Metallurgical Thermodynamics

MT – 2102 Credit:04

Instructors:

Dr. C. K. Behera
and
Mr. J. K. Singh
 Marks Distribution

Total Marks 100

Sessional Test - I 15

Sessional Test - II 15

Assignments / Attdn. 10

End Semester 60
 Grading System

S 90 -100
A 80-89

B 70-79
C 60-69
D 50-59
E 40-49
F < 40
 Course Content
●
Basic Principles
Extensive and intensive properties, thermodynamic systems and processes. First Law of
Thermodynamics, enthalpy, Hess’ Law, heat capacity, Kirchhoff’s law. Second Law of
Thermodynamics, entropy, entropy change in gases, significance of sign change of entropy.
Trouton’s and Richard’s rules. Driving force of a chemical reaction, combined statement of first and
second laws of thermodynamics, Helmholtz and Gibbs free energies. Ellingham diagram,
Equilibrium constants, van’t Hoff’s isotherm, Le Chatelier principle. Clausius-Clapeyron equation.
Maxwell’s equations, Third Law of Thermodynamics.
●
Solution Thermodynamics
Solution, mixture and compound. Raoult’s law: activity, ideal solution, standard state. Partial
molar quantities, Gibbs-Duhem equation, chemical potential, fugacity, activity and equilibrium
constant. Free energy of mixing, excess and integral quantities. Regular solutions, α -function.
Dilute solutions: Henry’s and Sievert’s laws. Alternative standard states. Gibbs-Duhem integration
●
Statistical concept of entropy. Elements of Gibbs Phase Rule and its applications.
●
Experimental Techniques
Determination of thermodynamic quantities by different techniques, viz. calorimetry, chemical
equilibria, vapour pressure and electrochemical: aqueous, fused and solid electrolytes; formation,
concentration and displacement cells.
 Suggested Reading

1. D.R. Gaskell: Introduction to Metallurgical Thermodynamics, McGraw-Hill.

2. L.S. Darken and R.W. Gurry: Physical Chemistry of Metals, McGraw-Hill.

3. G.S. Upadhyaya and R.K. Dube: Problems in Metallurgical Thermodynamics and

Kinetics, Pergamon.

4. J. Mekowiak: Physical Chemistry for Metallurgists, George Allen & Unwin.

5. J.J. Moore: Chemical Metallurgy, Butterworths.

6. R.H. Parker: An Introduction to Chemical Metallurgy, Pergamon.

 Scope, Basic Concepts and
Definitions
●
Thermodynamics is that branch of science which deals with the study of the
transfer and conversion of energy from one form into other and its conversion to
work.
●
It deals with only conventional forms of energies like electrical, mechanical,
chemical. etc.
●
The non-conventional energy like nuclear energy related to atomic and sub-
atomic particle forms has to be dealt separately because in that case all matter
would have to be considered as per the famous Einstein’s equation :
E = mC2 .
 Scope, Basic Concepts and
Definitions
●
Here the subject matter of discussion is chemical and/or metallurgical
thermodynamics alone.
●
The systems under discussions consisting of large no. of particles i. e
macro systems.
Classification
Thermodynamics may be broadly classified into three :
 Classical: it treats a substance as continuum, ignoring behavior of atoms
and molecules. It consists of first, second and third laws of thermodynamics
 Scope, Basic Concepts and
Definitions
 Statistical thermodynamics: The application of probability theory, quantum
theory and statistical mechanics allowed it to arrive at macroscopic
thermodynamic relations from atomistic point of view.
 Irreversible Thermodynamics: Irreversible thermodynamics deals with the
application of thermodynamics to irreversible processes such as chemical
reactions.

The thermodynamics generally means classical thermodynamics

 Scope, Basic Concepts and
Definitions
●
Chemical thermodynamics is based on the three laws of thermodynamics
systematically applied to various physico-chemical processes in physical
chemistry.
●
Broadly speaking, the application primarily chemical thermodynamics to
metals and materials lead to the development and growth of Metallurgical
thermodynamics or its later generalization as Thermodynamics of materials.
●
Processing of ceramics and metals is carried out primarily at high temperatures
which led to the development of metallurgical thermodynamics.
 Energy
It is the ability to do work. This is too mechanical an answer.
The broader definition is : it is the capacity to bring about changes in the
existing materials as per the requirements.
Forms of energies
 Mechanical: Kinetic, potential and configurational.
 Thermal: Heat exchanged.
 Electrical: Electrical energy = current x time x potential difference.
 Chemical: Chemical energy = no. of chemical bonds x bond strength
 Scope, Basic Concepts and
System
Definitions
and Surrounding
●
Any portion of the universe selected for consideration is known as the system or
thermodynamic system.
●
A thermodynamic system must, of necessity be stable with respect to its chemistry
during its study. If the system is undergoing continuously some chemical change
cannot be considered as system
●
For example a live animate body like tree and human being are not system. All
inanimate aggregates are called systems as they have their fixed chemistry
●
The rest of the universe excluding system is called surrounding.
 Classification of
thermodynamic systems
Thermodynamic Systems

In terms of Based on Based on

interaction with Material composition
surrounding Distribution

Single Multi

Homogeneous
component component

Heterogeneous
Isolated Open
Closed

Heterogeneous
Neither Both

Homogeneous
Heterogeneous
Homogeneous
matter nor matter Can
energy is and exchange
exchanged energy energy
with exchange not the
surrounding occurs matter
 Homogeneous and
Heterogeneous system
●
Homogeneous system consists of single phase only.
●
Heterogeneous consists of more than one phase.
 State of a system
●
As the position of a point in the space is described by its coordinates w.r.t
some prefixed axes, similarly the state of a system is described by some
experimentally determinable parameter which can lead to the complete
reproduction of the system.
●
These parameters are temperature, pressure and volume.
●
The minimum number of variable required to describe the state of the system
are called independent state variables.
 State of a system (cont.)
●
Incase of a multicomponent system the independent state variables are i)
composition ii) two of the three variables T, P, V.
●
All other variables whose values get fixed with the specification of
independent state variables are referred to as dependent state variables.
●
State variables are also known as state properties or state functions.
 Extensive and Intensive
State properties
●
If a state variable, whether dependent or independent, is a function of the mass
of the system it is known as extensive state property. For example: Mass,
Volume, weight, length, energy etc.
●
If a state variable is independent of the mass or size of the system it is called
intensive state property. For example: temperature, pressure, conductivity,
density, colour, odor, malleabilty, hardness, specific heat, molar volume etc.
 Extensive and Intensive
State properties
● Product of an intensive and an extensive state variable is also an
extensive state variable.
● Ratio of two extensive properties yields an intensive properties.
For example: Density = m / V
● The general convention in chemical thermodynamics is to go for
molar properties, which are intensive and become independent of
quantity of matter and hence of more general applicability.
 Equation of State
● The state of the system can be described in the form of some
mathematical equation involving some state variables. The analytical
form as applicable to the system under consideration is known as
equation of state e.g. for an ideal gas PV = nRT.
● The above relationship is an expression which correlates the P, T and
V. In fact this is found to be true in case of solids as well as liquids
though exact form of this relationship may not be known.
● The same can be described in generalized form:
F(P,V,T) = 0
 Thermodynamic Processes
● A material system may under go a change, under externally or
internally imposed constraints, in terms of their state variables from
the existing one to some different values. Such a change in the
state of the system is known as thermodynamic processes.
● For example: Expansion of a gas from V1 to V2 may be called as a
thermodynamic process. Many a times such processes are carried
out under additionally imposed conditions and are named
accordingly. Such processes are:
 Thermodynamic Processes
● Isothermal processes: These are the processes which proceed
without any change in temperature of the system e. g. melting
of ice or metal. dT = 0
● Isobaric process: These are the processes which proceed
without any change in pressure of the system e.g. processes
carried out in open atmosphere. dP = 0
● Isochoric Processes: These are the processes which proceed
without any change in volume of the system e.g. the processes
carried out in vessel of known volume . dV = 0
 Thermodynamic Processes
●
Adiabatic processes: These are the processes
which proceed without any exchange of heat by
the system with its surrounding e. g. the system is
completely insulated from the surrounding . dq =
0. for ideal gas PVγ = const. γ = Cp/Cv
●
Polytropic Processes: Those processes which
obey equation PVn = const where n is any positive
number between 1 and γ.
 Path and State Functions
• The property whose change depends on only the initial and final
states of the system not on the path adopted to bring about the
change is called state function. Mathematically therefore if the
property is a state function (X) then in a cyclic process, when
system under goes a change and returns to original state then
Ф dX = 0
• If Y is not a state function
Ф δY ≠ 0
So Y is called a path function
 Properties of State Function
• If a system has two independent variables say x and y and any
other function or property can be expressed in its total differential
form
dz = Mdx + Ndy
where M and N may be function of x and y then the function z is a
state variable if and only if
 ∂M   ∂N 
  =  
 ∂ y X  ∂ x Y
• For an ideal gas T = PV/R wherein P and V are independent
variables and T as dependent variable. It can be expressed in total
differential as
 ∂T   ∂T 
dT = dV +  dP
 ∂V   ∂P 
 Relationship among
state variables
Let there be three state functions X, Y and Z and two of these as
independent state variables. Once Z and once Y as dependent variables. Thus
Z = Z (X, Y)
Y = Y (X, Z)
Total differential can be written as

And  ∂Z  ∂Z

dZ =   dX +   dY
 ∂ X Y  ∂ Y X
∂Y ∂Y
dY =   dX +   dZ
 ∂ X Z  ∂ Z X
 Relationship among
state variables
Putting the value of dY in first expression leads to
 ∂ Z   ∂Z  ∂Y    ∂Z  ∂Y 
dZ =   +      dX +      dZ 
 ∂ X  Y  ∂ Y  X  ∂ X  Z    ∂ Y  X  ∂ Z  X 

equating the coefficients of dX and dZ on both

Sides, we get
 ∂Z ∂Y  ∂Z 1
    = 1 ⇒   =
 ∂ Y X  ∂ Z X  ∂ Y  X  ∂ Y 
 ∂Z
 X
 ∂Z  ∂Z ∂Y  ∂Z  ∂Z ∂Y

and  
 
+ 
 
 
 
=0 ⇒  
 = −    
 ∂ X Y  ∂ Y X  ∂ X Z  ∂ X Y  ∂ Y X  ∂ X Z
 Relationship among
Similarly,
state variables
∂Y 1
  =  ∂Z 1
 ∂ X  Z  ∂ X  and   =
∂Y  ∂ X  Y  ∂ X 
 Z  ∂Z
 Y
Finally after substitution we can write
 ∂Z ∂Y ∂X
      = − 1
 ∂ Y X  ∂ X Z  ∂ Z Y
similarly
∂X ∂Y  ∂Z 
      = − 1
 ∂ Y Z  ∂ Z X  ∂ X Y
The above two expressions correlate the partial differentials of three state
variables w.r.t one another and are popularly called reciprocity theorem.
 Thermodynamic Equilibrium
●
Mechanical Equilibrium: if there is no pressure gradient in
the system.
●
Thermal Equilibrium: if there is no temperature gradient in
the system.
●
Chemical Equilibrium: if the rate of forward reaction is
equal to rate of backward reaction.
●
Complete thermodynamic equilibrium is thus that situation
where the system is in equilibrium with respect to all such
potentials like mechanical, thermal and chemical.
 Reversible and
Irreversible Processes
● A process that can be reversed in its direction by an infinetesimal change
in one or more of the state variables is said to be a reversible process.
● A classical example of this is the gas cylinder and piston. If the pressure
of the gas is say P atm and (p+dp) is exerted from outside on the piston,
the gas inside the piston shall be compressed. However, if the external
pressure is (p-dp) then the gas shall expand.
 Reversible and
Irreversible Processes
●
On the contrary a matchstick when it burns, the process
can not be reversed by changing one or other
parameters. Once burnt can not be reproduced by
reversing the process. This is typically a Irreversible
process.
●
Other examples are mixing of two gases, mixing of two
liquids to form a solution or flow of electric current
through resistor.
●
All natural processes are irreversible.
 Experimental Evidence
Leading to First Law
• For number of
thermodynamic cycle each
consisting of number of
processes
∑W i
= 4.184
∑q i

• If , however work and heat

measured in same unit then
for a thermodynamic cycle
W=q
It is impossible to produce energy of any kind or form without
the disappearance of an equivalent amount of energy
 Experimental Evidence
Leading to First Law
System goes from state I to state II by
various path and returns to the initial
state by path r only. Then we can write
Wa +Wr = qa + qr
or Wa – qa = (qr - Wr)
Simillarly along other paths
Wb – qb = (qr - Wr)
Wc – qc = (qr - Wr)
Wd – qd = (qr - Wr)
Or qa – Wa = qb – Wb= The difference between q and W shall
remain constant as long as initial and
qc – Wc= qd – Wd
final states are not changed.
 Experimental Evidence
Leading to First Law
From the previous discussion, the following conclusions can be drawn:
i) The amount of heat exchanged and work done for taking the system from
state I to II is different for different paths thus these functions are path
functions. These are denoted by symbol δq and δw for infinetesimal change.
ii) The difference between the heat input q and work done W can be equated to
change in another variable, say U i.e
q-W =U
Since q-W is independent of path, U is a state function. It has
further been proved that for a thermodynamic cycle
ΔU = 0
It is denoted by dU for infinetesimal change.
 Experimental Evidence
Leading to First Law
Let us consider that the system goes from state I to II by absorption of

heat from the surrounding and doing work on the surrounding. As we

know that q and W cannot be equal we can consider two distinct cases:

i) q < W: system partly imparts energy for the work done.

ii) q > W: The heat is partly retained by the system itself and partly returned to
the surrounding in the form of work done.

In both the cases system acts as a reservoir of energy. This stored energy

in the system which can change during a thermodynamic process is called

internal energy and denoted by symbol U.

 Internal Energy
It consists of
 macroscopic kinetic energy due to motion of the
system as a whole.
 potential energy of the system due to its position in
the force field.
 kinetic energy of atoms and molecules in the form of
translation, rotation and vibration.
 energy of interaction amongst atoms and molecules
 columbic energy of interaction amongst electrons and
nucleii in atoms
 energy contents of the electrons and nucleii of atoms
 Internal Energy
●
In conventional chemical thermodynamics which we shall be concerned
with only kinetic energies of atoms and molecules and interaction amongst
atoms and molecules i. e. items (3) and (4) are considered to be important
since changes occurring in them principally contribute to ΔU.
●
Absolute value of the energy is not known. All we can determine is change
in internal energy.
●
Internal energy will depend on temperature for a material of fixed mass,
composition and structure.
●
U is function of Temperature only.
 Statement of First law
For an infinetesimal process, the statement is:
dU = δq – δW
‘Sum of all forms of energy exchanged by a system
with its surrounding is equal to the change in internal
energy of the system which is a function of state’.

‘Energy can neither be created nor can be destroyed’

 Significance of the First Law
● It is based on the law of conservation of energy.
● It brought in the concept of the internal energy.
● It separates heat and work interactions between the system and
surroundings as two different terms.
● It treats internal energy as a state property is an exact differential.
 Internal energy in terms
of Partial Derivatives
● For given homogeneous system consisting of given amount
of substance of fixed composition;
● U = F(P,V,T)
● If any two variables are independent third will be
automatically fixed. This also therfore can be stated as:
● U = F(P,V); U = F(V,T) ; U = F(P,T)
 Internal energy in terms
of Partial Derivatives
From the theorem of partial derivatives
 Enthalpy
● If pressure is maintained constant during change of system
from state I to state II the work done
dV = P (V II − V I )
II II
w=∫ PdV = P ∫
I I

From the first law:

UII – UI = δq – P(VII – VI )
On rearranging these terms
(UII + PVII ) - (UI + PVI ) = δq
Or HII - Hi = ΔH = δq
Where H = U + PV is called entalpy. The heat content at
constant pressure is called enthalpy.
 Enthalpy
●
Enthalpy is a state property but heat is not.
As we know H = U + PV
dH = dU + PdV + VdP
As U is a function of state so one can write
 ∂U   ∂U 
dU =   dP +   dV
 ∂ P V  ∂V P
  ∂U     ∂U  
dH = V +    dP +  P +    dV
Hence   ∂ P V    ∂ V  P 

= M dP + N dV (Say)
 Enthalpy
●
Differential of coefficient of dP w.r.t V at constant P is given by the relation
∂M   ∂2 U 
  = 1 +  
 ∂V   ∂ V∂ P 
●
Differential of coefficient of dV w.r.t P at constant V is given by the relation

∂N   ∂2 U 
  = 1 +  
 ∂P   ∂ P∂ V 
●
Hence the above two partial differentials are equal proving thereby that the
equation for dH is an exact differential equation and thus leading to the
conclusion that H is a function of state.
 Enthalpy
●
As Internal energy of an ideal gas is a function of
temperature only.
●
At constant temperature
 ∂ U  dT = 0 and therefore dU
  = 0
= 0 so ∂P T

H = U + PV
∂H ∂U  ∂( P V ) 
  =   +  
 ∂ P T  ∂ P T  ∂ P  T
●
As we know:
●

●
For an ideal gas at Constant T, PV = constant, d
 Enthalpy

∂H  ∂U 
  =   = 0
 ∂ P T  ∂ P T

In other words enthalpy of an ideal gas is independent of

pressure at constant temperature. Similarly, enthalpy is
independent of volume. Hence H is a function of T only
for
the fixed mass of the substance.
 Internal Energy Vs Enthalpy
 Internal energy is all that energy stored in the system. But, What does enthalpy
mean? This can best illustrated by the example of calcination of calcium
carbonate.
CaCO3 = CaO + CO2
 The enthalpy change of the process will be equal to invested
bond energy to break the bond between CaO and CO2 or internal energy provided
both CaO and CO2 are solids.
 However if CO2 is allowed to form gas then breaking of one mole of CaCo3 nearly
22.4 ltrs. of CO2 will be formed. The expansion in volume will take place.
 In this process of expansion the system will do work equivalent to ∫ PdV as
mechanical work on the surrounding.
 Internal Energy Vs Enthalpy
 Hence in addition to the requirement of energy for breaking the bond of
Cao-CO2 additional energy equivalent to ∫ PdV will have to be supplied to
the system making a total of U + ∫ PdV and this is the enthalpy change of
the system on calcination.
 For chemical processes where there is no significant change in volume as
in
2CaO3. SiO2 = 2CaO + SiO2
 The ∫ PdV is practically absent and U and H are almost the same.
 In chemical and metallurgical world, even if term ∫ PdV is absent, it
worthwhile to refer to H which is more appropriate.
 Heat Capacity
● In chemical and metallurgical processes, materials get heated or cooled and
therefore it is necessary to know the amount of heat required to heat or amount
of heat liberated on cooling a material over a certain temperature range.
● Different materials require different amounts of heat to get heated through the
same temperature rise. This is because the materials have different heat
capacities.
● This is so because of the variation in the crystal structure of the materials and
their related parameters.
 Heat Capacity
● The heat capacity of a substance is the amount of heat
required to raise its temperature by one degree.
● In thermodynamics the molar heat capacity (C) i.e. heat
capacity of 1 g-mole of a substance is most widely
employed. Thus C = δ q
∂T
The molar heat capacity at constant volume is given by
δ q   ∂U 
CV =   =  
 ∂ T V  ∂ T V
Since at constant volume δq = dU.
 Heat Capacity
Similarly molar heat capacity at constant pressure is given by

δ q   ∂H 

CP =  
 =  
 ∂ T P  ∂ T P
Since at constant pressure δq = dH. Further we can write
dH = CP dT
T2
Or H T2 − H T1 = ∫ T1
C P dT

CP > CV since CP includes heat required to do work against

pressure also besides raising temperature
 Interrelationship of CP and CV
 ∂H   ∂U   ∂ (U + PV )   ∂U 
C P − CV =   −   =   −  
 ∂ T  P  ∂ T V  ∂T V  ∂ T V
 ∂U   ∂U   ∂V 
=   −   + P  
 ∂ T  P  ∂ T V  ∂T P

 ∂U   ∂U 
dU =   dV +   dT
And we know  ∂ V T  ∂ T V

differentiating w.r.t T at constant P we get

 ∂U   ∂U   ∂V   ∂U 
  =     +  
 ∂ T  P  ∂ V T  ∂T P  ∂ T V
 Interrelationship of CP and CV
 ∂U 
Putting the value of   we get
 ∂ T P

 ∂U   ∂V   ∂V   ∂ V   ∂ U  
C P − CV =     + P   =     + P 
 ∂V T  ∂T P  ∂T P  ∂ T  P  ∂ V T 

For an ideal gas rate of change of U with V is zero at const T.

 ∂V 
C P − CV =   P
 ∂T P
RT
For ideal gas V =
P
So CP – CV = R
 Application of First law
to Thermodynamic Processes
●
With the help of the first law, one is able to calculate
the changes taking place in internal energy and
enthalpy of a system during a thermodynamic process.
●
Processes which are frequently studied and to which
this law will be applied include: i) Isothermal process
ii) Adiabatic process iii) polytropic processes.
 In all these cases working substance of the system
shall be considered to be an ideal gas
 Application of First law
to Thermodynamic Processes
i) Isothermal
Process: The process is carried out when
dT = 0 thus dU = 0 . Hence
δq = δW = PdV
It is also true that in this Rcase
Vf T Vf Vf dV
q = w = ∫ PdV = ∫ dV = R T ∫
Vi V Vi Vi V
Vf Vf 
= RT ∫ d ln V = R T ln  
 Vi
Vi


If Vf > Vi i.e. for expansion of gas q is positive i.e.

the system will absorb heat from its surroundings
 Application of First law
to Thermodynamic Processes
 Application of First law
to Thermodynamic Processes
 If Vf < Vi i.e. for compression of gas q is negative i.e. the system will impart heat to
the surroundings at the same time absorbing mechanical energy from them in the
form of mechanical work done on it.
 The change in enthalpy of the system will be:

∆H = H f − H i = ∆U + ( Pf V f − PiVi )
= R (T f − Ti ) = 0

Tf = Ti in the isothermal process.

 Thus in an isothermal process with an ideal gas internal energy and enthalpy
remains unchanged and work done is equal to the heat exchanged.
 Application of First law
to Thermodynamic Processes
ii) Adiabatic Process: There is no exchange of heat between the system and
surrounding i. e. δq = 0. Hence first law takes the form
dU = - δW = - P dV
Or dU = CV dT = - P dV
This indicate that system will perform work at the cost
of its internal energy and therefore the lowering of
temperature of the system will result.
dT = − CV (T f − Ti )
Tf
Adiabatic work done (w) = − CV ∫
Ti

Change in Internal energy = CV (Tf – Ti)

 Adiabatic Process

Relationship between P and V and T and V in

adiabatic process.
dV
CV dT = − R T
V
Or CV dT dV
=−
R T V

Integration of this equation under the limiting

condition
V = Vi at T = Ti
And
Adiabatic Process
And substituting the expression for R in above
Expression CV Tf Vf
ln = − ln
C P − CV Ti Vi
γ −1 γ −1
Or T f V f = T V
i i where γ =
CP
CV

Or T V γ −1 = Const Or P V γ = Const

Also since by definition H = U + P V

Or dH = dU + P dV + V dP
As dU = - P dV
So dH = V dP
Adiabatic Process
Enthalpy change in a adiabatic process is
Pf Vf
∆H = ∫ Pi
V dP = − γ ∫ Vi
P dV

P V γ = Const
As for such process.
This on integration lead to the expression

γ Pi Vi  Vi 
γ −1

∆H =  − 1
γ −1  V f 
 
 
Adiabatic Process
Work done in reversible adiabatic expansion can
be deduced as follows
V2 V2 dV
w= ∫ V1
PdV = m ∫
V1 Vγ
 V21− γ − V11− γ 
= m 
 1 −γ 
Or
P2V2 − P1V1
w=
1− γ
Where
P V γ = m = a const.
Polytropic Process
iii) Polytropic process: The general expression for this process is

P V n = const.

The work done in this process is similar to adiabatic process but

γ ≠n
PiVi − Pf V f
w=
n −1

PiVi  Vi 
n −1

=−  − 1
n − 1  V f 
 
 
Polytrophic Process
Change in Internal energy = CV (Tf – Ti)
Internal energy can also be expressed in terms of P and V as follows:
dT = − CV (T f − Ti )
Tf
∆U = − CV ∫
Ti

 Pf V f PV  C P V  Pf V f 
= CV  − i i  = V i i  − 1
 R R  R  PiVi 
 
CV Pi Vi  V i 
n −1

= − 1
R  V f  
 
From the first law heat exchanged q is obtained as
[ C ( n − 1) − R] Pi Vi  V 
n −1

q= V  i  − 1
R ( n + 1)  V f 
 
 

For n = γ; q = 0 obtained from the above expression which is true for adiabatic
process.
Polytropic Process
Change in enthalpy of the system is given by
∆H = ∆U + ( Pf V f − Pi Vi )
Substituting the expression for ΔU in above expression

CV + R ] Pi Vi  Vi 
n −1

∆H =
[ 

 − 1
R  V f 
 
 
Or
C P Pi Vi  Vi 
n −1

∆H =   − 1
R  V f 
 
 

Above equation show that for n = 1 i.e. isothermal process with ideal gas , both
change in internal energy and enthalpy are equal to zero.
 Summary of Thermodynamic
Processes
Process characteristics P-V-T Work done Heat exchange
relationship
Isothermal dT = 0 PV = const RT ln (Vf / Vi) RT ln (Vf / Vi)
Isochoric dV = 0 P/T = const 0 Cv (Tf – Ti)
Isobaric dP = 0 V/T = const Pi(Vf – Vi) Cp (Tf – Ti) +
Pi(Vf – Vi)
Adiabatic q=0 PVγ = const (PfVf - Pi Vi) / (1- γ) 0
polytropic - PVn = Const (PfVf - Pi Vi) / (1- n) Cv (Tf – Ti).
(γ - n)/(1-n)
 Thermo chemistry

●
It may be defined as the branch of science which deals
with the study of heat exchanges associated either with
chemical reaction or physical changes in the state of
matter such as melting, sublimation or evaporation etc.

●
If heat is produced by a chemical reaction it is denoted by
– ve sign (Exothermic reaction)
●
If heat is absorbed during a chemical reaction it is denoted
by +ve sign (endothermic reaction).
 Hess’s Law

It states that the total heat exchanged in a given chemical reaction, which may take place under
constant pressure, volume or temperature is the same irrespective of the fact whether it is
made to take place over a path involving formation of number of intermediate products or
over the one involving the formation of final product from the reactant directly in one stage.

ΔH =ΔH1+ΔH2+ΔHx+ΔHy
Hess’s Law
 Variation of heat Capacity
with Temperature
● Experimental data consists of CP as function of temperature.
● For the liquid and solid, The P V term is very small. Hence H is
taken as equal to U and CP as equal to CV.
● In other words no distinction is made between CP and CV so far as
applications are concerned.
● It has been found that experimental CP Vs. T data for elements and
compounds fit best with an equation of type:
CP = a + b T + c T-2
 Variation of heat Capacity
with Temperature
● Where a, b, c are empirically fitted constant and differ from
substance to substance.
● The last term is the smallest and therefore often ignored.
● In some cases, such as liquid metals, both bT and cT-2 are
usually ignored.
● The above expression is also valid for diatomic and
polyatomic gases as well.
 Variation of Enthalpy
with Temperature
● Change in enthalpy during the course of process (ΔH) is equal to
the heat supplied to the system (q) at constant pressure.
● The constant pressure restriction is mostly not important for
example H is not function of P for ideal gases.
● Energies of solid and liquids are hardly affected by some changes
in pressure due to their very small molar volumes. In other words,
the VdP term is negligible.
● In most metallurgical and materials processing, gases are ideal and
pressure is maximum a few atmosphere. Therefore ΔH = q
approximation is quite all right.
 Classification of
Enthalpy change

●
Absolute value of enthalpy change of a
substance is not known. Only we can
measure are changes of enthalpy.
●
Enthalpy change occur due to various causes.
●
Sensible heat: enthalpy change due to change
of temperature of a substance is known as
sensible heat. It is divided into:
 Classification of
Enthalpy change
i) change in enthalpy without any change in aggregation of the
substance:
As a universal convention, thermo chemical data books take
sensible heat at 298 K (250C) as zero for any substance. Hence
sensible heat at temperature T, per mole of a substance is given as:
T
H T − H 298 = ∫ 298
C P dT

298 K is known as reference temperature

 Classification of
Enthalpy change
Putting the expression for heat capacity, we get

∫ ( a + b T + c T ) dT
T
−2
H T − H 298 =
298

= a ( T − 298) + (T − 298 ) − c (
b
2
2 2 1
T − 1
298
)
= A T + B T 2 − C T −1 + D
Where A, B, C and D are lumped parameters and functions
of empirical constants a, b, c
 Classification of
Enthalpy change
ii) Enthalpy change due to changes in state of aggregation of substance :
These are isothermal processes. By convention enthalpy change s for
all isothermal processes are designated by ΔH. For example,
ΔHm = enthalpy change of one mole of solid due to melting (i. e. latent
heat of fusion per mole )
ΔHv = enthalpy change of one mole of liquid due to vaporization (i. e.
latent heat of vaporization per mole )
 Classification of
Enthalpy change
Consider a pure substance A, which is undergoing
following changes during heating from 298 to T K

A (Solid) → A (Liquid) → A (Gas) → A (Gas)

at 298 K at Tm at Tb at T
Tm and Tb are the melting and boiling points of A.Then
Tm Tb
H T − H 298 = ∫ 298
C P ( s) dT + ∆H m + ∫ Tm
C P (l ) dT
Tm
+ ∆H V + ∫ C P ( g ) dT
Tb

Cp (s), Cp (l) and Cp (g), are for solid liquid and

gaseous A. it is only applicable for pure substance.
 Classification of
Enthalpy change
Heat of reaction (ΔH): This is the change of enthalpy that occurs
when a reaction takes place. By convention reaction is considered to
be isothermal. Consider the following reaction occurs at
temperature T:
A (pure) + BC (pure) = AB (pure) + C (pure)
Then
ΔH (at T) = ΔHAB (at T) + ΔHC (at T) - ΔHA (at T) - ΔHBC (at T)

Where ΔHAB , ΔHBC , ΔHA and ΔHc are molar enthalpies

of pure Ab, BC, A and C, respectively.
 Classification of
Enthalpy change
Heat of mixing (ΔHmix ): This is the change of enthalpy that
occurs when a substance is dissolved in solvent.
This process is generalized as
A (pure) = A (in solution)
This process is also accompanied by a change of enthalpy
(ΔHmix ), where
(ΔHmix ) = HA (in solution) – HA (pure)

Again by convention, the process is assumed to be isothermal for

thermodynamic calculations
Some comments:
• For calculation of enthalpy change, reactions, dissolutions and
phase transformations has been assumed to occur isothermally.
Since enthalpy is a state property, it depends only on initial and
final states and not the path.
• For a reversible isothermal process, the temperature remains
constant all through. If the process is not reversible, then
temperature at the beginning and end of a process would be
same. In between, temperature can vary significantly.
Sign convention for ΔH:

The process accompanied by liberation of heat are called

exothermic. This happens if the enthalpy in the final state
(state 2) is lower than the initial state (State 1) i. e. H2 < H1
so
for the process
state 1 → state 2
we have ΔH = H2 – H1 < 0
Therefore ΔH is negative. The opposite is an
endothermic process which is characterized by
absorption of heat and positive value of ΔH.
Standard state of enthalpy

• The stable state of a substance changes with the temperature. The

stable state of H2O is ice which is below 0 oC, liquid water 0-100
o
C and a stable gas at 1 atm pressure above 100 oC.
• Considering all these points a standard state has been defined as a
pure element or compound at its stable state at the temperature
under consideration and at 1 atm pressure. Thus the standard state
of H2O at 50 oC is pure water at 1 atm pressure.
• By convention enthalpy changes at standard state are denoted by
subscript ‘0’ e. g.

H T0 and ∆H T0
Standard state of enthalpy
As already mentioned, 298 K is the universal reference
temperature for compilation of sensible heats. By this
convention, sensible heat at standard state of a substance is
arbitrarily taken as zero at 298 K. This is solely for
calculation
of sensible heats not ΔH0 for a process occurring at 298 K
 Kirchoff’s Law
Utility:

It allows us to calculate the enthalpy changes at

various temperatures, provided the enthalpy is
known at some other temperature, and the heat
capacity of the reactants and products are known in
the range of temperatures under consideration.
Derivation:

Consider a chemical reaction at temperature T1

whose enthalpy change is ΔH1. Calculate the
 Kirchoff’s Law

The product of this reaction at T2 can be obtained in

many
different ways. Let us, however, consider the reaction to
be
carried out first by reacting the reactants (x+y) at T1 and
then
raising the temperature of the products from T1 to T2
along ABC.
 Kirchoff’s Law
The heat absorbed by this process will be
T2
∆H1 + ∫ T1
C Pz dT

The second way of obtaining the same result is to raise the

temperature of the reactants from T1 T2 and then react them
together at T2 i. e. along ADC.The heat absorbed by this process is

( )
T2

∆H 2 +
∫ T1
C Px + C P + dT
y
 Kirchoff’s Law
According to Hess’s law the heats absorbed during the two ways of
producing z must be the same since the initial conditions of the
reactants and final conditions of the products are in each case the
same. T2
( ) ∫
T2

∆H 2 +
∫T1
C Px + C P + dT
y = ∆H 1 +
T1
C Pz dT

Or
∆H 2 − ∆H 1 = ∫
T2

T1
[C Pz (
− C Px + C Py dT )]
T2
Or ∆H 2 − ∆H 1 = ∫ T1
∆ C P dT
Or T2
∆H 2 = ∆H 1 + ∫ T1
∆ C P dT
 Kirchoff’s Law
Since all the terms are known in the right hand of the equation, ΔH2
can be calculated. We know
T2
∆H 2 − ∆H 1 = ∫ T1
∆ C P dT

 ∂ ∆H 
Or   = ∆ C P
 ∂T P

This is the statement of the Kirchoff’s law. It means the rate of

change of enthalpy of a process or a reaction with temperature is
given by the difference of the heat capacity at constant pressure of
products and reactants taking part in the reaction
Problem-1
Problem-2
Enthalpy change:
∆ H (a → c) = ∆ U (a→c) + (Pc Vc – Pa Va)
= - 9.13 + n R (Tc – Ta)
= - 9.13 + 4.09 x 8.3144 x (119 - 298)
= - 9.13 - 6.0870 kJ = - 15.2170 kJ
Problem-3
 Problem - 5
Calculate the heat of the following reaction at 1000K
Fe2O3(s) + 3C (s) = 2Feα (s) + 3CO(g) from the following data:
Cp( α ,Fe) = 4.18 + 5.92 x 10-3 T caldeg-1 mol-1
Cp(CO) = 6.79 + 0.98 x 10-3 T – 0.11 x 105 T-2 caldeg-1 mol-1
Cp(Fe2O3) = 4.10 + 1.02 x 10-3 T – 2.10 x 105T-2 caldeg-1 mol-1
The heats of formation of Fe2O3 and CO at 298 K are
-197000 and – 26400 cal/mol. respectively.
 Solution
∆ Cp = Cp (product) – Cp (reactant) = 2.Cp(α -Fe)+ 3 Cp(CO) – Cp(Fe2O3) – 3Cp(C)
2 x Cp(α -Fe) = 8.36 + 11.84 x 10-3T
3 x Cp(CO) =20.37 + 2.94 x 10-3 T -0.33 x 105 T-2
__________________________________________
Cp (product) = 28.73 + 14.78 x 10-3T – 0.33 x 105 T-2
Cp = 23.49 + 18.60 x 10-3T – 3.55 x 105 T-2
3Cp(C) = 12.30 + 3.06 x 10-3T – 6.30 x 105 T-2
__________________________________________
Cp (reactant) = 35.79 + 21.66 x 10-3T -4.85 x 105 T-2
∆ Cp = -7.06 - 6.88 x 10-3T + 9.52 x 105 T-2
 Solution
1000
∆H 1000 = ∆H 298 + ∫ ∆C
298
p .dT

1000

= 117800 + ∫( 7.06 6.88 x10 3

) T + 9.52 x105 T 2
)dT
298

= 117800 – 7.06(1000-298) -6.88. (10002 – 2982)

x 10-3 – 9.52 x 105 (1000-1 – 298-1)
= 117800 – 5850 = 111950 cals.
 Problem-6
The standard heat of formation, of ammonia gas
is -11.03
kcal/mol. at 250C utilizing the data given below
derive a −3 −6 2 −1 −1
C p
, NH 3 = 6.189 + 7.787 x 10 T − 0.728 x 10 T cal deg mol
general expression for heat of formation
C p , N 2 = 6.450 + 1.414 x 10 −3 T − 0.0808 x 10 −6 T 2 cal deg −1 mol −1
applicable in the
−3 −6 2 −1 −1
C N =
temperature
p, 2 6 .947 − 0. 2 x 10 T +
range 273 – 1500K. 0. 4808 x10 T cal deg mol
 Solution
The reaction is
1 3
N 2 ( g ) + H 2 ( g ) = NH 3 ( g ) ∆H 298
0
= − 11030 cal / mol
2 2
1 3
∆C p = C p , NH − C p N2 − C p H 2
3 2 2
298

ΔH 273 + ∫+Δ7.38
ΔH 298== -7.457 C p .dT x 10-3T – 1.409 x 10-6T2
273
298

ΔH 273 = ΔH 298 - ∫ ΔC dT
273
p
298

-11030 - ∫(
273
7.457 + 7.38 x 10 3 T 1.409 x10 6 T 2 ) dT
 Solution
=-11030 + 7.457 (298 – 273) - x 7.38 x 10-3 (2982-2732) + x 10-6 (2983-2733)
= -11030 + 186.4 – 52.7 +2.9 = -10893 cal.
T

∫ ( − 7.457 + 7.38 x10 )

−3
∆H T = ∆H 273 + T − 1.409 x10 −6 T 2 dT
273
= -10893 – 7.457 T + 3.69 x 10-3 T2 – 0.47 x 10-6 T3 – (-7.457 x 273 + 3.69 x 10-3 x
2732 – 0.47 x 10-6 2733)
= -10893 +2036 – 275 + 10 – 7.457 T + 3.69 x 10-3 T2 – 0.47 x 10-6 T3
= - 9122 – 7.457T + 3.69 x 10-3 T2 – 0.47 x 10-6 T3
= -9122 – 7.457T + 3.69 x 10-3 T2 – 0.47 x 10-6 T3 cal/mol

For ∆ H1000K solution T = 1000 in the above

equation
∆ H1000K = -9122 -7457 + 3690 – 470 = -13359
 Solution
1000

ΔH1000 = ΔH 298 + ∫ ΔC dT
p
298
1000

= -11030 + ∫(
298
7.7457 + 7.38 x10 3 T 1.409 x10 6 T 3 ) dT

= - 11030 – 7.457 (1000-298) + 3.69 x 10-3 (10002-2982) – 0.47 x 10-6 (10003-2983)

= -11030 – 5234.8 + 3362.3 – 457.6 = -13360.1 cal/mol
Problem- 4
Problem
 CT-I
Solution
Solution for Q-2: Fe + ½ O2 = FeO
ΔH 298 = ΔH FeO = - 63200 Cal
1033 1123

ΔH1123 = ΔH 298 + ∫ ΔC
298
p1dT - ΔH tr + ∫ ΔC
1033
p2 dT

1 3
ΔC p1 = C p ,Feo - C p ,Fe ,mag - C p ,O 2 = 3.9 -4.42 ×10 T -0.47 ×105 T 2
2
1 3
ΔC p 2 = C p ,Feo -C p ,Fe,nonmag - C p ,O 2 = -0.92 +1.5 ×10 T -0.47 ×105 T 2
2

ΔH1123 = - 63.208 kcal

 CT-I
Solution
Solution for Q-3:
(a)
As U, T, ans S are dependent state functions

dU = ( ∂∂UP ) V dP + ( ∂∂UV ) P dV
dS = ( ∂∂PS ) V dP + ( ∂∂VS ) P dV

dT = ( ∂∂TP ) V dP + ( ∂∂VT ) P dV
We can express G in the following manner
dG = dU + PdV + VdP – TdS – SdT
 CT-I
Solution
dG = [ ( ∂∂Vu ) p + P -T ( ∂∂VS ) p -S( ∂∂VT ) p ] dV + [ ( ∂∂Pu ) V + V -T ( ∂∂PS ) V -S( ∂∂TP ) V ] dP
= MdP + NdV

( )
∂M
∂P v = ∂ 2U
∂P∂V + 1 -( ∂T
) ( )
∂S
∂P v ∂V p -T ∂ 2S
∂P∂V -( ∂S
) ( )
∂T
∂P v ∂ V p -S ( ∂ 2T
∂P∂V )

( )
∂N
∂V P = ∂2U
∂P∂V + 1 -( ∂T
) ( )
∂S
∂P v ∂V p -T ∂ 2S
∂P∂V -( ∂S
) ( )
∂T
∂P v ∂V p -S ( ∂ 2T
∂P∂V )

So G is a function of state
 CT-I
Solution
(b)
dH = TdS + VdP
dH = [ T ( ∂P
∂S
) v + V] dP + T ( ∂V∂S ) P dV
= MdP + NdV

( ) = ( ) ( ) + T( ) + 1
∂M
∂V P
∂T ∂S
∂V P ∂P V
∂ 2S
∂P∂V

( ∂P ) V = ( ∂P ) V ( ∂V ) P + T ( ∂P∂V )
∂N ∂T ∂S ∂ S 2

So H is not a function of state

 Second law of
Thermodynamics
Introduction
● System which are away from equilibrium, upon initiation, shall move towards
equilibrium and such processes are referred to as natural or spontaneous or
irreversible processes.

● Examples: heat flow from hotter to colder body or depressurisation of inflated

tube in a low pressure surroundings or free fall under gravity and so on.
 Second law of
Thermodynamics
●
The spontaneous change from an existing state to
equilibrium state is possible because in the
existing state the system happens to be at higher
potential which is the driving force for the change
to occur.
●
Higher temperature is therefore the higher thermal
potential which makes heat flow from higher to a
lower temperature. Similarly higher pressure is a
higher mechanical potential and so on.
●
If the system is in equilibrium and if it is to be
moved in the reverse direction in the above
examples it would be termed as unnatural or non-
spontaneous processes.

●
Therefore water can not be raised to an overhead
tank unless energy in the form of motor pump set is
provided to the system from the surroundings.
●
Similarly heat can not flow from a colder to a hotter body
unless aided by the surroundings in the form of compressor
energy as in the refrigerator.
●
But in chemical processes it is not readily possible to assess
as to what is a natural or unnatural process. This can only
be evaluated from the equilibrium state of the system.
● The knowledge of equilibrium CO / CO2 ratio in contact
with Fe or FeO can only guide us as to how to prevent
oxidation of iron or effect reduction of iron oxide by
providing a suitable CO / CO gas mixture as surroundings.
Heat Engines
•Heat engines operate in
a cycle, converting heat HOT
to work then returning to
original state at end of
cycle. Q1
•A gun (for example)
converts heat to work Engine W
but isn’t a heat engine
because it doesn’t
operate in a cycle.
Q2
•In each cycle the
engine takes in heat Q1
from a “hot reservoir”, COLD
converts some of it into
work W, then dumps the
●
This whole process for conversion of heat to work
necessarily produces a permanent change in the cold
reservoir by way of release of heat into it. This is
called compensation.
●
It means the entire heat that is absorbed initially is
not converted to useful work but a part of it is
rejected to a cold reservoir as of necessity.
●
In other words ‘in a cyclic process it is just not
possible to convert all heat into mechanical work. In
Efficiency of a heat engine
Definition:
HOT
work done per cycle
efficiency η =
heat input per cycle
Q1
W
=
Q1
Engine W
•Because engine returns to
original state at the end of
each cycle, ∆ U(cycle) = 0, Q2
so W = Q1 - Q2
•Thus: η = Q1 − Q 2 = 1 − Q 2
Q1 Q1 COLD
Efficiency of a heat engine

•According to the first law of

thermodynamics (energy conservation)
you can (in principle) make a 100%
efficient heat engine.

BUT………….

•The second law of thermodynamics says

you can’t:
 Kelvin Statement of Second
Law:

“No process is possible whose

SOLE RESULT is the complete
conversion of heat into work”

 William Thomson, Lord Kelvin  (1824-1907)

Heat flow

Both processes
opposite are COLD HOT
Q
perfectly OK
according to First
Law (energy
WARM WARM
conservation)

But we know only COLD HOT

Q
one of them would
really happen –
Second Law COLDER HOTTER
Clausius Statement of Second Law:

“No process is possible whose SOLE RESULT is the

net transfer of heat from an object at temperature
T1 to another object at temperature T2, if T2 > T1”

Rudolf Clausius (1822-1888)
How to design a “perfect”
heat engine
1)Don’t waste any work
So make sure engine operates reversibly
(always equilibrium conditions, and no friction).
2)Don’t waste any heat
So make sure no heat is used up changing the
temperature of the engine or working
substance, ie ensure heat input/output takes
place isothermally

 Sadi Carnot (1796-1832)
The Carnot Cycle (I):
isothermal expansion
Working substance Gas
Hot
(gas) expands Source
isothermally at Q1 T1
T1
temperature T1,
absorbing heat Q1 a Piston
from hot source.

P Q1
a
b
b
T1

V
The Carnot Cycle (II):
adiabatic expansion
Gas isolated from hot
Gas isolated
source, from hot
expands Gas
source, expands
adiabatically, and
adiabatically falls
temperature and from
temperature
T falls from T1
1 to T2
to T2.

P
a

b b Piston
T1
c
T2 c
V
 The Carnot Cycle (III):
isothermal compression
Gas is compressed Gas
isothermally at Cold
temperature T2 expelling Sink
T2
heat Q2 to cold sink. Q2 T2

P
a d

b
T1
d c
T2 c Piston
V
Q2
The Carnot Cycle (IV):
adiabatic compression
Gas
Gas is
is compressed
compressed Gas
adiabatically,
adiabatically, temperature
rises from T2 to
temperature T1 and
rises fromthe
T2
piston is returned
to T1 and the pistonto its
is
original
returned position. Work
to its original a
done is the
position. shaded
The area.
work done
per cycle is the shaded
area. d Piston
P
a

b
W T1
d c
T2
V
Efficiency of ideal gas
Carnot engine

P Q1
Q1 − Q 2 Q2 a
η= = 1−
Q1 Q1 b
W T1
d c
T2
V
Q2

•We can calculate the efficiency using our

knowledge of the properties of ideal gases
Isothermal expansion
(ideal gas)

P Q1
a

b
T1

Va Vb V

V
Q1 = Wab = nRT1 ln b
Va
Isothermal compression
(ideal gas)

P
a

b
T1
d c
T2
V
Q2

V
Q2 = Wcd = nRT2 ln c
Vd
Efficiency of ideal gas
Carnot engine
V
Q1 nRT2 ln c
P Q Vd
a η = 1− 2 = 1−
Q1 Vb
b nRT1 ln
T1
Va
W
d c
T2
V
Q2
T1Vb
γ −1
= T 2Vc
γ −1
(1) T2
Vb Vc η = 1−
γ −1 γ −1
(1) ÷ (2) = T1
T1Va = T 2Vd (2) Va Vd
Q1 Q2
=
T1 T 2
Adiabatic processes
 So……..
For all Carnot Cycles, the following results hold:
Tc
η = 1−
Th
Qc Qh Qc Qh Conservatio
= ⇒ − =0 n of “Q/T”
Tc T h Tc T h

What about more general cases?????

The expression
Qc Qh Qc Qh
= ⇒ − =0
Tc T h Tc T h
Was derived from expressions for efficiency,
where only the magnitude of the heat
input/output matters. If we now adopt the
convention that heat input is positive, and heat
output is negativeQwe Qh
c have: + =0
Tc Th
dQ
In other words ∫ T
cycle
=0
For any reversible cycle:
The Carnot Cycle
The Importance of the Carnot Engine
1. All Carnot cycles that operate between
the same two temperatures have the
same efficiency.

2. The Carnot engine is the most efficient

engine possible that operates between
any two given temperatures.
Entropy

To emphasise the fact that the relationship we

have just derived is true for reversible
processes only, we write:
dQrev
∫
cycle
T
=0

We now introduce a new quantity, called

ENTROPY (S)
dQrev
dS =
T

Entropy is conserved for a reversible cycle

Is entropy a function of state?
Reversible cycle
For whole cycle:
dQrev B
∆S =
∫
T
cycle
=0 P

path1

B  A 
 dQrev   dQrev 
∫

A
T   + 

 path1  B
∫T  
 path2
=0 A path2

V
B  B 
 dQrev   dQrev 
∫

A
T 
=
∫

 path1  A
T 
 path2
Entropy change
is path
independent →
entropy is a
thermodynamic
∆ SBA(path1) = ∆ SBA(path2) = SB − S A function of state
Irreversible processes
Carnot Engine Irreversible Engine

 Qc  Tc  Qc  Tc
ηc = 1 −   = 1− η irrev = 1 −   < 1−
 Qh  rev Th  Qh  irrev Th

For irreversible case:

 Qc  Tc  Qc  Tc  Qc  Qh
−   < − ⇒   >   >
 Qh  irrev Th  Qh  irrev Th  Tc  irrev Th

 Qh   Qc 
  +   < 0
 Th  irrev  Tc  irrev
Irreversible processes
Following similar argument to that for arbitrary cycle:

dQirrev
∫
cycle
T
< 0 For irreversible cycle

Irreversible cycle
Path 1 B( irrev) A( rev)
B
dQirrev dQrev
∫ ∫
(irreversible)
P + <0
T T
Path 2 A( irrev) B( rev)
(reversible)
B( irrev) B( rev)
dQirrev dQrev
A
∫
A( irrev)
T
<
∫
A( rev)
T
V
Irreversible processes

B( irrev) B( rev) B( irrev) B( rev)

dQirrev
∫
dQirrev
T
<
∫
dQrev
T ∫
A( irrev)
T
<
∫ dS
A(rev)
A( irrev) A( rev)

dQirrev
dS >
General Case T

dQ
dS ≥
T

Equality holds for reversible change, inequality holds for irreversible

change
 “Entropy statement”
of Second Law
We have shown that:
dQ
dS ≥
T
a thermally isolated (or completely isolated) system, dQ = 0

dS ≥ 0

“The entropy of an isolated system cannot

decrease”
What is an “isolated system”

The Universe itself is the ultimate “isolated

system”, so you sometimes see the second law
written:

“The entropy of the Universe cannot

(butdecrease”
it can, in principle, stay the same (for a reversible process))

It’s usually a sufficiently good enough

approximation to assume that a given system,
together with its immediate surroundings
constitute our “isolated system” (or universe)
………
Entropy changes: a summary

For a reversible cycle:

∆ S (system) = ∆ S (surroundings) =0
∆ S (universe) = ∆ S (system) + ∆ S (surroundings) =0
For a reversible change of state (A→B):
∆ S (system) = -∆ S (surroundings) = not necessarily 0
∆ S (universe) = ∆ S (system) + ∆ S (surroundings) =0
For an irreversible cycle
∆ S (system) = 0; ∆ S (surroundings) >0
∆ S (universe) = ∆ S (system) + ∆ S (surroundings) >0
For a irreversible change of state (A→B):
∆ S (system) ≠ - ∆ S (surroundings)
∆ S (universe) = ∆ S (system) + ∆ S (surroundings) >0
 Other Types of Engines
Schematic diagram of a refrigerator:
Refrigerator removes heat from cold reservoir, puts it into
surroundings, keeping food in reservoir cold.

Heat transfer takes

place from cold to
hot body
 Dependence of entropy
on temperature
Dependence of entropy on temperature can becalculated at constant
volume as follow: δ q rev dU PdV C V
dS = = + = dT = C V d ln T
T T T T
T2
∆SV = S2 − S1 = ∫ C V d ln T
T1

Dependence of entropy on temperature can becalculated at constant

pressure as follow:
δ q rev 1 1 1 C dT
dS = = [ dU + d ( PV ) ] = d ( U + PV ) = dH = P = C P d ln T
T T T T T
T2
∆SP = S2 − S1 = ∫ C p d ln T
T1
 Volume dependency
of entropy
δ q rev 1
We know; dS =
T
= [ dU + d ( PV ) ]
T

∂U ∂U
dU =   dT +   dV
and  ∂ T V  ∂ V T

1 ∂U 1  ∂ U  
So dS =   dT +   + P  dV
T  ∂ T V T  ∂ V  T 

As ‘S’ is function of state therefore the above

expression forms an exact differentials. Hence
∂ 1 ∂U  ∂ 1 ∂U P 
    =    + 
∂ V  T  ∂ T  V  ∂ T  T  ∂ V  T T  V
T
On simplification the above expression yields:
∂P ∂U
T   =   + P
 ∂ T V  ∂ V T

So we can write
1 ∂U ∂P
dS =   dT +   dV
T  ∂ T V  ∂ T V

And under isothermal condition dT = 0 lead to the following

expression: ∂P
dST =   dV
 ∂ T V
●
In case of gas one can directly integrate the above expression to calculate the
change in entropy during a process.
●
However, in case of solid and liquids, the equation of state is not known and
 ∂P
canalso not be determined experimentally. Hence in such cases this
 ∂ T V
partial differential is required to be expressed in terms of some experimentally
determinable parameters. For this purpose the reciprocity theorem is used to
write the following:

∂P ∂V  ∂P 
  = −   . 
 ∂ T V  ∂ T P  ∂ V T
●
Isobaric coefficient of volumetric thermal expansion of a material (α ) is
given as
1 ∂V
α =  
V  ∂ T P
●
Isothermal compressibility of a material (β ) is given as
1 ∂V
β = −  
V  ∂ P T
●
So
α
dS = dV
β
Which on integration will yield the change in entropy for a change in volume
from V1 to V2 under isothermal condition
 Pressure dependency of entropy

●
We know: δ q rev 1 P 1
dS = = dU + dV = ( dU + P dV )
T T T T
●
From the definition of the enthalpy, one can get

●
Therefore, dH = dU + P dV + VdP

●
The total differential dH can also be expressed as

1 V
dS = dH − dP
T T
∂H ∂H
dH =   dT +   dP
 ∂ T P  ∂ P T
●
After substitution, we get
1 ∂H 1  ∂ H  V
dS =   dT +    −  dP
T  ∂ T P  T  ∂ P  T T 
●
The equation is an exact differential because entropy being function of
state. Therefore,
∂ 1 ∂H  ∂ 1  ∂H  V
    =    − 
∂ P  T  ∂ T  P  T ∂ T  T  ∂ P  T T  P
●
On simplification this yields

1 ∂H  ∂V
   − V  =  
T   ∂ P  T  P  ∂ T  P
• So after substitution we can write
1 ∂H ∂V
dS =   dT +   dP
T  ∂ T P  ∂ T P

• For an isothermal process the above expression yields,

 ∂V 
dST = −   P dP = − α V dP
 ∂T 
• On integration, one can calculate the change in entropy for a
change in pressure from P1 to P2 under isothermal conditions.
 Relationship between CP&CV
• We have derived the following relationship:
∂U ∂P ∂H ∂V
  = T   − P   = V − T  
 ∂ V T  ∂ T V  ∂ P T  ∂ T P

∂P ∂V  ∂P 
  = −   . 
 ∂ T V  ∂ T P  ∂ V T

1 ∂V 1 ∂V
α =   β = −  
V  ∂ T P V  ∂ P T
• We know the following expression
 ∂U   ∂V   ∂V   ∂ V   ∂ U  
C P − CV =     + P   =     + P 
 ∂V T  ∂T P  ∂T P  ∂ T  P  ∂ V T 

∂U
 
• Elimination of  ∂ V T from the above equation leads to the relation

∂P  ∂V 
C P − C V = T    
 ∂ T V  ∂ T P
• Or
α2 V T
CP − CV =
β
 Entropy Change in Gases
S1 p1 Change S2 p2
v1 T1 → v2 T2

Ideal gas
dq/T = Cv .dT/T + R dV/V = dS

∆ S = S2 –S1 = T2 v2
dT dv
Cv ∫ +R ∫
ln1 T+ R ln v1 v
On integration ∆ S = C T
v
T2 v2
T1when temperature
Entropy change can be calculated v1 and volume change
take place on heating an ideal gas
 Entropy Change in Gases
∆ S = Cv ln (T2/T1) + R ln (T2p1/T1p2)
= Cv ln (T2/T1) + R ln (T2/T1 )+ R ln (p1/p2 )
Or ∆ S = Cp ln (T2/T1 )– R ln p2/p1

In an isothermal process i.e. at constant temp T = T1 = T2.

∆ ST = - R ln p2/p1 = R ln p1/p2 = R ln (v2/v1)
For an isobaric process p1 = p2 = p
∆ Sp = Cp ln (T2/T1)
For an isochoric process v1 = v2 = v
∆ Sv = Cv ln (T2/T1)
 Entropy Change in Gases
As the system absorbs heat, its entropy will increase
e.g. with
melting and boiling.
T2

∫ Cpd ln T
T1

∆ S= S2 – S1 =

∆ S is the area beneath the

curve between temperature,
T1 and T2(graphical method).
 Significance of sign of entropy
change of a process in closed system

• Two identical copper vessel

T1 > T 2
touching each other, full of
water and each at different
temperature.
I q II
• Vessels are completely
insulated so that heat can T1 T2
neither enter nor leave this
system.

• T1 – T2 is the measure of
irreversibility of this process.
This also denote the how much
heat will flow Insulation
Entropy change of vessel I = - q1 / T1
Entropy change of vessel I = q / T2
Total change of entropy will be the sum of entropy changes of the two
q q
vessels. Thus ∆SPr ocess = ∆S1 + ∆S2 =  − 

 T2 T1 
q ( T1 − T2 )
∆SPr ocess =
T1 T2

When q is +ve and T1 – T2 is +ve then the entropy

change for a real irreversible process in a closed
system must also be positive.
 ● T1 > T2 ; ∆ Sirr > 0 (+ve) : The entropy change of a real process is greater than
zero(+ve).
● T1 = T2 ; ∆ Srev = 0 (zero): Dynamic equilibrium exists between two vessels and
there is no heat transfer.
● T1 < T2 ; ∆ Sirr < 0 (-ve). : Entropy change is negative and the process proceeds
in the reverse direction.
Sign of entropy change shows the direction of flow of heat energy.
 Calculation of entropy change

• Entropy is a state property. Hence the basis and procedure for

calculation of entropy changes are similar to those for the enthalpy
changes.
• Hess’s law and Kirchoff’s law are applicable here too.
• A pure substance at its stablest state also constitutes standard state
0
for entropy at that temperature which is designated as ST .
Following significant difference are to be noted
between entropy and enthalpy.
– Entropy changes are to be calculated only through the
reversible path. This restriction is not there for any other state
property, including enthalpy.
– Absolute value of entropy can be determined. Thermodynamic
data sources provide the values of entropy of a substance
for pure substance. This is in contrast with the energy where
only changes are available in the data sources.
 Entropy changes associated
with phase transformation

For a pure substance, reversible phase changes

(melting, boiling etc.) at a constant pressure occurs at
a constant temperature. Therefore,
∆ H 0m for melting
∆S =0
m
Tm
for boiling
∆ H 0V
∆ SV =
0

TV

∆ H 0
∆ S 0tr = tr

Ttr in general for phase trans.

A (Solid) → A (Liquid) → A (Gas) → A (Gas)
at 298 K at Tm at Tb at T
Tm and Tb are the melting and boiling points of A. Then

Tm C 0P ( s ) ∆H 0m Tb C 0P ( l )
S0T − S0298 = ∫ 298 T
dT +
Tm
+ ∫ Tm T
dT

∆H 0V T C ( g)
0
+ +∫ P
dT
TV Tb T
 Entropy changes in
chemical processes

By nature, reactions and mixing are irreversible. Like enthalpy

changes, entropy changes are considered only for the isothermal
process. However, they cannot be calculated from enthalpy as done for
the phase transformation in view of irreversibility. Consider the
reaction A + BC = AB + C
The entropy change of the reaction at temperature T

∆S = S
0
T
0
AB (at T ) + S (at T ) − S (at T ) − S
0
C
0
A
0
BC (at T )
The entropy change of the reaction with temperature
can be calculated as

∆S0T2 = ∆S0T1 + ∑ (S
product
0
T2 − S0T1 −) ∑ (S
Re ac tan t
0
T2 − S0T1 )
T2 ( C P ) product T2 ( C P ) reac tan t
= ∆S + ∫0
T1 dT − ∫ dT
T1 T T1 T
∆ CP
T2
= ∆S + ∫0
T1 dT
T1 T
 Various interpretations of entropy
δ q rev
●dS =
for an infinitesimal, isothermal reversible
T

process.
●
Entropy is times arrow i. e. a fundamental
indicator of time.
●
Entropy has the relationship with heat not
available for work.
●
Entropy is a measure of disorder of a system.
 Combined statement of
first and second law

●
If a system is capable of doing only mechanical work the first law equation can be put as:
dU = δq – P dV. It is not exact differential. Holds true for the reversible processes.
 The second law for the reversible process gives
dS = δq rev / T or δq = T dS
 The two laws therefore can lead to
dU = TdS – P dV or TdS = dU + PdV
This is the combined statement of first and second law.
It includes only those terms which are state functions only and
hence is exact differential equation.
●
For irreversible process second law gives
dS > 0
Or therefore, TdS > dU + PdV
 For a unnatural or non spontaneous process
dS < 0
Or therefore TdS < dU + P dV
 Thermodynamic Potentials

● A system by itself, in isolated state or in contact with surrounding shall

stay in equilibrium unless acted upon by some constraints.

● If a system tends to move as a result of being not in equilibrium or as a

result of external constraint, there must be a driving force making the
system move from within itself or under the applied constraints.

● This driving force is referred to as thermodynamic potential driving the

system to change to a new state.
●
Is this driving force or potential the same under all conditions of the system or it
varies from condition to condition of the system ?

●
Heat flow s from higher to lower temperature. The flow is possible due to higher
thermal potential.

●
Similarly the higher pressure is the driving mechanical potential.

●
Also higher electrical voltage is driving the electrons under the influence of
electrical potential as voltage.
●
However the question remains as to what is that potential, forcing a thermodynamic
process to take place?
●
It is easy to imagine that a system with higher associated energy will be relatively
unstable as compared to the one having lower energy.
●
In other words, when a natural changes take occurs the system moves from higher to
lower energy levels or moves from higher to lower thermodynamic potentials.
●
It also means that the energy is a potential driving the system for change to occur.
●
It also means that for equilibrium to exist the potential of all the systems or sub-systems
within it must be at the same potential.
●
So far the internal energy, enthalpy and entropy have been evolved as
energy parameters but it is not yet known as to whether these act as
potential in driving a particular process?

●
It must be noted that for natural process the system moves from lower to a
higher entropy level hence entropy can not be considered as a driving
force.
●
Can internal energy and enthalpy qualify as potentials capable of driving the process
towards equilibrium if already at higher levels ?

●
If internal energy and enthalpy are potential terms then changes in them will have to be
zero at equilibrium and these will have to decrease for natural changes and increase for
unnatural changes.

●
Let us therefore see if criteria can be evolved mathematically to evaluate what
constitute as thermodynamic potential and if so under what conditions?
 Potentials under constant volume
and constant entropy conditions

Mathematically these conditions are expressed as

dV = 0 and dS = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
dU = 0
iii) TdS < dU + P dV for unnatural process
So under above conditions we can write
dU > 0
●
As internal energy decreases for natural process, remains same at equilibrium
and increases for unnatural process thus fully qualifies to be called as
thermodynamic potential under the conditions of constant volume and entropy.
●
As a corollary, the internal energy must be the function of entropy and volume
can be expressed:
U = F (S, V)
Total differential of internal energy is given by

∂U ∂U
dU =   dS +   dV
 ∂ S V  ∂ V S
●
We know: dU = TdS – P dV
●
On comparison this leads to
∂U
●
and ∂U
  = T   = − P
 ∂ S V  ∂ V S
●
By specifying U as function of S and V it is possible to evaluate T and P
thereby describing the system fully.
●
By describing U as a function of any other two variables, it is not possible
to describe the system fully.
 Potentials under constant pressure
and constant entropy conditions

Mathematically these conditions are expressed as

dP = 0 and dS = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU + d (PV ) < 0
Or d (U + P V) < 0
Or dH < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
dU + d (PV ) = 0
Or dH = 0
iii) TdS < dU + P dV for unnatural process
So under above conditions we can write
dU + d (PV ) > 0
Or dH > 0
So on the whole dH > = < 0 for unnatural, equilibrium
and natural processes as the case may be.

Therefore, the term enthalpy qualifies as being called

a potential term under constant pressure and entropy
conditions.
●
Enthalpy can therefore be described mathematically as: H = F (P, S)
●
Total differential of enthalpy can be written as
∂H ∂H
dH =   dS +   dP
 ∂ S P  ∂ P S
●
Also by definition: dH = d (U + P V)
●
= dU + P dV + V dP
●
= T dS + V dP
●
On comparison we get

∂H ∂H
  = T and   = V
 ∂ S P  ∂ P S
 Potentials under constant volume
and constant temperature conditions

Mathematically these conditions are

expressed as
dV = 0 and dT = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU - TdS < 0
Or d ( U – T S) < 0
Let us define new mathematical term
A=U–TS
then dA < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
d ( U – T S) = 0
Or dA = 0
iii) TdS < dU + P dV for the unnatural process
So under above conditions we can write
d ( U – T S) > 0
Or dA > 0
The newly defined function qualifies for being referred as a
potential term under constant volume and temperature
conditions
‘A’ being the function of all state variables ‘A’ also
must be state function. Expressing as before
∂A ∂A
A = F (V, T) dA =   dT +   dV
Total differential of ‘A’  ∂ T V  ∂ V T
●
Now A=U–TS
dA = dU – TdS – S dT
And since, TdS = dU + P dV
Therefore dA = - S dT – P dV
On comparison we get

∂A ∂A
  = − S and   = − P
 ∂ T V  ∂ V T
This function ‘A’ was first defined by Helmholtz and
therefore is known as Helmholtz free energy.
We know dA = dU – T dS
And for reversible process qrev = T dS
An therefore qrev = dU – dA
From the First law dU = qrev – W
And hence qrev = dU + W
Comparing the two equations for qrev we get
- dA = W
Or dA = - W
That the change in Helmholtz free energy in a process is equal
to the amount of work done by the system on the surrounding
or is equal to the amount of work the system is capable of doing.
 Potentials under constant pressure
and constant temperature conditions

These are by far the most commonly adopted

conditions in chemical and metallurgical engineering
practices. It means
dP = 0 and dT = 0
i) TdS > dU + P dV for natural process
So under above condition we can write
dU + d (P V) - TdS < 0
Or d ( U + P V– T S) < 0
Let us define new mathematical term
G = U + P V– T S
then dG < 0
ii) TdS = dU + P dV for the equilibrium process
So under above conditions we can write
d ( U + P V– T S) = 0
Or dG = 0
iii) TdS < dU + P dV for the unnatural process
So under above conditions we can write
d ( U + P V– T S) > 0
Or dG > 0

The function defined above thus qualifies for being

called as a potential term under constant pressure
and temperature conditions
‘G’ is a function of all state variable. so it is a state function.
The function ‘G’ is referred to as Gibbs free energy.
Now G=U+PV–TS
And H=U+PV
Then G=H–TS
Or ∆ G = ∆ H – T ∆ S for a finite change
Or dG = dH – T dS – SdT in differential form
At constant pressure dP = 0 and dH = q = TdS
And hence dG = - SdT
Or
 dG 
  = − S
 d T P
Again dG = dH – T dS – SdT
On putting dH = dU + P dV + V dP
dG = dU + P dV + VdP – T dS – SdT
Putting in this dU + P dV = T dS
dG = T dS + V dP – T dS – S dT
= V dP – S dT
At constant temperature when dT = 0 ; dG = V dP
Or dG 
  = V
 d P T
Since G is a state function any change in G can be
represented as ∆ G = ∆ U – T ∆ S + ∆ (P V)
= - Wrev + ∆ (P V)
The change of Gibbs free energy during a process is equal and opposite in sign to the
net reversible work obtainable from the process occurring under isothermal condition
when corrected for change in volume under isobaric condition.
Since G is a state function any change in G can be
represented as
∆ G = ∆ U – T ∆ S + ∆ (P V)
= - Wrev + ∆ (P V)
The change of Gibbs free energy during a process is
equal and opposite in sign to the net reversible work
obtainable from the process occurring under
isothermal condition when corrected for change in
volume under isobaric condition.
 Important thermodynamic relations

For closed and isolated systems have fixed mass and

composition and the reversible work is done against
pressure.
dU = T dS - PdV
dH = T dS + V dP
dA = - S dT – P dV
dG = - S dT + V dP
 Criteria for thermodynamic equilibria

Differential form Finite difference form

(dU)S,V = 0 (∆ U)S,V = 0
(dH)S,P = 0 (∆ H)S,P = 0
(dA)T,V = 0 (∆ A)T,V = 0
(dG)T,P = 0 (∆ G)T,P = 0

Since it is easy to maintain temperature and pressure

constant the Gibbs free energy criteria is employed in
chemical and metallurgical processes. However, in other
areas, other criteria are also employed.
 Maxwell’s equations

From the properties of the exact differential

equation: dZ = M dX + N dY,  ∂M   ∂N 
  =  
 ∂y  X  ∂ x  Y
 ∂T  ∂P
  = −  
 ∂ V S  ∂ S V
∂T ∂V
  =  
 ∂ P S  ∂ S  P Maxwell’s relations are used
frequently in thermodynamics
 ∂S  ∂P
  =   for the calculation of changes in
 ∂ V T  ∂ T  V
thermodynamic variables for
 ∂S  ∂V
  = −   different processes.
 ∂ P T  ∂ T P
 The Driving Force
of a Chemical Reaction
● Why does a chemical reaction take place?
● It was believed that the energy change accompanying a reaction
can be measured directly by the enthalpy change at constant
pressure, or change in intrinsic energy (∆ U) at constant volume.
● The reasoning behind this would be apparent – if a system losses
energy as a result of a chemical reaction, that reaction will take
place spontaneously – and the greater the quantity of heat lost, the
greater the driving force behind the reaction.
 The Driving Force
of a Chemical Reaction (cont.)
● C (s)+ O2 (g) = CO2(g) with evolution of heat energy, i.e.
∆H 298
0
= −94050cal/mol which happens to be a driving force in this case.
● 2 Fe (s) + O (g) = 2FeO(s) and
2

3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)

Both have negative heats of reaction at 16000C and both take place
spontaneously
● On the other hand, if we consider the reaction;

ZnO(s) + C(s) = Zn(g) + CO (g)

and
● This reaction will not take place at 250C but if the system is heated to

11000C,
0 carbon will reduce zinc0 oxide to produce zinc metal.
∆ H 1373 = +83200 ∆ H 298 = +56800
 The Driving Force
of a Chemical Reaction (cont.)
● we cannot use heats of formation as a criterion of their tendency to
take place. We must therefore search for a more consistent rule for
the driving force of a reaction.
● Consider the reaction: ZnO(s) + C(s) = Zn(g) + CO (g)
● At 11000C, i.e above the boiling point of Zn (9070C), the reaction will
take place between phases indicated above. At 250C, zinc is a solid
(melting point 419.60C) so that the reaction is
ZnO(s) + C(s) = Zn (s) + CO (g)
 The Driving Force
of a Chemical Reaction (cont.)
● The most obvious difference in these reactions apart from
their temperature, is the difference in the physical state,
means a difference in the state of order of a system and
consequently in the entropy of the system.

● ∆ S0 at 250C should be much less than that 11000C, because

at 11000C two molecules of gas are being produced from two
solid molecules whereas at 250C two solid moles only
produce one gaseous mole.
 The Driving Force
of a Chemical Reaction (cont.)
●
A solid to gas transformation means a comparatively large entropy
increase and the following figures for the reduction of ZnO by C:
ΔS298 = 46 cal / mol deg and ΔS1373 = 68 cal / mol deg
●
Why not use entropy change of a reaction as a measure of the driving
force behind a chemical reaction?
●
The idea is immediately contradicted if we consider the formation of the
oxide of any metal:
1
Fe(s ) + O 2 (g ) = FeO (s ) , ΔS0298 = - 17 cal / deg mol
2
●
We know that this reaction is spontaneous – an oxide film forms readily
on iron at room temperature. Thus a positive entropy change is not the
criterion of a chemical reaction.
 The Driving Force
of a Chemical Reaction (cont.)
● The Second Law of thermodynamics states that a spontaneous
process is always accompanied by an increase in entropy of the
system and its surroundings.
● The surroundings receive e a quantity of heat - ∆ H at constant

temperature and pressure

∴ entropy increase of the surroundings = − ∆H
● If ∆ S is the entropy change of the system, total T
entropy change of
the system and surroundings = ∆ S – ∆H
T
● For the 2nd Law to be obeyed (∆ S - ) must be +ve
∆H
TΔS - ΔH T
= + ve
T
 The Driving Force
of a Chemical Reaction (cont.)
●
we can say that (∆ H – T ∆ S) must always be –ve for a reaction to proceed
spontaneously in order that the total entropy change of the system and
surroundings can be +ve, when the reaction proceeds.
●
We should examine the factor (∆ H – T ∆ S) for the above three reactions in
question. For the reduction of ZnO by C at 250C

ΔH 298 - TΔS298 = 56800 -298( 46) = +43100 cal / deg mol

●
The reaction cannot proceed because this factor is +ve, and the total entropy
change of the system and its surroundings is –ve

1100is0 C
atThis ΔH1373 -so
TΔthat
S1373 the
= 83300 -1373( ) = - 10200 cal
●
negative reaction will68take place spontaneously at 11000C.
This explains why zinc oxide smelting must be carried out at temperature of the
order of 11000C in order that reduction of the oxide by carbon can proceed.
 The Driving Force
of a Chemical Reaction (cont.)
● For the oxidation of iron at 250C
∆H 298 − T∆S 298 = − 63200 − 298( − 17 ) = − 57140 cal.

● Again it is negative, and the reaction takes place spontaneously at

250C.
Consistent Rule
● The driving force of a reaction can be calculated as (∆ H - T∆ S);

the more negative this factor, the greater the driving force and if
the factor is +ve, the reaction will not proceed spontaneously.
● ∆ G = ∆ H - T∆ S called Gibbs Free energy
 The Driving Force
of a Chemical Reaction (cont.)
● It is the maximum work available from a system at constant pressure
other than that due to a volume change. Most metallurgical
processes work at constant pressure.

● We had already seen the fundamental importance of the factor (∆ H-

T∆ S), so that ∆ G is a measure of the ‘driving force’ behind a
chemical reaction. For a spontaneous change in the system, ∆ G
must be negative, the more negative, the greater the driving force.
 Thermodynamic Mnemonic Square

In order to memorize important thermodynamic relationship

involving the different thermodynamic potentials Max Born
suggested a diagram known as Thermodynamic Mnemonic
Square. V A T
●
Four sides of the square are leveled
in alphabetical order starting from the
top and moving in clock-wise direction
with four thermodynamic potentials U G
namely A, G, H, U.

S H P
●
The other four primary functions namely V, T, P, S are placed at the four corners in such a way that
each thermodynamic potential is surrounded by the condition under which it acts
We can write the total differentials of each of
potentials with help of this diagram as follows:
 Differential of any potential is equal to the sum of the differentials of its
adjoining variables with their coefficients equal to diagonally opposite
variables.

 This coefficients are taken to be positive if arrow points away from the
variable and negative if it points towards the variable.

dG = - S dT + V dP
Maxwell’s relations can also be read from the
diagram as follows:
 It is required to consider the corners only
 The square is rotated in anti clock-wise direction in such a way that the
function whose partial differential is to be arrived it appears on the top
left hand corner of the square.
 The partial derivative of this variable w.r. t variable on the bottom left
hand corner keeping the lower right hand corner variable as constant is
equal to the partial derivative of the top right hand corner variable w.r.t
bottom right hand corner variable with bottom left hand corner variable
as constant.
 Negative sign on the right hand side of the equation is put if the arrows
are placed unsymmetrically with respect to vertical axis drawn from
centre of the square on rotation.

 ∂T  ∂P
  = −  
 ∂ V S  ∂ S V
 Standard state of free energy

Standard state is pure element or compound at 1

atm pressure and at its stablest state at the
temperature under consideration.

Free energy change of the reaction are generally

calculated when the reactants and products are
present in their standard states is called the standard
free energy change.

The standard free energy is designated by ∆ G0T.

Like enthalpy, we cannot measure the absolute

value of free energy but change in free energy is
quite possible to measure.
● Therefore, there must be some reference point with
respect to which the actual values of various substance
can be calculated.
● The free energies of stable form of the elements at 298 K
and 1 atm pressure are arbitrarily assigned as zero
value.
● The free energy of formation of compound are
calculated on the basis of the above assumption and the
value is described as standard free energy of formation.
 ●
This quantity is generally reported at 298 K and for compound say MO, it
would be written as ∆ G0298, MO.
●
The Hess’s law is applicable for calculation of free energy change as it is
a state property.
●
The standard free energy of formation of compound and the standard free
energy of compound are same.
0
M + ½ O2 = MO 0

∆ G0298 = G0298,MO - G0298,M - ½ G0298, O2

∆ G0298,MO = G0298,MO
For the reaction
a A+ bB → cC + d D
the s tan dard free energy change ∆G 0 at 298 K is given by

∆G 0298 = ∑ G 0298, Pr oduct − ∑ G 0298, Re ac tan t

= c G 0298, C + d G 0298, D − a G 0298, A − b G 0298, B

inorder to calculate the s tan dard free energy change of a reaction

the s tan dard free energies of reac tan t and products must be known
 Some thermodynamic
relationships
By definition G = H – TS = U + PV –TS
differentiating dG =dU + PdV + VdP – TdS – S.dT (1)
Assuming a reversible process involving work due only to
expansion at constant pressure
According to First Law: dU = dq – PdV and from Second
Law: dq = TdS
∴ dU = TdS – PdV (2)
From (1) and (2) we get dG = (TdS – PdV) + PdV + VdP – TdS – SdT
or dG = VdP – SdT(3)
 Some thermodynamic
relationships
At constant pressure, dP = 0, so that  δG=- S
 δT 
and at constant temperature, dT = 0 and ∴ dGP = VdP
from PV = RT for ideal gas, dG = RT
dP
Integrating between the limits PA and PPB at constant
Temperature
PB
dP PB
∆G = G B − G A = RT ∫ = RT ln ( 4)
PA
P PA
if GA is the free energy of the system in its initial state and GB
the free energy in its final state when the system undergoes a
change at constant pressure
 Some thermodynamic
relationships
dG A = − S A .dT and dG B = − S B dT
d ( G B -G A ) = (S B - SA ) dT

but ∆ G = GB – GA and ∆ S = SB – SA and so that d (∆ G) = -∆ S.dT

 δ∆G 
 δT  = − ∆S  δ ( ∆G ) 
 P ∆ G = ∆H − T ∆S = ∆H +  δT 
on substitution   P ,T

known on Gibbs – Helmholtz equation

 Calculation of ∆ G0 at high temperature

It is possible to calculate ∆ G0 of a reaction at high

temperature from the ∆ H0 and ∆ S0 values at 298 K
(available in the literature ) in this way

∆G 0T = ∆H 0T − T ∆S 0T
 0 T
  0 T
∆C P 
or ∆G 0T = ∆H 298 +

∫298 ∆C P dT  − T ∆S 298 + 298∫ T dT 
It must be remembered that if any transformation
takes place between 298 and T K in reactants and
products must be introduced in the above equation.
 Fugacity
The variation of Molar Gibbs free energy of a
closed system of fixed composition, with pressure
at constant temperature is given by
dG = V dP
For one mole of ideal gas
dG = (RT / P) dP = RT d ln P
For isothermal change of pressure from P1 to P2
at T
G (P2, T) – G (P1, T) = RT ln (P2 / P1)
 Fugacity
contd……
AS Gibbs free energy do not have absolute values,
it is convenient to choose an arbitrary reference
state from which changes in Gibbs free energy can
be measured. This reference state is called
standard state and chosen as being the state of
one mole of pure gas at one atm pressure and the
temperature of interest.
The Gibbs free energy of the ideal gas in the
standard state G (P = 1, T) is designated as G0 (T).
 Fugacity contd..
Thus the Gibbs free energy of 1 mole of gas at any
other pressure P is given as
G (P, T) = G0 (T) + RT ln P
Simply
G = G0 + RT ln P
So the molar Gibbs free energy of the ideal gas is
a linear function of the logarithm of the pressure of
the gas
 Fugacity contd…
●
If the gas is not ideal then the relation of molar free energy and logarithm
of pressure is not linear.
●
A function is invented which when used in place of pressure gives a linear
relationship.
●
This function is called ‘Fugacity ( f )’ is partially defined as
dG = RT dln f
 Fugacity contd…
In addition, as the real gas and the ideal gas
behave the same at very low pressure, it is
obvious that (f / P) → 1 as P → 0.
after integration from standard state to any arbitrary state we can write
G - G0 = RT ln (f / f0)
Where G0 is the Gibbs free energy of the real gas
in the standard state. f is the fugacity at a
specified state and f0 is standard state fugacity.
Fugacity is the measure of escaping tendency of a gas.
Fugacity is the effective pressure corrected for non-ideality
 Activity
Activity (a) is defined as

f fi
a= 0 or a i = 0
f fi
So we can write

G − G 0 = RT ln a Or G i − G i0 = RT ln a i

Partial molar free energy of

component i in the state
of interest. free energy of component I
in the standard state.
●
The standard state of a substance are generally chosen as the pure solid or
liquid form of the substance at 1 atm pressure and temperature under
consideration or as the gases at 1 atm pressure at the temperature under
consideration.

●
The activity of a substance in its standard state is seen to be unity.
 Equilibrium Constant

Let us consider a general chemical reaction at

constant temperature and pressure
lL + mM+ ⋅ ⋅ ⋅ ⋅ = qQ + rR + ⋅ ⋅ ⋅ ⋅

Capital letters for chemical element and small

letters for the number of gram mole. The general
free energy change of the reaction may be written as

∆G = q G Q + r G R + ⋅ ⋅ ⋅ − l G L − m G M + ⋅ ⋅ ⋅
The standard free energy change can be written as
0 0 0 0
∆G = q G + r G + ⋅ ⋅ ⋅ − l G + m G
0
Q R L M + ⋅⋅⋅

Subtracting these two equations,

( 0
) (
∆G − ∆G = q G − G Q + r G − G R + ⋅ ⋅ ⋅
0
Q
0
R )
−l( G
0
L )
−GL − m G ( 0
M )
−GM ⋅ ⋅ ⋅
Or
∆G 0 − ∆G = − q RT ln a Q − r RT ln a R + ⋅ ⋅ ⋅
+ l RT ln a L + m RT ln a M ⋅ ⋅ ⋅
Or a qQ a rR ⋅ ⋅ ⋅
∆G 0 − ∆G = − RT ln = − RT ln J
a a ⋅⋅⋅ l
L
m
M
The parameter J is called activity quotient
Or ∆G = ∆G 0 + RT ln J
Which is known as van’t Hoff isotherm.
Let us consider the equilibrium in which all the reactant and
products are in equilibrium. In this case the activity product
defined as K, the thermodynamic equilibrium constant.

eq
 a a ⋅ ⋅ ⋅
q r

At equilibrium ∆ G = 0, K =  Q

R

 a a ⋅
l
L ⋅ ⋅m
M

Or ∆G 0 = − RT ln [ J ] at eq. = − RT ln K
J
∆G = RT ln  
K
(J / K) < 1 reaction is in forward direction.
(J / K) > 1 reaction is in backward direction.

Since the standard state of a substance is at 1atm

pressure the ∆ G0 of a reaction is function of
temperature only. Therefore, the equilibrium
constant K also function of temperature only.
 Gibbs – Helmholtz Equation
For this process, mass, composition and pressure are
assumed to be constant only variation of temperature
is considered.
Derivation of Gibbs – Helmholtz Equation

∂G 
  = − S
 ∂ T P
∂G 
0r G = H − T S = H + T  
 ∂ T P
Deviding bothsides by T 2 we obtain
G H 1 ∂G 
= +  
T 2
T 2
T  ∂ T P
 1 ∂G  G H
or   − 2 = − 2
T  ∂ T P T T
 ∂ ( G T)  H
or   =− 2
 ∂ T P T

This is one of the form of Gibbs – Helmholtz Equation.

The
 alternative
 form can be derived as follows.
 ∂ ( G T)  1  ∂G  1  ∂G  ∂T
  =  + G =   +G
 1  T  ∂ (1 T )  P T  ∂ T  P ∂ (1 T )
 ∂  T  
 P
 
 ∂ ( G T)  1 ∂G  1 ∂G  G 
or   = − T 2   + G = − T 2    − 2 
 1  T  ∂ T P  T  ∂ T  P T 
∂ 
 T  
 P
  
 ∂ ( G T)   H 
  = − T2  − 2  = H
 1   T 

 ∂  T  
 P

This is the alternative form of Gibbs – Helmholtz Equation .

We can write Gibbs – Helmholtz Equation for a process as
 ∂ ( ∆G T )  ∆H
  = −
 ∂ T P T2 Utility
 Evaluation of enthalpy of reaction from
  free energy change.
 ∂ ( ∆G T )   Evaluation of free energy change from
  = ∆H
 1  calorimetric data.
 ∂  T  
 P
∆G 0T ∆H 0T
T
=− ∫ T2 d T
 ∆H 1 
or ∆G 0T = − T ∫  2 0 + 2 ∫ ∆C P d T  d T
 T T 
 ∆H 1
( ) 
= − T ∫  2 0 + 2 ∫ ∆a + ∆b T + ∆c T − 2 d T  d T
 T T 
 ∆H ∆a ∆b ∆c 
= − T ∫  20 + + − 3  dT
 T T 2 T 
∆b 2 ∆c 1
= ∆H 0 − ∆a T ln T − T − + IT
2 2 T
Where ∆H 0 and I are int egration cons tan t. These are det er min ed
from the knowledge of either ∆G 0 at two temperatures or ∆G 0 and
∆H 0 at one temperature.
 Trouton’s and
Rechard’s Rules
Rechard’s rule: it states that the ratio of latent heat of melting
to the temperature of the normal melting point of the F.C.C
metal is approximately 9.61 J / K and that of BCC metal is
approximately 8.25 J / K. i.e
∆ Hm
= 9.61 J / K for F.C.C metal
Tm
∆ Hm
= 8.25 J / K for B.C.C metal
Tm
Trouton’s Rule: it states that the ratio of latent heat of boiling to the temperature of
the normal boiling point of the F.C.C metal is approximately 87 J / K.

∆ HV
= 87 J / K
TV
Problem
The initial state of one mole of an ideal gas is P = 10 atm and
T = 300 K. Calculate the entropy change in the gas for
a) Reversible isothermal decrease of pressure to 1 atm.
b) Reversible Adiabatic decrease of pressure to 1 atm.
c) Reversible constant volume decrease of pressure to 1 atm.
Solution
P1 = 10 atm and T1 = 300 K
R T1 0.08207 × 300
P1 V1 = R T1 ⇒V1 = = = 2.462 ltrs .
P1 10
a ) P2 = 1 atm and T2 = T1 = 300 K as per isothermal process
P1 V1 10 × 2.462
P1 V1 = P2 V2 ⇒V2 = = = 24 .62 ltrs .
P2 1
 2 2 V2 V2
δ q rev d U + P dV P R
∆S = ∫
1
T
= ∫
1
T
= ∫
V1
T
dV = ∫
V1
V
dV

V   24.62 
= R ln  2  = 8.314 ln   = 19.14 J / K
 V1   2.462 
δ q rev
b) dS = = 0 as δ q rev = 0 for adiabatic process
T
3 P V 1× 2.462
c) P2 = 1 atm., C V = R , T2 = 2 2 = = 30 K
2 R 0.08207
2 2 2 T2
δ q rev d U + P dV dU CV
∆S = ∫
1
T
= ∫
1
T
= ∫
1
T
= ∫
T1
T
dT

T  3  30 
= C V ln  2  = × 8.314 ln   = − 28.71 J / K
 T1  2  300 
Problem
Calculate the entropy change of the universe in isothermal
freezing of 1 gm-mole of super cooled liquid gold at 1250 K
from the following data for gold.
Tm = 1336 K,∆ H0m = 12.36 kJ/mol,
CP(s) = 23.68 + 5.19 x 10-3 T J / mol / K, CP(l) = 29.29 J / mol / K
Solution
∆S Universe = ∆SSystem + ∆SSurroundin g
i) ∆ SSystem
In this case freezing process is isothermal but irreversible,
sin ce it is not occuring at the equilibrium freezing temperature.
But, ∆ SSystem is to be calculated only along a reversible path.
It makes no difference as to which reversible path we choose sin ce
entropy is a state property.
 The simplest reversible path is
Au (l) Heating
→ Au (l) Freezing
 → Au (s) Cooling
→ Au (s)
at 1250 K at 1336 K at 1336 K at 1250 K
(State − 1) ( State − 2)
1336 1250
C P ( l) ∆ H 0m C P (s)
∆SSystem = S2 − S1 = ∫
1250
T
dT −
Tm
+ ∫
1336
T
dT

1336
29 .69 12360
1250
(23 .68 + 5.19 × 10 −3
T ) dT
= ∫
1250
T
dT −
1336
+ ∫
1336
T

=−9.327 J K −1
ii) ∆ SSurrounding
Both the initial and final state of the system have been assumed to be at 1250 K.
This is possible only if the surrounding is at 1250 K and it has inf inite heat capacity.
Surrrounding absorbs heat released during freezing reversibly at 1250 K. Hence
δ q ∆ H System
∆ SSurrounding = =
T T
1336 1250
∆ H System = H 2 − H 1 = ∫
1250
C P (l)d T − ∆ H 0m + ∫
1336
C P (s) d T

1336 1250

∫ ∫ ( 23.68 + 5.19 × 10 )
−3
= 29.69 d T − 12360 + T dT
1250 1336

= − 12460 J
∆ H System 12460 ∆ Suniverse is positive since
∆ SSurrounding = = = 9.967 J K −1
T 1250 the process is irreversible.
∆ SUniverse = − 9.327 + 9.967 = 0.64 J K −1
Problem
one gram of liquid ThO2 at 2900 0C is mixed with 5 gm of ThO2
at 3400 0C adiabatically. a) what is the final temperature
b) What is the entropy change of the system and surrounding
Combined c) is the process spontaneous? Assume CP to be
Independent
Solution
of temperature.
a ) Heat released by hotter body = heat absorbed by colder body
( m C P d T ) Hot = ( m C P d T ) cold
5 C P ( Tf − 3173) = 1 C P ( 3673 − Tf )
Tf = 3589 K
Tf
dT
entropy change of cold body (∆ SC ) = C P ∫T
TC
Tf
dT
entropy change of hot body (∆ SH ) = 5 C P ∫T
TH
b) Total entropy change of the system (∆ SSystem ) = ∆ SH + ∆ SC
Tf T
dT f
dT
= 5 CP ∫ + CP ∫
TH
T TC
T
 Tf   Tf 
= 5 C P ln   + C P ln  
 TH   TC 
= 0.00752 C P
c) Entropy change of the surrounding is zero
as process is carried out adiabatically.
∆SUniverse = ∆SSystem + ∆SSurrounding > 0
So the process is spon tan eous
Problem
Calculate the standard entropy change of the following reaction
at 1000 K.
Pb (l) + 0.5 O2(g) = PbO (s)
and also calculate the entropy change of the Universe.
Given: Tm,Pb = 600K, ∆ H0m,Pb = 4812 J mol-1, ∆ H0PbO,298 = -219 kJ
S298,PbO = 67.78 J K-1 , S298,Pb = 64.85 J K-1 , S298,O2 = 205.09 J K-1
CP,PbO(s) = 44.35 + 16.74x10-3 T J K-1 mol-1
CP,Pb(s) = 23.55 + 9.75X10-3 T J K-1 mol-1
CP,Pb(l) = 32.43 – 3.09X10-3 T J K-1 mol-1
CP,O2 = 29.96 + 4.184X10-3 T - 1.67x 105 T-2 J K-1 mol-1
Solution
The Pr oblem physically consists of evaluation
∆S1000
0
for the reaction
1
Pb (l) + O 2 (g ) = PbO (s) ................(1)
2
from ∆S0298 and ∆C P values for the reaction
1
Pb (s) + O 2 (g ) = PbO (s) .................(2)
2
1 0
∆S0298 = S0298, PbO − S0298, Pb − S298, O 2
2
1
= 67.78 − 64.85 − × 205.09 = − 99.615 J K −1
2
∆C P (1) = − 3.05 + 17.72 × 10 −3 T + 0.836 × 10 5 T − 2 J K −1 mol −1
∆C P (2) = 5.81 + 4.89 × 10 −3 T + 0.836 × 10 5 T − 2 J K −1 mol −1

Noting that Pb melts at 600 K , we can write

600 1000
∆C P (2) ∆H 0m ∆C P (1)
∆S = ∆S + ∫ dT − + ∫
0 0
1000 298 dT
298
T Tm 600
T
 600 
 + 17.72 ×10 ( 600 − 298)
−3
= ∆S0298 − 3.05 ln 
 298 
0.836 × 105  1 1  4812  1000 
−  2
− 2  − + 5.81 ln  
2  600 298  600  600 
0.836 ×105  1 1 
+ 4.89 ×10 (1000 − 600 ) −
−3
 2
− 2 
2  1000 600 
= − 99.615 − 2.13 + 5.35 + 0.35 − 8.02 + 2.96 + 1.956 + 0.07
= − 99.079 J K −1
Heat released by the reaction or heat of reaction at 1000 K is
600 1000
∆H = ∆H + ∫ ∆C P (1) d T − ∆H + ∫ ∆C P ( 2) d T ∴ ∆H 0298 = ∆H 0298, PbO
0 0 0
1000 298 m
298 600

17.72 × 10 −3
= ∆H − 3.05 ( 600 − 298) +
0
298
2
600 2 − 298 2( )
 1 1 
− 0.836 × 10 5  −  − 4812 + 5.81(1000 − 600 )
 600 298 
4.89 × 10 −3
+
2
( )  1
1000 2 − 600 2 − 0.836 × 10 5  −
1 

 1000 600 
= − 219 × 10 −3 − 9 21.10 + 2402.79 + 141.20 − 4812 + 2324 + 1564.80 + 55.73
= − 218.244 kJ
Assu min g that the surr ounding is at 1000 K having l arg e heat capacity.
∆H1000
0
218.244
∆Ssurrounding = = = 218 J K −1
T 1000
∆SUniverse = ∆SSystem + ∆SSurrounding
= − 99.079 + 218 = 119 J K −1
Problem
From the data given for different phases involved, calculate the
change in entropy of one mole of manganese when it is heated
from 298 K to 1873 K under one atmospheric pressure.
(CP)α -Mn = 5.7 + 3.4 x 10-3 T – 0.4 x 105 T –2 cal / deg/ mol
(CP)β -Mn = 8.3 + 0.73 x 10-3 T cal / deg/ mol
(CP )γ-Mn = 10.70 cal / deg/ mol
(CP )δ-Mn = 11.3 cal / deg/ mol
(CP )Mn , l = 11.0 cal / deg/ mol
Transformation Temperature / K Latent heat in Cal / mol.

α →β 990 535
β →γ 1360 525
γ →δ 1410 430
δ→l 1517 3500
The total change in entropy will be equal to the sum of the
changes in entropy due to the rise of temperature and those
due to the phase transformation occurring on heating. Thus

α − Mn 990
→ β − Mn 1360
→
 γ − Mn 1410
→
 δ − Mn 1517
→ l − Mn

990
( C P ) α − Mn 535
1360
( C P ) β − Mn 525
∆S = ∫
298
T
dT +
990
+ ∫
990
T
dT +
1360
1410
( C P ) γ − Mn 430
1517
( C P ) δ − Mn
+ ∫
1360
T
dT + + ∫
1410 1410 T
dT

3500
1873
( C P ) l − Mn
+ + ∫ dT
1517 1517 T
 5.7 + 3.4 ×10 − 3 T − 0.4 ×10 5 T − 2
990
∆S = ∫
298
T
dT + 0.5404

8.3 + 0.7 ×10 − 3 T

1360 1410
10.7
+ ∫
990
T
dT + 0.3860 + ∫
1360
T
dT

1517 1873
11.3 11
+ 0.3049 + ∫
1410
T
dT + 2.3071 + ∫
1517
T
dT

∆S = 9.4010 + 0.5404 + 2.8945 + 0.3860 + 0.3863 + 0.3049

+ 0.8265 + 2.3071 + 2.3188 = 19.3655 cal / K / mol.
Problem
Using the following values, calculate the standard free energy change per
mole of the metal at 1000 K for the reduction of molybdic oxide and chromic
oxide by hydrogen:

∆ G 1000
0
, Cr2 O 3 ( s ) = − 205.5 kcal / mol.

∆ G 1000
0
, MoO 3 ( s ) = − 120.0 kcal / mol.

∆ G 1000
0
, H 2 O ( g ) = − 45.5 kcal / mol.
Solution
3
2 Cr + O 2 → Cr2 O 3 ; ∆ G1000
0
= − 205.5 kcal / mol.
2
3
Mo + O 2 → MoO 3 ; ∆ G1000
0
= − 120.0 kcal / mol
2
1
H 2 + O 2 → H 2 O; ∆ G1000
0
= − 45.5 kcal / mol
2
The reduction reaction can be written as
Cr2 O 3 + 3 H 2 → 2 Cr + 3 H 2 O

∆G 0
=
[ 3 × ( − 45.5) − ( − 205.5) ]
= 34.5 kcal / mol.
1000
2
MoO 3 + 3 H 2 → Mo + 3 H 2 O
∆ G1000
0
= 3 × ( − 45.5) − ( − 120 ) = − 16.5 kcal / mol.
sin ce the free energy change for the reduction of chromium
oxide is + ve , it can not be reduced by hydrogen at this
temperature. But, molybdenum can be reduced at this
temperature as the free energy change is − ve.
Problem
The standard heat of formation of solid HgO at 298 K is – 21.56
kcal / mol. The standard entropies of solid HgO, liquid Hg and
O2 at 298 K are 17.5, 18.5 and 49.0 cal /deg/mol, respectively.
Assuming that ∆ H0 and ∆ S0 are independent of temperature,
calculate the temperature at which solid HgO will dissociate
into liquid Hg and O2.

Solution
∆H 0298, HgO ( s ) = − 21.56 kcal / mol
S0298, HgO ( s ) = 17.5 cal / deg/ mol /
S0298, Hg ( l ) = 18.5 cal / deg/ mol /
S0298, O 2 ( g ) = 49 cal / deg/ mol /
The reaction can be written as
1
Hg (l) + O 2 (g ) = HgO (s)
2
∆H 0298 = ∆H 0298, HgO (s ) = − 21.56 kcal / mol.
1 o
∆S 0298 = S o298, HgO ( s ) − S o298, Hg ( l ) − S 298,O 2 ( g )
2
1
= 17.5 − 18.5 − × 49 = − 25.5 J K −1
2
sin ce ∆H 0 and ∆S 0 are independent of T
We can write ∆G 0T = ∆H 0298 − T ∆S 0298
The solid HgO will start to dissociate when ∆G 0 = 0
∆G 0T = ∆H 0298 − T ∆S 0298 = − 21560 + 25.5 T cal / mol
21560
0 = − 21560 + 25.5 T ⇒ T = = 845 K = 572 0 C
25.5
 Problem
For the reaction WO3 + 3H2(g) =W(s) + 3H2O(g)
a)Calculate ∆ G0 and K at 400, 700 and 1000K
b)What is the maximum moisture content of H2 needed for the
reaction given:
3
WO3(s) = W(s) + O2 ( g ), ∆G = 201500 + 10.2 T log T − 91.7 T cals
0

2
3H2 + 3
O 2 (g ) = 3H 2 O(g ) , ΔG 0 = -176700 + + 39.3 T cals.
2
Solution:

WO3(s) = W(s) + 3
O2 ( g ), ∆G 0 = 201500 + 10.2 T log T − 91.7 T cals
H2 + 1 2
O2 ( g ) = H 2 O( g ) , ∆G 0 = − 58900 + 13.1T cals.
2
∴ WO3(s) + 3H2(g)W(s) + 3H2O(g),
∆G 0 = 24800 + 10.2 T log T − 52.4 T cals
 Problem-2
a) i) ∆G 0 at 400 0 K ∆G 400
0
= 24800 + 10. x 400 log 400 − 52.4 x 400 =14460 cals.
∆G at 700 K
0 0
ΔG 0700 = 5122 cals.
ii)
∆G at1000 K
0 0 0
ΔG1000 = 3000 cals.
iii)
∆G 0
− ∆G 0 RT
∆G = − RT ln K i.e. ln K = −
0
or K = e
RT

K400= 1.26x10-8
K700= 2.5x10-2 3
 p H 2O 
K1000== 0.22
K 
 pH 
b)  2 
 solution
p H 2O
= K14003 = (1.253 x 10-8 )
1 3
= 2.472 x 10-3
pH2
p H 2O pH2
pH2 + =1
1
p H 2 =(0.00247+1)
= 0.=9975
1 atm.
1.002472
and ∴p H 2O = 0.002466 atm

%p
moisture = 0.24 %
=700( 2=.52.317x10
x 10-2 ) -3 = 0.296
H 2O 1 3
At 700K,
pH2 K
 solution
p H (0.296
2
+1) =1

1
pH2 = = 0.7716 and p H 2O = 0.2283
1.132

∴% H 2 O at 700K = 22.83%
at 1000K K1000 = 0.22

p H 2O
= ( 0.22) 1 3 = 0.6067
p H2
1
pH2 = = 0.6223
1.6067
pH2O = 0.3776
% H2O at 1000K = 37.76 %
 Problem-3
What is the maximum partial pressure of moisture which can
be tolerated in H2 – H2O mixture at 1atmospheric total
pressure without oxidation of nickel at 7500C?
1
Ni(s ) + O 2 (g ) = NiO(s ) ΔG10 = - 58450 + 23.55T cals.
2
1
H 2 (g ) + O 2 (g ) = H 2 O(g ) ΔG 02 = - 58900 + 13.1T cals.
2

Solution
Equation under question Ni + H2O = NiO(s) +H2

ΔG 0r = ΔG10 - ΔG 02
= 450 + 10.45 T cals.
 solution
∴ ∆ G 01023 = 450 + 10.45 x 1023
= 11140
= - RT lnK
11140
1.987 × 1023
ln k = - pH2
=-5.48006 p H O
2

Kp H=2 =+ 00.0041669
.0041669 p H 2O= (1)  p H 2 + p H 2O = 1 (2)

1
or p H 2O = = 0.99585
0.0041669 p H 2O + p H 2O = 1 1.0041669
from
∴ p =10.00415
H2
&2: Hence maximum tolerable partial pressure of
moisture is 0.99585 atm
 problem
The standard free energy change for reaction at 1125K NiO(s) +
CO(g) = Ni(s) + CO2(g) is -5147 cals. Would an atmosphere of 15% CO2,
5% CO and 80% N2 oxidise nickel at 1125K?

Solution:
∆ G0 = -RTlnK = -4.575 x 1125 log K = -5147

K = 10
5147
Klog K above
for the = reaction is = 1.000
4.575 x1125

p CO 2 a Ni a Ni = 1 = a NiO
K= .
In the given atmosphere
p <1 so anoNiO
i.e J/K is CO oxidation of nickel
p CO 2
= = 10
p CO 2
p CO
=3= J
p CO
 Problem
For the reaction NiO(s) + H2(g) = Ni(s) + H2O(g)
calculate the equilibrium constant at 7500C from the following
data:
1
Ni (s ) + O 2 ( g ) = NiO (s ), ΔG 0 = - 58450 + 23 .55 Tcals .
2
1
H 2 (g ) + O 2 (g ) = H 2 O(g ), ΔG 0 = - 58900 + 13.1Tcals.
2
Could pure nickel be annealed at 750 C in an atmosphere
0

containing 95% H2O and 5% H2 by volume without oxidation?

 solution
∆ G0 for the required reaction would be ∆ G0 = ∆G 20 − ∆G10
∆ G0 = -RT lnK = -4.575T log K

ΔG 0 p H 2O a Ni p H 2O
log K = = . =
4.575T p H 2 a NiO p H 2
11140
= = 2.38 (aNi = 1 = aNiO )
4.575 x 1023

p H 2O
K = 240 = i.e. p H 2O = 240 p H 2
pH2
p H 2O 95
given : = = 19 = J
p H2 5 J/K <1 rxn in forward direction
So no oxidation will take place
Problem
Calculate the standard enthalpy and entropy changes at 298 K
for the reaction
2 Cu (s) + ½ O2 = Cu2O (s)
∆ G0 = - 40500 -3.92 T log T + 29.5 T cal / mol

Solution
∆G 0 = − 40500 − 3.92 × 0.4343 T ln T + 29.5 T
= − 40500 − 1.702 T ln T + 29.5 T
∆G 0 40500
=− − 1.702 ln T + 29.5
T T
Differentiating,
(
∂ ∆G 0 T
=
)
40500 1.702
−
∂T T 2
T
By G − H equation, we can write
∆H 0 40500 1.702
− 2 = 2
−
T T T
or ∆H 0 = − 40500 + 1.70 T cal / mol
at 298 K ∆H 0298 = − 40500 + 1.70 × 298
= − 39.99 kcal / mol.
∂ ∆G 0
= − ∆S0 = − 1.702 − 1.702 ln T + 29.5
∂T
= 27.798 − 1.702 ln T
or ∆S0 = − 27.798 + 1.702 ln T
at 298 K, ∆S0298 = − 27.798 + 1.702 ln 298
= − 18.10 cal / K
Problem
Enthalpy of the solid platinum at any temperature is given by
the expression:
H T = H 298 + 5.8 T + 0.64 × 10 −3 T 2 − 1785 cal / mol.
Derive an expression for the change in free energy when one
mole of platinum is heated from 298 K to any temperature T K.

Solution
According to G − H equation of any system at
temperature T.
G  HT 
  = − ∫ 2  dT + C
T T 
Thus
 GT 

H
 = − ∫  298
2
+
5. 8
+ 0(.64 ×10 −3
−) 1785 
2 
dT + C
 T   T T T 
G  H − 1785
or  T  = − 298 − 5.8 ln T − 0.64 ×10 −3 T + C
 T  T
or G T = ( H 298 − 1785) − 5.8 T ln T − 0.64 ×10 −3 T 2 + C T

The free energy change ∆G on heating to temperature T

from 298 K will therefore be given by
∆G = G T − G 298

G 298 = ( H 298 − 1785) − 5.85 × 298 × ln 298 − 0.64 ×10 −3 2982 + 298 C

or ∆G = C T − 5.8 T ln T − 0.64 ×10 −3 T 2 − 298 C + 9903.69 cal / mole

 Problem-1
Calculate (1) the elevation of the boiling point of zinc when the external pressure
is 2 atm. and (ii) the depression of the freezong point when the external
pressure is 50 atm. The latent heat of vaporization of zinc is 27.3 kcal/g atom
and the normal temperature of boiling is 9070C. The corresponding heat of
fusion is 1.74 kcal/gatom and the normal temperature of fusion is 419.50C.
The density of solid zinc is 7.0 g/cc and that of liquid zinc is 6.48 g/ce at 1
atm. pressure.
Solution
Using the Clausius-Clapeyron equation for this problem we have dP ∆S e
=
dT ∆V
e
dP L
= e where v g is the volume of 1 gatom of zinc vapour and v l is the volume of 1 g atom of
dT T ( v g − vl ) )
liquid
To zinc this problem we have also to know the values of the volume of 1
solve
gatom of zinc in the vapour and liquid states. The volume occupied by 1 gatom
of a perfect gas at STD in 22400 cc.
The volume occupied by 1 g.atom of zinc vapours at 9070C
(1180K) is
22400
vg = ( 1180) cc.
273
65.38
Volume occupied by 1 gatom of liquid zinc = = 10.09 cc.
6.48

Substituting these values in the equation dP = 1 atm.

(
dP.T e v g - v l )
dT = e
1 cc atm = 0.024212 cals.
L
 v g >> vl ∴ v g − vl = v g
 solution
1×1180 × 22400 ×1180 cc .atm.K
=
27300 × 273 cal
1×1180 ×1180 × 22400 × 0.024212 cal K
= = 101.3 K
27300 × 273 cal
dP Lf 65.38
(ii) = vl = ,
dT T f
( vl − v s ) 6.48
65.38
vs =
f
7
dP.T
∴ dT = ( vl − v s )
Lf
 65.38 65.38 
49 × 692.5  − 
 6.48 7.0  cc atm K
1cc atm = 0.024212 cal.
1740 cal.
 Problem-2
49 × 692.5
= (10.089 - 9.34) × 0.024212
1740
49 × 692.5
= × 0.75 × 0.024212
1740
= 0.354 K Ans
 Problem-2
The latent heat of vaporization of zinc is 27.3 k cal/mole at the boiling point of
9070C. Find the vapour pressure over pure zinc at 8500C.
Solution:
for l → g transformation we have
dP Le Le RT
= e = e v g >> . vl ; v=
dT T ( v g − vl ) T v g P
dP LP
= p 1 = 1 atm., T1 =1180 K , p 2 = ? , T2 =1123 K
dT RT 2

dP L 1 p2 L  T2 − T1 
∫ P = R ∫T2 or ln
p1
=
R

 T1T2 

 Solution
27300  1123 − 1180 
ln p2 – 0 =   = -0.5909869
1.987  1180 ×1123 

p2= 0.55378 atm

 Lechatelier’s Principle
Statement
It states that if an equilibrium in a system is upset,
the system will tend to react in a direction that will
reestablish the equilibrium.
Factors
i) Concentration of reactant and product
ii) Pressure
iii) Temperature
 Effect of concentration
Consider the reaction
A+B=C+D K=
[ C] [ D]
At equilibrium for which [ A] [ B]
●
If the concentration of any one of the reactant or product is altered the concentration of
others must alter to keep K constant.
●
If for example [D] is increased by adding more D to the system then [C] will decrease
(by reaction with D to form A and B) preserving the value of K.
●
In general, If the product is added, the system will shift towards left to reestablish the
equilibrium and converse is true for the reactant.
●
If the reactant is removed, the equilibrium will shift towards reactant and same
is true for the product.
●
This shift of equilibrium may be used to advantage in some commercial
processes since continuous removal of product will drive the reaction to
completion. This is more easily achieved if one of the product is a gas e.g.
CaCO3 = CaO + CO2
In the lime kiln removal of CO2 in an air current drives the reaction towards
right.
●
Other example is the production of magnesium:
2 MgO(s) + Si(s) = 2Mg (g) + SiO2(s)
At the temperature employed the magnesium vapour can be evacuated.
 Effect of Pressure
●
Changes in pressure have no effect on the position of equilibrium when only
solids or liquids are involved or in gaseous reactions involving no volume
change e.g.
FeO(s) + CO(g) = Fe(s) + CO2((g)
●
Since equal volumes of gas appear in both sides.
●
However, the equilibrium position for a reaction in which changes in
gaseous volume occur may be displaced by pressure
●
We can consider following examples
● N2(g) + 3 H2(g) = 2 NH3(g)
1 vol + 3 vol = 2 vol
Here in this case there is an overall volume decrease( 4 → 2).
●
If the system is subjected to a pressure increase the system will move in
such a direction as to lessen this increase in pressure .
●
By moving to the right the volume diminution results in reduction in
pressure i. e increasing pressure drives the reaction to the right.
●
Ammonia is commercially produced at 350 atm.
 Effect of Temperature
●
‘K’ is unaffected by concentration and pressure change but dependent on
temperature.
●
Exothermic reaction:
N2 +3 H2 = 2 NH3 ∆ H = - 92.37 kJ
●
If the temperature is increased the system reacts in such a way as to
oppose this constraint by removing heat. Which can be done by shifting to
the left.
●
Exothermic reactions are favoured by low temperature
●
Endothermic reaction:
●
ZnO + C = Zn + CO ∆ H = +349 kJ
●
Increase in temperature will again shift the equilibrium in the direction
which absorbs heat
i. e. to the right in this case.
●
Endothermic reactions are therefore, favoured by high temperatures.
 Clausius-Clapeyron Equation
●
It is extremely important for calculating the effect of
change of pressure on the equilibrium transformation
temperature.
Derivation
●
Let us consider a single solid substance in equilibrium with its liquid at its
temperature of melting and under one atm pressure.

●
There is a natural tendency for the molecule to pass from solid into liquid or
vice versa.
●
The number of atoms passing at any time from one state to other will depend
on the temperature and pressure.
Let us assume that the molar free
Energy of the solid at constant T, P
Is GA and of the liquid is GB; then
If GA > GB the solid metal can
Me (l)
decrease its free energy by
GB
dissolving, i. e. if
GA > GB Solid → Liquid; solid melts since ∆ G = -ve
Me (s)
GA = GB Solid = Liquid; Equlibrium since ∆ G = 0 GA
GA < GB Solid ← Liquid; liquid solidifies since ∆ G = +ve
The condition for a dynamic equilibrium between the
solid and the liquid metal is
GA = GB
and dGA = dGB
The change in the free energy of either phase may
caused by the change in temperature and pressure
of the phases.
dG = f ( T, P)
 ∂ GA   ∂GA 
dG A =   . dT +   . dP
 ∂T P  ∂P T
 ∂GB   ∂GB 
dG B =   . dT +   . dP
 ∂ T P  ∂ P T
At equilibrium dGA = dGB

 ∂ GA   ∂ GA   ∂ GB   ∂ GB 
  . dT +   . dP =  ∂ T  . dT +  ∂ P  . dP
 ∂ T P  ∂ P T  P  T
− S A dT + v A dP = − S B dT + v B dP
Or

Or
( vB − v A ) dP = ( S B − S A ) dT

Or ∆v . dP = ∆S . dT
Or dP ∆S ∆H tr
= as ∆S =
dT ∆V Ttr
dP ∆ H tr
=
d T Ttr ( v B − v A )
Or dP ∆ H tr
= Clausius – Clapeyron
dT Ttr ∆v Equation
● If ∆ v is +ve as is normally in the case of melting and ∆ Htr will be +ve quantity i. e as
the pressure increases the transition temperature should also increase. In other words
the equilibrium melting point shall increase with pressure and vice versa.

●
However, for ice – water system ∆ v is – ve and hence (dP / dT) is –ve and which is
fully exploited in the game of skating on ice wherein the skate pressure increase shall
decrease the melting point of ice and hence help skating by providing fluid for
lubrication.
 Applications of Clausius – Clapeyron Equation

Liquid − Vapour Equilibia

dP ∆ HV
=
d T T ( v vap − v liq )
where ∆ H V is the latent heat of vapourization
and v vap and v liq are the molar volumes of vapor
and liquid respectively.
 Applications of Clausius – Clapeyron Equation

Contd….

v vap >> v liq hence

dP ∆HV
=
dT T v vap
Assu min g that the vapor behaves as an
ideal gas
RT
v vap =
P
after substituti on we get
dP P ∆HV d ( ln P ) ∆HV
= 2
⇒ =
dT RT dT R T2
 Assu min g ∆ H V is cons tan t then
int egration of above eq.
∆ HV
ln P = − +C
RT
where C is int egration cons tan t
 1 ∆ HV
The slope of the plot ln P vs.  is − and
 T R
int ercept is C. The heat of vapourization of liquid
metal calculated by this method will be the mean
value over the temp int erval concerned
Integration of C − C equation can be done within
the lim its P1 and P2 corresponding to the temps
T1 and T2 respectively. Assu min g that ∆H V is
independent of temperature.
P2 T2
∆ HV dT
∫ d ( ln P ) =
P1
R ∫T T 2
1

P2 ∆ HV  1 1
or ln =−  − 
P1 R  T2 T1 
This equation can be used to calculate the vapour pressure at
any temperature if the vapour pressure at another temperature
and heat of vapourization are known.
Solid – Vapour (sublimation) Equilibria
On the basis of assumptions similar to those made
in liquid – vapour equilibria, one can obtain the
similar expression for solid – vapour equilibria.

d ( ln P ) ∆ HS
=
dT R T2
Where ∆ Hs is the heat of sublimation
Solid – liquid (Fusion) equilibria
d T Tf ( v liq − v solid )
Applying C – C equation to so solid liquid equilibria
dP ∆ Hf
= ⇒ =
d T Tf ( v liq − v solid ) dP ∆ Hf

∆ Hf is the molar heat of fusion, vliq and vsolid are the

molar volumes of liquid and solid respectively.

This equation may be applied to calculate the change

in melting point of a metal with change of pressure.
Solid – Solid equilibria
The rate of change of transition temperature at
which two crystalline forms of a solid are in
equilibrium with pressure is given by following
expressions: α → β Ttr

dP ∆ H tr d T Ttr ( v β − v α )
= ⇒ =
d T Ttr ( v β − v α ) dP ∆ H tr
Where ∆ Htr is the molar heat of transition, vα and
vβ are the molar volume of the indicated forms of
solid measured at Ttr.
 Ellingham Diagram
●
Ellingham diagrams are basically graphical representation of ∆ G0 vs. T
relations for the chemical reactions of chemical and metallurgical engineering
interest.
●
H. J. T. Ellingham in 1944, was first to plot the standard free energy of
formation of oxides against temperature and these later became known as
Ellingham diagram.
●
Later on the same plotting was applied for sulphides, chlorides, fluorides etc.
●
Oxide diagrams are mostly used in metallurgy.
 Features of Ellingham diagram
1) Formation reaction for oxides may be generalized as

2x 2
M + O2 ( g) = M x Oy
y y
Where the values of x and y will depend on the specific
compound. M and M x O y are general symbols for metal
and metal oxides, respectively.
Specific examples are
2 Ni + O 2 (g ) = 2 NiO
4 2
Al + O 2 (g) = Al2 O 3
3 3
Free energy is an extensive property
hence value ∆G 0 of a reaction would
depend on the no. of moles involved.
In the Ellingham diagram 1 mole of O 2
constitutes the basis in the oxide formation
reaction. Thus the value of ∆G 0 are per mole
of oxygen. S tan dard free energy means the
reac tan t (metal) and product are in their
s tan dard state or pure states e.g. at unit
activity
2) Since ∆ G0 = ∆ H0 - T ∆ S0
The variation of ∆ H0 not being large, it can be treated as constant over a wide range of
temperatures. ∆ S0 however, changes with temperature particularly when gaseous
phases are involved with the condensed phases.
The plot of ∆ G0 against temperature is a straight line. So the slope of the line is
- ∆ S0 . Let us consider the reaction
M(s) + O2 (g) = MO(s)
∆ S0 = S0 (oxide) - S0 (metal) - S0 (oxygen gas)
since S0 (oxide) and S0 (metal) are practically the same, the
entropy change (∆ S0) arises predominantly due to disappearance of one mole of oxygen
gas and hence it is -ve. So the slope of the line is positive.
 The entropy changes of various such metal oxidation process are expected to be
substantially of the same value. Therefore, the most of the oxide lines slope
upwards and parallel to each other.

3) The plot of ∆ G0 against temperature is a straight line as long as there is no

phase change (melting, boiling, phase transformation) in either the reactant and
products. The reason is that when such phase change takes place, there is a
change in entropy and since the change entropy is the slope of the line, therefore
when such changes takes place, the straight line will change its slope. Let us
consider the reaction
let us consider the melting of reactant. The reaction is
M(l) + O2(g) = MO(s)
∆ S0 = S0 (oxide) - S0 (metal (l)) - S0 (oxygen gas)
Since S0 (metal (l)) > S0 (metal (s))
∆ S0 = more negative than when both were solid
Hence the slope of the line will be further upwards from
the temperature of melting.
if the reactant boils. We can write
S0 (metal (g)) > S0 (metal (l))
∆ S0 = more negative than when metal oxide was solid
and metal was liquid
Hence the slope of the line will be further upwards from
the boiling point..
let us consider the melting of product. The reaction is
M(s) + O2(g) = MO(l)
∆ S0 = S0 (oxide(l)) - S0 (metal (s)) - S0 (oxygen gas)
Since S0 (oxide (l)) > S0 (oxide (s))
∆ S0 = les negative than when both were solid
Hence the line will be bend downward with +ve slope from
the temperature of melting.
if the product boils. We can write
S0 (oxide (g)) > S0 (oxide (l))
∆ S0 = less negative than when metal oxide was liquid
and metal was solid
Hence the line will be bend further downward with +ve slope from the temperature of
melting.
4) The intercept of the straight line with the ordinate at absolute zero gives
approximately the value of ∆ H0, since from the equation ∆ G0 = ∆ H0 - T ∆ S0
when T = 0, ∆ G0 = ∆ H0
5) since ∆ G0 must have a negative value for the reaction to take place, it can be seen
from this plot that all metals shown below the negative areas of ∆ G0 are oxidized
spontaneously by oxygen while those above are not e. g. gold
6) When a line touches the positive regions of ∆ G0 this means beyond that temperature
no further oxidation can take place or the oxide formed in that region is unstable or
oxides will start decomposing when ∆ G0 = 0. i. e Ag2O will decompose at 15000C.
7) The stability of an oxide is directly related to its - ∆ G0 values; less stable oxides
have a small - ∆ G0 and more stable oxides have a high - ∆ G0 value.

8) An oxide can be reduced by only those metals below it in Ellingham diagram; the
reverse cannot take place. For example at 8000C, Cr2O3 can be reduced by
aluminium but Al2O3 cannot reduced by chromium:
4/3 Al + O2 = 2/3 Al2O3 ∆ G0 = - 800 kJ
4/3 Cr + O2 = 2/3 Cr2O3 ∆ G0 = - 500 kJ
2/3 Cr2O3 + 4/3 Al = 2/3 Al2O3 + 4/3 Cr; ∆ G0 = - 300 kJ
9) ∆ G0 of an oxide may be greater than another at low temperature but becomes
less than the other at higher temperature. Thus while the MnO is reduced by Na
below 2200C, the reverse is true above that temperature.
10) The line of the reaction C + O2 = CO2 runs nearly horizontally on the chart i.e its
slope is zero or practically there is no entropy change for this reaction. This can
be seen from the fact that the initial and final volumes are practically the same
which is the one volume of oxygen gas and one volume of CO2, respectively;
entropy of the solid being negligible.
11) The line for the reaction 2 C + O2 = 2CO runs downwards i.e. it has a negative slope,
this is due to the large increase in entropy: two volume of gaseous CO are formed
from one volume of oxygen gas. In this case ∆ G0 become more negative as the
temperature increases.

12) That the line for CO formation runs downward is of great importance in
pyrometallurgy. It enables almost all the metal – metal oxide lines meet C – CO lines
at high temperature. This makes most the oxides unstable beyond point of
intersection. This is called reversion of stability. This means that reduction of most
metal oxides by carbon is possible at high temperature.
13) Carbon monoxide can reduce all oxides above the CO2 lines. For example at
7000C NiO can be reduced by CO
2 CO + O2 = 2 CO2 ∆ G0 = - 95 kcal.
2 Ni + O2 = 2 NiO ∆ G0 = - 75 kcal.
2CO + 2NiO = 2Ni + 2CO2 ∆ G0 = - 20 kcal.
14) All oxides above H2O lines can be reduced by H2 e.g at 7000C
2 H2 + O2 = 2 H2O ∆ G0 = - 92 kcal.
2 Co + O2 = 2 CoO ∆ G0 = - 75 kcal.
2CoO + 2 H2 = 2Co+ 2 H2O ∆ G0 = - 17 kcal.
 Nomographic scale on Ellingham diagram

The diagram already described can be made more useful

by superimposing grids or nomographic scales around
them.
1. PO2 grid : Consider the reaction involving the oxidation of pure solid metal to pure
solid oxide
2 M (s) + O2 (g) = 2 MO (s)
∆ G0 = - R T ln (1 / PO2) = R T ln PO2
Hence knowing ∆ G0 and T the corresponding equilibrium PO2 can be calculated for
any such reaction.
When ∆ G0 = 0, PO2 = 1 atm and the equilibrium PO2 values radiate from the point ‘O’
on the ∆ G0 axis. For the fixed values of PO2 the ∆ G0 is plotted as a function of T
2) CO / CO2 grid: For the reaction
2 CO + O2 = 2 CO2
∆ G0 = - 135000 + 41.57 T cal / mole
∆ G0 = - R T ln K = - R T ln (P2CO2 / P2CO . PO2)
RT ln PO2 = ∆ G0 - 2 R T ln (PCO / PCO2)
= - 135000 + 41.57 T - 2 R T ln (PCO / PCO2)
RT ln PO2 can be plotted as a function of temperature for fixed values of CO / CO2.
When T = 0 , RT ln PO2 = - 135000 cal / mole. The equilibrium (PCO / PCO2) values
radiate from the point ‘C’ on the ∆ G0 axis.
3. H2 / H2O grid: For the reaction
2 H2 + O2 = 2 H2O
∆ G0 = - 118000 + 26.57 T cal / mole
RT ln PO2 = ∆ G0 - 2 R T ln (PH2 / PH2O)
= - - 118000 + 26.57 - 2 R T ln (PH2 / PH2O)
RT ln PO2 can be plotted as a function of temperature for fixed values of H2 / H2O. When
T = 0 , RT ln PO2 = - 118000 cal / mole. The equilibrium (PH2 / PH2O) values radiate from
the point ‘H’ on the ∆ G0 axis.
Use of Nomographic Scale
 Disadvantages of Ellingham diagram

1) The diagram is applicable only for the substances present in their standard states.
But practically activity may not be unity.
2) Compound whose formation lines are represented in the diagram are assumed to
be stoichiometric only which often is not true.
3) The information regarding rate of the reaction can not be obtained.
4) The diagram do not show the condition under which the reaction tend to occur.
5) Where oxide formation lines in the diagram are close together accurate
measurement and subsequent calculation is difficult.
6) The possibility of formation of intermetallic compound between reactants and
products is ignored
 Non-standard state condition
●
If any one of the constituents of the reaction is not present in its standard state is
called non-standard state condition.
●
The activity of that substance will be less than one.
●
It can be best illustrated by the reduction MgO by silicon.
2 MgO(s) + Si(s) = 2 Mg(g) + SiO2(s)
∆ G01473 = + 272 kJ
●
So there appears to be very little chance of using silicon as a reducing agent to
produce magnesium from magnesia.
●
From the van’t Hoff isotherm, the actual free energy change of the this reaction is
given by
 p 2
Mg . a SiO 2


∆G = ∆G + R T ln 2
0 
 a MgO . a Si 
 
● If pMg and aSiO2 can be lowered sufficiently, ∆ G can be made negative even though
∆ G0 is positive.
● PMg is lowered by working at a pressure of 10 – 4 atm.
● aSiO2 is lowered by adding sufficient CaO to form orthosilicate (2 CaO. SiO2). A
basic slag would give aSiO2 < 0.001.
 Third law of Thermodynamics
Enunciation of third law
The change in entropy with constant pressure and constant
volume is given by following equations
CP
dS = dT
T
CV
and dS = dT
T
Integration ofTthese two leads to the following
CP
S= ∫
0
T
dT + S0, P

T
CV
S= ∫
0
T
dT + S0, V Where S0,P, and S0,V are the
integration constant.
●
These equations also state that for calculation of absolute value of entropy of any
substance, these constants should be known.

●
In order to evaluate the constant, Nernst analyzed the low temperature data on free
energy and enthalpy of chemical reactions.

●
The analysis lead to the formulation of first, the Nernst heat theorem and later the
third law of thermodynamics.
 Nernst heat theorem
• Nernst collected enthalpy of
formation of various reactions
by calorimetric method and
determined free energies as a
function of temperature by emf
method.

• These free energies and

enthalpy when plotted against
temperature yielded curves as
shown.
It is seen from the figure that at low temperature that both
enthalpy and free energy of a reaction approaches each
other asymptotically with the asymptote laying parallel to
temperature axis. This lead Nernst to arrive at the following
conclusions: ∂ ( ∆ G)
( i ) Lim =0
T →0 ∂T
∂ ( ∆ H)
( ii ) Lim =0
As
T →0 ∂T
∂ ( ∆ G) 
  = − ∆S
Therefore, one can ∂ T P
 write
Lim ∆ S = 0
T →0
Statement of Nernst heat theorem
It states that both entropy change and temperature
coefficients of enthalpy and free energy changes for the
reaction tends to zero as temperature approaches 0 0K.
Entropy of a pure substance
A pure substance is a pure element or pure compound.
Consider the formation of compound AB from elements A
and B i.e
A(s) + B(s) = AB(s)
For which 0 0 0 0
Δ S = S
At absolute zero temperature ∆AB - S -
S = 0 it is possible
0
A Sprovided
B
either i)
0 0 0
Or ii) S AB = (S A + S B)
S0AB , S0A and S0B are all individually zero
● From a probability point of view, the first alternative is very unlikely as a general
feature. It may be true, by chance, in a few cases.

● Hence alternative (ii) is accepted as of general validity and it may be concluded

that “entropies of pure solids at T = 0 are zero”

● Therefore, the absolute value of entropy of a pure substance at any temperature

can be determined by taking T = 0, S = 0 as the lower limit.
 Various statements of third law
“All reactions involving substances in the condensed state
∆ S is zero at absolute zero”

“The entropy of any homogeneous crystalline substance

which is in complete internal equilibrium may be taken as
zero at 0 0K”

“The entropy of any phase whose quantum states and

atomic arrangement corresponds to a unique lowest energy
state at the absolute zero is zero”
 Experimental verification
of the third law
●
Third law is not so obvious as first and second law; hence it is required to describe
some of the evidence by which it was established.

●
The so called direct verification of the third law involves the application of the
second law, namely the principle that the entropy of the system is a function of
state and the net entropy change experienced by a system undergoing a cycle is
therefore zero.
• Let us consider the cycle shown T
in the figure.
II
• The starting point is a system
composed of reactants at the
absolute zero.
K
0
• The first step of the cycle
I
consists in heating the reactants III
to temperature T.
• The reaction is allowed to
completion at T in the second
step. IV
• The products are cooled to 0
0 % reacted 100
absolute zero in the third step.
• The fourth step which imaginary,
the reverse reaction is allowed to
proceed
●
We have from the second law
∆ SI + ∆ SII + ∆ SIII + ∆ SIV = 0
Or ∆ SIV = - (∆ SI + ∆ SII + ∆ SIII )
●
Since the entropy change in the first three steps measured experimentally, the
entropy change at absolute zero can be determined.
●
Let us consider the following transformation reaction
190 C
Sn (gray) ←
→ Sn ( white)
292
∆S I = ∫C
0
P (gray) d ln T = 9.11 EU

Qr 541
∆S II = = = 1.85 EU
Tr 292
0
∆S III =
292
∫C P ( white) d ln T = − 11.04 EU
● The entropy change at absolute zero ‘∆ S0’ is
∆ S0 = ∆ SIV = - (∆ SI + ∆ SII + ∆ SIII )
= - (9.11 + 1.85 – 11.04) = 0.08 EU
●
This is probably smaller than the experimental error and thus it has been shown
that in this case ∆ S0 is zero within the experimental error.
 Consequences of the third law
Third law leads to following important consequences
1. CP, CV and α will be zero at absolute zero.

G=H−TS
 ∂G  ∂H  ∂S 
  =   − T   − S
 ∂ T P  ∂ T P  ∂ T P
∂G  ∂H
As we know   = − S and   = C P
 ∂ T P  ∂ T P
 ∂S 
we can write C P = T  
 ∂ T P
 ∂S  Prove that CV is zero
as   is finite , at T = 0 ⇒ C P = 0
 ∂ T P at absolute zero
 1  ∂V
α =  
V  ∂ T P
according to max well' s equation
 ∂V  ∂S 
  = −  
 ∂ T P  ∂ P T
 ∂S 
as T → 0 , S → 0 so   =0
 ∂ P  T →0
 ∂V
⇒   = 0 ⇒ α = 0
 ∂ T P
2. Unattainability of absolute zero temperature
let us consider a carnot cycle in which heat is absorbed at temperature T (T > 00K)
delivered to cold reservoir maintained at 00K. Entropy change during such a cycle will
be equal to zero i. e.
∆ SI + ∆ SIII = 0

where ∆ SI is the entropy change during isothermal expansion and ∆ SIII is the entropy
change during isothermal compression.
 According to third law the entropy change during isothermal
volume change (∆ SIII ) at 00K is zero. Hence ∆ SI will be zero.

But this not true as both heat exchange and temperature for
this is finite non-zero and positive.

Hence one cannot design a cycle in which the temperature of

the working substance descend to the absolute zero.

Thus it can be concluded that the temperature of 00K cannot

be attained.
3. Calculation of entropy and free energy from calorimetric data.
Entropy of a substance at constant volume is given by
T
SV = ∫ C V d ln T + S0,V
0

As per third law S0,V = 0

T
therefore, SV = ∫ C V d ln T
0
From the knowledge of heat capacity which can be
determined by calorimetric techniques, one can
calculate the absolute value of entropy of a component
at any temperature T.
Third law also helps in the calculation of free energy during the
chemical reaction from the calorimetric data obtained in the
form of enthalpy of a reaction as a function of temperature. We
know ∆ G=∆ H–T∆ S

T T
∆C P
∆S = ∫ d T and ∆H = ∆H 0 + ∫ ∆C P d T
0
T 0

Where ∆ H0 is the enthalpy of reaction at 00K.

Or T
∆C P T
∆G = ∆H 0 + ∫ ∆C P d T − T ∫ dT
0 0
T
All the quantities present in the above expression can be
determined by calorimetric techniques. Thus, one can calculate
the change in free energy of any reaction at desired temperature
Problem
Calculate the standard free energy change ∆ G0
and free energy change ∆ G for the following
reaction at 1000 K.
Ca (a = 0.9 ) = Ca (a = 0.5 )
Solution
∆ G0 is calculated by measuring the free energy
change of both reactants and products in their
standard states. Since calcium is solid at 1000 K
the standard state for both reactant and products
is pure solid Calcium as indicated and thus
∆ G0 = 0
we know
∆ G = ∆ G0 + RT ln K
= ∆ G0 + RT ln (aproduct / aproduct)
= ∆ G0 + RT ln (aCa0.5 / aCa0.9)
= 0 + 8.314 x 1273 ln (0.5 / 0.9)
∆ G = - 4.88 kJ / mol
Problem
Consider the equilibrium reaction of pure solid CaSi at 1000 K
with Ca and Si dissolved in a solvent. Suppose that activity of
calcium is 0.5 in the solution and CaSi is pure. Find
i) aSi in equilibrium with Ca (a = 0.5) and pure CaSi
ii) PCa in equilibrium with dissolved Ca.
ι ι ι )∆ G1000K of the reaction:
Ca (a = 0.5) + Si(a= 0.4) = CaSi (a = 0.8)
Given : Ca(s) + Si(s) = CaSi (s); ∆ G01000k = - 172 kJ / mol
P0Ca = 14.6 N / m2
Solution
i)For the reaction: Ca(s) + Si(s) = CaSi (s)
∆ G0 = - RT ln K
K = exp (- ∆ G0 / RT)
= exp( 172000 / 8.314 x 1273 ) = 8.92 x 108
Or K = (aCaSi / aCa. aSi) = 8.92 x 108
since CaSi exists in pure states, aCaSi = 1 and
putting aCa = 0.5 we get aSi = 2.24 x 10-9

ii) It is given that aCa = 0.5, since aCa = PCa / P0Ca .

We can obtain PCa if the value of P0Ca is known.
Since our standard states for Ca is pure solid at
1000K, P0Ca is simply the vapour pressure of pure Ca at
1000 K. It is given that P0Ca = 14.6 N / m2, So PCa =
7.3 N / m2
iii) For the reaction
Ca (a = 0.5) + Si(a= 0.4) = CaSi (a = 0.8)
∆ G = ∆ G0 + R T ln K
= - 172000 + 8.314 x 1273 ln (0.8 / 0.5 x 0.4)
= - 160 kJ / mol
Problem
Solid TiO2 is converted into gaseous TiCl4 by treatment with
chlorine in presence of carbon. Calculate the thermodynamic
utilization of chlorine gas at 10000C. Assume the oxidation of
carbon into CO and total pressure as 1 atm.
Given: TiO2(s) + 2 C (s) + 2 Cl2 (g) = TiCl4(g) + 2 CO (g)
∆ G0 = - 318 kJ / mol at 10000C.
Solution
∆ G0 = - R T ln K
Or – 318 000 = - 8.316 x 1273 ln K
Or K = 1.11 x 1013 = (P2CO . PTiCl4) / (aTiO2 . a2C . P2Cl2)
Assuming TiO2 and carbon as pure solid aTiO2 = 1= aC
From the stoichiometry of the reaction production of one mole
of TiCl4 leads to the production of 2 moles of CO i.e.
PCO = 2 PTiCl4
Making all the substitution
P3TiCl4 / P2Cl2 = 0.275 x 1013 i.e PTiCl4 >> PCl2
So as a first approximation let us take PTiCl4= PT = 1atm. Then
we get PCl2 = 6 x 10 -7 atm. This is truly negligible. Therefore,
the thermodynamic utilization of Cl2 is 100%.
Problem
A gas consisting of 60.2% H2 , and 39.8 % H2O at 1
atmospheric pressure is in equilibrium with pure γ – iron at
9100C. At the same temperature the gas composition in
equilibrium with an iron – nickel alloy (0.71 atom fraction of
iron) is 51.9% H2 and 48.1% H2O. Determine the activity of
iron in the alloy.

Solution
In equilibrium with pure iron the reaction is:
Fe (s) + H2O(g) = FeO(g) + H2(g)
For which: K = (aFeO . PH2) / (aFe . PH2O)
Fe and FeO are in their standard state (aFe = 1 = aFeO)
K = (PH2 / PH2O)Fe, Pure
The corresponding reaction with the alloy is:
Fe (Fe - Ni) + H2O(g) = FeO(g) + H2(g)
The activity of pure FeO is again unity. But the activity of iron is
less than unity in the alloy. Thus :
K = (PH2 / aFe . PH2O)Fe – Ni
However the value of the equilibrium constant is unchanged on
the solution of the iron in the alloy, then:
(PH2 / PH2O)Fe, Pure = (PH2 / aFe . PH2O)Fe – Ni
Or aFe = (PH2 / aFe . PH2O)Fe – Ni / (PH2 / PH2O)Fe, Pure
Substituting the gas composition
aFe = (0.519 / 0.481) / (0.602 / 0.398) = 0.713
Problem
Chromium plates are bright annealed at 7270C in wet
hydrogen atmosphere. The pressure of wet hydrogen is 1 atm.
i) Calculate the permissible water content in the hydrogen if there is to be no oxidation at
7270C.
ii) Will annealed chromium plates be oxidized when cooled to 2270C in the furnace
atmosphere as calculated in (i).
Given: 2 Cr (s) + 3 H2O(g) = Cr2O3(s) + 3 H2
∆ G0 = - 91050 + 22.80 T cals.

Solution
i)For the reaction: 2 Cr (s) + 3 H2O(g) = Cr2O3(s) + 3 H2
∆ G01000K = - 68250 cal = - R T ln K
K = exp( - ∆ G01000K / 1.987 x 1000) = 8.26 x 10 14
K = (PH2 / PH2O)3 = 8.26 x 10 14
(PH2 / PH2O) = 9.384 x 10 4
As PH2 + PH2O = 1
After solving above equations we get:
PH2O = 1 / (1 + 9.384 x 10 4 ) = 1.065 x 10 – 5 atm.
Since total pressure is 1 atm, the volume percent of H2O
is1.065 x 10 – 3. This the maximum water content of H2 to
avoid any oxidation of chromium.
ii) ∆ G0500K = - 79650 cal = - R T ln K
K = 6.57 x 10 34
The activity quotient is :
J = (PH2 / PH2O)3 = (1 / 1.065 x 10 – 5 )3 = 8.25 x 1014
J / K = 8.25 x 1014 / 6.57 x 10 34 < 1 so forward reaction
will oxidise the Cr
Problem
The lowest temperature at which copper oxide (Cu2O)can
dissociate in a vacuum of 10 – 5 mm Hg.
Given : Cu2O(s)= 2 Cu(s) + ½ O2(g)
∆ G0 = 40500 + 3.92 T log T – 29.5 T cal
Solution:
For the reaction: Cu2O(s)= 2 Cu(s) + ½ O2(g)
∆ G = ∆ G0 + (RT /2) ln PO2 = ∆ G0 -2.288 T log PO2
PO2 = (0.2 x 10 -5 ) / 760 = 2.635 x 10 – 9 atm.
At equilibrium ∆ G = 0
∆ G0 = -2.288 T log (2.635 x 10 – 9 ) = 19.6 T
Or 40500 + 3.92 TD log TD – 29.5 TD =19.6 TD
Or 3.92 TD log TD = 49.1 TD – 40500
This is best solved graphically and TD = 1085 K.
Problem
i. At what temps will carbon reduce a) SnO2(s) b) Cr2O3 (s) and c) SiO2(s)?
ii. Steam blown through hot coke gives rise to the fuel gas mixture called water gas
(CO+H2): C + H2O = CO + H2. calculate the temperature the coke must be maintained
for the reaction to be feasible?
iii. At what temperature the Ag2O just begin to decompose at one atmospheric pressure?
iv. In what temperature range can hydrogen be used to reduce SnO2 to Sn?
v. Deduce the standard free energy change for the reduction of Al2O3 by Mg at 1000 0C.
vi. Explain the reasons for the change in slope of the following lines:
 2Mg + O2 = 2 MgO at 1100 0C.
2Pb + O2 = 2 PbO at 1470 0C
4 Li + O2 = 2 Li2O at 1300 0C
VII. Estimate the standard free energy change for the following reaction at 1200 K.
a) reduction of copper (I) oxide with hydrogen and b)
reduction copper oxide (I) with carbon.
VIII. At what temperature is the reaction: 4/3 Cr + O2 = 2/3 Cr2O3 at
equilibrium when PO2 is 10-14 atm.
IX. Calculate the equilibrium oxygen pressure between Al2O3 and Al at 1000 K. Could a vacuum
of 10-10 mm Hg prevent the oxidation of aluminum?
X. Suppose CaO is placed in a vacuume in which the partial pressure of oxygen is 10-5 mm Hg.
Will CaO be reduced.
XI. Which is the suitable material for the steam pipe Ni or Al?
XII. What is the equilibrium CO / CO2 ratio for the following reaction: MnO + CO = Mn + CO2
XIII. At what temperature is the reaction PbO + H2 = Pb + H2O at equilibrium when the H2 / H2O
ratio is 1/104?
Problem
Calculate the vapour pressure of liquid silver at its melting
point, 960 0C, making use of Trouton’s rule. Boiling point of
silver is 2210 0C.
Solution: According to Trouton ' s rule
∆H V
= 87 J / K
Tb
Hence ∆H V = 87 × 2483 = 216.021 kJ / mol.
We know for the liquid vapour equilibria
∆H V
ln p = − +C
RT
C can be evaluated by the condition P = 1 at T = 2483 K
C comes out to be 10.46.
∆H V
So ln p = − + 10.46
RT
216021
or ln p = − + 10.46 = 2.459 ×10 − 5 atm
8.314 × (960 + 273)
Problem
The equilibrium vapour pressure in atm. of a solid is given by the
expression: ln p = - 4.085 + 1.57x10 -4 ln T – 2.83x10- 3 T
Calculate the heat of sublimation of solid at 300 0C.
Solution:

We know for the solid − vapour equilibria

d ln p ∆H S 2 d ln p
= 2
⇒ ∆H S = R T
dT RT dT
it is given that for the solid
ln p = − 4.085 + 1.57 ×10 − 4 ln T
− 2.83 ×10 − 3 T
d ln p 1.57 ×10 − 4
So = − 2.83×10 − 3
dT T
putting this in the aboveequation we get
  1. 57 ×10 −4
−3 

∆H S = RT 
2
− 2.83 ×10 
 (300 + 273) 
= 1.987 ( 573)
2
( 2.7399 ×10 −7
− 2.83×10 − 3 )
= − 1846.085 cal.
Heat of sub lim ation is 1846.085 cal. at 573 K
Problem
Calculate the melting point of ice under a pressure of 2 atm.
From the following data.
Density of water at 00C = 1.0 gm /cc
Density of ice at 00C = 0.9174 gm /cc
Latent heat of fusion of ice = 80 cal / gm
Assume that the above data to be independent of temperature
and pressure and also that the ice melts at 0 0C under 1 atm.
Pressure.
Solution
molecularweight 18
Molar volume of water at 0 0 C = = = 18 c.c
density 1
molecularweight 18
Molar volume of ice 0 0 C = = = 19.62 c.c
density 0.9174
We know for the solid − liquid equilibria
V − Vs
ln T = l P+C
∆H M

for the conversion from cal to c.c atm

1 cal = 41.293 c.c atm

ln T =
(18 − 19.62) P+C
80 × 18 × 41.293
= − 2.7 × 10 − 5 P + C
From the given condition T = 273 K , P = 1 atm
So ln 273 = − 2.7 × 10 − 5 × 1 + C or C = 5.6095
 For the calculation of melting po int of ice at
2 atm. . We can put the value of C = 5.6095
and P = 2 atm.in the above equation and we get
−5
ln T = (− 2.7 × 10 × 2 ) + 5.6095 = 5.6094
or T = 272.98 K
Problem
Calculate the rate of change of melting point of iron with
pressure with the help of the following:
M. P of iron = 1535 0C.
Density of solid iron at melting point = 7.86 gm/cc
Density of liquid iron at melting point = 7.55 gm/cc
Latent heat of fusion of iron = 3.3 kcal / mol
Atomic weight of iron = 56
 molecular wt. 56
Molar volume of solid iron = = 7.124 cc / mol
density 7.86
molecular wt. 56
Molar volume of liquid iron = = 7.4172 cc / mol
density 7.55
1 cal = 41.293 c.c atm
we know for the solis − liquid equilibria
d T ( Vl − Vs ) ( 7.4172 − 7.1246) ×1808 = 3.88 × 10 − 3 deg ree / atm.
= Tm =
dP ∆H m 3300 × 41.293

Problem
Rhombic sulphure transform to monoclinic sulphure at 368.5
K. with an enthalpy changes of 96 cal / mol. test the validity of
the third law of thermodynamics for this transition from the
following data:
i) CP of the rhombic sulphure at 15 K = 0.3 cal/deg/mol
ii) Area under the curve drawn between (Cp / T ) and T for rhombic sulphure between T
iii) For monoclinic sulphure: S368.5 – S0 = 9.07 cal /deg / mol
Assume that the entropy contribution of rhombic sulphure
below 15 K follows Debye’s equation. SR → SM
Solution: T
II

III
0
K I

0 IV

0 100
% reacted
 15 368.5
 CP   CP 
= ∫
0

 T 
 dT + ∫
15

 T 
 dT

Debye' s law is obyed below 15 K ⇒ C P = a T 3

15
 a T3  368.5
 CP 
∆SI = ∫
0

 T 
 dT + ∫
15

 T 
 dT
15 368.5
 CP 
= ∫ aT dT + ∫
2
  dT
0 15  T 

[ ]
368.5
1 3 15  CP 
= aT 0 +
3 15
∫ 
 T 
 dT
368.5
1  CP 
= [ CP ] 0 + ∫
15
  dT
3 15  T 
Entropy change during first step =
368.5
 CP 
∆SI = S368.5 − S0 = ∫
0

 T 
 dT
15 368.5
 CP   CP 
= ∫
0

 T 
 dT + ∫
15

 T 
 dT

Debye' s law is obyed below 15 K ⇒ C P = a T 3

15
 a T3  368.5
 CP 
∆SI = ∫ 0

 T 
 dT +
15
∫ 
 T 
 dT
 368.5
1  CP 
= [ CP ] 0 + ∫
15
  dT
3 15  T 
368.5
1  CP 
= [ C P ]15 + ∫   dT
3 15  T 
1
= × 0.3 + 8.71 = 8.81 cal / deg / mole
3
∆H tr 96
∆SII = = = 0.2605
Ttr 368.5
∆SIII = S0 − S0368.5 = − (S368.5 − S0 ) = − 9.07
According to sec ond law
∆SIV = − ( ∆SI + ∆SII + ∆SIII ) = − 0.0005 cal / deg/ mol
it means that the entropy change of the reaction at absolute zero
is zero. Thus the third law is verified.
 Statistical Interpretation of Entropy

Statistical Thermodynamics:
It deals with the interpretation and derivation of thermodynamic
properties based on the properties of the particles constituting
the system and their distribution in the system.

Elementary Statistical Concepts

Microstates: In a gaseous system, each particle shall have
three position coordinates namely x, y, and z and three velocity
coordinates vx, vy, and vz. If at any instant one is able to specify
value of all these six coordinates for each of the particle
constituting the system, such a complete specification is said to
define the microstate of the system.
• A set which defines all the possible microstates of a system
is called an ENSEMBLE.
• A set of microstates having same characteristics is called a
MACROSTATE.
let us consider an example a system consisting of three
distinguishable balls A, B and C contained in a box consisting
of two compartments I and II. Let us construct an ensemble.
Microstates No.
Position of
the Particles 1 2 3 4 5 6 7 8

Compartment I A, B,C A,B A,C B,C A B C -

Compartment II - C B A B,C A,C A,B A,B,C

These eight microstates can be grouped into the following four
macrostates:
I. All the three particles lie in compartment I – only one No.1 microstates
corresponds to this macrostates.
II. Two particles present in compartment I and only one in compartment II: three
microstates namely 2, 3, 4 correspond to this macrostates.
III. one particle present in compartment I and two in compartment II: three microstates
namely 5, 6, 7 correspond to this macrostates.
IV. All the three particles present in compartment II corresponds to Microstate no.8
 In actual practice a system consists of a large no. of particles and hence for every
macrostates there are large no. of microstates and no. of such macrostates are also large.
For the calculation microstates for a macrostates, one uses the technique of permutation
and combination.
 Next, how to calculate the no. of microstates or maximum no. of possible arrangement
of particles in a system.
 This can be illustrated by an example: let us consider first where we have, say, eight
object numbered 1 through 8 and four boxes.
 Let us attempt to answer the question: in how many different ways can these objects are
placed in these boxes assuming that each box is large enough to contain the all of the
objects.
 We may put object labeled 1 in any of the four boxes. Similarly, since each event is
independent we may do likewise for the object 2 etc.
 The total no of ways of putting object 1 is four . The total no of ways of putting object 2
is four, etc up through object 8.
 The total no of ways of arranging all the balls is therefore 48.
● In the situation we will be dealing with (atoms in crystals) we can differentiate atoms.
We can in principle distinguish a gold atom from a copper atom. However we can not
distinguish within the given type one from other.
● The situation discussed above therefore is not completely applicable to our case: we
shall not be interested in which object is in given box but, how many of the same type
of object are in each box.
● To illustrate, let us calculate the number of ways for which there are two balls in each
box. Such a total is called the total no. of microstates in the given macrostate.
● Thus we need to calculate how many ways we have of arranging two objects in box 1
two of the remaining six in box 2 and two of the remaining four in box 3 etc.
● The first step is to calculate the no of ways of picking two objects out of eight for box
1. This is done by combination of N objects taken n at a time i.e 8C2 = 8! / (2! 6!).
● We have six objects left. So no. of ways of putting two object out of remaining six in
box 2 is 6C2 = 6! / (2! 4!).
● Similarly for box 3 we have four objects left and
4
C2 = 4! / (2! 4!) and so on..
● Now we are ready to answer: the total no of ways putting two balls in each box is (W)
W = 8C2 x 6C2 x 4C2 x 2C2 = N! = 8! = 2520
n1!n2!n3!n4! (2!)4
● What is the probability of achieving the macrostate in which we have two objects
in each box. The answer is:
2520 / 48.
● The probability of a system to be present in a particular macrostate is directly
proportional to the no. of microstates which it has.
● In other wards we can say a system will spend highest time fraction in the
macrostate which has highest no of microstates (W).
● It can be further simplified as it is this macrostate of highest probability which
determines all the macroscopic properties of the system.
 Entropy and Most Probable Macrostate

●
Properties of a system depends on the most probable macrostate i. e the one
having highest no. of microstates (W).
●
It has been proved that for the isolated system of constant volume have
maximum entropy at equilibrium.
●
So one can conclude that both W and entropy must be related to each other.
●
Let such a relation be expressed as:
S = f(W)
In order to arrive at the analytical form of this function, let us
consider a system divided into two sub-system A and B. The
no of microstates W in any macrostate will be equal to the
product of the microstates WA and WB of the sub-system.
Hence
W = Wa . W B
Total entropy of the system is
S = SA+ SB
As we can write
SA = f (WA)
SB = f (WB)
So f(WA. WB) = f(WA) + f(WB)
Differentiantion with respect to WB gives
∂ f (W A .WB ) ∂ (W A .WB ) ∂ f (W A ) ∂ f (WB )
= +
∂ (W A .WB ) ∂ WB ∂ WB ∂ WB
which on simplification yields
∂ f (W A .WB ) ∂ f (WB )
WA . =
∂ (W A .WB ) ∂ WB
Differentiation w. r. t.W A gives
∂ 2 f (W A .WB ) ∂ (W A .WB ) ∂ f (W A .WB ) ∂ 2 f (WB )
WA . + =
∂ (W A .WB ) 2
∂ WA ∂ (W A .WB ) ∂ W A .∂ WB
or
∂ 2 f (W A .WB ) ∂ f (W A .WB ) ∂ 2 f (WB ) ∂  ∂ f (W B ) 
WA . WB + = =   = 0
∂ (W A .WB ) 2
∂ (W A .WB ) ∂ W A .∂ WB ∂ WB  ∂WA 
 ∂ 2 f (W A .WB ) ∂ f (W A .WB )
W A .WB + =0
∂ (W A .WB ) 2
∂ (W A .WB )
or
∂ 2 f (W ) ∂ f (W )
W. + =0
∂ (W ) 2
∂ (W )
A general solution to the sec ond order diff . eq. is
f (W ) = C1 ln W + C 2
for a perfect crystal S = 0 for W = 1, we get C2 = 0
Thus S = C ln W + C
and C1 can be determined from the throttling of one mole of
1 2
ideal gas. The gas expands by throttling process to double its volume. The
throttling process is isenthalpic process.
The entropy change during this process is
Pf
R Pf
∆S = S f − S i = − ∫ dP = − R ln
Pi
P Pi
In this process of throttling Pi = Pf / 2
Therefore − SW
S f the
Let us calculate i =inRthe
lninitial
2 and final state

N!
Wf =
( N / 2) ! ( N / 2) !
N!
Wi = =1
N!
According to sterling approximation i.e ln N ! = N ln N − N
S f − Si = C1 ( ln W f − ln Wi ) ;
 N N N 
 N ln N − N −  ln −  
 2 2 2  R
or ln 2 = C1  ⇒ C1 = = K
 N N N N
 −  ln − 
  2 2 2 
putting the value of C1 we get S = K ln W
 Entropy of Mixing for a Binary Solution

(N0-n) A + n B = solution [(N0- n) A, n B]

Component A Component B
(N0 –n) atoms n atoms

∆ Sm

Solution
N0 atoms
In 1 mole of solution
there are N0 lattice sites
∆ Sm = SA,B – SA – SB (Avogadro's no.)

Or ∆ Sm = K (ln W – ln W – ln W )
● WA,B is the no.of ways of arranging (N0 – n) A atoms and n B atoms on N0 sites so

N 0!
W A, B =
Since, in purenmetal 0 −
! ( Nthe n)!are indistinguishable so
atoms
●

WA = WB= 1. Thus

N 0!
∆S m = K ln
n ! ( N 0 − n)!
Applying sterling approximation
entropy of mixing

 n n N 0 − n of idealNsolution

∆S = N 0 K 
m
ln + ln 0

N
 0 N 0 N 0 N 0 − n 
N0 − n n
as x A = and x B =
N0 N0
So ∆S m = − R [ x A ln x A + x B ln x B ]
 THERMODYNAMICS
OF SOLUTIONS
● A solution may be defined as a homogeneous phase composed of different chemical
substances, whose concentration may be varied without the precipitation of a new phase.
● It differs from a mixture by its homogeneity and from a compound by being able to
possess variable composition.
● Solution may be gaseous, liquid or solid. It may be classified as binary or ternary
solution depending on whether it contains two or three components.
● A binary solution has two chemical substances (elements or compounds), e.g. molten
cadmium and zinc miscible in all proportions.
 Composition of solution
● Composition of solution may be expressed in a number of
ways. In metallurgy usually by weight, mol or atom percent,
for example, if w1 and w2 are weights of the solvent and solute
in the solution:
 w2 
wt % solute =   × 100
 w1 + w2 
 wA 
 MA 
atom% / mol % A =   ×100
 wA + wB 
 MA MB 
● where WA and WB are weights of components A and B having
atomic/molecular weights MA and MB, respectively.
 Composition of a solution
● If nA number of moles of A and nB number of moles of B
form a solution, A-B. atom fractions of A and B are
given as n
xA = A
n A + nB
nB
xB =
n A + nB

● and xA + xB = 1
 Raoult’s law
● The law states that the relative lowering of the vapour pressure a
solvent due to the addition of a solute is equal to the mole
fraction of the solute in the solution.
● Imagine A and B forming a solution, each one exerts its own
vapour pressure, pA and pB in the solution, respectively.
● Suppose p is the total pressure of the solution and xA and xB are
atom/mole fractions. If p0A and p0B are the partial pressure of pure
A and pure B, respectively at the same temperature at which
solution exists.

p A0 − p A p B0 − p B
0
= xB = xA
pA pB0
 Ideal Solution
● pA
1 − 0 = xB
pA

pA pB
0
=1 − x B = x A and 0 = x B
pA pB

i.e. p A = p 0A .x A or ( p A α x A )
and p B = p B0 .x B or ( p B α x B )
A solution which obeys Raoult’s law is called an
ideal solution.
( A ↔ A) = ( B ↔ B ) 1
= { ( A ↔ A) + ( B ↔ B ) }
2
Ideal Solutions
 Non-ideal or real solutions
● Deviations from Raoult’s law occur when the attractive forces between the
molecules of components A and B of the solution are stronger or weaker than those
existing between A and A or B and B in their pure states.
● For example, if there were a stronger attractive force between components A and B
in solution than the mutual attraction between molecules of A-A and of B-B, there
would be less tendency for these components to leave the solution is observed.
● In this case the vapour pressure whould be less than that predicted by Raoult’s law .
This is called negative deviation from Raoult’s law.
Non-ideal or real solutions
 Non-ideal or real solutions
● Using the same argument if the attractive force between A and B was less than
that between A and A or B and B in their pure states there would be a greater
tendency for these components to leave the solution as a gas, thereby increasing
the vapour pressure above the liquid. This is represented in Fig and is called
positive deviation from Raoult’s law.
● Immiscible liquids exhibit positive deviation since the attractive force between
the components in the liquid is low.
 Activity
●
We have already defined activity as
pA
aA = 0
pA
●
For ideal solutions we have:

p A = p 0A .x A
● For an ideal solution it will be seen that aA = xA, xA the mole fraction of A in
the solution.
●
if the solution deviates from Raoult’s law we write

a A = γ A .x A
● where γA is a fraction greater or less than unity for a positive or negative
deviation, respectively is called Raoultian activity coefficient.
● For a pure substance: xA = 1 and γA = 1, so that we have unit activity of the
substance A which is said to be in its ‘standard state’
 Activity
● If we return to our original argument that the vapour pressure of a
substance is a measure of its attraction to the solution in which it
exists and hence a measure of its availability for reaction, perhaps
with another phase, we can state that this fundamental definition of
activity, as that fraction of molar concentration “available” for
reaction, is universally applicable.
 Activity
Let us now consider the physical significance of
both Raoult’s
ideal and non-ideal behaviour of binary systems.
1. Raoult’s ideal behaviour: If in a solution composed of A and B (atoms or
molecules) the attractive forces between A and B are the same as between A
and A or between B and B, then the activities of A and B in the solution at all
concentrations will be equal to their mole fractions and the solution is said to
be ideal. The system Bi-Sn can serve as an example of such a solution at a
particular temperature. In this case the net attractive force between Bi and Sn
1
in the solution can be represented by the equation:
( A ↔ B ) = ( A ↔ A) = ( B ↔ B ) = { ( A ↔ A) + ( B ↔ B ) }
2
 Activity
2. Positive deviation: When the net attractive force between the substances
A and B is less than between A-A and B-B, then the solution of A and B
exhibits positive deviation from Raoult’s law. In this case the Raoultian
activity coefficient is always greater than unity except when approaching
the concentration of xA→ 1 Pb and Zn liquid solutions show such
behaviour at temperature above 1071K. The heat of solution in systems
showing positive deviation is endothermic. In general a solution, A-B
exhibiting positive deviation has
1
A ↔ B < {( A ↔ A + ( B ↔ B ))}
2
 Activity
3. Negative deviations occur when the attractive force between the two
components A and B is higher than between A-A and B-B. For example
Mg-Bi system shows such a behaviour. Negative deviations generally
indicate a tendency for compound formation (Mg3Bi2). The heat of
solution for systems exhibiting negative deviatias is usually exothermic.
Occasionally both negative and positive deviations from Raoult’s law
occur in the same binary system. An outstanding example of this
behaviour is found in the Zn-Sb, Cd-Bi and Cd-Sb systems. In general in
case of negative deviation in the system, A-B we have

1
A ↔ B > { ( A ↔ A) + ( B ↔ B )}
2
 Activity

Fig.: Relationship between activity and mole fraction of substance

A in three solutions-one ideal, the second showing a positive
deviation and the third a negative deviation from ideal behavior.
 PARTIAL MOLAR
QUANTITIES

●
In dealing with solutions, one of the first questions which naturally arises is
how to express molar quantities of a substance in solution when two liquids
are mixed, the total volume of the solution is, in general, not equal to the sum
of the individual volumes before mixing, this reflects the difference of the
interatomic forces in the pure substance and in the solution.
●
The problem presented is not solved directly but is avoided by the introduction
of partial molar quantities. Since the same general treatment is applicable to
any extensive thermodynamic quantity such as volume, energy, entropy and
free energy, we shall use the symbol Q to represent any one of these.
 PARTIAL MOLAR
QUANTITIES
● Prime is used to indicate any arbitrary amount of solution rather
than one mole, molar quantities are represented as unprimed.
● Thus Q′ is the total quantity of solution, Q the molar.
● If n1, n2 , n3, ………are number of moles of components 1,2 3,
……. respectively in the solution, we have

Q′
Q= (1)
n1 + n 2 + n3 + ..........
 PARTIAL MOLAR
QUANTITIES
● Let us imagine that to an arbitrary quantity of a solution an
infinitesimal number of moles, dn1, of component 1 is added at
constant temperature and pressure without changing the amount
of other constituents. The corresponding increment in the
property Q′ is dQ′ , the ratio

 ∂Q ′ 
 
 ∂n1  P ,T ,n2 , n3 ......
● Is known as the as the partial molar quantity of components 1
and designated as

 ∂Q ′ 
Q1 =   P ,T ,n2 ,n3 ,....... (2)
 ∂n1 
 PARTIAL MOLAR
QUANTITIES

● Q1
may be represented equally well as the increment of Q′ when 1 mol
of the first component is added to a very large quantity of the solution for
example, if the volume increase accompanying the addition of 1 gm
mol/atom of Cu to a large quantity of a liquid alloy is observed to be 8.5
cc, the partial molar volume of copper in the alloy at the particular
composition, temperature and pressure is 8.5 cc. This is written as
VCu = 8.5 cc

● We know Q’ =Q’(T,P, n1, n2, ……)

●
From the fundamentals of partial differentiation we have at constant
pressure and temperature dQ ′ =  ∂Q ′   ∂Q ′ 
dn +   dn + ..........(3)
 ∂n  1  ∂n  2
 1  n2 , n3  2  n1 , n3
dQ' = Q1 dn1 + Q2 dn2 + Q3 dn3 + .................................(4)
 PARTIAL MOLAR
QUANTITIES
● If we add to a large quantity of solution n1 moles of component 1, n2
moles of component 2 etc the increment in Q′ after mixing is given as

n1Q1 + n 2 Q2 + ...........

● If we now mechanically remove a portion containing n1 + n2 + n3 ….moles,

the extensive quantity Q′ for the main body of solution is now decreased
by ( n1 + n2 + …) Q.
●
Since at the end of these processes the main body of the solution is the
same in composition and amount as it was initially, Q′ has the same value
finally as initially and the increment in Q′ accompanying the individual
addition is equal to the decrement accompanying their mass withdrawal
 PARTIAL MOLAR
QUANTITIES
(n1 + n2 + .....) Q = n1Q1 + n2Q2 + ..................
 ni 
● Dividing by (n1 + n2+………) and noting that n + n + n = x i
 1 2 3 
Q = x1Q1 + x 2 Q2 + ..........(5)

● on multiplying by (n1+ n2 + n3 ……..) we can write as

Q ′ = n1Q1 + n 2 Q2 + ......................(6)

● In a binary solution we can write equations 5 and 6 as

Q = x1Q1 + x 2 Q2 (5)
Q ′ = n1Q1 + n2 Q2 (6)
 PARTIAL MOLAR
QUANTITIES
● On differentiating equation 6, we get

dQ ′ = n1 dQ1 + n2 dQ2 + Q1 dn1 + Q2 dn2 (7 )

● Subtracting (4) from (7) we get

n1dQ1 + n2 dQ2 = 0 (8)

x1 dQ1 + x 2 dQ2 = 0 (9)

● Equation (9) is known as one of the forms of Gibbs – Duhem
equation.
 Method of obtaining partial
molar quantities from molar quantities

● Differentiate equation (5)

dQ = x1 dQ1 + x 2 dQ2 + Q1 dx1 + Q2 dx 2 (10)

● Combining equation (9) and (10)

dQ = Q1dx1 + Q2 dx2 (11)

● Multiplying (11) by (x1/dx2)and putting dx1 = -dx2,(x1 + x2 = 1)

dQ dx1
x1 = x1Q1 . + x1Q2 = − x1Q1 + x1Q2
● dx 2this to (5)dx
Adding we2 get

dQ
Q + x1 = x1Q2 + x2Q2 = Q2
dx2
 Method of obtaining partial
molar quantities from molar quantities

dQ dQ
∴Q2 = Q + x1 = Q + (1 − x 2 ) (12)
dx 2 dx 2

dQ
QSimilarly,
( )
●
1 = Q + 1 − x1 (12a)
dx1
 Tangent intercept method
dQ CH − CF y − y1
A E C = ( slope = 2 )
dx 2 1 − x2 x 2 − x1
0
dQ
Q2 = Q + (1 − x 2 )
Q1 dx 2
CH − CF
↑ Q2 = CF + (1 − x 2 ).
1 − x2
Q G
B = CF + CH − CF = CH
D F
dQ AG − AD y −y
H = ( slope = 2 1 )
dx1 1 − x1 x2 − x1
dQ
Q1 = Q + (1 − x1 )
dx1
1 x2 2 AG − AD
= AD + (1 − x1 ).
1 − x1
= AD + AG − AD = AG
 Method of obtaining one partial
molar quantities from another partial
molar quantities

Integration of this equation from x1 =1 to x1 = x1

will result
 Method of obtaining one partial
molar quantities from another partial
molar quantities
If the input in the calculation is the functional relationship
between ⎯ and x2, then

If the input in the calculation is the functional relationship

between ⎯ and x1, then
Problem
 Obtaining Molar property
from Partial molar properties
 Problem
The enthalpies of mixing of Cd-Sn alloys at 5000C are given below:
xCd 0 0.1 0.3 0.5 0.7 0.9 1.0
∆ HMCal/mole 0 298.2 652.4 800.0 620.5 251.5 0
Calculate the values of the partial molar enthalpies of mixing of cadmium and
tin in a Cd-Sn alloy containing 60 at % cadmium.
Solution:
To find the value of partial molar enthalpies of mixing of cadmium,
Draw a tangent at xCd = 0.6. The
∆H Cd and that of tin i.e. ∆H Sn , plot∆H vs xCd
M M M
values of and are obtained by intersection of the tangent with the
axes at xCd = 1 and xSn =∆1, ∆H Cd
M M
H Snrespectively.
●

∆H Cd = 320 cal / mol and ∆H Sn = 1360 cal / mol .

 Problem
In the formation of liquid brass: (1-x) Cu(l) + x Zn(l) =
Cu-Zn (l), the molar heat of formation is given by
∆ H = - 7100 x (1-x) cals, where x is the atom fraction
of zinc. Derive expressions for partial molar heat of
mixing of Cu and Zn in the liquid brass as a function
of composition.
 Solution
∆ H = - 7100 x (1-x)
∂∆H
∆H Zn = ∆H + (1 − x Zn ) .
∂x Zn
∂∆H ∂∆H d
= = [ − 7100 x(1 − x ) ]
∂x Zn ∂x dx

[ ]
= d − 7100 ( x − x 2 ) = − 7100 (1 − 2 x )
dx
∴∆H Zn = − 7100 x(1 − x ) + (1 − x ) [ − 7100 (1 − 2 x ) ]
= (1 − x ) [ − 7100 x + ( − 7100)(1 − 2 x ) ]
= −7100 (1 − x ) [ x + 1 − 2 x ] = − 7100 (1 − x ) (1 − x ) = − 7100 (1 − x )
2
 solution
 ∂∆H   ∂∆H   ∂∆H  ∂∆H
∆H Cu = ∆H + (1 − xCu )   = ∆H + x Zn   = ∆H + x Zn   = ∆H − x.
 ∂xCu   ∂xCu   − ∂x Zn  ∂x

= -7100 x (1-x) – x [ -7100 (1-2x)]

= -7100 x [1-x – (1-2x)]
= -7100 x [1-x -1 + 2x] = -7100 x (x) = -7100 x2 Ans.
 Problem

●
A 30% mole by methanol –water solution is to be prepared. How
many m3 of pure methanol (molar volume =40.7x10-3m3/mol) and
pure water (molar volume = 18.068x10-6m3/mol) are to be mixed to
prepare 2m3 of desired solution. The partial molar volume of
methanol and water in 30% solution are 38.36x10-6 m3/mol and
17.765x10-6 m3/mol respectively.
Solution

Methanol =0.3 mole fraction

Water=0.7 mole fraction

V=0.3 x38.36x10-6 +0.7x17.765x10-6

=24.025x10-6 m3/mol

For 2 m3 solution
2
= −6
= 83.246 × 10 mol
3

24.025 × 10
Solution

Number of moles of methanol in 2m3solution

=83.246x103x0.3= 24.97x103mol

Number of moles of water in 2m3solution

=83.246x103x07= 58.272x103mol
Volume of pure methanol to be taken
= 24.97x103 x 40.7x10-3 =1.0717 m3

Volume of pure water to be taken

= 58.272x103 x 18.068x10-6 =1.0529 m3
 Problem

Find weather the equation given below is thermodynamically

consistent
G = 100 x1 + 150 x 2 + x1 x 2 ( 10 x1 + x 2 )
∂G
G1 = G + ( 1 − x 1 ) 3 2
∂x 1 G1 = 18 x1 + 35 x1 + 16 x1 + 101
∂G
G2 = G − x1 3 2
∂x 1 G2 = 18 x1 − 8 x1 + 150
 d G1 2
= 54 x1 − 70 x1 + 16
dx1
d G2 2
= 54 x1 − 16 x1
dx1
G D equation
d G1 d G2
x1 + (1 − x1 ) =0
dx1 dx1
2 2
x1 ( 54 x1 − 70 x1 + 16 ) + ( 1 − x1 )( 54 x1 − 16 x1 ) = 0
It satisfies the GD equation, the above equation is consistent.
 The Free Energy Change due to
the Formation of a solution

● The pure component i, occurring in a condensed state at the temperature

T exerts an equilibrium partial pressure, pi0 . When occurring in a
condensed solution at temperature T, it exerts a low equilibrium
pressure pi. Consider the following steps:
1. evaporation of 1 mole of pure condensed i to pure i at the pressure pi0 at T.
2. change in the pressure of 1 mole of vapour i from pi0 to pi at the temperature T.
3. Condensation of 1 mole of vapour i from the pressure pi into the condensed
solution at T.
 The Free Energy Change due to
the Formation of a solution
● The difference in molar free energy between pure i and i in the solution
= ∆ Ga + ∆ Gb +∆ Gc.
● However as steps a and c are equilibrium processes, ∆ Ga and ∆ Gc are
both zero.
● The overall free energy change for the three step process thus equals
∆ Gb which can be written as
● ∆ Gb = Gi(in sol)-Gi (pure) = RT ln pi – RTln pi0
= RT ln (pi /pi0) = RT ln ai
● but Gi (in solution) is simply the partial molar free energy of i in the
solution, (pure) is the molar free energy of pure i, Gi0 .
Gi and G i
 The Free Energy Change due to
the Formation of a solution
● The difference between the two is the free energy change accompanying
the dissolution of 1 mole of i in the solution.
● The quantity is designated as the partial molar free energy
M
of the solution of i.
●
ΔG,i
Hence
● ∆ G M
= G − G i = RT ln
0
If at constant Ti and P,i nA number ofamole
i of A and nB of moles of B are
mixed to form a binary solution,
● free energy before mixing = nAGA0 + nBGB0
● free energy after mixing =
The free energy change due to mixing, ∆ G′ M, referred to the integral
A + n B Gthe
●
n A Gbetween
free energy of mixing, is the difference B two quantities, i.e.
 The Free Energy Change due to
the Formation of a solution
( ) ( )
∆G ′ M = ( n A G A + n B G B ) − n A G A0 − n B G B0 = n A G A − G A0 + n B G B − G B0 ( )
= n A ΔG AM + n B ΔG BM
= RT (nA ln aA + nB ln aB)

In terms of one mole of solution,

i. e. integral molar free energy

for an ideal solution ai = xi, ∴ ∆G M = RT ( x A ln a A + x B ln a B )

∆ GM,id = RT (xAln xA + xB ln xB)
 Properties of Raoultian
Ideal solution
Change in volume accompanying the formation of ideal solution.
∆ GM,id = RT (xAln xA + xB ln xB)
M ,id
∆G A = RT ln x A ∆G
M ,id
B = RT ln x B

We can write,
 ∂ Gi   ∂ G 0i 
  =V i   = V 0
 ∂P   ∂P  i
  T ,Comp   T ,Comp

 ∂ (G i − G 0i ) 

∂ P
 = V i(− Vi
0
)
  T ,Comp

∂ ΔG i M M
= Δ Vi
∂P
T , Comp
 Properties of Raoultian
Ideal solution
M ,id
for an ideal solution , ∆G i = RT ln xi

As xi is not a function of pressure, then

M ,id
∆Vi =0

( )
∆V ′ M = ( n AV A + n B VB ) − n AV A0 + n B VB0
Integral volume of the solution (mixing)
= n (V -V ) +n (V -V )
A A
0
A B B
0
B

= n A ΔVAM + n B ΔVB = 0 M

M ,id M ,id
∆V M ,id
= x A ∆V A + xB ∆V B =0 or ΔV M,id = 0
 Properties of Raoultian
Ideal solution
The heat of formation of an ideal solution
For a component in the solution, G - H equation

(
 ∂ Gi / T )  = -
Hi
 ∂T  P , comp T 2
 

∂ (
For the
G i
0
/ T )
pure component
H i
o

P , comp = -
∂T T2

  G i − G 0i  
 ∂  
  T

 =−
(H i − H i0 )
 ∂T  T2
 
  P ,Comp
 Properties of Raoultian
Ideal solution
  ∆G iM 
∂  
  T  M
 ∆H i
  =− 2
 ∂T  T
 
  P ,Comp

M
● ∆H i is the partial Molar heat of solution (mixing) of i
M ,id
● In an ideal solution, ∆G i = RT ln xi

 ∂ ( R ln xi ) 
M ,id
∆H i
 ∂T  =− 2
  P ,Comp T
M ,id
or ∆ H i =0
M ,id M ,id
Integral molar heat of mixing, ∆H M ,id
= xA ∆ H + xB ∆ H =0
●

A B

∆H M ,id = 0
 Properties of Raoultian
Ideal solution
The entropy of formation of an ideal solution
 ∂G 
  =−S
 ∂ T  P ,omp

For the
∂ ∆Gformation
M
 ofM a solution
  = − ∆S
 ∂T  P ,omp

For an ideal solution

∆ MG,idM,id = ∂RT
∆G M(x
,id ln x
 A + xB ln xB)
∆S = −  A  = − R( x A ln x A + x B ln x B )
 ∂T  P ,omp
M ,id
∆S i = −R ln xi
 Properties of Real Solution
● Real solutions do not obey Raoult’s law (ai = γi. xi)
● Integral molar free energy of mixing :
∆G M = RT ( x A ln a A + x B ln a B )
∆G M = RT ( x A ln γ A + xB ln γ B ) + RT ( x A ln x A + xB ln xB )
= G XS + G M ,id

● Partial molar free energy of mixing:

M
∆G i = RT ln ai
= RT ln γ i + RT ln xi
XS M ,id
= Gi + Gi
 Properties of Real Solution
Change in volume accompanying the formation of Real solution.

●
Partial molar volume of mixing
∆Vi
M
=
(
 ∂ ∆G M
i ) 
 ∂ P 
T , Comp

∂ ( ln ai )
= RT
∂P

●
Integral∆Molar Volume
M of mixing
V = x ∆V A + x ∆V B
M M
A B

 ∂ ( ln a A ) ∂ ( ln a B ) 
∆V M
= RT  x A + xB 
 ∂ P ∂ P 
 Properties of Real Solution
Change in Entropy accompanying the formation of real solution.
●
Partial molar entropy of mixing
∆ Si
M
=−
(
 ∂ ∆G M
i ) 
 ∂ T  P , Comp
∂ ( ln ai )
= − RT − R ln ai
∂P

M M
∆S M
= x A ∆S A + xB ∆S B
●
Integral molar entropy of mixing
 ∂ ( ln a A ) ∂ ( ln a B ) 
∆S M = − RT  x A + xB  − R [ x A ln a A + x B ln a B ]
 ∂T ∂T 
 Properties of Real Solution
Change in enthalpy accompanying the formation of real solution.
●
Partial molar enthalpy of mixing
  ∆G iM 
∂  
  T  M
 ∆ H i
  =− 2
 ∂T  T
 
  P ,Comp

 ∂ ( R ln ai ) 
M
∆H i
= − 
T2  ∂ T  P ,Comp
M  ∂ ( ln ai ) 
∆H i = −RT 2  
 ∂ T  P ,Comp
 Properties of Real Solution
●
Integral molar enthalpy of mixing
M M
∆H M
= xA ∆ H A + xB ∆ H B

 ∂ ( ln a A ) ∂ ( ln a B ) 
∆H M
= − RT  x A
2
+ xB  P , comp
 ∂T ∂T 
 Regular Solution
●
In the case of non ideal solutions it is still possible to assume random
mixing in certain cases but the enthalpy of mixing will no longer be zero
because there will be heat changes due to changes in binding energy.
●
This assumption of random mixing can only be made where there is a
small deviation from ideal behaviour, so that the enthalpy of mixing is
quite small. Solutions of this type are called regular solution. For regular
solutions the entropy of mixing is the same as for ideal solution, so that
∆H M = ∆G M + T∆S M = RT ( x A ln a A + xB ln aB ) − RT ( x A ln x A + xB ln xB )
= RT ( x A ln γ A + xB ln γ B )
●
where and are the actively coefficient of A and B, respectively.
 Regular Solution
●
In 1895 Margules suggested that activity coefficients, A and B of a binary solution
at any given temperature can be represented by power series equations as follows:

1 1
ln γ A = α 1 x B + α 2 x B2 + α 3 x B3 + ..........
2 3
1 1
ln γ
By the= β x +
B application
1 A β
of x 2
+ β
2theA Gibbs – x A + ..........
3
3 Duhem equation xA d lnγA = - xB d ln γB, it can
2 3
●

be shown, for the system to hold over the entire range of composition, .

●
By similar comparison of co-efficients of the power series, Margules further
demonstrated that the variation of the γ’s can be represented by the quadratic
terms only, when
α 1 = β1 = 0

α2 = β2
 Regular Solution
●
For regular solutions Hildebrand
in 1929 established that
RT ln γ B = α′ x 2A and RT ln γ A = α′ x 2B

●
α- function is defined as:
ln γ A = α A xB2 and ln γ B = α B x A2
●
From comparison of the above
expressions we get
α′
● αA = αB = α and α =
RT

●
α is independent of composition
which indicates that Tl – Sn system
follows regular solution model.
 Properties of Regular Solution

● Thermodynamic properties of solutions may be divided into two

parts: ideal and excess.
● Properties of regular solutions can be discussed by the excess

parts.
QReal = Qid + QXS
● The change in property during mixing:

ΔQ M ,R = ΔQ M ,id + Q XS
● Hence we can write for integral molar free energy of mixing as

ΔG M ,R = ΔG M ,id + G XS

ΔG XS = ΔG M ,R - ΔG M ,id
 Properties of Regular Solution

it may be shown as  ∂G XS 
●
  = − S XS
 ∂T p
●
ΔGxs = ΔHxs - TΔSxs = (ΔHM,R – ΔHM,id ) – T (ΔSM,R – ΔSM,id )
= ΔHM,R (as ΔHM,id =0 and ΔSM,R = ΔSM,id )

ΔGxs = ΔHM,R

ΔG XS = ΔG M ,R - ΔG M ,id
= RT ( x A ln a A + xB ln aB ) − RT ( x A ln x A + xB ln xB )
= RT ( x A ln γ A + xB ln γ B ) = ∆H M , R
XS XS
= xA G A + xB G B
M M
∴G A
XS
= RT ln γ A = ∆ H A and G B
XS
= RT ln γ B = ∆ H B
 Properties of Regular Solution
∆G XS = RT ( x A ln γ A + xB ln γ B )

(
= RT x Aα xB2 + xB α x A2 )
= RT α x A xB ( x A + xB )
= RTα x A x B
Hence for regular solution
∆G XS = ∆H M = RTα x A xB
α′
= α ′x A xB where
This means GXS for a regular solution is independent of α =
RT
temperature
 Properties of Regular Solution
This can also be shown as  ∂G XS 
  = − S XS
●

 ∂T p
●
As SXS for a regular solution is zero, then GXS and ΔHM are independent of
XS
temperature. Similarly, is also independent
G of temperature.

G AXS = RT1 ln γ A ( T1 ) = RT2 ln γ A ( T2 ) = α ′xB2

●
This equation is of considerable importance and of practical use in
connecting activity data at one temperature to activity data at another
temperature. Hence for a regular solution we have.

ln γ A at temperatureT2 T1
=
ln γ A at temperatureT1 T2
 Properties of Regular Solution
ln γ A at temperature T2 T1
= ; dividing by (1 − x A ) 2 we get
ln γ A at temperature T1 T2
ln γ A
at T2 α (T2 ) T1
(1 − x A ) 2
T ∴ =
= 1 α (T1 ) T2
ln γ A T2
at T1 or α 1T1 = α 2T2
(1 − x A ) 2

For strict adherence to this

model αT should be
independent of temperature.
Thus Tl – Sn is not strictly
regular in behaviour
 Properties of Regular Solution
Change in volume accompanying the formation of regular solution.
●
Partial molar volume of mixing

∆Vi
M
=
(
 ∂ ∆G M
i ) 
 ∂ P  T , Comp

 ∂ ( ln ai ) 
= RT  
 ∂ P  T ,omp
●
Integral molar volume of mixing

M M
∆V M
= x A ∆V A + x B ∆V B

 ∂ ( ln a A ) ∂ ( ln a B ) 
∆V M
= RT  x A + xB 
 ∂ P ∂ P  T ,omp
 Properties of Regular Solution
Change in Entropy accompanying the formation of real solution.
●
Partial molar entropy of mixing
M
∆ Si = − R ln xi

●
Integral molar entropy
M of mixing
M
∆S
M
= x A ∆S A + xB ∆S B

∆S M = − R [ x A ln x A + xB ln xB ]
 Properties of Regular Solution
Change in enthalpy accompanying the formation of real solution.
●
Partial molar enthalpy of mixing
M
∆ H = RT ln γ i = Gi XS
i

●
Integral molar enthalpy of mixing
M M
∆H M
= xA ∆ H A + xB ∆ H B

∆H M = − RT [ x A ln γ A + xB ln γ B ]
 Regular solution behaviour:

1. linear variation of ln γA vs xB2 (slope = α ) at a

given temperature indicates regular solution
behaviour of the system: A-B.
2. However for strict adherence to the model, α T
should be independent of T but not so in many
cases. In general we find ln varying linearly
with x but α iT decreases with temperature.
Thermodynamic properties
of Solutions
Thermodynamic properties
of Solutions
(Q = ∑ x . Q )
k K

(Q XS
= Q M − Q M ,id )
 GIBBS – DUHEM INTEGRATION

●
Thermodynamic equations for calculation of excess free energy
and integral molar free energy of a solution need activity coefficient
and activity of all the components of the solution. However,
experimental techniques viz. chemical equilibria, vapour pressure
and electrochemical can measure activity of only one component.
●
In order to get activity of the second component in a binary solution
we must couple activity and atom/mole fractions of both the
components with the aid of Gibbs-Duhem equation as follows:

∑ Xi dQ = 0,
i
●
Q is any extensive property.
 GIBBS – DUHEM INTEGRATION –
METHOD -I

●
Since activity of a component is related to the
partial molar free energy, we can write Gibbs-
Duhem equation as under:
x A d∆G AM + xd∆G BM = 0 (1)

∴ x A d ln a A + x B d ln a B = 0 (2)
xB
or d ln a A = d ln a B (3)
xA
xA = xA
 xB 
ln a A | x A = x A = − ∫   d ln aB
x
x A =1  A 
GIBBS – DUHEM INTEGRATION
METHOD -I
 GIBBS – DUHEM INTEGRATION –
METHOD -II

(4)
Eq.(4) Eq.(2)

(5)
 GIBBS – DUHEM INTEGRATION

xB
as xB →1, a A → 1, ln γ B → 0 but →∞
xA

xB
as xB → 0, aB → 0, γ B is finite and ln γ B is also finite for →0
xA
 GIBBS – DUHEM INTEGRATION – METHOD -III

● As a further aid to the integration of the Gibbs Duhem equation, the

is introduced as
ln γ i
α − function αi = γ i → 1 as xi → 1
(1 − x i ) 2
● α -function is always finite because
● For the components of a binary solution
ln γ A ln γ B
αA = 2 , and α B = 2 ln γ B = α B x A2
xB xA
● α B is known as a function of composition:
● On differentiation we get

d ln γ B = 2α B x A .dx A + x A2 .dα B ,
 GIBBS – DUHEM INTEGRATION –
METHOD -III
xB
● d ln γ A = − d ln γ B
substituting this into xA
xB xB 2
d ln γ A = − 2α B x A dx A − .x A .dα B = −2 x Bα B .dx A − x B x A dα B
xA xA

x A = xA α B at x A = x A
●
Onlnintegration
γ A = − ∫ 2 xBα B dx A − ∫x x d αB
B A ( A)
x A =1 α B at x A =1
GIBBS – DUHEM INTEGRATION –
METHOD -III

(A)
 GIBBS – DUHEM INTEGRATION –
METHOD -III

● Thus ln at xA=xA is obtained as – xBxAα B minus the area under the plot of
α B vs xA from xA=xA to xA = 1. Since α B is everywhere finite, this
integration does not involve a tail to infinity.
 Problem
The activity coefficient of zinc in liquid Cd-Zn alloys at
4350C
have been expressed as ln γ Zn = 0.87 x2 Cd – 0.30 x3 Cd
(a) Calculate the activity of cadmium in a 30 at % Cd at
4350C.
(b) Develop a corresponding equation for the activity
coefficient of cadmium in the alloy system at this
temperature.
 Solution
From Gibbs-Duhem equation we can write as
xZn d ln γ Zn +xCd d ln γ Cd = 0
on integration
x = xwe get
xZn Cd Cd

ln γ Cd = − ∫ d ln γ Zn
xCd =1
xCd
xCd = xCd

=− ∫
1 - xCd
xCd
( 2
1.74 xCd - 0.90 xCd )
dxCd
xCd =1
xCd = xCd

=− ∫ Cd
(1 - x ) 1.74(xCd - 0.90 x 2
Cd dxCd )
xCd =1
 Solution
xCd = 0.3

=− ∫ (1.74 - 2.64 x + 0.90 x )dx

2
Cd Cd Cd
xCd =1
2 3 0.3
= - [1.74 x Cd - 1.32 x Cd + 0 .3 x ] Cd 1

= [ - 1.74 x Cd + 1.32 x 2
Cd - 0.3 x 3 0.3
Cd 1
]

ln γ Cd = 1.218 - 1.201 + 0.292 = 0.309

= -1.74(0.3-0.1) + 1.32 (0.09-1)-0.3 (0.027-1)
∴ γ Cd =1.362
a Cd = γ Cd .x Cd = 1.362 × 0.3 = 0.4086 Ans.
 Solution
xCd = xCd
xZn
(b) ln γ Cd = − ∫
xCd =
xCd
d ln γ Zn

xCd = xCd

=− ∫
1 - xCd
xCd
( 2
1.74 xCd - 0.90 xCd dxCd )
xCd =1

xCd = xCd

=− ∫ Cd
(1 - x ) 1 .74(xCd - 0.90 x 2
Cd dxCd )
xCd =1

= − ∫ (1 - xCd ) (1.74 - 0.9 xCd )dxCd = − ∫ (1.74 - 2.64 xCd + 0.9 xCd
2
)dxCd
xCd = xCd

=− ∫ + 2
( -1 .74 2. 64 xCd - 0 . 90 xCd ) dxCd
xCd =1
 Solution
2 3 x Cd = x Cd
[-1.74 x CD + 1.32 x Cd - 0.3 x ] Cd x Cd =1

= −1.74 xCd + 1.32 xCd

2
− 0.3 xCd
3
− (−1.74 + 1.32 − 0.3)
= 0.72 − 1.74 xCd + 1.32 xCd
2
− 0.3 xCd
3

put xCd = 1 − x Zn to get the desired form

2 3
= 0.72 - 1.74(1 - x Zn )+ 1.32(1 - x Zn ) - 0.3(1 - x Zn )
= 0.72 − 1.74 + 1.74 x Zn + 1.32 − 2.64 x Zn + 1.32 x Zn
2
− 0.3(1 − 3 x Zn + 3 x Zn
2
− x Zn
3
)

= 0.3x 3Zn + x 2Zn (-0.9+ 1.32) + x Zn (0.9 - 2.64 + 1.74) - 0.3 + 1.32 - 1.74 + 0.72

= 0.3x 3Zn + 0.42 x 2Zn Ans.

 Solution
Alternatively, we can also solve as
xZn
ln γ Cd =−∫ 2
(1.74 xCd - 0.9 xCd )dxCd = ∫ xZn (1.74 - 0.9 xCd )(-dxCd )
xCd
xCd = xCd xZn = xZn

= ∫x
xCd =1
Zn (1.74 - 0.9 xCd ).dxZn = ∫ [1.74 x
xZn = 0
Zn dxZn - 0.9 xZn (1 - xZn )] dxZn

= ∫ 1.74 xZn dxZn − 0.9 xZn dxZn + ∫ 0.9 xZn

2
dxZn

3
x
= ∫ 0.84 x Zn dxZn + 0.9 ∫ xZn
2
dxZn = [0.42 xZn ]0 + [0.90. Zn ]0xZn = 0.42 xZn
2 x Zn 2
+ 0.3 xZn
3

3
 Problem
At 746K the activity coefficient of lead in liquid Pb-Bi alloy is expressed as
Making use of the Gibbs-Duhem equation 2 develop the corresponding equation
ln γ Pbof=bismuth
for the activity coefficient - 0.74in
(1the
- x alloy
Pb ) .at 746K. (a) Calculate the activity of
lead at 746K and 1000K in the Pb-Bi alloy containing 50at % lead (b) Calculate the
integral molar heat of mixing /excess free energy of the alloy containing 40at% Pb at 746
K (c) What is the integral molar free energy of mixing of the above alloy in (b) at 1000K
(d) Calculate the difference in change in free energy when 1 gatom of lead dissolves in a
very large amount of the above alloy at 746 and 1000K
 Solution
(a)For Pb-Bi system the Gibb-Duhem equation
may be written as:
x Bi d ln γ Bi + x Pb d ln γ Pb = 0

ln γ Pb at x Bi = x Bi
on integration we get
xPb ln γ Pb = −0.74(1 − x Pb ) 2
ln γ Bi = - ∫
ln γ Pb at x Bi =1
xBi
d ln γ Pb
d ln γ Pb = 1.48(1 − x Pb ) dx Pb

xPb
=−∫ 1.48(1 - xPb ) dxPb
(1 - xPb )
 Solution
x Bi 2 x Pb = (1 x Bi )
x
= − 1.48 ∫x
x Bi =1
Pb dxPb = -1.48 Pb
2 x Pb = 0

= - 0.74(1-xBi )2

So the solution is a regular solution

γ Pb (746 K ) = 0.83, a Pb = 0.5 × 0.83 = 0.415(746 K ) Ans.
 Solution
for regular solution

ln γ Pb ln γ Bi
( b ) α Pb = α Bi = =
x Bi 2 x Pb 2
 Solution
at 746 K

ln γ Pb = αx Bi 2 = -0.74x 2Bi

ln γ Bi = αx Pb 2 = -0.74x 2Pb
G XS = ∆H M = RT ( x Pb ln γ Pb + xbI ln γ Bi )
= RT α xAxB
= - 1.987 × 746 × 0.74 × 0.4 × 0.6
= -263.3 cal/mole. Ans.
(C) for regular solution α 1T1 = α 2T2
α 1 = -0.74 (746 = T1)
α1T1 - 0.74 × 746
α 2 (1000K ) = = = -0.55
T2 1000
At 1000K
ln γ Pb = αx Bi 2 = - 0.55x 2Bi ==> γ Pb = 0.8715
a Pb = 0.8715 x 0.5 = 0.435
2
ln γ Bi = αx Pb = -0.55x 2Pb ==> γ Bi = 0.8715
a Bi = 0.8715 x 0.5 = 0.435
 Solution
∆G M = RT ( x Pb ln a Pb + x Bi ln a Bi )
=1.987 × 1000 (0.5 ln 0.435 + 0.5 ln 0.435)
= 1.987 × 1000 × ln 0.435 = 1987 × (-0.8324)
= -1654 cal/m. Ans.
(d) difference in free energy =
= RT ln aPb (1000K) –RT ln aPb (746K) M M
= 1.987 (1000 × ln 0.435 – 746 ln 0.415) Δ G Pb (1000 K ) - Δ G Pb ( 746 K )
= 1.987 [1000(-0.8325) – 746 (-0.8795)]
= 1.987 (-176.4) = -350.5 cal/mole. Ans.
 Problem
Al-Zn alloys exhibit the following relationship at 4770C:
RT ln γZn = 1750 (1-xZn)2 where R and T an expressed in cal/deg.gatom
and K, respectively.

i) Develop the corresponding expression ln γ Al

(ii) Calculate the heat of mixing of the alloy containing 40 at % Zn at 4770C.

What would be excess molar free energy of the alloy at this temperature?
(iii) Calculate the integral molar free energy of the above alloy at 5070C.
 Solution
1750 3500
ln γ Zn = (1 − xZn ) , d ln γ Zn = -
2
(1 - x Zn ) dx Zn
RT RT
appropriate form of the Gibbs-Duhem equation.
x Al d ln γ Al + x Zn d ln γ Zn = 0
xZn
ln γ Al = − ∫ .d ln γ Zn
x =x
x Al
Al Al
xZn  3500 
=− ∫
x Al =1
−
(1 − xZn )  RT
(1 − x Zn ) dx Zn 

x Al = x Al 2
3500 3500 xZn xZn =(1− x Al )

=
RT ∫
x Al =1
x Al dxZn = .
RT 2 xZn =0

1750
= (1 − x Al ) 2
RT
 Solution
(ii) The above form of equation show that α is independent of composition. Thus Al-
Zn system follows regular solution model, hence

α Zn = α Al
ln γ Zn 1750
α Zn = = = α Al
(1 − xZn ) RT
2

∴ ∆H M = G XS = RTαx Al x Znx = 0.4, xAl = 0.6

Zn
1750
= RT . 0.6 × 0.4
RT
= 1750 × 0.24 = 420 cal/gatom Ans.
 Solution
(iii) ∆G M = RT ( x Al ln a Al + x Zn .a Zn )

for regular solutions, α 1T1 = α 2T2

T1 = 477 + 273 = 750 K , T2 = 507 + 273 = 780 K .
ln γ Zn 1750 1750 7
α 750 = = = = = 1.174
(1 − x Zn ) 2
RT R750 3 × 1.987
α 750 × 750 1750 750 175
α 780 = = x = = 1.129
780 R 750 780 78 x1.987
ln γ Zn
α 780 = xZn =0.4
(1 − x Zn ) 2
 Solution
∴ ln γ Zn ( 780 ) = α 780 × (1 − x Zn ) = 1.129 × 0.36 = 0.40644
2

∴ γ Zn ( 780 ) = 1.50146

∴ a Zn = γ Zn .x Zn = 1.50146 × 0.4 = 0.6005

ln γ Al
∴ α 780 =
(1 − x Al ) 2
ln γ Al = α 780 (1 − 0.6) 2 = 1.129 × 0.16 = 0.18664
γAl= 1.19798
aAl = 1.19798 × 0.6 = 0.71879

∆G M = RT (0.6 ln 0.718979 + 0.4 ln 0.6008)

 Solution
=1.987 × 780 (0.6 × (-0.3301856) + 0.4
(0.5075)
= 1.987 × 780 [-0.1981 – 0.2038] = 1.987 ×
780 (-0.4019)
= -622.8 cal.mole.
Ans.
 Problem
In liquid Fe-Ni solution at 1873 K the activity of nickel as a function of
composition is listed below:
xNi 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
aNi 0.067 0.137 0.208 0.287 0.376 0.492 0.620 0.776 0.89
(i) Calculate the activity of iron in an alloy containing 60 at% iron by Gibbs - Duhem integration.
(ii) Calculate in the above alloy at 1873 K.

M M
∆G Ni , ∆G Fe , ∆GiM , ∆GiXS
 Solution
Solution:
By third method of integration calculate α Ni

xNi 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
aNi 0.067 0.137 0.208 0.287 0.376 0.492 0.620 0.776 0.89
γNi 0.67 0.685 0.69 0.72 0.75 0.82 0.986 0.96 0.99
(1-xNi )2 0.81 0.64 0.49 0.36 0.25 0.16 0.09 0.04 0.01
α Ni -0.49 -0.59 -0.75 -0.92 -1.14 -1.24 -1.35 -1.07 -1.01
Making use of α function we have

x Fe = x Fe

ln γ Fe = −α Ni .xFe x Ni − ∫α
x Fe =1
Ni .dxFe

= − [α x x + ∫ α dx ]
= - (-0.92 × 0.6Ni× 0.4
Fe– 0.08)
Ni = 0.301 Ni
i.e. γNi Fe
= 1.35, aFe = 0.6 × 1.35 = 0.81
 Solution
M
∆G = RT ln a Ni = 8.314 ×1873 ln(0.287) = −19438 J / mole.
Ni

M
∆G Fei = RT ln a Fei = 8.314 ×1873 ln(0.81) = −3281 J / mole.
∆G M = ( x Ni G Ni + xFe G Fe ) = 0.4 × (−19438) + 0.6(−3281) = −9744 J / mole.

G XS = ∆G M − ∆GidM , = RT ( x Ni ln γ Ni + xFe ln γ Fe ) = 8.314 ×1873 (0.4 ln 0.72 + 0.6 ln 1.35)

= 758 J/mole
 Problem
At 1200K the activity coefficient of zinc in liquid brass is
expressed as
ln γZn = - 1.929 (1-xZn)2
(a) Calculate the integral molar heat of mixing and the excess free energy of
brass containing 40 at % copper at 12000 K.
(b) What is the integral molar free energy of mixing of the above alloy at 1300
K. Check your answer.
(c) Calculate the difference in change of free energy when one g. atom of
liquid Zinc dissolves in a large amount of liquid brass at 1200 and 1300 K.
 Solution
The variation of activity coefficient with composition shows that α Zn =-1.929, is independent of composition.
This indicates that brass behaves regularly at 1200K.

∴α Zn =α Cu

ln γ Zn ln γ Cu
α Zn = = = α Cu = −1.929
(1 − x Zn ) 2
(1 − xCu ) 2

we know that for regular solution we have ∆H M = G XS = RT ( x A ln γ A + x B ln γ B )

∴ Integral molar heat of mixing (or excess molar free energy) of brass,

T = 1200 K , x = 0.4, x ==0.6RT ( xZn ln γ Zn + x Cu ln γ Cu )

∆ =
M XS
H Cu
G Zn

ln γ Zn = − 1.929 xCu
2
= −1.929 × 0.4 2 = −0.30864
 Solution
∴ γ Zn = 0.7344 and a Zn = 0.7344 × 0.6 = 0.4406

ln γ Cu = −1.929 xZn
2
= −1.929 x 0.6 2 = − 0.6944

∴ γ Cu = 0.4993 and aCu = 0.4993 × 0.4 = 0.1997

∴ ∆H M = G XS = 1.987 ×1200 (0.6 ln γ Zn + 0.4 ln γ Cu )

= - 2384.4 (0.6 × 0.30864 + 0.4 × 0.6944)

= -2384.4 × 0.4629 = -1103.8 cal/mol.
or GXS = (RTα ) xCu xZn = (-4600) × 0.24 = -1104 Ans.
 Solution
(b) ∆G M = RT ( x A ln a A + x B ln a B ), sin ce ∆G M for brass is needed at 1300
K, hence aCuand aZn should be first calculated at 1300K by making use of
properties of regular solution.
α Zn = α Cu = −1.929(at1200 K ) and α 1T1 = α 2T2

∴ α 1200 .1200 = α 1300 .1300

12 12
α 1300 = α 1200 . = −1.929 × = −1.781
13 13
ln γ Zn = α 1300 .xCu
2
= −1.781× (0.4) 2 = 0.2849
∴γ Zn = 0.7520 and a Zn = 0.7520 × 0.6 = 0.45125

ln γ Cu = α1300 .xZn = −1.781× ( 0.6) = 0.6412

2 2
 Solution
∴γ Cu = 0.5267, aCu = 0.5267 × 0.4 = 0.21071

∆G M = 1.987 × 1300(0.6 ln 0.45125 + 0.4 ln 0.21071)

=
G XS (1300) ×
1.987 1300
= RT αxCu (-1.10034) = -2842.3
.x Zn = 1.987 × 1300 (−1.781) ×cal/mol.
0.24 = −1103.5
G XS (1200) = G XS (1300) = −1104 cal / mol. (Re gular solution )

∆G M ,id = RT ( xZn ln xZn + xCu ln xCu ) = 1.987 ×1300 (0.6 ln 0.6 + 0.4 ln 0.4)
= −1738.5 cal / mol.

G XS = ∆H M = ∆G M − ∆GidM = −2842.3 − (−1738.5) = −1103.8cal / mol.

 Solution
M M
Difference in change in free energy = G (1300 ) - G (1200)
Zn Zn
=RT ln aZn(1300) – RT ln aZn (1200)
=1.987 (1300 ln 0.4513 – 1200 ln 0.4406)
=1.987 (-1034.31 + 984.54) = -98.9 cal/mol. Ans.
Dilute Solution –
Henry’s Law
Henry’s Law
 Henry’s Law
p Aα x A
i.e. p A = kx A (1)
pA k
dividing by p A0 we have 0
= 0 .x A i.e.a A = const x A or a A α x A
pA pA

●
γ A0to
The constant is equal the slope of the curve at zero concentration of A,
(activity
designated by coefficient of the solute A at infinite dilution).

a A = γ A0 . x A
●
Like Raoult’s law, Henry’s law is valid within a concentration range where the
extent varies from one system to another, but it is valid only at low
concentration.
 Henry’s Law

aA

γ0A → Henry’s law constant

xA
 Henry’s Law
●
In concentratrated solution the standard has been defined as unit
atmospheric pressure and unit activity i.e. pure substance at any
temperature.
●
In dilute solutions relative standard states other than pure substance being
used. Henry’s law offers two such standard states, called alternative
standard states.
(1) Infinitely dilute, atom/mole fraction standard state.
(2) Infinitely dilute, wt% (w/o or %) standard state.
 Solubility of Gases
 It is important to note that the validity of Henry’s law depend upon the
proper choice of solute species. For example, consider
(a) solution of nitrogen in water
(b) solution of nitrogen in liquid iron
 In the first case nitrogen dissolves molecularly as N2
aN 2
N 2 ( g ) ↔ N 2 ( dissolved in water) K=
pN2
 As solubility of N2 in water is low according to Henry’s law we have
kxN 2
aN 2 = k xN 2 or K =
pN2

K
xN 2 ( so lub ility ) = p N 2 = k ′ p N 2
k
 Solubility of Gases
●
Thus the solubility of nitrogen in water is proportional to the partial
pressure of nitrogen gas in equilibrium with water.
●
Solubility can be expressed as mole fraction, cc per 100 g of water or any
other unit.
●
(2) In the second case under consideration
nitrogen dissolves atomically in solid or liquid
N 2 ( g ) ↔ 2 N (in Fe)
metals:
a 2
N ( inFe ) (kx N ) 2
K= =
pN2 pN2
K
or x N (inFe ) ( so lub ility ) = pN2 = k ' pN2
k
 Solubility of Gases –
Sievert’s law
● Since all the common diatomic gases N2, O2, H2 etc.
dissolve atomically in metals, the general expression for
solubility is given as:

S =k pN2

● This is known as Sievert’s law and can be stated as –

solubility of diatomic gases in metals is directly
proportional to the square root of partial pressure of the gas
in equilibrium with the metal.
 Problem
At 8000C, 100g of silver dissolves 3.3 cm3 (STP) of oxygen at one
atmosphere pressure. How much oxygen does silver dissolve from air at
8000C?

Solution:
According to Sieverts law: S =k pO2 i.e. 3.3 = k 1 = = >k = 3.3

In air pO2= 0.21 atm, S =k pO2 = 3.3 0.21 = 1.51cm3

 Problem
The following solubility of oxygen in 100 g of silver at 10750C have been
measured.
pO2 (mmHg ) 128 488 760 1203

Oxygen dissolved cm3/100gAg 81.5 156.9 193.6 247.8

a) Show whether these observations agree with Sievert’s law for the
solubility of oxygen in metals.
b) How much oxygen does 100g of silver absorb at 10750C from air?
c) What pressure of air corresponds to one atm of O2 with respect to the
solubility of oxygen in silver at 10750C.
 Solution
solubility
Sievert' s cons tan t k s =
pO2
81.5
kS = = 7.2037
128
156.9
ks = = 7.1025
488
193.6
ks = = 7.0226
760
247.8
kS = = 7.1444
1203
 Solution
Almost constant values of ks demonstrate that solubility of oxygen in
silver is proportional to the square root of partial pressure of oxygen in
equilibrium. Hence the observations agree with Sievert’s law. Average
value of ks = 7.1183.

(b) In air, pO2 = 0.21 atm. = 0.21 × 760

So lub ility = k S 0.21× 760 = 7.1183 159.6 = 89.93cc per 100 gm Ag
1
(c ) pair = ( pair =1 atm, pO2 = 0.21)
0.21
= 4.7629
 Problem
At 15400C liquid iron dissolves 0.04% nitrogen in equilibrium with
nitrogen gas at one atmospheric gas pressure and 0.23% oxygen in
equilibrium with oxygen gas at one atmosphere gas pressure. At that
temperature nitrogen pentoxide gas was passed over liquid iron such
that equilibrium was attained with fully dissociated gas at a net pressure
of one atmosphere. What is the nitrogen and oxygen contents of the melt?
 Solution
5
N 2O5 ( g ) ↔ N 2 ( g ) + O2 ( g ) = 2 N + 5 O
2

N2 gas : O2 gas
1 mol : (5/2) mols
2 mol : 5 mols.
2 vol 2: 5 vol. 5
p N 2 = atm and pO2 = atm
7 7
S N = K N p N 2 = 0.04 = K N 1 = > K N = 0.04

S N' (dissociated N 2 O5 ) = K N p′
2
= 0.04 = 0.02138% Ans.
7
 Solution
SO = K O p
0.23 = K O 1
K O = 0.23
S O′ (dissociated N 2O5 ) = 0.23 5 = 0.19439%
7
 Alternative Standard States
1. Infinitely dilute, atom fraction standard state
Henerian standard state is obtained from Henry’s law which, strictly being
limiting law obeyed by the solute in the dilute solution is expressed by

aA
→ γ A0 as x A → 0
xA
where a A is the activity of A w.r.t Roultian
s tan dard state and γ 0
is the Henery' s law cons tan t
If the solute obeys Henry’s law overAa finite concentration range, then

a A → γ A0 . x A
 Alternative Standard States
●
Henerian standard state is obtained by the extending the Henry’s law line
to xA = 1.
●
This state represents pure solute in the hypothetical, nonphysical state in
which it would exist as a pure component if it obeyed Henry’s law over
the entire composition range (i.e., as it does for a dilute solution)

h A = 1 = γ 0A at x A = 1 .
This is the henerian s tan dard state and
h A is the henerian activity
●
Having defined the Henrian standard state, the activity of A in solution
with respect to the Henrian standard state is given by:

hA = f A . x A
where f A is the henerian activity coefficient
 Alternative Standard States
● In the range of composition in which the solute obeys Henry’s Law, fA =1 and solute exhibit the
Henerian ideality

hA = xA

 a A x A .γ A γ A 
 = = 
 hA x A . f A f A  x A = cons tan t

● In the range of composition in which the solute obeys Henry’s Law, fA =1 and γA = γA0

aA 0 
 =γA 
 hA  x A = cons tan t
 Alternative Standard States
● The free energy change accompanying the transfer of one mole of solute A from pure
substance standard state (Raoultian standard state) to Henerian standard state, that is:

A (intheRaoultianstandardstate) → A(inthe Henerianstandardstate )

is given by

∆G A0 ( R → H ) = G 0A ( H ) − G 0A ( R )
● The partial molar free energy of the solute at constant concentration is independent of
standard state. The value of ΔGA0 remains unchanged if is added and is
subtracted from the right hand side of the above equation
G A (R) G A(H )

∆G A0 ( R → H ) = G 0A ( H ) − G 0A ( R ) + G A ( R ) − G A ( H )
( ) (
= G A ( R ) − G 0A ( R ) − G A ( H ) − G 0A ( H ) )
 Alternative Standard States
But G A − G A0 = R T ln a A

a 
Hence, ∆G A0 ( R → H ) = RT ln  A 
 hA  x A =cons tan t
= RT ln γ A0
 Alternative Standard States
2. Infinitely dilute, wt% standard state.
●
The use of this standard state eliminates the necessity of converting

weight percentages, obtained via chemical analysis, to mole fractions for

the purpose of thermodynamic calculations. This standard state is

particularly convenient to use in metallurgical systems containing dilute

solutes. This standard state can formally be defined as:

aA
→ 1 as wt.% A → 0
wt.% A
or a A = wt.% A( wt .% A →0 )
 Alternative Standard States
● If the concentration up to 1 weight-percent of solute A,
then aA = 1 at wt%A =1 and this 1 weight-percent solution
is then the standard state
● W.r. t 1 weight-percent standard state, the activity of
solute A is given hby = f . wt.% A
A (1 wt %) A (1 wt %)

● Where fA(1wt%) is the 1 wt.% activity coefficient and in the

range of composition in which A obeys the Henry’s law
fA(1wt%) hA (1wt %) = wt .% A
 Alternative Standard States
●
We can also write

 aA x A .γ A 
 = 
 hA(1wt %) f A(1wt %) .wt % A  cons tan t composition
● In the range of composition in which the solute obeys Henry’s Law, fA(1wt%)
=1 and γA = γA0 , therefore,

 aA xA. 
 =γ A
0

 hA(1wt %) wt % A  cons tan t composition
 Alternative Standard States
●
We know that wt.% A
MA
xA =
wt.% A 100 − wt .% A
+
MA MB
● Where MA and MB are the molecular weight of A and B. the first term in
the denominator is small compared to the second and the relation may be
simplified as
wt.% A
MA wt.% A . M B
xA ≈ =
100 100. M A
MB
xA MB
Therefore, =
wt.% A 100. M A
 Alternative Standard States
●
The free energy change accompanying the transfer of one mole of solute
A from pure substance standard state (Raoultian standard state) to 1 wt.%
standard state, that is:
A (in the Raoultian standard state) → A( in the 1 wt.% standard state)

is given by
 aA 
∆G ( R →1 wt. %) = RT ln 
0
A 
h
 A (1Wt .%)  x A = const
MB
= RT ln γ + RT ln
0
A
100.M A
 Alternative Standard States
●
The free energy change accompanying the transfer of one
mole of solute A from Henerian standard state to 1 wt.%
standard state, that is:
A (in the Henerian standard state) → A( in the 1 wt.% standard state)
is given by
∆G A0 ( H →1 wt. %) = ∆G A0 ( R →1 wt. %) − ∆G A0 ( R → H )
 MB 
=  RT ln γ A0 + RT ln  − RT ln γ A
0

 100.M A 
MB
= RT ln
100.M A
 Problem
Calculate the free energy change when the standard state of manganese is
transferred from pure liquid state to infinitely dilute wt% solution of
manganese in iron at 16270C melting point of Mn =12450C, at wt of Mn =
54.94, Fe = 55.85. Assume ideal behaviour of the solution.
Solution:
T = 1627 + 273 = 1900, MMn = 54.94, MFe = 55.85 γ Mn
0
= 1(ideal )
Mn (pure substance standard state) → Mn (dilute wt% standard state)
aMn  0 M Fe 
∆G ( R → H ) = RT ln
0
Mn = RT ln γ Mn 
hMn (1wt %)  100 M Mn 

 55.85 
= 8.314 ×1900 × ln 1× 
 100 × 54. 94 
= − 72455 J / mol
 Problem
From experimental measurements of the equilibria between H2-H2O gas
mixtures pure silica and silicon dissolved in liquid iron, the free energy
accompanying the transfer of standard state from pure silicon to the
infinitely dilute, wt.% solution of silicon in iron i.e.:
Si (pure, 1) ↔ Si (wt% dil. in Fe) has been expressed as ∆ G0 = -28500 –
5.8T cal./mol. At 16000C, the activity coefficient of silicon in iron ,
relative to pure silicon as the standard state is 0.0014 at 1 atomic% Si.
Calculate the activity coefficient of silicon, relative to the wt% standard
state at this concentration.
 Solution
∆ G0 = -28500 – 5.8T = -28500 -5.8 × 1873 = -39360 cal.

wt % Si
atom% si = 0.01 = 28.09
wt % Si + 100 − wt % Si
28.09 55.85
wt% Si = 0.50
Si (pure, 1) ↔ Si (1wt% in Fe)

γ 0
M γ 0
Si .55.85
∆GSi ( R → 1 wt %) = RT ln
0 Si Fe
= RT ln = − 39360
100M Si 100 × 28.07
∴ γ Si = 0.00128
0

This is the activity coefficient of Si at infinite dilution, relative to pure Si as the standard
state.
 Solution
Hence the activity coefficient of Si at 1 at% Si, relative to pure Si as the
standard state is calculated as follows:
aSi ( pure) = γ Si .xSi = 0.0014 × 0.01 = 0.000014
aSi γ Si0 M Fe
=
hSi (1wt %) 100 M Si
aSi .100M Si 0.000014 ×100 × 28.09
∴ hSi (1 wt %) = = = 0.55
γ Si0 M Fe 0.00128 × 55.85
wt % Si
M Si
xSi =
wt % Si + (100 − wt % Si )
M Si M Fe
 Solution
wt % Si
0r 0.01 = 28.09
wt % Si + (100 − wt % Si )
28.09 55.85
or wt % Si = 0.50

hSi = fSi . wt% Si

hSi 0.55
∴ f Si = = = 1.1 Ans.
wt % Si 0.50
 Problem
γ Al0
The Raoultian activity coefficient of Al at infinite dilution, in liquid
Fe-Al alloys is reported to be 0.063 at 16000C. Calculate the standard free
energy of formation of Al2O3(s) at 16000C for each of the three standard
states for solution of Al in Fe.
MAl = 26.98 and MFe = 55.85
given 1. 2 Al(l) + 3/2O2(g) = Al2O3(s) ∆ G0 = -1682927 – 323.24TJ
2. 2 Al(l, H) + 3/2O2(g) = Al2O3(s)
3. 2 Al(l, wt %) + 3/2O2(g) = Al2O3(s)
 Solution
(1) 3
2 Al (l ) + O2 ( g ) = Al2O3 ( s ) (1)
2
∆ G0 = -1082927 +323.24 × 1873 = -1077498.5 J

3
2 Al (l , H ) + O2 ( g ) = Al2O3 ( s ) ( 2)
2
Al (l ) = Al (l , H ) (3)

For reaction (3)

a Al
∆G Al0 ( R → H ) = RT = RT ln γ Al0
hAl

Total free energy change for reaction (2) = ∆G(0H ) = ∆G(0R ) − 2∆G(0R → H )
 Solution
= ∆G(0R ) − 2 RT ln γ Al0
= -1077498 – 2 × 8.314 × 1873 ln (0.063)
= -1077498 – (-86102) = -991396 J.
3
2 Al (l ,1wt %) + O2 ( g ) = Al2O3 ( s ) (4)
2
Al (l ) = Al (l ,1wt %) (5)

For reaction (5)

a Al  γ Al0 M Fe 
∆G Al0 ( R → 1wt %) = RT = RT ln  
hAl (1wt %) 100 M Al 

Total fre energy change for the reaction (4) = ∆G(01wt %) = ∆G(0R ) − 2∆G(0R →1wt %)
 γ Al0 M Fe 
= ∆G 0
( R) − 2 RT ln  
 100 M Al 
 Solution
 0.063 × 55.85 
= -1077498 – 2 × 8.314 × 1873 ln  
 100 × 26.98 

= -1077498 – 2 × 8.314 × 1873× (-6.6422)

= -1077498+206866.8
= -870631J Ans.
 Problem

Vanadiam melts at 1720oC. The raoultion activity coefficient of vanadian

at infinite dilution in liquid iron at 1620oC is 0.069. Calculate the free
energy change accompanying the transfer of standard state from pure solid
vanadium to the infinitely dilute wt% solution of V in pure iron at 1620oC.
Given: heat of fusion of V = 4800 cal/g atom
MFe = 55.85 and MV = 50.95.

Solution:
TVf = 1993 K γ V0 = 0.069 at 1893K .
∆H f
4800
∆S =
f
f
= = 2.4084 cal / deg .mol.
T 1993
 Solution
Free energy of fusion of vanadium (s →l) at the operating temperature
1893K.

∆G f = ∆H f − T∆S f = 4800 − 1893 × 2.4084 = 240.9 cal / mole.

We calculate ∆ Gf for fusion because the melting point of V is more than the
operating temperature (at which V is in solid state).
V (pure l) → V (wt%)
 γ 0
M   0.069 × 55.85 
∆GV0 ( R − 1wt %) = RT ln V Fe  = 1.987 ×1983 ln  
 100 M V   100 × 50.95 
= -27033 cal/mol

For energy change V (pure solid) → V infinitely dilute wt% solution

= ΔGf + ΔGV0 (R →H) = 240.9 – 27033
= -26792.1 cal/mol.
 Chemical Potential
● The general equation for the free energy change of a system with temperature and pressure
dG = VdP – SdT, does not take into account any variation in free energy due to
concentration changes.
● We know
G ′ = G ′(T , P, n , n , ....)
● From the fundamentals of partial1 differentiation
2
we have

 ∂G′   ∂G′   ∂G ′   ∂G′ 

′
dG =   dT +  
 dP +  
 dn1 +   dn2 + ......
 ∂T  P ,ni  ∂P T ,ni  ∂n1 Texcept
, P , n2 ....
n1
 ∂n2 Texcept
, P , n1 ....
n2

∂G '
= S'.dT + V' dP + ∑ dn i
● The coefficient ∂called
n i Tthe
, P , n1 ....
‘chemical potential’ and is denoted by µ
except n i
hence
 ∂ G′ 
 
 ∂ ni  ePx,Tc ,epn1n.......
ti
 Chemical Potential
 ∂G′ 
  = µi
∂n
 i  Except1 ni
T , P , n .....

µ is an intensive variable
This gives a new sets of fundamental equations for the open systems.
dG ′ = − S ′dT + V ′dP + ∑ µ i dni

dA′ = − S ′dT − PdV ′ + ∑ µ i dni

dH ′ = TdS ′ + V ′dP + ∑ µ i dni

dU ′ = TdS ′ − PdV ′ + ∑ µ i dni

 Physical Meaning of
Chemical potential
●
Consider the change in free energy (dG/) of a system produced by the
addition of dnA mole of component A at constant pressure and temperature.
The change in free energy of a system is given by dG ′ = µ A dn A = G A dn A is
the partial molar free energy of component A in solution

 ∂G ′ 
G A =   = µ A for a large quantity of solution
 ∂n A  P ,T , n B
 ∂G 
G A =   = µ A for one mole of solution
 ∂n A  P ,T , n B
●
Chemical potential of either 1 g mol or 1 g atom of a substance dissolved in
a solution of definite concentration is the partial molar free energy. Thus
 Equality of chemical potential
amongst phases at equilibrium
We know: dG ′ = − S ′dT + V ′dP + ∑ µ i dni
At constant T and P: dG′ = ∑ μ i dn i
Consider two phases(I and II) in the system. Then,

Consider moving an infinitesimal of quantity dn1 from phase

I to phase II. Then,
 Equality of chemical potential
amongst phases at equilibrium
Therefore, total free energy change of the system is

For equilibrium at constant temp and pressure

Hence,

It can be generalized for all components at constant T and

P when phase I and II are at equilibrium as
 Equality of chemical potential
amongst phases at equilibrium

Where P is the total no. of phases in the system

 Phase Rule
Phase(P)
A phase is defined as any homogeneous and physically distinct part of a system
which is separated from other part of the system by a bounding surface. For
example, at 273.15K, three phases ice, water and water vapour can exist in
equilibrium. When ice exists in more than one crystalline form, each form will
represent a separate phase because it is clearly distinguishable from each other.

Components(C)
The number of components in a system at equilibrium is the smallest number of
independently variable constituents by means of which the composition of each

phase present can be expressed directly or in the form of a chemical equation.

 Phase Rule
As an example let us consider decomposition of calcium carbonate :
CaCO3 (s) = CaO(s) + CO2(g)
●
According to the above definition, at equilibrium this system will consist
of two components since the third one is fixed by the equilibrium
conditions.
●
Thus we have three phases – two solids (CaCO3 and CaO) and a gas
(CO2) and the system has only two components.
● If CaO and CO2 are taken, the composition of calcium carbonate phase can
be expressed as xCaO + xCO2 giving xCaCO3 (by the chemical reaction).
●
The composition of the three phases could be expressed equally by taking
CaCO3 and CaO or CaCO3 and CO2 as the components.
 Phase Rule
●
The dissociation of any carbonate, oxide or similar compounds involves
two components; the same is true in the case of salt hydrate equilibria, for
example : CuSO4.5H2O(s) = CuSO4.3H2O(s) + 2H2O(g) when the simplest

components are evidently CuSO4 and H2O.

● In the slightly more complicated equilibrium : Fe(s) + H2O(g) = FeO(s) +
H2(g) it is necessary to choose three components in order that the
composition of each of the three phases can be expressed.
●
The composition of the two solid phases could be given in terms of Fe and
O, but these alone are insufficient to define the gaseous phase which is a
mixture of hydrogen and water vapour, a third component, viz., H2O is
necessary.
 Phase Rule
● The water system for example consists of one component, viz., H2O each
of the phases in equilibrium i.e. solid, liquid and vapour may be regarded
as being made of this component only.

Degrees of freedom(F)
●
The number of degrees of freedom is the number of variable factors, such
as temperature, pressure and concentration that need to be fixed in order
that the condition of a system at equilibrium may be completely defined
when referring to its equilibrium phase diagrams.
Derivation of the Phase
Rule Equation
Derivation of the Phase
Rule Equation
Derivation of the Phase
Rule Equation
 Application of phase rule
to single component system
 Application of phase rule
to two component system
For two component system: F = 3 – P as the pressure is kept
constant

P=1  F= 2 can vary T and composition - bivariant

P=2  F= 1 can vary either T or P – monovariant

P=3  F= 0 no free variables it is a fixed point. - invarient

Two components
Eutectic system
 Phase rule in Reactive
Components
●
Consider a system consisting of N chemical species and there
are P number of phases.
●
In this case the number of components differ from number of
species.
●
Let us consider there are three out of N species are chemically
active and participate in the following reaction:
AB(s) = A(g) + B(g).
●
The number of total variables = P(N-1) + 2
●
Total number of constraints due to phase equilibrium= N(P-1).
●
There is another additional constraints: AB(s) = A(g) + B(g).
 Phase rule in Reactive
Components
●
Additional, in the absence of A(g) and B(g) in the starting
reactant mixtures, stoichiometric consideration requires that
PA= PB.
●
Some times, special constraints are placed on the system. For
example, the system under consideration, the partial pressure
of A has been fixed at 2 atm.
●
So this way total no. of constraints are = N(P-1)+1+1+1.
●
F = [P(N-1)+2] – [N(P-1)+1+1+1] = (N-2) – P +1 = C – P +1
●
Generalizing, for a system in which there are ‘r’ independent
chemical equilibria, ‘s’ stoichiometric relation and ‘t’ special
constraints we have
F = (N – r – s - t) – P +2 = C- P + 2 –t
where C = N - r - s
 Application of Phase rule
in Reactive Components
Problem:
A system is composed of a solid phase CaCO3, a solid phase CaO,
and a gas phase CO2 . The following equilibrium occurs:
CaCO3(s) = CaO(s) + CO2(g)
How many components are there and what are the degrees of
freedom?
Solution:
Species: CaCO3(s) , CaO(s), CO2(g) : N =3, Phases : two solid and a gas phase P =
3. No. of independent reaction equilibria r = 1. There is no
stoichiometric or special constraints.
So s = 0 and t = 0
C = N-r-s = 3-1-0= 2
F = C-P+2-t = 2-3+2-0 = 1
Either temperature or pressure must be specified.
 Application of Phase rule
in Reactive Components
Problem:
A pure solid NH4Cl is introduced into an evacuated chamber. It is
then allowed to decompose and equilibrium has been established by
following reaction:
NH4Cl(s) = NH3(g) + HCl(g)
Calculate the number of components and degrees of freedom.
Solution:
N = 3 (NH4Cl(s) , NH3(g) , HCl(g) )
P = 1 solid (NH4Cl(s) ) + 1 gases (NH3(g) + HCl(g ) = 2
r=1
s = 1 as P NH3(g) = P HCl(g)
t=0
C = N – r – s = 3 – 1 -1 = 1
F = C – P + 2 – t = 1 -2 + 2 – 0 = 1
 Application of Phase rule
in Reactive Components
Problem:
Show that the system in which the reaction
Mn(s) + 2/3 AlCl3(g, 1atm) = MnCl2(l) + 2/3 Al (l)
is at equilibrium is invariant.
Solution:
N = 4 (Mn(s), AlCl3(g), MnCl2(l), Al (l))
P = 1 solid (Mn) + 2 liquids(MnCl2(l)and Al (l)) + 1 gas (AlCl3(g)) = 4
r=1
s=0
t = 1 (1 atm of AlCl3(g))
C = N –r – s = 4 – 1 – 0 = 3
F=C–P+2–t=3–4+2–1=0
This is an invariant system
 Application of Phase rule
in
Problem:
Reactive Components
Consider reduction of FeO with CO under standard conditions
i.e. P = 1 atm.
FeO(s) + CO(g) = Fe(s) + CO2(g).
Calculate the number of components and degrees of freedom.
Solution:
In this system we have P = 3 (i.e. two solids FeO and Fe
and a gaseous phase CO+CO2) and N = 4, r = 1, s = 0 and
t = 1 (PCO + PCO2 =1 atm)
C = N –r –s = 4 -1 -0 = 3
F = C - P + 2-t = 3 – 3 + 2 -1 = 1
Thus the above system has only one degree of freedom, either
temperature or pressure.
 Phase Diagram
Graphical representation of what phases
are present
in materials systems at various
temperatures,
pressures and compositions are called
phase diagrams
Solid Solution
Solid Solution
Types of Solid Solubility
 Phase Diagram
Solidus
The phase boundary between solid and two phase region.
Liquidus
The phase boundary between liquid and two phase
region.
Solvus
The solid state phase boundary between terminal solid
solution and two phase region.
 Single – Component System –
Variation of Free energy with
Temperature

 ∂ G( s ) 
  = − S ( s )
 ∂ T P
 ∂ G( l ) 
  = − S ( l )
 ∂ T P

S(l) > S(s), So slope of the line

for liquid H2O is greater than
solid H2O
 Single – Component System –
Variation of Free energy with
Temperature

 ∂ ∆G 
  = − ∆S
 ∂T P

●
Where ΔS is the change in
molar entropy which occurs
as a result of the change of
state.
●
The slope od the line is –ve
which shows that at all temp
SH2O(l) > SH2O(s)
 Single – Component System –
Variation of Free energy with
Pressure
 ∂ G( l ) 
  = V( l )
 ∂ P T
 ∂ G( s ) 
  = V( s )
 ∂ P T

V(l) < S(s) for H2O So slope

of the line for solid H2O
is greater than liquid H2O
at all pressure
 Variation of Free energies of
solid liquid and vapour H2O with
Temperature and Pressure
 Binary Phase Diagrams
Isomorphous System: The system which exhibits complete solid solubility
and liquid solubility is called an isomorphous sytem. The crystal
structure of both the components as well as solid solution are same.
Eutectic system: The system which exhibit limited solid solubility or
terminal solid solution is called an eutectic system.
Isomorphous system
Eutectic system
 Experimental Determination of
Liquidus and Solidus– Cooling Curve Method

● T = f(t) cooling curves measurements for several

compositions
● Pure metal : melts /solidifies /allotropic transformation
takes place at one temperature.
● Binary solutions: melts /solidifies over a range of
temperature.
● The temperature at which the start of solidification
takes place is called liquidus.
● The temperature at which the end of solidification
takes place is called solidus.
 Experimental Determination of
Liqidus and Solidus– Cooling Curve Method
 Experimental Determination of
Solvus– Cooling Curve Method
● The common methods for the determining the solvus are microscopic
examination and X-ray diffraction methods.
● A series of small ingots of alloys of different compositions are prepared
and homogenized.
● They are annealed at various temperatures for prolonged time (a few
days) and then quenched.
● High temperature phases may be retained on quenching.
● Subsequent, metallographic studies and X-ray diffraction reveals the
various phases present at that temperature for given alloys
 Experimental Determination of
Solvus– Cooling Curve Method
●
A phase boundary is first bracketed
between two compositions.
●
The exact location of the boundary is
determined by studying a more alloys of
closely varying compositions in the
boundary region.
 Free energy – Composition
Diagram

● X 2α energy
The intercepts of the two axes by the tangent of the Gibbs free
curve of the µ α1αphase µ 2αthe composition
and at represent
●
similarly, for the β phase
 Free – Energy Composition
Diagram for Binary Systems

Isomorphous
System
 Free – Energy Composition
Diagram for Binary Systems

Eutectic System