Thermodynamics

of Materials

 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,MetallurgicalThermodynamics and
Kinetics
Boris S.Bokstein,. Mikhail I. Mendelev, and David J.
Srolovitz, Thermodynamics and Kinetics in Materials
Science.

Komponen Penilaian

 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.

 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.

SIC 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.

Termodinamika material

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Termodinamika material
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Termodinamika material
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Termodinamika material
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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
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describe the state

 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)
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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.
T
P V
V
Considering the path 1a2, the change in volume is
(
)
dT

P ( P )T dP
V = V2 V1 = (Va V1) + (V2 Va) = T T P
Similarly for the path 1b2,
P2 V
T 2 V
(
)
dP

P1 P T1
T1 ( T ) P2 dT
V = (Vb V1) + (V2 Vb) =
2

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).

Figure 1.2 A quantity of gas contained in a

cylinder by a piston.

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.

Gas

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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
Figure 1.4
for H2O. two components, a
phase
If the diagram
system contains
composition axis 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
Figure 1.5 The phase diagram for the
atm. Figure 1.5 shows the phase relationships
occurring in the system Al O -Cr O at 1 atmsystem Al2O3Cr2O3.

Schematic representation of part

of the phase diagram for H2O.

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FIRST LAW OF THERMODYNAMICS

20

EROTH 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

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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.
Difference between the total energy and the internal energy?

system
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.
For an ideal gas (no interactions) :

U = U (T) - pure kinetic

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Introduction

Internal Energy of an Ideal Gas

The internal energy of an ideal
gas with f degrees of freedom:

f
U Nk BT
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
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
emphasize this fact, it is better to use the term
heating rather than heat)

WORK

HEATING

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
A the
piston
area

The work done by an external force on a gas enclosed within a cylinder

fitted with a piston:

W = (PA) dx = P (Adx) = - PdV

force

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

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
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determining the mechanical equivalent of heat, the system (water) was heated by stirring.

Introduction

W and Q are not State Functions

- we can bring the system from state 1 to
state 2 along infinite # of paths, and for each
path P(T,V) will be different.

V2

W1 2 P (T , V )dV
V1

Since the work done on a system depends not

only on the initial and final states, but also on the
intermediate states, it is not a state function.

U = Q + W

U is a state function, W - is not

thus, Q is not a state function either.

Wnet WAB WCD P2 V2 V1 P1 V1 V2

P
P2
P1

P2 P1 V2 V1 0

V1

PV diagram

V2

- the work is negative for the clockwise cycle; if

the cyclic process were carried out in the reverse
order (counterclockwise), the net work done on
the gas would be positive.

Introduc
tion

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
functions, we will use sometimes the curled symbols (instead of d)
for their increments (Q and W).

d U T d S P dV
y

- an exact differential

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)
dz z x dx, y dy z x, y
z(x,y) at these points:
Ax x, y Ay x, y
x

A necessary and sufficient condition for this:

y
x
z x, y
z x, y
z
If this condition
z
Ax x, y
Ay x, y
dy
d z
dx

holds:
x
y
x y
y x
T
f

- cross derivatives
dT dV
e.g., for an ideal gas: Q dU PdV Nk B
V
2

are not equal

z(x1,y1)

V
S

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 quasiequilibrium 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 quasiequilibrium processes:

isochoric:
isobaric:
isothermal:
adiabatic:

V = const
P = const
T = const
Q=0

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

well-defined the path between two states is
a continuous lines in the P, V, T space.
P

V
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The First Law of

Thermodynamics
How a system participates in a thermodynamic processes is
characterized by two quantities: work W, and heat Q.
Sign
Assume that we want to expand a system
convention
in
Then, the work of expansion
thermodyna
associated with an infinitesimal
mics:
process that changes the volume is
Work done by the
given by
For a finite change in volume, the work of
expansion is

system is (+), work

done on the system
is (-) and the heat
supplied to the
system is (+).

However, work
depends on the path
so W is not a state
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function.

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)

a)
b)
c)

CO2(g) + 2H2O + energy

Reaction gives off energy as heat

Potential energy stored in chemical bonds is lowered
Total energy is unchanged

2. Uses and Shortcomings

a)
b)
c)

Lets us keep track of energy flow in processes

Does not tell us if or why a given process occurs
Does not tell us direction of a chemical reaction

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Implications of the first law of

thermodynamics

oric 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
isobaric and
processes

between
isochoric

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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
2

Step

T=const
1

A B

--

BC

--

--

CA

B
C

f
U Nk BT
2

V, m3

PV Nk B T

Quasistatic Processes in an Ideal Gas

isochoric ( V = const )

W12 0

2
PV= NkBT2
PV= NkBT1

1
V1,2

3
Q12 Nk B T2 T1 0
2

(see the last slide)

dU Q12
isobaric

CV T

( P = const )

W12 P(V , T )dV PV2 V1 0

2
1
V1

PV= NkBT2
PV= NkBT1
V2

5
Q12 Nk B T2 T1 0
2

dU W12 Q12

CP T

Isothermal Process in an Ideal Gas

isothermal ( T = const ) :
PV= NkBT

W
V2

Wi f

dU 0
V2

V1

V
Nk BT ln i
Vf

Wi-f > 0 if Vi >Vf (compression)

Wi-f < 0 if Vi <Vf (expansion)

V2

dV
V
Nk BT ln 2
V
V1
V1

W12 P (V , T )dV Nk BT
V1

Q12 W12

Adiabatic Process in an Ideal Gas

Q12 0

adiabatic (thermally isolated system)

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

V2

PV Nk BT
dV
V

V1

to calculate W1-2 , we need to know P (V,T)

1

PV= NkBT2
PV= NkBT1

V1

for an adiabatic process

f
Nk BT
2

ln
V1

f
Nk B dT PdV
2

( f the # of unfrozen degrees of freedom )

PdV VdP Nk B dT

2 dP
0

f
P

dU

P1
ln

2
PdV
PV
f
V
P
dV
dP

0
V
P
V1
P1

PdV VdP
2 Adiabatic
f exponent

PV P1V1 const

Adiabatic Process in an Ideal Gas (cont.)

PV P1V1 const

V2

PV= NkBT2
PV= NkBT1

V1

An adiabatic is steeper than an isotherma:

in an adiabatic process, the work flowing out
of the gas comes at the expense of its
thermal energy its temperature will
decrease.

V2

V2

V1

V1

W12 P (V , T )dV

1 1

V2

PV
1

dV PV
V 1
1 1
V
1
V1

1 1
1
PV
1 1
1 V2
V1

1 1

1+2/31.67 (monatomic), 1+2/5 =1.4 (diatomic), 1+2/6 1.33 (polyatomic)

(again, neglecting the vibrational degrees of freedom)

Prove W12

f
f
PV Nk B 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.
2.
3.
4.

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.
Heat of Formation : is the heat evolved or absorbed (i.e. change in enthalpy) when one mole
of the compound is formed from its constituent elements
Heat of Combustion: is the enthalpy change when one mole of the substance is completely
burnt in oxygen.
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 of 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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42

Set of Problems

43

45

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:

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48

ation 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.

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

Example:

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52

53

Solution:
The problem basically consists of calculating the standard enthalpy change of the
reaction
at 527C from the standard enthalpy change of the reaction

at 25C and heat capacity data.

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55

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 ) .
i. Fuel + Oxidant (at 298 K) Combustion products (at 298 K).
or

Exothermic

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

q is the heat evolved in step

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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.
Given

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

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
58

59

60

61

62

The Second Law of Thermodynamics

63

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.
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Second Law of Thermodynamics

Difficult
definition ............
First we should know the definition of
Entropy measures the spontaneous dispersal of
entropy
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.
65

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
(reversible) process, and T is the temperature of the system in kelvins.

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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.

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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)
68

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
| QH |
Senv

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)

69

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.
70

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

Entropy Change for a Irreversible Process

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

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 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

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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

no phase transformation or change of
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state between T1 and T2

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

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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 = 0, the system is at equilibrium and no spontaneous change will
occur.
ii. If > 0, the reaction will tend to occur spontaneously from state A to
state B.
iii. If <0, the reaction will tend to occur spontaneously In the reverse
The above statements apply for the total entropy change, i.e. that of
direction, i.e. from state B to state A.
system and of its surroundings.
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 Example:

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

Solution:

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 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).

G iven, heat fusion of Zn at the m elting 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.

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 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:

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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:

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 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
2. At 1063C, liquid gold is transformed reversibly to solid gold. {Au} at 1063C <Au>
at 1063C;
3. The solid gold is brought from 1063C to 833C. <Au> at 1063C <Au> at 833C;

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 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

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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

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 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

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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.

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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.
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 In the same way as the enthalpy change, the free energy change of a system depends upon the initial
and final states of the system, and does not depend on the path taken to bring about the change.
Also, it is an extensive property of the system - depending upon the amount of substances present in
the system.
The free energy changes of reactions can be added or subtracted. Thus, for instance, the free energy
changes of the two reactions at 25C are given below.

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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.

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 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
it is possible to reduce MoO3 by H2 at that T and P.

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 nickel will not form

nickel oxide in a steam
atmosphere at 827C.
chromium will form
chromic oxide in a
steam atmosphere at
827C.
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Calculation of G at High Temperatures

Since the standard enthalpies of formation and standard entropies of compounds are usually reported
in the literature at 25C, the standard enthalpy and entropy change, and hence standard free energy
change, of a reaction at 25C can be easily calculated.
However, metallurgists are generally interested in calculating G and G for reactions at high
temperatures.
It is possible to calculate G of a reaction at a high temperature from the H 0 and S values at
25C in the following way:

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 Calculate the standard free energy change of the reaction

at 327C (600 K) from the following data:

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 Gibbs Free Energy and the Thermodynamic Functions

At constant pressure and variable temperature

At constant temperature and variable pressure

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 Similarly, for any reaction

Gibbs-Helmholtz Equation

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THE THIRD LAW OF

THERMODYNAMICS
The entropy of a system at absolute zero in a state
of
thermodynamic equilibrium is zero.
The entropy of a pure, perfect and crystalline solid at
absolute zero is zero.
Nernst heat theorem

the heat capacity of any substance goes to zero

as T0K.
all processes that take a system from one
equilibrium state to another occur with no
change of entropy Planck will always be
valid provided that the entropy of any

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Application
One of the important applications of this law is to determine the absolute value
of entropy, S, at any temperature, provided that the heat capacities are known
within the range of temperature under consideration and that the substance is
crystalline at absolute zero.

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