Contents

1 Chapter 1. Introduction 1
1.1 Classical Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1
1.1.2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 3
1.1.3 Branches of description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 4
1.1.4 Thermodynamic equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 6
1.1.5 Non-equilibrium thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.6 Laws of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 7
1.1.7 System models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 8
1.1.8 States and processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 9
1.1.9 Instrumentation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 12
1.1.10 Conjugate variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.1.11 Potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.1.12 Axiomatics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 13
1.1.13 Scope of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 14
1.1.14 Applied fields . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.1.15 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.1.16 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 15
1.1.17 Cited bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 18
1.1.18 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 19
1.1.19 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.2 Statistical Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.2.1 Principles: mechanics and ensembles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 20
1.2.2 Statistical thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 21
1.2.3 Non-equilibrium statistical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 23
1.2.4 Applications outside thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.2.5 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 24
1.2.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.2.7 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25

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1.2.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 25
1.2.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.3 Chemical Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.3.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 26
1.3.2 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3.3 Chemical energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3.4 Chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 27
1.3.5 Non equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 29
1.3.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.3.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.3.8 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.3.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.4 Equilibrium Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 30
1.4.1 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.4.2 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.5 Non-equilibrium Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 31
1.5.1 Scope of non-equilibrium thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.5.2 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 32
1.5.3 Basic concepts . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 33
1.5.4 Stationary states, fluctuations, and stability . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.5.5 Local thermodynamic equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 34
1.5.6 Entropy in evolving systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.5.7 Flows and forces . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 35
1.5.8 The Onsager relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.5.9 Speculated extremal principles for non-equilibrium processes . . . . . . . . . . . . . . . . . . 36
1.5.10 Applications of non-equilibrium thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . 36
1.5.11 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 36
1.5.12 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 37
1.5.13 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 38
1.5.14 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 39

2 Chapter 2. Laws of Thermodynamics 40

2.1 Zeroth law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.1.1 Zeroth law as equivalence relation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 40
2.1.2 Foundation of temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 41
2.1.3 Physical meaning of the usual statement of the zeroth law . . . . . . . . . . . . . . . . . . . . 41
2.1.4 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.1.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 42
2.1.6 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
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2.2 First law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43

2.2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 43
2.2.2 Conceptually revised statement, according to the mechanical approach . . . . . . . . . . . . . 45
2.2.3 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 45
2.2.4 Various statements of the law for closed systems . . . . . . . . . . . . . . . . . . . . . . . . . 46
2.2.5 Evidence for the first law of thermodynamics for closed systems . . . . . . . . . . . . . . . . . 48
2.2.6 State functional formulation for infinitesimal processes . . . . . . . . . . . . . . . . . . . . . . 51
2.2.7 Spatially inhomogeneous systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.8 First law of thermodynamics for open systems . . . . . . . . . . . . . . . . . . . . . . . . . . 52
2.2.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 56
2.2.11 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 59
2.2.12 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.3 Second law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 60
2.3.2 Various statements of the law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 61
2.3.3 Corollaries . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 64
2.3.4 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 66
2.3.5 Statistical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.3.6 Derivation from statistical mechanics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 68
2.3.7 Living organisms . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.3.8 Gravitational systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 70
2.3.9 Non-equilibrium states . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.3.10 Arrow of time . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.3.11 Irreversibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 71
2.3.12 Quotations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 72
2.3.13 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.3.14 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 73
2.3.15 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.3.16 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.4 Third law of Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 78
2.4.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.4.2 Explanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 79
2.4.3 Mathematical formulation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 80
2.4.4 Consequences of the third law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 81
2.4.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.4.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
2.4.7 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 82
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3 Chapter 3. History 83
3.1 History of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 83
3.1.2 Branches of . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 87
3.1.3 Entropy and the second law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.1.4 Heat transfer . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.1.5 Cryogenics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.1.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 88
3.1.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.1.8 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.1.9 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.2 An Experimental Enquiry Concerning the Source of the Heat which is Excited by Friction . . . . . . . 89
3.2.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 89
3.2.2 Experiments . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.3 Reception . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.4 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 90
3.2.5 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 91

4 Chapter 4. System State 92

4.1 Control volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.1.2 Substantive derivative . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 92
4.1.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.1.4 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.1.5 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2 Ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2.1 Types of ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 93
4.2.2 Classical thermodynamic ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 94
4.2.3 Heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.2.4 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 95
4.2.5 Thermodynamic potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.2.6 Speed of sound . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 96
4.2.7 Table of ideal gas equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.2.8 Ideal quantum gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.2.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.3 Real gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 97
4.3.1 Models . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 98
4.3.2 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
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4.3.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 99
4.3.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 100

5 Chapter 5. System Processes 101

5.1 Thermodynamic process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.1.1 Kinds of process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 101
5.1.2 A cycle of quasi-static processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.1.3 Conjugate variable processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 102
5.1.4 Thermodynamic potentials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.1.5 Polytropic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 103
5.1.6 Processes classified by the second law of thermodynamics . . . . . . . . . . . . . . . . . . . . 103
5.1.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5.1.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5.1.9 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5.2 Isobaric process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 104
5.2.1 Specific heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
5.2.2 Sign convention for work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 105
5.2.3 Defining enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.2.4 Variable density viewpoint . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.2.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.2.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.3 Isochoric process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.3.1 Formalism . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 106
5.3.2 Ideal Otto cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.3.3 Etymology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.3.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.3.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.3.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 107
5.4 Isothermal process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.4.1 Examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.4.2 Details for an ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.4.3 Calculation of work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 108
5.4.4 Entropy changes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 109
5.4.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.4.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.5 Adiabatic process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.5.1 Description . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 110
5.5.2 Adiabatic heating and cooling . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 111
5.5.3 Ideal gas (reversible process) . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 112
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5.5.4 Graphing adiabats . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 115

5.5.5 Etymology . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.5.6 Conceptual significance in thermodynamic theory . . . . . . . . . . . . . . . . . . . . . . . . 116
5.5.7 Divergent usages of the word adiabatic . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 116
5.5.8 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.5.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 117
5.5.10 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.6 Isenthalpic process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.6.1 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.6.2 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.7 Isentropic process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 118
5.7.1 Background . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.7.2 Isentropic processes in thermodynamic systems . . . . . . . . . . . . . . . . . . . . . . . . . 119
5.7.3 Isentropic flow . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 120
5.7.4 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.7.5 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.7.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 121
5.8 Polytropic process . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.8.1 Derivation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 122
5.8.2 Applicability . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.3 Polytropic Specific Heat Capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.4 Relationship to ideal processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.5 Notation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.6 Other . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.7 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 123
5.8.8 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 124

6 Chapter 6. System Properties 125

6.1 Introduction to entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
6.1.1 Explanation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 125
6.1.2 Example of increasing entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
6.1.3 Origins and uses . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
6.1.4 Heat and entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 127
6.1.5 Introductory descriptions of entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.1.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.1.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.1.8 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.2 Entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 129
6.2.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130
CONTENTS vii

6.2.2 Definitions and descriptions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 130

6.2.3 Second law of thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
6.2.4 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 135
6.2.5 Entropy change formulas for simple processes . . . . . . . . . . . . . . . . . . . . . . . . . . 137
6.2.6 Approaches to understanding entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 138
6.2.7 Interdisciplinary applications of entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 140
6.2.8 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 141
6.2.9 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
6.2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 142
6.2.11 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 144
6.2.12 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
6.3 Pressure . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 145
6.3.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 146
6.3.2 Types . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 149
6.3.3 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 152
6.3.4 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.3.5 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.3.6 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.4 Thermodynamic temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 153
6.4.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 154
6.4.2 The relationship of temperature, motions, conduction, and thermal energy . . . . . . . . . . . 154
6.4.3 Practical applications for thermodynamic temperature . . . . . . . . . . . . . . . . . . . . . . 160
6.4.4 Definition of thermodynamic temperature . . . . . . . . . . . . . . . . . . . . . . . . . . . . 160
6.4.5 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 162
6.4.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 166
6.4.7 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 167
6.4.8 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
6.5 Volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 171
6.5.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.5.2 Heat and work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.5.3 Specific volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 172
6.5.4 Gas volume . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 173
6.5.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174
6.5.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 174

7 Chapter 7 175
7.1 Thermodynamic system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7.1.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 175
7.1.2 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176
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7.1.3 Systems in equilibrium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 176

7.1.4 Walls . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
7.1.5 Surroundings . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
7.1.6 Closed system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 177
7.1.7 Isolated system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 178
7.1.8 Selective transfer of matter . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7.1.9 Open system . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7.1.10 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179
7.1.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 179

8 Chapter 8. Material Properties 181

8.1 Heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
8.1.1 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
8.1.2 Units . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 181
8.1.3 Measurement of heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 182
8.1.4 Theory of heat capacity . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 186
8.1.5 Table of specific heat capacities . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
8.1.6 Mass heat capacity of building materials . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
8.1.7 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 194
8.1.8 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.1.9 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.1.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 195
8.1.11 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
8.2 Compressibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
8.2.1 Definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 196
8.2.2 Thermodynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 197
8.2.3 Earth science . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
8.2.4 Fluid dynamics . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
8.2.5 Negative compressibility . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
8.2.6 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
8.2.7 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 198
8.3 Thermal expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8.3.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8.3.2 Coefficient of thermal expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 199
8.3.3 Expansion in solids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 200
8.3.4 Isobaric expansion in gases . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
8.3.5 Expansion in liquids . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
8.3.6 Expansion in mixtures and alloys . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 202
8.3.7 Apparent and absolute expansion . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203
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8.3.8 Examples and applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 203

8.3.9 Thermal expansion coefficients for various materials . . . . . . . . . . . . . . . . . . . . . . . 204
8.3.10 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.3.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 205
8.3.12 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 206

9 Chapter 9. Potentials 207

9.1 Thermodynamic potential . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
9.1.1 Description and interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 207
9.1.2 Natural variables . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
9.1.3 The fundamental equations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 208
9.1.4 The equations of state . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
9.1.5 The Maxwell relations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 209
9.1.6 Euler integrals . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.7 The Gibbs–Duhem relation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.8 Chemical reactions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 210
9.1.10 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.1.11 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.1.12 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.1.13 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.2 Enthalpy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 211
9.2.1 Origins . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
9.2.2 Formal definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 212
9.2.3 Other expressions . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2.4 Physical interpretation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2.5 Relationship to heat . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2.6 Applications . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 213
9.2.7 Diagrams . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 216
9.2.8 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
9.2.9 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
9.2.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
9.2.11 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 218
9.2.12 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
9.3 Internal energy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
9.3.1 Introduction . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 219
9.3.2 Description and definition . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 220
9.3.3 Internal energy of the ideal gas . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 221
9.3.4 Internal energy of a closed thermodynamic system . . . . . . . . . . . . . . . . . . . . . . . . 222
x CONTENTS

9.3.5 Internal energy of multi-component systems . . . . . . . . . . . . . . . . . . . . . . . . . . . 223

9.3.6 Internal energy in an elastic medium . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
9.3.7 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 224
9.3.8 Notes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
9.3.9 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
9.3.10 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225
9.3.11 Bibliography . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 225

10 Chapter 10. Equations 226

10.1 Ideal gas law . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
10.1.1 Equation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 226
10.1.2 Applications to thermodynamic processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . 227
10.1.3 Deviations from ideal behavior of real gases . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
10.1.4 Derivations . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 228
10.1.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.1.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.1.7 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229
10.1.8 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 229

11 Chapter 11. Fundamentals 230

11.1 Fundamental thermodynamic relation . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 230
11.1.1 Derivation from the first and second laws of thermodynamics . . . . . . . . . . . . . . . . . . 230
11.1.2 Derivation from statistical mechanical principles . . . . . . . . . . . . . . . . . . . . . . . . . 231
11.1.3 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
11.1.4 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
11.2 Heat engine . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 232
11.2.1 Overview . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
11.2.2 Everyday examples . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
11.2.3 Examples of heat engines . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 233
11.2.4 Efficiency . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 235
11.2.5 History . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
11.2.6 Heat engine enhancements . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
11.2.7 Heat engine processes . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 236
11.2.8 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
11.2.9 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
11.3 Thermodynamic cycle . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 237
11.3.1 Heat and work . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 238
11.3.2 Modelling real systems . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
11.3.3 Well-known thermodynamic cycles . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 240
CONTENTS xi

11.3.4 State functions and entropy . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 241

11.3.5 See also . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
11.3.6 References . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
11.3.7 Further reading . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242
11.3.8 External links . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 242

12 Text and image sources, contributors, and licenses 243

12.1 Text . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 243
12.2 Images . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 253
12.3 Content license . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 257
Chapter 1

Chapter 1. Introduction

1.1 Classical Thermodynamics Its laws are explained by statistical mechanics, in terms of
the microscopic constituents.
Thermodynamics applies to a wide variety of topics in
science and engineering, especially physical chemistry,
chemical engineering and mechanical engineering.
Historically, the distinction between heat and temperature
was studied in the 1750s by Joseph Black. Characteristi-
cally thermodynamic thinking began in the work of Carnot
(1824) who believed that the efficiency of heat engines was
the key that could help France win the Napoleonic Wars.[1]
The Irish-born British physicist Lord Kelvin was the first
to formulate a concise definition of thermodynamics in
1854:[2]

Thermo-dynamics is the subject of the rela-

tion of heat to forces acting between contiguous
parts of bodies, and the relation of heat to elec-
trical agency.

Initially, thermodynamics, as applied to heat engines, was

concerned with the thermal properties of their 'working ma-
terials’, such as steam, in an effort to increase the efficiency
Annotated color version of the original 1824 Carnot heat engine and power output of engines. Thermodynamics was later
showing the hot body (boiler), working body (system, steam), and expanded to the study of energy transfers in chemical pro-
cold body (water), the letter-labels indicate the stopping points in cesses, such as the investigation, published in 1840, of the
Carnot cycle heats of chemical reactions[3] by Germain Hess, which was
not originally explicitly concerned with the relation between
Thermodynamics is a branch of physics concerned with energy exchanges by heat and work. From this evolved the
heat and temperature and their relation to energy and work. study of chemical thermodynamics and the role of entropy
It defines macroscopic variables, such as internal energy, in chemical reactions.[4][5][6][7][8][9][10][11]
entropy, and pressure, that partly describe a body of matter
or radiation. It states that the behavior of those variables is
subject to general constraints, that are common to all mate- 1.1.1 Introduction
rials, beyond the peculiar properties of particular materials.
These general constraints are expressed in the four laws of Historically, thermodynamics arose from the study of two
thermodynamics. Thermodynamics describes the bulk be- distinct kinds of transfer of energy, as heat and as work,
havior of the body, not the microscopic behaviors of the and the relation of those to the system’s macroscopic vari-
very large numbers of its microscopic constituents, such as ables of volume, pressure and temperature.[12][13] As it de-
molecules. The basic results of thermodynamics rely on the veloped, thermodynamics began also to study transfers of
existence of idealized states of thermodynamic equilibrium. matter.

1
2 CHAPTER 1. CHAPTER 1. INTRODUCTION

The plain term 'thermodynamics’ refers to a macro- empirical work in physics and chemistry.[9] Always associ-
scopic description of bodies and processes.[14] Ref- ated with the material that constitutes a system, its working
erence to atomic constitution is foreign to classical substance, are the walls that delimit the system, and connect
thermodynamics.[15] Usually the plain term 'thermodynam- it with its surroundings. The state variables chosen for the
ics’ refers by default to equilibrium as opposed to non- system should be appropriate for the natures of the walls
equilibrium thermodynamics. The qualified term 'statistical and surroundings.[24]
thermodynamics’ refers to descriptions of bodies and pro- A thermodynamic operation is an artificial physical manip-
cesses in terms of the atomic or other microscopic constitu- ulation that changes the definition of a system or its sur-
tion of matter, using statistical and probabilistic reasoning.
roundings. Usually it is a change of the permeability of a
Thermodynamic equilibrium is one of the most important wall of the system,[25] that allows energy (as heat or work) or
concepts for thermodynamics.[16][17] The temperature of a matter (mass) to be exchanged with the environment. For
thermodynamic system is well defined, and is perhaps the example, the partition between two thermodynamic sys-
most characteristic quantity of thermodynamics. As the tems can be removed so as to produce a single system. A
systems and processes of interest are taken further from thermodynamic operation that increases the range of pos-
thermodynamic equilibrium, their exact thermodynamical sible transfers usually leads to a thermodynamic process of
study becomes more difficult. Relatively simple approxi- transfer of mass or energy that changes the state of the sys-
mate calculations, however, using the variables of equilib- tem, and the transfer occurs in natural accord with the laws
rium thermodynamics, are of much practical value. Many of thermodynamics. But if the operation simply reduces the
important practical engineering cases, as in heat engines or possible range of transfers, in general it does not initiate a
refrigerators, can be approximated as systems consisting of process. The states of the system’s surrounding systems are
many subsystems at different temperatures and pressures. assumed to be unchanging in time except when they are
If a physical process is too fast, the equilibrium thermody- changed by a thermodynamic operation, whereupon a ther-
namic variables, for example temperature, may not be well modynamic process can be initiated.
enough defined to provide a useful approximation. A thermodynamic system can also be defined in terms of
Central to thermodynamic analysis are the definitions of the the cyclic processes that it can undergo.[26] A cyclic pro-
system, which is of interest, and of its surroundings.[8][18] cess is a cyclic sequence of thermodynamic operations and
The surroundings of a thermodynamic system consist of processes that can be repeated indefinitely often without
physical devices and of other thermodynamic systems that changing the final state of the system.
can interact with it. An example of a thermodynamic sur- For thermodynamics and statistical thermodynamics to
rounding is a heat bath, which is held at a prescribed tem- apply to a physical system, it is necessary that its inter-
perature, regardless of how much heat might be drawn from nal atomic mechanisms fall into one of two classes:
it.
There are four fundamental kinds of physical entities • those so rapid that, in the time frame of the process of
in thermodynamics: interest, the atomic states rapidly bring system to its
own state of internal thermodynamic equilibrium; and
• states of a system, and the states of its surrounding • those so slow that, in the time frame of the process of
systems interest, they leave the system unchanged.[27][28]
• walls of a system,[19][20][21][22][23]
The rapid atomic mechanisms account for the internal
• thermodynamic processes of a system, and energy of the system. They mediate the macroscopic
changes that are of interest for thermodynamics and statisti-
• thermodynamic operations. cal thermodynamics, because they quickly bring the system
near enough to thermodynamic equilibrium. “When inter-
This allows two fundamental approaches to thermodynamic mediate rates are present, thermodynamics and statistical
reasoning, that in terms of states of a system, and that in mechanics cannot be applied.”[27] Such intermediate rate
terms of cyclic processes of a system. atomic processes do not bring the system near enough to
A thermodynamic system can be defined in terms of thermodynamic equilibrium in the time frame of the macro-
its states.[17] In this way, a thermodynamic system is a scopic process of interest. This separation of time scales of
macroscopic physical object, explicitly specified in terms of atomic processes is a theme that recurs throughout the sub-
macroscopic physical and chemical variables that describe ject.
its macroscopic properties. The macroscopic state variables For example, classical thermodynamics is characterized by
of thermodynamics have been recognized in the course of its study of materials that have equations of state or char-
1.1. CLASSICAL THERMODYNAMICS
acteristic equations. They express equilibrium relations be-
tween macroscopic mechanical variables and temperature
and internal energy. They express the constitutive pecu-
liarities of the material of the system. A classical material
can usually be described by a function that makes pressure
dependent on volume and temperature, the resulting pres-
sure being established much more rapidly than any imposed
change of volume or temperature.[29][30][31][32]
The present article takes a gradual approach to the sub-
ject, starting with a focus on cyclic processes and thermody-
namic equilibrium, and then gradually beginning to further
consider non-equilibrium systems.
Thermodynamic facts can often be explained by viewing
macroscopic objects as assemblies of very many micro-
scopic or atomic objects that obey Hamiltonian dynam-
ics.[8][33][34] The microscopic or atomic objects exist in
species, the objects of each species being all alike. Because
of this likeness, statistical methods can be used to account
for the macroscopic properties of the thermodynamic sys-
tem in terms of the properties of the microscopic species.
Such explanation is called statistical thermodynamics; also
often it is referred to by the term 'statistical mechanics',
though this term can have a wider meaning, referring to 'mi-
croscopic objects’, such as economic quantities, that do not
obey Hamiltonian dynamics.[33]
1.1.2 History
The history of thermodynamics as a scientific discipline
generally begins with Otto von Guericke who, in about
1650,[35] built and designed the world’s first vacuum pump
and demonstrated a vacuum using his Magdeburg hemi-
spheres. Guericke was driven to make a vacuum in or-
der to disprove Aristotle's long-held supposition that 'na-
ture abhors a vacuum'. Shortly after Guericke, the physi-
cist and chemist Robert Boyle had learned of Guericke’s de-
signs and, in 1656, in coordination with the scientist Robert
Hooke, built an air pump.[36] Using this pump, Boyle and
Hooke noticed a correlation between pressure, temperature,
and volume. In time, they formulated Boyle’s Law, which
states that for a gas at constant temperature, its pressure
and volume are inversely proportional. In 1679, based on
these concepts, an associate of Boyle’s named Denis Pa-
pin built a steam digester, which was a closed vessel with
a tightly fitting lid that confined steam until a high pres-
sure was generated. Later versions of this design imple-
mented a steam release valve that kept the machine from
exploding. By watching the valve rhythmically move up
and down, Papin conceived of the idea of a piston and a
cylinder engine. He did not, however, follow through with
his design. Nevertheless, in 1697, based on Papin’s designs,
the engineer Thomas Savery built the first engine, followed
3
The thermodynamicists representative of the original eight found-
ing schools of thermodynamics. The schools with the most-lasting
effect in founding the modern versions of thermodynamics are the
Berlin school, particularly as established in Rudolf Clausius’s 1865
textbook The Mechanical Theory of Heat, the Vienna school, while
the statistical mechanics of Ludwig Boltzmann, and the Gibbsian
school at Yale University, led by the American engineer Willard
Gibbs' 1876 On the Equilibrium of Heterogeneous Substances
launched chemical thermodynamics.
by Thomas Newcomen in 1712. Although these early en-
gines were crude and inefficient, they attracted the attention
of the leading scientists of the time.
The concepts of heat capacity and latent heat, which were
necessary for development of thermodynamics, were devel-
oped by Professor Joseph Black at the University of Glas-
gow, where James Watt worked as an instrument maker.
Watt consulted with Black on tests of his steam engine, but
it was Watt who conceived the idea of the external con-
denser, greatly raising the steam engine's efficiency.[37] All
the previous work led Sadi Carnot, the “father of thermody-
namics”, to publish Reflections on the Motive Power of Fire
(1824), a discourse on heat, power, energy, and engine ef-
ficiency. The paper outlined the basic energetic relations
between the Carnot engine, the Carnot cycle, and motive
power. It marked the start of thermodynamics as a modern
science.[11]
The first thermodynamic textbook was written in 1859 by
William Rankine, originally trained as a physicist and a pro-
fessor of civil and mechanical engineering at the University
of Glasgow.[38] The first and second laws of thermody-
namics emerged simultaneously in the 1850s, primarily out
of the works of William Rankine, Rudolf Clausius, and
William Thomson (Lord Kelvin).
The foundations of statistical thermodynamics were set out
by physicists such as James Clerk Maxwell, Ludwig Boltz-
4 CHAPTER 1. CHAPTER 1. INTRODUCTION

mann, Max Planck, Rudolf Clausius and J. Willard Gibbs. engine in reference to Thomson’s 1849 phraseology,[42]:545
From 1873 to '76, the American mathematical physicist and Thomson’s note on Joules’ 1851 paper On the Air-
Josiah Willard Gibbs published a series of three papers, Engine.
the most famous being "On the equilibrium of heteroge- In 1854, thermo-dynamics, as a functional term to denote
neous substances".[4] Gibbs showed how thermodynamic the general study of the action of heat, was first used by
processes, including chemical reactions, could be graphi- William Thomson in his paper “On the Dynamical Theory
cally analyzed. By studying the energy, entropy, volume, of Heat”.[2]
chemical potential, temperature and pressure of the In 1859, the closed compound form thermodynamics was
thermodynamic system, one can determine whether a pro- first used by William Rankine in A Manual of the Steam En-
cess would occur spontaneously.[39] Chemical thermody- gine in a chapter on the Principles of Thermodynamics.[43]
namics was further developed by Pierre Duhem,[5] Gilbert
N. Lewis, Merle Randall,[6] and E. A. Guggenheim,[7][8]
who applied the mathematical methods of Gibbs. 1.1.3 Branches of description

Thermodynamic systems are theoretical constructions used

to model physical systems that exchange matter and en-
ergy in terms of the laws of thermodynamics. The study
of thermodynamical systems has developed into several re-
lated branches, each using a different fundamental model
as a theoretical or experimental basis, or applying the prin-
ciples to varying types of systems.

Classical thermodynamics

Classical thermodynamics accounts for the adventures of a

thermodynamic system in terms, either of its time-invariant
equilibrium states, or else of its continually repeated cyclic
The lifetimes of some of the most important contributors to thermo-
processes, but, formally, not both in the same account.
dynamics
It uses only time-invariant, or equilibrium, macroscopic
quantities measurable in the laboratory, counting as time-
invariant a long-term time-average of a quantity, such as
Etymology a flow, generated by a continually repetitive process.[44][45]
In classical thermodynamics, rates of change are not ad-
The etymology of thermodynamics has an intricate history. mitted as variables of interest. An equilibrium state stands
It was first spelled in a hyphenated form as an adjective endlessly without change over time, while a continually re-
(thermo-dynamic) in 1849 and from 1854 to 1859 as the peated cyclic process runs endlessly without a net change in
hyphenated noun thermo-dynamics to represent the science the system over time.
of heat and motive power and thereafter as thermodynamics.
In the account in terms of equilibrium states of a system, a
The components of the word thermo-dynamic are derived state of thermodynamic equilibrium in a simple system is
from the Greek words θέρμη therme, meaning “heat,” and spatially homogeneous.
δύναμις dynamis, meaning “power” (Haynie claims that the
word was coined around 1840).[40][41] In the classical account solely in terms of a cyclic process,
the spatial interior of the 'working body' of that process is
The term thermo-dynamic was first used in January 1849 not considered; the 'working body' thus does not have a de-
by William Thomson, later Lord Kelvin, in the phrase a per- fined internal thermodynamic state of its own because no as-
fect thermo-dynamic engine to describe Sadi Carnot’s heat sumption is made that it should be in thermodynamic equi-
engine.[42]:545 In April 1849, Thomson added an appendix librium; only its inputs and outputs of energy as heat and
to his paper and used the term thermodynamic in the phrase work are considered.[46] It is common to describe a cycle
the object of a thermodynamic engine.[42]:569 theoretically as composed of a sequence of very many ther-
Pierre Perrot claims that the term thermodynamics was modynamic operations and processes. This creates a link to
coined by James Joule in 1858 to designate the science of the description in terms of equilibrium states. The cycle is
relations between heat and power.[11] Joule, however, never then theoretically described as a continuous progression of
used that term, but did use the term perfect thermo-dynamic equilibrium states.
1.1. CLASSICAL THERMODYNAMICS
Classical thermodynamics was originally concerned with
the transformation of energy in a cyclic process, and the
exchange of energy between closed systems defined only by
their equilibrium states. The distinction between transfers
of energy as heat and as work was central.
As classical thermodynamics developed, the distinction be-
tween heat and work became less central. This was because
there was more interest in open systems, for which the dis-
tinction between heat and work is not simple, and is be-
yond the scope of the present article. Alongside the amount
of heat transferred as a fundamental quantity, entropy was
gradually found to be a more generally applicable concept,
especially when considering chemical reactions. Massieu in
1869 considered entropy as the basic dependent thermody-
namic variable, with energy potentials and the reciprocal of
the thermodynamic temperature as fundamental indepen-
dent variables. Massieu functions can be useful in present-
day non-equilibrium thermodynamics. In 1875, in the work
of Josiah Willard Gibbs, entropy was considered a funda-
mental independent variable, while internal energy was a
dependent variable.[47]
All actual physical processes are to some degree irre-
versible. Classical thermodynamics can consider irre-
versible processes, but its account in exact terms is re-
stricted to variables that refer only to initial and final states
of thermodynamic equilibrium, or to rates of input and out-
put that do not change with time. For example, classical
thermodynamics can consider time-average rates of flows
generated by continually repeated irreversible cyclic pro-
cesses. Also it can consider irreversible changes between
equilibrium states of systems consisting of several phases
(as defined below in this article), or with removable or re-
placeable partitions. But for systems that are described in
terms of equilibrium states, it considers neither flows, nor
spatial inhomogeneities in simple systems with no exter-
nally imposed force fields such as gravity. In the account in
terms of equilibrium states of a system, descriptions of ir-
reversible processes refer only to initial and final static equi-
librium states; the time it takes to change thermodynamic
state is not considered.[48][49]
Local equilibrium thermodynamics
Local equilibrium thermodynamics is concerned with the
time courses and rates of progress of irreversible processes
in systems that are smoothly spatially inhomogeneous. It
admits time as a fundamental quantity, but only in a re-
stricted way. Rather than considering time-invariant flows
as long-term-average rates of cyclic processes, local equilib-
rium thermodynamics considers time-varying flows in sys-
tems that are described by states of local thermodynamic For generalized or extended thermodynamics, the defini-
equilibrium, as follows. tion of the quantity known as the entropy of a small local
5
For processes that involve only suitably small and smooth
spatial inhomogeneities and suitably small changes with
time, a good approximation can be found through the as-
sumption of local thermodynamic equilibrium. Within the
large or global region of a process, for a suitably small local
region, this approximation assumes that a quantity known
as the entropy of the small local region can be defined in a
particular way. That particular way of definition of entropy
is largely beyond the scope of the present article, but here it
may be said that it is entirely derived from the concepts of
classical thermodynamics; in particular, neither flow rates
nor changes over time are admitted into the definition of
the entropy of the small local region. It is assumed with-
out proof that the instantaneous global entropy of a non-
equilibrium system can be found by adding up the simulta-
neous instantaneous entropies of its constituent small local
regions. Local equilibrium thermodynamics considers pro-
cesses that involve the time-dependent production of en-
tropy by dissipative processes, in which kinetic energy of
bulk flow and chemical potential energy are converted into
internal energy at time-rates that are explicitly accounted
for. Time-varying bulk flows and specific diffusional flows
are considered, but they are required to be dependent vari-
ables, derived only from material properties described only
by static macroscopic equilibrium states of small local re-
gions. The independent state variables of a small local re-
gion are only those of classical thermodynamics.
Generalized or extended thermodynamics
Like local equilibrium thermodynamics, generalized or ex-
tended thermodynamics also is concerned with the time
courses and rates of progress of irreversible processes in
systems that are smoothly spatially inhomogeneous. It de-
scribes time-varying flows in terms of states of suitably
small local regions within a global region that is smoothly
spatially inhomogeneous, rather than considering flows as
time-invariant long-term-average rates of cyclic processes.
In its accounts of processes, generalized or extended ther-
modynamics admits time as a fundamental quantity in a
more far-reaching way than does local equilibrium thermo-
dynamics. The states of small local regions are defined by
macroscopic quantities that are explicitly allowed to vary
with time, including time-varying flows. Generalized ther-
modynamics might tackle such problems as ultrasound or
shock waves, in which there are strong spatial inhomo-
geneities and changes in time fast enough to outpace a ten-
dency towards local thermodynamic equilibrium. General-
ized or extended thermodynamics is a diverse and develop-
ing project, rather than a more or less completed subject
such as is classical thermodynamics.[50][51]
6 CHAPTER 1. CHAPTER 1. INTRODUCTION

region is in terms beyond those of classical thermodynam- equilibrium. In thermodynamic equilibrium, a system’s
ics; in particular, flow rates are admitted into the definition properties are, by definition, unchanging in time. In ther-
of the entropy of a small local region. The independent state modynamic equilibrium no macroscopic change is occur-
variables of a small local region include flow rates, which ring or can be triggered; within the system, every micro-
are not admitted as independent variables for the small lo- scopic process is balanced by its opposite; this is called the
cal regions of local equilibrium thermodynamics. principle of detailed balance. A central aim in equilibrium
Outside the range of classical thermodynamics, the def- thermodynamics is: given a system in a well-defined initial
inition of the entropy of a small local region is no sim- state, subject to specified constraints, to calculate what the
equilibrium state of the system is.[53]
ple matter. For a thermodynamic account of a process in
terms of the entropies of small local regions, the defini- In theoretical studies, it is often convenient to consider the
tion of entropy should be such as to ensure that the second simplest kind of thermodynamic system. This is defined
law of thermodynamics applies in each small local region. variously by different authors.[48][54][55][56][57][58] For the
It is often assumed without proof that the instantaneous present article, the following definition is convenient, as
global entropy of a non-equilibrium system can be found abstracted from the definitions of various authors. A re-
by adding up the simultaneous instantaneous entropies of gion of material with all intensive properties continuous in
its constituent small local regions. For a given physical space and time is called a phase. A simple system is for the
process, the selection of suitable independent local non- present article defined as one that consists of a single phase
equilibrium macroscopic state variables for the construc- of a pure chemical substance, with no interior partitions.
tion of a thermodynamic description calls for qualitative Within a simple isolated thermodynamic system in thermo-
physical understanding, rather than being a simply math- dynamic equilibrium, in the absence of externally imposed
ematical problem concerned with a uniquely determined force fields, all properties of the material of the system are
thermodynamic description. A suitable definition of the spatially homogeneous.[59] Much of the basic theory of ther-
entropy of a small local region depends on the physically modynamics is concerned with homogeneous systems in
insightful and judicious selection of the independent local thermodynamic equilibrium.[4][60]
non-equilibrium macroscopic state variables, and different
selections provide different generalized or extended ther- Most systems found in nature or considered in engineer-
modynamical accounts of one and the same given physical ing are not in thermodynamic equilibrium, exactly consid-
process. This is one of the several good reasons for con- ered. They are changing or can be triggered to change over
sidering entropy as an epistemic physical variable, rather time, and are continuously and discontinuously subject to
[22]
than as a simply material quantity. According to a respected flux of matter and energy to and from other systems.
author: “There is no compelling reason to believe that the For example, according to Callen, “in absolute thermody-
classical thermodynamic entropy is a measurable property namic equilibrium all radioactive materials would have de-
of nonequilibrium phenomena, ...”[52] cayed completely and nuclear reactions would have trans-
muted all nuclei to the most stable isotopes. Such processes,
which would take cosmic times to complete, generally can
Statistical thermodynamics be ignored.”.[22] Such processes being ignored, many sys-
tems in nature are close enough to thermodynamic equilib-
Statistical thermodynamics, also called statistical mechan- rium that for many purposes their behaviour can be well
ics, emerged with the development of atomic and molecu- approximated by equilibrium calculations.
lar theories in the second half of the 19th century and early
20th century. It provides an explanation of classical ther-
modynamics. It considers the microscopic interactions be-
tween individual particles and their collective motions, in
terms of classical or of quantum mechanics. Its explana- Quasi-static transfers between simple systems are
tion is in terms of statistics that rest on the fact the sys- nearly in thermodynamic equilibrium and are re-
tem is composed of several species of particles or collective versible
motions, the members of each species respectively being in
some sense all alike. It very much eases and simplifies theoretical thermodynam-
ical studies to imagine transfers of energy and matter be-
tween two simple systems that proceed so slowly that at
1.1.4 Thermodynamic equilibrium all times each simple system considered separately is near
enough to thermodynamic equilibrium. Such processes are
Equilibrium thermodynamics studies transformations of sometimes called quasi-static and are near enough to being
matter and energy in systems at or near thermodynamic reversible.[61][62]
1.1. CLASSICAL THERMODYNAMICS 7

Natural processes are partly described by tendency to- bringing them into contact and measuring any changes of
wards thermodynamic equilibrium and are irreversible their observable properties in time.[65] In traditional state-
ments, the law provides an empirical definition of temper-
If not initially in thermodynamic equilibrium, simple iso- ature and justification for the construction of practical ther-
lated thermodynamic systems, as time passes, tend to evolve mometers. In contrast to absolute thermodynamic tempera-
naturally towards thermodynamic equilibrium. In the ab- tures, empirical temperatures are measured just by the me-
sence of externally imposed force fields, they become ho- chanical properties of bodies, such as their volumes, with-
mogeneous in all their local properties. Such homogene- out reliance on the concepts of energy, entropy or the first,
ity is an important characteristic of a system in thermo- second, or third laws of thermodynamics.[56][66] Empirical
dynamic equilibrium in the absence of externally imposed temperatures lead to calorimetry for heat transfer in terms
force fields. of the mechanical properties of bodies, without reliance on
mechanical concepts of energy.
Many thermodynamic processes can be modeled by com-
pound or composite systems, consisting of several or many The physical content of the zeroth law has long been rec-
contiguous component simple systems, initially not in ther- ognized. For example, Rankine in 1853 defined temper-
modynamic equilibrium, but allowed to transfer mass and ature as follows: “Two portions of matter are said to have
energy between them. Natural thermodynamic processes equal temperatures when neither tends to communicate heat
are described in terms of a tendency towards thermody- to the other.”[67] Maxwell in 1872 stated a “Law of Equal
namic equilibrium within simple systems and in transfers Temperatures”.[68] He also stated: “All Heat is of the same
between contiguous simple systems. Such natural processes kind.”[69] Planck explicitly assumed and stated it in its cus-
are irreversible.[63] tomary present-day wording in his formulation of the first
two laws.[70] By the time the desire arose to number it as
a law, the other three had already been assigned numbers,
1.1.5 Non-equilibrium thermodynamics and so it was designated the zeroth law.

Non-equilibrium thermodynamics[64] is a branch of ther-
modynamics that deals with systems that are not in
thermodynamic equilibrium; it is also called thermodynam-
ics of irreversible processes.
1.1.6 Laws of thermodynamics
• First law of thermodynamics: The increase in internal
energy of a closed system is equal to the difference of
the heat supplied to the system and the work done by the
system: ΔU = Q − W [71][72][73][74][75][76][77][78][79][80]
(Note that due to the ambiguity of what constitutes
positive work, some sources state that ΔU = Q + W,
in which case work done on the system is positive.)

Main article: Laws of thermodynamics The first law of thermodynamics asserts the existence of
a state variable for a system, the internal energy, and tells
how it changes in thermodynamic processes. The law al-
Thermodynamics states a set of four laws that are valid for
lows a given internal energy of a system to be reached by
all systems that fall within the constraints implied by each.
any combination of heat and work. It is important that
In the various theoretical descriptions of thermodynamics
internal energy is a variable of state of the system (see
these laws may be expressed in seemingly differing forms,
Thermodynamic state) whereas heat and work are variables
but the most prominent formulations are the following:
that describe processes or changes of the state of systems.
The first law observes that the internal energy of an iso-
• Zeroth law of thermodynamics: If two systems are
lated system obeys the principle of conservation of en-
each in thermal equilibrium with a third, they are also
ergy, which states that energy can be transformed (changed
in thermal equilibrium with each other.
from one form to another), but cannot be created or
destroyed.[81][82][83][84][85]
This statement implies that thermal equilibrium is an
equivalence relation on the set of thermodynamic systems • Second law of thermodynamics: Heat cannot sponta-
under consideration. Systems are said to be in thermal equi- neously flow from a colder location to a hotter location.
librium with each other if spontaneous molecular thermal
energy exchanges between them do not lead to a net ex- The second law of thermodynamics is an expression of the
change of energy. This law is tacitly assumed in every mea- universal principle of dissipation of kinetic and potential
surement of temperature. For two bodies known to be at the energy observable in nature. The second law is an obser-
same temperature, deciding if they are in thermal equilib- vation of the fact that over time, differences in tempera-
rium when put into thermal contact does not require actually ture, pressure, and chemical potential tend to even out in
8 CHAPTER 1. CHAPTER 1. INTRODUCTION

a physical system that is isolated from the outside world. under study. Everything in the universe except the system
Entropy is a measure of how much this process has pro- is known as the surroundings. A system is separated from
gressed. The entropy of an isolated system that is not in the remainder of the universe by a boundary, which may
equilibrium tends to increase over time, approaching a max- be actual, or merely notional and fictive, but by convention
imum value at equilibrium. delimits a finite volume. Transfers of work, heat, or matter
In classical thermodynamics, the second law is a basic pos- between the system and the surroundings take place across
tulate applicable to any system involving heat energy trans- this boundary, which may or may not have properties that
fer; in statistical thermodynamics, the second law is a con- restrict what can be transferred across it. A system may
have several distinct boundary sectors or partitions separat-
sequence of the assumed randomness of molecular chaos.
There are many versions of the second law, but they all ing it from the surroundings, each characterized by how it
restricts transfers, and being permeable to its characteristic
have the same effect, which is to explain the phenomenon
of irreversibility in nature. transferred quantities.
The volume can be the region surrounding a single atom res-
• Third law of thermodynamics: As a system approaches onating energy, as Max Planck defined in 1900; it can be a
absolute zero the entropy of the system approaches a body of steam or air in a steam engine, such as Sadi Carnot
minimum value. defined in 1824; it can be the body of a tropical cyclone, as
Kerry Emanuel theorized in 1986 in the field of atmospheric
The third law of thermodynamics is a statistical law of na- thermodynamics; it could also be just one nuclide (i.e. a
ture regarding entropy and the impossibility of reaching system of quarks) as hypothesized in quantum thermody-
absolute zero of temperature. This law provides an abso- namics.
lute reference point for the determination of entropy. The
entropy determined relative to this point is the absolute en- Anything that passes across the boundary needs to be ac-
tropy. Alternate definitions of the third law are, “the en- counted for in a proper transfer balance equation. Thermo-
tropy of all systems and of all states of a system is smallest dynamics is largely about such transfers.
at absolute zero,” or equivalently “it is impossible to reach Boundary sectors are of various characters: rigid, flexible,
the absolute zero of temperature by any finite number of fixed, moveable, actually restrictive, and fictive or not actu-
processes”. ally restrictive. For example, in an engine, a fixed bound-
Absolute zero is −273.15 °C (degrees Celsius), −459.67 °F ary sector means the piston is locked at its position; then
(degrees Fahrenheit), 0 K (kelvin), or 0 R (Rankine). no pressure-volume work is done across it. In that same
engine, a moveable boundary allows the piston to move in
and out, permitting pressure-volume work. There is no re-
1.1.7 System models strictive boundary sector for the whole earth including its
atmosphere, and so roughly speaking, no pressure-volume
work is done on or by the whole earth system. Such a sys-
tem is sometimes said to be diabatically heated or cooled
SURROUNDINGS by radiation.[86][87]
Thermodynamics distinguishes classes of systems by their
boundary sectors.

• An open system has a boundary sector that is per-

SYSTEM meable to matter; such a sector is usually permeable
also to energy, but the energy that passes cannot in
general be uniquely sorted into heat and work compo-
nents. Open system boundaries may be either actually
restrictive, or else non-restrictive.

• A closed system has no boundary sector that is perme-

BOUNDARY able to matter, but in general its boundary is permeable
to energy. For closed systems, boundaries are totally
A diagram of a generic thermodynamic system prohibitive of matter transfer.

The thermodynamic system is an important concept of ther- • An adiabatically isolated system has only adiabatic
modynamics. It is a precisely defined region of the universe boundary sectors. Energy can be transferred as work,
1.1. CLASSICAL THERMODYNAMICS 9

but transfers of matter and of energy as heat are pro- cannot be adequately accounted for in terms of equilibrium
hibited. states or classical cyclic processes.[93][94]
• A purely diathermically isolated system has only The notion of a cyclic process does not require a full ac-
boundary sectors permeable only to heat; it is some- count of the state of the system, but does require a full
times said to be adynamically isolated and closed to account of how the process occasions transfers of matter
matter transfer. A process in which no work is trans- and energy between the principal system (which is often
ferred is sometimes called adynamic.[88] called the working body) and its surroundings, which must
include at least two heat reservoirs at different known and
• An isolated system has only isolating boundary sec- fixed temperatures, one hotter than the principal system and
tors. Nothing can be transferred into or out of it. the other colder than it, as well as a reservoir that can re-
ceive energy from the system as work and can do work on
Engineering and natural processes are often described as the system. The reservoirs can alternatively be regarded as
composites of many different component simple systems, auxiliary idealized component systems, alongside the prin-
sometimes with unchanging or changing partitions be- cipal system. Thus an account in terms of cyclic processes
tween them. A change of partition is an example of a requires at least four contributory component systems. The
thermodynamic operation. independent variables of this account are the amounts of
energy that enter and leave the idealized auxiliary systems.
In this kind of account, the working body is often regarded
1.1.8 States and processes as a “black box”,[95] and its own state is not specified. In this
approach, the notion of a properly numerical scale of em-
There are four fundamental kinds of entity in pirical temperature is a presupposition of thermodynamics,
thermodynamics—states of a system, walls between not a notion constructed by or derived from it.
systems, thermodynamic processes, and thermodynamic
operations. This allows three fundamental approaches
to thermodynamic reasoning—that in terms of states of
thermodynamic equilibrium of a system, and that in terms Account in terms of states of thermodynamic equilib-
of time-invariant processes of a system, and that in terms rium
of cyclic processes of a system.
When a system is at thermodynamic equilibrium under a
The approach through states of thermodynamic equilibrium given set of conditions of its surroundings, it is said to be in
of a system requires a full account of the state of the system a definite thermodynamic state, which is fully described by
as well as a notion of process from one state to another of a its state variables.
system, but may require only an idealized or partial account
of the state of the surroundings of the system or of other If a system is simple as defined above, and is in thermody-
systems. namic equilibrium, and is not subject to an externally im-
posed force field, such as gravity, electricity, or magnetism,
The method of description in terms of states of thermo- then it is homogeneous, that is say, spatially uniform in all
dynamic equilibrium has limitations. For example, pro- respects.[96]
cesses in a region of turbulent flow, or in a burning gas mix-
ture, or in a Knudsen gas may be beyond “the province of In a sense, a homogeneous system can be regarded as spa-
thermodynamics”.[89][90][91] This problem can sometimes tially zero-dimensional, because it has no spatial variation.
be circumvented through the method of description in terms If a system in thermodynamic equilibrium is homogeneous,
of cyclic or of time-invariant flow processes. This is part of then its state can be described by a few physical vari-
the reason why the founders of thermodynamics often pre- ables, which are mostly classifiable as intensive variables
ferred the cyclic process description. and extensive variables.[8][33][97][98][99]
Approaches through processes of time-invariant flow of a An intensive variable is one that is unchanged with the ther-
system are used for some studies. Some processes, for modynamic operation of scaling of a system.
example Joule-Thomson expansion, are studied through
steady-flow experiments, but can be accounted for by distin- An extensive variable is one that simply scales with the scal-
guishing the steady bulk flow kinetic energy from the inter- ing of a system, without the further requirement used just
nal energy, and thus can be regarded as within the scope of below here, of additivity even when there is inhomogeneity
classical thermodynamics defined in terms of equilibrium of the added systems.
states or of cyclic processes.[44][92] Other flow processes, for Examples of extensive thermodynamic variables are total
example thermoelectric effects, are essentially defined by mass and total volume. Under the above definition, entropy
the presence of differential flows or diffusion so that they is also regarded as an extensive variable. Examples of in-
10
tensive thermodynamic variables are temperature, pressure,
and chemical concentration; intensive thermodynamic vari-
ables are defined at each spatial point and each instant of
time in a system. Physical macroscopic variables can be
mechanical, material, or thermal.[33] Temperature is a ther-
mal variable; according to Guggenheim, “the most impor-
tant conception in thermodynamics is temperature.”[8]
Intensive variables have the property that if any number of
systems, each in its own separate homogeneous thermody-
namic equilibrium state, all with the same respective values
of all of their intensive variables, regardless of the values
of their extensive variables, are laid contiguously with no
partition between them, so as to form a new system, then
the values of the intensive variables of the new system are
the same as those of the separate constituent systems. Such
a composite system is in a homogeneous thermodynamic
equilibrium. Examples of intensive variables are temper-
ature, chemical concentration, pressure, density of mass,
density of internal energy, and, when it can be properly
defined, density of entropy.[100] In other words, intensive
variables are not altered by the thermodynamic operation
of scaling.
For the immediately present account just below, an al-
ternative definition of extensive variables is considered,
that requires that if any number of systems, regardless of
their possible separate thermodynamic equilibrium or non-
equilibrium states or intensive variables, are laid side by side
with no partition between them so as to form a new system,
then the values of the extensive variables of the new system
are the sums of the values of the respective extensive vari-
ables of the individual separate constituent systems. Ob-
viously, there is no reason to expect such a composite sys-
tem to be in a homogeneous thermodynamic equilibrium.
Examples of extensive variables in this alternative defini-
tion are mass, volume, and internal energy. They depend
on the total quantity of mass in the system.[101] In other
words, although extensive variables scale with the system
under the thermodynamic operation of scaling, neverthe-
less the present alternative definition of an extensive vari-
able requires more than this: it requires also its additivity
regardless of the inhomogeneity (or equality or inequality
of the values of the intensive variables) of the component
systems.
Though, when it can be properly defined, density of en-
tropy is an intensive variable, for inhomogeneous systems,
entropy itself does not fit into this alternative classification
of state variables.[102][103] The reason is that entropy is a
property of a system as a whole, and not necessarily related
simply to its constituents separately. It is true that for any
number of systems each in its own separate homogeneous
thermodynamic equilibrium, all with the same values of in-
tensive variables, removal of the partitions between the sep-
arate systems results in a composite homogeneous system in
CHAPTER 1. CHAPTER 1. INTRODUCTION
thermodynamic equilibrium, with all the values of its inten-
sive variables the same as those of the constituent systems,
and it is reservedly or conditionally true that the entropy
of such a restrictively defined composite system is the sum
of the entropies of the constituent systems. But if the con-
stituent systems do not satisfy these restrictive conditions,
the entropy of a composite system cannot be expected to
be the sum of the entropies of the constituent systems, be-
cause the entropy is a property of the composite system as
a whole. Therefore, though under these restrictive reser-
vations, entropy satisfies some requirements for extensivity
defined just above, entropy in general does not fit the im-
mediately present definition of an extensive variable.
Being neither an intensive variable nor an extensive variable
according to the immediately present definition, entropy is
thus a stand-out variable, because it is a state variable of a
system as a whole.[102] A non-equilibrium system can have a
very inhomogeneous dynamical structure. This is one rea-
son for distinguishing the study of equilibrium thermody-
namics from the study of non-equilibrium thermodynamics.
The physical reason for the existence of extensive variables
is the time-invariance of volume in a given inertial reference
frame, and the strictly local conservation of mass, momen-
tum, angular momentum, and energy. As noted by Gibbs,
entropy is unlike energy and mass, because it is not locally
conserved.[102] The stand-out quantity entropy is never con-
served in real physical processes; all real physical processes
are irreversible.[104] The motion of planets seems reversible
on a short time scale (millions of years), but their motion,
according to Newton’s laws, is mathematically an example
of deterministic chaos. Eventually a planet suffers an un-
predictable collision with an object from its surroundings,
outer space in this case, and consequently its future course
is radically unpredictable. Theoretically this can be ex-
pressed by saying that every natural process dissipates some
information from the predictable part of its activity into
the unpredictable part. The predictable part is expressed in
the generalized mechanical variables, and the unpredictable
part in heat.
Other state variables can be regarded as conditionally 'ex-
tensive' subject to reservation as above, but not extensive as
defined above. Examples are the Gibbs free energy, the
Helmholtz free energy, and the enthalpy. Consequently,
just because for some systems under particular conditions
of their surroundings such state variables are conditionally
conjugate to intensive variables, such conjugacy does not
make such state variables extensive as defined above. This
is another reason for distinguishing the study of equilibrium
thermodynamics from the study of non-equilibrium ther-
modynamics. In another way of thinking, this explains why
heat is to be regarded as a quantity that refers to a process
and not to a state of a system.
1.1. CLASSICAL THERMODYNAMICS 11

A system with no internal partitions, and in thermodynamic other independent variable, and then changes in volume are
equilibrium, can be inhomogeneous in the following re- considered as dependent. Careful attention to this principle
spect: it can consist of several so-called 'phases’, each ho- is necessary in thermodynamics.[107][108]
mogeneous in itself, in immediate contiguity with other
phases of the system, but distinguishable by their having
various respectively different physical characters, with dis- Changes of state of a system In the approach through
continuity of intensive variables at the boundaries between equilibrium states of the system, a process can be described
the phases; a mixture of different chemical species is con- in two main ways.
sidered homogeneous for this purpose if it is physically In one way, the system is considered to be connected to the
homogeneous.[105] For example, a vessel can contain a sys- surroundings by some kind of more or less separating par-
tem consisting of water vapour overlying liquid water; then tition, and allowed to reach equilibrium with the surround-
there is a vapour phase and a liquid phase, each homo- ings with that partition in place. Then, while the separative
geneous in itself, but still in thermodynamic equilibrium character of the partition is kept unchanged, the conditions
with the other phase. For the immediately present account, of the surroundings are changed, and exert their influence
systems with multiple phases are not considered, though on the system again through the separating partition, or the
for many thermodynamic questions, multiphase systems are partition is moved so as to change the volume of the system;
important. and a new equilibrium is reached. For example, a system is
allowed to reach equilibrium with a heat bath at one tem-
perature; then the temperature of the heat bath is changed
Equation of state The macroscopic variables of a ther-
and the system is allowed to reach a new equilibrium; if the
modynamic system in thermodynamic equilibrium, in
partition allows conduction of heat, the new equilibrium is
which temperature is well defined, can be related to
different from the old equilibrium.
one another through equations of state or characteristic
[29][30][31][32]
equations. They express the constitutive pe- In the other way, several systems are connected to one an-
culiarities of the material of the system. The equation of other by various kinds of more or less separating partitions,
state must comply with some thermodynamic constraints, and to reach equilibrium with each other, with those parti-
but cannot be derived from the general principles of ther- tions in place. In this way, one may speak of a 'compound
modynamics alone. system'. Then one or more partitions is removed or changed
in its separative properties or moved, and a new equilibrium
is reached. The Joule-Thomson experiment is an example
Thermodynamic processes between states of thermody- of this; a tube of gas is separated from another tube by a
namic equilibrium porous partition; the volume available in each of the tubes is
determined by respective pistons; equilibrium is established
A thermodynamic process is defined by changes of state in- with an initial set of volumes; the volumes are changed and
ternal to the system of interest, combined with transfers of a new equilibrium is established.[109][110][111][112][113] An-
matter and energy to and from the surroundings of the sys- other example is in separation and mixing of gases, with
tem or to and from other systems. A system is demarcated use of chemically semi-permeable membranes.[114]
from its surroundings or from other systems by partitions
that more or less separate them, and may move as a piston
to change the volume of the system and thus transfer work. Commonly considered thermodynamic processes It
is often convenient to study a thermodynamic process in
which a single variable, such as temperature, pressure, or
Dependent and independent variables for a process A volume, etc., is held fixed. Furthermore, it is useful to group
process is described by changes in values of state variables these processes into pairs, in which each variable held con-
of systems or by quantities of exchange of matter and en- stant is one member of a conjugate pair.
ergy between systems and surroundings. The change must
be specified in terms of prescribed variables. The choice Several commonly studied thermodynamic processes
of which variables are to be used is made in advance of are:
consideration of the course of the process, and cannot be
changed. Certain of the variables chosen in advance are • Isobaric process: occurs at constant pressure
called the independent variables.[106] From changes in in-
dependent variables may be derived changes in other vari- • Isochoric process: occurs at constant volume (also
ables called dependent variables. For example, a process called isometric/isovolumetric)
may occur at constant pressure with pressure prescribed as
an independent variable, and temperature changed as an- • Isothermal process: occurs at a constant temperature
12 CHAPTER 1. CHAPTER 1. INTRODUCTION

• Adiabatic process: occurs without loss or gain of en- A cyclic process of a system requires in its surroundings
ergy as heat at least two heat reservoirs at different temperatures, one
at a higher temperature that supplies heat to the system,
• Isentropic process: a reversible adiabatic process oc- the other at a lower temperature that accepts heat from
curs at a constant entropy, but is a fictional idealization. the system. The early work on thermodynamics tended to
Conceptually it is possible to actually physically con- use the cyclic process approach, because it was interested
duct a process that keeps the entropy of the system in machines that converted some of the heat from the sur-
constant, allowing systematically controlled removal roundings into mechanical power delivered to the surround-
of heat, by conduction to a cooler body, to compensate ings, without too much concern about the internal work-
for entropy produced within the system by irreversible ings of the machine. Such a machine, while receiving an
work done on the system. Such isentropic conduct of a amount of heat from a higher temperature reservoir, al-
process seems called for when the entropy of the sys- ways needs a lower temperature reservoir that accepts some
tem is considered as an independent variable, as for lesser amount of heat. The difference in amounts of heat
example when the internal energy is considered as a is equal to the amount of heat converted to work.[83] Later,
function of the entropy and volume of the system, the the internal workings of a system became of interest, and
natural variables of the internal energy as studied by they are described by the states of the system. Nowadays,
Gibbs. instead of arguing in terms of cyclic processes, some writers
are inclined to derive the concept of absolute temperature
• Isenthalpic process: occurs at a constant enthalpy
from the concept of entropy, a variable of state.
• Isolated process: no matter or energy (neither as work
nor as heat) is transferred into or out of the system

It is sometimes of interest to study a process in which sev-

eral variables are controlled, subject to some specified con-
straint. In a system in which a chemical reaction can occur,
for example, in which the pressure and temperature can af-
fect the equilibrium composition, a process might occur in
which temperature is held constant but pressure is slowly al-
tered, just so that chemical equilibrium is maintained all the
way. There is a corresponding process at constant temper-
ature in which the final pressure is the same but is reached
by a rapid jump. Then it can be shown that the volume
change resulting from the rapid jump process is smaller than
that from the slow equilibrium process.[115] The work trans-
ferred differs between the two processes.
Account in terms of cyclic processes
A cyclic process[26] is a process that can be repeated in-
definitely often without changing the final state of the sys-
tem in which the process occurs. The only traces of the
effects of a cyclic process are to be found in the surround-
ings of the system or in other systems. This is the kind
of process that concerned early thermodynamicists such as
Sadi Carnot, and in terms of which Kelvin defined absolute
temperature,[116] before the use of the quantity of entropy
by Rankine and its clear identification by Clausius.[117] For
some systems, for example with some plastic working sub-
stances, cyclic processes are practically nearly unfeasible
because the working substance undergoes practically irre-
versible changes.[118] This is why mechanical devices are
lubricated with oil and one of the reasons why electrical
devices are often useful.
1.1.9 Instrumentation
There are two types of thermodynamic instruments, the
meter and the reservoir. A thermodynamic meter is any
device that measures any parameter of a thermodynamic
system. In some cases, the thermodynamic parameter is
actually defined in terms of an idealized measuring instru-
ment. For example, the zeroth law states that if two bodies
are in thermal equilibrium with a third body, they are also
in thermal equilibrium with each other. This principle, as
noted by James Maxwell in 1872, asserts that it is possi-
ble to measure temperature. An idealized thermometer is
a sample of an ideal gas at constant pressure. From the
ideal gas law PV=nRT, the volume of such a sample can
be used as an indicator of temperature; in this manner it
defines temperature. Although pressure is defined mechan-
ically, a pressure-measuring device, called a barometer may
also be constructed from a sample of an ideal gas held at a
constant temperature. A calorimeter is a device that mea-
sures and define the internal energy of a system.
A thermodynamic reservoir is a system so large that it does
not appreciably alter its state parameters when brought into
contact with the test system. It is used to impose a particu-
lar value of a state parameter upon the system. For exam-
ple, a pressure reservoir is a system at a particular pressure,
which imposes that pressure upon any test system that it is
mechanically connected to. The Earth’s atmosphere is often
used as a pressure reservoir.
1.1. CLASSICAL THERMODYNAMICS 13

1.1.10 Conjugate variables times without,[120][121] explicit mention. Particular atten-

tion is paid to the law in accounts of non-equilibrium
Main article: Conjugate variables thermodynamics.[122][123] One statement of this law is “The
total mass of a closed system remains constant.”[9] Another
A central concept of thermodynamics is that of energy. By statement of it is “In a chemical reaction, matter is neither
the First Law, the total energy of a system and its surround- created nor destroyed.”[124] Implied in this is that matter
ings is conserved. Energy may be transferred into a sys- and energy are not considered to be interconverted in such
tem by heating, compression, or addition of matter, and accounts. The full generality of the law of conservation of
extracted from a system by cooling, expansion, or extrac- energy is thus not used in such accounts.
tion of matter. In mechanics, for example, energy transfer In 1909, Constantin Carathéodory presented[56] a purely
equals the product of the force applied to a body and the mathematical axiomatic formulation, a description often
resulting displacement. referred to as geometrical thermodynamics, and sometimes
[79]
Conjugate variables are pairs of thermodynamic concepts, said to take the “mechanical approach” to thermodynam-
with the first being akin to a “force” applied to some ics. The Carathéodory formulation is restricted to equilib-
thermodynamic system, the second being akin to the re- rium thermodynamics and does not attempt to deal with
sulting “displacement,” and the product of the two equalling non-equilibrium thermodynamics, forces that act at a dis-
[125]
the amount of energy transferred. The common conjugate tance on the system, or surface tension effects. More-
variables are: over, Carathéodory’s formulation does not deal with mate-
rials like water near 4 °C, which have a density extremum
as a function of temperature at constant pressure.[126][127]
• Pressure-volume (the mechanical parameters); Carathéodory used the law of conservation of energy
• Temperature-entropy (thermal parameters); as an axiom from which, along with the contents of
the zeroth law, and some other assumptions including
• Chemical potential-particle number (material param- his own version of the second law, he derived the first
eters). law of thermodynamics.[128] Consequently, one might also
describe Carathėodory’s work as lying in the field of
energetics,[129] which is broader than thermodynamics.
1.1.11 Potentials Carathéodory presupposed the law of conservation of mass
without explicit mention of it.
Thermodynamic potentials are different quantitative mea-
Since the time of Carathėodory, other influential axiomatic
sures of the stored energy in a system. Potentials are used
formulations of thermodynamics have appeared, which like
to measure energy changes in systems as they evolve from
Carathéodory’s, use their own respective axioms, different
an initial state to a final state. The potential used depends
from the usual statements of the four laws, to derive the four
on the constraints of the system, such as constant temper-
usually stated laws.[130][131][132]
ature or pressure. For example, the Helmholtz and Gibbs
energies are the energies available in a system to do useful Many axiomatic developments assume the existence of
work when the temperature and volume or the pressure and states of thermodynamic equilibrium and of states of ther-
temperature are fixed, respectively. mal equilibrium. States of thermodynamic equilibrium of
compound systems allow their component simple systems
The five most well known potentials are:
to exchange heat and matter and to do work on each other
where T is the temperature, S the entropy, p the pressure, on their way to overall joint equilibrium. Thermal equi-
V the volume, µ the chemical potential, N the number of librium allows them only to exchange heat. The physical
particles in the system, and i is the count of particles types properties of glass depend on its history of being heated and
in the system. cooled and, strictly speaking, glass is not in thermodynamic
[133]
Thermodynamic potentials can be derived from the en- equilibrium.
ergy balance equation applied to a thermodynamic sys- According to Herbert Callen's widely cited 1985 text on
tem. Other thermodynamic potentials can also be obtained thermodynamics: “An essential prerequisite for the mea-
through Legendre transformation. surability of energy is the existence of walls that do not per-
mit transfer of energy in the form of heat.”.[134] According
to Werner Heisenberg's mature and careful examination of
1.1.12 Axiomatics the basic concepts of physics, the theory of heat has a self-
standing place.[135]
Most accounts of thermodynamics presuppose the law
of conservation of mass, sometimes with,[119] and some- From the viewpoint of the axiomatist, there are several dif-
14
ferent ways of thinking about heat, temperature, and the
second law of thermodynamics. The Clausius way rests on
the empirical fact that heat is conducted always down, never
up, a temperature gradient. The Kelvin way is to assert the
empirical fact that conversion of heat into work by cyclic
processes is never perfectly efficient. A more mathemati-
cal way is to assert the existence of a function of state called
the entropy that tells whether a hypothesized process oc-
curs spontaneously in nature. A more abstract way is that
of Carathéodory that in effect asserts the irreversibility of
some adiabatic processes. For these different ways, there
are respective corresponding different ways of viewing heat
and temperature.
The Clausius–Kelvin–Planck way This way prefers ideas
close to the empirical origins of thermodynamics. It
presupposes transfer of energy as heat, and empirical
temperature as a scalar function of state. According
to Gislason and Craig (2005): “Most thermodynamic
data come from calorimetry...”[136] According to Kon-
depudi (2008): “Calorimetry is widely used in present day
laboratories.”[137] In this approach, what is often currently
called the zeroth law of thermodynamics is deduced as a
simple consequence of the presupposition of the nature of
heat and empirical temperature, but it is not named as a
numbered law of thermodynamics. Planck attributed this
point of view to Clausius, Kelvin, and Maxwell. Planck
wrote (on page 90 of the seventh edition, dated 1922, of
his treatise) that he thought that no proof of the second law
of thermodynamics could ever work that was not based on
the impossibility of a perpetual motion machine of the sec-
ond kind. In that treatise, Planck makes no mention of the
1909 Carathéodory way, which was well known by 1922.
Planck for himself chose a version of what is just above
called the Kelvin way.[138] The development by Truesdell
and Bharatha (1977) is so constructed that it can deal natu-
rally with cases like that of water near 4 °C.[131]
The way that assumes the existence of entropy as a
function of state This way also presupposes transfer of
energy as heat, and it presupposes the usually stated form
of the zeroth law of thermodynamics, and from these two it
deduces the existence of empirical temperature. Then from
the existence of entropy it deduces the existence of absolute
thermodynamic temperature.[8][130]
The Carathéodory way This way presupposes that the
state of a simple one-phase system is fully specifiable by
just one more state variable than the known exhaustive
list of mechanical variables of state. It does not explic-
itly name empirical temperature, but speaks of the one-
dimensional “non-deformation coordinate”. This satisfies
the definition of an empirical temperature, that lies on a
one-dimensional manifold. The Carathéodory way needs
to assume moreover that the one-dimensional manifold has
a definite sense, which determines the direction of irre-
CHAPTER 1. CHAPTER 1. INTRODUCTION
versible adiabatic process, which is effectively assuming
that heat is conducted from hot to cold. This way presup-
poses the often currently stated version of the zeroth law,
but does not actually name it as one of its axioms.[125] Ac-
cording to one author, Carathéodory’s principle, which is
his version of the second law of thermodynamics, does not
imply the increase of entropy when work is done under
adiabatic conditions (as was noted by Planck[139] ). Thus
Carathéodory’s way leaves unstated a further empirical fact
that is needed for a full expression of the second law of
thermodynamics.[140]
1.1.13 Scope of thermodynamics
Originally thermodynamics concerned material and radia-
tive phenomena that are experimentally reproducible. For
example, a state of thermodynamic equilibrium is a steady
state reached after a system has aged so that it no longer
changes with the passage of time. But more than that, for
thermodynamics, a system, defined by its being prepared
in a certain way must, consequent on every particular oc-
casion of preparation, upon aging, reach one and the same
eventual state of thermodynamic equilibrium, entirely de-
termined by the way of preparation. Such reproducibility is
because the systems consist of so many molecules that the
molecular variations between particular occasions of prepa-
ration have negligible or scarcely discernable effects on the
macroscopic variables that are used in thermodynamic de-
scriptions. This led to Boltzmann’s discovery that entropy
had a statistical or probabilistic nature. Probabilistic and
statistical explanations arise from the experimental repro-
ducibility of the phenomena.[141]
Gradually, the laws of thermodynamics came to be used
to explain phenomena that occur outside the experimen-
tal laboratory. For example, phenomena on the scale of
the earth’s atmosphere cannot be reproduced in a lab-
oratory experiment. But processes in the atmosphere
can be modeled by use of thermodynamic ideas, ex-
tended well beyond the scope of laboratory equilibrium
thermodynamics.[142][143][144] A parcel of air can, near
enough for many studies, be considered as a closed ther-
modynamic system, one that is allowed to move over sig-
nificant distances. The pressure exerted by the surround-
ing air on the lower face of a parcel of air may differ from
that on its upper face. If this results in rising of the parcel
of air, it can be considered to have gained potential energy
as a result of work being done on it by the combined sur-
rounding air below and above it. As it rises, such a parcel
usually expands because the pressure is lower at the higher
altitudes that it reaches. In that way, the rising parcel also
does work on the surrounding atmosphere. For many stud-
ies, such a parcel can be considered nearly to neither gain
nor lose energy by heat conduction to its surrounding at-
1.1. CLASSICAL THERMODYNAMICS 15

mosphere, and its rise is rapid enough to leave negligible Wikibooks

time for it to gain or lose heat by radiation; consequently
the rising of the parcel is near enough adiabatic. Thus the • Engineering Thermodynamics
adiabatic gas law accounts for its internal state variables,
• Entropy for Beginners
provided that there is no precipitation into water droplets,
no evaporation of water droplets, and no sublimation in the
process. More precisely, the rising of the parcel is likely 1.1.16 References
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[8] Guggenheim, E.A. (1949/1967)

1.1.15 See also
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Lists and timelines
[10] Enrico Fermi (1956). Thermodynamics. Courier Dover
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230763036.
• List of textbooks in statistical mechanics
[11] Perrot, Pierre (1998). A to Z of Thermodynamics. Ox-
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123283342.
• List of thermodynamic properties
[12] Bridgman, P.W. (1943). The Nature of Thermodynamics,
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• Timeline of thermodynamics [13] Partington, J.R. (1949), page 118.

16
[14] Reif, F. (1965). Fundamentals of Statistical and Thermal
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[17] Marsland, R. III, Brown, H.R., Valente, G. (2015).
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[20] Guggenheim, E.A. (1949/1967), pp. 7–8.
[21] Tisza, L. (1966), pp. 109, 112.
[22] Callen, p. 15.
[23] Bailyn, M. (1994), p. 21.
[24] Callen, H.B. (1960/1985), p. 427.
[25] Tisza, L. (1966), pp. 41, 109, 121, originally published
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[26] Serrin, J. (1986). Chapter 1, 'An Outline of Thermodynami-
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[27] Fowler, R., Guggenheim, E.A. (1939), p. 13.
[28] Tisza, L. (1966), pp. 79–80.
[29] Planck, M. 1923/1926, page 5.
[30] Partington, p. 121.
[31] Adkins, pp. 19–20.
[32] Haase, R. (1971), pages 11–16.
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[35] Partington, J.R. (1949), p. 551.
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[37] The Newcomen engine was improved from 1711 until Watt’s
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[41] Donald T. Haynie (2001). Biological Thermodynamics (2
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S. Carnot and F. Reech, Springer, New York, ISBN 0-387-
07971-8.
CHAPTER 1. CHAPTER 1. INTRODUCTION
[132] Wright, P.G. (1980). Conceptually distinct types of thermo-
dynamics, Eur. J. Phys. 1: 81–84.
[133] Callen, H.B. (1960/1985), p. 14.
Row, New York, pp. 98–99.
[136] Gislason, E.A., Craig, N.C. (2005). Cementing the founda-
tions of thermodynamics:comparison of system-based and
surroundings-based definitions of work and heat, J. Chem.
Thermodynamics 37: 954–966.
[137] Kondepudi, D. (2008). Introduction to Modern Thermody-
namics, Wiley, Chichester, ISBN 978-0-470-01598-8, p.
63.
[138] Planck, M. (1922/1927).
[139] Planck, M. (1926). Über die Begründung des zweiten
Hauptsatzes der Thermodynamik, Sitzungsberichte der
Preußischen Akademie der Wissenschaften, physikalisch-
mathematischen Klasse, pp. 453–463.
[140] Münster, A. (1970). Classical Thermodynamics, translated
by E.S. Halberstadt, Wiley–Interscience, London, ISBN 0-
471-62430-6, p 41.
[141] Grandy, W.T., Jr (2008). Entropy and the Time Evolution of
Macroscopic Systems, Oxford University Press, Oxford UK,
ISBN 978-0-19-954617-6. p. 49.
[142] Iribarne, J.V., Godson, W.L. (1973/1989). Atmospheric
thermodynamics, second edition, reprinted 1989, Kluwer
Academic Publishers, Dordrecht, ISBN 90-277-1296-4.
ican Institute of Physics, New York, ISBN 0-88318-712-4
[144] North, G.R., Erukhimova, T.L. (2009). Atmospheric Ther-
modynamics. Elementary Physics and Chemistry, Cambridge
University Press, Cambridge UK, ISBN 978-0-521-89963-
5.
ogy, fourth edition, Elsevier, Amsterdam, ISBN 978-0-12-
354015-7.
versity Press, Cambridge UK, ISBN 978-0-521-19573-7.
1.1.17 Cited bibliography
• Adkins, C.J. (1968/1975). Equilibrium Thermody-
namics, second edition, McGraw-Hill, London, ISBN
0-07-084057-1.
• Bailyn, M. (1994). A Survey of Thermodynamics,
American Institute of Physics Press, New York, ISBN
0-88318-797-3.
1.1. CLASSICAL THERMODYNAMICS
• Born, M. (1949). Natural Philosophy of Cause and
Chance, Oxford University Press, London.
• Bryan, G.H. (1907). Thermodynamics. An Introduc-
tory Treatise dealing mainly with First Principles and
their Direct Applications, B.G. Teubner, Leipzig.
• Callen, H.B. (1960/1985). Thermodynamics and an
Introduction to Thermostatistics, (1st edition 1960) 2nd
edition 1985, Wiley, New York, ISBN 0-471-86256-
8.
• Eu, B.C. (2002). Generalized Thermodynamics. The
Thermodynamics of Irreversible Processes and Gener-
alized Hydrodynamics, Kluwer Academic Publishers,
Dordrecht, ISBN 1-4020-0788-4.
• Fowler, R., Guggenheim, E.A. (1939). Statistical
Thermodynamics, Cambridge University Press, Cam-
bridge UK.
• Gibbs, J.W. (1875). On the equilibrium of hetero-
geneous substances, Transactions of the Connecticut
Academy of Arts and Sciences, 3: 108–248.
• Grandy, W.T., Jr (2008). Entropy and the Time Evolu-
tion of Macroscopic Systems, Oxford University Press,
Oxford, ISBN 978-0-19-954617-6.
• Guggenheim, E.A. (1949/1967). Thermodynamics.
An Advanced Treatment for Chemists and Physicists, 1.1.18 Further reading
(1st edition 1949) 5th edition 1967, North-Holland,
Amsterdam.
• Haase, R. (1971). Survey of Fundamental Laws,
chapter 1 of Thermodynamics, pages 1–97 of volume
1, ed. W. Jost, of Physical Chemistry. An Advanced
Treatise, ed. H. Eyring, D. Henderson, W. Jost, Aca-
demic Press, New York, lcn 73–117081.
• Kondepudi, D., Prigogine, I. (1998). Modern Thermo-
dynamics. From Heat Engines to Dissipative Structures,
John Wiley & Sons, ISBN 0-471-97393-9.
• Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Under-
standing Non-equilibrium Thermodynamics, Springer,
Berlin, ISBN 978-3-540-74251-7.
• Marsland, R. III, Brown, H.R., Valente, G. (2015).
Time and irreversibility in axiomatic thermodynam-
ics, Am. J. Phys., 83(7): 628–634.
• Partington, J.R. (1949). An Advanced Treatise on
Physical Chemistry, volume 1, Fundamental Princi-
ples. The Properties of Gases, Longmans, Green and
Co., London.
• Pippard, A.B. (1957). The Elements of Classical Ther-
modynamics, Cambridge University Press.
19
• Planck, M.(1897/1903). Treatise on Thermodynam-
ics, translated by A. Ogg, Longmans, Green & Co.,
London.
• Planck, M. (1923/1926). Treatise on Thermodynam-
ics, third English edition translated by A. Ogg from
the seventh German edition, Longmans, Green & Co.,
London.
• Serrin, J. (1986). New Perspectives in Thermodynam-
ics, edited by J. Serrin, Springer, Berlin, ISBN 3-540-
15931-2.
• Sommerfeld, A. (1952/1956). Thermodynamics and
Statistical Mechanics, Academic Press, New York.
• Tschoegl, N.W. (2000). Fundamentals of Equilibrium
and Steady-State Thermodynamics, Elsevier, Amster-
dam, ISBN 0-444-50426-5.
• Tisza, L. (1966). Generalized Thermodynamics, M.I.T
Press, Cambridge MA.
• Truesdell, C.A. (1980). The Tragicomical History of
Thermodynamics, 1822–1854, Springer, New York,
ISBN 0-387-90403-4.
• Goldstein, Martin, and Inge F. (1993). The Refrigera-
tor and the Universe. Harvard University Press. ISBN
0-674-75325-9. OCLC 32826343. A nontechnical
introduction, good on historical and interpretive mat-
ters.
• Kazakov, Andrei (July–August 2008). “Web Thermo
Tables – an On-Line Version of the TRC Thermody-
namic Tables” (PDF). Journal of Research of the Na-
tional Institutes of Standards and Technology 113 (4):
209–220. doi:10.6028/jres.113.016.
The following titles are more technical:
• Cengel, Yunus A., & Boles, Michael A. (2002). Ther-
modynamics – an Engineering Approach. McGraw
Hill. ISBN 0-07-238332-1. OCLC 45791449.
• Fermi, E. (1956). Thermodynamics, Dover, New
York.
• Kittel, Charles & Kroemer, Herbert (1980). Thermal
Physics. W. H. Freeman Company. ISBN 0-7167-
1088-9. OCLC 32932988.
20 CHAPTER 1. CHAPTER 1. INTRODUCTION

1.1.19 External links 1.2.1 Principles: mechanics and ensembles

• Thermodynamics Data & Property Calculation Web- Main articles: Mechanics and Statistical ensemble
sites
In physics there are two types of mechanics usually exam-
• Thermodynamics OpenCourseWare from the
ined: classical mechanics and quantum mechanics. For
University of Notre Dame Archived March 4, 2011,
both types of mechanics, the standard mathematical ap-
at the Wayback Machine.
proach is to consider two ingredients:
• Thermodynamics at ScienceWorld
1. The complete state of the mechanical system at a given
• Biochemistry Thermodynamics time, mathematically encoded as a phase point (classi-
cal mechanics) or a pure quantum state vector (quan-
• Engineering Thermodynamics – A Graphical Ap- tum mechanics).
proach
2. An equation of motion which carries the state forward
in time: Hamilton’s equations (classical mechanics)
or the time-dependent Schrödinger equation (quantum
1.2 Statistical Thermodynamics mechanics)

Statistical mechanics is a branch of theoretical physics that Using these two ingredients, the state at any other time, past
studies, using probability theory, the average behaviour of or future, can in principle be calculated. There is however a
a mechanical system made up of a large number of equiv- disconnection between these laws and everyday life experi-
alent components where the microscopic realization of the ences, as we do not find it necessary (nor even theoretically
system is uncertain or undefined.[1][2][3][note 1] possible) to know exactly at a microscopic level the simul-
A common use of statistical mechanics is in explaining the taneous positions and velocities of each molecule while car-
thermodynamic behaviour of large systems. This branch rying out processes at the human scale (for example, when
of statistical mechanics which treats and extends classical performing a chemical reaction). Statistical mechanics fills
thermodynamics is known as statistical thermodynamics this disconnection between the laws of mechanics and the
or equilibrium statistical mechanics. Microscopic me- practical experience of incomplete knowledge, by adding
chanical laws do not contain concepts such as temperature, some uncertainty about which state the system is in.
heat, or entropy; however, statistical mechanics shows how Whereas ordinary mechanics only considers the behaviour
these concepts arise from the natural uncertainty about the of a single state, statistical mechanics introduces the
state of a system when that system is prepared in prac- statistical ensemble, which is a large collection of virtual,
tice. The benefit of using statistical mechanics is that it pro- independent copies of the system in various states. The sta-
vides exact methods to connect thermodynamic quantities tistical ensemble is a probability distribution over all pos-
(such as heat capacity) to microscopic behaviour, whereas sible states of the system. In classical statistical mechan-
in classical thermodynamics the only available option would ics, the ensemble is a probability distribution over phase
be to just measure and tabulate such quantities for various points (as opposed to a single phase point in ordinary me-
materials. Statistical mechanics also makes it possible to ex- chanics), usually represented as a distribution in a phase
tend the laws of thermodynamics to cases which are not con- space with canonical coordinates. In quantum statistical
sidered in classical thermodynamics, such as microscopic mechanics, the ensemble is a probability distribution over
systems and other mechanical systems with few degrees of pure states,[note 2] and can be compactly summarized as a
freedom.[1] density matrix.
Statistical mechanics also finds use outside equilibrium. An As is usual for probabilities, the ensemble can be interpreted
important subbranch known as non-equilibrium statisti- in different ways:[1]
cal mechanics deals with the issue of microscopically mod-
elling the speed of irreversible processes that are driven by • an ensemble can be taken to represent the various pos-
imbalances. Examples of such processes include chemical sible states that a single system could be in (epistemic
reactions or flows of particles and heat. Unlike with equi- probability, a form of knowledge), or
librium, there is no exact formalism that applies to non-
equilibrium statistical mechanics in general, and so this • the members of the ensemble can be understood as
branch of statistical mechanics remains an active area of the states of the systems in experiments repeated on
theoretical research. independent systems which have been prepared in a
1.2. STATISTICAL THERMODYNAMICS 21

similar but imperfectly controlled manner (empirical different equilibrium ensembles that can be considered, and
probability), in the limit of an infinite number of trials. only some of them correspond to thermodynamics.[1] Addi-
tional postulates are necessary to motivate why the ensem-
These two meanings are equivalent for many purposes, and ble for a given system should have one form or another.
will be used interchangeably in this article.
A common approach found in many textbooks is to take the
However the probability is interpreted, each state in the en- equal a priori probability postulate.[2] This postulate states
semble evolves over time according to the equation of mo- that
tion. Thus, the ensemble itself (the probability distribution
over states) also evolves, as the virtual systems in the en- For an isolated system with an exactly known
semble continually leave one state and enter another. The energy and exactly known composition, the sys-
ensemble evolution is given by the Liouville equation (clas- tem can be found with equal probability in any
sical mechanics) or the von Neumann equation (quantum microstate consistent with that knowledge.
mechanics). These equations are simply derived by the ap-
plication of the mechanical equation of motion separately The equal a priori probability postulate therefore provides a
to each virtual system contained in the ensemble, with the motivation for the microcanonical ensemble described be-
probability of the virtual system being conserved over time low. There are various arguments in favour of the equal a
as it evolves from state to state. priori probability postulate:
One special class of ensemble is those ensembles that do
not evolve over time. These ensembles are known as equi- • Ergodic hypothesis: An ergodic state is one that
librium ensembles and their condition is known as statistical evolves over time to explore “all accessible” states: all
equilibrium. Statistical equilibrium occurs if, for each state those with the same energy and composition. In an er-
in the ensemble, the ensemble also contains all of its future godic system, the microcanonical ensemble is the only
and past states with probabilities equal to the probability of possible equilibrium ensemble with fixed energy. This
being in that state.[note 3] The study of equilibrium ensem- approach has limited applicability, since most systems
bles of isolated systems is the focus of statistical thermo- are not ergodic.
dynamics. Non-equilibrium statistical mechanics addresses
the more general case of ensembles that change over time, • Principle of indifference: In the absence of any further
and/or ensembles of non-isolated systems. information, we can only assign equal probabilities to
each compatible situation.

1.2.2 Statistical thermodynamics • Maximum information entropy: A more elaborate ver-

sion of the principle of indifference states that the cor-
The primary goal of statistical thermodynamics (also rect ensemble is the ensemble that is compatible with
known as equilibrium statistical mechanics) is to derive the the known information and that has the largest Gibbs
classical thermodynamics of materials in terms of the prop- entropy (information entropy).[4]
erties of their constituent particles and the interactions be-
tween them. In other words, statistical thermodynamics Other fundamental postulates for statistical mechanics have
[5]
provides a connection between the macroscopic properties also been proposed.
of materials in thermodynamic equilibrium, and the micro-
scopic behaviours and motions occurring inside the mate-
Three thermodynamic ensembles
rial.
Whereas statistical mechanics proper involves dynamics, Main articles: Microcanonical ensemble, Canonical en-
here the attention is focussed on statistical equilibrium semble and Grand canonical ensemble
(steady state). Statistical equilibrium does not mean that the
particles have stopped moving (mechanical equilibrium), There are three equilibrium ensembles with a simple form
rather, only that the ensemble is not evolving. that can be defined for any isolated system bounded inside
a finite volume.[1] These are the most often discussed en-
Fundamental postulate sembles in statistical thermodynamics. In the macroscopic
limit (defined below) they all correspond to classical ther-
A sufficient (but not necessary) condition for statistical modynamics.
equilibrium with an isolated system is that the probability
distribution is a function only of conserved properties (to- Microcanonical ensemble describes a system with a pre-
tal energy, total particle numbers, etc.).[1] There are many cisely given energy and fixed composition (precise
22 CHAPTER 1. CHAPTER 1. INTRODUCTION

number of particles). The microcanonical ensemble a simple task, however, since it involves considering every
contains with equal probability each possible state that possible state of the system. While some hypothetical sys-
is consistent with that energy and composition. tems have been exactly solved, the most general (and real-
istic) case is too complex for exact solution. Various ap-
Canonical ensemble describes a system of fixed compo- proaches exist to approximate the true ensemble and allow
sition that is in thermal equilibrium[note 4] with a heat calculation of average quantities.
bath of a precise temperature. The canonical ensem-
ble contains states of varying energy but identical com-
position; the different states in the ensemble are ac- Exact There are some cases which allow exact solutions.
corded different probabilities depending on their total
energy. • For very small microscopic systems, the ensembles
Grand canonical ensemble describes a system with non- can be directly computed by simply enumerating over
fixed composition (uncertain particle numbers) that is all possible states of the system (using exact diago-
in thermal and chemical equilibrium with a thermo- nalization in quantum mechanics, or integral over all
dynamic reservoir. The reservoir has a precise tem- phase space in classical mechanics).
perature, and precise chemical potentials for various
• Some large systems consist of many separable mi-
types of particle. The grand canonical ensemble con-
croscopic systems, and each of the subsystems can
tains states of varying energy and varying numbers of
be analysed independently. Notably, idealized gases
particles; the different states in the ensemble are ac-
of non-interacting particles have this property, allow-
corded different probabilities depending on their total
ing exact derivations of Maxwell–Boltzmann statistics,
energy and total particle numbers.
Fermi–Dirac statistics, and Bose–Einstein statistics.[2]

For systems containing many particles (the thermodynamic
limit), all three of the ensembles listed above tend to give
identical behaviour. It is then simply a matter of mathemat-
ical convenience which ensemble is used.[6]
Important cases where the thermodynamic ensembles do
not give identical results include:
• Microscopic systems.
• Large systems at a phase transition.
• Large systems with long-range interactions.
In these cases the correct thermodynamic ensemble must be
chosen as there are observable differences between these
ensembles not just in the size of fluctuations, but also
in average quantities such as the distribution of particles.
The correct ensemble is that which corresponds to the way
the system has been prepared and characterized—in other
words, the ensemble that reflects the knowledge about that
system.[2]
• A few large systems with interaction have been solved.
By the use of subtle mathematical techniques, exact
solutions have been found for a few toy models.[7]
Some examples include the Bethe ansatz, square-
lattice Ising model in zero field, hard hexagon model.
Monte Carlo Main article: Monte Carlo method
One approximate approach that is particularly well suited
to computers is the Monte Carlo method, which examines
just a few of the possible states of the system, with the states
chosen randomly (with a fair weight). As long as these states
form a representative sample of the whole set of states of the
system, the approximate characteristic function is obtained.
As more and more random samples are included, the errors
are reduced to an arbitrarily low level.
• The Metropolis–Hastings algorithm is a classic Monte
Carlo method which was initially used to sample the
canonical ensemble.

• Path integral Monte Carlo, also used to sample the

canonical ensemble.

Calculation methods
Other
Once the characteristic state function for an ensemble has
been calculated for a given system, that system is 'solved' • For rarefied non-ideal gases, approaches such as the
(macroscopic observables can be extracted from the charac- cluster expansion use perturbation theory to include
teristic state function). Calculating the characteristic state the effect of weak interactions, leading to a virial ex-
function of a thermodynamic ensemble is not necessarily pansion.[3]
1.2. STATISTICAL THERMODYNAMICS 23

• For dense fluids, another approximate approach is equations are fully reversible and do not destroy informa-
based on reduced distribution functions, in particular tion (the ensemble’s Gibbs entropy is preserved). In order
the radial distribution function.[3] to make headway in modelling irreversible processes, it is
necessary to add additional ingredients besides probability
• Molecular dynamics computer simulations can be used and reversible mechanics.
to calculate microcanonical ensemble averages, in er-
godic systems. With the inclusion of a connection to Non-equilibrium mechanics is therefore an active area of
a stochastic heat bath, they can also model canonical theoretical research as the range of validity of these ad-
and grand canonical conditions. ditional assumptions continues to be explored. A few ap-
proaches are described in the following subsections.
• Mixed methods involving non-equilibrium statistical
mechanical results (see below) may be useful.
Stochastic methods

1.2.3 Non-equilibrium statistical mechanics One approach to non-equilibrium statistical mechanics is to

See also: Non-equilibrium thermodynamics
There are many physical phenomena of interest that involve
quasi-thermodynamic processes out of equilibrium, for ex-
ample:
• heat transport by the internal motions in a material,
driven by a temperature imbalance,
• electric currents carried by the motion of charges in a
conductor, driven by a voltage imbalance,
incorporate stochastic (random) behaviour into the system.
Stochastic behaviour destroys information contained in the
ensemble. While this is technically inaccurate (aside from
hypothetical situations involving black holes, a system can-
not in itself cause loss of information), the randomness is
added to reflect that information of interest becomes con-
verted over time into subtle correlations within the system,
or to correlations between the system and environment.
These correlations appear as chaotic or pseudorandom in-
fluences on the variables of interest. By replacing these cor-
relations with randomness proper, the calculations can be
made much easier.

• spontaneous chemical reactions driven by a decrease
in free energy,
• friction, dissipation, quantum decoherence,
• systems being pumped by external forces (optical
pumping, etc.),
• and irreversible processes in general.
All of these processes occur over time with characteristic
rates, and these rates are of importance for engineering.
The field of non-equilibrium statistical mechanics is con-
cerned with understanding these non-equilibrium processes
at the microscopic level. (Statistical thermodynamics can
only be used to calculate the final result, after the external
imbalances have been removed and the ensemble has set-
tled back down to equilibrium.)
In principle, non-equilibrium statistical mechanics could
be mathematically exact: ensembles for an isolated system
evolve over time according to deterministic equations such
as Liouville’s equation or its quantum equivalent, the von
Neumann equation. These equations are the result of ap-
plying the mechanical equations of motion independently to
each state in the ensemble. Unfortunately, these ensemble
evolution equations inherit much of the complexity of the
underlying mechanical motion, and so exact solutions are
very difficult to obtain. Moreover, the ensemble evolution
• Boltzmann transport equation: An early form of
stochastic mechanics appeared even before the term
“statistical mechanics” had been coined, in studies of
kinetic theory. James Clerk Maxwell had demon-
strated that molecular collisions would lead to appar-
ently chaotic motion inside a gas. Ludwig Boltzmann
subsequently showed that, by taking this molecular
chaos for granted as a complete randomization, the
motions of particles in a gas would follow a simple
Boltzmann transport equation that would rapidly re-
store a gas to an equilibrium state (see H-theorem).
The Boltzmann transport equation and related ap-
proaches are important tools in non-equilibrium statis-
tical mechanics due to their extreme simplicity. These
approximations work well in systems where the “in-
teresting” information is immediately (after just one
collision) scrambled up into subtle correlations, which
essentially restricts them to rarefied gases. The Boltz-
mann transport equation has been found to be very
useful in simulations of electron transport in lightly
doped semiconductors (in transistors), where the elec-
trons are indeed analogous to a rarefied gas.
A quantum technique related in theme is the random
phase approximation.
• BBGKY hierarchy: In liquids and dense gases, it is
not valid to immediately discard the correlations be-
24 CHAPTER 1. CHAPTER 1. INTRODUCTION

tween particles after one collision. The BBGKY hier-
archy (Bogoliubov–Born–Green–Kirkwood–Yvon hi-
erarchy) gives a method for deriving Boltzmann-type
equations but also extending them beyond the dilute
gas case, to include correlations after a few collisions.
• Keldysh formalism (a.k.a. NEGF—non-equilibrium
Green functions): A quantum approach to including
stochastic dynamics is found in the Keldysh formal-
ism. This approach often used in electronic quantum
transport calculations.
an electronic system is the use of the Green-Kubo rela-
tions, with the inclusion of stochastic dephasing by inter-
actions between various electrons by use of the Keldysh
method.[8][9]
1.2.4 Applications outside thermodynamics
The ensemble formalism also can be used to analyze general
mechanical systems with uncertainty in knowledge about
the state of a system. Ensembles are also used in:

Near-equilibrium methods • propagation of uncertainty over time,[1]

Another important class of non-equilibrium statistical me- • regression analysis of gravitational orbits,
chanical models deals with systems that are only very
slightly perturbed from equilibrium. With very small • ensemble forecasting of weather,
perturbations, the response can be analysed in linear re-
• dynamics of neural networks,
sponse theory. A remarkable result, as formalized by the
fluctuation-dissipation theorem, is that the response of a • bounded-rational potential games in game theory and
system when near equilibrium is precisely related to the economics.
fluctuations that occur when the system is in total equi-
librium. Essentially, a system that is slightly away from
equilibrium—whether put there by external forces or by 1.2.5 History
fluctuations—relaxes towards equilibrium in the same way,
since the system cannot tell the difference or “know” how In 1738, Swiss physicist and mathematician Daniel
it came to be away from equilibrium.[3]:664 Bernoulli published Hydrodynamica which laid the basis for
This provides an indirect avenue for obtaining numbers the kinetic theory of gases. In this work, Bernoulli posited
such as ohmic conductivity and thermal conductivity by the argument, still used to this day, that gases consist of
extracting results from equilibrium statistical mechanics. great numbers of molecules moving in all directions, that
Since equilibrium statistical mechanics is mathematically their impact on a surface causes the gas pressure that we
well defined and (in some cases) more amenable for calcu- feel, and that what we experience as heat is simply the ki-
lations, the fluctuation-dissipation connection can be a con- netic energy of their motion.[5]
venient shortcut for calculations in near-equilibrium statis- In 1859, after reading a paper on the diffusion of molecules
tical mechanics. by Rudolf Clausius, Scottish physicist James Clerk Maxwell
A few of the theoretical tools used to make this connection formulated the Maxwell distribution of molecular veloc-
include: ities, which gave the proportion of molecules having a
certain velocity in a specific range. This was the first-
• Fluctuation–dissipation theorem ever statistical law in physics.[10] Five years later, in 1864,
Ludwig Boltzmann, a young student in Vienna, came across
• Onsager reciprocal relations Maxwell’s paper and spent much of his life developing the
subject further.
• Green–Kubo relations
Statistical mechanics proper was initiated in the 1870s with
• Landauer–Büttiker formalism the work of Boltzmann, much of which was collectively
• Mori–Zwanzig formalism published in his 1896 Lectures on Gas Theory.[11] Boltz-
mann’s original papers on the statistical interpretation of
thermodynamics, the H-theorem, transport theory, thermal
Hybrid methods equilibrium, the equation of state of gases, and similar sub-
jects, occupy about 2,000 pages in the proceedings of the
An advanced approach uses a combination of stochastic Vienna Academy and other societies. Boltzmann intro-
methods and linear response theory. As an example, one duced the concept of an equilibrium statistical ensemble
approach to compute quantum coherence effects (weak lo- and also investigated for the first time non-equilibrium sta-
calization, conductance fluctuations) in the conductance of tistical mechanics, with his H-theorem.
1.2. STATISTICAL THERMODYNAMICS
The term “statistical mechanics” was coined by the
American mathematical physicist J. Willard Gibbs in
1884.[12][note 5] “Probabilistic mechanics” might today seem
a more appropriate term, but “statistical mechanics” is
firmly entrenched.[13] Shortly before his death, Gibbs pub-
lished in 1902 Elementary Principles in Statistical Mechan-
ics, a book which formalized statistical mechanics as a
fully general approach to address all mechanical systems—
macroscopic or microscopic, gaseous or non-gaseous.[1]
Gibbs’ methods were initially derived in the framework
classical mechanics, however they were of such generality
that they were found to adapt easily to the later quantum
mechanics, and still form the foundation of statistical me-
chanics to this day.[2]
1.2.6 See also
• Thermodynamics: non-equilibrium, chemical
• Mechanics: classical, quantum
• Probability, statistical ensemble
• Numerical methods: Monte Carlo method, molecular
dynamics
• Statistical physics
• Quantum statistical mechanics
• List of notable textbooks in statistical mechanics
• List of important publications in statistical mechanics
Fundamentals of Statistical Mechanics – Wikipedia book
1.2.7 Notes
[1] The term statistical mechanics is sometimes used to refer
to only statistical thermodynamics. This article takes the
broader view. By some definitions, statistical physics is an
even broader term which statistically studies any type of
physical system, but is often taken to be synonymous with
statistical mechanics.
[2] The probabilities in quantum statistical mechanics should
not be confused with quantum superposition. While a quan-
tum ensemble can contain states with quantum superposi-
tions, a single quantum state cannot be used to represent an
ensemble.
[3] Statistical equilibrium should not be confused with
mechanical equilibrium. The latter occurs when a me-
chanical system has completely ceased to evolve even on a
microscopic scale, due to being in a state with a perfect bal-
ancing of forces. Statistical equilibrium generally involves
states that are very far from mechanical equilibrium.
25
[4] The transitive thermal equilibrium (as in, “X is thermal equi-
librium with Y”) used here means that the ensemble for the
first system is not perturbed when the system is allowed to
weakly interact with the second system.
[5] According to Gibbs, the term “statistical”, in the context of
mechanics, i.e. statistical mechanics, was first used by the
Scottish physicist James Clerk Maxwell in 1871. From: J.
Clerk Maxwell, Theory of Heat (London, England: Long-
mans, Green, and Co., 1871), p. 309: “In dealing with
masses of matter, while we do not perceive the individual
molecules, we are compelled to adopt what I have described
as the statistical method of calculation, and to abandon the
strict dynamical method, in which we follow every motion
by the calculus.”
1.2.8 References
[1] Gibbs, Josiah Willard (1902). Elementary Principles in Sta-
tistical Mechanics. New York: Charles Scribner’s Sons.
[2] Tolman, R. C. (1938). The Principles of Statistical Mechan-
ics. Dover Publications. ISBN 9780486638966.
[3] Balescu, Radu (1975). Equilibrium and Non-Equilibrium
Statistical Mechanics. John Wiley & Sons. ISBN
9780471046004.
[4] Jaynes, E. (1957). “Information Theory and Statis-
tical Mechanics”. Physical Review 106 (4): 620.
doi:10.1103/PhysRev.106.620.
[5] J. Uffink, "Compendium of the foundations of classical sta-
tistical physics." (2006)
[6] Reif, F. (1965). Fundamentals of Statistical and Thermal
Physics. McGraw–Hill. p. 227. ISBN 9780070518001.
[7] Baxter, Rodney J. (1982). Exactly solved models in statistical
mechanics. Academic Press Inc. ISBN 9780120831807.
[8] Altshuler, B. L.; Aronov, A. G.; Khmelnitsky, D. E. (1982).
“Effects of electron-electron collisions with small energy
transfers on quantum localisation”. Journal of Physics
C: Solid State Physics 15 (36): 7367. doi:10.1088/0022-
3719/15/36/018.
[9] Aleiner, I.; Blanter, Y. (2002). “Inelastic scattering time
for conductance fluctuations”. Physical Review B 65 (11).
doi:10.1103/PhysRevB.65.115317.
[10] Mahon, Basil (2003). The Man Who Changed Everything –
the Life of James Clerk Maxwell. Hoboken, NJ: Wiley. ISBN
0-470-86171-1. OCLC 52358254.
[11] Ebeling, Werner; Sokolov, Igor M. (2005). Statistical Ther-
modynamics and Stochastic Theory of Nonequilibrium Sys-
tems. World Scientific Publishing Co. Pte. Ltd. pp. 3–12.
ISBN 978-90-277-1674-3. (section 1.2)
26 CHAPTER 1. CHAPTER 1. INTRODUCTION

[12] J. W. Gibbs, “On the Fundamental Formula of Statistical 1.3.1 History

Mechanics, with Applications to Astronomy and Thermo-
dynamics.” Proceedings of the American Association for the
Advancement of Science, 33, 57-58 (1884). Reproduced in
The Scientific Papers of J. Willard Gibbs, Vol II (1906), pp.
16.

[13] Mayants, Lazar (1984). The enigma of probability and

physics. Springer. p. 174. ISBN 978-90-277-1674-3.

1.2.9 External links

• Philosophy of Statistical Mechanics article by
Lawrence Sklar for the Stanford Encyclopedia of
Philosophy.

• Sklogwiki - Thermodynamics, statistical mechanics,

and the computer simulation of materials. SklogWiki
is particularly orientated towards liquids and soft con-
densed matter.

• Statistical Thermodynamics - Historical Timeline

• Thermodynamics and Statistical Mechanics by

Richard Fitzpatrick

• Lecture Notes in Statistical Mechanics and Mesoscop-

ics by Doron Cohen J. Willard Gibbs - founder of chemical thermodynamics

• Videos of lecture series in statistical mechanics on In 1865, the German physicist Rudolf Clausius, in his
YouTube taught by Leonard Susskind. Mechanical Theory of Heat, suggested that the prin-
• Vu-Quoc, L., Configuration integral (statistical me- ciples of thermochemistry, e.g. the heat evolved in
chanics), 2008. this wiki site is down; see this article combustion reactions,
[2]
could be applied to the principles of
in the web archive on 2012 April 28. thermodynamics. Building on the work of Clausius, be-
tween the years 1873-76 the American mathematical physi-
cist Willard Gibbs published a series of three papers, the
most famous one being the paper On the Equilibrium of
1.3 Chemical Thermodynamics Heterogeneous Substances. In these papers, Gibbs showed
how the first two laws of thermodynamics could be mea-
Chemical thermodynamics is the study of the interrela- sured graphically and mathematically to determine both the
tion of heat and work with chemical reactions or with phys- thermodynamic equilibrium of chemical reactions as well
ical changes of state within the confines of the laws of ther- as their tendencies to occur or proceed. Gibbs’ collection
modynamics. Chemical thermodynamics involves not only of papers provided the first unified body of thermodynamic
laboratory measurements of various thermodynamic prop- theorems from the principles developed by others, such as
erties, but also the application of mathematical methods to Clausius and Sadi Carnot.
the study of chemical questions and the spontaneity of pro- During the early 20th century, two major publications
cesses. successfully applied the principles developed by Gibbs to
The structure of chemical thermodynamics is based on the chemical processes, and thus established the foundation of
first two laws of thermodynamics. Starting from the first the science of chemical thermodynamics. The first was
and second laws of thermodynamics, four equations called the 1923 textbook Thermodynamics and the Free Energy
the “fundamental equations of Gibbs” can be derived. From of Chemical Substances by Gilbert N. Lewis and Merle
these four, a multitude of equations, relating the thermody- Randall. This book was responsible for supplanting the
namic properties of the thermodynamic system can be de- chemical affinity for the term free energy in the English-
rived using relatively simple mathematics. This outlines the speaking world. The second was the 1933 book Modern
mathematical framework of chemical thermodynamics.[1] Thermodynamics by the methods of Willard Gibbs written
1.3. CHEMICAL THERMODYNAMICS 27

by E. A. Guggenheim. In this manner, Lewis, Randall, of chemical bonds involves energy or heat, which may be
and Guggenheim are considered as the founders of mod- either absorbed or evolved from a chemical system.
ern chemical thermodynamics because of the major con- Energy that can be released (or absorbed) because of a re-
tribution of these two books in unifying the application of action between a set of chemical substances is equal to the
thermodynamics to chemistry.[1] difference between the energy content of the products and
the reactants. This change in energy is called the change in
1.3.2 Overview internal energy of a chemical reaction. Where ∆Uf◦ reactants
is the internal energy of formation of the reactant molecules
The primary objective of chemical thermodynamics is the that can be calculated from the bond energies of the vari-
establishment of a criterion for the determination of the fea- ous chemical bonds of the molecules under consideration
sibility or spontaneity of a given transformation.[3] In this and ∆Uf◦ products is the internal energy of formation of the
manner, chemical thermodynamics is typically used to pre- product molecules. The change in internal energy is a pro-
dict the energy exchanges that occur in the following pro- cess which is equal to the heat change if it is measured un-
cesses: der conditions of constant volume(at STP condition), as
in a closed rigid container such as a bomb calorimeter.
However, under conditions of constant pressure, as in reac-
1. Chemical reactions
tions in vessels open to the atmosphere, the measured heat
2. Phase changes change is not always equal to the internal energy change,
because pressure-volume work also releases or absorbs en-
3. The formation of solutions ergy. (The heat change at constant pressure is called the
enthalpy change; in this case the enthalpy of formation).
The following state functions are of primary concern in Another useful term is the heat of combustion, which is the
chemical thermodynamics: energy released due to a combustion reaction and often ap-
plied in the study of fuels. Food is similar to hydrocar-
• Internal energy (U) bon fuel and carbohydrate fuels, and when it is oxidized, its
caloric content is similar (though not assessed in the same
• Enthalpy (H)
way as a hydrocarbon fuel — see food energy).
• Entropy (S) In chemical thermodynamics the term used for the chemi-
cal potential energy is chemical potential, and for chemical
• Gibbs free energy (G)
transformation an equation most often used is the Gibbs-
Duhem equation.
Most identities in chemical thermodynamics arise from ap-
plication of the first and second laws of thermodynamics,
particularly the law of conservation of energy, to these state
functions.
The 3 laws of thermodynamics: 1.3.4 Chemical reactions

1. The energy of the universe is constant. Main article: Chemical reaction

2. In any spontaneous process, there is always an increase
in entropy of the universe In most cases of interest in chemical thermodynamics there
are internal degrees of freedom and processes, such as
3. The entropy of a perfect crystal(well ordered) at 0 chemical reactions and phase transitions, which always cre-
Kelvin is zero ate entropy unless they are at equilibrium, or are maintained
at a “running equilibrium” through “quasi-static” changes
by being coupled to constraining devices, such as pistons
1.3.3 Chemical energy or electrodes, to deliver and receive external work. Even
for homogeneous “bulk” materials, the free energy func-
Main article: Chemical energy tions depend on the composition, as do all the extensive
thermodynamic potentials, including the internal energy. If
Chemical energy is the potential of a chemical substance to the quantities { Ni }, the number of chemical species, are
undergo a transformation through a chemical reaction or to omitted from the formulae, it is impossible to describe com-
transform other chemical substances. Breaking or making positional changes.
28
Gibbs function or Gibbs Energy
For a “bulk” (unstructured) system they are the last remain-
ing extensive variables. For an unstructured, homogeneous
“bulk” system, there are still various extensive composi-
tional variables { Ni } that G depends on, which specify
the composition, the amounts of each chemical substance,
expressed as the numbers of molecules present or (divid-
ing by Avogadro’s number = 6.023× 1023 ), the numbers of
moles
G = G(T, P, {Ni }) .
For the case where only PV work is possible
∑
dG = −SdT + V dP + µi dNi
i
in which μi is the chemical potential for the i-th component derivative
in the system
( )
∂G
µi = .
∂Ni T,P,Nj̸=i ,etc.
The expression for dG is especially useful at constant T and
P, conditions which are easy to achieve experimentally and
which approximates the condition in living creatures
∑ change in the Gibbs free energy of the process is negative,
(dG)T,P = µi dNi .
i
Chemical affinity
Main article: Chemical affinity
While this formulation is mathematically defensible, it is
not particularly transparent since one does not simply add or
remove molecules from a system. There is always a process
involved in changing the composition; e.g., a chemical reac-
tion (or many), or movement of molecules from one phase
(liquid) to another (gas or solid). We should find a nota-
tion which does not seem to imply that the amounts of the
components ( Ni } can be changed independently. All real
processes obey conservation of mass, and in addition, con-
servation of the numbers of atoms of each kind. Whatever
molecules are transferred to or from should be considered
part of the “system”.
Consequently, we introduce an explicit variable to represent dξj/dt. For each and every physically independent process
the degree of advancement of a process, a progress variable (Prigogine & Defay, p. 38; Prigogine, p. 24)
CHAPTER 1. CHAPTER 1. INTRODUCTION
ξ for the extent of reaction (Prigogine & Defay, p. 18; Pri-
gogine, pp. 4–7; Guggenheim, p. 37.62), and to the use
of the partial derivative ∂G/∂ξ (in place of the widely used
"ΔG", since the quantity at issue is not a finite change). The
result is an understandable expression for the dependence of
dG on chemical reactions (or other processes). If there is
just one reaction
( )
∂G
(dG)T,P = dξ.
∂ξ T,P
If we introduce the stoichiometric coefficient for the i-th
component in the reaction
νi = ∂Ni /∂ξ
which tells how many molecules of i are produced or con-
sumed, we obtain an algebraic expression for the partial
( ) ∑
∂G
= µi νi = −A
∂ξ T,P i
where, (De Donder; Progoine & Defay, p. 69; Guggen-
heim, pp. 37,240), we introduce a concise and historical
name for this quantity, the "affinity", symbolized by A, as
introduced by Théophile de Donder in 1923. The minus
sign comes from the fact the affinity was defined to represent
the rule that spontaneous changes will ensue only when the
meaning that the chemical species have a positive affinity
for each other. The differential for G takes on a simple form
which displays its dependence on compositional change
(dG)T,P = −A dξ .
If there are a number of chemical reactions going on simul-
taneously, as is usually the case
∑
(dG)T,P = − Ak dξk .
k
a set of reaction coordinates { ξj }, avoiding the notion that
the amounts of the components ( Ni } can be changed in-
dependently. The expressions above are equal to zero at
thermodynamic equilibrium, while in the general case for
real systems, they are negative because all chemical reac-
tions proceeding at a finite rate produce entropy. This can
be made even more explicit by introducing the reaction rates
1.3. CHEMICAL THERMODYNAMICS
A ξ˙ ≤ 0 .
This is a remarkable result since the chemical potentials
are intensive system variables, depending only on the local
molecular milieu. They cannot “know” whether the temper-
ature and pressure (or any other system variables) are going
to be held constant over time. It is a purely local criterion
and must hold regardless of any such constraints. Of course,
it could have been obtained by taking partial derivatives of
any of the other fundamental state functions, but nonethe-
less is a general criterion for (−T times) the entropy pro-
duction from that spontaneous process; or at least any part
of it that is not captured as external work. (See Constraints
below.)
We now relax the requirement of a homogeneous “bulk”
system by letting the chemical potentials and the affinity
apply to any locality in which a chemical reaction (or any
other process) is occurring. By accounting for the entropy
production due to irreversible processes, the inequality for
dG is now replaced by an equality
∑ explaining how ordered structures e.g. the biological sys-
dG = −SdT + V dP − Ak dξk + W ′
k tions are utilized, the classical principles of equilibrium in
or
∑ ordered structures.
dGT,P = − Ak dξk + W ′ .
k Prigogine called these systems dissipative systems, because
Any decrease in the Gibbs function of a system is the upper
limit for any isothermal, isobaric work that can be captured
in the surroundings, or it may simply be dissipated, appear-
ing as T times a corresponding increase in the entropy of
the system and/or its surrounding. Or it may go partly to-
ward doing external work and partly toward creating en-
tropy. The important point is that the extent of reaction for
a chemical reaction may be coupled to the displacement of
some external mechanical or electrical quantity in such a
way that one can advance only if the other one also does.
The coupling may occasionally be rigid, but it is often flex-
ible and variable.
Solutions
In solution chemistry and biochemistry, the Gibbs free en-
ergy decrease (∂G/∂ξ, in molar units, denoted cryptically
by ΔG) is commonly used as a surrogate for (−T times) the
entropy produced by spontaneous chemical reactions in sit-
uations where there is no work being done; or at least no
“useful” work; i.e., other than perhaps some ± PdV. The
29
assertion that all spontaneous reactions have a negative ΔG
is merely a restatement of the fundamental thermodynamic
relation, giving it the physical dimensions of energy and
somewhat obscuring its significance in terms of entropy.
When there is no useful work being done, it would be less
misleading to use the Legendre transforms of the entropy
appropriate for constant T, or for constant T and P, the
Massieu functions −F/T and −G/T respectively.
1.3.5 Non equilibrium
Main article: non-equilibrium thermodynamics
Generally the systems treated with the conventional chemi-
cal thermodynamics are either at equilibrium or near equi-
librium. Ilya Prigogine developed the thermodynamic treat-
ment of open systems that are far from equilibrium. In do-
ing so he has discovered phenomena and structures of com-
pletely new and completely unexpected types. His general-
ized, nonlinear and irreversible thermodynamics has found
surprising applications in a wide variety of fields.
The non equilibrium thermodynamics has been applied for
tems, can develop from disorder. Even if Onsager’s rela-
thermodynamics still show that linear systems close to equi-
librium always develop into states of disorder which are sta-
ble to perturbations and cannot explain the occurrence of
they are formed and maintained by the dissipative processes
which take place because of the exchange of energy be-
tween the system and its environment and because they dis-
appear if that exchange ceases. They may be said to live in
symbiosis with their environment.
The method which Prigogine used to study the stability of
the dissipative structures to perturbations is of very great
general interest. It makes it possible to study the most var-
ied problems, such as city traffic problems, the stability of
insect communities, the development of ordered biological
structures and the growth of cancer cells to mention but a
few examples.
System constraints
In this regard, it is crucial to understand the role of walls
and other constraints, and the distinction between indepen-
dent processes and coupling. Contrary to the clear implica-
tions of many reference sources, the previous analysis is not
restricted to homogeneous, isotropic bulk systems which
can deliver only PdV work to the outside world, but ap-
30
plies even to the most structured systems. There are com-
plex systems with many chemical “reactions” going on at the
same time, some of which are really only parts of the same,
overall process. An independent process is one that could
proceed even if all others were unaccountably stopped in
their tracks. Understanding this is perhaps a “thought ex-
periment” in chemical kinetics, but actual examples exist.
A gas reaction which results in an increase in the number 1.3.8 Further reading
of molecules will lead to an increase in volume at constant
external pressure. If it occurs inside a cylinder closed with • Herbert B. Callen (1960). Thermodynamics. Wiley
a piston, the equilibrated reaction can proceed only by do-
ing work against an external force on the piston. The ex-
tent variable for the reaction can increase only if the piston
moves, and conversely, if the piston is pushed inward, the
reaction is driven backwards.
Similarly, a redox reaction might occur in an
electrochemical cell with the passage of current in
wires connecting the electrodes. The half-cell reactions at
the electrodes are constrained if no current is allowed to
flow. The current might be dissipated as joule heating, or
it might in turn run an electrical device like a motor doing
mechanical work. An automobile lead-acid battery can
be recharged, driving the chemical reaction backwards.
In this case as well, the reaction is not an independent
process. Some, perhaps most, of the Gibbs free energy of
reaction may be delivered as external work.
The hydrolysis of ATP to ADP and phosphate can drive
the force times distance work delivered by living muscles,
and synthesis of ATP is in turn driven by a redox chain in
mitochondria and chloroplasts, which involves the transport
of ions across the membranes of these cellular organelles.
The coupling of processes here, and in the previous exam-
ples, is often not complete. Gas can leak slowly past a pis- 1.3.9 External links
ton, just as it can slowly leak out of a rubber balloon. Some
reaction may occur in a battery even if no external current is • Chemical Thermodynamics - University of North Car-
flowing. There is usually a coupling coefficient, which may
depend on relative rates, which determines what percent-
age of the driving free energy is turned into external work,
or captured as “chemical work"; a misnomer for the free
energy of another chemical process.
1.3.6 See also
• Thermodynamic databases for pure substances
1.3.7 References
[1] Ott, Bevan J.; Boerio-Goates, Juliana (2000). Chemical
Thermodynamics – Principles and Applications. Academic
Press. ISBN 0-12-530990-2.
[2] Clausius, R. (1865). The Mechanical Theory of Heat – with in its own state of internal thermodynamic equilibrium, is
CHAPTER 1. CHAPTER 1. INTRODUCTION
its Applications to the Steam Engine and to Physical Properties
of Bodies. London: John van Voorst, 1 Paternoster Row.
MDCCCLXVII.
[3] Klotz, I. (1950). Chemical Thermodynamics. New York:
Prentice-Hall, Inc.
& Sons. The clearest account of the logical founda-
tions of the subject. ISBN 0-471-13035-4. Library of
Congress Catalog No. 60-5597
• Ilya Prigogine & R. Defay, translated by D.H. Ev-
erett; Chapter IV (1954). Chemical Thermodynamics.
Longmans, Green & Co. Exceptionally clear on the
logical foundations as applied to chemistry; includes
non-equilibrium thermodynamics.
• Ilya Prigogine (1967). Thermodynamics of Irreversible
Processes, 3rd ed. Interscience: John Wiley & Sons.
A simple, concise monograph explaining all the basic
ideas. Library of Congress Catalog No. 67-29540
• E.A. Guggenheim (1967). Thermodynamics: An Ad-
vanced Treatment for Chemists and Physicists, 5th ed.
North Holland; John Wiley & Sons (Interscience). A
remarkably astute treatise. Library of Congress Cata-
log No. 67-20003
• Th. De Donder (1922). Bull. Ac. Roy. Belg. (Cl. Sc.)
(5) 7: 197, 205. Missing or empty |title= (help)
olina
• Chemical energetics (Introduction to thermodynamics
and the First Law)
• Thermodynamics of chemical equilibrium (Entropy,
Second Law and free energy)
1.4 Equilibrium Thermodynamics
Equilibrium Thermodynamics is the systematic study of
transformations of matter and energy in systems in terms
of a concept called thermodynamic equilibrium. The word
equilibrium implies a state of balance. Equilibrium ther-
modynamics, in origins, derives from analysis of the Carnot
cycle. Here, typically a system, as cylinder of gas, initially
1.5. NON-EQUILIBRIUM THERMODYNAMICS 31

set out of balance via heat input from a combustion reac- • Kondepudi, D. & Prigogine, I. (2004). Modern Ther-
tion. Then, through a series of steps, as the system settles modynamics – From Heat Engines to Dissipative Struc-
into its final equilibrium state, work is extracted. tures (textbook). New York: John Wiley & Sons.
In an equilibrium state the potentials, or driving forces,
within the system, are in exact balance. A central aim in
equilibrium thermodynamics is: given a system in a well- • Perrot, P. (1998). A to Z of Thermodynamics (dictio-
defined initial state of thermodynamic equilibrium, subject nary). New York: Oxford University Press.
to accurately specified constraints, to calculate, when the
constraints are changed by an externally imposed interven-
tion, what the state of the system will be once it has reached
a new equilibrium. An equilibrium state is mathematically
ascertained by seeking the extrema of a thermodynamic po- 1.5 Non-equilibrium Thermody-
tential function, whose nature depends on the constraints
imposed on the system. For example, a chemical reaction
namics
at constant temperature and pressure will reach equilibrium
at a minimum of its components’ Gibbs free energy and a Non-equilibrium thermodynamics is a branch of
maximum of their entropy. thermodynamics that deals with physical systems that are
Equilibrium thermodynamics differs from non-equilibrium not in thermodynamic equilibrium but can be adequately
thermodynamics, in that, with the latter, the state of the sys- described in terms of variables (non-equilibrium state
tem under investigation will typically not be uniform but variables) that represent an extrapolation of the variables
will vary locally in those as energy, entropy, and temper- used to specify the system in thermodynamic equilibrium.
ature distributions as gradients are imposed by dissipative Non-equilibrium thermodynamics is concerned with
thermodynamic fluxes. In equilibrium thermodynamics, by transport processes and with the rates of chemical reac-
contrast, the state of the system will be considered uniform tions. It relies on what may be thought of as more or less
throughout, defined macroscopically by such quantities as nearness to thermodynamic equilibrium. Non-equilibrium
temperature, pressure, or volume. Systems are studied in thermodynamics is a work in progress, not an established
terms of change from one equilibrium state to another; such edifice. This article will try to sketch some approaches to
a change is called a thermodynamic process. it and some concepts important for it.

Ruppeiner geometry is a type of information geometry Almost all systems found in nature are not in thermody-
used to study thermodynamics. It claims that thermody- namic equilibrium; for they are changing or can be trig-
namic systems can be represented by Riemannian geome- gered to change over time, and are continuously and dis-
try, and that statistical properties can be derived from the continuously subject to flux of matter and energy to and
model. This geometrical model is based on the idea that from other systems and to chemical reactions. Some sys-
there exist equilibrium states which can be represented by tems and processes are, however, in a useful sense, near
points on two-dimensional surface and the distance between enough to thermodynamic equilibrium to allow description
these equilibrium states is related to the fluctuation between with useful accuracy by currently known non-equilibrium
them. thermodynamics. Nevertheless, many natural systems and
processes will always remain far beyond the scope of non-
equilibrium thermodynamic methods. This is because of
1.4.1 See also the very small size of atoms, as compared with macroscopic
systems.
• Non-equilibrium thermodynamics The thermodynamic study of non-equilibrium systems re-
quires more general concepts than are dealt with by
• Thermodynamics
equilibrium thermodynamics. One fundamental difference
between equilibrium thermodynamics and non-equilibrium
1.4.2 References thermodynamics lies in the behaviour of inhomogeneous
systems, which require for their study knowledge of rates of
• Adkins, C.J. (1983). Equilibrium Thermodynamics, reaction which are not considered in equilibrium thermody-
3rd Ed. Cambridge: Cambridge University Press. namics of homogeneous systems. This is discussed below.
Another fundamental and very important difference is the
• Cengel, Y. & Boles, M. (2002). Thermodynamics – difficulty or impossibility in defining entropy at an instant
an Engineering Approach, 4th Ed. (textbook). New of time in macroscopic terms for systems not in thermody-
York: McGraw Hill. namic equilibrium.[1][2]
32
1.5.1 Scope of non-equilibrium thermody- spond to extensive thermodynamic state variables have to
namics be defined as spatial densities of the corresponding exten-
Difference between equilibrium and non-equilibrium
thermodynamics
A profound difference separates equilibrium from non-
equilibrium thermodynamics. Equilibrium thermodynam-
ics ignores the time-courses of physical processes. In
contrast, non-equilibrium thermodynamics attempts to de-
scribe their time-courses in continuous detail.
Equilibrium thermodynamics restricts its considerations to
processes that have initial and final states of thermodynamic
equilibrium; the time-courses of processes are deliberately
ignored. Consequently, equilibrium thermodynamics al-
lows processes that pass through states far from thermody-
namic equilibrium, that cannot be described even by the
variables admitted for non-equilibrium thermodynamics,[3]
such as time rates of change of temperature and pressure.[4]
For example, in equilibrium thermodynamics, a process is
allowed to include even a violent explosion that cannot be
described by non-equilibrium thermodynamics.[3] Equilib-
rium thermodynamics does, however, for theoretical de-
velopment, use the idealized concept of the “quasi-static
process”. A quasi-static process is a conceptual (time-
less and physically impossible) smooth mathematical pas-
sage along a continuous path of states of thermodynamic
equilibrium.[5] It is an exercise in differential geometry
rather than a process that could occur in actuality.
Non-equilibrium thermodynamics, on the other hand, at-
tempting to describe continuous time-courses, need its state
variables to have a very close connection with those of
equilibrium thermodynamics.[6] This profoundly restricts
the scope of non-equilibrium thermodynamics, and places
heavy demands on its conceptual framework.
Non-equilibrium state variables
The suitable relationship that defines non-equilibrium ther-
modynamic state variables is as follows. On occasions when
the system happens to be in states that are sufficiently close
to thermodynamic equilibrium, non-equilibrium state vari-
ables are such that they can be measured locally with suffi-
cient accuracy by the same techniques as are used to mea-
sure thermodynamic state variables, or by corresponding
and time and space derivatives, including fluxes of matter
and energy. In general, non-equilibrium thermodynamic
systems are spatially and temporally non-uniform, but their
non-uniformity still has a sufficient degree of smoothness to
support the existence of suitable time and space derivatives
of non-equilibrium state variables. Because of the spatial
non-uniformity, non-equilibrium state variables that corre-
CHAPTER 1. CHAPTER 1. INTRODUCTION
sive equilibrium state variables. On occasions when the sys-
tem is sufficiently close to thermodynamic equilibrium, in-
tensive non-equilibrium state variables, for example tem-
perature and pressure, correspond closely with equilibrium
state variables. It is necessary that measuring probes be
small enough, and rapidly enough responding, to capture
relevant non-uniformity. Further, the non-equilibrium state
variables are required to be mathematically functionally re-
lated to one another in ways that suitably resemble cor-
responding relations between equilibrium thermodynamic
state variables.[7] In reality, these requirements are very de-
manding, and it may be difficult or practically, or even the-
oretically, impossible to satisfy them. This is part of why
non-equilibrium thermodynamics is a work in progress.
1.5.2 Overview
Non-equilibrium thermodynamics is a work in progress, not
an established edifice. This article will try to sketch some
approaches to it and some concepts important for it.
Some concepts of particular importance for non-
equilibrium thermodynamics include time rate of dis-
sipation of energy (Rayleigh 1873,[8] Onsager 1931,[9]
also[7][10] ), time rate of entropy production (Onsager
1931),[9] thermodynamic fields,[11][12][13] dissipative
structure,[14] and non-linear dynamical structure.[10]
One problem of interest is the thermodynamic study of non-
equilibrium steady states, in which entropy production and
some flows are non-zero, but there is no time variation of
physical variables.
One initial approach to non-equilibrium thermodynamics is
sometimes called 'classical irreversible thermodynamics’.[2]
There are other approaches to non-equilibrium thermody-
namics, for example extended irreversible thermodynam-
ics,[2][15] and generalized thermodynamics,[16] but they are
hardly touched on in the present article.
Quasi-radiationless non-equilibrium thermodynamics
of matter in laboratory conditions
According to Wildt[17] (see also Essex[18][19][20] ), current
versions of non-equilibrium thermodynamics ignore radiant
heat; they can do so because they refer to laboratory quan-
tities of matter under laboratory conditions with tempera-
tures well below those of stars. At laboratory temperatures,
in laboratory quantities of matter, thermal radiation is weak
and can be practically nearly ignored. But, for example, at-
mospheric physics is concerned with large amounts of mat-
ter, occupying cubic kilometers, that, taken as a whole, are
1.5. NON-EQUILIBRIUM THERMODYNAMICS
not within the range of laboratory quantities; then thermal tively treated as two-dimensional surfaces, with no spatial
radiation cannot be ignored. volume, and no spatial variation.
Local equilibrium thermodynamics
The terms 'classical irreversible thermodynamics’[2] and 'lo-
cal equilibrium thermodynamics’ are sometimes used to re-
fer to a version of non-equilibrium thermodynamics that de-
mands certain simplifying assumptions, as follows. The as-
sumptions have the effect of making each very small vol-
ume element of the system effectively homogeneous, or
well-mixed, or without an effective spatial structure, and
without kinetic energy of bulk flow or of diffusive flux.
Even within the thought-frame of classical irreversible ther-
modynamics, care[10] is needed in choosing the independent
variables[21] for systems. In some writings, it is assumed
that the intensive variables of equilibrium thermodynam-
ics are sufficient as the independent variables for the task
(such variables are considered to have no 'memory', and do
not show hysteresis); in particular, local flow intensive vari-
ables are not admitted as independent variables; local flows
are considered as dependent on quasi-static local intensive
variables.
Also it is assumed that the local entropy density is the same
function of the other local intensive variables as in equi-
librium; this is called the local thermodynamic equilib-
rium assumption[7][10][14][15][22][23][24][25] (see also Keizer
(1987)[26] ). Radiation is ignored because it is transfer of
energy between regions, which can be remote from one
another. In the classical irreversible thermodynamic ap-
proach, there is allowed very small spatial variation, from
very small volume element to adjacent very small volume
element, but it is assumed that the global entropy of the
system can be found by simple spatial integration of the lo-
cal entropy density; this means that spatial structure can-
not contribute as it properly should to the global entropy
assessment for the system. This approach assumes spatial
and temporal continuity and even differentiability of locally
defined intensive variables such as temperature and internal
energy density. All of these are very stringent demands.
Consequently, this approach can deal with only a very lim-
ited range of phenomena. This approach is nevertheless
valuable because it can deal well with some macroscopi-
cally observable phenomena.
In other writings, local flow variables are considered; these
might be considered as classical by analogy with the time-
invariant long-term time-averages of flows produced by
endlessly repeated cyclic processes; examples with flows are
in the thermoelectric phenomena known as the Seebeck and
the Peltier effects, considered by Kelvin in the nineteenth
century and by Onsager in the twentieth.[22][27] These ef-
fects occur at metal junctions, which were originally effec-
33
Local equilibrium thermodynamics with materials
with “memory” A further extension of local equilibrium
thermodynamics is to allow that materials may have “mem-
ory”, so that their constitutive equations depend not only on
present values but also on past values of local equilibrium
variables. Thus time comes into the picture more deeply
than for time-dependent local equilibrium thermodynamics
with memoryless materials, but fluxes are not independent
variables of state.[28]
Extended irreversible thermodynamics
Extended irreversible thermodynamics is a branch of
non-equilibrium thermodynamics that goes outside the re-
striction to the local equilibrium hypothesis. The space of
state variables is enlarged by including the fluxes of mass,
momentum and energy and eventually higher order fluxes.
The formalism is well-suited for describing high-frequency
processes and small-length scales materials.
1.5.3 Basic concepts
There are many examples of stationary non-equilibrium
systems, some very simple, like a system confined between
two thermostats at different temperatures or the ordinary
Couette flow, a fluid enclosed between two flat walls moving
in opposite directions and defining non-equilibrium condi-
tions at the walls. Laser action is also a non-equilibrium
process, but it depends on departure from local thermody-
namic equilibrium and is thus beyond the scope of clas-
sical irreversible thermodynamics; here a strong tempera-
ture difference is maintained between two molecular de-
grees of freedom (with molecular laser, vibrational and ro-
tational molecular motion), the requirement for two com-
ponent 'temperatures’ in the one small region of space, pre-
cluding local thermodynamic equilibrium, which demands
that only one temperature be needed. Damping of acous-
tic perturbations or shock waves are non-stationary non-
equilibrium processes. Driven complex fluids, turbulent
systems and glasses are other examples of non-equilibrium
systems.
The mechanics of macroscopic systems depends on a num-
ber of extensive quantities. It should be stressed that all sys-
tems are permanently interacting with their surroundings,
thereby causing unavoidable fluctuations of extensive quan-
tities. Equilibrium conditions of thermodynamic systems
are related to the maximum property of the entropy. If the
only extensive quantity that is allowed to fluctuate is the in-
ternal energy, all the other ones being kept strictly constant,
34 CHAPTER 1. CHAPTER 1. INTRODUCTION

the temperature of the system is measurable and meaning- 1.5.4 Stationary states, fluctuations, and
ful. The system’s properties are then most conveniently de- stability
scribed using the thermodynamic potential Helmholtz free
energy (A = U - TS), a Legendre transformation of the en- In thermodynamics one is often interested in a stationary
ergy. If, next to fluctuations of the energy, the macroscopic state of a process, allowing that the stationary state include
dimensions (volume) of the system are left fluctuating, we the occurrence of unpredictable and experimentally unre-
use the Gibbs free energy (G = U + PV - TS), where the producible fluctuations in the state of the system. The fluc-
system’s properties are determined both by the temperature tuations are due to the system’s internal sub-processes and
and by the pressure. to exchange of matter or energy with the system’s surround-
Non-equilibrium systems are much more complex and they ings that create the constraints that define the process.
may undergo fluctuations of more extensive quantities. The If the stationary state of the process is stable, then the unre-
boundary conditions impose on them particular intensive producible fluctuations involve local transient decreases of
variables, like temperature gradients or distorted collective entropy. The reproducible response of the system is then
motions (shear motions, vortices, etc.), often called ther- to increase the entropy back to its maximum by irreversible
modynamic forces. If free energies are very useful in equi- processes: the fluctuation cannot be reproduced with a sig-
librium thermodynamics, it must be stressed that there is no nificant level of probability. Fluctuations about stable sta-
general law defining stationary non-equilibrium properties tionary states are extremely small except near critical points
of the energy as is the second law of thermodynamics for (Kondepudi and Prigogine 1998, page 323).[29] The stable
the entropy in equilibrium thermodynamics. That is why stationary state has a local maximum of entropy and is lo-
in such cases a more generalized Legendre transformation cally the most reproducible state of the system. There are
should be considered. This is the extended Massieu poten- theorems about the irreversible dissipation of fluctuations.
tial. By definition, the entropy (S) is a function of the col- Here 'local' means local with respect to the abstract space
lection of extensive quantities Ei . Each extensive quantity of thermodynamic coordinates of state of the system.
has a conjugate intensive variable Ii (a restricted definition
If the stationary state is unstable, then any fluctuation will
of intensive variable is used here by comparison to the def-
almost surely trigger the virtually explosive departure of the
inition given in this link) so that:
system from the unstable stationary state. This can be ac-
companied by increased export of entropy.
Ii = ∂S/∂Ei .
We then define the extended Massieu function as follows: 1.5.5 Local thermodynamic equilibrium

∑ The scope of present-day non-equilibrium thermodynamics

kb M = S − (Ii Ei ), does not cover all physical processes. A condition for the
i validity of many studies in non-equilibrium thermodynam-
ics of matter is that they deal with what is known as local
where kb is Boltzmann’s constant, whence
thermodynamic equilibrium.

∑
kb dM = (Ei dIi ).
i ter
The independent variables are the intensities.
Intensities are global values, valid for the system as a whole.
When boundaries impose to the system different local con-
ditions, (e.g. temperature differences), there are intensive
variables representing the average value and others repre-
senting gradients or higher moments. The latter are the
thermodynamic forces driving fluxes of extensive proper-
ties through the system.
It may be shown that the Legendre transformation changes
the maximum condition of the entropy (valid at equilib-
rium) in a minimum condition of the extended Massieu
function for stationary states, no matter whether at equi-
librium or not.
Local thermodynamic equilibrium of ponderable mat-
Local thermodynamic equilibrium of matter[7][14][23][24][25]
(see also Keizer (1987)[26] means that conceptually, for
study and analysis, the system can be spatially and tempo-
rally divided into 'cells’ or 'micro-phases’ of small (infinites-
imal) size, in which classical thermodynamical equilibrium
conditions for matter are fulfilled to good approximation.
These conditions are unfulfilled, for example, in very rar-
efied gases, in which molecular collisions are infrequent;
and in the boundary layers of a star, where radiation is pass-
ing energy to space; and for interacting fermions at very low
temperature, where dissipative processes become ineffec-
tive. When these 'cells’ are defined, one admits that mat-
ter and energy may pass freely between contiguous 'cells’,
1.5. NON-EQUILIBRIUM THERMODYNAMICS 35

slowly enough to leave the 'cells’ in their respective individ- thermomechanics,[36][37][38][39] which evolved completely
ual local thermodynamic equilibria with respect to intensive independently of statistical mechanics and maximum-
variables. entropy principles.
One can think here of two 'relaxation times’ separated by
order of magnitude.[30] The longer relaxation time is of the 1.5.7 Flows and forces
order of magnitude of times taken for the macroscopic dy-
namical structure of the system to change. The shorter The fundamental relation of classical equilibrium thermo-
is of the order of magnitude of times taken for a single dynamics [40]
'cell' to reach local thermodynamic equilibrium. If these
two relaxation times are not well separated, then the classi-
cal non-equilibrium thermodynamical concept of local ther- 1 p ∑ µi s
modynamic equilibrium loses its meaning[30] and other ap- dS = dU + dV − dNi
T T T
proaches have to be proposed, see for instance Extended i=1
irreversible thermodynamics. For example, in the atmo-
expresses the change in entropy dS of a system as a func-
sphere, the speed of sound is much greater than the wind
tion of the intensive quantities temperature T , pressure p
speed; this favours the idea of local thermodynamic equi-
and ith chemical potential µi and of the differentials of the
librium of matter for atmospheric heat transfer studies at
extensive quantities energy U , volume V and ith particle
altitudes below about 60 km where sound propagates, but
number Ni .
not above 100 km, where, because of the paucity of inter-
molecular collisions, sound does not propagate. Following Onsager (1931,I),[9] let us extend our consider-
ations to thermodynamically non-equilibrium systems. As
a basis, we need locally defined versions of the extensive
Milne’s 1928 definition of local thermodynamic equi- macroscopic quantities U , V and Ni and of the intensive
librium in terms of radiative equilibrium macroscopic quantities T , p and µi .

Milne (1928),[31] thinking about stars, gave a definition of For classical non-equilibrium studies, we will consider some
'local thermodynamic equilibrium' in terms of the thermal new locally defined intensive macroscopic variables. We
radiation of the matter in each small local 'cell'. He defined can, under suitable conditions, derive these new variables
'local thermodynamic equilibrium' in a 'cell' by requiring by locally defining the gradients and flux densities of the
that it macroscopically absorb and spontaneously emit ra- basic locally defined macroscopic quantities.
diation as if it were in radiative equilibrium in a cavity at Such locally defined gradients of intensive macroscopic
the temperature of the matter of the 'cell'. Then it strictly variables are called 'thermodynamic forces’. They 'drive'
obeys Kirchhoff’s law of equality of radiative emissivity and flux densities, perhaps misleadingly often called 'fluxes’,
absorptivity, with a black body source function. The key which are dual to the forces. These quantities are defined
to local thermodynamic equilibrium here is that the rate of in the article on Onsager reciprocal relations.
collisions of ponderable matter particles such as molecules
Establishing the relation between such forces and flux den-
should far exceed the rates of creation and annihilation of
sities is a problem in statistical mechanics. Flux densities (
photons.
Ji ) may be coupled. The article on Onsager reciprocal re-
lations considers the stable near-steady thermodynamically
non-equilibrium regime, which has dynamics linear in the
1.5.6 Entropy in evolving systems
forces and flux densities.
It is pointed out[32][33][34][35] by W.T. Grandy Jr that en- In stationary conditions, such forces and associated flux
tropy, though it may be defined for a non-equilibrium sys- densities are by definition time invariant, as also are the
tem, is when strictly considered, only a macroscopic quan- system’s locally defined entropy and rate of entropy pro-
tity that refers to the whole system, and is not a dynami- duction. Notably, according to Ilya Prigogine and others,
cal variable and in general does not act as a local potential when an open system is in conditions that allow it to reach a
that describes local physical forces. Under special circum- stable stationary thermodynamically non-equilibrium state,
stances, however, one can metaphorically think as if the it organizes itself so as to minimize total entropy production
thermal variables behaved like local physical forces. The defined locally. This is considered further below.
approximation that constitutes classical irreversible ther-
One wants to take the analysis to the further stage of de-
modynamics is built on this metaphoric thinking. scribing the behaviour of surface and volume integrals of
This point of view shares many points in common non-stationary local quantities; these integrals are macro-
with the concept and the use of entropy in continuum scopic fluxes and production rates. In general the dynam-
36 CHAPTER 1. CHAPTER 1. INTRODUCTION

ics of these integrals are not adequately described by linear discussion of the possibilities for principles of extrema of
equations, though in special cases they can be so described. entropy production and of dissipation of energy: Chapter
12 of Grandy (2008)[1] is very cautious, and finds difficulty
in defining the 'rate of internal entropy production' in many
1.5.8 The Onsager relations cases, and finds that sometimes for the prediction of the
course of a process, an extremum of the quantity called the
Main article: Onsager reciprocal relations rate of dissipation of energy may be more useful than that
of the rate of entropy production; this quantity appeared in
[9]
Following Section III of Rayleigh (1873),[8] Onsager (1931, Onsager’s 1931 origination of this subject. Other writ-
I)[9] showed that in the regime where both the flows ( Ji ) ers have also felt that prospects for general global extremal
are small and the thermodynamic forces ( Fi ) vary slowly, principles are clouded. Such writers include Glansdorff and
the rate of creation of entropy (σ) is linearly related to the Prigogine (1971), Lebon, Jou and Casas-Vásquez (2008),
flows: and Šilhavý (1997).
A recent proposal may perhaps by-pass those clouded
∑ prospects.[42][43]
∂Fi
σ= Ji
i
∂xi
1.5.10 Applications of non-equilibrium
and the flows are related to the gradient of the forces, thermodynamics
parametrized by a matrix of coefficients conventionally de-
noted L : Non-equilibrium thermodynamics has been successfully
applied to describe biological processes such as protein
∑ folding/unfolding and transport through membranes.
∂Fj
Ji = Lij Also, ideas from non-equilibrium thermodynamics and the
j
∂xj
informatic theory of entropy have been adapted to describe
from which it follows that: general economic systems.[44] [45]

∑ ∂Fi ∂Fj 1.5.11 See also

σ= Lij
∂xi ∂xj
i,j • Dissipative system
The second law of thermodynamics requires that the matrix • Entropy production
L be positive definite. Statistical mechanics considerations
involving microscopic reversibility of dynamics imply that • Extremal principles in non-equilibrium thermodynam-
the matrix L is symmetric. This fact is called the Onsager ics
reciprocal relations.
• Self-organization

1.5.9 Speculated extremal principles for • Autocatalytic reactions and order creation
non-equilibrium processes • Self-organizing criticality
Main article: Extremal principles in non-equilibrium • Bogoliubov-Born-Green-Kirkwood-Yvon hierarchy
thermodynamics of equations

• Boltzmann equation
Until recently, prospects for useful extremal principles in
this area have seemed clouded. C. Nicolis (1999)[41] con- • Vlasov equation
cludes that one model of atmospheric dynamics has an at-
tractor which is not a regime of maximum or minimum • Maxwell’s demon
dissipation; she says this seems to rule out the existence
• Information entropy
of a global organizing principle, and comments that this
is to some extent disappointing; she also points to the dif- • Constructal theory
ficulty of finding a thermodynamically consistent form of
entropy production. Another top expert offers an extensive • Spontaneous symmetry breaking
1.5. NON-EQUILIBRIUM THERMODYNAMICS
1.5.12 References
[1] Grandy, W.T., Jr (2008).
[2] Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Understand-
ing Non-equilibrium Thermodynamics: Foundations, Appli-
cations, Frontiers, Springer-Verlag, Berlin, e-ISBN 978-3-
540-74252-4.
[3] Lieb, E.H., Yngvason, J. (1999), p. 5.
[4] Gyarmati, I. (1967/1970), pp. 8–12.
[5] Callen, H.B. (1960/1985), § 4–2.
[6] Glansdorff, P., Prigogine, I. (1971), Ch. II,§ 2.
[7] Gyarmati, I. (1967/1970).
[8] Strutt, J. W. (1871). “Some General Theorems relating to
Vibrations”. Proceedings of the London Mathematical Soci-
ety s1–4: 357–368. doi:10.1112/plms/s1-4.1.357.
[9] Onsager, L. (1931). “Reciprocal relations in ir-
reversible processes, I”. Physical Review 37
(4): 405–426. Bibcode:1931PhRv...37..405O.
doi:10.1103/PhysRev.37.405.
[10] Lavenda, B.H. (1978). Thermodynamics of Irreversible Pro-
cesses, Macmillan, London, ISBN 0-333-21616-4.
[11] Gyarmati, I. (1967/1970), pages 4-14.
[12] Ziegler, H., (1983). An Introduction to Thermomechanics,
North-Holland, Amsterdam, ISBN 0-444-86503-9.
[13] Balescu, R. (1975). Equilibrium and Non-equilibrium Sta-
tistical Mechanics, Wiley-Interscience, New York, ISBN 0-
471-04600-0, Section 3.2, pages 64-72.
[14] Glansdorff, P., Prigogine, I. (1971). Thermodynamic
Theory of Structure, Stability, and Fluctuations, Wiley-
Interscience, London, 1971, ISBN 0-471-30280-5.
[15] Jou, D., Casas-Vázquez, J., Lebon, G. (1993). Extended Ir-
reversible Thermodynamics, Springer, Berlin, ISBN 3-540-
55874-8, ISBN 0-387-55874-8.
[16] Eu, B.C. (2002).
[17] Wildt, R. (1972). “Thermodynamics of the gray atmo-
sphere. IV. Entropy transfer and production”. Astrophys-
ical Journal 174: 69–77. Bibcode:1972ApJ...174...69W.
doi:10.1086/151469
[18] Essex, C. (1984a). “Radiation and the irre-
versible thermodynamics of climate”. Journal of
the Atmospheric Sciences 41 (12): 1985–1991.
Bibcode:1984JAtS...41.1985E. doi:10.1175/1520-
0469(1984)041<1985:RATITO>2.0.CO;2.
[19] Essex, C. (1984b). “Minimum entropy production in
the steady state and radiative transfer”. Astrophysical
Journal 285: 279–293. Bibcode:1984ApJ...285..279E.
doi:10.1086/162504
37
[20] Essex, C. (1984c). “Radiation and the violation of bi-
linearity in the irreversible thermodynamics of irreversible
processes”. Planetary and Space Science 32 (8): 1035–
1043. Bibcode:1984P&SS...32.1035E. doi:10.1016/0032-
0633(84)90060-6
[21] Prigogine, I., Defay, R. (1950/1954). Chemical Thermody-
namics, Longmans, Green & Co, London, page 1.
[22] De Groot, S.R., Mazur, P. (1962). Non-equilibrium Ther-
modynamics, North-Holland, Amsterdam.
[23] Balescu, R. (1975). Equilibrium and Non-equilibrium Sta-
tistical Mechanics, John Wiley & Sons, New York, ISBN 0-
471-04600-0.
[24] Mihalas, D., Weibel-Mihalas, B. (1984). Foundations of
Radiation Hydrodynamics, Oxford University Press, New
York, ISBN 0-19-503437-6.
[25] Schloegl, F. (1989). Probability and Heat: Fundamentals
of Thermostatistics, Freidr. Vieweg & Sohn, Brausnchweig,
ISBN 3-528-06343-2.
[26] Keizer, J. (1987). Statistical Thermodynamics of Nonequi-
librium Processes, Springer-Verlag, New York, ISBN 0-387-
96501-7.
[27] Kondepudi, D. (2008). Introduction to Modern Thermody-
namics, Wiley, Chichester UK, ISBN 978-0-470-01598-8,
pages 333-338.
[28] Coleman, B.D., Noll, W. (1963). The thermodynamics of
elastic materials with heat conduction and viscosity, Arch.
Ration. Mach. Analysis, 13: 167–178.
[29] Kondepudi, D., Prigogine, I, (1998). Modern Thermody-
namics. From Heat Engines to Dissipative Structures, Wiley,
Chichester, 1998, ISBN 0-471-97394-7.
[30] Zubarev D. N.,(1974). Nonequilibrium Statistical Thermody-
namics, translated from the Russian by P.J. Shepherd, New
York, Consultants Bureau. ISBN 0-306-10895-X; ISBN
978-0-306-10895-2.
[31] Milne, E.A. (1928). “The effect of collisions on
monochromatic radiative equilibrium”. Monthly
Notices of the Royal Astronomical Society 88:
493–502. Bibcode:1928MNRAS..88..493M.
doi:10.1093/mnras/88.6.493.
[32] Grandy, W.T., Jr. (2004). “Time Evolution
in Macroscopic Systems. I. Equations of Mo-
tion”. Foundations of Physics 34: 1. arXiv:cond-
mat/0303290. Bibcode:2004FoPh...34....1G.
doi:10.1023/B:FOOP.0000012007.06843.ed.
[33] Grandy, W.T., Jr. (2004). “Time Evolution in Macroscopic
Systems. II. The Entropy”. Foundations of Physics 34: 21.
arXiv:cond-mat/0303291. Bibcode:2004FoPh...34...21G.
doi:10.1023/B:FOOP.0000012008.36856.c1.
38
[34] Grandy, W. T., Jr (2004). “Time Evolution in Macro-
scopic Systems. III: Selected Applications”. Foundations
of Physics 34 (5): 771. Bibcode:2004FoPh...34..771G.
doi:10.1023/B:FOOP.0000022187.45866.81.
[35] Grandy 2004 see also .
[36] Truesdell, Clifford (1984). Rational Thermodynamics (2
ed.). Springer.
[37] Maugin, Gérard A. (2002). Continuum Thermomechanics.
Kluwer.
[38] Gurtin, Morton E. (2010). The Mechanics and Thermody-
namics of Continua. Cambridge University Press.
[39] Amendola, Giovambattista (2012). Thermodynamics of
Materials with Memory: Theory and Applications. Springer.
[40] W. Greiner, L. Neise, and H. Stöcker (1997), Ther-
modynamics and Statistical Mechanics (Classical Theo-
retical Physics) ,Springer-Verlag, New York, P85, 91,
101,108,116, ISBN 0-387-94299-8.
[41] Nicolis, C. (1999). “Entropy production and dynamical
complexity in a low-order atmospheric model”. Quar-
terly Journal of the Royal Meteorological Society 125
(557): 1859–1878. Bibcode:1999QJRMS.125.1859N.
doi:10.1002/qj.49712555718.
[42] Attard, P. (2012). “Optimising Principle for Non-
Equilibrium Phase Transitions and Pattern Formation with
Results for Heat Convection”. arXiv:1208.5105.
[43] Attard, P. (2012). Non-Equilibrium Thermodynamics and
Statistical Mechanics: Foundations and Applications, Oxford
University Press, Oxford UK, ISBN 978-0-19-966276-0.
[44] Pokrovskii, Vladimir (2011). Econodynamics. The
Theory of Social Production. http://www.springer.com/
physics/complexity/book/978-94-007-2095-4: Springer,
Dordrecht-Heidelberg-London-New York.
[45] Chen, Jing (2015). The Unity of Science and Economics: A
New Foundation of Economic Theory. http://www.springer.
com/us/book/9781493934645: Springer.
Bibliography of cited references
• Callen, H.B. (1960/1985). Thermodynamics and an
Introduction to Thermostatistics, (1st edition 1960) 2nd
edition 1985, Wiley, New York, ISBN 0-471-86256-
8.
• Eu, B.C. (2002). Generalized Thermodynamics. The
Thermodynamics of Irreversible Processes and Gener-
alized Hydrodynamics, Kluwer Academic Publishers,
Dordrecht, ISBN 1-4020-0788-4.
• Glansdorff, P., Prigogine, I. (1971). Thermodynamic
Theory of Structure, Stability, and Fluctuations, Wiley-
Interscience, London, 1971, ISBN 0-471-30280-5.
CHAPTER 1. CHAPTER 1. INTRODUCTION
• Grandy, W.T., Jr (2008). Entropy and the Time Evolu-
tion of Macroscopic Systems. Oxford University Press.
ISBN 978-0-19-954617-6.
• Gyarmati, I. (1967/1970). Non-equilibrium Thermo-
dynamics. Field Theory and Variational Principles,
translated from the Hungarian (1967) by E. Gyarmati
and W.F. Heinz, Springer, Berlin.
• Lieb, E.H., Yngvason, J. (1999). 'The physics and
mathematics of the second law of thermodynamics’,
Physics Reports, 310: 1–96. See also this.
1.5.13 Further reading
• Ziegler, Hans (1977): An introduction to Thermome-
chanics. North Holland, Amsterdam. ISBN 0-444-
11080-1. Second edition (1983) ISBN 0-444-86503-
9.
• Kleidon, A., Lorenz, R.D., editors (2005). Non-
equilibrium Thermodynamics and the Production of
Entropy, Springer, Berlin. ISBN 3-540-22495-5.
• Prigogine, I. (1955/1961/1967). Introduction to Ther-
modynamics of Irreversible Processes. 3rd edition, Wi-
ley Interscience, New York.
• Zubarev D. N. (1974): Nonequilibrium Statistical
Thermodynamics. New York, Consultants Bureau.
ISBN 0-306-10895-X; ISBN 978-0-306-10895-2.
• Keizer, J. (1987). Statistical Thermodynamics
of Nonequilibrium Processes, Springer-Verlag, New
York, ISBN 0-387-96501-7.
• Zubarev D. N., Morozov V., Ropke G. (1996): Sta-
tistical Mechanics of Nonequilibrium Processes: Basic
Concepts, Kinetic Theory. John Wiley & Sons. ISBN
3-05-501708-0.
• Zubarev D. N., Morozov V., Ropke G. (1997): Statis-
tical Mechanics of Nonequilibrium Processes: Relax-
ation and Hydrodynamic Processes. John Wiley &
Sons. ISBN 3-527-40084-2.
• Tuck, Adrian F. (2008). Atmospheric turbulence : a
molecular dynamics perspective. Oxford University
Press. ISBN 978-0-19-923653-4.
• Grandy, W.T., Jr (2008). Entropy and the Time Evolu-
tion of Macroscopic Systems. Oxford University Press.
ISBN 978-0-19-954617-6.
• Kondepudi, D., Prigogine, I. (1998). Modern Thermo-
dynamics: From Heat Engines to Dissipative Structures.
John Wiley & Sons, Chichester. ISBN 0-471-97393-
9.
1.5. NON-EQUILIBRIUM THERMODYNAMICS 39

• de Groot S.R., Mazur P. (1984). Non-Equilibrium

Thermodynamics (Dover). ISBN 0-486-64741-2

1.5.14 External links

• Stephan Herminghaus’ Dynamics of Complex Fluids
Department at the Max Planck Institute for Dynamics
and Self Organization

• Non-equilibrium Statistical Thermodynamics applied

to Fluid Dynamics and Laser Physics - 1992- book by
Xavier de Hemptinne.
• Nonequilibrium Thermodynamics of Small Systems -
PhysicsToday.org
• Into the Cool - 2005 book by Dorion Sagan and Eric
D. Schneider, on nonequilibrium thermodynamics and
evolutionary theory.

• Thermodynamics ‘‘beyond’’ local equilibrium

Chapter 2

Chapter 2. Laws of Thermodynamics

2.1 Zeroth law of Thermodynamics a member of any other subset. This means that a unique
“tag” can be assigned to every system, and if the “tags” of
The zeroth law of thermodynamics states that if two two systems are the same, they are in thermal equilibrium
thermodynamic systems are each in thermal equilibrium with each other, and if different, they are not. This prop-
with a third, then they are in thermal equilibrium with each erty is used to justify the use of empirical temperature as a
other. tagging system. Empirical temperature provides further re-
lations of thermally equilibrated systems, such as order and
Two systems are said to be in the relation of thermal equilib- continuity with regard to “hotness” or “coldness”, but these
rium if they are linked by a wall permeable only to heat and are not implied by the standard statement of the zeroth law.
they do not change over time.[1] As a convenience of lan-
guage, systems are sometimes also said to be in a relation of If it is defined that a thermodynamic system is in thermal
thermal equilibrium if they are not linked so as to be able equilibrium with itself (i.e., thermal equilibrium [6] is reflex-
to transfer heat to each other, but would not do so if they ive), then the zeroth law may be stated as follows:
were connected by a wall permeable only to heat. Thermal
equilibrium between two systems is a transitive relation. If a body A, be in thermal equilibrium with
two other bodies, B and C, then B and C are in
The physical meaning of the law was expressed by Maxwell thermal equilibrium with one another.
in the words: “All heat is of the same kind”.[2] For this rea-
son, another statement of the law is “All diathermal walls
This statement asserts that thermal equilibrium is a left-
are equivalent”.[3]
Euclidean relation between thermodynamic systems. If we
The law is important for the mathematical formulation of also define that every thermodynamic system is in thermal
thermodynamics, which needs the assertion that the rela- equilibrium with itself, then thermal equilibrium is also a
tion of thermal equilibrium is an equivalence relation. This reflexive relation. Binary relations that are both reflexive
information is needed for a mathematical definition of tem- and Euclidean are equivalence relations. Thus, again im-
perature that will agree with the physical existence of valid plicitly assuming reflexivity, the zeroth law is therefore of-
thermometers.[4] ten expressed as a right-Euclidean statement:[7]

If two systems are in thermal equilibrium with

2.1.1 Zeroth law as equivalence relation
A thermodynamic system is by definition in its own state
of internal thermodynamic equilibrium, that is to say, there
is no change in its observable state (i.e. macrostate) over
time and no flows occur in it. One precise statement of the
zeroth law is that the relation of thermal equilibrium is an
equivalence relation on pairs of thermodynamic systems.[5]
In other words, the set of all systems each in its own state
of internal thermodynamic equilibrium may be divided into
subsets in which every system belongs to one and only one
subset, and is in thermal equilibrium with every other mem-
ber of that subset, and is not in thermal equilibrium with
a third system, then they are in thermal equilib-
rium with each other.
One consequence of an equivalence relationship is that the
equilibrium relationship is symmetric: If A is in thermal
equilibrium with B, then B is in thermal equilibrium with
A. Thus we may say that two systems are in thermal equi-
librium with each other, or that they are in mutual equilib-
rium. Another consequence of equivalence is that thermal
equilibrium is a transitive relationship and is occasionally
expressed as such:[4][8]
If A is in thermal equilibrium with B and if

40
2.1. ZEROTH LAW OF THERMODYNAMICS
B is in thermal equilibrium with C, then A is in
thermal equilibrium with C .
A reflexive, transitive relationship does not guarantee an
equivalence relationship. In order for the above statement
to be true, both reflexivity and symmetry must be implicitly
assumed.
It is the Euclidean relationships which apply directly to
thermometry. An ideal thermometer is a thermometer
which does not measurably change the state of the system it
is measuring. Assuming that the unchanging reading of an
ideal thermometer is a valid “tagging” system for the equiv-
alence classes of a set of equilibrated thermodynamic sys-
tems, then if a thermometer gives the same reading for two
systems, those two systems are in thermal equilibrium, and
if we thermally connect the two systems, there will be no
subsequent change in the state of either one. If the read-
ings are different, then thermally connecting the two sys-
tems will cause a change in the states of both systems and
when the change is complete, they will both yield the same
thermometer reading. The zeroth law provides no informa-
tion regarding this final reading.
2.1.2 Foundation of temperature
The zeroth law establishes thermal equilibrium as an equiv-
alence relationship. An equivalence relationship on a set
(such as the set of all systems each in its own state of in-
ternal thermodynamic equilibrium) divides that set into a
collection of distinct subsets (“disjoint subsets”) where any
member of the set is a member of one and only one such
subset. In the case of the zeroth law, these subsets con-
sist of systems which are in mutual equilibrium. This par-
titioning allows any member of the subset to be uniquely
“tagged” with a label identifying the subset to which it be-
longs. Although the labeling may be quite arbitrary,[9] tem-
perature is just such a labeling process which uses the real
number system for tagging. The zeroth law justifies the
use of suitable thermodynamic systems as thermometers to
provide such a labeling, which yield any number of pos-
sible empirical temperature scales, and justifies the use of
the second law of thermodynamics to provide an absolute,
or thermodynamic temperature scale. Such temperature
scales bring additional continuity and ordering (i.e., “hot”
and “cold”) properties to the concept of temperature.[7]
In the space of thermodynamic parameters, zones of con-
stant temperature form a surface, that provides a natural
order of nearby surfaces. One may therefore construct a
global temperature function that provides a continuous or-
dering of states. The dimensionality of a surface of constant
temperature is one less than the number of thermodynamic
parameters, thus, for an ideal gas described with three ther-
41
modynamic parameters P, V and N, it is a two-dimensional
surface.
For example, if two systems of ideal gases are in equilib-
rium, then P 1 V 1 /N 1 = P 2 V 2 /N 2 where Pi is the pressure
in the ith system, Vi is the volume, and Ni is the amount (in
moles, or simply the number of atoms) of gas.
The surface PV/N = const defines surfaces of equal thermo-
dynamic temperature, and one may label defining T so that
PV/N = RT, where R is some constant. These systems can
now be used as a thermometer to calibrate other systems.
Such systems are known as “ideal gas thermometers”.
In a sense, focused on in the zeroth law, there is only one
kind of diathermal wall or one kind of heat, as expressed by
Maxwell’s dictum that “All heat is of the same kind”.[2] But
in another sense, heat is transferred in different ranks, as
expressed by Sommerfeld’s dictum “Thermodynamics in-
vestigates the conditions that govern the transformation of
heat into work. It teaches us to recognize temperature as
the measure of the work-value of heat. Heat of higher tem-
perature is richer, is capable of doing more work. Work
may be regarded as heat of an infinitely high temperature,
as unconditionally available heat.”[10] This is why tempera-
ture is the particular variable indicated by the zeroth law’s
statement of equivalence.
2.1.3 Physical meaning of the usual state-
ment of the zeroth law
The present article states the zeroth law as it is often sum-
marized in textbooks. Nevertheless, this usual statement
perhaps does not explicitly convey the full physical mean-
ing that underlies it. The underlying physical meaning was
perhaps first clarified by Maxwell in his 1871 textbook.[2]
In Carathéodory’s (1909) theory, it is postulated that there
exist walls “permeable only to heat”, though heat is not ex-
plicitly defined in that paper. This postulate is a physical
postulate of existence. It does not, however, as worded just
previously, say that there is only one kind of heat. This
paper of Carathéodory states as proviso 4 of its account
of such walls: “Whenever each of the systems S 1 and S 2
is made to reach equilibrium with a third system S 3 un-
der identical conditions, systems S 1 and S 2 are in mutual
equilibrium”.[11] It is the function of this statement in the
paper, not there labeled as the zeroth law, to provide not
only for the existence of transfer of energy other than by
work or transfer of matter, but further to provide that such
transfer is unique in the sense that there is only one kind
of such wall, and one kind of such transfer. This is sig-
naled in the postulate of this paper of Carathéodory that
precisely one non-deformation variable is needed to com-
plete the specification of a thermodynamic state, beyond the
42 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

necessary deformation variables, which are not restricted in namics’. Fowler, with co-author Edward A. Guggenheim,
number. It is therefore not exactly clear what Carathéodory wrote of the zeroth law as follows:
means when in the introduction of this paper he writes "It
is possible to develop the whole theory without assuming the ...we introduce the postulate: If two
existence of heat, that is of a quantity that is of a different assemblies are each in thermal equilib-
nature from the normal mechanical quantities." rium with a third assembly, they are in
thermal equilibrium with each other.
Maxwell (1871) discusses at some length ideas which he
summarizes by the words “All heat is of the same kind”.[2] They then proposed that “it may be shown to follow that
Modern theorists sometimes express this idea by postulat- the condition for thermal equilibrium between several as-
ing the existence of a unique one-dimensional hotness mani- semblies is the equality of a certain single-valued function
fold, into which every proper temperature scale has a mono- of the thermodynamic states of the assemblies, which may
tonic mapping.[12] This may be expressed by the statement be called the temperature t, any one of the assemblies be-
that there is only one kind of temperature, regardless of the ing used as a “thermometer” reading the temperature t on
variety of scales in which it is expressed. Another mod- a suitable scale. This postulate of the "Existence of temper-
ern expression of this idea is that “All diathermal walls are ature" could with advantage be known as the zeroth law of
equivalent”.[13] This might also be expressed by saying that thermodynamics". The first sentence of this present article
there is precisely one kind of non-mechanical, non-matter- is a version of this statement.[18] It is not explicitly evident
transferring contact equilibrium between thermodynamic in the existence statement of Fowler and Guggenheim that
systems. temperature refers to a unique attribute of a state of a sys-
These ideas may be regarded as helping to clarify the physi- tem, such as is expressed in the idea of the hotness manifold.
cal meaning of the usual statement of the zeroth law of ther- Also their statement refers explicitly to statistical mechani-
modynamics. It is the opinion of Lieb and Yngvason (1999) cal assemblies, not explicitly to macroscopic thermodynam-
that the derivation from statistical mechanics of the law of ically defined systems.
entropy increase is a goal that has so far eluded the deep-
est thinkers.[14] Thus the idea remains open to considera-
tion that the existence of heat and temperature are needed 2.1.5 References
as coherent primitive concepts for thermodynamics, as ex-
pressed, for example, by Maxwell and Planck. On the other Citations
hand, Planck in 1926 clarified how the second law can be [1] Carathéodory, C. (1909).
stated without reference to heat or temperature, by refer-
ring to the irreversible and universal nature of friction in [2] Maxwell, J.C. (1871), p. 57.
natural thermodynamic processes.[15] [3] Bailyn, M. (1994), pp. 24, 144.
[4] Lieb, E.H., Yngvason, J. (1999), p. 56.
[5] Lieb, E.H., Yngvason, J. (1999), p. 52.
2.1.4 History
[6] Planck. M. (1914), p. 2.
According to Arnold Sommerfeld, Ralph H. Fowler in- [7] Buchdahl, H.A. (1966), p. 73.
vented the title 'the zeroth law of thermodynamics’ when he
was discussing the 1935 text of Saha and Srivastava. They [8] Kondepudi, D. (2008), p. 7.
write on page 1 that “every physical quantity must be mea- [9] Dugdale, J.S. (1996), p. 35.
surable in numerical terms”. They presume that tempera-
[10] Sommerfeld, A. (1923), p. 36.
ture is a physical quantity and then deduce the statement
“If a body A is in temperature equilibrium with two bodies [11] Carathéodory, C. (1909), Section 6.
B and C, then B and C themselves will be in temperature
[12] Serrin, J. (1986), p. 6.
equilibrium with each other”. They then in a self-standing
paragraph italicize as if to state their basic postulate: "Any [13] Bailyn, M. (1994), p. 23.
of the physical properties of A which change with the appli- [14] Lieb, E.H., Yngvason, J. (1999), p. 5.
cation of heat may be observed and utilised for the measure-
ment of temperature." They do not themselves here use the [15] Planck, M. (1926).
term 'zeroth law of thermodynamics’.[16][17] There are very [16] Sommerfeld, A. (1951/1955), p. 1.
many statements of these physical ideas in the physics liter-
[17] Saha, M.N., Srivastava, B.N. (1935), p. 1.
ature long before this text, in very similar language. What
was new here was just the label 'zeroth law of thermody- [18] Fowler, R., Guggenheim, E.A. (1939/1965), p. 56.
2.2. FIRST LAW OF THERMODYNAMICS 43

Works cited • Sommerfeld, A. (1951/1955). Thermodynamics and

Statistical Mechanics, vol. 5 of Lectures on Theoretical
• Bailyn, M. (1994). A Survey of Thermodynamics, Physics, edited by F. Bopp, J. Meixner, translated by
American Institute of Physics Press, New York, ISBN J. Kestin, Academic Press, New York.
978-0-88318-797-5.
• H.A. Buchdahl (1966). The Concepts of Classical 2.1.6 Further reading
Thermodynamics. Cambridge University Press.
• C. Carathéodory (1909). “Untersuchungen über • Atkins, Peter (2007). Four Laws That Drive the Uni-
die Grundlagen der Thermodynamik”. Math- verse. New York: Oxford University Press. ISBN
ematische Annalen (in German) 67: 355–386. 978-0-19-923236-9.
doi:10.1007/BF01450409. A translation may be
found here. A partly reliable translation is to be found
at Kestin, J. (1976). The Second Law of Thermody- 2.2 First law of Thermodynamics
namics, Dowden, Hutchinson & Ross, Stroudsburg
PA. The first law of thermodynamics is a version of the law
of conservation of energy, adapted for thermodynamic sys-
• Dugdale, J. S. (1996). Entropy and its Physical Inter-
tems. The law of conservation of energy states that the to-
pretation. Taylor & Francis. ISBN 0-7484-0569-0.
tal energy of an isolated system is constant; energy can be
• Fowler, R., Guggenheim, E.A. (1939/1965). Statisti- transformed from one form to another, but cannot be cre-
cal Thermodynamics. A version of Statistical Mechan- ated or destroyed. The first law is often formulated by stat-
ics for Students of Physics and Chemistry, first print- ing that the change in the internal energy of a closed system
ing 1939, reprinted with corrections 1965, Cambridge is equal to the amount of heat supplied to the system, minus
University Press, Cambridge UK. the amount of work done by the system on its surroundings.
Equivalently, perpetual motion machines of the first kind
• D. Kondepudi (2008). Introduction to Modern Ther- are impossible.
modynamics. Wiley. ISBN 978-0470-01598-8.
• Lieb, E.H., Yngvason, J. (1999). The physics and
mathematics of the second law of thermodynamics,
2.2.1 History
Physics Reports, 310: 1–96.
Investigations into the nature of heat and work and their re-
• Maxwell, J.C. (1871). Theory of Heat, Longmans, lationship began with the invention of the first engines used
Green, and Co., London. to extract water from mines. Improvements to such engines
so as to increase their efficiency and power output came first
• Planck. M. (1914). The Theory of Heat Radiation, a from mechanics that tinkered with such machines but only
translation by Masius, M. of the second German edi- slowly advanced the art. Deeper investigations that placed
tion, P. Blakiston’s Son & Co., Philadelphia. those on a mathematical and physics basis came later.
• Planck, M. (1926). Über die Begründing des zweiten The process of development of the first law of thermody-
Hauptsatzes der Thermodynamik, S.B. Preuß. Akad. namics was by way of much investigative trial and error
Wiss. phys. math. Kl.: 453–463. over a period of about half a century. The first full state-
ments of the law came in 1850 from Rudolf Clausius and
• Saha, M.N., Srivastava, B.N. (1935). A Treatise on from William Rankine; Rankine’s statement was perhaps
Heat. (Including Kinetic Theory of Gases, Thermody- not quite as clear and distinct as was Clausius’.[1] A main
namics and Recent Advances in Statistical Thermody- aspect of the struggle was to deal with the previously pro-
namics), the second and revised edition of A Text Book posed caloric theory of heat.
of Heat, The Indian Press, Allahabad and Calcutta.
Germain Hess in 1840 stated a conservation law for the so-
• Serrin, J. (1986). Chapter 1, 'An Outline of Ther- called 'heat of reaction' for chemical reactions.[2] His law
modynamical Structure', pages 3–32, in New Perspec- was later recognized as a consequence of the first law of
tives in Thermodynamics, edited by J. Serrin, Springer, thermodynamics, but Hess’s statement was not explicitly
Berlin, ISBN 3-540-15931-2. concerned with the relation between energy exchanges by
• Sommerfeld, A. (1923). Atomic Structure and Spec- heat and work.
tral Lines, translated from the third German edition According to Truesdell (1980), Julius Robert von Mayer in
by H.L. Brose, Methuen, London. 1841 made a statement that meant that “in a process at con-
44 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

stant pressure, the heat used to produce expansion is univer- The concept of internal energy is considered by Bailyn to
sally interconvertible with work”, but this is not a general be of “enormous interest”. Its quantity cannot be immedi-
statement of the first law.[3][4] ately measured, but can only be inferred, by differencing
actual immediate measurements. Bailyn likens it to the en-
ergy states of an atom, that were revealed by Bohr’s energy
Original statements: the “thermodynamic approach”
relation hν = En'' − En'. In each case, an unmeasurable
quantity (the internal energy, the atomic energy level) is re-
The original nineteenth century statements of the first law
vealed by considering the difference of measured quantities
of thermodynamics appeared in a conceptual framework in
(increments of internal energy, quantities of emitted or ab-
which transfer of energy as heat was taken as a primitive
sorbed radiative energy).[8]
notion, not defined or constructed by the theoretical devel-
opment of the framework, but rather presupposed as prior
to it and already accepted. The primitive notion of heat
was taken as empirically established, especially through Conceptual revision: the “mechanical approach”
calorimetry regarded as a subject in its own right, prior
to thermodynamics. Jointly primitive with this notion of In 1907, George H. Bryan wrote about systems between
heat were the notions of empirical temperature and thermal which there is no transfer of matter (closed systems):
equilibrium. This framework also took as primitive the no- "Definition. When energy flows from one system or part
tion of transfer of energy as work. This framework did not of a system to another otherwise than by the performance
presume a concept of energy in general, but regarded it as of mechanical work, the energy so transferred is called
derived or synthesized from the prior notions of heat and heat.”[9] This definition may be regarded as expressing a
work. By one author, this framework has been called the conceptual revision, as follows. This was systematically
“thermodynamic” approach.[5] expounded in 1909 by Constantin Carathéodory, whose
attention had been drawn to it by Max Born. Largely
The first explicit statement of the first law of thermodynam-
through Born’s[10] influence, this revised conceptual ap-
ics, by Rudolf Clausius in 1850, referred to cyclic thermo-
proach to the definition of heat came to be preferred by
dynamic processes.
many twentieth-century writers. It might be called the “me-
In all cases in which work is pro- chanical approach”.[11]
duced by the agency of heat, a quan- Energy can also be transferred from one thermodynamic
tity of heat is consumed which is pro- system to another in association with transfer of matter.
portional to the work done; and con- Born points out that in general such energy transfer is not
versely, by the expenditure of an equal resolvable uniquely into work and heat moieties. In gen-
quantity of work an equal quantity of eral, when there is transfer of energy associated with matter
heat is produced.[6] transfer, work and heat transfers can be distinguished only
when they pass through walls physically separate from those
Clausius also stated the law in another form, referring to the for matter transfer.
existence of a function of state of the system, the internal
energy, and expressed it in terms of a differential equa- The “mechanical” approach postulates the law of conserva-
tion for the increments of a thermodynamic process.[7] This tion of energy. It also postulates that energy can be trans-
equation may described as follows: ferred from one thermodynamic system to another adiabati-
cally as work, and that energy can be held as the internal en-
In a thermodynamic process involving ergy of a thermodynamic system. It also postulates that en-
a closed system, the increment in the ergy can be transferred from one thermodynamic system to
internal energy is equal to the differ- another by a path that is non-adiabatic, and is unaccompa-
ence between the heat accumulated by nied by matter transfer. Initially, it “cleverly” (according to
the system and the work done by it. Bailyn) refrains from labelling as 'heat' such non-adiabatic,
unaccompanied transfer of energy. It rests on the primitive
Because of its definition in terms of increments, the value notion of walls, especially adiabatic walls and non-adiabatic
of the internal energy of a system is not uniquely defined. walls, defined as follows. Temporarily, only for purpose of
It is defined only up to an arbitrary additive constant of in- this definition, one can prohibit transfer of energy as work
tegration, which can be adjusted to give arbitrary reference across a wall of interest. Then walls of interest fall into two
zero levels. This non-uniqueness is in keeping with the ab- classes, (a) those such that arbitrary systems separated by
stract mathematical nature of the internal energy. The in- them remain independently in their own previously estab-
ternal energy is customarily stated relative to a convention- lished respective states of internal thermodynamic equilib-
ally chosen standard reference state of the system. rium; they are defined as adiabatic; and (b) those without
2.2. FIRST LAW OF THERMODYNAMICS
such independence; they are defined as non-adiabatic.[12]
This approach derives the notions of transfer of energy as
heat, and of temperature, as theoretical developments, not
taking them as primitives. It regards calorimetry as a de-
rived theory. It has an early origin in the nineteenth cen-
tury, for example in the work of Helmholtz,[13] but also in
the work of many others.[5]
2.2.2 Conceptually revised statement, ac-
cording to the mechanical approach 2.2.3
The revised statement of the first law postulates that a
change in the internal energy of a system due to any ar-
bitrary process, that takes the system from a given initial
thermodynamic state to a given final equilibrium thermo-
dynamic state, can be determined through the physical ex-
istence, for those given states, of a reference process that
occurs purely through stages of adiabatic work.
The revised statement is then
For a closed system, in any arbitrary
process of interest that takes it from an
initial to a final state of internal ther-
modynamic equilibrium, the change of
internal energy is the same as that
for a reference adiabatic work pro-
cess that links those two states. This
is so regardless of the path of the
process of interest, and regardless of
whether it is an adiabatic or a non-
adiabatic process. The reference adi-
abatic work process may be chosen ar-
bitrarily from amongst the class of all
such processes.
This statement is much less close to the empirical basis than
are the original statements,[14] but is often regarded as con-
ceptually parsimonious in that it rests only on the concepts
of adiabatic work and of non-adiabatic processes, not on
the concepts of transfer of energy as heat and of empiri-
cal temperature that are presupposed by the original state-
ments. Largely through the influence of Max Born, it is
often regarded as theoretically preferable because of this
conceptual parsimony. Born particularly observes that the
revised approach avoids thinking in terms of what he calls
the “imported engineering” concept of heat engines.[10]
Basing his thinking on the mechanical approach, Born in
1921, and again in 1949, proposed to revise the defini-
tion of heat.[10][15] In particular, he referred to the work
of Constantin Carathéodory, who had in 1909 stated the
first law without defining quantity of heat.[16] Born’s defini- Often nowadays, however, writers use the IUPAC conven-
tion was specifically for transfers of energy without trans- tion by which the first law is formulated with work done on
45
fer of matter, and it has been widely followed in textbooks
(examples:[17][18][19] ). Born observes that a transfer of mat-
ter between two systems is accompanied by a transfer of
internal energy that cannot be resolved into heat and work
components. There can be pathways to other systems, spa-
tially separate from that of the matter transfer, that allow
heat and work transfer independent of and simultaneous
with the matter transfer. Energy is conserved in such trans-
fers.
Description
The first law of thermodynamics for a closed system was
expressed in two ways by Clausius. One way referred to
cyclic processes and the inputs and outputs of the system,
but did not refer to increments in the internal state of the
system. The other way referred to an incremental change
in the internal state of the system, and did not expect the
process to be cyclic.
A cyclic process is one that can be repeated indefinitely of-
ten, returning the system to its initial state. Of particular
interest for single cycle of a cyclic process are the net work
done, and the net heat taken in (or 'consumed', in Clausius’
statement), by the system.
In a cyclic process in which the system does net work on
its surroundings, it is observed to be physically necessary
not only that heat be taken into the system, but also, impor-
tantly, that some heat leave the system. The difference is
the heat converted by the cycle into work. In each repeti-
tion of a cyclic process, the net work done by the system,
measured in mechanical units, is proportional to the heat
consumed, measured in calorimetric units.
The constant of proportionality is universal and independent
of the system and in 1845 and 1847 was measured by James
Joule, who described it as the mechanical equivalent of heat.
In a non-cyclic process, the change in the internal energy of
a system is equal to net energy added as heat to the system
minus the net work done by the system, both being mea-
sured in mechanical units. Taking ΔU as a change in inter-
nal energy, one writes
∆U = Q − W (sign convention of Clausius and generally in this article) ,
where Q denotes the net quantity of heat supplied to the sys-
tem by its surroundings and W denotes the net work done
by the system. This sign convention is implicit in Clausius’
statement of the law given above. It originated with the
study of heat engines that produce useful work by consump-
tion of heat.
46 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

the system by its surroundings having a positive sign. With are made on it in the section below headed 'First law of ther-
this now often used sign convention for work, the first law modynamics for open systems’.
for a closed system may be written: There are two main ways of stating a law of thermodynam-
ics, physically or mathematically. They should be logically
∆U = Q + W (sign convention of IUPAC) . coherent and consistent with one another.[23]
[20]
An example of a physical statement is that of Planck
(1897/1903):
This convention follows physicists such as Max Planck,[21]
and considers all net energy transfers to the system as posi- It is in no way possible, either by mechani-
tive and all net energy transfers from the system as negative, cal, thermal, chemical, or other devices, to ob-
irrespective of any use for the system as an engine or other tain perpetual motion, i.e. it is impossible to
device. construct an engine which will work in a cycle
When a system expands in a fictive quasistatic process, the and produce continuous work, or kinetic energy,
work done by the system on the environment is the product, from nothing.[24]
P dV, of pressure, P, and volume change, dV, whereas the
work done on the system is -P dV. Using either sign conven- This physical statement is restricted neither to closed sys-
tion for work, the change in internal energy of the system tems nor to systems with states that are strictly defined only
is: for thermodynamic equilibrium; it has meaning also for
open systems and for systems with states that are not in ther-
modynamic equilibrium.
dU = δQ − P dV process) (quasi-static, An example of a mathematical statement is that of Craw-
ford (1963):
where δQ denotes the infinitesimal increment of heat sup-
plied to the system from its surroundings. For a given
Work and heat are expressions of actual physical processes system we
of supply or removal of energy, while the internal energy let ΔE kin =
U is a mathematical abstraction that keeps account of the large-scale
exchanges of energy that befall the system. Thus the term mechani-
heat for Q means “that amount of energy added or removed cal energy,
by conduction of heat or by thermal radiation”, rather than ΔE pot =
referring to a form of energy within the system. Likewise, large-scale
the term work energy for W means “that amount of energy potential
gained or lost as the result of work”. Internal energy is a energy, and
property of the system whereas work done and heat supplied ΔE tot = total
are not. A significant result of this distinction is that a given energy. The
internal energy change ΔU can be achieved by, in principle, first two
many combinations of heat and work. quantities are
specifiable
in terms of
2.2.4 Various statements of the law for appropriate
mechanical
closed systems
variables, and
by definition
The law is of great importance and generality and is conse-
quently thought of from several points of view. Most care-
ful textbook statements of the law express it for closed sys-
tems. It is stated in several ways, sometimes even by the E tot = E kin + E pot + U .
same author.[5][22]
For the thermodynamics of closed systems, the distinction For any finite
between transfers of energy as work and as heat is central process,
and is within the scope of the present article. For the ther- whether re-
modynamics of open systems, such a distinction is beyond versible or
the scope of the present article, but some limited comments irreversible,
2.2. FIRST LAW OF THERMODYNAMICS 47

in equilibrium is a function of state, that the sum of the in-

ternal energies of the phases is the total internal energy of
∆E tot = ∆E kin + ∆E pot + ∆U . the system, and that the value of the total internal energy
of the system is changed by the amount of work done adia-
The first law batically on it, considering work as a form of energy. That
in a form article considered this statement to be an expression of the
that involves law of conservation of energy for such systems. This version
the principle is nowadays widely accepted as authoritative, but is stated
of conser- in slightly varied ways by different authors.
vation of
energy more Such statements of the first law for closed systems assert
generally is the existence of internal energy as a function of state de-
fined in terms of adiabatic work. Thus heat is not defined
calorimetrically or as due to temperature difference. It is
defined as a residual difference between change of internal
∆E tot = Q + W . energy and work done on the system, when that work does
not account for the whole of the change of internal energy
Here Q and and the system is not adiabatically isolated.[17][18][19]
W are heat The 1909 Carathéodory statement of the law in ax-
and work iomatic form does not mention heat or temperature, but
added, with the equilibrium states to which it refers are explicitly
no restric- defined by variable sets that necessarily include “non-
tions as to deformation variables”, such as pressures, which, within
whether the reasonable restrictions, can be rightly interpreted as empiri-
process is cal temperatures,[27] and the walls connecting the phases of
reversible, the system are explicitly defined as possibly impermeable
quasistatic, to heat or permeable only to heat.
or irre-
versible.[Warner, According to Münster (1970), “A somewhat unsatisfactory
Am. J. Phys., aspect of Carathéodory’s theory is that a consequence of
29, 124 the Second Law must be considered at this point [in the
(1961)][25] statement of the first law], i.e. that it is not always possi-
ble to reach any state 2 from any other state 1 by means of
This statement by Crawford, for W, uses the sign convention an adiabatic process.” Münster instances that no adiabatic
of IUPAC, not that of Clausius. Though it does not explic- process can reduce the internal energy of a system at con-
itly say so, this statement refers to closed systems, and to stant volume.[17] Carathéodory’s paper asserts that its state-
internal energy U defined for bodies in states of thermo- ment of the first law corresponds exactly to Joule’s exper-
dynamic equilibrium, which possess well-defined tempera- imental arrangement, regarded as an instance of adiabatic
tures. work. It does not point out that Joule’s experimental ar-
rangement performed essentially irreversible work, through
The history of statements of the law for closed systems friction of paddles in a liquid, or passage of electric current
has two main periods, before and after the work of Bryan through a resistance inside the system, driven by motion of a
(1907),[26] of Carathéodory (1909),[16] and the approval of coil and inductive heating, or by an external current source,
Carathéodory’s work given by Born (1921).[15] The earlier which can access the system only by the passage of elec-
traditional versions of the law for closed systems are nowa- trons, and so is not strictly adiabatic, because electrons are
days often considered to be out of date. a form of matter, which cannot penetrate adiabatic walls.
Carathéodory’s celebrated presentation of equilibrium The paper goes on to base its main argument on the pos-
thermodynamics[16] refers to closed systems, which are al- sibility of quasi-static adiabatic work, which is essentially
lowed to contain several phases connected by internal walls reversible. The paper asserts that it will avoid reference to
of various kinds of impermeability and permeability (ex- Carnot cycles, and then proceeds to base its argument on cy-
plicitly including walls that are permeable only to heat). cles of forward and backward quasi-static adiabatic stages,
Carathéodory’s 1909 version of the first law of thermody- with isothermal stages of zero magnitude.
namics was stated in an axiom which refrained from defin- Sometimes the concept of internal energy is not made ex-
ing or mentioning temperature or quantity of heat trans- plicit in the statement.[28][29][30]
ferred. That axiom stated that the internal energy of a phase
48 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

Sometimes the existence of the internal energy is made ex- Adiabatic processes
plicit but work is not explicitly mentioned in the statement
of the first postulate of thermodynamics. Heat supplied is
then defined as the residual change in internal energy af- In an adiabatic process, there is transfer of energy as work
ter work has been taken into account, in a non-adiabatic but not as heat. For all adiabatic process that takes a sys-
process.[31] tem from a given initial state to a given final state, irrespec-
tive of how the work is done, the respective eventual to-
A respected modern author states the first law of thermody- tal quantities of energy transferred as work are one and the
namics as “Heat is a form of energy”, which explicitly men- same, determined just by the given initial and final states.
tions neither internal energy nor adiabatic work. Heat is de- The work done on the system is defined and measured by
fined as energy transferred by thermal contact with a reser- changes in mechanical or quasi-mechanical variables exter-
voir, which has a temperature, and is generally so large that nal to the system. Physically, adiabatic transfer of energy
addition and removal of heat do not alter its temperature.[32] as work requires the existence of adiabatic enclosures.
A current student text on chemistry defines heat thus: "heat
is the exchange of thermal energy between a system and For instance, in Joule’s experiment, the initial system is a
its surroundings caused by a temperature difference.” The tank of water with a paddle wheel inside. If we isolate
author then explains how heat is defined or measured by the tank thermally, and move the paddle wheel with a pul-
calorimetry, in terms of heat capacity, specific heat capac- ley and a weight, we can relate the increase in temperature
ity, molar heat capacity, and temperature.[33] with the distance descended by the mass. Next, the system
is returned to its initial state, isolated again, and the same
A respected text disregards the Carathéodory’s exclusion of amount of work is done on the tank using different devices
mention of heat from the statement of the first law for closed (an electric motor, a chemical battery, a spring,...). In every
systems, and admits heat calorimetrically defined along with case, the amount of work can be measured independently.
work and internal energy.[34] Another respected text defines The return to the initial state is not conducted by doing adia-
heat exchange as determined by temperature difference, but batic work on the system. The evidence shows that the final
also mentions that the Born (1921) version is “completely state of the water (in particular, its temperature and vol-
rigorous”.[35] These versions follow the traditional approach ume) is the same in every case. It is irrelevant if the work
that is now considered out of date, exemplified by that of is electrical, mechanical, chemical,... or if done suddenly or
Planck (1897/1903).[36] slowly, as long as it is performed in an adiabatic way, that
is to say, without heat transfer into or out of the system.
Evidence of this kind shows that to increase the tempera-
ture of the water in the tank, the qualitative kind of adia-
batically performed work does not matter. No qualitative
kind of adiabatic work has ever been observed to decrease
2.2.5 Evidence for the first law of thermody- the temperature of the water in the tank.
namics for closed systems A change from one state to another, for example an in-
crease of both temperature and volume, may be conducted
in several stages, for example by externally supplied electri-
The first law of thermodynamics for closed systems was cal work on a resistor in the body, and adiabatic expansion
originally induced from empirically observed evidence, in- allowing the body to do work on the surroundings. It needs
cluding calorimetric evidence. It is nowadays, however, to be shown that the time order of the stages, and their rel-
taken to provide the definition of heat via the law of con- ative magnitudes, does not affect the amount of adiabatic
servation of energy and the definition of work in terms of work that needs to be done for the change of state. Accord-
changes in the external parameters of a system. The original ing to one respected scholar: “Unfortunately, it does not
discovery of the law was gradual over a period of perhaps seem that experiments of this kind have ever been carried
half a century or more, and some early studies were in terms out carefully. ... We must therefore admit that the statement
of cyclic processes.[1] which we have enunciated here, and which is equivalent to
The following is an account in terms of changes of state of the first law of thermodynamics, [14]
is not well founded on di-
a closed system through compound processes that are not rect experimental evidence.” Another expression of this
necessarily cyclic. This account first considers processes for view is "... no systematic precise experiments to verify this
[37]
which the first law is easily verified because of their simplic- generalization directly have ever been attempted.”
ity, namely adiabatic processes (in which there is no transfer This kind of evidence, of independence of sequence of
as heat) and adynamic processes (in which there is no trans- stages, combined with the above-mentioned evidence, of
fer as work). independence of qualitative kind of work, would show the
2.2. FIRST LAW OF THERMODYNAMICS 49

existence of an important state variable that corresponds slowly, the frictional or viscous dissipation is less. In
with adiabatic work, but not that such a state variable rep- the limit of infinitely slow performance, the dissipation
resented a conserved quantity. For the latter, another step tends to zero and then the limiting process, though fic-
of evidence is needed, which may be related to the concept tional rather than actual, is notionally reversible, and
of reversibility, as mentioned below. is called quasi-static. Throughout the course of the
That important state variable was first recognized and de- fictional limiting quasi-static process, the internal in-
noted U by Clausius in 1850, but he did not then name it, tensive variables of the system are equal to the exter-
and he defined it in terms not only of work but also of heat nal intensive variables, those that describe the reac-
tive forces exerted by the surroundings.[44] This can
transfer in the same process. It was also independently rec-
ognized in 1850 by Rankine, who also denoted it U ; and be taken to justify the formula
in 1851 by Kelvin who then called it “mechanical energy”, quasi-static adiabatic, quasi-static adiabatic,
and later “intrinsic energy”. In 1865, after some hestitation, (1) WA→O = −WO→A .
Clausius began calling his state function U “energy”. In
1882 it was named as the internal energy by Helmholtz.[38] • Another way to deal with it is to allow that experiments
If only adiabatic processes were of interest, and heat could with processes of heat transfer to or from the system
be ignored, the concept of internal energy would hardly may be used to justify the formula (1) above. More-
arise or be needed. The relevant physics would be largely over, it deals to some extent with the problem of lack
covered by the concept of potential energy, as was intended of direct experimental evidence that the time order of
in the 1847 paper of Helmholtz on the principle of conser- stages of a process does not matter in the determina-
vation of energy, though that did not deal with forces that tion of internal energy. This way does not provide the-
cannot be described by a potential, and thus did not fully oretical purity in terms of adiabatic work processes,
justify the principle. Moreover, that paper was critical of but is empirically feasible, and is in accord with ex-
the early work of Joule that had by then been performed. [39] periments actually done, such as the Joule experiments
A great merit of the internal energy concept is that it frees mentioned just above, and with older traditions.
thermodynamics from a restriction to cyclic processes, and
allows a treatment in terms of thermodynamic states. The formula (1) above allows that to go by processes of
quasi-static adiabatic work from the state A to the state B
In an adiabatic process, adiabatic work takes the system ei- we can take a path that goes through the reference state O
ther from a reference state O with internal energy U (O) to , since the quasi-static adiabatic work is independent of the
an arbitrary one A with internal energy U (A) , or from the path
state A to the state O :

adiabatic, quasi−static adiabatic, quasi−static adiabatic, quasi−static adiab

adiabatic adiabatic −WA→B = −WA→O −WO→B = WO→A
U (A) = U (O)−WO→A or U (O) = U (A)−WA→O .
This kind of empirical evidence, coupled with theory of this
Except under the special, and strictly speaking, fictional, kind, largely justifies the following statement:
condition of reversibility, only one of the processes
adiabatic, O → A or adiabatic, A → O is empirically fea-
For all adiabatic processes between two specified
sible by a simple application of externally supplied work.
states of a closed system of any nature, the net
The reason for this is given as the second law of thermody-
work done is the same regardless the details of the
namics and is not considered in the present article.
process, and determines a state function called in-
The fact of such irreversibility may be dealt with in two ternal energy, U .”
main ways, according to different points of view:

• Since the work of Bryan (1907), the most ac-
cepted way to deal with it nowadays, followed by
Carathéodory,[16][19][40] is to rely on the previously es-
tablished concept of quasi-static processes,[41][42][43]
as follows. Actual physical processes of transfer of
energy as work are always at least to some degree ir-
reversible. The irreversibility is often due to mech-
anisms known as dissipative, that transform bulk ki-
netic energy into internal energy. Examples are fric-
tion and viscosity. If the process is performed more
Adynamic processes
See also: Thermodynamic processes
A complementary observable aspect of the first law is about
heat transfer. Adynamic transfer of energy as heat can be
measured empirically by changes in the surroundings of the
system of interest by calorimetry. This again requires the
existence of adiabatic enclosure of the entire process, sys-
tem and surroundings, though the separating wall between
50 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

the surroundings and the system is thermally conductive
or radiatively permeable, not adiabatic. A calorimeter can
rely on measurement of sensible heat, which requires the
existence of thermometers and measurement of tempera-
ture change in bodies of known sensible heat capacity un-
der specified conditions; or it can rely on the measurement
of latent heat, through measurement of masses of material
that change phase, at temperatures fixed by the occurrence
of phase changes under specified conditions in bodies of
known latent heat of phase change. The calorimeter can
be calibrated by adiabatically doing externally determined
work on it. The most accurate method is by passing an
electric current from outside through a resistance inside the
calorimeter. The calibration allows comparison of calori-
metric measurement of quantity of heat transferred with
quantity of energy transferred as work. According to one
textbook, “The most common device for measuring ∆U
is an adiabatic bomb calorimeter.”[45] According to an-
other textbook, “Calorimetry is widely used in present day
laboratories.”[46] According to one opinion, “Most thermo-
dynamic data come from calorimetry...”[47] According to
another opinion, “The most common method of measuring
“heat” is with a calorimeter.”[48]
When the system evolves with transfer of energy as heat, cult to calculate, and irreversible thermodynamics is called
without energy being transferred as work, in an adynamic for. Nevertheless, the first law still holds and provides a
process,[49] the heat transferred to the system is equal to the check on the measurements and calculations
increase in its internal energy:
This combined statement is the expression the first law
of thermodynamics for reversible processes for closed sys-
tems.
In particular, if no work is done on a thermally isolated
closed system we have
∆U = 0
This is one aspect of the law of conservation of energy and
can be stated:
The internal energy of an isolated system remains
constant.
General case for irreversible processes
If, in a process of change of state of a closed system, the
energy transfer is not under a practically zero temperature
gradient and practically frictionless, then the process is ir-
reversible. Then the heat and work transfers may be diffi-
of the work
path P1 , irreversible
done irreversibly on the system, W A→B , and the
heat transferred irreversibly to the system, Qpath A→B
P1 , irreversible

, which belong to the same particular process defined by its

particular irreversible path, P1 , through the space of ther-
Qadynamic
A→B = ∆U . modynamic states.

General case for reversible processes

path P1 , irreversible
−WA→B + Qpath
A→B
P1 , irreversible
= ∆U .
Heat transfer is practically reversible when it is driven by
practically negligibly small temperature gradients. Work This means that the internal energy U is a function of state
transfer is practically reversible when it occurs so slowly and that the internal energy change ∆U between two states
that there are no frictional effects within the system; fric- is a function only of the two states.
tional effects outside the system should also be zero if the
process is to be globally reversible. For a particular re-
versible process in general, the work done reversibly on Overview of the weight of evidence for the law
path P0 , reversible
the system, WA→B , and the heat transferred re-
versibly to the system, Qpath P0 , reversible The first law of thermodynamics is so general that its pre-
are not required to
A→B
dictions cannot all be directly tested. In many properly
occur respectively adiabatically or adynamically, but they
must belong to the same particular process defined by its conducted experiments it has been precisely supported, and
never violated. Indeed, within its scope of applicability, the
particular reversible path, P0 , through the space of ther-
modynamic states. Then the work and heat transfers can law is so reliably established, that, nowadays, rather than
occur and be calculated simultaneously. experiment being considered as testing the accuracy of the
law, it is more practical and realistic to think of the law as
Putting the two complementary aspects together, the first testing the accuracy of experiment. An experimental result
law for a particular reversible process can be written that seems to violate the law may be assumed to be inac-
curate or wrongly conceived, for example due to failure to
account for an important physical factor. Thus, some may
path P0 , reversible path P0 , reversible
−WA→B + QA→B = ∆U . regard it as a principle more abstract than a law.
2.2. FIRST LAW OF THERMODYNAMICS 51

2.2.6 State functional formulation for in- which the defining state variables are S and V, with respect
finitesimal processes to which T and P are partial derivatives of U.[50][51][52] It
is only in the fictive reversible case, when isochoric work is
When the heat and work transfers in the equations above excluded, that the work done and heat transferred are given
are infinitesimal in magnitude, they are often denoted by δ, by −P dV and T dS.
rather than exact differentials denoted by d, as a reminder In the case of a closed system in which the particles of the
that heat and work do not describe the state of any system. system are of different types and, because chemical reac-
The integral of an inexact differential depends upon the par- tions may occur, their respective numbers are not necessar-
ticular path taken through the space of thermodynamic pa- ily constant, the fundamental thermodynamic relation for
rameters while the integral of an exact differential depends dU becomes:
only upon the initial and final states. If the initial and final
states are the same, then the integral of an inexact differ-
∑
ential may or may not be zero, but the integral of an exact dU = T dS − P dV + µi dNi .
differential is always zero. The path taken by a thermo- i
dynamic system through a chemical or physical change is
where dNᵢ is the (small) increase in amount of type-i par-
known as a thermodynamic process.
ticles in the reaction, and μᵢ is known as the chemical po-
The first law for a closed homogeneous system may be tential of the type-i particles in the system. If dNᵢ is ex-
stated in terms that include concepts that are established pressed in mol then μᵢ is expressed in J/mol. If the system
in the second law. The internal energy U may then be ex- has more external mechanical variables than just the volume
pressed as a function of the system’s defining state variables that can change, the fundamental thermodynamic relation
S, entropy, and V, volume: U = U (S, V). In these terms, further generalizes to:
T, the system’s temperature, and P, its pressure, are partial
derivatives of U with respect to S and V. These variables ∑ ∑
are important throughout thermodynamics, though not nec- dU = T dS − Xi dxi + µj dNj .
essary for the statement of the first law. Rigorously, they i j
are defined only when the system is in its own state of in-
Here the Xᵢ are the generalized forces corresponding to the
ternal thermodynamic equilibrium. For some purposes, the
external variables xᵢ. The parameters Xᵢ are independent of
concepts provide good approximations for scenarios suffi-
the size of the system and are called intensive parameters
ciently near to the system’s internal thermodynamic equi-
and the xᵢ are proportional to the size and called extensive
librium.
parameters.
The first law requires that:
For an open system, there can be transfers of particles as
well as energy into or out of the system during a process.
dU = δQ−δW irreversible). or quasi-static process,For this case,
general the(closed
system, first law of thermodynamics still holds, in
the form that the internal energy is a function of state and
Then, for the fictive case of a reversible process, dU can be the change of internal energy in a process is a function only
written in terms of exact differentials. One may imagine re- of its initial and final states, as noted in the section below
versible changes, such that there is at each instant negligible headed First law of thermodynamics for open systems.
departure from thermodynamic equilibrium within the sys-
A useful idea from mechanics is that the energy gained by
tem. This excludes isochoric work. Then, mechanical work
a particle is equal to the force applied to the particle mul-
is given by δW = - P dV and the quantity of heat added can
tiplied by the displacement of the particle while that force
be expressed as δQ = T dS. For these conditions
is applied. Now consider the first law without the heating
term: dU = -PdV. The pressure P can be viewed as a force
(and in fact has units of force per unit area) while dVis the
dU = T ds−P dV process). reversible system, (closed
displacement (with units of distance times area). We may
While this has been shown here for reversible changes, it is say, with respect to this work term, that a pressure differ-
valid in general, as U can be considered as a thermodynamic ence forces a transfer of volume, and that the product of
state function of the defining state variables S and V: the two (work) is the amount of energy transferred out of
the system as a result of the process. If one were to make
this term negative then this would be the work done on the
(2) dU = T dS−P dV irreversible). or quasi-static process, general system, (closed
system.
Equation (2) is known as the fundamental thermodynamic It is useful to view the TdS term in the same light: here the
relation for a closed system in the energy representation, for temperature is known as a “generalized” force (rather than
52 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

pot
an actual mechanical force) and the entropy is a generalized of interaction E12 between the subsystems. Thus, in an ob-
displacement. vious notation, one may write
Similarly, a difference in chemical potential between
groups of particles in the system drives a chemical reac-
tion that changes the numbers of particles, and the corre- E = E1kin + E1pot + U1 + E2kin + E2pot + U2 + E12
pot

sponding product is the amount of chemical potential en- pot

The quantity E12 in general lacks an assignment to either
ergy transformed in process. For example, consider a sys-
subsystem in a way that is not arbitrary, and this stands in
tem consisting of two phases: liquid water and water vapor.
the way of a general non-arbitrary definition of transfer of
There is a generalized “force” of evaporation that drives
energy as work. On occasions, authors make their various
water molecules out of the liquid. There is a generalized
respective arbitrary assignments.[55]
“force” of condensation that drives vapor molecules out of
the vapor. Only when these two “forces” (or chemical po- The distinction between internal and kinetic energy is hard
tentials) are equal is there equilibrium, and the net rate of to make in the presence of turbulent motion within the sys-
transfer zero. tem, as friction gradually dissipates macroscopic kinetic en-
ergy of localised bulk flow into molecular random motion
The two thermodynamic parameters that form a gener-
of molecules that is classified as internal energy.[56] The
alized force-displacement pair are called “conjugate vari-
rate of dissipation by friction of kinetic energy of localised
ables”. The two most familiar pairs are, of course, pressure-
bulk flow into internal energy,[57][58][59] whether in turbu-
volume, and temperature-entropy.
lent or in streamlined flow, is an important quantity in non-
equilibrium thermodynamics. This is a serious difficulty for
2.2.7 Spatially inhomogeneous systems attempts to define entropy for time-varying spatially inho-
mogeneous systems.
Classical thermodynamics is initially focused on closed ho-
mogeneous systems (e.g. Planck 1897/1903[36] ), which
might be regarded as 'zero-dimensional' in the sense that 2.2.8 First law of thermodynamics for open
they have no spatial variation. But it is desired to study also systems
systems with distinct internal motion and spatial inhomo-
geneity. For such systems, the principle of conservation of For the first law of thermodynamics, there is no trivial pas-
energy is expressed in terms not only of internal energy as sage of physical conception from the closed system view
[60][61]
defined for homogeneous systems, but also in terms of ki- to an open system view. For closed systems, the con-
netic energy and potential energies of parts of the inhomo- cepts of an adiabatic enclosure and of an adiabatic wall are
geneous system with respect to each other and with respect fundamental. Matter and internal energy cannot permeate
to long-range external forces.[53] How the total energy of a or penetrate such a wall. For an open system, there is a
system is allocated between these three more specific kinds wall that allows penetration by matter. In general, matter in
of energy varies according to the purposes of different writ- diffusive motion carries with it some internal energy, and
ers; this is because these components of energy are to some some microscopic potential energy changes accompany the
extent mathematical artefacts rather than actually measured motion. An open system is not adiabatically enclosed.
physical quantities. For any closed homogeneous compo- There are some cases in which a process for an open system
nent of an inhomogeneous closed system, if E denotes the can, for particular purposes, be considered as if it were for a
total energy of that component system, one may write closed system. In an open system, by definition hypotheti-
cally or potentially, matter can pass between the system and
its surroundings. But when, in a particular case, the process
E = E kin + E pot + U of interest involves only hypothetical or potential but no ac-
tual passage of matter, the process can be considered as if
where E kin and E pot denote respectively the total kinetic it were for a closed system.
energy and the total potential energy of the component
closed homogeneous system, and U denotes its internal
energy.[25][54] Internal energy for an open system
Potential energy can be exchanged with the surroundings of Since the revised and more rigorous definition of the inter-
the system when the surroundings impose a force field, such nal energy of a closed system rests upon the possibility of
as gravitational or electromagnetic, on the system. processes by which adiabatic work takes the system from
A compound system consisting of two interacting closed one state to another, this leaves a problem for the definition
homogeneous component subsystems has a potential energy of internal energy for an open system, for which adiabatic
2.2. FIRST LAW OF THERMODYNAMICS
work is not in general possible. According to Max Born,
the transfer of matter and energy across an open connec-
tion “cannot be reduced to mechanics”.[62] In contrast to
the case of closed systems, for open systems, in the pres-
ence of diffusion, there is no unconstrained and uncondi-
tional physical distinction between convective transfer of
internal energy by bulk flow of matter, the transfer of in-
ternal energy without transfer of matter (usually called heat
conduction and work transfer), and change of various po-
tential energies.[63][64][65] The older traditional way and the
conceptually revised (Carathéodory) way agree that there
is no physically unique definition of heat and work transfer
processes between open systems.[66][67][68][69][70][71]
In particular, between two otherwise isolated open systems
an adiabatic wall is by definition impossible.[72] This prob-
lem is solved by recourse to the principle of conservation of
energy. This principle allows a composite isolated system to
be derived from two other component non-interacting iso-
lated systems, in such a way that the total energy of the com-
posite isolated system is equal to the sum of the total ener-
gies of the two component isolated systems. Two previously
isolated systems can be subjected to the thermodynamic
operation of placement between them of a wall permeable
to matter and energy, followed by a time for establishment
of a new thermodynamic state of internal equilibrium in
the new single unpartitioned system.[73] The internal ener-
gies of the initial two systems and of the final new system,
considered respectively as closed systems as above, can be
measured.[60] Then the law of conservation of energy re-
quires that
∆Us + ∆Uo = 0 , [74][75]
where ΔU and ΔUₒ denote the changes in internal energy
of the system and of its surroundings respectively. This is a
statement of the first law of thermodynamics for a transfer
between two otherwise isolated open systems,[76] that fits
well with the conceptually revised and rigorous statement
of the law stated above.
For the thermodynamic operation of adding two systems
with internal energies U 1 and U 2 , to produce a new sys-
tem with internal energy U, one may write U = U 1 + U 2 ;
the reference states for U, U 1 and U 2 should be specified
accordingly, maintaining also that the internal energy of a
system be proportional to its mass, so that the internal en-
ergies are extensive variables.[60][77]
There is a sense in which this kind of additivity expresses a
fundamental postulate that goes beyond the simplest ideas
of classical closed system thermodynamics; the extensivity
of some variables is not obvious, and needs explicit expres-
sion; indeed one author goes so far as to say that it could be
recognized as a fourth law of thermodynamics, though this
is not repeated by other authors.[78][79]
53
Also of course
∆Ns + ∆No = 0 , [74][75]
where ΔN and ΔNₒ denote the changes in mole number of a
component substance of the system and of its surroundings
respectively. This is a statement of the law of conservation
of mass.
Process of transfer of matter between an open system
and its surroundings
A system connected to its surroundings only through con-
tact by a single permeable wall, but otherwise isolated, is an
open system. If it is initially in a state of contact equilib-
rium with a surrounding subsystem, a thermodynamic pro-
cess of transfer of matter can be made to occur between
them if the surrounding subsystem is subjected to some
thermodynamic operation, for example, removal of a par-
tition between it and some further surrounding subsystem.
The removal of the partition in the surroundings initiates a
process of exchange between the system and its contiguous
surrounding subsystem.
An example is evaporation. One may consider an open sys-
tem consisting of a collection of liquid, enclosed except
where it is allowed to evaporate into or to receive conden-
sate from its vapor above it, which may be considered as its
contiguous surrounding subsystem, and subject to control
of its volume and temperature.
A thermodynamic process might be initiated by a thermo-
dynamic operation in the surroundings, that mechanically
increases in the controlled volume of the vapor. Some me-
chanical work will be done within the surroundings by the
vapor, but also some of the parent liquid will evaporate and
enter the vapor collection which is the contiguous surround-
ing subsystem. Some internal energy will accompany the
vapor that leaves the system, but it will not make sense to
try to uniquely identify part of that internal energy as heat
and part of it as work. Consequently, the energy transfer
that accompanies the transfer of matter between the sys-
tem and its surrounding subsystem cannot be uniquely split
into heat and work transfers to or from the open system.
The component of total energy transfer that accompanies
the transfer of vapor into the surrounding subsystem is cus-
tomarily called 'latent heat of evaporation', but this use of
the word heat is a quirk of customary historical language,
not in strict compliance with the thermodynamic definition
of transfer of energy as heat. In this example, kinetic en-
ergy of bulk flow and potential energy with respect to long-
range external forces such as gravity are both considered
to be zero. The first law of thermodynamics refers to the
change of internal energy of the open system, between its
initial and final states of internal equilibrium.
54
Open system with multiple contacts
An open system can be in contact equilibrium with several
other systems at once.[16][80][81][82][83][84][85][86]
This includes cases in which there is contact equilibrium
between the system, and several subsystems in its sur-
roundings, including separate connections with subsystems
through walls that are permeable to the transfer of matter
and internal energy as heat and allowing friction of passage
of the transferred matter, but immovable, and separate con-
nections through adiabatic walls with others, and separate
connections through diathermic walls impermeable to mat-
ter with yet others. Because there are physically separate
connections that are permeable to energy but impermeable
to matter, between the system and its surroundings, energy
transfers between them can occur with definite heat and
work characters. Conceptually essential here is that the in-
ternal energy transferred with the transfer of matter is mea-
sured by a variable that is mathematically independent of
the variables that measure heat and work.[87]
With such independence of variables, the total increase of
internal energy in the process is then determined as the
sum of the internal energy transferred from the surround-
ings with the transfer of matter through the walls that are
permeable to it, and of the internal energy transferred to
the system as heat through the diathermic walls, and of the
energy transferred to the system as work through the adi-
abatic walls, including the energy transferred to the sys-
tem by long-range forces. These simultaneously transferred
quantities of energy are defined by events in the surround-
ings of the system. Because the internal energy trans-
ferred with matter is not in general uniquely resolvable
into heat and work components, the total energy transfer
cannot in general be uniquely resolved into heat and work
components.[88] Under these conditions, the following for-
mula can describe the process in terms of externally defined
thermodynamic variables, as a statement of the first law of
thermodynamics:
∑
m
(3) ∆U0 = Q − W −
∆Ui irreversible), or quasi-static fictive quasi-static
i=1
where ΔU 0 denotes the change of internal energy of the
system, and ΔUi denotes the change of internal energy of
the ith of the m surrounding subsystems that are in open
contact with the system, due to transfer between the system (5) dU0 = δQ − δW +
and that ith surrounding subsystem, and Q denotes the in-
ternal energy transferred as heat from the heat reservoir of
the surroundings to the system, and W denotes the energy The reference
transferred from the system to the surrounding subsystems
that are in adiabatic connection with it. The case of a wall ful account
that is permeable to matter and can move so as to allow There are several other accounts of this, in apparent mutual
transfer of energy as work is not considered here.
CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS
Combination of first and second laws If the system
is described by the energetic fundamental equation, U 0 =
U 0 (S, V, Nj), and if the process can be described in the
quasi-static formalism, in terms of the internal state vari-
ables of the system, then the process can also be described
by a combination of the first and second laws of thermody-
namics, by the formula
∑
n
(4) dU0 = T dS − P dV + µj dNj
j=1
where there are n chemical constituents of the system and
permeably connected surrounding subsystems, and where
T, S, P, V, Nj, and μj, are defined as above.[89]
For a general natural process, there is no immediate term-
wise correspondence between equations (3) and (4), be-
cause they describe the process in different conceptual
frames.
Nevertheless, a conditional correspondence exists. There
are three relevant kinds of wall here: purely diathermal, adi-
abatic, and permeable to matter. If two of those kinds of
wall are sealed off, leaving only one that permits transfers of
energy, as work, as heat, or with matter, then the remaining
permitted terms correspond precisely. If two of the kinds
of wall are left unsealed, then energy transfer can be shared
between them, so that the two remaining permitted terms
do not correspond precisely.
For the special fictive case of quasi-static transfers, there
is a simple correspondence.[90] For this, it is supposed that
the system has multiple areas of contact with its surround-
ings. There are pistons that allow adiabatic work, purely
diathermal walls, and open connections with surrounding
subsystems of completely controllable chemical potential
(or equivalent controls for charged species). Then, for a
suitable fictive quasi-static transfer, one can write
δQ = T dS and δW = P dV energy) of transfers quasi-static subsystems
For process,
transfers for
general subsystems, which the defined
surrounding chemical po-
(suitably
tentials in the connected surrounding subsystems are suit-
ably controlled, these can be put into equation (4) to yield
∑n
µj dNj transfers) quasi-static subsystems, s
j=1
[90]
does not actually write equation (5), but
what it does write is fully compatible with it. Another help-
is given by Tschoegl.[91]
conflict.[69][92][93]
2.2. FIRST LAW OF THERMODYNAMICS 55

Non-equilibrium transfers non-conservation of internal energy because of local con-

version of kinetic energy of bulk flow to internal energy by
The transfer of energy between an open system and a sin- viscosity.
gle contiguous subsystem of its surroundings is considered Gyarmati shows that his definition of “the heat flow vector”
also in non-equilibrium thermodynamics. The problem of is strictly speaking a definition of flow of internal energy,
definition arises also in this case. It may be allowed that not specifically of heat, and so it turns out that his use here
the wall between the system and the subsystem is not only of the word heat is contrary to the strict thermodynamic
permeable to matter and to internal energy, but also may definition of heat, though it is more or less compatible with
be movable so as to allow work to be done when the two historical custom, that often enough did not clearly distin-
systems have different pressures. In this case, the transfer guish between heat and internal energy; he writes “that this
of energy as heat is not defined. relation must be considered to be the exact definition of
Methods for study of non-equilibrium processes mostly deal the concept of heat flow, fairly loosely used in experimen-
with spatially continuous flow systems. In this case, the tal physics and heat technics.”[95] Apparently in a different
open connection between system and surroundings is usu- frame of thinking from that of the above-mentioned para-
ally taken to fully surround the system, so that there are no doxical usage in the earlier sections of the historic 1947
separate connections impermeable to matter but permeable work by Prigogine, about discrete systems, this usage of
to heat. Except for the special case mentioned above when Gyarmati is consistent with the later sections of the same
there is no actual transfer of matter, which can be treated 1947 work by Prigogine, about continuous-flow systems,
as if for a closed system, in strictly defined thermodynamic which use the term “heat flux” in just this way. This usage
terms, it follows that transfer of energy as heat is not de- is also followed by Glansdorff and Prigogine in their 1971
fined. In this sense, there is no such thing as 'heat flow' for text about continuous-flow systems. They write: “Again
a continuous-flow open system. Properly, for closed sys- the flow of internal energy may be split into a convection
tems, one speaks of transfer of internal energy as heat, but flow ρuv and a conduction flow. This conduction flow is
in general, for open systems, one can speak safely only of by definition the heat flow W. Therefore: j[U] = ρuv + W
transfer of internal energy. A factor here is that there are where u denotes the [internal] energy per unit mass. [These
often cross-effects between distinct transfers, for example authors actually use the symbols E and e to denote inter-
that transfer of one substance may cause transfer of another nal energy but their notation has been changed here to ac-
even when the latter has zero chemical potential gradient. cord with the notation of the present article. These authors
actually use the symbol U to refer to total energy, includ-
Usually transfer between a system and its surroundings ap-
ing kinetic energy of bulk flow.]"[96] This usage is followed
plies to transfer of a state variable, and obeys a balance law,
also by other writers on non-equilibrium thermodynamics
that the amount lost by the donor system is equal to the
such as Lebon, Jou, and Casas-Vásquez,[97] and de Groot
amount gained by the receptor system. Heat is not a state
and Mazur.[98] This usage is described by Bailyn as stat-
variable. For his 1947 definition of “heat transfer” for dis-
ing the non-convective flow of internal energy, and is listed
crete open systems, the author Prigogine carefully explains
as his definition number 1, according to the first law of
at some length that his definition of it does not obey a bal-
thermodynamics.[70] This usage is also followed by work-
ance law. He describes this as paradoxical.[94]
ers in the kinetic theory of gases.[99][100][101] This is not the
The situation is clarified by Gyarmati, who shows that his ad hoc definition of “reduced heat flux” of Haase.[102]
definition of “heat transfer”, for continuous-flow systems,
In the case of a flowing system of only one chemical con-
really refers not specifically to heat, but rather to transfer
stituent, in the Lagrangian representation, there is no dis-
of internal energy, as follows. He considers a conceptual
tinction between bulk flow and diffusion of matter. More-
small cell in a situation of continuous-flow as a system de-
over, the flow of matter is zero into or out of the cell that
fined in the so-called Lagrangian way, moving with the local
moves with the local center of mass. In effect, in this de-
center of mass. The flow of matter across the boundary is
scription, one is dealing with a system effectively closed to
zero when considered as a flow of total mass. Nevertheless,
the transfer of matter. But still one can validly talk of a
if the material constitution is of several chemically distinct
distinction between bulk flow and diffusive flow of internal
components that can diffuse with respect to one another,
energy, the latter driven by a temperature gradient within
the system is considered to be open, the diffusive flows of
the flowing material, and being defined with respect to the
the components being defined with respect to the center of
local center of mass of the bulk flow. In this case of a vir-
mass of the system, and balancing one another as to mass
tually closed system, because of the zero matter transfer, as
transfer. Still there can be a distinction between bulk flow
noted above, one can safely distinguish between transfer of
of internal energy and diffusive flow of internal energy in
energy as work, and transfer of internal energy as heat.[103]
this case, because the internal energy density does not have
to be constant per unit mass of material, and allowing for
56 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

2.2.9 See also [16] Carathéodory, C. (1909).

• Laws of thermodynamics [17] Münster, A. (1970), pp. 23–24.

[18] Reif, F. (1965), p. 122.

• Perpetual motion
• Microstate (statistical mechanics) – includes Micro-
scopic definitions of internal energy, heat and work
• Entropy production
[19] Haase, R. (1971), pp. 24–25.
[20] Quantities, Units and Symbols in Physical Chemistry (IU-
PAC Green Book) See Sec. 2.11 Chemical Thermodynam-
ics

• Relativistic heat conduction [21] Planck, M. (1897/1903). Treatise on Thermodynamics,

translated by A. Ogg, Longmans, Green & Co., London.,
p. 43
2.2.10 References [22] Münster, A. (1970).
[1] Truesdell, C. A. (1980). [23] Kirkwood, J. G., Oppenheim, I. (1961), pp. 31–33.
[2] Hess, H. (1840). “Thermochemische Unter- [24] Planck, M. (1897/1903), p. 86.
suchungen”. Annalen der Physik und Chemie 126
(6): 385–404. Bibcode:1840AnP...126..385H. [25] Crawford, F. H. (1963), pp. 106–107.
doi:10.1002/andp.18401260620.
[26] Bryan, G. H. (1907), p. 47.
[3] Truesdell, C. A. (1980), pp. 157–158.
[27] Buchdahl, H. A. (1966), p. 34.
[4] Mayer, Robert (1841). Paper: 'Remarks on the Forces of [28] Pippard, A. B. (1957/1966), p. 14.
Nature"; as quoted in: Lehninger, A. (1971). Bioenerget-
ics – the Molecular Basis of Biological Energy Transforma- [29] Reif, F. (1965), p. 82.
tions, 2nd. Ed. London: The Benjamin/Cummings Publish-
ing Company. [30] Adkins, C. J. (1968/1983), p. 31.

[5] Bailyn, M. (1994), p. 79. [31] Callen, H. B. (1960/1985), pp. 13, 17.

[6] Clausius, R. (1850), page 373, translation here taken from
Truesdell, C. A. (1980), pp. 188–189.
[7] Clausius, R. (1850), page 384, equation (IIa.).
[8] Bailyn, M. (1994), p. 80.
[9] Bryan, G. H. (1907), p.47. Also Bryan had written about
this in the Enzyklopädie der Mathematischen Wissenschaften,
volume 3, p. 81. Also in 1906 Jean Baptiste Perrin wrote
about it in Bull. de la société français de philosophie, volume
6, p. 81.
[10] Born, M. (1949), Lecture V, pp. 31–45.
[11] Bailyn, M. (1994), pp. 65, 79.
[12] Bailyn, (1994), p. 82.
[13] Helmholtz, H. (1847).
[14] Pippard, A. B. (1957/1966), p. 15. According to Herbert
Callen, in his most widely cited text, Pippard’s text gives
a “scholarly and rigorous treatment"; see Callen, H. B.
(1960/1985), p. 485. It is also recommended by Münster,
A. (1970), p. 376.
[32] Kittel, C. Kroemer, H. (1980). Thermal Physics, (first edi-
tion by Kittel alone 1969), second edition, W. H. Freeman,
San Francisco, ISBN 0-7167-1088-9, pp. 49, 227.
[33] Tro, N. J. (2008). Chemistry. A Molecular Approach,
Pearson/Prentice Hall, Upper Saddle River NJ, ISBN 0-13-
100065-9, p. 246.
[34] Kirkwood, J. G., Oppenheim, I. (1961), pp. 17–18. Kirk-
wood & Oppenheim 1961 is recommended by Münster,
A. (1970), p. 376. It is also cited by Eu, B. C. (2002),
Generalized Thermodynamics, the Thermodynamics of Irre-
versible Processes and Generalized Hydrodynamics, Kluwer
Academic Publishers, Dordrecht, ISBN 1-4020-0788-4, pp.
18, 29, 66.
[35] Guggenheim, E. A. (1949/1967). Thermodynamics. An Ad-
vanced Treatment for Chemists and Physicists, (first edition
1949), fifth edition 1967, North-Holland, Amsterdam, pp.
9–10. Guggenheim 1949/1965 is recommended by Buch-
dahl, H. A. (1966), p. 218. It is also recommended by Mün-
ster, A. (1970), p. 376.
[36] Planck, M. (1897/1903).
[37] Kestin, J. (1966), p. 156.

[15] Born, M. (1921). “Kritische Betrachtungen zur tradi- [38] Cropper, W. H. (1986). “Rudolf Clausius and the
tionellen Darstellung der Thermodynamik”. Physik. Zeitschr road to entropy”. Am. J. Phys. 54: 1068–1074.
22: 218–224. Bibcode:1986AmJPh..54.1068C. doi:10.1119/1.14740.
2.2. FIRST LAW OF THERMODYNAMICS
[39] Truesdell, C. A. (1980), pp. 161–162.
[40] Buchdahl, H. A. (1966), p. 43.
[41] Maxwell, J. C. (1871). Theory of Heat, Longmans, Green,
and Co., London, p. 150.
[42] Planck, M. (1897/1903), Section 71, p. 52.
[43] Bailyn, M. (1994), p. 95.
[44] Adkins, C. J. (1968/1983), p. 35.
[45] Atkins, P., de Paula, J. (1978/2010). Physical Chemistry,
(first edition 1978), ninth edition 2010, Oxford University
Press, Oxford UK, ISBN 978-0-19-954337-3, p. 54.
[46] Kondepudi, D. (2008). Introduction to Modern Thermody-
namics, Wiley, Chichester, ISBN 978-0-470-01598-8, p.
63.
[47] Gislason, E. A.; Craig, N. C. (2005). “Cement-
ing the foundations of thermodynamics:comparison of
system-based and surroundings-based definitions of work
and heat”. J. Chem. Thermodynamics 37: 954–966.
doi:10.1016/j.jct.2004.12.012.
[48] Rosenberg, R. M. (2010). “From Joule to Caratheodory
and Born: A conceptual evolution of the first law of
thermodynamics”. J. Chem. Edu. 87: 691–693.
Bibcode:2010JChEd..87..691R. doi:10.1021/ed1001976.
[49] Partington, J.R. (1949), p. 183: "Rankine calls the curves
representing changes without performance of work, ady-
namics.”
[50] Denbigh, K. (1954/1981), p. 45.
[51] Adkins, C. J. (1968/1983), p. 75.
[52] Callen, H. B. (1960/1985), pp. 36, 41, 63.
[53] Bailyn, M. (1994), 254–256.
[54] Glansdorff, P., Prigogine, I. (1971), page 8.
[55] Tisza, L. (1966), p. 91.
[56] Denbigh, K. G. (1951), p. 50.
[57] Thomson, W. (1852 a). "On a Universal Tendency in Nature
to the Dissipation of Mechanical Energy" Proceedings of the
Royal Society of Edinburgh for April 19, 1852 [This version
from Mathematical and Physical Papers, vol. i, art. 59, pp.
511.]
[58] Thomson, W. (1852 b). On a universal tendency in nature
to the dissipation of mechanical energy, Philosophical Mag-
azine 4: 304–306.
[59] Helmholtz, H. (1869/1871). Zur Theorie der stationären
Ströme in reibenden Flüssigkeiten, Verhandlungen des
naturhistorisch-medizinischen Vereins zu Heidelberg, Band
V: 1–7. Reprinted in Helmholtz, H. (1882), Wis-
senschaftliche Abhandlungen, volume 1, Johann Ambrosius
Barth, Leipzig, pages 223–230
57
[60] Münster A. (1970), Sections 14, 15, pp. 45–51.
[61] Landsberg, P. T. (1978), p. 78.
[62] Born, M. (1949), p. 44.
[63] Denbigh, K. G. (1951), p. 56. Denbigh states in a footnote
that he is indebted to correspondence with E. A. Guggen-
heim and with N. K. Adam. From this, Denbigh concludes
“It seems, however, that when a system is able to exchange
both heat and matter with its environment, it is impossible
to make an unambiguous distinction between energy trans-
ported as heat and by the migration of matter, without al-
ready assuming the existence of the 'heat of transport'.”
[64] Fitts, D. D. (1962), p. 28.
[65] Denbigh, K. (1954/1971), pp. 81–82.
[66] Münster, A. (1970), p. 50.
[67] Haase, R. (1963/1969), p. 15.
[68] Haase, R. (1971), p. 20.
[69] Smith, D. A. (1980). Definition of heat in open systems,
Aust. J. Phys., 33: 95–105.
[70] Bailyn, M. (1994), p. 308.
[71] Balian, R. (1991/2007), p. 217
[72] Münster, A. (1970), p. 46.
[73] Tisza, L. (1966), p. 41.
[74] Callen H. B. (1960/1985), p. 54.
[75] Tisza, L. (1966), p. 110.
[76] Tisza, L. (1966), p. 111.
[77] Prigogine, I., (1955/1967), p. 12.
[78] Landsberg, P. T. (1961), pp. 142, 387.
[79] Landsberg, P. T. (1978), pp. 79,102.
[80] Prigogine, I. (1947), p. 48.
[81] Born, M. (1949), Appendix 8, pp. 146–149.
[82] Aston, J. G., Fritz, J. J. (1959), Chapter 9.
[83] Kestin, J. (1961).
[84] Landsberg, P. T. (1961), pp. 128–142.
[85] Tisza, L. (1966), p. 108.
[86] Tschoegl, N. W. (2000), p. 201.
[87] Born, M. (1949), pp. 146–147.
[88] Haase, R. (1971), p. 35.
[89] Callen, H. B., (1960/1985), p. 35.
 58
[90] Aston, J. G., Fritz, J. J. (1959), Chapter 9. This is an unusu-
ally explicit account of some of the physical meaning of the
Gibbs formalism.
[91] Tschoegl, N. W. (2000), pp. 12–14.
[92] Buchdahl, H. A. (1966), Section 66, pp. 121–125.
[93] Callen, J. B. (1960/1985), Section 2-1, pp. 35–37.
[94] Prigogine, I., (1947), pp. 48–49.
[95] Gyarmati, I. (1970), p. 68.
[96] Glansdorff, P, Prigogine, I, (1971), p. 9.
[97] Lebon, G., Jou, D., Casas-Vázquez, J. (2008), p. 45.
[98] de Groot, S. R., Mazur, P. (1962), p. 18.
[99] de Groot, S. R., Mazur, P. (1962), p. 169.
[100] Truesdell, C., Muncaster, R. G. (1980), p. 3.
[101] Balescu, R. (1997), p. 9.
[102] Haase, R. (1963/1969), p. 18.
[103] Eckart, C. (1940).
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Kinetic Theory of Gases. An Anthology of Classic Pa-
pers with Historical Commentary, volume 1 of History
of Modern Physical Sciences, edited by N. S. Hall, Im-
perial College Press, London, ISBN 1-86094-347-0,
pp. 89–110.
• Kestin, J. (1961). “On intersecting isen-
tropics”. Am. J. Phys. 29: 329–
331. Bibcode:1961AmJPh..29..329K.
doi:10.1119/1.1937763.
• Kestin, J. (1966). A Course in Thermodynamics, Blais-
dell Publishing Company, Waltham MA.
• Kirkwood, J. G., Oppenheim, I. (1961). Chemical
Thermodynamics, McGraw-Hill Book Company, New
York.
• Landsberg, P. T. (1961). Thermodynamics with Quan-
tum Statistical Illustrations, Interscience, New York.
• Landsberg, P. T. (1978). Thermodynamics and Statis-
tical Mechanics, Oxford University Press, Oxford UK,
ISBN 0-19-851142-6.
• Lebon, G., Jou, D., Casas-Vázquez, J. (2008). Under-
standing Non-equilibrium Thermodynamics, Springer,
Berlin, ISBN 978-3-540-74251-7.
• Münster, A. (1970), Classical Thermodynamics, trans-
lated by E. S. Halberstadt, Wiley–Interscience, Lon-
don, ISBN 0-471-62430-6.
59
• Partington, J.R. (1949). An Advanced Treatise on
Physical Chemistry, volume 1, Fundamental Princi-
ples. The Properties of Gases, Longmans, Green and
Co., London.
• Pippard, A. B. (1957/1966). Elements of Classical
Thermodynamics for Advanced Students of Physics,
original publication 1957, reprint 1966, Cambridge
University Press, Cambridge UK.
• Planck, M.(1897/1903). Treatise on Thermodynam-
ics, translated by A. Ogg, Longmans, Green & Co.,
London.
• Prigogine, I. (1947). Étude Thermodynamique des
Phénomènes irréversibles, Dunod, Paris, and Desoers,
Liège.
• Prigogine, I., (1955/1967). Introduction to Thermody-
namics of Irreversible Processes, third edition, Inter-
science Publishers, New York.
• Reif, F. (1965). Fundamentals of Statistical and
Thermal Physics, McGraw-Hill Book Company, New
York.
• Tisza, L. (1966). Generalized Thermodynamics,
M.I.T. Press, Cambridge MA.
• Truesdell, C. A. (1980). The Tragicomical History of
Thermodynamics, 1822–1854, Springer, New York,
ISBN 0-387-90403-4.
• Truesdell, C. A., Muncaster, R. G. (1980). Fun-
damentals of Maxwell’s Kinetic Theory of a Simple
Monatomic Gas, Treated as a branch of Rational Me-
chanics, Academic Press, New York, ISBN 0-12-
701350-4.
• Tschoegl, N. W. (2000). Fundamentals of Equilibrium
and Steady-State Thermodynamics, Elsevier, Amster-
dam, ISBN 0-444-50426-5.
2.2.11 Further reading
• Goldstein, Martin, and Inge F. (1993). The Refrigera-
tor and the Universe. Harvard University Press. ISBN
0-674-75325-9. OCLC 32826343. Chpts. 2 and 3
contain a nontechnical treatment of the first law.
• Çengel Y. A. and Boles M. (2007). Thermodynamics:
an engineering approach. McGraw-Hill Higher Edu-
cation. ISBN 0-07-125771-3. Chapter 2.
• Atkins P. (2007). Four Laws that drive the Universe.
OUP Oxford. ISBN 0-19-923236-9.
60 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

2.2.12 External links of heat to work in a cyclic heat engine operating between
two given temperatures.
• MISN-0-158, The First Law of Thermodynamics
(PDF file) by Jerzy Borysowicz for Project PHYS-
NET. 2.3.1 Introduction
Intuitive meaning of the law
• First law of thermodynamics in the MIT Course
Unified Thermodynamics and Propulsion from Prof.
The second law is about thermodynamic systems or bod-
Z. S. Spakovszky
ies of matter and radiation, initially each in its own
state of internal thermodynamic equilibrium, and sepa-
rated from one another by walls that partly or wholly
2.3 Second law of Thermodynamics allow or prevent the passage of matter and energy be-
tween them, or make them mutually inaccessible for their
[8][9][10][11][12][13]
The second law of thermodynamics states that for a ther- constituents.
modynamically defined process to actually occur, the sum The law envisages that the walls are changed by some ex-
of the entropies of the participating bodies must increase. ternal agency, making them less restrictive or constraining
In an idealized limiting case, that of a reversible process, and more permeable in various ways, and increasing the
this sum remains unchanged. A simplified version of the accessibility, to parts of the overall system, of matter and
law states that the flow of heat is from a hotter to a colder energy.[14][15][16][17] Thereby a process is defined, establish-
body. ing new equilibrium states.
A thermodynamically defined process consists of transfers The process invariably spreads,[18][19][20][21] disperses,[22]
of matter and energy between bodies of matter and radia- and dissipates[6][23] matter or energy, or both, amongst the
tion, each participating body being initially in its own state bodies. Some energy, inside or outside the system, is de-
of internal thermodynamic equilibrium. The bodies are ini- graded in its ability to do work.[24] This is quantitatively
tially separated from one another by walls that obstruct the described by increase of entropy. It is the consequence of
passage of matter and energy between them. The transfers decrease of constraint by a wall, with a corresponding in-
are initiated by a thermodynamic operation: some external crease in the accessibility, to the parts of the system, of
agency intervenes[1] to make one or more of the walls less matter and energy. An increase of constraint by a wall has
obstructive.[2] This establishes new equilibrium states in the no effect on an established thermodynamic equilibrium.
bodies. If, instead of making the walls less obstructive, the For an example of the spreading of matter due to increase
thermodynamic operation makes them more obstructive, no of accessibility, one may consider a gas initially confined
transfers are occasioned, and there is no effect on an estab-
by an impermeable wall to one of two compartments of
lished thermodynamic equilibrium. an isolated system. The wall is then removed. The gas
The law expresses the irreversibility of the process. The spreads throughout both compartments.[17] The sum of the
transfers invariably bring about spread,[3][4][5] dispersal, entropies of the two compartments increases. Reinsertion
or dissipation[6] of matter or energy, or both, amongst of the impermeable wall does not change the spread of the
the bodies. They occur because more kinds of transfer gas between the compartments. For an example of the
through the walls have become possible.[7] Irreversibility spreading of energy due to increase of accessibility, one
in thermodynamic processes is a consequence of the asym- may consider a wall impermeable to matter and energy ini-
metric character of thermodynamic operations, and not of tially separating two otherwise isolated bodies at different
any internally irreversible microscopic properties of the temperatures. A thermodynamic operation makes the wall
bodies. become permeable only to heat, which then passes from the
The second law is an empirical finding that has been ac- hotter to the colder body, until their temperatures become
cepted as an axiom of thermodynamic theory. When its equal. The sum of the entropies of the two bodies increases.
presuppositions may be only approximately fulfilled, often Restoration of the complete impermeability of the wall does
enough, the law can give a very useful approximation to not change the equality of the temperatures. The spreading
the observed facts. Statistical thermodynamics, classical or is a change from heterogeneity towards homogeneity.
quantum, explains the microscopic origin of the law. The It is the unconstraining of the initial equilibrium that
second law has been expressed in many ways. Its first for- causes the increase of entropy and the change towards
mulation is credited to the French scientist Sadi Carnot in homogeneity.[15] The following reasoning offers intuitive
1824 (see Timeline of thermodynamics). Carnot showed understanding of this fact. One may imagine that the freshly
that there is an upper limit to the efficiency of conversion unconstrained system, still relatively heterogeneous, imme-
2.3. SECOND LAW OF THERMODYNAMICS 61

diately after the intervention that increased the wall per- ies, and never the reverse, unless external work is performed
meability, in its transient condition, arose by spontaneous on the system. The key concept for the explanation of this
evolution from an unconstrained previous transient condi- phenomenon through the second law of thermodynamics is
tion of the system. One can then ask, what is the probable the definition of a new physical quantity, the entropy.[33][34]
such imagined previous condition. The answer is that, over- For mathematical analysis of processes, entropy is intro-
whelmingly probably, it is just the very same kind of homo- duced as follows. In a fictive reversible process, an infinites-
geneous condition as that to which the relatively heteroge- imal increment in the entropy (dS) of a system results from
neous condition will overwhelmingly probably evolve. Ob- an infinitesimal transfer of heat (δQ) to a closed system di-
viously, this is possible only in the imagined absence of the
vided by the common temperature (T) of the system and
constraint that was actually present until its removal. In this the surroundings which supply the heat:[35]
light, the reversibility of the dynamics of the evolution of
the unconstrained system is evident, in accord with the ordi-
nary laws of microscopic dynamics. It is the removal of the
δQ
constraint that is effective in causing the change towards ho- dS = process) reversible fictive idealized system, (closed.
T
mogeneity, not some imagined or apparent “irreversibility”
of the laws of spontaneous evolution.[25] This reasoning is For an actually possible infinitesimal process without ex-
of intuitive interest, but is essentially about microstates, and change of matter with the surroundings, the second law re-
therefore does not belong to macroscopic equilibrium ther- quires that the increment in system entropy be greater than
modynamics, which studiously ignores consideration of mi- that:
crostates, and non-equilibrium considerations of this kind.
It does, however, forestall futile puzzling about some fa-
mous proposed “paradoxes”, imagining of a “derivation” of δQ
an “arrow of time” from the second law,[26] and meaning- dS > process). irreversible possible, actually system, (closed
T
less speculation about an imagined “low entropy state” of
the early universe.[27] This is because a general process for this case may include
work being done on the system by its surroundings, which
Though it is more or less intuitive to imagine 'spread-
must have frictional or viscous effects inside the system,
ing', such loose intuition is, for many thermodynamic pro-
and because heat transfer actually occurs only irreversibly,
cesses, too vague or imprecise to be usefully quantitatively
driven by a finite temperature difference.[36][37]
informative, because competing possibilities of spreading
can coexist, for example due to an increase of some con- The zeroth law of thermodynamics in its usual short state-
straint combined with decrease of another. The second ment allows recognition that two bodies in a relation of
law justifies the concept of entropy, which makes the no- thermal equilibrium have the same temperature, especially
tion of 'spreading' suitably precise, allowing quantitative that a test body has the same temperature as a reference
predictions of just how spreading will occur in partic- thermometric body.[38] For a body in thermal equilibrium
ular circumstances. It is characteristic of the physical with another, there are indefinitely many empirical temper-
quantity entropy that it refers to states of thermodynamic ature scales, in general respectively depending on the prop-
equilibrium.[28][29][30] erties of a particular reference thermometric body. The
second law allows a distinguished temperature scale, which
defines an absolute, thermodynamic temperature, indepen-
dent of the properties of any particular reference thermo-
General significance of the law
metric body.[39][40]
The first law of thermodynamics provides the basic defini-
tion of thermodynamic energy, also called internal energy, 2.3.2 Various statements of the law
associated with all thermodynamic systems, but unknown
in classical mechanics, and states the rule of conservation The second law of thermodynamics may be expressed
of energy in nature.[31][32] in many specific ways,[41] the most prominent classi-
The concept of energy in the first law does not, however, cal statements[42] being the statement by Rudolf Clau-
account for the observation that natural processes have a sius (1854), the statement by Lord Kelvin (1851), and
preferred direction of progress. The first law is symmetri- the statement in axiomatic thermodynamics by Constantin
cal with respect to the initial and final states of an evolving Carathéodory (1909). These statements cast the law in gen-
system. But the second law asserts that a natural process eral physical terms citing the impossibility of certain pro-
runs only in one sense, and is not reversible. For example, cesses. The Clausius and the Kelvin statements have been
heat always flows spontaneously from hotter to colder bod- shown to be equivalent.[43]
62 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

Carnot’s principle It is impossible, by means of inanimate mate-

rial agency, to derive mechanical effect from any
The historical origin of the second law of thermodynamics portion of matter by cooling it below the temper-
was in Carnot’s principle. It refers to a cycle of a Carnot ature of the coldest of the surrounding objects.[53]
heat engine, fictively operated in the limiting mode of ex-
treme slowness known as quasi-static, so that the heat and
work transfers are between subsystems that are always in Equivalence of the Clausius and the Kelvin statements
their own internal states of thermodynamic equilibrium.
The Carnot engine is an idealized device of special inter-
est to engineers who are concerned with the efficiency of
heat engines. Carnot’s principle was recognized by Carnot
at a time when the caloric theory of heat was seriously con-
sidered, before the recognition of the first law of thermo-
dynamics, and before the mathematical expression of the
concept of entropy. Interpreted in the light of the first law,
it is physically equivalent to the second law of thermody- Imagined Carnot
namics, and remains valid today. It states Engine Engine

The efficiency of a quasi-static or reversible

Carnot cycle depends only on the temperatures
of the two heat reservoirs, and is the same,
whatever the working substance. A Carnot
engine operated in this way is the most ef-
ficient possible heat engine using those two
temperatures.[44][45][46][47][48][49][50]
Derive Kelvin Statement from Clausius Statement

Clausius statement Suppose there is an engine violating the Kelvin statement:

The German scientist Rudolf Clausius laid the foundation
for the second law of thermodynamics in 1850 by examin-
ing the relation between heat transfer and work.[51] His for-
mulation of the second law, which was published in German
in 1854, is known as the Clausius statement:
Heat can never pass from a colder to a
warmer body without some other change, con-
nected therewith, occurring at the same time.[52]
The statement by Clausius uses the concept of 'passage of
heat'. As is usual in thermodynamic discussions, this means
'net transfer of energy as heat', and does not refer to con-
tributory transfers one way and the other.
Heat cannot spontaneously flow from cold regions to hot re-
gions without external work being performed on the system,
which is evident from ordinary experience of refrigeration,
for example. In a refrigerator, heat flows from cold to hot,
but only when forced by an external agent, the refrigeration
system.
Kelvin statement
Lord Kelvin expressed the second law as
i.e., one that drains heat and converts it completely into
work in a cyclic fashion without any other result. Now pair
it with a reversed Carnot engine as shown by the figure.
The net and sole effect of this newly created engine con-
sisting of the
( two )engines mentioned is transferring heat
∆Q = Q η1 − 1 from the cooler reservoir to the hot-
ter one, which violates the Clausius statement. Thus a vi-
olation of the Kelvin statement implies a violation of the
Clausius statement, i.e. the Clausius statement implies the
Kelvin statement. We can prove in a similar manner that the
Kelvin statement implies the Clausius statement, and hence
the two are equivalent.
Planck’s proposition
Planck offered the following proposition as derived directly
from experience. This is sometimes regarded as his state-
ment of the second law, but he regarded it as a starting point
for the derivation of the second law.
It is impossible to construct an engine
which will work in a complete cycle,
and produce no effect except the rais-
ing of a weight and cooling of a heat
reservoir.[54][55]
2.3. SECOND LAW OF THERMODYNAMICS 63

Relation between Kelvin’s statement and Planck’s Though it is almost customary in textbooks to say that
proposition Carathéodory’s principle expresses the second law and to
treat it as equivalent to the Clausius or to the Kelvin-
It is almost customary in textbooks to speak of the “Kelvin- Planck statements, such is not the case. To get all the
Planck statement” of the law, as for example in the text by content of the second law, Carathéodory’s principle needs
ter Haar and Wergeland.[56] One text gives a statement very to be supplemented by Planck’s principle, that isochoric
like Planck’s proposition, but attributes it to Kelvin with- work always increases the internal energy of a closed sys-
out mention of Planck.[57] One monograph quotes Planck’s tem that was initially in its own internal thermodynamic
proposition as the “Kelvin-Planck” formulation, the text equilibrium.[37][66][67][68]
naming Kelvin as its author, though it correctly cites Planck
in its references.[58] The reader may compare the two state-
ments quoted just above here. Planck’s Principle

Planck’s statement In 1926, Max Planck wrote an important paper on the basics
of thermodynamics.[67][69] He indicated the principle
Planck stated the second law as follows.

Every process occurring in nature pro- The internal energy of a closed system
ceeds in the sense in which the sum is increased by an adiabatic process,
of the entropies of all bodies taking throughout the duration of which,
part in the process is increased. In the volume of the system remains
the limit, i.e. for reversible processes, constant.[37][66]
the sum of the entropies remains un-
changed.[59][60][61]
This formulation does not mention heat and does not men-
tion temperature, nor even entropy, and does not necessar-
Rather like Planck’s statement is that of Uhlenbeck and ily implicitly rely on those concepts, but it implies the con-
Ford for irreversible phenomena. tent of the second law. A closely related statement is that
“Frictional pressure never does positive work.”[70] Using a
... in an irreversible or spontaneous now-obsolete form of words, Planck himself wrote: “The
change from one equilibrium state to production of heat by friction is irreversible.”[71][72]
another (as for example the equaliza-
tion of temperature of two bodies A Not mentioning entropy, this principle of Planck is stated
and B, when brought in contact) the in physical terms. It is very closely related to the Kelvin
entropy always increases. [62] statement given just above.[73] It is relevant that for a sys-
tem at constant volume and mole numbers, the entropy is
a monotonic function of the internal energy. Nevertheless,
Principle of Carathéodory this principle of Planck is not actually Planck’s preferred
statement of the second law, which is quoted above, in a
Constantin Carathéodory formulated thermodynamics on previous sub-section of the present section of this present
a purely mathematical axiomatic foundation. His state- article, and relies on the concept of entropy.
ment of the second law is known as the Principle of
Carathéodory, which may be formulated as follows:[63] A statement that in a sense is complementary to Planck’s
principle is made by Borgnakke and Sonntag. They do not
offer it as a full statement of the second law:
In every neighborhood of any state S of an
adiabatically enclosed system there are states in-
accessible from S.[64] ... there is only one way in which the
entropy of a [closed] system can be
With this formulation, he described the concept of adiabatic decreased, and that is to transfer heat
accessibility for the first time and provided the founda- from the system.[74]
tion for a new subfield of classical thermodynamics, of-
ten called geometrical thermodynamics. It follows from
Carathéodory’s principle that quantity of energy quasi- Differing from Planck’s just foregoing principle, this one is
statically transferred as heat is a holonomic process func- explicitly in terms of entropy change. Of course, removal
tion, in other words, δQ = T dS .[65] of matter from a system can also decrease its entropy.
64 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

Statement for a system that has a known expression of Clausius Inequality

its internal energy as a function of its extensive state
variables The Clausius theorem (1854) states that in a cyclic process

The second law has been shown to be equivalent to the I

internal energy U being a weakly convex function, when
written as a function of extensive properties (mass, volume,
entropy, ...).[75][76]
2.3.3 Corollaries
Perpetual motion of the second kind
δQ
≤ 0.
T
The equality holds in the reversible case[77] and the '<' is in
the irreversible case. The reversible case is used to intro-
duce the state function entropy. This is because in cyclic
processes the variation of a state function is zero from state
functionality.

Thermodynamic temperature
Main article: Perpetual motion
Main article: Thermodynamic temperature
Before the establishment of the Second Law, many people
who were interested in inventing a perpetual motion ma-
For an arbitrary heat engine, the efficiency is:
chine had tried to circumvent the restrictions of first law of
thermodynamics by extracting the massive internal energy
of the environment as the power of the machine. Such a Wn qH − qC qC
machine is called a “perpetual motion machine of the sec- η = = =1− (1)
qH qH qH
ond kind”. The second law declared the impossibility of
such machines. where W is for the net work done per cycle. Thus the effi-
ciency depends only on qC/qH.
Carnot’s theorem states that all reversible engines operating
Carnot theorem between the same heat reservoirs are equally efficient. Thus,
any reversible heat engine operating between temperatures
Carnot’s theorem (1824) is a principle that limits the max- T 1 and T 2 must have the same efficiency, that is to say,
imum efficiency for any possible engine. The efficiency the efficiency is the function of temperatures only: qC =
qH
solely depends on the temperature difference between the f (T , T ) (2).
H C
hot and cold thermal reservoirs. Carnot’s theorem states:
In addition, a reversible heat engine operating between tem-
peratures T 1 and T 3 must have the same efficiency as one
• All irreversible heat engines between two heat reser- consisting of two cycles, one between T 1 and another (in-
voirs are less efficient than a Carnot engine operating termediate) temperature T 2 , and the second between T 2
between the same reservoirs. andT 3 . This can only be the case if

• All reversible heat engines between two heat reservoirs

q q q
are equally efficient with a Carnot engine operating be- f (T1 , T3 ) = 3 = 2 3 = f (T1 , T2 )f (T2 , T3 ).
tween the same reservoirs. q 1 q1 q2
Now consider the case where T1 is a fixed reference tem-
perature: the temperature of the triple point of water. Then
In his ideal model, the heat of caloric converted into work
for any T 2 and T 3 ,
could be reinstated by reversing the motion of the cycle, a
concept subsequently known as thermodynamic reversibil-
ity. Carnot, however, further postulated that some caloric
f (T1 , T3 ) 273.16 · f (T1 , T3 )
is lost, not being converted to mechanical work. Hence, no f (T2 , T3 ) = = .
real heat engine could realise the Carnot cycle's reversibility f (T 1 , T2 ) 273.16 · f (T1 , T2 )
and was condemned to be less efficient. Therefore, if thermodynamic temperature is defined by
Though formulated in terms of caloric (see the obsolete
caloric theory), rather than entropy, this was an early in-
sight into the second law. T = 273.16 · f (T1 , T )
2.3. SECOND LAW OF THERMODYNAMICS 65

then the function f, viewed as a function of thermodynamic Energy, available useful work
temperature, is simply
See also: Exergy

T3
f (T2 , T3 ) = , An important and revealing idealized special case is to con-
T2
sider applying the Second Law to the scenario of an iso-
and the reference temperature T 1 will have the value lated system (called the total system or universe), made up
273.16. (Of course any reference temperature and any pos- of two parts: a sub-system of interest, and the sub-system’s
itive numerical value could be used—the choice here cor- surroundings. These surroundings are imagined to be so
responds to the Kelvin scale.) large that they can be considered as an unlimited heat reser-
voir at temperature TR and pressure PR — so that no matter
how much heat is transferred to (or from) the sub-system,
Entropy
the temperature of the surroundings will remain TR; and no
matter how much the volume of the sub-system expands (or
Main article: entropy (classical thermodynamics)
contracts), the pressure of the surroundings will remain PR.
Whatever changes to dS and dSR occur in the entropies of
According to the Clausius equality, for a reversible process
the sub-system and the surroundings individually, accord-
ing to the Second Law the entropy Stot of the isolated total
I system must not decrease:
δQ
=0
T
∫ δQ
That means the line integral L T
is path independent. dStot = dS + dSR ≥ 0
So we can define a state function S called entropy, which
According to the First Law of Thermodynamics, the change
satisfies
dU in the internal energy of the sub-system is the sum of the
heat δq added to the sub-system, less any work δw done by
δQ the sub-system, plus any net chemical energy entering the
dS = sub-system d ∑μiRNi, so that:
T
With this we can only obtain the difference of entropy by
integrating the above formula. To obtain the absolute value, dU = δq − δw + d(∑ µ N )
iR i
we need the Third Law of Thermodynamics, which states
that S=0 at absolute zero for perfect crystals. where μᵢR are the chemical potentials of chemical species
For any irreversible process, since entropy is a state func- in the external surroundings.
tion, we can always connect the initial and terminal states Now the heat leaving the reservoir and entering the sub-
with an imaginary reversible process and integrating on that system is
path to calculate the difference in entropy.
Now reverse the reversible process and combine it with the
said irreversible process. Applying Clausius inequality on δq = TR (−dSR ) ≤ TR dS
this loop,
where we have first used the definition of entropy in classi-
cal thermodynamics (alternatively, in statistical thermody-
∫ I
δQ δQ namics, the relation between entropy change, temperature
−∆S + = <0 and absorbed heat can be derived); and then the Second
T T
Law inequality from above.
Thus,
It therefore follows that any net work δw done by the sub-
∫ system must obey
δQ
∆S ≥
T ∑
δw ≤ −dU + TR dS + µiR dNi
where the equality holds if the transformation is reversible.
Notice that if the process is an adiabatic process, then δQ = It is useful to separate the work δw done by the subsystem
0 , so ∆S ≥ 0 . into the useful work δwu that can be done by the sub-system,
66 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

over and beyond the work pR dV done merely by the sub-

system expanding against the surrounding external pressure,
giving the following relation for the useful work (exergy)
that can be done:

∑
δwu ≤ −d(U − TR S + pR V − µiR Ni )

It is convenient to define the right-hand-side as the exact

derivative of a thermodynamic potential, called the avail-
ability or exergy E of the subsystem,

∑
E = U − TR S + pR V − µiR Ni

The Second Law therefore implies that for any process

which can be considered as divided simply into a subsys-
tem, and an unlimited temperature and pressure reservoir
with which it is in contact,

dE + δwu ≤ 0
i.e. the change in the subsystem’s exergy plus the useful
work done by the subsystem (or, the change in the subsys- Nicolas Léonard Sadi Carnot in the traditional uniform of a student
tem’s exergy less any work, additional to that done by the of the École Polytechnique.
pressure reservoir, done on the system) must be less than or
equal to zero.
In sum, if a proper infinite-reservoir-like reference state is
cal work is due to Nicolas Léonard Sadi Carnot in 1824.
chosen as the system surroundings in the real world, then
He was the first to realize correctly that the efficiency of
the Second Law predicts a decrease in E for an irreversible
this conversion depends on the difference of temperature
process and no change for a reversible process.
between an engine and its environment.
dStot ≥ 0 Is equivalent to dE + δwu ≤ 0 Recognizing the significance of James Prescott Joule's work
on the conservation of energy, Rudolf Clausius was the first
This expression together with the associated reference state to formulate the second law during 1850, in this form: heat
permits a design engineer working at the macroscopic scale does not flow spontaneously from cold to hot bodies. While
(above the thermodynamic limit) to utilize the Second Law common knowledge now, this was contrary to the caloric
without directly measuring or considering entropy change in theory of heat popular at the time, which considered heat
a total isolated system. (Also, see process engineer). Those as a fluid. From there he was able to infer the principle of
changes have already been considered by the assumption Sadi Carnot and the definition of entropy (1865).
that the system under consideration can reach equilibrium Established during the 19th century, the Kelvin-Planck
with the reference state without altering the reference state. statement of the Second Law says, “It is impossible for any
An efficiency for a process or collection of processes that device that operates on a cycle to receive heat from a sin-
compares it to the reversible ideal may also be found (See gle reservoir and produce a net amount of work.” This was
second law efficiency.) shown to be equivalent to the statement of Clausius.
This approach to the Second Law is widely utilized in The ergodic hypothesis is also important for the Boltzmann
engineering practice, environmental accounting, systems approach. It says that, over long periods of time, the time
ecology, and other disciplines. spent in some region of the phase space of microstates with
the same energy is proportional to the volume of this region,
i.e. that all accessible microstates are equally probable over
2.3.4 History
a long period of time. Equivalently, it says that time average
See also: History of entropy and average over the statistical ensemble are the same.
The first theory of the conversion of heat into mechani- There is a traditional doctrine, starting with Clausius, that
2.3. SECOND LAW OF THERMODYNAMICS 67

entropy can be understood in terms of molecular 'dis- This statement is the best-known phrasing of the second
order' within a macroscopic system. This doctrine is law. Because of the looseness of its language, e.g. universe,
obsolescent.[78][79][80] as well as lack of specific conditions, e.g. open, closed, or
isolated, many people take this simple statement to mean
that the second law of thermodynamics applies virtually to
Account given by Clausius every subject imaginable. This, of course, is not true; this
statement is only a simplified version of a more extended
and precise description.
In terms of time variation, the mathematical statement of
the second law for an isolated system undergoing an arbi-
trary transformation is:

dS
≥0
dt
where

S is the entropy of the system and

t is time.

The equality sign applies after equilibration. An alternative

way of formulating of the second law for isolated systems
is:

dS
dt = Ṡi with Ṡi ≥ 0

with Ṡi the sum of the rate of entropy production by all

processes inside the system. The advantage of this formu-
lation is that it shows the effect of the entropy production.
The rate of entropy production is a very important concept
since it determines (limits) the efficiency of thermal ma-
chines. Multiplied with ambient temperature Ta it gives
the so-called dissipated energy Pdiss = Ta Ṡi .
Rudolf Clausius
The expression of the second law for closed systems (so,
In 1856, the German physicist Rudolf Clausius stated allowing heat exchange and moving boundaries, but not ex-
what he called the “second fundamental theorem in the change of matter) is:
mechanical theory of heat" in the following form:[81]
dt = T + Ṡi with Ṡi ≥ 0
dS Q̇

∫
δQ Here
= −N
T
where Q is heat, T is temperature and N is the “equivalence-
value” of all uncompensated transformations involved in a
cyclical process. Later, in 1865, Clausius would come to
define “equivalence-value” as entropy. On the heels of this
definition, that same year, the most famous version of the
second law was read in a presentation at the Philosophical
Society of Zurich on April 24, in which, in the end of his
presentation, Clausius concludes:
The entropy of the universe tends to a maxi-
mum.
Q̇
T
The equality sign holds in the case that only reversible pro-
cesses take place inside the system. If irreversible processes
take place (which is the case in real systems in operation)
the >-sign holds. If heat is supplied to the system at several
places we have to take the algebraic sum of the correspond-
ing terms.
For open systems (also allowing exchange of matter):
68 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

dS
dt = Q̇
T + Ṡ + Ṡi with Ṡi ≥ 0 which states that the entropy of a thermally isolated system
can only increase, is a trivial consequence of the equal prior
probability postulate, if we restrict the notion of the entropy
Here Ṡ is the flow of entropy into the system associated
to systems in thermal equilibrium. The entropy of an iso-
with the flow of matter entering the system. It should not be
lated system in thermal equilibrium containing an amount
confused with the time derivative of the entropy. If matter
of energy of E is:
is supplied at several places we have to take the algebraic
sum of these contributions.

2.3.5 Statistical mechanics
Statistical mechanics gives an explanation for the second
law by postulating that a material is composed of atoms
and molecules which are in constant motion. A particular
set of positions and velocities for each particle in the sys-
tem is called a microstate of the system and because of the
constant motion, the system is constantly changing its mi-
crostate. Statistical mechanics postulates that, in equilib-
rium, each microstate that the system might be in is equally
likely to occur, and when this assumption is made, it leads
directly to the conclusion that the second law must hold in a
statistical sense. That is, the second law will hold on aver-
age, with a statistical variation on the order of 1/√N where
N is the number of particles in the system. For everyday
(macroscopic) situations, the probability that the second law
will be violated is practically zero. However, for systems
with a small number of particles, thermodynamic parame-
ters, including the entropy, may show significant statistical
deviations from that predicted by the second law. Classical
thermodynamic theory does not deal with these statistical
variations.
2.3.6 Derivation from statistical mechanics
Further information: H-theorem
Due to Loschmidt’s paradox, derivations of the Second Law
have to make an assumption regarding the past, namely that
the system is uncorrelated at some time in the past; this al-
lows for simple probabilistic treatment. This assumption is
usually thought as a boundary condition, and thus the sec-
ond Law is ultimately a consequence of the initial condi-
tions somewhere in the past, probably at the beginning of
the universe (the Big Bang), though other scenarios have
also been suggested.[82][83][84]
Given these assumptions, in statistical mechanics, the Sec-
ond Law is not a postulate, rather it is a consequence of the
fundamental postulate, also known as the equal prior prob-
ability postulate, so long as one is clear that simple proba-
bility arguments are applied only to the future, while for the
past there are auxiliary sources of information which tell us
that it was low entropy. The first part of the second law,
S = kB ln [Ω (E)]
where Ω (E) is the number of quantum states in a small
interval between E and E + δE . Here δE is a macroscop-
ically small energy interval that is kept fixed. Strictly speak-
ing this means that the entropy depends on the choice of δE
. However, in the thermodynamic limit (i.e. in the limit of
infinitely large system size), the specific entropy (entropy
per unit volume or per unit mass) does not depend on δE .
Suppose we have an isolated system whose macroscopic
state is specified by a number of variables. These macro-
scopic variables can, e.g., refer to the total volume, the po-
sitions of pistons in the system, etc. Then Ω will depend
on the values of these variables. If a variable is not fixed,
(e.g. we do not clamp a piston in a certain position), then
because all the accessible states are equally likely in equi-
librium, the free variable in equilibrium will be such that Ω
is maximized as that is the most probable situation in equi-
librium.
If the variable was initially fixed to some value then upon
release and when the new equilibrium has been reached, the
fact the variable will adjust itself so that Ω is maximized,
implies that the entropy will have increased or it will have
stayed the same (if the value at which the variable was fixed
happened to be the equilibrium value). Suppose we start
from an equilibrium situation and we suddenly remove a
constraint on a variable. Then right after we do this, there
are a number Ω of accessible microstates, but equilibrium
has not yet been reached, so the actual probabilities of the
system being in some accessible state are not yet equal to
the prior probability of 1/Ω . We have already seen that in
the final equilibrium state, the entropy will have increased
or have stayed the same relative to the previous equilibrium
state. Boltzmann’s H-theorem, however, proves that the
quantity H increases monotonically as a function of time
during the intermediate out of equilibrium state.
Derivation of the entropy change for reversible pro-
cesses
The second part of the Second Law states that the entropy
change of a system undergoing a reversible process is given
by:
2.3. SECOND LAW OF THERMODYNAMICS 69

change x to x + dx. Then Ω (E) will change because the

δQ
dS =
T . Let’s focus again on the energy eigenstates for which dE r
where the temperature is defined as:
1 d ln [Ω (E)]
≡β≡
kB T dE
See here for the justification for this definition. Suppose
that the system has some external parameter, x, that can be
changed. In general, the energy eigenstates of the system
will depend on x. According to the adiabatic theorem of
quantum mechanics, in the limit of an infinitely slow change
of the system’s Hamiltonian, the system will stay in the same
energy eigenstate and thus change its energy according to
the change in energy of the energy eigenstate it is in.
energy eigenstates depend on x, causing energy eigenstates
to move into or out of the range between E and E + δE
dx
lies within the range between Y and Y + δY . Since these
energy eigenstates increase in energy by Y dx, all such en-
ergy eigenstates that are in the interval ranging from E – Y
dx to E move from below E to above E. There are
ΩY (E)
NY (E) = Y dx
δE
such energy eigenstates. If Y dx ≤ δE , all these energy
eigenstates will move into the range between E and E +δE
and contribute to an increase in Ω . The number of energy
eigenstates that move from below E + δE to above E + δE
is, of course, given by NY (E + δE) . The difference

The generalized force, X, corresponding to the external

variable x is defined such that Xdx is the work performed
NY (E) − NY (E + δE)
by the system if x is increased by an amount dx. E.g., if x
is the volume, then X is the pressure. The generalized force is thus the net contribution to the increase in Ω . Note that
for a system known to be in energy eigenstate Er is given if Y dx is larger than δE there will be the energy eigenstates
by: that move from below E to above E+δE . They are counted
in both NY (E) and NY (E + δE) , therefore the above
expression is also valid in that case.
dEr
X=− Expressing the above expression as a derivative with respect
dx
to E and summing over Y yields the expression:
Since the system can be in any energy eigenstate within an
interval of δE , we define the generalized force for the sys-
( ) ∑ ( ∂ΩY ) ( )
tem as the expectation value of the above expression: ∂Ω ∂ (ΩX)
=− Y =
∂x E ∂E x ∂E x
Y
⟨ ⟩
dEr The logarithmic derivative of Ω with respect to x is thus
X=−
dx given by:
To evaluate the average, we partition the Ω (E) energy
eigenstates by counting how many of them have a value for ( ∂ ln (Ω) ) (
∂X
)
dEr = βX +
dx within a range between Y and Y + δY . Calling this ∂x ∂E x
E
number ΩY (E) , we have:
The first term is intensive, i.e. it does not scale with system
∑ size. In contrast, the last term scales as the inverse system
Ω (E) = ΩY (E) size and will thus vanishes in the thermodynamic limit. We
Y have thus found that:

The average defining the generalized force can now be writ-

ten: ( )
∂S X
=
∂x E T
1 ∑ Combining this with
X=− Y ΩY (E)
Ω (E)
Y
( )
We can relate this to the derivative of the entropy with re- ∂S 1
spect to x at constant energy E as follows. Suppose we =
∂E x T
70 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

Gives: To a fair approximation, living organisms may be consid-

ered as examples of (b). Approximately, an animal’s phys-
( ) ( ) ical state cycles by the day, leaving the animal nearly un-
∂S ∂S dE X δQ changed. Animals take in food, water, and oxygen, and, as
dS = dE + dx = + dx =
∂E x ∂x E T T T a result of metabolism, give out breakdown products and
heat. Plants take in radiative energy from the sun, which
may be regarded as heat, and carbon dioxide and water.
Derivation for systems described by the canonical en-
They give out oxygen. In this way they grow. Eventually
semble
they die, and their remains rot. This can be regarded as a
cyclic process. Overall, the sunlight is from a high temper-
If a system is in thermal contact with a heat bath at some
ature source, the sun, and its energy is passed to a lower
temperature T then, in equilibrium, the probability distribu-
temperature sink, the soil. This is an increase of entropy of
tion over the energy eigenvalues are given by the canonical
the surroundings of the plant. Thus animals and plants obey
ensemble:
the second law of thermodynamics, considered in terms of
cyclic processes. Simple concepts of efficiency of heat en-
( ) gines are hardly applicable to this problem because they as-
E
exp − kB Tj
sume closed systems.
Pj =
Z From the thermodynamic viewpoint that considers (a), pas-
Here Z is a factor that normalizes the sum of all the proba- sages from one equilibrium state to another, only a roughly
bilities to 1, this function is known as the partition function. approximate picture appears, because living organisms are
We now consider an infinitesimal reversible change in the never in states of thermodynamic equilibrium. Living or-
temperature and in the external parameters on which the ganisms must often be considered as open systems, because
energy levels depend. It follows from the general formula they take in nutrients and give out waste products. Thermo-
for the entropy: dynamics of open systems is currently often considered in
terms of passages from one state of thermodynamic equilib-
∑ rium to another, or in terms of flows in the approximation of
S = −kB Pj ln (Pj ) local thermodynamic equilibrium. The problem for living
j organisms may be further simplified by the approximation
of assuming a steady state with unchanging flows. General
that
principles of entropy production for such approximations
are subject to unsettled current debate or research. Never-
∑ theless, ideas derived from this viewpoint on the second law
dS = −kB ln (Pj ) dPj of thermodynamics are enlightening about living creatures.
j

Inserting the formula for Pj for the canonical ensemble in

here gives:
2.3.8 Gravitational systems
1∑ 1∑ 1∑ dE + δW δQ
dS = Ej dPj = d (Ej Pj )− Pj dEj = =
T j T j T j In systems
T thatTdo not require for their descriptions the gen-
eral theory of relativity, bodies always have positive heat
capacity, meaning that the temperature rises with energy.
2.3.7 Living organisms Therefore, when energy flows from a high-temperature ob-
ject to a low-temperature object, the source temperature is
There are two principal ways of formulating thermodynam- decreased while the sink temperature is increased; hence
ics, (a) through passages from one state of thermodynamic temperature differences tend to diminish over time. This is
equilibrium to another, and (b) through cyclic processes, by not always the case for systems in which the gravitational
which the system is left unchanged, while the total entropy force is important and the general theory of relativity is re-
of the surroundings is increased. These two ways help to un- quired. Such systems can spontaneously change towards
derstand the processes of life. This topic is mostly beyond uneven spread of mass and energy. This applies to the uni-
the scope of this present article, but has been considered verse in large scale, and consequently it may be difficult or
by several authors, such as Erwin Schrödinger, Léon Bril- impossible to apply the second law to it.[27] Beyond this, the
louin[85] and Isaac Asimov. It is also the topic of current thermodynamics of systems described by the general theory
research. of relativity is beyond the scope of the present article.
2.3. SECOND LAW OF THERMODYNAMICS 71

2.3.9 Non-equilibrium states beyond the scope of this article.

Main article: Non-equilibrium thermodynamics 2.3.10 Arrow of time

The theory of classical or equilibrium thermodynamics is Further information: Entropy (arrow of time)
idealized. A main postulate or assumption, often not even See also: Arrow of time
explicitly stated, is the existence of systems in their own
internal states of thermodynamic equilibrium. In general, a The second law of thermodynamics is a physical law that is
region of space containing a physical system at a given time, not symmetric to reversal of the time direction.
that may be found in nature, is not in thermodynamic equi-
The second law has been proposed to supply an explanation
librium, read in the most stringent terms. In looser terms,
of the difference between moving forward and backwards in
nothing in the entire universe is or has ever been truly in
time, such as why the cause precedes the effect (the causal
exact thermodynamic equilibrium.[27][86]
arrow of time).[92]
For purposes of physical analysis, it is often enough con-
venient to make an assumption of thermodynamic equilib-
rium. Such an assumption may rely on trial and error for 2.3.11 Irreversibility
its justification. If the assumption is justified, it can of-
ten be very valuable and useful because it makes available Irreversibility in thermodynamic processes is a consequence
the theory of thermodynamics. Elements of the equilib- of the asymmetric character of thermodynamic operations,
rium assumption are that a system is observed to be un- and not of any internally irreversible microscopic proper-
changing over an indefinitely long time, and that there are ties of the bodies. Thermodynamic operations are macro-
so many particles in a system, that its particulate nature can scopic external interventions imposed on the participating
be entirely ignored. Under such an equilibrium assump- bodies, not derived from their internal properties. There
tion, in general, there are no macroscopically detectable are reputed “paradoxes” that arise from failure to recognize
fluctuations. There is an exception, the case of critical this.
states, which exhibit to the naked eye the phenomenon
of critical opalescence. For laboratory studies of critical
states, exceptionally long observation times are needed. Loschmidt’s paradox
In all cases, the assumption of thermodynamic equilibrium, Main article: Loschmidt’s paradox
once made, implies as a consequence that no putative can-
didate “fluctuation” alters the entropy of the system.
Loschmidt’s paradox, also known as the reversibility para-
It can easily happen that a physical system exhibits internal dox, is the objection that it should not be possible to deduce
macroscopic changes that are fast enough to invalidate the
an irreversible process from the time-symmetric dynamics
assumption of the constancy of the entropy. Or that a phys- that describe the microscopic evolution of a macroscopic
ical system has so few particles that the particulate nature
system.
is manifest in observable fluctuations. Then the assump-
tion of thermodynamic equilibrium is to be abandoned. In the opinion of Schrödinger, “It is now quite obvious in
There is no unqualified general definition of entropy for what manner you have to reformulate the law of entropy—
non-equilibrium states.[87] or for that matter, all other irreversible statements—so that
they be capable of being derived from reversible models.
There are intermediate cases, in which the assump- You must not speak of one isolated system but at least of
tion of local thermodynamic equilibrium is a very good two, which you may for the moment consider isolated from
approximation,[88][89][90][91] but strictly speaking it is still an the rest of the world, but not always from each other.”[93]
approximation, not theoretically ideal. For non-equilibrium The two systems are isolated from each other by the wall,
situations in general, it may be useful to consider statistical until it is removed by the thermodynamic operation, as en-
mechanical definitions of other quantities that may be con- visaged by the law. The thermodynamic operation is ex-
veniently called 'entropy', but they should not be confused ternally imposed, not subject to the reversible microscopic
or conflated with thermodynamic entropy properly defined dynamical laws that govern the constituents of the systems.
for the second law. These other quantities indeed belong to It is the cause of the irreversibility. The statement of the law
statistical mechanics, not to thermodynamics, the primary in this present article complies with Schrödinger’s advice.
realm of the second law. The cause–effect relation is logically prior to the second law,
The physics of macroscopically observable fluctuations is not derived from it.
72 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

Poincaré recurrence theorem

Main article: Poincaré recurrence theorem

The Poincaré recurrence theorem considers a theoretical

microscopic description of an isolated physical system.
This may be considered as a model of a thermodynamic sys-
tem after a thermodynamic operation has removed an inter-
nal wall. The system will, after a sufficiently long time, re-
turn to a microscopically defined state very close to the ini-
tial one. The Poincaré recurrence time is the length of time
elapsed until the return. It is exceedingly long, likely longer
than the life of the universe, and depends sensitively on the
geometry of the wall that was removed by the thermody-
namic operation. The recurrence theorem may be perceived
as apparently contradicting the second law of thermody-
namics. More obviously, however, it is simply a micro-
scopic model of thermodynamic equilibrium in an isolated
system formed by removal of a wall between two systems.
For a typical thermodynamical system, the recurrence time
is so large (many many times longer than the lifetime of the
universe) that, for all practical purposes, one cannot observe
the recurrence. One might wish, nevertheless, to imagine
that one could wait for the Poincaré recurrence, and then
re-insert the wall that was removed by the thermodynamic
operation. It is then evident that the appearance of irre- James Clerk Maxwell
versibility is due to the utter unpredictability of the Poincaré
recurrence given only that the initial state was one of ther- in B, contrary to the second law of thermodynamics.
modynamic equilibrium, as is the case in macroscopic ther-
modynamics. Even if one could wait for it, one has no prac- One response to this question was suggested in 1929 by Leó
tical possibility of picking the right instant at which to re- Szilárd and later by Léon Brillouin. Szilárd pointed out
insert the wall. The Poincaré recurrence theorem provides that a real-life Maxwell’s demon would need to have some
a solution to Loschmidt’s paradox. If an isolated thermo- means of measuring molecular speed, and that the act of
dynamic system could be monitored over increasingly many acquiring information would require an expenditure of en-
multiples of the average Poincaré recurrence time, the ther- ergy.
modynamic behavior of the system would become invariant Maxwell’s demon repeatedly alters the permeability of
under time reversal. the wall between A and B. It is therefore performing
thermodynamic operations on a microscopic scale, not just
observing ordinary spontaneous or natural macroscopic
Maxwell’s demon
thermodynamic processes.
Main article: Maxwell’s demon

2.3.12
James Clerk Maxwell imagined one container divided into
two parts, A and B. Both parts are filled with the same gas
at equal temperatures and placed next to each other, sep-
arated by a wall. Observing the molecules on both sides,
an imaginary demon guards a microscopic trapdoor in the
wall. When a faster-than-average molecule from A flies to-
wards the trapdoor, the demon opens it, and the molecule
will fly from A to B. The average speed of the molecules in
B will have increased while in A they will have slowed down
on average. Since average molecular speed corresponds to
temperature, the temperature decreases in A and increases
Quotations
The law that entropy always increases holds,
I think, the supreme position among the laws of
Nature. If someone points out to you that your
pet theory of the universe is in disagreement
with Maxwell’s equations — then so much the
worse for Maxwell’s equations. If it is found to
be contradicted by observation — well, these
experimentalists do bungle things sometimes.
But if your theory is found to be against the
second law of thermodynamics I can give you
2.3. SECOND LAW OF THERMODYNAMICS
no hope; there is nothing for it but to collapse in
deepest humiliation.
— Sir Arthur Stanley Eddington, The Nature of
the Physical World (1927)
There have been nearly as many formulations
of the second law as there have been discussions
of it.
— Philosopher / Physicist P.W. Bridgman,
(1941)
Clausius is the author of the sibyllic utter-
ance, “The energy of the universe is constant; the
entropy of the universe tends to a maximum.”
The objectives of continuum thermomechanics
stop far short of explaining the “universe”,
but within that theory we may easily derive an
explicit statement in some ways reminiscent of
Clausius, but referring only to a modest object:
an isolated body of finite size.
— Truesdell, C., Muncaster, R.G. (1980).
Fundamentals of Maxwell’s Kinetic Theory of
a Simple Monatomic Gas, Treated as a Branch
of Rational Mechanics, Academic Press, New
York, ISBN 0-12-701350-4, p.17.
2.3.13 See also
• Clausius–Duhem inequality
• Fluctuation theorem
• History of thermodynamics
• Jarzynski equality
• Laws of thermodynamics
• Maximum entropy thermodynamics
• Reflections on the Motive Power of Fire
• Thermal diode
• Relativistic heat conduction
2.3.14 References
[1] Guggenheim, E.A. (1949), p.454: “It is usually when a sys-
tem is tampered with that changes take place.”
73
[2] Pippard, A.B. (1957/1966), p. 96: “In the first two examples
the changes treated involved the transition from one equilib-
rium state to another, and were effected by altering the con-
straints imposed upon the systems, in the first by removal of
an adiabatic wall and in the second by altering the volume to
which the gas was confined.”
[3] Guggenheim, E.A. (1949).
[4] Denbigh, K. (1954/1981), p. 75.
[5] Atkins, P.W., de Paula, J. (2006), p. 78: “The opposite
change, the spreading of the object’s energy into the sur-
roundings as thermal motion, is natural. It may seem very
puzzling that the spreading out of energy and matter, the
collapse into disorder, can lead to the formation of such or-
dered structures as crystals or proteins. Nevertheless, in due
course, we shall see that dispersal of energy and matter ac-
counts for change in all its forms.”
[6] W. Thomson (1852).
[7] Pippard, A.B. (1957/1966), p. 97: “it is the act of removing
the wall and not the subsequent flow of heat which increases
the entropy.”
[8] Adkins, C.J. (1968/1983), p. 4: “contain the system within
walls of some special kind that allow or prevent various sorts
of interaction between the system and its surroundings"; p.
5: “a section of wall through which one or more of the com-
ponents may pass while others are contained; such a wall
is called semipermeable; p. 49: “Take the walls to be ther-
mally insulating"; p. 144: “If isotropic radiation is trapped
in a vessel with perfectly reflecting walls ...”
[9] Callen, H.B. (1960/1985), p. 16: “In general, a wall that
constrains an extensive parameter of a system is said to be
restrictive with respect to that parameter.”
[10] Baierlein, R. (1999), p. 22: “no energy passes through any
walls"; p. 118: “cubical cavity with perfectly reflecting metal
walls”.
[11] Pippard, A.B. (1957/1966), p. 106: “In this example we
have considered the constraint to take the form of a me-
chanical barrier"; p. 108: “We shall consider the equilib-
rium between a liquid and its vapour, under two different
constraints: first, with the vessel immersed in a constant-
temperature bath, and open to a constant external pressure;
and secondly, with the vessel closed and thermally isolated.”
[12] Buchdahl, H.A. (1966), p. 72: “It should be noted that there
need be no restriction on heat exchange within the system.”
[13] Blundell, S.J., Blundell, K.M. (2006), p. 16: “we are ap-
plying a constraint to the system, either constraining the
volume of the gas to be fixed, or constraining the pressure
of the gas to be fixed"; p. 108: “The first constraint is that
of keeping the volume constant.”
[14] Guggenheim, E.A. (1949), p.454: “It is usually when a sys-
tem is tampered with that changes take place.”
74
[15] Pippard, A.B. (1957/1966), p. 96: “In the first two examples
the changes treated involved the transition from one equilib-
rium state to another, and were effected by altering the con-
straints imposed upon the systems, in the first by removal of
an adiabatic wall and in the second by altering the volume
to which the gas was confined"; "It is not possible to vary the
constraints of an isolated system in such a way as to decrease
the entropy"; p. 97: “It will be seen then that our second
statement of the entropy law has much to recommend it in
that it concentrates upon the essential feature of a thermo-
dynamic change, the variation of the constraints to which
a system is subjected"; “In the same way when two bodies
at different temperatures are placed in thermal contact by
removal of an adiabatic wall, it is the act of removing the
wall and not the subsequent flow of heat which increases the
entropy”.
[16] Kittel, C., Kroemer, H. (1969/1980), p. 46: “the entropy of
a closed system tends to remain constant or to increase when
a constraint internal to the system is removed.”
[17] Uffink, J. (2003), p. 133: “A process is then conceived of
as being triggered by the cancellation of one or more of
these constraints (e.g. mixing or expansion of gases after
the removal of a partition, loosening a previously fixed pis-
ton, etc.).”
[18] Bridgman, P.W. (1943), p. 153: “The entropy increase
arising from this process, that is, exchange of radiation be-
tween bodies at different temperatures, is not to be sought
in the initial act of absorption, which may be non-entropy-
increasing, but is to be found after the initial absorption in
the spreading out of the spectrum of the absorbed energy
from the distribution characteristic of the higher temper-
ature of its source to the distribution characteristic of the
lower temperature of the sink.”
[19] Guggenheim, E.A. (1949), p. 452: “To the question what in
one word does entropy really mean, the author would have
no hesitation in replying 'Accessibility' or 'Spread'.”
[20] Denbigh, K. (1954/1981), p. 75.
[21] Atkins, P.W., de Paula, J. (2006), p. 78: “The opposite
change, the spreading of the object’s energy into the sur-
roundings as thermal motion, is natural. It may seem very
puzzling that the spreading out of energy and matter, the
collapse into disorder, can lead to the formation of such or-
dered structures as crystals or proteins. Nevertheless, in due
course, we shall see that dispersal of energy and matter ac-
counts for change in all its forms.”
[22] Tisza, L., Quay, P.M. (1963), 'The statistical thermodynam-
ics of equilibrium', Annals of Physics, 26: 48–90; p. 65;
p. 88: “The dispersal of the d.f.[distribution function] over
these states is their entropy”.
[23] Callen, H.B. (1960/1985). P. 63: “In order for the change to
be quasi-static, this compression must be dissipated through-
out the entire volume of gas before the next appreciable com-
pression occurs"; p. 69: “The excess work done in an ir-
reversible process over that done in a reversible process, is
CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS
called dissipative work"; p. 321: “But in any real case the
motion of the piston will cause viscous damping within the
systems and the kinetic energy of the piston will eventually
be dissipated.”
[24] Adkins, C.J. (1968/1983), p. 76.
[25] Phil Attard (2012). Non-equilibrium Thermodynamics and
Statistical Mechanics: Foundations and Applications. Oxford
University Press. p. 24. ISBN 0-19-163977-X.: “Physi-
cally, the result means that for every fluctuation from equi-
librium, there is a reverse fluctuation back to equilibrium,
where equilibrium means the most likely macrostate.”
[26] Uffink, J. (2001).
[27] Grandy, W.T. (Jr) (2008), p. 151.
[28] • Tisza, L. (1966), p. 40: “This conforms to the no-
tion that entropy, a state function, is associated with
equilibrium states.”
[29] Callen, H.B. (1960/1985), p. 27: “It must be stressed that
we postulate the existence of the entropy only for equilib-
rium states and that our postulate makes no reference what-
soever to nonequilibrium states.”
[30] Uffink, J. (2001), p. 306: “A common and preliminary de-
scription of the Second Law is that it guarantees that all phys-
ical systems in thermal equilibrium can be characterised by
a quantity called entropy"; p. 308: “In thermodynamics, en-
tropy is not defined for arbitrary states out of equilibrium.”
[31] Planck, M. (1897/1903), pp. 40–41.
[32] Munster A. (1970), pp. 8–9, 50–51.
[33] Planck, M. (1897/1903), pp. 79–107.
[34] Bailyn, M. (1994), Section 71, pp. 113–154.
[35] Bailyn, M. (1994), p. 120.
[36] Adkins, C.J. (1968/1983), p. 75.
[37] Münster, A. (1970), p. 45.
[38] J. S. Dugdale (1996). Entropy and its Physical Meaning.
Taylor & Francis. p. 13. ISBN 0-7484-0569-0. This law is
the basis of temperature.
[39] Zemansky, M.W. (1968), pp. 207–209.
[40] Quinn, T.J. (1983), p. 8.
[41] “Concept and Statements of the Second Law”. web.mit.edu.
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[42] Lieb & Yngvason (1999).
[43] Rao (2004), p. 213.
[44] Carnot, S. (1824/1986).
[45] Truesdell, C. (1980), Chapter 5.
2.3. SECOND LAW OF THERMODYNAMICS 75

[46] Adkins, C.J. (1968/1983), pp. 56–58. [75] van Gool, W.; Bruggink, J.J.C. (Eds) (1985). Energy and
time in the economic and physical sciences. North-Holland.
[47] Münster, A. (1970), p. 11. pp. 41–56. ISBN 0-444-87748-7.
[48] Kondepudi, D., Prigogine, I. (1998), pp.67–75.
[76] Grubbström, Robert W. (2007). “An Attempt
[49] Lebon, G., Jou, D., Casas-Vázquez, J. (2008), p. 10. to Introduce Dynamics Into Generalised Exergy
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[50] Eu, B.C. (2002), pp. 32–35. doi:10.1016/j.apenergy.2007.01.003.

[51] Clausius (1850).

[77] Clausius theorem at Wolfram Research
[52] Clausius (1854), p. 86.
[78] Denbigh, K.G., Denbigh, J.S. (1985). Entropy in Relation to
[53] Thomson (1851). Incomplete Knowledge, Cambridge University Press, Cam-
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[54] Planck, M. (1897/1903), p. 86.

[55] Roberts, J.K., Miller, A.R. (1928/1960), p. 319. [79] Grandy, W.T., Jr (2008). Entropy and the Time Evolution
of Macroscopic Systems, Oxford University Press, Oxford,
[56] ter Haar, D., Wergeland, H. (1966), p. 17. ISBN 978-0-19-954617-6, pp. 55–58.

[57] Pippard, A.B. (1957/1966), p. 30. [80] Entropy Sites — A Guide Content selected by Frank L.
Lambert
[58] Čápek, V., Sheehan, D.P. (2005), p. 3

[59] Planck, M. (1897/1903), p. 100. [81] Clausius (1867).

[60] Planck, M. (1926), p. 463, translation by Uffink, J. (2003), [82] Hawking, SW (1985). “Arrow of time
p. 131. in cosmology”. Phys. Rev. D 32 (10):
2489–2495. Bibcode:1985PhRvD..32.2489H.
[61] Roberts, J.K., Miller, A.R. (1928/1960), p. 382. This
doi:10.1103/PhysRevD.32.2489. Retrieved 2013-02-
source is partly verbatim from Planck’s statement, but does
15.
not cite Planck. This source calls the statement the principle
of the increase of entropy.
[83] Greene, Brian (2004). The Fabric of the Cosmos. Alfred A.
[62] Uhlenbeck, G.E., Ford, G.W. (1963), p. 16. Knopf. p. 171. ISBN 0-375-41288-3.

[63] Carathéodory, C. (1909). [84] Lebowitz, Joel L. (September 1993). “Boltzmann’s Entropy
and Time’s Arrow” (PDF). Physics Today 46 (9): 32–38.
[64] Buchdahl, H.A. (1966), p. 68.
Bibcode:1993PhT....46i..32L. doi:10.1063/1.881363. Re-
[65] Sychev, V. V. (1991). The Differential Equations of Ther- trieved 2013-02-22.
modynamics. Taylor & Francis. ISBN 978-1-56032-121-7.
Retrieved 2012-11-26. [85] Léon Brillouin Science and Information Theory (Academic
Press, 1962) (Dover, 2004)
[66] Lieb & Yngvason (1999), p. 49.
[86] Callen, H.B. (1960/1985), p. 15.
[67] Planck, M. (1926).

[68] Buchdahl, H.A. (1966), p. 69. [87] Lieb, E.H., Yngvason, J. (2003), p. 190.

[69] Uffink, J. (2003), pp. 129–132. [88] Gyarmati, I. (1967/1970), pp. 4-14.
[70] Truesdell, C., Muncaster, R.G. (1980). Fundamentals
[89] Glansdorff, P., Prigogine, I. (1971).
of Maxwell’s Kinetic Theory of a Simple Monatomic Gas,
Treated as a Branch of Rational Mechanics, Academic Press,
New York, ISBN 0-12-701350-4, p. 15. [90] Müller, I. (1985).

[71] Planck, M. (1897/1903), p. 81. [91] Müller, I. (2003).

[72] Planck, M. (1926), p. 457, Wikipedia editor’s translation. [92] Halliwell, J.J.; et al. (1994). Physical Origins of Time Asym-
[73] Lieb, E.H., Yngvason, J. (2003), p. 149. metry. Cambridge. ISBN 0-521-56837-4. chapter 6

[74] Borgnakke, C., Sonntag., R.E. (2009), p. 304. [93] Schrödinger, E. (1950), p. 192.
76
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78 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

• Thomson, W. (1852). On the universal tendency in • Kostic, M (2011). “Revisiting The Second Law
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Statistical Mechanics" – by Lawrence Sklar.
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• Caratheodory, C., “Examination of the foundations of
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2.4 Third law of Thermodynamics

2.3.15 Further reading
The third law of thermodynamics is sometimes stated as
• Goldstein, Martin, and Inge F., 1993. The Refrigerator follows, regarding the properties of systems in equilibrium
and the Universe. Harvard Univ. Press. Chpts. 4– at absolute zero temperature:
9 contain an introduction to the Second Law, one a
bit less technical than this entry. ISBN 978-0-674-
75324-2 The entropy of a perfect crystal at absolute
zero is exactly equal to zero.
• Leff, Harvey S., and Rex, Andrew F. (eds.) 2003.
Maxwell’s Demon 2 : Entropy, classical and quantum At absolute zero (zero kelvin), the system must be in a state
information, computing. Bristol UK; Philadelphia PA: with the minimum possible energy, and the above statement
Institute of Physics. ISBN 978-0-585-49237-7 of the third law holds true provided that the perfect crys-
tal has only one minimum energy state. Entropy is related
• Halliwell, J.J. (1994). Physical Origins of Time Asym-
to the number of accessible microstates, and for a system
metry. Cambridge. ISBN 0-521-56837-4.(technical).
consisting of many particles, quantum mechanics indicates
that there is only one unique state (called the ground state)
• Carnot, Sadi; Thurston, Robert Henry (editor and
with minimum energy.[1] If the system does not have a well-
translator) (1890). Reflections on the Motive Power of
defined order (if its order is glassy, for example), then in
Heat and on Machines Fitted to Develop That Power.
practice there will remain some finite entropy as the system
New York: J. Wiley & Sons. Cite uses deprecated
is brought to very low temperatures as the system becomes
parameter |coauthors= (help) (full text of 1897 ed.)
locked into a configuration with non-minimal energy. The
(html)
constant value is called the residual entropy of the system.[2]
• Stephen Jay Kline (1999). The Low-Down on En- The Nernst–Simon statement of the third law of thermody-
tropy and Interpretive Thermodynamics, La Cañada, namics concerns thermodynamic processes at a fixed, low
CA: DCW Industries. ISBN 1-928729-01-0. temperature:
2.4. THIRD LAW OF THERMODYNAMICS 79

The entropy change associated with any con- (derived from even more basic laws). The basic law from
densed system undergoing a reversible isother- which it is primarily derived is the statistical-mechanics def-
mal process approaches zero as the temperature inition of entropy for a large system:
at which it is performed approaches 0 K.

Here a condensed system refers to liquids and solids. A S − S0 = kB ln Ω

classical formulation by Nernst (actually a consequence of
the Third Law) is: where S is entropy, kB is the Boltzmann constant, and Ω is
the number of microstates consistent with the macroscopic
configuration. The counting of states is from the reference
It is impossible for any process, no matter
state of absolute zero, which corresponds to the entropy of
how idealized, to reduce the entropy of a system
S0 .
to its absolute-zero value in a finite number of
operations.
2.4.2 Explanation
Physically, the Nernst–Simon statement implies that it is
impossible for any procedure to bring a system to the abso- In simple terms, the third law states that the entropy of a
lute zero of temperature in a finite number of steps.[3] perfect crystal of a pure substance approaches zero as the
temperature approaches zero. The alignment of a perfect
crystal leaves no ambiguity as to the location and orientation
2.4.1 History of each part of the crystal. As the energy of the crystal is
reduced, the vibrations of the individual atoms are reduced
The 3rd law was developed by the chemist Walther Nernst to nothing, and the crystal becomes the same everywhere.
during the years 1906–12, and is therefore often referred
to as Nernst’s theorem or Nernst’s postulate. The third The third law provides an absolute reference point for the
law of thermodynamics states that the entropy of a system determination of entropy at any other temperature. The en-
at absolute zero is a well-defined constant. This is because tropy of a system, determined relative to this zero point,
a system at zero temperature exists in its ground state, so is then the absolute entropy of that system. Mathemati-
that its entropy is determined only by the degeneracy of the cally, the absolute entropy of any system at zero tempera-
ground state. ture is the natural log of the number of ground states times
Boltzmann’s constant kB=1.38x10−23, JK−1 .
In 1912 Nernst stated the law thus: “It is impossible for any
procedure to lead to the isotherm T = 0 in a finite number The entropy of a perfect crystal lattice as defined by Nernst’s
of steps.”[4] theorem is zero provided that its ground state is unique, be-
cause ln(1) = 0. If the system is composed of one-billion
An alternative version of the third law of thermodynamics atoms, all alike, and lie within the matrix of a perfect crys-
as stated by Gilbert N. Lewis and Merle Randall in 1923: tal, the number of permutations of one-billion identical
things taken one-billion at a time is Ω = 1. Hence:
If the entropy of each element in some (perfect)
crystalline state be taken as zero at the absolute
zero of temperature, every substance has a finite S − S0 = kB ln Ω = kB ln 1 = 0
positive entropy; but at the absolute zero of tem-
perature the entropy may become zero, and does The difference is zero, hence the initial entropy S0 can be
so become in the case of perfect crystalline sub- any selected value so long as all other such calculations in-
stances. clude that as the initial entropy. As a result the initial en-
tropy value of zero is selected S0 = 0 is used for conve-
This version states not only ΔS will reach zero at 0 K, but S nience.
itself will also reach zero as long as the crystal has a ground
state with only one configuration. Some crystals form de-
fects which causes a residual entropy. This residual entropy S − S0 = S − 0 = 0
disappears when the kinetic barriers to transitioning to one
ground state are overcome.[5] S=0
With the development of statistical mechanics, the third law By way of example, suppose a system consists of 1 cm3 of
of thermodynamics (like the other laws) changed from a matter with a mass of 1 g and 20 g/mol. The system consists
fundamental law (justified by experiments) to a derived law of 3x1022 identical atoms at 0 K. If one atom should absorb
80 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

a photon of wavelength of 1 cm that atom is then unique and
the permutations of one unique atom among the 3x1022 is
N=3x1022 . The entropy, energy, and temperature of the
system rises and can be calculated. The entropy change is:
∆S = S − S0 = kB ln Ω
From the second law of thermodynamics:
δQ
∆S = S − S0 =
T contrast, may have many nearly-degenerate ground states
Hence:
ground states, trapped out of equilibrium, is ice Ih, which
has “proton disorder”.
For the entropy at absolute zero to be zero, the magnetic
moments of a perfectly ordered crystal must themselves
be perfectly ordered; from an entropic perspective, this
can be considered to be part of the definition of a “per-
fect crystal”. Only ferromagnetic, antiferromagnetic, and
diamagnetic materials can satisfy this condition. However,
ferromagnetic materials do not in fact have zero entropy at
zero temperature, because the spins of the unpaired elec-
trons are all aligned and this gives a ground-state spin de-
generacy. Materials that remain paramagnetic at 0 K, by
(for example, in a spin glass), or may retain dynamic disor-
der (a quantum spin liquid).

δQ
∆S = S − S0 = kB ln(Ω) =
T 2.4.3 Mathematical formulation
Calculating entropy change:
Consider a closed system in internal equilibrium. As the
system is in equilibrium, there are no irreversible processes
so −1
the entropy production is zero. During slow heating,
S−0 = kB ln N = 1.38×10−23 ×ln 3 × 1022 = 70×10−23 Jsmall K temperature gradients are generated in the material,
but the associated entropy production can be kept arbitrar-
The energy change of the system as a result of absorbing ily low if the heat is supplied slowly enough. The increase
the single photon whose energy is ε: in entropy due to the added heat δQ is then given by the
second part of the Second law of thermodynamics which
states that the entropy change of a system is given by
hc 6.62 × 10−34 J · s × 3 × 108 m s−1 −23
δQ = ϵ = = = 2×10 J
The temperature rise dT due to the heat δQ is determined
λ 0.01 m
by the heat capacity C(T,X) according to
The temperature of the system rises by:
The parameter X is a symbolic notation for all parameters
(such as pressure, magnetic field, liquid/solid fraction, etc.)
ϵ 2 × 10 −23
J 1 which are kept constant during the heat supply. E.g. if the
T = = = K volume is constant we get the heat capacity at constant vol-
∆S 70 × 10−23 J K−1 35
ume CV. In the case of a phase transition from liquid to
This can be interpreted as the average temperature of the solid, or from gas to liquid the parameter X can be one of
system over the range from 0 < S < 70x10−23 J/K[6] A single the two components. Combining relations (1) and (2) gives
atom was assumed to absorb the photon but the temperature Integration of Eq.(3) from a reference temperature T to an
0
and entropy change characterizes the entire system. arbitrary temperature T gives the entropy at temperature T
An example of a system which does not have a unique We now come to the mathematical formulation of the third
ground state is one whose net spin is a half-integer, for law. There are three steps:
which time-reversal symmetry gives two degenerate ground
states. For such systems, the entropy at zero temperature 1: in the limit T 0 →0 the integral in Eq.(4) is finite. So that
is at least kB*ln(2) (which is negligible on a macroscopic we may take T 0 =0 and write
scale). Some crystalline systems exhibit geometrical frus- 2. the value of S(0,X) is independent of X. In mathematical
tration, where the structure of the crystal lattice prevents the form
emergence of a unique ground state. Ground-state helium
(unless under pressure) remains liquid. So Eq.(5) can be further simplified to

In addition, glasses and solid solutions retain large entropy Equation (6) can also be formulated as
at 0 K, because they are large collections of nearly degener- In words: at absolute zero all isothermal processes are isen-
ate states, in which they become trapped out of equilibrium. tropic. Eq.(8) is the mathematical formulation of the third
Another example of a solid with many nearly-degenerate law.
2.4. THIRD LAW OF THERMODYNAMICS 81

3: Classically, one is free to choose the zero of the entropy, can always be made zero by cooling the material down far
and it is convenient to take enough.[9] A modern, quantitative analysis follows.
so that Eq.(7) reduces to the final form Suppose that the heat capacity of a sample in the low tem-
α
However, reinterpreting Eq. (9) in view of the quantized perature region has the form of a power law C(T,X)=C 0 T
asymptotically as T→0, and we wish to find which values
nature of the lowest-lying energy states, the physical mean-
ing of Eq.(9) goes deeper than just a convenient selection of α are compatible with the third law. We have
of the zero of the entropy. It is due to the perfect order at By the discussion of third law (above), this integral must be
zero kelvin as explained above. bounded as T 0 →0, which is only possible if α>0. So the
heat capacity must go to zero at absolute zero

2.4.4 Consequences of the third law if it has the form of a power law. The same argument shows
that it cannot be bounded below by a positive constant, even
if we drop the power-law assumption.
On the other hand, the molar specific heat at constant vol-
ume of a monatomic classical ideal gas, such as helium at
room temperature, is given by CV=(3/2)R with R the molar
ideal gas constant. But clearly a constant heat capacity does
not satisfy Eq. (12). That is, a gas with a constant heat ca-
pacity all the way to absolute zero violates the third law of
thermodynamics. We can verify this more fundamentally
by substituting CV in Eq. (4), which yields
In the limit T 0 →0 this expression diverges, again contra-
dicting the third law of thermodynamics.
Fig.1 Left side: Absolute zero can be reached in a finite number of The conflict is resolved as follows: At a certain temperature
steps if S(0,X1 )≠S(0, X2 ). Right: An infinite number of steps is the quantum nature of matter starts to dominate the behav-
needed since S(0,X1 )= S(0,X2 ). ior. Fermi particles follow Fermi–Dirac statistics and Bose
particles follow Bose–Einstein statistics. In both cases the
heat capacity at low temperatures is no longer temperature
Absolute zero independent, even for ideal gases. For Fermi gases
with the Fermi temperature TF given by
The third law is equivalent to the statement that
Here NA is Avogadro’s number, V the molar volume, and
“It is impossible by any procedure, no matter how M the molar mass.
idealized, to reduce the temperature of any sys- For Bose gases
tem to zero temperature in a finite number of fi-
nite operations”.[7] with TB given by
The specific heats given by Eq.(14) and (16) both satisfy
The reason that T=0 cannot be reached according to the Eq.(12). Indeed, they are power laws with α=1 and α=3/2
third law is explained as follows: Suppose that the temper- respectively.
ature of a substance can be reduced in an isentropic pro-
cess by changing the parameter X from X2 to X1 . One can
think of a multistage nuclear demagnetization setup where a Vapor pressure
magnetic field is switched on and off in a controlled way.[8]
If there were an entropy difference at absolute zero, T=0 The only liquids near absolute zero are ³He and ⁴He. Their
could be reached in a finite number of steps. However, at heat of evaporation has a limiting value given by
T=0 there is no entropy difference so an infinite number of with L0 and C constant. If we consider a container, partly
steps would be needed. The process is illustrated in Fig.1. filled with liquid and partly gas, the entropy of the liquid–
gas mixture is
Specific heat where S (T) is the entropy of the liquid and x is the gas frac-
tion. Clearly the entropy change during the liquid–gas tran-
A non-quantitative description of his third law that Nernst sition (x from 0 to 1) diverges in the limit of T→0. This
gave at the very beginning was simply that the specific heat violates Eq.(8). Nature solves this paradox as follows: at
82 CHAPTER 2. CHAPTER 2. LAWS OF THERMODYNAMICS

temperatures below about 50 mK the vapor pressure is so
low that the gas density is lower than the best vacuum in the
universe. In other words: below 50 mK there is simply no
gas above the liquid.
Latent heat of melting
[4] Bailyn, M. (1994). A Survey of Thermodynamics, American
Institute of Physics, New York, ISBN 0-88318-797-3, page
342.
[5] Kozliak, Evguenii; Lambert, Frank L. (2008). “Resid-
ual Entropy, the Third Law and Latent Heat”. En-
tropy 10 (3): 274–84. Bibcode:2008Entrp..10..274K.
doi:10.3390/e10030274.

The melting curves of ³He and ⁴He both extend down to
absolute zero at finite pressure. At the melting pressure liq-
uid and solid are in equilibrium. The third law demands
that the entropies of the solid and liquid are equal at T=0.
As a result the latent heat of melting is zero and the slope
of the melting curve extrapolates to zero as a result of the
Clausius–Clapeyron equation.
[6] Reynolds and Perkins (1977). Engineering Thermodynam-
icsq. McGraw Hill. p. 438. ISBN 0-07-052046-1.
[7] Guggenheim, E.A. (1967). Thermodynamics. An Advanced
Treatment for Chemists and Physicists, fifth revised edition,
North-Holland Publishing Company, Amsterdam, page 157.
[8] F. Pobell, Matter and Methods at Low Temperatures,
(Springer-Verlag, Berlin, 2007)

Thermal expansion coefficient [9] Einstein and the Quantum, A. Douglas Stone, Princeton Uni-
versity Press, 2013.
The thermal expansion coefficient is defined as
J. Wilks The Third Law of Thermodynamics Oxford Uni-
With the Maxwell relation
versity Press (1961)p 83.
and Eq.(8) with X=p it is shown that
So the thermal expansion coefficient of all materials must
2.4.7 Further reading
go to zero at zero kelvin.
• Goldstein, Martin & Inge F. (1993) The Refrigerator
and the Universe. Cambridge MA: Harvard University
2.4.5 See also Press. ISBN 0-674-75324-0. Chpt. 14 is a nontech-
nical discussion of the Third Law, one including the
• Adiabatic process
requisite elementary quantum mechanics.
• Ground state
• Braun, S.; Ronzheimer, J. P.; Schreiber, M.; Hodg-
• Laws of thermodynamics man, S. S.; Rom, T.; Bloch, I.; Schneider, U.
(2013). “Negative Absolute Temperature for Mo-
• Quantum thermodynamics tional Degrees of Freedom”. Science 339 (6115): 52–
5. arXiv:1211.0545. Bibcode:2013Sci...339...52B.
• Residual entropy doi:10.1126/science.1227831. PMID 23288533. Lay
summary – New Scientist (3 January 2013).
• Thermodynamic entropy
• Levy, A.; Alicki, R.; Kosloff, R. (2012). “Quan-
• Timeline of thermodynamics, statistical mechanics,
tum refrigerators and the third law of thermo-
and random processes
dynamics”. Phys. Rev. E 85: 061126.
• Quantum refrigerators arXiv:1205.1347. Bibcode:2012PhRvE..85f1126L.
doi:10.1103/PhysRevE.85.061126.

2.4.6 References
[1] J. Wilks The Third Law of Thermodynamics Oxford Univer-
sity Press (1961).

[2] Kittel and Kroemer, Thermal Physics (2nd ed.), page 49.

[3] Wilks, J. (1971). The Third Law of Thermodynamics,

Chapter 6 in Thermodynamics, volume 1, ed. W. Jost, of
H. Eyring, D. Henderson, W. Jost, Physical Chemistry. An
Advanced Treatise, Academic Press, New York, page 477.
Chapter 3
Chapter 3. History
3.1 History of thermodynamics
The 1698 Savery Engine – the world’s first commercially-useful
steam engine: built by Thomas Savery
The history of thermodynamics is a fundamental strand
in the history of physics, the history of chemistry, and
the history of science in general. Owing to the relevance
of thermodynamics in much of science and technology,
its history is finely woven with the developments of
classical mechanics, quantum mechanics, magnetism, and
chemical kinetics, to more distant applied fields such as
meteorology, information theory, and biology (physiology),
and to technological developments such as the steam engine,
internal combustion engine, cryogenics and electricity gen-
83
eration. The development of thermodynamics both drove
and was driven by atomic theory. It also, albeit in a sub-
tle manner, motivated new directions in probability and
statistics; see, for example, the timeline of thermodynam-
ics.
3.1.1 History
See also: Timeline of thermodynamics
Contributions from ancient and medieval times
See also: History of heat and Vacuum
The ancients viewed heat as that related to fire. In 3000
BC, the ancient Egyptians viewed heat as related to origin
mythologies.[1] In the Western philosophical tradition, af-
ter much debate about the primal element among earlier
pre-Socratic philosophers, Empedocles proposed a four-
element theory, in which all substances derive from earth,
water, air, and fire. The Empedoclean element of fire
is perhaps the principal ancestor of later concepts such
as phlogiston and caloric. Around 500 BC, the Greek
philosopher Heraclitus became famous as the “flux and
fire” philosopher for his proverbial utterance: “All things
are flowing.” Heraclitus argued that the three principal ele-
ments in nature were fire, earth, and water.
Atomism is a central part of today’s relationship be-
tween thermodynamics and statistical mechanics. Ancient
thinkers such as Leucippus and Democritus, and later the
Epicureans, by advancing atomism, laid the foundations for
the later atomic theory. Until experimental proof of atoms
was later provided in the 20th century, the atomic theory
was driven largely by philosophical considerations and sci-
entific intuition.
The 5th century BC, Greek philosopher Parmenides, in his
only known work, a poem conventionally titled On Nature,
84 CHAPTER 3. CHAPTER 3. HISTORY

To prove this theory, he filled a long glass tube (sealed at one

end) with mercury and upended it into a dish also contain-
ing mercury. Only a portion of the tube emptied (as shown
adjacent); ~30 inches of the liquid remained. As the mer-
cury emptied, and a partial vacuum was created at the top
of the tube. The gravitational force on the heavy element
Mercury prevented it from filling the vacuum.

Transition from chemistry to thermochemistry

See also: History of chemistry

The theory of phlogiston arose in the 17th century, late

Heating a body, such as a segment of protein alpha helix (above),

tends to cause its atoms to vibrate more, and to expand or change
phase, if heating is continued; an axiom of nature noted by Herman
Boerhaave in the 1700s.

uses verbal reasoning to postulate that a void, essentially

what is now known as a vacuum, in nature could not occur.
This view was supported by the arguments of Aristotle, but
was criticized by Leucippus and Hero of Alexandria. From
antiquity to the Middle Ages various arguments were put
forward to prove or disapprove the existence of a vacuum
and several attempts were made to construct a vacuum but
all proved unsuccessful.
The European scientists Cornelius Drebbel, Robert Fludd,
Galileo Galilei and Santorio Santorio in the 16th and 17th
centuries were able to gauge the relative "coldness" or
"hotness" of air, using a rudimentary air thermometer (or
thermoscope). This may have been influenced by an earlier
device which could expand and contract the air constructed
by Philo of Byzantium and Hero of Alexandria.
Around 1600, the English philosopher and scientist Francis
Bacon surmised: “Heat itself, its essence and quiddity is
motion and nothing else.” In 1643, Galileo Galilei, while
generally accepting the 'sucking' explanation of horror
vacui proposed by Aristotle, believed that nature’s vacuum-
The world’s first ice-calorimeter, used in the winter of 1782-83,
abhorrence is limited. Pumps operating in mines had al- by Antoine Lavoisier and Pierre-Simon Laplace, to determine the
ready proven that nature would only fill a vacuum with wa- heat evolved in various chemical changes; calculations which were
ter up to a height of ~30 feet. Knowing this curious fact, based on Joseph Black's prior discovery of latent heat. These ex-
Galileo encouraged his former pupil Evangelista Torricelli periments mark the foundation of thermochemistry.
to investigate these supposed limitations. Torricelli did not
believe that vacuum-abhorrence (Horror vacui) in the sense in the period of alchemy. Its replacement by caloric the-
of Aristotle’s 'sucking' perspective, was responsible for rais- ory in the 18th century is one of the historical markers of
ing the water. Rather, he reasoned, it was the result of the the transition from alchemy to chemistry. Phlogiston was
pressure exerted on the liquid by the surrounding air. a hypothetical substance that was presumed to be liberated
3.1. HISTORY OF THERMODYNAMICS 85

from combustible substances during burning, and from met-

als during the process of rusting. Caloric, like phlogiston,
was also presumed to be the “substance” of heat that would
flow from a hotter body to a cooler body, thus warming it.
The first substantial experimental challenges to caloric the-
ory arose in Rumford's 1798 work, when he showed that
boring cast iron cannons produced great amounts of heat
which he ascribed to friction, and his work was among the
first to undermine the caloric theory. The development of
the steam engine also focused attention on calorimetry and
the amount of heat produced from different types of coal.
The first quantitative research on the heat changes during
chemical reactions was initiated by Lavoisier using an ice
calorimeter following research by Joseph Black on the latent
heat of water.
More quantitative studies by James Prescott Joule in 1843
onwards provided soundly reproducible phenomena, and
helped to place the subject of thermodynamics on a solid
footing. William Thomson, for example, was still trying to
explain Joule’s observations within a caloric framework as
late as 1850. The utility and explanatory power of kinetic
theory, however, soon started to displace caloric and it was
largely obsolete by the end of the 19th century. Joseph
Black and Lavoisier made important contributions in the Robert Boyle. 1627-1691
precise measurement of heat changes using the calorimeter,
a subject which became known as thermochemistry.

assumed to be a system of motionless particles, and not in-

Phenomenological thermodynamics
• Boyle’s law (1662)
• Charles’s law was first published by Joseph Louis Gay-
Lussac in 1802, but he referenced unpublished work
by Jacques Charles from around 1787. The relation-
ship had been anticipated by the work of Guillaume
Amontons in 1702.
• Gay-Lussac’s law (1802)
Birth of thermodynamics as science
At its origins, thermodynamics was the study of engines. A
precursor of the engine was designed by the German sci-
entist Otto von Guericke who, in 1650, designed and built
the world’s first vacuum pump and created the world’s first
ever vacuum known as the Magdeburg hemispheres. He
was driven to make a vacuum in order to disprove Aristotle's
long-held supposition that 'Nature abhors a vacuum'.
Shortly thereafter, Irish physicist and chemist Robert Boyle
had learned of Guericke’s designs and in 1656, in coordina-
tion with English scientist Robert Hooke, built an air pump.
Using this pump, Boyle and Hooke noticed the pressure-
volume correlation: P.V=constant. In that time, air was Hence, prior to 1698 and the invention of the Savery En-
terpreted as a system of moving molecules. The concept of
thermal motion came two centuries later. Therefore Boyle’s
publication in 1660 speaks about a mechanical concept: the
air spring.[2] Later, after the invention of the thermome-
ter, the property temperature could be quantified. This tool
gave Gay-Lussac the opportunity to derive his law, which
led shortly later to the ideal gas law. But, already before the
establishment of the ideal gas law, an associate of Boyle’s
named Denis Papin built in 1679 a bone digester, which is
a closed vessel with a tightly fitting lid that confines steam
until a high pressure is generated.
Later designs implemented a steam release valve to keep
the machine from exploding. By watching the valve rhyth-
mically move up and down, Papin conceived of the idea
of a piston and cylinder engine. He did not however fol-
low through with his design. Nevertheless, in 1697, based
on Papin’s designs, engineer Thomas Savery built the first
engine. Although these early engines were crude and inef-
ficient, they attracted the attention of the leading scientists
of the time. One such scientist was Sadi Carnot, the “father
of thermodynamics”, who in 1824 published Reflections on
the Motive Power of Fire, a discourse on heat, power, and
engine efficiency. This marks the start of thermodynamics
as a modern science.
86 CHAPTER 3. CHAPTER 3. HISTORY

A Watt steam engine, the steam engine that propelled the Industrial
Revolution in Britain and the world

gine, horses were used to power pulleys, attached to buck-

ets, which lifted water out of flooded salt mines in Eng-
land. In the years to follow, more variations of steam en-
gines were built, such as the Newcomen Engine, and later
the Watt Engine. In time, these early engines would eventu-
ally be utilized in place of horses. Thus, each engine began
to be associated with a certain amount of “horse power” de-
pending upon how many horses it had replaced. The main
problem with these first engines was that they were slow and
clumsy, converting less than 2% of the input fuel into useful Sadi Carnot (1796-1832): the “father” of thermodynamics
work. In other words, large quantities of coal (or wood) had
to be burned to yield only a small fraction of work output.
The name “thermodynamics”, however, did not arrive un-
Hence the need for a new science of engine dynamics was
til 1854, when the British mathematician and physicist
born.
William Thomson (Lord Kelvin) coined the term thermo-
Most cite Sadi Carnot’s 1824 book Reflections on the Mo- dynamics in his paper On the Dynamical Theory of Heat.[3]
tive Power of Fire as the starting point for thermodynamics
In association with Clausius, in 1871, the Scottish mathe-
as a modern science. Carnot defined “motive power” to be
matician and physicist James Clerk Maxwell formulated a
the expression of the useful effect that a motor is capable of
new branch of thermodynamics called Statistical Thermody-
producing. Herein, Carnot introduced us to the first mod-
namics, which functions to analyze large numbers of parti-
ern day definition of "work": weight lifted through a height.
cles at equilibrium, i.e., systems where no changes are oc-
The desire to understand, via formulation, this useful effect
curring, such that only their average properties as tempera-
in relation to “work” is at the core of all modern day ther-
ture T, pressure P, and volume V become important.
modynamics.
Soon thereafter, in 1875, the Austrian physicist Ludwig
In 1843, James Joule experimentally found the mechanical
Boltzmann formulated a precise connection between en-
equivalent of heat. In 1845, Joule reported his best-known
tropy S and molecular motion:
experiment, involving the use of a falling weight to spin a
paddle-wheel in a barrel of water, which allowed him to
estimate a mechanical equivalent of heat of 819 ft·lbf/Btu
S = k log W
(4.41 J/cal). This led to the theory of conservation of energy
and explained why heat can do work. being defined in terms of the number of possible states [W]
In 1850, the famed mathematical physicist Rudolf Clausius such motion could occupy, where k is the Boltzmann’s con-
defined the term entropy S to be the heat lost or turned into stant.
waste, stemming from the Greek word entrepein meaning The following year, 1876, was a seminal point in the de-
to turn. velopment of human thought. During this essential period,
3.1. HISTORY OF THERMODYNAMICS 87

chemical engineer Willard Gibbs, the first person in Amer- John Herapath later independently formulated a kinetic the-
ica to be awarded a PhD in engineering (Yale), published ory in 1820, but mistakenly associated temperature with
an obscure 300-page paper titled: On the Equilibrium of momentum rather than vis viva or kinetic energy. His
Heterogeneous Substances, wherein he formulated one grand work ultimately failed peer review and was neglected. John
equality, the Gibbs free energy equation, which suggested James Waterston in 1843 provided a largely accurate ac-
a measure of the amount of “useful work” attainable in re- count, again independently, but his work received the same
acting systems. Gibbs also originated the concept we now reception, failing peer review even from someone as well-
know as enthalpy H, calling it “a heat function for constant disposed to the kinetic principle as Davy.
pressure”.[4] The modern word enthalpy would be coined
Further progress in kinetic theory started only in the mid-
many years later by Heike Kamerlingh Onnes,[5] who based dle of the 19th century, with the works of Rudolf Clausius,
it on the Greek word enthalpein meaning to warm.
James Clerk Maxwell, and Ludwig Boltzmann. In his 1857
Building on these foundations, those as Lars Onsager, work On the nature of the motion called heat, Clausius for
Erwin Schrödinger, and Ilya Prigogine, and others, func- the first time clearly states that heat is the average kinetic
tioned to bring these engine “concepts” into the thorough- energy of molecules. This interested Maxwell, who in 1859
fare of almost every modern-day branch of science. derived the momentum distribution later named after him.
Boltzmann subsequently generalized his distribution for the
case of gases in external fields.
Kinetic theory
Boltzmann is perhaps the most significant contributor to ki-
Main article: Kinetic theory of gases netic theory, as he introduced many of the fundamental con-
cepts in the theory. Besides the Maxwell–Boltzmann dis-
tribution mentioned above, he also associated the kinetic
The idea that heat is a form of motion is perhaps an ancient energy of particles with their degrees of freedom. The
one and is certainly discussed by Francis Bacon in 1620 in Boltzmann equation for the distribution function of a gas
his Novum Organum. The first written scientific reflection in non-equilibrium states is still the most effective equa-
on the microscopic nature of heat is probably to be found tion for studying transport phenomena in gases and metals.
in a work by Mikhail Lomonosov, in which he wrote: By introducing the concept of thermodynamic probability
as the number of microstates corresponding to the current
"(..) movement should not be denied based on macrostate, he showed that its logarithm is proportional to
the fact it is not seen. Who would deny that the entropy.
leaves of trees move when rustled by a wind, de-
spite it being unobservable from large distances?
Just as in this case motion remains hidden due 3.1.2 Branches of
to perspective, it remains hidden in warm bodies
due to the extremely small sizes of the moving The following list gives a rough outline as to when the major
particles. In both cases, the viewing angle is so branches of thermodynamics came into inception:
small that neither the object nor their movement
can be seen.” • Thermochemistry - 1780s
• Classical thermodynamics - 1824
During the same years, Daniel Bernoulli published his book
Hydrodynamics (1738), in which he derived an equation for • Chemical thermodynamics - 1876
the pressure of a gas considering the collisions of its atoms
• Statistical mechanics - c. 1880s
with the walls of a container. He proves that this pressure
is two thirds the average kinetic energy of the gas in a unit • Equilibrium thermodynamics
volume. Bernoulli’s ideas, however, made little impact on
the dominant caloric culture. Bernoulli made a connection • Engineering thermodynamics
with Gottfried Leibniz's vis viva principle, an early formula- • Chemical engineering thermodynamics - c. 1940s
tion of the principle of conservation of energy, and the two
theories became intimately entwined throughout their his- • Non-equilibrium thermodynamics - 1941
tory. Though Benjamin Thompson suggested that heat was
a form of motion as a result of his experiments in 1798, no • Small systems thermodynamics - 1960s
attempt was made to reconcile theoretical and experimental • Biological thermodynamics - 1957
approaches, and it is unlikely that he was thinking of the vis
viva principle. • Ecosystem thermodynamics - 1959
88 CHAPTER 3. CHAPTER 3. HISTORY

• Relativistic thermodynamics - 1965 The phenomenon of heat conduction is immediately

grasped in everyday life. In 1701, Sir Isaac Newton pub-
• Quantum thermodynamics - 1968 lished his law of cooling. However, in the 17th century, it
came to be believed that all materials had an identical con-
• Black hole thermodynamics - c. 1970s ductivity and that differences in sensation arose from their
different heat capacities.
• Geological thermodynamics - c. 1970s
Suggestions that this might not be the case came from the
• Biological evolution thermodynamics - 1978 new science of electricity in which it was easily apparent
that some materials were good electrical conductors while
• Geochemical thermodynamics - c. 1980s others were effective insulators. Jan Ingen-Housz in 1785-9
made some of the earliest measurements, as did Benjamin
• Atmospheric thermodynamics - c. 1980s
Thompson during the same period.
• Natural systems thermodynamics - 1990s The fact that warm air rises and the importance of the phe-
nomenon to meteorology was first realised by Edmund Hal-
• Supramolecular thermodynamics - 1990s ley in 1686. Sir John Leslie observed that the cooling effect
of a stream of air increased with its speed, in 1804.
• Earthquake thermodynamics - 2000
Carl Wilhelm Scheele distinguished heat transfer by
• Drug-receptor thermodynamics - 2001 thermal radiation (radiant heat) from that by convection and
conduction in 1777. In 1791, Pierre Prévost showed that
• Pharmaceutical systems thermodynamics – 2002 all bodies radiate heat, no matter how hot or cold they are.
In 1804, Leslie observed that a matte black surface radi-
Ideas from thermodynamics have also been applied in other ates heat more effectively than a polished surface, suggest-
fields, for example: ing the importance of black body radiation. Though it had
become to be suspected even from Scheele’s work, in 1831
• Thermoeconomics - c. 1970s Macedonio Melloni demonstrated that black body radiation
could be reflected, refracted and polarised in the same way
as light.
3.1.3 Entropy and the second law James Clerk Maxwell's 1862 insight that both light and ra-
diant heat were forms of electromagnetic wave led to the
Main article: History of entropy start of the quantitative analysis of thermal radiation. In
1879, Jožef Stefan observed that the total radiant flux from
Even though he was working with the caloric theory, Sadi a blackbody is proportional to the fourth power of its tem-
Carnot in 1824 suggested that some of the caloric avail- perature and stated the Stefan–Boltzmann law. The law was
able for generating useful work is lost in any real process. derived theoretically by Ludwig Boltzmann in 1884.
In March 1851, while grappling to come to terms with the
work of James Prescott Joule, Lord Kelvin started to spec-
ulate that there was an inevitable loss of useful heat in all
3.1.5 Cryogenics
processes. The idea was framed even more dramatically by
In 1702 Guillaume Amontons introduced the concept of
Hermann von Helmholtz in 1854, giving birth to the spectre
absolute zero based on observations of gases. In 1810, Sir
of the heat death of the universe.
John Leslie froze water to ice artificially. The idea of abso-
In 1854, William John Macquorn Rankine started to make lute zero was generalised in 1848 by Lord Kelvin. In 1906,
use in calculation of what he called his thermodynamic func- Walther Nernst stated the third law of thermodynamics.
tion. This has subsequently been shown to be identical to the
concept of entropy formulated by Rudolf Clausius in 1865.
Clausius used the concept to develop his classic statement 3.1.6 See also
of the second law of thermodynamics the same year.
• Conservation of energy: Historical development

3.1.4 Heat transfer • History of Chemistry

• History of Physics
Main article: Heat transfer
• Maxwell’s thermodynamic surface
3.2. AN EXPERIMENTAL ENQUIRY CONCERNING THE SOURCE OF THE HEAT WHICH IS EXCITED BY FRICTION89

• Timeline of thermodynamics, statistical mechanics, • Brief History of Thermodynamics - Berkeley [PDF]

and random processes
• History of Thermodynamics - Thermodynamic-
• Thermodynamics Study.net
• Timeline of heat engine technology • Historical Background of Thermodynamics -
Carnegie-Mellon University
• Timeline of low-temperature technology
• History of Thermodynamics - In Pictures

3.1.7 References
[1] J. Gwyn Griffiths (1955). “The Orders of Gods in Greece
3.2 An Experimental Enquiry Con-
and Egypt (According to Herodotus)". The Journal of Hel- cerning the Source of the Heat
lenic Studies 75: 21–23. doi:10.2307/629164. JSTOR
629164. which is Excited by Friction
[2] New Experiments physico-mechanicall, Touching the
Spring of the Air and its Effects (1660).

[3] Thomson, W. (1854). “On the Dynamical Theory of Heat”.

Transactions of the Royal Society of Edinburgh 21 (part I):
123. doi:10.1017/s0080456800032014. |chapter= ignored
(help) reprinted in Sir William Thomson, LL.D. D.C.L.,
F.R.S. (1882). Mathematical and Physical Papers 1. Lon-
don, Cambridge: C.J. Clay, M.A. & Son, Cambridge Uni-
versity Press. p. 232. Hence Thermo-dynamics falls nat-
urally into two Divisions, of which the subjects are respec-
tively, the relation of heat to the forces acting between con-
tiguous parts of bodies, and the relation of heat to electrical
agency.

[4] Laidler, Keith (1995). The World of Physical Chemistry.

Oxford University Press. p. 110.

[5] Howard, Irmgard (2002). “H Is for Enthalpy, Thanks to

Heike Kamerlingh Onnes and Alfred W. Porter”. Jour-
nal of Chemical Education (ACS Publications) 79 (6): 697.
Bibcode:2002JChEd..79..697H. doi:10.1021/ed079p697.

3.1.8 Further reading

• Cardwell, D.S.L. (1971). From Watt to Clausius: The
Rise of Thermodynamics in the Early Industrial Age.
London: Heinemann. ISBN 0-435-54150-1. Benjamin Thompson

• Leff, H.S. & Rex, A.F. (eds) (1990). Maxwell’s De- An Experimental Enquiry Concerning the Source of the
mon: Entropy, Information and Computing. Bristol: Heat which is Excited by Friction (1798), which was
Adam Hilger. ISBN 0-7503-0057-4. published in the Philosophical Transactions of the Royal
Society, is a scientific paper by Benjamin Thompson,
Count Rumford that provided a substantial challenge to
3.1.9 External links established theories of heat and began the 19th century
revolution in thermodynamics.
• History of Statistical Mechanics and Thermodynamics
- Timeline (1575 to 1980) @ Hyperjeff.net
• History of Thermodynamics - University of Waterloo 3.2.1 Background
• Thermodynamic History Notes - Wolfram- Main article: Caloric theory
Science.com
90 CHAPTER 3. CHAPTER 3. HISTORY

Rumford was an opponent of the caloric theory of heat

which held that heat was a fluid that could be neither cre-
ated nor destroyed. He had further developed the view that
all gases and liquids were absolute non-conductors of heat.
His views were out of step with the accepted science of the
time and the latter theory had particularly been attacked by
John Dalton and John Leslie.
Rumford was heavily influenced by the argument from de-
sign and it is likely that he wished to grant water a privileged
and providential status in the regulation of human life.
Though Rumford was to come to associate heat with
motion, there is no evidence that he was committed to the
kinetic theory or the principle of vis viva.
In his 1798 paper, Rumford acknowledged that he had pre-
decessors in the notion that heat was a form of motion.
Those predecessors included Francis Bacon, Robert Boyle, Joule’s apparatus for measuring the mechanical equivalent of heat.
Robert Hooke, John Locke, and Henry Cavendish.
Charles Haldat made some penetrating criticisms of the
reproducibility of Rumford’s results and it is possible to see
3.2.2 Experiments the whole experiment as somewhat tendentious.

Rumford had observed the frictional heat generated by
boring cannon at the arsenal in Munich. Rumford im-
mersed a cannon barrel in water and arranged for a spe-
cially blunted boring tool. He showed that the water could
be boiled within roughly two and a half hours and that the
supply of frictional heat was seemingly inexhaustible. Rum-
ford confirmed that no physical change had taken place in
the material of the cannon by comparing the specific heats
of the material machined away and that remaining were the
same.
Rumford argued that the seemingly indefinite generation
of heat was incompatible with the caloric theory. He con-
tended that the only thing communicated to the barrel was
motion.
Rumford made no attempt to further quantify the heat gen-
erated or to measure the mechanical equivalent of heat.
3.2.3 Reception
However, the experiment inspired the work of James
Prescott Joule in the 1840s. Joule’s more exact measure-
ments were pivotal in establishing the kinetic theory at the
expense of caloric.
3.2.4 Notes
1. ^ Benjamin Count of Rumford (1798) “An in-
quiry concerning the source of the heat which
is excited by friction,” Philosophical Transactions
of the Royal Society of London, 88 : 80–102.
doi:10.1098/rstl.1798.0006
2. ^ Cardwell (1971) p.99
3. ^ Leslie, J. (1804). An Experimental Enquiry into the
Nature and Propagation of Heat. London.
4. ^ Rumford (1804) "An enquiry concerning the nature
of heat and the mode of its communication" Philo-
sophical Transactions of the Royal Society p.77

Most established scientists, such as William Henry, as well
as Thomas Thomson, believed that there was enough un-
certainty in the caloric theory to allow its adaptation to ac-
count for the new results. It had certainly proved robust and
adaptable up to that time. Furthermore, Thomson, Jöns
Jakob Berzelius, and Antoine César Becquerel observed
that electricity could be indefinitely generated by friction.
No educated scientist of the time was willing to hold that
electricity was not a fluid.
Ultimately, Rumford’s claim of the “inexhaustible” sup-
ply of heat was a reckless extrapolation from the study.
5. ^ Cardwell (1971) pp99-100
6. ^ From p. 100 of Rumford’s paper of 1798: “Before
I finish this paper, I would beg leave to observe, that
although, in treating the subject I have endeavoured to
investigate, I have made no mention of the names of
those who have gone over the same ground before me,
nor of the success of their labours; this omission has
not been owing to any want of respect for my predeces-
sors, but was merely to avoid prolixity, and to be more
at liberty to pursue, without interruption, the natural
train of my own ideas.”
3.2. AN EXPERIMENTAL ENQUIRY CONCERNING THE SOURCE OF THE HEAT WHICH IS EXCITED BY FRICTION91

7. ^ In his Novum Organum (1620), Francis Bacon con- Transactions of the Royal Society of London, 73 : 303-
cludes that heat is the motion of the particles compos- 328. From the footnote continued on p. 313: " … I
ing matter. In Francis Bacon, Novum Organum (Lon- think Sir Isaac Newton’s opinion, that heat consists in
don, England: William Pickering, 1850), from page the internal motion of the particles of bodies, much
164: " … Heat appears to be Motion.” From p. 165: " the most probable … "
… the very essence of Heat, or the Substantial self of
Heat, is motion and nothing else, … " From p. 168: 12. ^ Henry, W. (1802) “A review of some experiments
" … Heat is not a uniform Expansive Motion of the which have been supposed to disprove the materiality
whole, but of the small particles of the body; … " of heat”, Manchester Memoirs v, p.603
13. ^ Thomson, T. “Caloric”, Supplement on Chemistry,
8. ^ “Of the mechanical origin of heat and cold” in:
Encyclopædia Britannica, 3rd ed.
Robert Boyle, Experiments, Notes, &c. About the Me-
chanical Origine or Production of Divers Particular 14. ^ Haldat, C.N.A (1810) “Inquiries concerning the heat
Qualities: … (London, England: E. Flesher (printer), produced by friction”, Journal de Physique lxv, p.213
1675). At the conclusion of Experiment VI, Boyle
notes that if a nail is driven completely into a piece of 15. ^ Cardwell (1971) p.102
wood, then further blows with the hammer cause it to
become hot as the hammer’s force is transformed into
random motion of the nail’s atoms. From pp. 61-62: " 3.2.5 Bibliography
… the impulse given by the stroke, being unable either
• Cardwell, D.S.L. (1971). From Watt to Clausius: The
to drive the nail further on, or destroy its interness [i.e.,
Rise of Thermodynamics in the Early Industrial Age.
entireness, integrity], must be spent in making various
Heinemann: London. ISBN 0-435-54150-1.
vehement and intestine commotion of the parts among
themselves, and in such an one we formerly observed
the nature of heat to consist.”

9. ^ “Lectures of Light” (May 1681) in: Robert Hooke

with R. Waller, ed., The Posthumous Works of Robert
Hooke … (London, England: Samuel Smith and Ben-
jamin Walford, 1705). From page 116: “Now Heat,
as I shall afterward prove, is nothing but the internal
Motion of the Particles of [a] Body; and the hotter a
Body is, the more violently are the Particles moved,
…"

10. ^ Sometime during the period 1698-1704, John Locke

wrote his book Elements of Natural Philosophy, which
was first published in 1720: John Locke with Pierre
Des Maizeaux, ed., A Collection of Several Pieces of
Mr. John Locke, Never Before Printed, Or Not Extant
in His Works (London, England: R. Francklin, 1720).
From p. 224: "Heat, is a very brisk agitation of the
insensible parts of the object, which produces in us that
sensation, from whence we denominate the object hot:
so what in our sensation is heat, in the object is nothing
but motion. This appears by the way, whereby heat is
produc'd: for we see that the rubbing of a brass-nail
upon a board, will make it very hot; and the axle-trees
of carts and coaches are often hot, and sometimes to a
degree, that it sets them on fire, by rubbing of the nave
of the wheel upon it.”

11. ^ Henry Cavendish (1783) “Observations on Mr.

Hutchins’s experiments for determining the degree
of cold at which quicksilver freezes,” Philosophical
Chapter 4

Chapter 4. System State

4.1 Control volume They therefore apply on volumes. Finding forms of the
equation that are independent of the control volumes allows
In continuum mechanics and thermodynamics, a control simplification of the integral signs.
volume is a mathematical abstraction employed in the pro-
cess of creating mathematical models of physical processes. 4.1.2 Substantive derivative
In an inertial frame of reference, it is a volume fixed in space
or moving with constant flow velocity through which the Main article: Material derivative
continuum (gas, liquid or solid) flows. The surface enclos-
ing the control volume is referred to as the control sur-
face.[1] Computations in continuum mechanics often require that
the regular time derivation operator d/dt is replaced by the
At steady state, a control volume can be thought of as an substantive derivative operator D/Dt . This can be seen as
arbitrary volume in which the mass of the continuum re- follows.
mains constant. As a continuum moves through the control
volume, the mass entering the control volume is equal to Consider a bug that is moving through a volume where there
the mass leaving the control volume. At steady state, and is some scalar, e.g. pressure, that varies with time and po-
in the absence of work and heat transfer, the energy within sition: p = p(t, x, y, z) .
the control volume remains constant. It is analogous to the If the bug during the time interval from t to t + dt moves
classical mechanics concept of the free body diagram. from (x, y, z) to (x + dx, y + dy, z + dz), then the bug
experiences a change dp in the scalar value,

4.1.1 Overview
∂p ∂p ∂p ∂p
dp = dt + dx + dy + dz
Typically, to understand how a given physical law applies to ∂t ∂x ∂y ∂z
the system under consideration, one first begins by consid- (the total differential). If the bug is moving with a velocity
ering how it applies to a small, control volume, or “repre- v = (vx , vy , vz ), the change in particle position is vdt =
sentative volume”. There is nothing special about a partic- (vx dt, vy dt, vz dt), and we may write
ular control volume, it simply represents a small part of the
system to which physical laws can be easily applied. This
gives rise to what is termed a volumetric, or volume-wise ∂p ∂p ∂p ∂p
dp = dt + vx dt + vy dt + vz dt
formulation of the mathematical model. ∂t ∂x ∂y ∂z
( )
One can then argue that since the physical laws behave in a ∂p ∂p ∂p ∂p
= + vx + vy + vz dt
certain way on a particular control volume, they behave the ∂t ∂x ∂y ∂z
( )
same way on all such volumes, since that particular con- ∂p
trol volume was not special in any way. In this way, the = + v · ∇p dt.
∂t
corresponding point-wise formulation of the mathematical
model can be developed so it can describe the physical be- where ∇p is the gradient of the scalar field p. So:
haviour of an entire (and maybe more complex) system.
In continuum mechanics the conservation equations (for in- d ∂
stance, the Navier-Stokes equations) are in integral form. = + v · ∇.
dt ∂t

92
4.2. IDEAL GAS 93

If the bug is just moving with the flow, the same formula be treated like ideal gases within reasonable tolerances.[1]
applies, but now the velocity vector,v, is that of the flow, u. Generally, a gas behaves more like an ideal gas at higher
The last parenthesized expression is the substantive deriva- temperature and lower pressure,[1] as the potential energy
tive of the scalar pressure. Since the pressure p in this com- due to intermolecular forces becomes less significant com-
putation is an arbitrary scalar field, we may abstract it and pared with the particles’ kinetic energy, and the size of the
write the substantive derivative operator as molecules becomes less significant compared to the empty
space between them.
The ideal gas model tends to fail at lower temperatures or
D ∂
= + u · ∇. higher pressures, when intermolecular forces and molecular
Dt ∂t size become important. It also fails for most heavy gases,
such as many refrigerants,[1] and for gases with strong inter-
4.1.3 See also molecular forces, notably water vapor. At high pressures,
the volume of a real gas is often considerably greater than
• Continuum mechanics that of an ideal gas. At low temperatures, the pressure of
a real gas is often considerably less than that of an ideal
• Cauchy momentum equation gas. At some point of low temperature and high pressure,
real gases undergo a phase transition, such as to a liquid or
• Special relativity
a solid. The model of an ideal gas, however, does not de-
• Substantive derivative scribe or allow phase transitions. These must be modeled
by more complex equations of state. The deviation from
the ideal gas behaviour can be described by a dimensionless
4.1.4 References quantity, the compressibility factor, Z.
The ideal gas model has been explored in both the
• James R. Welty, Charles E. Wicks, Robert E. Wilson
Newtonian dynamics (as in "kinetic theory") and in
& Gregory Rorrer Fundamentals of Momentum, Heat,
quantum mechanics (as a "gas in a box"). The ideal gas
and Mass Transfer ISBN 0-471-38149-7
model has also been used to model the behavior of elec-
trons in a metal (in the Drude model and the free electron
Notes model), and it is one of the most important models in sta-
tistical mechanics.
[1] G.J. Van Wylen and R.E. Sonntag (1985), Fundamentals of
Classical Thermodynamics, Section 2.1 (3rd edition), John
Wiley & Sons, Inc., New York ISBN 0-471-82933-1 4.2.1 Types of ideal gas
There are three basic classes of ideal gas:
4.1.5 External links
• the classical or Maxwell–Boltzmann ideal gas,
• Integral Approach to the Control Volume analysis of
Fluid Flow • the ideal quantum Bose gas, composed of bosons, and
• the ideal quantum Fermi gas, composed of fermions.
4.2 Ideal gas
The classical ideal gas can be separated into two types: The
classical thermodynamic ideal gas and the ideal quantum
An ideal gas is a theoretical gas composed of many ran- Boltzmann gas. Both are essentially the same, except that
domly moving point particles that do not interact except the classical thermodynamic ideal gas is based on classical
when they collide elastically. The ideal gas concept is useful statistical mechanics, and certain thermodynamic parame-
because it obeys the ideal gas law, a simplified equation of ters such as the entropy are only specified to within an un-
state, and is amenable to analysis under statistical mechan- determined additive constant. The ideal quantum Boltz-
ics. One mole of an ideal gas has a volume of 22.7 L at STP mann gas overcomes this limitation by taking the limit of
as defined by IUPAC. the quantum Bose gas and quantum Fermi gas in the limit
At normal conditions such as standard temperature and of high temperature to specify these additive constants. The
pressure, most real gases behave qualitatively like an ideal behavior of a quantum Boltzmann gas is the same as that of
gas. Many gases such as nitrogen, oxygen, hydrogen, noble a classical ideal gas except for the specification of these con-
gases, and some heavier gases like carbon dioxide can stants. The results of the quantum Boltzmann gas are used
94 CHAPTER 4. CHAPTER 4. SYSTEM STATE

in a number of cases including the Sackur–Tetrode equa- gas is a function only of its temperature. For the present
tion for the entropy of an ideal gas and the Saha ionization purposes it is convenient to postulate an exemplary version
equation for a weakly ionized plasma. of this law by writing:

4.2.2 Classical thermodynamic ideal gas U = ĉV nRT

Macroscopic account where

The ideal gas law is an extension of experimentally dis- • U is the internal energy
covered gas laws. Real fluids at low density and high • ĉV is the dimensionless specific heat capac-
temperature approximate the behavior of a classical ideal ity at constant volume, ≈ 3/2 for monatomic
gas. However, at lower temperatures or a higher density, a gas, 5/2 for diatomic gas and 3 for more
real fluid deviates strongly from the behavior of an ideal gas, complex molecules.
particularly as it condenses from a gas into a liquid or as it
deposits from a gas into a solid. This deviation is expressed
as a compressibility factor. Microscopic model
The classical thermodynamic properties of an ideal gas can In order to switch from macroscopic quantities (left hand
be described by two equations of state:.[2][3] side of the following equation) to microscopic ones (right
One of them is the well known ideal gas law hand side), we use

P V = nRT nR = N kB

where where

• P is the pressure • N is the number of gas particles

• V is the volume • kB is the Boltzmann constant
(1.381×10−23 J·K−1 ).
• n is the amount of substance of the gas (in
moles) The probability distribution of particles by velocity or en-
• R is the gas constant (8.314 J·K−1 mol−1 ) ergy is given by the Maxwell speed distribution.
• T is the absolute temperature. The ideal gas model depends on the following assumptions:

This equation is derived from Boyle’s law: V = k/P (at • The molecules of the gas are indistinguish-
constant T and n); Charles’s law: V = bT (at constant P able, small, hard spheres
and n); and Avogadro’s law: V = an (at constant T and P); • All collisions are elastic and all motion is
where frictionless (no energy loss in motion or col-
lision)
• k is a constant used in Boyle’s law
• Newton’s laws apply
• b is a proportionality constant; equal to
• The average distance between molecules is
V /T
much larger than the size of the molecules
• a is a proportionality constant; equal to
• The molecules are constantly moving in
V /n .
random directions with a distribution of
speeds
By combining
( the) three laws, it would demonstrate
( ) ( Tthat
)
3V = kba TPn which would mean that V = kba n • There are no attractive or repulsive forces
3 P
. between the molecules apart from those
( ) that determine their point-like collisions
Under ideal conditions, V = R TPn ; that is, P V = nRT • The only forces between the gas molecules
. and the surroundings are those that de-
The other equation of state of an ideal gas must express termine the point-like collisions of the
Joule’s law, that the internal energy of a fixed mass of ideal molecules with the walls
4.2. IDEAL GAS 95

• In the simplest case, there are no long-range ideal gas. This is an important step since, according to the
forces between the molecules of the gas and theory of thermodynamic potentials, if we can express the
the surroundings. entropy as a function of U (U is a thermodynamic poten-
tial), volume V and the number of particles N, then we will
The assumption of spherical particles is necessary so that have a complete statement of the thermodynamic behavior
there are no rotational modes allowed, unlike in a diatomic of the ideal gas. We will be able to derive both the ideal gas
gas. The following three assumptions are very related: law and the expression for internal energy from it.
molecules are hard, collisions are elastic, and there are no Since the entropy is an exact differential, using the chain
inter-molecular forces. The assumption that the space be- rule, the change in entropy when going from a reference
tween particles is much larger than the particles themselves state 0 to some other state with entropy S may be written as
is of paramount importance, and explains why the ideal gas ∆S where:
approximation fails at high pressures.

∫ S ∫ T ( ) ∫ V ( )
∂S ∂S
4.2.3 Heat capacity ∆S = dS = dT + dV
S0 T0 ∂T V V0 ∂V T
The heat capacity at constant volume, including an ideal gas where the reference variables may be functions of the
is: number of particles N. Using the definition of the heat ca-
pacity at constant volume for the first differential and the
( ) ( ) appropriate Maxwell relation for the second we have:
1 ∂S 1 ∂U
ĉV = T =
nR ∂T V nR ∂T V
∫ T ∫ V( )
where S is the entropy. This is the dimensionless heat ca- ∆S = Cv ∂P
dT + dV.
pacity at constant volume, which is generally a function T0 T V0 ∂T V
of temperature due to intermolecular forces. For mod-
Expressing CV in terms of ĉV as developed in the above
erate temperatures, the constant for a monatomic gas is
section, differentiating the ideal gas equation of state, and
ĉV = 3/2 while for a diatomic gas it is ĉV = 5/2 . It is seen
integrating yields:
that macroscopic measurements on heat capacity provide
information on the microscopic structure of the molecules.
( ) ( )
The heat capacity at constant pressure of 1/R mole of ideal T V
∆S = ĉV N k ln + N k ln
gas is: T0 V0
which implies that the entropy may be expressed as:
( ) ( )
1 ∂S 1 ∂H
ĉp = T = = ĉV + 1
nR ∂T p nR ∂T p ( )
V T ĉv
S = N k ln
where H = U + pV is the enthalpy of the gas. f (N )
Sometimes, a distinction is made between an ideal gas, where all constants have been incorporated into the loga-
where ĉV and ĉp could vary with temperature, and a perfect rithm as f(N) which is some function of the particle num-
gas, for which this is not the case. ber N having the same dimensions as V T ĉv in order that
The ratio of the constant volume and constant pressure heat the argument of the logarithm be dimensionless. We now
capacity is impose the constraint that the entropy be extensive. This
will mean that when the extensive parameters (V and N)
are multiplied by a constant, the entropy will be multiplied
cP by the same constant. Mathematically:
γ=
cV
For air, which is a mixture of gases, this ratio is 1.4.
S(T, aV, aN ) = aS(T, V, N ).

4.2.4 Entropy From this we find an equation for the function f(N)

Using the results of thermodynamics only, we can go a long

way in determining the expression for the entropy of an af (N ) = f (aN ).
96 CHAPTER 4. CHAPTER 4. SYSTEM STATE

Differentiating this with respect to a, setting a equal to

unity, and then solving the differential equation yields f(N): ( )
S V T ĉV
= ln
kN NΦ
f (N ) = ΦN The chemical potential of the ideal gas is calculated from
the corresponding equation of state (see thermodynamic
where Φ may vary for different gases, but will be indepen-
potential):
dent of the thermodynamic state of the gas. It will have the
dimensions of V T ĉv /N . Substituting into the equation for
the entropy: ( )
∂G
µ=
∂N T,P
( )
S V T ĉv where G is the Gibbs free energy and is equal to U + P V −
= ln .
Nk NΦ T S so that:
and using the expression for the internal energy of an ideal
gas, the entropy may be written: ( ( ))
V T ĉV
µ(T, V, N ) = kT ĉP − ln
NΦ
[ ( )ĉv ]
S V U 1 The thermodynamic potentials for an ideal gas can now be
= ln
Nk N ĉv kN Φ written as functions of T, V, and N as:

Since this is an expression for entropy in terms of U, V,

and N, it is a fundamental equation from which all other
properties of the ideal gas may be derived.
where, as before, ĉP = ĉV + 1 . The most informative way
This is about as far as we can go using thermodynamics of writing the potentials is in terms of their natural variables,
alone. Note that the above equation is flawed — as the tem- since each of these equations can be used to derive all of the
perature approaches zero, the entropy approaches negative other thermodynamic variables of the system. In terms of
infinity, in contradiction to the third law of thermodynam- their natural variables, the thermodynamic potentials of a
ics. In the above “ideal” development, there is a critical single-species ideal gas are:
point, not at absolute zero, at which the argument of the
logarithm becomes unity, and the entropy becomes zero.
This is unphysical. The above equation is a good approx- ( )1/ĉV
N Φ S/N k
imation only when the argument of the logarithm is much U (S, V, N ) = ĉV N k e
V
larger than unity — the concept of an ideal gas breaks down
( ( ))
at low values of V/N. Nevertheless, there will be a “best” V T ĉV
value of the constant in the sense that the predicted en- A(T, V, N ) = N kT ĉV − ln
NΦ
tropy is as close as possible to the actual entropy, given ( )1/ĉP
the flawed assumption of ideality. A quantum-mechanical P Φ S/N k
H(S, P, N ) = ĉP N k e
derivation of this constant is developed in the derivation of k
the Sackur–Tetrode equation which expresses the entropy ( ( ĉP ))
kT
of a monatomic (ĉv = 3/2) ideal gas. In the Sackur- G(T, P, N ) = N kT ĉP − ln
Tetrode theory the constant depends only upon the mass PΦ
of the gas particle. The Sackur–Tetrode equation also suf- In statistical mechanics, the relationship between the
fers from a divergent entropy at absolute zero, but is a good Helmholtz free energy and the partition function is funda-
approximation for the entropy of a monatomic ideal gas for mental, and is used to calculate the thermodynamic proper-
high enough temperatures. ties of matter; see configuration integral for more details.

4.2.5 Thermodynamic potentials 4.2.6 Speed of sound

Main article: Thermodynamic potential Main article: Speed of sound

Expressing the entropy as a function of T, V, and N: The speed of sound in an ideal gas is given by
4.3. REAL GAS 97

Ideal Bose and Fermi gases

√( ) √ √
∂P γP γRT An ideal gas of bosons (e.g. a photon gas) will be governed
csound = = =
∂ρ s ρ M by Bose–Einstein statistics and the distribution of energy
will be in the form of a Bose–Einstein distribution. An ideal
where gas of fermions will be governed by Fermi–Dirac statis-
tics and the distribution of energy will be in the form of
γ is the adiabatic index (ĉP /ĉV ) a Fermi–Dirac distribution.
s is the entropy per particle of the gas.
ρ is the mass density of the gas. 4.2.9 See also
P is the pressure of the gas.
R is the universal gas constant • Compressibility factor
T is the temperature
• Dynamical billiards - billiard balls as a model of an
M is the molar mass of the gas. ideal gas

• Table of thermodynamic equations

4.2.7 Table of ideal gas equations
• Scale-free ideal gas
See Table of thermodynamic equations: Ideal gas.

4.2.8 Ideal quantum gases 4.2.10 References

[1] Cengel, Yunus A.; Boles, Michael A. Thermodynamics: An

In the above-mentioned Sackur–Tetrode equation, the best
Engineering Approach (Fourth ed.). p. 89. ISBN 0-07-
choice of the entropy constant was found to be proportional 238332-1.
to the quantum thermal wavelength of a particle, and the
point at which the argument of the logarithm becomes zero [2] Adkins, C.J. (1968/1983). Equilibrium Thermodynamics,
is roughly equal to the point at which the average distance (1st edition 1968), third edition 1983, Cambridge University
between particles becomes equal to the thermal wavelength. Press, Cambridge UK, ISBN 0-521-25445-0, pp. 116–120.
In fact, quantum theory itself predicts the same thing. Any
gas behaves as an ideal gas at high enough temperature and [3] Tschoegl, N.W. (2000). Fundamentals of Equilibrium and
low enough density, but at the point where the Sackur– Steady-State Thermodynamics, Elsevier, Amsterdam, ISBN
Tetrode equation begins to break down, the gas will begin 0-444-50426-5, p 88.
to behave as a quantum gas, composed of either bosons or
fermions. (See the gas in a box article for a derivation of the
ideal quantum gases, including the ideal Boltzmann gas.) 4.3 Real gas
Gases tend to behave as an ideal gas over a wider range of
pressures when the temperature reaches the Boyle temper- Real gases are non-hypothetical gases whose molecules oc-
ature. cupy space and have interactions; consequently, they adhere
to gas laws. To understand the behaviour of real gases, the
following must be taken into account:
Ideal Boltzmann gas

The ideal Boltzmann gas yields the same results as the clas- • compressibility effects;
sical thermodynamic gas, but makes the following identifi-
cation for the undetermined constant Φ: • variable specific heat capacity;

• van der Waals forces;

T 3/2 Λ3
Φ= • non-equilibrium thermodynamic effects;
g
where Λ is the thermal de Broglie wavelength of the gas and • issues with molecular dissociation and elementary re-
g is the degeneracy of states. actions with variable composition
98 CHAPTER 4. CHAPTER 4. SYSTEM STATE

For most applications, such a detailed analysis is unnec- van der Waals model
essary, and the ideal gas approximation can be used with
reasonable accuracy. On the other hand, real-gas models Main article: van der Waals equation
have to be used near the condensation point of gases, near
critical points, at very high pressures, to explain the Joule– Real gases are often modeled by taking into account their
Thomson effect and in other less usual cases. The deviation molar weight and molar volume
from ideality can be described by the compressibility factor
Z.
( )
a
RT = P+ 2 (Vm − b)
Vm
Where P is the pressure, T is the temperature, R the ideal
4.3.1 Models gas constant, and V the molar volume. a and b are param-
eters that are determined empirically for each gas, but are
sometimes estimated from their critical temperature (T )
and critical pressure (P ) using these relations:

27R2 Tc2
a=
64Pc
RTc
b=
8Pc

Redlich–Kwong model

The Redlich–Kwong equation is another two-parameter

equation that is used to model real gases. It is almost al-
ways more accurate than the van der Waals equation, and
often more accurate than some equations with more than
two parameters. The equation is

( )
a
RT = P+√ (Vm − b)
T Vm (Vm + b)
Isotherms of real gas where a and b two empirical parameters that are not the
Dark blue curves – isotherms below the critical temperature. Green
same parameters as in the van der Waals equation. These
sections – metastable states.
parameters can be determined:
The section to the left of point F – normal liquid.
Point F – boiling point.
Line FG – equilibrium of liquid and gaseous phases.
Section FA – superheated liquid. R2 Tc 5/2
a = 0.42748
Section F′A – stretched liquid (p<0). Pc
Section AC – analytic continuation of isotherm, physically impossi-
RTc
ble. b = 0.08664
Section CG – supercooled vapor. Pc
Point G – dew point.
The plot to the right of point G – normal gas. Berthelot and modified Berthelot model
Areas FAB and GCB are equal.
Red curve – Critical isotherm.
The Berthelot equation (named after D. Berthelot[1] is very
Point K – critical point.
rarely used,
Light blue curves – supercritical isotherms
P = RT
Vm −b − a
T Vm2

but the modified version is somewhat more accurate

Main article: Equation of state [ ( )]
9P /Pc
P = RTVm 1 + 128T /Tc 1 − 6
(T /Tc ) 2
4.3. REAL GAS 99

Dieterici model c = 4Pc Tc2 Vc3 .

This model (named after C. Dieterici[2] ) fell out of usage in

recent years Beattie–Bridgeman model
exp ( Vm−a
RT ) [5]
P = RT Vm −b .
This equation is based on five experimentally determined
Clausius model constants. It is expressed as
( )
P = RTv 2 1 − vT 3 (v + B) − v 2
c A

The Clausius equation (named after Rudolf Clausius) is a

where
very simple three-parameter equation used to model gases.
( )
RT = P + T (Vma+c)2 (Vm − b) ( a)
A = A0 1 −
where v
27R2 Tc3 ( )
a = 64Pc b
B = B0 1 −
b = Vc − RT c v
4Pc
This equation is known to be reasonably accurate for den-
8Pc − Vc
c = 3RT c
sities up to about 0.8 ρ ᵣ, where ρ ᵣ is the density of the
where V is critical volume. substance at its critical point. The constants appearing in
the above equation are available in following table when P
3 3
is in KPa, v is in Kmmol , T is in K and R=8.314 KkPa·m
mol·K
[6]
Virial model

The Virial equation derives from a perturbative treatment Benedict–Webb–Rubin model

of statistical mechanics.
( )
P Vm = RT 1 + B(T )
+ C(T )
+ D(T )
+ ... Main article: Benedict–Webb–Rubin equation
Vm V 2 V 3
m m

or alternatively
( The BWR equation, sometimes referred to as the BWRS
)
B ′ (T ) C ′ (T ) D ′ (T ) equation,
P Vm = RT 1 + + + + ...
P P2 P3
(
where A, B, C, A′, B′, and C′ are temperature dependent P = RT d+d RT (B + bd) − (A + ad − aαd ) − T 2 [C − cd(1 + γd ) e
2 4 1 2

constants. where d is the molar density and where a, b, c, A, B, C, α,

and γ are empirical constants. Note that the γ constant is a
derivative of constant α and therefore almost identical to 1.
Peng–Robinson model

Peng–Robinson equation of state (named after D.-Y. Peng 4.3.2 See also
and D. B. Robinson[3] ) has the interesting property being
useful in modeling some liquids as well as real gases. • Gas laws
a(T )
P = RT
Vm −b − Vm (Vm +b)+b(Vm −b) • Ideal gas law by Boyle & Gay-Lussac
• Compressibility factor
Wohl model
• Equation of state
The Wohl equation (named after A. Wohl[4] ) is formulated
in terms of critical values, making it useful when real gas
constants are not available. 4.3.3 References
( )
RT = P + T Vm (Va m −b) − T 2cV 3 (Vm − b) [1] D. Berthelot in Travaux et Mémoires du Bureau international
m
des Poids et Mesures – Tome XIII (Paris: Gauthier-Villars,
where 1907)
a = 6Pc Tc Vc2
[2] C. Dieterici, Ann. Phys. Chem. Wiedemanns Ann. 69, 685
Vc
b= 4 (1899)
100 CHAPTER 4. CHAPTER 4. SYSTEM STATE

[3] Peng, D. Y., and Robinson, D. B. (1976). “A New

Two-Constant Equation of State”. Industrial and
Engineering Chemistry: Fundamentals 15: 59–64.
doi:10.1021/i160057a011.

[4] A. Wohl “Investigation of the condition equation”, Zeitschrift

für Physikalische Chemie (Leipzig) 87 pp. 1–39 (1914)

[5] Yunus A. Cengel and Michael A. Boles, Thermodynamics:

An Engineering Approach 7th Edition, McGraw-Hill, 2010,
ISBN 007-352932-X

[6] Gordan J. Van Wylen and Richard E. Sonntage, Fundamen-

tal of Classical Thermodynamics, 3rd ed, New York, John
Wiley & Sons, 1986 P46 table 3.3

• Dilip Kondepudi, Ilya Prigogine, Modern Thermo-

dynamics, John Wiley & Sons, 1998, ISBN 0-471-
97393-9

• Hsieh, Jui Sheng, Engineering Thermodynamics,

Prentice-Hall Inc., Englewood Cliffs, New Jersey
07632, 1993. ISBN 0-13-275702-8
• Stanley M. Walas, Phase Equilibria in Chemical Engi-
neering, Butterworth Publishers, 1985. ISBN 0-409-
95162-5

• M. Aznar, and A. Silva Telles, A Data Bank of Pa-

rameters for the Attractive Coefficient of the Peng–
Robinson Equation of State, Braz. J. Chem. Eng. vol.
14 no. 1 São Paulo Mar. 1997, ISSN 0104-6632

• An introduction to thermodynamics by Y. V. C. Rao

• The corresponding-states principle and its practice:
thermodynamic, transport and surface properties of
fluids by Hong Wei Xiang

4.3.4 External links

• http://www.ccl.net/cca/documents/dyoung/
topics-orig/eq_state.html
Chapter 5

Chapter 5. System Processes

5.1 Thermodynamic process Thermodynamic process

Defined by change in a system, a thermodynamic process

Classical thermodynamics considers three main kinds of is a passage of a thermodynamic system from an initial
thermodynamic process: change in a system, cycles in a sys- to a final state of thermodynamic equilibrium. The ini-
tem, and flow processes. tial and final states are the defining elements of the pro-
Defined by change in a system , a thermodynamic process cess. The actual course of the process is not the primary
is a passage of a thermodynamic system from an initial to concern, and often is ignored. A state of thermodynamic
a final state of thermodynamic equilibrium. The initial and equilibrium endures unchangingly unless it is interrupted
final states are the defining elements of the process. The by a thermodynamic operation that initiates a thermody-
actual course of the process is not the primary concern, and namic process. The equilibrium states are each respectively
often is ignored. This is the customary default meaning fully specified by a suitable set of thermodynamic state vari-
of the term 'thermodynamic process’. In general, during ables, that depend only on the current state of the system,
the actual course of a thermodynamic process, the system not the path taken by the processes that produce that state.
passes through physical states which are not describable as In general, during the actual course of a thermodynamic
thermodynamic states, because they are far from internal process, the system passes through physical states which are
thermodynamic equilibrium. Such processes are useful for not describable as thermodynamic states, because they are
thermodynamic theory. far from internal thermodynamic equilibrium. Such a pro-
cess may therefore be admitted for equilibrium thermody-
Defined by a cycle of transfers into and out of a system, a
namics, but not be admitted for non-equilibrium thermo-
cyclic process is described by the quantities transferred in
dynamics, which primarily aims to describe the continuous
the several stages of the cycle, which recur unchangingly.
passage along the path, at definite rates of progress.
The descriptions of the staged states of the system are not
the primary concern. Cyclic processes were important con- Though not so in general, it is, however, possible, that a
ceptual devices in the early days of thermodynamical in- process may take place slowly or smoothly enough to allow
vestigation, while the concept of the thermodynamic state its description to be usefully approximated by a continu-
variable was being developed. ous path of equilibrium thermodynamic states. Then it may
be approximately described by a process function that does
Defined by flows through a system, a flow process is a
depend on the path. Such a process may be idealized as a
steady state of flows into and out of a vessel with definite
“quasi-static” process, which is infinitely slow, and which
wall properties. The internal state of the vessel contents is
is really a theoretical exercise in differential geometry, as
not the primary concern. The quantities of primary concern
opposed to an actually possible physical process; in this ide-
describe the states of the inflow and the outflow materials,
alized case, the calculation may be exact, though the process
and, on the side, the transfers of heat, work, and kinetic
does not actually occur in nature. Such idealized processes
and potential energies for the vessel. Flow processes are of
are useful in the theory of thermodynamics.
interest in engineering.

Cyclic process

Defined by a cycle of transfers into and out of a system,

5.1.1 Kinds of process a cyclic process is described by the quantities transferred
in the several stages of the cycle. The descriptions of the

101
102 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

staged states of the system may be of little or even no inter-

est. A cycle is a sequence of a small number of thermody-
namic processes that indefinitely often repeatedly returns
the system to its original state. For this, the staged states
themselves are not necessarily described, because it is the
transfers that are of interest. It is reasoned that if the cycle
can be repeated indefinitely often, then it can be assumed
that the states are recurrently unchanged. The condition of
the system during the several staged processes may be of
even less interest than is the precise nature of the recurrent
states. If, however, the several staged processes are ideal-
ized and quasi-static, then the cycle is described by a path
through a continuous progression of equilibrium states.

Flow process

Defined by flows through a system, a flow process is a steady

state of flow into and out of a vessel with definite wall prop-
erties. The internal state of the vessel contents is not the pri-
mary concern. The quantities of primary concern describe
the states of the inflow and the outflow materials, and, on
the side, the transfers of heat, work, and kinetic and po-
tential energies for the vessel. The states of the inflow and
outflow materials consist of their internal states, and of their
kinetic and potential energies as whole bodies. Very often,
the quantities that describe the internal states of the input
and output materials are estimated on the assumption that
they are bodies in their own states of internal thermody-
namic equilibrium. Because rapid reactions are permitted,
the thermodynamic treatment may be approximate, not ex-
act.
An example of a cycle of idealized thermodynamic processes which
make up the Stirling cycle
5.1.3 Conjugate variable processes
It is often useful to group processes into pairs, in which each
variable held constant is one member of a conjugate pair.
Pressure - volume
The pressure-volume conjugate pair is concerned with the
transfer of mechanical or dynamic energy as the result of
work.

• An isobaric process occurs at constant pressure. An

5.1.2 A cycle of quasi-static processes
Main article: Stirling cycle
A quasi-static thermodynamic process can be visualized
by graphically plotting the path of idealized changes to the
system’s state variables. In the example, a cycle consisting
of four quasi-static processes is shown. Each process has
a well-defined start and end point in the pressure-volume
state space. In this particular example, processes 1 and 3
are isothermal, whereas processes 2 and 4 are isochoric.
The PV diagram is a particularly useful visualization of a
quasi-static process, because the area under the curve of a
process is the amount of work done by the system during
that process. Thus work is considered to be a process vari-
able, as its exact value depends on the particular path taken
between the start and end points of the process. Similarly,
heat may be transferred during a process, and it too is a
process variable.
example would be to have a movable piston in a cylin-
der, so that the pressure inside the cylinder is always
at atmospheric pressure, although it is separated from
the atmosphere. In other words, the system is dy-
namically connected, by a movable boundary, to a
constant-pressure reservoir.
• An isochoric process is one in which the volume is
held constant, with the result that the mechanical PV
work done by the system will be zero. On the other
hand, work can be done isochorically on the system,
for example by a shaft that drives a rotary paddle lo-
cated inside the system. It follows that, for the simple
system of one deformation variable, any heat energy
transferred to the system externally will be absorbed as
internal energy. An isochoric process is also known as
an isometric process or an isovolumetric process. An
example would be to place a closed tin can of material
into a fire. To a first approximation, the can will not
5.1. THERMODYNAMIC PROCESS 103

expand, and the only change will be that the contents There is no energy added or subtracted from the
gain internal energy, evidenced by increase in temper- system by particle transfer. The system is particle-
ature and pressure. Mathematically, δQ = dU . The transfer-insulated from its environment by a bound-
system is dynamically insulated, by a rigid boundary, ary that is impermeable to particles, but permissive
from the environment. of transfers of energy as work or heat. These pro-
cesses are the ones by which thermodynamic work and
heat are defined, and for them, the system is said to be
Temperature - entropy closed.
The temperature-entropy conjugate pair is concerned with
the transfer of energy, especially for a closed system.
5.1.4 Thermodynamic potentials
• An isothermal process occurs at a constant tem-
Any of the thermodynamic potentials may be held constant
perature. An example would be a closed system
during a process. For example:
immersed in and thermally connected with a large
constant-temperature bath. Energy gained by the sys-
tem, through work done on it, is lost to the bath, so • An isenthalpic process introduces no change in
that its temperature remains constant. enthalpy in the system.
• An adiabatic process is a process in which there is no
matter or heat transfer, because a thermally insulat-
ing wall separates the system from its surroundings. 5.1.5 Polytropic processes
For the process to be natural, either (a) work must be
done on the system at a finite rate, so that the inter- Main article: Polytropic process
nal energy of the system increases; the entropy of the
system increases even though it is thermally insulated; A polytropic process is a thermodynamic process that
or (b) the system must do work on the surroundings, obeys the relation:
which then suffer increase of entropy, as well as gain-
ing energy from the system.
n
• An isentropic process is customarily defined as an PV = C,
idealized quasi-static reversible adiabatic process, of
transfer of energy as work. Otherwise, for a constant- where P is the pressure, V is volume, n is any real number
entropy process, if work is done irreversibly, heat (the “polytropic index”), and C is a constant. This equation
transfer is necessary, so that the process is not adi- can be used to accurately characterize processes of certain
abatic, and an accurate artificial control mechanism systems, notably the compression or expansion of a gas, but
is necessary; such is therefore not an ordinary natural in some cases, liquids and solids.
thermodynamic process.

5.1.6 Processes classified by the second law

Chemical potential - particle number
of thermodynamics
The processes just above have assumed that the boundaries
are also impermeable to particles. Otherwise, we may as- According to Planck, one may think of three main classes
sume boundaries that are rigid, but are permeable to one of thermodynamic process: natural, fictively reversible, and
or more types of particle. Similar considerations then hold impossible or unnatural.[1][2]
for the chemical potential–particle number conjugate pair,
which is concerned with the transfer of energy via this trans-
fer of particles. Natural process

• In a constant chemical potential process the system Only natural processes occur in nature. For thermodynam-
is particle-transfer connected, by a particle-permeable ics, a natural process is a transfer between systems that[1]
in-
boundary, to a constant-µ reservoir. creases the sum of their entropies, and is irreversible. Nat-
ural processes may occur spontaneously, or may be trig-
• The conjugate here is a constant particle number pro- gered in a metastable or unstable system, as for example
cess. These are the processes outlined just above. in the condensation of a supersaturated vapour.[3]
104
Fictively reversible process
To describe the geometry of graphical surfaces that illus-
trate equilibrium relations between thermodynamic func-
tions of state, one can fictively think of so-called “reversible
processes”. They are convenient theoretical objects that
trace paths across graphical surfaces. They are called “pro-
cesses” but do not describe naturally occurring processes,
which are always irreversible. Because the points on the
paths are points of thermodynamic equilibrium, it is cus-
tomary to think of the “processes” described by the paths
as fictively “reversible”.[1]
Unnatural process
Unnatural processes are logically conceivable but do not oc-
cur in nature. They would decrease the sum of the entropies
if they occurred.[1]
Quasistatic process
Main article: Quasistatic process
A quasistatic process is an idealized or fictive model of
a thermodynamic “process” considered in theoretical stud-
ies. It does not occur in physical reality. It may be imag-
ined as happening infinitely slowly so that the system passes
through a continuum of states that are infinitesimally close
to equilibrium. The fictive “process” can be regarded as
reversible.
5.1.7 See also
• Flow process
• Heat
• Kalina cycle
• Phase transition
• Work (thermodynamics)
5.1.8 References
[1] Guggenheim, E.A. (1949/1967). Thermodynamics. An Ad-
vanced Treatment for Chemists and Physicists, fifth revised
edition, North-Holland, Amsterdam, p. 12.
[2] Tisza, L. (1966). Generalized Thermodynamics, M.I.T.
Press, Cambridge MA, p. 32.
[3] Planck, M.(1897/1903). Treatise on Thermodynamics,
translated by A. Ogg, Longmans, Green & Co., London, p.
82.
CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES
5.1.9 Further reading
• Physics for Scientists and Engineers - with Modern
Physics (6th Edition), P. A. Tipler, G. Mosca, Free-
man, 2008, ISBN 0-7167-8964-7
• Encyclopaedia of Physics (2nd Edition), R.G. Lerner,
G.L. Trigg, VHC publishers, 1991, ISBN 3-527-
26954-1 (Verlagsgesellschaft), ISBN 0-89573-752-3
(VHC Inc.)
• McGraw Hill Encyclopaedia of Physics (2nd Edition),
C.B. Parker, 1994, ISBN 0-07-051400-3
• Physics with Modern Applications, L.H. Greenberg,
Holt-Saunders International W.B. Saunders and Co,
1978, ISBN 0-7216-4247-0
• Essential Principles of Physics, P.M. Whelan, M.J.
Hodgeson, 2nd Edition, 1978, John Murray, ISBN 0-
7195-3382-1
• Thermodynamics, From Concepts to Applications
(2nd Edition), A. Shavit, C. Gutfinger, CRC Press
(Taylor and Francis Group, USA), 2009, ISBN
9781420073683
• Chemical Thermodynamics, D.J.G. Ives, Univer-
sity Chemistry, Macdonald Technical and Scientific,
1971, ISBN 0-356-03736-3
• Elements of Statistical Thermodynamics (2nd Edition),
L.K. Nash, Principles of Chemistry, Addison-Wesley,
1974, ISBN 0-201-05229-6
• Statistical Physics (2nd Edition), F. Mandl, Manch-
ester Physics, John Wiley & Sons, 2008, ISBN
9780471915331
5.2 Isobaric process
An isobaric process is a thermodynamic process in which
the pressure stays constant: ΔP = 0. The term derives from
the Greek iso- (equal) and baros (weight). The heat trans-
ferred to the system does work, but also changes the internal
energy of the system:
Q = ∆U − W
According to the first law of thermodynamics, W is work
done by the system, U is internal energy, and Q is heat.[1]
Pressure-volume work by the closed system is defined as:
∫
W = p dV
5.2. ISOBARIC PROCESS 105

P = n cP ∆T

where cP is specific heat at a constant pressure.

5.2.1 Specific heat capacity

P A B To find the molar specific heat capacity of the gas involved,

the following equations apply for any general gas that is
calorically perfect. The property γ is either called the adi-
abatic index or the heat capacity ratio. Some published
W sources might use k instead of γ .
Molar isochoric specific heat:

R
O VA VB V
cV =
γ−1
Molar isobaric specific heat:

The yellow area represents the work done

γR
cp =
γ−1
where Δ means change over the whole process, whereas d
denotes a differential. Since pressure is constant, this means The values for γ are γ = 1.4 for diatomic gasses like air
that and its major components, and γ = 35 for monatomic gasses
like the noble gasses. The formulas for specific heats would
reduce in these special cases:
W = −p∆V Monatomic:

Applying the ideal gas law, this becomes cV = 3R

and cP = 5R
2 2

Diatomic:
W = −n R ∆T
cV = 5R 2 and cP = 2
7R
assuming that the quantity of gas stays constant, e.g., there
is no phase transition during a chemical reaction. According
An isobaric process is shown on a P-V diagram as a straight
to the equipartition theorem, the change in internal energy
horizontal line, connecting the initial and final thermostatic
is related to the temperature of the system by
states. If the process moves towards the right, then it is an
expansion. If the process moves towards the left, then it is
a compression.
∆U = n cV ∆T

where cV is specific heat at a constant volume. 5.2.2 Sign convention for work
Substituting the last two equations into the first equation
produces: The motivation for the specific sign conventions of
thermodynamics comes from early development of heat en-
gines. When designing a heat engine, the goal is to have the
system produce and deliver work output. The source of en-
Q = n cV ∆T + n R ∆T
ergy in a heat engine, is a heat input.
If the volume compresses (delta V = final volume - initial
volume < 0), then W < 0. That is, during isobaric com-
= n (cV + R) ∆T pression the gas does negative work, or the environment
106 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

does positive work. Restated, the environment does pos- can stay constant as the density-temperature quadrant (ρ,T
itive work on the gas. ) undergoes a squeeze mapping.[2]
If the volume expands (delta V = final volume - initial vol-
ume > 0), then W > 0. That is, during isobaric expansion 5.2.5 See also
the gas does positive work, or equivalently, the environment
does negative work. Restated, the gas does positive work on • Adiabatic process
the environment.
• Cyclic process
If heat is added to the system, then Q > 0. That is, during
isobaric expansion/heating, positive heat is added to the gas, • Isochoric process
or equivalently, the environment receives negative heat. Re-
stated, the gas receives positive heat from the environment. • Isothermal process
If the system rejects heat, then Q < 0. That is, during iso- • Polytropic process
baric compression/cooling, negative heat is added to the
gas, or equivalently, the environment receives positive heat. • Isenthalpic process
Restated, the environment receives positive heat from the
gas.
5.2.6 References
[1] “First Law of Thermodynamics”. Hyperphysics.
5.2.3 Defining enthalpy
[2] Peter Olver (1999), Classical Invariant Theory, p. 217
An isochoric process is described by the equation Q = ∆U
. It would be convenient to have a similar equation for iso-
baric processes. Substituting the second equation into the
first yields
5.3 Isochoric process
An isochoric process, also called a constant-volume pro-
Q = ∆U + ∆(p V ) = ∆(U + p V ) cess, an isovolumetric process, or an isometric process,
is a thermodynamic process during which the volume of the
The quantity U + p V is a state function so that it can be closed system undergoing such a process remains constant.
given a name. It is called enthalpy, and is denoted as H. An isochoric process is exemplified by the heating or the
Therefore an isobaric process can be more succinctly de- cooling of the contents of a sealed, inelastic container: The
scribed as thermodynamic process is the addition or removal of heat;
the isolation of the contents of the container establishes the
closed system; and the inability of the container to deform
Q = ∆H imposes the constant-volume condition. The isochoric pro-
Enthalpy and isochoric specific heat capacity are very useful cess here should be a quasi-static process.
mathematical constructs, since when analyzing a process in
an open system, the situation of zero work occurs when the 5.3.1 Formalism
fluid flows at constant pressure. In an open system, enthalpy
is the quantity which is useful to use to keep track of energy An isochoric thermodynamic process is characterized by
content of the fluid. constant volume, i.e., ∆V = 0 . The process does no
pressure-volume work, since such work is defined by
5.2.4 Variable density viewpoint
A given quantity (mass m) of gas in a changing volume pro- ∆W = P ∆V
duces a change in density ρ. In this context the ideal gas law
is written where P is pressure. The sign convention is such that posi-
tive work is performed by the system on the environment.
If the process is not quasi-static, the work can perhaps be
R(T ρ) = M P done in a volume constant thermodynamic process.[1]
where T is thermodynamic temperature and M is molar For a reversible process, the first law of thermodynamics
mass. When R and M are taken as constant, then pressure P gives the change in the system’s internal energy:
5.3. ISOCHORIC PROCESS 107

dU = dQ − dW
P
Replacing work with a change in volume gives
Final State
dU = dQ − P dV
PB B
Since the process is isochoric, dV = 0 , the previous equa-
tion now gives

Initial State
dU = dQ
Using the definition of specific heat capacity at constant
volume, PA A
Cv = dU /dT
dQ = mcv dT O V V
Integrating both sides yields
Isochoric process in the pressure volume diagram. In this diagram,
∫ T2 pressure increases, but volume remains constant.
∆Q = m cv dT.
T1

Where cv is the specific heat capacity at constant volume, 5.3.3 Etymology

T1 is the initial temperature and T2 is the final temperature.
We conclude with: The noun isochor and the adjective isochoric are derived
from the Greek words ἴσος (isos) meaning “equal”, and
χώρος (choros) meaning “space.”
∆Q = mcv ∆T
On a pressure volume diagram, an isochoric process ap- 5.3.4 See also
pears as a straight vertical line. Its thermodynamic conju-
gate, an isobaric process would appear as a straight horizon- • Isobaric process
tal line.
• Adiabatic process
Ideal gas
• Cyclic process
If an ideal gas is used in an isochoric process, and the quan- • Isothermal process
tity of gas stays constant, then the increase in energy is pro-
portional to an increase in temperature and pressure. Take • Polytropic process
for example a gas heated in a rigid container: the pressure
and temperature of the gas will increase, but the volume
will remain the same. 5.3.5 References
[1] https://www.physicsforums.com/threads/
5.3.2 Ideal Otto cycle if-gas-volume-remains-constant-it-can-does-work-to-others.
765131/
The ideal Otto cycle is an example of an isochoric process
when it is assumed that the burning of the gasoline-air mix-
ture in an internal combustion engine car is instantaneous. 5.3.6 External links
There is an increase in the temperature and the pressure of
the gas inside the cylinder while the volume remains the • http://lorien.ncl.ac.uk/ming/webnotes/Therm1/
same. revers/isocho.htm
108 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

5.4 Isothermal process that the process is also isothermal.[7] Thus, specifying that
a process is isothermal is not sufficient to specify a unique
An isothermal process is a change of a system, in which process.
the temperature remains constant: ΔT = 0. This typically
occurs when a system is in contact with an outside thermal
5.4.2 Details for an ideal gas
reservoir (heat bath), and the change occurs slowly enough
to allow the system to continually adjust to the tempera-
ture of the reservoir through heat exchange. In contrast, an
adiabatic process is where a system exchanges no heat with
its surroundings (Q = 0). In other words, in an isothermal
process, the value ΔT = 0 and therefore ΔU = 0 (only for
an ideal gas) but Q ≠ 0, while in an adiabatic process, ΔT ≠
0 but Q = 0.

5.4.1 Examples
Isothermal processes can occur in any kind of system that
has some means of regulating the temperature, including
highly structured machines, and even living cells. Some
parts of the cycles of some heat engines are carried out
isothermally (for example, in the Carnot cycle).[1] In the
thermodynamic analysis of chemical reactions, it is usual to
first analyze what happens under isothermal conditions and
then consider the effect of temperature.[2] Phase changes,
such as melting or evaporation, are also isothermal pro- Several isotherms of an ideal gas on a p-V diagram
cesses when, as is usually the case, they occur at constant
pressure.[3] Isothermal processes are often used and a start- For the special case of a gas to which Boyle’s law[7] applies,
ing point in analyzing more complex, non-isothermal pro- the product pV is a constant if the gas is kept at isothermal
cesses. conditions. The value of the constant is nRT, where n is the
number of moles of gas present and R is the ideal gas con-
Isothermal processes are of special interest for ideal gases. stant. In other words, the ideal gas law pV = nRT applies.[8]
This is a consequence of Joule’s second law which states that This means that
the internal energy of a fixed amount of an ideal gas depends
only on its temperature.[4] Thus, in an isothermal process
the internal energy of an ideal gas is constant. This is a result nRT constant
p= =
of the fact that in an ideal gas there are no intermolecular V V
forces.[5] Note that this is true only for ideal gases; the in- holds. The family of curves generated by this equation is
ternal energy depends on pressure as well as on temperature shown in the graph presented at the bottom right-hand of the
for liquids, solids, and real gases.[6] page.[or the upper part of section when viewed in mobile]
In the isothermal compression of a gas there is work is Each curve is called an isotherm. Such graphs are termed
done on the system to decrease the volume and increase indicator diagrams and were first used by James Watt and
the pressure.[7] Doing work on the gas increases the inter- others to monitor the efficiency of engines. The temper-
nal energy and will tend to increase the temperature. To ature corresponding to each curve in the figure increases
maintain the constant temperature energy must leave the from the lower left to the upper right.
system as heat and enter the environment. If the gas is ideal,
the amount of energy entering the environment is equal to
the work done on the gas, because internal energy does not 5.4.3 Calculation of work
change. For details of the calculations, see calculation of
work. In thermodynamics, the reversible work involved when a gas
changes from state A to state B is[9]
For an adiabatic process, in which no heat flows into or out
of the gas because its container is well insulated, Q = 0 .
∫ VB
If there is also no work done, i.e. a free expansion, there is
WA→B = − p dV
no change in internal energy. For an ideal gas, this means VA
5.4. ISOTHERMAL PROCESS 109

where Qrev is the heat transferred reversibly to the system

and T is absolute temperature.[10] This formula is valid only
for a hypothetical reversible process; that is, a process in
which equilibrium is maintained at all times.
A simple example is an equilibrium phase transition (such
as melting or evaporation) taking place at constant tem-
perature and pressure. For a phase transition at constant
pressure, the heat transferred to the system is equal to the
enthalpy of transformation, ∆Htr , thus Q = ∆Htr . [11] At
any given pressure, there will be a transition temperature,
Ttr , for which the two phases are in equilibrium (for exam-
ple, the normal boiling point for vaporization of a liquid at
one atmosphere pressure). If the transition takes place un-
der such equilibrium conditions, the formula above may be
used to directly calculate the entropy change[12]
𝐴

∆Htr
∆Str =
Ttr
The purple area represents “work” for this isothermal change
Another example is the reversible isothermal expansion (or
compression) of an ideal gas from an initial volume VA and
For an isothermal, reversible process, this integral equals
pressure PA to a final volume VB and pressure PB . As
the area under the relevant pressure-volume isotherm, and
shown in Calculation of work, the heat transferred to the
is indicated in purple in the figure (at the bottom right-hand
gas is
of the page) for an ideal gas. Again, p = nRT /V applies
and with T being constant (as this is an isothermal process),
the expression for work becomes:
VB
Q = −W = nRT ln
VA
∫ VB ∫ VB ∫ VB
nRT 1 result is for a reversible
This VB process, so it may be substi-
WA→B = − p dV = − dV = −nRT dV = −nRT ln
VA VA V V VAthe entropy change to obtain [13]
VA tuted in the formula for

By convention, work is defined as the work on the system

by its surroundings. If, for example, the system is com-
pressed, then the work is positive and the internal energy of ∆S = nR ln VB
the system increases. Conversely, if the system expands, it VA
does work on the surroundings and the internal energy of Since an ideal gas obey’s Boyle’s Law, this can be rewritten,
the system decreases. if desired, as
It is also worth noting that for ideal gases, if the tempera-
ture is held constant, the internal energy of the system also is
constant, and so ∆U = 0 . Since the First Law of Thermo- PA
∆S = nR ln
dynamics states that ∆U = Q + W (IUPAC convention), PB
it follows that Q = −W for the isothermal compression or
expansion of ideal gases. Once obtained, these formulas can be applied to an
irreversible process, such as the free expansion of an ideal
gas. Such an expansion is also isothermal and may have the
5.4.4 Entropy changes same initial and final states as in the reversible expansion.
Since entropy is a state function, the change in entropy of
Isothermal processes are especially convenient for calculat- the system is the same as in the reversible process and is
ing changes in entropy since, in this case, the formula for given by the formulas above. Note that the result Q = 0 for
the entropy change, ∆S , is simply the free expansion can not be used in the formula for the
entropy change since the process is not reversible.

Qrev The difference between the reversible and free expansions

∆S = is found in the entropy of the surroundings. In both cases,
T
110 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

the surroundings are at a constant temperature, T , so that [11] Petrucci, op cit.

∆Ssur = −Q/T ; the minus sign is used since the heat
transferred to the surroundings is equal in magnitude and [12] Atkins, Chapter 4, op.cit.
opposite in sign to the heat, Q , transferred to the system. In
[13] Ibid
the reversible case, the change in entropy of the surround-
ings is equal and opposite to the change in the system, so the
change in entropy of the universe is zero. In the free expan-
sion, Q = 0 , so the entropy of the surroundings does not 5.5 Adiabatic process
change and the change in entropy of the universe is equal
to ∆S for the system. An adiabatic process is one that occurs without transfer of
heat or matter between a thermodynamic system and its sur-
roundings. In an adiabatic process, energy is transferred
5.4.5 See also only as work.[1][2] The adiabatic process provides a rigor-
ous conceptual basis for the theory used to expound the first
• Joule–Thomson effect
law of thermodynamics, and as such it is a key concept in
• Joule expansion (also called free expansion) thermodynamics.
Some chemical and physical processes occur so rapidly that
• Adiabatic process
they may be conveniently described by the “adiabatic ap-
• Cyclic process proximation”, meaning that there is not enough time for
the transfer of energy as heat to take place to or from the
• Isobaric process system.[3]
• Isochoric process By way of example, the adiabatic flame temperature is an
idealization that uses the “adiabatic approximation” so as to
• Polytropic process provide an upper limit calculation of temperatures produced
by combustion of a fuel. The adiabatic flame temperature
is the temperature that would be achieved by a flame if the
5.4.6 References
process of combustion took place in the absence of heat loss
[1] Keenan, J.H. (1970). Thermodynamics, Chapter 12: “Heat- to the surroundings.
engine cycles”. M.I.T. Press, Cambridge, Massachusetts.

[2] Rock, P. A. (1983). Chemical Thermodynamics, Chapter 5.5.1 Description

11: “Thermodynamics of chemical reactions”. University
Science Books, Mill Valley, CA. ISBN 0-935702-12-1
A process that does not involve the transfer of heat or mat-
[3] Petrucci, R. H., W.S. Harwood, F.G Herring, J.D. Madura ter into or out of a system, so that Q = 0, is called an adia-
(2007). General Chemistry, Chapter 12. Pearson,Upper batic process, and such a system is said to be adiabatically
Saddle River, New Jersey. ISBN 0-13-149330-2 isolated.[4][5] The assumption that a process is adiabatic is
a frequently made simplifying assumption. For example,
[4] Klotz, I.M. and R. M. Rosenberg (1991). Chemical Thermo-
the compression of a gas within a cylinder of an engine is
dynamics, Chapter 6, “Application of the first law to gases”.
Benjamin, Meno Park, California.
assumed to occur so rapidly that on the time scale of the
compression process, little of the system’s energy can be
[5] Ibid transferred out as heat. Even though the cylinders are not
insulated and are quite conductive, that process is idealized
[6] Adkins, C. J.(1983). Equilibrium Thermodynamics. Cam-
to be adiabatic. The same can be said to be true for the
bridge University Press.
expansion process of such a system.
[7] Klotz and Rosenberg. op. cit..
The assumption of adiabatic isolation of a system is a use-
[8] Ibid. ful one, and is often combined with others so as to make
the calculation of the system’s behaviour possible. Such
[9] Atkins, Peter (1997). Physical Chemistry (6th ed.). Chapter assumptions are idealizations. The behaviour of actual ma-
2, “The first law: the concepts”. New York: W.H. Freeman chines deviates from these idealizations, but the assumption
and Co. ISBN 0-7167-2871-0.
of such “perfect” behaviour provide a useful first approxi-
[10] Atkins, Peter (1997). Physical Chemistry (6th ed.). Chap- mation of how the real world works. According to Laplace,
ter 4, “The second law: the concepts”. New York: W.H. when sound travels in a gas, there is no loss of heat in the
Freeman and Co. ISBN 0-7167-2871-0. medium and the propagation of sound is adiabatic. For this
5.5. ADIABATIC PROCESS 111

adiabatic process, the modulus of elasticity E = γP where The transfer of energy as work into an adiabatically isolated
γ is the ratio of specific heats at constant pressure and at system can be imagined as being of two idealized extreme
constant volume (γ = Cp /Cv ) and P is the pressure of the kinds. In one such kind, there is no entropy produced within
gas . the system (no friction, viscous dissipation, etc.), and the
work is only pressure-volume work (denoted by P dV). In
nature, this ideal kind occurs only approximately, because
Various applications of the adiabatic assumption it demands an infinitely slow process and no sources of dis-
sipation.
For a closed system, one may write the first law of ther-
modynamics thus: ΔU = Q + W, where ΔU denotes the The other extreme kind of work is isochoric work (dV = 0),
change of the system’s internal energy, Q the quantity of for which energy is added as work solely through friction or
energy added to it as heat, and W the work done on it by its viscous dissipation within the system. A stirrer that trans-
surroundings. fers energy to a viscous fluid of an adiabatically isolated
system with rigid walls, without phase change, will cause a
• If the system has rigid walls such that work cannot be rise in temperature of the fluid, but that work is not recov-
transferred in or out (W = 0), and the walls of the sys- erable. Isochoric work is irreversible.[6] The second law of
tem are not adiabatic and energy is added in the form thermodynamics observes that a natural process, of trans-
of heat (Q > 0), and there is no phase change, the tem- fer of energy as work, always consists at least of isochoric
perature of the system will rise. work and often both of these extreme kinds of work. Every
natural process, adiabatic or not, is irreversible, with ΔS >
• If the system has rigid walls such that pressure–volume 0, as friction or viscosity are always present to some extent.
work cannot be done, and the system walls are adia-
batic (Q = 0), but energy is added as isochoric work
in the form of friction or the stirring of a viscous
fluid within the system (W > 0), and there is no phase 5.5.2 Adiabatic heating and cooling
change, the temperature of the system will rise.
The adiabatic compression of a gas causes a rise in tem-
• If the system walls are adiabatic (Q = 0), but not rigid perature of the gas. Adiabatic expansion against pressure,
(W ≠ 0), and, in a fictive idealized process, energy is or a spring, causes a drop in temperature. In contrast, free
added to the system in the form of frictionless, non- expansion is an isothermal process for an ideal gas.
viscous pressure–volume work, and there is no phase
change, the temperature of the system will rise. Such Adiabatic heating occurs when the pressure of a gas is
a process is called an isentropic process and is said to increased from work done on it by its surroundings, e.g.,
be “reversible”. Fictively, if the process is reversed, a piston compressing a gas contained within an adiabatic
the energy added as work can be recovered entirely cylinder. This finds practical application in diesel engines
as work done by the system. If the system contains a which rely on the lack of quick heat dissipation during their
compressible gas and is reduced in volume, the un- compression stroke to elevate the fuel vapor temperature
certainty of the position of the gas is reduced, and sufficiently to ignite it.
seemingly would reduce the entropy of the system, but Adiabatic heating occurs in the Earth’s atmosphere when an
the temperature of the system will rise as the process air mass descends, for example, in a katabatic wind, Foehn
is isentropic (ΔS = 0). Should the work be added in wind, or chinook wind flowing downhill over a mountain
such a way that friction or viscous forces are operating range. When a parcel of air descends, the pressure on
within the system, then the process is not isentropic, the parcel increases. Due to this increase in pressure, the
and if there is no phase change, then the temperature parcel’s volume decreases and its temperature increases as
of the system will rise, the process is said to be “ir- work is done on the parcel of air, thus increasing its internal
reversible”, and the work added to the system is not energy, which manifests itself by a rise in the temperature
entirely recoverable in the form of work. of that mass of air. The parcel of air can only slowly dis-
• If the walls of a system are not adiabatic, and energy sipate the energy by conduction or radiation (heat), and to
is transferred in as heat, entropy is transferred into the a first approximation it can be considered adiabatically iso-
system with the heat. Such a process is neither adia- lated and the process an adiabatic process.
batic nor isentropic, having Q > 0, and ΔS > 0 accord- Adiabatic cooling occurs when the pressure on an adiabat-
ing to the second law of thermodynamics. ically isolated system is decreased, allowing it to expand,
thus causing it to do work on its surroundings. When the
Naturally occurring adiabatic processes are irreversible (en- pressure applied on a parcel of air is reduced, the air in the
tropy is produced). parcel is allowed to expand; as the volume increases, the
112 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

[3]
temperature falls as its internal energy decreases. Adiabatic P V n = constant
cooling occurs in the Earth’s atmosphere with orographic
lifting and lee waves, and this can form pileus or lenticular where P is pressure, V is volume, and for this case n = γ
clouds. where
Adiabatic cooling does not have to involve a fluid. One
technique used to reach very low temperatures (thousandths
and even millionths of a degree above absolute zero) is via γ = CP = f + 2 ,
adiabatic demagnetisation, where the change in magnetic CV f
field on a magnetic material is used to provide adiabatic C being the specific heat for constant pressure, C be-
P V
cooling. Also, the contents of an expanding universe can ing the specific heat for constant volume, γ is the adiabatic
be described (to first order) as an adiabatically cooling fluid. index, and f is the number of degrees of freedom (3 for
(See - Heat death of the universe) monatomic gas, 5 for diatomic gas and collinear molecules
Rising magma also undergoes adiabatic cooling before e.g. carbon dioxide).
eruption, particularly significant in the case of magmas that For a monatomic ideal gas, γ = 5/3 , and for a diatomic
rise quickly from great depths such as kimberlites.[7] gas (such as nitrogen and oxygen, the main components of
[8]
Such temperature changes can be quantified using the ideal air) γ = 7/5 . Note that the above formula is only ap-
gas law, or the hydrostatic equation for atmospheric pro- plicable to classical ideal gases and not Bose–Einstein or
cesses. Fermi gases.
In practice, no process is truly adiabatic. Many processes For reversible adiabatic processes, it is also true that
rely on a large difference in time scales of the process of in-
terest and the rate of heat dissipation across a system bound- P 1−γ T γ = constant [3]
ary, and thus are approximated by using an adiabatic as-
sumption. There is always some heat loss, as no perfect V T f /2 = constant
insulators exist.
where T is an absolute temperature. This can also be writ-
ten as
5.5.3 Ideal gas (reversible process)
T V γ−1 = constant [3]
Main article: Reversible adiabatic process
The mathematical equation for an ideal gas undergoing a
Example of adiabatic compression

The compression stroke in a gasoline engine can be used as

an example of adiabatic compression. The simplifying as-
sumptions are: the uncompressed volume of the cylinder is
1000 cm3 (one litre); the gas within is nearly pure nitrogen
(thus a diatomic gas with five degrees of freedom and so γ
= 7/5); the compression ratio of the engine is 10:1 (that is,
the 1000 cm3 volume of uncompressed gas be reduced to
100 cm3 by the piston); and that the uncompressed gas is
at approximately room temperature and pressure (a warm
room temperature of ~27 °C or 300 K, and a pressure of
1 bar ~ 100 kPa, or about 14.7 PSI, i.e. typical sea-level
atmospheric pressure).
P V γ = constant = 100, 000 pa ×10007/5 = 100 × 103 ×
15.8 × 103 = 1.58 × 109
so our adiabatic constant for this example is about 1.58 bil-
For a simple substance, during an adiabatic process in which the lion.
volume increases, the internal energy of the working substance must
decrease The gas is now compressed to a 100 cm3 volume (we will
assume this happens quickly enough that no heat can en-
reversible (i.e., no entropy generation) adiabatic process can ter or leave the gas). The new volume is 100 cm3 , but the
be represented by the polytropic process equation constant for this experiment is still 1.58 billion:
5.5. ADIABATIC PROCESS 113

P V γ = constant = 1.58 × 109 = P × 1007/5 portional to the volume, the entropy increases in this case,
so solving for P: therefore this process is irreversible.

P = 1.58 × 109 /1007/5 = 1.58 × 109 /630.9 = 2.50 ×

106 Pa Derivation of P-V relation for adiabatic heating and
cooling
or about 362 PSI or 24.5 atm. Note that this pressure in-
crease is more than a simple 10:1 compression ratio would The definition of an adiabatic process is that heat transfer
indicate; this is because the gas is not only compressed, but to the system is zero, δQ = 0 . Then, according to the first
the work done to compress the gas also increases its internal law of thermodynamics,
energy which manifests itself by a rise in the gas’s temper-
ature and an additional rise in pressure above what would
result from a simplistic calculation of 10 times the original
pressure. (1) dU + δW = δQ = 0,

We can solve for the temperature of the compressed gas in where dU is the change in the internal energy of the system
the engine cylinder as well, using the ideal gas law, PV=RT and δW is work done by the system. Any work ( δW )
(R the specific gas constant for that gas). Our initial con- done must be done at the expense of internal energy U ,
ditions are 100,000 pa of pressure, 1000 cm3 volume, and since no heat δQ is being supplied from the surroundings.
300 K of temperature, so our experimental constant is: Pressure-volume work δW done by the system is defined as
105 ×103
PV
T = constant = 300 = 3.33 × 105
We know the compressed gas has V = 100 cm3 and P = (2) δW = P dV.
2.50E6 pascals, so we can solve for temperature by simple
algebra: However, P does not remain constant during an adiabatic
PV 2.50×106 ×100 process but instead changes along with V .
constant = T = 3.33×105 = 751
It is desired to know how the values of dP and dV relate to
That is a final temperature of 751 K, or 477 °C, or 892 °F,
each other as the adiabatic process proceeds. For an ideal
well above the ignition point of many fuels. This is why
gas the internal energy is given by
a high compression engine requires fuels specially formu-
lated to not self-ignite (which would cause engine knock-
ing when operated under these conditions of temperature
and pressure), or that a supercharger with an intercooler (3) U = αnRT,
to provide a pressure boost but with a lower temperature
rise would be advantageous. A diesel engine operates un- where α is the number of degrees of freedom divided by
der even more extreme conditions, with compression ratios two, R is the universal gas constant and n is the number of
of 20:1 or more being typical, in order to provide a very moles in the system (a constant).
high gas temperature which ensures immediate ignition of Differentiating Equation (3) and use of the ideal gas law,
the injected fuel. P V = nRT , yields

Adiabatic free expansion of a gas (4) dU = αnR dT = α d(P V ) = α(P dV + V dP ).

See also: Free expansion Equation (4) is often expressed as dU = nCV dT because
CV = αR .

For an adiabatic free expansion of an ideal gas, the gas is Now substitute equations (2) and (4) into equation (1) to
contained in an insulated container and then allowed to ex- obtain
pand in a vacuum. Because there is no external pressure
for the gas to expand against, the work done by or on the
system is zero. Since this process does not involve any heat −P dV = αP dV + αV dP,
transfer or work, the First Law of Thermodynamics then
implies that the net internal energy change of the system is factorize : −P dV, :
zero. For an ideal gas, the temperature remains constant
because the internal energy only depends on temperature in
that case. Since at constant temperature, the entropy is pro- −(α + 1)P dV = αV dP,
114 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

and divide both sides by PV:

(1) ∆U = αRnT2 − αRnT1 = αRn∆T

dV dP
−(α + 1) =α . At the same time, the work done by the pressure-volume
V P
changes as a result from this process, is equal to
After integrating the left and right sides from V0 to V and
from P0 to P and changing the sides respectively,
∫ V2

( ) ( ) (2) W = P dV
P α+1 V V1
ln =− ln .
P0 α V0 Since we require the process to be adiabatic, the following
α+1 equation needs to be true
Exponentiate both sides, and substitute α with γ , the
heat capacity ratio

(3) ∆U + W = 0
( ) ( )−γ
P V
= , By the previous derivation,
P0 V0
and eliminate the negative sign to obtain
(4) P V γ = constant = P1 V1γ
( ) ( )γ
P V0 Rearranging (4) gives
= .
P0 V
Therefore, ( )γ
V1
P = P1
V
( )( )γ
P V Substituting this into (2) gives
=1
P0 V0
and ∫ V2 ( )γ
V1
W = P1 dV
V1 V
P0 V0γ = P V γ = constant .
Integrating,

Derivation of P-T relation for adiabatic heating and

cooling V21−γ − V11−γ
W = P1 V1γ
1−γ
Substituting the ideal gas law into the above, we obtain
α+1
Substituting γ = α ,

P (nRT /P )γ = constant . ( )
W = −αP1 V1γ V21−γ − V11−γ
which simplifies to
Rearranging,

P (1−γ) T γ = constant .
(( )1−γ )
V2
W = −αP1 V1 −1
Derivation of discrete formula V1

The change in internal energy of a system, measured from Using the ideal gas law and assuming a constant molar quan-
state 1 to state 2, is equal to tity (as often happens in practical cases),
5.5. ADIABATIC PROCESS 115

1. Every adiabat asymptotically approaches both the V

(( )1−γ ) axis and the P axis (just like isotherms).
V2
W = −αnRT1 −1
V1 2. Each adiabat intersects each isotherm exactly once.

By the continuous formula, 3. An adiabat looks similar to an isotherm, except that

during an expansion, an adiabat loses more pressure
than an isotherm, so it has a steeper inclination (more
( )−γ vertical).
P2 V2
=
P1 V1 4. If isotherms are concave towards the “north-east” di-
Or, rection (45°), then adiabats are concave towards the
“east north-east” (31°).

( ) −1 5. If adiabats and isotherms are graphed at regular inter-

P2 γ
V2 vals of entropy and temperature, respectively (like alti-
=
P1 V1 tude on a contour map), then as the eye moves towards
Substituting into the previous expression for W , the axes (towards the south-west), it sees the density of
isotherms stay constant, but it sees the density of adi-
abats grow. The exception is very near absolute zero,
(( ) γ−1 ) where the density of adiabats drops sharply and they
P2 γ
W = −αnRT1 −1 become rare (see Nernst’s theorem).
P1

Substituting this expression and (1) in (3) gives The following diagram is a P-V diagram with a superposi-
tion of adiabats and isotherms:
(( ) γ−1 )
P2 γ
αnR(T2 − T1 ) = αnRT1 −1
P1

Simplifying,

(( ) γ−1 )
P2 γ
T2 − T1 = T1 −1
P1

Simplifying,

( ) γ−1
T2 P2 γ
−1= −1
T1 P1
Simplifying,

( ) γ−1
P2 γ
T2 = T1
P1

5.5.4 Graphing adiabats

An adiabat is a curve of constant entropy on the P-V dia-
gram. Some properties of adiabats on a P-V diagram are
indicated. These properties may be read from the classi-
cal behaviour of ideal gases, except in the region where PV
becomes small (low temperature), where quantum effects
become important.
116 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

The isotherms are the red curves and the adiabats are the In the eighteenth century, the law of conservation of energy
black curves. was yet to be fully formulated or established, and the nature
The adiabats are isentropic. of heat was debated. One approach to these problems was
to regard heat, measured by calorimetry, as a primary sub-
Volume is the horizontal axis and pressure is the vertical stance that is conserved in quantity. By the middle of the
axis. nineteenth century, it was recognized as a form of energy,
and the law of conservation of energy was thereby also rec-
ognized. The view that eventually established itself, and is
5.5.5 Etymology currently regarded as right, is that the law of conservation
of energy is a primary axiom, and that heat is to be analyzed
The term adiabatic/ˌædiəˈbætɪk/, literally means 'not to as consequential. In this light, heat cannot be a component
be passed through'. It is formed from the ancient Greek of the total energy of a single body because it is not a state
privative "α" (“not”) + διαβατός, “able to be passed variable, but, rather, is a variable that describes a process
through”, in turn deriving from διὰ- (“through”), and of transfer between two bodies. The abiabatic process is
βαῖνειν (“to walk, go, come”), thus ἀδιάβατος .[9] Accord- important because it is a logical ingredient of this current
ing to Maxwell,[10] and to Partington,[11] the term was in- view.[17]
troduced by Rankine.[12]
The etymological origin corresponds here to an impossibil-
ity of transfer of energy as heat and of transfer of matter 5.5.7 Divergent usages of the word adiabatic
across the wall.
This present article is written from the viewpoint of macro-
scopic thermodynamics, and the word adiabatic is used in
5.5.6 Conceptual significance in thermody- this article in the traditional way of thermodynamics, intro-
namic theory duced by Rankine. It is pointed out in the present article
that, for example, if a compression of a gas is rapid, then
The adiabatic process has been important for thermody- there is little time for heat transfer to occur, even when the
namics since its early days. It was important in the work gas is not adiabatically isolated by a definite wall. In this
of Joule, because it provided a way of nearly directly relat- sense, a rapid compression of a gas is sometimes approxi-
ing quantities of heat and work. mately or loosely said to be adiabatic, though often far from
For a thermodynamic system that is enclosed by walls that isentropic, even when the gas is not adiabatically isolated by
do not pass matter, energy can pass in and out only as heat a definite wall.
or work. Thus a quantity of work can be related almost Quantum mechanics and quantum statistical mechanics,
directly to an equivalent quantity of heat in a cycle of two however, use the word adiabatic in a very different sense,
limbs. The first is an isochoric adiabatic work process that one that can at times seem almost opposite to the classical
adds to the system’s internal energy. Then an isochoric and thermodynamic sense. In quantum theory, the word adia-
workless heat transfer returns the system to its original state. batic can mean something perhaps near isentropic, or per-
The first limb adds a definite amount of energy and the haps near quasi-static, but the usage of the word is very dif-
second removes it. Accordingly, Rankine measured quan- ferent between the two disciplines.
tity of heat in units of work, rather than as a calorimetric On one hand in quantum theory, if a perturbative element
quantity.[13] In 1854, Rankine used a quantity that he called of compressive work is done almost infinitely slowly (that
“the thermodynamic function” that later was called entropy, is to say quasi-statically), it is said to have been done adia-
and at that time he wrote also of the “curve of no transmis- batically. The idea is that the shapes of the eigenfunctions
sion of heat”,[14] which he later called an adiabatic curve.[12] change slowly and continuously, so that no quantum jump
Besides it two isothermal limbs, Carnot’s cycle has two adi- is triggered, and the change is virtually reversible. While
abatic limbs. the occupation numbers are unchanged, nevertheless there
For the foundations of thermodynamics, the concep- is change in the energy levels of one-to-one corresponding,
tual importance of this was emphasized by Bryan,[15] pre-and post-compression, eigenstates. Thus a perturbative
by Carathéodory,[1] and by Born.[16] The reason is that element of work has been done without heat transfer and
calorimetry presupposes temperature as already defined be- without introduction of random change within the system.
fore the statement of the first law of thermodynamics. But For example, Max Born writes “Actually, it is usually the
it is better not to make such a presupposition. Rather, the 'adiabatic' case with which we have to do: i.e. the limiting
definition of absolute thermodynamic temperature is best case where the external force (or the reaction of the parts
left till the second law is available as a conceptual basis.[17] of the system on each other) acts very slowly. In this case,
5.5. ADIABATIC PROCESS
to a very high approximation
c21 = 1, c22 = 0, c23 = 0, ... ,
that is, there is no probability for a transition, and the sys- 5.5.9 References
tem is in the initial state after cessation of the perturba-
tion. Such a slow perturbation is therefore reversible, as it [1] Carathéodory, C. (1909). Untersuchungen über die Grund-
is classically.”[18]
On the other hand, in quantum theory, if a perturbative
element of compressive work is done rapidly, it randomly
changes the occupation numbers of the eigenstates, as well
as changing their shapes. In that theory, such a rapid change
is said not to be adiabatic, and the contrary word diabatic
is applied to it. One might guess that perhaps Clausius, if
he were confronted with this, in the now-obsolete language
he used in his day, would have said that “internal work” was
done and that 'heat was generated though not transferred'.
In classical thermodynamics, such a rapid change would still
be called adiabatic because the system is adiabatically iso-
lated, and there is no transfer of energy as heat. The strong
irreversibility of the change, due to viscosity or other en-
tropy production, does not impinge on this classical usage.
Thus for a mass of gas, in macroscopic thermodynamics,
words are so used that a compression is sometimes loosely
or approximately said to be adiabatic if it is rapid enough
to avoid heat transfer, even if the system is not adiabatically
isolated. But in quantum statistical theory, a compression
is not called adiabatic if it is rapid, even if the system is adi-
abatically isolated in the classical thermodynamic sense of
the term. The words are used differently in the two disci-
plines, as stated just above.
5.5.8 See also
• Cyclic process
• First law of thermodynamics
• Heat burst
• Isobaric process
• Isenthalpic process
• Isentropic process
• Isochoric process
• Isothermal process
• Polytropic process
• Entropy (classical thermodynamics)
117
• Quasistatic process
• Total air temperature
• Magnetic refrigeration
lagen der Thermodynamik, Mathematische Annalen, 67:
355–386, doi:10.1007/BF01450409. A translation may be
found here. Also a mostly reliable translation is to be found
at Kestin, J. (1976). The Second Law of Thermodynamics,
Dowden, Hutchinson & Ross, Stroudsburg PA.
[2] Bailyn, M. (1994). A Survey of Thermodynamics, American
Institute of Physics Press, New York, ISBN 0-88318-797-3,
p. 21.
[3] Bailyn, M. (1994), pp. 52–53.
[4] Tisza, L. (1966). Generalized Thermodynamics, M.I.T
Press, Cambridge MA: "(adiabatic partitions inhibit the
transfer of heat and mass)", p. 48.
[5] Münster, A. (1970), p. 48: “mass is an adiabatically inhib-
ited variable.”
[6] Münster, A. (1970), Classical Thermodynamics, translated
by E.S. Halberstadt, Wiley–Interscience, London, ISBN 0-
471-62430-6, p. 45.
[7] Kavanagh, J.L.; Sparks R.S.J. (2009). “Temperature
changes in ascending kimberlite magmas”. Earth
and Planetary Science Letters (Elsevier) 286 (3–
4): 404–413. Bibcode:2009E&PSL.286..404K.
doi:10.1016/j.epsl.2009.07.011. Retrieved 18 Febru-
ary 2012.
[8] Adiabatic Processes
[9] Liddell, H.G., Scott, R. (1940). A Greek-English Lexicon,
Clarendon Press, Oxford UK.
[10] Maxwell, J.C. (1871), Theory of Heat (first ed.), London:
Longmans, Green and Co., p. 129
[11] Partington, J.R. (1949), An Advanced Treatise on Physical
Chemistry., volume 1, Fundamental Principles. The Proper-
ties of Gases, London: Longmans, Green and Co., p. 122.
[12] Rankine, W.J.McQ. (1866). On the theory of explosive
gas engines, The Engineer, July 27, 1866; at page 467 of
the reprint in Miscellaneous Scientific Papers, edited by W.J.
Millar, 1881, Charles Griffin, London.
[13] Rankine, W.J.M. (1854). On the geometrical representa-
tion of the expansive action of heat, and theory of ther-
modynamic engines, Proc. Roy. Soc., 144: 115–175,
Miscellaneous Scientific Papers p. 339
118 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

[14] Rankine, W.J.M. (1854). On the geometrical representa- fluid as it escapes from the valve.[2] With a knowledge of the
tion of the expansive action of heat, and theory of ther- specific enthalpy of the fluid, and the pressure outside the
modynamic engines, Proc. Roy. Soc., 144: 115–175, pressure vessel, it is possible to determine the temperature
Miscellaneous Scientific Papers p. 341. and speed of the escaping fluid.
[15] Bryan, G.H. (1907). Thermodynamics. An Introductory In an isenthalpic process:
Treatise dealing mainly with First Principles and their Direct
Applications, B.G. Teubner, Leipzig. • h1 = h2
[16] Born, M. (1949). Natural Philosophy of Cause and Chance, • dh = 0
Oxford University Press, London.

[17] Bailyn, M. (1994). A Survey of Thermodynamics, Ameri- Isenthalpic processes on an ideal gas follow isotherms since
can Institute of Physics, New York, ISBN 0-88318-797-3, dh = 0 = cp dT .
Chapter 3.

[18] Born, M. (1927). Physical aspects of quantum mechan- 5.6.1 See also
ics, Nature, 119: 354–357. (Translation by Robert Oppen-
heimer.) • Isentropic process

• Silbey, Robert J.; et al. (2004). Physical chemistry. • Adiabatic process

Hoboken: Wiley. p. 55. ISBN 978-0-471-21504-2.

• Broholm, Collin. “Adiabatic free expansion.” Physics 5.6.2 References

& Astronomy @ Johns Hopkins University. N.p., 26
Nov. 1997. Web. 14 Apr. *Nave, Carl Rod. “Adi- G.J. Van Wylen and R.E. Sonntag (1985), Fundamentals of
abatic Processes.” HyperPhysics. N.p., n.d. Web. 14 Classical Thermodynamics, John Wiley & Sons, Inc., New
Apr. 2011. . York ISBN 0-471-82933-1

• Thorngren, Dr. Jane R.. “Adiabatic Processes.”

Daphne – A Palomar College Web Server. N.p., 21 Notes
July 1995. Web. 14 Apr. 2011. .
[1] Atkins, Peter; Julio de Paula (2006). Atkin’s Physical Chem-
istry. Oxford: Oxford University Press. p. 64. ISBN 978-
0-19-870072-2.
5.5.10 External links
[2] G.J. Van Wylen and R.E. Sonntag, Fundamentals of Classi-
• Article in HyperPhysics Encyclopaedia cal Thermodynamics, Section 5.13 (3rd edition)

[3] G.J. Van Wylen and R.E. Sonntag, Fundamentals of Classi-

cal Thermodynamics, Section 2.1 (3rd edition)
5.6 Isenthalpic process
An isenthalpic process or isoenthalpic process is a pro- 5.7 Isentropic process
cess that proceeds without any change in enthalpy, H; or
specific enthalpy, h.[1] In thermodynamics, an isentropic process is an ideal-
In a steady-state, steady-flow process, significant changes in ized thermodynamic process that is adiabatic and in which
pressure and temperature can occur to the fluid and yet the the work transfers of the system are frictionless; there
process will be isenthalpic if there is no transfer of heat to or is no transfer of heat or of matter and the process is
from the surroundings, no work done on or by the surround- reversible.[1][2][3][4][5][6] Such an idealized process is useful
ings, and no change in the kinetic energy of the fluid.[2] (If a in engineering as a model of and basis of comparison for
steady-state, steady-flow process is analysed using a control real processes.[7]
volume everything outside the control volume is considered The word 'isentropic' is occasionally, though not customar-
to be the surroundings.[3] ) ily, interpreted in another way, reading it as if its meaning
The throttling process is a good example of an isenthalpic were deducible from its etymology. This is contrary to its
process. Consider the lifting of a relief valve or safety valve original and customarily used definition. In this occasional
on a pressure vessel. The specific enthalpy of the fluid inside reading, it means a process in which the entropy of the sys-
the pressure vessel is the same as the specific enthalpy of the tem remains unchanged, for example because work done
5.7. ISENTROPIC PROCESS 119

on the system includes friction internal to the system, and

heat is withdrawn from the system, in just the right amount
to compensate for the internal friction, so as to leave the
entropy unchanged.[8]

5.7.1 Background

The second law of thermodynamics states that,

T dS ≥ δQ

where δQ is the amount of energy the system gains by

heating, T is the temperature of the system, and dS is the
change in entropy. The equal sign refers to a reversible pro-
cess, which is an imagined idealized theoretical limit, never
actually occurring in physical reality.[9][10] For an isentropic
process, which by definition is reversible, there is no trans- T-s (Entropy vs. Temperature) diagram of an isentropic process,
fer of energy as heat because the process is adiabatic. In which is a vertical line segment.
an irreversible process of transfer of energy as work, en-
tropy is produced within the system; consequently, in order
to maintain constant entropy within the system, energy must
be removed from the system as heat during the process. Work Turbine Actual Wa ∼ h1 − h2a
η = = =
For reversible processes, an isentropic transformation is T Work Turbine Isentropic Ws h1 − h2s
carried out by thermally “insulating” the system from its sur-
roundings. Temperature is the thermodynamic conjugate Isentropic efficiency of Compressors
variable to entropy, thus the conjugate process would be an
isothermal process in which the system is thermally “con-
nected” to a constant-temperature heat bath. Work Compressor Isentropic Ws ∼ h2s − h1
ηC = = =
Work Compressor Actual Wa h2a − h1

Isentropic efficiency of Nozzles

5.7.2 Isentropic processes in thermody-
namic systems
Exit Nozzle at KE Actual V2a2
∼ h1 − h2a
The entropy of a given mass does not change during a pro- η N = = =
Exit Nozzle at KE Isentropic V2s2 h1 − h2s
cess that is internally reversible and adiabatic. A process
during which the entropy remains constant is called an isen- For all the above equations:
tropic process, written △s = 0 or s1 = s2 . [11] Some isen-
tropic thermodynamic devices include: pumps, gas com- h1 is the enthalpy at the entrance state
pressors, turbines, nozzles, and diffusers.
h2a is the enthalpy at the exit state for the actual
process
Isentropic efficiencies of steady-flow devices in thermo- h2s is the enthalpy at the exit state for the isen-
dynamic systems tropic process

Most steady-flow devices operate under adiabatic condi-

tions, and the ideal process for these devices is the isen-
tropic process.The parameter that describes how efficiently
a device approximates a corresponding isentropic device is
called isentropic or adiabatic efficiency.[12]
Isentropic efficiency of Turbines:
Isentropic devices in thermodynamic cycles
Ideal Rankine Cycle 1->2 Isentropic compression in a pump
Ideal Rankine Cycle 3->4 Isentropic expansion in a turbine
Ideal Carnot Cycle 2->3 Isentropic expansion
Ideal Carnot Cycle 4->1 Isentropic compression
120 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

Ideal Otto Cycle 1->2 Isentropic compression
Ideal Otto Cycle 3->4 Isentropic expansion
Ideal Diesel Cycle 1->2 Isentropic compression
Ideal Diesel Cycle 3->4 Isentropic expansion
Ideal Brayton Cycle 1->2 Isentropic compression in a
compressor
Ideal Brayton Cycle 3->4 Isentropic expansion in a turbine
Ideal Vapor-compression refrigeration Cycle 1->2 Isen-
tropic compression in a compressor
NOTE: The isentropic assumptions are only applicable with
ideal cycles. Real world cycles have inherent losses due to
inefficient compressors and turbines. The real world system
are not truly isentropic but are rather idealized as isentropic
for calculation purposes.
Then for a process that is both reversible and adiabatic
(i.e. no heat transfer occurs), δQrev = 0 , and so dS =
δQrev /T = 0 . All reversible adiabatic processes are isen-
tropic. This leads to two important observations,
dU = δW + δQ = −pdV + 0
dH = δW +δQ+pdV +V dp = −pdV +0+pdV +V dp = V dp
Next, a great deal can be computed for isentropic processes
of an ideal gas. For any transformation of an ideal gas, it is
always true that
dU = nCv dT , and dH = nCp dT .

Using the general results derived above for dU and dH ,

5.7.3 Isentropic flow then

In fluid dynamics, an isentropic flow is a fluid flow that is

both adiabatic and reversible. That is, no heat is added to dU = nCv dT = −pdV
the flow, and no energy transformations occur due to friction
or dissipative effects. For an isentropic flow of a perfect dH = nCp dT = V dp
gas, several relations can be derived to define the pressure, So for an ideal gas, the heat capacity ratio can be written as,
density and temperature along a streamline.
Note that energy can be exchanged with the flow in an isen- Cp dp/p
tropic transformation, as long as it doesn't happen as heat γ = =−
CV dV /V
exchange. An example of such an exchange would be an
isentropic expansion or compression that entails work done For an ideal gas γ is constant. Hence on integrating the
on or by the flow. above equation, assuming a perfect gas, we get
For an isentropic flow, entropy density can vary between
different streamlines. If the entropy density is the same ev-
pV γ = constant
erywhere, then flow is said to be homentropic.
( )γ
p2 V1
=
p1 V2
Derivation of the isentropic relations
Using the equation of state for an ideal gas, pV = nRT ,
For a closed system, the total change in energy of a system
is the sum of the work done and the heat added,
T V γ−1 = constant
pγ−1
= constant
dU = δW + δQ Tγ
also, for constant Cp = Cv + R (per mole),
The reversible work done on a system by changing the vol-
V nR nRT
ume is, T = p and p = V

) ( ( )
T2 p2
S2 − S1 = nCp ln − nR ln
dW = −pdV T1 p1
( ) ( ) ( ) ( )
S2 − S1 T2 T2 V1 T2 V2
where p is the pressure and V is the volume. The change in = C p ln −R ln = C v ln +R ln
n T1 T1 V2 T1 V1
enthalpy ( H = U + pV ) is given by,
Thus for isentropic processes with an ideal gas,
( )(R/Cv ) ( )(Cv /R)
V1 T1
dH = dU + pdV + V dp T2 = T1 V2 or V2 = V1 T2
5.7. ISENTROPIC PROCESS 121

Table of isentropic relations for an ideal gas [3] Münster, A. (1970). Classical Thermodynamics, translated
by E.S. Halberstadt, Wiley–Interscience, London, ISBN 0-
471-62430-6, p. 13.

[4] Haase, R. (1971). Survey of Fundamental Laws, chapter 1

Derived from: of Thermodynamics, pages 1–97 of volume 1, ed. W. Jost,
of Physical Chemistry. An Advanced Treatise, ed. H. Eyring,
D. Henderson, W. Jost, Academic Press, New York, lcn 73–
pV γ = constant 117081, p. 71.

pV = mRs T [5] Borgnakke, C., Sonntag., R.E. (2009). Fundamentals of

Thermodynamics, seventh edition, Wiley, ISBN 978-0-470-
p = ρRs T 04192-5, p. 310.

Where: [6] Massey, B.S. (1970), Mechanics of Fluids, Section 12.2 (2nd
edition) Van Nostrand Reinhold Company, London. Library
of Congress Catalog Card Number: 67-25005, p. 19.
• p = Pressure
[7] Çengel, Y.A., Boles, M.A. (2015). Thermodynamics: An
• V = Volume
Engineering Approach, 8th edition, McGraw-Hill, New
York, ISBN 978-0-07-339817-4, p. 340.
• γ = Ratio of specific heats = Cp /Cv

• T = Temperature [8] Çengel, Y.A., Boles, M.A. (2015). Thermodynamics: An

Engineering Approach, 8th edition, McGraw-Hill, New
• m = Mass York, ISBN 978-0-07-339817-4, pp. 340–341.

• Rs = Gas constant for the specific gas = R/M [9] Guggenheim, E.A. (1985). Thermodynamics. An Ad-
vanced Treatment for Chemists and Physicists, seventh edi-
• R = Universal gas constant tion, North Holland, Amsterdam, ISBN 0444869514, p. 12:
“As a limiting case between natural and unnatural processes
• M = Molecular weight of the specific gas we have reversible processes, which consist of the passage in
either direction through a continuous series of equilibrium
• ρ = Density states. Reversible processes do not actually occur ....”
• Cp = Specific heat at constant pressure
[10] Kestin, J. (1966). A Course in Thermodynamics, Blaisdell
• Cv = Specific heat at constant volume Publishing Company, Waltham MA, p. 127: “However, by
a stretch of imagination, it was accepted that a process, com-
pression or expansion, as desired, could be performed “in-
finitely slowly” or as is sometimes said, quasistatically." P.
5.7.4 See also 130: “It is clear that all natural processes are irreversible and
that reversible processes constitute convenient idealizations
• Gas laws only.”
• Adiabatic process
[11] Cengel, Yunus A., and Michaeul A. Boles. Thermodynam-
• Isenthalpic process ics: An Engineering Approach. 7th Edition ed. New York:
Mcgraw-Hill, 2012. Print.
• Isentropic analysis
[12] Cengel, Yunus A., and Michaeul A. Boles. Thermodynam-
• Polytropic process ics: An Engineering Approach. 7th Edition ed. New York:
Mcgraw-Hill, 2012. Print.

5.7.5 Notes
5.7.6 References
[1] Partington, J.R. (1949), An Advanced Treatise on Physical
Chemistry., volume 1, Fundamental Principles. The Proper-
• Van Wylen, G.J. and Sonntag, R.E. (1965), Funda-
ties of Gases, London: Longmans, Green and Co., p. 122.
mentals of Classical Thermodynamics, John Wiley &
[2] Kestin, J. (1966). A Course in Thermodynamics, Blaisdell Sons, Inc., New York. Library of Congress Catalog
Publishing Company, Waltham MA, p. 196. Card Number: 65-19470
122 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

5.8 Polytropic process

“Pantropic” redirects here. For the term used in distribu-
tions, see pantropical.

A polytropic process is a thermodynamic process that

obeys the relation:

pv n = C

where p is the pressure, v is specific volume, n is the poly-

tropic index (any real number), and C is a constant. All
processes that can be expressed as a pressure and vol-
ume product are polytropic processes. Some of those pro-
cesses (n=0,1, γ, ∞ ), are unique. This equation can ac-
curately characterize a very wide range of thermodynamic
processes, that range from n=0 to n= ∞ which covers,
n=0 (isobaric), n=1 (isothermal), n=γ (isentropic), n= ∞ Polytropic processes behave differently with various polytropic in-
dice. Polytropic process can generate other basic thermodynamic
(isochoric) processes and all values of n in between. Hence
processes.
the equation is polytropic in the sense that it describes many
lines or many processes. In addition to the behavior of
gases, it can in some cases represent some liquids and solids. Energy entering the system increases the energy of the sys-
The polytropic process equation is particularly useful for tem, and energy leaving the system decreases the energy of
characterizing expansion and compression processes which the system. The sign convention is that heat transfer into the
include heat transfer. The one restriction is that the process system is positive. Work done by the system is also positive.
should display a constant energy transfer ratio K during that With this sign convention, the heat transfer term is added
process: to du , and the work term is subtracted from du .
Define the energy transfer ratio,
K = δQ/δW = constant
δq
If it deviates from that restriction it suggests the exponent is K =
not a constant. δw

For a particular exponent, other points along the curve that δq = Kδw
describes that thermodynamic process can be calculated: For an internally reversible process the only type of work
interaction is moving boundary work, given by δw = pdv .
By substituting the above expressions for δw , and δq into
p1 v1n = p2 v2n = ... = C
The First Law it can then be written

5.8.1 Derivation
The following derivation is taken from Christians.[1] Con-
sider a gas in a closed system undergoing an internally re-
versible process with negligible changes in kinetic and po-
tential energy. The First Law of Thermodynamics states
that the energy added to a system as heat, minus the energy
that leaves the system as work, is equal to the change in the
internal energy of the system:
(K − 1)pdv = c v dT
Consider the Ideal Gas equation of state with the well-
known compressibility factor, Z: pv = ZRT. Assume the
compressibility factor is constant for the process. Assume
the gas constant is also fixed (i.e. no chemical reactions are
occurring, hence R is constant). The pv = ZRT equation of
state can be differentiated to give

δq − δw = du pdv + vdp = ZRdT

5.8. POLYTROPIC PROCESS 123

Based on the well-known specific heat relationship arising 5.8.3 Polytropic Specific Heat Capacity
from the definition of enthalpy, the term ZR can be replaced
by cp - cv. With these observations the First Law (Eq. 1) It is denoted by cn and it is equal to cn = cv γ−n
1−n
becomes

5.8.4 Relationship to ideal processes

vdp
− = (1 − γ)K + γ
pdv For certain values of the polytropic index, the process will
where γ is the ratio of specific heats c /cᵥ. This equation be synonymous with other common processes. Some ex-
will be important for understanding the basis of the poly- amples of the effects of varying index values are given in
tropic process equation. Now consider the polytropic pro- the table.
cess equation itself: When the index n is between any two of the former values
(0, 1, γ, or ∞), it means that the polytropic curve will be
bounded by the curves of the two corresponding indices.
pv n = C c
Note that 1 < γ < 2 , since γ = cvp = cvc+Rv
= 1 + cRv =
cp
Taking the natural log of both sides (recognizing that the cp −R .
exponent n is constant for a polytropic process) gives

ln p + n ln v = C
which can be differentiated and re-arranged to give
vdp
n=−
pdv
By comparing this result to the result obtained from the First
Law, it is concluded that when the energy transfer ratio
is constant for the process, the polytropic exponent is a
constant and therefore the process is polytropic. In fact
the polytropic exponent can be expressed in terms of the
energy transfer ratio:
5.8.5 Notation
In the case of an isentropic ideal gas, γ is the ratio of spe-
cific heats, known as the adiabatic index or as adiabatic ex-
ponent.
An isothermal ideal gas is also a polytropic gas. Here, the
polytropic index is equal to one, and differs from the adia-
batic index γ .
In order to discriminate between the two gammas, the poly-
tropic gamma is sometimes capitalized, Γ .
To confuse matters further, some authors refer to Γ as the
polytropic index, rather than n . Note that
1
n= Γ−1 .

n = (1 − γ)K + γ
5.8.6 Other
where the term (1 − γ) is negative for an ideal gas.
A solution to the Lane-Emden equation using a polytropic
This derivation can be expanded to include polytropic pro-
fluid is known as a polytrope.
cesses in open systems, including instances where the ki-
netic energy (i.e. Mach Number) is significant. It can also
be expanded to include irreversible polytropic processes
5.8.7 See also
(see Ref [1] ).
• Polytrope
5.8.2 Applicability • Adiabatic process
The polytropic process equation is usually applicable for re- • Isentropic process
versible or irreversible processes of ideal or near-ideal gases
involving heat transfer and/or work interactions when the • Isobaric process
energy transfer ratio δq/δw is constant for the process. The
• Isochoric process
equation may not be applicable for processes in an open sys-
tem if the kinetic energy (i.e. Mach Number) is significant. • Isothermal process
The polytropic process equation may also be applicable in
some cases to processes involving liquids, or even solids. • Vapor compression refrigeration
124 CHAPTER 5. CHAPTER 5. SYSTEM PROCESSES

• Gas compressor

• Internal combustion engine

• Quasistatic equilibrium

• Thermodynamics

5.8.8 References
[1] Christians, Joseph, “Approach for Teaching Polytropic Pro-
cesses Based on the Energy Transfer Ratio, International
Journal of Mechanical Engineering Education, Volume 40,
Number 1 (January 2012), Manchester University Press

[2] G. P. Horedt Polytropes: Applications In Astrophysics And

Related Fields, Springer, 10/08/2004, pp.24.

[3] GPSA book section 13

Chapter 6

Chapter 6. System Properties

6.1 Introduction to entropy of the fact that the entropy of the Universe never decreases
is found in the second law of thermodynamics.
In a physical system, entropy provides a measure of the
This article is a non-technical introduction to the subject. amount of thermal energy that cannot be used to do work.
For the main encyclopedia article, see Entropy. In some other definitions of entropy, it is a measure of how
evenly energy (or some analogous property) is distributed
The idea of "irreversibility" is central to the understanding in a system. Work and heat are determined by a process
of entropy. Everyone has an intuitive understanding of ir- that a system undergoes, and only occur at the boundary of
reversibility (a dissipative process) - if one watches a movie a system. Entropy is a function of the state of a system, and
of everyday life running forward and in reverse, it is easy to has a value determined by the state variables of the system.
distinguish between the two. The movie running in reverse The concept of entropy is central to the second law of ther-
shows impossible things happening - water jumping out of modynamics. The second law determines which physical
a glass into a pitcher above it, smoke going down a chimney, processes can occur. For example, it predicts that the flow
water in a glass freezing to form ice cubes, crashed cars re- of heat from a region of high temperature to a region of
assembling themselves, and so on. The intuitive meaning of low temperature is a spontaneous process – it can proceed
expressions such as “you can't unscramble an egg”, “don't along by itself without needing any extra external energy.
cry over spilled milk” or “you can't take the cream out of When this process occurs, the hot region becomes cooler
the coffee” is that these are irreversible processes. There is and the cold region becomes warmer. Heat is distributed
a direction in time by which spilled milk does not go back more evenly throughout the system and the system’s ability
into the glass. to do work has decreased because the temperature differ-
In thermodynamics, one says that the “forward” processes ence between the hot region and the cold region has de-
– pouring water from a pitcher, smoke going up a chimney, creased. Referring back to our definition of entropy, we
etc. – are “irreversible": they cannot happen in reverse, can see that the entropy of this system has increased. Thus,
even though, on a microscopic level, no laws of physics the second law of thermodynamics can be stated to say that
would be violated if they did. All real physical processes the entropy of an isolated system always increases, and such
involving systems in everyday life, with many atoms or processes which increase entropy can occur spontaneously.
molecules, are irreversible. For an irreversible process in an The entropy of a system increases as its components have
isolated system, the thermodynamic state variable known as the range of their momentum and/or position increased.
entropy is always increasing. The reason that the movie in The term entropy was coined in 1865 by the German physi-
reverse is so easily recognized is because it shows processes cist Rudolf Clausius, from the Greek words en-, “in”, and
for which entropy is decreasing, which is physically impos- trope “a turning”, in analogy with energy.[1]
sible. In everyday life, there may be processes in which the
increase of entropy is practically unobservable, almost zero.
In these cases, a movie of the process run in reverse will not 6.1.1 Explanation
seem unlikely. For example, in a 1-second video of the col-
lision of two billiard balls, it will be hard to distinguish the The concept of thermodynamic entropy arises from the
forward and the backward case, because the increase of en- second law of thermodynamics. By this law of entropy in-
tropy during that time is relatively small. In thermodynam- crease it quantifies the reduction in the capacity of a system
ics, one says that this process is practically “reversible”, with for change, for example heat always flows from a region
an entropy increase that is practically zero. The statement of higher temperature to one with lower temperature un-

125
126 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

til temperature becomes uniform or determines whether a which result in those values. The number of arrangements
thermodynamic process may occur. of molecules which could result in the same values for tem-
Entropy is calculated in two ways, the first is the entropy perature, pressure and volume is the number of microstates.
change (ΔS) to a system containing a sub-system which un- The concept of energy is related to the first law of ther-
dergoes heat transfer to its surroundings (inside the system modynamics, which deals with the conservation of energy
of interest). It is based on the macroscopic relationship be- and under which the loss in heat will result in a decrease
tween heat flow into the sub-system and the temperature in the internal energy of the thermodynamic system. Ther-
at which it occurs summed over the boundary of that sub- modynamic entropy provides a comparative measure of the
system. The second calculates the absolute entropy (S) of amount of this decrease in internal energy of the system
a system based on the microscopic behaviour of its individ- and the corresponding increase in internal energy of the sur-
ual particles. This is based on the natural logarithm of the roundings at a given temperature. A simple and more con-
number of microstates possible in a particular macrostate crete visualization of the second law is that energy of all
(W or Ω) called the thermodynamic probability. Roughly, types changes from being localized to becoming dispersed
it gives the probability of the system’s being in that state. In or spread out, if it is not hindered from doing so. Entropy
this sense it effectively defines entropy independently from change is the quantitative measure of that kind of a sponta-
its effects due to changes which may involve heat, mechan- neous process: how much energy has flowed or how widely
ical, electrical, chemical energies etc. but also includes log- it has become spread out at a specific temperature.
ical states such as information. The concept of entropy has been developed to describe any
Following the formalism of Clausius, the first calculation of several phenomena, depending on the field and the con-
can be mathematically stated as:[2] text in which it is being used. Information entropy takes the
mathematical concepts of statistical thermodynamics into
areas of probability theory unconnected with heat and en-
δq ergy.
δS = .
T
Where δS is the increase or decrease in entropy, δq is the
heat added to the system or subtracted from it, and T is
temperature. The equal sign indicates that the change is re-
versible . If the temperature is allowed to vary, the equation
must be integrated over the temperature path. This calcula-
tion of entropy change does not allow the determination of
absolute value, only differences. In this context, the Sec-
ond Law of Thermodynamics may be stated that for heat
transferred over any valid process for any system, whether
isolated or not,

δq
δS ≥ .
T
The second calculation defines entropy in absolute terms
and comes from statistical mechanics. The entropy of a
particular macrostate is defined to be Boltzmann’s constant
times the natural logarithm of the number of microstates
corresponding to that macrostate, or mathematically

S = kB ln Ω,
Where S is the entropy, kB is Boltzmann’s constant, and Ω
is the number of microstates.
The macrostate of a system is what we know about the sys-
tem, for example the temperature, pressure, and volume of Ice melting provides an example of entropy increasing
a gas in a box. For each set of values of temperature, pres-
sure, and volume there are many arrangements of molecules
6.1. INTRODUCTION TO ENTROPY
6.1.2 Example of increasing entropy
Main article: Disgregation
Ice melting provides an example in which entropy increases
in a small system, a thermodynamic system consisting of
the surroundings (the warm room) and the entity of glass
container, ice, water which has been allowed to reach
thermodynamic equilibrium at the melting temperature of
ice. In this system, some heat (δQ) from the warmer sur-
roundings at 298 K (77 °F, 25 °C) transfers to the cooler
system of ice and water at its constant temperature (T)
of 273 K (32 °F, 0 °C), the melting temperature of ice.
The entropy of the system, which is δQ/T, increases by
δQ/273K. The heat δQ for this process is the energy re-
quired to change water from the solid state to the liquid
state, and is called the enthalpy of fusion, i.e. ΔH for ice
fusion.
It is important to realize that the entropy of the surrounding
room decreases less than the entropy of the ice and water
increases: the room temperature of 298 K is larger than 273
K and therefore the ratio, (entropy change), of δQ/298K for
the surroundings is smaller than the ratio (entropy change),
of δQ/273K for the ice and water system. This is always
true in spontaneous events in a thermodynamic system and
it shows the predictive importance of entropy: the final net
entropy after such an event is always greater than was the
initial entropy.
As the temperature of the cool water rises to that of the
room and the room further cools imperceptibly, the sum
of the δQ/T over the continuous range, “at many incre-
ments”, in the initially cool to finally warm water can be
found by calculus. The entire miniature ‘universe’, i.e. this
thermodynamic system, has increased in entropy. Energy
has spontaneously become more dispersed and spread out
in that ‘universe’ than when the glass of ice and water was
introduced and became a 'system' within it.
6.1.3 Origins and uses
Originally, entropy was named to describe the “waste heat,”
or more accurately, energy loss, from heat engines and other
mechanical devices which could never run with 100% ef-
ficiency in converting energy into work. Later, the term
came to acquire several additional descriptions, as more was
understood about the behavior of molecules on the micro-
scopic level. In the late 19th century, the word “disorder”
was used by Ludwig Boltzmann in developing statistical
views of entropy using probability theory to describe the
increased molecular movement on the microscopic level.
That was before quantum behavior came to be better un-
derstood by Werner Heisenberg and those who followed.
127
Descriptions of thermodynamic (heat) entropy on the mi-
croscopic level are found in statistical thermodynamics and
statistical mechanics.
For most of the 20th century, textbooks tended to de-
scribe entropy as “disorder”, following Boltzmann’s early
conceptualisation of the “motional” (i.e. kinetic) energy of
molecules. More recently, there has been a trend in chem-
istry and physics textbooks to describe entropy as energy
dispersal.[3] Entropy can also involve the dispersal of par-
ticles, which are themselves energetic. Thus there are in-
stances where both particles and energy disperse at differ-
ent rates when substances are mixed together.
The mathematics developed in statistical thermodynam-
ics were found to be applicable in other disciplines. In
particular, information sciences developed the concept of
information entropy where a constant replaces the temper-
ature which is inherent in thermodynamic entropy.
6.1.4 Heat and entropy
At a microscopic level, kinetic energy of molecules is re-
sponsible for the temperature of a substance or a system.
“Heat” is the kinetic energy of molecules being transferred:
when motional energy is transferred from hotter surround-
ings to a cooler system, faster-moving molecules in the
surroundings collide with the walls of the system which
transfers some of their energy to the molecules of the sys-
tem and makes them move faster.
• Molecules in a gas like nitrogen at room temperature
at any instant are moving at an average speed of nearly
500 miles per hour (210 m/s), repeatedly colliding
and therefore exchanging energy so that their individ-
ual speeds are always changing. Assuming an ideal-
gas model, average kinetic energy increases linearly
with temperature, so the average speed increases as
the square root of temperature.
• Thus motional molecular energy (‘heat energy’)
from hotter surroundings, like faster-moving
molecules in a flame or violently vibrating iron
atoms in a hot plate, will melt or boil a substance
(the system) at the temperature of its melting or
boiling point. That amount of motional energy
from the surroundings that is required for melt-
ing or boiling is called the phase-change energy,
specifically the enthalpy of fusion or of vapor-
ization, respectively. This phase-change energy
breaks bonds between the molecules in the sys-
tem (not chemical bonds inside the molecules
that hold the atoms together) rather than con-
tributing to the motional energy and making
the molecules move any faster – so it does not
128
raise the temperature, but instead enables the
molecules to break free to move as a liquid or
as a vapor.
• In terms of energy, when a solid becomes a liq-
uid or a vapor, motional energy coming from the
surroundings is changed to ‘potential energy‘ in
the substance (phase change energy, which is re-
leased back to the surroundings when the sur-
roundings become cooler than the substance’s
boiling or melting temperature, respectively).
Phase-change energy increases the entropy of
a substance or system because it is energy that
must be spread out in the system from the sur-
roundings so that the substance can exist as a liq-
uid or vapor at a temperature above its melting
or boiling point. When this process occurs in a
'universe' that consists of the surroundings plus
the system, the total energy of the 'universe' be-
comes more dispersed or spread out as part of
the greater energy that was only in the hotter sur-
roundings transfers so that some is in the cooler
system. This energy dispersal increases the en-
tropy of the 'universe'.
The important overall principle is that ”Energy of all types
changes from being localized to becoming dispersed or
spread out, if not hindered from doing so. Entropy (or bet-
ter, entropy change) is the quantitative measure of that kind
of a spontaneous process: how much energy has been trans-
ferred/T or how widely it has become spread out at a specific
temperature.”
Classical calculation of entropy
When entropy was first defined and used in 1865 the very
existence of atoms was still controversial and there was no
concept that temperature was due to the motional energy
of molecules or that “heat” was actually the transferring of
that motional molecular energy from one place to another.
Entropy change, ∆S , was described in macroscopic terms
that could be directly measured, such as volume, temper-
ature, or pressure. However, today the classical equation
of entropy, ∆S = qrev T can be explained, part by part, in
modern terms describing how molecules are responsible for
what is happening:
• ∆S is the change in entropy of a system (some phys-
ical substance of interest) after some motional en-
ergy (“heat”) has been transferred to it by fast-moving
molecules. So, ∆S = Sf inal − Sinitial .
• Then, ∆S = Sf inal − Sinitial = qrev
T , the quotient
of the motional energy (“heat”) q that is transferred
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
“reversibly” (rev) to the system from the surroundings
(or from another system in contact with the first sys-
tem) divided by T, the absolute temperature at which
the transfer occurs.
• “Reversible” or “reversibly” (rev) simply means
that T, the temperature of the system, has to stay
(almost) exactly the same while any energy is be-
ing transferred to or from it. That’s easy in the
case of phase changes, where the system abso-
lutely must stay in the solid or liquid form un-
til enough energy is given to it to break bonds
between the molecules before it can change to
a liquid or a gas. For example in the melting
of ice at 273.15 K, no matter what temperature
the surroundings are – from 273.20 K to 500 K
or even higher, the temperature of the ice will
stay at 273.15 K until the last molecules in the
ice are changed to liquid water, i.e., until all the
hydrogen bonds between the water molecules in
ice are broken and new, less-exactly fixed hydro-
gen bonds between liquid water molecules are
formed. This amount of energy necessary for
ice melting per mole has been found to be 6008
joules at 273 K. Therefore, the entropy change
per mole is qrev 6008J
T = 273K , or 22 J/K.
• When the temperature isn't at the melting or
boiling point of a substance no intermolecular
bond-breaking is possible, and so any motional
molecular energy (“heat”) from the surroundings
transferred to a system raises its temperature,
making its molecules move faster and faster. As
the temperature is constantly rising, there is no
longer a particular value of “T” at which energy
is transferred. However, a “reversible” energy
transfer can be measured at a very small tem-
perature increase, and a cumulative total can be
found by adding each of many small temperature
intervals or increments. For example, to find the
entropy change qrev
T from 300 K to 310 K, mea-
sure the amount of energy transferred at dozens
or hundreds of temperature increments, say from
300.00 K to 300.01 K and then 300.01 to 300.02
and so on, dividing the q by each T, and finally
adding them all.
• Calculus can be used to make this calculation
easier if the effect of energy input to the system
is linearly dependent on the temperature change,
as in simple heating of a system at moderate
to relatively high temperatures. Thus, the en-
ergy being transferred “per incremental change
in temperature” (the heat capacity, Cp ), mul-
tiplied by the integral of dT T from Tinitial to
Tf inal
Tf inal , is directly given by ∆S = Cp ln Tinitial
6.2. ENTROPY 129

. a measure of molecular disorder within a macroscopic sys-

tem. The second law of thermodynamics states that an iso-
lated system’s entropy never decreases. Such a system spon-
6.1.5 Introductory descriptions of entropy taneously evolves towards thermodynamic equilibrium, the
state with maximum entropy. Non-isolated systems may
Traditionally, 20th century textbooks have introduced lose entropy, provided they increase their environment’s en-
entropy as order and disorder so that it provides “a mea- tropy by that increment. Since entropy is a state function,
surement of the disorder or randomness of a system”. It the change in entropy of a system is constant for any process
has been argued that ambiguities in the terms used (such with known initial and final states. This applies whether the
as “disorder” and “chaos”) contribute to widespread con- process is reversible or irreversible. However, irreversible
fusion and can hinder comprehension of entropy for most processes increase the combined entropy of the system and
students. A more recent formulation associated with Frank its environment.
L. Lambert describing entropy as energy dispersal.[3]
The change in entropy (ΔS) of a system was originally de-
fined for a thermodynamically reversible process as
6.1.6 See also
∫
• Entropy (energy dispersal) δQrev
∆S =
T
• Second law of thermodynamics
where T is the absolute temperature of the system, divid-
• Statistical mechanics
ing an incremental reversible transfer of heat into that sys-
• Thermodynamics tem (δQᵣₑᵥ). (If heat is transferred out the sign would be
reversed giving a decrease in entropy of the system.) The
above definition is sometimes called the macroscopic def-
6.1.7 References inition of entropy because it can be used without regard to
any microscopic description of the contents of a system.
[1] “etymonline.com:entropy". Retrieved 2009-06-15. The concept of entropy has been found to be generally use-
[2] I. Klotz, R. Rosenberg, Chemical Thermodynamics - Basic ful and has several other formulations. Entropy was discov-
Concepts and Methods, 7th ed., Wiley (2008), p. 125 ered when it was noticed to be a quantity that behaves as
a function of state, as a consequence of the second law of
[3] Entropy Sites — A Guide Content selected by Frank L. thermodynamics.
Lambert
Entropy is an extensive property. It has the dimension of
energy divided by temperature, which has a unit of joules
6.1.8 Further reading per kelvin (J K−1 ) in the International System of Units (or
kg m2 s−2 K−1 in terms of base units). But the entropy of a
• Goldstein, Martin and Inge F. (1993). The Refrigera- pure substance is usually given as an intensive property —
tor and the Universe: Understanding the Laws of En- either entropy per unit mass (SI unit: J K−1 kg−1 ) or entropy
ergy. Harvard Univ. Press. ISBN 9780674753259. per unit amount of substance (SI unit: J K−1 mol−1 ).
chapters=4-12 touch on entropy
The absolute entropy (S rather than ΔS) was defined later,
using either statistical mechanics or the third law of ther-
modynamics.
6.2 Entropy
In the modern microscopic interpretation of entropy in sta-
tistical mechanics, entropy is the amount of additional in-
This article is about entropy in thermodynamics. For other formation needed to specify the exact physical state of a sys-
uses, see Entropy (disambiguation). tem, given its thermodynamic specification. Understanding
Not to be confused with Enthalpy. the role of thermodynamic entropy in various processes re-
For a more accessible and less technical introduction to quires an understanding of how and why that information
this topic, see Introduction to entropy. changes as the system evolves from its initial to its final con-
dition. It is often said that entropy is an expression of the
In thermodynamics, entropy (usual symbol S) is a measure disorder, or randomness of a system, or of our lack of in-
of the number of specific realizations or microstates that formation about it. The second law is now often seen as an
may realize a thermodynamic system in a defined state spec- expression of the fundamental postulate of statistical me-
ified by macroscopic variables. Most understand entropy as chanics through the modern definition of entropy.
130
6.2.1 History
Rudolf Clausius (1822–1888), originator of the concept of entropy
Main article: History of entropy
The French mathematician Lazare Carnot proposed in his
1803 paper Fundamental Principles of Equilibrium and
Movement that in any machine the accelerations and shocks
of the moving parts represent losses of moment of activ-
ity. In other words, in any natural process there exists an
inherent tendency towards the dissipation of useful energy.
Building on this work, in 1824 Lazare’s son Sadi Carnot
published Reflections on the Motive Power of Fire which
posited that in all heat-engines, whenever "caloric" (what is
now known as heat) falls through a temperature difference,
work or motive power can be produced from the actions of
its fall from a hot to cold body. He made the analogy with
that of how water falls in a water wheel. This was an early
insight into the second law of thermodynamics.[1] Carnot
based his views of heat partially on the early 18th cen-
tury “Newtonian hypothesis” that both heat and light were
types of indestructible forms of matter, which are attracted
and repelled by other matter, and partially on the contem-
porary views of Count Rumford who showed (1789) that
heat could be created by friction as when cannon bores are
machined.[2] Carnot reasoned that if the body of the work-
ing substance, such as a body of steam, is returned to its
original state at the end of a complete engine cycle, that “no
change occurs in the condition of the working body”.
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
The first law of thermodynamics, deduced from the heat-
friction experiments of James Joule in 1843, expresses the
concept of energy, and its conservation in all processes; the
first law, however, is unable to quantify the effects of friction
and dissipation.
In the 1850s and 1860s, German physicist Rudolf Clau-
sius objected to the supposition that no change occurs in
the working body, and gave this “change” a mathemati-
cal interpretation by questioning the nature of the inher-
ent loss of usable heat when work is done, e.g. heat
produced by friction.[3] Clausius described entropy as the
transformation-content, i.e. dissipative energy use, of
a thermodynamic system or working body of chemical
species during a change of state.[3] This was in contrast to
earlier views, based on the theories of Isaac Newton, that
heat was an indestructible particle that had mass.
Later, scientists such as Ludwig Boltzmann, Josiah Willard
Gibbs, and James Clerk Maxwell gave entropy a statistical
basis. In 1877 Boltzmann visualized a probabilistic way to
measure the entropy of an ensemble of ideal gas particles,
in which he defined entropy to be proportional to the log-
arithm of the number of microstates such a gas could oc-
cupy. Henceforth, the essential problem in statistical ther-
modynamics, i.e. according to Erwin Schrödinger, has been
to determine the distribution of a given amount of energy
E over N identical systems. Carathéodory linked entropy
with a mathematical definition of irreversibility, in terms
of trajectories and integrability.
6.2.2 Definitions and descriptions
Any method involving the notion of entropy, the very ex-
istence of which depends on the second law of thermody-
namics, will doubtless seem to many far-fetched, and may
repel beginners as obscure and difficult of comprehension.
Willard Gibbs, Graphical Methods in the Thermodynamics
of Fluids[4]
There are two related definitions of entropy: the
thermodynamic definition and the statistical mechanics def-
inition. Historically, the classical thermodynamics defini-
tion developed first. In the classical thermodynamics view-
point, the system is composed of very large numbers of
constituents (atoms, molecules) and the state of the system
is described by the average thermodynamic properties of
those constituents; the details of the system’s constituents
are not directly considered, but their behavior is described
by macroscopically averaged properties, e.g. temperature,
pressure, entropy, heat capacity. The early classical def-
inition of the properties of the system assumed equilib-
rium. The classical thermodynamic definition of entropy
has more recently been extended into the area of non-
6.2. ENTROPY 131

equilibrium thermodynamics. Later, the thermodynamic treated as an irreversible process, which is usually a com-
properties, including entropy, were given an alternative def- plex task. An irreversible process increases entropy.[7]
inition in terms of the statistics of the motions of the mi- Heat transfer situations require two or more non-isolated
croscopic constituents of a system — modeled at first classi- systems in thermal contact. In irreversible heat trans-
cally, e.g. Newtonian particles constituting a gas, and later fer, heat energy is irreversibly transferred from the higher
quantum-mechanically (photons, phonons, spins, etc.). The temperature system to the lower temperature system, and
statistical mechanics description of the behavior of a system the combined entropy of the systems increases. Each sys-
is necessary as the definition of the properties of a system tem, by definition, must have its own absolute temperature
using classical thermodynamics become an increasingly un-
applicable within all areas in each respective system in or-
reliable method of predicting the final state of a system that der to calculate the entropy transfer. Thus, when a system
is subject to some process.
at higher temperature TH transfers heat dQ to a system of
lower temperature TC, the former loses entropy dQ/TH and
Function of state the latter gains entropy dQ/TC. Since TH > TC, it follows
that dQ/TH < dQ/TC, whence there is a net gain in the com-
There are many thermodynamic properties that are bined entropy.
functions of state. This means that at a particular ther-
modynamic state (which should not be confused with the Carnot cycle
microscopic state of a system), these properties have a cer-
tain value. Often, if two properties of the system are deter- The concept of entropy arose from Rudolf Clausius's study
mined, then the state is determined and the other proper- of the Carnot cycle.[8] In a Carnot cycle, heat QH is ab-
ties’ values can also be determined. For instance, a quantity sorbed at temperature TH from a 'hot' reservoir (an isother-
of gas at a particular temperature and pressure has its state mal process), and given up as heat QC to a 'cold' reservoir
fixed by those values, and has a particular volume that is (isothermal process) at TC. According to Carnot’s princi-
determined by those values. As another instance, a system ple, work can only be produced by the system when there
composed of a pure substance of a single phase at a particu- is a temperature difference, and the work should be some
lar uniform temperature and pressure is determined (and is function of the difference in temperature and the heat ab-
thus a particular state) and is at not only a particular volume sorbed (QH). Carnot did not distinguish between QH and
but also at a particular entropy.[5] The fact that entropy is QC, since he was using the incorrect hypothesis that caloric
a function of state is one reason it is useful. In the Carnot theory was valid, and hence heat was conserved (the incor-
cycle, the working fluid returns to the same state it had at rect assumption that QH and QC were equal) when, in fact,
the start of the cycle, hence the line integral of any state QH is greater than QC.[9] Through the efforts of Clausius
function, such as entropy, over the cycle is zero. and Kelvin, it is now known that the maximum work that a
system can produce is the product of the Carnot efficiency
and the heat absorbed from the hot reservoir:
Reversible process

Entropy is defined for a reversible process and for a sys-

tem that, at all times, can be treated as being at a uniform
state and thus at a uniform temperature. Reversibility is an
ideal that some real processes approximate and that is of-
ten presented in study exercises. For a reversible process,
entropy behaves as a conserved quantity and no change oc-
curs in total entropy. More specifically, total entropy is
conserved in a reversible process and not conserved in an
irreversible process.[6] One has to be careful about system
boundaries. For example, in the Carnot cycle, while the
heat flow from the hot reservoir to the cold reservoir repre-
sents an increase in entropy, the work output, if reversibly
and perfectly stored in some energy storage mechanism,
represents a decrease in entropy that could be used to op-
erate the heat engine in reverse and return to the previous
state, thus the total entropy change is still zero at all times
if the entire process is reversible. Any process that does
not meet the requirements of a reversible process must be
In order to derive the Carnot efficiency, 1-(TC/TH) (a num-
ber less than one), Kelvin had to evaluate the ratio of the
work output to the heat absorbed during the isothermal ex-
pansion with the help of the Carnot-Clapeyron equation
which contained an unknown function, known as the Carnot
function. The possibility that the Carnot function could
be the temperature as measured from a zero temperature,
was suggested by Joule in a letter to Kelvin. This allowed
Kelvin to establish his absolute temperature scale.[10] It is
also known that the work produced by the system is the dif-
ference between the heat absorbed from the hot reservoir
and the heat given up to the cold reservoir:
Since the latter is valid over the entire cycle, this gave Clau-
sius the hint that at each stage of the cycle, work and heat
132 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

would not be equal, but rather their difference would be a irreversible process prevents the cycle from outputting the
state function that would vanish upon completion of the cy- maximum amount of work as predicted by the Carnot equa-
cle. The state function was called the internal energy and it tion.
became the first law of thermodynamics.[11] The Carnot cycle and efficiency are useful because they de-
Now equating (1) and (2) gives fine the upper bound of the possible work output and the
efficiency of any classical thermodynamic system. Other
cycles, such as the Otto cycle, Diesel cycle and Brayton
QH QC cycle, can be analyzed from the standpoint of the Carnot
− =0
TH TC cycle. Any machine or process that is claimed to produce
an efficiency greater than the Carnot efficiency is not vi-
or
able because it violates the second law of thermodynamics.
For very small numbers of particles in the system, statis-
QH QC tical thermodynamics must be used. The efficiency of de-
= vices such as photovoltaic cells require an analysis from the
TH TC
standpoint of quantum mechanics.
This implies that there is a function of state which is con-
served over a complete cycle of the Carnot cycle. Clausius
called this state function entropy. One can see that entropy Classical thermodynamics
was discovered through mathematics rather than through
laboratory results. It is a mathematical construct and has Main article: Entropy (classical thermodynamics)
no easy physical analogy. This makes the concept some-
what obscure or abstract, akin to how the concept of energy
The thermodynamic definition of entropy was developed
arose.
in the early 1850s by Rudolf Clausius and essentially de-
Clausius then asked what would happen if there should be scribes how to measure the entropy of an isolated system in
less work produced by the system than that predicted by thermodynamic equilibrium with its parts. Clausius created
Carnot’s principle. The right-hand side of the first equation the term entropy as an extensive thermodynamic variable
would be the upper bound of the work output by the system, that was shown to be useful in characterizing the Carnot
which would now be converted into an inequality cycle. Heat transfer along the isotherm steps of the Carnot
cycle was found to be proportional to the temperature of a
( ) system (known as its absolute temperature). This relation-
TC ship was expressed in increments of entropy equal to the
W < 1− QH
TH ratio of incremental heat transfer divided by temperature,
which was found to vary in the thermodynamic cycle but
When the second equation is used to express the work as a eventually return to the same value at the end of every cy-
difference in heats, we get cle. Thus it was found to be a function of state, specifically
( ) a thermodynamic state of the system. Clausius wrote that
QH − QC < 1 − TTH C
QH he “intentionally formed the word Entropy as similar as pos-
sible to the word Energy”, basing the term on the Greek ἡ
or
τροπή tropē, “transformation”.[12][note 1]
QC > TTH C
QH
While Clausius based his definition on a reversible process,
there are also irreversible processes that change entropy.
So more heat is given up to the cold reservoir than in the Following the second law of thermodynamics, entropy of an
Carnot cycle. If we denote the entropies by Sᵢ=Qᵢ/Tᵢ for isolated system always increases. The difference between
the two states, then the above inequality can be written as a an isolated system and closed system is that heat may not
decrease in the entropy flow to and from an isolated system, but heat flow to and
from a closed system is possible. Nevertheless, for both
SH − SC < 0 closed and isolated systems, and indeed, also in open sys-
or tems, irreversible thermodynamics processes may occur.
SH < SC According H to the Clausius equality, for a reversible
∫ cyclic
process: δQTrev = 0. This means the line integral L δQTrev
In other words, the entropy that leaves the system is greater is path-independent.
than the entropy that enters the system, implying that some So we can define a state function S called entropy, which
6.2. ENTROPY 133

δQrev
satisfies dS = T .
To find the entropy difference between any two states of a
system, the integral must be evaluated for some reversible
path between the initial and final states.[13] Since entropy
is a state function, the entropy change of the system for an
irreversible path will be the same as for a reversible path be-
tween the same two states.[14] However, the entropy change
of the surroundings will be different.
sure of “disorder” (the higher the entropy, the higher the
disorder).[15][16][17] This definition describes the entropy as
being proportional to the natural logarithm of the number of
possible microscopic configurations of the individual atoms
and molecules of the system (microstates) which could give
rise to the observed macroscopic state (macrostate) of the
system. The constant of proportionality is the Boltzmann
constant.

We can only obtain the change of entropy by integrating the Specifically, entropy is a logarithmic measure of the number
above formula. To obtain the absolute value of the entropy, of states with significant probability of being occupied:
we need the third law of thermodynamics, which states that
S = 0 at absolute zero for perfect crystals. ∑
S = −kB pi ln pi ,
From a macroscopic perspective, in classical thermody-
i
namics the entropy is interpreted as a state function of a
thermodynamic system: that is, a property depending only where kB is the Boltzmann constant, equal to
on the current state of the system, independent of how that 1.38065×10−23 J/K. The summation is over all the
state came to be achieved. In any process where the system possible microstates of the system, and pi is the probability
gives up energy ΔE, and its entropy falls by ΔS, a quantity that the system is in the i-th microstate.[18] This definition
at least TR ΔS of that energy must be given up to the sys- assumes that the basis set of states has been picked so
tem’s surroundings as unusable heat (TR is the temperature that there is no information on their relative phases. In a
of the system’s external surroundings). Otherwise the pro- different basis set, the more general expression is
cess will not go forward. In classical thermodynamics, the
entropy of a system is defined only if it is in thermodynamic
equilibrium. S = −k Tr (b ρ ln(bρ)),
B

where ρb is the density matrix, Tr is trace (linear algebra)

Statistical mechanics
and ln is the matrix logarithm. This density matrix formu-
lation is not needed in cases of thermal equilibrium so long
The statistical definition was developed by Ludwig Boltz-
as the basis states are chosen to be energy eigenstates. For
mann in the 1870s by analyzing the statistical behavior of
most practical purposes, this can be taken as the fundamen-
the microscopic components of the system. Boltzmann
tal definition of entropy since all other formulas for S can
showed that this definition of entropy was equivalent to the
be mathematically derived from it, but not vice versa.
thermodynamic entropy to within a constant number which
has since been known as Boltzmann’s constant. In sum- In what has been called the fundamental assumption of sta-
mary, the thermodynamic definition of entropy provides tistical thermodynamics or the fundamental postulate in sta-
the experimental definition of entropy, while the statisti- tistical mechanics, the occupation of any microstate is as-
cal definition of entropy extends the concept, providing an sumed to be equally probable (i.e. Pi = 1/Ω, where Ω is the
explanation and a deeper understanding of its nature. number of microstates); this assumption is usually justified
for an isolated system in equilibrium.[19] Then the previous
The interpretation of entropy in statistical mechanics is the
equation reduces to
measure of uncertainty, or mixedupness in the phrase of
Gibbs, which remains about a system after its observable
macroscopic properties, such as temperature, pressure and
volume, have been taken into account. For a given set of S = kB ln Ω.
macroscopic variables, the entropy measures the degree to
which the probability of the system is spread out over dif- In thermodynamics, such a system is one in which the vol-
ferent possible microstates. In contrast to the macrostate, ume, number of molecules, and internal energy are fixed
which characterizes plainly observable average quantities, (the microcanonical ensemble).
a microstate specifies all molecular details about the sys- The most general interpretation of entropy is as a measure
tem including the position and velocity of every molecule. of our uncertainty about a system. The equilibrium state
The more such states available to the system with apprecia- of a system maximizes the entropy because we have lost all
ble probability, the greater the entropy. In statistical me- information about the initial conditions except for the con-
chanics, entropy is a measure of the number of ways in served variables; maximizing the entropy maximizes our ig-
which a system may be arranged, often taken to be a mea- norance about the details of the system.[20] This uncertainty
134 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

100,000 ft^3/lbm
10,000 ft^3/lbm

20,000 ft^3/lbm

50,000 ft^3/lbm
is not of the everyday subjective kind, but rather the uncer-

1000 ft^3/lbm

2000 ft^3/lbm

5000 ft^3/lbm
100 ft^3/lbm

200 ft^3/lbm

500 ft^3/lbm
100,000 psi
.02 ft^3/lbm

.05 ft^3/lbm

10 ft^3/lbm

20 ft^3/lbm

50 ft^3/lbm
50,000 psi

20,000 psi

10,000 psi
.1 ft^3/lbm

.2 ft^3/lbm

.5 ft^3/lbm

1 ft^3/lbm

2 ft^3/lbm

5 ft^3/lbm
5000 psi

2000 psi

1000 psi

500 psi

200 psi

100 psi

.05 psi

.02 psi

.01 psi
50 psi

20 psi
10 psi

.5 psi

.2 psi

.1 psi
5 psi

2 psi

1 psi
tainty inherent to the experimental method and interpreta-
2200

2100

tive model. 2000

The interpretative model has a central role in determining 1900

entropy. The qualifier “for a given set of macroscopic vari- 1800

ables” above has deep implications: if two observers use 1700

supercritical region

different sets of macroscopic variables, they will observe 1600

different entropies. For example, if observer A uses the 1500

variables U, V and W, and observer B uses U, V, W, X,

1400

temperature, R
then, by changing X, observer B can cause an effect that
1300

vapor region
liquid region

1200

looks like a violation of the second law of thermodynam- 1100

ics to observer A. In other words: the set of macroscopic 1000

variables one chooses must include everything that may 900

change in the experiment, otherwise one might see decreas- 800

ing entropy![21] 700

saturated region

Entropy can be defined for any Markov processes with 600

reversible dynamics and the detailed balance property.

500

10%

100%
70%
0%

30%

50%

60%

80%

90%
20%

quality
40%
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0 2.2 2.4 2.6 2.8 3.0 3.2
entropy, Btu/lbm-R

In Boltzmann’s 1896 Lectures on Gas Theory, he showed

that this expression gives a measure of entropy for systems A temperature–entropy diagram for steam. The vertical axis repre-
of atoms and molecules in the gas phase, thus providing a sents uniform temperature, and the horizontal axis represents spe-
measure for the entropy of classical thermodynamics. cific entropy. Each dark line on the graph represents constant pres-
sure, and these form a mesh with light gray lines of constant volume.
(Dark-blue is liquid water, light-blue is liquid-steam mixture, and
Entropy of a system faint-blue is steam. Grey-blue represents supercritical liquid water.)

mechanics. As an example, for a glass of ice water in air at

SURROUNDINGS room temperature, the difference in temperature between
a warm room (the surroundings) and cold glass of ice and
water (the system and not part of the room), begins to be
equalized as portions of the thermal energy from the warm
surroundings spread to the cooler system of ice and wa-
ter. Over time the temperature of the glass and its contents
and the temperature of the room become equal. The en-
SYSTEM tropy of the room has decreased as some of its energy has
been dispersed to the ice and water. However, as calcu-
lated in the example, the entropy of the system of ice and
water has increased more than the entropy of the surround-
ing room has decreased. In an isolated system such as the
room and ice water taken together, the dispersal of energy
BOUNDARY from warmer to cooler always results in a net increase in en-
tropy. Thus, when the “universe” of the room and ice water
system has reached a temperature equilibrium, the entropy
A thermodynamic system change from the initial state is at a maximum. The entropy
of the thermodynamic system is a measure of how far the
Entropy is the above-mentioned unexpected and, to some, equalization has progressed.
obscure integral that arises directly from the Carnot cycle. Thermodynamic entropy is a non-conserved state func-
It is reversible heat divided by temperature. It is also, re- tion that is of great importance in the sciences of physics
markably, a fundamental and very useful function of state. and chemistry.[15][22] Historically, the concept of entropy
In a thermodynamic system, pressure, density, and tem- evolved in order to explain why some processes (per-
perature tend to become uniform over time because this mitted by conservation laws) occur spontaneously while
equilibrium state has higher probability (more possible their time reversals (also permitted by conservation laws)
combinations of microstates) than any other; see statistical do not; systems tend to progress in the direction of in-
6.2. ENTROPY
creasing entropy.[23][24] For isolated systems, entropy never
decreases.[22] This fact has several important consequences
in science: first, it prohibits "perpetual motion" machines;
and second, it implies the arrow of entropy has the same
direction as the arrow of time. Increases in entropy cor-
respond to irreversible changes in a system, because some
energy is expended as waste heat, limiting the amount of
work a system can do.[15][16][25][26]
Unlike many other functions of state, entropy cannot be di-
rectly observed but must be calculated. Entropy can be cal-
culated for a substance as the standard molar entropy from
absolute zero (also known as absolute entropy) or as a dif-
ference in entropy from some other reference state which
is defined as zero entropy. Entropy has the dimension of
energy divided by temperature, which has a unit of joules
per kelvin (J/K) in the International System of Units. While
these are the same units as heat capacity, the two concepts
are distinct.[27] Entropy is not a conserved quantity: for ex-
ample, in an isolated system with non-uniform temperature,
heat might irreversibly flow and the temperature become
more uniform such that entropy increases. The second law
of thermodynamics, states that a closed system has entropy
which may increase or otherwise remain constant. Chemi-
cal reactions cause changes in entropy and entropy plays an
important role in determining in which direction a chemical
reaction spontaneously proceeds.
One dictionary definition of entropy is that it is “a measure
of thermal energy per unit temperature that is not available
for useful work”. For instance, a substance at uniform tem-
perature is at maximum entropy and cannot drive a heat en-
gine. A substance at non-uniform temperature is at a lower
entropy (than if the heat distribution is allowed to even out)
and some of the thermal energy can drive a heat engine.
A special case of entropy increase, the entropy of mixing, by probability, thus allowing for a decrease in disorder
occurs when two or more different substances are mixed. even in an isolated system. Although this is possible, such
If the substances are at the same temperature and pres- an event has a small probability of occurring, making it
sure, there will be no net exchange of heat or work – the unlikely.[30]
entropy change will be entirely due to the mixing of the
different substances. At a statistical mechanical level, this
results due to the change in available volume per particle 6.2.4 Applications
with mixing.[28]
6.2.3 Second law of thermodynamics
Main article: Second law of thermodynamics
The second law of thermodynamics requires that, in gen-
eral, the total entropy of any system will not decrease
other than by increasing the entropy of some other system.
Hence, in a system isolated from its environment, the en-
tropy of that system will tend not to decrease. It follows
135
that heat will not flow from a colder body to a hotter body
without the application of work (the imposition of order)
to the colder body. Secondly, it is impossible for any de-
vice operating on a cycle to produce net work from a single
temperature reservoir; the production of net work requires
flow of heat from a hotter reservoir to a colder reservoir,
or a single expanding reservoir undergoing adiabatic cool-
ing, which performs adiabatic work. As a result, there is no
possibility of a perpetual motion system. It follows that a
reduction in the increase of entropy in a specified process,
such as a chemical reaction, means that it is energetically
more efficient.
It follows from the second law of thermodynamics that the
entropy of a system that is not isolated may decrease. An air
conditioner, for example, may cool the air in a room, thus
reducing the entropy of the air of that system. The heat
expelled from the room (the system), which the air con-
ditioner transports and discharges to the outside air, will
always make a bigger contribution to the entropy of the en-
vironment than will the decrease of the entropy of the air
of that system. Thus, the total of entropy of the room plus
the entropy of the environment increases, in agreement with
the second law of thermodynamics.
In mechanics, the second law in conjunction with the
fundamental thermodynamic relation places limits on a sys-
tem’s ability to do useful work.[29] The entropy change of a
system at temperature T absorbing an infinitesimal amount
of heat δq in a reversible way, is given by δq/T. More explic-
itly, an energy TR S is not available to do useful work, where
TR is the temperature of the coldest accessible reservoir or
heat sink external to the system. For further discussion, see
Exergy.
Statistical mechanics demonstrates that entropy is governed
The fundamental thermodynamic relation
Main article: Fundamental thermodynamic relation
The entropy of a system depends on its internal energy and
its external parameters, such as its volume. In the ther-
modynamic limit, this fact leads to an equation relating the
change in the internal energy U to changes in the entropy
and the external parameters. This relation is known as the
fundamental thermodynamic relation. If external pressure
P bears on the volume V as the only external parameter,
this relation is:
136 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

rection of complex chemical reactions. For such applica-

dU = T dS − P dV
Since both internal energy and entropy are monotonic func-
tions of temperature T, implying that the internal energy is
fixed when one specifies the entropy and the volume, this re-
lation is valid even if the change from one state of thermal
equilibrium to another with infinitesimally larger entropy
and volume happens in a non-quasistatic way (so during this
change the system may be very far out of thermal equilib- Entropy balance equation for open systems
rium and then the entropy, pressure and temperature may
not exist).
The fundamental thermodynamic relation implies many
thermodynamic identities that are valid in general, indepen-
dent of the microscopic details of the system. Important ex-
amples are the Maxwell relations and the relations between
heat capacities.
tions, ΔS must be incorporated in an expression that in-
cludes both the system and its surroundings, ΔSᵤ ᵢᵥₑᵣ ₑ =
ΔS ᵤᵣᵣₒᵤ ᵢ + ΔS ₑ . This expression becomes, via some
steps, the Gibbs free energy equation for reactants and
products in the system: ΔG [the Gibbs free energy change
of the system] = ΔH [the enthalpy change] −T ΔS [the en-
tropy change].[31]
Heat added
Q
Work performed
external to boundary
Wshaft

Hout
Entropy in chemical thermodynamics

Thermodynamic entropy is central in chemical thermody- Hin

namics, enabling changes to be quantified and the outcome System boundary (open)
of reactions predicted. The second law of thermodynam-
ics states that entropy in an isolated system – the combi-
nation of a subsystem under study and its surroundings – During steady-state continuous operation, an entropy balance ap-
increases during all spontaneous chemical and physical pro- plied to an open system accounts for system entropy changes related
cesses. The Clausius equation of δqᵣₑᵥ/T = ΔS introduces to heat flow and mass flow across the system boundary.
the measurement of entropy change, ΔS. Entropy change
describes the direction and quantifies the magnitude of sim- In chemical engineering, the principles of thermodynam-
ple changes such as heat transfer between systems – always ics are commonly applied to "open systems", i.e. those in
from hotter to cooler spontaneously. which heat, work, and mass flow across the system bound-
The thermodynamic entropy therefore has the dimension of ary. Flows of both heat ( Q̇ ) and work, i.e. ẆS (shaft
energy divided by temperature, and the unit joule per kelvin work) and P(dV/dt) (pressure-volume work), across the sys-
(J/K) in the International System of Units (SI). tem boundaries, in general cause changes in the entropy of
the system. Transfer as heat entails entropy transfer Q̇/T,
Thermodynamic entropy is an extensive property, meaning
where T is the absolute thermodynamic temperature of the
that it scales with the size or extent of a system. In many system at the point of the heat flow. If there are mass flows
processes it is useful to specify the entropy as an intensive across the system boundaries, they will also influence the
property independent of the size, as a specific entropy char- total entropy of the system. This account, in terms of heat
acteristic of the type of system studied. Specific entropy and work, is valid only for cases in which the work and heat
may be expressed relative to a unit of mass, typically the transfers are by paths physically distinct from the paths of
kilogram (unit: Jkg−1 K−1 ). Alternatively, in chemistry, it isentry and exit of matter from the system.[34][35]
also referred to one mole of substance, in which case it is
called the molar entropy with a unit of Jmol−1 K−1 . To derive a generalized entropy balanced equation, we start
with the general balance equation for the change in any
Thus, when one mole of substance at about 0K is warmed extensive quantity Θ in a thermodynamic system, a quan-
by its surroundings to 298K, the sum of the incremental val- tity that may be either conserved, such as energy, or non-
ues of qᵣₑᵥ/T constitute each element’s or compound’s stan- conserved, such as entropy. The basic generic balance ex-
dard molar entropy, an indicator of the amount of energy pression states that dΘ/dt, i.e. the rate of change of Θ in
stored by a substance at 298K.[31][32] Entropy change also the system, equals the rate at which Θ enters the system at
measures the mixing of substances as a summation of their the boundaries, minus the rate at which Θ leaves the sys-
relative quantities in the final mixture.[33] tem across the system boundaries, plus the rate at which
Entropy is equally essential in predicting the extent and di- Θ is generated within the system. For an open thermody-
6.2. ENTROPY 137

namic system in which heat and work are transferred by
paths separate from the paths for transfer of matter, using
this generic balance equation, with respect to the rate of
change with time t of the extensive quantity entropy S, the
entropy balance equation is:[36][note 2]
Cooling and heating
For heating or cooling of any system (gas, liquid or solid) at
constant pressure from an initial temperature T0 to a final
temperature T , the entropy change is

dS ∑ K
Q̇ ∆S = nCP ln
T
= Ṁk Ŝk + + Ṡgen T0
dt T
k=1
provided that the constant-pressure molar heat capacity (or
where specific heat) CP is constant and that no phase transition
∑K occurs in this temperature interval.
k=1 Ṁk Ŝk = the net rate of entropy flow due
to the flows of mass into and out of the system Similarly at constant volume, the entropy change is
(where Ŝ = entropy per unit mass).
Q̇ T
= the rate of entropy flow due to the flow of
T ∆S = nCv ln
heat across the system boundary. T0
Ṡgen = the rate of entropy production within the where the constant-volume heat capacity Cᵥ is constant and
system. This entropy production arises from pro- there is no phase change.
cesses within the system, including chemical re-
At low temperatures near absolute zero, heat capacities of
actions, internal matter diffusion, internal heat
solids quickly drop off to near zero, so the assumption of
transfer, and frictional effects such as viscos-
constant heat capacity does not apply.[38]
ity occurring within the system from mechanical
work transfer to or from the system. Since entropy is a state function, the entropy change of any
process in which temperature and volume both vary is the
Note, also, that if there are
∑ multiple heat flows, the term same as for a path divided into two steps - heating at con-
Q̇/T will be replaced by Q̇j /Tj , where Q̇j is the heat stant volume and expansion at constant temperature. For an
flow and Tj is the temperature at the jth heat flow port into ideal gas, the total entropy change is[39]
the system.

T V
∆S = nC ln + nR ln
6.2.5 Entropy change formulas for simple v
T0 V0
processes Similarly if the temperature and pressure of an ideal gas
both vary,
For certain simple transformations in systems of constant
composition, the entropy changes are given by simple
formulas.[37] T P
∆S = nCP ln − nR ln
T0 P0
Isothermal expansion or compression of an ideal gas
Phase transitions
For the expansion (or compression) of an ideal gas from
an initial volume V0 and pressure P0 to a final volume V Reversible phase transitions occur at constant temperature
and pressure P at any constant temperature, the change in and pressure. The reversible heat is the enthalpy change
entropy is given by: for the transition, and the entropy change is the enthalpy
change divided by the thermodynamic temperature. For fu-
sion (melting) of a solid to a liquid at the melting point T ,
V P the entropy of fusion is
∆S = nR ln = −nR ln .
V0 P0
Here n is the number of moles of gas and R is the ideal
∆Hfus
gas constant. These equations also apply for expansion into ∆Sfus = .
a finite vacuum or a throttling process, where the temper- Tm
ature, internal energy and enthalpy for an ideal gas remain Similarly, for vaporization of a liquid to a gas at the boiling
constant. point T , the entropy of vaporization is
138 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

measure of the total amount of “disorder” in the system is

given by:[43][44]
∆Hvap
∆Svap = .
Tb
CD
Disorder = .
6.2.6 Approaches to understanding entropy CI
Similarly, the total amount of “order” in the system is given
As a fundamental aspect of thermodynamics and physics, by:
several different approaches to entropy beyond that of Clau-
sius and Boltzmann are valid.
CO
Order = 1 − .
Standard textbook definitions CI
In which CD is the “disorder” capacity of the system, which
The following is a list of additional definitions of entropy is the entropy of the parts contained in the permitted en-
from a collection of textbooks: semble, CI is the “information” capacity of the system, an
expression similar to Shannon’s channel capacity, and CO
• a measure of energy dispersal at a specific tempera- is the “order” capacity of the system.[42]
ture.

• a measure of disorder in the universe or of the avail- Energy dispersal

ability of the energy in a system to do work.[40]
Main article: Entropy (energy dispersal)
• a measure of a system’s thermal energy per unit tem-
perature that is unavailable for doing useful work.[41]
The concept of entropy can be described qualitatively as a
measure of energy dispersal at a specific temperature.[45]
In Boltzmann’s definition, entropy is a measure of the num- Similar terms have been in use from early in the history
ber of possible microscopic states (or microstates) of a sys- of classical thermodynamics, and with the development of
tem in thermodynamic equilibrium. Consistent with the statistical thermodynamics and quantum theory, entropy
Boltzmann definition, the second law of thermodynamics changes have been described in terms of the mixing or
needs to be re-worded as such that entropy increases over “spreading” of the total energy of each constituent of a sys-
time, though the underlying principle remains the same. tem over its particular quantized energy levels.
Ambiguities in the terms disorder and chaos, which usu-
Order and disorder ally have meanings directly opposed to equilibrium, con-
tribute to widespread confusion and hamper comprehen-
Main article: Entropy (order and disorder) sion of entropy for most students.[46] As the second law of
thermodynamics shows, in an isolated system internal por-
tions at different temperatures will tend to adjust to a sin-
Entropy has often been loosely associated with the amount gle uniform temperature and thus produce equilibrium. A
of order or disorder, or of chaos, in a thermodynamic sys- recently developed educational approach avoids ambiguous
tem. The traditional qualitative description of entropy is terms and describes such spreading out of energy as dis-
that it refers to changes in the status quo of the system andpersal, which leads to loss of the differentials required for
is a measure of “molecular disorder” and the amount of work even though the total energy remains constant in ac-
wasted energy in a dynamical energy transformation from cordance with the first law of thermodynamics[47] (compare
one state or form to another. In this direction, several re- discussion in next section). Physical chemist Peter Atkins,
cent authors have derived exact entropy formulas to account for example, who previously wrote of dispersal leading to a
for and measure disorder and order in atomic and molec- disordered state, now writes that “spontaneous changes are
ular assemblies.[42][43][44] One of the simpler entropy or- always accompanied by a dispersal of energy”.[48]
der/disorder formulas is that derived in 1984 by thermody-
namic physicist Peter Landsberg, based on a combination
of thermodynamics and information theory arguments. He Relating entropy to energy usefulness
argues that when constraints operate on a system, such that
it is prevented from entering one or more of its possible or Following on from the above, it is possible (in a thermal
permitted states, as contrasted with its forbidden states, the context) to regard entropy as an indicator or measure of
6.2. ENTROPY 139

the effectiveness or usefulness of a particular quantity of

energy.[49] This is because energy supplied at a high tem- ∑
perature (i.e. with low entropy) tends to be more useful S = −kB pi log pi
than the same amount of energy available at room tempera- i

ture. Mixing a hot parcel of a fluid with a cold one produces i.e. in such a basis the density matrix is diagonal.
a parcel of intermediate temperature, in which the overall
increase in entropy represents a “loss” which can never be Von Neumann established a rigorous mathematical frame-
replaced. work for quantum mechanics with his work Mathematis-
che Grundlagen der Quantenmechanik. He provided in this
Thus, the fact that the entropy of the universe is steadily in- work a theory of measurement, where the usual notion of
creasing, means that its total energy is becoming less useful: wave function collapse is described as an irreversible pro-
eventually, this will lead to the "heat death of the Universe". cess (the so-called von Neumann or projective measure-
ment). Using this concept, in conjunction with the density
Entropy and adiabatic accessibility matrix he extended the classical concept of entropy into the
quantum domain.
A definition of entropy based entirely on the relation of
adiabatic accessibility between equilibrium states was given Information theory
by E.H.Lieb and J. Yngvason in 1999.[50] This approach
has several predecessors, including the pioneering work of I thought of calling it “information”, but the word was overly
Constantin Carathéodory from 1909 [51] and the monograph used, so I decided to call it “uncertainty”. [...] Von Neu-
by R. Giles from 1964.[52] In the setting of Lieb and Yngva- mann told me, “You should call it entropy, for two reasons.
son one starts by picking, for a unit amount of the substance In the first place your uncertainty function has been used
under consideration, two reference states X0 and X1 such in statistical mechanics under that name, so it already has
that the latter is adiabatically accessible from the former a name. In the second place, and more important, nobody
but not vice versa. Defining the entropies of the reference knows what entropy really is, so in a debate you will always
states to be 0 and 1 respectively the entropy of a state X is have the advantage.”
defined as the largest number λ such that X is adiabatically
accessible from a composite state consisting of an amount Conversation between Claude Shannon and John von Neu-
λ in the state X1 and a complementary amount, (1 − λ) , mann regarding what name to give to the attenuation in
in the state X0 . A simple but important result within this phone-line signals[53]
setting is that entropy is uniquely determined, apart from a Main articles: Entropy (information theory), Entropy in
choice of unit and an additive constant for each chemical thermodynamics and information theory and Entropic
element, by the following properties: It is monotonic with uncertainty
respect to the relation of adiabatic accessibility, additive on
composite systems, and extensive under scaling.
When viewed in terms of information theory, the entropy
state function is simply the amount of information (in the
Entropy in quantum mechanics Shannon sense) that would be needed to specify the full mi-
crostate of the system. This is left unspecified by the macro-
Main article: von Neumann entropy scopic description.
In information theory, entropy is the measure of the amount
In quantum statistical mechanics, the concept of entropy of information that is missing before reception and is some-
was developed by John von Neumann and is generally re- times referred to as Shannon entropy.[54] Shannon entropy
ferred to as "von Neumann entropy", is a broad and general concept which finds applications
in information theory as well as thermodynamics. It was
originally devised by Claude Shannon in 1948 to study the
S = −kB Tr(ρ log ρ) amount of information in a transmitted message. The defi-
nition of the information entropy is, however, quite general,
where ρ is the density matrix and Tr is the trace operator. and is expressed in terms of a discrete set of probabilities
This upholds the correspondence principle, because in the pi so that
classical limit, when the phases between the basis states
used for the classical probabilities are purely random, this
∑n
expression is equivalent to the familiar classical definition H(X) = − p(xi ) log p(xi ).
of entropy, i=1
140
In the case of transmitted messages, these probabilities Thermodynamic and statistical mechanics concepts
were the probabilities that a particular message was actu-
ally transmitted, and the entropy of the message system was
a measure of the average amount of information in a mes-
sage. For the case of equal probabilities (i.e. each message
is equally probable), the Shannon entropy (in bits) is just the
number of yes/no questions needed to determine the con-
tent of the message.[18]
The question of the link between information entropy
and thermodynamic entropy is a debated topic. While
most authors argue that there is a link between the
two,[55][56][57][58][59] a few argue that they have nothing to
do with each other.[18]
The expressions for the two entropies are similar. If W is
the number of microstates that can yield a given macrostate,
and each microstate has the same A priori probability, then
that probability is p=1/W. The Shannon entropy (in nats)
will be:
∑
W • Residual entropy – the entropy present after a sub-
H=− p log(p) = log(W )
i=1
and if entropy is measured in units of k per nat, then the
entropy is given[60] by:
H = k log(W )
which is the famous Boltzmann entropy formula when k
is Boltzmann’s constant, which may be interpreted as the
thermodynamic entropy per nat. There are many ways
of demonstrating the equivalence of “information entropy”
and “physics entropy”, that is, the equivalence of “Shannon
entropy” and “Boltzmann entropy”. Nevertheless, some au-
thors argue for dropping the word entropy for the H func-
tion of information theory and using Shannon’s other term
“uncertainty” instead.[61]
6.2.7 Interdisciplinary applications of en-
tropy
Although the concept of entropy was originally a
thermodynamic construct, it has been adapted in
other fields of study, including information theory,
psychodynamics, thermoeconomics/ecological economics,
and evolution.[42][62][63][64][65] For instance, an entropic
argument has been recently proposed for explaining the
preference of cave spiders in choosing a suitable area for
laying their eggs.[66]
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
• Entropy unit – a non-S.I. unit of thermodynamic en-
tropy, usually denoted “e.u.” and equal to one calorie
per Kelvin per mole, or 4.184 Joules per Kelvin per
mole.[67]
• Gibbs entropy – the usual statistical mechanical en-
tropy of a thermodynamic system.
• Boltzmann entropy – a type of Gibbs entropy, which
neglects internal statistical correlations in the overall
particle distribution.
• Tsallis entropy – a generalization of the standard
Boltzmann-Gibbs entropy.
• Standard molar entropy – is the entropy content of one
mole of substance, under conditions of standard tem-
perature and pressure.
stance is cooled arbitrarily close to absolute zero.
• Entropy of mixing – the change in the entropy when
two different chemical substances or components are
mixed.
• Loop entropy – is the entropy lost upon bringing to-
gether two residues of a polymer within a prescribed
distance.
• Conformational entropy – is the entropy associated
with the physical arrangement of a polymer chain that
assumes a compact or globular state in solution.
• Entropic force – a microscopic force or reaction ten-
dency related to system organization changes, molecu-
lar frictional considerations, and statistical variations.
• Free entropy – an entropic thermodynamic potential
analogous to the free energy.
• Entropic explosion – an explosion in which the reac-
tants undergo a large change in volume without releas-
ing a large amount of heat.
• Entropy change – a change in entropy dS between
two equilibrium states is given by the heat transferred
dQrev divided by the absolute temperature T of the
system in this interval.
• Sackur-Tetrode entropy – the entropy of a monatomic
classical ideal gas determined via quantum considera-
tions.
6.2. ENTROPY 141

The arrow of time The entropy gap is widely believed to have been originally
opened up by the early rapid exponential expansion of the
Main article: Entropy (arrow of time) universe.

Entropy is the only quantity in the physical sciences that Economics

seems to imply a particular direction of progress, some-
times called an arrow of time. As time progresses, the sec- See also: Nicholas Georgescu-Roegen § The relevance of
ond law of thermodynamics states that the entropy of an thermodynamics to economics and Ecological economics §
isolated system never decreases. Hence, from this perspec- Methodology
tive, entropy measurement is thought of as a kind of clock.
Romanian American economist Nicholas Georgescu-
Roegen, a progenitor in economics and a paradigm founder
Cosmology of ecological economics, made extensive use of the entropy
concept in his magnum opus on The Entropy Law and the
Main article: Heat death of the universe Economic Process.[75] Due to Georgescu-Roegen’s work,
the laws of thermodynamics now form an integral part of
the ecological economics school.[76]:204f [77]:29-35 Although
Since a finite universe is an isolated system, the Second Law
his work was blemished somewhat by mistakes, a full chap-
of Thermodynamics states that its total entropy is constantly
ter on the economics of Georgescu-Roegen has approvingly
increasing. It has been speculated, since the 19th century,
been included in one elementary physics textbook on the
that the universe is fated to a heat death in which all the
historical development of thermodynamics.[78]:95-112
energy ends up as a homogeneous distribution of thermal
energy, so that no more work can be extracted from any In economics, Georgescu-Roegen’s work has generated the
source. term 'entropy pessimism'.[79]:116 Since the 1990s, lead-
ing ecological economist and steady-state theorist Herman
If the universe can be considered to have generally increas-
Daly — a student of Georgescu-Roegen — has been the
ing entropy, then – as Sir Roger Penrose has pointed out –
economists profession’s most influential proponent of the
gravity plays an important role in the increase because grav-
entropy pessimism position.[80]:545f
ity causes dispersed matter to accumulate into stars, which
collapse eventually into black holes. The entropy of a black
hole is proportional to the surface area of the black hole’s 6.2.8 See also
event horizon.[68] Jacob Bekenstein and Stephen Hawking
have shown that black holes have the maximum possible • Autocatalytic reactions and order creation
entropy of any object of equal size. This makes them likely
end points of all entropy-increasing processes, if they are • Brownian ratchet
totally effective matter and energy traps. However, the es-
• Clausius–Duhem inequality
cape of energy from black holes might be possible due to
quantum activity, see Hawking radiation. Hawking has re- • Configuration entropy
cently changed his stance on some details, in a paper which
largely redefined the event horizons of black holes.[69] • Departure function

The role of entropy in cosmology remains a controversial • Enthalpy

subject since the time of Ludwig Boltzmann. Recent work
• Entropic force
has cast some doubt on the heat death hypothesis and the
applicability of any simple thermodynamic model to the • Entropy (information theory)
universe in general. Although entropy does increase in the
model of an expanding universe, the maximum possible en- • Entropy (computing)
tropy rises much more rapidly, moving the universe further
• Entropy and life
from the heat death with time, not closer.[70][71][72] This re-
sults in an “entropy gap” pushing the system further away • Entropy (order and disorder)
from the posited heat death equilibrium.[73] Other compli-
cating factors, such as the energy density of the vacuum and • Entropy rate
macroscopic quantum effects, are difficult to reconcile with • Geometrical frustration
thermodynamical models, making any predictions of large-
scale thermodynamics extremely difficult.[74] • Laws of thermodynamics
142
• Multiplicity function
• Negentropy (negative entropy)
• Orders of magnitude (entropy)
• Stirling’s formula
• Thermodynamic databases for pure substances
• Thermodynamic potential
• Wavelet entropy
6.2.9 Notes
[1] A machine in this context includes engineered devices as
well as biological organisms.
[2] The overdots represent derivatives of the quantities with re-
spect to time.
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[78] Schmitz, John E.J. (2007). The Second Law of Life: Energy,
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6.2.11 Further reading
• Atkins, Peter; Julio De Paula (2006). Physical Chem-
istry, 8th ed. Oxford University Press. ISBN 0-19-
870072-5.
• Baierlein, Ralph (2003). Thermal Physics. Cambridge
University Press. ISBN 0-521-65838-1.
• Ben-Naim, Arieh (2007). Entropy Demystified. World
Scientific. ISBN 981-270-055-2.
• Callen, Herbert, B (2001). Thermodynamics and an
Introduction to Thermostatistics, 2nd Ed. John Wiley
and Sons. ISBN 0-471-86256-8.
• Chang, Raymond (1998). Chemistry, 6th Ed. New
York: McGraw Hill. ISBN 0-07-115221-0.
• Cutnell, John, D.; Johnson, Kenneth, J. (1998).
Physics, 4th ed. John Wiley and Sons, Inc. ISBN 0-
471-19113-2. Cite uses deprecated parameter |coau-
thor= (help)
• Dugdale, J. S. (1996). Entropy and its Physical Mean-
ing (2nd ed.). Taylor and Francis (UK); CRC (US).
ISBN 0-7484-0569-0.
• Fermi, Enrico (1937). Thermodynamics. Prentice
Hall. ISBN 0-486-60361-X.
• Goldstein, Martin; Inge, F (1993). The Refrigerator
and the Universe. Harvard University Press. ISBN 0-
674-75325-9.
• Gyftopoulos, E.P.; G.P. Beretta (1991, 2005, 2010).
Thermodynamics. Foundations and Applications.
Dover. ISBN 0-486-43932-1. Check date values in:
|date= (help)
• Haddad, Wassim M.; Chellaboina, VijaySekhar;
Nersesov, Sergey G. (2005). Thermodynamics – A
Dynamical Systems Approach. Princeton University
Press. ISBN 0-691-12327-6.
6.3. PRESSURE 145

• Kroemer, Herbert; Charles Kittel (1980). Thermal • The Discovery of Entropy by Adam Shulman. Hour-
Physics (2nd ed.). W. H. Freeman Company. ISBN long video, January 2013.
0-7167-1088-9.
• Lambert, Frank L.; entropysite.oxy.edu • Moriarty, Philip; Merrifield, Michael (2009). “S En-
tropy”. Sixty Symbols. Brady Haran for the University
• Penrose, Roger (2005). The Road to Reality: A Com- of Nottingham.
plete Guide to the Laws of the Universe. New York: A.
A. Knopf. ISBN 0-679-45443-8.
• Entropy Scholarpedia
• Reif, F. (1965). Fundamentals of statistical and ther-
mal physics. McGraw-Hill. ISBN 0-07-051800-9.
• Schroeder, Daniel V. (2000). Introduction to Thermal 6.3 Pressure
Physics. New York: Addison Wesley Longman. ISBN
0-201-38027-7.
This article is about pressure in the physical sciences. For
• Serway, Raymond, A. (1992). Physics for Scientists other uses, see Pressure (disambiguation).
and Engineers. Saunders Golden Subburst Series. Pressure (symbol: p or P) is the force applied perpen-
ISBN 0-03-096026-6.
• Spirax-Sarco Limited, Entropy – A Basic Understand-
ing A primer on entropy tables for steam engineering
• vonBaeyer; Hans Christian (1998). Maxwell’s Demon:
Why Warmth Disperses and Time Passes. Random
House. ISBN 0-679-43342-2.
• Entropy for beginners – a wikibook
• An Intuitive Guide to the Concept of Entropy Arising
in Various Sectors of Science – a wikibook

6.2.12 External links

• Entropy and the Second Law of Thermodynamics - an
A-level physics lecture with detailed derivation of en-
tropy based on Carnot cycle
Pressure as exerted by particle collisions inside a closed container.
• Khan Academy: entropy lectures, part of Chemistry
playlist
dicular to the surface of an object per unit area over which
• Proof: S (or Entropy) is a valid state variable
that force is distributed. Gauge pressure (also spelled gage
[lower-alpha 1]
• Thermodynamic Entropy Definition Clarifica- pressure) is the pressure relative to the ambient
tion pressure.
• Reconciling Thermodynamic and State Defini- Various units are used to express pressure. Some of these
tions of Entropy derive from a unit of force divided by a unit of area; the SI
• Entropy Intuition unit of pressure, the pascal (Pa), for example, is one newton
per square metre; similarly, the pound-force per square inch
• More on Entropy (psi) is the traditional unit of pressure in the imperial and
• The Second Law of Thermodynamics and Entropy - US customary systems. Pressure may also be expressed
Yale OYC lecture, part of Fundamentals of Physics I in terms of standard atmospheric pressure; the atmosphere
(PHYS 200) (atm) is equal to this pressure and the torr is defined as 1 ⁄760
of this. Manometric units such as the centimetre of wa-
• Entropy and the Clausius inequality MIT OCW lec- ter, millimetre of mercury, and inch of mercury are used
ture, part of 5.60 Thermodynamics & Kinetics, Spring to express pressures in terms of the height of column of a
2008 particular fluid in a manometer.
146 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

6.3.1 Definition
Pressure is the amount of force acting per unit area. The the fluid on that surface is the surface integral over S of the
symbol for pressure is p or P.[1] The IUPAC recommenda- right-hand side of the above equation.
tion for pressure is a lower-case p.[2] However, upper-case
P is widely used. The usage of P vs p depends on the field
in which one is working, on the nearby presence of other
symbols for quantities such as power and momentum, and
on writing style.
Formula
points outward. The equation has meaning in that, for any
surface S in contact with the fluid, the total force exerted by
It is incorrect (although rather usual) to say “the pressure
is directed in such or such direction”. The pressure, as a
scalar, has no direction. The force given by the previous
relationship to the quantity has a direction, but the pres-
sure does not. If we change the orientation of the surface
element, the direction of the normal force changes accord-
ingly, but the pressure remains the same.
Pressure is transmitted to solid boundaries or across arbi-
trary sections of fluid normal to these boundaries or sec-
tions at every point. It is a fundamental parameter in
thermodynamics, and it is conjugate to volume.

Units

Mathematically:

F
p=
A
where:

p is the pressure,
F is the normal force,
A is the area of the surface on contact.

Pressure is a scalar quantity. It relates the vector surface

element (a vector normal to the surface) with the normal
force acting on it. The pressure is the scalar proportionality Mercury column
constant that relates the two normal vectors:
The SI unit for pressure is the pascal (Pa), equal to one
newton per square metre (N/m2 or kg·m−1 ·s−2 ). This name
dFn = −p dA = −p n dA for the unit was added in 1971;[3] before that, pressure in SI
The minus sign comes from the fact that the force is consid- was expressed simply in newtons per square metre.
ered towards the surface element, while the normal vector Other units of pressure, such as pounds per square inch and
6.3. PRESSURE
bar, are also in common use. The CGS unit of pressure is
the barye (Ba), equal to 1 dyn·cm−2 or 0.1 Pa. Pressure is
sometimes expressed in grams-force or kilograms-force per
square centimetre (g/cm2 or kg/cm2 ) and the like without
properly identifying the force units. But using the names
kilogram, gram, kilogram-force, or gram-force (or their
symbols) as units of force is expressly forbidden in SI. The
technical atmosphere (symbol: at) is 1 kgf/cm2 (98.0665
kPa or 14.223 psi).
Since a system under pressure has potential to perform work
on its surroundings, pressure is a measure of potential en-
ergy stored per unit volume. It is therefore related to energy
density and may be expressed in units such as joules per cu-
bic metre (J/m3 , which is equal to Pa).
Some meteorologists prefer the hectopascal (hPa) for atmo-
spheric air pressure, which is equivalent to the older unit
millibar (mbar). Similar pressures are given in kilopas-
cals (kPa) in most other fields, where the hecto- prefix is
rarely used. The inch of mercury is still used in the United
States. Oceanographers usually measure underwater pres-
sure in decibars (dbar) because pressure in the ocean in-
creases by approximately one decibar per metre depth.
The standard atmosphere (atm) is an established constant. It
is approximately equal to typical air pressure at earth mean
sea level and is defined as 101325 Pa.
Because pressure is commonly measured by its ability to
displace a column of liquid in a manometer, pressures
are often expressed as a depth of a particular fluid (e.g.,
centimetres of water, millimetres of mercury or inches of
mercury). The most common choices are mercury (Hg) and
water; water is nontoxic and readily available, while mer-
cury’s high density allows a shorter column (and so a smaller
manometer) to be used to measure a given pressure. The
pressure exerted by a column of liquid of height h and den-
sity ρ is given by the hydrostatic pressure equation p = ρgh,
where g is the gravitational acceleration. Fluid density and
local gravity can vary from one reading to another depend-
ing on local factors, so the height of a fluid column does
not define pressure precisely. When millimetres of mer-
cury or inches of mercury are quoted today, these units are
not based on a physical column of mercury; rather, they
have been given precise definitions that can be expressed
in terms of SI units. One millimetre of mercury is approxi-
mately equal to one torr. The water-based units still depend
on the density of water, a measured, rather than defined,
quantity. These manometric units are still encountered in
many fields. Blood pressure is measured in millimetres of
mercury in most of the world, and lung pressures in cen-
timetres of water are still common.
Underwater divers use the metre sea water (msw or MSW)
and foot sea water (fsw or FSW) units of pressure, and these
are the standard units for pressure gauges used to measure
147
pressure exposure in diving chambers and personal decom-
pression computers. A msw is defined as 0.1 bar, and is not
the same as a linear metre of depth, and 33.066 fsw = 1
atm.[4] Note that the pressure conversion from msw to fsw
is different from the length conversion: 10 msw = 32.6336
fsw, while 10 m = 32.8083 ft
Gauge pressure is often given in units with 'g' appended,
e.g. 'kPag', 'barg' or 'psig', and units for measurements of
absolute pressure are sometimes given a suffix of 'a', to
avoid confusion, for example 'kPaa', 'psia'. However, the
US National Institute of Standards and Technology recom-
mends that, to avoid confusion, any modifiers be instead
applied to the quantity being measured rather than the unit
of measure[5] For example, "p = 100 psi” rather than "p =
100 psig”.
Differential pressure is expressed in units with 'd' appended;
this type of measurement is useful when considering sealing
performance or whether a valve will open or close.
Presently or formerly popular pressure units include the fol-
lowing:
• atmosphere (atm)
• manometric units:
• centimetre, inch, millimetre (torr) and microme-
tre (mTorr, micron) of mercury
• Height of equivalent column of water, including
millimetre (mm H
2O), centimetre (cm H
2O), metre, inch, and foot of water
• imperial and customary units:
• kip, short ton-force, long ton-force, pound-force,
ounce-force, and poundal per square inch
• short ton-force and long ton-force per square
inch
• fsw (feet sea water) used in underwater diving,
particularly in connection with diving pressure
exposure and decompression
• non-SI metric units:
• bar, decibar, millibar
• msw (metres sea water), used in underwater
diving, particularly in connection with div-
ing pressure exposure and decompression
• kilogram-force, or kilopond, per square cen-
timetre (technical atmosphere)
• gram-force and tonne-force (metric ton-force)
per square centimetre
• barye (dyne per square centimetre)
148 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

• kilogram-force and tonne-force per square metre fruit with the flat side it obviously will not cut. But if we
• sthene per square metre (pieze) take the thin side, it will cut smoothly. The reason is that
the flat side has a greater surface area (less pressure) and so
it does not cut the fruit. When we take the thin side, the
Examples surface area is reduced and so it cuts the fruit easily and
quickly. This is one example of a practical application of
pressure.
For gases, pressure is sometimes measured not as an ab-
solute pressure, but relative to atmospheric pressure; such
measurements are called gauge pressure. An example of
this is the air pressure in an automobile tire, which might be
said to be “220 kPa (32 psi)", but is actually 220 kPa (32
psi) above atmospheric pressure. Since atmospheric pres-
sure at sea level is about 100 kPa (14.7 psi), the absolute
pressure in the tire is therefore about 320 kPa (46.7 psi).
In technical work, this is written “a gauge pressure of 220
kPa (32 psi)". Where space is limited, such as on pressure
gauges, name plates, graph labels, and table headings, the
use of a modifier in parentheses, such as “kPa (gauge)" or
“kPa (absolute)", is permitted. In non-SI technical work, a
gauge pressure of 32 psi is sometimes written as “32 psig”
and an absolute pressure as “32 psia”, though the other
methods explained above that avoid attaching characters to
the unit of pressure are preferred.[6]
Gauge pressure is the relevant measure of pressure wher-
ever one is interested in the stress on storage vessels and
the plumbing components of fluidics systems. However,
whenever equation-of-state properties, such as densities or
changes in densities, must be calculated, pressures must be
expressed in terms of their absolute values. For instance, if
the atmospheric pressure is 100 kPa, a gas (such as helium)
at 200 kPa (gauge) (300 kPa [absolute]) is 50% denser than
the same gas at 100 kPa (gauge) (200 kPa [absolute]). Fo-
cusing on gauge values, one might erroneously conclude the
first sample had twice the density of the second one.

Scalar nature

The effects of an external pressure of 700bar on an aluminum

cylinder with 5mm wall thickness
As an example of varying pressures, a finger can be pressed
against a wall without making any lasting impression; how-
ever, the same finger pushing a thumbtack can easily dam-
age the wall. Although the force applied to the surface is
the same, the thumbtack applies more pressure because the
point concentrates that force into a smaller area. Pressure
is transmitted to solid boundaries or across arbitrary sec-
tions of fluid normal to these boundaries or sections at every
point. Unlike stress, pressure is defined as a scalar quantity.
The negative gradient of pressure is called the force density.
Another example is of a common knife. If we try to cut a
In a static gas, the gas as a whole does not appear to move.
The individual molecules of the gas, however, are in con-
stant random motion. Because we are dealing with an ex-
tremely large number of molecules and because the motion
of the individual molecules is random in every direction, we
do not detect any motion. If we enclose the gas within a con-
tainer, we detect a pressure in the gas from the molecules
colliding with the walls of our container. We can put the
walls of our container anywhere inside the gas, and the force
per unit area (the pressure) is the same. We can shrink the
size of our “container” down to a very small point (becom-
ing less true as we approach the atomic scale), and the pres-
sure will still have a single value at that point. Therefore,
pressure is a scalar quantity, not a vector quantity. It has
6.3. PRESSURE 149

magnitude but no direction sense associated with it. Pres- fluid being ideal[8] and incompressible.[8] An ideal fluid is
sure acts in all directions at a point inside a gas. At the a fluid in which there is no friction, it is inviscid,[8] zero
surface of a gas, the pressure force acts perpendicular (at viscosity.[8] The equation for all points of a system filled
right angle) to the surface. with a constant-density fluid is
A closely related quantity is the stress tensor σ, which relates
the vector force F⃗ to the vector area A⃗ via the linear relation p
γ + v2
2g + z = const [9]
F⃗ = σ A⃗ .
This tensor may be expressed as the sum of the viscous where:
stress tensor minus the hydrostatic pressure. The negative
of the stress tensor is sometimes called the pressure tensor,
p = pressure of the fluid
but in the following, the term “pressure” will refer only to
the scalar pressure. γ = ρg = density·acceleration of gravity = specific
According to the theory of general relativity, pressure in- weight of the fluid.[8]
creases the strength of a gravitational field (see stress– v = velocity of the fluid
energy tensor) and so adds to the mass-energy cause of
g = acceleration of gravity
gravity. This effect is unnoticeable at everyday pressures
but is significant in neutron stars, although it has not been z = elevation
experimentally tested.[7] p
= pressure head
γ
2
v
= velocity head
6.3.2 Types 2g

Fluid pressure Applications

Fluid pressure is the pressure at some point within a fluid,
• Hydraulic brakes
such as water or air (for more information specifically about
liquid pressure, see section below).
• Artesian well
Fluid pressure occurs in one of two situations:
• Blood pressure
1. an open condition, called “open channel flow”, e.g. the
ocean, a swimming pool, or the atmosphere. • Hydraulic head

2. a closed condition, called “closed conduit”, e.g. a wa- • Plant cell turgidity
ter line or gas line.
• Pythagorean cup
Pressure in open conditions usually can be approximated as
the pressure in “static” or non-moving conditions (even in
Explosion or deflagration pressures
the ocean where there are waves and currents), because the
motions create only negligible changes in the pressure. Such
Explosion or deflagration pressures are the result of the ig-
conditions conform with principles of fluid statics. The
nition of explosive gases, mists, dust/air suspensions, in un-
pressure at any given point of a non-moving (static) fluid
confined and confined spaces.
is called the hydrostatic pressure.
Closed bodies of fluid are either “static”, when the fluid is
not moving, or “dynamic”, when the fluid can move as in Negative pressures
either a pipe or by compressing an air gap in a closed con-
tainer. The pressure in closed conditions conforms with the While pressures are, in general, positive, there are several
principles of fluid dynamics. situations in which negative pressures may be encountered:
The concepts of fluid pressure are predominantly attributed
to the discoveries of Blaise Pascal and Daniel Bernoulli. • When dealing in relative (gauge) pressures. For in-
Bernoulli’s equation can be used in almost any situation to stance, an absolute pressure of 80 kPa may be de-
determine the pressure at any point in a fluid. The equa- scribed as a gauge pressure of −21 kPa (i.e., 21 kPa
tion makes some assumptions about the fluid, such as the below an atmospheric pressure of 101 kPa).
150 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

1 2
p0 = ρv + p
2
where

p0 is the stagnation pressure

v is the flow velocity
p is the static pressure.

The pressure of a moving fluid can be measured using a

Pitot tube, or one of its variations such as a Kiel probe or
low pressure chamber in Bundesleistungszentrum Kienbaum, Ger-
Cobra probe, connected to a manometer. Depending on
many
where the inlet holes are located on the probe, it can mea-
sure static pressures or stagnation pressures.
• When attractive intermolecular forces (e.g., van der
Waals forces or hydrogen bonds) between the parti-
Surface pressure and surface tension
cles of a fluid exceed repulsive forces due to ther-
mal motion. These forces explain ascent of sap in tall
There is a two-dimensional analog of pressure – the lateral
plants. An apparent negative pressure must act on wa-
force per unit length applied on a line perpendicular to the
ter molecules at the top of any tree taller than 10 m,
force.
which is the pressure head of water that balances the
atmospheric pressure. Intermolecular forces maintain Surface pressure is denoted by π and shares many sim-
cohesion of columns of sap that run continuously in ilar properties with three-dimensional pressure. Proper-
xylem from the roots to the top leaves.[10] ties of surface chemicals can be investigated by measuring
pressure/area isotherms, as the two-dimensional analog of
• The Casimir effect can create a small attractive force Boyle’s law, πA = k, at constant temperature.
due to interactions with vacuum energy; this force is
sometimes termed “vacuum pressure” (not to be con-
fused with the negative gauge pressure of a vacuum). F
π=
l
• For non-isotropic stresses in rigid bodies, depending
on how the orientation of a surface is chosen, the same Surface tension is another example of surface pressure, but
distribution of forces may have a component of pos- with a reversed sign, because “tension” is the opposite to
itive pressure along one surface normal, with a com- “pressure”.
ponent of negative pressure acting along the another
surface normal.
Pressure of an ideal gas
• The stresses in an electromagnetic field are gen-
erally non-isotropic, with the pressure normal to Main article: Ideal gas law
one surface element (the normal stress) being
negative, and positive for surface elements per- In an ideal gas, molecules have no volume and do not inter-
pendicular to this. act. According to the ideal gas law, pressure varies linearly
with temperature and quantity, and inversely with volume.
• In the cosmological constant.

Stagnation pressure nRT

p=
V
Stagnation pressure is the pressure a fluid exerts when it is where:
forced to stop moving. Consequently, although a fluid mov-
ing at higher speed will have a lower static pressure, it may
have a higher stagnation pressure when forced to a standstill. p is the absolute pressure of the gas
Static pressure and stagnation pressure are related by: n is the amount of substance
6.3. PRESSURE 151

T is the absolute temperature where:

V is the volume
R is the ideal gas constant. p is liquid pressure
g is gravity at the surface of overlaying material
Real gases exhibit a more complex dependence on the vari- ρ is density of liquid
ables of state.[11] h is height of liquid column or depth within a sub-
stance
Vapor pressure
Another way of saying this same formula is the following:
Main article: Vapor pressure

Vapor pressure is the pressure of a vapor in thermodynamic p = density weight × depth

equilibrium with its condensed phases in a closed system.
All liquids and solids have a tendency to evaporate into a The pressure a liquid exerts against the sides and bottom of a
gaseous form, and all gases have a tendency to condense container depends on the density and the depth of the liquid.
back to their liquid or solid form. If atmospheric pressure is neglected, liquid pressure against
the bottom is twice as great at twice the depth; at three times
The atmospheric pressure boiling point of a liquid (also the depth, the liquid pressure is threefold; etc. Or, if the
known as the normal boiling point) is the temperature at liquid is two or three times as dense, the liquid pressure is
which the vapor pressure equals the ambient atmospheric correspondingly two or three times as great for any given
pressure. With any incremental increase in that tempera- depth. Liquids are practically incompressible – that is, their
ture, the vapor pressure becomes sufficient to overcome at- volume can hardly be changed by pressure (water volume
mospheric pressure and lift the liquid to form vapor bubbles decreases by only 50 millionths of its original volume for
inside the bulk of the substance. Bubble formation deeper each atmospheric increase in pressure). Thus, except for
in the liquid requires a higher pressure, and therefore higher small changes produced by temperature, the density of a
temperature, because the fluid pressure increases above the particular liquid is practically the same at all depths.
atmospheric pressure as the depth increases.
Atmospheric pressure pressing on the surface of a liquid
The vapor pressure that a single component in a mixture must be taken into account when trying to discover the total
contributes to the total pressure in the system is called pressure acting on a liquid. The total pressure of a liquid,
partial vapor pressure. then, is ρgh plus the pressure of the atmosphere. When this
distinction is important, the term total pressure is used. Oth-
Liquid pressure erwise, discussions of liquid pressure refer to pressure with-
out regard to the normally ever-present atmospheric pres-
See also: Fluid statics § Pressure in fluids at rest sure.
It is important to recognize that the pressure does not de-
When a person swims under the water, water pressure is pend on the amount of liquid present. Volume is not the im-
felt acting on the person’s eardrums. The deeper that per- portant factor – depth is. The average water pressure acting
son swims, the greater the pressure. The pressure felt is due against a dam depends on the average depth of the water and
to the weight of the water above the person. As someone not on the volume of water held back. For example, a wide
swims deeper, there is more water above the person and but shallow lake with a depth of 3 m (10 ft) exerts only half
therefore greater pressure. The pressure a liquid exerts de- the average pressure that a small 6 m (20 ft) deep pond does
pends on its depth. (note that the total force applied to the longer dam will be
greater, due to the greater total surface area for the pressure
Liquid pressure also depends on the density of the liquid. If to act upon, but for a given 5 foot section of each dam, the
someone was submerged in a liquid more dense than water, 10ft deep water will apply half the force of 20ft deep wa-
the pressure would be correspondingly greater. The pres- ter). A person will feel the same pressure whether his/her
sure due to a liquid in liquid columns of constant density or head is dunked a metre beneath the surface of the water in
at a depth within a substance is represented by the following a small pool or to the same depth in the middle of a large
formula: lake. If four vases contain different amounts of water but
are all filled to equal depths, then a fish with its head dunked
a few centimetres under the surface will be acted on by wa-
p = ρgh ter pressure that is the same in any of the vases. If the fish
152 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

swims a few centimetres deeper, the pressure on the fish will
increase with depth and be the same no matter which vase
the fish is in. If the fish swims to the bottom, the pressure
will be greater, but it makes no difference what vase it is in.
All vases are filled to equal depths, so the water pressure is
the same at the bottom of each vase, regardless of its shape
or volume. If water pressure at the bottom of a vase were
greater than water pressure at the bottom of a neighboring
vase, the greater pressure would force water sideways and
then up the narrower vase to a higher level until the pres-
sures at the bottom were equalized. Pressure is depth de-
pendent, not volume dependent, so there is a reason that
water seeks its own level.
Restating this as energy equation, the energy per unit vol-
ume in an ideal, incompressible liquid is constant through-
out its vessel. At the surface, gravitational potential energy
is large but liquid pressure energy is low. At the bottom
of the vessel, all the gravitational potential energy is con-
verted to pressure energy. The sum of pressure energy and
gravitational potential energy per unit volume is constant
throughout the volume of the fluid and the two energy com-
ponents change linearly with the depth.[12] Mathematically,
it is described by Bernoulli’s equation where velocity head
is zero and comparisons per unit volume in the vessel are:
the hole is located. Then it curves downward due to grav-
ity. If there are three holes in a bucket (top, bottom, and
middle), then the force vectors perpendicular to the inner
container surface will increase with increasing depth – that
is, a greater pressure at the bottom makes it so that the bot-
tom hole will shoot water out the farthest. The force exerted
by a fluid on a smooth surface is always at right angles to the
√
surface. The speed of liquid out of the hole is 2gh , where
[13]
h is the depth below the free surface. Interestingly, this
is the same speed the water (or anything else) would have
if freely falling the same vertical distance h.
Kinematic pressure
P = p/ρ0
is the kinematic pressure, where p is the pressure and ρ0
constant mass density. The SI unit of P is m2 /s2 . Kinematic
pressure is used in the same manner as kinematic viscosity
ν in order to compute Navier–Stokes equation without ex-
plicitly showing the density ρ0 .
Navier–Stokes equation with kinematic quantities
∂t + (u∇)u = −∇P + ν∇ u
∂u 2

p 6.3.3 See also

+ z = const
γ
• Atmospheric pressure
Terms have the same meaning as in section Fluid pressure.
• Blood pressure

• Boyle’s Law
Direction of liquid pressure
• Combined gas law
An experimentally determined fact about liquid pressure is
that it is exerted equally in all directions.[13] If someone is • Conversion of units
submerged in water, no matter which way that person tilts
his/her head, the person will feel the same amount of wa- • Critical point (thermodynamics)
ter pressure on his/her ears. Because a liquid can flow, this • Dynamic pressure
pressure isn't only downward. Pressure is seen acting side-
ways when water spurts sideways from a leak in the side of • Hydraulics
an upright can. Pressure also acts upward, as demonstrated
when someone tries to push a beach ball beneath the sur- • Internal pressure
face of the water. The bottom of a boat is pushed upward • Kinetic theory
by water pressure (buoyancy).
When a liquid presses against a surface, there is a net force • Microphone
that is perpendicular to the surface. Although pressure • Orders of magnitude (pressure)
doesn't have a specific direction, force does. A submerged
triangular block has water forced against each point from • Partial pressure
many directions, but components of the force that are not
perpendicular to the surface cancel each other out, leaving • Pressure measurement
only a net perpendicular point.[13] This is why water spurt- • Pressure sensor
ing from a hole in a bucket initially exits the bucket in a di-
rection at right angles to the surface of the bucket in which • Sound pressure
6.4. THERMODYNAMIC TEMPERATURE 153

• Spouting can [12] Streeter, V.L., Fluid Mechanics, Example 3.5, McGraw–Hill
Inc. (1966), New York.
• Timeline of temperature and pressure measurement
technology [13] Hewitt 251 (2006)

• Units conversion by factor-label

• Vacuum 6.3.6 External links
• Vacuum pump • Introduction to Fluid Statics and Dynamics on Project
PHYSNET
• Vertical pressure variation
• Pressure being a scalar quantity
6.3.4 Notes
[1] The preferred spelling varies by country and even by indus- 6.4 Thermodynamic temperature
try. Further, both spellings are often used within a particular
industry or country. Industries in British English-speaking
Thermodynamic temperature is the absolute measure
countries typically use the “gauge” spelling.
of temperature and is one of the principal parameters of
thermodynamics.
6.3.5 References Thermodynamic temperature is defined by the third law of
thermodynamics in which the theoretically lowest tempera-
[1] Giancoli, Douglas G. (2004). Physics: principles with ap- ture is the null or zero point. At this point, absolute zero, the
plications. Upper Saddle River, N.J.: Pearson Education.
particle constituents of matter have minimal motion and can
ISBN 0-13-060620-0.
become no colder.[1][2] In the quantum-mechanical descrip-
[2] McNaught, A. D.; Wilkinson, A.; Nic, M.; Jirat, tion, matter at absolute zero is in its ground state, which is its
J.; Kosata, B.; Jenkins, A. (2014). IUPAC. Com- state of lowest energy. Thermodynamic temperature is of-
pendium of Chemical Terminology, 2nd ed. (the “Gold ten also called absolute temperature, for two reasons: one,
Book”). 2.3.3. Oxford: Blackwell Scientific Publications. proposed by Kelvin, that it does not depend on the proper-
doi:10.1351/goldbook.P04819. ISBN 0-9678550-9-8. ties of a particular material; two that it refers to an absolute
[3] “14th Conference of the International Bureau of Weights and zero according to the properties of the ideal gas.
Measures”. Bipm.fr. Retrieved 2012-03-27. The International System of Units specifies a particular
[4] US Navy (2006). US Navy Diving Manual, 6th revision. scale for thermodynamic temperature. It uses the Kelvin
United States: US Naval Sea Systems Command. pp. 2– scale for measurement and selects the triple point of water
32. Retrieved 2008-06-15. at 273.16K as the fundamental fixing point. Other scales
have been in use historically. The Rankine scale, using the
[5] “Rules and Style Conventions for Expressing Values of degree Fahrenheit as its unit interval, is still in use as part of
Quantities”. NIST. Retrieved 2009-07-07. the English Engineering Units in the United States in some
[6] NIST, Rules and Style Conventions for Expressing Values of engineering fields. ITS-90 gives a practical means of esti-
Quantities, Sect. 7.4. mating the thermodynamic temperature to a very high de-
gree of accuracy.
[7] “Einstein’s gravity under pressure”. Springerlink.com. Re-
trieved 2012-03-27. Roughly, the temperature of a body at rest is a measure of
the mean of the energy of the translational, vibrational and
[8] Finnemore, John, E. and Joseph B. Franzini (2002). Fluid rotational motions of matter's particle constituents, such as
Mechanics: With Engineering Applications. New York: Mc- molecules, atoms, and subatomic particles. The full variety
Graw Hill, Inc. pp. 14–29. ISBN 978-0-07-243202-2. of these kinetic motions, along with potential energies of
[9] NCEES (2011). Fundamentals of Engineering: Supplied particles, and also occasionally certain other types of par-
Reference Handbook. Clemson, South Carolina: NCEES. ticle energy in equilibrium with these, make up the total
p. 64. ISBN 978-1-932613-59-9. internal energy of a substance. Internal energy is loosely
called the heat energy or thermal energy in conditions when
[10] Karen Wright (March 2003). “The Physics of Negative
no work is done upon the substance by its surroundings, or
Pressure”. Discover. Retrieved 31 January 2015.
by the substance upon the surroundings. Internal energy
[11] P. Atkins, J. de Paula Elements of Physical Chemistry, 4th may be stored in a number of ways within a substance, each
Ed, W.H. Freeman, 2006. ISBN 0-7167-7329-5. way constituting a “degree of freedom”. At equilibrium,
154
each degree of freedom will have on average the same en-
ergy: kB T /2 where kB is the Boltzmann constant, unless
that degree of freedom is in the quantum regime. The in-
ternal degrees of freedom (rotation, vibration, etc.) may be
in the quantum regime at room temperature, but the trans-
lational degrees of freedom will be in the classical regime
except at extremely low temperatures (fractions of kelvins)
and it may be said that, for most situations, the thermody-
namic temperature is specified by the average translational
kinetic energy of the particles.
6.4.1 Overview
Temperature is a measure of the random submicroscopic
motions and vibrations of the particle constituents of
matter. These motions comprise the internal energy of a
substance. More specifically, the thermodynamic temper-
ature of any bulk quantity of matter is the measure of the
average kinetic energy per classical (i.e., non-quantum) de-
gree of freedom of its constituent particles. “Translational
motions” are almost always in the classical regime. Trans-
lational motions are ordinary, whole-body movements in
three-dimensional space in which particles move about and
exchange energy in collisions. Figure 1 below shows trans-
lational motion in gases; Figure 4 below shows translational
motion in solids. Thermodynamic temperature’s null point,
absolute zero, is the temperature at which the particle con-
stituents of matter are as close as possible to complete rest;
that is, they have minimal motion, retaining only quantum
mechanical motion.[3] Zero kinetic energy remains in a sub-
stance at absolute zero (see Thermal energy at absolute zero,
below).
Throughout the scientific world where measurements are
made in SI units, thermodynamic temperature is measured
in kelvins (symbol: K). Many engineering fields in the U.S.
however, measure thermodynamic temperature using the
Rankine scale.
By international agreement, the unit kelvin and its scale are
defined by two points: absolute zero, and the triple point of
Vienna Standard Mean Ocean Water (water with a specified
blend of hydrogen and oxygen isotopes). Absolute zero, the
lowest possible temperature, is defined as being precisely 0
K and −273.15 °C. The triple point of water is defined as
being precisely 273.16 K and 0.01 °C. This definition does
three things:
1. It fixes the magnitude of the kelvin unit as being pre-
cisely 1 part in 273.16 parts the difference between
absolute zero and the triple point of water;
2. It establishes that one kelvin has precisely the same
magnitude as a one-degree increment on the Celsius
scale; and
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
3. It establishes the difference between the two scales’
null points as being precisely 273.15 kelvins (0 K =
−273.15 °C and 273.16 K = 0.01 °C).
Temperatures expressed in kelvins are converted to degrees
Rankine simply by multiplying by 1.8 as follows: T°R =
1.8TK, where TK and T°R are temperatures in kelvin and
degrees Rankine respectively. Temperatures expressed in
degrees Rankine are converted to kelvins by dividing by 1.8
as follows: TK = T°R ⁄₁.₈.
Practical realization
Main article: ITS-90
Although the Kelvin and Celsius scales are defined using ab-
solute zero (0 K) and the triple point of water (273.16 K and
0.01 °C), it is impractical to use this definition at tempera-
tures that are very different from the triple point of water.
ITS-90 is then designed to represent the thermodynamic
temperature as closely as possible throughout its range.
Many different thermometer designs are required to cover
the entire range. These include helium vapor pressure ther-
mometers, helium gas thermometers, standard platinum re-
sistance thermometers (known as SPRTs, PRTs or Plat-
inum RTDs) and monochromatic radiation thermometers.
For some types of thermometer the relationship between
the property observed (e.g., length of a mercury column)
and temperature, is close to linear, so for most purposes a
linear scale is sufficient, without point-by-point calibration.
For others a calibration curve or equation is required. The
mercury thermometer, invented before the thermodynamic
temperature was understood, originally defined the temper-
ature scale; its linearity made readings correlate well with
true temperature, i.e. the “mercury” temperature scale was
a close fit to the true scale.
6.4.2 The relationship of temperature, mo-
tions, conduction, and thermal energy
The nature of kinetic energy, translational motion, and
temperature
The thermodynamic temperature is a measure of the av-
erage energy of the translational, vibrational, and rotational
motions of matter's particle constituents (molecules, atoms,
and subatomic particles). The full variety of these kinetic
motions, along with potential energies of particles, and
also occasionally certain other types of particle energy in
equilibrium with these, contribute the total internal energy
(loosely, the thermal energy) of a substance. Thus, inter-
nal energy may be stored in a number of ways (degrees of
6.4. THERMODYNAMIC TEMPERATURE 155

Since there are three translational degrees of freedom (e.g.,

motion along the x, y, and z axes), the translational kinetic
energy is related to the kinetic temperature by:

3
Ē = kB Tk
2
where:

• Ē is the mean kinetic energy in joules (J) and is pro-

nounced “E bar”
• kB = 1.3806504(24)×10−23 J/K is the Boltzmann con-
stant and is pronounced “Kay sub bee”
• Tk is the kinetic temperature in kelvins (K) and is pro-
nounced “Tee sub kay”
Fig. 1 The translational motion of fundamental particles of na-
ture such as atoms and molecules are directly related to temper-
ature. Here, the size of helium atoms relative to their spacing is
shown to scale under 1950 atmospheres of pressure. These room-
temperature atoms have a certain average speed (slowed down here
two trillion-fold). At any given instant however, a particular helium
atom may be moving much faster than average while another may
be nearly motionless. Five atoms are colored red to facilitate fol-
lowing their motions.

freedom) within a substance. When the degrees of freedom

are in the classical regime (“unfrozen”) the temperature is
very simply related to the average energy of those degrees
of freedom at equilibrium. The three translational degrees
of freedom are unfrozen except for the very lowest tempera-
tures, and their kinetic energy is simply related to the ther-
modynamic temperature over the widest range. The heat
capacity, which relates heat input and temperature change,
is discussed below.
The relationship of kinetic energy, mass, and velocity is
given by the formula Ek = 1 ⁄2 mv2 .[4] Accordingly, particles
with one unit of mass moving at one unit of velocity have
precisely the same kinetic energy, and precisely the same
temperature, as those with four times the mass but half the Fig. 2 The translational motions of helium atoms occur across a
range of speeds. Compare the shape of this curve to that of a Planck
velocity.
curve in Fig. 5 below.
Except in the quantum regime at extremely low tempera-
tures, the thermodynamic temperature of any bulk quantity While the Boltzmann constant is useful for finding the mean
of a substance (a statistically significant quantity of parti- kinetic energy of a particle, it’s important to note that even
cles) is directly proportional to the mean average kinetic when a substance is isolated and in thermodynamic equi-
energy of a specific kind of particle motion known as trans- librium (all parts are at a uniform temperature and no heat
lational motion. These simple movements in the three x, y, is going into or out of it), the translational motions of in-
and z–axis dimensions of space means the particles move in dividual atoms and molecules occur across a wide range of
the three spatial degrees of freedom. The temperature de- speeds (see animation in Figure 1 above). At any one in-
rived from this translational kinetic energy is sometimes re- stant, the proportion of particles moving at a given speed
ferred to as kinetic temperature and is equal to the thermody- within this range is determined by probability as described
namic temperature over a very wide range of temperatures. by the Maxwell–Boltzmann distribution. The graph shown
156 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

here in Fig. 2 shows the speed distribution of 5500 K

helium atoms. They have a most probable speed of 4.780
km/s. However, a certain proportion of atoms at any given
instant are moving faster while others are moving relatively
slowly; some are momentarily at a virtual standstill (off the
x–axis to the right). This graph uses inverse speed for its
x–axis so the shape of the curve can easily be compared to
the curves in Figure 5 below. In both graphs, zero on the
x–axis represents infinite temperature. Additionally, the x
and y–axis on both graphs are scaled proportionally.

The high speeds of translational motion

Although very specialized laboratory equipment is required

to directly detect translational motions, the resultant col-
lisions by atoms or molecules with small particles sus-
pended in a fluid produces Brownian motion that can be
seen with an ordinary microscope. The translational mo-
tions of elementary particles are very fast[5] and tempera-
Fig. 3 Because of their internal structure and flexibility, molecules
tures close to absolute zero are required to directly observe can store kinetic energy in internal degrees of freedom which con-
them. For instance, when scientists at the NIST achieved a tribute to the heat capacity.
record-setting cold temperature of 700 nK (billionths of a
kelvin) in 1994, they used optical lattice laser equipment to
adiabatically cool caesium atoms. They then turned off the
entrapment lasers and directly measured atom velocities of rem, which states that for any bulk quantity of a substance in
7 mm per second in order to calculate their temperature.[6] equilibrium, the kinetic energy of particle motion is evenly
Formulas for calculating the velocity and speed of transla- distributed among all the active (i.e. unfrozen) degrees of
tional motion are given in the following footnote.[7] freedom available to the particles. Since the internal tem-
perature of molecules are usually equal to their kinetic tem-
perature, the distinction is usually of interest only in the de-
The internal motions of molecules and specific heat tailed study of non-local thermodynamic equilibrium (LTE)
phenomena such as combustion, the sublimation of solids,
There are other forms of internal energy besides the ki- and the diffusion of hot gases in a partial vacuum.
netic energy of translational motion. As can be seen in
the animation at right, molecules are complex objects; they The kinetic energy stored internally in molecules causes
are a population of atoms and thermal agitation can strain substances to contain more internal energy at any given tem-
their internal chemical bonds in three different ways: via perature and to absorb additional internal energy for a given
rotation, bond length, and bond angle movements. These temperature increase. This is because any kinetic energy
are all types of internal degrees of freedom. This makes that is, at a given instant, bound in internal motions is not at
molecules distinct from monatomic substances (consisting that same[8]instant contributing to the molecules’ translational
of individual atoms) like the noble gases helium and argon, motions. This extra thermal energy simply increases the
which have only the three translational degrees of free- amount of energy a substance absorbs for a given temper-
dom. Kinetic energy is stored in molecules’ internal de- ature rise. This property is known as a substance’s specific
grees of freedom, which gives them an internal tempera- heat capacity.
ture. Even though these motions are called internal, the ex- Different molecules absorb different amounts of thermal
ternal portions of molecules still move—rather like the jig- energy for each incremental increase in temperature; that
gling of a stationary water balloon. This permits the two- is, they have different specific heat capacities. High specific
way exchange of kinetic energy between internal motions heat capacity arises, in part, because certain substances’
and translational motions with each molecular collision. molecules possess more internal degrees of freedom than
Accordingly, as energy is removed from molecules, both others do. For instance, nitrogen, which is a diatomic
their kinetic temperature (the temperature derived from the molecule, has five active degrees of freedom at room tem-
kinetic energy of translational motion) and their internal perature: the three comprising translational motion plus
temperature simultaneously diminish in equal proportions. two rotational degrees of freedom internally. Since the two
This phenomenon is described by the equipartition theo- internal degrees of freedom are essentially unfrozen, in ac-
6.4. THERMODYNAMIC TEMPERATURE 157

cordance with the equipartition theorem, nitrogen has five- lisions, but entire molecules or atoms can move forward
thirds the specific heat capacity per mole (a specific number into new territory, bringing their kinetic energy with them.
of molecules) as do the monatomic gases.[9] Another exam- Consequently, temperature differences equalize throughout
ple is gasoline (see table showing its specific heat capacity). gases very quickly—especially for light atoms or molecules;
Gasoline can absorb a large amount of thermal energy per convection speeds this process even more.[10]
mole with only a modest temperature change because each
Translational motion in solids, however, takes the form of
molecule comprises an average of 21 atoms and therefore
phonons (see Fig. 4 at right). Phonons are constrained,
has many internal degrees of freedom. Even larger, more
quantized wave packets that travel at a given substance’s
complex molecules can have dozens of internal degrees of
speed of sound. The manner in which phonons interact
freedom. within a solid determines a variety of its properties, includ-
ing its thermal conductivity. In electrically insulating solids,
[11]
The diffusion of thermal energy: Entropy, phonons, phonon-based heat conduction is usually inefficient and
and mobile conduction electrons such solids are considered thermal insulators (such as glass,
plastic, rubber, ceramic, and rock). This is because in
solids, atoms and molecules are locked into place relative
to their neighbors and are not free to roam.
Metals however, are not restricted to only phonon-based
heat conduction. Thermal energy conducts through metals
extraordinarily quickly because instead of direct molecule-
to-molecule collisions, the vast majority of thermal energy
is mediated via very light, mobile conduction electrons. This
is why there is a near-perfect correlation between metals’
thermal conductivity and their electrical conductivity.[12]
Conduction electrons imbue metals with their extraordinary
conductivity because they are delocalized (i.e., not tied to a
specific atom) and behave rather like a sort of quantum gas
due to the effects of zero-point energy (for more on ZPE, see
Note 1 below). Furthermore, electrons are relatively light
with a rest mass only 1 ⁄1836 th that of a proton. This is about
the same ratio as a .22 Short bullet (29 grains or 1.88 g)
compared to the rifle that shoots it. As Isaac Newton wrote
with his third law of motion,

Fig. 4 The temperature-induced translational motion of particles Law #3: All forces occur in pairs, and these
in solids takes the form of phonons. Shown here are phonons with two forces are equal in magnitude and opposite
identical amplitudes but with wavelengths ranging from 2 to 12 in direction.
molecules.

Heat conduction is the diffusion of thermal energy from hotHowever, a bullet accelerates faster than a rifle given an
parts of a system to cold. A system can be either a sin- equal force. Since kinetic energy increases as the square of
velocity, nearly all the kinetic energy goes into the bullet,
gle bulk entity or a plurality of discrete bulk entities. The
term bulk in this context means a statistically significantnot the rifle, even though both experience the same force
quantity of particles (which can be a microscopic amount).from the expanding propellant gases. In the same manner,
Whenever thermal energy diffuses within an isolated sys- because they are much less massive, thermal energy is read-
tem, temperature differences within the system decrease ily borne by mobile conduction electrons. Additionally, be-
(and entropy increases). cause they're delocalized and very fast, kinetic thermal en-
ergy conducts extremely quickly through metals with abun-
One particular heat conduction mechanism occurs when dant conduction electrons.
translational motion, the particle motion underlying tem-
perature, transfers momentum from particle to particle
in collisions. In gases, these translational motions are The diffusion of thermal energy: Black-body radiation
of the nature shown above in Fig. 1. As can be seen
in that animation, not only does momentum (heat) dif- Thermal radiation is a byproduct of the collisions arising
fuse throughout the volume of the gas through serial col- from various vibrational motions of atoms. These collisions
158
5500K
8E+11
Spectral energy density / kJ/m3 nm
6E+11
5000K
4E+11
4500K
2E+11 4000K
3500K
0
0 500
Wavelength / nm
Fig. 5 The spectrum of black-body radiation has the form of a
Planck curve. A 5500 K black-body has a peak emittance wave-
length of 527 nm. Compare the shape of this curve to that of a
Maxwell distribution in Fig. 2 above.
cause the electrons of the atoms to emit thermal photons
(known as black-body radiation). Photons are emitted any-
time an electric charge is accelerated (as happens when
electron clouds of two atoms collide). Even individual
molecules with internal temperatures greater than absolute
zero also emit black-body radiation from their atoms. In
any bulk quantity of a substance at equilibrium, black-body
photons are emitted across a range of wavelengths in a spec-
trum that has a bell curve-like shape called a Planck curve
(see graph in Fig. 5 at right). The top of a Planck curve (the
peak emittance wavelength) is located in a particular part
of the electromagnetic spectrum depending on the temper-
ature of the black-body. Substances at extreme cryogenic
temperatures emit at long radio wavelengths whereas ex-
tremely hot temperatures produce short gamma rays (see
Table of common temperatures).
Black-body radiation diffuses thermal energy throughout
a substance as the photons are absorbed by neighboring
atoms, transferring momentum in the process. Black-body
photons also easily escape from a substance and can be ab-
sorbed by the ambient environment; kinetic energy is lost
in the process.
As established by the Stefan–Boltzmann law, the intensity
of black-body radiation increases as the fourth power of ab-
solute temperature. Thus, a black-body at 824 K (just short
of glowing dull red) emits 60 times the radiant power as it
does at 296 K (room temperature). This is why one can so
easily feel the radiant heat from hot objects at a distance. At
higher temperatures, such as those found in an incandescent
lamp, black-body radiation can be the principal mechanism
by which thermal energy escapes a system.
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
Table of thermodynamic temperatures The full range
of the thermodynamic temperature scale, from absolute
zero to absolute hot, and some notable points between them
are shown in the table below.
A
The 2500 K value is approximate.
B
For a true blackbody (which tungsten filaments are not).
Tungsten filaments’ emissivity is greater at shorter wave-
lengths, which makes them appear whiter.
C
Effective photosphere temperature.
D
For a true blackbody (which the plasma was not). The Z
machine’s dominant emission originated from 40 MK elec-
trons (soft x–ray emissions) within the plasma.
1000 1500 2000
Fig. 6 Ice and water: two phases of the same substance
The heat of phase changes The kinetic energy of parti-
cle motion is just one contributor to the total thermal energy
in a substance; another is phase transitions, which are the
potential energy of molecular bonds that can form in a sub-
stance as it cools (such as during condensing and freezing).
The thermal energy required for a phase transition is called
latent heat. This phenomenon may more easily be grasped
by considering it in the reverse direction: latent heat is the
energy required to break chemical bonds (such as during
evaporation and melting). Almost everyone is familiar with
the effects of phase transitions; for instance, steam at 100
°C can cause severe burns much faster than the 100 °C air
from a hair dryer. This occurs because a large amount of
latent heat is liberated as steam condenses into liquid water
on the skin.
Even though thermal energy is liberated or absorbed dur-
ing phase transitions, pure chemical elements, compounds,
and eutectic alloys exhibit no temperature change whatso-
ever while they undergo them (see Fig. 7, below right).
Consider one particular type of phase transition: melting.
When a solid is melting, crystal lattice chemical bonds are
being broken apart; the substance is transitioning from what
is known as a more ordered state to a less ordered state. In
Fig. 7, the melting of ice is shown within the lower left box
6.4. THERMODYNAMIC TEMPERATURE 159

heading from blue to green. known as enthalpy of vaporization) is roughly 540 times that
required for a one-degree increase.[29]
Water’s sizable enthalpy of vaporization is why one’s skin
can be burned so quickly as steam condenses on it (head-
ing from red to green in Fig. 7 above). In the opposite
direction, this is why one’s skin feels cool as liquid water on
it evaporates (a process that occurs at a sub-ambient wet-
bulb temperature that is dependent on relative humidity).
Water’s highly energetic enthalpy of vaporization is also an
important factor underlying why solar pool covers (floating,
insulated blankets that cover swimming pools when not in
use) are so effective at reducing heating costs: they prevent
evaporation. For instance, the evaporation of just 20 mm
of water from a 1.29-meter-deep pool chills its water 8.4
degrees Celsius (15.1 °F).
Fig. 7 Water’s temperature does not change during phase transi-
tions as heat flows into or out of it. The total heat capacity of a
mole of water in its liquid phase (the green line) is 7.5507 kJ.
Internal energy The total energy of all particle motion
translational and internal, including that of conduction elec-
At one specific thermodynamic point, the melting point trons, plus the potential energy of phase changes, plus zero-
(which is 0 °C across a wide pressure range in the case point energy[3] comprise the internal energy of a substance.
of water), all the atoms or molecules are, on average, at
the maximum energy threshold their chemical bonds can
withstand without breaking away from the lattice. Chemi-
cal bonds are all-or-nothing forces: they either hold fast, or
break; there is no in-between state. Consequently, when a
substance is at its melting point, every joule of added ther-
mal energy only breaks the bonds of a specific quantity of
its atoms or molecules,[25] converting them into a liquid of
precisely the same temperature; no kinetic energy is added
to translational motion (which is what gives substances their
temperature). The effect is rather like popcorn: at a certain
temperature, additional thermal energy can't make the ker-
nels any hotter until the transition (popping) is complete.
If the process is reversed (as in the freezing of a liquid),
thermal energy must be removed from a substance.
As stated above, the thermal energy required for a phase
transition is called latent heat. In the specific cases of melt-
ing and freezing, it’s called enthalpy of fusion or heat of fu-
sion. If the molecular bonds in a crystal lattice are strong,
the heat of fusion can be relatively great, typically in the
range of 6 to 30 kJ per mole for water and most of the metal- Fig. 8 When many of the chemical elements, such as the noble gases
lic elements.[26] If the substance is one of the monatomic and platinum-group metals, freeze to a solid — the most ordered
gases, (which have little tendency to form molecular bonds) state of matter — their crystal structures have a closest-packed ar-
rangement. This yields the greatest possible packing density and the
the heat of fusion is more modest, ranging from 0.021 to
lowest energy state.
2.3 kJ per mole.[27] Relatively speaking, phase transitions
can be truly energetic events. To completely melt ice at 0
°C into water at 0 °C, one must add roughly 80 times the
thermal energy as is required to increase the temperature Internal energy at absolute zero As a substance cools,
of the same mass of liquid water by one degree Celsius. different forms of internal energy and their related ef-
The metals’ ratios are even greater, typically in the range of fects simultaneously decrease in magnitude: the latent heat
400 to 1200 times.[28] And the phase transition of boiling of available phase transitions is liberated as a substance
is much more energetic than freezing. For instance, the en- changes from a less ordered state to a more ordered state;
ergy required to completely boil or vaporize water (what is the translational motions of atoms and molecules dimin-
160 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

ish (their kinetic temperature decreases); the internal mo-

tions of molecules diminish (their internal temperature de-
creases); conduction electrons (if the substance is an electri-
cal conductor) travel somewhat slower;[30] and black-body
radiation’s peak emittance wavelength increases (the pho-
tons’ energy decreases). When the particles of a substance
are as close as possible to complete rest and retain only
ZPE-induced quantum mechanical motion, the substance
is at the temperature of absolute zero (T=0).
Note that whereas absolute zero is the point of zero thermo-
dynamic temperature and is also the point at which the par-
ticle constituents of matter have minimal motion, absolute
zero is not necessarily the point at which a substance con-
tains zero thermal energy; one must be very precise with Helium-4, is a superfluid at or below 2.17 kelvins, (2.17 Celsius
what one means by internal energy. Often, all the phase degrees above absolute zero)
changes that can occur in a substance, will have occurred
by the time it reaches absolute zero. However, this is not
always the case. Notably, T=0 helium remains liquid at involving gases. By expressing variables in absolute terms
room pressure and must be under a pressure of at least 25 and applying Gay–Lussac’s law of temperature/pressure
bar (2.5 MPa) to crystallize. This is because helium’s heat proportionality, solutions to everyday problems are straight-
of fusion (the energy required to melt helium ice) is so low forward; for instance, calculating how a temperature change
(only 21 joules per mole) that the motion-inducing effect affects the pressure inside an automobile tire. If the tire has
of zero-point energy is sufficient to prevent it from freezing a relatively cold pressure of 200 kPa-gage , then in abso-
at lower pressures. Only if under at least 25 bar (2.5 MPa) lute terms (relative to a vacuum), its pressure is 300 kPa-
of pressure will this latent thermal energy be liberated as absolute.[33][34][35] Room temperature (“cold” in tire terms)
helium freezes while approaching absolute zero. A further is 296 K. If the tire pressure is 20 °C hotter (20 kelvins),
complication is that many solids change their crystal struc- the solution is calculated as 316 K ⁄₂₉₆ K = 6.8% greater ther-
ture to more compact arrangements at extremely high pres- modynamic temperature and absolute pressure; that is, a
sures (up to millions of bars, or hundreds of gigapascals). pressure of 320 kPa-absolute, which is 220 kPa-gage.
These are known as solid-solid phase transitions wherein la-
tent heat is liberated as a crystal lattice changes to a more
thermodynamically favorable, compact one. 6.4.4 Definition of thermodynamic tempera-
The above complexities make for rather cumbersome ture
blanket statements regarding the internal energy in T=0
substances. Regardless of pressure though, what can be The thermodynamic temperature is defined by the second
said is that at absolute zero, all solids with a lowest-energy law of thermodynamics and its consequences. The thermo-
crystal lattice such those with a closest-packed arrangement dynamic temperature can be shown to have special proper-
(see Fig. 8, above left) contain minimal internal energy, ties, and in particular can be seen to be uniquely defined (up
retaining only that due to the ever-present background to some constant multiplicative factor) by considering the
of zero-point energy.[3] [31] One can also say that for a efficiency of idealized heat engines. Thus the ratio T 2 /T 1
given substance at constant pressure, absolute zero is the of two temperaturesT 1 andT 2 is the same in all absolute
point of lowest enthalpy (a measure of work potential scales.
that takes internal energy, pressure, and volume into Strictly speaking, the temperature of a system is well-
consideration).[32] Lastly, it is always true to say that all defined only if it is at thermal equilibrium. From a mi-
T=0 substances contain zero kinetic thermal energy.[3] [7] croscopic viewpoint, a material is at thermal equilibrium if
the quantity of heat between its individual particles cancel
out. There are many possible scales of temperature, derived
from a variety of observations of physical phenomena.
6.4.3 Practical applications for thermody- Loosely stated, temperature differences dictate the direc-
namic temperature tion of heat between two systems such that their combined
energy is maximally distributed among their lowest possi-
Thermodynamic temperature is useful not only for scien- ble states. We call this distribution "entropy". To better un-
tists, it can also be useful for lay-people in many disciplines derstand the relationship between temperature and entropy,
6.4. THERMODYNAMIC TEMPERATURE 161

consider the relationship between heat, work and tempera- so that

ture illustrated in the Carnot heat engine. The engine con-
verts heat into work by directing a temperature gradient be-
tween a higher temperature heat source, TH, and a lower g(T3 ) q3
f (T1 , T3 ) = = .
temperature heat sync, TC, through a gas filled piston. The g(T1 ) q1
work done per cycle is equal to the difference between the
i.e. The ratio of heat exchanged is a function of the respec-
heat supplied to the engine by TH, qH, and the heat sup-
tive temperatures at which they occur. We can choose any
plied to TC by the engine, qC. The efficiency of the engine
monotonic function for our g(T ) ; it is a matter of conve-
is the work divided by the heat put into the system or
nience and convention that we choose g(T ) = T . Choos-
ing then one fixed reference temperature (i.e. triple point of
wcy qH − qC qC water), we establish the thermodynamic temperature scale.
Efficiency = = =1− (1)
qH qH qH It is to be noted that such a definition coincides with that
of the ideal gas derivation; also it is this definition of the
where w is the work done per cycle. Thus the efficiency
thermodynamic temperature that enables us to represent the
depends only on qC/qH.
Carnot efficiency in terms of TH and TC, and hence derive
Carnot’s theorem states that all reversible engines operating that the (complete) Carnot cycle is isentropic:
between the same heat reservoirs are equally efficient. Thus,
any reversible heat engine operating between temperatures
T 1 and T 2 must have the same efficiency, that is to say, the qC TC
= f (TH , TC ) = . (3).
efficiency is the function of only temperatures qH TH
Substituting this back into our first formula for efficiency
qC yields a relationship in terms of temperature:
= f (TH , TC ) (2).
qH
In addition, a reversible heat engine operating between tem- qC TC
peratures T 1 and T 3 must have the same efficiency as one Efficiency = 1 − =1− (4).
qH TH
consisting of two cycles, one between T 1 and another (in-
termediate) temperature T 2 , and the second between T 2 Notice that for TC=0 the efficiency is 100% and that effi-
andT 3 . If this were not the case, then energy (in the form ciency becomes greater than 100% for TC<0, which cases
of Q) will be wasted or gained, resulting in different over- are unrealistic. Subtracting the right hand side of Equation
all efficiencies every time a cycle is split into component 4 from the middle portion and rearranging gives
cycles; clearly a cycle can be composed of any number of
smaller cycles. qH qC
− = 0,
With this understanding of Q1 , Q2 and Q3 , we note also that TH TC
mathematically,
where the negative sign indicates heat ejected from the sys-
tem. The generalization of this equation is Clausius theo-
q3 q2 q3 rem, which suggests the existence of a state function S (i.e.,
f (T1 , T3 ) = = = f (T1 , T2 )f (T2 , T3 ). a function which depends only on the state of the system,
q1 q1 q2
not on how it reached that state) defined (up to an additive
But the first function is NOT a function of T 2 , therefore constant) by
the product of the final two functions MUST result in the
removal of T 2 as a variable. The only way is therefore to
define the function f as follows: dqrev
dS = (5),
T
where the subscript indicates heat transfer in a reversible
g(T2 )
f (T1 , T2 ) = . process. The function S corresponds to the entropy of the
g(T1 )
system, mentioned previously, and the change of S around
and any cycle is zero (as is necessary for any state function).
Equation 5 can be rearranged to get an alternative defini-
tion for temperature in terms of entropy and heat (to avoid
g(T3 ) logic loop, we should first define entropy through statistical
f (T2 , T3 ) = . mechanics):
g(T2 )
162 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

dqrev
T = .
dS
For a system in which the entropy S is a function S(E) of
its energy E, the thermodynamic temperature T is therefore
given by

1 dS
= ,
T dE
so that the reciprocal of the thermodynamic temperature is
the rate of increase of entropy with energy.

6.4.5 History
• Ca. 485 BC: Parmenides in his treatise “On Nature”

Guillaume Amontons

endeavoring to improve upon the air thermometers in

use at the time. His J-tube thermometers comprised
a mercury column that was supported by a fixed mass
of air entrapped within the sensing portion of the ther-
mometer. In thermodynamic terms, his thermome-
ters relied upon the volume / temperature relationship
of gas under constant pressure. His measurements of
the boiling point of water and the melting point of ice
showed that regardless of the mass of air trapped in-
side his thermometers or the weight of mercury the air
was supporting, the reduction in air volume at the ice
point was always the same ratio. This observation led
him to posit that a sufficient reduction in temperature
would reduce the air volume to zero. In fact, his calcu-
lations projected that absolute zero was equivalent to
−240 °C—only 33.15 degrees short of the true value
of −273.15 °C.

• 1742: Anders Celsius (1701–1744) created a “back-

Parmenides
postulated the existente of primum frigidum, a hypo-
thetical elementary substance source of all cooling or
cold in the world.[36]
• 1702–1703: Guillaume Amontons (1663–1705) pub-
lished two papers that may be used to credit him as
being the first researcher to deduce the existence of a
fundamental (thermodynamic) temperature scale fea-
turing an absolute zero. He made the discovery while
wards” version of the modern Celsius temperature
scale. In Celsius’s original scale, zero represented the
boiling point of water and 100 represented the melting
point of ice. In his paper Observations of two persis-
tent degrees on a thermometer, he recounted his exper-
iments showing that ice’s melting point was effectively
unaffected by pressure. He also determined with re-
markable precision how water’s boiling point varied as
a function of atmospheric pressure. He proposed that
zero on his temperature scale (water’s boiling point)
would be calibrated at the mean barometric pressure
6.4. THERMODYNAMIC TEMPERATURE
Carl Linnaeus
Anders Celsius
at mean sea level.
• 1744: Coincident with the death of Anders Celsius,
the famous botanist Carl Linnaeus (1707–1778) ef-
fectively reversed[37] Celsius’s scale upon receipt of his
first thermometer featuring a scale where zero repre-
sented the melting point of ice and 100 represented
water’s boiling point. The custom-made linnaeus-
thermometer, for use in his greenhouses, was made
by Daniel Ekström, Sweden’s leading maker of scien-
tific instruments at the time. For the next 204 years,
the scientific and thermometry communities world-
wide referred to this scale as the centigrade scale.
Temperatures on the centigrade scale were often re-
ported simply as degrees or, when greater specificity
was desired, degrees centigrade. The symbol for tem-
perature values on this scale was °C (in several for-
mats over the years). Because the term centigrade
was also the French-language name for a unit of an-
gular measurement (one-hundredth of a right angle)
and had a similar connotation in other languages, the
term "centesimal degree" was used when very precise,
unambiguous language was required by international
standards bodies such as the International Bureau of
Weights and Measures (Bureau international des poids
et mesures) (BIPM). The 9th CGPM (General Confer-
ence on Weights and Measures (Conférence générale
163
des poids et mesures) and the CIPM (International
Committee for Weights and Measures (Comité interna-
tional des poids et mesures) formally adopted[38] degree
Celsius (symbol: °C) in 1948.[39]
• 1777: In his book Pyrometrie (Berlin: Haude &
Spener, 1779) completed four months before his
death, Johann Heinrich Lambert (1728–1777), some-
times incorrectly referred to as Joseph Lambert, pro-
posed an absolute temperature scale based on the pres-
sure/temperature relationship of a fixed volume of
gas. This is distinct from the volume/temperature re-
lationship of gas under constant pressure that Guil-
laume Amontons discovered 75 years earlier. Lambert
stated that absolute zero was the point where a sim-
ple straight-line extrapolation reached zero gas pres-
sure and was equal to −270 °C.
• Circa 1787: Notwithstanding the work of Guillaume
Amontons 85 years earlier, Jacques Alexandre César
Charles (1746–1823) is often credited with discover-
ing, but not publishing, that the volume of a gas under
constant pressure is proportional to its absolute tem-
perature. The formula he created was V 1 /T 1 = V 2 /T 2 .
• 1802: Joseph Louis Gay-Lussac (1778–1850) pub-
lished work (acknowledging the unpublished lab notes
of Jacques Charles fifteen years earlier) describ-
ing how the volume of gas under constant pressure
changes linearly with its absolute (thermodynamic)
164 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

Johann Heinrich Lambert

Jacques Alexandre César Charles
temperature. This behavior is called Charles’s Law
and is one of the gas laws. His are the first known
formulas to use the number 273 for the expansion co-
efficient of gas relative to the melting point of ice (in-
dicating that absolute zero was equivalent to −273 °C).
• 1848: William Thomson, (1824–1907) also known as
Lord Kelvin, wrote in his paper, On an Absolute Ther-
mometric Scale, of the need for a scale whereby infi-
nite cold (absolute zero) was the scale’s null point, and
which used the degree Celsius for its unit increment.
Like Gay-Lussac, Thomson calculated that absolute
zero was equivalent to −273 °C on the air thermome-
ters of the time. This absolute scale is known today
as the Kelvin thermodynamic temperature scale. It’s
noteworthy that Thomson’s value of −273 was actually
derived from 0.00366, which was the accepted expan-
sion coefficient of gas per degree Celsius relative to the
ice point. The inverse of −0.00366 expressed to five
significant digits is −273.22 °C which is remarkably
close to the true value of −273.15 °C.
• 1859: William John Macquorn Rankine (1820–1872)
proposed a thermodynamic temperature scale simi-
lar to William Thomson’s but which used the degree
Fahrenheit for its unit increment. This absolute scale Joseph Louis Gay-Lussac
is known today as the Rankine thermodynamic tem-
perature scale.
6.4. THERMODYNAMIC TEMPERATURE
Lord Kelvin
• 1877–1884: Ludwig Boltzmann (1844–1906) made William John Macquorn Rankine
major contributions to thermodynamics through an
understanding of the role that particle kinetics and
black body radiation played. His name is now attached
to several of the formulas used today in thermodynam-
ics.
• Circa 1930s: Gas thermometry experiments carefully
calibrated to the melting point of ice and boiling point
of water showed that absolute zero was equivalent to
−273.15 °C.
• 1948: Resolution 3 of the 9th CGPM (Conférence
Générale des Poids et Mesures, also known as the
General Conference on Weights and Measures) fixed
the triple point of water at precisely 0.01 °C. At this
time, the triple point still had no formal definition for
its equivalent kelvin value, which the resolution de-
clared “will be fixed at a later date”. The implication
is that if the value of absolute zero measured in the
1930s was truly −273.15 °C, then the triple point of
water (0.01 °C) was equivalent to 273.16 K. Addition-
ally, both the CIPM (Comité international des poids et
mesures, also known as the International Committee
for Weights and Measures) and the CGPM formally
adopted the name Celsius for the degree Celsius and
165
the Celsius temperature scale. [39]
• 1954: Resolution 3 of the 10th CGPM gave the Kelvin
scale its modern definition by choosing the triple point
of water as its second defining point and assigned it a
temperature of precisely 273.16 kelvin (what was ac-
tually written 273.16 degrees Kelvin at the time). This,
in combination with Resolution 3 of the 9th CGPM,
had the effect of defining absolute zero as being pre-
cisely zero kelvin and −273.15 °C.
• 1967/1968: Resolution 3 of the 13th CGPM renamed
the unit increment of thermodynamic temperature
kelvin, symbol K, replacing degree absolute, symbol
°K. Further, feeling it useful to more explicitly define
the magnitude of the unit increment, the 13th CGPM
also decided in Resolution 4 that “The kelvin, unit of
thermodynamic temperature, is the fraction 1/273.16
of the thermodynamic temperature of the triple point
of water”.
• 2005: The CIPM (Comité International des Poids et
Mesures, also known as the International Committee
for Weights and Measures) affirmed that for the pur-
166 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

• Delocalized electron

• Diffusion

• Elastic collision

• Electron

• Energy

• Energy conversion efficiency

• Enthalpy

• Entropy

• Equipartition theorem

• Evaporation

• Fahrenheit

• First law of thermodynamics

• Freezing

• Gas laws
Ludwig Boltzmann • Heat

• Heat conduction
poses of delineating the temperature of the triple point
of water, the definition of the Kelvin thermodynamic • Heat engine
temperature scale would refer to water having an iso-
• Internal energy
topic composition defined as being precisely equal to
the nominal specification of Vienna Standard Mean • International System of Quantities
Ocean Water.
• ITS-90

6.4.6 See also • Ideal gas law

• Joule
• Absolute hot
• Absolute zero • Kelvin

• Adiabatic process • Kinetic energy

• Black-body • Latent heat

• Boiling • Laws of thermodynamics

• Boltzmann constant • Maxwell–Boltzmann distribution

• Brownian motion • Melting

• Carnot heat engine • Mole

• Chemical bond • Molecule

• Condensation • Orders of magnitude (temperature)

• Convection • Phase transition

• Degrees of freedom • Phonon

6.4. THERMODYNAMIC TEMPERATURE 167

• Planck’s law of black-body radiation 6.4.7 Notes

• Potential energy In the following notes, wherever numeric equal-
ities are shown in concise form, such as
• Quantum mechanics: 1.85487(14)×1043 , the two digits between the
parentheses denotes the uncertainty at 1-σ (1
• Introduction to quantum mechanics standard deviation, 68% confidence level) in the
• Quantum mechanics (main article) two least significant digits of the significand.

• Rankine scale [1] Rankine, W.J.M., “A manual of the steam engine and other
prime movers”, Richard Griffin and Co., London (1859), p.
• Specific heat capacity 306-7

• Standard enthalpy change of fusion [2] William Thomson, 1st Baron Kelvin, “Heat”, Adam and
Charles Black, Edinburgh (1880), p. 39
• Standard enthalpy change of vaporization

• Stefan–Boltzmann law

• Sublimation

• Temperature

• Temperature conversion formulas

• Thermal conductivity

• Thermal radiation

• Thermodynamic beta

• Thermodynamic equations

• Thermodynamic equilibrium
[3]
• Thermodynamics
Absolute zero’s relationship to zero-point energy
• Thermodynamics Category (list of articles)
While scientists are achieving temperatures ever closer to
absolute zero, they can not fully achieve a state of zero tem-
• Timeline of heat engine technology
perature. However, even if scientists could remove all ki-
netic thermal energy from matter, quantum mechanical zero-
• Timeline of temperature and pressure measurement
point energy (ZPE) causes particle motion that can never be
technology eliminated. Encyclopædia Britannica Online defines zero-
point energy as the “vibrational energy that molecules re-
• Triple point tain even at the absolute zero of temperature”. ZPE is the
result of all-pervasive energy fields in the vacuum between
• Universal gas constant the fundamental particles of nature; it is responsible for the
Casimir effect and other phenomena. See Zero Point Energy
• Vienna Standard Mean Ocean Water (VSMOW) and Zero Point Field. See also Solid Helium by the Univer-
sity of Alberta’s Department of Physics to learn more about
• Wien’s displacement law ZPE’s effect on Bose–Einstein condensates of helium. Al-
though absolute zero (T=0) is not a state of zero molecular
• Work (Mechanical) motion, it is the point of zero temperature and, in accor-
dance with the Boltzmann constant, is also the point of zero
• Work (thermodynamics) particle kinetic energy and zero kinetic velocity. To under-
stand how atoms can have zero kinetic velocity and simul-
• Zero-point energy taneously be vibrating due to ZPE, consider the following
168
thought experiment: two T=0 helium atoms in zero grav-
ity are carefully positioned and observed to have an average
separation of 620 pm between them (a gap of ten atomic di-
ameters). It’s an “average” separation because ZPE causes
them to jostle about their fixed positions. Then one atom
is given a kinetic kick of precisely 83 yoctokelvins (1 yK =
1×10−24 K). This is done in a way that directs this atom’s
velocity vector at the other atom. With 83 yK of kinetic
energy between them, the 620 pm gap through their com-
mon barycenter would close at a rate of 719 pm/s and they
would collide after 0.862 second. This is the same speed as
shown in the Fig. 1 animation above. Before being given
the kinetic kick, both T=0 atoms had zero kinetic energy
and zero kinetic velocity because they could persist indefi-
nitely in that state and relative orientation even though both
were being jostled by ZPE. At T=0, no kinetic energy is
available for transfer to other systems. The Boltzmann con-
stant and its related formulas describe the realm of particle
kinetics and velocity vectors whereas ZPE is an energy field
that jostles particles in ways described by the mathematics of
quantum mechanics. In atomic and molecular collisions in
gases, ZPE introduces a degree of chaos, i.e., unpredictabil-
ity, to rebound kinetics; it is as likely that there will be less
ZPE-induced particle motion after a given collision as more.
This random nature of ZPE is why it has no net effect upon
either the pressure or volume of any bulk quantity (a statisti-
cally significant quantity of particles) of T>0 K gases. How-
ever, in T=0 condensed matter; e.g., solids and liquids, ZPE
causes inter-atomic jostling where atoms would otherwise
be perfectly stationary. Inasmuch as the real-world effects
that ZPE has on substances can vary as one alters a ther-
modynamic system (for example, due to ZPE, helium won't
freeze unless under a pressure of at least 25 bar or 2.5 MPa),
ZPE is very much a form of thermal energy and may prop-
erly be included when tallying a substance’s internal energy.
Note too that absolute zero serves as the baseline atop which
thermodynamics and its equations are founded because they
deal with the exchange of thermal energy between “systems”
(a plurality of particles and fields modeled as an average).
Accordingly, one may examine ZPE-induced particle mo-
tion within a system that is at absolute zero but there can
never be a net outflow of thermal energy from such a sys-
tem. Also, the peak emittance wavelength of black-body
radiation shifts to infinity at absolute zero; indeed, a peak
no longer exists and black-body photons can no longer es-
cape. Because of ZPE, however, virtual photons are still
emitted at T=0. Such photons are called “virtual” because
they can't be intercepted and observed. Furthermore, this
zero-point radiation has a unique zero-point spectrum. How-
ever, even though a T=0 system emits zero-point radiation,
no net heat flow Q out of such a system can occur because if
the surrounding environment is at a temperature greater than
T=0, heat will flow inward, and if the surrounding environ-
ment is at T=0, there will be an equal flux of ZP radiation
both inward and outward. A similar Q equilibrium exists at
T=0 with the ZPE-induced spontaneous emission of photons
(which is more properly called a stimulated emission in this
context). The graph at upper right illustrates the relationship
of absolute zero to zero-point energy. The graph also helps
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
in the understanding of how zero-point energy got its name:
it is the vibrational energy matter retains at the zero kelvin
point. Derivation of the classical electromagnetic zero-point
radiation spectrum via a classical thermodynamic operation
involving van der Waals forces, Daniel C. Cole, Physical Re-
view A, 42 (1990) 1847.
[4] At non-relativistic temperatures of less than about 30 GK,
classical mechanics are sufficient to calculate the velocity of
particles. At 30 GK, individual neutrons (the constituent of
neutron stars and one of the few materials in the universe
with temperatures in this range) have a 1.0042 γ (gamma
or Lorentz factor). Thus, the classic Newtonian formula for
kinetic energy is in error less than half a percent for temper-
atures less than 30 GK.
[5] Even room–temperature air has an average molecular
translational speed (not vector-isolated velocity) of 1822
km/hour. This is relatively fast for something the size of a
molecule considering there are roughly 2.42×1016 of them
crowded into a single cubic millimeter. Assumptions: Av-
erage molecular weight of wet air = 28.838 g/mol and T =
296.15 K. Assumption’s primary variables: An altitude of
194 meters above mean sea level (the world–wide median
altitude of human habitation), an indoor temperature of 23
°C, a dewpoint of 9 °C (40.85% relative humidity), and 760
mmHg (101.325 kPa) sea level–corrected barometric pres-
sure.
[6] Adiabatic Cooling of Cesium to 700 nK in an Optical Lattice,
A. Kastberg et al., Physical Review Letters 74 (1995) 1542
doi:10.1103/PhysRevLett.74.1542. It’s noteworthy that a
record cold temperature of 450 pK in a Bose–Einstein con-
densate of sodium atoms (achieved by A. E. Leanhardt et al..
of MIT) equates to an average vector-isolated atom velocity
of 0.4 mm/s and an average atom speed of 0.7 mm/s.
[7] The rate of translational motion of atoms and molecules is
calculated based on thermodynamic temperature as follows:
√
kB T
v̄ =
m
where:
• v̄ is the vector-isolated mean velocity of translational
particle motion in m/s
• kB is the Boltzmann constant = 1.3806504(24)×10−23
J/K
• T is the thermodynamic temperature in kelvins
• m is the molecular mass of substance in kilograms
In the above formula, molecular mass, m, in kilograms per
particle is the quotient of a substance’s molar mass (also
known as atomic weight, atomic mass, relative atomic mass,
and unified atomic mass units) in g/mol or daltons divided
by 6.02214179(30)×1026 (which is the Avogadro constant
times one thousand). For diatomic molecules such as H2 ,
N2 , and O2 , multiply atomic weight by two before plugging it
into the above formula. The mean speed (not vector-isolated
6.4. THERMODYNAMIC TEMPERATURE
velocity) of an atom or molecule along any arbitrary path is
calculated as follows:
√
s̄ = v̄ 3
where:
• s̄ is the mean speed of translational particle motion in
m/s
Note that the mean energy of the translational motions of
a substance’s constituent particles correlates to their mean
speed, not velocity. Thus, substituting s̄ for v in the classic
formula for kinetic energy, Ek = 1 ⁄2 m • v 2 produces pre-
cisely the same value as does Emean = 3/2kBT (as shown in
the section titled The nature of kinetic energy, translational
motion, and temperature). Note too that the Boltzmann con-
stant and its related formulas establish that absolute zero is
the point of both zero kinetic energy of particle motion and
zero kinetic velocity (see also Note 1 above).
[8] The internal degrees of freedom of molecules cause their ex-
ternal surfaces to vibrate and can also produce overall spin-
ning motions (what can be likened to the jiggling and spin-
ning of an otherwise stationary water balloon). If one exam-
ines a single molecule as it impacts a containers’ wall, some
of the kinetic energy borne in the molecule’s internal de-
grees of freedom can constructively add to its translational
motion during the instant of the collision and extra kinetic
energy will be transferred into the container’s wall. This
would induce an extra, localized, impulse-like contribution
to the average pressure on the container. However, since
the internal motions of molecules are random, they have
an equal probability of destructively interfering with trans-
lational motion during a collision with a container’s walls or
another molecule. Averaged across any bulk quantity of a
gas, the internal thermal motions of molecules have zero net
effect upon the temperature, pressure, or volume of a gas.
Molecules’ internal degrees of freedom simply provide ad-
ditional locations where internal energy is stored. This is
precisely why molecular-based gases have greater specific
heat capacity than monatomic gases (where additional ther-
mal energy must be added to achieve a given temperature
rise).
[9] When measured at constant-volume since different amounts
of work must be performed if measured at constant-pressure.
Nitrogen’s CvH (100 kPa, 20 °C) equals 20.8 J mol−1 K−1 vs.
the monatomic gases, which equal 12.4717 J mol−1 K−1 . Ci-
tations: W.H. Freeman’s Physical Chemistry, Part 3: Change
(422 kB PDF, here), Exercise 21.20b, p. 787. Also Georgia
State University’s Molar Specific Heats of Gases.
[10] The speed at which thermal energy equalizes throughout the
volume of a gas is very rapid. However, since gases have
extremely low density relative to solids, the heat flux (the
thermal power passing per area) through gases is compar-
atively low. This is why the dead-air spaces in multi-pane
windows have insulating qualities.
[11] Diamond is a notable exception. Highly quantized modes of
phonon vibration occur in its rigid crystal lattice. Therefore,
169
not only does diamond have exceptionally poor specific heat
capacity, it also has exceptionally high thermal conductivity.
[12] Correlation is 752 (W m−1 K−1 ) /(MS·cm), σ = 81, through
a 7:1 range in conductivity. Value and standard deviation
based on data for Ag, Cu, Au, Al, Ca, Be, Mg, Rh, Ir, Zn,
Co, Ni, Os, Fe, Pa, Pt, and Sn. Citation: Data from CRC
Handbook of Chemistry and Physics, 1st Student Edition and
this link to Web Elements’ home page.
[13] The cited emission wavelengths are for true black bodies in
equilibrium. In this table, only the sun so qualifies. CO-
DATA 2006 recommended value of 2.897 7685(51) × 10−3
m K used for Wien displacement law constant b.
[14] A record cold temperature of 450 ±80 pK in a Bose–
Einstein condensate (BEC) of sodium atoms was achieved in
2003 by researchers at MIT. Citation: Cooling Bose–Einstein
Condensates Below 500 Picokelvin, A. E. Leanhardt et al.,
Science 301, 12 Sept. 2003, Pg. 1515. It’s noteworthy that
this record’s peak emittance black-body wavelength of 6,400
kilometers is roughly the radius of Earth.
[15] The peak emittance wavelength of 2.897 77 m is a frequency
of 103.456 MHz
[16] Measurement was made in 2002 and has an uncertainty of
±3 kelvins. A 1989 measurement produced a value of
5777 ±2.5 K. Citation: Overview of the Sun (Chapter 1
lecture notes on Solar Physics by Division of Theoretical
Physics, Dept. of Physical Sciences, University of Helsinki).
Download paper (252 kB PDF)
[17] The 350 MK value is the maximum peak fusion fuel temper-
ature in a thermonuclear weapon of the Teller–Ulam con-
figuration (commonly known as a “hydrogen bomb”). Peak
temperatures in Gadget-style fission bomb cores (commonly
known as an “atomic bomb”) are in the range of 50 to 100
MK. Citation: Nuclear Weapons Frequently Asked Ques-
tions, 3.2.5 Matter At High Temperatures. Link to relevant
Web page. All referenced data was compiled from publicly
available sources.
[18] Peak temperature for a bulk quantity of matter was achieved
by a pulsed-power machine used in fusion physics experi-
ments. The term “bulk quantity” draws a distinction from
collisions in particle accelerators wherein high “tempera-
ture” applies only to the debris from two subatomic parti-
cles or nuclei at any given instant. The >2 GK temperature
was achieved over a period of about ten nanoseconds dur-
ing “shot Z1137.” In fact, the iron and manganese ions in
the plasma averaged 3.58 ±0.41 GK (309 ±35 keV) for 3
ns (ns 112 through 115). Citation: Ion Viscous Heating in
a Magnetohydrodynamically Unstable Z Pinch at Over 2 ×
109 Kelvin, M. G. Haines et al., Physical Review Letters 96,
Issue 7, id. 075003. Link to Sandia’s news release.
[19] Core temperature of a high–mass (>8–11 solar masses) star
after it leaves the main sequence on the Hertzsprung–Russell
diagram and begins the alpha process (which lasts one day)
of fusing silicon–28 into heavier elements in the following
170
steps: sulfur–32 → argon–36 → calcium–40 → titanium–
44 → chromium–48 → iron–52 → nickel–56. Within min-
utes of finishing the sequence, the star explodes as a Type II
supernova. Citation: Stellar Evolution: The Life and Death
of Our Luminous Neighbors (by Arthur Holland and Mark
Williams of the University of Michigan). Link to Web site.
More informative links can be found here, and here, and a
concise treatise on stars by NASA is here. Archived July 20,
2015, at the Wayback Machine.
[20] Based on a computer model that predicted a peak internal
temperature of 30 MeV (350 GK) during the merger of a
binary neutron star system (which produces a gamma–ray
burst). The neutron stars in the model were 1.2 and 1.6
solar masses respectively, were roughly 20 km in diameter,
and were orbiting around their barycenter (common center
of mass) at about 390 Hz during the last several milliseconds
before they completely merged. The 350 GK portion was a
small volume located at the pair’s developing common core
and varied from roughly 1 to 7 km across over a time span
of around 5 ms. Imagine two city-sized objects of unimag-
inable density orbiting each other at the same frequency as
the G4 musical note (the 28th white key on a piano). It’s
also noteworthy that at 350 GK, the average neutron has a
vibrational speed of 30% the speed of light and a relativistic
mass (m) 5% greater than its rest mass (m0 ). Citation: Torus
Formation in Neutron Star Mergers and Well-Localized Short
Gamma-Ray Bursts, R. Oechslin et al. of Max Planck Insti-
tute for Astrophysics., arXiv:astro-ph/0507099 v2, 22 Feb.
2006. Download paper (725 kB PDF) (from Cornell Uni-
versity Library’s arXiv.org server). To view a browser-based
summary of the research, click here.
[21] NewScientist: Eight extremes: The hottest thing in the uni-
verse, 07 March 2011, which stated “While the details of
this process are currently unknown, it must involve a fireball
of relativistic particles heated to something in the region of
a trillion kelvin”
[22] Results of research by Stefan Bathe using the PHENIX de-
tector on the Relativistic Heavy Ion Collider at Brookhaven
National Laboratory in Upton, New York, U.S.A. Bathe has
studied gold-gold, deuteron-gold, and proton-proton colli-
sions to test the theory of quantum chromodynamics, the
theory of the strong force that holds atomic nuclei together.
Link to news release.
[23] Citation: How do physicists study particles? by CERN.
[24] The Planck frequency equals 1.854 87(14) × 1043 Hz (which
is the reciprocal of one Planck time). Photons at the Planck
frequency have a wavelength of one Planck length. The
Planck temperature of 1.416 79(11) × 1032 K equates to a
calculated b /T = λmax wavelength of 2.045 31(16) × 10−26
nm. However, the actual peak emittance wavelength quan-
tizes to the Planck length of 1.616 24(12) × 10−26 nm.
[25] Water’s enthalpy of fusion (0 °C, 101.325 kPa) equates to
0.062284 eV per molecule so adding one joule of ther-
mal energy to 0 °C water ice causes 1.0021×1020 water
CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES
molecules to break away from the crystal lattice and become
liquid.
[26] Water’s enthalpy of fusion is 6.0095 kJ mol−1 K−1 (0 °C,
101.325 kPa). Citation: Water Structure and Science, Wa-
ter Properties, Enthalpy of fusion, (0 °C, 101.325 kPa) (by
London South Bank University). Link to Web site. The only
metals with enthalpies of fusion not in the range of 6–30 J
mol−1 K−1 are (on the high side): Ta, W, and Re; and (on the
low side) most of the group 1 (alkaline) metals plus Ga, In,
Hg, Tl, Pb, and Np. Citation: This link to Web Elements’
home page.
[27] Xenon value citation: This link to WebElements’ xenon data
(available values range from 2.3 to 3.1 kJ/mol). It is also
noteworthy that helium’s heat of fusion of only 0.021 kJ/mol
is so weak of a bonding force that zero-point energy prevents
helium from freezing unless it is under a pressure of at least
25 atmospheres.
[28] CRC Handbook of Chemistry and Physics, 1st Student Edi-
tion and Web Elements.
[29] H2 Ospecific heat capacity, Cp = 0.075327 kJ mol−1 K−1 (25
°C); Enthalpy of fusion = 6.0095 kJ/mol (0 °C, 101.325
kPa); Enthalpy of vaporization (liquid) = 40.657 kJ/mol
(100 °C). Citation: Water Structure and Science, Water Prop-
erties (by London South Bank University). Link to Web site.
[30] Mobile conduction electrons are delocalized, i.e. not tied to
a specific atom, and behave rather like a sort of quantum
gas due to the effects of zero-point energy. Consequently,
even at absolute zero, conduction electrons still move be-
tween atoms at the Fermi velocity of about 1.6×106 m/s.
Kinetic thermal energy adds to this speed and also causes
delocalized electrons to travel farther away from the nuclei.
[31] No other crystal structure can exceed the 74.048% pack-
ing density of a closest-packed arrangement. The two reg-
ular crystal lattices found in nature that have this density
are hexagonal close packed (HCP) and face-centered cubic
(FCC). These regular lattices are at the lowest possible en-
ergy state. Diamond is a closest-packed structure with an
FCC crystal lattice. Note too that suitable crystalline chem-
ical compounds, although usually composed of atoms of dif-
ferent sizes, can be considered as closest-packed structures
when considered at the molecular level. One such com-
pound is the common mineral known as magnesium alu-
minum spinel (MgAl2 O4 ). It has a face-centered cubic crys-
tal lattice and no change in pressure can produce a lattice
with a lower energy state.
[32] Nearly half of the 92 naturally occurring chemical elements
that can freeze under a vacuum also have a closest-packed
crystal lattice. This set includes beryllium, osmium, neon,
and iridium (but excludes helium), and therefore have zero
latent heat of phase transitions to contribute to internal en-
ergy (symbol: U). In the calculation of enthalpy (formula:
H = U + pV), internal energy may exclude different sources
of thermal energy (particularly ZPE) depending on the na-
ture of the analysis. Accordingly, all T=0 closest-packed
6.5. VOLUME
matter under a perfect vacuum has either minimal or zero
enthalpy, depending on the nature of the analysis. Use Of
Legendre Transforms In Chemical Thermodynamics, Robert
A. Alberty, Pure Appl.Chem., 73 (2001) 1349.
[33] Pressure also must be in absolute terms. The air still in a tire
at 0 kPa-gage expands too as it gets hotter. It’s not uncom-
mon for engineers to overlook that one must work in terms
of absolute pressure when compensating for temperature.
For instance, a dominant manufacturer of aircraft tires pub-
lished a document on temperature-compensating tire pres-
sure, which used gage pressure in the formula. However, the
high gage pressures involved (180 psi; 12.4 bar; 1.24 MPa)
means the error would be quite small. With low-pressure au-
tomobile tires, where gage pressures are typically around 2
bar (200 kPa), failing to adjust to absolute pressure results
in a significant error. Referenced document: Aircraft Tire
Ratings (155 kB PDF, here).
[34] Regarding the spelling “gage” vs. “gauge” in the context
of pressures measured relative to atmospheric pressure, the
preferred spelling varies by country and even by industry.
Further, both spellings are often used within a particular
industry or country. Industries in British English-speaking
countries typically use the spelling “gauge pressure” to dis-
tinguish it from the pressure-measuring instrument, which in
the U.K., is spelled pressure gage. For the same reason, many
of the largest American manufacturers of pressure transduc-
ers and instrumentation use the spelling gage pressure (the
convention used here) in their formal documentation to dis-
tinguish it from the instrument, which is spelled pressure
gauge. (see Honeywell-Sensotec’s FAQ page and Fluke Cor-
poration’s product search page).
[35] A difference of 100 kPa is used here instead of the 101.325
kPa value of one standard atmosphere. In 1982, the
International Union of Pure and Applied Chemistry (IU-
PAC) recommended that for the purposes of specifying the
physical properties of substances, the standard pressure (at-
mospheric pressure) should be defined as precisely 100 kPa
(≈750.062 Torr). Besides being a round number, this had a
very practical effect: relatively few people live and work at
precisely sea level; 100 kPa equates to the mean pressure at
an altitude of about 112 meters, which is closer to the 194–
meter, worldwide median altitude of human habitation. For
especially low-pressure or high-accuracy work, true atmo-
spheric pressure must be measured. Citation: IUPAC.org,
Gold Book, Standard Pressure
[36] Absolute Zero and the Conquest of Cold , Shachtman, Tom.,
Mariner Books, 1999.
[37] A Brief History of Temperature Measurement and; Uppsala
University (Sweden), Linnaeus’ thermometer
[38] bipm.org
[39] According to The Oxford English Dictionary (OED), the
term “Celsius’s thermometer” had been used at least as early
as 1797. Further, the term “The Celsius or Centigrade ther-
mometer” was again used in reference to a particular type
171
of thermometer at least as early as 1850. The OED also
cites this 1928 reporting of a temperature: “My altitude was
about 5,800 metres, the temperature was 28° Celsius”. How-
ever, dictionaries seek to find the earliest use of a word or
term and are not a useful resource as regards the terminology
used throughout the history of science. According to sev-
eral writings of Dr. Terry Quinn CBE FRS, Director of the
BIPM (1988–2004), including Temperature Scales from the
early days of thermometry to the 21st century (148 kB PDF,
here) as well as Temperature (2nd Edition / 1990 / Academic
Press / 0125696817), the term Celsius in connection with the
centigrade scale was not used whatsoever by the scientific or
thermometry communities until after the CIPM and CGPM
adopted the term in 1948. The BIPM wasn't even aware that
degree Celsius was in sporadic, non-scientific use before that
time. It’s also noteworthy that the twelve-volume, 1933 edi-
tion of OED did not even have a listing for the word Celsius
(but did have listings for both centigrade and centesimal in
the context of temperature measurement). The 1948 adop-
tion of Celsius accomplished three objectives:
(a) All common temperature scales would have their units
named after someone closely associated with them;
namely, Kelvin, Celsius, Fahrenheit, Réaumur and
Rankine.
(b) Notwithstanding the important contribution of Lin-
naeus who gave the Celsius scale its modern form,
Celsius’s name was the obvious choice because it be-
gan with the letter C. Thus, the symbol °C that for
centuries had been used in association with the name
centigrade could continue to be used and would simul-
taneously inherit an intuitive association with the new
name.
(c) The new name eliminated the ambiguity of the term
centigrade, freeing it to refer exclusively to the French-
language name for the unit of angular measurement.
6.4.8 External links
• Kinetic Molecular Theory of Gases. An explanation
(with interactive animations) of the kinetic motion of
molecules and how it affects matter. By David N.
Blauch, Department of Chemistry, Davidson College.
• Zero Point Energy and Zero Point Field. A Web site
with in-depth explanations of a variety of quantum ef-
fects. By Bernard Haisch, of Calphysics Institute.
6.5 Volume
For the general geometric concept, see volume.
In thermodynamics, the volume of a system is an impor-
tant extensive parameter for describing its thermodynamic
172 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

state. The specific volume, an intensive property, is the sys- Volume is one of a pair of conjugate variables, the other
tem’s volume per unit of mass. Volume is a function of state being pressure. As with all conjugate pairs, the product is
and is interdependent with other thermodynamic properties a form of energy. The product pV is the energy lost to a
such as pressure and temperature. For example, volume is system due to mechanical work. This product is one term
related to the pressure and temperature of an ideal gas by which makes up enthalpy H :
the ideal gas law.
The physical volume of a system may or may not coincide
with a control volume used to analyze the system. H = U + pV,
where U is the internal energy of the system.
The second law of thermodynamics describes constraints on
6.5.1 Overview the amount of useful work which can be extracted from a
thermodynamic system. In thermodynamic systems where
The volume of a thermodynamic system typically refers the temperature and volume are held constant, the measure
to the volume of the working fluid, such as, for example, of “useful” work attainable is the Helmholtz free energy;
the fluid within a piston. Changes to this volume may be and in systems where the volume is not held constant, the
made through an application of work, or may be used to measure of useful work attainable is the Gibbs free energy.
produce work. An isochoric process however operates at
a constant-volume, thus no work can be produced. Many Similarly, the appropriate value of heat capacity to use in
other thermodynamic processes will result in a change in a given process depends on whether the process produces
volume. A polytropic process, in particular, causes changes a change in volume. The heat capacity is a function of the
to the system so that the quantity pV n is constant (where p amount of heat added to a system. In the case of a constant-
is pressure, V is volume, and n is the polytropic index, a volume process, all the heat affects the internal energy of
constant). Note that for specific polytropic indexes a poly- the system (i.e., there is no pV-work, and all the heat af-
tropic process will be equivalent to a constant-property pro- fects the temperature). However in a process without a con-
cess. For instance, for very large values of n approaching stant volume, the heat addition affects both the internal en-
infinity, the process becomes constant-volume. ergy and the work (i.e., the enthalpy); thus the temperature
changes by a different amount than in the constant-volume
Gases are compressible, thus their volumes (and specific case and a different heat capacity value is required.
volumes) may be subject to change during thermodynamic
processes. Liquids, however, are nearly incompressible,
thus their volumes can be often taken as constant. In 6.5.3 Specific volume
general, compressibility is defined as the relative volume
change of a fluid or solid as a response to a pressure, and See also: Specific volume
may be determined for substances in any phase. Similarly,
thermal expansion is the tendency of matter to change in
Specific volume ( ν ) is the volume occupied by a unit of
volume in response to a change in temperature.
mass of a material.[1] In many cases the specific volume is a
Many thermodynamic cycles are made up of varying pro- useful quantity to determine because, as an intensive prop-
cesses, some which maintain a constant volume and some erty, it can be used to determine the complete state of a sys-
which do not. A vapor-compression refrigeration cycle, tem in conjunction with another independent intensive vari-
for example, follows a sequence where the refrigerant fluid able. The specific volume also allows systems to be studied
transitions between the liquid and vapor states of matter. without reference to an exact operating volume, which may
Typical units for volume are m (cubic meters), l (liters), not be known (nor significant) at some stages of analysis.
3

and ft3 (cubic feet). The specific volume of a substance is equal to the reciprocal
3
of its mass density. Specific volume may be expressed in mkg
ft3 ft3 mL
, lbm , slug , or g .
6.5.2 Heat and work

Mechanical work performed on a working fluid causes a V 1

ν= =
change in the mechanical constraints of the system; in other m ρ
words, for work to occur, the volume must be altered.
Hence volume is an important parameter in characterizing where, V is the volume, m is the mass and ρ is the density
many thermodynamic processes where an exchange of en- of the material.
ergy in the form of work is involved. For an ideal gas,
6.5. VOLUME
R̄T
ν=
P ent temperature or pressure (1 and 2), assuming nR are the
where, R̄ is the specific gas constant, T is the temperature same, the following equation uses humidity exclusion in ad-
and P is the pressure of the gas.
Specific volume may also refer to molar volume.
6.5.4 Gas volume
Dependence on pressure and temperature
The volume of gas increases proportionally to absolute tem- For example, calculating how much 1 liter of air (a) at 0 °C,
perature and decreases inversely proportionally to pressure, 100 kPa, pw = 0 kPa (known as STPD, see below) would fill
approximately according to the ideal gas law:
V = nRTp
where:
• p is the pressure
• V is the volume
• n is the amount of substance of gas (moles)
• R is the gas constant, 8.314 J·K mol
−1 −1
• T is the absolute temperature
To simplify, a volume of gas may be expressed as the vol-
ume it would have in standard conditions for temperature
and pressure, which are 0 °C and 100 kPa.[2]
Humidity exclusion
In contrast to other gas components, water content in air,
or humidity, to a higher degree depends on vaporization
and condensation from or into water, which, in turn, mainly
depends on temperature. Therefore, when applying more
pressure to a gas saturated with water, all components will
initially decrease in volume approximately according to
the ideal gas law. However, some of the water will con-
dense until returning to almost the same humidity as be-
fore, giving the resulting total volume deviating from what
the ideal gas law predicted. Conversely, decreasing temper-
ature would also make some water condense, again making
the final volume deviating from predicted by the ideal gas
law.
Therefore, gas volume may alternatively be expressed ex-
cluding the humidity content: V (volume dry). This frac-
tion more accurately follows the ideal gas law. On the con-
trary V (volume saturated) is the volume a gas mixture
would have if humidity was added to it until saturation (or
100% relative humidity).
173
General conversion
To compare gas volume between two conditions of differ-
dition to the ideal gas law:
p1 −pw,1
V2 = V1 × T2
T1 × p2 −pw,2
Where, in addition to terms used in the ideal gas law:
• pw is the partial pressure of gaseous water
during condition 1 and 2, respectively
when breathed into the lungs where it is mixed with water
vapor (l), where it quickly becomes 37 °C, 100 kPa, pw =
6.2 kPa (BTPS):
310 K 100 kPa−0 kPa
Vl = 1 l × 273 K × 100 kPa−6.2 kPa = 1.21 l
Common conditions
Some common expressions of gas volume with defined or
variable temperature, pressure and humidity inclusion are:
• ATPS: Ambient temperature (variable) and pressure
(variable), saturated (humidity depends on tempera-
ture)
• ATPD: Ambient temperature (variable) and pressure
(variable), dry (no humidity)
• BTPS: Body Temperature (37 °C or 310 K) and pres-
sure (generally same as ambient), saturated (47 mmHg
or 6.2 kPa)
• STPD: Standard temperature (0 °C or 273 K) and
pressure (760 mmHg (101.33 kPa) or 100 kPa (750.06
mmHg)), dry (no humidity)
Conversion factors
The following conversion factors can be used to convert be-
tween expressions for volume of a gas:[3]
Partial volume
See also: Partial pressure
The partial volume of a particular gas is the volume which
the gas would have if it alone occupied the volume, with
unchanged pressure and temperature, and is useful in gas
174 CHAPTER 6. CHAPTER 6. SYSTEM PROPERTIES

mixtures, e.g. air, to focus on one particular gas component,

e.g. oxygen.
It can be approximated both from partial pressure and molar
fraction:[4]

Vx = Vtot × Px
Ptot = Vtot × nx
ntot

• Vx is the partial volume of any individual

gas component (X)
• Vtot is the total volume in gas mixture
• Px is the partial pressure of gas X
• Ptot is the total pressure in gas mixture
• nx is the amount of substance of a gas (X)
• ntot is the total amount of substance in gas
mixture

6.5.5 See also

• Volumetric flow rate

6.5.6 References
[1] Cengel, Yunus A.; Boles, Michael A. (2002). Thermody-
namics: an engineering approach. Boston: McGraw-Hill. p.
11. ISBN 0-07-238332-1.

[2] A. D. McNaught, A. Wilkinson (1997). Compendium of

Chemical Terminology, The Gold Book (2nd ed.). Blackwell
Science. ISBN 0-86542-684-8.

[3] Brown, Stanley; Miller, Wayne; Eason, M (2006). Exercise

Physiology: Basis of Human Movement in Health and Dis-
ease. Lippincott Williams & Wilkins. p. 113. ISBN 0-
7817-3592-0. Retrieved 13 February 2014.

[4] Page 200 in: Medical biophysics. Flemming Cornelius. 6th

Edition, 2008.
Chapter 7

Chapter 7

7.1 Thermodynamic system rather than of states of the system; such were historically
important in the conceptual development of the subject; and
(b) systems considered in terms of processes described by
A thermodynamic system is the material and radiative steady flows; such are important in engineering.
content of a macroscopic volume in space, that can be ade- In 1824 Sadi Carnot described a thermodynamic system as
quately described by thermodynamic state variables such as the working substance (such as the volume of steam) of
temperature, entropy, internal energy and pressure. Usu- any heat engine under study. The very existence of such
ally, by default, a thermodynamic system is taken to be thermodynamic systems may be considered a fundamental
in its own internal state of thermodynamic equilibrium, postulate of equilibrium thermodynamics, though it is only
as opposed to a non-equilibrium state. The thermody- rarely cited as a numbered law.[1][2][3] According to Bai-
namic system is always enclosed by walls that separate lyn, the commonly rehearsed statement of the zeroth law
it from its surroundings; these constrain the system. A of thermodynamics is a consequence of this fundamental
thermodynamic system is subject to external interventions postulate.[4]
called thermodynamic operations; these alter the system’s
walls or its surroundings; as a result, the system under- In equilibrium thermodynamics the state variables do not
goes thermodynamic processes according to the principles include fluxes because in a state of thermodynamic equilib-
of thermodynamics. (This account mainly refers to the sim- rium all fluxes have zero values by postulation. Equilibrium
plest kind of thermodynamic system; compositions of sim- thermodynamic processes may of course involve fluxes but
ple systems may also be considered.) these must have ceased by the time a thermodynamic pro-
cess or operation is complete bringing a system to its even-
The thermodynamic state of a thermodynamic system is its tual thermodynamic state. Non-equilibrium thermodynam-
internal state as specified by its state variables. In addi- ics allows its state variables to include non-zero fluxes, that
tion to the state variables, a thermodynamic account also describe transfers of matter or energy or entropy between a
requires a special kind of quantity called a state function, system and its surroundings.[5]
which is a function of the defining state variables. For ex-
ample, if the state variables are internal energy, volume and
mole amounts, that special function is the entropy. These 7.1.1 Overview
quantities are inter-related by one or more functional rela-
tionships called equations of state, and by the system’s char- Thermodynamic equilibrium is characterized by absence of
acteristic equation. Thermodynamics imposes restrictions flow of matter or energy. Equilibrium thermodynamics, as
on the possible equations of state and on the characteris- a subject in physics, considers macroscopic bodies of mat-
tic equation. The restrictions are imposed by the laws of ter and energy in states of internal thermodynamic equi-
thermodynamics. librium. It uses the concept of thermodynamic processes,
According to the permeabilities of the walls of a system, by which bodies pass from one equilibrium state to another
transfers of energy and matter occur between it and its by transfer of matter and energy between them. The term
surroundings, which are assumed to be unchanging over 'thermodynamic system' is used to refer to bodies of mat-
time, until a state of thermodynamic equilibrium is attained. ter and energy in the special context of thermodynamics.
The only states considered in equilibrium thermodynamics The possible equilibria between bodies are determined by
are equilibrium states. Classical thermodynamics includes the physical properties of the walls that separate the bodies.
equilibrium thermodynamics. It also considers: (a) sys- Equilibrium thermodynamics in general does not measure
tems considered in terms of cyclic sequences of processes time. Equilibrium thermodynamics is a relatively simple

175
176
SURROUNDINGS
SYSTEM
BOUNDARY
and well settled subject. One reason for this is the exis-
tence of a well defined physical quantity called 'the entropy
of a body'.
Non-equilibrium thermodynamics, as a subject in physics,
considers bodies of matter and energy that are not in states
of internal thermodynamic equilibrium, but are usually par-
ticipating in processes of transfer that are slow enough to
allow description in terms of quantities that are closely re-
lated to thermodynamic state variables. It is characterized
by presence of flows of matter and energy. For this topic,
very often the bodies considered have smooth spatial inho-
mogeneities, so that spatial gradients, for example a tem-
perature gradient, are well enough defined. Thus the de-
scription of non-equilibrium thermodynamic systems is a
field theory, more complicated than the theory of equilib-
rium thermodynamics. Non-equilibrium thermodynamics
is a growing subject, not an established edifice. In gen-
eral, it is not possible to find an exactly defined entropy for
non-equilibrium problems. For many non-equilibrium ther-
modynamical problems, an approximately defined quantity
called 'time rate of entropy production' is very useful. Non-
equilibrium thermodynamics is mostly beyond the scope of
the present article.
Another kind of thermodynamic system is considered in
engineering. It takes part in a flow process. The account
is in terms that approximate, well enough in practice in
many cases, equilibrium thermodynamical concepts. This
is mostly beyond the scope of the present article, and is set
out in other articles, for example the article Flow process.
7.1.2 History
The first to create the concept of a thermodynamic sys- At thermodynamic equilibrium, a system’s properties are,
tem was the French physicist Sadi Carnot whose 1824 by definition, unchanging in time. Systems in equilib-
CHAPTER 7. CHAPTER 7
Reflections on the Motive Power of Fire studied what he
called the working substance, e.g., typically a body of water
vapor, in steam engines, in regards to the system’s ability
to do work when heat is applied to it. The working sub-
stance could be put in contact with either a heat reservoir (a
boiler), a cold reservoir (a stream of cold water), or a piston
(to which the working body could do work by pushing on
it). In 1850, the German physicist Rudolf Clausius general-
ized this picture to include the concept of the surroundings,
and began referring to the system as a “working body.” In
his 1850 manuscript On the Motive Power of Fire, Clausius
wrote:
The article Carnot heat engine shows the original piston-
and-cylinder diagram used by Carnot in discussing his ideal
engine; below, we see the Carnot engine as is typically mod-
eled in current use:
Carnot engine diagram (modern) - where heat flows from a high
temperature TH furnace through the fluid of the “working body”
(working substance) and into the cold sink TC, thus forcing the
working substance to do mechanical work W on the surroundings,
via cycles of contractions and expansions.
In the diagram shown, the “working body” (system), a term
introduced by Clausius in 1850, can be any fluid or vapor
body through which heat Q can be introduced or transmit-
ted through to produce work. In 1824, Sadi Carnot, in his
famous paper Reflections on the Motive Power of Fire, had
postulated that the fluid body could be any substance capa-
ble of expansion, such as vapor of water, vapor of alcohol,
vapor of mercury, a permanent gas, or air, etc. Though,
in these early years, engines came in a number of config-
urations, typically QH was supplied by a boiler, wherein
water boiled over a furnace; QC was typically a stream of
cold flowing water in the form of a condenser located on
a separate part of the engine. The output work W was the
movement of the piston as it turned a crank-arm, which typ-
ically turned a pulley to lift water out of flooded salt mines.
Carnot defined work as “weight lifted through a height.”
7.1.3 Systems in equilibrium
7.1. THERMODYNAMIC SYSTEM 177

rium are much simpler and easier to understand than sys- contact, such as conduction of heat, or by long-range forces
tems not in equilibrium. In some cases, when analyzing a such as an electric field in the surroundings.
thermodynamic process, one can assume that each interme- A system with walls that prevent all transfers is said to be
diate state in the process is at equilibrium. This consider- isolated. This is an idealized conception, because in prac-
ably simplifies the analysis. tice some transfer is always possible, for example by grav-
In isolated systems it is consistently observed that as time itational forces. It is an axiom of thermodynamics that an
goes on internal rearrangements diminish and stable condi- isolated system eventually reaches internal thermodynamic
tions are approached. Pressures and temperatures tend to equilibrium, when its state no longer changes with time.
equalize, and matter arranges itself into one or a few rela- The walls of a closed system allow transfer of energy as heat
tively homogeneous phases. A system in which all processes and as work, but not of matter, between it and its surround-
of change have gone practically to completion is considered ings. The walls of an open system allow transfer both of
in a state of thermodynamic equilibrium. The thermody- matter and of energy.[12][13][14][15][16][17][18] This scheme of
namic properties of a system in equilibrium are unchang- definition of terms is not uniformly used, though it is con-
ing in time. Equilibrium system states are much easier to venient for some purposes. In particular, some writers use
describe in a deterministic manner than non-equilibrium 'closed system' where 'isolated system' is here used.[19][20]
states.
Anything that passes across the boundary and effects a
For a process to be reversible, each step in the process must change in the contents of the system must be accounted for
be reversible. For a step in a process to be reversible, the in an appropriate balance equation. The volume can be the
system must be in equilibrium throughout the step. That region surrounding a single atom resonating energy, such as
ideal cannot be accomplished in practice because no step Max Planck defined in 1900; it can be a body of steam or
can be taken without perturbing the system from equilib- air in a steam engine, such as Sadi Carnot defined in 1824.
rium, but the ideal can be approached by making changes
It could also be just one nuclide (i.e. a system of quarks) as
slowly. hypothesized in quantum thermodynamics.

7.1.4 Walls 7.1.5 Surroundings

See also: Environment (systems)
A system is enclosed by walls that bound it and connect
it to its surroundings.[6][7][8][9][10][11] Often a wall restricts
passage across it by some form of matter or energy, mak- The system is the part of the universe being studied, while
ing the connection indirect. Sometimes a wall is no more the surroundings is the remainder of the universe that lies
than an imaginary two-dimensional closed surface through outside the boundaries of the system. It is also known
which the connection to the surroundings is direct. as the environment, and the reservoir. Depending on the
type of system, it may interact with the system by exchang-
A wall can be fixed (e.g. a constant volume reactor) or
ing mass, energy (including heat and work), momentum,
moveable (e.g. a piston). For example, in a reciprocat-
electric charge, or other conserved properties. The environ-
ing engine, a fixed wall means the piston is locked at its
ment is ignored in analysis of the system, except in regards
position; then, a constant volume process may occur. In
to these interactions.
that same engine, a piston may be unlocked and allowed to
move in and out. Ideally, a wall may be declared adiabatic,
diathermal, impermeable, permeable, or semi-permeable. 7.1.6 Closed system
Actual physical materials that provide walls with such ide-
alized properties are not always readily available. Main article: Closed system § In thermodynamics
The system is delimited by walls or boundaries, either actual
or notional, across which conserved (such as matter and en- In a closed system, no mass may be transferred in or out
ergy) or unconserved (such as entropy) quantities can pass of the system boundaries. The system always contains the
into and out of the system. The space outside the thermo- same amount of matter, but heat and work can be ex-
dynamic system is known as the surroundings, a reservoir, changed across the boundary of the system. Whether a sys-
or the environment. The properties of the walls determine tem can exchange heat, work, or both is dependent on the
what transfers can occur. A wall that allows transfer of a property of its boundary.
quantity is said to be permeable to it, and a thermodynamic
system is classified by the permeabilities of its several walls. • Adiabatic boundary – not allowing any heat exchange:
A transfer between system and surroundings can arise by A thermally isolated system
178 CHAPTER 7. CHAPTER 7

• Rigid boundary – not allowing exchange of work: A particles. However, for systems undergoing a chemical re-
mechanically isolated system action, there may be all sorts of molecules being generated
and destroyed by the reaction process. In this case, the fact
One example is fluid being compressed by a piston in a that the system is closed is expressed by stating that the to-
cylinder. Another example of a closed system is a bomb tal number of each elemental atom is conserved, no matter
calorimeter, a type of constant-volume calorimeter used in what kind of molecule it may be a part of. Mathematically:
measuring the heat of combustion of a particular reaction.
Electrical energy travels across the boundary to produce m
∑
a spark between the electrodes and initiates combustion. aij Nj = b0i
Heat transfer occurs across the boundary after combustion j=1
but no mass transfer takes place either way.
where N is the number of j-type molecules, aᵢ is the num-
Beginning with the first law of thermodynamics for an open ber of atoms of element i in molecule j and bᵢ0 is the total
system, this is expressed as: number of atoms of element i in the system, which remains
constant, since the system is closed. There is one such equa-
tion for each element in the system.
1 1
∆U = Q−W +mi (h+ v 2 +gz)i −me (h+ v 2 +gz)e
2 2
where U is internal energy, Q is the heat added to the sys- 7.1.7 Isolated system
tem, W is the work done by the system, and since no mass is
Main article: Isolated system
transferred in or out of the system, both expressions involv-
ing mass flow are zero and the first law of thermodynamics
for a closed system is derived. The first law of thermody- An isolated system is more restrictive than a closed system
namics for a closed system states that the increase of inter- as it does not interact with its surroundings in any way. Mass
nal energy of the system equals the amount of heat added and energy remains constant within the system, and no en-
to the system minus the work done by the system. For in- ergy or mass transfer takes place across the boundary. As
finitesimal changes the first law for closed systems is stated time passes in an isolated system, internal differences in the
by: system tend to even out and pressures and temperatures tend
to equalize, as do density differences. A system in which all
equalizing processes have gone practically to completion is
dU = δQ − δW. in a state of thermodynamic equilibrium.
Truly isolated physical systems do not exist in reality (ex-
If the work is due to a volume expansion by dV at a pressure cept perhaps for the universe as a whole), because, for ex-
P then: ample, there is always gravity between a system with mass
and masses elsewhere.[21][22][23][24][25] However, real sys-
tems may behave nearly as an isolated system for finite (pos-
δW = P dV. sibly very long) times. The concept of an isolated system
can serve as a useful model approximating many real-world
For a homogeneous system undergoing a reversible process, situations. It is an acceptable idealization used in construct-
the second law of thermodynamics reads: ing mathematical models of certain natural phenomena.
In the attempt to justify the postulate of entropy increase
in the second law of thermodynamics, Boltzmann’s H-
δQ = T dS
theorem used equations, which assumed that a system (for
where T is the absolute temperature and S is the entropy example, a gas) was isolated. That is all the mechanical
of the system. With these relations the fundamental ther- degrees of freedom could be specified, treating the walls
modynamic relation, used to compute changes in internal simply as mirror boundary conditions. This inevitably led
energy, is expressed as: to Loschmidt’s paradox. However, if the stochastic behav-
ior of the molecules in actual walls is considered, along with
the randomizing effect of the ambient, background thermal
radiation, Boltzmann’s assumption of molecular chaos can
dU = T dS − P dV. be justified.
For a simple system, with only one type of particle (atom or The second law of thermodynamics for isolated systems
molecule), a closed system amounts to a constant number of states that the entropy of an isolated system not in equi-
7.1. THERMODYNAMIC SYSTEM
librium tends to increase over time, approaching maximum
value at equilibrium. Overall, in an isolated system, the
internal energy is constant and the entropy can never de-
crease. A closed system’s entropy can decrease e.g. when
heat is extracted from the system.
It is important to note that isolated systems are not equiv-
alent to closed systems. Closed systems cannot exchange
matter with the surroundings, but can exchange energy. Iso-
lated systems can exchange neither matter nor energy with
their surroundings, and as such are only theoretical and do
not exist in reality (except, possibly, the entire universe). 7.1.10 See also
It is worth noting that 'closed system' is often used in ther-
modynamics discussions when 'isolated system' would be
correct - i.e. there is an assumption that energy does not
enter or leave the system.
7.1.8 Selective transfer of matter
For a thermodynamic process, the precise physical proper-
ties of the walls and surroundings of the system are impor-
tant, because they determine the possible processes.
An open system has one or several walls that allow transfer
of matter. To account for the internal energy of the open
system, this requires energy transfer terms in addition to
those for heat and work. It also leads to the idea of the
chemical potential.
A wall selectively permeable only to a pure substance can
put the system in diffusive contact with a reservoir of that
pure substance in the surroundings. Then a process is possi-
ble in which that pure substance is transferred between sys-
tem and surroundings. Also, across that wall a contact equi-
librium with respect to that substance is possible. By suit-
able thermodynamic operations, the pure substance reser-
voir can be dealt with as a closed system. Its internal en-
ergy and its entropy can be determined as functions of its
temperature, pressure, and mole number.
A thermodynamic operation can render impermeable to
matter all system walls other than the contact equilibrium
wall for that substance. This allows the definition of an in-
tensive state variable, with respect to a reference state of the
surroundings, for that substance. The intensive variable is
called the chemical potential; for component substance i it
is usually denoted μi. The corresponding extensive variable
can be the number of moles Ni of the component substance
in the system.
For a contact equilibrium across a wall permeable to a sub- [14] Guggenheim, E.A. (1949/1967). Thermodynamics. An Ad-
stance, the chemical potentials of the substance must be
same on either side of the wall. This is part of the nature
of thermodynamic equilibrium, and may be regarded as re- [15] Münster, A. (1970). Classical Thermodynamics, translated
lated to the zeroth law of thermodynamics.[26]
179
7.1.9 Open system
In an open system, matter may pass in and out of some
segments of the system boundaries. There may be other
segments of the system boundaries that pass heat or work
but not matter. Respective account is kept of the transfers
of energy across those and any other several boundary seg-
ments. In thermodynamic equilibrium, all flows have van-
ished.
• Physical system
7.1.11 References
[1] Bailyn, M. (1994). A Survey of Thermodynamics, American
Institute of Physics Press, New York, ISBN 0-88318-797-3,
p. 20.
[2] Tisza, L. (1966). Generalized Thermodynamics, M.I.T
Press, Cambridge MA, p. 119.
[3] Marsland, R. III, Brown, H.R., Valente, G. (2015). Time
and irreversibility in axiomatic thermodynamics, Am. J.
Phys., 83(7): 628–634.
[4] Bailyn, M. (1994). A Survey of Thermodynamics, American
Institute of Physics Press, New York, ISBN 0-88318-797-3,
p. 22.
[5] Eu, B.C. (2002). Generalized Thermodynamics. The
Thermodynamics of Irreversible Processes and Generalized
Hydrodynamics, Kluwer Academic Publishers, Dordrecht,
ISBN 1-4020-0788-4.
[6] Born, M. (1949). Natural Philosophy of Cause and Chance,
Oxford University Press, London, p.44
[7] Tisza, L. (1966), pp. 109, 112.
[8] Haase, R. (1971), p. 7.
[9] Adkins, C.J. (1968/1975), p. 4
[10] Callen, H.B. (1960/1985), pp. 15, 17.
[11] Tschoegl, N.W. (2000), p. 5.
[12] Prigogine, I., Defay, R. (1950/1954). Chemical Thermody-
namics, Longmans, Green & Co, London, p. 66.
[13] Tisza, L. (1966). Generalized Thermodynamics, M.I.T
Press, Cambridge MA, pp. 112–113.
vanced Treatment for Chemists and Physicists, (1st edition
1949) 5th edition 1967, North-Holland, Amsterdam, p. 14.
by E.S. Halberstadt, Wiley–Interscience, London, pp. 6–7.
180 CHAPTER 7. CHAPTER 7

[16] Haase, R. (1971). Survey of Fundamental Laws, chapter 1

of Thermodynamics, pages 1–97 of volume 1, ed. W. Jost,
of Physical Chemistry. An Advanced Treatise, ed. H. Eyring,
D. Henderson, W. Jost, Academic Press, New York, lcn 73–
117081, p. 3.

[17] Tschoegl, N.W. (2000). Fundamentals of Equilibrium and

Steady-State Thermodynamics, Elsevier, Amsterdam, ISBN
0-444-50426-5, p. 5.

[18] Silbey, R.J., Alberty, R.A., Bawendi, M.G. (1955/2005).

Physical Chemistry, fourth edition, Wiley, Hoboken NJ, p.
4.

[19] Callen, H.B. (1960/1985). Thermodynamics and an Intro-

duction to Thermostatistics, (1st edition 1960) 2nd edition
1985, Wiley, New York, ISBN 0-471-86256-8, p. 17.

[20] ter Haar, D., Wergeland, H. (1966). Elements of Thermody-

namics, Addison-Wesley Publishing, Reading MA, p. 43.

[21] I.M.Kolesnikov; V.A.Vinokurov; S.I.Kolesnikov (2001).

Thermodynamics of Spontaneous and Non-Spontaneous Pro-
cesses. Nova science Publishers. p. 136. ISBN 1-56072-
904-X.

[22] “A System and Its Surroundings”. ChemWiki. University of

California - Davis. Retrieved May 2012.

[23] “Hyperphysics”. The Department of Physics and Astronomy

of Georgia State University. Retrieved May 2012.

[24] Bryan Sanctuary. “Open, Closed and Isolated Systems in

Physical Chemistry,”. Foundations of Quantum Mechanics
and Physical Chemistry. McGill University (Montreal). Re-
trieved May 2012.

[25] Material and Energy Balances for Engineers and Environ-

mentalists (PDF). Imperial College Press. p. 7. Retrieved
May 2012.

[26] Bailyn, M. (1994). A Survey of Thermodynamics, American

Institute of Physics Press, New York, ISBN 0-88318-797-3,
pp. 19–23.

• Abbott, M.M.; van Hess, H.G. (1989). Thermody-

namics with Chemical Applications (2nd ed.). McGraw
Hill.
• Callen, H.B. (1960/1985). Thermodynamics and an
Introduction to Thermostatistics, (1st edition 1960) 2nd
edition 1985, Wiley, New York, ISBN 0-471-86256-
8.
• Halliday, David; Resnick, Robert; Walker, Jearl
(2008). Fundamentals of Physics (8th ed.). Wiley.
• Moran, Michael J.; Shapiro, Howard N. (2008). Fun-
damentals of Engineering Thermodynamics (6th ed.).
Wiley.
Chapter 8

Chapter 8. Material Properties

8.1 Heat capacity be used to quantitatively predict the specific heat capacity
of simple systems.

Heat capacity or thermal capacity is a measurable

physical quantity equal to the ratio of the heat added to 8.1.1 History
(or removed from) an object to the resulting temperature
change.[1] The SI unit of heat capacity is joule per kelvin KJ Main article: History of heat
and the dimensional form is L2 MT−2 Θ−1 . Specific heat is
the amount of heat needed to raise the temperature of one In a previous theory of heat common in the early modern
gram of mass by 1 degree Celsius. period, heat was thought to be a measurement of an invis-
Heat capacity is an extensive property of matter, meaning ible fluid, known as the caloric. Bodies were capable of
it is proportional to the size of the system. When express- holding a certain amount of this fluid, hence the term heat
ing the same phenomenon as an intensive property, the heat capacity, named and first investigated by Scottish chemist
capacity is divided by the amount of substance, mass, or Joseph Black in the 1750s.[5]
volume, so that the quantity is independent of the size or Since the development of thermodynamics during the 18th
extent of the sample. The molar heat capacity is the heat and 19th centuries, scientists have abandoned the idea of a
capacity per unit amount (SI unit: mole) of a pure substance physical caloric, and instead understand heat as changes in
and the specific heat capacity, often simply called specific a system’s internal energy. That is, heat is no longer consid-
heat, is the heat capacity per unit mass of a material. Oc- ered a fluid; rather, heat is a transfer of disordered energy.
casionally, in engineering contexts, the volumetric heat ca- Nevertheless, at least in English, the term “heat capacity”
pacity is used. survives. In some other languages, the term thermal capac-
Temperature reflects the average randomized kinetic energy ity is preferred, and it is also sometimes used in English.
of constituent particles of matter (e.g. atoms or molecules)
relative to the centre of mass of the system, while heat is the
transfer of energy across a system boundary into the body 8.1.2 Units
other than by work or matter transfer. Translation, rotation,
and vibration of atoms represent the degrees of freedom of Extensive properties
motion which classically contribute to the heat capacity of
gases, while only vibrations are needed to describe the heat In the International System of Units, heat capacity has the
capacities of most solids[2] , as shown by the Dulong–Petit unit joules per kelvin. An object’s heat capacity (symbol C)
law. Other contributions can come from magnetic[3] and is defined as the ratio of the amount of heat energy trans-
electronic[4] degrees of freedom in solids, but these rarely ferred to an object and the resulting increase in temperature
make substantial contributions. of the object,

For quantum mechanical reasons, at any given temperature,

some of these degrees of freedom may be unavailable, or Q
C= ,
only partially available, to store thermal energy. In such ∆T
cases, the specific heat capacity is a fraction of the max- assuming that the temperature range is sufficiently small so
imum. As the temperature approaches absolute zero, the that the heat capacity is constant. More generally, because
specific heat capacity of a system approaches zero, due to heat capacity does depend upon temperature, it should be
loss of available degrees of freedom. Quantum theory can written as

181
182
δQ
C(T ) = , the pound calorie (lb-cal), defined as the amount of heat re-
dT
where the symbol δ is used to imply that heat is a path func-
tion. Heat capacity is an extensive property, meaning it de-
pends on the extent or size of the physical system in ques-
tion. A sample containing twice the amount of substance as
another sample requires the transfer of twice the amount of
heat ( Q ) to achieve the same change in temperature ( ∆T
).
Intensive properties
For many experimental and theoretical purposes it is more
convenient to report heat capacity as an intensive property
– an intrinsic characteristic of a particular substance. This
is most often accomplished by expressing the property in
relation to a unit of mass. In science and engineering, such
properties are often prefixed with the term specific.[6] In-
ternational standards now recommend that specific heat ca-
pacity always refer to division by mass.[7] The units for the
specific heat capacity are [c] = kg·K J
. as the pressure and the volume of the system before and af-
In chemistry, heat capacity is often specified relative to one
mole, the unit of amount of substance, and is called the mo-
J
lar heat capacity. It has the unit [Cmol ] = mol·K .
For some considerations it is useful to specify the volume-
specific heat capacity, commonly called volumetric heat ca-
pacity, which is the heat capacity per unit volume and has
SI units [s] = m3J·K . This is used almost exclusively for
liquids and solids, since for gases it may be confused with
specific heat capacity at constant volume.
Alternative unit systems
While SI units are the most widely used, some countries
and industries also use other systems of measurement. One
older unit of heat is the kilogram-calorie (Cal), originally
defined as the energy required to raise the temperature of
one kilogram of water by one degree Celsius, typically from
14.5 to 15.5 °C. The specific average heat capacity of wa-
ter on this scale would therefore be exactly 1 Cal/(C°⋅kg).
However, due to the temperature-dependence of the spe-
cific heat, a large number of different definitions of the
calorie came into being. Whilst once it was very prevalent,
especially its smaller cgs variant the gram-calorie (cal), de-
fined so that the specific heat of water would be 1 cal/(K⋅g),
in most fields the use of the calorie is now archaic.
In the United States other units of measure for heat capacity
may be quoted in disciplines such as construction, civil en-
gineering, and chemical engineering. A still common sys-
tem is the English Engineering Units in which the mass ref-
CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES
erence is pound mass and the temperature is specified in
degrees Fahrenheit or Rankine. One (rare) unit of heat is
quired to raise the temperature of one pound of water by
one degree Celsius. On this scale the specific heat of wa-
ter would be 1 lb-cal/(K⋅lbm). More common is the British
thermal unit, the standard unit of heat in the U.S. construc-
tion industry. This is defined such that the specific heat of
water is 1 BTU/(F°⋅lb).
8.1.3 Measurement of heat capacity
It may appear that the way to measure heat capacity is to
add a known amount of heat to an object, and measure
the change in temperature. This works reasonably well for
many solids. However, for precise measurements, and es-
pecially for gasses, other aspects of measurement become
critical.
The heat capacity can be affected by many of the state vari-
ables that describe the thermodynamic system under study.
These include the starting and ending temperature, as well
ter heat is added. So rather than a single way to measure
heat capacity, there are actually several slightly different
measurements of heat capacity. The most commonly used
methods for measurement are to hold the object either at
constant pressure (CP) or at constant volume (CV). Gases
and liquids are typically also measured at constant volume.
Measurements under constant pressure produce larger val-
ues than those at constant volume because the constant pres-
sure values also include heat energy that is used to do work
to expand the substance against the constant pressure as its
temperature increases. This difference is particularly no-
table in gases where values under constant pressure are typ-
ically 30% to 66.7% greater than those at constant volume.
Hence the heat capacity ratio of gases is typically between
1.3 and 1.67.[8]
The specific heat capacities of substances comprising
molecules (as distinct from monatomic gases) are not fixed
constants and vary somewhat depending on temperature.
Accordingly, the temperature at which the measurement is
made is usually also specified. Examples of two common
ways to cite the specific heat of a substance are as follows:[9]
• Water (liquid): CP = 4185.5 J/(kg⋅K) (15 °C, 101.325
kPa)
• Water (liquid): CVH = 74.539 J/(mol⋅K) (25 °C)
For liquids and gases, it is important to know the pressure to
which given heat capacity data refer. Most published data
are given for standard pressure. However, quite different
standard conditions for temperature and pressure have been
8.1. HEAT CAPACITY 183

defined by different organizations. The International Union

of Pure and Applied Chemistry (IUPAC) changed its rec-
ommendation from one atmosphere to the round value 100 H = U + PV .
kPa (≈750.062 Torr).[notes 1]
A small change in the enthalpy can be expressed as

Calculation from first principles

dH = δQ + V dP ,
The path integral Monte Carlo method is a numerical ap-
proach for determining the values of heat capacity, based and therefore, at constant pressure, we have
on quantum dynamical principles. However, good approx-
imations can be made for gases in many states using sim- ( ) ( )
pler methods outlined below. For many solids composed ∂H ∂Q
= = CP .
of relatively heavy atoms (atomic number > iron), at non- ∂T P ∂T P
cryogenic temperatures, the heat capacity at room temper-
ature approaches 3R = 24.94 joules per kelvin per mole These two equations:
of atoms (Dulong–Petit law, R is the gas constant). Low
temperature approximations for both gases and solids at ( ) ( )
∂U ∂Q
temperatures less than their characteristic Einstein temper- = = CV .
atures or Debye temperatures can be made by the methods ∂T V ∂T V
of Einstein and Debye discussed below. ( ) ( )
∂H ∂Q
= = CP .
∂T P ∂T P
Thermodynamic relations and definition of heat capac- are property relations and are therefore independent of the
ity type of process. In other words, they are valid for any sub-
stance going through any process. Both the internal energy
The internal energy of a closed system changes either by and enthalpy of a substance can change with the transfer of
adding heat to the system or by the system performing work. energy in many forms i.e., heat.[10]
Written mathematically we have

Relation between heat capacities

∆esystem = ein − eout
Main article: Relations between heat capacities
Or
Measuring the heat capacity, sometimes referred to as spe-
cific heat, at constant volume can be prohibitively difficult
dU = δQ − δW . for liquids and solids. That is, small temperature changes
For work as a result of an increase of the system volume we typically require large pressures to maintain a liquid or solid
may write, at constant volume implying the containing vessel must be
nearly rigid or at least very strong (see coefficient of ther-
mal expansion and compressibility). Instead it is easier to
measure the heat capacity at constant pressure (allowing the
dU = δQ − P dV .
material to expand or contract freely) and solve for the heat
If the heat is added at constant volume, then the second term capacity at constant volume using mathematical relation-
of this relation vanishes and one readily obtains ships derived from the basic thermodynamic laws. Start-
ing from the fundamental thermodynamic relation one can
show
( ) ( )
∂U ∂Q
= = CV .
∂T V ∂T V ( ) ( )
∂P ∂V
This defines the heat capacity at constant volume, CV, which CP − CV = T ∂T ∂T P,n
V,n
is also related to changes in internal energy. Another useful
quantity is the heat capacity at constant pressure, CP. This where the partial derivatives are taken at constant volume
quantity refers to the change in the enthalpy of the system, and constant number of particles, and constant pressure and
which is given by constant number of particles, respectively.
184 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

This can also be rewritten

C C
c = Em = = ,
α2 m ρV
CP − CV = V T
βT where
where

C
α is the coefficient of thermal expansion,
βT is the isothermal compressibility. m
V
The heat capacity ratio or adiabatic index is the ratio of the m
heat capacity at constant pressure to heat capacity at con- ρ = V
stant volume. It is sometimes also known as the isentropic For gases, and also for other materials under high pressures,
expansion factor. there is need to distinguish between different boundary con-
ditions for the processes under consideration (since values
Ideal gas [11] For an ideal gas, evaluating the partial differ significantly between different conditions). Typical
derivatives above according to the equation of state where processes for which a heat capacity may be defined include
R is the gas constant for an ideal gas isobaric (constant pressure, dP = 0 ) or isochoric (constant
volume, dV = 0 ) processes. The corresponding specific
heat capacities are expressed as
P V = nRT
() ( ) ( )
∂P ∂V ∂C
CP − CV = T cP = ,
∂T V,n ∂T P,n ∂m P
( ) ( )
nRT ∂P nR ∂C
P = ⇒ = cV = .
V ∂T V,n V ∂m V
( ) From the results of the previous section, dividing through
nRT ∂V nR
V = ⇒ = by the mass gives the relation
P ∂T P,n P
substituting
α2 T
cP − cV = .
( ) ( ) ( )( ) ( )( ) ρβT )
(
∂P ∂V nR nR nRT nR nR
T =T = = Pparameter=tonR
AP related c is CV −1 , the volumetric heat
∂T V,n ∂T P,n V P V P
capacity. In engineering practice, cV for solids or liquids
this equation reduces simply to Mayer's relation, often signifies a volumetric heat capacity, rather than a
constant-volume one. In such cases, the mass-specific heat
capacity (specific heat) is often explicitly written with the
CP,m − CV,m = R subscript m , as cm . Of course, from the above relation-
ships, for solids one writes

Specific heat capacity

C cvolumetric
cm = = .
The specific heat capacity of a material on a per mass basis m ρ
is
For pure homogeneous chemical compounds with estab-
lished molecular or molar mass or a molar quantity is es-
∂C tablished, heat capacity as an intensive property can be ex-
c= , pressed on a per mole basis instead of a per mass basis by
∂m
the following equations analogous to the per mass equa-
which in the absence of phase transitions is equivalent to tions:
8.1. HEAT CAPACITY 185

dimensionless entropy per particle S ∗ = S/N k , measured

( ) in nats.
∂C
CP,m =
∂n P
( ) dS ∗
∂C C∗ =
CV,m = d ln T
∂n V
Alternatively, using base 2 logarithms, C * relates the base-
where n is the number of moles in the body or
2 logarithmic increase in temperature to the increase in the
thermodynamic system. One may refer to such a per mole
dimensionless entropy measured in bits.[12]
quantity as molar heat capacity to distinguish it from spe-
cific heat capacity on a per mass basis.
Heat capacity at absolute zero
Polytropic heat capacity From the definition of entropy
The polytropic heat capacity is calculated at processes if all
the thermodynamic properties (pressure, volume, tempera-
ture) change T dS = δQ

the absolute entropy can be calculated by integrating from

( ) zero kelvins temperature to the final temperature T
∂C
Ci,m =
∂n
∫ Tf ∫ Tf ∫ Tf
The most important polytropic processes run between the S(Tf ) = δQ δQ dT dT
= = C(T ) .
adiabatic and the isotherm functions, the polytropic index T =0 T 0 dT T 0 T
is between 1 and the adiabatic exponent (γ or κ)
The heat capacity must be zero at zero temperature in or-
der for the above integral not to yield an infinite absolute
Dimensionless heat capacity entropy, which would violate the third law of thermody-
namics. One of the strengths of the Debye model is that
The dimensionless heat capacity of a material is (unlike the preceding Einstein model) it predicts the proper
mathematical form of the approach of heat capacity toward
zero, as absolute zero temperature is approached.
C C
C∗ = =
nR Nk
Negative heat capacity (stars)
where
Most physical systems exhibit a positive heat capacity.
C is the heat capacity of a body made of the ma- However, even though it can seem paradoxical at first,[13][14]
terial in question (J/K) there are some systems for which the heat capacity is nega-
tive. These are inhomogeneous systems which do not meet
n is the amount of substance in the body (mol) the strict definition of thermodynamic equilibrium. They
R is the gas constant (J/(K⋅mol)) include gravitating objects such as stars, galaxies; and also
sometimes some nano-scale clusters of a few tens of atoms,
N is the number of molecules in the body. (di-
close to a phase transition.[15] A negative heat capacity can
mensionless)
result in a negative temperature.
k is Boltzmann’s constant (J/(K⋅molecule))
According to the virial theorem, for a self-gravitating body
like a star or an interstellar gas cloud, the average potential
In the ideal gas article, dimensionless heat capacity C ∗ is energy UPₒ and the average kinetic energy UKᵢ are locked
expressed as ĉ , and is related there directly to half the num- together in the relation
ber of degrees of freedom per particle. This holds true
for quadratic degrees of freedom, a consequence of the
equipartition theorem.
UPot = −2UKin ,
More generally, the dimensionless heat capacity relates the
logarithmic increase in temperature to the increase in the The total energy U (= UPₒ + UKᵢ ) therefore obeys
186
U = −UKin ,
If the system loses energy, for example by radiating en-
ergy away into space, the average kinetic energy actually
increases. If a temperature is defined by the average ki-
netic energy, then the system therefore can be said to have
a negative heat capacity.[16]
A more extreme version of this occurs with black holes.
According to black hole thermodynamics, the more mass
and energy a black hole absorbs, the colder it becomes. In
contrast, if it is a net emitter of energy, through Hawking
radiation, it will become hotter and hotter until it boils away.
8.1.4 Theory of heat capacity
Factors that affect specific heat capacity
Molecules undergo many characteristic internal vibrations. Poten-
tial energy stored in these internal degrees of freedom contributes to
a sample’s energy content, [17] [18] but not to its temperature. More
internal degrees of freedom tend to increase a substance’s specific
heat capacity, so long as temperatures are high enough to overcome
quantum effects.
For any given substance, the heat capacity of a body is di-
rectly proportional to the amount of substance it contains
(measured in terms of mass or moles or volume). Doubling
the amount of substance in a body doubles its heat capacity,
etc. As to rotation about an atom’s axis (again, whether the atom
However, when this effect has been corrected for, by divid- is bound or free), its energy of rotation is proportional to the
ing the heat capacity by the quantity of substance in a body, moment of inertia for the atom, which is extremely small
CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES
the resulting specific heat capacity is a function of the struc-
ture of the substance itself. In particular, it depends on the
number of degrees of freedom that are available to the parti-
cles in the substance; each independent degree of freedom
allows the particles to store thermal energy. The transla-
tional kinetic energy of substance particles is only one of
the many possible degrees of freedom which manifests as
temperature change, and thus the larger the number of de-
grees of freedom available to the particles of a substance
other than translational kinetic energy, the larger will be the
specific heat capacity for the substance. For example, ro-
tational kinetic energy of gas molecules stores heat energy
in a way that increases heat capacity, since this energy does
not contribute to temperature.
In addition, quantum effects require that whenever energy
be stored in any mechanism associated with a bound system
which confers a degree of freedom, it must be stored in cer-
tain minimal-sized deposits (quanta) of energy, or else not
stored at all. Such effects limit the full ability of some de-
grees of freedom to store energy when their lowest energy
storage quantum amount is not easily supplied at the aver-
age energy of particles at a given temperature. In general,
for this reason, specific heat capacities tend to fall at lower
temperatures where the average thermal energy available to
each particle degree of freedom is smaller, and thermal en-
ergy storage begins to be limited by these quantum effects.
Due to this process, as temperature falls toward absolute
zero, so also does heat capacity.
Degrees of freedom Main article: degrees of freedom
(physics and chemistry)
Molecules are quite different from the monatomic gases
like helium and argon. With monatomic gases, thermal
energy comprises only translational motions. Translational
motions are ordinary, whole-body movements in 3D space
whereby particles move about and exchange energy in
collisions—like rubber balls in a vigorously shaken con-
tainer (see animation here [19] ). These simple movements in
the three dimensions of space mean individual atoms have
three translational degrees of freedom. A degree of free-
dom is any form of energy in which heat transferred into
an object can be stored. This can be in translational ki-
netic energy, rotational kinetic energy, or other forms such
as potential energy in vibrational modes. Only three transla-
tional degrees of freedom (corresponding to the three inde-
pendent directions in space) are available for any individual
atom, whether it is free, as a monatomic molecule, or bound
into a polyatomic molecule.
8.1. HEAT CAPACITY 187

compared to moments of inertia of collections of atoms. perature of the solid), especially in solids with light and
This is because almost all of the mass of a single atom is tightly bound atoms (e.g., beryllium metal or diamond).
concentrated in its nucleus, which has a radius too small to Polyatomic gases store intermediate amounts of energy,
give a significant moment of inertia. In contrast, the spacing giving them a “per-atom” heat capacity that is between that
of quantum energy levels for a rotating object is inversely of monatomic gases (3 ⁄2 R per mole of atoms, where R is
proportional to its moment of inertia, and so this spacing the ideal gas constant), and the maximum of fully excited
becomes very large for objects with very small moments warmer solids (3 R per mole of atoms). For gases, heat ca-
of inertia. For these reasons, the contribution from rota- pacity never falls below the minimum of 3 ⁄2 R per mole (of
tion of atoms on their axes is essentially zero in monatomic molecules), since the kinetic energy of gas molecules is al-
gases, because the energy spacing of the associated quan- ways available to store at least this much thermal energy.
tum levels is too large for significant thermal energy to be However, at cryogenic temperatures in solids, heat capacity
stored in rotation of systems with such small moments of falls toward zero, as temperature approaches absolute zero.
inertia. For similar reasons, axial rotation around bonds
joining atoms in diatomic gases (or along the linear axis
in a linear molecule of any length) can also be neglected as Example of temperature-dependent specific heat ca-
a possible “degree of freedom” as well, since such rotation pacity, in a diatomic gas To illustrate the role of var-
is similar to rotation of monatomic atoms, and so occurs ious degrees of freedom in storing heat, we may consider
about an axis with a moment of inertia too small to be able nitrogen, a diatomic molecule that has five active degrees of
to store significant heat energy. freedom at room temperature: the three comprising transla-
tional motion plus two rotational degrees of freedom inter-
In polyatomic molecules, other rotational modes may be-
nally. Although the constant-volume molar heat capacity of
come active, due to the much higher moments of inertia
nitrogen at this temperature is five-thirds that of monatomic
about certain axes which do not coincide with the linear
gases, on a per-mole of atoms basis, it is five-sixths that of a
axis of a linear molecule. These modes take the place of
monatomic gas. The reason for this is the loss of a degree of
some translational degrees of freedom for individual atoms,
freedom due to the bond when it does not allow storage of
since the atoms are moving in 3-D space, as the molecule ro-
thermal energy. Two separate nitrogen atoms would have a
tates. The narrowing of quantum mechanically determined
total of six degrees of freedom—the three translational de-
energy spacing between rotational states results from situa-
grees of freedom of each atom. When the atoms are bonded
tions where atoms are rotating around an axis that does not
the molecule will still only have three translational degrees
connect them, and thus form an assembly that has a large
of freedom, as the two atoms in the molecule move as one.
moment of inertia. This small difference between energy
However, the molecule cannot be treated as a point object,
states allows the kinetic energy of this type of rotational
and the moment of inertia has increased sufficiently about
motion to store heat energy at ambient temperatures. Fur-
two axes to allow two rotational degrees of freedom to be
thermore, internal vibrational degrees of freedom also may
active at room temperature to give five degrees of freedom.
become active (these are also a type of translation, as seen
The moment of inertia about the third axis remains small, as
from the view of each atom). In summary, molecules are
this is the axis passing through the centres of the two atoms,
complex objects with a population of atoms that may move
and so is similar to the small moment of inertia for atoms of
about within the molecule in a number of different ways
a monatomic gas. Thus, this degree of freedom does not act
(see animation at right), and each of these ways of moving
to store heat, and does not contribute to the heat capacity
is capable of storing energy if the temperature is sufficient.
of nitrogen. The heat capacity per atom for nitrogen (5/2
The heat capacity of molecular substances (on a “per-atom” R per mole molecules = 5/4 R per mole atoms) is therefore
or atom-molar, basis) does not exceed the heat capacity of less than for a monatomic gas (3/2 R per mole molecules or
monatomic gases, unless vibrational modes are brought into atoms), so long as the temperature remains low enough that
play. The reason for this is that vibrational modes allow en- no vibrational degrees of freedom are activated.[20]
ergy to be stored as potential energy in intra-atomic bonds in
At higher temperatures, however, nitrogen gas gains one
a molecule, which are not available to atoms in monatomic
more degree of internal freedom, as the molecule is excited
gases. Up to about twice as much energy (on a per-atom
into higher vibrational modes that store thermal energy. A
basis) per unit of temperature increase can be stored in a
vibrational degree of freedom contributes a heat capacity
solid as in a monatomic gas, by this mechanism of storing
of 1/2 R each for kinetic and potential energy, for a to-
energy in the potentials of interatomic bonds. This gives
tal of R. Now the bond is contributing heat capacity, and
many solids about twice the atom-molar heat capacity at
(because of storage of energy in potential energy) is con-
room temperature of monatomic gases.
tributing more than if the atoms were not bonded. With
However, quantum effects heavily affect the actual ratio at full thermal excitation of bond vibration, the heat capac-
lower temperatures (i.e., much lower than the melting tem- ity per volume, or per mole of gas molecules approaches
188
seven-thirds that of monatomic gases. Significantly, this
is seven-sixths of the monatomic gas value on a mole-of-
atoms basis, so this is now a higher heat capacity per atom
than the monatomic figure, because the vibrational mode
enables for diatomic gases allows an extra degree of poten-
tial energy freedom per pair of atoms, which monatomic
gases cannot possess.[21][22] See thermodynamic tempera-
ture for more information on translational motions, kinetic
(heat) energy, and their relationship to temperature.
However, even at these large temperatures where gaseous
nitrogen is able to store 7/6ths of the energy per atom of
a monatomic gas (making it more efficient at storing en-
ergy on an atomic basis), it still only stores 7/12 ths of the
maximal per-atom heat capacity of a solid, meaning it is not
nearly as efficient at storing thermal energy on an atomic ba-
sis, as solid substances can be. This is typical of gases, and
results because many of the potential bonds which might be
storing potential energy in gaseous nitrogen (as opposed to
solid nitrogen) are lacking, because only one of the spatial
dimensions for each nitrogen atom offers a bond into which
potential energy can be stored without increasing the kinetic
energy of the atom. In general, solids are most efficient, on
an atomic basis, at storing thermal energy (that is, they have
the highest per-atom or per-mole-of-atoms heat capacity).
Per mole of different units
Per mole of molecules When the specific heat capac-
ity, c, of a material is measured (lowercase c means the
unit quantity is in terms of mass), different values arise be-
cause different substances have different molar masses (es-
sentially, the weight of the individual atoms or molecules).
In solids, thermal energy arises due to the number of atoms
that are vibrating. “Molar” heat capacity per mole of
molecules, for both gases and solids, offer figures which are
arbitrarily large, since molecules may be arbitrarily large.
Such heat capacities are thus not intensive quantities for this
reason, since the quantity of mass being considered can be
increased without limit.
Per mole of atoms Conversely, for molecular-based sub-
stances (which also absorb heat into their internal degrees
of freedom), massive, complex molecules with high atomic
count—like octane—can store a great deal of energy per
mole and yet are quite unremarkable on a mass basis, or on
a per-atom basis. This is because, in fully excited systems, For a list of heat capacities per atom-mole of various sub-
heat is stored independently by each atom in a substance, stances, in terms of R, see the last column of the table of
not primarily by the bulk motion of molecules. heat capacities below.
Thus, it is the heat capacity per-mole-of-atoms, not per-
mole-of-molecules, which is the intensive quantity, and Corollaries of these considerations for solids (volume-
which comes closest to being a constant for all substances specific heat capacity) Since the bulk density of a solid
CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES
at high temperatures. This relationship was noticed empir-
ically in 1819, and is called the Dulong–Petit law, after its
two discoverers.[23] Historically, the fact that specific heat
capacities are approximately equal when corrected by the
presumed weight of the atoms of solids, was an important
piece of data in favor of the atomic theory of matter.
Because of the connection of heat capacity to the number
of atoms, some care should be taken to specify a mole-of-
molecules basis vs. a mole-of-atoms basis, when compar-
ing specific heat capacities of molecular solids and gases.
Ideal gases have the same numbers of molecules per vol-
ume, so increasing molecular complexity adds heat capacity
on a per-volume and per-mole-of-molecules basis, but may
lower or raise heat capacity on a per-atom basis, depending
on whether the temperature is sufficient to store energy as
atomic vibration.
In solids, the quantitative limit of heat capacity in general is
about 3 R per mole of atoms, where R is the ideal gas con-
stant. This 3 R value is about 24.9 J/mole.K. Six degrees of
freedom (three kinetic and three potential) are available to
each atom. Each of these six contributes 1 ⁄2 R specific heat
capacity per mole of atoms.[24] This limit of 3 R per mole
specific heat capacity is approached at room temperature
for most solids, with significant departures at this temper-
ature only for solids composed of the lightest atoms which
are bound very strongly, such as beryllium (where the value
is only of 66% of 3 R), or diamond (where it is only 24%
of 3 R). These large departures are due to quantum ef-
fects which prevent full distribution of heat into all vibra-
tional modes, when the energy difference between vibra-
tional quantum states is very large compared to the average
energy available to each atom from the ambient tempera-
ture.
For monatomic gases, the specific heat is only half of 3 R
per mole, i.e. (3 ⁄2 R per mole) due to loss of all potential
energy degrees of freedom in these gases. For polyatomic
gases, the heat capacity will be intermediate between these
values on a per-mole-of-atoms basis, and (for heat-stable
molecules) would approach the limit of 3 R per mole of
atoms, for gases composed of complex molecules, and at
higher temperatures at which all vibrational modes accept
excitational energy. This is because very large and complex
gas molecules may be thought of as relatively large blocks of
solid matter which have lost only a relatively small fraction
of degrees of freedom, as compared to a fully integrated
solid.
8.1. HEAT CAPACITY
chemical element is strongly related to its molar mass (usu-
ally about 3 R per mole, as noted above), there exists a no-
ticeable inverse correlation between a solid’s density and its
specific heat capacity on a per-mass basis. This is due to
a very approximate tendency of atoms of most elements to
be about the same size, and constancy of mole-specific heat
capacity) result in a good correlation between the volume of
any given solid chemical element and its total heat capac-
ity. Another way of stating this, is that the volume-specific
heat capacity (volumetric heat capacity) of solid elements
is roughly a constant. The molar volume of solid elements
is very roughly constant, and (even more reliably) so also
is the molar heat capacity for most solid substances. These
two factors determine the volumetric heat capacity, which
as a bulk property may be striking in consistency. For ex-
ample, the element uranium is a metal which has a density
almost 36 times that of the metal lithium, but uranium’s
specific heat capacity on a volumetric basis (i.e. per given
volume of metal) is only 18% larger than lithium’s.
Since the volume-specific corollary of the Dulong–Petit of momentum, which leads to 3N total degrees of freedom.
specific heat capacity relationship requires that atoms of all This gives:
elements take up (on average) the same volume in solids,
there are many departures from it, with most of these due
to variations in atomic size. For instance, arsenic, which is
only 14.5% less dense than antimony, has nearly 59% more
specific heat capacity on a mass basis. In other words; even
though an ingot of arsenic is only about 17% larger than
an antimony one of the same mass, it absorbs about 59% CV,m = n = 2 R
more heat for a given temperature rise. The heat capac-
ity ratios of the two substances closely follows the ratios of
their molar volumes (the ratios of numbers of atoms in the
same volume of each substance); the departure from the
correlation to simple volumes in this case is due to lighter
arsenic atoms being significantly more closely packed than
antimony atoms, instead of similar size. In other words,
similar-sized atoms would cause a mole of arsenic to be
63% larger than a mole of antimony, with a correspondingly
lower density, allowing its volume to more closely mirror its
heat capacity behavior.
Other factors
Hydrogen bonds Hydrogen-containing polar molecules
like ethanol, ammonia, and water have powerful, inter-
molecular hydrogen bonds when in their liquid phase.
These bonds provide another place where heat may be
stored as potential energy of vibration, even at compara-
tively low temperatures. Hydrogen bonds account for the
fact that liquid water stores nearly the theoretical limit of
3 R per mole of atoms, even at relatively low temperatures
(i.e. near the freezing point of water).
189
Impurities In the case of alloys, there are several condi-
tions in which small impurity concentrations can greatly af-
fect the specific heat. Alloys may exhibit marked difference
in behaviour even in the case of small amounts of impuri-
ties being one element of the alloy; for example impurities
in semiconducting ferromagnetic alloys may lead to quite
different specific heat properties.[25]
The simple case of the monatomic gas
In the case of a monatomic gas such as helium under con-
stant volume, if it is assumed that no electronic or nuclear
quantum excitations occur, each atom in the gas has only
3 degrees of freedom, all of a translational type. No en-
ergy dependence is associated with the degrees of freedom
which define the position of the atoms. While, in fact, the
degrees of freedom corresponding to the momenta of the
atoms are quadratic, and thus contribute to the heat capac-
ity. There are N atoms, each of which has 3 components
( )
∂U 3 3
C V = = N kB = n R
∂T V 2 2
CV 3
where
CV is the heat capacity at constant volume of the
gas
CV,m is the molar heat capacity at constant vol-
ume of the gas
N is the total number of atoms present in the con-
tainer
n is the number of moles of atoms present in
the container (n is the ratio of N and Avogadro’s
number)
R is the ideal gas constant, (8.3144621[75]
J/(mol⋅K). R is equal to the product of
Boltzmann’s constant kB and Avogadro’s
number
The following table shows experimental molar constant
volume heat capacity measurements taken for each noble
monatomic gas (at 1 atm and 25 °C):
It is apparent from the table that the experimental heat ca-
pacities of the monatomic noble gases agrees with this sim-
ple application of statistical mechanics to a very high de-
gree.
190 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

The molar heat capacity of a monatomic gas at constant inertia about the internuclear axis is vanishingly small rela-
pressure is then tive to the other two rotational axes, the energy spacing can
be considered so high that no excitations of the rotational
state can occur unless the temperature is extremely high. It
5 is easy to calculate the expected number of vibrational de-
Cp,m = CV,m + R = R
2 grees of freedom (or vibrational modes). There are three
degrees of translational freedom, and two degrees of rota-
Diatomic gas tional freedom, therefore

fvib = f − ftrans − frot = 6 − 3 − 2 = 1

Each rotational and translational degree of freedom will

contribute R/2 in the total molar heat capacity of the gas.
Each vibrational mode will contribute R to the total molar
heat capacity, however. This is because for each vibrational
mode, there is a potential and kinetic energy component.
Both the potential and kinetic components will contribute
R/2 to the total molar heat capacity of the gas. Therefore,
a diatomic molecule would be expected to have a molar
constant-volume heat capacity of

3R 7R
CV,m = +R+R= = 3.5R
2 2
Constant volume specific heat capacity of a diatomic gas (ide-
alised). As temperature increases, heat capacity goes from 3/2 R where the terms originate from the translational, rotational,
(translation contribution only), to 5/2 R (translation plus rotation), and vibrational degrees of freedom, respectively.
finally to a maximum of 7/2 R (translation + rotation + vibration)
The following is a table of some molar constant-volume heat
capacities of various diatomic gases at standard temperature
In the somewhat more complex case of an ideal gas of (25 °C = 298 K)
diatomic molecules, the presence of internal degrees of
freedom are apparent. In addition to the three translational From the above table, clearly there is a problem with
degrees of freedom, there are rotational and vibrational de- the above theory. All of the diatomics examined have
grees of freedom. In general, the number of degrees of heat capacities that are lower than those predicted by the
freedom, f, in a molecule with na atoms is 3na: equipartition theorem, except Br2 . However, as the atoms
composing the molecules become heavier, the heat capaci-
ties move closer to their expected values. One of the reasons
for this phenomenon is the quantization of vibrational, and
f = 3na
to a lesser extent, rotational states. In fact, if it is assumed
Mathematically, there are a total of three rotational degrees that the molecules remain in their lowest energy vibrational
of freedom, one corresponding to rotation about each of the state because the inter-level energy spacings for vibration-
axes of three-dimensional space. However, in practice only energies are large, the predicted molar constant volume heat
the existence of two degrees of rotational freedom for linear capacity for a diatomic molecule becomes just that from the
molecules will be considered. This approximation is valid contributions of translation and rotation:
because the moment of inertia about the internuclear axis is
vanishingly small with respect to other moments of inertia
3R 5R
in the molecule (this is due to the very small rotational mo- CV,m = +R= = 2.5R
ments of single atoms, due to the concentration of almost 2 2
all their mass at their centers; compare also the extremely which is a fairly close approximation of the heat capac-
small radii of the atomic nuclei compared to the distance ities of the lighter molecules in the above table. If the
between them in a diatomic molecule). Quantum mechan- quantum harmonic oscillator approximation is made, it
ically, it can be shown that the interval between successive turns out that the quantum vibrational energy level spac-
rotational energy eigenstates is inversely proportional to the ings are actually inversely proportional to the square root
moment of inertia about that axis. Because the moment of of the reduced mass of the atoms composing the diatomic
8.1. HEAT CAPACITY 191

In addition, a molecule may have rotational motion. The

kinetic energy of rotational motion is generally expressed
as

1 ( )
E= I1 ω12 + I2 ω22 + I3 ω32
2

where I is the moment of inertia tensor of the molecule,

and [ω1 , ω2 , ω3 ] is the angular velocity pseudo-vector (in
a coordinate system aligned with the principal axes of the
molecule). In general, then, there will be three additional
degrees of freedom corresponding to the rotational motion
Constant volume specific heat capacity of diatomic gases (real
gases) between about 200 K and 2000 K. This temperature range of the molecule, (For linear molecules one of the inertia
is not large enough to include both quantum transitions in all gases. tensor terms vanishes and there are only two rotational de-
Instead, at 200 K, all but hydrogen are fully rotationally excited, so grees of freedom). The degrees of freedom corresponding
all have at least 5/2 R heat capacity. (Hydrogen is already below to translations and rotations are called the rigid degrees of
5/2, but it will require cryogenic conditions for even H2 to fall to 3/2 freedom, since they do not involve any deformation of the
R). Further, only the heavier gases fully reach 7/2 R at the highest molecule.
temperature, due to the relatively small vibrational energy spacing
of these molecules. HCl and H2 begin to make the transition above The motions of the atoms in a molecule which are not part
500 K, but have not achieved it by 1000 K, since their vibrational of its gross translational motion or rotation may be classified
energy level spacing is too wide to fully participate in heat capacity, as vibrational motions. It can be shown that if there are n
even at this temperature. atoms in the molecule, there will be as many as v = 3n−3−
nr vibrational degrees of freedom, where nr is the number
of rotational degrees of freedom. A vibrational degree of
molecule. Therefore, in the case of the heavier diatomic freedom corresponds to a specific way in which all the atoms
molecules such as chlorine or bromine, the quantum vi- of a molecule can vibrate. The actual number of possible
brational energy level spacings become finer, which allows vibrations may be less than this maximal one, due to various
more excitations into higher vibrational levels at lower tem- symmetries.
peratures. This limit for storing heat capacity in vibrational
modes, as discussed above, becomes 7R/2 = 3.5 R per mole For example, triatomic nitrous oxide N2 O will have only 2
of gas molecules, which is fairly consistent with the mea- degrees of rotational freedom (since it is a linear molecule)
sured value for Br2 at room temperature. As temperatures and contains n=3 atoms: thus the number of possible vi-
rise, all diatomic gases approach this value. brational degrees of freedom will be v = (3⋅3) − 3 − 2 = 4.
There are four ways or “modes” in which the three atoms
can vibrate, corresponding to 1) A mode in which an atom
General gas phase at each end of the molecule moves away from, or towards,
the center atom at the same time, 2) a mode in which either
The specific heat of the gas is best conceptualized in terms end atom moves asynchronously with regard to the other
of the degrees of freedom of an individual molecule. The two, and 3) and 4) two modes in which the molecule bends
different degrees of freedom correspond to the different out of line, from the center, in the two possible planar direc-
ways in which the molecule may store energy. The molecule tions that are orthogonal to its axis. Each vibrational degree
may store energy in its translational motion according to the of freedom confers TWO total degrees of freedom, since
formula: vibrational energy mode partitions into 1 kinetic and 1 po-
tential mode. This would give nitrous oxide 3 translational,
2 rotational, and 4 vibrational modes (but these last giving
1 ( 2 ) 8 vibrational degrees of freedom), for storing energy. This
E= m vx + vy2 + vz2
2 is a total of f = 3 + 2 + 8 = 13 total energy-storing degrees
where m is the mass of the molecule and [vx , vy , vz ] is ve- of freedom, for N2 O.
locity of the center of mass of the molecule. Each direction For a bent molecule like water H2 O, a similar calculation
of motion constitutes a degree of freedom, so that there are gives 9 − 3 − 3 = 3 modes of vibration, and 3 (translational)
three translational degrees of freedom. + 3 (rotational) + 6 (vibrational) = 12 degrees of freedom.
192 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

The storage of energy into degrees of freedom If the temperature of the substance is so low that the
equipartition energy of (1/2)kT is much smaller than this
If the molecule could be entirely described using classi- excitation energy, then there will be little or no energy in
cal mechanics, then the theorem of equipartition of energy this degree of freedom. This degree of freedom is then said
could be used to predict that each degree of freedom would to be “frozen out”. As mentioned above, the temperature
have an average energy in the amount of (1/2)kT where corresponding to the first excited vibrational state of HCl is
k is Boltzmann’s constant and T is the temperature. Our about 4156 K. For temperatures well below this value, the
calculation of the constant-volume heat capacity would be vibrational degrees of freedom of the HCl molecule will be
straightforward. Each molecule would be holding, on aver- frozen out. They will contain little energy and will not con-
age, an energy of (f/2)kT where f is the total number of tribute to the thermal energy or the heat capacity of HCl
degrees of freedom in the molecule. Note that Nk = R if gas.
N is Avogadro’s number, which is the case in considering
the heat capacity of a mole of molecules. Thus, the total in-
ternal energy of the gas would be (f/2)NkT where N is the
Energy storage mode “freeze-out” temperatures
total number of molecules. The heat capacity (at constant
volume) would then be a constant (f/ 2)Nk the mole-specific
It can be seen that for each degree of freedom there is a
heat capacity would be (f/ 2)R the molecule-specific heat
critical temperature at which the degree of freedom “un-
capacity would be (f/2)k and the dimensionless heat capac-
freezes” and begins to accept energy in a classical way. In
ity would be just f/2. Here again, each vibrational degree
the case of translational degrees of freedom, this tempera-
of freedom contributes 2f. Thus, a mole of nitrous oxide
ture is that temperature at which the thermal wavelength of
would have a total constant-volume heat capacity (includ-
the molecules is roughly equal to the size of the container.
ing vibration) of (13/2)R by this calculation.
For a container of macroscopic size (e.g. 10 cm) this tem-
In summary, the molar heat capacity (mole-specific heat ca- perature is extremely small and has no significance, since
pacity) of an ideal gas with f degrees of freedom is given the gas will certainly liquify or freeze before this low tem-
by perature is reached. For any real gas translational degrees
of freedom may be considered to always be classical and
contain an average energy of (3/2)kT per molecule.
f
CV,m = R The rotational degrees of freedom are the next to “un-
2
freeze”. In a diatomic gas, for example, the critical tem-
This equation applies to all polyatomic gases, if the degrees
[26] perature for this transition is usually a few tens of kelvins,
of freedom are known.
although with a very light molecule such as hydrogen the
The constant-pressure heat capacity for any gas would ex- rotational energy levels will be spaced so widely that ro-
ceed this by an extra factor of R (see Mayer's relation, tational heat capacity may not completely “unfreeze” until
above). As example C would be a total of (15/2)R/mole considerably higher temperatures are reached. Finally, the
for nitrous oxide. vibrational degrees of freedom are generally the last to un-
freeze. As an example, for diatomic gases, the critical tem-
perature for the vibrational motion is usually a few thou-
The effect of quantum energy levels in storing energy in
sands of kelvins, and thus for the nitrogen in our example
degrees of freedom
at room temperature, no vibration modes would be excited,
The various degrees of freedom cannot generally be consid- and the constant-volume heat capacity at room temperature
ered to obey classical mechanics, however. Classically, the is (5/2)R/mole, not (7/2)R/mole. As seen above, with some
energy residing in each degree of freedom is assumed to be unusually heavy gases such as iodine gas I2 , or bromine gas
continuous—it can take on any positive value, depending on Br2 , some vibrational heat capacity may be observed even
the temperature. In reality, the amount of energy that may at room temperatures.
reside in a particular degree of freedom is quantized: It may It should be noted that it has been assumed that atoms have
only be increased and decreased in finite amounts. A good no rotational or internal degrees of freedom. This is in fact
estimate of the size of this minimum amount is the energy untrue. For example, atomic electrons can exist in excited
of the first excited state of that degree of freedom above its states and even the atomic nucleus can have excited states
ground state. For example, the first vibrational state of the as well. Each of these internal degrees of freedom are as-
hydrogen chloride (HCl) molecule has an energy of about sumed to be frozen out due to their relatively high excitation
5.74 × 10−20 joule. If this amount of energy were deposited energy. Nevertheless, for sufficiently high temperatures,
in a classical degree of freedom, it would correspond to a these degrees of freedom cannot be ignored. In a few ex-
temperature of about 4156 K. ceptional cases, such molecular electronic transitions are of
8.1. HEAT CAPACITY 193

sufficiently low energy that they contribute to heat capac- Solid phase
ity at room temperature, or even at cryogenic temperatures.
One example of an electronic transition degree of freedom Main articles: Einstein solid, Debye model and Kinetic the-
which contributes heat capacity at standard temperature is ory of solids
that of nitric oxide (NO), in which the single electron in an For matter in a crystalline solid phase, the Dulong–Petit
anti-bonding molecular orbital has energy transitions which
contribute to the heat capacity of the gas even at room tem-
perature.
An example of a nuclear magnetic transition degree of free-
dom which is of importance to heat capacity, is the transi-
tion which converts the spin isomers of hydrogen gas (H2 )
into each other. At room temperature, the proton spins
of hydrogen gas are aligned 75% of the time, resulting
in orthohydrogen when they are. Thus, some thermal en-
ergy has been stored in the degree of freedom available
when parahydrogen (in which spins are anti-aligned) ab-
sorbs energy, and is converted to the higher energy ortho
form. However, at the temperature of liquid hydrogen,
not enough heat energy is available to produce orthohydro-
gen (that is, the transition energy between forms is large
enough to “freeze out” at this low temperature), and thus
the parahydrogen form predominates. The heat capacity
of the transition is sufficient to release enough heat, as or- The dimensionless heat capacity divided by three, as a function of
thohydrogen converts to the lower-energy parahydrogen, to temperature as predicted by the Debye model and by Einstein’s ear-
boil the hydrogen liquid to gas again, if this evolved heat is lier model. The horizontal axis is the temperature divided by the
not removed with a catalyst after the gas has been cooled Debye temperature. Note that, as expected, the dimensionless heat
and condensed. This example also illustrates the fact that capacity is zero at absolute zero, and rises to a value of three as the
some modes of storage of heat may not be in constant equi- temperature becomes much larger than the Debye temperature. The
red line corresponds to the classical limit of the Dulong–Petit law
librium with each other in substances, and heat absorbed or
released from such phase changes may “catch up” with tem-
law, which was discovered empirically, states that the molar
perature changes of substances, only after a certain time. In
heat capacity assumes the value 3 R. Indeed, for solid metal-
other words, the heat evolved and absorbed from the ortho-
lic chemical elements at room temperature, molar heat ca-
para isomeric transition contributes to the heat capacity of
pacities range from about 2.8 R to 3.4 R. Large exceptions
hydrogen on long time-scales, but not on short time-scales.
at the lower end involve solids composed of relatively low-
These time scales may also depend on the presence of a cat-
mass, tightly bonded atoms, such as beryllium at 2.0 R, and
alyst.
diamond at only 0.735 R. The latter conditions create larger
Less exotic phase-changes may contribute to the heat- quantum vibrational energy spacing, so that many vibra-
capacity of substances and systems, as well, as (for exam- tional modes have energies too high to be populated (and
ple) when water is converted back and forth from solid to thus are “frozen out”) at room temperature. At the higher
liquid or gas form. Phase changes store heat energy entirely end of possible heat capacities, heat capacity may exceed R
in breaking the bonds of the potential energy interactions by modest amounts, due to contributions from anharmonic
between molecules of a substance. As in the case of hy- vibrations in solids, and sometimes a modest contribution
drogen, it is also possible for phase changes to be hindered from conduction electrons in metals. These are not degrees
as the temperature drops, so that they do not catch up and of freedom treated in the Einstein or Debye theories.
become apparent, without a catalyst. For example, it is pos-
The theoretical maximum heat capacity for multi-atomic
sible to supercool liquid water to below the freezing point,
gases at higher temperatures, as the molecules become
and not observe the heat evolved when the water changes to
larger, also approaches the Dulong–Petit limit of 3 R, so
ice, so long as the water remains liquid. This heat appears
long as this is calculated per mole of atoms, not molecules.
instantly when the water freezes.
The reason for this behavior is that, in theory, gases
with very large molecules have almost the same high-
temperature heat capacity as solids, lacking only the (small)
heat capacity contribution that comes from potential energy
that cannot be stored between separate molecules in a gas.
194
The Dulong–Petit limit results from the equipartition the-
orem, and as such is only valid in the classical limit of a
microstate continuum, which is a high temperature limit.
For light and non-metallic elements, as well as most of the
common molecular solids based on carbon compounds at
standard ambient temperature, quantum effects may also
play an important role, as they do in multi-atomic gases.
These effects usually combine to give heat capacities lower
than 3 R per mole of atoms in the solid, although in molec-
ular solids, heat capacities calculated per mole of molecules
in molecular solids may be more than 3 R. For example,
the heat capacity of water ice at the melting point is about
4.6 R per mole of molecules, but only 1.5 R per mole of
atoms. As noted, heat capacity values far lower than 3 R
“per atom” (as is the case with diamond and beryllium) re-
sult from “freezing out” of possible vibration modes for light
atoms at suitably low temperatures, just as happens in many
low-mass-atom gases at room temperatures (where vibra-
tional modes are all frozen out). Because of high crystal
binding energies, the effects of vibrational mode freezing
are observed in solids more often than liquids: for example
the heat capacity of liquid water is twice that of ice at near
the same temperature, and is again close to the 3 R per mole
of atoms of the Dulong–Petit theoretical maximum.
Liquid phase
A general theory of the heat capacity of liquids has not yet
been achieved, and is still an active area of research. It was
long thought that phonon theory is not able to explain the
heat capacity of liquids, since liquids only sustain longitu-
dinal, but not transverse phonons, which in solids are re-
sponsible for 2/3 of the heat capacity. However, Brillouin
scattering experiments with neutrons and with X-rays, con-
firming an intuition of Yakov Frenkel,[27] have shown that
transverse phonons do exist in liquids, albeit restricted to 8.1.6 Mass heat capacity of building materi-
frequencies above a threshold called the Frenkel frequency.
Since most energy is contained in these high-frequency
modes, a simple modification of the Debye model is suf- See also: Thermal mass
ficient to yield a good approximation to experimental heat
capacities of simple liquids.[28]
Amorphous materials can be considered a type of liquid.
The specific heat of amorphous materials has characteris-
tic discontinuities at the glass transition temperature. These 8.1.7 Further reading
discontinuities are frequently used to detect the glass transi-
tion temperature where a supercooled liquid transforms to
[29]
a glass.
8.1.5 Table of specific heat capacities
See also: List of thermal conductivities
CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES
Note that the especially high molar values, as for paraffin,
gasoline, water and ammonia, result from calculating spe-
cific heats in terms of moles of molecules. If specific heat is
expressed per mole of atoms for these substances, none of
the constant-volume values exceed, to any large extent, the
theoretical Dulong–Petit limit of 25 J⋅mol−1 ⋅K−1 = 3 R per
mole of atoms (see the last column of this table). Paraffin,
for example, has very large molecules and thus a high heat
capacity per mole, but as a substance it does not have re-
markable heat capacity in terms of volume, mass, or atom-
mol (which is just 1.41 R per mole of atoms, or less than
half of most solids, in terms of heat capacity per atom).
In the last column, major departures of solids at standard
temperatures from the Dulong–Petit law value of 3 R, are
usually due to low atomic weight plus high bond strength
(as in diamond) causing some vibration modes to have too
much energy to be available to store thermal energy at the
measured temperature. For gases, departure from 3 R per
mole of atoms in this table is generally due to two factors:
(1) failure of the higher quantum-energy-spaced vibration
modes in gas molecules to be excited at room temperature,
and (2) loss of potential energy degree of freedom for small
gas molecules, simply because most of their atoms are not
bonded maximally in space to other atoms, as happens in
many solids.
A
Assuming an altitude of 194 metres above mean sea level (the
world–wide median altitude of human habitation), an indoor tem-
perature of 23 °C, a dewpoint of 9 °C (40.85% relative humidity),
and 760 mm–Hg sea level–corrected barometric pressure (molar
water vapor content = 1.16%).
*Derived data by calculation. This is for water-rich tissues such
as brain. The whole-body average figure for mammals is approx-
imately 2.9 J⋅cm−3 ⋅K−1 [38]
als
(Usually of interest to builders and solar designers)
• Encyclopædia Britannica, 2015, “Heat capacity (Al-
ternate title: thermal capacity),” see , accessed 14
February 2015.
• Emmerich Wilhelm & Trevor M. Letcher, Eds., 2010,
Heat Capacities: Liquids, Solutions and Vapours, Cam-
bridge, U.K.:Royal Society of Chemistry, ISBN 0-
85404-176-1, see , accessed 14 February 2014. A
very recent outline of selected traditional aspects of
8.1. HEAT CAPACITY 195

the title subject, including a recent specialist introduc- 8.1.10 References

tion to its theory, Emmerich Wilhelm, “Heat Capac-
ities: Introduction, Concepts, and Selected Applica- [1] Halliday, David; Resnick, Robert (2013). Fundamentals of
tions” (Chapter 1, pp. 1–27), chapters on traditional Physics. Wiley. p. 524.
and more contemporary experimental methods such [2] Kittel, Charles (2005). Introduction to Solid State Physics
as photoacoustic methods, e.g., Jan Thoen & Christ (8th ed.). Hoboken, New Jesery, USA: John Wiley & Sons.
Glorieux, “Photothermal Techniques for Heat Capac- p. 141. ISBN 0-471-41526-X.
ities,” and chapters on newer research interests, includ-
[3] Blundell, Stephen (2001). Magnetism in Condensed Matter.
ing on the heat capacities of proteins and other poly- Oxford Master Series in Condensed Matter Physics (1st ed.).
meric systems (Chs. 16, 15), of liquid crystals (Ch. Hoboken, New Jesery, USA: Oxford University Press. p.
17), etc. 27. ISBN 978-0-19-850591-4.
[4] Kittel, Charles (2005). Introduction to Solid State Physics
(8th ed.). Hoboken, New Jesery, USA: John Wiley & Sons.
8.1.8 See also
p. 141. ISBN 0-471-41526-X.
• Quantum statistical mechanics [5] Laider, Keith J. (1993). The World of Physical Chemistry.
Oxford University Press. ISBN 0-19-855919-4.
• Heat capacity ratio
[6] International Union of Pure and Applied Chemistry, Physi-
• Statistical mechanics cal Chemistry Division. “Quantities, Units and Symbols in
Physical Chemistry” (PDF). Blackwell Sciences. p. 7. The
• Thermodynamic equations adjective specific before the name of an extensive quantity
is often used to mean divided by mass.
• Thermodynamic databases for pure substances [7] International Bureau of Weights and Measures (2006), The
International System of Units (SI) (PDF) (8th ed.), ISBN 92-
• Heat equation 822-2213-6

• Heat transfer coefficient [8] Lange’s Handbook of Chemistry, 10th ed. page 1524
[9] “Water – Thermal Properties”. Engineeringtoolbox.com.
• Latent heat
Retrieved 2013-10-31.
• Material properties (thermodynamics) [10] Thermodynamics: An Engineering Approach by Yunus A.
Cengal and Michael A. Boles
• Joback method (Estimation of heat capacities)
[11] Yunus A. Cengel and Michael A. Boles,Thermodynamics:
• Specific melting heat An Engineering Approach 7th Edition, , McGraw-Hill,
2010,ISBN 007-352932-X
• Specific heat of vaporization [12] Fraundorf, P. (2003). “Heat capacity in bits”. American
Journal of Physics 71 (11): 1142. arXiv:cond-mat/9711074.
• Volumetric heat capacity Bibcode:2003AmJPh..71.1142F. doi:10.1119/1.1593658.
• Thermal mass [13] D. Lynden-Bell & R. M. Lynden-Bell (Nov
1977). “On the negative specific heat paradox”.
• R-value (insulation) Monthly Notices of the Royal Astronomical Society
181: 405–419. Bibcode:1977MNRAS.181..405L.
• Storage heater doi:10.1093/mnras/181.3.405.
[14] Lynden-Bell, D. (Dec 1998). “Negative Specific
Heat in Astronomy, Physics and Chemistry”. Phys-
8.1.9 Notes ica A 263: 293–304. arXiv:cond-mat/9812172v1.
Bibcode:1999PhyA..263..293L. doi:10.1016/S0378-
[1] IUPAC, Compendium of Chemical Terminology, 2nd ed. 4371(98)00518-4.
(the “Gold Book”) (1997). Online corrected version:
(2006–) "Standard Pressure".. Besides being a round num- [15] Schmidt, Martin; Kusche, Robert; Hippler, Thomas;
ber, this had a very practical effect: relatively few people Donges, Jörn; Kronmüller, Werner; Issendorff, von, Bernd;
live and work at precisely sea level; 100 kPa equates to the Haberland, Hellmut (2001). “Negative Heat Capacity
mean pressure at an altitude of about 112 metres (which is for a Cluster of 147 Sodium Atoms”. Physical Review
closer to the 194–metre, world–wide median altitude of hu- Letters 86 (7): 1191–4. Bibcode:2001PhRvL..86.1191S.
man habitation). doi:10.1103/PhysRevLett.86.1191. PMID 11178041.
196 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

[16] See e.g., Wallace, David (2010). “Gravity, entropy, and cos-
mology: in search of clarity” (preprint). British Journal for
the Philosophy of Science 61 (3): 513. arXiv:0907.0659.
Bibcode:2010BJPS...61..513W. doi:10.1093/bjps/axp048.
Section 4 and onwards.
[17] Reif, F. (1965). Fundamentals of statistical and thermal
physics. McGraw-Hill. pp. 253–254.
[18] Charles Kittel; Herbert Kroemer (2000). Thermal physics.
Freeman. p. 78. ISBN 0-7167-1088-9.
[19] Media:Translational motion.gif
[20] Smith, C. G. (2008). Quantum Physics and the Physics of
large systems, Part 1A Physics. University of Cambridge.
[35] “Heat Storage in Materials”. The Engineering Toolbox.
[36] Crawford, R. J. Rotational molding of plastics. ISBN 1-
59124-192-8.
[37] Gaur, Umesh; Wunderlich, Bernhard (1981). “Heat
capacity and other thermodynamic properties of lin-
ear macromolecules. II. Polyethylene” (PDF). Jour-
nal of Physical and Chemical Reference Data 10: 119.
Bibcode:1981JPCRD..10..119G. doi:10.1063/1.555636.
[38] Faber, P.; Garby, L. (1995). “Fat content affects heat ca-
pacity: a study in mice”. Acta Physiologica Scandinavica
153 (2): 185–7. doi:10.1111/j.1748-1716.1995.tb09850.x.
PMID 7778459.

[21] The comparison must be made under constant-volume

conditions—CvH—so that no work is performed. Nitro-
8.1.11 External links
gen’s CvH (100 kPa, 20 °C) = 20.8 J mol−1 K−1 vs. the
monatomic gases which equal 12.4717 J mol−1 K−1 . Cita- 8.2 Compressibility
tions: Freeman’s, W. H. “Physical Chemistry Part 3: Change
Exercise 21.20b, Pg. 787” (PDF).
“Incompressible” redirects here. For the property of vector
[22] Georgia State University. “Molar Specific Heats of Gases”. fields, see Solenoidal vector field. For the topological
[23] Petit A.-T., Dulong P.-L. (1819). “Recherches sur quelques property, see Incompressible surface.
points importants de la Théorie de la Chaleur”. Annales de
Chimie et de Physique 10: 395–413. In thermodynamics and fluid mechanics, compressibility is
[24] “The Heat Capacity of a Solid” (PDF). a measure of the relative volume change of a fluid or solid
as a response to a pressure (or mean stress) change.
[25] Hogan, C. (1969). “Density of States of an In-
sulating Ferromagnetic Alloy”. Physical Review
188 (2): 870. Bibcode:1969PhRv..188..870H. 1 ∂V
doi:10.1103/PhysRev.188.870. β=−
V ∂p
[26] Young; Geller (2008). Young and Geller College Physics (8th where V is volume and p is pressure.
ed.). Pearson Education. ISBN 0-8053-9218-1.

[27] In his textbook Kinetic Theory of Liquids (engl. 1947)

8.2.1 Definition
[28] Bolmatov, D.; Brazhkin, V. V.; Trachenko, K. (2012). “The
The specification above is incomplete, because for any ob-
phonon theory of liquid thermodynamics”. Scientific Reports
2. doi:10.1038/srep00421. Lay summary. ject or system the magnitude of the compressibility depends
strongly on whether the process is adiabatic or isothermal.
[29] Ojovan, Michael I. (2008). “Viscosity and Glass Tran-
sition in Amorphous Oxides”. Advances in Condensed Accordingly isothermal compressibility is defined:
Matter Physics 2008: 1. Bibcode:2008AdCMP2008....1O.
doi:10.1155/2008/817829. ( )
1 ∂V
[30] Page 183 in: Cornelius, Flemming (2008). Medical bio- βT = −
V ∂p T
physics (6th ed.). ISBN 1-4020-7110-8. (also giving a den-
sity of 1.06 kg/L) where the subscript T indicates that the partial differential
is to be taken at constant temperature
[31] “Table of Specific Heats”.
Isentropic compressibility is defined:
[32] “Iron”. National Institute of Standards and Technology.

[33] “Materials Properties Handbook, Material: Lithium” ( )

(PDF). Archived from the original (PDF) on September 5, 1 ∂V
βS = −
2006. V ∂p S

[34] “HCV (Molar Heat Capacity (cV)) Data for Methanol”. where S is entropy. For a solid, the distinction between the
Dortmund Data Bank Software and Separation Technology. two is usually negligible.
8.2. COMPRESSIBILITY 197

The minus sign makes the compressibility positive in the The deviation from ideal gas behavior tends to become par-
(usual) case that an increase in pressure induces a reduction ticularly significant (or, equivalently, the compressibility
in volume. factor strays far from unity) near the critical point, or in the
case of high pressure or low temperature. In these cases, a
generalized compressibility chart or an alternative equation
Relation to speed of sound of state better suited to the problem must be utilized to pro-
duce accurate results.
The speed of sound is defined in classical mechanics as:
A related situation occurs in hypersonic aerodynamics,
where dissociation causes an increase in the “notational”
( )
∂p molar volume, because a mole of oxygen, as O2 , becomes
c2 = 2 moles of monatomic oxygen and N2 similarly dissociates
∂ρ S
to 2N. Since this occurs dynamically as air flows over the
where ρ is the density of the material. It follows, by re- aerospace object, it is convenient to alter Z, defined for an
placing partial derivatives, that the isentropic compressibil- initial 30 gram mole of air, rather than track the varying
ity can be expressed as: mean molecular weight, millisecond by millisecond. This
pressure dependent transition occurs for atmospheric oxy-
gen in the 2500 K to 4000 K temperature range, and in the
1 5000 K to 10,000 K range for nitrogen.[1]
βS = 2
ρc
In transition regions, where this pressure dependent disso-
ciation is incomplete, both beta (the volume/pressure dif-
Relation to bulk modulus ferential ratio) and the differential, constant pressure heat
capacity will greatly increase.
The inverse of the compressibility is called the bulk modu-
For moderate pressures, above 10,000 K the gas further
lus, often denoted K (sometimes B). That page also contains
dissociates into free electrons and ions. Z for the result-
some examples for different materials.
ing plasma can similarly be computed for a mole of initial
The compressibility equation relates the isothermal com- air, producing values between 2 and 4 for partially or singly
pressibility (and indirectly the pressure) to the structure of ionized gas. Each dissociation absorbs a great deal of en-
the liquid. ergy in a reversible process and this greatly reduces the ther-
modynamic temperature of hypersonic gas decelerated near
the aerospace object. Ions or free radicals transported to
8.2.2 Thermodynamics the object surface by diffusion may release this extra (non-
thermal) energy if the surface catalyzes the slower recom-
Main article: Compressibility factor bination process.
The isothermal compressibility is related to the isentropic
The term “compressibility” is also used in thermodynamics (or adiabatic) compressibility by the relation,
to describe the deviance in the thermodynamic properties
of a real gas from those expected from an ideal gas. The
compressibility factor is defined as
α2 T
βS = βT −
ρcp
pV
Z=
RT via Maxwell’s relations. More simply stated,
where p is the pressure of the gas, T is its temperature, and
V is its molar volume. In the case of an ideal gas, the com-
pressibility factor Z is equal to unity, and the familiar ideal βT
gas law is recovered: =γ
βS

RT where,
p=
V
Z can, in general, be either greater or less than unity for a γ is the heat capacity ratio. See here for a deriva-
real gas. tion.
198 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

8.2.3 Earth science 8.2.5 Negative compressibility

Compressibility is used in the Earth sciences to quantify In general, the bulk compressibility (sum of the linear com-
the ability of a soil or rock to reduce in volume with applied pressibilities on the three axes) is positive, i.e. an increase
pressure. This concept is important for specific storage, in pressure squeezes the material to a smaller volume. This
when estimating groundwater reserves in confined aquifers. condition is required for mechanical stability.[5] However,
Geologic materials are made up of two portions: solids and under very specific conditions the compressibility can be
voids (or same as porosity). The void space can be full of negative.[6]
liquid or gas. Geologic materials reduces in volume only
when the void spaces are reduced, which expel the liquid or
gas from the voids. This can happen over a period of time, 8.2.6 See also
resulting in settlement.
• Poisson ratio
It is an important concept in geotechnical engineering in the
design of certain structural foundations. For example, the • Mach number
construction of high-rise structures over underlying layers
of highly compressible bay mud poses a considerable design • Prandtl-Glauert singularity, associated with super-
constraint, and often leads to use of driven piles or other sonic flight.
innovative techniques. • Shear strength

8.2.4 Fluid dynamics 8.2.7 References

[1] Regan, Frank J. Dynamics of Atmospheric Re-entry. p. 313.
Main article: Navier-Stokes equations § Compressible flow
ISBN 1-56347-048-9.
of Newtonian fluids
[2] Domenico, P. A.; Mifflin, M. D. (1965). “Wa-
ter from low permeability sediments and land
The degree of compressibility of a fluid has strong impli-
subsidence”. Water Resources Research 1
cations for its dynamics. Most notably, the propagation of (4): 563–576. Bibcode:1965WRR.....1..563D.
sound is dependent on the compressibility of the medium. doi:10.1029/WR001i004p00563. OSTI 5917760.

[3] Hugh D. Young; Roger A. Freedman. University Physics

Aeronautical dynamics with Modern Physics. Addison-Wesley; 2012. ISBN 978-
0-321-69686-1. p. 356.
Main article: Aerodynamics § De- [4] Fine, Rana A.; Millero, F. J. (1973). “Compressibil-
sign_issues_with_increasing_speed ity of water as a function of temperature and pres-
sure”. Journal of Chemical Physics 59 (10): 5529–5536.
Bibcode:1973JChPh..59.5529F. doi:10.1063/1.1679903.
Compressibility is an important factor in aerodynamics. At
low speeds, the compressibility of air is not significant in [5] Munn, R. W. (1971). “Role of the elastic con-
relation to aircraft design, but as the airflow nears and ex- stants in negative thermal expansion of axial solids”.
ceeds the speed of sound, a host of new aerodynamic effects Journal of Physics C: Solid State Physics 5: 535–
become important in the design of aircraft. These effects, 542. Bibcode:1972JPhC....5..535M. doi:10.1088/0022-
often several of them at a time, made it very difficult for 3719/5/5/005.
World War II era aircraft to reach speeds much beyond 800 [6] Lakes, Rod; Wojciechowski, K. W. (2008).
km/h (500 mph). “Negative compressibility, negative Poisson’s ra-
Many effects are often mentioned in conjunction with the tio, and stability”. Physica Status Solidi (b)
term “compressibility”, but regularly have little to do with 245 (3): 545. Bibcode:2008PSSBR.245..545L.
doi:10.1002/pssb.200777708.
the compressible nature of air. From a strictly aerodynamic
Gatt, Ruben; Grima, Joseph N. (2008). “Negative com-
point of view, the term should refer only to those side-
pressibility”. Physica status solidi (RRL) - Rapid Research
effects arising as a result of the changes in airflow from an Letters 2 (5): 236. Bibcode:2008PSSRR...2..236G.
incompressible fluid (similar in effect to water) to a com- doi:10.1002/pssr.200802101.
pressible fluid (acting as a gas) as the speed of sound is ap- Kornblatt, J. A. (1998). “Materials with
proached. There are two effects in particular, wave drag Negative Compressibilities”. Science 281
and critical mach. (5374): 143a. Bibcode:1998Sci...281..143K.
8.3. THERMAL EXPANSION 199

doi:10.1126/science.281.5374.143a. change in temperature is called the material’s coefficient of

Moore, B.; Jaglinski, T.; Stone, D. S.; Lakes, thermal expansion and generally varies with temperature.
R. S. (2006). “Negative incremental bulk mod-
ulus in foams”. Philosophical Magazine Letters
86 (10): 651. Bibcode:2006PMagL..86..651M. 8.3.1 Overview
doi:10.1080/09500830600957340.
Predicting expansion

8.3 Thermal expansion If an equation of state is available, it can be used to predict

the values of the thermal expansion at all the required tem-
peratures and pressures, along with many other state func-
tions.

Contraction effects (negative thermal expansion)

A number of materials contract on heating within certain

temperature ranges; this is usually called negative thermal
expansion, rather than “thermal contraction”. For exam-
ple, the coefficient of thermal expansion of water drops to
zero as it is cooled to 3.983 °C and then becomes negative
below this temperature; this means that water has a max-
imum density at this temperature, and this leads to bodies
of water maintaining this temperature at their lower depths
during extended periods of sub-zero weather. Also, fairly
pure silicon has a negative coefficient of thermal expansion
for temperatures between about 18 and 120 Kelvin.[2]

Factors affecting thermal expansion

Unlike gases or liquids, solid materials tend to keep their

shape when undergoing thermal expansion.
Thermal expansion generally decreases with increasing
bond energy, which also has an effect on the melting point
of solids, so, high melting point materials are more likely to
have lower thermal expansion. In general, liquids expand
slightly more than solids. The thermal expansion of glasses
is higher compared to that of crystals.[3] At the glass tran-
sition temperature, rearrangements that occur in an amor-
phous material lead to characteristic discontinuities of coef-
Expansion joint in a road bridge used to avoid damage from ther- ficient of thermal expansion or specific heat. These discon-
mal expansion. tinuities allow detection of the glass transition temperature
where a supercooled liquid transforms to a glass.[4]
Thermal expansion is the tendency of matter to change
in shape, area, and volume in response to a change in Absorption or desorption of water (or other solvents) can
temperature,[1] through heat transfer. change the size of many common materials; many organic
materials change size much more due to this effect than they
Temperature is a monotonic function of the average molec- do to thermal expansion. Common plastics exposed to wa-
ular kinetic energy of a substance. When a substance is ter can, in the long term, expand by many percent.
heated, the kinetic energy of its molecules increases. Thus,
the molecules begin moving more and usually maintain a
greater average separation. Materials which contract with 8.3.2 Coefficient of thermal expansion
increasing temperature are unusual; this effect is limited in
size, and only occurs within limited temperature ranges (see The coefficient of thermal expansion describes how the
examples below). The degree of expansion divided by the size of an object changes with a change in temperature.
200 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

Specifically, it measures the fractional change in size per the size of an object and so it is not usually necessary to
degree change in temperature at a constant pressure. Sev- consider the effect of pressure changes.
eral types of coefficients have been developed: volumet- Common engineering solids usually have coefficients of
ric, area, and linear. Which is used depends on the partic- thermal expansion that do not vary significantly over the
ular application and which dimensions are considered im- range of temperatures where they are designed to be used,
portant. For solids, one might only be concerned with the so where extremely high accuracy is not required, practical
change along a length, or over some area. calculations can be based on a constant, average, value of
The volumetric thermal expansion coefficient is the most the coefficient of expansion.
basic thermal expansion coefficient, and the most rele-
vant for fluids. In general, substances expand or contract
when their temperature changes, with expansion or contrac- Linear expansion
tion occurring in all directions. Substances that expand at
the same rate in every direction are called isotropic. For
isotropic materials, the area and volumetric thermal expan-
sion coefficient are, respectively, approximately twice and
three times larger than the linear thermal expansion coeffi-
cient.
Mathematical definitions of these coefficients are defined
below for solids, liquids, and gases. Change in length of a rod due to thermal expansion.

Linear expansion means change in one dimension (length)

General volumetric thermal expansion coefficient as opposed to change in volume (volumetric expansion). To
a first approximation, the change in length measurements of
In the general case of a gas, liquid, or solid, the volumetric an object due to thermal expansion is related to temperature
coefficient of thermal expansion is given by change by a “linear expansion coefficient”. It is the frac-
tional change in length per degree of temperature change.
( ) Assuming negligible effect of pressure, we may write:
1 ∂V
αV =
V ∂T p
1 dL
The subscript p indicates that the pressure is held constant αL = L dT
during the expansion, and the subscript V stresses that it is
the volumetric (not linear) expansion that enters this general where L is a particular length measurement and dL/dT is
definition. In the case of a gas, the fact that the pressure is the rate of change of that linear dimension per unit change
held constant is important, because the volume of a gas will in temperature.
vary appreciably with pressure as well as temperature. For The change in the linear dimension can be estimated to be:
a gas of low density this can be seen from the ideal gas law

∆L
= αL ∆T
8.3.3 Expansion in solids L
This equation works well as long as the linear-expansion
When calculating thermal expansion it is necessary to con- coefficient does not change much over the change in tem-
sider whether the body is free to expand or is constrained. If perature ∆T , and the fractional change in length is small
the body is free to expand, the expansion or strain resulting ∆L/L ≪ 1 . If either of these conditions does not hold,
from an increase in temperature can be simply calculated the equation must be integrated.
by using the applicable coefficient of thermal expansion
If the body is constrained so that it cannot expand, then
Effects on strain For solid materials with a significant
internal stress will be caused (or changed) by a change in
length, like rods or cables, an estimate of the amount of
temperature. This stress can be calculated by considering
thermal expansion can be described by the material strain,
the strain that would occur if the body were free to expand
given by ϵthermal and defined as:
and the stress required to reduce that strain to zero, through
the stress/strain relationship characterised by the elastic or
Young’s modulus. In the special case of solid materials, ex- (Lfinal − Linitial )
ternal ambient pressure does not usually appreciably affect ϵthermal =
Linitial
8.3. THERMAL EXPANSION 201

where Linitial is the length before the change of temperature Volume expansion
and Lfinal is the length after the change of temperature.
For a solid, we can ignore the effects of pressure on the
For most solids, thermal expansion is proportional to the
material, and the volumetric thermal expansion coefficient
change in temperature:
can be written:[5]

ϵthermal ∝ ∆T 1 dV
αV =
V dT
Thus, the change in either the strain or temperature can be
estimated by: where V is the volume of the material, and dV /dT is the
rate of change of that volume with temperature.
This means that the volume of a material changes by some
ϵthermal = αL ∆T fixed fractional amount. For example, a steel block with a
volume of 1 cubic meter might expand to 1.002 cubic me-
where ters when the temperature is raised by 50 K. This is an ex-
pansion of 0.2%. If we had a block of steel with a volume
of 2 cubic meters, then under the same conditions, it would
expand to 2.004 cubic meters, again an expansion of 0.2%.
∆T = (Tfinal − Tinitial )
The volumetric expansion coefficient would be 0.2% for 50
−1
is the difference of the temperature between the two K, or 0.004% K .
recorded strains, measured in degrees Celsius or Kelvin, and If we already know the expansion coefficient, then we can
αL is the linear coefficient of thermal expansion in “per calculate the change in volume
degree Celsius” or “per Kelvin”, denoted by °C−1 or K−1 ,
respectively. In the field of continuum mechanics, the ther-
mal expansion and its effects are treated as eigenstrain and ∆V
= αV ∆T
eigenstress. V
where ∆V /V is the fractional change in volume (e.g.,
Area expansion 0.002) and ∆T is the change in temperature (50 °C).
The above example assumes that the expansion coefficient
The area thermal expansion coefficient relates the change in did not change as the temperature changed and the increase
a material’s area dimensions to a change in temperature. It in volume is small compared to the original volume. This
is the fractional change in area per degree of temperature is not always true, but for small changes in temperature, it
change. Ignoring pressure, we may write: is a good approximation. If the volumetric expansion co-
efficient does change appreciably with temperature, or the
increase in volume is significant, then the above equation
1 dA will have to be integrated:
αA =
A dT
where A is some area of interest on the object, and dA/dT ( ) ∫ Tf
V + ∆V
is the rate of change of that area per unit change in temper- ln = αV (T ) dT
V Ti
ature.
(∫ )
The change in the area can be estimated as: ∆V Tf
= exp αV (T ) dT − 1
V Ti

∆A where αV (T ) is the volumetric expansion coefficient as a

= αA ∆T
A function of temperature T, and Ti , Tf are the initial and
final temperatures respectively.
This equation works well as long as the area expansion co-
efficient does not change much over the change in tem-
perature ∆T , and the fractional change in area is small Isotropic materials For isotropic materials the volumet-
∆A/A ≪ 1 . If either of these conditions does not hold, ric thermal expansion coefficient is three times the linear
the equation must be integrated. coefficient:
202 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

8.3.4 Isobaric expansion in gases

αV = 3αL For an ideal gas, the volumetric thermal expansion (i.e., rel-
ative change in volume due to temperature change) depends
This ratio arises because volume is composed of three mu- on the type of process in which temperature is changed.
tually orthogonal directions. Thus, in an isotropic material,Two simple cases are isobaric change, where pressure is
for small differential changes, one-third of the volumetric held constant, and adiabatic change, where no heat is ex-
expansion is in a single axis. As an example, take a cube of changed with the environment.
steel that has sides of length L. The original volume will be
V = L3 and the new volume, after a temperature increase, The ideal gas law can be written as:
will be

pv = T
∆L
V +∆V = (L+∆L) = L +3L ∆L+3L∆L +∆L ≈ L where
3 3 2 2 3
+3L2 ∆L3
p is =
theVpressure,
+3V
L v is the specific volume, and t is
temperature measured in energy units. By taking the loga-
We can make the substitutions ∆V = αV L3 ∆T and, for rithm of this equation:
isotropic materials, ∆L = αL L∆T . We now have:

ln (v) + ln (p) = ln (T )
V +∆V = (L+LαL ∆T )3 = L3 +3L3 αL ∆T +3L3 αL 2
∆T 2 +L3 αL3
∆T 3 ≈ L3 +3L3 αL ∆T
Then by definition of isobaric thermal expansion coefficient,
Since the volumetric and linear coefficients are defined only with the above equation of state:
for extremely small temperature and dimensional changes
(that is, when ∆T and ∆L are small), the last two terms ( ) ( )
can be ignored and we get the above relationship between γ ≡ 1 ∂v =
d(ln v)
=
d(ln T )
= .
1
p
the two coefficients. If we are trying to go back and forth v ∂T p dT p dT T
between volumetric and linear coefficients using larger val-
ues of ∆T then we will need to take into account the third The index p denotes an isobaric process.
term, and sometimes even the fourth term.
Similarly, the area thermal expansion coefficient is two 8.3.5 Expansion in liquids
times the linear coefficient:
Theoretically, the coefficient of linear expansion can be
found from the coefficient of volumetric expansion (αV ≈
αA = 2αL 3α). However, for liquids, α is calculated through the ex-
perimental determination of αV.
This ratio can be found in a way similar to that in the linear
example above, noting that the area of a face on the cube is
just L2 . Also, the same considerations must be made when 8.3.6 Expansion in mixtures and alloys
dealing with large values of ∆T .
The expansivity of the components of the mixture can can-
cel each other like in invar.
Anisotropic materials
The thermal expansivity of a mixture from the expansivi-
Materials with anisotropic structures, such as crystals (with ties of the pure components and their excess expansivities
less than cubic symmetry) and many composites, will gener- follow from:
ally have different linear expansion coefficients αL in dif-
ferent directions. As a result, the total volumetric expan- ∑ ∂Vi ∑ ∂V E
sion is distributed unequally among the three axes. If the ∂V = + i

crystal symmetry is monoclinic or triclinic, even the angles ∂T i

∂T i
∂T
between these axes are subject to thermal changes. In such ∑ ∑
cases it is necessary to treat the coefficient of thermal ex- α = αi Vi + αiE ViE
pansion as a tensor with up to six independent elements. A i i
good way to determine the elements of the tensor is to study ∂ V¯E i ∂(ln(γi )) ∂2
the expansion by powder diffraction. = R + RT ln(γi )
∂T ∂P ∂T ∂P
8.3. THERMAL EXPANSION
8.3.7 Apparent and absolute expansion
When measuring the expansion of a liquid, the measure-
ment must account for the expansion of the container as
well. For example, a flask that has been constructed with
a long narrow stem filled with enough liquid that the stem
itself is partially filled, when placed in a heat bath will ini-
tially show the column of liquid in the stem to drop fol-
lowed by the immediate increase of that column until the
flask-liquid-heat bath system has thermalized. The initial
observation of the column of liquid dropping is not due to
an initial contraction of the liquid but rather the expansion
of the flask as it contacts the heat bath first. Soon after,
the liquid in the flask is heated by the flask itself and begins
to expand. Since liquids typically have a greater expansion
over solids, the liquid in the flask eventually exceeds that of
the flask, causing the column of liquid in the flask to rise. A
direct measurement of the height of the liquid column is a
measurement of the apparent expansion of the liquid. The
absolute expansion of the liquid is the apparent expansion
corrected for the expansion of the containing vessel.[6]
8.3.8 Examples and applications
For applications using the thermal expansion property, see
bi-metal and mercury-in-glass thermometer.
The expansion and contraction of materials must be con-
Thermal expansion of long continuous sections of rail tracks is the
driving force for rail buckling. This phenomenon resulted in 190
train derailments during 1998–2002 in the US alone.[7]
sidered when designing large structures, when using tape or
chain to measure distances for land surveys, when design-
ing molds for casting hot material, and in other engineering
applications when large changes in dimension due to tem-
perature are expected.
Thermal expansion is also used in mechanical applications
to fit parts over one another, e.g. a bushing can be fitted over
a shaft by making its inner diameter slightly smaller than
the diameter of the shaft, then heating it until it fits over the
203
shaft, and allowing it to cool after it has been pushed over
the shaft, thus achieving a 'shrink fit'. Induction shrink fit-
ting is a common industrial method to pre-heat metal com-
ponents between 150 °C and 300 °C thereby causing them
to expand and allow for the insertion or removal of another
component.
There exist some alloys with a very small linear expansion
coefficient, used in applications that demand very small
changes in physical dimension over a range of tempera-
tures. One of these is Invar 36, with α approximately equal
to 0.6×10−6 K−1 . These alloys are useful in aerospace ap-
plications where wide temperature swings may occur.
Pullinger’s apparatus is used to determine the linear expan-
sion of a metallic rod in the laboratory. The apparatus con-
sists of a metal cylinder closed at both ends (called a steam
jacket). It is provided with an inlet and outlet for the steam.
The steam for heating the rod is supplied by a boiler which
is connected by a rubber tube to the inlet. The center of
the cylinder contains a hole to insert a thermometer. The
rod under investigation is enclosed in a steam jacket. One
of its ends is free, but the other end is pressed against a
fixed screw. The position of the rod is determined by a
micrometer screw gauge or spherometer.
Drinking glass with fracture due to uneven thermal expansion after
pouring of hot liquid into the otherwise cool glass
The control of thermal expansion in brittle materials is a
key concern for a wide range of reasons. For example,
both glass and ceramics are brittle and uneven temperature
causes uneven expansion which again causes thermal stress
and this might lead to fracture. Ceramics need to be joined
or work in consort with a wide range of materials and there-
fore their expansion must be matched to the application.
Because glazes need to be firmly attached to the underly-
ing porcelain (or other body type) their thermal expansion
must be tuned to 'fit' the body so that crazing or shivering
do not occur. Good example of products whose thermal
expansion is the key to their success are CorningWare and
204 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

the spark plug. The thermal expansion of ceramic bodies which is constrained to flow in only one direction (along the
can be controlled by firing to create crystalline species that tube) due to changes in volume brought about by changes
will influence the overall expansion of the material in the in temperature. A bi-metal mechanical thermometer uses a
desired direction. In addition or instead the formulation of bimetallic strip and bends due to the differing thermal ex-
the body can employ materials delivering particles of the pansion of the two metals.
desired expansion to the matrix. The thermal expansion of Metal pipes made of different materials are heated by pass-
glazes is controlled by their chemical composition and the ing steam through them. While each pipe is being tested,
firing schedule to which they were subjected. In most cases one end is securely fixed and the other rests on a rotating
there are complex issues involved in controlling body and
shaft, the motion of which is indicated with a pointer. The
glaze expansion, adjusting for thermal expansion must be linear expansion of the different metals is compared qual-
done with an eye to other properties that will be affected,
itatively and the coefficient of linear thermal expansion is
generally trade-offs are required. calculated.
Thermal expansion can have a noticeable effect in gasoline
stored in above ground storage tanks which can cause gaso-
line pumps to dispense gasoline which may be more com- 8.3.9 Thermal expansion coefficients for
pressed than gasoline held in underground storage tanks in various materials
the winter time or less compressed than gasoline held in un-
derground storage tanks in the summer time.[8] Main article: Thermal expansion coefficients of the ele-
Heat-induced expansion has to be taken into account in ments (data page)
most areas of engineering. A few examples are: This section summarizes the coefficients for some common
Coefficient de dilatation volumique isobare (modèle Tait)

• Metal framed windows need rubber spacers 2 000

0 bar
125 bar
1 800 250 bar

• Rubber tires
375 bar
500 bar
1 600

• Metal hot water heating pipes should not be used in 1 400

long straight lengths
1 200

• Large structures such as railways and bridges need 1 000

expansion joints in the structures to avoid sun kink
800

• One of the reasons for the poor performance of

600
cold car engines is that parts have inefficiently large
spacings until the normal operating temperature is 400

achieved. 200
20 40 60 80 100 120 140 160 180 200 220 240 260

• A gridiron pendulum uses an arrangement of different

metals to maintain a more temperature stable pendu- Volumetric thermal expansion coefficient for a semicrystalline
lum length. polypropylene.
• A power line on a hot day is droopy, but on a cold day
it is tight. This is because the metals expand under materials.
heat. For isotropic materials the coefficients linear thermal ex-
• Expansion joints that absorb the thermal expansion in pansion α and volumetric thermal expansion αV are related
a piping system.[9] by αV = 3α. For liquids usually the coefficient of volu-
metric expansion is listed and linear expansion is calculated
• Precision engineering nearly always requires the engi- here for comparison.
neer to pay attention to the thermal expansion of the For common materials like many metals and compounds,
product. For example, when using a scanning electron the thermal expansion coefficient is inversely proportional
microscope even small changes in temperature such as to the melting point.[10] In particular for metals the relation
1 degree can cause a sample to change its position rel- is:
ative to the focus point.

Thermometers are another application of thermal expan- 0.020

sion – most contain a liquid (usually mercury or alcohol) α ≈ MP
8.3. THERMAL EXPANSION 205

Coefficients de dilatation linéiques

18 [2] Bullis, W. Murray (1990). “Chapter 6”. In O'Mara, William
17.5 C.; Herring, Robert B.; Hunt, Lee P. Handbook of semicon-
X2CrNi12 (1.4003, 403)
17
X20Cr13 (1.4021, 420) ductor silicon technology. Park Ridge, New Jersey: Noyes
16.5 C35E (1.1181, 1035)

16
X2CrNiMoN22-5-3 (1.4462, 2205) Publications. p. 431. ISBN 0-8155-1237-6. Retrieved
X2CrNiMo17-12-2 (1.4404, 316L)
15.5 2010-07-11.
15

14.5 [3] Varshneya, A. K. (2006). Fundamentals of inorganic

14
glasses. Sheffield: Society of Glass Technology. ISBN 0-
13.5
12-714970-8.
13

12.5

12
[4] Ojovan, M. I. (2008). “Configurons: thermodynamic pa-
11.5 rameters and symmetry changes at glass transition”. En-
11 tropy 10 (3): 334–364. Bibcode:2008Entrp..10..334O.
10.5
doi:10.3390/e10030334.
10
100 150 200 250 300 350 400 450 500 550 600

[5] Turcotte, Donald L.; Schubert, Gerald (2002). Geodynamics

(2nd ed.). Cambridge. ISBN 0-521-66624-4.
Linear thermal expansion coefficient for some steel grades.
[6] Ganot, A., Atkinson, E. (1883). Elementary treatise on
physics experimental and applied for the use of colleges and
for halides and oxides schools, William and Wood & Co, New York, pp. 272–73.

[7] Track Buckling Research. Volpe Center, U.S. Department

0.038 of Transportation
α≈ − 7.0 · 10−6 K−1
MP
[8] Cost or savings of thermal expansion in above ground tanks.
In the table below, the range for α is from 10−7 K−1 for Artofbeingcheap.com (2013-09-06). Retrieved 2014-01-
hard solids to 10−3 K−1 for organic liquids. The coeffi- 19.
cient α varies with the temperature and some materials have
[9] Lateral, Angular and Combined Movements U.S. Bellows.
a very high variation ; see for example the variation vs.
temperature of the volumetric coefficient for a semicrys- [10] MIT Lecture Sheer and Thermal Expansion Tensors – Part 1
talline polypropylene (PP) at different pressure, and the
variation of the linear coefficient vs. temperature for some [11] “Thermal Expansion”. Western Washington University.
steel grades (from bottom to top: ferritic stainless steel, Archived from the original on 2009-04-17.
martensitic stainless steel, carbon steel, duplex stainless
steel, austenitic steel). [12] Ahmed, Ashraf; Tavakol, Behrouz; Das, Rony; Joven,
Ronald; Roozbehjavan, Pooneh; Minaie, Bob (2012). Study
(The formula αV ≈ 3α is usually used for solids.)[11] of Thermal Expansion in Carbon Fiber Reinforced Polymer
Composites. Proceedings of SAMPE International Sympo-
sium. Charleston, SC.
8.3.10 See also
[13] Young; Geller. Young and Geller College Physics (8th ed.).
• Negative thermal expansion ISBN 0-8053-9218-1.

• Mie-Gruneisen equation of state [14] “Technical Glasses Data Sheet” (PDF). schott.com.

• Autovent [15] Raymond Serway; John Jewett (2005), Principles of Physics:

A Calculus-Based Text, Cengage Learning, p. 506, ISBN
• Grüneisen parameter 0-534-49143-X
• Apparent molar property [16] “DuPont™ Kapton® 200EN Polyimide Film”.
matweb.com.

8.3.11 References [17] “Macor data sheet” (PDF). corning.com.

[1] when the body is heated its dimension(size) increase.This in-
crease in dimension is called thermal expansion . Paul A.,
Tipler; Gene Mosca (2008). Physics for Scientists and Engi-
neers, Volume 1 (6th ed.). New York, NY: Worth Publishers.
pp. 666–670. ISBN 1-4292-0132-0.
[18] “Properties of Common Liquid Materials”.
[19] “WDSC 340. Class Notes on Thermal Properties of Wood”.
forestry.caf.wvu.edu. Archived from the original on 2009-
03-30.
206 CHAPTER 8. CHAPTER 8. MATERIAL PROPERTIES

[20] Richard C. Weatherwax; Alfred J. Stamm (1956). The co-

efficients of thermal expansion of wood and wood prod-
ucts (PDF) (Technical report). Forest Products Laboratory,
United States Forest Service. 1487.

[21] “Sapphire” (PDF). kyocera.com.

[22] “Basic Parameters of Silicon Carbide (SiC)". Ioffe Institute.

[23] Becker, P.; Seyfried, P.; Siegert, H. (1982). “The lattice

parameter of highly pure silicon single crystals”. Zeitschrift
für Physik B 48: 17. Bibcode:1982ZPhyB..48...17B.
doi:10.1007/BF02026423.

[24] Nave, Rod. “Thermal Expansion Coefficients at 20 C”.

Georgia State University.

[25] “Sitall CO-115M (Astrositall)". Star Instruments.

[26] Thermal Expansion table

[27] Salvador, James R.; Guo, Fu; Hogan, Tim; Kanatzidis,

Mercouri G. (2003). “Zero thermal expansion in Yb-
GaGe due to an electronic valence transition”. Na-
ture 425 (6959): 702–5. Bibcode:2003Natur.425..702S.
doi:10.1038/nature02011. PMID 14562099.

[28] Janssen, Y.; Change, S.; Cho, B.K.; Llobet, A.; Den-
nis, K.W.; McCallum, R.W.; Mc Queeney, R.J.; Can-
feld, P.C. (2005). “YbGaGe: normal thermal expan-
sion”. Journal of Alloys and Compounds 389: 10–13.
doi:10.1016/j.jallcom.2004.08.012.

8.3.12 External links

• Glass Thermal Expansion Thermal expansion mea-
surement, definitions, thermal expansion calculation
from the glass composition

• Water thermal expansion calculator

• DoITPoMS Teaching and Learning Package on Ther-
mal Expansion and the Bi-material Strip
• Engineering Toolbox – List of coefficients of Linear
Expansion for some common materials
• Article on how αV is determined

• MatWeb: Free database of engineering properties for

over 79,000 materials

• USA NIST Website – Temperature and Dimensional

Measurement workshop
• Hyperphysics: Thermal expansion

• Understanding Thermal Expansion in Ceramic Glazes

Chapter 9

Chapter 9. Potentials

9.1 Thermodynamic potential Just as in mechanics, where potential energy is defined as

capacity to do work, similarly different potentials have dif-
ferent meanings:
A thermodynamic potential is a scalar quantity used to
represent the thermodynamic state of a system. The con-
cept of thermodynamic potentials was introduced by Pierre • Internal energy (U) is the capacity to do work plus the
Duhem in 1886. Josiah Willard Gibbs in his papers used capacity to release heat.
the term fundamental functions. One main thermodynamic
potential that has a physical interpretation is the internal en- • Gibbs energy (G) is the capacity to do non-mechanical
ergy U. It is the energy of configuration of a given system of work.
conservative forces (that is why it is a potential) and only has
meaning with respect to a defined set of references (or data). • Enthalpy (H) is the capacity to do non-mechanical
Expressions for all other thermodynamic energy potentials work plus the capacity to release heat.
are derivable via Legendre transforms from an expression
• Helmholtz free energy (F) is the capacity to do me-
for U. In thermodynamics, certain forces, such as gravity,
chanical work (useful work).
are typically disregarded when formulating expressions for
potentials. For example, while all the working fluid in a
steam engine may have higher energy due to gravity while From these definitions we can say that ΔU is the energy
sitting on top of Mount Everest than it would at the bottom added to the system, ΔF is the total work done on it, ΔG is
of the Mariana Trench, the gravitational potential energy the non-mechanical work done on it, and ΔH is the sum of
term in the formula for the internal energy would usually non-mechanical work done on the system and the heat given
be ignored because changes in gravitational potential within to it. Thermodynamic potentials are very useful when cal-
the engine during operation would be negligible. culating the equilibrium results of a chemical reaction, or
when measuring the properties of materials in a chemical
reaction. The chemical reactions usually take place under
some simple constraints such as constant pressure and tem-
9.1.1 Description and interpretation perature, or constant entropy and volume, and when this is
true, there is a corresponding thermodynamic potential that
Five common thermodynamic potentials are:[1] comes into play. Just as in mechanics, the system will tend
where T = temperature, S = entropy, p = pressure, V = towards lower values of potential and at equilibrium, under
volume. The Helmholtz free energy is often denoted by these constraints, the potential will take on an unchanging
the symbol F, but the use of A is preferred by IUPAC,[2] minimum value. The thermodynamic potentials can also be
ISO and IEC.[3] Nᵢ is the number of particles of type i in used to estimate the total amount of energy available from
the system and μᵢ is the chemical potential for an i-type par- a thermodynamic system under the appropriate constraint.
ticle. For the sake of completeness, the set of all Nᵢ are also In particular: (see principle of minimum energy for a
included as natural variables, although they are sometimes derivation)[4]
ignored.
These five common potentials are all energy potentials, • When the entropy (S ) and “external parameters” (e.g.
but there are also entropy potentials. The thermodynamic volume) of a closed system are held constant, the in-
square can be used as a tool to recall and derive some of the ternal energy (U ) decreases and reaches a minimum
potentials. value at equilibrium. This follows from the first and

207
208 CHAPTER 9. CHAPTER 9. POTENTIALS

second laws of thermodynamics and is called the prin- The definitions of the thermodynamic potentials may be
ciple of minimum energy. The following three state- differentiated and, along with the first and second laws of
ments are directly derivable from this principle. thermodynamics, a set of differential equations known as
the fundamental equations follow.[7] (Actually they are all
• When the temperature (T ) and external parameters of expressions of the same fundamental thermodynamic rela-
a closed system are held constant, the Helmholtz free tion, but are expressed in different variables.) By the first
energy (F ) decreases and reaches a minimum value at law of thermodynamics, any differential change in the inter-
equilibrium. nal energy U of a system can be written as the sum of heat
flowing into the system and work done by the system on the
• When the pressure (p) and external parameters of a environment, along with any change due to the addition of
closed system are held constant, the enthalpy (H ) de- new particles to the system:
creases and reaches a minimum value at equilibrium.

• When the temperature (T ), pressure (p) and external ∑

dU = δQ − δW + µi dNi
parameters of a closed system are held constant, the
i
Gibbs free energy (G ) decreases and reaches a mini-
mum value at equilibrium. where δQ is the infinitesimal heat flow into the system, and
δW is the infinitesimal work done by the system, μᵢ is the
chemical potential of particle type i and Nᵢ is the number of
9.1.2 Natural variables type i particles. (Note that neither δQ nor δW are exact dif-
ferentials. Small changes in these variables are, therefore,
The variables that are held constant in this process are represented with δ rather than d.)
termed the natural variables of that potential.[5] The natu- By the second law of thermodynamics, we can express the
ral variables are important not only for the above-mentioned internal energy change in terms of state functions and their
reason, but also because if a thermodynamic potential can differentials. In case of reversible changes we have:
be determined as a function of its natural variables, all of
the thermodynamic properties of the system can be found
by taking partial derivatives of that potential with respect to δQ = T dS
its natural variables and this is true for no other combination
of variables. On the converse, if a thermodynamic potential δW = p dV
is not given as a function of its natural variables, it will not,
where
in general, yield all of the thermodynamic properties of the
system.
T is temperature,
Notice that the set of natural variables for the above four po- S is entropy,
tentials are formed from every combination of the T-S and
P-V variables, excluding any pairs of conjugate variables. p is pressure,
There is no reason to ignore the Ni − μi conjugate pairs,
and in fact we may define four additional potentials for and V is volume, and the equality holds for reversible pro-
each species.[6] Using IUPAC notation in which the brack- cesses.
ets contain the natural variables (other than the main four), This leads to the standard differential form of the internal
we have: energy in case of a quasistatic reversible change:
If there is only one species, then we are done. But, if there
are, say, two species, then there will be additional potentials ∑
such as U [µ1 , µ2 ] = U − µ1 N1 − µ2 N2 and so on. If there dU = T dS − pdV + µi dNi
are D dimensions to the thermodynamic space, then there i

are 2D unique thermodynamic potentials. For the most sim- Since U, S and V are thermodynamic functions of state,
ple case, a single phase ideal gas, there will be three dimen- the above relation holds also for arbitrary non-reversible
sions, yielding eight thermodynamic potentials. changes. If the system has more external variables than
just the volume that can change, the fundamental thermo-
dynamic relation generalizes to:
9.1.3 The fundamental equations
∑ ∑
Main article: Fundamental thermodynamic relation dU = T dS − Xi dxi + µj dNj
i j
9.1. THERMODYNAMIC POTENTIAL 209

( ) ( )
Here the Xᵢ are the generalized forces corresponding to the +V = ∂H ∂G
=
external variables xᵢ. ∂p S,{Ni } ∂p T,{Ni }
Applying Legendre transforms repeatedly, the following ( ) ( )
∂G ∂F
differential relations hold for the four potentials: −S = =
∂T p,{Ni } ∂T V,{Ni }
Note that the infinitesimals on the right-hand side of each ( )
of the above equations are of the natural variables of the ∂ϕ
µj =
potential on the left-hand side. Similar equations can be de- ∂Nj X,Y,{Ni̸=j }
veloped for all of the other thermodynamic potentials of the
system. There will be one fundamental equation for each where, in the last equation, ϕ is any of the thermodynamic
thermodynamic potential, resulting in a total of 2D funda- potentials U, F, H, G and X, Y, {Nj̸=i } are the set of nat-
mental equations. ural variables for that potential, excluding Nᵢ . If we use all
potentials, then we will have more equations of state such
The differences between the four thermodynamic potentials as
can be summarized as follows:

( )
∂U [µj ]
d(pV ) = dH − dU = dG − dF −Nj =
∂µj S,V,{Ni̸=j }

d(T S) = dU − dF = dH − dG
9.1.4 The equations of state
We can use the above equations to derive some differen-
tial definitions of some thermodynamic parameters. If we
define Φ to stand for any of the thermodynamic potentials,
then the above equations are of the form:
and so on. In all, there will be D equations for each poten-
tial, resulting in a total of D 2D equations of state. If the
D equations of state for a particular potential are known,
then the fundamental equation for that potential can be de-
termined. This means that all thermodynamic information
about the system will be known, and that the fundamental
equations for any other potential can be found, along with
the corresponding equations of state.

∑ 9.1.5 The Maxwell relations

dΦ = xi dyi
i Main article: Maxwell relations
where xᵢ and yᵢ are conjugate pairs, and the yᵢ are the natural
variables of the potential Φ. From the chain rule it follows Again, define xᵢ and yᵢ to be conjugate pairs, and the yᵢ to
that: be the natural variables of some potential Φ. We may take
the “cross differentials” of the state equations, which obey
( ) the following relationship:
∂Φ
xj =
∂yj {yi̸=j } ( ) ( )
( ) ( )
∂ ∂Φ ∂ ∂Φ
Where yi ≠ j is the set of all natural variables of Φ except yᵢ . =
∂yj ∂yk {yi̸=k } ∂yk ∂yj {yi̸=j }
This yields expressions for various thermodynamic param- {yi̸=j } {yi̸=k }
eters in terms of the derivatives of the potentials with re-
[1][9]
spect to their natural variables. These equations are known From these we get the Maxwell relations. There will be
as equations of state since they specify parameters of the (D − 1)/2 of them for each potential giving a total of D(D
[8]
thermodynamic state. If we restrict ourselves to the po- − 1)/2 equations in all. If we restrict ourselves the U, F, H,
tentials U, F, H and G, then we have: G

( ) ( ) ( ) ( )
∂U ∂H ∂T ∂p
+T = = =−
∂S V,{Ni } ∂S p,{Ni }
∂V S,{Ni } ∂S V,{Ni }

( ) ( ) ( ) ( )
∂U ∂F ∂T ∂V
−p = = =+
∂V S,{Ni } ∂V T,{Ni } ∂p S,{Ni } ∂S p,{Ni }
210 CHAPTER 9. CHAPTER 9. POTENTIALS

( ) ( ) ∑
∂S ∂p G= µi Ni
=+
∂V T,{Ni } ∂T V,{Ni } i
( ) ( ) As in the above sections, this process can be carried out on
∂S ∂V
=− all of the other thermodynamic potentials. Note that the Eu-
∂p T,{Ni } ∂T
p,{Ni } ler integrals are sometimes also referred to as fundamental
Using the equations of state involving the chemical potential equations.
we get equations such as:
9.1.7 The Gibbs–Duhem relation
( ) ( )
∂T ∂µj
= Deriving the Gibbs–Duhem equation from basic thermody-
∂Nj ∂S
V,S,{Ni̸=j } V,{Ni } namic state equations is straightforward.[7][10][11] Equating
any thermodynamic potential definition with its Euler inte-
and using the other potentials we can get equations such as:
gral expression yields:

( ) ( ) ∑
∂Nj ∂p
=− U = TS − PV + µi Ni
∂V S,µj ,{Ni̸=j } ∂µj S,V {Ni̸=j } i
( ) ( ) Differentiating, and using the second law:
∂Nj ∂µk
=−
∂Nk S,V,µj ,{Ni̸=j,k } ∂µj S,V {Ni̸=j }
∑
dU = T dS − P dV + µi dNi
i
9.1.6 Euler integrals
yields:
Again, define xᵢ and yᵢ to be conjugate pairs, and the yᵢ to
be the natural variables of the internal energy. Since all of ∑
the natural variables of the internal energy U are extensive 0 = SdT − V dP + Ni dµi
quantities i

Which is the Gibbs–Duhem relation. The Gibbs–Duhem

is a relationship among the intensive parameters of the sys-
U ({αyi }) = αU ({yi }) tem. It follows that for a simple system with I components,
there will be I + 1 independent parameters, or degrees of
it follows from Euler’s homogeneous function theorem that freedom. For example, a simple system with a single com-
the internal energy can be written as: ponent will have two degrees of freedom, and may be spec-
ified by only two parameters, such as pressure and volume
for example. The law is named after Josiah Willard Gibbs
∑ ( ∂U ) and Pierre Duhem.
U ({yi }) = yj
j
∂yj {yi̸=j }

From the equations of state, we then have: 9.1.8 Chemical reactions

Changes in these quantities are useful for assessing the de-
∑ gree to which a chemical reaction will proceed. The rele-
U = T S − pV + µ i Ni vant quantity depends on the reaction conditions, as shown
i
in the following table. Δ denotes the change in the potential
Substituting into the expressions for the other main poten- and at equilibrium the change will be zero.
tials we have: Most commonly one considers reactions at constant p and
T, so the Gibbs free energy is the most useful potential in
∑ studies of chemical reactions.
F = −pV + µi Ni
i
∑ 9.1.9 See also
H = TS + µi Ni
i
• Coomber’s relationship
9.2. ENTHALPY 211

9.1.10 Notes 9.1.13 External links

[1] Alberty (2001) p. 1353 • Thermodynamic Potentials – Georgia State University
[2] Alberty (2001) p. 1376 • Chemical Potential Energy: The 'Characteristic' vs the
[3] ISO/IEC 80000-5:2007, item 5-20.4 Concentration-Dependent Kind

[4] Callen (1985) p. 153

[5] Alberty (2001) p. 1352 9.2 Enthalpy

[6] Alberty (2001) p. 1355
Not to be confused with Entropy.
[7] Alberty (2001) p. 1354

[8] Callen (1985) p. 37 Enthalpy i /ˈɛnθəlpi/ is a measurement of energy in a

thermodynamic system. It includes the internal energy,
[9] Callen (1985) p. 181
which is the energy required to create a system, and the
[10] Moran & Shapiro, p. 538 amount of energy required to make room for it by displacing
its environment and establishing its volume and pressure.[1]
[11] Callen (1985) p. 60
Enthalpy is defined as a state function that depends only on
the prevailing equilibrium state identified by the variables
9.1.11 References internal energy, pressure, and volume. It is an extensive
quantity. The unit of measurement for enthalpy in the
• Alberty, R. A. (2001). “Use of Legendre transforms in International System of Units (SI) is the joule, but other his-
chemical thermodynamics” (PDF). Pure Appl. Chem. torical, conventional units are still in use, such as the British
73 (8): 1349–1380. doi:10.1351/pac200173081349. thermal unit and the calorie.
• Callen, Herbert B. (1985). Thermodynamics and an The enthalpy is the preferred expression of system energy
Introduction to Thermostatistics (2nd ed.). New York: changes in many chemical, biological, and physical mea-
John Wiley & Sons. ISBN 0-471-86256-8. surements at constant pressure, because it simplifies the de-
scription of energy transfer. At constant pressure, the en-
• Moran, Michael J.; Shapiro, Howard N. (1996). Fun- thalpy change equals the energy transferred from the en-
damentals of Engineering Thermodynamics (3rd ed.). vironment through heating or work other than expansion
New York ; Toronto: J. Wiley & Sons. ISBN 0-471- work.
07681-3.
The total enthalpy, H, of a system cannot be measured
directly. The same situation exists in classical mechan-
9.1.12 Further reading ics: only a change or difference in energy carries physi-
cal meaning. Enthalpy itself is a thermodynamic poten-
• McGraw Hill Encyclopaedia of Physics (2nd Edition), tial, so in order to measure the enthalpy of a system, we
C.B. Parker, 1994, ISBN 0-07-051400-3 must refer to a defined reference point; therefore what we
measure is the change in enthalpy, ΔH. The ΔH is a posi-
• Thermodynamics, From Concepts to Applications
tive change in endothermic reactions, and negative in heat-
(2nd Edition), A. Shavit, C. Gutfinger, CRC Press
releasing exothermic processes.
(Taylor and Francis Group, USA), 2009, ISBN
9781420073683 For processes under constant pressure, ΔH is equal to
the change in the internal energy of the system, plus the
• Chemical Thermodynamics, D.J.G. Ives, Univer- pressure-volume work that the system has done on its
sity Chemistry, Macdonald Technical and Scientific, surroundings.[2] This means that the change in enthalpy un-
1971, ISBN 0-356-03736-3 der such conditions is the heat absorbed (or released) by
• Elements of Statistical Thermodynamics (2nd Edition), the material through a chemical reaction or by external
L.K. Nash, Principles of Chemistry, Addison-Wesley, heat transfer. Enthalpies for chemical substances at con-
1974, ISBN 0-201-05229-6 stant pressure assume standard state: most commonly 1 bar
pressure. Standard state does not, strictly speaking, specify
• Statistical Physics (2nd Edition), F. Mandl, Manch- a temperature (see standard state), but expressions for en-
ester Physics, John Wiley & Sons, 2008, ISBN thalpy generally reference the standard heat of formation at
9780471566588 25 °C.
212 CHAPTER 9. CHAPTER 9. POTENTIALS

Enthalpy of ideal gases and incompressible solids and liq- enthalpy h = H/m, where m is the mass of the system, or
uids does not depend on pressure, unlike entropy and the molar enthalpy H = H/n, where n is the number of
Gibbs energy. Real materials at common temperatures and moles (h and H are intensive properties). For inhomoge-
pressures usually closely approximate this behavior, which neous systems the enthalpy is the sum of the enthalpies of
greatly simplifies enthalpy calculation and use in practical the composing subsystems:
designs and analyses.
∑
9.2.1 Origins H= Hk ,
k

The word enthalpy is based on the Ancient Greek verb where the label k refers to the various subsystems. In case
enthalpein (ἐνθάλπειν), which means “to warm in”.[3] It of continuously varying p, T, and/or composition, the sum-
comes from the Classical Greek prefix ἐν- en-, meaning mation becomes an integral:
“to put into”, and the verb θάλπειν thalpein, meaning “to
heat”. The word enthalpy is often incorrectly attributed to
Benoît Paul Émile Clapeyron and Rudolf Clausius through ∫
the 1850 publication of their Clausius–Clapeyron relation. H= ρh dV,
This misconception was popularized by the 1927 publica-
tion of The Mollier Steam Tables and Diagrams. However, where ρ is the density.
neither the concept, the word, nor the symbol for enthalpy
existed until well after Clapeyron’s death. The enthalpy of homogeneous systems can be viewed as
function H(S,p) of the entropy S and the pressure p, and a
The earliest writings to contain the concept of enthalpy did differential relation for it can be derived as follows. We start
not appear until 1875,[4] when Josiah Willard Gibbs intro- from the first law of thermodynamics for closed systems for
duced “a heat function for constant pressure”. However, an infinitesimal process:
Gibbs did not use the word “enthalpy” in his writings.[note 1]
The actual word first appears in the scientific literature in a
1909 publication by J. P. Dalton. According to that pub- dU = δQ − δW.
lication, Heike Kamerlingh Onnes (1853–1926) actually
coined the word.[5] Here, δQ is a small amount of heat added to the system, and
Over the years, many different symbols were used to de- δW a small amount of work performed by the system. In
note enthalpy. It was not until 1922 that Alfred W. Porter a homogeneous system only reversible processes can take
proposed the symbol "H" as the accepted standard,[6] thus place, so the second law of thermodynamics gives δQ = T
finalizing the terminology still in use today. dS, with T the absolute temperature of the system. Further-
more, if only pV work is done, δW = p dV. As a result,

9.2.2 Formal definition

dU = T dS − p dV.
The enthalpy of a homogeneous system is defined as[7][8]
Adding d(pV) to both sides of this expression gives

H = U + pV,

where dU + d(pV ) = T dS − p dV + d(pV ),

or
H is the enthalpy of the system,
U is the internal energy of the system,
p is the pressure of the system, d(U + pV ) = T dS + V dp.
V is the volume of the system.
So
The enthalpy is an extensive property. This means that, for
homogeneous systems, the enthalpy is proportional to the
size of the system. It is convenient to introduce the specific dH(S, p) = T dS + V dp.
9.2. ENTHALPY 213

9.2.3 Other expressions and therefore the internal energy is used.[10][11] In basic
chemistry, experiments are often conducted at constant
The above expression of dH in terms of entropy and pres- atmospheric pressure, and the pressure-volume work rep-
sure may be unfamiliar to some readers. However, there resents an energy exchange with the atmosphere that can-
are expressions in terms of more familiar variables such as not be accessed or controlled, so that ΔH is the expression
temperature and pressure:[9][7]:88 chosen for the heat of reaction.

dH = Cp dT + V (1 − αT ) dp. 9.2.5 Relationship to heat

Here Cp is the heat capacity at constant pressure and α is In order to discuss the relation between the enthalpy in-
the coefficient of (cubic) thermal expansion: crease and heat supply, we return to the first law for closed
systems: dU = δQ − δW. We apply it to the special case with
( ) a uniform pressure at the surface. In this case the work term
1 ∂V can be split into two contributions, the so-called pV work,
α= .
V ∂T p given by p dV (where here p is the pressure at the surface,
dV is the increase of the volume of the system) and all other
With this expression one can, in principle, determine the types of work δW′, such as by a shaft or by electromagnetic
enthalpy if Cp and V are known as functions of p and T. interaction. So we write δW = p dV + δW′. In this case the
Note that for an ideal gas, αT = 1,[note 2] so that first law reads:

dH = Cp dT. dU = δQ − p dV − δW ′ ,

In a more general form, the first law describes the internal or

energy with additional terms involving the chemical poten-
tial and the number of particles of various types. The dif-
ferential statement for dH then becomes dH = δQ + V dp − δW ′ .

From this relation we see that the increase in enthalpy of a

∑ system is equal to the added heat:
dH = T dS + V dp + µi dNi ,
i

where μi is the chemical potential per particle for an i-type dH = δQ,

particle, and Ni is the number of such particles. The last
term can also be written as μi dni (with dni the number of provided that the system is under constant pressure (dp =
moles of component i added to the system and, in this case, 0) and that the only work done by the system is expansion
μi the molar chemical potential) or as μi dmi (with dmi the work (δW = 0).[12]
mass of component i added to the system and, in this case,
μi the specific chemical potential).
9.2.6 Applications
9.2.4 Physical interpretation In thermodynamics, one can calculate enthalpy by deter-
mining the requirements for creating a system from “noth-
The U term can be interpreted as the energy required to ingness"; the mechanical work required, pV, differs based
create the system, and the pV term as the energy that would upon the conditions that obtain during the creation of the
be required to “make room” for the system if the pressure thermodynamic system.
of the environment remained constant. When a system, for Energy must be supplied to remove particles from the sur-
example, n moles of a gas of volume V at pressure p and roundings to make space for the creation of the system, as-
temperature T, is created or brought to its present state from suming that the pressure p remains constant; this is the pV
absolute zero, energy must be supplied equal to its internal term. The supplied energy must also provide the change
energy U plus pV, where pV is the work done in pushing in internal energy, U, which includes activation energies,
against the ambient (atmospheric) pressure. ionization energies, mixing energies, vaporization energies,
In basic physics and statistical mechanics it may be more chemical bond energies, and so forth. Together, these con-
interesting to study the internal properties of the system stitute the change in the enthalpy U + pV. For systems at
214 CHAPTER 9. CHAPTER 9. POTENTIALS

constant pressure, with no external work done other than Enthalpy changes
the pV work, the change in enthalpy is the heat received by
the system. An enthalpy change describes the change in enthalpy ob-
served in the constituents of a thermodynamic system when
For a simple system, with a constant number of particles,
undergoing a transformation or chemical reaction. It is the
the difference in enthalpy is the maximum amount of ther-
difference between the enthalpy after the process has com-
mal energy derivable from a thermodynamic process in
pleted, i.e. the enthalpy of the products, and the initial en-
which the pressure is held constant.
thalpy of the system, i.e. the reactants. These processes are
reversible and the enthalpy for the reverse process is the
Heat of reaction negative value of the forward change.
A common standard enthalpy change is the enthalpy of for-
Main article: Standard enthalpy of reaction mation, which has been determined for a large number of
substances. Enthalpy changes are routinely measured and
The total enthalpy of a system cannot be measured directly, compiled in chemical and physical reference works, such as
the enthalpy change of a system is measured instead. En- the CRC Handbook of Chemistry and Physics. The follow-
thalpy change is defined by the following equation: ing is a selection of enthalpy changes commonly recognized
in thermodynamics.
When used in these recognized terms the qualifier change
∆H = Hf − Hi , is usually dropped and the property is simply termed en-
thalpy of 'process’. Since these properties are often used
where as reference values it is very common to quote them for a
standardized set of environmental parameters, or standard
ΔH is the “enthalpy change”, conditions, including:
H is the final enthalpy of the system (in a chem-
ical reaction, the enthalpy of the products), • A temperature of 25 °C or 298 K,
Hᵢ is the initial enthalpy of the system (in a chem- • A pressure of one atmosphere (1 atm or 101.325 kPa),
ical reaction, the enthalpy of the reactants).
• A concentration of 1.0 M when the element or com-
pound is present in solution,
For an exothermic reaction at constant pressure, the sys-
tem’s change in enthalpy equals the energy released in the • Elements or compounds in their normal physical
reaction, including the energy retained in the system and states, i.e. standard state.
lost through expansion against its surroundings. In a similar
manner, for an endothermic reaction, the system’s change For such standardized values the name of the enthalpy is
in enthalpy is equal to the energy absorbed in the reaction, commonly prefixed with the term standard, e.g. standard
including the energy lost by the system and gained from enthalpy of formation.
compression from its surroundings. A relatively easy way
to determine whether or not a reaction is exothermic or en- Chemical properties:
dothermic is to determine the sign of ΔH. If ΔH is positive,
the reaction is endothermic, that is heat is absorbed by the • Enthalpy of reaction, defined as the enthalpy change
system due to the products of the reaction having a greater observed in a constituent of a thermodynamic system
enthalpy than the reactants. On the other hand, if ΔH is when one mole of substance reacts completely.
negative, the reaction is exothermic, that is the overall de- • Enthalpy of formation, defined as the enthalpy change
crease in enthalpy is achieved by the generation of heat. observed in a constituent of a thermodynamic system
when one mole of a compound is formed from its ele-
Specific enthalpy mentary antecedents.
• Enthalpy of combustion, defined as the enthalpy
The specific enthalpy of a uniform system is defined as h change observed in a constituent of a thermodynamic
= H/m where m is the mass of the system. The SI unit for system when one mole of a substance burns completely
specific enthalpy is joule per kilogram. It can be expressed with oxygen.
in other specific quantities by h = u + pv, where u is the
specific internal energy, p is the pressure, and v is specific • Enthalpy of hydrogenation, defined as the enthalpy
volume, which is equal to 1/ρ, where ρ is the density. change observed in a constituent of a thermodynamic
9.2. ENTHALPY 215

system when one mole of an unsaturated compound energy of a system is equal to the amount of energy added
reacts completely with an excess of hydrogen to form to the system by matter flowing in and by heating, minus the
a saturated compound. amount lost by matter flowing out and in the form of work
done by the system:
• Enthalpy of atomization, defined as the enthalpy
change required to atomize one mole of compound
completely.
dU = δQ + dUin − dUout − δW,
• Enthalpy of neutralization, defined as the enthalpy
where Uᵢ is the average internal energy entering the system,
change observed in a constituent of a thermodynamic
and Uₒᵤ is the average internal energy leaving the system.
system when one mole of water is formed when an acid
and a base react. Heat added
Q
• Standard Enthalpy of solution, defined as the enthalpy
Work performed
change observed in a constituent of a thermodynamic external to boundary
system when one mole of a solute is dissolved com- Wshaft
pletely in an excess of solvent, so that the solution is
at infinite dilution.

• Standard enthalpy of Denaturation (biochemistry), de- Hout

fined as the enthalpy change required to denature one

mole of compound. Hin

System boundary (open)

• Enthalpy of hydration, defined as the enthalpy change
observed when one mole of gaseous ions are com-
pletely dissolved in water forming one mole of aqueous
ions. During steady, continuous operation, an energy balance applied to
an open system equates shaft work performed by the system to heat
added plus net enthalpy added
Physical properties:
The region of space enclosed by the boundaries if the open
• Enthalpy of fusion, defined as the enthalpy change re- system is usually called a control volume, and it may or may
quired to completely change the state of one mole of not correspond to physical walls. If we choose the shape
substance between solid and liquid states. of the control volume such that all flow in or out occurs
perpendicular to its surface, then the flow of matter into the
• Enthalpy of vaporization, defined as the enthalpy
system performs work as if it were a piston of fluid pushing
change required to completely change the state of one
mass into the system, and the system performs work on the
mole of substance between liquid and gaseous states.
flow of matter out as if it were driving a piston of fluid.
• Enthalpy of sublimation, defined as the enthalpy There are then two types of work performed: flow work
change required to completely change the state of one described above, which is performed on the fluid (this is
mole of substance between solid and gaseous states. also often called pV work), and shaft work, which may be
performed on some mechanical device.
• Lattice enthalpy, defined as the energy required to sep-
These two types of work are expressed in the equation
arate one mole of an ionic compound into separated
gaseous ions to an infinite distance apart (meaning no
force of attraction).
δW = d(pout Vout ) − d(pin Vin ) + δWshaft .
• Enthalpy of mixing, defined as the enthalpy change
upon mixing of two (non-reacting) chemical sub- Substitution into the equation above for the control volume
stances. (cv) yields:

Open systems dUcv = δQ+dUin +d(pin Vin )−dUout −d(pout Vout )−δWshaft .

In thermodynamic open systems, matter may flow in and The definition of enthalpy, H, permits us to use this
out of the system boundaries. The first law of thermody- thermodynamic potential to account for both internal en-
namics for open systems states: The increase in the internal ergy and pV work in fluids for open systems:
216 CHAPTER 9. CHAPTER 9. POTENTIALS

dUcv = δQ + dHin − dHout − δWshaft .

If we allow also the system boundary to move (e.g. due to

moving pistons), we get a rather general form of the first law
for open systems.[13] In terms of time derivatives it reads:

dU ∑ ∑ ∑ dVk
= Q̇k + Ḣk − pk − P,
dt dt
k k k

with sums over the various places k where heat is supplied,

matter flows into the system, and boundaries are moving.
The Ḣk terms represent enthalpy flows, which can be writ- T–s diagram of nitrogen.[14] The red curve at the left is the melt-
ten as ing curve. The red dome represents the two-phase region with the
low-entropy side the saturated liquid and the high-entropy side the
saturated gas. The black curves give the T–s relation along isobars.
The pressures are indicated in bar. The blue curves are isenthalps
Ḣk = hk ṁk = Hm ṅk ,
(curves of constant enthalpy). The values are indicated in blue in
with ṁk the mass flow and ṅk the molar flow at position k kJ/kg. The specific points a, b, etc., are treated in the main text.
respectively. The term dVk/dt represents the rate of change
of the system volume at position k that results in pV power
of the most common diagrams is the temperature–specific
done by the system. The parameter P represents all other
entropy diagram (T–s-diagram). It gives the melting curve
forms of power done by the system such as shaft power, but
and saturated liquid and vapor values together with isobars
it can also be e.g. electric power produced by an electrical
and isenthalps. These diagrams are powerful tools in the
power plant.
hands of the thermal engineer.
Note that the previous expression holds true only if the ki-
netic energy flow rate is conserved between system inlet and
outlet. Otherwise, it has to be included in the enthalpy bal- Some basic applications
ance. During steady-state operation of a device (see turbine,
pump, and engine), the average dU/dt may be set equal to The points a through h in the figure play a role in the dis-
zero. This yields a useful expression for the average power cussion in this section.
generation for these devices in the absence of chemical re-
actions:
a: T = 300 K, p = 1 bar, s = 6.85 kJ/(kg K), h =
461 kJ/kg;
∑ ⟨ ⟩ ∑ ⟨ ⟩ ∑ ⟨ dVk ⟩
P = Q̇k + Ḣk − pk , b: T = 380 K, p = 2 bar, s = 6.85 kJ/(kg K), h =
dt 530 kJ/kg;
k k k

where the angle brackets denote time averages. The tech-
nical importance of the enthalpy is directly related to its
presence in the first law for open systems, as formulated
above.
9.2.7 Diagrams
Nowadays the enthalpy values of important substances can
be obtained using commercial software. Practically all rel-
evant material properties can be obtained either in tabular
or in graphical form. There are many types of diagrams,
such as h–T diagrams, which give the specific enthalpy as
function of temperature for various pressures, and h–p di-
agrams, which give h as function of p for various T. One
c: T = 300 K, p = 200 bar, s = 5.16 kJ/(kg K), h
= 430 kJ/kg;
d: T = 270 K, p = 1 bar, s = 6.79 kJ/(kg K), h =
430 kJ/kg;
e: T = 108 K, p = 13 bar, s = 3.55 kJ/(kg K), h =
100 kJ/kg (saturated liquid at 13 bar);
f: T = 77.2 K, p = 1 bar, s = 3.75 kJ/(kg K), h =
100 kJ/kg;
g: T = 77.2 K, p = 1 bar, s = 2.83 kJ/(kg K), h =
28 kJ/kg (saturated liquid at 1 bar);
h: T = 77.2 K, p = 1 bar, s = 5.41 kJ/(kg K), h =
230 kJ/kg (saturated gas at 1 bar);
9.2. ENTHALPY 217

Throttling and T = 108 K. Throttling from this point to a pressure of

1 bar ends in the two-phase region (point f). This means
Main article: Joule–Thomson effect that a mixture of gas and liquid leaves the throttling valve.
One of the simple applications of the concept of enthalpy Since the enthalpy is an extensive parameter, the enthalpy
in f (h ) is equal to the enthalpy in g (h ) multiplied by the
liquid fraction in f (x ) plus the enthalpy in h (h ) multiplied
by the gas fraction in f (1 − x ). So

hf = xf hg + (1 − xf )hh .
With numbers: 100 = x × 28 + (1 − x ) × 230, so x =
0.64. This means that the mass fraction of the liquid in the
liquid–gas mixture that leaves the throttling valve is 64%.
Schematic diagram of a throttling in the steady state. Fluid enters
the system (dotted rectangle) at point 1 and leaves it at point 2. The Compressors
mass flow is ṁ.
Main article: Gas compressor
is the so-called throttling process, also known as Joule- A power P is applied e.g. as electrical power. If the com-
Thomson expansion. It concerns a steady adiabatic flow of
a fluid through a flow resistance (valve, porous plug, or any
other type of flow resistance) as shown in the figure. This
process is very important, since it is at the heart of domes-
tic refrigerators, where it is responsible for the temperature
drop between ambient temperature and the interior of the
refrigerator. It is also the final stage in many types of lique-
fiers.
In the first law for open systems (see above) applied to the
system, all terms are zero, except the terms for the enthalpy
flow. Hence
Schematic diagram of a compressor in the steady state. Fluid enters
the system (dotted rectangle) at point 1 and leaves it at point 2. The
mass flow is ṁ. A power P is applied and a heat flow Q̇ is released
0 = ṁh1 − ṁh2 . to the surroundings at ambient temperature Ta.

Since the mass flow is constant, the specific enthalpies at the pression is adiabatic, the gas temperature goes up. In the
two sides of the flow resistance are the same: reversible case it would be at constant entropy, which cor-
responds with a vertical line in the T–s diagram. For ex-
ample, compressing nitrogen from 1 bar (point a) to 2 bar
h1 = h2 , (point b) would result in a temperature increase from 300
K to 380 K. In order to let the compressed gas exit at ambi-
that is, the enthalpy per unit mass does not change during ent temperature Tₐ, heat exchange, e.g. by cooling water, is
the throttling. The consequences of this relation can be necessary. In the ideal case the compression is isothermal.
demonstrated using the T–s diagram above. Point c is at The average heat flow to the surroundings is Q̇. Since the
200 bar and room temperature (300 K). A Joule–Thomson system is in the steady state the first law gives
expansion from 200 bar to 1 bar follows a curve of constant
enthalpy of roughly 425 kJ/kg (not shown in the diagram)
lying between the 400 and 450 kJ/kg isenthalps and ends in 0 = −Q̇ + ṁh − ṁh + P.
1 2
point d, which is at a temperature of about 270 K. Hence
the expansion from 200 bar to 1 bar cools nitrogen from The minimal power needed for the compression is realized
300 K to 270 K. In the valve, there is a lot of friction, and if the compression is reversible. In that case the second law
a lot of entropy is produced, but still the final temperature of thermodynamics for open systems gives
is below the starting value!
Point e is chosen so that it is on the saturated liquid line Q̇
with h = 100 kJ/kg. It corresponds roughly with p = 13 bar 0 = − Ta + ṁs1 − ṁs2 .
218 CHAPTER 9. CHAPTER 9. POTENTIALS

Eliminating Q̇ gives for the minimal power 9.2.10 References

Pmin
= h2 − h1 − Ta (s2 − s1 ).
ṁ
For example, compressing 1 kg of nitrogen from 1 bar to
200 bar costs at least (h − hₐ) − Tₐ(s − sₐ). With the data,
obtained with the T–s diagram, we find a value of (430 −
461) − 300 × (5.16 − 6.85) = 476 kJ/kg.
[1] Zemansky, Mark W. (1968). “Chapter 11”. Heat and Ther-
modynamics (5th ed.). New York, NY: McGraw-Hill. p.
275.
[2] Van Wylen, G. J.; Sonntag, R. E. (1985). “Section 5.5”.
Fundamentals of Classical Thermodynamics (3rd ed.). New
York, NY: John Wiley & Sons. ISBN 0-471-82933-1.
[3] "ἐνθάλπω". A Greek–English Lexicon.

The relation for the power can be further simplified by writ- [4] Henderson, Douglas; Eyring, Henry; Jost, Wilhelm (1967).
ing it as Physical Chemistry: An Advanced Treatise. Academic Press.
p. 29.

∫ [5] Laidler, Keith (1995). The World of Physical Chemistry.

2
Pmin Oxford University Press. p. 110.
= (dh − Ta ds).
ṁ 1
[6] Howard, Irmgard (2002). "H Is for Enthalpy, Thanks to
Heike Kamerlingh Onnes and Alfred W. Porter”. Jour-
With dh = T ds + v dp, this results in the final relation
nal of Chemical Education (ACS Publications) 79 (6): 697.
Bibcode:2002JChEd..79..697H. doi:10.1021/ed079p697.
∫ 2 [7] Guggenheim, E. A. (1959). Thermodynamics. Amsterdam:
Pmin
= v dp. North-Holland Publishing Company.
ṁ 1
[8] Zumdahl, Steven S. (2008). “Thermochemistry”.
Chemistry. Cengage Learning. p. 243. ISBN 978-0-
9.2.8 See also 547-12532-9.

[9] Moran, M. J.; Shapiro, H. N. (2006). Fundamentals of En-

• Standard enthalpy change of formation (data table) gineering Thermodynamics (5th ed.). John Wiley & Sons. p.
511.
• Calorimetry
[10] Reif, F. (1967). Statistical Physics. London: McGraw-Hill.
• Calorimeter [11] Kittel, C.; Kroemer, H. (1980). Thermal Physics. London:
Freeman.
• Departure function
[12] Ebbing, Darrel; Gammon, Steven (2010). General Chem-
istry. Cengage Learning. p. 231. ISBN 978-0-538-49752-
• Hess’s law
7.

• Isenthalpic process [13] Moran, M. J.; Shapiro, H. N. (2006). Fundamentals of En-

gineering Thermodynamics (5th ed.). John Wiley & Sons. p.
• Stagnation enthalpy 129.

[14] Figure composed with data obtained with RefProp, NIST

• Thermodynamic databases for pure substances Standard Reference Database 23.

• Entropy
9.2.11 Bibliography

9.2.9 Notes • Dalton, J.P. (1909). “Researches on the Joule–Kelvin

effect, especially at low temperatures. I. Calculations
[1] The Collected Works of J. Willard Gibbs, Vol. I do not con-
for hydrogen” (PDF). KNAW Proceedings 11: 863–
tain reference to the word enthalpy, but rather reference the 873.
heat function for constant pressure.
• Haase, R. (1971). Jost, W., ed. Physical Chemistry:
( ) An Advanced Treatise. New York, NY: Academic. p.
T ∂( nRT ) nRT
[2] αT = V
P
∂T
= PV
=1 29.
p
9.3. INTERNAL ENERGY 219

• Gibbs, J. W. The Collected Works of J. Willard Gibbs, chain of thermodynamic operations and thermodynamic
Vol. I (1948 ed.). New Haven, CT: Yale University processes by which the given state can be prepared, start-
Press. p. 88.. ing with a reference state which is customarily assigned a
reference value for its internal energy. Such a chain, or
• Howard, I. K. (2002). "H Is for Enthalpy, Thanks to path, can be theoretically described by certain extensive
Heike Kamerlingh Onnes and Alfred W. Porter”. J. state variables of the system, namely, its entropy, S, its vol-
Chem. Educ. 79: 697–698. doi:10.1021/ed079p697. ume, V, and its mole numbers, {Nj}. The internal energy,
• Laidler, K. (1995). The World of Physical Chemistry. U(S,V,{Nj}), is a function of those. Sometimes, to that
Oxford: Oxford University Press. p. 110. list are appended other extensive state variables, for exam-
ple electric dipole moment. For practical considerations in
• Kittel, C.; Kroemer, H. (1980). Thermal Physics. thermodynamics and engineering it is rarely necessary or
New York, NY: S. R. Furphy & Co. p. 246. convenient to consider all energies belonging to the total
intrinsic energy of a system, such as the energy given by
• DeHoff, R. (2006). Thermodynamics in Materials Sci-
the equivalence of mass. Customarily, thermodynamic de-
ence (2nd ed.). New York, NY: Taylor and Francis
scriptions include only items relevant to the processes un-
Group.
der study. Thermodynamics is chiefly concerned only with
changes in the internal energy, not with its absolute value.
9.2.12 External links The internal energy is a state function of a system, because
its value depends only on the current state of the system
• Enthalpy - Eric Weisstein’s World of Physics and not on the path taken or processes undergone to pre-
• Enthalpy - Georgia State University pare it. It is an extensive quantity. It is the one and only
cardinal thermodynamic potential.[4] Through it, by use of
• Enthalpy example calculations - Texas A&M Univer- Legendre transforms, are mathematically constructed the
sity Chemistry Department other thermodynamic potentials. These are functions of
variable lists in which some extensive variables are replaced
by their conjugate intensive variables. Legendre transfor-
9.3 Internal energy mation is necessary because mere substitutive replacement
of extensive variables by intensive variables does not lead
In thermodynamics, the internal energy of a system is the to thermodynamic potentials. Mere substitution leads to a
energy contained within the system, excluding the kinetic less informative formula, an equation of state.
energy of motion of the system as a whole and the potential Though it is a macroscopic quantity, internal energy can
energy of the system as a whole due to external force fields. be explained in microscopic terms by two theoretical vir-
It keeps account of the gains and losses of energy of the tual components. One is the microscopic kinetic energy
system that are due to changes in its internal state.[1][2] due to the microscopic motion of the system’s particles
The internal energy of a system can be changed by transfers (translations, rotations, vibrations). The other is the poten-
of matter and by work and heat transfer.[3] When matter tial energy associated with the microscopic forces, includ-
transfer is prevented by impermeable containing walls, the ing the chemical bonds, between the particles; this is for
system is said to be closed. Then the first law of thermo- ordinary physics and chemistry. If thermonuclear reactions
dynamics states that the increase in internal energy is equal are specified as a topic of concern, then the static rest mass
to the total heat added plus the work done on the system by energy of the constituents of matter is also counted. There
its surroundings. If the containing walls pass neither mat- is no simple universal relation between these quantities of
ter nor energy, the system is said to be isolated. Then its microscopic energy and the quantities of energy gained or
internal energy cannot change. The first law of thermody- lost by the system in work, heat, or matter transfer.
namics may be regarded as establishing the existence of the The SI unit of energy is the joule (J). Sometimes it is conve-
internal energy. nient to use a corresponding density called specific internal
The internal energy is one of the two cardinal state functions energy which is internal energy per unit of mass (kilogram)
of the state variables of a thermodynamic system. of the system in question. The SI unit of specific internal
energy is J/kg. If the specific internal energy is expressed
relative to units of amount of substance (mol), then it is re-
9.3.1 Introduction ferred to as molar internal energy and the unit is J/mol.
From the standpoint of statistical mechanics, the internal
The internal energy of a given state of a system cannot be di- energy is equal to the ensemble average of the sum of the
rectly measured. It is determined through some convenient
220 CHAPTER 9. CHAPTER 9. POTENTIALS

microscopic kinetic and potential energies of the system. energy needed to create the given state of the system from
the reference state.
Cardinal functions From a non-relativistic microscopic point of view, it may
be divided into microscopic potential energy, U ᵢ ᵣₒ ₒ , and
The internal energy, U(S,V,{Nj}), expresses the thermody- microscopic kinetic energy, U ᵢ ᵣₒ ᵢ , components:
namics of a system in the energy-language, or in the en-
ergy representation. Its arguments are exclusively extensive
variables of state. Alongside the internal energy, the other U = Umicro pot + Umicro kin
cardinal function of state of a thermodynamic system is its
entropy, as a function, S(U,V,{Nj}), of the same list of ex- The microscopic kinetic energy of a system arises as the
tensive variables of state, except that the entropy, S, is re- sum of the motions of all the system’s particles with re-
placed in the list by the internal energy, U. It expresses the spect to the center-of-mass frame, whether it be the mo-
entropy representation.[4][5][6] tion of atoms, molecules, atomic nuclei, electrons, or other
Each cardinal function is a monotonic function of each particles. The microscopic potential energy algebraic sum-
of its natural or canonical variables. Each provides its mative components are those of the chemical and nuclear
characteristic or fundamental equation, for example U = particle bonds, and the physical force fields within the sys-
U(S,V,{Nj}), that by itself contains all thermodynamic in- tem, such as due to internal induced electric or magnetic
formation about the system. The fundamental equations for dipole moment, as well as the energy of deformation of
the two cardinal functions can in principle be interconverted solids (stress-strain). Usually, the split into microscopic ki-
by solving, for example, U = U(S,V,{Nj}) for S, to get S = netic and potential energies is outside the scope of macro-
S(U,V,{Nj}). scopic thermodynamics.

In contrast, Legendre transforms are necessary to derive Internal energy does not include the energy due to motion
fundamental equations for other thermodynamic potentials or location of a system as a whole. That is to say, it ex-
and Massieu functions. The entropy as a function only of cludes any kinetic or potential energy the body may have
extensive state variables is the one and only cardinal func- because of its motion or location in external gravitational,
tion of state for the generation of Massieu functions. It is not electrostatic, or electromagnetic fields. It does, however, in-
itself customarily designated a 'Massieu function', though clude the contribution of such a field to the energy due to
rationally it might be thought of as such, corresponding to the coupling of the internal degrees of freedom of the ob-
the term 'thermodynamic potential', which includes the in- ject with the field. In such a case, the field is included in the
ternal energy.[5][7][8] thermodynamic description of the object in the form of an
additional external parameter.
For real and practical systems, explicit expressions of the
fundamental equations are almost always unavailable, but For practical considerations in thermodynamics or engi-
neering, it is rarely necessary, convenient, nor even possi-
the functional relations exist in principle. Formal, in princi-
ple, manipulations of them are valuable for the understand- ble, to consider all energies belonging to the total intrinsic
ing of thermodynamics. energy of a sample system, such as the energy given by the
equivalence of mass. Typically, descriptions only include
components relevant to the system under study. Indeed, in
9.3.2 Description and definition most systems under consideration, especially through ther-
modynamics, it is impossible to calculate the total internal
The internal energy U of a given state of the system is de- energy.[9] Therefore, a convenient null reference point may
termined relative to that of a standard state of the system, be chosen for the internal energy.
by adding up the macroscopic transfers of energy that ac- The internal energy is an extensive property: it depends on
company a change of state from the reference state to the the size of the system, or on the amount of substance it con-
given state: tains.
At any temperature greater than absolute zero, microscopic
∑ potential energy and kinetic energy are constantly converted
∆U = Ei
into one another, but the sum remains constant in an isolated
i
system (cf. table). In the classical picture of thermody-
where ΔU denotes the difference between the internal en- namics, kinetic energy vanishes at zero temperature and the
ergy of the given state and that of the reference state, and internal energy is purely potential energy. However, quan-
the Ei are the various energies transferred to the system in tum mechanics has demonstrated that even at zero tempera-
the steps from the reference state to the given state. It is the ture particles maintain a residual energy of motion, the zero
9.3. INTERNAL ENERGY 221

point energy. A system at absolute zero is merely in its A second mechanism of change of internal energy of a
quantum-mechanical ground state, the lowest energy state closed system is the doing of work on the system, either
available. At absolute zero a system of given composition in mechanical form by changing pressure or volume, or by
has attained its minimum attainable entropy. other perturbations, such as directing an electric current
The microscopic kinetic energy portion of the internal en- through the system.
ergy gives rise to the temperature of the system. Statistical If the system is not closed, the third mechanism that can in-
mechanics relates the pseudo-random kinetic energy of in- crease the internal energy is transfer of matter into the sys-
dividual particles to the mean kinetic energy of the entire tem. This increase, ΔU ₐ ₑᵣ cannot be split into heat and
ensemble of particles comprising a system. Furthermore, it work components. If the system is so set up physically that
relates the mean microscopic kinetic energy to the macro- heat and work can be done on it by pathways separate from
scopically observed empirical property that is expressed as and independent of matter transfer, then the transfers of en-
temperature of the system. This energy is often referred to ergy add to change the internal energy:
as the thermal energy of a system,[10] relating this energy,
like the temperature, to the human experience of hot and
cold. ∆U = Q + Wpressure−volume + Wisochoric + ∆Umatter
Statistical mechanics considers any system to be statistically
(separate pathway for matter transfer from heat and work transfer pathway
distributed across an ensemble of N microstates. Each mi-
crostate has an energy Eᵢ and is associated with a probabil- If a system undergoes certain phase transformations while
ity pᵢ. The internal energy is the mean value of the system’s being heated, such as melting and vaporization, it may
total energy, i.e., the sum of all microstate energies, each be observed that the temperature of the system does not
weighted by their probability of occurrence: change until the entire sample has completed the transfor-
mation. The energy introduced into the system while the
temperature did not change is called a latent energy, or latent
∑N
heat, in contrast to sensible heat, which is associated with
U= p i Ei .
temperature change.
i=1

This is the statistical expression of the first law of thermo-

dynamics.
Internal energy changes
Thermodynamics is chiefly concerned only with the
changes, ΔU, in internal energy.
For a closed system, with matter transfer excluded, the
changes in internal energy are due to heat transfer Q and
due to work. The latter can be split into two kinds, pressure- noble gases. Here the kinetic energy consists only of the
volume work W ᵣₑ ᵤᵣₑ-ᵥₒ ᵤ ₑ, and frictional and other kinds,
such as electrical polarization, which do not alter the vol-
ume of the system, and are called isochoric, Wᵢ ₒ ₒᵣᵢ . Ac-
cordingly, the internal energy change ΔU for a process may
be written[3]
∆U = Q + Wpressure−volume +
Wisochoric (closed system, no transfer of matter).
[note 1]
When a closed system receives energy as heat, this energy
increases the internal energy. It is distributed between mi-
croscopic kinetic and microscopic potential energies. In
general, thermodynamics does not trace this distribution.
In an ideal gas all of the extra energy results in a temper-
ature increase, as it is stored solely as microscopic kinetic
energy; such heating is said to be sensible.
9.3.3 Internal energy of the ideal gas
Thermodynamics often uses the concept of the ideal gas
for teaching purposes, and as an approximation for work-
ing systems. The ideal gas is a gas of particles considered as
point objects that interact only by elastic collisions and fill
a volume such that their free mean path between collisions
is much larger than their diameter. Such systems are ap-
proximated by the monatomic gases, helium and the other
translational energy of the individual atoms. Monatomic
particles do not rotate or vibrate, and are not electronically
excited to higher energies except at very high temperatures.
Therefore, internal energy changes in an ideal gas may
be described solely by changes in its kinetic energy. Ki-
netic energy is simply the internal energy of the per-
fect gas and depends entirely on its pressure, volume and
thermodynamic temperature.
The internal energy of an ideal gas is proportional to its mass
(number of moles) N and to its temperature T
U = cN T,
where c is the heat capacity (at constant volume) of the gas.
The internal energy may be written as a function of the three
222 CHAPTER 9. CHAPTER 9. POTENTIALS

extensive properties S, V, N (entropy, volume, mass) in the and the change in internal energy becomes
following way [11][12]

S −R R+c
dU = T dS − pdV
U (S, V, N ) = const · e cN V c N c ,
where const is an arbitrary positive constant and where R is Changes due to temperature and volume
the universal gas constant. It is easily seen that U is a lin-
early homogeneous function of the three variables (that is, it The expression relating changes in internal energy to
is extensive in these variables), and that it is weakly convex. changes in temperature and volume is
Knowing temperature and pressure to be the derivatives
T = ∂U ∂S , p = − ∂V , the ideal gas law pV = RN T imme-
∂U
[ ( ) ]
diately follows. ∂p
dU = CV dT + T − p dV (1) .
∂T V

9.3.4 Internal energy of a closed thermody- This is useful if the equation of state is known.
namic system In case of an ideal gas, we can derive that dU = Cv dT ,
i.e. the internal energy of an ideal gas can be written as a
This above summation of all components of change in inter- function that depends only on the temperature.
nal energy assume that a positive energy denotes heat added
to the system or work done on the system, while a negative Proof of pressure independence for an ideal gas
energy denotes work of the system on the environment.
Typically this relationship is expressed in infinitesimal The expression relating changes in internal energy to
terms using the differentials of each term. Only the inter- changes in temperature and volume is
nal energy is an exact differential. For a system undergoing
only thermodynamics processes, i.e. a closed system that [ ( ) ]
∂p
can exchange only heat and work, the change in the internal dU = CV dT + T − p dV.
energy is ∂T V
The equation of state is the ideal gas law

dU = δQ + δW
which constitutes the first law of thermodynamics.[note 1] It pV = nRT.
may be expressed in terms of other thermodynamic param-
Solve for pressure:
eters. Each term is composed of an intensive variable (a
generalized force) and its conjugate infinitesimal extensive
variable (a generalized displacement). nRT
p= .
For example, for a non-viscous fluid, the mechanical work V
done on the system may be related to the pressure p and Substitute in to internal energy expression:
volume V. The pressure is the intensive generalized force,
while the volume is the extensive generalized displacement:
[ ( ) ]
∂p nRT
dU = CV dT + T − dV.
∂T V V
δW = −pdV
Take the derivative of pressure with respect to temperature:
This defines the direction of work, W, to be energy flow
from the working system to the surroundings, indicated by
( )
a negative term.[note 1] Taking the direction of heat transfer ∂p nR
Q to be into the working fluid and assuming a reversible = .
∂T V V
process, the heat is
Replace:
δQ = T dS .
[ ]
T is temperature nRT nRT
S is entropy dU = C V dT + − dV.
V V
9.3. INTERNAL ENERGY 223

And simplify:
α2
Cp = CV + V T
dU = CV dT. βT

Derivation of dU in terms of dT and dP

Derivation of dU in terms of dT and dV

The partial derivative of the pressure with respect to tem-

To express dU in terms of dT and dV, the term
perature at constant volume can be expressed in terms of
the coefficient of thermal expansion
( ) ( )
∂S ∂S
dS = dT + dV
∂T V ∂V T
( )
1 ∂V
α≡
is substituted in the fundamental thermodynamic relation V ∂T p

and the isothermal compressibility

dU = T dS − pdV.
( )
This gives: 1 ∂V
βT ≡ −
V ∂p T
( ) [ ( ) ]
∂S ∂S by writing:
dU = T dT + T − p dV.
∂T V ∂V T
( ∂S ) ( ) ( )
The term T ∂T is the heat capacity at constant volume ∂V ∂V
V dV = dp+ dT = V (αdT − βT dp) (2)
CV . ∂p T ∂T p
The partial derivative of S with respect to V can be evalu-
ated if the equation of state is known. From the fundamen- and equating dV to zero and solving for the ratio dp/dT.
tal thermodynamic relation, it follows that the differential This gives:
of the Helmholtz free energy A is given by:
( ) ( ∂V )
∂p ∂T p α
= −( ) = (3)
dA = −SdT − pdV. ∂T V
∂V βT
∂p
T
The symmetry of second derivatives of A with respect to T
Substituting (2) and (3) in (1) gives the above expression.
and V yields the Maxwell relation:

( ) ( ) Changes due to volume at constant temperature

∂S ∂p
= .
∂V T ∂T V The internal pressure is defined as a partial derivative of
the internal energy with respect to the volume at constant
This gives the expression above.
temperature:

Changes due to temperature and pressure ( )

∂U
πT =
When dealing with fluids or solids, an expression in terms ∂V T
of the temperature and pressure is usually more useful:

9.3.5 Internal energy of multi-component

dU = (Cp − αpV ) dT + (βT p − αT ) V dp systems
where it is assumed that the heat capacity at constant pres- In addition to including the entropy S and volume V terms in
sure is related to the heat capacity at constant volume ac- the internal energy, a system is often described also in terms
cording to: of the number of particles or chemical species it contains:
224 CHAPTER 9. CHAPTER 9. POTENTIALS

The sum over the composition of the system is the Gibbs

free energy:
U = U (S, V, N1 , . . . , Nn )

where N are the molar amounts of constituents of type j in ∑

the system. The internal energy is an extensive function of G =
the extensive variables S, V, and the amounts N , the internal
energy may be written as a linearly homogeneous function
of first degree:
U (αS, αV, αN1 , αN2 , . . .) = αU (S, V, N1 , N2 , . . .)
µi Ni
i
that arises from changing the composition of the system at
constant temperature and pressure. For a single component
system, the chemical potential equals the Gibbs energy per
amount of substance, i.e. particles or moles according to
the original definition of the unit for {Nj } .

where α is a factor describing the growth of the system. The

differential internal energy may be written as
9.3.6 Internal energy in an elastic medium

For an elastic medium the mechanical energy term of the

∑ ∂U internal energy must be replaced by the more general ex-
dU
∑ = ∂U
∂S dS + ∂U
∂V dV + i ∂Ni dNi = T dS − p dV + pression involving the stress σij and strain εij . The in-
i µ i dN i finitesimal statement is:
which shows (or defines) temperature T to be the partial
derivative of U with respect to entropy S and pressure p
to be the negative of the similar derivative with respect to dU = T dS + V σij dεij
volume V
where Einstein notation has been used for the tensors, in
which there is a summation over all repeated indices in the
product term. The Euler theorem yields for the internal
energy:[13]
T = ∂U∂S ,

1
U = T S + σij εij
2
p = − ∂V
∂U
,
For a linearly elastic material, the stress is related to the
and where the coefficients µi are the chemical potentials strain by:
for the components of type i in the system. The chemical
potentials are defined as the partial derivatives of the energy
with respect to the variations in composition:
σij = Cijkl εkl
( ) where the Cᵢ are the components of the 4th-rank elastic
∂U
µi = constant tensor of the medium.
∂Ni S,V,Nj̸=i

As conjugate variables to the composition {Nj } , the chem-

ical potentials are intensive properties, intrinsically charac-
teristic of the qualitative nature of the system, and not pro-
portional to its extent. Because of the extensive nature of
U and its independent variables, using Euler’s homogeneous
function theorem, the differential dU may be integrated and
yields an expression for the internal energy:
∑
U = T S − pV + µ i Ni
i
9.3.7 History
James Joule studied the relationship between heat, work,
and temperature. He observed that if he did mechanical
work on a fluid, such as water, by agitating the fluid, its
temperature increased. He proposed that the mechanical
work he was doing on the system was converted to thermal
energy. Specifically, he found that 4185.5 joules of energy
were needed to raise the temperature of a kilogram of water
by one degree Celsius.
9.3. INTERNAL ENERGY 225

9.3.8 Notes Bibliography of cited references

[1] In this article we choose the sign convention of the mechan-
ical work as typically defined in chemistry, which is differ-
ent from the convention used in physics. In chemistry, work
performed by the system against the environment, e.g., a sys-
tem expansion, is negative, while in physics this is taken to
be positive.
• Adkins, C.J. (1968/1975). Equilibrium Thermody-
namics, second edition, McGraw-Hill, London, ISBN
0-07-084057-1.
• Bailyn, M. (1994). A Survey of Thermodynamics,
American Institute of Physics Press, New York, ISBN
0-88318-797-3.

• Born, M. (1949). Natural Philosophy of Cause and

9.3.9 See also Chance, Oxford University Press, London.

• Calorimetry • Callen, H.B. (1960/1985), Thermodynamics and an

Introduction to Thermostatistics, (first edition 1960),
• Enthalpy second edition 1985, John Wiley & Sons, New York,
ISBN 0-471-86256-8.
• Exergy
• Crawford, F. H. (1963). Heat, Thermodynamics, and
• Thermodynamic equations Statistical Physics, Rupert Hart-Davis, London, Har-
court, Brace & World, Inc.
• Thermodynamic potentials • Haase, R. (1971). Survey of Fundamental Laws,
chapter 1 of Thermodynamics, pages 1–97 of volume
1, ed. W. Jost, of Physical Chemistry. An Advanced
9.3.10 References Treatise, ed. H. Eyring, D. Henderson, W. Jost, Aca-
demic Press, New York, lcn 73–117081.
[1] Crawford, F. H. (1963), pp. 106–107.
• Münster, A. (1970), Classical Thermodynamics,
[2] Haase, R. (1971), pp. 24–28. translated by E.S. Halberstadt, Wiley–Interscience,
London, ISBN 0-471-62430-6.
[3] Born, M. (1949), Appendix 8, pp. 146–149.
• Tschoegl, N.W. (2000). Fundamentals of Equilibrium
[4] Tschoegl, N.W. (2000), p. 17. and Steady-State Thermodynamics, Elsevier, Amster-
dam, ISBN 0-444-50426-5.
[5] Callen, H.B. (1960/1985), Chapter 5.

[6] Münster, A. (1970), p. 6. 9.3.11 Bibliography

[7] Münster, A. (1970), Chapter 3. • Alberty, R. A. (2001). “Use of Legendre transforms in

chemical thermodynamics” (PDF). Pure Appl. Chem.
[8] Bailyn, M. (1994), pp. 206–209. 73 (8): 1349–1380. doi:10.1351/pac200173081349.

[9] I. Klotz, R. Rosenberg, Chemical Thermodynamics - Basic • Lewis, Gilbert Newton; Randall, Merle: Revised by
Concepts and Methods, 7th ed., Wiley (2008), p.39 Pitzer, Kenneth S. & Brewer, Leo (1961). Thermody-
namics (2nd ed.). New York, NY USA: McGraw-Hill
[10] Thermal energy – Hyperphysics Book Co. ISBN 0-07-113809-9.

[11] van Gool, W.; Bruggink, J.J.C. (Eds) (1985). Energy and
• Landau, L. D.; Lifshitz, E. M. (1986). Theory of
time in the economic and physical sciences. North-Holland. Elasticity (Course of Theoretical Physics Volume 7).
pp. 41–56. ISBN 0444877487. (Translated from Russian by J.B. Sykes and W.H.
Reid) (Third ed.). Boston, MA: Butterworth Heine-
[12] Grubbström, Robert W. (2007). “An Attempt mann. ISBN 0-7506-2633-X.
to Introduce Dynamics Into Generalised Exergy
Considerations”. Applied Energy 84: 701–718.
doi:10.1016/j.apenergy.2007.01.003.

[13] Landau & Lifshitz 1986

Chapter 10

Chapter 10. Equations

10.1 Ideal gas law • V is the volume of the gas

• n is the amount of substance of gas (in moles)

• R is the ideal, or universal, gas constant, equal to the

product of the Boltzmann constant and the Avogadro
constant.

• T is the temperature of the gas

It can also be derived microscopically from kinetic the-

ory, as was achieved (apparently independently) by August
Krönig in 1856[2] and Rudolf Clausius in 1857.[3]

10.1.1 Equation

The state of an amount of gas is determined by its pressure,

volume, and temperature. The modern form of the equation
relates these simply in two main forms. The temperature
used in the equation of state is an absolute temperature: in
[4]
Isotherms of an ideal gas. The curved lines represent the relation- the SI system of units, Kelvin.
ship between pressure (on the vertical, y-axis) and volume (on the
horizontal, x-axis) for an ideal gas at different temperatures: lines
which are farther away from the origin (that is, lines that are nearer Common form
to the top right-hand corner of the diagram) represent higher tem-
peratures. The most frequently introduced form is

The ideal gas law is the equation of state of a hypotheti-

cal ideal gas. It is a good approximation to the behavior of
P V = nRT
many gases under many conditions, although it has several
limitations. It was first stated by Émile Clapeyron in 1834 as where:
a combination of Boyle’s law, Charles’ law and Avogadro’s
Law.[1] The ideal gas law is often written as:
• P is the pressure of the gas

P V = nRT • V is the volume of the gas

where:
• n is the amount of substance of gas (also known as
• P is the pressure of the gas number of moles)

226
10.1. IDEAL GAS LAW 227

• R is the ideal, or universal, gas constant, equal to the Statistical mechanics

product of the Boltzmann constant and the Avogadro
constant. In statistical mechanics the following molecular equation is
derived from first principles:
• T is the temperature of the gas

In SI units, P is measured in pascals, V is measured in cubic P V = N kB T

metres, n is measured in moles, and T in Kelvin (The Kelvin
scale is a shifted Celsius scale where 0.00 Kelvin = −273.15 where P is the absolute pressure of the gas measured in
degrees Celsius, the lowest possible temperature). R has the pascals; N is the number of molecules in the given volume
value 8.314 J·K−1 ·mol−1 or 0.08206 L·atm·mol−1 ·K−1 or ≈2 V. The number density is given by the ratio N/V; kB is the
calories if using pressure in standard atmospheres (atm) in- Boltzmann constant relating temperature and energy; and T
stead of pascals, and volume in litres instead of cubic me- is the absolute temperature in Kelvin .
tres. The number density contrasts to the other formulation,
which uses n, the number of moles and V, the volume. This
Molar form relation implies that R=NAkB where NA is Avogadro’s con-
stant, and the consistency of this result with experiment is
How much gas is present could be specified by giving the a good check on the principles of statistical mechanics.
mass instead of the chemical amount of gas. Therefore, an From this we can notice that for an average particle mass of
alternative form of the ideal gas law may be useful. The μ times the atomic mass constant mᵤ (i.e., the mass is μ u)
chemical amount (n) (in moles) is equal to the mass (m) (in
grams) divided by the molar mass (M) (in grams per mole):
m
Y =
µmu
m
n=
M and since ρ = mn, we find that the ideal gas law can be
By replacing n with m / M, and subsequently introducing rewritten as:
density ρ = m/V, we get:
1 m k
m P = kT = ρT.
PV = RT V µmu µmu
M
In SI units, P is measured in pascals; V in cubic metres; Y
R
P =ρ T is a dimensionless number; and T in Kelvin. k has the value
M 1.38·10−23 J·K−1 in SI units.
Defining the specific gas constant R ₑ ᵢfi as the ratio R/M,

10.1.2 Applications to thermodynamic pro-

P = ρRspecific T cesses
This form of the ideal gas law is very useful because it links
pressure, density, and temperature in a unique formula in- The table below essentially simplifies the ideal gas equation
dependent of the quantity of the considered gas. Alterna- for a particular processes, thus making this equation easier
tively, the law may be written in terms of the specific vol- to solve using numerical methods.
ume v, the reciprocal of density, as A thermodynamic process is defined as a system that moves
from state 1 to state 2, where the state number is denoted
by subscript. As shown in the first column of the table, ba-
P v = Rspecific T sic thermodynamic processes are defined such that one of
It is common, especially in engineering applications, to rep- the gas properties (P, V, T, or S) is constant throughout the
resent the specific gas constant by the symbol R. In such process.
cases, the universal gas constant is usually given a differ- For a given thermodynamics process, in order to specify the
ent symbol such as R to distinguish it. In any case, the con- extent of a particular process, one of the properties ratios
text and/or units of the gas constant should make it clear (which are listed under the column labeled “known ratio”)
as to whether the universal or specific gas constant is being must be specified (either directly or indirectly). Also, the
referred to.[5] property for which the ratio is known must be distinct from
228 CHAPTER 10. CHAPTER 10. EQUATIONS

the property held constant in the previous column (other- where C is a constant which is directly proportional to the
wise the ratio would be unity, and not enough information amount of gas, n (Avogadro’s law). The proportionality fac-
would be available to simplify the gas law equation). tor is the universal gas constant, R, i.e. C = nR.
In the final three columns, the properties (P, V, or T) at state Hence the ideal gas law
2 can be calculated from the properties at state 1 using the
equations listed.
^
a. In an isentropic process, system entropy (S) is con- P V = nRT
stant. Under these conditions, P 1 V 1 γ = P 2 V 2 γ , where γ
is defined as the heat capacity ratio, which is constant for Theoretical
a calorifically perfect gas. The value used for γ is typically
1.4 for diatomic gases like nitrogen (N2 ) and oxygen (O2 ), Kinetic theory Main article: Kinetic theory of gases
(and air, which is 99% diatomic). Also γ is typically 1.6
for monatomic gases like the noble gases helium (He), and
The ideal gas law can also be derived from first principles
argon (Ar). In internal combustion engines γ varies between
using the kinetic theory of gases, in which several simpli-
1.35 and 1.15, depending on constitution gases and temper-
ature. fying assumptions are made, chief among which are that
the molecules, or atoms, of the gas are point masses, pos-
sessing mass but no significant volume, and undergo only
10.1.3 Deviations from ideal behavior of real elastic collisions with each other and the sides of the con-
tainer in which both linear momentum and kinetic energy
gases are conserved.
The equation of state given here applies only to an ideal
gas, or as an approximation to a real gas that behaves suf- Statistical mechanics Main article: Statistical mechan-
ficiently like an ideal gas. There are in fact many different ics
forms of the equation of state. Since the ideal gas law ne-
glects both molecular size and intermolecular attractions, it Let q = (qₓ, q , q ) and p = (pₓ, p , p ) denote the position
is most accurate for monatomic gases at high temperatures vector and momentum vector of a particle of an ideal gas,
and low pressures. The neglect of molecular size becomes respectively. Let F denote the net force on that particle.
less important for lower densities, i.e. for larger volumes at Then the time-averaged potential energy of the particle is:
lower pressures, because the average distance between ad-
jacent molecules becomes much larger than the molecular
size. The relative importance of intermolecular attractions
diminishes with increasing thermal kinetic energy, i.e., with ⟨ dp ⟩ ⟨ dp ⟩ ⟨ dp ⟩
x y z
increasing temperatures. More detailed equations of state, ⟨q · F⟩ = qx + qy + qz
dt dt dt
such as the van der Waals equation, account for deviations ⟨ ∂H ⟩ ⟨ ∂H ⟩ ⟨ ∂H ⟩
from ideality caused by molecular size and intermolecular = − qx − qy − qz = −3kB T,
∂qx ∂qy ∂qz
forces.
where the first equality is Newton’s second law, and the
A residual property is defined as the difference between a
second line uses Hamilton’s equations and the equipartition
real gas property and an ideal gas property, both considered
theorem. Summing over a system of N particles yields
at the same pressure, temperature, and composition.

⟨∑
N ⟩
10.1.4 Derivations 3N kB T = − qk · Fk .
k=1
Empirical
By Newton’s third law and the ideal gas assumption, the net
force of the system is the force applied by the walls of the
The ideal gas law can be derived from combining two em- container, and this force is given by the pressure P of the
pirical gas laws: the combined gas law and Avogadro’s law. gas. Hence
The combined gas law states that

⟨∑
N ⟩ I
PV − qk · F k =P q · dS,
=C surface
T k=1
10.1. IDEAL GAS LAW 229

where dS is the infinitesimal area element along the walls of [3] Clausius, R. (1857). “Ueber die Art der Bewegung, welche
the container. Since the divergence of the position vector q wir Wärme nennen”. Annalen der Physik und Chemie (in
is German) 176 (3): 353–79. Bibcode:1857AnP...176..353C.
doi:10.1002/andp.18571760302. Facsimile at the Biblio-
thèque nationale de France (pp. 353–79).
∂qx ∂qy ∂qz [4] “Equation of State”.
∇·q= + + = 3,
∂qx ∂qy ∂qz
[5] Moran and Shapiro, Fundamentals of Engineering Thermo-
the divergence theorem implies that dynamics, Wiley, 4th Ed, 2000

I ∫ 10.1.7 Further reading

P q · dS = P (∇ · q) dV = 3P V,
surface volume
• Davis and Masten Principles of Environmental Engi-
where dV is an infinitesimal volume within the container neering and Science, McGraw-Hill Companies, Inc.
and V is the total volume of the container. New York (2002) ISBN 0-07-235053-9
Putting these equalities together yields • Website giving credit to Benoît Paul Émile Clapeyron,
(1799–1864) in 1834

⟨∑
N ⟩
3N kB T = − qk · Fk = 3P V, 10.1.8 External links
k=1
• Configuration integral (statistical mechanics) where
which immediately implies the ideal gas law for N particles: an alternative statistical mechanics derivation of the
ideal-gas law, using the relationship between the
Helmholtz free energy and the partition function, but
P V = N kB T = nRT, without using the equipartition theorem, is provided.
Vu-Quoc, L., Configuration integral (statistical me-
where n = N/NA is the number of moles of gas and R = chanics), 2008. this wiki site is down; see this article
NAkB is the gas constant. in the web archive on 2012 April 28.

• Online Ideal Gas law Calculator

10.1.5 See also
• Van der Waals equation

• Boltzmann constant

• Configuration integral

• Dynamic pressure

• Internal energy

10.1.6 References
[1] Clapeyron, E (1834). “Mémoire sur la puissance motrice
de la chaleur”. Journal de l'École Polytechnique (in French)
XIV: 153–90. Facsimile at the Bibliothèque nationale de
France (pp. 153–90).

[2] Krönig, A. (1856). “Grundzüge einer Theorie der

Gase”. Annalen der Physik und Chemie (in Ger-
man) 99 (10): 315–22. Bibcode:1856AnP...175..315K.
doi:10.1002/andp.18561751008. Facsimile at the Biblio-
thèque nationale de France (pp. 315–22).
Chapter 11

Chapter 11. Fundamentals

11.1 Fundamental thermodynamic

relation dU = δQ − δW

In thermodynamics, the fundamental thermodynamic re-
lation is generally expressed as an infinitesimal change in
internal energy in terms of infinitesimal changes in entropy,
and volume for a closed system in thermal equilibrium in
the following way.
where δQ and δW are infinitesimal amounts of heat sup-
plied to the system by its surroundings and work done by
the system on its surroundings, respectively.
According to the second law of thermodynamics we have
for a reversible process:

dU = T dS − P dV δQ
dS =
T
Here, U is internal energy, T is absolute temperature, S
is entropy, P is pressure, and V is volume. This relation Hence:
applies to a reversible change, or to a change in a closed
system of uniform temperature and pressure at constant
composition.[1] δQ = T dS
This is only one expression of the fundamental thermody- By substituting this into the first law, we have:
namic relation. It may be expressed in other ways, using
different variables (e.g. using thermodynamic potentials).
For example, the fundamental relation may be expressed in
terms of the enthalpy as dU = T dS − δW

Letting δW be reversible pressure-volume work done by the

system on its surroundings,
dH = T dS + V dP
in terms of the Helmholtz free energy (F) as
δW = P dV

dF = −S dT − P dV we have:

and in terms of the Gibbs free energy (G) as

dU = T dS − P dV

dG = −S dT + V dP This equation has been derived in the case of reversible

changes. However, since U, S, and V are thermody-
namic state functions, the above relation holds also for non-
11.1.1 Derivation from the first and second reversible changes in a system of uniform pressure and tem-
laws of thermodynamics perature at constant composition.[1] If the composition, i.e.
the amounts ni of the chemical components, in a system of
The first law of thermodynamics states that: uniform temperature and pressure can also change, e.g. due

230
11.1. FUNDAMENTAL THERMODYNAMIC RELATION 231

to a chemical reaction, the fundamental thermodynamic re- The fundamental assumption of statistical mechanics is that
lation generalizes to: all the Ω (E) states are equally likely. This allows us to
extract all the thermodynamical quantities of interest. The
∑ temperature is defined as:
dU = T dS − P dV + µi dni d log[Ω(E)]
kT ≡ β ≡
1
i dE

The µj are the chemical potentials corresponding to parti- This definition can be derived from the microcanonical en-
cles of type j . The last term must be zero for a reversible semble, which is a system of a constant number of particles,
process. a constant volume and that does not exchange energy with
its environment. Suppose that the system has some external
If the system has more external parameters than just the parameter, x, that can be changed. In general, the energy
volume that can change, the fundamental thermodynamic eigenstates of the system will depend on x. According to
relation generalizes to the adiabatic theorem of quantum mechanics, in the limit
of an infinitely slow change of the system’s Hamiltonian,
∑ ∑ the system will stay in the same energy eigenstate and thus
dU = T dS − Xj dxj + µi dni change its energy according to the change in energy of the
j i
energy eigenstate it is in.
Here the Xi are the generalized forces corresponding to the
The generalized force, X, corresponding to the external pa-
external parameters xi .
rameter x is defined such that Xdx is the work performed
by the system if x is increased by an amount dx. E.g., if x
11.1.2 Derivation from statistical mechani- is the volume, then X is the pressure. The generalized force
for a system known to be in energy eigenstate Er is given
cal principles
by:
The above derivation uses the first and second laws of ther-
modynamics. The first law of thermodynamics is essentially
dE
a definition of heat, i.e. heat is the change in the internal X = − r
energy of a system that is not caused by a change of the dx
external parameters of the system. Since the system can be in any energy eigenstate within an
However, the second law of thermodynamics is not a defin- interval of δE , we define the generalized force for the sys-
ing relation for the entropy. The fundamental definition of tem as the expectation value of the above expression:
entropy of an isolated system containing an amount of en-
ergy of E is: ⟨ ⟩
dEr
X=−
dx
S = k log [Ω (E)]
To evaluate the average, we partition the Ω (E) energy
where Ω (E) is the number of quantum states in a small eigenstates by counting how many of them have a value for
dEr
interval between E and E + δE . Here δE is a macroscop- dx within a range between Y and Y + δY . Calling this
ically small energy interval that is kept fixed. Strictly speak- number ΩY (E) , we have:
ing this means that the entropy depends on the choice of δE
. However, in the thermodynamic limit (i.e. in the limit of
∑
infinitely large system size), the specific entropy (entropy Ω (E) = ΩY (E)
per unit volume or per unit mass) does not depend on δE Y
. The entropy is thus a measure of the uncertainty about
exactly which quantum state the system is in, given that we The average defining the generalized force can now be writ-
know its energy to be in some interval of size δE . ten:
Deriving the fundamental thermodynamic relation from
first principles thus amounts to proving that the above def- 1 ∑
inition of entropy implies that for reversible processes we X = − Ω (E) Y ΩY (E)
have: Y

We can relate this to the derivative of the entropy with re-

δQ spect to x at constant energy E as follows. Suppose we
dS = change x to x + dx. Then Ω (E) will change because the
T
232 CHAPTER 11. CHAPTER 11. FUNDAMENTALS

energy eigenstates depend on x, causing energy eigenstates

to move into or out of the range between E and E + δE ( ) ( )
. Let’s focus again on the energy eigenstates for which dE r ∂S ∂S dE X
dx dS = dE + dx = + dx
lies within the range between Y and Y + δY . Since these ∂E x ∂x E T T
energy eigenstates increase in energy by Y dx, all such en-
which we can write as:
ergy eigenstates that are in the interval ranging from E - Y
dx to E move from below E to above E. There are

dE = T dS − Xdx
ΩY (E)
NY (E) = Y dx
δE
11.1.3 References
such energy eigenstates. If Y dx ≤ δE , all these energy
eigenstates will move into the range between E and E +δE [1] Schmidt-Rohr, K. (2014). “Expansion Work without the
and contribute to an increase in Ω . The number of energy External Pressure, and Thermodynamics in Terms of Qua-
eigenstates that move from below E + δE to above E + δE sistatic Irreversible Processes” J. Chem. Educ. 91: 402-409.
is, of course, given by NY (E + δE) . The difference http://dx.doi.org/10.1021/ed3008704

NY (E) − NY (E + δE) 11.1.4 External links

is thus the net contribution to the increase in Ω . Note that if • The Fundamental Thermodynamic Relation
Y dx is larger than δE there will be energy eigenstates that
move from below E to above E + δE . They are counted • Thermodynamics and Heat Transfer
in both NY (E) and NY (E + δE) , therefore the above
expression is also valid in that case.
Expressing the above expression as a derivative with respect 11.2 Heat engine
to E and summing over Y yields the expression:
See also: Thermodynamic cycle
( ) ∑ ( ) ( )
∂Ω ∂ΩY ∂ (ΩX)
=− Y = In thermodynamics, a heat engine is a system that con-
∂x E ∂E x ∂E x verts heat or thermal energy—and chemical energy—
Y
to mechanical energy, which can then be used to do
The logarithmic derivative of Ω with respect to x is thus
mechanical work.[1][2] It does this by bringing a working
given by:
substance from a higher state temperature to a lower state
temperature. A heat “source” generates thermal energy that
( ) ( ) brings the working substance to the high temperature state.
∂ log (Ω) ∂X
= βX + The working substance generates work in the "working
∂x ∂E
E x body" of the engine while transferring heat to the colder
The first term is intensive, i.e. it does not scale with system "sink" until it reaches a low temperature state. During this
size. In contrast, the last term scales as the inverse system process some of the thermal energy is converted into work
size and thus vanishes in the thermodynamic limit. We have by exploiting the properties of the working substance. The
thus found that: working substance can be any system with a non-zero heat
capacity, but it usually is a gas or liquid. During this pro-
( ) cess, a lot of heat is lost to the surroundings, i.e. it cannot
∂S X be used.
=
∂x E T In general an engine converts energy to mechanical work.
Combining this with Heat engines distinguish themselves from other types of en-
gines by the fact that their efficiency is fundamentally lim-
ited by Carnot’s theorem.[3] Although this efficiency lim-
( ) itation can be a drawback, an advantage of heat engines
∂S 1
= is that most forms of energy can be easily converted to
∂E x T
heat by processes like exothermic reactions (such as com-
Gives: bustion), absorption of light or energetic particles, friction,
11.2. HEAT ENGINE 233

dissipation and resistance. Since the heat source that sup- (which no engine ever attains) is equal to the temperature
plies thermal energy to the engine can thus be powered by difference between the hot and cold ends divided by the
virtually any kind of energy, heat engines are very versatile temperature at the hot end, all expressed in absolute tem-
and have a wide range of applicability. perature or kelvins.
Heat engines are often confused with the cycles they attempt The efficiency of various heat engines proposed or used to-
to implement. Typically, the term “engine” is used for a day has a large range:
physical device and “cycle” for the model.
• 3 percent[4] (97 percent waste heat using low quality
heat) for the OTEC ocean power proposal.
11.2.1 Overview
• 25 percent for most automotive gasoline engines [5]

• 49 percent for a supercritical coal-fired power station

such as the Avedøre Power Station, and many others

• 60 percent for a steam-cooled combined cycle gas tur-

bine.[6]

All these processes gain their efficiency (or lack thereof)

from the temperature drop across them. Significant energy
may be used for auxiliary equipment, such as pumps, which
effectively reduces efficiency.

Power

Heat engines can be characterized by their specific power,

which is typically given in kilowatts per litre of engine dis-
placement (in the U.S. also horsepower per cubic inch). The
result offers an approximation of the peak power output of
an engine. This is not to be confused with fuel efficiency,
Figure 1: Heat engine diagram since high efficiency often requires a lean fuel-air ratio, and
thus lower power density. A modern high-performance car
3
In thermodynamics, heat engines are often modeled using engine makes in excess of 75 kW/l (1.65 hp/in ).
a standard engineering model such as the Otto cycle. The
theoretical model can be refined and augmented with ac-
tual data from an operating engine, using tools such as an 11.2.2 Everyday examples
indicator diagram. Since very few actual implementations
of heat engines exactly match their underlying thermody- Examples of everyday heat engines include the steam en-
namic cycles, one could say that a thermodynamic cycle is gine (for example most of the world’s power plants use
an ideal case of a mechanical engine. In any case, fully steam turbines, a modern form of steam engine), and the
understanding an engine and its efficiency requires gaining internal combustion engine , gasoline (petrol) engine the
a good understanding of the (possibly simplified or ideal- diesel engine, in an automobile or truck. A common toy that
ized) theoretical model, the practical nuances of an actual is also a heat engine is a drinking bird. Also the stirling en-
mechanical engine, and the discrepancies between the two. gine is a heat engine. All of these familiar heat engines are
powered by the expansion of heated gases. The general sur-
In general terms, the larger the difference in temperature roundings are the heat sink, which provides relatively cool
between the hot source and the cold sink, the larger is the gases that, when heated, expand rapidly to drive the me-
potential thermal efficiency of the cycle. On Earth, the cold chanical motion of the engine.
side of any heat engine is limited to being close to the am-
bient temperature of the environment, or not much lower
than 300 Kelvin, so most efforts to improve the thermo- 11.2.3 Examples of heat engines
dynamic efficiencies of various heat engines focus on in-
creasing the temperature of the source, within material lim- It is important to note that although some cycles have a typ-
its. The maximum theoretical efficiency of a heat engine ical combustion location (internal or external), they often
234 CHAPTER 11. CHAPTER 11. FUNDAMENTALS

can be implemented with the other. For example, John Er- • Stirling cycle (Stirling engine, thermoacoustic devices)
icsson developed an external heated engine running on a
cycle very much like the earlier Diesel cycle. In addition, • Internal combustion engine (ICE):
externally heated engines can often be implemented in open • Otto cycle (e.g. Gasoline/Petrol engine)
or closed cycles.
• Diesel cycle (e.g. Diesel engine)
• Atkinson cycle (Atkinson engine)
Earth’s heat engine
• Brayton cycle or Joule cycle originally Ericsson
Earth’s atmosphere and hydrosphere—Earth’s heat cycle (gas turbine)
engine—are coupled processes that constantly even out • Lenoir cycle (e.g., pulse jet engine)
solar heating imbalances through evaporation of surface • Miller cycle (Miller engine)
water, convection, rainfall, winds, and ocean circulation,
when distributing heat around the globe.[7]
Liquid only cycle
The Hadley system provides an example of a heat engine.
The Hadley circulation is identified with rising of warm and
In these cycles and engines the working fluid are always like
moist air in the equatorial region with descent of colder air
liquid:
in the subtropics corresponding to a thermally driven di-
rect circulation, with consequent net production of kinetic
energy.[8] • Stirling cycle (Malone engine)
• Heat Regenerative Cyclone[9]
Phase-change cycles
Electron cycles
In these cycles and engines, the working fluids are gases and
liquids. The engine converts the working fluid from a gas to • Johnson thermoelectric energy converter
a liquid, from liquid to gas, or both, generating work from
the fluid expansion or compression. • Thermoelectric (Peltier–Seebeck effect)
• Thermogalvanic cell
• Rankine cycle (classical steam engine)
• Thermionic emission
• Regenerative cycle (steam engine more efficient than
Rankine cycle) • Thermotunnel cooling

• Organic Rankine cycle (Coolant changing phase in

temperature ranges of ice and hot liquid water) Magnetic cycles

• Vapor to liquid cycle (Drinking bird, Injector, Minto • Thermo-magnetic motor (Tesla)
wheel)

• Liquid to solid cycle (Frost heaving — water changing Cycles used for refrigeration
from ice to liquid and back again can lift rock up to 60
cm.) Main article: refrigeration

• Solid to gas cycle (Dry ice cannon — Dry ice sublimes A domestic refrigerator is an example of a heat pump: a heat
to gas.) engine in reverse. Work is used to create a heat differential.
Many cycles can run in reverse to move heat from the cold
Gas-only cycles side to the hot side, making the cold side cooler and the hot
side hotter. Internal combustion engine versions of these
In these cycles and engines the working fluid is always a gas cycles are, by their nature, not reversible.
(i.e., there is no phase change): Refrigeration cycles include:

• Carnot cycle (Carnot heat engine) • Vapor-compression refrigeration

• Ericsson cycle (Caloric Ship John Ericsson) • Stirling cryocoolers
11.2. HEAT ENGINE 235

• Gas-absorption refrigerator work and delivering the rest to the cold temperature heat
sink.
• Air cycle machine
In general, the efficiency of a given heat transfer process
• Vuilleumier refrigeration (whether it be a refrigerator, a heat pump or an engine)
is defined informally by the ratio of “what you get out” to
• Magnetic refrigeration
“what you put in”.
In the case of an engine, one desires to extract work and
Evaporative heat engines puts in a heat transfer.

The Barton evaporation engine is a heat engine based on a

cycle producing power and cooled moist air from the evap-
oration of water into hot dry air. −W −Qh − Qc Qc
η= = =1−
−Qh −Qh −Qh

Mesoscopic heat engines
Mesoscopic heat engines are nanoscale devices that may
serve the goal of processing heat fluxes and perform use-
ful work at small scales. Potential applications include e.g.
electric cooling devices. In such mesoscopic heat engines,
work per cycle of operation fluctuates due to thermal noise.
There is exact equality that relates average of exponents of
work performed by any heat engine and the heat transfer
from the hotter heat bath.[10] This relation transforms the
Carnot’s inequality into exact equality.
The theoretical maximum efficiency of any heat engine de-
pends only on the temperatures it operates between. This
efficiency is usually derived using an ideal imaginary heat
engine such as the Carnot heat engine, although other en-
gines using different cycles can also attain maximum effi-
ciency. Mathematically, this is because in reversible pro-
cesses, the change in entropy of the cold reservoir is the
negative of that of the hot reservoir (i.e., ∆Sc = −∆Sh ),
keeping the overall change of entropy zero. Thus:

Tc ∆Sc Tc
11.2.4 Efficiency ηmax = 1 − =1−
−Th ∆Sh Th

The efficiency of a heat engine relates how much useful where Th is the absolute temperature of the hot source and
work is output for a given amount of heat energy input. Tc that of the cold sink, usually measured in kelvin. Note
From the laws of thermodynamics, after a completed cycle: that dSc is positive while dSh is negative; in any reversible
work-extracting process, entropy is overall not increased,
but rather is moved from a hot (high-entropy) system to a
cold (low-entropy one), decreasing the entropy of the heat
W = Qc − (−Qh ) source and increasing that of the heat sink.
The reasoning behind this being the maximal efficiency
where goes as follows. It is first assumed that if a more efficient
H heat engine than a Carnot engine is possible, then it could
W = − P dV is the work extracted
from the engine. (It is negative since be driven in reverse as a heat pump. Mathematical analysis
work is done by the engine.) can be used to show that this assumed combination would
result in a net decrease in entropy. Since, by the second
Qh = Th ∆Sh is the heat en-
law of thermodynamics, this is statistically improbable to
ergy taken from the high tempera-
the point of exclusion, the Carnot efficiency is a theoretical
ture system. (It is negative since heat
upper bound on the reliable efficiency of any process.
is extracted from the source, hence
(−Qh ) is positive.) Empirically, no heat engine has ever been shown to run at a
Qc = Tc ∆Sc is the heat energy deliv- greater efficiency than a Carnot cycle heat engine.
ered to the cold temperature system. Figure 2 and Figure 3 show variations on Carnot cycle ef-
(It is positive since heat is added to the ficiency. Figure 2 indicates how efficiency changes with
sink.) an increase in the heat addition temperature for a constant
compressor inlet temperature. Figure 3 indicates how the
In other words, a heat engine absorbs heat energy from the efficiency changes with an increase in the heat rejection
high temperature heat source, converting part of it to useful temperature for a constant turbine inlet temperature.
236
Endoreversible heat engines
The most Carnot efficiency as a criterion of heat engine
performance is the fact that by its nature, any maximally
efficient Carnot cycle must operate at an infinitesimal tem-
perature gradient. This is because any transfer of heat be-
tween two bodies at differing temperatures is irreversible,
and therefore the Carnot efficiency expression only applies
in the infinitesimal limit. The major problem with that is
that the object of most heat engines is to output some sort
of power, and infinitesimal power is usually not what is be-
ing sought.
A different measure of ideal heat engine efficiency is
given by considerations of endoreversible thermodynamics,
where the cycle is identical to the Carnot cycle except in that
the two processes of heat transfer are not reversible (Callen
1985):
√ The most common such exploitation is the use of water
η = 1− Tc
Th (Note: Units K or °R)
This model does a better job of predicting how well
real-world heat engines can do (Callen 1985, see also
endoreversible thermodynamics):
As shown, the endoreversible efficiency much more closely
models the observed data.
11.2.5 History
Main article: Timeline of heat engine technology
See also: History of the internal combustion engine and
History of thermodynamics
Heat engines have been known since antiquity but were only
made into useful devices at the time of the industrial revo-
lution in the 18th century. They continue to be developed
today.
11.2.6 Heat engine enhancements
Engineers have studied the various heat engine cycles ex-
tensively in effort to improve the amount of usable work
they could extract from a given power source. The Carnot
cycle limit cannot be reached with any gas-based cycle, but
engineers have worked out at least two ways to possibly go
around that limit, and one way to get better efficiency with-
out bending any rules.
1. Increase the temperature difference in the heat engine. 11.2.7 Heat engine processes
The simplest way to do this is to increase the hot side
temperature, which is the approach used in modern Each process is one of the following:
CHAPTER 11. CHAPTER 11. FUNDAMENTALS
combined-cycle gas turbines. Unfortunately, physical
limits (such as the melting point of the materials used
to build the engine) and environmental concerns re-
garding NOₓ production restrict the maximum tem-
perature on workable heat engines. Modern gas tur-
bines run at temperatures as high as possible within
the range of temperatures necessary to maintain ac-
ceptable NOₓ output . Another way of increasing ef-
ficiency is to lower the output temperature. One new
method of doing so is to use mixed chemical work-
ing fluids, and then exploit the changing behavior of
the mixtures. One of the most famous is the so-called
Kalina cycle, which uses a 70/30 mix of ammonia and
water as its working fluid. This mixture allows the cy-
cle to generate useful power at considerably lower tem-
peratures than most other processes.
2. Exploit the physical properties of the working fluid.
above the so-called critical point, or so-called super-
critical steam. The behavior of fluids above their crit-
ical point changes radically, and with materials such
as water and carbon dioxide it is possible to exploit
those changes in behavior to extract greater thermo-
dynamic efficiency from the heat engine, even if it is
using a fairly conventional Brayton or Rankine cycle.
A newer and very promising material for such appli-
cations is CO2 . SO2 and xenon have also been con-
sidered for such applications, although SO2 is a little
toxic for most.
3. Exploit the chemical properties of the working fluid.
A fairly new and novel exploit is to use exotic work-
ing fluids with advantageous chemical properties. One
such is nitrogen dioxide (NO2 ), a toxic component
of smog, which has a natural dimer as di-nitrogen
tetraoxide (N2 O4 ). At low temperature, the N2 O4
is compressed and then heated. The increasing tem-
perature causes each N2 O4 to break apart into two
NO2 molecules. This lowers the molecular weight of
the working fluid, which drastically increases the ef-
ficiency of the cycle. Once the NO2 has expanded
through the turbine, it is cooled by the heat sink, which
makes it recombine into N2 O4 . This is then fed back
by the compressor for another cycle. Such species
as aluminium bromide (Al2 Br6 ), NOCl, and Ga2 I6
have all been investigated for such uses. To date, their
drawbacks have not warranted their use, despite the
efficiency gains that can be realized.[12]
11.3. THERMODYNAMIC CYCLE
• isothermal (at constant temperature, maintained with
heat added or removed from a heat source or sink)
• isobaric (at constant pressure)
• isometric/isochoric (at constant volume), also referred
to as iso-volumetric
• adiabatic (no heat is added or removed from the system
during adiabatic process)
• isentropic (reversible adiabatic process, no heat is
added or removed during isentropic process)
11.2.8 See also
• Heat pump
• Reciprocating engine for a general description of the
mechanics of piston engines
• Thermosynthesis
• Timeline of heat engine technology
11.2.9 References
[1] Fundamentals of Classical Thermodynamics, 3rd ed. p. 159,
(1985) by G. J. Van Wylen and R. E. Sonntag: “A heat en-
gine may be defined as a device that operates in a thermody-
namic cycle and does a certain amount of net positive work
as a result of heat transfer from a high-temperature body
and to a low-temperature body. Often the term heat engine
is used in a broader sense to include all devices that pro-
duce work, either through heat transfer or combustion, even
though the device does not operate in a thermodynamic cy-
cle. The internal-combustion engine and the gas turbine are
examples of such devices, and calling these heat engines is
an acceptable use of the term.”
[2] Mechanical efficiency of heat engines, p. 1 (2007) by James
R. Senf: “Heat engines are made to provide mechanical en-
ergy from thermal energy.”
[3] Thermal physics: entropy and free energies, by Joon Chang
Lee (2002), Appendix A, p. 183: “A heat engine absorbs
energy from a heat source and then converts it into work for
us.... When the engine absorbs heat energy, the absorbed
heat energy comes with entropy.” (heat energy ∆Q = T ∆S
), “When the engine performs work, on the other hand, no
entropy leaves the engine. This is problematic. We would
like the engine to repeat the process again and again to pro-
vide us with a steady work source. ... to do so, the working
substance inside the engine must return to its initial thermo-
dynamic condition after a cycle, which requires to remove
the remaining entropy. The engine can do this only in one
way. It must let part of the absorbed heat energy leave with-
out converting it into work. Therefore the engine cannot
convert all of the input energy into work!"
237
[4] M. Emam, Experimental Investigations on a Standing-Wave
Thermoacoustic Engine, M.Sc. Thesis, Cairo University,
Egypt (2013).
[5] Where the Energy Goes: Gasoline Vehicles, US Dept of En-
ergy
[6] “Efficiency by the Numbers” by Lee S. Langston
[7] Lindsey, Rebecca (2009). “Climate and Earth’s Energy
Budget”. NASA Earth Observatory.
[8] Junling Huang and Michael B. McElroy (2014).
“Contributions of the Hadley and Ferrel Circulations
to the Energetics of the Atmosphere over the Past
32 Years”. Journal of Climate 27 (7): 2656–2666.
Bibcode:2014JCli...27.2656H. doi:10.1175/jcli-d-13-
00538.1.
[9] “Cyclone Power Technologies Website”. Cy-
clonepower.com. Retrieved 2012-03-22.
[10] N. A. Sinitsyn (2011). “Fluctuation Relation for Heat
Engines”. J. Phys. A: Math. Theor. 44: 405001.
arXiv:1111.7014. Bibcode:2011JPhA...44N5001S.
doi:10.1088/1751-8113/44/40/405001.
[11] F. L. Curzon, B. Ahlborn (1975). “Efficiency of a Carnot
Engine at Maximum Power Output”. Am. J. Phys., Vol. 43,
pp. 24.
[12] “Nuclear Reactors Concepts and Thermodynamic Cycles”
(PDF). Retrieved 2012-03-22.
• Kroemer, Herbert; Kittel, Charles (1980). Thermal
Physics (2nd ed.). W. H. Freeman Company. ISBN
0-7167-1088-9.
• Callen, Herbert B. (1985). Thermodynamics and an
Introduction to Thermostatistics (2nd ed.). John Wiley
& Sons, Inc. ISBN 0-471-86256-8.
11.3 Thermodynamic cycle
A thermodynamic cycle consists of a linked sequence of
thermodynamic processes that involve transfer of heat and
work into and out of the system, while varying pressure,
temperature, and other state variables within the system,
and that eventually returns the system to its initial state.[1]
In the process of passing through a cycle, the working fluid
(system) may convert heat from a warm source into use-
ful work, and dispose of the remaining heat to a cold sink,
thereby acting as a heat engine. Conversely, the cycle may
be reversed and use work to move heat from a cold source
and transfer it to a warm sink thereby acting as a heat pump.
During a closed cycle, the system returns to its original
thermodynamic state of temperature and pressure. Process
238 CHAPTER 11. CHAPTER 11. FUNDAMENTALS

quantities (or path quantities), such as heat and work are

process dependent. For a cycle for which the system returns
to its initial state the first law of thermodynamics applies:

∆E = Eout − Ein = 0

The above states that there is no change of the energy of the

system over the cycle. Eᵢ might be the work and heat in-
put during the cycle and Eₒᵤ would be the work and heat
output during the cycle. The first law of thermodynam-
ics also dictates that the net heat input is equal to the net
work output over a cycle (we account for heat, Qᵢ , as posi-
tive and Qₒᵤ as negative). The repeating nature of the pro-
cess path allows for continuous operation, making the cycle
an important concept in thermodynamics. Thermodynamic
cycles are often represented mathematically as quasistatic
processes in the modeling of the workings of an actual de-
vice.
The net work equals the area inside because it is (a) the Riemann
sum of work done on the substance due to expansion, minus (b) the
11.3.1 Heat and work work done to re-compress.

Two primary classes of thermodynamic cycles are power

cycles and heat pump cycles. Power cycles are cycles
which convert some heat input into a mechanical work out-
put, while heat pump cycles transfer heat from low to high
temperatures by using mechanical work as the input. Cycles
composed entirely of quasistatic processes can operate as
power or heat pump cycles by controlling the process direc-
tion. On a pressure-volume (PV) diagram or temperature-
entropy diagram, the clockwise and counterclockwise di-
rections indicate power and heat pump cycles, respectively.
course of the cyclic process, when the cyclic process finishes
the system’s energy is the same as the energy it had when
the process began.
If the cyclic process moves clockwise around the loop, then
W will be positive, and it represents a heat engine. If it
moves counterclockwise, then W will be negative, and it
represents a heat pump.
Each Point in the Cycle

Relationship to work Otto Cycle:

Because the net variation in state properties during a ther- 1→2: Isentropic Expansion: Constant entropy (s), De-
modynamic cycle is zero, it forms a closed loop on a PV crease in pressure (P), Increase in volume (v), Decrease in
diagram. A PV diagram’s Y axis shows pressure (P) and X temperature (T)
axis shows volume (V). The area enclosed by the loop is the 2→3: Isochoric Cooling: Constant volume(v), Decrease in
work (W) done by the process: pressure (P), Decrease in entropy (S), Decrease in temper-
ature (T)
I 3→4: Isentropic Compression: Constant entropy (s), In-
(1) W = P dV crease in pressure (P), Decrease in volume (v), Increase in
temperature (T)
This work is equal to the balance of heat (Q) transferred 4→1: Isochoric Heating: Constant volume (v), Increase in
into the system: pressure (P), Increase in entropy (S), Increase in tempera-
ture (T)
A List of Thermodynamic Processes:
(2) W = Q = Qin − Qout
Adiabatic : No energy transfer as heat (Q) during that part
Equation (2) makes a cyclic process similar to an isothermal of the cycle would amount to δQ=0. This does not exclude
process: even though the internal energy changes during the energy transfer as work.
11.3. THERMODYNAMIC CYCLE
Description of each point in the thermodynamic cycles.
Isothermal : The process is at a constant temperature during
that part of the cycle (T=constant, δT=0). This does not
exclude energy transfer as heat or work.
Isobaric : Pressure in that part of the cycle will remain con-
stant. (P=constant, δP=0). This does not exclude energy
transfer as heat or work.
Isochoric : The process is constant volume (V=constant,
δV=0). This does not exclude energy transfer as heat or
work.
Isentropic : The process is one of constant entropy
(S=constant, δS=0). This excludes the transfer of heat but
not work.
Power cycles
Heat engine diagram.
Main article: Heat engine
Thermodynamic power cycles are the basis for the operation
W1→2 =
of heat engines, which supply most of the world’s electric
239
power and run the vast majority of motor vehicles. Power
cycles can be organized into two categories: real cycles and
ideal cycles. Cycles encountered in real world devices (real
cycles) are difficult to analyze because of the presence of
complicating effects (friction), and the absence of sufficient
time for the establishment of equilibrium conditions. For
the purpose of analysis and design, idealized models (ideal
cycles) are created; these ideal models allow engineers to
study the effects of major parameters that dominate the cy-
cle without having to spend significant time working out
intricate details present in the real cycle model.
Power cycles can also be divided according to the type of
heat engine they seek to model. The most common cycles
used to model internal combustion engines are the Otto cy-
cle, which models gasoline engines, and the Diesel cycle,
which models diesel engines. Cycles that model external
combustion engines include the Brayton cycle, which mod-
els gas turbines, the Rankine cycle, which models steam tur-
bines, the Stirling cycle, which models hot air engines, and
the Ericsson cycle, which also models hot air engines.
The clockwise thermodynamic cycle indicated by the arrows shows
that the cycle represents a heat engine. The cycle consists of four
states (the point shown by crosses) and four thermodynamic pro-
cesses (lines).
For example, the pressure-volume mechanical work output
from the heat engine cycle (net work out), consisting of 4
thermodynamic processes, is:
(3) Wnet = W1→2 + W2→3 + W3→4 + W4→1
∫ V2
P dV, system on done work negative,
V1
240 CHAPTER 11. CHAPTER 11. FUNDAMENTALS

∫ V3
images illustrate the differences in work output predicted
W2→3 = P dV, V3 equal V2 if work zero
V2 by an ideal Stirling cycle and the actual performance of a
∫ V4
Stirling engine:
W3→4 = P dV, system by done work positive, As the net work output for a cycle is represented by the in-
V3
∫ V1 terior of the cycle, there is a significant difference between
the predicted work output of the ideal cycle and the actual
W4→1 = P dV, V1 equal V4 if work zero
V4
work output shown by a real engine. It may also be observed
that the real individual processes diverge from their ideal-
If no volume change happens in process 4-1 and 2-3, equa-
ized counterparts; e.g., isochoric expansion (process 1-2)
tion (3) simplifies to:
occurs with some actual volume change.

(4) Wnet = W1→2 + W3→4

11.3.3 Well-known thermodynamic cycles

Heat pump cycles In practice, simple idealized thermodynamic cycles are usu-
ally made out of four thermodynamic processes. Any ther-
Main article: Heat pump and refrigeration cycle modynamic processes may be used. However, when ideal-
ized cycles are modeled, often processes where one state
variable is kept constant are used, such as an isothermal
Thermodynamic heat pump cycles are the models for
process (constant temperature), isobaric process (constant
household heat pumps and refrigerators. There is no dif-
pressure), isochoric process (constant volume), isentropic
ference between the two except the purpose of the refriger-
process (constant entropy), or an isenthalpic process (con-
ator is to cool a very small space while the household heat
stant enthalpy). Often adiabatic processes are also used,
pump is intended to warm a house. Both work by moving
where no heat is exchanged.
heat from a cold space to a warm space. The most common
refrigeration cycle is the vapor compression cycle, which Some example thermodynamic cycles and their constituent
models systems using refrigerants that change phase. The processes are as follows:
absorption refrigeration cycle is an alternative that absorbs
the refrigerant in a liquid solution rather than evaporating it.
Gas refrigeration cycles include the reversed Brayton cycle Ideal cycle
and the Hampson-Linde cycle. Multiple compression and
expansion cycles allow gas refrigeration systems to liquify
gases. p
11.3.2 Modelling real systems
Thermodynamic cycles may be used to model real devices 1 2
and systems, typically by making a series of assumptions.[2]
simplifying assumptions are often necessary to reduce the
A
D B
[2]
problem to a more manageable form. For example, as
shown in the figure, devices such a gas turbine or jet en-
gine can be modeled as a Brayton cycle. The actual device C
is made up of a series of stages, each of which is itself mod-
eled as an idealized thermodynamic process. Although each 4 3
stage which acts on the working fluid is a complex real de-
vice, they may be modelled as idealized processes which ap-
proximate their real behavior. If energy is added by means
other than combustion, then a further assumption is that the
exhaust gases would be passed from the exhaust to a heat ex- v
changer that would sink the waste heat to the environment
and the working gas would be reused at the inlet stage. An illustration of an ideal cycle heat engine (arrows clockwise).
The difference between an idealized cycle and actual per-
formance may be significant.[2] For example, the following An ideal cycle is constructed out of:
11.3. THERMODYNAMIC CYCLE 241

1. TOP and BOTTOM of the loop: a pair of parallel iso- A Stirling cycle is like an Otto cycle, except that the adi-
baric processes abats are replaced by isotherms. It is also the same as an
Ericsson cycle with the isobaric processes substituted for
2. LEFT and RIGHT of the loop: a pair of parallel iso- constant volume processes.
choric processes
1. TOP and BOTTOM of the loop: a pair of quasi-
Internal energy of a perfect gas undergoing different por- parallel isothermal processes
tions of a cycle:
2. LEFT and RIGHT sides of the loop: a pair of parallel
Isothermal: ∆U = RT ln VV21 − RT ln VV12 =
isochoric processes
00) equal to has process isothermal an of U (Note:
Isochoric: ∆U = Cv ∆T − 0 = Cv ∆T Heat flows into the loop through the top isotherm and the
Isobaric: ∆U = Cp ∆T − R∆T ( or P ∆V ) = Cv ∆T left isochore, and some of this heat flows back out through
the bottom isotherm and the right isochore, but most of
the heat flow is through the pair of isotherms. This makes
Carnot cycle sense since all the work done by the cycle is done by the
pair of isothermal processes, which are described by Q=W.
Main article: Carnot cycle This suggests that all the net heat comes in through the top
isotherm. In fact, all of the heat which comes in through the
The Carnot cycle is a cycle composed of the totally left isochore comes out through the right isochore: since the
reversible processes of isentropic compression and expan- top isotherm is all at the same warmer temperature TH and
sion and isothermal heat addition and rejection. The the bottom isotherm is all at the same cooler temperature
thermal efficiency of a Carnot cycle depends only on the TC , and since change in energy for an isochore is propor-
absolute temperatures of the two reservoirs in which heat tional to change in temperature, then all of the heat coming
transfer takes place, and for a power cycle is: in through the left isochore is cancelled out exactly by the
heat going out the right isochore.

TL
η =1− 11.3.4 State functions and entropy
TH
where TL is the lowest cycle temperature and TH the high- If Z is a state function then the balance of Z remains un-
est. For Carnot power cycles the coefficient of performance changed during a cyclic process:
for a heat pump is:
I
dZ = 0
TL
COP = 1 +
TH − TL Entropy is a state function and is defined as
and for a refrigerator the coefficient of performance is:
Q
S=
TL T
COP =
TH − TL so that
The second law of thermodynamics limits the efficiency
and COP for all cyclic devices to levels at or below the
∆Q
Carnot efficiency. The Stirling cycle and Ericsson cycle are ∆S =
T
two other reversible cycles that use regeneration to obtain
isothermal heat transfer. then it is clear that for any cyclic process,

Stirling cycle I I
dQ
dS = =0
T
Main article: Stirling cycle
meaning that the net entropy change over a cycle is 0.
242 CHAPTER 11. CHAPTER 11. FUNDAMENTALS

11.3.5 See also

• Entropy
• Economizer

11.3.6 References
[1] Cengel, Yunus A.; Boles, Michael A. (2002). Thermody-
namics: an engineering approach. Boston: McGraw-Hill. p.
14. ISBN 0-07-238332-1.

[2] Cengel, Yunus A.; Boles, Michael A. (2002). Thermody-

namics: an engineering approach. Boston: McGraw-Hill.
pp. 452. ISBN 0-07-238332-1.

11.3.7 Further reading

• Halliday, Resnick & Walker. Fundamentals of
Physics, 5th edition. John Wiley & Sons, 1997. Chap-
ter 21, Entropy and the Second Law of Thermodynam-
ics.
• Çengel, Yunus A., and Michael A. Boles. Thermody-
namics: An Engineering Approach, 7th ed. New York:
McGraw-Hill, 2011. Print.

• Hill and Peterson. “Mechanics and Thermodynamics

of Propulsion”, 2nd ed. Prentice Hall, 1991. 760 pp.

11.3.8 External links

Chapter 12

Text and image sources, contributors, and

licenses

12.1 Text
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Engels, Danny, Miguel~enwiki, Roadrunner, Jdpipe, Heron, Arj, Olivier, Ram-Man, Michael Hardy, Tim Starling, Kku, Menchi, Jedimike,
TakuyaMurata, Dgrant, Looxix~enwiki, Ahoerstemeier, CatherineMunro, Glenn, Victor Gijsbers, Jeff Relf, Mxn, Smack, Ehn, Tantalate, Reddi,
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Wwoods, Dratman, Curps, Michael Devore, Bensaccount, Abqwildcat, Macrakis, Foobar, Physicist, Louis Labrèche, Daen, Antandrus, BozMo,
OverlordQ, Karol Langner, APH, H Padleckas, Icairns, Monn0016, Sam Hocevar, MulderX, Agro r, Edsanville, Klemen Kocjancic, Mike Rosoft,
Poccil, CALR, EugeneZelenko, Masudr, Llh, Vsmith, Jpk, Pavel Vozenilek, Dmr2, Bender235, Eric Forste, Pmetzger, El C, Hayabusa future,
Femto, CDN99, Bobo192, Jung dalglish, SpeedyGonsales, Sasquatch, MPerel, Helix84, Haham hanuka, Pearle, Jumbuck, Ixfalia, Alansohn,
Gary, Dbeardsl, Atlant, PAR, Cdc, Malo, Cortonin, Wtmitchell, NAshbery, Docboat, Jheald, Gene Nygaard, Falcorian, Zntrip, Alyblaith, Miaow
Miaow, Uncle G, Plek, Carcharoth, Kzollman, Jwulsin, Sympleko, Pkeck, Tylerni7, Jwanders, Keta, Mido, Cbdorsett, Dzordzm, Frankie1969,
Prashanthns, Mandarax, Graham87, Jclemens, Melesse, Rjwilmsi, DrTorstenHenning, SMC, Ligulem, Dar-Ape, JohnnoShadbolt, Sango123,
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Rambling Man, Siddhant, RobotE, Pip2andahalf, Sillybilly, Anonymous editor, Anubis1975, JabberWok, Casey56, Wavesmikey, Stephenb, Oke-
dem, The1physicist, CambridgeBayWeather, Rsrikanth05, Wiki alf, Hagiographer, UDScott, Nick, Dhollm, Abb3w, DeadEyeArrow, Ms2ger,
Spinkysam, Enormousdude, Lt-wiki-bot, Arthur Rubin, Pb30, KGasso, MaNeMeBasat, Banus, RG2, Bo Jacoby, DVD R W, That Guy, From
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monkey, Sundaryourfriend, Gilliam, Hmains, Skizzik, ThorinMuglindir, Saros136, Bluebot, Bduke, Silly rabbit, SchfiftyThree, Complexica,
DHN-bot~enwiki, Antonrojo, Stedder, Sholto Maud, EvelinaB, HGS, Nakon, Lagrangian, Dreadstar, Richard001, Hammer1980, BryanG, Jk-
lin, DMacks, Sadi Carnot, Kukini, SashatoBot, Ocee, ML5, CatastrophicToad~enwiki, JoseREMY, Nonsuch, Pflatau, Ben Moore, CyrilB,
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isi, Tawkerbot2, Dlohcierekim, Daniel5127, Deathcrap, Spudcrazy, Meisam.fa, CRGreathouse, Dycedarg, Scohoust, Albert.white, TVC 15,
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Tpot2688, Omicronpersei8, Freak in the bunnysuit, Thijs!bot, MuTau, Barticus88, Bill Nye the wheelin' guy, Coelacan, Knakts, Kablammo,
Headbomb, Pjvpjv, Gerry Ashton, James086, D.H, Stannered, Spud Gun, Austin Maxwell, AntiVandalBot, Gioto, Luna Santin, Jnyanydts,
FrankLambert, Dylan Lake, JAnDbot, MER-C, Matthew Fennell, Acroterion, Lidnariq, Bongwarrior, VoABot II, JNW, Indon, Loonymon-
key, User A1, Pax:Vobiscum, Oneileri, A666666, Jtir, BetBot~enwiki, Mermaid from the Baltic Sea, NAHID, Rettetast, Ravichandar84,
R'n'B, LittleOldMe old, Mausy5043, Ludatha, Rhinestone K, Uncle Dick, Maurice Carbonaro, Yonidebot, Brien Clark, Ian.thomson, Dis-
penser, Katalaveno, MikeEagling, Notreallydavid, AntiSpamBot, Wariner, NewEnglandYankee, Nwbeeson, Ontarioboy, Rumpelstiltskin223,
WilfriedC, KylieTastic, Bob, Joshmt, Lyctc, Vagr7, Biff Laserfire, CA387, Idioma-bot, Funandtrvl, VolkovBot, Macedonian, Orthologist, Philip
Trueman, TXiKiBoT, Rei-bot, Anonymous Dissident, Sankalpdravid, Baatarchuluun~enwiki, Qxz, Anna Lincoln, CaptinJohn, Sillygoosemo,
JhsBot, Leafyplant, Jackfork, Psyche825, Nny12345, Zion biñas, Appieters, Whbstare, Enigmaman, Sploonie, Synthebot, Falcon8765, Envi-
roboy, Phmoreno, A Raider Like Indiana, Furious.baz, SvNH, Jianni, EmxBot, Kbrose, Arjun024, SieBot, Damorbel, Paradoctor, Jason Patton,
LeadSongDog, JerrySteal, Hoax user, Ddsmartie, Bentogoa, Happysailor, Flyer22 Reborn, Dhatfield, BrianGregory86, Oxymoron83, Anto-
nio Lopez, CultureShock582, OKBot, Correogsk, Mygerardromance, Hamiltondaniel, JL-Bot, Tomasz Prochownik, Loren.wilton, ClueBot,
Namasi, The Thing That Should Not Be, DesertAngel, Taroaldo, Therealmilton, Pak umrfrq, Kdruhl, LizardJr8, Whoever101, ChandlerMap-
Bot, Notburnt, GrapeSmuckers, Aua, Djr32, Jusdafax, LaosLos, Chrisban0314, Pmronchi, Eeekster, Lartoven, Brews ohare, NuclearWarfare,
Jotterbot, PhySusie, Scog, Sidsawsome, SoxBot, Razorflame, DEMOLISHOR, CheddarMan, Aitias, Dank, MagDude101, Galor612, Cable-
man1112, SoxBot III, RexxS, Faulcon DeLacy, Spitfire, Shres58tha, Avoided, Snapperman2, Thatguyflint, Mls1492, Thebestofall007, Addbot,
Power.corrupts, DOI bot, Morri028, DougsTech, Patrosnoopy, Glane23, Bob K31416, Numbo3-bot, Landofthedead2, Lightbot, OlEnglish,
Gatewayofintrigue, Ben Ben, Luckas-bot, Yobot, THEN WHO WAS PHONE?, Bos7, QueenCake, IW.HG, Magog the Ogre, AnomieBOT,
Paranoidhuman, IncidentalPoint, Daniele Pugliesi, Jim1138, Flewis, Materialscientist, Celtis123, Citation bot, Fredde 99, LilHelpa, Xqbot, Ad-

243
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bot, Wickey-nl, Looie496, Netzwerkerin, , SPat, Gail, Loupeter, Yobot, Ht686rg90, TaBOT-zerem, ^musaz, Xqbot, P99am, ChristopherKing-
Chemist, Charvest, Hlfhjwlrdglsp, Baz.77.243.99.32, Anterior1, Jonesey95, RjwilmsiBot, Pullister, EmausBot, Dcirovic, Michael assis, JSquish,
ZéroBot, Wikfr, AManWithNoPlan, Kyucasio, Hpubliclibrary, Keulian, Rashhypothesis, IBensone, RockMagnetist, EdoBot, Amviotd, ClueBot
NG, CocuBot, Landregn, Frietjes, Theopolisme, Helpful Pixie Bot, Mulhollant, Robwf, PhnomPencil, Op47, Acmedogs, F=q(E+v^B), JZCL,
Roshan220195, Egm4313.s12, Illia Connell, Dexbot, Mogism, Mark viking, Alefbenedetti, W. P. Uzer, KeithFratus, Michael Lee Baker, Philip-
peTilly, ԱշոտՏՆՂ, Udus97, Scientific Adviser, Izkala, VexorAbVikipædia, Dymaio, KasparBot, Spinrade, JosiahWilard, Gray76007600 and
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Jeffq, Robbot, Giftlite, H Padleckas, Icairns, Discospinster, Vsmith, Nk, Alansohn, PAR, Count Iblis, LukeSurl, StradivariusTV, Jeff3000,
Ketiltrout, Srleffler, Sanguinity, Dhollm, Arthur Rubin, Elfer~enwiki, Itub, SmackBot, Fuzzform, MalafayaBot, Hallenrm, SteveLower, Sadi
Carnot, JzG, Beetstra, Optakeover, Myasuda, AndrewHowse, Astrochemist, ErrantX, Thijs!bot, Barticus88, Headbomb, Marek69, D.H, User
A1, Thermbal, AtholM, Avitohol, Yuorme, Thisisborin9, Philip Trueman, The Original Wildbear, Seb az86556, Damorbel, Caltas, ClueBot, The
Thing That Should Not Be, Ectomaniac, DragonBot, Excirial, Tnxman307, SchreiberBike, Avoided, Ronhjones, LaaknorBot, EconoPhysicist,
Bwrs, Legobot, Luckas-bot, Yobot, Gdewilde, Daniele Pugliesi, Unara, Materialscientist, The High Fin Sperm Whale, Citation bot, J G Campbell,
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pha, Karol Langner, Pjacobi, Vsmith, ChrisChiasson, Wavesmikey, Dhollm, Sadi Carnot, Alphachimpbot, OKBot, Daniele Pugliesi, ‫قلی زادگان‬,
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Bot, 7methylguanosine, Bibcode Bot, BG19bot, Mn-imhotep, Taylanmath, Pfd1986, Cyberbot II, Laberkiste, Adwaele, JYBot, Duncanpark,
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Anome, Michael Hardy, Tim Starling, Ellywa, Victor Gijsbers, Reddi, Wik, Jeepien, Fibonacci, Sokane, Raul654, Bkell, Seth Ilys, Cutler, Alan
12.1. TEXT 245

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Miaow Miaow, Tutmosis, Palica, Yurik, Jehochman, Fresheneesz, Chobot, YurikBot, Splintercellguy, NTBot~enwiki, Wavesmikey, SCZenz,
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tunius, Knowhow, Müslimix, ThorinMuglindir, MalafayaBot, DHN-bot~enwiki, Tsca.bot, Sholto Maud, Chlewbot, Quadparty, Cybercobra,
Richard001, Marosszék, Sadi Carnot, Lambiam, Wikipedialuva, Frokor, Dicklyon, Ginkgo100, K, Hyperquantization, Achoo5000, Equendil,
Kareemjee, Astrochemist, Meno25, Ring0, Odie5533, Christian75, Hernlund, Mawfive, Headbomb, Pfranson, Widefox, JAnDbot, JamesBWat-
son, WLU, Anaxial, Yonidebot, SubwayEater, DorganBot, Gpetrov, Funandtrvl, ACSE, Amikake3, Lear’s Fool, Davwillev, Wenli, Anna512,
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Dave souza, Bender235, ESkog, Pjrich, Marx Gomes, Shanes, Smalljim, AtomicDragon, Pazouzou, Helix84, Orzetto, Alansohn, Arthena,
PAR, Jheald, Count Iblis, Kazvorpal, KTC, SmthManly, ChrisNoe, Zealander, WadeSimMiser, Hdante, Mandarax, Rjwilmsi, The wub, Fish
and karate, Gurch, Fresheneesz, SteveBaker, Srleffler, Mcavoys, Flying Jazz, ChrisChiasson, DVdm, Bgwhite, YurikBot, 4C~enwiki, Arado,
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JDspeeder1, Mejor Los Indios, Vojta2, Sbyrnes321, Itub, SmackBot, Aido2002, Philx, Rex the first, McGeddon, Gilliam, The Gnome, Keegan,
Complexica, Sadads, Gracenotes, VMS Mosaic, Marosszék, Sadi Carnot, Loodog, AstroChemist, Nonsuch, Pflatau, Wikster72, 2T, Irides-
cent, K, TwistOfCain, IvanLanin, Charlieb003, Rhetth, Mikiemike, Makeemlighter, Equendil, Cydebot, Kareemjee, Astrochemist, Meno25,
Christian75, DumbBOT, LeBofSportif, Headbomb, BirdKr, EdJohnston, Perpetual motion machine, Pgagge, Luna Santin, MichaelHenley,
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eyca, Bongwarrior, Wikidudeman, Usien6, Dirac66, TheBusiness, Hbent, Valthalas, Stafo86, Pharaoh of the Wizards, Abecedare, McDScott,
Akmunna, Littlecanargie, Sunderland06, VolkovBot, TXiKiBoT, NPrice, JhsBot, LeaveSleaves, Cremepuff222, Venny85, Koen Van de moor-
tel~enwiki, Blurpeace, Logan, Kbrose, SieBot, Caltas, Adamaja456, Happysailor, CombatCraig, Belinrahs, Momo san, Cloudjunkie, Shally87,
ClueBot, Mild Bill Hiccup, NewYorkDreams, NuclearWarfare, PhySusie, TCGrenfell, MigFP, Erodium, Nathan Johnson, Wertuose, Gonfer,
Addbot, Rishabhgoel, Lightbot, PV=nRT, Echinoidea, Luckas-bot, Yobot, Fraggle81, TaBOT-zerem, GMTA, Worm That Turned, AnomieBOT,
Jim1138, Materialscientist, 90 Auto, ArthurBot, LilHelpa, Lh389, Xqbot, Popx3rocks, Nanog, GrouchoBot, ‫حامد میرزاحسینی‬, Waleswatcher,
A. di M., Chjoaygame, FrescoBot, Tobby72, Pepper, Cannolis, Redrose64, Pinethicket, I dream of horses, Jonesey95, Martinvl, Jschnur, Vin-
cenzo Malvestuto, Piandcompany, FoxBot, Tehfu, Fox Wilson, Skk146, Tbhotch, Isrl.abel, Ripchip Bot, EmausBot, Llewkcalbyram, 478jjjz,
Passionless, Netheril96, Wikipelli, JSquish, Moravveji, Thine Antique Pen, Jay-Sebastos, Mentibot, BF6-NJITWILL, 912doctorwho, Wiki-
wind, Spicemix, ClueBot NG, Sag010793, Widr, Helpful Pixie Bot, Novusuna, Ninja-bunny.webs, Bibcode Bot, Lowercase sigmabot, Ditto51,
NZLS11, ISTB351, Hallows AG, Wiki13, MusikAnimal, Mark Arsten, Ushakaron, Mn-imhotep, Rs2360, Zedshort, Glacialfox, Anbu121,
Therealrockstar007, Coldestgecko, Alchemice, Keitam, Pmmanley, Fatimah M, Arcandam, Adwaele, Webclient101, Mogism, Ninjamen1234,
Zmicier P., Chessmad1, Nerlost, Babitaarora, Zenibus, PhoenixPub, JaconaFrere, Ordessa, Isambard Kingdom, Timothya101., Captain Chesa-
peake, Das O2, Kolaberry, Awyeahlol, Klaus Schmidt-Rohr and Anonymous: 326

• Second law of thermodynamics Source: https://en.wikipedia.org/wiki/Second_law_of_thermodynamics?oldid=715820238 Contributors: The

Anome, Jeronimo, XJaM, Roadrunner, Jdpipe, David spector, Lorenzarius, Michael Hardy, Ixfd64, Ahoerstemeier, Cyp, Theresa knott,
Snoyes, Jebba, AugPi, Cherkash, Ilyanep, Tantalate, Reddi, Terse, Tb, Timc, IceKarma, DJ Clayworth, Tpbradbury, Phys, Omegatron, Marc
Girod~enwiki, Jeffq, ScienceGuy, ChrisO~enwiki, Fredrik, Romanm, Gandalf61, Postdlf, Ashley Y, Sunray, Hadal, Robinh, Johnstone, Cutler,
Tea2min, Stirling Newberry, Giftlite, ComaVN, N12345n, Karn, FunnyMan3595, Curps, FeloniousMonk, Chinasaur, Dav4is, Duncharris, Bob-
blewik, Edcolins, LiDaobing, Pcarbonn, Antandrus, Eroica, Ravikiran r, Kaldari, Jossi, Karol Langner, Wikimol, Rdsmith4, Panzi, Sam Hocevar,
Neutrality, Ratiocinate, Trevor MacInnis, Grstain, DanielCD, Brianhe, Rich Farmbrough, KillerChihuahua, Rhobite, Pjacobi, Vsmith, Arnol-
dReinhold, Dave souza, Ivan Bajlo, Number 0, Bender235, Ignignot, Sietse Snel, Euyyn, SteveCoast, Bobo192, I9Q79oL78KiL0QTFHgyc,
Aquillion, Nk, Maebmij, Helix84, AppleJuggler, Cpcjr, Jason One, Kingsindian, Zenosparadox, Arthena, Mineralogy, PAR, Wtshymanski,
Evil Monkey, Jheald, Count Iblis, Dominic, Pauli133, Alai, KTC, Oleg Alexandrov, Crosbiesmith, ChrisNoe, Madmardigan53, Miaow Miaow,
Keta, Denevans, Funhistory, Christopher Thomas, Gerbrant, GSlicer, Kbdank71, Nanite, Rjwilmsi, Koavf, Eyu100, Yamamoto Ichiro, Ni-
hiltres, Dantecubed, Fresheneesz, Srleffler, Jittat~enwiki, Chobot, Flying Jazz, ChrisChiasson, Wavelength, Michaeladenner, RobotE, Hairy
Dude, Bobby1011, Wavesmikey, Akamad, Stephenb, Gaius Cornelius, CambridgeBayWeather, Aeusoes1, SCZenz, Ragesoss, Dhollm, Abb3w,
Mgrierson, Dna-webmaster, WAS 4.250, Enormousdude, 2over0, Dieseldrinker, Arthur Rubin, BorgQueen, Ilmari Karonen, Fluent aphasia,
Profero, Infinity0, Sbyrnes321, DVD R W, Knowledgeum, Luk, SmackBot, Cirejcon, Ashenai, ChXu, CarbonCopy, McGeddon, Palinurus,
WebDrake, Jim62sch, David Shear, Neptunius, Adrian232, Gunnar.Kaestle, Lsommerer, Bmord, Jab843, Yamaguchi , Gilliam, The Gnome,
ThorinMuglindir, Kmarinas86, Chris the speller, Bduke, Tisthammerw, MalafayaBot, Complexica, Bonaparte, Desp~enwiki, Zmanish, Ver-
rai, Ben Rogers, Sholto Maud, Andyparkins, H-J-Niemann, EPM, Dreadstar, DMacks, Henning Makholm, Sadi Carnot, Mikaduki, Zchenyu,
AThing, Miftime, Rklawton, Doanison, JorisvS, Mgiganteus1, Nonsuch, IronGargoyle, AwesomeMachine, Stikonas, MrArt, Peyre, Xionbox,
Astrobradley, Dan Gluck, Seqsea, K, Michaelbusch, CzarB, Kommando797, Spk ben, George100, Tubbyspencer, Josedanielc, Mikiemike, Ale
jrb, Wafulz, AlbertSM, Father Ignatius, Jucati, Emilio Juanatey, Myasuda, Cydebot, Rifleman 82, Meno25, Ring0, Miguel de Servet, Michael C
Price, DumbBOT, JodyB, Spookpadda, Daa89563, LeBofSportif, DMZ, Headbomb, Marek69, John254, EdJohnston, AntiVandalBot, Wide-
fox, Gökhan, Canadian-Bacon, Narssarssuaq, MER-C, Physical Chemist, Acroterion, Meeples, Magioladitis, VoABot II, Mbarbier, Hubbardaie,
Daarznieks, Dirac66, Hbent, Heqwm, Tercer, Wkussmaul, Jtir, Aeternium, Hweimer, R'n'B, Mbweissman, Time traveller, J.delanoy, Pharaoh of
the Wizards, Musaran, Ian.thomson, Bluecheese333, Salih, LordAnubisBOT, Frisettes, Stootoon, Ppithermo, VolkovBot, Larryisgood, Joeoet-
tinger, ABF, Speaker to Lampposts, JayEsJay, Rei-bot, Anonymous Dissident, Michael H 34, LeaveSleaves, Natg 19, Maxim, Antixt, Enviroboy,
San Diablo, Zebas, Kbrose, Subh83, SieBot, YonaBot, BotMultichill, Dawn Bard, Caltas, Jewk, Crash Underride, Arjun r acharya, Discrete,
246 CHAPTER 12. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

Nrsmith, Jdaloner, Barry Fruitman, Sunrise, Denisarona, Vanished user qkqknjitkcse45u3, ClueBot, PaulLowrance, The Thing That Should Not
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wayofintrigue, Teles, Arbitrarily0, Hartz, Luckas-bot, Yobot, Fraggle81, Sanyi4, Egbertus, AnomieBOT, Rubinbot, Jim1138, Jacob2718, Ma-
terialscientist, Citation bot, Chemeditor, LilHelpa, Xqbot, Nanog, Aa77zz, GrouchoBot, ChristopherKingChemist, Rhettballew, Waleswatcher,
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dream of horses, Jonesey95, AnandaDaldal, Serols, Alfredwongpuhk, ‫کاشف عقیل‬, Howzeman, Klangenfurt, Naji Khaleel, Yappy2bhere,
LoStrangolatore, RjwilmsiBot, Ptbptb, Aircorn, EmausBot, John of Reading, Lea phys, Da500063, Netheril96, Dcirovic, Arjun S Ariyil,
Evanh2008, JSquish, John Cline, Bollyjeff, Mattedia, Kenan82, Tls60, WikiPidi, Ems2715, BF6-NJITWILL, Spicemix, Rocketrod1960, Clue-
Bot NG, Snoid Headly, Jj1236, Mormequill, Widr, WikiPuppies, Helpful Pixie Bot, Bibcode Bot, Lowercase sigmabot, BG19bot, Savarona1,
Cdh1001, Ugncreative Usergname, Glevum, Rs2360, Crio, Rowan Adams, Pratyya Ghosh, LeeMcLoughlin1975, Adwaele, Mdkssner, Jcham-
mel, Pterodactyloid, Lugia2453, Zmicier P., Jochen Burghardt, Reatlas, Nerlost, Nicksola, Glenn Tamblyn, Mre env, The-vegan-muser, Aspro89,
Prokaryotes, Nakitu, PhoenixPub, Ammamaretu, Skr15081997, Burnandquiver, Monkbot, Douglas Cotton, Wiki jeri, IagoQnsi, Trackteur,
Tylerleeredd, Theeditinprogress, BiologicalMe, Jorge Guerra Pires, KH-1, Crystallizedcarbon, Yusefghouth, Captain Chesapeake, CAPTAIN
RAJU, Klaus Schmidt-Rohr and Anonymous: 561
• Third law of thermodynamics Source: https://en.wikipedia.org/wiki/Third_law_of_thermodynamics?oldid=709781075 Contributors: The
Anome, XJaM, Cherkash, Rob Hooft, Reddi, Stismail, Grendelkhan, Vamos, Fredrik, Guy Peters, Cutler, Giftlite, Smjg, Tom harrison, Ev-
eryking, Ned Morrell, Karol Langner, D6, Pjacobi, Bender235, Duk, Helix84, Keenan Pepper, Andrewpmk, PAR, Jheald, Gene Nygaard,
Miaow Miaow, SeventyThree, Nanite, Chobot, YurikBot, Chris Capoccia, Wavesmikey, Okedem, Salsb, SCZenz, Dhollm, E2mb0t~enwiki,
Tony1, CWenger, Sbyrnes321, McGeddon, Unyoyega, Gilliam, Sandycx, Colonies Chris, Malosse, Rrburke, Marosszék, BZegarski, Sadi Carnot,
Majorclanger, 2T, K, Richard75, Einstein runner, Astrochemist, Gogo Dodo, Ring0, Khattab01~enwiki, Dchristle, Thijs!bot, Barticus88, Wide-
fox, MER-C, Magioladitis, Alan Holyday, Edward321, Canberra User, Masaki K, Mbweissman, Time traveller, Ssault, Olulade, CardinalDan,
VolkovBot, Malinaccier, A4bot, Wolfrock, Zebas, Kbrose, Natox, SieBot, Gerakibot, Oxymoron83, OKBot, Bewporteous, Mygerardromance,
WikiLaurent, TSRL, ClueBot, LAX, Wikijens, MigFP, Happysam92, Spitfire, Addbot, CarsracBot, Luckas-bot, Sanyi4, AnomieBOT, Rubin-
bot, Jim1138, JackieBot, Citation bot, Xqbot, Draxtreme, GrouchoBot, RibotBOT, Waleswatcher, Erik9, Chjoaygame, D'ohBot, Jonesey95,
Nobleness of Mind, Hb2007, EmausBot, John of Reading, 8digits, Shuipzv3, Wmayner, Nexia asx, Spicemix, ClueBot NG, Alchemist314,
Helpful Pixie Bot, Bibcode Bot, BG19bot, CityOfSilver, Bush6984, Rs2360, Zedshort, Nitcho1as12, SimmeD, Patton622, Adwaele, Cup o'
Java, Cesaranieto~enwiki, Ankitdwivedimi6, FiredanceThroughTheNight, Dakkagon, Sball004, Garfield Garfield, Krishtafar, Wikixenia and
Anonymous: 109
• History of thermodynamics Source: https://en.wikipedia.org/wiki/History_of_thermodynamics?oldid=713637911 Contributors: Collabi, Lu-
mos3, Arkuat, Gandalf61, Cutler, Karol Langner, Eric Forste, PAR, Marianika~enwiki, Carcharoth, Benbest, Rjwilmsi, Ligulem, Srleffler,
Chobot, Gaius Cornelius, CambridgeBayWeather, Ragesoss, Dhollm, Moe Epsilon, Rayc, Netrapt, Tropylium, SmackBot, Jagged 85, Tim-
Bentley, Colonies Chris, A.R., DMacks, Ligulembot, Mion, Sadi Carnot, Pilotguy, JzG, JorisvS, Peterlewis, Special-T, AdultSwim, Lottamiata,
Myasuda, FilipeS, Gtxfrance, Doug Weller, M karzarj, Barticus88, D.H, Greg L, EdJogg, VoABot II, Cardamon, Jtir, Inwind, ElinorD, Riick,
Enviroboy, Radagast3, Natox, SieBot, I Love Pi, Anchor Link Bot, Tomasz Prochownik, MCCRogers, Taroaldo, J8079s, Djr32, CohesionBot,
Eeekster, XLinkBot, Saeed.Veradi, Ariconte, Kwjbot, Addbot, Lightbot, Wikkidd, Luckas-bot, Yobot, Ptbotgourou, Ajh16, AnomieBOT, Ci-
tation bot, ArthurBot, Xqbot, J04n, GrouchoBot, ChristopherKingChemist, SassoBot, Geraldo61, Fortdj33, Machine Elf 1735, Citation bot
1, TobeBot, Marie Poise, Syncategoremata, ClueBot NG, Helpful Pixie Bot, Bibcode Bot, Ludi Romani, Bfong2828, SoledadKabocha, Belief
action, Nerlost, Sibyl Gray, Yikkayaya, CleanEnergyPundit and Anonymous: 32
• An Experimental Enquiry Concerning the Source of the Heat which is Excited by Friction Source: https://en.wikipedia.org/wiki/An_
Experimental_Enquiry_Concerning_the_Source_of_the_Heat_which_is_Excited_by_Friction?oldid=715176110 Contributors: Jdpipe, Domi-
nus, Charles Matthews, Bloodshedder, Cutler, MakeRocketGoNow, Mdd, Wijnand, GregorB, Rjwilmsi, Tim!, Ligulem, Vclaw, Jaraalbe, Russ-
Bot, Dhollm, Qero, Itub, SmackBot, Localzuk, Peterlewis, Wizard191, Cydebot, Mrmrbeaniepiece, Gioto, Nyttend, PC78, TomyDuby, Inwind,
Guillaume2303, Kdruhl, Good Olfactory, Airplaneman, Tassedethe, Lightbot, Citation bot, ChristopherKingChemist, ClueBot NG, Saehry,
Nerlost, VexorAbVikipædia and Anonymous: 2
• Control volume Source: https://en.wikipedia.org/wiki/Control_volume?oldid=642129926 Contributors: Jdpipe, Silverfish, Rich Farmbrough,
Xezbeth, Mairi, Mdd, RJFJR, Kbdank71, Mathbot, Siddhant, Matador, Dhollm, Bjs1234, Plober, Chris the speller, Bluebot, HydrogenSu, Sadi
Carnot, Wanstr, Wolfram.Tungsten, STBot, FelixTheCat85, Salih, Dolphin51, Cacadril, Crowsnest, Addbot, Iwfyita, ZéroBot and Anonymous:
11
• Ideal gas Source: https://en.wikipedia.org/wiki/Ideal_gas?oldid=716419913 Contributors: SimonP, Peterlin~enwiki, Ben-Zin~enwiki, Florian-
Marquardt, Patrick, Michael Hardy, Wshun, GTBacchus, Looxix~enwiki, Ellywa, Nikai, Schneelocke, Bamos, Robbot, Hankwang, Kizor, COG-
DEN, Soilguy3, Tea2min, Enochlau, Giftlite, Wolfkeeper, Herbee, Brona, Bensaccount, Louis Labrèche, Kraton, Karol Langner, H Padleckas,
Tsemii, Edsanville, Brianjd, Pjacobi, Vsmith, Altmany, SpookyMulder, Bender235, Chewie, Nigelj, Avathar~enwiki, Nk, Keenan Pepper, PAR,
Cdc, Rebroad, H2g2bob, -kkm, Gene Nygaard, BillC, GregorB, Palica, Nanite, Margospl, Chobot, ChrisChiasson, YurikBot, Hairy Dude, Jab-
berWok, CambridgeBayWeather, Rick lightburn, D. F. Schmidt, Dhollm, Aaron Schulz, Bota47, 2over0, Aleksas, TBadger, CWenger, Paul
D. Anderson, Bo Jacoby, CrniBombarder!!!, SmackBot, Kmarinas86, Chris the speller, ViceroyInterus, GregRM, MalafayaBot, Complexica,
Colonies Chris, Moosesheppy, Whpq, Michael Ross, Just plain Bill, Sadi Carnot, Lambiam, Kpengboy, MTSbot~enwiki, Tawkerbot2, OlexiyO,
Joelholdsworth, Cydebot, Nonagonal Spider, Headbomb, Bigbill2303, JustAGal, Escarbot, Leftynm, Nosbig, JAnDbot, Davidtwu, Bongwar-
rior, Corpeter~enwiki, User A1, Mythealias, CommonsDelinker, Leyo, Slugger, Huzzlet the bot, Davidr222, Landarski, Bigjoestalin, Stan J
Klimas, Tarotcards, Hesam 8529022, VolkovBot, DSRH, Theosch, Malinaccier, Tsi43318, Riick, Nosferatütr, SieBot, Gerakibot, Man It’s So
Loud In Here, Adamtester, Thekingofspain, Qmantoast, ClueBot, Razimantv, Mild Bill Hiccup, Turbojet, Vql, CarlosPatiño, Katanada, Khun-
glongcon, WikiDao, Prowikipedians, Addbot, Power.corrupts, Fieldday-sunday, EconoPhysicist, Ckk253, PranksterTurtle, Mean Free Path,
Tide rolls, Zorrobot, Luckas-bot, Yobot, Fraggle81, Kipoc, Paranoidhuman, Materialscientist, Xqbot, Nickkid5, GrouchoBot, ChristopherKing-
Chemist, RibotBOT, E0steven, SD5, BoomerAB, Chjoaygame, Nagoltastic, FrescoBot, FoxBot, சஞ்சீவி சிவகுமார், EmausBot, WikitanvirBot,
Mrericsully, HiW-Bot, Kiwi128, AManWithNoPlan, Donner60, ClueBot NG, CocuBot, Movses-bot, Tr00rle, Kevinjasm, Piguy101, Brad7777,
12.1. TEXT 247

Aisteco, Uopchem25asdf, BeaumontTaz, YDelta, Mike666234, HiYahhFriend, MantleMeat, Trackteur, Macofe, Carlojoseph14, Alligator420,
Mtthwknnd4 and Anonymous: 181
• Real gas Source: https://en.wikipedia.org/wiki/Real_gas?oldid=709413052 Contributors: Charles Matthews, Robbot, Giftlite, Brianjd, PAR,
Velella, Jost Riedel, Rjwilmsi, Boccobrock, Dhollm, Tony1, Closedmouth, SmackBot, Colonies Chris, Anakata, Gogo Dodo, Raoul NK, Head-
bomb, Fayenatic london, Olaf, Stan J Klimas, Heero Kirashami, Vanished user 39948282, TXiKiBoT, Theosch, LeaveSleaves, Meters, Logan, J-
puppy, StaticGull, Marco zannotti, ClueBot, Ideal gas equation, Alexbot, Katanada, Crowsnest, Addbot, Power.corrupts, Download, LinkFA-Bot,
84user, Krano, Luckas-bot, Takuma-sa, Azylber, Sonia, Gumok, Omnipaedista, Shadowjams, BenzolBot, Pinethicket, MinkeyBuddy, MastiBot,
Jauhienij, EmausBot, Klbrain, Dcirovic, ZéroBot, Zl1corvette, ClueBot NG, Jwchong, UAwiki, Ushakaron, Mn-imhotep, Sarah george mesiha,
Marvin W. Hile, Zrephel, Jianhui67, VIKRAMGUPTAJI and Anonymous: 65
• Thermodynamic process Source: https://en.wikipedia.org/wiki/Thermodynamic_process?oldid=715721366 Contributors: Glenn, Giftlite,
Andycjp, Karol Langner, Paul August, Alansohn, PAR, GangofOne, YurikBot, Bhny, Wavesmikey, Dhollm, Bota47, Jeh, SmackBot,
MalafayaBot, Chlewbot, Lambiam, Karenjc, Thijs!bot, JAnDbot, R'n'B, Spshu, DorganBot, VolkovBot, ABF, Philip Trueman, Lechatjaune,
Jackfork, AlleborgoBot, Natox, SieBot, Gerakibot, OKBot, FearChild, Cerireid, Addbot, Amirber, BepBot, Luckas-bot, Ptbotgourou, Choij,
Daniele Pugliesi, ArthurBot, Erik9bot, Chjoaygame, Jauhienij, EmausBot, Mmeijeri, ClueBot NG, Pcarmour, Helpful Pixie Bot, J824h,
BG19bot, F=q(E+v^B), Glacialfox, Prokaryotes, DavRosen, Quenhitran, Dhyannesh Dev, BadFaithEditor, Metlapalli sai kiran kanth, K Sikdar,
Shrodinger X and Anonymous: 31
• Isobaric process Source: https://en.wikipedia.org/wiki/Isobaric_process?oldid=717073640 Contributors: Peterlin~enwiki, Ellywa, Glenn,
AugPi, Wik, Robbot, Karol Langner, Discospinster, Rgdboer, Duk, Orzetto, Keenan Pepper, Margosbot~enwiki, YurikBot, Dhollm, Plober,
SmackBot, Loodog, Pflatau, Sabate, Damouns, Thijs!bot, Gökhan, JAnDbot, JaGa, El Belga, VolkovBot, Lechatjaune, T0lk, Insanity Incarnate,
Kbrose, SieBot, Mike2vil, WikiBotas, Hjlim, Auntof6, Crowsnest, MystBot, Addbot, Jncraton, PV=nRT, Luckas-bot, Yobot, TaBOT-zerem,
Sanyi4, Rubinbot, GrouchoBot, Pyther, FrescoBot, ‫عبد المؤمن‬, LucienBOT, Simeon89, Pinethicket, Dance-a-day, TjBot, Ripchip Bot, Emaus-
Bot, WikitanvirBot, Carultch, ClueBot NG, Anagogist, AvocatoBot, BattyBot, IkamusumeFan, CarrieVS, Zziccardi, Ebag7125, Tyler.neysmith
and Anonymous: 41
• Isochoric process Source: https://en.wikipedia.org/wiki/Isochoric_process?oldid=715485863 Contributors: Peterlin~enwiki, Ixfd64, Ellywa,
Glenn, AugPi, Robbot, BenFrantzDale, Karol Langner, ArneBab, Rich Farmbrough, CDN99, DanielNuyu, Duk, Gene Nygaard, Knuckles,
YurikBot, Dhollm, Bota47, StuRat, Plober, Mejor Los Indios, KocjoBot~enwiki, Ortho, A.Z., David Legrand, Mahlerite, ALittleSlow, Thijs!bot,
Kerotan, Nyq, Freddyd945, JaGa, Ydw, Shoessss, VolkovBot, LokiClock, JhsBot, Nightkhaos, AlleborgoBot, Kbrose, SieBot, BotMultichill,
Lara bran, ClueBot, Wikijens, DragonBot, MystBot, Addbot, Skyezx, Nachoj, PV=nRT, Zorrobot, Luckas-bot, Yobot, Sanyi4, Xqbot, Grou-
choBot, Pyther, Erik9bot, OgreBot, RedBot, Thái Nhi, Jeffrd10, TjBot, Ifly6, Chuchung712, Voltaire169, ClueBot NG, IkamusumeFan, Gin-
suloft, JJMC89 and Anonymous: 46
• Isothermal process Source: https://en.wikipedia.org/wiki/Isothermal_process?oldid=717175757 Contributors: Roadrunner, Peterlin~enwiki,
Glenn, Cyan, AugPi, Dcoetzee, Robbot, HaeB, Karol Langner, Rich Farmbrough, Robotje, Duk, Dungodung, LOL, Shpoffo, Nneonneo, Gelo71,
Yuta Aoki, Margosbot~enwiki, Chobot, Bgwhite, RussBot, Postglock, CambridgeBayWeather, Adamrush, Dhollm, Plober, SmackBot, David
Shear, Mcduff, Coffin, Akriasas, Lambiam, Pflatau, Vanisaac, OlexiyO, Astrochemist, Mtpaley, John254, Kathovo, JAnDbot, JaGa, JCraw,
R'n'B, Lechatjaune, Pedvi, !dea4u, Romeoracz, SieBot, Yintan, WikiBotas, EoGuy, DragonBot, Forbes72, MystBot, Addbot, Jncraton, Tide
rolls, PV=nRT, Legobot, Luckas-bot, Ptbotgourou, Sanyi4, Nallimbot, Rtanz, Rubinbot, Jim1138, Xqbot, Trueravenfan, GrouchoBot, Erik9bot,
Jwilson75503, Thái Nhi, EmausBot, Netheril96, A2soup, AManWithNoPlan, ClueBot NG, KrDa, AnkurBargotra, Uopchem0251, BattyBot,
ChrisGualtieri, Dexbot, Namige, Evan585619, Rajawaseem6, Retired Pchem Prof, Eden-K121D and Anonymous: 95
• Adiabatic process Source: https://en.wikipedia.org/wiki/Adiabatic_process?oldid=717492687 Contributors: AxelBoldt, CYD, Bryan Derksen,
AdamW, Andre Engels, JeLuF, Roadrunner, Peterlin~enwiki, Icarus~enwiki, Edward, Michael Hardy, Tim Starling, Glenn, AugPi, Hike395,
Ec5618, Steinsky, Kaare, Grendelkhan, Phys, Raul654, Donarreiskoffer, Robbot, Chancemill, Sverdrup, Moink, Wereon, Enochlau, Giftlite,
Mat-C, BenFrantzDale, Mboverload, Andycjp, Gunnar Larsson, Karol Langner, Klemen Kocjancic, Discospinster, Rich Farmbrough, Guanabot,
Vsmith, Bender235, Evand, Gershwinrb, Bobo192, Kghose, Duk, Giraffedata, Jtalledo, PAR, BernardH, Count Iblis, Artur adib, Gene Nygaard,
Dan100, Linas, SeventyThree, Palica, Rjwilmsi, JLM~enwiki, Ucucha, Chobot, DVdm, Bgwhite, Triku~enwiki, YurikBot, Hairy Dude, Russ-
Bot, Stassats, NawlinWiki, Dhollm, Mlouns, Tony1, Fsiler, Plober, Mejor Los Indios, SmackBot, Slashme, InverseHypercube, Giraldusfaber,
The Gnome, Dauto, ThorinMuglindir, Bluebot, Kevinbevin9, Sbharris, Tschwenn, Smokefoot, Hgilbert, Dr. Crash, SashatoBot, Shrew, Loodog,
KostasG, Breno, Mgiganteus1, NongBot~enwiki, Pflatau, Rm w a vu, Joe Frickin Friday, Tac2z, Phuzion, Tawkerbot2, Mika1h, W.F.Galway,
Rracecarr, Thijs!bot, E. Ripley, Thljcl, Escarbot, Stannered, Mikenorton, TAnthony, MSBOT, Magioladitis, AuburnPilot, Aka042, Dirac66,
User A1, Dbrunner, Pgriffin, AstroHurricane001, Choihei, Stan J Klimas, NewEnglandYankee, Molly-in-md, Balawd, Dhaluza, STBotD, Deor,
VolkovBot, Kyle the bot, Plenumchamber~enwiki, Venny85, MajorHazard, Kbrose, David Straight, SieBot, Ivan Štambuk, Damorbel, VVVBot,
Oxymoron83, Anchor Link Bot, Hamiltondaniel, Breeet, Dolphin51, Denisarona, ClueBot, IceUnshattered, Mild Bill Hiccup, Heathmoor,
Alexbot, JLewis98856, Pcmproducts, Amaruca, Ecomesh, NevemTeve, Stefano Schiavon, ChrisHodgesUK, Mscript, Bannerts, Addbot, The
Geologist, Alkonblanko, Masegado, Sarasknight, Lindert, EconoPhysicist, BepBot, AnnaFrance, Ginosbot, Emilio juanatey, Zorrobot, Ettrig,
Legobot, Luckas-bot, Yobot, Tohd8BohaithuGh1, Sirsparksalot, Sanyi4, Synchronism, AnomieBOT, Ciphers, Xtreme219, Darkroll, Mate-
rialscientist, Xqbot, GrouchoBot, Sheeson, Chjoaygame, FrescoBot, Sapphirus, Jschnur, RedBot, Serols, FoxBot, Eracer55, TCarey, Tbhotch,
RjwilmsiBot, EmausBot, John of Reading, DacodaNelson, Mobius Bot, Carultch, Donner60, Eg-T2g, ClueBot NG, Pvnuffel, KL56-NJITWILL,
Clive.gregory, Rogerwillismillsii, Bibcode Bot, Alexgotsis, Bauka91 91, Royourboat, Lynskyder, YumOooze, Zedshort, Warrenrob50, Armasd,
Dexbot, C5st4wr6ch, Coolitic, Destroyer130, Jodosma, Samgo27, Bcheah, Toyalima, JCMPC, Femkemilene, Monkbot, Krishtafar, Appleuseryu
and Anonymous: 222
• Isenthalpic process Source: https://en.wikipedia.org/wiki/Isenthalpic_process?oldid=645636432 Contributors: Glenn, Karol Langner, Count
Iblis, Gene Nygaard, NawlinWiki, Dhollm, Hirudo, Thorney¿?, SmackBot, Bduke, Xyabc, Rracecarr, Hasanpasha, StuartF, Stan J Klimas,
Davecrosby uk, Dolphin51, Editor2020, MystBot, Addbot, LatitudeBot, Zorrobot, Amirobot, Citation bot, EmausBot, WikitanvirBot, ZéroBot,
Rmashhadi, Helpful Pixie Bot, Titodutta, MusikAnimal, Monkbot and Anonymous: 10
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Auntof6, Excirial, PixelBot, Wdford, Mikaey, SchreiberBike, Addbot, CarsracBot, Redheylin, Glane23, Ht686rg90, Fraggle81, Becky Sayles,
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FrantzDale, Bensaccount, Jason Quinn, Bobblewik, ThePhantom, Karol Langner, Icairns, Gscshoyru, Tsemii, Edsanville, Vsmith, Xezbeth,
Nabla, Joanjoc~enwiki, Kwamikagami, RAM, Jung dalglish, Pearle, I-hunter, Yhr, Mc6809e, PAR, Jheald, Gene Nygaard, Ian Moody, Kelly
Martin, Pol098, Palica, Marudubshinki, Rjwilmsi, FlaBot, Margosbot~enwiki, Yrfeloran, Chobot, DVdm, YurikBot, Wavelength, RobotE,
Jimp, RussBot, Madkayaker, Gaius Cornelius, Grafen, Trovatore, Dhollm, Voidxor, E2mb0t~enwiki, Poppy, JPushkarH, Mumuwenwu, SDS,
GrinBot~enwiki, Bo Jacoby, Tom Morris, Hansonrstolaf, Edgar181, Skizzik, ThorinMuglindir, Chris the speller, Complexica, Sbharris, Sct72,
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board, Myasuda, Cydebot, Christian75, Mikewax, Thijs!bot, Memty Bot, Andyjsmith, Marek69, Greg L, Vincent88~enwiki, Ste4k, JAnDbot,
BenB4, Magioladitis, Riceplaytexas, Engineman, Chemical Engineer, Dirac66, Mythealias, Anaxial, Alro, R'n'B, Leyo, Mausy5043, Thermbal,
Brien Clark, Notreallydavid, NewEnglandYankee, RayForma, Ojovan, Brvman, AlnoktaBOT, TheOtherJesse, 8thstar, Philip Trueman, Osh-
wah, Aymatth2, Meters, Demize, Kbrose, JDHeinzmann, Damorbel, BotMultichill, Cwkmail, Revent, Flyer22 Reborn, Allmightyduck, Anchor
Link Bot, Dolphin51, Denisarona, Elassint, ClueBot, Bbanerje, Auntof6, Dh78~enwiki, Djr32, KyuubiSeal, Rathemis, Peacheshead, Johnuniq,
TimothyRias, Forbes72, WikHead, NellieBly, Alberisch~enwiki, Gniemeyer, Addbot, Boomur, CanadianLinuxUser, Keds0, Snaily, Yobot,
AnomieBOT, DemocraticLuntz, Rubinbot, Daniele Pugliesi, Materialscientist, Citation bot, Eumolpo, Ulf Heinsohn, Chthonicdaemon, Grou-
choBot, Ccmwiki~enwiki, Tufor, A. di M., Thehelpfulbot, Khakiandmauve, Chjoaygame, Banak, Italianice84, Bergdohle, Mfwitten, Cannolis,
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imac, J36miles, EmausBot, John of Reading, Ajraddatz, Tpudlik, Dewritech, Gowtham vmj, Onegumas, Wikipelli, K6ka, Hhhippo, Ronk01,
Offsure, Quondum, Mmww123, AManWithNoPlan, Wayne Slam, Hpubliclibrary, Donner60, ChuispastonBot, RockMagnetist, 28bot, Puls-
fordp, ClueBot NG, Cwmhiraeth, Ulflund, School of Stone, Physics is all gnomes, The Master of Mayhem, O.Koslowski, Rezabot, Danim,
MerlIwBot, ImminentFate, Magneticmoment, Helpful Pixie Bot, Lolm8, Calabe1992, Bibcode Bot, ElZarco, BG19bot, Yafjj215, AvocatoBot,
Ushakaron, Tcep, Jschmalzel, Saiprasadrm, Zedshort, Physicsch, Martkat08, MathewTownsend, Anthonymcnug, BattyBot, David.moreno72,
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P., Mgibby5, Reatlas, Joeinwiki, C5st4wr6ch, Epicgenius, Luke arnold16, Akiaterry, AresLiam, Kogge, Newestcastleman, JCMPC, Kernkkk,
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Aarchiba, Moriori, Chris Roy, Mor~enwiki, Mintleaf~enwiki, BenFrantzDale, Leonard G., Pne, Sam Hocevar, HasharBot~enwiki, AMR, PAR,
Count Iblis, Gene Nygaard, GregorB, Rjwilmsi, Cryonic Mammoth, Deklund, RobotE, RussBot, Twin Bird, Dhollm, Valeriecoffman, Hearto-
faDog, Commander Keane bot, Rpspeck, Powerfool, COMPFUNK2, Wiz9999, Mwtoews, John, Iepeulas, Lenoxus, Pacerlaser, Courcelles,
Covalent, Novous, TheTito, Basar, Thijs!bot, Headbomb, JustAGal, EarthPerson, JAnDbot, Tigga, Ibjt4ever, Magioladitis, Ehdr, Msd3k, Red
Sunset, R'n'B, Deans-nl, Zygimantus, Uncle Dick, KudzuVine, Sandman619, CWii, YuryKirienko, Wiae, Andy Dingley, Gerakibot, Ra'ike,
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12.1. TEXT 251

Citation bot 1, Pinethicket, Agrasa, RjwilmsiBot, Ankid, EmausBot, ZéroBot, Redhanker, AManWithNoPlan, Stwalczyk, Whoop whoop pull
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drewman327, Cdang, Giftlite, BenFrantzDale, Alexf, Deewiant, Thorsten1, Grm wnr, ChrisRuvolo, Vsmith, Bender235, Quietly, Art LaPella,
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ter, Pol098, Firien, Knuckles, Prashanthns, Susato, Paxsimius, Mandarax, NCdave, Jclemens, Nanite, Rjwilmsi, Matt Deres, ACrush, Gurch,
Chobot, YurikBot, Charles Gaudette, Akamad, Alex Bakharev, ArcticFlame, Grafen, Dhollm, Moe Epsilon, DeadEyeArrow, CWenger, Grin-
Bot~enwiki, That Guy, From That Show!, Luk, Yvwv, SmackBot, Slashme, Da2ce7, Eupedia, Gilliam, Reza1615, EndingPop, Mion, Harry-
boyles, ML5, Paladinwannabe2, Dan Gluck, Wizard191, Iridescent, Courcelles, Mcginnly, Ironmagma, Saintrain, Thijs!bot, Epbr123, Head-
bomb, Nick Number, Escarbot, Porqin, QuiteUnusual, RogueNinja, JAnDbot, Ibjt4ever, Jinxinzzi, Asplace, Bongwarrior, VoABot II, JamesB-
Watson, Christophe.Finot, Raggiante~enwiki, Cardamon, R'n'B, Zygimantus, Eybot~enwiki, J.delanoy, Trusilver, Dani setiawan, Mike.lifeguard,
Davidprior, Afluegel, Jcwf, TomasBat, In Transit, STBotD, Ojovan, AntoniusJ~enwiki, Squids and Chips, WOSlinker, Hqb, Leaf of Silver,
Claidheamohmor, Gerakibot, Yintan, Mothmolevna, Chromaticity, Masgatotkaca, Csloomis, OKBot, AllHailZeppelin, Kanonkas, ClueBot,
Sealsrock!, The Thing That Should Not Be, Ken l lee, Mild Bill Hiccup, Harland1, Largedizkool, Adrian dakota, DragonBot, Awickert, Cohe-
sionBot, PixelBot, Leonard^Bloom, P1415926535, La Pianista, Ammm3478, 1ForTheMoney, Ngebbett, David.Boettcher, Addbot, Xp54321,
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fession0791, AManWithNoPlan, Puffin, RockMagnetist, Teaktl17, ClueBot NG, Ronaldjo, Gareth Griffith-Jones, Satellizer, Ulrich67, Mmarre,
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Lektio, Prokaryotes, Ginsuloft, Stamptrader, JOb, VolpeCenter, Emaw61, Monkbot, Jkutil18, Mybalonyhasafirstname, Trackteur, R-joven,
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Chaos, Dhollm, Bota47, That Guy, From That Show!, SmackBot, Incnis Mrsi, Pavlovič, Bomac, Kmarinas86, MalafayaBot, Huwmanbeing,
Cybercobra, Drphilharmonic, Sadi Carnot, Eli84, Kareemjee, Ring0, LeBofSportif, Headbomb, JAnDbot, Magioladitis, Joshua Davis, Dorgan,
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Cydebot, Kupirijo, Llort, Christian75, Viridae, Tunheim, Chandni chn, Thijs!bot, Runch, Odyssey1989, Headbomb, John254, F l a n k e r,
Dawnseeker2000, Escarbot, The Obento Musubi, Teentje, Gioto, Seaphoto, Madbehemoth, Ani td, JAnDbot, Hans Mayer, MER-C, Larry-
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252 CHAPTER 12. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

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Trueman, Rbingama, TXiKiBoT, Malinaccier, Comtraya, Rexeken, LanceBarber, Hanjabba, Riick, Brianga, Hoopssheaffer, Givegains, SieBot,
Flyer22 Reborn, Baxter9, Oxymoron83, Smaug123, 123ilikecheese, Lightmouse, JerroldPease-Atlanta, Nskillen, COBot, Adamtester, Thom-
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RP459, QuantumGlow, Dj-dios-del-sol, SkyLined, Dnvrfantj, Addbot, Power.corrupts, LaaknorBot, Eelpop, CarsracBot, LinkFA-Bot, Light-
bot, Loupeter, Legobot, Yobot, Ptbotgourou, Daniele Pugliesi, JackieBot, Materialscientist, Nickkid5, Quark1005, Craftyminion, GrouchoBot,
ChristopherKingChemist, RibotBOT, ‫قلی زادگان‬, Dougofborg, Kamran28, Khakiandmauve, StephenWade, EntropyTrap, Lambda(T), Hap-
pydude69 yo, Mrahner, Michael93555, D'ohBot, RWG00, Zmcdargh, Citation bot 1, Kishmakov, I dream of horses, RedBot, Pbsouthwood,
Cramyourspam, Orenburg1, Geraldo62, Diblidabliduu, Jade Harley, RjwilmsiBot, MagnInd, Steve Belkins, EmausBot, Tdindorf, Razor2988,
RA0808, Jerry858, Dcirovic, Ssp37097, JSquish, ZéroBot, Susfele, MarkclX, Stovl, SporkBot, YnnusOiramo, Donner60, Odysseus1479, The-
islikerice, RockMagnetist, George Makepeace, ClueBot NG, BubblyWantedXx, Helloimriley, Wrecker1431, Rezabot, Widr, Bibcode Bot, Mar-
iansavu, MusikAnimal, AvocatoBot, Mark Arsten, Trevayne08, F=q(E+v^B), Klilidiplomus, TechNickL1, Egm4313.s12, NJIT HUMrudyh,
NJIT HUMNV, Waterproof-breathable, AlanParkerFrance, Dexbot, Epicgenius, I am One of Many, Blackbombchu, Zenibus, JustBerry, Gin-
suloft, Keojukwu, DudeWithAFeud, Whizzy1999, Fuguangwei, Evanrelf, Monkbot, Nojedi, Trackteur, ChaquiraM, Smanojprabhakar, Ériu-
gena, CAPTAIN RAJU, Pwags3147, The Master 6969, Qzd, KapteynCook and Anonymous: 400
• Fundamental thermodynamic relation Source: https://en.wikipedia.org/wiki/Fundamental_thermodynamic_relation?oldid=704331825 Con-
tributors: PAR, Batmanand, Count Iblis, John Baez, Dhollm, Katieh5584, SmackBot, Betacommand, Sadi Carnot, Dicklyon, Robomojo,
Ahjulsta, Towerman86, Gogobera, BertSen, Kbrose, SieBot, ClueBot, CohesionBot, Addbot, Tnowotny, PV=nRT, LucienBOT, KHamsun,
Netheril96, ZéroBot, Makecat, BG19bot, Liquidityinsta, Mela widiawati, Klaus Schmidt-Rohr and Anonymous: 23
• Heat engine Source: https://en.wikipedia.org/wiki/Heat_engine?oldid=716542100 Contributors: Mav, The Anome, Stokerm, Mirwin, Roadrun-
ner, Jdpipe, Heron, Icarus~enwiki, Isis~enwiki, Ram-Man, Ubiquity, Kku, Delirium, Ronz, CatherineMunro, Glenn, GCarty, Charles Matthews,
Tantalate, Far neil, Greenrd, Omegatron, Lumos3, Phil Boswell, Robbot, Academic Challenger, Cyrius, Cutler, Buster2058, Ancheta Wis,
Mat-C, Wolfkeeper, Tom harrison, Mcapdevila, Pashute, PlatinumX, LiDaobing, Karol Langner, Oneiros, NathanHurst, Rich Farmbrough,
Vsmith, Liberatus, Femto, Rbj, Jwonder, Jung dalglish, Giraffedata, Nk, Exomnium, Alansohn, PAR, Gene Nygaard, Oleg Alexandrov, Garyl-
hewitt, Fingers-of-Pyrex, Peter Beard, WadeSimMiser, Rtdrury, Rjwilmsi, Lionelbrits, Maustrauser, Fresheneesz, Lmatt, Scimitar, Chobot,
DVdm, Triku~enwiki, Siddhant, YurikBot, Wavelength, Borgx, JabberWok, Gaius Cornelius, Wimt, Anomalocaris, Eb Oesch, Dhollm, Scs,
Tony1, Bota47, Nikkimaria, Lio , Back ache, A Doon, ArielGold, RG2, Eric Norby, GrinBot~enwiki, SkerHawx, SmackBot, Gilliam, Blue-
bot, Exprexxo, Complexica, Mbertsch, SundarBot, Bob Castle, Sadi Carnot, Adsllc, Loodog, Beetstra, Stikonas, Dodo bird, Mfield, Hu12,
MFago, GDallimore, IanOfNorwich, Mikiemike, BFD1, CuriousEric, Dwolsten, Chris23~enwiki, Cydebot, Odie5533, Michael C Price, Dumb-
BOT, RottweilerCS, Efranco~enwiki, Ϙ, Gralo, Headbomb, Paquitotrek, Strongriley, Northumbrian, EdJogg, TimVickers, Aspensti, JAnDbot,
Andrew Swallow, Mauk2, VoABot II, Rich257, JMBryant, Catgut, Animum, Allstarecho, Jtir, Rettetast, Tom Gundtofte-Bruun, Fredrosse,
Nono64, FactsAndFigures, Ignacio Icke, Lbeaumont, Andejons, STBotD, WarFox, Engware, Lseixas, Funandtrvl, VolkovBot, Larryisgood,
TXiKiBoT, NPrice, LeaveSleaves, Abjkf, Senpai71, Why Not A Duck, SieBot, Gerakibot, Viskonsas, Flyer22 Reborn, Oxymoron83, Ani-
magi1981, YinZhang, Robvanbasten, Dolphin51, Martarius, ClueBot, Toy 121, Arunsingh16, AdrianAbel, Thingg, Vilkapi, YouRang?, Gonfer,
Kbdankbot, Klundarr, Addbot, LaaknorBot, CarsracBot, Vyom25, Tide rolls, Lightbot, ‫ماني‬, Loupeter, Megaman en m, Legobot, Luckas-bot,
Yobot, Pentajism, Typenolies, AnomieBOT, Daniele Pugliesi, Jim1138, Piano non troppo, Theseeker4, Bluerasberry, Citation bot, LovesMacs,
Jeriee, In fact, Shadowjams, GliderMaven, Thayts, ‫محمد طاهر عيسى‬, Steve Quinn, HamburgerRadio, Lotje, Antipastor, Jfmantis, Orphan
Wiki, Sheeana, Hhhippo, ZéroBot, DavidMCEddy, Matt tuke, Wagino 20100516, Yerocus, Peterh5322, Teapeat, Rememberway, ClueBot
NG, Anagogist, Loopy48, Teep111, Widr, Calabe1992, Bibcode Bot, Lowercase sigmabot, BG19bot, MusikAnimal, Zedshort, O8h7w, Batty-
Bot, Bangjiwoo, TooComplicated, Prokaryotes, Monkbot, Tashi19, IvanZhilin, KasparBot, Valaratar, Klaus Schmidt-Rohr, Azamali1947 and
Anonymous: 205
• Thermodynamic cycle Source: https://en.wikipedia.org/wiki/Thermodynamic_cycle?oldid=687246415 Contributors: Glenn, Robbot, Wolf-
keeper, Dratman, H Padleckas, CDN99, Kjkolb, Gene Nygaard, Palica, Ttjoseph, Siddhant, YurikBot, Borgx, Dhollm, Troodon~enwiki, Cov-
12.2. IMAGES 253

ington, KnightRider~enwiki, SmackBot, Gilliam, Bluebot, Tsca.bot, Ryan Roos, DMacks, Mion, Sadi Carnot, UberCryxic, Mbeychok, EmreDu-
ran, Mig8tr, Ring0, Teratornis, Zanhsieh, Thijs!bot, Headbomb, MSBOT, JamesBWatson, Akhil999in, Jtir, MartinBot, Sigmundg, Felipebm,
Andy Dingley, Kropotkine 113, Treekids, Ariadacapo, Turbojet, Sylvain.quoilin, Erodium, Cerireid, Skarebo, Addbot, CarsracBot, Yobot,
AnomieBOT, Shadowjams, Samwb123, I dream of horses, Bluefist, AXRL, EmausBot, WikitanvirBot, Frostbite sailor, Allforrous, Donner60,
ChuispastonBot, ClueBot NG, Incompetence, Guy vandegrift, Zedshort, APerson, Anushrut93, Faizan, Scie8, Hjd28 and Anonymous: 45

12.2 Images
• File:13-07-23-kienbaum-unterdruckkammer-33.jpg Source: https://upload.wikimedia.org/wikipedia/commons/e/eb/
13-07-23-kienbaum-unterdruckkammer-33.jpg License: CC BY 3.0 Contributors: Own work Original artist: Ralf Roletschek
• File:1D_normal_modes_(280_kB).gif Source: https://upload.wikimedia.org/wikipedia/commons/9/9b/1D_normal_modes_%28280_kB%
29.gif License: CC-BY-SA-3.0 Contributors: This is a compressed version of the Image:1D normal modes.gif phonon animation on Wikipedia
Commons that was originally created by Régis Lachaume and freely licensed. The original was 6,039,343 bytes and required long-duration
downloads for any article which included it. This version is 4.7% the size of the original and loads much faster. This version also has an inter-
frame delay of 40 ms (v.s. the original’s 100 ms). Including processing time for each frame, this version runs at a frame rate of about 20–22.5
Hz on a typical computer, which yields a more fluid motion. Greg L 00:41, 4 October 2006 (UTC). (from http://en.wikipedia.org/wiki/Image:
1D_normal_modes_%28280_kB%29.gif) Original artist: Original Uploader was Greg L (talk) at 00:41, 4 October 2006.
• File:Adiabatic.svg Source: https://upload.wikimedia.org/wikipedia/commons/4/49/Adiabatic.svg License: CC-BY-SA-3.0 Contributors:
Image:Adiabatic.png Original artist: User:Stannered
• File:Aluminium_cylinder.jpg Source: https://upload.wikimedia.org/wikipedia/commons/8/8a/Aluminium_cylinder.jpg License: CC BY-SA
3.0 Contributors: Own work Original artist:
• File:Ambox_important.svg Source: https://upload.wikimedia.org/wikipedia/commons/b/b4/Ambox_important.svg License: Public domain
Contributors: Own work, based off of Image:Ambox scales.svg Original artist: Dsmurat (talk · contribs)
• File:Anders_Celsius.jpg Source: https://upload.wikimedia.org/wikipedia/commons/9/9f/Anders_Celsius.jpg License: Public domain Contrib-
utors: This is a cleaned up version of what appears at The Uppsala Astronomical Observatory, which is part of Uppsala University. The full-size
original image of the painting appears here, which can be accessed via this history page at the observatory’s Web site.
Original artist: Olof Arenius
• File:Barometer_mercury_column_hg.jpg Source: https://upload.wikimedia.org/wikipedia/commons/b/b9/Barometer_mercury_column_hg.
jpg License: CC BY-SA 2.5 Contributors: Own work Original artist: Hannes Grobe 19:02, 3 September 2006 (UTC)
• File:Benjamin_Thompson.jpg Source: https://upload.wikimedia.org/wikipedia/commons/3/3c/Benjamin_Thompson.jpg License: Public do-
main Contributors:
http://www.sil.si.edu/imagegalaxy/imagegalaxy_imageDetail.cfm?id_image=3087
http://www.sil.si.edu/digitalcollections/hst/scientific-identity/CF/by_name_display_results.cfm?scientist=Rumford,%20Benjamin%
20Thompson,%20Count

Original artist: Not specified[1][2]

• File:Boltzmann2.jpg Source: https://upload.wikimedia.org/wikipedia/commons/a/ad/Boltzmann2.jpg License: Public domain Con-
tributors: Uni Frankfurt Original artist: Unknown<a href='//www.wikidata.org/wiki/Q4233718' title='wikidata:Q4233718'><img
alt='wikidata:Q4233718' src='https://upload.wikimedia.org/wikipedia/commons/thumb/f/ff/Wikidata-logo.svg/20px-Wikidata-logo.svg.png'
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• File:Brayton_cycle.svg Source: https://upload.wikimedia.org/wikipedia/commons/3/3c/Brayton_cycle.svg License: CC-BY-SA-3.0 Contribu-
tors: ? Original artist: ?
• File:Can_T=0_be_reached.jpg Source: https://upload.wikimedia.org/wikipedia/en/c/c7/Can_T%3D0_be_reached.jpg License: CC-BY-SA-
3.0 Contributors:
Made by SliteWrite
Original artist:
Adwaele
• File:Carl_von_Linné.jpg Source: https://upload.wikimedia.org/wikipedia/commons/6/68/Carl_von_Linn%C3%A9.jpg License: Public do-
main Contributors: Nationalmuseum press photo, cropped with colors slightly adjusted Original artist: Alexander Roslin
• File:Carnot2.jpg Source: https://upload.wikimedia.org/wikipedia/commons/e/ec/Carnot2.jpg License: Public domain Contributors: ? Original
artist: ?
• File:Carnot_engine_(hot_body_-_working_body_-_cold_body).jpg Source: https://upload.wikimedia.org/wikipedia/commons/c/c7/
Carnot_engine_%28hot_body_-_working_body_-_cold_body%29.jpg License: Public domain Contributors: Own work (Original text: I (Libb
Thims (talk)) created this work entirely by myself.) Original artist: Libb Thims (talk)
• File:Carnot_heat_engine_2.svg Source: https://upload.wikimedia.org/wikipedia/commons/2/22/Carnot_heat_engine_2.svg License: Public
domain Contributors: Based upon Image:Carnot-engine.png Original artist: Eric Gaba (Sting - fr:Sting)
254 CHAPTER 12. TEXT AND IMAGE SOURCES, CONTRIBUTORS, AND LICENSES

• File:Clausius-1.jpg Source: https://upload.wikimedia.org/wikipedia/commons/3/34/Clausius-1.jpg License: Public domain Contributors:

unknown Original artist: Unknown<a href='//www.wikidata.org/wiki/Q4233718' title='wikidata:Q4233718'><img alt='wikidata:Q4233718'
src='https://upload.wikimedia.org/wikipedia/commons/thumb/f/ff/Wikidata-logo.svg/20px-Wikidata-logo.svg.png' width='20'
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• File:Clausius.jpg Source: https://upload.wikimedia.org/wikipedia/commons/4/40/Clausius.jpg License: Public domain Contributors: http://
www-history.mcs.st-andrews.ac.uk/history/Posters2/Clausius.html Original artist: Original uploader was user:Sadi Carnot at en.wikipedia
• File:Close-packed_spheres.jpg Source: https://upload.wikimedia.org/wikipedia/commons/8/8e/Close-packed_spheres.jpg License: CC-BY-
SA-3.0 Contributors: English Wikipedia Original artist: User:Greg L
• File:Coefficient_dilatation_lineique_aciers.svg Source: https://upload.wikimedia.org/wikipedia/commons/b/b2/Coefficient_dilatation_
lineique_aciers.svg License: CC0 Contributors: Own work, data from OTUA Original artist: Cdang
• File:Coefficient_dilatation_volumique_isobare_PP_semicristallin_Tait.svg Source: https://upload.wikimedia.org/wikipedia/commons/6/
6e/Coefficient_dilatation_volumique_isobare_PP_semicristallin_Tait.svg License: CC BY-SA 3.0 Contributors: Own work Original artist:
Cdang
• File:Commons-logo.svg Source: https://upload.wikimedia.org/wikipedia/en/4/4a/Commons-logo.svg License: CC-BY-SA-3.0 Contributors: ?
Original artist: ?
• File:Crystal_energy.svg Source: https://upload.wikimedia.org/wikipedia/commons/1/14/Crystal_energy.svg License: LGPL Contributors:
Own work conversion of Image:Crystal_128_energy.png Original artist: Dhatfield
• File:DebyeVSEinstein.jpg Source: https://upload.wikimedia.org/wikipedia/commons/5/54/DebyeVSEinstein.jpg License: Public domain
Contributors: ? Original artist: ?
• File:Dehnungsfuge.jpg Source: https://upload.wikimedia.org/wikipedia/commons/d/d6/Dehnungsfuge.jpg License: CC-BY-SA-3.0 Contrib-
utors: ? Original artist: ?
• File:Deriving_Kelvin_Statement_from_Clausius_Statement.svg Source: https://upload.wikimedia.org/wikipedia/commons/8/83/
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• File:DiatomicSpecHeat1.png Source: https://upload.wikimedia.org/wikipedia/commons/0/07/DiatomicSpecHeat1.png License: Public do-
main Contributors: Own work Original artist: User:PAR
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main Contributors: Own work Original artist: User:PAR
• File:Drikkeglas_med_brud-1.JPG Source: https://upload.wikimedia.org/wikipedia/commons/e/eb/Drikkeglas_med_brud-1.JPG License:
CC BY-SA 3.0 Contributors: Own work Original artist: Arc1977
• File:Edit-clear.svg Source: https://upload.wikimedia.org/wikipedia/en/f/f2/Edit-clear.svg License: Public domain Contributors: The Tango!
Desktop Project. Original artist:
The people from the Tango! project. And according to the meta-data in the file, specifically: “Andreas Nilsson, and Jakub Steiner (although
minimally).”
• File:Eight_founding_schools.png Source: https://upload.wikimedia.org/wikipedia/commons/8/85/Eight_founding_schools.png License:
Public domain Contributors: Own work Original artist: Libb Thims
• File:Energy_thru_phase_changes.png Source: https://upload.wikimedia.org/wikipedia/en/1/18/Energy_thru_phase_changes.png License:
Cc-by-sa-3.0 Contributors: ? Original artist: ?
• File:Entropyandtemp.PNG Source: https://upload.wikimedia.org/wikipedia/commons/9/91/Entropyandtemp.PNG License: CC-BY-SA-3.0
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• File:First_law_open_system.svg Source: https://upload.wikimedia.org/wikipedia/commons/8/86/First_law_open_system.svg License: Public
domain Contributors:
• First_law_open_system.png Original artist:
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Contributors: ? Original artist: ?
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from en.wikipedia to Commons by Sreejithk2000 using CommonsHelper. Original artist: Engware at English Wikipedia
• File:Gaylussac.jpg Source: https://upload.wikimedia.org/wikipedia/commons/2/2f/Gaylussac.jpg License: Public domain Contributors:
chemistryland.com Original artist: François Séraphin Delpech
• File:Green_check.svg Source: https://upload.wikimedia.org/wikipedia/commons/0/03/Green_check.svg License: Public domain Contributors:
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12.2. IMAGES 255

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domain Contributors: circa 1870: French physicist Guillaume Amontons (1663 - 1705) demonstrates the semaphore in the Luxembourg Gar-
dens, Paris in 1690. Original Publication: From an illustration published in Paris circa 1870. Close-up approximating bust. Original artist: Un-
known<a href='//www.wikidata.org/wiki/Q4233718' title='wikidata:Q4233718'><img alt='wikidata:Q4233718' src='https://upload.wikimedia.
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tographs division under the digital ID ppmsca.02185.
This tag does not indicate the copyright status of the attached work. A normal copyright tag is still required. See Commons:Licensing for more information.
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