Thermodynamics of

Materials

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 Termodinamika Material (3 SKS)
Program Studi Teknik Metalurgi dan Material

Text Book
David R. Gaskell, Introduction to The Thermodynamics of Materials,
Fourth Edition, Taylor & Francis Books, Inc. 2003.
G.S. Upadhyaya, Metallurgical Thermodynamics and Kinetics
Boris S. Bokstein,. Mikhail I. Mendelev, and David J. Srolovitz,
Thermodynamics and Kinetics in Materials Science.

Komponen Penilaian
1. Kuis dan Tugas (20 %)
2. Ujian Tengah Semester (30 %)
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 What is thermodynamics?
Thermodynamics is the branch of science that deals with the heat and the temperature and their relations with
energy and work and the conversions of one into the other.
Thermodynamics can be beroken down into two subjects with different approach:
1. Classical Thermodynamics : Focuses on the thermal behavior of macroscopic systems and phenomenological
nature of the systems and discuss properties (Pressure, Temperature, Volume) and their relationships.
2. Statistical Thermodynamics : Focuses on the microsopic properties of the system in the form of statistical
average of atomic scale behavior.

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 For materials science and engineering, thermodynamics can be used to:
1. Understand how the properties of materials are affected by the thermodynamic
processes (processes that involve changes in the energy of materials).
2. To control properties through its determination of materials structure.

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 BASIC DEFINITIONS IN THERMODYNAMICS
A system is an ensemble (collection) of bodies that can
either be extracted from its surroundings.
A system is called to as isolated if it neither exchanges
energy nor matter with its surroundings and its volume is
constant.
A system which does not exchange matter with its
surroundings is called as closed system; otherwise it is
called as open system.

The state of a system is determined by a set of system parameters such as:

volume V,
temperature T,
pressure p,
and concentration of each of its components Ci.
So, the State function is a function that depend on the system parameters. 6
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 Properties
Quantities which can be used to describe a system, e.g. density, volume,
(1) Intensive properties
not additive, independent of size or mass of the system. e.g. temperature, pressure,
density,
(2) Extensive properties
additive, dependent of the size of the system. e.g. volume, no. of moles,
extensive/extensive = intensive
e.g. density = mass/volume, pressure = force/area.

State
Microscopic state: If it is possible to know the masses, velocities, positions, and all modes of
all of the constituent particles in a system, this mass of knowledge would serve to describe
the state of the system, which would determine all of the properties of the system.

Macroscopic state: A specific condition of a system, which is completely and precisely

described through its properties.

Generally, only the minimum number of properties necessary to completely describe the
state 14
 State Function (State Variable)
A variable which depends only on the state of the system. If a change in the system
occurs, the change in such a function depends only on the initial and final state, and is
independent of the path of the change. e.g. T, V, P, U, H, S, G.

Equation of State
A mathematical relationship between the state functions.
Example: Consider the volume V of a fixed quantity of a pure gas as a property, the value
of which is dependent on the values of P and T. The relationship between the dependent
variable V and the independent variables P and T can be expressed as
V = V(P,T)
This is called an equation of state. 15
 In a three-dimensional diagram, the coordinates of which are volume, temperature, and pressure, the points in
P-V-T space which represent the equilibrium states of existence of the system lie on a surface.

Figure 1.1 The Equilibrium States of existence

of a Fixed Quantity of gas in P-V-T space.

Fixing the values of any two of the three variables fixes the value of the third variable. Consider a process which
moves the gas from state 1 to state 2. This process causes the volume of the gas to change by
V = V2 V1
This process could proceed along an infinite number of paths on the P-V-T surface, two of which, 1a2 and
1b2, are shown in Fig. 1.1.
Considering the path 1a2, the change in volume is T2 V P2 V

V = V2 V1 = (Va V1) + (V2 Va) = T1 T P1

( ) dT P1 ( P )T2 dP
Similarly for the path 1b2, P2 V T 2 V
V = (Vb V1) + (V2 Vb) = P ( ) dP T ( ) P2 dT
P T
T1
1 1

The change in volume caused by moving the state of the gas from state 1 to state 2 depends only on the volume at state
1 and the volume at state 2 and is independent of the path.
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 Equilibrium
A system shows no further tendency to change its properties with time.
(1) Stable equilibrium
(2) Meta-stable equilibrium

Phase
A phase is defined as being a finite volume in the physical system within which
the properties are uniformly constant. i.e. It does not experience any abrupt
change in passing from one point to another.

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A particularly simple system is illustrated in Fig. 1.2. This is a fixed quantity of gas contained in a
cylinder by a movable piston. The system is at rest, i.e. is at equilibrium, when:
1. The pressure exerted by the gas on the piston equals the pressure exerted by the piston on the gas,
and
2. The temperature of the gas is the same as the temperature of the surroundings (provided that
heat can be transported through the wall). W

Figure 1.2 A quantity of gas contained in a

cylinder by a piston.

Gas
Equilibrium occurs as a result of the establishment of a balance between the tendency
of the external influences acting on the system to cause a change in the system and the
tendency of the system to resist change.
The fixing of the pressure of the gas at P1 and the temperature T1 determines the state
of the system and hence fixes the volume at the value V1. If, by suitable decrease in
the weight placed on the piston, the pressure exerted on the gas is decreased to P2, the
resulting imbalance between the pressure exerted by the gas and the pressure exerted
on the gas causes the piston to move out of the cylinder. This process increases the
volume of the gas and hence decreases the pressure which it exerts on the piston until
equalization of the pressure is restored.
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 Phase Diagrams and Thermodynamic Components

The phase diagram of a one-component system (i.e. a system of fixed

composition) is a two-dimensional representation of the dependence
of the equilibrium state of existence of the system on the two
independent variables.
T and P are normally chosen as the two independent variables. Fig.
1.4 shows a schematic of part of the phase diagram for H2O.

Figure 1.4 Schematic representation of part

If the system contains two components, a composition axis of the phase diagram for H2O.
must be included and the complete diagram is three-
dimensional with the coordinates composition,
temperature, and pressure.
In most cases, however, it is sufficient to present a binary
phase diagram as a constant pressure section of the three-
dimensional diagram.
The constant pressure chosen is normally 1 atm. Figure 1.5
shows the phase relationships occurring in the system
Al2O3-Cr2O3 at 1 atm pressure.
Figure 1.5 The phase diagram for the
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system Al2O3-Cr2O3.
ZEROTH LAW OF THERMODYNAMICS
The Zeroth Law of Thermodynamics states that if two bodies, a and b, are each in thermal equilibrium
with a third body, c, then they are in thermal equilibrium with each other.

Hotness Temperature

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Introduction
Internal Energy
The internal energy of a system of particles, U, is the sum of the kinetic energy in the reference frame in
which the center of mass is at rest and the potential energy arising from the forces of the particles on each
other.

system Difference between the total energy and the internal energy?
boundary system
U = kinetic + potential
environment
The internal energy is a state function it depends only on the values
of macroparameters (the state of a system), not on the method of
preparation of this state (the path in the macroparameter space is
irrelevant).

In equilibrium [ f (P,V,T)=0 ] : U = U (V, T)

U depends on the kinetic energy of particles in a system and an average
inter-particle distance (~ V-1/3) interactions.
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For an ideal gas (no interactions) : U = U (T) - pure kinetic
Introduction
Internal Energy of an Ideal Gas

The internal energy of an ideal f

gas with f degrees of freedom: U NkBT
2
f 3 (monatomic), 5 (diatomic), 6 (polyatomic)

(here we consider only trans.+rotat. degrees of freedom, and neglect

the vibrational ones that can be excited at very high temperatures)

How does the internal energy of air in this (not-air-tight) room change with T if the
external P = const?

f PV f
U N in roomk BT N in room PV
2 k BT 2

- does not change at all, an increase of the kinetic energy of individual

molecules with T is compensated by a decrease of their number.
Introduction
Work and Heating (Heat)

We are often interested in U , not U. U is due to:

Q - energy flow between a system and its
WORK
environment due to T across a boundary and a finite
thermal conductivity of the boundary
heating (Q > 0) /cooling (Q < 0)
(there is no such physical quantity as heat; to HEATING
emphasize this fact, it is better to use the term
heating rather than heat)
W - any other kind of energy transfer across
boundary - work

Work and Heating are both defined to describe energy transfer

across a system boundary.
Heating/cooling processes:
conduction: the energy transfer by molecular contact fast-moving
molecules transfer energy to slow-moving molecules by collisions;
convection: by macroscopic motion of gas or liquid
radiation: by emission/absorption of electromagnetic radiation.
 Introduction
Work
The work done by an external force on a gas enclosed within a cylinder
A the fitted with a piston:
piston
area W = (PA) dx = P (Adx) = - PdV
force

The sign: if the volume is decreased, W is positive (by compressing gas, we

x
increase its internal energy); if the volume is increased, W is negative (the gas
decreases its internal energy by doing some work on the environment).

P
V2
W1-2 - P(T ,V )dV
V1
W = - PdV - applies to any
shape of system boundary dU = Q PdV

The work is not necessarily associated with the volume changes e.g., in the Joules experiments on
determining the mechanical equivalent of heat, the system (water) was heated by stirring. 24
Introduction
W and Q are not State Functions
V2 - we can bring the system from state 1 to
W1-2 - P(T ,V )dV state 2 along infinite # of paths, and for each
V1
path P(T,V) will be different.
P 2
Since the work done on a system depends not
only on the initial and final states, but also on the
1 V intermediate states, it is not a state function.
T

U = Q + W U is a state function, W - is not

thus, Q is not a state function either.
P

P2
A B Wnet WAB WCD - P2 V2 - V1 - P1 V1 - V2
-P2 - P1 V2 - V1 0
P1 D C
- the work is negative for the clockwise cycle; if
the cyclic process were carried out in the reverse
V1 V2 V order (counterclockwise), the net work done on
the gas would be positive.
PV diagram
Introduction Comment on State Functions
U, P, T, and V are the state functions, Q and W are not. Specifying an initial and final states of a
system does not fix the values of Q and W, we need to know the whole process (the intermediate
states). Analogy: in classical mechanics, if a force is not conservative (e.g., friction), the initial and
final positions do not determine the work, the entire path must be specified.
In math terms, Q and W are not exact differentials of some functions
of macroparameters. To emphasize that W and Q are NOT the state U
functions, we will use sometimes the curled symbols (instead of d)
for their increments (Q and W).
V
d U T d S - P dV - an exact differential S

y z(x1,y1) dz Ax x, y dx Ay x, y dy - it is an exact differential if it is

the difference between the values of some (state) function
z(x2,y2)
z(x,y) at these points: dz z x dx, y dy - z x, y
x Ax x, y Ay x, y
A necessary and sufficient condition for this:
y x
z x, y z x, y z z
Ax x, y Ay x, y
If this condition
d z dx dy
holds: x y x y y x
f T
e.g., for an ideal gas: Q dU PdV NkB dT dV - cross derivatives
2 V are not equal
Introduction
Quasi-Static Processes
Quasi-static (quasi-equilibrium) processes sufficiently slow processes, any
intermediate state can be considered as an equilibrium state (the macroparamers are
well-defined for all intermediate states).

Advantage: the state of a system that participates in a quasi-equilibrium process can be described with the
same (small) number of macro parameters as for a system in equilibrium (e.g., for an ideal gas in quasi-
equilibrium processes, this could be T and P). By contrast, for non-equilibrium processes (e.g. turbulent
flow of gas), we need a huge number of macro parameters.

Examples of quasi- For quasi-equilibrium processes, P, V, T are

equilibrium processes: well-defined the path between two states
is a continuous lines in the P, V, T space.
isochoric: V = const P 2
isobaric: P = const
isothermal: T = const
1 V
adiabatic: Q=0 T 27
The First Law of Thermodynamics
How a system participates in a thermodynamic processes is characterized by two
quantities: work W, and heat Q.
Sign convention in
Assume that we want to expand a system thermodynamics:
Work done by the system
Then, the work of expansion associated with
is (+), work done on the
an infinitesimal process that changes the system is (-) and the heat
volume is given by supplied to the system is
(+).

For a finite change in volume, the work of expansion is

However, work depends on

the path so W is not a state
function.
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 The First Law of Thermodynamics
The first law of thermodynamics states that
Energy can neither be create nor destroyed in a system of constant mass, although it may be
converted from one form to another.
In other words, the first law postulates that for any system there is a state function, U,
called the internal energy, which increases by a quantity equal to the heat added to
the system and decreases by the work done by the system.

This equation can be rearranged as

This implies that all heat added to the system is either used by the system to perform
work or to increase the internal energy of the system.
The full differential equation for the first law can be written as

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1. Example: CH4(g) + 2O2(g) CO2(g) + 2H2O + energy
a) Reaction gives off energy as heat
b) Potential energy stored in chemical bonds is lowered
c) Total energy is unchanged

2. Uses and Shortcomings

a) Lets us keep track of energy flow in processes
b) Does not tell us if or why a given process occurs
c) Does not tell us direction of a chemical reaction

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Implications of the first law of thermodynamics
Isochoric processes : is a process that does not change the Volume of the system.
In this processes, the work done is equal to zero and all heat entering the system
is used to change the internal energy

In this case we can define heat capacity as

or

The heat capacity per mole is called the molar heat capacity and the heat capacity
per gram is called the specific heat capacity.
Since the U is a state function, so heat capacity too. The change in U associated with
any isochoric process to the heat capacity can be written as

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 Isobaric processes : is a process that leaves pressure unchanged.
In this case

H is the enthalpi of the system state function

The isobaric heat capacity is defined as

So the entalphy change can be given as

The relation between isobaric

and isochoric processes

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Adiabatic process: processes that occur without exchanging heat between the system and its
surroundings. In such processes, all of the work performed by the system leads to a decrement of the
internal energy.

Exercise
1. 1 g of ice at T=0C and 10 g of water at T=100C are mixed in an adiabatic container. What is the
temperature within the container when its contents reach equilibrium? Express your answer in K.
For H2O, the change in enthalpy on melting Hmelt=6.01 kJ/mole and Cp=75.3 J/K mole.

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Case in ideal gas
Problem

Imagine that an ideal monatomic gas is taken from its initial state A to state
B by an isothermal process, from B to C by an isobaric process, and from
C back to its initial state A by an isochoric process. Fill in the signs of Q,
W, and U for each step.
P,
105 Pa Step Q W U
A
2
AB + -- 0
T=const
BC -- + --
B
1 C
CA + 0 +
1 2 V, m3

f PV NkBT
U NkBT
2
Quasistatic Processes in an Ideal Gas

isochoric ( V = const )
P
2 W12 0

Q12 NkB T2 - T1 0 CV T
PV= NkBT2 3
1 PV= NkBT1 2
(see the last slide)
V1,2 V dU Q12
isobaric ( P = const )
P 2
W12 - P(V , T )dV - PV2 - V1 0
2 1
1 PV= NkBT2
Q12 NkB T2 - T1 0 CP T
5
PV= NkBT1
2
V1 V2 V
dU W12 Q12
 Isothermal Process in an Ideal Gas

P isothermal ( T = const ) :

PV= NkBT
dU 0
W V2 V2
dV V
V2 V1 W12 - P(V , T )dV - NkBT - NkBT ln 2
V V V1
V1 V1

V Q12 -W12
Wi - f NkBT ln i
Vf
Wi-f > 0 if Vi >Vf (compression)
Wi-f < 0 if Vi <Vf (expansion)
 Adiabatic Process in an Ideal Gas
adiabatic (thermally isolated system) Q12 0 dU W12
The amount of work needed to change the state of a thermally isolated system
depends only on the initial and final states and not on the intermediate states.
V2

W12 - P(V , T )dV

P V1
2
to calculate W1-2 , we need to know P (V,T)
for an adiabatic process
PV= NkBT2
1 f f
PV= NkBT1 U NkBT dU NkB dT - PdV
2 2
V2 V1 V ( f the # of unfrozen degrees of freedom )

2
PV NkBT PdV VdP NkB dT PdV VdP - PdV PV
f
2 dP
V P
dV 2 Adiabatic dV dP
1 0 , 1 0
V f P f exponent V1
V P1
P

V P
ln ln 1 PV P1V1 const
V1 P
Adiabatic Process in an Ideal Gas (cont.)

P PV P1V1 const
2
An adiabatic is steeper than an isotherma:
PV= NkBT2 in an adiabatic process, the work flowing
1 out of the gas comes at the expense of its
PV= NkBT1
thermal energy its temperature will
V2 V1 V decrease.
V2 V2 V2
PV 1
W12 - P(V , T )dV - 1 1
dV - PV
V - 1

V - 1
1 1
V1 V1 V1

1 1 1
PV -1 - -1
- 1 V2
1 1
V1
1+2/31.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 1.33 (polyatomic)
(again, neglecting the vibrational degrees of freedom)
f f
Prove W12 PV NkB T U
2 2
Application in Metallurgy (Thermochemistry)
Thermochemistry is the study of heat effects acompanying chemical reactions,
the formation of solutions and changes in the state of matter such as melting or
vaporization, and other physicochemical processes.

1. Heat of Reaction : is the heat evolved or absorbed when the reactants react completely to
produce products. It could be expressed in terms of either per mole of any reactant or any
product.
2. Heat of Formation : The heat of formation per mole of a compound is the heat evolved or
absorbed (i.e. change in enthalpy) when one mole of the compound is formed from its
constituent elements
3. Heat of Combustion: is the enthalpy change when one mole of the substance is completely
burnt in oxygen.
4. Heat of Solution : When one substance dissolves in another, there will be a change in enthalpy.
This is called the heat of solution, and depends on the concentration cf the solution.

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 More in Heat of Formation.

Its value depends upon the temperature, pressure, and the chemical state of the
reactants and products; and for this reason it is generally expressed in terms of 'standard
heat of formation.

The heat of formation of a compound from its elements in their standard states is called
'standard heat of formation'.

The standard state of an element is the most stable form under the chosen standard
conditions of temperature and pressure.

Thus, the most commonly used standard state for a solid, liquid, and gas at a particular
temperature is as follows:
Solid : at 1 atmosphere pressure (101325 N/m2).
Liquid : at 1 atmosphere pressure (101325N/m2).
Gas : at 1 atmosphere pressure (101325 N/m ) .

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Set of Problems
1. Calculate the standard heat of reaction at 25C (298 K) andl atm pressure of

3<FeO> + 2<Al> = <Al2O3> + 3<Fe> (1)

in terms of per mole of Al2O3 formed, per mole of Fe formed, per mole of FeO
reacted, per mole of Al reacted and per gram of Fe formed.
Given that:
298 <FeO> = -6 3 . 3 k c a l / m o l e (-264.84 kJ/mol).
H298 <Al203 > = - 4 0 0 . 0 kcal/mole (-1673.6 kJ/mol).
Atomic weight of Fe = 56.

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Solution:
3<FeO> + 2<Al> = <Al2O3> + 3<Fe>
The standard heat of reaction of (1.A.1) at 25C and 1 atm pressure, 298 (1) can be written as
298,(1) = 298,product - 298,reactant
= 298,<Al203> + 3H 298,<Fe> - 3H 298,<FeO> - 2H 298,<Al>
Since the standard heat content of a pure element is zero and the standard heat content of a
compound is equal to its standard heat of formation, we have
298,(1) = 298,<Al203> - 3H 298,<FeO>
= -400.00 (3 x -63.3) = -210.1 kcal
To form 1 mole of solid Al2O3 and 3 moles of solid Fe at 25C and 1 atm pressure, the heat of reaction is
-210.1 kcal/mole of Al2O3 formed.
Since 3 moles of Fe are formed, the heat of reaction is -210.1/3 = -70.03 kcal/mole of Fe formed.
The heat of reaction is -70.03 kcal/mole of FeO reacted and -105.05 kcal/mole of Al reacted.
In order to calculate the heat of reaction per g of Fe formed, the heat of reaction per mole of Fe formed
should be divided by its atomic weight.
Hence, the heat of reaction is -70.03/56 = -1.255 kcal/g of Fe formed. 42
 Hess's Law
The law states that the heat
content change in a
chemical reaction is the
same whether it takes place
in one or several stages,
provided the temperature
and either pressure or
volume remain constant.

Example: 1. Calculate the standard heat of formation of solid W03 from solid W and 02 gas at 25C (298 K)
and 1 atm pressure from the following data at 25C (298 K) and 1 atm pressure:

<W> + (02) = <W02> ; 298 = -134 kcal (-560.66 kJ).

3<W02> + (02) = < W308> ; 2 9 8 = -131.5 kcal (-550.20 kJ).
<W3O8> +1/2(O2) = 3<WO3> ; 298 = -66.5 (-278.24 kJ).

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Solution:
The problem consists of calculating the standard heat of the following reaction at 25C and 1
atm pressure:
<W> + 3/2(02) = < W03> (2)
Eq. 2 could be regarded as being made up of the following reactions:

3<W> + 3<02> = 3< W03> (3)

3<W02> + <02> = < W308> (4)
<W3O8> +1/2<O2> = 3<WO3> (5)

Adding all the equations above we get

3<W> + 9/2<O2> = 3<WO3> (6)

According to Hesss law Dividing the heat of reaction of Eq. (6) by 3,

we get the heat of reaction of Eq. (2). Thus
298,(6) = 298,<3> + H 298,<4> + H 298,<5>
298,<2> = -200 kcal
= (3X-134.0) + (-131.5) + (-66.5)
= -600 kcal

Therefore, the standard heat of formation of solid W03 at 25 C and 1 atm pressure is -200.0
kcal/mole.
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Variation of Enthalpy Change with Temperature
The standard enthalpy change of a reaction can be easily
calculated at 25C from the data; but the kinetics of many
reactions are not fast enough at 25C for the changes to be
complete in a measurable period of time.

Therefore it often becomes necessary to find out the

enthalpy change of the reactions at a higher temperature.
0 2 2
(0
= (0 =

0 1 1
2

0 2 = 0 1 +
1
2

0 2 = 0 1 + ,product ,reactant (7)

1

Thus, if the standard enthalpy change of a reaction at a temperature is known, Eq. (7) could be applied to calculate
the standard enthalpy change at some other temperature. 45
Example:

Calculate the standard heat of formation of PbO from Pb and O2 at 227C (500 K) from the following data:

Solution: For the reaction 1

<Pb>+ (O 2 )=<PbO> (8)
2
H 0 298,(8) -52.400 kcal

Applying eq. (7) we have 2

0 500 8 = 0 298 8 + ,product ,reactant

1
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 500
1
0 (500 8 = 0 (298 8+ ,<PbO> ,<Pb> ,<O >
2 2
298
500

10.6 + 4 103 T 5.63 + 2.33 103 T

=52400 + 1
7.16 + 1 103 T 0.4 105 T 2
2
298
500

=52400 + 1.39 + 1.17 103 T + 0.2 105 T 2

298
1.17 103 2 2 5
1 1
=52400 + 1.39(500298 + 500 298 0.2 10
2 500 298
= -51998 kcal

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 Maximum Reaction Temperature : Flame Temperature
It is possible to consider a reaction taking place under adiabatic conditions so that no heat enters or leaves the system.
For a constant pressure, this means enthalpy change zero.
The temperature changes, so that the T products will be at a different from T reactants.
If the enthalpy change is positive, i.e. heat is absorbed, the temperature of the adiabatic system will fall.
In case the enthalpy change is negative, the temperature will rise during the course of the reaction.
From a knowledge of heat of reaction and the variation of the heat capacities of the reactants and products with
temperature, it is possible to calculate the final temperature of the system.

Assuming that the process is adiabatic, the combustion of a fuel can be represented as

Fuel + Oxidant (at 298 K) + Combustion products (at a very high temperature, Tm ) .

or i. Fuel + Oxidant (at 298 K) Combustion products (at 298 K). Exothermic
ii. Combustion products (at 298 K) Combustion products (at T ) .
The available thermal energy is then used to heat up the combustion products from 298 K to their final temperature T .

= ,product q is the heat evolved in step

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298
Example :
The combustion of acetylene fuel with nitrous oxide as oxidant at 25C (298 K) is widely performed in flame
emission spectrophotometry. Calculate the maximum temperature attained if the best mixture corresponds to
the reaction. Assume that water is undissociated.
2 2 + 3(2 = 2( + (2 + 3(2
Given

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Solution :
The first step calculate the standard enthalpy change of the reaction

2 2 + 3(2 = 2( + (2 + 3(2 (20.1)

H0 298(20.1 =2H 0 0
298(CO + H 298(H2 O H
0 0
298(C2 H2 3H 298(N2 O
= (2 26.42 + (57.8 (54.23 (3 19.70
= 223.97 kcal

In other words, 223.97 kcal of heat is evolved during the reaction which is used to heat up 2 moles of
CO, 1 mole of H2O and 3 moles of N 2 from 25C to the final maximum temperature

50


heat evolved = ,product

298

223970 = 2(CO + (H O + 3(N2

2
298

13.6 + 2.0 103 0.22 105 2 + 7.17 + 2.56 103 + 0.08 105 2
=
+ 19.5 + 3.0 103
298

= 40.27 + 7.56 103 0.14 105 2

298

= 40.27 + 3.78 102 2 + 0.14 105 1 298
2 1
= 3.78 102 + 40.27 + 0.14 105 12383
2
> 3.78 102 + 40.27 236353 = 0
> = 4207K

51
The Second Law of Thermodynamics

52
Second Law of Thermodynamics
While the first law of thermodynamics tells us that energy is conserved, it tells us nothing
about whether a reaction will proceed and, if so, in which direction.

We observe that heat always flows spontaneously

from a warmer object to a cooler one, although the
opposite would not violate the conservation of
energy.
This direction of heat flow is one of the ways of
expressing the second law of thermodynamics:

Simple definition
When objects of different temperatures are brought into
thermal contact, the spontaneous flow of heat that results is
always from the high temperature object to the low
temperature object. Spontaneous heat flow never proceeds
in the reverse direction.

53
Second Law of Thermodynamics
Difficult definition ............

First we should know the definition of entropy

Entropy measures the spontaneous dispersal of energy: or how
much energy is spread out in a process as a function of temperature.

Entropy is a measure
of disorder in the
physical system.

the second law of thermodynamics the universe, or in any

isolated system, the degree of disorder (entropy) can only increase.
54
 If a process occurs in a closed system, the entropy of the system increases for
irreversible processes and remains constant for reversible processes. It never decreases.

Here the greater-than sign applies to irreversible processes and the equals sign to
reversible processes. This relation applies only to closed systems.
The reversible processes as dictated in a P-V diagram, however, can have any signs of
entropy change since they describe only part of a closed system, which includes the
environment.
Irreversible Processes and Entropy:
Entropy Postulate:
If an irreversible process occurs in a closed system, the entropy S of the system
always increases; it never decreases.

Here Q is the energy transferred as heat to or from the system during the
55
(reversible) process, and T is the temperature of the system in kelvins.
56
Change in Entropy: Entropy is a State Function (gas ideal example)
Suppose that an ideal gas is taken through a reversible process, with the gas in an equilibrium state at the end
of each step.

For each small step, the energy transferred as heat to or from the gas is dQ, the work done by the gas is dW,
and the change in internal energy is dEint.

We have:

Since the process is reversible, dW = p dV and dEint = nCV dT.

Therefore,

Using ideal gas law, we obtain:

Integrating,

Finally,

The change in entropy S between the initial and final states of an ideal gas depends only on
properties of the initial and final states; S does not depend on how the gas changes between the
two states.
57
Entropy in the Real World: Perfect Refrigerators
The entropy change for the cold reservoir is -|Q|/TL, and that for the
warm reservoir is +|Q|/TH. Thus, the net entropy change for the entire
system is:

TH >TL, and the right side of this equation is negative and thus the net
change in entropy per cycle for the closed system refrigerator reservoirs
is also negative. This violates the second law of thermodynamics, and
therefore a perfect refrigerator does not exist.

The 2nd law of thermodynamics can be stated as:

No perfect refrigerators!

(The Clausius statement)

58
Entropy in the Real World: Perfect Refrigerators

To have a prefect engine, i.e., all the

absorbed heat transferred to work, we require
QL=0. With the engine entropy change being
zero, and the environment entropy change
being |Q |
DSenv = - H
<0
TH

the total entropy change for such an engine to

work will be negative, violating the 2nd law.

The 2nd law of thermodynamics can be stated as:

No perfect engine!

(The Kelvin-Planck statement) 59

Entropy in the Real World: Engine Efficiency

Not only there are no perfect engines and refrigerators, but also their
efficiency has an upper limit!

Carnots theorem:
(1)All reversible engines have the same efficiency.
(2) No engines have an efficiency higher than that of a reversible engine.

# Ideal engines
= Reversible engines

# A Carnot engine is
an ideal engine
undergoing a Carnot
cycle.
60
More about entropy
Entropy Change for a Reversible Process

For a reversible process, the sum of the entropy change of the system and of the surroundings is always zero
system + surrounding = 0
Entropy Change for a Irreversible Process
system + surrounding > 0

Entropy Change for a chemical reaction

The entropy change accompanying a chemical reaction is defined as the difference between the sum
of the entropies of all products and the sum of the entropies of all reactants.

aA + bB +... = mM + nN + ...
S = (m SM + n SN + ) - (a SA + b SB+ ),
If the reactants and products of a reaction are in their standard states, S will be written as
S0
61
 Example: Calculate the standard entropy change for the reaction at 25C
<Cr2O3> + 3<C> 2<Cr> + 3(CO)
Given:

Solution:

The standard entropy change of the given reaction at 25C can be written as

62
Variation of Entropy Change with Temperature
To calculate the change in entropy accompanying a finite change in a system, entropy equation should
be integrated between the limits of temperature involved in the change.

Since heat capacity is

We get equation that permits the calculation of entropy

of a substance at a temperature from its value at
another temperature.

The entropy values are generally stated at 25C (298 K),

thus

Standard state True for the substances in which there is no phase

transformation or change of state between T1 and T2
63
 In the case of a chemical reaction involving reactants and products in their standard states, the
changes in the standard entropies and heat capacities must be considered

If there is a phase transformation such as melting, vaporization, etc., at a temperature T in

between T1 and T2

after transformation

Entalphi change
Before transformation

64
Criterion of Spontaneity Based on Entropy
For a chemical reaction proceeding from the initial state A to the final state B, the total entropy change,
i.e. that of the system and its surroundings, can be written as

Under the restricted conditions of constant E and V, or constant H and P, the following criteria can be
utilized in assessing the probability of spontaneous change in the system:

i. If S total = 0, the system is at equilibrium and no spontaneous change will occur.

ii. If S total > 0, the reaction will tend to occur spontaneously from state A to state B.
iii. If S total <0, the reaction will tend to occur spontaneously In the reverse direction, i.e.
from state B to state A.

The above statements apply for the total entropy change, i.e. that of system and of its
surroundings.

65
 Example:
Calculate the standard entropy of solid copper at 1073C (1346 K) from the following data:

Solution:

66
 Example:
Zinc melts at 420C (693 K) and its standard entropy at 25C (298 K) is 9.95 cal/deg/mole (41.63
J/K/mol). Calculate the standard entropy of zinc at 750C (1023 K).

Given, heat fusion of Zn at the melting point

Solution:
There is a phase change at 420C, and hence in order to calculate the standard entropy of zinc at
750C, the entropy change of this phase change, i.e. Melting at 420 C must be considered.

67
68
 Example:
The phase transformation in pure iron may be represented as follows

Calculate the standard entropy of pure iron at 1627C (1900 K) if its standard entropy at 25C (298
K) is 6.50 cal/deg/mole (27.20 J/K/mol),

Given:

69
 Solution:
In the present example, several phase transformations are taking place in iron between 25C and 1627C,
and therefore the entropy change of these must be considered in order to calculate the standard entropy
of iron at 1627C.

70
Example:
Small droplets of gold have been observed to supercool by a maximum amount of approximately
230C. What is the entropy change associated with the isothermal solidification of 1 g-atom of such
supercooled gold? What is the entropy change of the surroundings if they are assumed to remain at
the same temperature as the supercooled gold? Also, calculate the total entropy change.

Given:

71
 Solution:
This is an example of irreversible process. The entropy change of the system can be calculated by considering
a series of reversible steps leading from a supercooled gold at 1063 - 230 = 833C. One such series might be
as follows:
1. Supercooled liquid gold is transformed reversibly from 833 to 1063C (melting point of gold). {Au} at 833C
{Au} at 1063C 1
2. At 1063C, liquid gold is transformed reversibly to solid gold. {Au} at 1063C <Au> at 1063C; 2
3. The solid gold is brought from 1063C to 833C. <Au> at 1063C <Au> at 833C; 2

72
 Now consider the surroundings. The irreversible process is able to transfer heat reversibly to the
isothermal reservoir. The temperature of the surroundings is the same as that of the supercooled gold
i.e. 833C.

Absorbed by surroundings

73
Free energy
Chemical reactions are rarely studied under conditions of constant energy, and therefore the
criterion of spontaneity based on the entropy change is not of much practical use.

Most reactions of chemical and metallurgical interest are performed at constant P and T (or V
and T) closed system

No mass can be transferred across the boundary of the system, but the transfer of energy is
allowed

Such a criterion can be established by the use of 'Free Energy functions - Gibbs free energy
and Helmholtz free energy.

Gibbs free energy

Helmholtz free energy

74
 The free energy change for a reaction is the difference between the sum of the free energies of the
products and of the reactants.

At temperature T

Similarly for Helmholtz free energy can be written as

75
Criterion of Spontaneity Based on Free Energy
For a reaction at constant volume and constant temperature, the following criteria have been
established:
i. If A is zero, the system is in equilibrium.
ii. If A is negative, the reaction tends to proceed spontaneously.
iii. If is positive, the reaction will occur spontaneously in the opposite direction.

Similarly, for a reaction at constant pressure and constant temperature, the following criteria have
been established:
i. If G is zero, the system is in equilibrium.
ii. If G is negative, the reaction tends to proceed spontaneously.
iii. If G is positive, the reaction will occur spontaneously in the opposite direction.

If the reactants and products are present in their standard states, G will be replaced by
G.
Since most reactions of chemical and metallurgical interest are performed under constant
pressure and constant temperature conditions, the subsequent discussions will be concerned
only with the Gibbs free energy, G, and will be described simply as free energy. 76
Calculation of Free Energy Change
For simplicity, free energy change of reactions is generally calculated when the reactants and
products are in their standard states, and this is called the standard free energy change, G.

For this reaction

The standard free energy

can be given as

However, as in the case of enthalpy, the absolute values of the free energies of substances are
not known, and only differences can be dealt with. Free energies like enthalpies must have some
reference point

The free energies of the stable form of the elements at 25 C

and 1 atm pressure are arbitrarily assigned a zero value.

77
78
Example:

Calculate the standard free energy change of the reaction

at 727C (1,000 K) and 1 atm pressure from the following data:

Also, comment on the possibility of reducing MoO3 by H2 at 727C and 1 atm pressure.

79
 Solution:

Since free energy is extensive property

Substracting 2.F.1 with 2.F.3

Since the standard free energy change of (2.F.4) is negative at 727C and 1 atm, it follows that
80
it is possible to reduce MoO3 by H2 at that T and P.