CH 201 - CHEMICAL ENGINEERING THERMODYNAMICS PREAMBLE

Chemical Engineering Thermodynamics is primarily concerned with the application of thermodynamics to phase equilibria and reaction equilibria in multicomponent systems. Of secondary importance in this context is the application of Thermodynamics to heat-to-work and work-to-heat conversion devices. These applications are studied in greater detail by Mechanical Engineers. Chemical engineers are however seriously

concerned with the calculation of work in separation and in mixing processes. Phase and reaction equilibria involving two or more solid phases are of primary interest to metallurgists.

Thermodynamics plays a supervisory and often intangible role in engineering. Its applications are obvious in the design of Chemical engineering equipment in processes in which approach to equilibrium is nearly one hundred percent in practice. Even in those cases where the processes are governed by rate considerations, thermodynamics sets the boundaries of design. It is also of fundamental importance so far as the theory of rate processes is concerned in the sense that rate processes are often treated as departures from equilibrium. The mathematical abilities required for applying thermodynamics to practical problems are generally of second year undergraduate level.

Classical thermodynamics is generally taught without reference to molecular structure of matter. The incorporation of concepts from molecular theory is indeed of great help in clarifying some of the concepts in classical thermodynamics. However the quantitative use of molecular theory is a skill that can be acquired only after considerable concerted effort on the part of the student. It is therefore impractical to try to include molecular theory for use as a quantitative tool as part of an undergraduate classical thermodynamics.

TOPICS

I. BASIC CONCEPTS :

The first law and conservation of energy, the second law,

application to engineering problems relating to equilibrium and extrema in work. II. PROPERTIES OF PURE SUBSTANCES: Changes in thermodynamic properties and their inter-relationships. Fugacities and fagacity coefficients. III. PROPERTIES OF MIXTURES: Partial molal properties. Mathematical models for the chemical potential. Ideal and nonideal solutions. Activity and activity coefficients. The Gibbs Duhem Equation. Excess properties of mixtures. IV. PHASE EQUILIBRIA: Criteria for equilibrium between different phases in multicomponent non-reacting systems. Application to systems of engineering interest, particularly to vapour-liquid equilibria and solubility. V. REACTION EQUILIBRIA: The equilibrium constant and the variation of yield in chemical reactions with pressure, temperature and composition.

TEXT BOOKS I Smith, JM.,Van Ness, HC., &. Abbott, MM, Introduction to Chemical Engineering Thermodynamics, 6th Edition, McGraw Hill (2001) - a comprehensive book. II Denbigh, K., The Principles of Chemical Equilibria with Applications in Chemistry and Chemical Engineering, Cambridge University Press (1968) - has the best exposition of concepts, has no explicit treatment of open systems. REFERENCES III Prausnitz,J.M., Lichtenthaler,R.N.& Azevedo,E.G.,MolecularThermodynamics of Fluid-phase Equilibria, Ed. 2. Prentice Hall (1986) - a mixture of classical thermodynamics with molecular theory. Some of the chapters are written in a refreshing style and can be used to advantage in a classical thermodynamics course. Material in chs. 1,2,3,5,6,8,9 and 10 is of interest to UG students. IV Walas, S.M., Phase Equilibria in Chemical Engineering, Butterworths (1985) good as a reference, student can miss the woods for the trees. V Sandler, H.P., 'Chemical Engineering Thermodynamics', Prentice-Hall (1988) current and reasonably comprehensive

This table gives the pages numbers in the text books (I, II and III) which are relevant to the material covered in the class. Page numbers have been provided according to both Third and Sixth editions of Smith and Van ness. The italicized page numbers correspond to the other books.

Topic

Lect # Scope and results

Title expected in Chemical

Page #'s in Edition 3

Page #'s in Edition 6

1 2 3,4

engineering Review of elementary concepts, the first law The second law, extrema in work Criteria of thermodynamic equilibrium, the free

1 -- 15 20-22 II: 63-84

1--15 20-44 155-181

17

energy

290-93, II: 43 - 48

217-220, 195-198

5,6 7 8,9

Thermodynamic properties, thermodynamic charts The thermodynamics of ideal gas P-V-T behaviour of real gases; equations of state

168-92 66-79 5765,80 94

195-220 71-87 62-71, 87-100

Internal combustion engines : Otto and Diesel C 10 11 27,28 29 cycles Vapour compression cycle Enthalpies of solution, Absorption refrigeration Heat pumps and liquefaction processes 497-502 513-29 530-34 535-41 295-299 309-313 313-318 318-329

12 13 14 15 16,17 17,18 19,20 21,22

Thermodynamic properties of mixtures Partial molal properties, Integration of the basic equations Excess properties of mixtures, T & P dependence Gibbs-Duhem equations: composition dependence Ideal gaseous mixtures, real gases,fugacities Ideal and nonideal solutions, activity coefficients Theories of solution

213-15 216-17 II:92- 94,103-04 II: 99-103 221-23, II:215-43 227-39,II:270-78 245-69, II:244-91 III: 415-32

368-371 371-374,380-381

402-409 373-376 381-386 386-397,400-402

21

Criteria for equilibrium between different phases Vapour liquid equilibrium: completely miscible

219-94

370-371

22 23

liquids Thermodynamic consistency

296-344 345-56

329-367,538-554 427-431

25 24 26 F 35 36

Ideal solubility Partially miscible systems Change in freezing and boiling points, osmosis Stoichiometry, representation of reactions Criterion for chemical reaction equilibrium Homogeneous reaction equilibrium involving

II: 264-67 357-64, III: 415-32 II: 257-64 376-83, II: 133-38 383-89 560-576 600-603 467-472 472-475

37 38 39 40 41 G 42 43

gases Heterogeneous equilibria The equilibrium constant Homogeneous liquid phase reactions Multireaction equilibria Systems of Current Interest: Biological systems Chemical vapour deposition

398-400,II: 140-55 II: 56-63 389-98 400-11 419-28

482-483 494-502 473-483 483-486 502-513

NA NA

NA NA