Metallurgical Thermodynamics

D E P A R T M E NT O F
Metallurgical Engineering
Institute of Technology Banaras Hindu University
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 Institute of Technology Banaras Hindu University
 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, -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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
Definitions Institute of Technology Banaras Hindu University
 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 .
 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
 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
 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,
SystemBasic
and Concepts and
Surrounding D E P A R T M E NT O F
 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
Heterogeneous system
 Homogeneous system consists of single phase only.

 Heterogeneous consists of more than one phase.
State of a system Metallurgical Engineering

 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.) Metallurgical Engineering

 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 D E P A R T M E NT O F
State properties Institute of Technology Banaras Hindu University
 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 D E P A R T M E NT O F
State properties Institute of Technology Banaras Hindu University
 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 Metallurgical Engineering

 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 Metallurgical Engineering

 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:

 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

 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 D E P A R T M E NT O F
• 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 D E P A R T M E NT O F
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
 Z  Z
dZ    dX    dY
  X Y   Y X
And
Y Y
dY    dX    dZ
  X Z   Z X
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
state variables
Similarly, 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 Metallurgical Engineering

 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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

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.

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.

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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
 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 Metallurgical Engineering

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 Metallurgical Engineering

 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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
Hence   U     U  
dH  V     dP   P     dV
   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 

 P    1 
  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 dT = 0 and therefore dU = 0 so
 U 
   0
  P T
 As we know: H  U  PV
 H U   P V  
       
  P T   P T   P  T
 For an ideal gas at Constant T, PV = constant, d (PV) = 0
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 q
C
T
The molar heat capacity at constant volume is given by
 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
 q   H 
C P      
  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 Metallurgical Engineering

 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
And we know  U   U 
dU    dV    dT
  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 Metallurgical Engineering

 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 C P – CV = R
Application of First law D E P A R T M E NT O F
to Thermodynamic Processes Institute of Technology Banaras Hindu University
 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
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 case
Vf Vf RT V f dV
qw Vi
PdV  Vi V dV  R T 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
and produce an equivalent amount of work.
 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.
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 Metallurgical Engineering

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
V = Vf at T = Tf

And substituting the expression for R in above

Expression CV Tf Vf
ln   ln
C P  CV Ti Vi
 1  1
Or T f V f  T V
i i where  
CP
CV
Or T V  1  Const Or P V   Const
Also since by definition H = U + P V

Or dH = dU + P dV + V dP
As dU = - P dV
So dH = V dP

Enthalpy change in a adiabatic process is

Pf Vf
H   Pi
V dP     Vi
P dV
P V   Const
As for such process.
This on integration lead to the expression
 Pi Vi  Vi 
 1

H    1
 1  V f 
 
 

Work done in reversible adiabatic expansion can

be deduced as follows
V2 V2 dV
w  V1
PdV  m 
V1 V
 V21   V11  
 m 
 1  
Or
P2V2  P1V1
w
1 
Where
P V   m  a const.
Polytropic Process Metallurgical Engineering

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

 n
PiVi  Pf V f
w
n 1
PiVi  Vi 
n 1

   1
n  1  V f 
 
 
Polytrophic Process Metallurgical Engineering

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 Metallurgical Engineering

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
Metallurgical are equal to zero.
Thermodynamics
Summary of Thermodynamic D E P A R T M E NT O F
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 Metallurgical Engineering

 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
Variation of heat Capacity D E P A R T M E NT O F
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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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.
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:
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
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
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 )
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   CP ( g ) dT
Tb
Cp (s), Cp (l) and Cp (g), are for solid liquid and

gaseous A. it is only applicable for pure substance.
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.
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 D E P A R T M E NT O F
• 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
oC 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 Metallurgical Engineering

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 D E P A R T M E NT O F
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 enthalpy change ΔH2 at
temperature T2.
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.
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
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 = H1 
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
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 Metallurgical Engineering


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 - 5 Metallurgical Engineering

Calculate the heat of the following reaction at 1000K

Fe2O3(s) + 3C (s) = 2Fe(s) + 3CO(g) from the following data:
Cp(, Fe) = 4.18 + 5.92 x 10-3 T caldeg-1mol-1
Cp(CO) = 6.79 + 0.98 x 10-3T – 0.11 x 105 T-2 caldeg-1mol-1
Cp(Fe2O3) = 4.10 + 1.02 x 10-3 T – 2.10 x 105T-2 caldeg-1mol-1
The heats of formation of Fe2O3 and CO at 298 K are
-197000 and – 26400 cal/mol. respectively.
Solution Metallurgical Engineering

Cp = Cp (product) – Cp (reactant) = 2.Cp(-Fe)+ 3 Cp(CO) – Cp(Fe2O3) – 3Cp(C)

2 x Cp(-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

1000
H 1000  H 298   C
298
p .dT
1000
= 117800 + ∫(
298
7.06 6.88 x10 3
) T + 9.52 x105 T 2
)dT
= 117800 – 7.06(1000-298) -6.88. (10002 – 2982) x 10-3 – 9.52 x

105 (1000-1 – 298-1)
= 117800 – 5850 = 111950 cals.

The standard heat of formation, of ammonia gas is -11.03

kcal/mol. at 250C utilizing the data given below derive a
general expression for heat of formation applicable in the
temperature range 273 – 1500K.
3 6 2 1 1
Cp 3
, NH  6. 189  7 . 787 x 10 T  0. 728 x 10 T cal deg mol
C p , N 2  6.450  1.414 x 10 3 T  0.0808 x 10 6 T 2 cal deg 1 mol 1
C p , N 2  6.947  0.2 x 10 3 T  0.4808 x10 6 T 2 cal deg 1 mol 1

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 N 2  C p H 2
3 2 2
= -7.457 + 7.38 x 10-3T – 1.409 x 10-6T2
298
ΔH 298 = ΔH 273 + ∫ ΔC p .dT

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

=-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 10-3T2 – 0.47 x 10-6T3 – (-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 10-3T2 – 0.47 x 10-6T3
= - 9122 – 7.457T + 3.69 x 10-3T2 – 0.47 x 10-6 T3
= -9122 – 7.457T + 3.69 x 10-3T2 – 0.47 x 10-6 T3 cal/mol
For H1000K solution T = 1000 in the above equation
H1000K = -9122 -7457 + 3690 – 470 = -13359

1000
ΔH 1000 = 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 Institute of Technology Banaras Hindu University
Problem Metallurgical Engineering

CT-I D E P A R T M E NT O F
Solution
Solution for Q-2: Fe + ½ O2 = FeO

ΔH 298 = ΔH FeO = - 63200 Cal
1033 1123
ΔH1123 = ΔH 298 + ∫ ΔC
298
p1 dT - 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
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
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
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 D E P A R T M E NT O F
Thermodynamics Institute of Technology Banaras Hindu University
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 D E P A R T M E NT O F
Thermodynamics Institute of Technology Banaras Hindu University
 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 / CO2
gas mixture as surroundings.
Heat Engines Institute of Technology Banaras Hindu University
•Heat engines operate in a

cycle, converting heat to HOT
work then returning to
original state at end of cycle.
Q1
•A gun (for example)
converts heat to work but
isn’t a heat engine because Engine W
it doesn’t operate in a cycle.
•In each cycle the engine
takes in heat Q1 from a “hot Q2
reservoir”, converts some of
it into work W, then dumps
the remaining heat (Q2) into COLD
a “cold reservoir”
 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 a non-cyclic process it
may be possible.
Efficiency of a heat engine Institute of Technology Banaras Hindu University
Definition:
HOT
work done per cycle
efficiency  
heat input per cycle
Q1
W

Q1
Engine W
•Because engine returns to
original state at the end of each
cycle, U(cycle) = 0, so W = Q2
Q1 - Q2
•Thus:   Q 1  Q 2  1  Q 2
Q1 Q1 COLD
Efficiency of a heat engine Institute of Technology Banaras Hindu University
•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 perfectly COLD HOT
Q
OK according to First
Law (energy
conservation)
WARM WARM
But we know only one

of them would really COLD HOT
Q
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” D E P A R T M E NT O F
heat engine Institute of Technology Banaras Hindu University
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): D E P A R T M E NT O F
isothermal expansion Institute of Technology Banaras Hindu University
Working substance (gas) Gas

Hot
expands isothermally at Source
temperature T1, Q1 T1
T1
absorbing heat Q1 from
hot source. a Piston
P Q1
a
b
b
T1
The Carnot Cycle (II): D E P A R T M E NT O F
adiabatic expansion Institute of Technology Banaras Hindu University
Gas isolated from hot

Gas isolated
source, from hot source,
expands Gas
expands adiabatically
adiabatically , and and
temperature falls
temperature falls from
from TT1 to
to
1
TT22.
P
a
b b Piston
T1
c
T2 c
V
The Carnot Cycle (III): D E P A R T M E NT O F
isothermal compression Institute of Technology Banaras Hindu University
Gas is compressed Gas

isothermally at temperature Cold
T2 expelling heat Q2 to cold Sink
T2
sink. Q2 T2
P
a d
b
T1
d c
T2 c Piston
V
Q2
The Carnot Cycle (IV): D E P A R T M E NT O F
adiabatic compression Institute of Technology Banaras Hindu University
Gas
Gas isis compressed
compressed Gas
adiabatically
adiabatically,, temperature
temperature
rises
rises from
from TT22to
to TT11and
andthe the
piston
piston isis returned
returnedto to its
its
original
original position.
position. Work done
The work a
isdone
the shaded
per cyclearea.
is the shaded
area.
d Piston
P
a
b
W T1
d c
T2
V
Efficiency of ideal gas D E P A R T M E NT O F
Carnot engine Institute of Technology Banaras Hindu University
P Q1
Q1  Q 2 Q2 a
 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 D E P A R T M E NT O F
(ideal gas) Institute of Technology Banaras Hindu University
P Q1
a
b
T1
Va Vb V
Vb
Q1  Wab  nRT1 ln
Va
Isothermal compression D E P A R T M E NT O F
(ideal gas) Institute of Technology Banaras Hindu University
P
a
b
T1
d c
T2
V
Q2
Vc
Q 2  Wcd  nRT 2 ln
Vd
Efficiency of ideal gas D E P A R T M E NT O F
Carnot engine Institute of Technology Banaras Hindu University
V
Q1 nRT 2 ln c
P Q Vd
a  1 2 1
Q1 Vb
b nRT1 ln
T1
Va
W
d c
T2
V
Q2
T1V b  1  T 2Vc  1
(1) T2
V b Vc  1
 1  1
(1)  (2)  T1
T1V a  T 2Vd (2) V a Vd
Q1 Q 2

T1 T 2
Adiabatic processes
So……..
For all Carnot Cycles, the following results hold:
Tc
 1
Th
Qc Q h Qc Q h Conservation
   0
Tc T h Tc T h of “Q/T”
What about more general cases?????
The expression
Qc Q h Qc Q h
   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 negative we have:
Qc Q h
 0
Tc T h
dQ
In other words 
cycle
T
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 Metallurgical Engineering

To emphasise the fact that the relationship we have

just derived is true for reversible processes only, we
write: dQ rev
 T
cycle
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? D E P A R T M E NT O F
Reversible cycle
For whole cycle:
dQ rev B
S 
 T
cycle
0 P
path1
B  A 
 dQrev   dQ rev 


A
T  

path 1  B
T 
path 2
0 A
path2
V
B  B 
 dQ rev   dQ rev 


A
T   


path 1  A
T 
path 2
Entropy change is
path independent
→ entropy is a
thermodynamic
function of state
S BA (path 1)  S BA (path 2)  S B  S A
Irreversible processes
Carnot Engine Irreversible Engine
 Qc  Tc  Qc  Tc
c  1     1  irrev  1    1
 Qh rev Th  Qh irrev Th
For irreversible case:
 Qc  Tc  Qc  Tc  Qc  Qh
           
 Qh irrev Th  Q h irrev Th  Tc irrev Th
 Qh   Qc 
      0
 T h irrev  T c irrev
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 dQ rev
 
(irreversible)
P  0
T T
Path 2 A( irrev ) B ( rev )
(reversible)
B ( irrev ) B (rev )
dQirrev dQ rev
A

A( irrev )
T


A( rev )
T
V
B ( irrev ) B (rev ) B ( irrev ) B ( rev )

dQ irrev

dQirrev
T


dQ rev
T 
A( irrev )
T


A( rev )
dS
A(irrev ) A( rev )
dQ irrev
dS 
General Case T
dQ
dS 
T
Equality holds for reversible change, inequality holds for irreversible change
“Entropy statement” D E P A R T M E NT O F
of Second Law Institute of Technology Banaras Hindu University
We have shown that:

dQ
dS 
T
For 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 decrease”
(but 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 D E P A R T M E NT O F
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
+Thermodynamics
Metallurgical
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 D E P A R T M E NT O F
on temperature Institute of Technology Banaras Hindu University
Dependence of entropy on temperature can becalculated at constant

volume as follow:  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:
 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 D E P A R T M E NT O F
of entropy Institute of Technology Banaras Hindu University
 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
P
and   T  can also not be determined experimentally. Hence in such cases
V
this 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 ()

is given as
1 V
   
V   T P
 Isothermal compressibility of a material () is given as
1 V
    
V   P T
 So

dS  dV

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 D E P A R T M E NT O F
 We know:
 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    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 D E P A R T M E NT O F
• 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
        
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
2 V T
CP  CV 

Entropy Change in Gases Metallurgical Engineering

S1 p1 Change S2 p2
v1 T1  v2 T2
Ideal gas
dq/T = Cv .dT/T + R dV/V = dS
T2 v2
S = S2 –S1 = dT dv
Cv ∫ +R ∫
T1
T v1
v
On integration S = Cv ln T+2 R ln v2
T1 v1
Entropy change can be calculated when temperature and volume
change take place on heating an ideal gas

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)

As the system absorbs heat, its entropy will increase e.g. with
melting and boiling.
T2
S= S2 – S1 =  Cpd ln T
T1
S is the area beneath the

curve between temperature,
T1 and T2(graphical method).
Significance of sign of entropy D E P A R T M E NT O F
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
vessels. Thus q q
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 Metallurgical Engineering

• 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
chemical processes Metallurgical Engineering

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 Metallurgical Engineering

 q rev
 dS  for an infinitesimal, isothermal reversible process.
T
 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 D E P A R T M E NT O F
first and second law Institute of Technology Banaras Hindu University
 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 Institute of Technology Banaras Hindu University
 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 D E P A R T M E NT O F
and constant entropy conditions Institute of Technology Banaras Hindu University
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
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 D E P A R T M E NT O F
and constant entropy conditions Metallurgical Engineering

Mathematically these conditions are expressed as

dP = 0 and dS = 0
dU + d (PV ) < 0
Or d (U + P V) < 0
Or dH < 0
dU + d (PV ) = 0
Or dH = 0
iii) TdS < dU + P dV for unnatural process

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 D E P A R T M E NT O F
and constant temperature conditions Institute of Technology Banaras Hindu University
Mathematically these conditions are

expressed as
dV = 0 and dT = 0
dU - TdS < 0
Or d ( U – T S) < 0
Let us define new mathematical term
A=U–TS
then dA < 0

d ( U – T S) = 0
Or dA = 0
iii) TdS < dU + P dV for the unnatural process
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 D E P A R T M E NT O F
and constant temperature conditions Institute of Technology Banaras Hindu University
These are by far the most commonly adopted

conditions in chemical and metallurgical engineering
practices. It means
dP = 0 and dT = 0
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

d ( U + P V– T S) = 0
Or dG = 0
iii) TdS < dU + P dV for the unnatural process
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 Institute of Technology Banaras Hindu University
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 Institute of Technology Banaras Hindu University
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 Institute of Technology Banaras Hindu University
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 D E P A R T M E NT O F
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.
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) + O2 (g) = 2FeO(s) and
3FeO(s) + 2 Al (l) = 2Fe(l) + Al2O3(s)
Both have negative heats of reaction at 1600 0C and both take place
spontaneously
 On the other hand, if we consider the reaction;
ZnO(s) + C(s) = Zn(g) + CO (g)
and
 This
 Hreaction
0
1373   will
83200 not take
 Hplace at 250C but if the system is heated
298  56800
0
to 11000C, carbon will reduce zinc oxide to produce zinc metal.

 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 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.

 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 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
 H
entropy increase of the surroundings =
T
 If S is the entropy change of the system, total entropy
change of the system and surroundings = S – H
T
 For the 2nd Law to be obeyed (S - H ) must be +ve

TΔS - ΔH T
= + ve
T

 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 25 0C
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
at 1100 0 C ΔH1373 - TΔS1373 = 83300 -1373( 68) = - 10200 cal

 This is negative so that the reaction will take place spontaneously at 1100 0C.
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.

 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

 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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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  dD
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 D E P A R T M E NT O F
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)
relationships
At constant pressure, dP = 0, so that  G  = - S

 T  P
and at constant temperature, dT = 0 and dG = VdP
from PV = RT for ideal gas, dG = RT dP
P
Integrating between the limits PA and PB at constant
Temperature PB
dP PB
G  G B  G A  RT P P  RT ln
PA
(4)
A
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
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
 G    G  
 T    S on substitution G  H  TS  H   
P
 T  P ,T
known on Gibbs – Helmholtz equation
Calculation of G0 at high temperature Metallurgical Engineering

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 S298  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 Metallurgical Engineering

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 D E P A R T M E NT O F
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.. Metallurgical Engineering

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… Metallurgical Engineering

 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… Metallurgical Engineering

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 Metallurgical Engineering

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 Metallurgical Engineering

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 Institute of Technology Banaras Hindu University
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 parameterMetallurgical
J is called activity quotient
Thermodynamics
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
K   

Q R
 a a    
l
L
m
M
At equilibrium G = 0,
G 0   RT ln  J  at eq.   RT ln K
J
Or 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 Metallurgical Engineering

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
  T   2 0  2   a  b T  c T  2  d T  d T
1 
 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 temperatur es or G 0 and
H 0 at one temperatur e.
Trouton’s and D E P A R T M E NT O F
Rechard’s Rules Institute of Technology Banaras Hindu University
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 Institute of Technology Banaras Hindu University
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
 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 
 q rev
b) dS   0 as  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
 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 
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   SSurrounding
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 . Thermodynamics
Metallurgical
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 
 
1250
T
dT 
1336
 
1336
T
dT
  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 surroundin g is at 1250 K and it has inf inite heat capacity.
Surrroundi ng absorbs heat released during freezing reversibly at 1250 K. Hence
 q  H System
 SSurrounding  
T T
1336 1250
 H System  H 2  H 1   C P ( l) d T   H  
0
m C P (s) d T
1250 1336
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-1mol-1
CP,Pb(s) = 23.55 + 9.75X10-3 T J K-1mol-1
CP,Pb(l) = 32.43 – 3.09X10-3 T J K-1mol-1
CP,O2 = 29.96 + 4.184X10-3 T - 1.67x 105 T-2 J K-1mol-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  2982  
 1 1 
 0.836  10 5     4812  5.811000  600
 600 298 
4.89  10 3

2
 
10002  600 2  0.836 10 5 
 1
1000

1 
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
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)-Mn = 5.7 + 3.4 x 10-3 T – 0.4 x 105 T – 2 cal / deg/ mol
(CP)-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.
→ 990 535

→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
  Mn 990
   Mn 1360

   Mn 1410

   Mn 1517
 l  Mn
990
 C P    Mn 535
1360
 C P    Mn 525
S  
298
T
dT 
990
 
990
T
dT 
1360
1410
 C P    Mn 430
1517
 C P    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 0
298 S o
298 , HgO ( s ) S o
298 , 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

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 0  201500  10.2 T log T  91.7 T cals
2
3
3H2 + O 2 (g ) = 3H 2 O(g ) , ΔG 0 = -176700 + + 39.3 T cals.
2
Solution:
3
WO3(s) = W(s) + O2 ( g ), G  201500  10.2 T log T  91.7 T cals
0
1 2
H2 + O 2 ( g )  H 2 O ( g ) , G 0
  58900  13.1T cals.
2
WO3(s) + 3H2(g)W(s) + 3H2O(g), G  24800  10.2 T log T  52.4 T cals

0

a) i) G 0 at 4000 K G4000
 24800  10. x 400 log 400  52.4 x 400 14460 cals.
ii) G 0 at 700 0 K ΔG 0700 = 5122 cals.
iii) G 0 at1000 0 K ΔG1000
0
= 3000 cals.
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
K1000= 0.22
3
b)  p H 2O 
K 
 pH 
 2 
solution Metallurgical Engineering

p H 2O
= K14003 = ( 1.253 x 10-8 )
1 3
= 2.472 x 10-3
pH2
p H 2O + pH2 = 1
p H 2 (0.00247+1) = 1
1
pH2 = = 0.9975 atm.
1.002472
and ∴p H 2O = 0.002466atm
% moisture = 0.24 %
At 700K, K700 = 2.317x10-3
p H 2O
= ( 2.5 x 10-2 )
1 3
= 0.296
pH2

p H 2 (0.296 +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 %

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.

 G 01023 = 450 + 10.45 x 1023

= 11140
= - RT lnK
11140
ln k = -
1.987  1023
=-5.48006 pH2
K = + 0.0041669 =
p H 2O
p H 2  0.0041669 p H 2O (1)  p H 2  p H 2O  1 (2)
from 1 & 2 :
1
or p H 2O   0.99585
0.0041669 p H 2O + p H 2O = 1 1.0041669
 p H 2  0.00415 Hence maximum tolerable partial pressure of
moisture is 0.99585 atm
problem Metallurgical Engineering

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
5147
log K = = 1.000 K = 10
4.575 x1125
K for the above reaction is
p CO 2 a Ni a Ni  1  a NiO
K= .
p CO a NiO
p CO 2
= = 10
p CO
In the given atmosphere p CO 2 i.e J/K is <1 so no oxidation of nickel
=3= J
p CO

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 + 23.55Tcals .
2
1
H 2 (g ) + O 2 (g ) = H 2 O(g ), ΔG 0 = - 58900 + 13.1Tcals .
2
Could pure nickel be annealed at 7500C in an atmosphere

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

G0 for the required reaction would be G0 = G20  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 J/K <1 rxn in forward direction
p H 2will take
So no oxidation 5 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 thereforebe 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


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 907 0C. The corresponding heat of
fusion is 1.74 kcal/gatom and the normal temperature of fusion is 419.5 0C.
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
dP Le
 where v g is the volume of 1gatom of zinc vapourand v l is the volumeof 1g atom of
dT T e  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 = 1 cc atm = 0.024212 cals.
Le
v g  vl  v g  vl  v g

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.

49 × 692.5
= (10.089 - 9.34) × 0.024212
1740
49 × 692.5
= × 0.75× 0.024212
1740
= 0.354 K Ans

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 1123K
dT RT 2
dP L 1 p2 L  T2  T1 
 P  R T2 or ln
p1

R

 T1T2 


ln p2 – 0 = 27300  1123 1180 = -0.5909869

 
1.987  1180 1123 
p2= 0.55378 atm
Lechatelier’s Principle Metallurgical Engineering

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 D E P A R T M E NT O F
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 Metallurgical Engineering

 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 Metallurgical Engineering

 ‘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 = G B
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
 vB  v A  dP   S B  S A  dT
Or
v . dP  S . dT
Or
dP S H tr
 as S 
Or 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 Institute of Technology Banaras Hindu University
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 Institute of Technology Banaras Hindu University
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 substitution 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:    Ttr
dP  H tr d T Ttr  v   v  
  
d T Ttr  v   v   dP  H tr
Where Htr is the molar heat of transition, v and
v are the molar volume of the indicated forms of
solid measured at Ttr.
Ellingham Diagram D E P A R T M E NT O F
 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 D E P A R T M E NT O F
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)  Al 2 O3
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 H 2 + O 2 = 2 H 2O 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 Metallurgical Engineering
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 H 2 + O 2 = 2 H2 O
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 Metallurgical Engineering

Disadvantages of Ellingham diagram D E P A R T M E NT O F
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 Metallurgical Engineering

 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. SiO 2). A
basic slag would give aSiO2 < 0.001.
Third law of Thermodynamics Metallurgical Engineering

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 of these two leads to the following
T
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 Metallurgical Engineering

• 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
   G
conclusions:  i  Lim 0
T 0 T
   H
 ii  Lim 0
T 0 T
As    G 
    S
  T P
Therefore, one can 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 ΔS0 = S0AB - S0A - S0B
At absolute zero temperature S0 = 0 it is possible provided
either i) S0AB = (S0A + S0B )
Or ii) 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 Metallurgical Engineering

“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 D E P A R T M E NT O F
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. 0
K
• 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 Metallurgical Engineering

Third law leads to following important consequences

1. CP, CV and  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
   
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    0
  T P
2. Unattainability of absolute zero temperature

let us consider a carnot cycle in which heat is absorbed at temperature T (T > 0 0K)
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.

T T
C P
Or 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

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 Metallurgical Engineering
G = G0 + RT ln K Institute of Technology Banaras Hindu University
= 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.
iii) 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

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 Metallurgical Engineering

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.
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%.
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) D E P A R T M E NT O F
K = (PH2 / PH2O)Fe, Pure Institute of Technology Banaras Hindu University
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
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 H 2O
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

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 Al 2O3 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 + O 2 = 2/3 Cr2O3
at equilibrium when PO2 is 10-14 atm.
IX. Calculate the equilibrium oxygen pressure between Al 2O3 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 D E P A R T M E NT O F
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 aboveequat ion we get
 1 .57 10 4
3 
 D E P A R T M E NT O F
H S  RT 
2
 2.8310  Metallurgical Engineering
 (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 D E P A R T M E NT O F
molecularweight 18Institute of Technology Banaras Hindu University
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
5
So ln 273   2.7  10  1 Thermodynamics
Metallurgical 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  Metallurgical
7.124 cc / mol
Engineering
density 7.86 Institute of Technology Banaras Hindu University
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 = 15 K to 368.5 K is 8.71 cal/deg/mol.
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
K
0
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 Metallurgical Engineering

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 Institute of Technology Banaras Hindu University
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. LetMicrostates
Position of
us construct
No. an
ensemble.
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 waysBanaras
canHindu
these
Institute of Technology
University
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
Metallurgical two objects in box
Engineering
1 two of the remaining six in box 2 and two of the remaining four in
Institute of Technology box
Banaras Hindu3University
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 inInstitute
which we have
of Technology Banarastwo
Hindu University
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 Metallurgical

us Engineering
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. WB
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)
Differenti antion 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 simplifica tion yields
 f (W A .WB )  f (WB )
WA . 
 (W A .WB )  WB
Differenti ation 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 WB  
WA . WB       0
 (W A .WB ) 2
 (W A .WB )  W A . WB  WB   WA 
 f (W A .WB )
2
 f (W A .WB ) Metallurgical Engineering
W A .WB  0 Institute of Technology Banaras Hindu University
 (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
Thus
for a perfect  CS1 =ln
S crystal W =
0 forW Cget2 C = 0
1, we 2
and C1 can be determined from the throttling of one mole of

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 D E P A R T M E NT O F
Pf
Pf
R
S  S f  S i    dP   R ln
Pi
P Pi
In this process of throttling Pi  Pf / 2
Therefore S f the
Let us calculate S iW in
R ln
the2initial 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  Thermodynamics
Metallurgical K ln W
Entropy of Mixing for a Binary Solution Institute of Technology Banaras Hindu University
(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 Metallurgical
= K (ln W Thermodynamics
– ln W – ln W )
 WA,B is the no.of ways of arranging (N0 – n) A atoms andMetallurgical
n DBE Patoms on N0 sites so
A R T M E NT O F
Engineering
N 0!
W A, B 
0  n)!
 Since, in purenmetal
! ( Nthe atoms are indistinguishable so
WA = WB= 1. Thus
N 0!
S m  K ln
n ! ( N 0  n)!
entropy of mixing
Applying sterling approximat ion
of ideal solution
 n n N n N0 
S m  N 0 K  ln  0 ln 
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 Metallurgical ln x B 
ln x A  x BThermodynamics
THERMODYNAMICS D E P A R T M E NT O F
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 Metallurgical Engineering

 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
w
 A w
 B 
 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 Metallurgical Engineering

 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
nA
xA 
n A  nB
nB
xB 
n A  nB
 and xA + xB = 1
Raoult’s law Metallurgical Engineering

 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 Metallurgical Engineering

 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  x A )
and p B  p B0 .x B or ( p B  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 Metallurgical Engineering

Non-ideal or real solutions Metallurgical Engineering

 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.


 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.

 We have already defined activity as

pA
aA  0
pA
 For ideal solutions we have:
p A  p A0 .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   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’

 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.

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 in the solution can be represented by the
equation:
1
( A  B )   A  A   B  B     A  A   B  B  
2

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

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

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 D E P A R T M E NT O F
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.
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  n2  n3  ..........
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 
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    
Q Q
dQ     dn1    dn2  ..........(3)
n
 1  n2 , n3 n
 2  n1 , n3
dQ'  Q1dn1  Q2 dn2  Q3 dn3  .................................(4)
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
QUANTITIES
(n1  n2  .....) Q  n1Q1  n2Q2  ..................

 ni 
 Dividing by (n1 + n2+………) and noting that   x i
n 
 1 2 n  n 3 
Q  x1Q1  x 2 Q2  ..........(5)
 on multiplying by (n1+ n2 + n3 ……..) we can write as

Q   n1Q1  n2 Q2  ......................(6)
 In a binary solution we can write equations 5 and 6 as
Q  x1Q1  x 2 Q2 (5)
Q   n1Q1  n 2 Q2 (6)
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 D E P A R T M E NT O F
molar quantities from molar quantities Institute of Technology Banaras Hindu University
 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
dx2 dx2
 Adding this to (5) we get
dQ
Q  x1  x1Q2  x2Q2  Q2
dx2
Method of obtaining partial D E P A R T M E NT O F
molar quantities from molar quantities Institute of Technology Banaras Hindu University
dQ dQ
Q2  Q  x1  Q  1  x 2  (12)
dx2 dx2
 Similarly,
dQ
Q1  Q  1  x1  (12a)
dx1
Tangent intercept method Metallurgical Engineering

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 D E P A R T M E NT O F
molar quantities from another partial Metallurgical Engineering

molar quantities
Integration of this equation from x1 =1 to x1 = x1 will result
Method of obtaining one partial D E P A R T M E NT O F
molar quantities from another partial Metallurgical Engineering

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

Obtaining Molar property D E P A R T M E NT O F
from Partial molar properties


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,
H Cd
M
and that of tin i.e. H SnM , plotH M vs xCd
H SnM H Cd
M
Draw a tangent at xCd =
0.6. The values of and are obtained by intersection of
the tangent with the axes at xCd = 1 and xSn = 1, respectively.
 H Cd  320 cal / mol and H Sn  1360 cal / mol.

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.

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
dx
  
 7100 x  x 2   7100 1  2 x 
H Zn   7100x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

 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.

 A 30% mole by methanol –water solution is to be prepared.

How many m3 of pure methanol (molar volume =40.7x10-
3 m3/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.


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

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

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 D E P A R T M E NT O F
the Formation of a solution Institute of Technology Banaras Hindu University
 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 p i0 to pi at the
temperature T.
3. Condensation of 1 mole of vapour i from the pressure p i into the
condensed solution at T.
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, Gi and(pure)
Gi is the molar free energy of
pure i, Gi0 .
 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
ΔG iM of the solution of i.
 Hence ,
Gi M  Gi  Gi0  RT ln ai
 If at constant T and P, nA number of mole 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 =
n A G A  n B G BM
 The free energy change due to mixing, G , referred to the
integral free energy of mixing, is the difference between the two
quantities, i.e.
  
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 BΔG BM
= RT (nA ln aA + nB ln aB)
In terms of one mole of solution,
i. e. integral molar free energy G M  RT  x A ln a A  x B ln a B 
for an ideal solution ai = xi,  GM,id = RT (xAln xA + xB ln xB)
Properties of Raoultian D E P A R T M E NT O F
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    Vi 0
 P 
  T ,Comp  P  T ,Comp
  (G i  G 0i ) 

 P
  V 
i  Vi
0

  T ,Comp
∂ ΔG i M M
= Δ Vi
∂P T ,Comp
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
Integral volume of the solution (mixing)

V  M   n AV A  n B VB    n AV A0  n B VB0 
= nA (V A -V 0
A
) +n B ( VB - V ) 0
B
= n A ΔVAM + n BΔVB M = 0
M ,id M ,id
V M ,id
 x A V A  xB V B 0 or ΔV M,id = 0
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 pure component
∂ ( G i 0 / T) Hi o
P , comp = -
∂T T2
  G i  G 0i  
   
  T

 

H i  H i0 
 T  T2
 
  P ,Comp
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  P ,Comp T 2
M ,id
or  H i 0
 Integral molar heat of mixing, H M ,id  x  H M
A
,id M ,id
 xB  H B  0
A
H M ,id  0
Ideal solution
The entropy of formation of an ideal solution

 G 
  S
  T  P ,omp
For the formation of a solution
  G M 
    S M
 T  P ,omp
For an ideal solution
GM,id = RT (xAln xA + xB ln xB)
  G M ,id 
S M ,id
      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 Metallurgical Engineering

 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  A  xB ln  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  i  RT ln xi
XS M ,id
 Gi  Gi

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 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 

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
 Integral molar entropy of mixing
M M
S M
 x A S A  xB S B
   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 

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

 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 Metallurgical Engineering

 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  A  xB ln  B 
 where and are the actively coefficient of A and B, respectively.

 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  A   1 x B   2 x B2   3 x B3  ..........
2 3
1 1
ln  B   1 x A   2 x A2   3 x 3A  ..........
2 3
 By the application of the Gibbs – Duhem equation xA d lnγA = - xB d ln γB,
it can be shown, for the system to hold over the entire range of composition, .
   0
 By similar comparison 1of co-efficients
1
of the power series, Margules further
demonstrated that the variation of the γ’s can be represented by the quadratic
terms only, when
2  2

 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  A   A xB2 and ln  B   B x A2
 From comparison of the above

expressions we get 
 αA = αB = α and  
RT
 α is independent of composition
which indicates that Tl – Sn
system follows regular solution
model.
Properties of Regular Solution Metallurgical Engineering

 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

 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  A  xB ln  B   H M , R
XS XS
 xA G A  xB G B
M M
G A
XS
 RT ln  A   H A and G B
XS
 RT ln  B   H B

G XS  RT  x A ln  A  xB ln  B 

 RT x A xB2  xB  x A2 
 RT  x A xB  x A  xB 
= RT α x A x B
Hence for regular solution
G XS  H M  RT x A xB

  x A xB where 
RT
This means GXS for a regular solution is independent of
temperature

 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 temperature. Similarly, G XS is also independent of
temperature.
G AXS  RT1 ln  A  T1   RT2 ln  A  T2    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  A at temperatureT2 T1

ln  A at temperatureT1 T2

ln  A at temperature T2 T1
 ; dividing by (1  x A ) 2 we get
ln  A at temperature T1 T2
ln  A
at T2  (T2 ) T1
(1  x A ) 2
T  
 1  (T1 ) T2
ln  A T2
at T1 or  1T1   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

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 aB  
V M
 RT  x A  xB 
  P  P  T ,omp

Change in Entropy accompanying the formation of real solution.

 Partial molar entropy of mixing
M
 Si   R ln xi
 Integral molar entropy of mixing

M M
S M
 x A S A  xB S B
S M   R  x A ln x A  xB ln xB 

Change in enthalpy accompanying the formation of real solution.

 Partial molar enthalpy of mixing
M
 H  RT ln  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  A  xB ln  B 
Regular solution behaviour: D E P A R T M E NT O F
1. linear variation of ln γA vs xB2 (slope = ) at a given

temperature indicates regular solution behaviour of the
system: A-B.
2. However for strict adherence to the model, T should be
independent of T but not so in many cases. In general we
find ln varying linearly with x but iT decreases with
temperature.
Thermodynamic properties D E P A R T M E NT O F
of Solutions
Thermodynamic properties D E P A R T M E NT O F
of Solutions
Q   x . Q 
k K
Q XS
 Q M  Q M ,id 
GIBBS – DUHEM INTEGRATION Institute of Technology Banaras Hindu University
 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 – D E P A R T M E NT O F
METHOD -I Institute of Technology Banaras Hindu University
 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 D E P A R T M E NT O F
METHOD -I Institute of Technology Banaras Hindu University
METHOD -II Institute of Technology Banaras Hindu University
(4)
Eq.(4) Eq.(2)
(5)
GIBBS – DUHEM INTEGRATION Institute of Technology Banaras Hindu University
xB
as xB 1, a A  1, ln  B  0 but 
xA
xB
as xB  0, aB  0,  B is finite and ln  B is also finite for 0
xA
METHOD -III Institute of Technology Banaras Hindu University
 As a further aid to the integration of the Gibbs Duhem

equation, the   function is introduced as
ln  i
i 
1  x i  2
  -function is always finite because  i  1 as xi  1
 For the components of a binary solution
ln  A ln 
 A  2 , and  B  2 B
xB xA
 B is known as a function of composition: ln  B   B x A2
 On differentiation we get
d ln  B  2 B x A .dx A  x A2 .d B ,
xB
 substituting this into d ln  A   d ln  B
xA
xB xB 2
d ln  A   2 B x A dx A  .x A .d B  2 x B B .dx A  x B x A d B
xA xA
 On integration
x A  xA  B at x A  x A
ln  A   
x A 1
2 xB B dx A  x
 B at x A 1
x d B
B A ( A)
(A)
 Thus ln at xA=xA is obtained as – xBxAB minus the area under the plot of
B vs xA from xA=xA to xA = 1. Since B is everywhere finite, this
integration does not involve a tail to infinity.

The activity coefficient of zinc in liquid Cd-Zn alloys at 4350C

have been expressed as ln 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.

From Gibbs-Duhem equation we can write as

xZn d ln Zn +xCd d ln Cd = 0
on integration we get
xCd  xCd
xZn
ln  Cd   
xCd 1
xCd
d ln  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 xCd  dxCd
2
xCd 1

xCd  0.3
  1.74 - 2.64 x  0.90 x dx

2
Cd Cd Cd
xCd 1
2 3 0.3
= - [1.74x Cd - 1.32x Cd + 0.3x ] Cd 1
= [ - 1.74x Cd + 1.32x 2
Cd - 0.3 x 3 0.3
Cd 1
]
= -1.74(0.3-0.1) + 1.32 (0.09-1)-0.3 (0.027-1)
ln γ Cd = 1.218 - 1.201+ 0.292 = 0.309
  Cd  1.362
a Cd = γ Cd .x Cd = 1.362 × 0.3 = 0.4086 Ans.

xCd  xCd
xZn
(b) ln  Cd   
xCd 
xCd
d ln  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 xCd  dxCd
2
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

2 3 x Cd= x Cd
[-1.74x CD +1.32x 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  3x Zn  3x 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 + 0.42x 2Zn Ans.


Alternatively, we can also solve as

xZn
ln  Cd  2
(1.74 xCd - 0.9 xCd )dxCd   xZn (1.74 - 0.9 xCd )(-dxCd )
xCd
xCd  xCd xZn  x Zn
 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 xZn 2
 0.3 xZn
3

At 746K the activity coefficient of lead in liquid Pb-Bi alloy is

expressed as ln γ Pb = - 0.74(1 - x Pb ) 2 . Making use of the Gibbs-
Duhem equation develop the corresponding equation for the
activity coefficient of bismuth in the alloy 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

(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
on integration we get
ln  Pb at x Bi  x Bi
xPb ln  Pb  0.74(1  x Pb ) 2
ln  Bi  - 
ln  Pb at x Bi 1
xBi
d ln  Pb
d ln  Pb  1.48(1  x Pb )dx Pb
xPb
 1.481 - xPb  dxPb
1 - xPb 

x Bi 2 x Pb  (1 x Bi )
x
 1.48 x
x Bi 1
Pb dxPb  -1.48
2
Pb
x Pb  0
= - 0.74(1-xBi)2
So the solution is a regular solution

 Pb (746K )  0.83, a Pb  0.5  0.83  0.415(746K ) Ans.

for regular solution
ln γ Pb ln γ Bi
( b ) α Pb = α Bi = =
x Bi 2 x Pb 2

at 746 K
ln γ Pb = αx Bi 2 = -0.74x 2Bi
ln γ Bi = αx Pb 2 = -0.74 x 2Pb
G XS  H M  RT  x Pb ln  Pb  xbI ln  Bi 
= RT  xAxB
= - 1.987  746  0.74  0.4 0.6
= -263.3 cal/mole. Ans.
(C) for regular solution 1T1 = 2T2

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

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 = M M
ΔG Pb (1000K ) - Δ G Pb (746K )
= RT ln aPb (1000K) –RT ln aPb(746K)
= 1.987 (1000  ln 0.435 – 746 ln 0.415)
= 1.987 [1000(-0.8325) – 746 (-0.8795)]
= 1.987 (-176.4) = -350.5 cal/mole. Ans.

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 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 507 0C.

1750 3500
ln  Zn  (1  xZn ) , d ln  Zn  -
2
(1 - x Zn ) dx Zn
RT RT
appropriate form of the Gibbs-Duhem equation.
x Al d ln  Al  x Zn d ln  Zn  0
xZn
ln  Al    .d ln  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

(ii) The above form of equation show that  is independent of

composition. Thus Al-Zn system follows regular solution model,
hence
 Zn   Al
ln  Zn 1750
 Zn     Al
1  xZn  RT
2
 H M  G XS  RTx Al x Zn
1750 xZn = 0.4, xAl = 0.6
 RT . 0.6  0.4
RT
= 1750  0.24 = 420 cal/gatom Ans.

(iii) G M  RT ( x Al ln a Al  x Zn .a Zn )
for regular solutions,  1T1   2T2

T1  477  273  750 K , T2  507  273  780 K .
ln  Zn 1750 1750 7
 750     1.174
(1  x Zn ) 2
RT R750 3  1.987
 750  750 1750 750 175
 780   x   1.129
780 R750 780 78 x1.987
ln  Zn
 780  xZn=0.4
1  x Zn  2

 ln  Zn ( 780)   780  1  x Zn   1.129  0.36  0.40644

2
  Zn ( 780)  1.50146
 a Zn   Zn .x Zn  1.50146  0.4  0.6005

ln  Al
  780 
(1  x Al ) 2
ln  Al   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)

=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.

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.
M M
(ii) Calculate G Ni , G Fe , GiM , GiXS in the above alloy at 1873 K.

Solution:
By third method of integration calculate 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
Ni -0.49 -0.59 -0.75 -0.92 -1.14 -1.24 -1.35 -1.07 -1.01
Making use of  function we have
x Fe  x Fe
ln  Fe   Ni .xFe x Ni  
x Fe 1
Ni .dxFe
  [ Ni xFe x Ni    Ni dxFe ]
= - (-0.92  0.6  0.4 – 0.08) = 0.301 i.e. γNi = 1.35, aFe = 0.6  1.35 = 0.81

M
G  RT ln a Ni  8.314 1873ln(0.287)  19438J / mole.
Ni
M
G Fei  RT ln aFei  8.314 1873 ln(0.81)  3281 J / mole.
G M  ( xNi G Ni  xFe G Fe )  0.4  (19438)  0.6(3281)  9744J / mole.
G XS  G M  GidM ,  RT ( x Ni ln  Ni  xFe ln  Fe )  8.314 1873 (0.4 ln 0.72  0.6 ln 1.35)
= 758 J/mole

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.

The variation of activity coefficient with composition shows that Zn =-

1.929, is independent of composition. This indicates that brass behaves
regularly at 1200K.
Zn=Cu
ln  Zn ln  Cu
 Zn     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  A  x B ln  B )

Integral molar heat of mixing (or excess molar free energy) of brass,
H M  G XS  RT ( xZn ln  Zn  xCu ln  Cu )
T = 1200 K , xCu = 0.4, xZn = 0.6
ln  Zn   1.929 xCu
2
 1.929  0.4 2  0.30864

  Zn  0.7344 and a Zn  0.7344 0.6  0.4406
ln  Cu  1.929 xZn
2
 1.929 x 0.6 2   0.6944
  Cu  0.4993 and aCu  0.4993 0.4  0.1997

 H M  G XS  1.987 1200 (0.6 ln  Zn  0.4 ln  Cu )
= - 2384.4 (0.6  0.30864 + 0.4  0.6944)

= -2384.4 0.4629 = -1103.8 cal/mol.
or GXS= (RT) xCu xZn = (-4600)  0.24 = -1104 Ans.

(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.
 Zn   Cu  1.929( at1200K ) and  1T1   2T2
  1200 .1200   1300 .1300

12 12
 1300   1200 .  1.929   1.781
13 13
ln  Zn   1300 .xCu
2
 1.781 (0.4) 2  0.2849
 Zn  0.7520 and a Zn  0.7520  0.6  0.45125
 1.781  0.6  0.6412

2
ln  Cu  1300 .xZn
2

 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)

= 1.987 1300 (-1.10034) = -2842.3 cal/mol.
G XS (1300)  RTxCu .x Zn  1.987  1300(1.781)  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.

M M
Difference in change in free energy = G Zn (1300) - G (1200)
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 – D E P A R T M E NT O F
Henry’s Law
Henry’s Law Metallurgical Engineering


p A x A
i.e. p A  kx A (1)
pA k
dividing by p 0A we have 0
 0 .x A i.e.a A  const x A or a A  x A
pA pA
 The constant is equal to the slope of the curve at zero concentration of
A, designated by  A0 (activity coefficient of the solute A at infinite
dilution).
a A   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.

aA
γ0A → Henry’s law constant
xA

 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 Metallurgical Engineering

 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 Metallurgical Engineering

 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 metals:
N 2 ( g )  2 N (in Fe)
a 2
N ( inFe ) (kx N ) 2
K 
pN 2 pN 2
K
or x N (inFe) ( so lub ility)  pN2  k ' pN2
k
Solubility of Gases – D E P A R T M E NT O F
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.

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

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.

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

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 100gm Ag
1
(c ) pair  ( pair 1 atm, pO2  0.21)
0.21
 4.7629

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?

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 : 5 vol.
2 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

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 Metallurgical Engineering

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
  A0 as x A  0
xA
where a A is the activity of A w.r.t Roultian
s tan dard state and  0
A is
If the solute obeys Henry’s law over the Henery
a finite ' s law
concentration cons
range, thentan t
a A   A0 . x A

 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

 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 . A  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 
 A 
 hA  x A  cons tan t

 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 (in the Raoultian standard state) → A( in the Henerian standard state)
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
G A (R)
equation 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 ) 

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  A0

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 

 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 by
h A (1 wt %)  f A (1 wt %) . wt.% A
 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

 We can also write
 aA x A . 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. 
  A
0

 hA(1wt %) wt % A  cons tan t composition

 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

 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   RT ln
0
A
100.M A

 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  A0  RT ln   RT ln  A
0
 100.M A 
MB
 RT ln
100.M A

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  Mn  1 (ideal )
0
Mn (pure substance standard state)  Mn (dilute wt% standard state)

aMn  0 M Fe 
G ( R  H )  RT ln
0
Mn  RT ln  Mn 
hMn (1wt %)  100 M Mn 
 55.85 
 8.314 1900  ln 1 
 100  54.94 
  72455 J / mol

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.

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)
 0
M  0
Si .55.85
GSi ( R  1 wt %)  RT ln
0 Si Fe
 RT ln   39360
100M Si 100  28.07
  Si  0.00128
0
This is the activity coefficient of Si at infinite dilution, relative to pure Si as the

standard state.

Hence the activity coefficient of Si at 1 at% Si, relative to pure Si as the

standard state is calculated as follows:
aSi ( pure )   Si .xSi  0.0014  0.01  0.000014
aSi  Si0 M Fe

hSi (1wt %) 100 M Si
aSi .100 M Si 0.000014 100  28.09
 hSi (1 wt %)    0.55
 Si0 M Fe 0.00128  55.85
wt % Si
M Si
xSi 
wt % Si  (100  wt % Si)
M Si M Fe

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

 0
The Raoultian activity coefficient of Al at infinite dilution, Al 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)

(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  Al0
hAl
Total free energy change for reaction (2) = G 0

(H )  G 0
( R)  2 G 0
( RH )

 G(0R )  2 RT ln  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   Al
0
M Fe 
G Al
0
( 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 %)
  Al0 M Fe 
 G 0
(R)  2 RT ln  
 100 M Al 

 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.

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  1993K  V0  0.069 at 1893K .

H f
4800
S 
f
f
  2.4084 cal / deg .mol.
T 1993

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%)
  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 Metallurgical Engineering

 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, n1 , n2 , ....)
 From the fundamentals of partial differentiation 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
∂n i T , P , n1 ....
except n i
 The coefficient  G  called the ‘chemical potential’ and is denoted

 
by  hence
 ni except
P ,T , n1 .......
ni
Chemical Potential Metallurgical Engineering

 G 
   i
n
 i  Except1 ni
T , P , n .....
 is an intensive variable
This gives a new sets of fundamental equations for the open systems.
dG    S dT  V dP    i dni
dA   S dT  PdV     i dni
dH   TdS   V dP    i dni
dU   TdS   PdV     i dni
Physical Meaning of D E P A R T M E NT O F
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    A dn A  G A dn A
is the partial molar free energy of component A in solution
 G  
G A      A for a large quantity of solution
 n A  P ,T , n B
 G 
G A      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 D E P A R T M E NT O F
amongst phases at equilibrium

We know: dG    S dT  V dP    dn i i
At constant T and P: dG′ = ∑ μ dn i 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,

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

Where P is the total no. of phases in the system
Phase Rule Metallurgical Engineering

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.

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.

 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., H 2O is
necessary.

 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 D E P A R T M E NT O F
Rule Equation
Rule Equation
Rule Equation
Application of phase rule D E P A R T M E NT O F
to single component system

Application of phase rule D E P A R T M E NT O F
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 D E P A R T M E NT O F
Eutectic system
Phase rule in Reactive D E P A R T M E NT O F
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 D E P A R T M E NT O F
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 D E P A R T M E NT O F
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.
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
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
Problem:
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
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)
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 D E P A R T M E NT O F
Liquidus and Solidus– Cooling Curve Method Institute of Technology Banaras Hindu University
 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.
Liqidus and Solidus– Cooling Curve Method Institute of Technology Banaras Hindu University
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
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 D E P A R T M E NT O F
Diagram
 The intercepts of the two axes by the tangent of the Gibbs

free energy curve of the α phase at the composition X 2
 
represent 1  and  2
 similarly, for the β phase
Free – Energy Composition D E P A R T M E NT O F
Diagram for Binary Systems Institute of Technology Banaras Hindu University
Isomorphous
System
Free – Energy Composition D E P A R T M E NT O F
Diagram for Binary Systems Institute of Technology Banaras Hindu University
Eutectic System

Metallurgical Thermodynamics

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Metallurgical Thermodynamics

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D E P A R T M E NT O F

Total Marks 100

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

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.

 Here the subject matter of discussion is chemical and/or metallurgical

 Statistical thermodynamics: The application of probability theory,

 Irreversible Thermodynamics: Irreversible thermodynamics deals

The thermodynamics generally means classical thermodynamics

 Chemical thermodynamics is based on the three laws of thermodynamics

It is the ability to do work. This is too mechanical an answer.

 A thermodynamic system must, of necessity be stable with respect to its

 The rest of the universe excluding system is called surrounding.

In terms of Based on Based on

 Homogeneous system consists of single phase only.

State of a system Metallurgical Engineering

 As the position of a point in the space is described by its coordinates w.r.t

 These parameters are temperature, pressure and volume.

 The minimum number of variable required to describe the state of the

State of a system (cont.) Metallurgical Engineering

 Incase of a multicomponent system the independent state variables are

 State variables are also known as state properties or state functions.

 If a state variable, whether dependent or independent, is a function of the

 If a state variable is independent of the mass or size of the system it is

 Product of an intensive and an extensive state variable is also

Equation of State Metallurgical Engineering

 The state of the system can be described in the form of some

Thermodynamic Processes Metallurgical Engineering

 A material system may under go a change, under externally or

 For example: Expansion of a gas from V1 to V2 may be called as

Thermodynamic Processes Metallurgical Engineering

 Isothermal processes: These are the processes which proceed

Thermodynamic Processes Metallurgical Engineering

 Adiabatic processes: These are the processes which

• The property whose change depends on only the initial and

• If a system has two independent variables say x and y and any

Let there be three state functions X, Y and Z and two of these as

Putting the value of dY in first expression leads to

equating the coefficients of dX and dZ on both

Thermodynamic Equilibrium Metallurgical Engineering

 Mechanical Equilibrium: if there is no pressure gradient in the

 A process that can be reversed in its direction by an

 On the contrary a matchstick when it burns, the process

• If , however work and

Leading to First Law

System goes from state I to state II by

Leading to First Law

From the previous discussion, the following conclusions can be drawn:

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

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

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

internal energy and denoted by symbol U.

 In conventional chemical thermodynamics which we shall be concerned

Statement of First law Metallurgical Engineering

For an infinetesimal process, the statement is:

‘Energy can neither be created nor can be destroyed’

Significance of the First Law Metallurgical Engineering

 It is based on the law of conservation of energy.

 It brought in the concept of the internal energy.