Metallurgical Thermodynamics & Kinetics

(B.Tech 3rd Semester)

Course Instructor
Dinesh Kumar Mishra

DEPARTMENT OF METALLURGICAL & MATERIALS ENGINEERING

VEER SURENDRA SAI UNIVERSITY OF TECHNOLOGY
BURLA
1
 DISCLAIMER
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disclaim any implied warranties of merchantability or fitness for a particular purpose.

2
 Metallurgical Thermodynamics and Kinetics
Module I
Importance of Thermodynamics, Definition of Thermodynamics; concept of state and path
functions, Equation of states, thermodynamic processes, Phase diagram of a single
component system, Internal energy, heat capacity, enthalpy.
Module II
First law of thermodynamics, Second law of thermodynamics, entropy, and entropy changes
for various processes, free energy and its significance, free energy change as a function of
temperature, reversible and irreversible process, criteria of equilibrium, auxiliary functions,
combined statements, Maxwell’s relations, transformation formula, Gibbs-Helmoltz equation,
Concept of standard state.
Module III
Fugacity, activity, equilibrium constant, Concept of Third law of thermodynamics, temperature
dependence of entropy, statistical interpretation of entropy, relation between Cp and Cv,
consequences of third law, Ellingham – Richardson diagrams.
Module IV
Solutions: partial molal quantities, ideal and non-ideal solutions, Roult’s law; Henry’s law,
Gibbs – Duhem equation, regular solution, Chemical potential, Free energy – composition
diagrams for binary alloy systems, determination of liquidus, solidus and solvus lines.
Module V
Introduction of metallurgical kinetics: heterogeneous reaction kinetics: gas-solid, solid-liquid,
liquid-liquid and solid-solid systems, Concept of Johnson-Mehl equation, thermal analysis,
3
Thermodynamics of electrochemical cells, solid electrolytes.
 LECTURE-1
THERMODYNAMICS : It is the subject which dealing with the relation between heat
and motion. Development of metallurgical Thermodynamic occurs due to the
application of chemical thermodynamics to the metals & materials which later on
known as Thermodynamics of materials.

Importance of Thermodynamics:

• It gives the idea about feasibility of the process.

• It gives the idea about end product & its stability.

• It is useful in calculation of heat values.

4
Continued…

Sl.No. Endothermic reaction Exothermic reaction

1 Heat absorbed into the system Heat released from the system

2 Temperature of the surrounding Temperature of the surrounding

increases decreases

3 Enthalpy of the reactant is lower Enthalpy of the reactant is greater

than the product i.e ∆H of than the product i.e ∆H of reaction
reaction=+ve = -ve

4 Ex: Calcium carbonate Ex: Combustion reactions like

decomposition C+O2=CO2

5
Continued…
Sl. No. Thermodynamics Kinetics
Tells whether or not a process or a How fast or slow a process or a
1
reaction can occur. reaction can occur.
Applicable to the systems in transition
Applicable to the systems in stable
2 from non-equilibrium to equilibrium
or metastable equilibrium.
or between two equilibrium states.
Kinetics of a process generally about
Sufficient driving force is needed to
3 how overcome the energy barrier to
enforce a favorable transformation.
finish the phase transformation.
It gives the idea about the reaction It gives the idea about
as o Reaction rate.
o Its Feasibility. o Reaction controlling step.
4
o Its stability.
o Its end product.
o Heat involved in it. 6
Continued…
System: It is defined as any portion of the universe or the quantity of matter that
chosen separately from the rest of the universe & closed by boundary surface.

Surrounding

System

Boundary Wall

Schematic of system, surrounding and boundary

7
Continued…
Surrounding: Except the system the rest of the universe is known as surrounding.
The previous schematic is showing how system and surrounding separated by a
boundary layer and also different showing what are different interactions
involved in it.

Boundary Wall: This is the wall which separated system from the surrounding.
• Adiabatic Wall: Not allow to any transparent.
• Diathermic Wall: Allow to any transparent.

8
Continued…
Definition of Thermodynamic Terms:
Types of System: Depending on various parameters system can be classified as
follows
1. Nature of Interaction
• Open system: Both heat & mass transfer possible. Example: Water vaporization
in the open atmosphere
• Closed system: Only heat transfer possible. Example: Water vaporization in a
closed chamber
• Isolated system: Neither heat nor mass transfer possible. Example: Thermo flask
2. Number of components
• Unary component system: System consists of single component. Example:
Water system
9
Continued…
• Multi component system: System consists of more than one component.
Example: Fe-C (binary component) system
3. Reactiveness
• Reactive system: System is chemically reactive. Example: Fe-C system
• Non-reactive system: System is chemically non-reactive. Example: SiO2-Water
system
4. Phase
• Homogeneous system: System consists of single phase. Example: Water
system in single phase like solid or liquid or vapour.
• Heterogeneous system: System consists of more than one phase. Example:
Chemical reactions in various metallurgical processes.

10
 LECTURE-2
State and Path Function

Sl. No. State Function Path Function

Independent of path followed Dependent of path followed and
1 and dependent on the initial independent on the initial and final
and final state of the system state of the system
Can be integrated using initial Need multiple integrals and limits to
2
and final values. integrate.
Usually expressed by an Usually expressed by a lowercase
3
uppercase letter. letter.
Examples: Internal energy,
4 Work done, heat change
enthalpy etc.

11
Continued…
Example: From state A to B

 Work done is different for all the three different paths

 Internal energy is same for all the three different paths

I
B
A II
III

Fig-Schematic of thermodynamic process occurs

from state A to state B through three different
paths

12
Continued…
Activated Complex
• As the chemical reaction is progressed, the reactant is converted into
product as shown in the figure, where a metastable complex is also
observed.

Potential energy vs Reaction coordinate diagram for above reaction

[Ref:https://chemistry.stackexchange.com/questions/6486/how-exactly-is-activation-energy-
defined ] 13
Continued…

 An activated complex is the transient unstable complex structure that results

at the maximum energy point during the reaction progress in between the
reactants and products of the reaction.

 The potential and/or free energy of the activated complex is always higher
than the both reactants or product.

 Activated complex is unstable complex that is temporary in nature.

14
Continued…
MOLECULARITY AND ORDER OF THE REACTION:

Sl. No. Molecularity Order of Reaction

It is the number of reacting
It is the sum of the power of the conc.
1 species undergoing collisions the
terms in the rate law expression.
reactions.
2 It is a theoretic value. It is determined experimentally
It has positive integral value 1, It can have negative & fractional value
3
2,3…n. also.
It does not change with change It may change with change in
4
in temperature and pressure. temperature and pressure.

15
Continued…
EQUATION OF STATES: Equations which depend on the state variables like P, V,
T, n are known as equation of states.
Universal Gas Law: 𝑃𝑉 = 𝑛𝑅𝑇 (1)
−𝑎
Dieterici Model: 𝑃 𝑉𝑚 − 𝑏 = 𝑅𝑇𝑒𝑥𝑝( (2)
𝑉𝑚 𝑅𝑇

PROPERTY: Generally properties (or state variables) are either extensive or

intensive.

Sl. No. Extensive Property Intensive Property

The properties which
The properties which depends on the
1 independent of size or mass of
size or mass of the system.
the system.
Example: Mass, Area, Volume, Length, Example: Density, Specific
2
Entropy, Enthalpy etc. volume, Molar volume etc. 16
Continued…
THERMODYNAMIC EQUILIBRIUM: If in a system both thermal & mechanical
equilibrium exists simultaneously. Then it is known as in thermodynamic
equilibrium.

• Thermal Equilibrium: Uniform temperature throughout the system.

• Mechanical Equilibrium: Uniform pressure throughout the system.

• Chemical Equilibrium: Uniform chemical potential throughout the system.

17
 LECTURE-3
PROCESS: When in a system there is two or more than two parameters get changed
then it is known as system gets changed and process occurs.

• Cyclic Process: Sequence of processes which return back to its initial point.

• Adiabatic Process: Process in which net heat change (𝛥𝑞) is equal to zero.

• Isothermal Process: Process in which net temperature change (𝛥𝑇) is equal to

zero.

1
Continued…
• Isobaric Process: Process in which net pressure change (𝛥𝑃) is equal to zero.

• Isochoric Process: Process in which net volume change (𝛥𝑉) is equal to zero.

• Quasi-static Process: It is the process in which every small steps are in

equilibrium, so that entire process is in equilibrium.

𝒋=𝑯

𝑷𝒓𝒐𝒄𝒆𝒔𝒔𝑨→𝑯 = 𝑷𝒓𝒐𝒄𝒆𝒔𝒔𝒊→𝒋
A B C D E F G H 𝑰=𝑨

2
Continued…

P-V graph for different thermodynamic processes

Ref: https://in.pinterest.com/pin/550705860678462036/?nic_v2=1a4vsVIc2
3
Continued…

P-V graph for quasi-static and non-quasi-static process

Ref: https://www.jobilize.com/physics2/course/3-4-thermodynamic-processes-the-first-
law-of-thermodynamics-by-opensta?qcr=www.quizover.com&page=1&=
4
Continued…

Equation table for different processes of an Ideal gas

Ref: https://www.brainkart.com/article/Ideal-and-Real-Gases,-Thermodynamic-
Relations_5474/
5
Continued…
ARRHENIUS EQUATION:
Arrhenius' equation represents the relationship between the rate
constant, k of the chemical reaction on the absolute temperature, T (in Kelvin) as
given by
− Ea RT
k= Ae (3)
where A is the pre-exponential factor, Ea is the activation energy and R is the
universal gas constant

Arrhenius equation can also be represented as

Ea
ln k = ln A − RT (4)

6
Continued…
Comparing equation (4) with the linear equation,

𝒍𝒏 𝐤
−𝑬𝒂
Slope 𝑹

𝟏
𝑻

𝐸𝑎
𝑙𝑛 𝑘1 = 𝑙𝑛 𝐴 − 𝑅𝑇1 (5)
𝐸𝑎
𝑙𝑛 𝑘2 = 𝑙𝑛 𝐴 − 𝑅𝑇2 (6)

𝑘1 Ea 1 1
Equation (5) – Equation (6) => ln = R −
𝑘2 𝑇2 𝑇1

7
Continued…
At constant rate constant:
E1 > E2 with k1=k2
=> Temp decrease from T1 to T2

ln k

1
T

Activation energy (Ea): It is defined as the minimum energy required

activate the reacting species to produce the product.
8
 LECTURE-4
PHASE DIAGRAM / CONSTITUTION DIAGRAM OF SINGLE COMPONENT SYSTEM
Phase: It is defined as a finite volume in the physical system within which the
properties are uniformly constant i.e. do not experience any abrupt change in
passing from one point in the volume to another.
Phase Diagram: The graphical representation of equilibrium states of existence of a
system is known as phase diagram/constitution diagram.
 The complexity of a phase diagram is primarily determined by a number of
components which occur in the system, where components are chemical species
of fixed composition.
 Phase Diagram for one-component System is a two dimensional representation
of the dependence of the equilibrium state of existence of the two independent
variables.
 Temperature & pressure are normally chosen as the two independent variables
9
Continued…
GIBBS PHASE RULE: It is used to find out the number of independent variables
associated with a system. At invariant point degree of freedom is zero.

Mathematically, Gibbs phase rule is given by

f=C−P+2 (7)
Where f – Degree of freedom, C – Number of components, P – Number of phases

• Components: It refers to the independent chemical species that constitute an

alloy.
Example: In Al-Cu system, there is two components involved as Al and Cu.

• Degree of Freedom: It refers to the number of independent variables

associated with the system. 10
Continued…
In the above figure represents
 Three areas BOC (solid), COA
(liquid), BOA (vapour)
represents single phase. Any
one out of this three phase
areas of the phase diagram is
said to be homogeneous
system and if more than one
Schematic representation of part of phase diagram
phase then it is said to be
for H2O
heterogeneous system.
Ref: https://www.ques10.com/p/29668/draw-and-
explain-neat-labeled-phase-diagram-for-wa/

11
Continued…

 The lines OA – (Solid-Liquid) line, OB – (Liquid-Vapour) line, OC – (Solid-Vapour)

line represents the simultaneously variations of P & T required for maintenance
of equilibrium between two phase.

 Point ‘O’ known as triple point where equilibrium lines meet which thus
represents the unique values of P & T required for the establishment of three-
phase equilibrium. It is central point that represents all the three phases i. e.
solid, liquid, vapour.

12
Continued…
Phase diagram and allotropes: Iron represents an example of allotropy in a
metal. There are at least four allotropic forms of iron, known as α, γ, δ, and ε; at
very high pressures and temperatures, some controversial experimental evidence
exists for a stable β phase.
• Low-pressure phase diagram of pure iron
• As molten iron cools past its freezing point of 1538 °C, it crystallizes into its δ
allotrope, which has a BCC crystal structure.
Fe (L, 1538 0C) →Fe (S, 1538 0C)
ΔHfreezing (L→S) =Hsolid−Hliquid=−ΔHfusion
• As it cools further to 1394 °C, it changes to its γ-iron allotrope (austenite), a FCC
crystal structure
ΔH (δ → γ) =Hγ-iron −H δ -iron
13
Continued…
• At 912 °C and below, the crystal structure again becomes the bcc α-iron
allotrope,
ΔH (γ → α) =H α -iron −H γ -iron
• At pressures above approximately 10 GPa and temperatures of a few hundred
kelvin or less, α-iron changes into a HCP crystal structure,
ΔH (α→ ε) =H ε -iron −H α -iron
The higher-temperature γ-phase also changes into ε-iron, but does so at higher
pressure.
ΔH (γ → ε) =H ε -iron −H γ -iron
• The β phase, if it exists, would appear at pressures of at least 50 GPa and
temperatures of at least 1500 K and have an orthorhombic or a double hcp
structure.
ΔH (γ → β) =H β -iron −H γ –iron 14
 LECTURE-5
INTERNAL ENERGY: It is defined as the inbuilt energy that responsible for the
existence of the matter.

Characteristics:
• It depends on state variables P, T, V, n.

• It is a state property and since the state of internal energy is same as the state of
the dependent parameters. So it is known as single valued function.

• Internal energy is the sum of the energy associated with translation motion,
vibration motion and electronic configuration.

15
Continued…
• For a cyclic process, change in internal energy (𝚫U) becomes zero.
• Internal energy is perfect differential i.e. 𝑈𝑖 = 𝑓(𝑃𝑖, 𝑉𝑖, 𝑇𝑖 )
At constant temperature,

𝜕𝑈 𝜕𝑈
𝛥𝑈 = 𝑑𝑉 + 𝑑𝑃 = 𝑓(𝑉, 𝑃) 𝑇
𝜕𝑉 𝑃
𝜕𝑃 𝑉
At constant volume,

𝜕𝑈 𝜕𝑈
𝛥𝑈 = 𝑑𝑃 + 𝑑𝑇 = 𝑓(𝑃, 𝑇)𝑉
𝜕𝑃 𝑇
𝜕𝑇 𝑃
At constant pressure,

𝜕𝑈 𝜕𝑈
𝛥𝑈 = 𝑑𝑉 + 𝑑𝑇 = 𝑓(𝑉, 𝑇)𝑃
𝜕𝑉 𝑇
𝜕𝑇 𝑉
16
Continued…
HEAT CAPACITY: Heat capacity(C) is the quantity of heat required to raise the
temperature of a substance by 10 C. Thus
q
C= (8)
ΔT

If the temperature change is made vanishingly small, then

δq
C= (9)
dT

Heat capacity at constant volume

δq dU+δW dU
CV = = = (10)
dT V dT V dT V

Heat capacity at constant pressure

δq dU+PdV+VdP dH
CP = = = (11)
dT P dT P dT P
17
Continued…
Factors affecting Heat Capacity :
Heat Capacity mainly depends on three factors

 Mass (m) of the substance i.e. number of moles of the substance: As increase
in the mass of the substance the heat requirement increases and vice-verse.

 Temperature change (∆T): It is directly proportional to heat requirement.

Increase in the Temperature change (∆T) of the substance increase the heat
requirement and vice-verse.

 Type of substance or matter: Solid or gas or liquid and further in particular

state, the different materials have different heat (c) absorbing capacity.
18
Continued…
Heat Capacity of Ideal Gases:
From the Kinetic theory of gases, we have the following knowledge given
below

Types of gases Examples 𝐜𝐯 value 𝐜𝐩 value

Monatomic He, Ne, Ar etc. 3 5

R R
2 2

Diatomic O2,N2,H2 etc. 5 7

R R
2 2

Triatomic O3 7 9
R R
2 2

19
 Continued…

Heat Capacity of Ideal Gases

Ref:
https://phys.libretexts.org/Bookshelves/University_Physics/Book%3A_University_Physics_(Open
Stax)/Map%3A_University_Physics_II_Thermodynamics%2C_Electricity%2C_and_Magnetism_(O
penStax)/02%3A_The_Kinetic_Theory_of_Gases/2.04%3A_Heat_Capacity_and_Equipartition_of
20
_Energy
Continued…
Heat capacity involvement in 1st law of Thermodynamics:

Heat Capacity of Ideal Gases along with internal energy calculation

Ref: https://www.embibe.com/study/molar-heat-capacities-of-ideal-gas-cv-m-cp-
m-concept 21
Continued… *Maximum Cp value for solid=3R

Heat Capacity for different solid materials

Ref: http://www.schoolphysics.co.uk/age16-
19/Thermal%20physics/Heat%20energy/text/Heat_energy/index.html 22
Continued…
• Molar Heat Capacity: Heat capacity per unit mol, unit-J/mol. K
• Specific Heat Capacity: Heat capacity per unit mass, unit-J/gm. K

Specific Heat Capacity change along with heat change during phase change
Ref: http://mcat-review.org/thermodynamics-thermochemistry.php 23
 QUIZ TEST-1
Q.1 – How the mass and energy are changes for closed and isolated system?

Q.2 – What do you mean by state and path function? Is there any path function
which seems to be a state function in certain case, Give example?

Q.3 – Is it possible to vaporize the water below 1000C, if possible then explain
how?

Q.4 –Density is which type of property and how, explain?

Q.5 –Define single valued function with an example.

24
 LECTURE-6
ENTHALPY: It is a defined thermodynamics potential designated by the letter “H”,
that consists of the internal energy (U) of the system plus the product of the
pressure (P) & volume (V) of the system. Mathematically it is given by
H = U + PV (12)

At constant pressure process

H2 U2 V2
H1
ΔH = H2 − H1 = (Δq)P = U1
ΔU +P V1
ΔV = U2 − U1 + P(V2 − V1 )

(13)
At constant volume process
H2 U2 P2
H1
ΔH = H2 − H1 = Δq V = U1
ΔU +𝑉 𝑃1
Δ𝑃

= (U2 −U1 ) + V(𝑃2 − 𝑃1 ) (14)

(Since at constant volume work done PdV becomes zero) 1
Continued…
HESS’S LAW: The law states that ”The total change of heat in a
chemical reaction is same irrespective whether it occurs in a single
step or in multiple steps provided that the reaction must be
isothermal or isobaric or isochoric.”

If a process occur from A to B, then

using Hess’s law we can write as
enthalpy change throughout the path
AB is equal to sum of the enthalpies
throughout AC, CD and DB.

HAB = ∆HAC + ∆HCD + ∆HD𝐵 (15)

2
Continued…

3
Continued…

KIRCHHOFF’S LAW: Kirchhoff’s law states that “If a system undergoes a change
from one state to another state then both internal energy & heat occur would
alter.”
Mathematically Kirchhoff’s law can be expressed as
T2 T2
T1
d ΔH = T1
ΔCP Reaction dT (16)

T2
ΔHT2 − ΔHT1 = T1
CP Product − CP Reactant dT

T2
ΔHT2 = ΔHT1 + T1
CP Product − CP Reactant dT (17)
4
Continued…
Kirchhoff’s law during phase change solid to liquid state can be expressed as
T𝑚 T2
ΔHT2 − ΔHT1 = T1
∆𝐶𝑝,𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 dT + 𝐿𝑓 + Tm
∆𝐶𝑝,𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 dT (18)
𝑠𝑜𝑙𝑖𝑑 𝑠𝑜𝑙𝑖𝑑

5
Continued…

Energy vs Temperature graph showing Enthalpy and free energy variation

Ref-http://hacker.faculty.geol.ucsb.edu/geo124T/lecture.html

6
Continued…
THERMO CHEMISTRY & ITS APPLICATIONS:
It is the study of heat effects accompanying chemical reactions, the
formation of solutions & changes in the state of matter such as melting or
vaporization & physico-chemical processes.
 Heat of Reaction: It is defined as the heat evolved or absorbed when the
reactants react completely to produce products.
Expressed in terms of either per mole of any reactant or any products.
 Heat of Formation: It is defined as the heat evolved or absorbed when one
mole of the compound is formed from its constituent elements.
• Expressed per mole of compound.
• Depends on temperature.
• In standard state, heat of formation of a compound out of its constituent
elements is called as standard heat of formation. 7
Continued…
 Heat of Combustion: Heat of combustion of a substance is the enthalpy
change when one mole of the substance is completely burnt in oxygen.
 Heat of Solution: When one substance dissolves in another there will be a
change in enthalpy that is known as heat of solution & it depends on the
concentration of the solution.

8
 LECTURE-7
FIRST LAW OF THERMODYNAMICS: First law of thermodynamics is also known as

conservation of energy, which states as the total energy of an isolated system is

always constant; energy can neither be created nor be destroyed, it can only be

transformed from one form to another.

Let us consider a body in the state A, which performs work W, absorbs

heat q & as a consequence moves to the state B. The absorption of heat increase

the internal energy of the body by the amount ∆𝑈 & the performance of work W

by the body decrease its internal energy by the amount W. Thus the total change

in the internal energy of the body, ∆𝑈 is

ΔU = UB − UA = q − W (19)
9
Continued…
This is the statement of 1st law of Thermodynamics.

For an infinitesimal change of state the equation (19) can be written as in

differential form as

dU = δq − δW (20)

10
Continued…
If we have considered that the process taking place in a closed
system. In particular, if no work is done on a thermally isolated
closed system. We have

ΔU = 0 (21)

This is one aspect of the law of conservation of energy &

can be stated as “The internal energy of an isolated system
remains constant.”

11
Continued…
Sign convention

Heat flow outward from the system=Negative sign

Work done on the system=Negative sign
Heat flow into the system=Positive sign

SYSTEM

Work done by the system=Positive sign

12
Continued…
Application of First Law of Thermodynamics:
Isobaric Processes: An isobaric process occurs at constant pressure. Since the pressure
is constant, the force exerted is constant and the work done is given as P𝚫V.

Boundary work is defined as:

For an isobaric process:

 An isobaric gas expansion of gas requires heat transfer to keep the pressure
constant.

 Best application of this isobaric process is movable piston in a cylinder, so

that pressure inside the cylinder is always at atmospheric pressure, although
it is isolated from the atmosphere. In other words, the system is dynamically
connected by a movable boundary, to a constant reservoir.
13
Continued…
 If a gas is to expand at a constant pressure, heat should be transferred
into the system at a certain rate. This process is called an isobaric
expansion.

Adiabatic Process:

 If the system has rigid walls such that work cannot be added (W = 0), and
the walls of the system are not adiabatic and energy is added in the form
of heat (Q > 0), the temperature of the system will rise.

 If the system has rigid walls such that work cannot be added (W = 0), and
the system boundaries are adiabatic (Q = 0), but energy is added as work
in the form of friction or the stirring of a viscous fluid within the system,
the temperature of the system will rise.

14
Continued…
 If the system walls are adiabatic (Q = 0), but not rigid (W ≠ 0), and energy
is added to the system in the form of frictionless, non-viscous work, the
temperature of the system will rise. The energy added, is stored within
the system, and is completely recoverable. Such a process of the
frictionless, non-viscous application of work to a system is called an
isentropic process.

 If the system contains a compressible gas and is reduced in volume, the

uncertainty of the position of the gas is reduced as it is compressed to a
smaller volume, and seemingly reduces the entropy of the system, but
the temperature of the system will rise as the process is isentropic (ΔS =
0).

15
Continued…
 The work Should be added in such a way that friction or viscous forces
are operating within the system, the process is not isentropic, the
temperature of the system will rise, and the work added to the system is
not entirely recoverable in the form of work.

 If the walls of a system are not adiabatic, and energy is transferred in as

heat, entropy is transferred into the system with the heat. Such a process
is neither adiabatic nor isentropic, having Q > 0, and ΔS > 0 according to
the second law of thermodynamics.

 Application in Carnot cycle: The engineer N. L. Sadi Carnot (1796–1832)

first proposed an ideal heat engine that operated through a cycle of
reversible isothermal and adiabatic steps

16
Continued…

Carnot cycle representation (a) P-V diagram (b) T-S diagram

Ref- https://www.tf.uni-
kiel.de/matwis/amat/td_kin_i/kap_1/pictures/carnot_cycle_pv_ts.png 17
 LECTURE-8
SECOND LAW OF THERMODYNAMICS: According to Clausius & Kelvin & as
reformulated by Max Plank, the following statement is significant: “It is impossible
to construct a cyclic engine that can convert heat from a reservoir at a uniform
temperature completely into mechanical energy without leaving any effect
elsewhere.”
The engine must be cyclic i.e. it returns to initial position after each stroke
or revolution.
Some Alternative Statements:
i. Heat absorbed at any one temperature can not completely transformed
into work without leaving some change in the system or its surrounding.
ii. Spontaneous processes are not thermodynamically reversible.

18
Continued…
Spontaneous Process: Spontaneous processes are the naturally occurring
processes which cannot be reversed without the interruption of external force.

Examples of Spontaneous processes: Flow of heat from higher to lower

temperature, diffusion process of a species from higher to lower concentration,
mixing of acid-base reactions, all natural processes that occurring in nature without
external intervention.

Generally 2nd law of TD mathematically expressed in terms of entropy (S) as

δqrev
dS = (22)
T

19
Continued…
ENTROPY: Entropy is a measure of randomness of a system. Entropy increases as
the number of possible microstates increases where microstate is the microscopic
arrangement of atoms or particles.
 Symbolically represented as by “S”.
 Standard Entropy (S0): The absolute entropy of a substance at 1atm pressure
and 298 K temperature.
 Unit: J/K.mol.
 Trends for standard entropy values
a. Entropy of solid < Liquid < Gas
b. More complexes molecules have higher entropy.

20
Continued…

Entropy comparison of two different phases using energy vs temperature graph

Ref: http://hacker.faculty.geol.ucsb.edu/geo124T/lecture.html 21
Continued…
Characteristics of Entropy:
 It depends on state variables.
 It is a perfect differentiable function, since it depends on the state
variables.
δqrev
 It is mathematically expressed as dS = .
T

 For absorption of heat δq is positive. So entropy change dS is

positive. Similarly for release of heat δq is negative. So entropy
change dS is negative.
 For adiabatic process, δq is equal to zero. Hence dS is equal to
zero. So adiabatic process also known as isotropic process. 22
Continued…
𝛅𝐪
𝐏𝐫𝐨𝐨𝐟 𝐨𝐟 𝛅𝐪 𝐢𝐬 𝐧𝐨𝐭 𝐏𝐞𝐫𝐟𝐞𝐜𝐭𝐥𝐲 𝐃𝐢𝐟𝐟𝐞𝐫𝐞𝐧𝐭𝐢𝐚𝐛𝐥𝐞, 𝐛𝐮𝐭 𝐓 𝐢𝐬 𝐏𝐞𝐫𝐟𝐞𝐜𝐭𝐥𝐲
𝐃𝐢𝐟𝐟𝐞𝐫𝐞𝐧𝐭𝐢𝐚𝐛𝐥𝐞:
Since, from 1st law of Thermodynamics, we know
δq = dU + δW (23)

Again, we know dU = CV dT & δW = PdV. So equation (23) becomes

dV
δq = CV dT + PdV = CV dT + RT (24)
V

RT
(Since molar quantity we have P = )
V

Now consider the process undergo from state-1 to state-2, we have equation (24)
becomes
2 T2 V2 dV
1
δq = C dT
T1 V
+ V1
RT = CV T2 − T1 + RT(ln V2 − ln V1 ) (25)
23
V
Continued…
2 V2
1
δq = CV ∆T + RT ln( ) (26)
V1

In above equation, we have

 For isothermal process, 1st term is zero. So δq depends on 2nd term.
 For non-isothermal process, both terms are not completely zero. So δq depends
on both terms.
Since δq not depends on state variables. So it is not a perfectly differentiable.
Again,
2 δq T2 dT V2 dV
1 T
= C
T1 V T
+ V1
R (27)
V

(Dividing equation (26) by T)

2 δq
1 T
= CV ln T2 − ln T1 + R ln V2 − ln V1 (28)
24
Continued…
2 δq T2 V2
1 T
= CV ln + R ln (29)
T1 V1

δq
Since, depends on at least one state varies when others remains constant.
T

δq
• For Isothermal process, depends on 2nd term.
T

δq
• For Isochoric process, depends on 1st term.
T

δq
So, is perfectly differentiable function.
T

ENTROPY OF A PERFECT GAS:

Dividing equation of 1st law by temperature (T), we have
2 δq S2 T2 dT V2 dV
1 T
= S1
dS = C
T1 V T
+ V1
R (30)
V

25
Continued…
T2 V2
ΔS = S2 − S1 = CV ln T2 − ln T1 + R ln V2 − ln V1 = CV ln + R ln (31)
T1 V1

T2 V2
S2 = CV ln + R ln + S1 (32)
T1 V1

RT
Now we know, CP − CV = R CV = CP − R & V= (33)
P

So using equation (33) in equation (32), it will become

T2 RT2 P2
S2 = Cp − R ln + R ln + S1
T1 RT1 P1

T2 T2 T2 P1
= CP ln − R ln + R ln + S1 (34)
T1 T1 T1 P2

T2 T2 T2 P1
S2 = CP ln − R ln + R ln + R ln + S1
T1 T1 T1 P2

T2 P2
= CP ln − R ln + S1 (35)
T1 P1

26
Continued…
In general the above equation (35) can be represented as
S = CP ln T − R ln P + So (36)
PV
Now putting T = in above equation (36) we have
R

PV
S = CP ln − R ln P + So = CP ln P + CP ln V − CP ln R − R ln P + So (37)
R

(Since CP ln R is a constant. So adding with So another constant get obtained SI)

S = CP ln P + CP ln V − R ln P + SI = CP − R ln P + CP ln V + SI

S = CV ln P + CP ln V + SI (38)
So for a process which undergoes from state (1) to state (2) equation (38) can be
expressed as
P2 V2
ΔS = S2 − S1 = CV ln + CP ln (39)
P1 V1
27
Continued…
At Isothermal condition (ΔT=0), equation (32) and (35) becomes
V2
S2 = R ln + S1 (40)
V1

P2
S2 = −R ln + S1 (41)
P1

From equation (40) & (41), we have got

V2 P2
ΔS = S2 − S1 = R ln = −R ln (42)
V1 P1

28
 LECTURE-9
FREE ENERGY: Free energy is defined as the part of energy that available for
useful work done & that part of energy which can not available for useful work
done is known as bound energy.
 Total energy (E) is the sum of free energy (A) and bound energy (B).
 The following two functions are employed in TD, according to the names of
the scientists who proposed them.
Helmholtz free energy (A) = U – TS (43)
Gibbs free energy (G) = H – TS (44)
 Since U, S, H etc. are the state properties & T is also a state variable. So F and
G are also state properties.
 Below Table is showing, how the nature of the reaction depends on sign of ∆H,
∆S & ∆G.
29
Continued…
∆H ∆S ∆G Reaction Outcome

Negative Positive Always Negative Reaction is Spontaneous at all

Temperature.

Positive Negative Always Positive Reaction is Non-spontaneous in

all Temperature

Negative Negative Negative at low Temperature Reaction is Spontaneous at low

Temperature.

Positive at high Temperature Reaction is Non-spontaneous in

high Temperature

Positive Positive Positive at low Temperature Reaction is Non-spontaneous in

low Temperature.

Negative at high Temperature Reaction is Spontaneous at high

30
Temperature
Continued…

Entropy change (ΔS), Gibbs free energy change (ΔG) and rate constant
(K) sign and values for different type of chemical reactions and conditions

Ref-https://www.clutchprep.com/analytical-chemistry/chemical-thermodynamics-gibbs-
free-energy

31
Continued…

Gibbs free energy change (ΔG) for different phases wrt to temperature: Maximum
for gaseous state and minimum for solid state at low temperature.

Ref-http://staff.um.edu.mt/jgri1/teaching/che2372/notes/04/g_props/g_props.html

32
Continued…

Ref-http://www.shodor.org/unchem/advanced/thermo/index.html

Direction of reaction on the basis of Gibbs free energy

• Forward reaction => Equilibrium energy level is lower than the reactant energy
level
• Backward reaction => Equilibrium energy level is lower than the product energy
level 33
Continued…
Free energy change as a function of temperature:

For Isothermal process, the Gibbs free energy change is given by

∆𝐺 = ∆𝐻 − 𝑇∆𝑆 (45)

Therefore
∆Gf0 T = ∆Hf0 T − T∆Sf0 T (46)

Now from Kirchhoff’s law

T
0
HT0 = H298
0
+ (∆CP,𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 )dT
298

34
Continued…
T
∆Hf0 T = ∆Hf0 298 + 298
∆CP
0
dT (47)

Again
0
T ∆CP,reaction
∆Sf0 T = ∆Sf0 298 + 298
dT (48)
T

Using equation (47) and (48) in equation (46), we have

∆Gf0 T =
0
T T ∆CP,reaction
∆Hf0 298 + 298
(∆C 0
P,𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 )dT −T ∆Sf0 298 + 298
dT (49)
T

0 0
For pure elements, 𝐻298 = 0, but 𝑆298 ≠ 0.
35
 LECTURE-10
REVERSIBLE & IRREVERSIBLE PROCESS
Sl no. Reversible Process Irreversible Process

It is defined as the hypothetical The process that can’t be reversed

1 passage of a system through a or changed back (permanent
series of equilibrium stages. damage).

Generally at normal condition it

Very slow & mostly impractible in
2 occurs. It may be very fast or fast or
nature.
slow & practically possible.

3 For isolated system 𝑑𝑆𝑠𝑦𝑠 = 0 For isolated system 𝑑𝑆𝑠𝑦𝑠 > 0

1
Continued…
Reversible Process:
Entropy change in a reversible process is given by
∆𝑆 = 𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑆𝑠𝑢𝑟𝑟 = 𝑆𝑠𝑢𝑟𝑟 (Since Ssystem = 0) (i)
𝑞1 𝑞2
𝑆𝑠𝑢𝑟𝑟 = 𝑆𝑠𝑜𝑢𝑟𝑐𝑒 + 𝑆𝑠𝑖𝑛𝑘 = + (ii)
𝑇1 𝑇2

Since Ssource equal and opposite to Ssink . So

Ssurr = 0 (iii)
So combining equation (i) & (iii), we have
∆𝑆 𝑟𝑒𝑣 =0

Irreversible Process:
• Entropy change in a irreversible process is given by, ∆𝑆 𝐼𝑟𝑣 = 𝑃𝑜𝑠𝑖𝑡𝑖𝑣𝑒
• Example: For a cyclic process (based on assumption) like Carnot Cycle, net
entropy change is always positive.
2
Continued…
Study of Graphitization of Petroleum Coke:
 The formation of synthetic graphite from amorphous carbon should
theoretically be accompanied by a continuous shrinkage of material. However, in
many instances an irreversible volume expansion, commonly referred to as
puffing, and is actually observed to occur at some point in the transformation.
 The addition of certain metals, particularly iron and calcium or their compounds,
is known to inhibit or eliminate this expansion. Although "puffing" has generally
been associated with the sulfur content of the petroleum coke.
 Since Graphitization of petroleum coke follows irreversible expansion. So
entropy change during this case is same as in case of irreversible process i.e.
∆𝑆 𝐺𝑟𝑎𝑝 = 𝑃𝑜𝑠𝑖𝑡𝑖𝑣𝑒

3
Continued…
Auxiliary Functions: The secondary derived functions as discussed in previous
section such as
dU = TdS − PdV (50)
dH = TdS + VdP (51)
dA = −SdT − PdV (52)
dG = −SdT + VdP (53)

CRITERIA OF THERMODYNAMICS EQUILIBRIA: Simply it is known as criteria of

equilibrium. At equilibrium, there is no change in the system i.e. system remains
stable. Again the reversible process occurs through a series of equilibrium stages.
Therefore, we keep the independent variables should be fixed to obtained
equilibrium criteria. So, in the previous four basic equations to get equilibrium
criteria we should have keep the right hand side independent variables as constant.
4
Continued…
Equilibrium Criteria
Basic Equations Differential Form Finite Difference Form
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 𝑑𝑈 𝑆,𝑉 =0 ∆𝑈 𝑆,𝑉 =0

𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 𝑑𝐻 𝑆,𝑃 =0 ∆𝐻 𝑆,𝑃 =0

𝑑𝐴 = −𝑆𝑑𝑇 − 𝑃𝑑𝑉 𝑑𝐴 𝑇,𝑉 =0 ∆𝐴 𝑇,𝑉 =0

𝑑𝐺 = −𝑆𝑑𝑇 + 𝑉𝑑𝑃 𝑑𝐺 𝑇,𝑃 =0 ∆𝐺 𝑇,𝑃 =0

N.B.: Since it is easy to maintain the temperature & pressure constant. So Gibbs
free energy criterion achieved which get employ in Chemical & Metallurgical
thermodynamics.

5
Continued…
MAXWELL’S RELATION
Considering equation (50):
(a) At constant entropy:
𝜕U
𝜕U = −P𝜕V = −P (54)
𝜕V S

𝜕2 U 𝜕P
=− (55)
𝜕S 𝜕V 𝜕S V

(b) At constant volume:

𝜕U
𝜕U = T𝜕S =T (56)
𝜕S V

𝜕2 U 𝜕T
= (57)
𝜕S 𝜕V 𝜕V S

6
Continued…
From equation (55) and (57), we have
𝜕T 𝜕P
= − (58)
𝜕V S 𝜕S V

In similar way
considering equation (51) at constant entropy and constant pressure, it will be
found
𝜕T 𝜕V
= (59)
𝜕P S 𝜕S P

considering equation (52) at constant temperature and constant volume, it will be

found
𝜕P 𝜕S
= (60)
𝜕T V 𝜕V T

7
Continued…
considering equation (53) at constant temperature and constant pressure, it will
be found
𝜕V 𝜕S
= − (61)
𝜕T P 𝜕P T

So the above equations (58), (59), (60) and (61) are known as Maxwell’s relations.

8
 QUIZ TEST-2
Q.1 –Write down the mathematical expression for enthalpy changes for the
following phase transformation
• Ɛ to β
• 𝞪 to ϒ
Q.2 – How the 1st law of Thermodynamics will be mathematically expressed, if in
a system heat flow occurs in the outward direction and work done on a system?
Q.3 – Write down the entropy expression for the reaction,
𝐻2 𝑔 + 1/2𝑂2 𝑔 = 𝐻2 𝑂 𝑔 ; Temperature varying from 300 K to 400 K
Q.4–What is the condition for free energy change (𝚫G) in case of forward
reaction, backward reaction and at equilibrium condition?
Q.5 –Spontaneous processes are reversible or irreversible, explain it with
suitable example.
9
 LECTURE-11
COMBINED EXPRESSIONS OF 1ST & 2ND LAW OF THERMODYNAMICS:

Assumptions:
• Closed System
• Reversible Process
• Work done against pressure

From 1st law of Thermodynamics, we know that

dU = δq − δW = δq − PdV (62)

From 2nd law of Thermodynamics, we know that

δq = TdS (63)
10
Continued…
Combining equation (62) and (63), we got
dU = TdS − PdV (64)
Again, we know
dH = dU + PdV + VdP (65)
Replacing the term dU from the equation (64) in the equation (65), it will become
dH = TdS − PdV + PdV + VdP = TdS + VdP (66)
From Helmholtz free energy equation, we know

A = U − TS dA = dU − TdS + SdT = TdS − PdV − (TdS + SdT) (67)

dA = TdS − PdV − TdS − SdT = −PdV − SdT (68)

11
Continued…
From Gibbs free energy equation, we know

G = H − TS dG = dH − TdS + SdT = TdS + VdP − (TdS + SdT) (69)

dG = TdS + VdP − TdS − SdT = VdP − SdT (70)

So, combining 1st & 2nd laws of Thermodynamics with considering the assumptions.
We got the following equations
dU = TdS − PdV (71)
dH = TdS + VdP (72)
dA = −PdV − SdT (73)
dG = VdP − SdT (74)
The above four basic differential equations (71-74) are valid under above
assumptions i.e. for closed and isolated systems which have fixed mass and
composition. The equations are also applicable for open systems provided under a
fixed mass and composition. 12
Continued…
Application of both 1st and 2nd law of thermodynamics
Major application in Carnot cycle
 Carnot cycle: During four steps on one down and upward stroke of the piston,
visualize the gas and cylinder sitting first on a heat source (heat is added), then
on an insulator (no heat exchange), next on a heat sink (heat is removed), and
finally back on the insulator.
 The pressure‐volume curve of Figure shows the Carnot cycle in the next slide.
The gas in the cylinder contains an ideal gas at pressure (P), volume (V), and
temperature (T).
 During this isothermal expansion, the gas did work lifting a load. Hence, the
work is represented by the area under the A–B segment of the curve

13
Continued…

Carnot cycle representation (a) P-V diagram (b) T-S diagram

Ref- https://www.tf.uni-
kiel.de/matwis/amat/td_kin_i/kap_1/pictures/carnot_cycle_pv_ts.png 14
Continued…
 As the gas expands adiabatically from point B to C on the P-V curve. So, the work
is done by the gas in terms of expansion on the piston as shown by the area
under the BC segment of P-V curve
 The gas is further isothermally compressed that gives up an heat to the sink. For
this, the work is done by the piston on the gas which shown as the area under
the CD segment of P-V curve
 At the end, the gas is compressed adiabatically further to reach at initial state as
at point A. For this part, the work is done on the gas, that is shown by the area
under the DA segment of P-V curve

15
Continued…
 The total work done by the gas on the piston is represented as the area under
the ABC section of the PV curve, whereas the total work done by the piston on
the gas is the area under the CDA section. The difference between these two
areas is the interior portion of the ABCD curve in the P-V graph that represents
the output of the Carnot engine.

 If the energy absorbed Q 1 heat from the source and given up Q 2 amount of
heat to sink , then the work output is expressed as W o/p = Q 1 − Q 2.

 The efficiency of the Carnot engine

𝑊𝑜/𝑝 Q1−Q2
𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 = × 100 % = × 100 %
𝑊𝑖/𝑝 Q1
16
Continued…
 As per the 2nd law of thermodynamics the efficiency of Carnot reversible cycle
depends on the temperatures of two heat reservoirs that operated within the
two temperatures in a most efficient way.

 Carnot cycle is the representation of the Carnot heat engine.

 It is operated in between two extreme points that is quasi-static in nature, so

that the heat transfer and work done in the Carnot engine always remains in
internal equilibrium

 It is equivalent to the second law of thermodynamics that states that

“Spontaneous processes are irreversible in nature”, and remains valid still yet.
17
Continued…
TRANSFORMATION FORMULA:
For state property x, y, z. The system X represented as

𝜕x 𝜕x
X = f x, y, z = dy + dz (75)
𝜕y z 𝜕z y

So for increase in change at constant composition X=0, so equation (75) becomes

𝜕𝑋 𝜕𝑋
0= dy + dz
𝜕y z
𝜕z y

𝜕𝑋 𝜕𝑋
dy = − dz
𝜕y z
𝜕z y

𝜕𝑋 𝜕y 𝜕z
= −1 (76)
𝜕y z 𝜕z x 𝜕x y

The above equation (76) is known as Transformation formula.

18
 LECTURE-12
GIBBS HELMHOLTZ EQUATION
From Helmholtz free energy equation, we have
dA = −PdV − SdT (77)
From Gibbs free energy equation, we have
dG = VdP − SdT (78)
1. Isochoric Process:
dA
dA = −SdT = −S (79)
dT V

A−U
Then as, A = U − TS −S= (80)
T

From equation (79) and (80), we have

dA A−U dF
= A−U=T (81)
dT V T dT V

dF
A=U+T (82)
19
dT V
Continued…

2. For Isobaric Process:

dG
dG = −SdT = −S (83)
dT P

G−H
Again we know, G = H − TS −S= (84)
T

From equation (83) and (84), we got

dG G−H dG
= G−H=T (85)
dT P T dT P

dG
G=H+T (86)
dT P

The above equations (82) and (86) are known as Gibbs Helmholtz equation.

20
Continued…
Importance of Gibbs-Helmholtz Equation:
 It measures the value of change in Gibbs free energy (∆G).
 The measurement of change in Gibbs free energy (∆G) determines the feasibility
& direction of the reaction.
a) If ∆G < 0, the reaction is feasible & it is a forward reaction.
b) If ∆G > 0, the reaction is not feasible & it is a backward reaction.
c) If ∆G = 0, the reaction is at equilibrium position & it is neither a forward
nor a backward reaction.

21
Continued…

22
Continued…

23
Continued…

24
Continued…

25
Continued…
Standard State:
 The standard state is the stablest state of pure substance at any specified
temperature and 1 atm pressure condition.

 At standard state, the enthalpy of a pure metal is always zero, but the entropy is
not equal to zero.

 At standard state, Gibbs free energy change for a chemical reaction is given by
d𝐺 0 = d𝐻 0 − 𝑇𝑑𝑆 0 (87)

 For any reaction to be spontaneous the Gibbs free energy change should be
negative.
26
 LECTURE-13
ESCAPING TENDENCY: It is the tendency of dissolution of one phase to another
phase on the measure of thermodynamic potential.
Let’s consider a system consists of liquid phase and a gaseous phase of
water. Then to express the escaping tendency or migration of molecules from one
phase to another, thermodynamic parameter molar thermodynamic potential is
used. In such cases, three cases arise
Case-1: When system is in equilibrium i. e. no migration of molecules from
one phase to another, Hence

Gvapour = Gliquid ∆G = 0 (88)

Case-2: Temperature is slightly increased, as a result liquid molecules

starts vaporizing then

Gvapour < Gliquid ∆G = +ve (89)

27
Continued…
Case-3: Suppose the temperature is lowered, in such case condensation of
gas molecules starts. So in that case

Gvapour > Gliquid ∆G = −ve (90)

FUGACITY: At P → 0, G = −∞ in this condition escaping tendency measure by a

term known as fugacity.

Fugacity related with pressure under the mathematical expression mentioned

below
−A
f = Pe RT (91)

28
Continued…
Graphical Representation of Fugacity:

Fig -Combined Pressure vs. Volume

graph for Ideal and Real gas

Since we know that

dG = VdP − SdT (92)
At constant temperature
dG = VdP (93)
29
Continued…
Now integrate from P1 to P2 pressure change
P2 P2
P1
dGideal =V P1
dP = Area A B′ C′ D (94)

P2 P2
P1
dGreal =V P1
dP = Area A BCD (95)

P2 P2
P1
dGideal = P1
dGreal + A′ (96)

For P1 → 0, P2 → P then equation (96) becomes

P P
Greal = Gideal − A′ (97)

RT ln f = RT ln P − A′ (98)
−A
f = Pe RT (99)

30
Continued…
ACTIVITY: The activity of a substance may be defined as the ratio of fugacity of the
substance to the fugacity in its standard state.
Mathematically it can be represented as,
𝑓
𝑎= (100)
𝑓0

At standard state, a=1, since f = f 0

Again for real gas,
Gi fi
G0i
dGreal = RT f0i
d ln f (101)

fi
Gi − Gi0 = RT ln f0i
(102)

𝑓𝑖
Since 𝑎𝑖 = , so equation (102) becomes
𝑓𝑖0

Gi − Gi0 = RT ln ai (103)
31
Continued…
In an ideal gas mixture, 𝑃𝑖 = 𝑓𝑖 . Hence
𝑃𝑖
𝐺𝑖 − 𝐺𝑖0 = 𝑅𝑇 ln 𝑃𝑖 − 𝑃𝑖0 = 𝑅𝑇 ln 𝑃𝑖0
(104)

Since 𝑃𝑖0 = 1 𝑎𝑡𝑚, So equation (104) becomes

𝐺𝑖 − 𝐺𝑖0 = 𝑅𝑇 ln 𝑃𝑖 (Since ln 𝑃𝑖0 = ln 1 = 0) (105)
From equation (103) and (105), we got

RT ln ai = RT ln Pi ai = Pi (106)
N. B.:
• 𝑎𝑖 is a dimensionless quantity.
• 𝑎𝑖 is numerically equivalent with 𝑃𝑖 (in atm) and its value is equal to the
value of 𝑃𝑖 (in atm).
32
Continued…

Activity determination in a chemical reaction

Ref- https://slideplayer.com/slide/4213696/
33
Continued…

Activity of different state of matters

Ref-
https://people.chem.umass.edu/botch/Chem122S08/Chapters/Ch9/Equilibriu
mConstant/Activity.html
34
Continued… LECTURE-14
EQUILIBRIUM CONSTANT: Generally Equilibrium constant for a chemical reaction
given by ‘K’.
Relationship of K with standard free energy of Reaction:
Consider the following reaction at constant temperature and pressure as
𝑙𝐿 + 𝑚𝑀 + ⋯ = 𝑞𝑄 + 𝑟𝑅 + ⋯ (107)
*Where l, m, q, r, …. represents number of moles
(L, M,…) and (Q, R,…) represents reactants and products respectively. ]
Then
∆𝐺 = 𝑞𝐺𝑄 + 𝑟𝐺𝑅 + ⋯ − 𝑙𝐺𝐿 + 𝑚𝐺𝑀 + ⋯ (108)

∆𝐺 0 = 𝑞𝐺𝑄0 + 𝑟𝐺𝑅0 + ⋯ − 𝑙𝐺𝐿0 + 𝑚𝐺𝑀

0
+⋯ (109)
∆𝐺 − ∆𝐺 0

= 𝑞 𝐺𝑄 − 𝐺𝑄0 + 𝑟 𝐺𝑅 − 𝐺𝑅0 + ⋯ − 𝑙 𝐺𝐿 − 𝐺𝐿0 + 𝑚 𝐺𝑀 − 𝐺𝑀

0
+⋯ (110)
Continued…
Since we know,
𝐺𝑖 − 𝐺𝑖0 = 𝑅𝑇 ln 𝑎𝑖 (111)
So equation (111) becomes
∆𝐺 − ∆𝐺 0 = 𝑅𝑇 𝑞 ln 𝑎𝑄 + 𝑟 ln 𝑎𝑅 + ⋯ − 𝑙 ln 𝑎𝐿 + 𝑚 ln 𝑎𝑀 + ⋯ (112)

𝑞 𝑟
𝑎𝑄 .𝑎𝑅 ….
∆𝐺 − ∆𝐺 0 = 𝑅𝑇 ln = 𝑅𝑇 ln 𝐽 (113)
𝑎𝐿𝑙 .𝑎𝑀
𝑚 ….

Where
𝑞
𝑟
𝑎𝑄 .𝑎𝑅 ….
𝐽 = 𝐴𝑐𝑡𝑖𝑣𝑖𝑡𝑦 𝑞𝑢𝑒𝑠𝑡𝑖𝑒𝑛𝑡 = (114)
𝑎𝐿𝑙 .𝑎𝑀
𝑚 ….
Continued…
At equilibrium,
∆𝐺 𝑃,𝑇 =0 (115)
So equation (113) becomes
−𝐺 0 = 𝑅𝑇 ln 𝐽 𝐴𝑡 𝑒𝑞𝑢𝑖𝑙𝑖𝑏𝑟𝑖𝑢𝑚 = 𝑅𝑇 ln 𝐾

∆𝐺 0 = 𝑅𝑇 ln 𝐾 (116)

Replacing equation (116) in equation (113) we have

∆𝐺 − −𝑅𝑇 ln 𝐾 = 𝑅𝑇 ln 𝐽
𝐽
∆𝐺 = 𝑅𝑇 ln 𝐽 − 𝑅𝑇 ln 𝐾 = 𝑅𝑇 ln (117)
𝐾
Continued…

Ref:
https://www.slideshare.net/wkkok1957/ib-chemistry-on-gibbs-free-energy-and-
equilibrium-constant-kc-52195265
Continued…

Ref:
https://www.slideshare.net/wkkok1957/ib-chemistry-on-gibbs-free-energy-and-
equilibrium-constant-kc-52195265
Continued…

Ref:
https://www.slideshare.net/wkkok1957/ib-chemistry-on-gibbs-free-energy-and-
equilibrium-constant-kc-52195265
Continued…

Ref:
https://www.slideshare.net/wkkok1957/ib-chemistry-on-gibbs-free-energy-and-
equilibrium-constant-kc-52195265
 LECTURE-15
THIRD LAW OF THERMODYNAMICS: In 1906, W. Nernst proposed his heat theory
on the basis of experimental evidence. It was later generalized by Max Plank as
“The entropy of any substance (which is at completely in internal equilibrium) may
take as Zero at 0K.” This is known as Third law of Thermodynamics.

 At T = 0K, thermal energy is zero. Thus this source of disorder gets eliminated.
But other sources remain there. In reality it is difficult to achieve exactly zero
entropy at T = 0 K.

 Actually, all disorders are caused by thermal energy which get lowered
continuously and vanish at T = 0K provided internal equilibrium exists.
Continued…

Thermal Entropy

Vibrational Configurational
Entropy Entropy

Total
Entropy

Electronic
Magnetic Entropy
Entropy
Continued…
 Out of different contributions towards the total entropy, configurational and
thermal entropy are the major contributors.
 Thermal entropy (∆𝑆𝑇 ) is equal to zero at absolute temperature, T = 0 K.
However the configurational entropy (∆𝑆𝑐 ) is dependent on configuration not on
absolute temperature, so not equals to zero even if at 0 K temperature. So total
entropy is not equals to zero at 0 K temperature.
 As per 3rd law of thermodynamics, “The entropy of any substance (which is at
completely in internal equilibrium) may take as Zero at 0K.” i.e. the total
entropy may be zero, if and only it is at complete internal equilibrium =>
∆𝑆𝑐 = Rln (n) = 0;
𝑤𝑕𝑒𝑟𝑒 𝑛 𝑖𝑠 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑒𝑙𝑒𝑚𝑒𝑛𝑡𝑠 𝑎𝑛𝑑 𝑅 𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑎𝑙 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡.
Continued…
TEMPERATURE DEPENDENCE OF ENTROPY:
We know
H = U + PV (118)

dH = d U + PV = dU + PdV + VdP = δq + VdP (119)

Now putting δq = TdS & dH = CP dT in equation (119) we have
CP dT = TdS + VdP (120)
Now dividing the equation (120) by T we have
^T V^P
CP = dS + (121)
T T

At constant pressure the above equation becomes

^T
CP = dS (122)
T
Continued…
Integrating equation (122) from state 1 to state 2, we have got

2 T2
dT
dS = CP
1 T1 T

ΔS = S2 − S1 = CP (ln T2 − ln T1 )
T2
ΔS = CP ln (123)
T1

Again, we know
δq = dU + PdV = CV dT + PdV (124)
Dividing equation (124) by T at constant volume, the equation becomes
δq ^T ^T
= CV dS = CV (125)
T T T

Integrating equation (125) from state-1 to state-2, we got

S2 T2 ^T T2
S1
dS = CV T1 T
∆S = S2 − S1 = CV ln (126)
T1
Continued…
STATISTICAL THERMODYNAMICS: It is originated from kinetic Theory of gases,
which related to average kinetic energy of molecules in an ideal gas. The application
of probability theory, quantum theory and statistical mechanics allowed it to arrive
at microscopic thermodynamics relations from atomistic (i. e. microscopic) point of
view.
Statistical interpretation of Entropy measurement follows as
 Entropy is additive in nature i.e. S = SA + SB
 Probability function is multiplicative in nature i.e.
𝑓 𝑤 = 𝑓(𝑤𝐴 . 𝑤𝐵 )
 Entropy can be represented as
𝑆 = 𝑓 𝑤 = 𝑓 𝑤𝐴 . 𝑤𝐵 = 𝑓 𝑤𝐴 + 𝑓 𝑤𝐵
Continued…
Micro-State of a system:
• Consider a system consisting of gas where particles are in a constant state of
motion which may be translational, rotational or vibrational.
• Due to these motions particles inside the system occupy different positions in
different instant of time. On the other hand due to collision among themselves
and wall of the container, velocities change with time.
• Thus particles inside a system has six different coordinates as (x, y, z) and three
are velocity co-ordinates as (VX, VY, VZ).
• If at any instant of time all these six co-ordinates are well-defined for each
particle present inside the system then such a complete specification define a
micro-state of a system.
Continued…
Ensemble: An Ensamble of a system can be defined by a set which consists of all
the possible micro-states of a system. This is because with the passage of time a
system passes from one micro-state to other as a result of which individual particles
within the system attains different set of position as well as velocity co-ordinates.

Micro-Cannonical Ensamble: Micro-state of an isolated system having constant

volume is called micro-Cannonical Ensamble.

Macro-state of a System: The different macro-state of Ensamble can be arranged

into a no. of subset in such a way that any one of the subset consists of such micro-
state which have same number of particles lying between the co-ordinates
X, Y, Z, VX , VY , VZ and ( X + δX, Y + δY, Z + δZ, VX + δVX , VY + δVY , VZ + δVZ ).
Thus subsets are called macro-state of a system.
Continued…
Let us assume without any restriction ni particles are allowed to move in gi
sections. So the ni particles arranged among themselves and that (gi-1) partitions
are among themselves in ni! and (gi-1)! Ways respectively. Then the particles and
partitions internally arranged among themselves in (ni+gi-1)! Ways.

So the number in which ni particles get allocated in gi state of degeneracy can be

expressed as
Total possible no. of degenration to accomodate nc particles
ni +ai −1 !
= (127)
ni ! ai −1 !

Number of microstates in a macrostate of an isolated system of constant volume

ni +ai −1 !
= (128)
ni ! ai −1 !
 QUIZ TEST-3
Q.1 –Write down the all the derived auxiliary equations from combined 1st and
2nd law of thermodynamics.
Q.2 – What is the importance of Gibbs-Helmoholtz equation in deciding the
feasibility of a chemical reaction?
Q.3 –How the escaping tendency is related with fugacity?
Q.4–Is it possible to predict the reaction direction and feasibility from rate
constant value? If yes, explain how?
Q.5 –What is the 3rd law of thermodynamics ?

Assignment-1
With the help of mathematical derivation proof the statement “The entropy of a
system in isolation can never decrease”.
 LECTURE-16
POSTULATES OF STATISTICAL THERMODYNAMICS:
First Postulate: It stated as “The time average of a mechanical variable such as
average energy of a system is equal to the Ensamble average representing the
Ensamble, provided the number of microstate representing the system are infinitely
large. ”

Derivation: Let the isolated system consists of n number of particles out of which n1
particles having energy U1. Similarly n2 particles having U2 ... up to ni particles
having Uc . Hence the total energy U which is constant for the system can be
expressed as
U = U1 n1 + U2 n2 + ⋯ + Uc nc = Uc nc (129)
As the total number of particles in the system is also constant i.e.
c
n = n1 + n2 + ⋯ + nc = c=1 nc (130)
Continued…
If ω be the number of microstate present in a macrostate

n! n!
w= = (131)
n1 ! n2 !……ni ! i ni !

Second Postulates: It is stated as “All microstate are equally probable therefore the
probability of a system to represent in a particular microstate is directly
proportional to the number of microstate present in the macrostate.” Hence
macrostate of higher number of microstate well define the macroscopic properties
of the system.
Maxwell-Boltzmann Statistics: It stated as “Particles in a microstate are
distinguished from each other on the basis of the total energy content by each
particle.”
Limitation: If there is an isolated system of constant volume then two or more
particles have same energy level. Then it is difficult to distinguish the particles from
each other. This problem gets solved under Boltzmann- Einstein statistics.
 Continued…
Boltzmann-Einstein Statistics: It stated as “Particles of same energy and size get
distinguished from each other on the basis of orientation or degeneracy principle.”
Suppose there are ni number of particles with energy UI in which there are gi states
of energy (degenerate state energy). To place ni particles in gi sections we need (gi-1)
partitions.
RELATIONSHIP BETWEEN STATISTICAL INTERPRETATIONS OF ENTROPY:
Entropy is additive in nature. For example, if we will take two particles A and B which
have entropy SA and SB. Then net entropy
S = SA + SB (132)
Probability function is multiplicative in nature i.e.
f w = f(wA . wB ) (133)
Entropy can be represented as
S = f w = f wA . wB = f wA + f wB (134)
Continued…
Now taking the derivative of equation (134) w.r.t. wB, we got
^`(w) ^`(wA ) ^`(wB )
= + (135)
^wB ^wB ^wB

^`(wA .wB ) ^(wA .wB ) ^`(wB )

× = (136)
^(wA .wB ) ^wB ^wB

^`(wA .wB ) ^`(wB )

wA = (137)
^(wA .wB ) ^wB

Now taking derivative of equation (137) w.r.t. wA , we got

df(wA .wB ) df(w )

^
d(wA .wB ) ^(wA .wB ) ^`(wA .wB ) ^w ^ dw B
wA × + × A = B
(138)
^(wA .wB ) ^wA ^(wA .wB ) ^wA ^wA

^2 `(wA .wB ) ^`(wA .wB )

wA . wB + =0 (139)
^ wA .wB 2 ^(wA .wB )

Putting wA . wB = w in equation (139), we got

^2 `(w) ^`(w)
w + =0 (140)
^w2 ^w
Continued…
So, equation (140) became a 2nd order differential equation.
For 2nd order differential equation the solution is

f w = c1 ln w + c2 S = c1 ln w + c2 (141)
Now for no disorderness , S=0, equation (141) will become
c1 ln w + c2 = 0 (142)

Again as we have S=0 i.e. there is only one microstate is possible,w ≅ 1 ln w = 0.

Hence equation (142) will become, c2 = 0 (143)
R
Now taking c1 = =k (144)
N0

[Where, R = Universal gas constant, N0= Avogadro’s number,

K = Boltzmann’s constant ]
Now using the equation (143) and (144) in equation (5.25), we got
S = k ln w (145)
 LECTURE-17
Consequences of 3rd Law of Thermodynamics: When disorder in a substance
completely vanishes, it becomes perfectly ordered and has only one possible
arrangement of atoms. Then a complete internal equilibrium is established. The
causes for deviation from perfect order are
 Thermal energy and resulting motion of atoms and molecules (at T = 0K).
 Non-crystallinity, as in amorphous solids and liquids.
 Crystal defects-vacancies, interstitial atoms, dislocation.
 Disordered compound structure.
 Disordered solid solution.
Continued…

Defects in crystalline solid materials

Ref-http://www.minaprem.com/materials-science/defects/point-defect-
imperfections-in-solids-materials-science/
Continued…

Points defects in crystalline solid material

Ref- https://www.differencebetween.com/difference-between-point-defect-
and-line-defect/
Continued…

Line defects in crystalline solid material

Ref-http://1.bp.blogspot.com/-UliOEYWbW5s/UHgkWQex3gI/AAAAAAAAACY/48_X38HeXl0/s1600/Materials-
Types-of-point-and-extended-defects.jpg

GB in crystalline solid material

Ref-http://www.engineeringarchives.com/les_matsci_surfacedefects.html
Continued…

Ref-https://slideplayer.com/slide/8125889/
Continued…

Ref- https://slideplayer.com/slide/10119709/
Continued…
Proof of 𝑪𝑷 − 𝑪𝑽 = 𝐑:
From 1st of law TD, we have
𝜕U 𝜕U
δq = dV + dT + PdV (146)
𝜕V T 𝜕T V

At constant pressure U can be expressed in differential form as

𝜕U 𝜕U
dU = dV + dT (147)
𝜕V T 𝜕T V

Put equation (147) in equation (146) we have

𝜕U 𝜕U
δq = dV + dT + PdV (148)
𝜕V T 𝜕T V

Taking derivative of equation (148) w.r.t. T, we got

δq 𝜕U ^V 𝜕U P^V
= + + (149)
^T 𝜕V T ^T 𝜕T V ^T

At constant pressure equation (149) becomes

δq ^U ^V P^V
= CP = + CV + (150)
^T P ^V T ^T ^T
Continued…
^U ^V P^V
CP − CV = + (151)
^V T ^T ^T

For ideal gas derivative of U w.r.t. V is zero. So equation (151) becomes

P^V
CP − CV = =R (152)
^T

RICHARDSON - ELLINGHAM (RE) DIAGRAM: R-E diagram is the simplest method of

representing free energy vs Temperature for compounds such as oxides and
sulphides. Temperature change in ∆𝐻 0 and ∆𝑆 0 tends to counterbalance each
other. Therefore it is possible to express ∆𝐺 0 in the form of a simple equation

∆G0 = a − bT (153)

[Where a and b are mean values of ∆𝐻0 and ∆𝑆 0 for temperature range under
consideration]
Continued…
 In this diagram, highly stable oxides are found at the bottom and less stable
oxides occupy higher positions.
 Therefore, an element present at the lower position will always reduce the
oxides of another metal lying above it, when all the reactants and products are in
their standard states. In the regions, since no phase transformation occur. So
plots are almost straight lines.
 Since 𝑑∆𝐺 0 = −∆𝑆 0 , slope of the line gives −∆𝑆 0 and extrapolated the plot
𝑑𝑇

to absolute zero gives intercept of line ∆𝐻0 on free energy axis.

 Again since free energy is an extensive property. Hence the value of ∆𝐺 of a
reaction would depend on number of moles involved.
 LECTURE-18
Characteristics of R-E Diagram:
• Different metals & its oxides of metallurgical processes are available in R-E
diagram.
• The zero free energy is at the top of the diagram & towards down in the Y-axis is
negative value is represented.
• This is a standard diagram because the reactant which are metal and products
which are oxides in general are in their standard state i.e. unity activity.
• Oxides or compounds which are placed at bottom of the graph indicate more
negative free energy i.e. is more stable & they can reduce the less stable oxides
that placed above it.
• Almost all oxides have negative free energy. However for noble metal case there
is some exception.
Continued…
• The line for CO2
would almost parallel
to the temperature
axis indicates the
value of −∆𝑆 0 (slope
of the line) is zero .
• Upward slope of most
of lines indicates that
the oxides become
less stable as the
temperature
increases. Ellingham Diagram of Selected Oxides
Ref- https://www.wikiwand.com/en/Ellingham_diagram
Continued…

• Increase in
reactivity towards
downward
direction
• CO is better
reducing agent
than H2O because
Increase in stability
with increase in
temperature and
cuts maximum
number of metal
oxide lines.

Ref- Julien, P., & Bergthorson, J. M. (2017). Enabling the metal fuel economy: green
recycling of metal fuels. Sustainable Energy & Fuels, 1(3), 615-625.
 Continued…
• Change in slope indicates phase transformation from one phase to another
phase.
a. Increase in slope indicates reactant undergoing phase transformation.
b. Decrease in slope indicates product undergoing phase transformation.
c. Large slope change indicates transformation from condensed phase to
gaseous phase.
d. Small slope phase change indicates melting or change of solid to other
phase.
e. No change in slope indicates no phase transformation.

• Carbothermic reactions involve the reduction of mostly metal oxides in the

presence of carbon as the reducing agent. These reactions are usually
conducted at temperatures of several hundred degrees Celsius.
Continued…
• Carbothermic based processes are used for production of the elemental
forms of many elements. Carbothermic reactions are not useful for few metal
oxides like sodium and potassium oxides. The ability of metals to takes part in
Carbothermic reactions is predicted mainly from R-E diagram.
• The reaction 2𝐶 𝑆 + 𝑂2 𝑔 = 2𝐶𝑂 𝑔 extremely important since in this case it
has downward slope cutting across the free energy diagram. This indicates,
why that all metal oxides can be reduced by CO above 10000 C.

C+O2=CO2
10000 C

• Below 10000 C, 2𝐶𝑂 𝑔 = 𝐶𝑂2 𝑔 + 𝐶 𝑠 occur. So below 10000 C carbon

monoxide is unstable.
Continued…
Limitations:

• Both products and reactants are in the standard state (i. e. pure substance at
1 atm).

• No Ellingham diagram for solution because thermodynamic activity data are

required.

• No reaction then difficult to predict the rate of reaction.

Continued…
Applications of R-E Diagram
Major applications in metallurgical processes such as
 Selection of efficient reducing agents
Example: Reducing agent for the reduction of Hematite and magnetite ore.
 Metal refining and purification.
Example: Various electro refining and purification of common metals Au, Cu, Fe
etc. and their oxides.
 Phase transformation and high temperature stability study
Example: phase transformation and temperature stability of metals oxides like
CaO, Al2O3 etc. can be predicted and compared.
 LECTURE-19
PARTIAL AND INTEGRAL MOLAR QUANTITIES:
For a closed system, where there is no possibility of mass and concentration
change, change of the components present in the system and the Thermodynamic
properties mainly depends on P, V and T, where as in case of open system
Thermodynamic properties essentially depends on P, V, T and mass of the system.
Let X be the Thermodynamic property
Case-1 (In case of closed system):
𝑋1′ = 𝑓 𝑃, 𝑉 (153)
𝑋2′ = 𝑓 𝑇, 𝑉 (154)
𝑋3′ = 𝑓 𝑃, 𝑇 (155)
Continued…
Case-II (In case of Open system):
Open system in which and chemical composition may change, the extensive
properties i. e. U, G, S, V, H etc. must depends on the amount of composition
present in the system.
So any extensive properties
𝑋 ′ = 𝑓 𝑃, 𝑇, 𝑛1 , 𝑛2 , … , 𝑛𝑖 (156)
Where 𝑛1 , 𝑛2 , … , 𝑛𝑖 are number of moles of the 1st, 2nd, … , ith component in the
system present as gm/mol.
Let us consider, there is a very small change in all the variables in all the systems.
dX ′ =

𝜕X 𝜕X 𝜕X
dP + 𝜕T + dn1 +
𝜕P T,n1 ,n2 ,…,ni 𝜕T P,n1 ,n2 ,…,ni 𝜕n1 P,T,n ,…,n
2 i

𝜕X 𝜕X
dn2 + ⋯ + dnc (157)
𝜕n2 P,T,n ,..,n 𝜕ni P,T,n ,..,n
1 i 1 i−1
Continued…
From the above relation, we have

𝜕𝑋
𝑋1 =
𝜕𝑛1 𝑃,𝑇,𝑛 ,…,𝑛
2 𝑖

𝜕𝑋
𝑋2 =
𝜕𝑛2 𝑃,𝑇,𝑛 ,…,𝑛
1 𝑖

. (158)

𝜕𝑋
𝑋𝑖 =
𝜕𝑛1 𝑃,𝑇,𝑛 ,…,𝑛
1 𝑖−1

Rate of change of Thermodynamic properties on addition of 1 mole of the

component when all other variables are unchanged. So we have at constant P, T
equation (158) becomes
𝑑𝑋 ′ = 𝑋1 𝑑𝑛1 + 𝑋2 𝑑𝑛2 + ⋯ + 𝑋𝑖 𝑑𝑛𝑖 = 𝑖 𝑋𝑖 𝑑𝑛𝑖 (159)
Continued…
Now if X mean to molar properties of a solution. Then X’ i. e. the value of quantity
X for the entire solution given by

𝑋 ′ = 𝑛 𝑇 𝑋 𝑑𝑋 ′ = 𝑛 𝑇 𝑑𝑋 (160)
[Where 𝑛𝑇 = 𝑖 𝑛𝑖 = 𝑛1 + 𝑛2 + ⋯ + 𝑛𝑖
X – Integral molar value of X in the solution]
Now from equation (159) and (160), we will have

c X c dnc = nT dX (161)
^ni
dX = c Xc = c X c dX c (162)
nT

^ni
[Where dXc = = Mole fraction of component i in the solution
nT

dX – Integral molar value of the solution

Xc – Partial molar value of X’ of component i in the solution ]
Continued…
CHEMICAL POTENTIAL: Thermodynamic equilibrium requires attainment of physic-chemical
equilibrium, besides mechanical & thermal equilibrium. This means chemical potential
should be uniform in the entire system in addition to uniformity of pressure & temperature.
There is a difference between the molar quantity (Q) & the same for system as
whole (Q’) as
𝑄′ = 𝑛 𝑇 𝑄 (163)
[Where, 𝑛 𝑇 = 𝑇𝑜𝑡𝑎𝑙 𝑛𝑢𝑚𝑏𝑒𝑟 𝑜𝑓 𝑚𝑜𝑙𝑒𝑠 = 𝑛1 + 𝑛2 + … … … + 𝑛𝑖 ]
By adopting the convention, let us consider a system with variable composition. Then the
auxiliary relation becomes

𝛿𝑈 ′ 𝛿𝑈 ′
𝑑𝑈 ′ = 𝑇𝑑𝑆 ′ − 𝑃𝑑𝑉 ′ + 𝛿𝑛1 𝑆 ′ ,𝑉 ′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛1 + ⋯ + 𝛿𝑛𝑖 𝑆 ′ ,𝑉 ′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛𝑖 (164)
2 1 1 𝑖

𝛿𝑈 ′
𝑑𝑈 ′ = 𝑇𝑑𝑆 ′ − 𝑃𝑑𝑉 ′ + 𝑖 𝛿𝑛 𝑑𝑛𝑖 (165)
𝑖

𝑑𝑈 ′ = 𝑇𝑑𝑆 ′ − 𝑃𝑑𝑉 ′ + 𝑖 𝜇𝑖 𝑑𝑛𝑖 (166)

Continued…
[Where, 𝜇𝑖 = Chemical potential for ith component for equation (167)
𝛿𝑈 ′
= s’,v’, n1, except ni ]
𝛿𝑛𝑖

Similarly, we have

𝛿𝐻 ′ 𝛿𝐻 ′
𝑑𝐻′ = 𝑇𝑑𝑆 ′ + 𝑉𝑑𝑃′ + 𝛿𝑛1 𝑆 ′ ,𝑃′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛1 + ⋯ + 𝛿𝑛𝑖 𝑆 ′ ,𝑃′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛𝑖 (167)
2 1 1 𝑖

𝑑𝐻′ = 𝑇𝑑𝑆 ′ + 𝑉𝑑𝑃′ + 𝑖 𝜇𝑖 𝑑𝑛𝑖 (168)

𝛿𝐴′ 𝛿𝐴′
𝑑𝐴′ = −𝑆 ′ 𝑑𝑇 − 𝑃𝑑𝑉 ′ + 𝑑𝑛1 + ⋯ + 𝑑𝑛𝑖
𝛿𝑛1 𝑇 ′ ,𝑉 ′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛 𝛿𝑛𝑖 𝑇 ′ ,𝑉 ′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
2 1 1 𝑖

(169)
Continued…
𝑑𝐴′ = −𝑆 ′ 𝑑𝑇 − 𝑃𝑑𝑉 ′ + 𝑖 𝜇𝑖 𝑑𝑛𝑖 (170)

′ ′ ′ 𝛿𝐺 ′ 𝛿𝐺 ′
𝑑𝐺 = −𝑆 𝑑𝑇 + 𝑉 𝑑𝑃 +
𝛿𝑛1 𝑇,𝑃,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛1 + ⋯ +
𝛿𝑛𝑖 𝑇,𝑃,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
𝑑𝑛𝑖 (171)
2 1 1 𝑖

𝑑𝐺 ′ = −𝑆 ′ 𝑑𝑇 + 𝑉 ′ 𝑑𝑃 + 𝑖 𝜇𝑖 𝑑𝑛𝑖 (172)
So, chemical potential for equation (168), (170) & (172) respectively are

𝛿𝐻 ′
𝜇𝑖 = (173)
𝛿𝑛𝑖 𝑆 ′ ,𝑃′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
1 𝑖

𝛿𝐴′
𝜇𝑖 = (174)
𝛿𝑛𝑖 𝑇 ′ ,𝑉 ′ ,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
1 𝑖

𝛿𝐺 ′
𝜇𝑖 = (175)
𝛿𝑛𝑖 𝑇,𝑃,𝑛 ,..,𝑒𝑥𝑐𝑒𝑝𝑡𝑛
1 𝑖

So, 𝜇𝑖 is same as the partial molar extensive properties of component i in a

solution.
Continued…
Application of Chemical Potential:

 Studies of phase equilibria

 In multi-component system, if we are interested in one component only. Then

easily can be obtained by considering the chemical potential of that
component.

 Allows easily visualization as to which way a species (element or compound)

would tend to get transferred
Continued…

Chemical potential refers to the sum of contribution from both ideal and excess. So
can be used to detect the deviation in ideality in real solution
Ref- https://en.wikipedia.org/wiki/Chemical_potential
Continued…

• Chemical potential change for

different phases followed the order
Solid<Liquid<Gas

Chemical potential used in phase transitions

Ref-https://socratic.org/questions/how-do-colligative-properties-affect-freezing-
point
 LECTURE-20
IDEAL & NON-IDEAL SOLUTIONS
Consider the vaporization of a component ‘A’ from a liquid solution at temp. T. if
the vapor behaves as ideal gas, then the equilibrium constant is given as
K = PA [A = PA0 (176)
The above process can be expressed as
𝐴(𝑙𝑖𝑞𝑢𝑖𝑑) → 𝐴(𝑣𝑎𝑝𝑜𝑢𝑟)
Equilibrium constant can be calculated for above reaction as

A]tcvcty o` pro^u]t (v[pour) PA

K= = (177)
A]tcvcty o` r_[]t[nt(Lcquc^) [t _ql\m [A

(Since ideal gas mixture case a=P)

Continued…
From above equation (176), we have

𝑃𝐴
𝑎𝐴 = (177)
𝑃𝐴0

Now taking the temperature as T, Let us consider there are two closed
containers out of which one contains a liquid solution, where A is the
component & another contains pure A. So if in case of solution the vapour
pressure is 𝑃𝐴 & in case of pure A the vapour pressure is 𝑃𝐴0 . Then for solution
case, we can expressed the mole fraction of component ‘A’ as

𝑋𝐴 = mole fraction of A in the solution = 𝑃𝐴 𝑃𝐴0

(178)
Continued…
Now, from equation (177) & (178), we have
𝑎𝐴 = 𝑥𝐴 (179)
If the solution obeys Raoult’s law then it is called an ideal solution & if the
solution does not obey Raoult’s law then it is called non-ideal solution.
There is a term known as activity co-efficient (γ) & mathematically it
represented as
[]tcvcty o` tb_ ]ompon_nt [i
γc = = (180)
Mol_ `r[]tcon o` tb_ ]ompon_nt xi

𝑎𝑖 = 𝛾𝑖. 𝑥𝑖 (181)
[Where 𝛾 𝑖 - Activity co-efficient of component in a solution]
Continued…
Now, if in a solution,
• 𝛾 𝑖 = 1, solution is ideal.
• 𝛾 𝑖 > 1 , solution exhibits positive departure from Raoult’s law.
• 𝛾 𝑖 < 1, solution exhibits negative departure from Raoult’s law.

In a solution, 𝑎𝑖 < 1, in contrast to pure i where 𝑎𝑖 = 1. This difference is due to

the following two effects
• Dilution of component i in a solution due to the presence of other
component (dilution effect).
• Interaction of component i with other components in a solution
(interaction effect).
Continued…
Activity:
 It is measure of free concentration i.e. concentration available for reaction.
 In an ideal solution, the entire concentration is available i.e. there is only
dilution effect. In case of binary solution like A-B, interaction effect more easily
followed. There is mainly three types of bonds between atoms (or molecules)
of A & B such as A – A and B – B are like bonds & A –B is unlike bond.
• If A – B bond stronger than the average of A – A & B – B bonds i.e. A & B
have the tendency to form a compound, then less numbers of A & B atoms
remains free. In this case the solution exhibit negative departure from the
Raoult’s law i.e. 𝛾𝐴 < 1 , 𝛾𝐵 < 1.
• If A –A & B – B bonds average is greater than A – B bonds then atoms (or
molecules) have the tendency more to form clusters. In this case the
solution would exhibit’s positive departure from Raoult’s law.
Continued…
Examples:
 Ideal solution: Cu – Ag, Fe – Ni, Fe – Mn, FeO – MnO.
 Negative Departure from Raoult’s Law: Silicates such as CaO – SiO2 &
MnO – SiO2.
 Positive Departure from Raoult’s Law: Cu – Fe.

QUASI-CHEMICAL APPROACH TO SOLUTIONS: Thermodynamics properties of

solutions are consequence of interaction amongst atoms molecules. Quasi-
chemical theory is the simplest & able to explain the properties approximately
from atomistic point of view. In a metallic solution, the components are assumed
to be present as atoms & not molecules due to nature of metallic bonds. So there
exit interaction energy between them.
Continued…
The quasi-chemical theory explained by considering some important
assumptions.
a) Atoms have chemical bonds amongst them.
b) Bonds get associated with some enthalpy which alone contributes to
enthalpy of solution.
c) Only bonds amongst nearest neighboring atoms are energetically significant.
 In, a binary A-B system, the bonds are A-A, B-B & A-B type. Assume that
enthalpies associated with these bonds are 𝐻𝐴𝐴 , 𝐻𝐵𝐵 & 𝐻𝐴𝐵 respectively.
 Let us consider one gm-atom of the solution. Let it have 𝑃𝐴𝐴 , 𝑃𝐵𝐵 & 𝑃𝐴𝐵
numbers of A-A, B-B and A-B bonds respectively.
 Then enthalpy of formation of the solution for one gm-atom from gaseous
state at temperature T is
𝐻 = 𝑃𝐴𝐴 𝐻𝐴𝐴 + 𝑃𝐵𝐵 𝐻𝐵𝐵 + 𝑃𝐴𝐵 𝐻𝐴𝐵 (182)
Continued…
If number of A atoms is 𝑁𝐴 & B atoms𝑁𝐵 , Then
𝑃𝐴𝐵 2𝑃𝐴𝐴
𝑁𝐴 = + (183)
𝑍 𝑍
𝑃𝐴𝐵 2𝑃𝐵𝐵
𝑁𝐵 = + (184)
𝑍 𝑍

[Where Z – Coordination number]

Thus 𝑃𝐴𝐴 & 𝑃𝐵𝐵 can be expressed in terms of 𝑃𝐴𝐵 ,𝑁𝐴 , 𝑁𝐵 and Z. Substituting these
terms in the equation (182), we will get
1 1 1
𝐻= 𝑍𝑁𝐴 𝐻𝐴𝐴 + 𝑍𝑁𝐵 𝐻𝐵𝐵 + 𝑃𝐴𝐵 [ 𝐻𝐴𝐵 − 𝐻𝐴𝐴 + 𝐻𝐵𝐵 ] (185)
2 2 2

Again enthalpy of mixture is

∆H m = [H − Enthaply of NA atoms in pure A + Enthaply of NB atoms in pure B ]
(186)
1
∆𝐻𝑚 = 𝑃𝐴𝐵 [ 𝐻𝐴𝐵 − (𝐻𝐴𝐴 + 𝐻𝐵𝐵 ) (187)
2
Continued…
Application to Ideal & Regular Solutions:
Since ∆H m = 0 for ideal solution. So from equation (187), we will have
1
𝐻𝐴𝐵 = (𝐻𝐴𝐴 + 𝐻𝐵𝐵 ) (188)
2

If 𝑁0 is the total number of atoms in a solution. Then

𝑁𝐴 𝑁𝐵
𝑥𝐴 = , 𝑥𝐵 = (189)
𝑁0 𝑁0

[Where 𝑁0 is the Avogadro’s number]

1
Again total number of bonds is 𝑍𝑁0 in 1 mole. Hence we have
2
1
𝑃𝐴𝐵 = 2 𝑥𝐴 𝑥𝐵 𝑍𝑁0 = 𝑍 𝑁0 𝑥𝐴 𝑥𝐵 (190)
2

[Where 𝑥𝐴 & 𝑥𝐵 are respective atoms]

Continued…
Putting the equation (190) in equation (187), we have
1
∆H m = 𝑍 𝑁0 𝑥𝐴 𝑥𝐵 [ 𝐻𝐴𝐵 − 𝐻𝐴𝐴 + 𝐻𝐵𝐵 ] (191)
2

Again we know
∆H m = xA xB Ω (192)

Comparing above equation (191) and (192), we will have

1
Ω = 𝑍 𝑁0 [ 𝐻𝐴𝐵 − 𝐻𝐴𝐴 + 𝐻𝐵𝐵 ] (193)
2
 QUIZ TEST-4
Q.1 –Write down the final expression for entropy from statistical interpretation
of entropy and define its relation with respect to the change in number of
microstates.
Q.2 –How the crystal defects affect the entropy change, explain its significance in
3rd law of thermodynamics.
Q.3 –State the major uses of R-E diagram in metallurgical processes.
Q.4–State the major difference between integral and partial molal quantities.
Q.5 –How the cluster formation affects the ideality, explain.
 LECTURE-21
GIBBS – DUHEM EQUATION [PARTIAL & INTEGRAL MOLAR PROPERTIES]
Relations amongst partial molar properties:
Imagine a very large quantity of solution, add 1 gm-mole of pure i into it.
Upon dissolution, the total quantity of solution increase by 1 gm – mole. As a
result without effective the composition so much the Q get increases. For constant
pressure & temperature the increase in Q’ is equal to 𝑄𝑖 . Therefore, 𝑄𝑖 .is the
value of Q per mole of i in the solution
Again, we know
m
Qi = 𝑄𝑖 − 𝑄𝑖0 (194)

[Where 𝑄𝑖0 = 𝑄 per mole for pure i

𝑄𝑖𝑚 = Partial molar value of Q of mixture of i in the solution
𝑄𝑖 = Partial molar value of Q of component in the solution ]
1
Continued…
So for Gibbs free energy per gm. mole of component i, we have
m
Gi = 𝐺𝑖 − 𝐺𝑖0 (195)
Again in general,
𝑑𝐻𝑖 = 𝑇 𝑑𝑠𝑖 + 𝑉𝑖 𝑑𝑃 (196)
𝑑𝐺𝑖 = −𝑆𝑖 𝑑𝑇 + 𝑉𝑖 𝑑𝑃 (197)
𝑑𝐻𝑚 = 𝑇 𝑑𝑆𝑖𝑚 + 𝑉𝑖𝑚 𝑑𝑃 (198)

𝑑𝐺𝑖𝑚 = −𝑆𝑖𝑚 𝑑𝑇 + 𝑉𝑖𝑚 𝑑𝑃 (199)

So, we have
𝐺𝑖 = 𝐻𝑖 − 𝑇𝑆𝑖 (200)
𝐺𝑖0 = 𝐻𝑖0 − 𝑇𝑆𝑖0 (201)
𝐺𝑖𝑚 = 𝐻𝑖𝑚 − 𝑇𝑆𝑚 (202)
2
Continued…
Using equation (200) and (201) in equation (195), we will get equation (203) as
follows

𝐺𝑖𝑚 = 𝐺𝑖 – Gi0 = 𝐻𝑖 − 𝑇 𝑆𝑖 − Hi0 − T𝑆𝑖0 (203)

Gim = 𝐻𝑖 − 𝐻𝑖0 − 𝑇𝑆𝑖 − 𝑇𝑆𝑖0 = 𝐻𝑖0 − 𝑇𝑆𝑖0 (204)

So considering some common extensive properties, we can write

𝜕G′
Gi′ = T, P, n1, n2…. except ni (205)
𝜕ηi

𝜕S′
Si = T, P, n1, n2…. except ni (206)
𝜕ηi

𝜕H′
Hi = T, P, n1, n2…. except ni (207)
𝜕ηi

𝜕V′
Vi = T, P, n1, n2…. except ni (208)
𝜕ηi
3
Continued…
Again, using equation (194), we can get the following equations
𝑆𝑖𝑚 = 𝑆𝑖 − 𝑆𝑖0 (209)

𝐻𝑖𝑚 = 𝐻𝑖 − 𝐻𝑖0 (210)

𝑉𝑖𝑚 = 𝑉𝑖 − 𝑉𝑖0 (211)

Common symbols that are used

Q – Extensive property of solution, it can refer as U, H, V, S, G etc.
𝑄𝑖 - Partial molar value of Q of component i in the solution.
𝑄𝑖0 - Q per mole for pure i.
𝑄𝑖𝑚 - Partial molar value of mixing of component i in the solution.
𝑄 ′ - Value of quantity in the entire solution
4
Continued…
Gibb’s – Duhem Equation:
Since we know, at constant T, P we have got
𝑑𝑄 ′ = 𝑄1 𝑑𝑛1 + 𝑄2 𝑑𝑛2 + −−−− + 𝑄𝑖 𝑑𝑛𝑖 (212)

𝑑𝑄′ = 𝑖 𝑄𝑖 𝑑𝑛𝑖 (213)

By adding small quantities of component (𝜕𝑛1, 𝜕𝑛2 , … , 𝜕𝑛𝑖 ) at constant T, P such

that overall composition of the solution remains same in all stages. Since 𝑄1 , 𝑄2 ,
………., 𝑄𝑖 are functions of T, P & compositions. So these are remained constant.
Therefore after the additions are complete, we get
𝑄 ′ = 𝑄1 𝑛1 + 𝑄2 𝑛2 + … … … … + 𝑄𝑖 𝑛𝑖 (214)
Differentiating equation (214), we will get
𝑑𝑄 ′ = (𝑄1 𝑑𝑛1 + 𝑛1 𝑑𝑄1 ) + ( 𝑄2 𝑑𝑛2 + 𝑛2 𝑑𝑄2 ) + … … … … … + (𝑄𝑖 𝑑𝑛𝑖 +
𝑛𝑖 𝑑𝑄𝑖 ) (215)
5
Continued…
𝑑𝑄 ′ = 𝑖 𝑄𝑖 𝑑𝑛𝑖 + 𝑖 𝑛𝑖 𝑑𝑄𝑖 ) (216)

Equating equation (213) and (216), we will get

𝑖 𝑛𝑖 𝑑𝑄𝑖 =0 (217)
Dividing the equation (217) by the total no. of moles(𝑛 𝑇 ), we will get
𝑛𝑖
𝑖 𝑋𝑖 𝑑𝑄𝑖 = 0 (Since,
𝑛𝑇
= 𝑋𝑖 ) (218)

[Where, Total no of moles (𝑛 𝑇 ) = 𝑛1 + 𝑛2 + … … … . + 𝑛𝑖 ]

In the above, equation (217) and (218) are the alternative forms of Gibb’s-Duhem
equation (G-D equation), which provide the principal foundation to
thermodynamic solutions.

6
Continued…
For Gibb’s free energy, the G-D equation can be written as

𝑖 𝑛𝑖 𝑑𝐺𝑖 =0 or 𝑖 𝑋𝑖 𝑑𝐺𝑖 =0 (219)

For pure component the values of Q such as 𝑄10 , 𝑄20 , ………., 𝑄𝑖0 are constants at
constant T & P. So 𝑑𝑄10 , 𝑑𝑄20 , …………., 𝑑𝑄𝑖0 are zero. Hence we have

𝑖 𝑛𝑖 𝑑𝑄𝑖0 =0 or 𝑖 𝑋𝑖 𝑑𝑄𝑖0 =0 (220)

Since we know that

𝑚
𝑖 𝑛𝑖 𝑑𝑄𝑖 = 𝑖 𝑛𝑖 𝑑(𝑄𝑖 − 𝑄0 ) = 0
Or (221)
𝑚
𝑖 𝑋𝑖 𝑑𝑄𝑖 = 𝑖 𝑋𝑖 𝑑(𝑄𝑖 − 𝑄0 ) = 0

7
Continued…
The G-D equation is usually applied to describe the effect temperature and
pressure changes on Gibbs free energy that well-known as Clausius-Clapeyron
equation.
Consider a phase transformation of an element or compound (designated as A)
A (phase I) = A (phase II)
For phase I: 𝑑𝐺𝐴 𝐼 = 𝑉𝐴 𝐼 𝑑𝑃 − 𝑆𝐴 𝐼 𝑑𝑇 (I)
For phase II: 𝑑𝐺𝐴 𝐼𝐼 = 𝑉𝐴 𝐼𝐼 𝑑𝑃 − 𝑆𝐴 𝐼𝐼 𝑑𝑇 (II)
At equilibrium phase transformation temp (𝑇𝑡𝑟 ) and pressure (𝑃𝑡𝑟 )
∆𝐺 = 𝐺𝐴 𝐼𝐼 − 𝐺𝐴 𝐼 = 0 (III)
So, due change the system have achieved new state of equilibrium where pressure
is 𝑃𝑡𝑟 + 𝑑𝑃, temp is 𝑇𝑡𝑟 + 𝑑𝑇 and also Gibb’s free energy change to 𝐺𝐴 𝐼 →
𝐺𝐴 𝐼 + 𝑑𝐺𝐴 𝐼 & 𝐺𝐴 𝐼𝐼 → 𝐺𝐴 𝐼𝐼 + 𝑑𝐺𝐴 𝐼𝐼 .
8
Continued…
Since, ∆𝐺 = 𝐺𝐴 𝐼𝐼 − 𝐺𝐴 𝐼 = 0 from equation (III),
So 𝐺𝐴 𝐼𝐼 = 𝐺𝐴 𝐼 =>𝑉𝐴 𝐼 𝑑𝑃 − 𝑆𝐴 𝐼 𝑑𝑇 = 𝑉𝐴 𝐼𝐼 𝑑𝑃 − 𝑆𝐴 𝐼𝐼 𝑑𝑇 (IV)
𝑆𝐴 𝐼𝐼 − 𝑆𝐴 𝐼 𝑑𝑇 = 𝑉𝐴 𝐼𝐼 − 𝑉𝐴 𝐼 𝑑𝑃 (V)

𝑑𝑇 𝑉𝐴 𝐼𝐼 − 𝑉𝐴 𝐼
= (VI)
𝑑𝑃 𝑒𝑞𝑙𝑏𝑚 𝑆𝐴 𝐼𝐼 − 𝑆𝐴 𝐼

𝑑𝑇 ∆𝑉𝑡𝑟 ∆𝑉𝑡𝑟 𝑇𝑡𝑟

= = (VII)
𝑑𝑃 𝑒𝑞𝑙𝑏𝑚 ∆𝑆𝑡𝑟 ∆𝐻𝑡𝑟

So it can be written as

𝜕𝑃 ∆𝑆𝑡𝑟 ∆𝐻𝑡𝑟 Note: tr stands for

= =
𝜕𝑇 ∆𝑉𝑡𝑟 ∆𝑉𝑡𝑟 𝑇𝑡𝑟 transformation
∆𝐺=0

Clausius-Clapeyron equation 9
 LECTURE-22
Raoult’s law of Ideal Solution:
Raoult's Law states that for an ideal solution the partial vapor pressure of a component in
solution is equal to the mole fraction of that component multiplied with its vapor pressure
at pure state. Mathematically, it can be expressed as

𝑃𝐴
𝑎𝑖 = = 𝑋𝑖 => 𝑃𝐴 = 𝑋𝑖 𝑃𝐴0 (where 𝛾𝑖 = 1 i. e. activity coefficient (γ) is 1) (222)
𝑃𝐴0

Properties of Ideal Solution:

 The enthalpy of solution (or "enthalpy of mixing") is zero as is the volume
change on mixing; the closer to zero the enthalpy of solution is, the more
"ideal" the behavior of the solution becomes.
 The vapor pressure of the solution obeys Raoult’s law
 The activity coefficient of each component (which measures deviation from
ideality) is equal to one. 10
Continued…
ACTIVITY VS MOLE FRACTION (HENRY’S LAW):
Henry’s Law: Henry’s law stated as, if 𝑋𝐵 → 0, then 𝛾𝐵 → 𝑎 constant value as
𝛾𝐵0 . In other words, in Henry’s law region for B.
𝑎𝐵 = 𝛾𝐵0 𝑋𝐵 (223)
[Where B is solute & A is solvent]
Similarly, to equation (223), we will also have
𝑎𝐴 = 𝛾𝐴0 𝑋𝐴 (224)
Where for
o 𝛾 𝑖 > 1 , solution exhibits positive departure from Raoult’s law.
o 𝛾 𝑖 < 1, solution exhibits negative departure from Raoult’s law.

11
Continued…
Fig (a) Positive & (b)
Negative deviations
from the Raoult’s law
for component B in
the binary A-B
solution; Henry’s law
lines for B are also
shown.

• The above Fig represents activity vs mole fraction curves for binary A-B
solutions at constant temperature.
• It shows Raoult’s law line component A & B. Positive & negative departures
from Raoult’s law are illustrated for aB with XB is leaner. This is basis for
Henry’s law for binary solution. 12
Continued…
• Solute in binary dilute solution obeys Henry’s Law. Henry’s law is expected to be
obeyed if solute atoms are far from each other then we can ignore solute-
solute interaction i.e. A-A & B-B interactions.
• In the previous Fig (a) & (b), we have the curves for aB merge with Raoult’s law
line if 𝑋𝐵 → 1. In other words, in the region where B obeys Henry’s law, A
tends to obey Raoult’s law & Vice versa.
Proof of the Above Statement:
From the Gibb’s-Duhem equation, we have
𝑋𝐴 𝑑𝐺𝐴𝑚 + 𝑋𝐵 𝑑𝐺𝐵𝑚 = 0 (225)
𝑅𝑇[𝑋𝐴 𝑑 𝑙𝑛𝑎𝐴 + 𝑋𝐵 𝑑 𝑙𝑛𝑎𝐵 ] = 0 (226)
𝑅𝑇 𝑋𝐴 𝑑 𝑙𝑛𝑎𝐴 + 𝑅𝑇 𝑋𝐵 𝑑 𝑙𝑛𝑎𝐵 = 0 (227)
𝑋𝐴 𝑑 𝑙𝑛𝑎𝐴 = − 𝑋𝐵 𝑑 𝑙𝑛𝑎𝐵 (228)
13
Continued…
𝑋𝐵
𝑑 𝑙𝑛𝑎𝐴 = − 𝑑 𝑙𝑛𝑎𝐵 (229)
𝑋𝐴

If B obeys Henry’s law, then

𝑑 𝑙𝑛𝑎𝐵 = 𝑑[ln 𝛾𝐵0 𝑋𝐵 = 𝑑 [ln 𝛾𝐵0 + 𝑙𝑛𝑋𝐵 ] (230)
[𝑎𝐵 = 𝛾𝐵0 𝑋𝐵 From equation (223)]

𝑑 ln 𝑎𝐵 = 𝑑 ln 𝛾𝐵0 + 𝑑 ln 𝑋𝐵 (231)

𝑑 ln 𝑎𝐵 = 𝑑 ln 𝑋𝐵 (232)
[Since 𝑑 ln 𝛾𝐵0 = 0 as 𝛾𝐵0 is constant]
Now from equation (229), we have
𝑥𝐵
𝑑 𝑙𝑛𝑎𝐴 = − 𝑑 𝑙𝑛𝑋𝐵 (233)
𝑥𝐴

14
Continued…
𝑋𝐵 𝑑𝑥𝐵
𝑑 ln 𝑎𝐴 = − (234)
𝑋𝐴 𝑋𝐵

𝑑𝑋𝐵
d ln aA = − (235)
𝑋𝐴

𝑑 ln 𝑋 1 𝑑𝑋
[Since = 𝑑𝑙𝑛X = ]
𝑑𝑋 𝑋 𝑋

Again we know,
𝑑𝑋𝐴 + 𝑑𝑋𝐵 = 0 (𝑆𝑖𝑛𝑐𝑒 𝑋𝐴 +𝑋𝐵 = 1) (236)
𝑑𝑋𝐵 = − 𝑑𝑋𝐴 (237)
So, using equation (237) in equation (235), we will get
𝑑𝑋𝐴
𝑑 𝑙𝑛𝑎𝐴 = = 𝑑 ln 𝑋𝐴 (238)
𝑋𝐴

Taking integration of equation (238), we have

ln 𝑎𝐴 = ln 𝑋𝐴 + 𝐶𝑜𝑛𝑠𝑡𝑎𝑛𝑡 (239)
15
Continued…
Let’s consider I as a constant, then ln 𝐼 will also a constant. Therefore, we can write
equation (239) as

ln 𝑎𝐴 = ln 𝑋𝐴 + ln 𝐼 (240)
ln 𝑎𝐴 = ln(𝐼𝑋𝐴 ) (241)
𝑎𝐴 = 𝐼𝑋𝐴 (242)

At 𝑋𝐴 → 1, 𝑎𝐴 → 1. Hence 𝐼 = 1

Hence, equation (242) will become

𝑎𝐴 = 𝑋𝐴 (243)
i.e. A obeys Raoult’s law when B obeys Henry’s law.

16
Continued…
REGULAR SOLUTIONS:
• Since most of the solutions are non-ideal so there is a great need to express the
thermodynamic quantity in these solutions in the form of analytical equations
i.e. function of temperature & composition.
• Regular solution model first proposed by Hildebrand, on approximation the
model is not much more consistent.
• Hildebrand defined a regular solution as one in which
m m,id
Si = Si But 𝐻𝑖𝑚 ≠ 0 (244)

i.e. ∆𝑠 𝑚 = ∆𝑠 𝑚,𝑖𝑑 But ∆𝐻 𝑚 ≠ 0 (245)

[Where “id” subscript refers to ideal solution]
• In other words, a regular solution has the same entropy as an ideal solution of
same composition, but enthalpy is different from ideal solution.
17
Continued…
Excess Function: For dealing with non-ideal solutions, a function known as
excess function (or molar excess property) and it is used only for extensive
properties & defined as
𝑄 𝑥𝑠 = 𝑄 − 𝑄 𝑖𝑑 (246)
Similarly, for partial molar excess properties the equation (246) will become

𝑄𝑖𝑥𝑠 = 𝑄𝑖 − 𝑄𝑖𝑖𝑑 (247)

[Here,
Q – Some extensive property (G, H, S……..) of the actual solution.
𝑄 𝑖𝑑 - Value of Q for ideal solution at same composition & temperature.
𝑄 𝑥𝑠 - Value of Q in excess of that of ideal solution. ]
For standard state, we can write equation (246) and (247) as
𝑄 𝑥𝑠 = (𝑄 − 𝑄 0 ) (248)

𝑄 𝑋𝑆 = ∆𝑄 𝑚 − ∆𝑄 𝑚,𝑖𝑑 (249)
18
Continued…
𝑄 𝑥𝑠 = 𝑄𝑖 − 𝑄𝑖0 − (𝑄𝑖𝑖𝑑 − 𝑄𝑖0 ) (250)

𝑄𝑖𝑋𝑆 = 𝑄𝑖𝑚 − 𝑄𝑖𝑚,𝑖𝑑 (251)

[Since, 𝑄 0 is added & 𝑄 0 subtracted. So, equation (249) & (251) are same as
equation (246) & (247) respectively.
Hence, for a regular solution
𝐺𝑖𝑥𝑠 = 𝐻𝑖𝑥𝑠 − 𝑇𝑆𝑖𝑥𝑠 = 𝐻𝑖𝑥𝑠 = 𝐻𝑖𝑚 (252)
𝐺 𝑥𝑠 = ∆𝐻 𝑚 (253)
[Since for a regular solution no excess entropy i.e.𝑆𝑖𝑥𝑠 = 0, 𝑆 𝑥𝑠 = 0 and also
𝐻𝑖𝑥𝑠 = 𝐻𝑖𝑚 , 𝐻 𝑥𝑠 = ∆𝐻 𝑚 ]
Again, 𝐺 𝑥𝑠 = ∆𝐺 𝑚 − ∆𝐺 𝑚,𝑖𝑑 = 𝑅𝑇 𝑖 𝑥𝑖 𝑙𝑛𝑎𝑖 − 𝑅𝑇 𝑖 𝑥𝑖 ln 𝑥𝑖 = 𝑅𝑇 𝑖 𝑥𝑖 𝑙𝑛𝛾𝑖
(254)
[Since, for ideal solution ( 𝑎𝑖 = 𝑥𝑖 )] 19
 LECTURE-23
Regular Binary Solutions:
For binary solution case, we have defined a function 𝛼 that is given by

ln 𝛾𝑖
𝛼𝑖 = (255)
(1−𝑋𝑖) )2

So, for A-B solution

ln 𝛾𝐵 ln 𝛾𝐵
𝛼𝐵 = = (256)
(1−𝑋𝐵) )2 𝑋𝐴2

ln 𝛾𝐵 = 𝛼𝐵 𝑋𝐴2 (257)
Similarly,
𝑙𝑛𝑥𝐴 = 𝛼𝐴 𝑋𝐵2 (258)
For binary regular solution
𝛼𝐴 = 𝛼𝐵 = 𝛼 = Constant (259)
20
Continued…
Since we know
∆𝐻 𝑚 = 𝐺 𝑥𝑠 = 𝑅𝑇 (𝑋𝐴 ln 𝛾𝐴 + 𝑋𝐵 ln 𝛾𝐵 ) (260)

∆𝐻𝑚 = 𝑅𝑇( 𝑋𝐴 𝛼𝐴 𝑋𝐵2 + 𝑋𝐵 𝛼𝐵 𝑋𝐴2 ) (261)

∆𝐻𝑚 = 𝑅𝑇𝛼 (𝑋𝐴 𝑋𝐵2 + 𝑋𝐵 𝑋𝐴2 ) (262)

(Using equation (258))

∆𝐻 𝑚 = 𝑅𝑇𝛼𝑋𝐴 𝑋𝐵 (𝑋𝐴 + 𝑋𝐵 ) (263)

∆𝐻𝑚 = 𝑅𝑇𝛼𝑋𝐴 𝑋𝐵 (264)

(𝑆𝑖𝑛𝑐𝑒 𝑋𝐴 + 𝑋𝐵 = 1)

∆𝐻 𝑚 = Ω 𝑋𝐴 𝑋𝐵 (Since Ω = 𝑅𝑇𝛼) (265)

[Where Ω is a parameter related to interaction energies in the solution]
21
Continued…
Again, we have
𝐻𝐴𝑚 = 𝐺𝐴𝑥𝑠 = 𝑅𝑇 ln 𝛾𝐴 = 𝑅𝑇𝛼𝑋𝐵2 = Ω𝑋𝐵2 (266)
𝐻𝐵𝑚 = 𝐺𝐵𝑥𝑠 = 𝑅𝑇 ln 𝛾𝐵 = 𝑅𝑇𝛼𝑋𝐴2 = Ω𝑋𝐴2 (267)

∆𝐻 𝑚 , 𝐻𝑖𝑚 of solutions mainly constant over a limited range approximately. So Ω

assumed to be independent of temperature.

Therefore
Ω 1
𝛼= 𝛼 ∝ (268)
𝑅𝑇 𝑇

22
Continued…
SIEVERT’S LAW: Statement of the law is “The atomic gases do not dissolve into the
metal in their molecular form rather they dissolve by dissociation i.e. in atomic
form.”
So dissolution of a diatomic gas into metal (condensed phase)
𝑥2 → 2𝑥 (In solution)
[Where 𝑥2 → diatomic gases]
Equilibrium constant of reaction

𝑕𝑥
𝐾𝑝 = 1 (269)
𝑃𝑥2 2
𝑒𝑞

[Where, 𝑕𝑥 → Henry activity of component x dissolve in condensed / solid phase.

𝑃𝑥2 → Partial pressure of 𝑥2 .
𝐾𝑝 → Sievert’s constant ]
23
Continued…
As the solubility of gases in condensed phase under moderate condition of
temperature and pressure is very small. So, the 𝑕𝑥 for the above expression for
gases are preferred to use in terms of wt. %. The above equation (269) changes to

𝑓𝑥 (𝑤𝑡.% 𝑥)
𝐾𝑝 = 1 (270)
𝑃𝑥 2
2

[Where, 𝑓𝑥 → Henry’s activity co-efficient ]

In Henry’s law if the activity co-efficient 𝑓𝑥 → 1, then equation (270) becomes

(𝑤𝑡.% 𝑥)
𝐾𝑝 = 1 (271)
𝑃𝑥 2
2

𝑤𝑡. % 𝑥 = 𝐾𝑝 𝑃𝑥2 (272)

wt. % x = Sievert ′ slaw constant × Px2 (273)

24
Continued…
From equation (272), Sievert’s law can be expressed as, at constant temperature,
the solubility of diatomic gases into the condensed phase is proportional to the
square root of partial pressure.
Limitation of Sievert’s Law: It is applicable only to the limiting type of solution
where Henerian activity 𝑕𝑥 → 1 (when (𝑓𝑥 ≠ 1)) in such case expression for
Sievert’s law take the form
1
ln wt. % x = ln K p + ln Px2 − ln fx (274)
2
1
[Since, 𝑓𝑥 𝑤𝑡. % 𝑥 = 𝐾𝑃 𝑃𝑥2 2 ]

The function 𝑓𝑥 can be expressed in terms of interaction co-efficient that means

ln fx =
ϵXX . wt% x + ϵ1X . wt% of 1st component + ϵ2X . wt% of 2nd component +
⋯ + ϵnX . wt% of nth component (275)
25
Continued…
[Where, 𝜖𝑋𝑋 −Self interaction parameter of the gas component “X”
𝜖𝑋1 , 𝜖𝑋2 , … , 𝜖𝑋𝑛 −Interaction parameter on component X of
component 1, 2,..., n]
Problem-Calculate the solubility of N2 gas under 1 atom pressure & 1600 0C in an
iron-based alloyed having the composition C = 3.5%, Mn = 1%, Si = 1.2%, P = 0.5%.
The interaction parameters for various components are
ϵCN = 0.25 × 2.3 , 𝜖𝑁𝑃 = 0.51 × 2.3, ϵMn
N 0.02 × 2.3

ϵN Si
N = 0, ϵN = 0.047 × 2.3

Sievert’s constant for N2 (KP) = 0.045

Solution: As we from limiting condition of Sievert’s law
ln fx = ϵCN . wt% of C + ϵPN . wt% of P + ϵMn
N . wt% of Mn + ⋯

+ ϵN
N . wt% of N
26
Continued…
= 0.25 × 3.5 + 0.51 × 0.5 + 0.02 × 1 + 0.047 × 1.2 × 2.3
[Since, 𝜖𝑁𝑁 = 0 ]
= 1.2064 × 2.3 = 2.77472 ≅ 2.775
Since, we know from Sievert’s law as

𝑓𝑥 × 𝑤𝑡. % 𝑁 = 𝑆𝑖𝑣𝑒𝑟𝑡 ′ 𝑠𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝐾𝑃 × 𝑃𝑁2

0.045 × 1
𝑤𝑡. % 𝑁 = = 2.8 × 10−3 (Ans)
16.04

27
Continued…
FREE ENERGY COMPOSITION DIAGRAM FOR BINARY ALLOYS SYSTEMS: The free
energy of each of phase’s presents on a phase diagram can be plotted as a function
of composition at a series of temperature. The phases co-exist in equilibrium are
those correspond to the lowest free energy of the system.

Fig -Free energy – composition relationships for an isomorphous system at three

temperatures, Ref-Raghavan, V. (2012). Physical metallurgy: principles and practice. PHI
Learning Pvt. Ltd. 28
Continued…

Fig -Free energy vs. composition relationships for a simple eutectic system at different
temperature, Ref-Raghavan, V. (2012). Physical metallurgy: principles and practice. PHI
Learning Pvt. Ltd. 29
 LECTURE-24
Binary Phase Diagram: The most commonly used phase diagrams are those that
depict the equilibrium between two components. These are known as binary
phase diagrams.
Example: (Fe-Fe3C) phase diagram, (Cu – Ni) phase diagram.
For graphical representation of the binary phase prelateships, we need a map with
three axes corresponding to temperature, pressure & composition. For binary
phase diagrams, we ignore the pressure variable & the vapor phase. As one of the
variables has been arbitrarily omitted the phase rule for condensed phases (i.e.
liquid & solids) only is written as
F= C−P+1 (276)

30
Continued…
Isomorphous system: An Isomorphous system defined as the simplest binary
phase diagram for a system that exhibiting complete liquid as well as solubility.
Example: Cu – Ni phase diagram
M. pt of Cu → 1083 0C, M. pt of Ni → 1455 0C

Fig-The Copper-Nickel
phase diagram, showing
complete solubility both
in the liquid and in the
solid states.

31
Continued…
 The liquid & solid regions are separated by a two-phase region, where
both the phase co-exists.
 The boundary between two-phase region & the liquid is called liquidous
line. The boundary between the two-phase region & the solid is called
solidus line.
 Solvus Line: It is the solid-state phase boundary between the terminal
solid solution & the two-phase region.
EXPERIMENTAL DETERMINATION OF PHASE DIAGRAMS: A variety of physical
techniques are used for the experimental determination of phase diagrams.
Among these the most important techniques are
1. Thermal analysis.
2. Microscopic examination.
3. X-ray diffraction. 32
Continued…
Determination of Liquidus and Solidus:
• Thermal analysis is the most important method for determination of the liquid-
solid transformations
• This method based on evolution or absorption of heat occurs during a phase
change
• When the temperature of an alloy sample is plotted as a function of time
during heating or cooling, abrupt changes in slope of plot occur at points
corresponding to the start or finish of a phase change
Cooling Curves: Curves of single composition for different conditions using thermal
analysis explained below.
Case – I: [For pure metal without super cooling] In this case, evolution of latent
heat due to start of solidification is equal to heat loss due to surroundings (refer
fig. (a)). Example: Pure metals like Fe, Cu, Ni etc. 33
Continued…

Fig-Thermal analysis. Cooling curves (a) for a pure metal without supercooling, (b) for a
pure metal with supercooling, (c) for a solid solution alloy, (d) for a hypoeutectic alloy,
Ref-Raghavan, V. (2012). Physical metallurgy: principles and practice. PHI Learning Pvt. Ltd.
34
Continued…
Case – II: [For a pure metal with super-cooling]
• In this case, evolution of latent heat due to the solidification less than heat lost
to the surroundings and this process is known as Super-cooling (refer fig. (b)).
• Once Solidification starts heat evolution raise the sample temperature back to
freezing point

Case – III: [For a solid solution alloys]

• From fig. (c) we have, first arrest indicating abrupt decrease in the cooling rate
occurs as the liquidus temperature 𝑇𝑙 is crossed. Since, over a range of
temperature the solidification occurs. So there is no horizontal part.
• The second arrest is observed at the solidus temperature 𝑇𝑠 , when the cooling
rate starts to increase again.
35
Continued…
Case – IV: [For a hypothetical alloy or pro-eutectic binary alloy]
• From fig. (d) we have, Peritectic alloy also shows the similar behavior as pro-
eutectic or hyper-eutectic alloy.
• First arrest occurs at the liquidus temperature & the cooling rate decreases.
• At the eutectic temperature 𝑇𝑒 , the cooling curve becomes horizontal as
invariant eutectic reaction occurs isothermally. The cooling rate increases again
when the eutectic solidification is complete.

36
Continued…
Following precautions are taken to determining cooling curves

 Local fluctuations of temperature in the furnace should be avoided.

 For the achievement of near equilibrium conditions, the rate of cooling must
be slow as feasible.

 To reduce super cooling, the molten alloy should be stirred for uniform
temperature.

 Composition analysis must be accurate.

 No contamination must occur from the crucible, thermocouple sheath etc. 37

Continued…
• Solidus is determined by approximate lines in cooling curve, as coring tends to
lower the solidus temperature.

• A more accurate determination can be carried out by holding the solidified

alloy for a long time for homogenization just below the approximate solidus
temperature determined from cooling curve.

• The alloy heated again to find the breaking in the heating curve. This break is at
a higher temp then that determined during cooling as coring effects are
removed by homogenization.

38
Continued…
Coring: Above solidus temperature same liquid remains without transfer to solid is
known as coring.

 Thermal analysis can be replaced with microscopic examination; the alloy is

heated close to the solidus & quenched to ascertain microscopically the
appearance of the first chilled liquid.

 Using the break in the cooling & heating curves for a series of compositions
covering the entire binary range, the liquidus & solidus boundaries can be fully
determined.

39
Continued…
Determination of the Solvus:

Fig-Determination of Solvus boundaries by the metallographic & X-ray methods, Ref-

Raghavan, V. (2012). Physical metallurgy: principles and practice. PHI Learning Pvt. Ltd.
40
Continued…
• The common methods for determining the Solvus are microscopic
examination & X-ray diffraction.
• A series of small ingots of alloys of different compositions are prepared and
homogenized. They are then annealed at various temperatures for prolonged
time (a few days) and quenched.
• In such cases, subsequent metallographic and X-ray studies at room
temperature disclose the appearance of second phase at some known
composition.
• In other cases, at high temperature phase may decompose on quenching, If
this happens room temperature, X-ray studies are not suitable. So a high
temperature X-ray camera used.

41
Continued…
• But even after the decomposition during quenching the metallographic
method may be useful, if the transformed phase is in an easily recognizable
form.
• A phase boundary is first bracketed between two compositions and then exact
location of boundary is determined by studying a few more alloys of closely
varying composition in the boundary region.

42
 LECTURE-25
TOPOCHEMICAL REACTION
It is defined as the solid-gas reaction or phase boundary controlled reactions that
occur by the movement of well-defined interface.
Diffusion steps:
I. Diffusion of reducing gas (CO, H2) from gas phase to the ore-pellet
through surface film.
II. Diffusion of reducing gas from ore-pellet to reductant layers.
III. Chemical reaction carry out as

𝑀𝑥 𝑂𝑦 + 𝑌𝐶𝑂 → 𝑋𝑀 + 𝑌𝐶𝑂2

𝑀𝑥 𝑂𝑦 + 𝐻2 → 𝑋𝑀 + 𝑌𝐻𝑂2

43
Continued…

Fe
FeO
𝑭𝒆𝟑 𝑶𝟒

𝑭𝒆𝟐 𝑶𝟑

CO2 gas

Fig- Reduction of iron ore presence of CO gas

IV. Diffusion of product gas (CO2, H2O) from reductant layer to ore-pellet
44
V. Diffusion of product gas from ore-pellet to surface film.
Continued…
Factors affecting the reaction rate kinetics:
 The physical state of both reactants and products.
 The concentrations of the reactants and products.
 The pressure or temperature at which the chemical reaction takes place.
 Presence of catalyst in the reaction.
Rate Controlling Step:
 The slowest step of a multi-step reaction is the rate determining step.
 The rate of the whole reaction = the rate of the rate determining step.
 The rate law corresponds to the components of the rate determining step.
 The chemical reaction included the process of diffusion of gaseous species and
that in intrinsic chemical reaction.
 If the effects of gas phase mass transfer being negligible and then the reaction
rate being controlled by intrinsic interfacial chemical reaction and the diffusion
45
of reactant and product gas species through solid product layer.
Continued…
Derivation: Let us assume the particle which is participating in reduction reaction
are spherical in nature for which the reaction is phase boundary type, then the
presence or absence of product layer the rate of reaction depends on the interface
area.
𝑑𝑤 𝑑𝑤
− ∝ 𝐴. 𝐶 − = 𝐾𝐴𝐶 (277)
𝑑𝑡 𝑑𝑡

N.B.: Negative sign indicates that with increase in time the wt. decreases
[Where, K → Reaction constant, A → Interface area for reaction
C → Concentration of the reagent fluid.]
If “r” be the radius of the spherical molecules, participating in the equation (277)
can be re-written as
𝑑 4
− 𝜋𝑟 3 . 𝜌 = 𝐾. 4𝜋𝑟 2 . 1 (278)
𝑑𝑡 3

[Where, 𝐴 = 4𝜋𝑟 2 , C=1]

46
Continued…
Reaction not started so, C = 1, for unreacted core sphere.
𝑑𝑟 3𝐾
− = (279)
𝑑𝑡 𝜌

𝑑𝑟 𝐾′
− = (280)
𝑑𝑡 𝜌

𝑟 𝐾′ 𝑡
− 𝑟0
𝑑𝑟 = 𝑑𝑡 (281)
𝜌 0

𝐾′
− 𝑟 − 𝑟0 = 𝑡 (282)
𝜌

𝐾′
𝑟0 − 𝑟 = 𝑡 (283)
𝜌

Again,
W0− W Change in wt.
α = [degree of reaction at (t = t 0 )] = = (284)
W0 Initial wt.
47
Continued…
Since, the weight decreases with time. So, degree of reduction (α) expressed as
Initial wt.−Final wt.
𝐷𝑒𝑔𝑟𝑒𝑒 𝑜𝑓𝑟𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛 𝛼 = (285)
Initial wt.

W0− W W 4 3ρ
3πr r 3
𝛼= =1− =1− 4 3 =1− r0 (286)
W0 W0 3πr ρ

r 3
=1− α (287)
r0

𝑟 1
𝑟0 = 1− 𝛼 3 (288)
1
𝑟 = 𝑟0 1 − 𝛼 3 (289)
Replacing the in equation (289) in equation (283), the equation becomes
1 𝐾′𝑡
𝑟0 − 𝑟0 1 − 𝛼 3 = (290)
𝜌

48
Continued…
1 𝐾′𝑡
𝑟0 1 − 1 − 𝛼 3 = (291)
𝜌

1 𝐾′𝑡
𝑟0 1 − 1 − 𝛼 3 = (292)
𝜌

The above equation (292) is known as Mckewan relation or model.

1
If we will take the experimental data and plot 1 − 1 − α 3 vs t and getting a
straight line, then we can say reduction reaction obeys Mckewan relation.
Factors affecting the reaction rate kinetics:
- The physical state of the reactants and products.
- The concentrations of the reactants and products.
- The temperature or pressure at which the reaction occurs.
- Whether or not any catalysts are present in the reaction.
49
Continued…
REACTION IN LUMPS: Steps followed during reaction in lump are given by
1. Diffusion of reducing gas CO/H2 through boundary surface.
2. Diffusion of reducing gas CO/H2 through macro pore.
3. Diffusion of reducing gas CO/H2 through micro pore.
4. Diffusion of reducing gas CO/H2 through product layer.
5. Reaction between CO/H2 gas & Metal Oxide
𝑀𝑥 𝑂𝑦 + 𝑌𝐶𝑂 → 𝑋𝑀 + 𝑌𝐶𝑂2

𝑀𝑥 𝑂𝑦 + 𝐻2 → 𝑋𝑀 + 𝑌𝐻𝑂2
Example: 𝐹𝑒2 𝑂3 + 3𝐶𝑂/𝐻2 = 2𝐹𝑒 + 3𝐶𝑂2 /𝐻2 𝑂(↑)
6. Diffusion of product gas CO2/H2O through product layer.
7. Diffusion of product gas CO2/H2O through micro pore.
8. Diffusion of product gas CO2/H2O through macro pore.
9. Diffusion of product gas CO2/H2O through boundary layer/surface. 50
Continued…
IMPORTANT NOTES:
 Reformed Natural Gas: It is defined as the gas that produces due to reaction
between CH4 with H2O using Ni catalyst at 8000 𝐶.
𝑁𝑖
𝐶𝐻4 + 𝐻2 𝑂 𝐶𝑂 + 3𝐻2
 Degree of Reduction: It is defined as the ratio of amount of O2 removed at any
time (t) to that of total possible amount of removal oxygen.

Amount of O2 removed at time t

Degree of reduction α =
Total possible O2 removal
 Metallization: It is defined as the ratio of metal Fe to that of total Fe present in
Fe and its oxides.

Metal Fe
Metallization =
Total Fe
Degree of Metallization = Metallization × 100 51
 QUIZ TEST-5
Q.1 –Explain the positive and negative deviation of real solutions from ideal
behavior with the help of suitable examples.

Q.2 –State the principal application of Gibbs-Duhem equation during phase

transformation.

Q.3 –Why most of the Gibbs free energy-composition curves are followed “U”
shape?

Q.4–State and explain the major techniques, that is mostly employed for solvus
curve determination.

Q.5 –How the rate-controlling step is determined and state its importance. 52
 LECTURE-26
TYPES OF REACTION:

There are basically two types of reactions existing. The differences

between two reactions are given below

Homogeneous Reaction Heterogeneous Reaction

- It takes place entirely within one phase - It involves more than one phase. Example:
where reactants and products both are slag-metal reaction; molten slag is in one
in one phase as well as reaction carry phase and molten metal in another phase,
out in that phase. reaction takes place at interface.
- Reaction occurs in the bulk i.e. within - Reaction occurs not in bulk but at the
the phase. interface.
- Rate of chemical reaction is - Rate of chemical reaction to the interfacial
proportional to the volume of the area between the two or more phases
phase.
53
Continued…
Homogeneous Reaction Heterogeneous Reaction
- No adsorption and desorption are - Heterogeneous reaction involves
involved in homogeneous reaction following steps
(a) Absorption of reactants into the
interfacial layer
(b) Chemical reaction between absorbed
components
(c) Desorption of products into the phase.

- Reaction mechanism is not complex - Reaction mechanism is complex.

Example: Reaction between gas Example: Transfer of a element or ion
molecules to produce gaseous products from molten slag to molten metal in a
refining process.

54
Continued…
Most of the metallurgical reactions are heterogeneous. The main types of
heterogeneous reactions are discussed below:

Gas – Solid : Reaction of oxide with CO gas oxidation of metal

H2

Example: Fe2 O3 s + 3CO g → 2Fe + 3CO2

2Fe + O2 → 2FeO

Gas –Liquid: Gaseous reduction in hydro-metallurgy.

Liquid – Liquid: Metal – slag reaction

55
Continued…
Liquid – Solid: Leaching and corrosion reactions
Example: Leaching of sulphide with liberation of elemental of S
CuS + + 2Fe3+ ferric → Cu2+ + S + 2 Fe2+ (ferrous)
Cementation process:
Cu2+ cupric + Fe → Cu metallic copper + Fe2+ (ferrous)

Solid – Solid:
Example: Reduction of ZnO with C as
ZnO + C → Zn + CO
Metallothermic reaction
Cr2 O3 + 2Al → Cr2 + Al2 O3

56
Continued…
In metallurgy,
• The reaction kinetics are principally employed to study the Solid-Gas reactions.
Till yet, the major studies have been done on Gas interaction with solid porous
pellets.
• The reduction of iron ore pellets by the reduct gas (CO, H2) mainly depends on
pellet size, composition of pellet and volume of pore spaces available for
reaction.
• Moreover the interface thickness, rate of gas diffusion, temperature and
pressure gradient plays very vital role during the reduction of pellets.

57
Continued…
Reaction of Flat Plate: Let us consider a small plate of material having area A
and thickness d. For the first instant let’s assume that any one of the surface has
been exposed to a reacting gas.
During the course of the reaction let’s assume the thickness of the
product produced is ‘y’ and with increase in time that thickness gets increased. If
the diffusion of reacting gas through the product layer is the rate controlling. Then
rate of the reaction is given as
𝑑𝑤 𝐷.𝐴.𝐶
𝑅𝑎𝑡𝑒 𝑜𝑓 𝑟𝑒𝑎𝑐𝑡𝑖𝑜𝑛 = = (293)
𝑑𝑡 𝑦

[Where, w – Weight of product after time t, D – Diffusion co-efficient

A – Area of the surface that available for reaction
C – Concentration ]
58
Continued…
Since , Weight (w) = volume × Density = (Area × Length) × Density
= A. y. ρ (294)
Put equation (294) in equation (293), we have
𝑑 𝐴.𝑦.𝜌 𝐷.𝐴.𝐶
= (295)
𝑑𝑡 𝑦

𝑑𝑦 𝐷.𝐶 1
= × (296)
𝑑𝑡 𝜌 𝑦

𝐷𝐶
Since = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 𝐾 (suppose), then equation (296) becomes
𝜌

𝑑𝑦 𝐾
= (297)
𝑑𝑡 𝑦

𝑦𝑑𝑦 = 𝐾 𝑑𝑡 (298)

𝑦 2 = 𝐾𝑡 (299)

The above equation (299) is known as Parabolic law. 59

 LECTURE-27
JOHNSON – MEHL’S EQUATION:

Fig- Graph of α vs t 60
Continued…
JOHNSON – MEHL’S EQUATION:
 It is based on 𝛼 vs t graph.
 Initially, rate of reaction 𝛼 increase with time to a fixed extent with a
faster rate. But, after maximum point the rate of reaction 𝛼 increase
with time with a slower rate.
 It is used to find out the dimension & order of reaction.
Relation between rate of reaction and time defined by the following equation
𝑑𝛼
= 𝐾 𝑛 𝑡 𝑛−1 1 − 𝛼 (300)
𝑑𝑡

𝑑𝛼
= 𝐾 𝑛 𝑡 𝑛−1 𝑑𝑡 (301)
1− 𝛼

𝐾𝑛𝑡 𝑛
− ln 1 − 𝛼 = (302)
𝑛

61
Continued…
−1 1 𝐾𝑛𝑡 𝑛
ln 1 − 𝛼 = ln = (303)
1−𝛼 𝑛

1 𝐾𝑛𝑡 𝑛
= exp (304)
1−𝛼 𝑛

𝛼 =1− 1 (305)
𝐾𝑛 𝑡𝑛
exp 𝑛

OR

From equation (303), we can also write as

1
log 1
1− 𝛼 = 𝐾 ′𝑡 𝑛 (306)
2.303

[Where 𝐾 ′ = 𝐾
1 ]
𝑛 𝑛
62
Continued…

log log 1
1−𝛼 = 𝑛 log 𝐾 ′ + 𝑛 log 𝑡 − log 2.303 (307)
𝑑𝛼
= 𝐾𝑛 𝑡 𝑛−1 𝑑𝑡 (308)
1− 𝛼

𝑛
1 𝐾′
ln = 1 = 𝐾′ 𝑛 𝑡𝑛 (309)
1− 𝛼 𝑛 𝑛

𝑛 𝑛𝑛
1 𝐾′ 𝑡
log = (310)
1− 𝛼 2.303

1
log log = 𝑛 log 𝐾 ′ + 𝑛 log 𝑡 − log 2.303 (311)
1− 𝛼

63
Continued…
Boundary Layer Thickness (t):
 When a fluid past to the rigid interface of an immersed body or flows over a
fixed impermeable wall, it is a necessary condition that the velocity is zero at any
fixed point or surface.
 The extent of modification in flow character depends upon the viscosity
magnitude.
 For the streamlined body along with fluid flow having very small viscosity value ,
the modification effect becomes confined within a very narrow region around
the solid surfaces is known as boundary layer.
 Within the boundary layer the fluid velocity changes rapidly changes that’s gives
a steep gradient in shearing stress

64
Continued…
 A more precise criterion of well-defined laminar boundary layer thickness is the
flow with high Reynolds number but within the laminar flow.

Controlling Factors to control the reduct gas diffusion

The different rate controlling factors which control the overall rate of reduction are
given below:
1) Boundary Layer Control
• In boundary layer control is based on control of diffusion gas and heat through
the boundary layer around each particle. The diffusion rate of the reduct gas
through the boundary layer is usually proportional to the concentration
gradient of the gas across the boundary layer and further the heat flow rate
through the particles is proportional with the temperature gradient across the
boundary layer. 65
Continued…
• In most direct reduction process contact among solids and gas is achieved by
means of counter current movement of preheated gas and solids movement.
The general application boundary layer control mechanism can be observed
during blast furnace operation
2) Phase Boundary Reaction Control
• The chemical reaction at the FeO-Fe interface is the rate controlling factor.
Since In this case the reduction rate per unit area of the rest iron oxides is
remained constant with time and this mechanism is known as “Phase Boundary
Reaction Control”.
• In this case, the counter diffusion of both reduct and product gas over the outer
reduced layer is very fast in spite of same reduct gas concentration over both
the reacting and particle surface.
66
Continued…
• In this case, the reaction rate at the Fe-FeO interface is controlled the overall
reduction rate and this mechanism is preferably happen at the beginning of
reduction known as phase boundary reaction.
3) Gaseous Diffusion Control
• The mass rate of inward reduct gas flow and outward product gas flow across
the reduced Fe layer can control the reduction rate of iron oxides is called as
“Gaseous Diffusion Control” which usually occurs in large sized particles.
• When rate controlling step is the gaseous diffusion, the inward diffusion rate of
reduct gas and outward diffusion rate of product gas through the porous outer
Fe layer is slower than the overall rate of reaction.
• In this case, the reduct gas concentration decreases with increase in product
gas concentration at the interface. The variation in the gas composition is lower
down the reduction rate till to prodece a pseudo steady state. 67
Continued…
4) Mixed Control
• The combination of both Phase Boundary Reaction Control and Gaseous
Diffusion Control mechanism in controlling the reduction rate is termed as
“Mixed Control”.
• In mixed control, the gas boundary layer acts along with two other such as
gaseous diffusion and phase boundary reaction to predict the overall rate of
reaction.

68
 LECTURE-28
THERMAL ANALYSIS
 Thermal analysis represents the group of techniques in which specific physical
properties of a material are measured as a function of temperature.
 These techniques are mainly based on the measurement of temperatures at
which phase changes or any other changes may occur, the measurement of the
energy absorbed (endothermic transition) or energy evolved (exothermic
transition) during a phase transition or a chemical reaction, and the assessment
of physical changes resulting from changes in temperature.
 Various environments such as vacuum, inert, or controlled gas composition and
heating rates from 0.1 to 500°C min −1 are used for temperatures in the range
of −190- 1400 °C.

69
Continued…
 The analysis of gases released by the specimen as a function of temperature is
possible when thermal analysis equipment is coupled with a mass
spectrometer.
 On the basis of applications of type of thermal analysis techniques are varied.
 For environmental measurements, these parameters can be measured: vapor
pressure, softening temperatures, thermal stability, flammability,, and boiling
points.
 Compositional analysis offers phase diagrams, solvent retention, mineral
characterization, free versus bound water, and polymer system analysis.
 In the important area of product reliability, thermal methods provide heat-
capacity data, liquid-crystal transitions, purity, polymer quality control, glass
transitions, Curie point, and fiber properties.
70
Continued…
 Information on stability can be obtained from modulus changes, creep studies,
expansion coefficients, and antioxidant evaluation.
 Dynamic properties of materials are found from cure characteristics, impact
resistance, elastic modulus, loss modulus, viscoelastic measurements, and
shear modulus.
 Eventually, the chemical reactions can be followed through catalyst evaluation,
reaction kinetics, metal–gas reactions, heats of transition, and crystallization
phenomena.

71
Continued…
There are usually three types of thermal analysis techniques are preferred such as

I. Differential scanning calorimetry (DSC)

II. Differential thermal analysis (DTA)

III. Thermo gravimetric analysis (TGA)

Differential scanning calorimetry (DSC) :

• It consists the measurement of power required to maintain ΔT equals to zero

with reference to temperature or time.

• Instrumentation: Use two separate furnaces below 650 °C and control both

specimen and reference temperature independently.

72
Continued…

Schematic of various transition under DSC analysis

Ref: https://www.particletesting.com/thermal-analysis/ 73
Continued…
• DSC is an accurate technique.

• Common applications are measurement of glass transition temperature, fusion

temperature, predict the chemical reaction and oxidative stability,

determination of curie point and crystallization temperature

Differential thermal analysis (DTA):

• It consists the measurement of heat change as a function of temperature or

time.

• Instrumentation: Use one furnace around 500 °C in which both the specimen

and reference temperature are simultaneously controlled.

74
Continued…
Tg : Temperature above glass
transition
Tc : Temperature below glass
crystallization temperature

Schematic DTA analysis for glass sample

Ref: Munishwar et al., 2018, Optical Materials, 86, 424-432.
75
Continued…
• DTA is less accurate technique as compare to DSC and TGA.

• Common applications of DTA technique are almost same as in case of DSC

technique such as predicting the chemical reaction and oxidative stability,

measurement of glass transition temperature, fusion temperature, curie point

and crystallization temperature.

Thermo gravimetric analysis (TGA)

• It consists the measurement of mass change as a function of temperature or

time by means of kinetic value determination and/or determination of of

moisture, diluent etc. loss rate using weight loss method.

76
Continued…

Schematic of TGA Grease (Greases, like oils, contain a variety of additives) Profile
Ref: https://www.machinerylubrication.com/Read/296/grease-analysis 77
Continued…
• Instrumentation: Use one furnace around 1000 °C with linear heating rate of

(5-10) °C/min. Most of the TGA techniques are followed isothermal monitoring

by controlling the both specimen and reference temperature change to zero.

• More accurate technique and overcome the difficulties of overlapping of both

endothermic and exothermic values as by weight loss method.

• Common applications of TGA technique are determination of moisture loss,

volatile materials loss, and oxidation temperature of specimen etc. Further

TGA technique is used for decomposition and compositional analysis of multi-

component system.
78
 LECTURE-29
INTRODUCTION TO ELECTROCHEMICAL CELLS
 Electrolysis implies the processes which utilize electrical energy for extraction
of metals (Example-Cu, Al, Zn etc) which known as electro winning and for
purification of metals (Example-Cu, Al, Pb etc) which known as electro refining.
 In case of electro winning, the anode is insoluble conductor while in electro
refining, it is impure metal itself. The electrolyte in each case is a solution with
sufficiently high electrical conductivity and solute concentration. The cathode
may be pure metal or a blank of another metal.
 Electrolytic dissociation of ionic media is governed by two laws, which are
known as Faraday’s laws of electrolysis.
I. Faraday’s First Law
II. Faraday’s Second Law
79
Continued…
Faraday’s First Law: It states that “The weight of material (W) deposited at an
electrode is directly proportional to the quantity of electricity (Q) passed through
the electrolyte”.
Mathematically can be expressed as

𝑊𝛼𝑄 𝑊𝛼 𝐼×𝑡 [ 𝑆𝑖𝑛𝑐𝑒 𝑄 = 𝐼 × 𝑡] (312)

𝑊 =𝑍×𝐼×𝑡 (313)
[Where , I – Electric Current (in amp), t – Time (in sec.)
W – Weight deposited (in gm.), Z – Electrochemical Equivalent ]
N. B.: Electrochemical Equivalent (Z): It is defined as the weight deposited by a
current of 1 amp during its passage for duration of 1 sec.
Faraday’s Second Law: It states that “The weight of material (W) deposited at an
electrode is directly proportional to the equivalent weight (E) of the material”.
80
Continued…
Mathematically can be expressed as

𝑊𝛼𝐸 𝐸𝛼𝑊 𝐸 =𝐹×𝑊 (314)

𝐸 𝐴 𝐴
𝑍
𝐹= = = (315)
𝑊 𝑊 𝑍×𝑊

𝐴𝑡𝑜𝑚𝑖𝑐 𝑤𝑡. 𝐴
(𝑆𝑖𝑛𝑐𝑒 𝐸 = )
𝑉𝑎𝑙𝑒𝑛𝑐𝑦 𝑍

[Where, 𝐹– Proportionality Constant known as Faraday’s constant 𝐹 ≈

96500 Coulomb/gm. eq.
A – Atomic Mass, W – Weight deposited (in gm.)
Z – Valency, E – Equivalent weight ]
Combined 1st and 2nd laws of Faraday, we have

𝑊𝛼𝑄×𝐸 𝑄×𝐸 𝛼𝑊 (316)

81
Continued…
𝑄×𝐸 =𝐹×𝑊 (317)
Now putting 𝐸 = 𝐴 𝑍 and 𝑄 = (𝐼 × 𝑡) in equation (318), we will get

𝐹×𝑊
𝐼×𝑡 = 𝐴 (318)
𝑍

𝐼×𝑡×𝐴
𝑊= (319)
𝐹×𝑍

Some Important Parameters in Electrometallurgy:

1. Current Efficiency: It is defined as the ratio of the actual mass of the substance
(metal) liberated from an electrolyte by the passage of current to the mass of the
substance liberated theoretically according to Faraday’s law.

82
Continued…
Mathematically it is represented as

𝑇𝑕𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 𝑟𝑒𝑞𝑢𝑖𝑟𝑒𝑑

𝐶𝑢𝑟𝑟𝑒𝑛𝑡 𝐸𝑓𝑓𝑖𝑐𝑖𝑒𝑛𝑐𝑦 𝜂𝐼 =
𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐𝑖𝑡𝑦 𝑐𝑜𝑛𝑠𝑢𝑚𝑒𝑑
𝐴𝑐𝑡𝑢𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑
= (320)
𝑇𝑕𝑒𝑜𝑟𝑒𝑡𝑖𝑐𝑎𝑙 𝑎𝑚𝑜𝑢𝑛𝑡 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑

2. Electric Power: It is defined as the ratio of electric power used per day with
actual weight of metal deposited.
Mathematically it is represented as

𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑝𝑜𝑤𝑒𝑟 𝑢𝑠𝑒𝑑 𝑝𝑒𝑟 𝑑𝑎𝑦

𝐸𝑙𝑒𝑐𝑡𝑟𝑖𝑐 𝑃𝑜𝑤𝑒𝑟 𝑖𝑛 𝑤𝑎𝑡𝑡𝑠 =
𝐴𝑐𝑡𝑢𝑎𝑙 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝑚𝑒𝑡𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑
𝑉𝑜𝑙𝑡𝑎𝑔𝑒 𝑑𝑟𝑜𝑝×𝐶𝑢𝑟𝑟𝑒𝑛𝑡
= (321)
𝐴𝑐𝑡𝑢𝑎𝑙 𝑤𝑒𝑖𝑔𝑕𝑡 𝑜𝑓 𝑡𝑕𝑒 𝑚𝑒𝑡𝑎𝑙 𝑑𝑒𝑝𝑜𝑠𝑖𝑡𝑒𝑑

83
Continued…
Thermodynamics of Electrochemical Cells:
 An Electrochemical reaction involves coupling of chemical reaction with the flow
of Electric current. Many metals are extracted and refined by electrolytic
process (Zn, Al, Mg etc.).
 Electroplating and anodizing are employed for surface protection of metals and
alloys from corrosion.
 Electrochemical reactions occur in Corrosion, Hydrometallurgy and slag-metal
reactions.
 Electrochemical method used for high temperature measurement tools.
 Batteries are Electrochemical cell.

84
Continued…
 Electrochemical cells are broadly classified into two categories
a. Galvanic Cells: In this case, stored chemical energy is converted into
electrical energy.
b. Electrolytic Cells: In this case, stored electrical energy is used to do
chemical work.
Thermodynamic studies/predictions/measurements can be done properly only for
Galvanic cells. These are can be made to operate reversibly.
Daniel Cell:
Most common example of Galvanic cell is Daniel cell.
Overall Reaction: 𝑍𝑛 𝑆 + 𝐶𝑢𝑆𝑂4 𝑎𝑞 = 𝐶𝑢 𝑆 + 𝑍𝑛𝑆𝑂4 (𝑎𝑞)
Overall reaction (Ionic form): 𝑍𝑛 𝑆 + 𝐶𝑢+2 𝑎𝑞 = 𝐶𝑢 𝑆 + 𝑍𝑛+2 (𝑎𝑞)

85
Continued…
Reaction Consists of
Anodic Reaction: 𝑍𝑛 𝑆 = 𝑍𝑛+2 𝑎𝑞 + 2𝑒(𝑂𝑥𝑖𝑑𝑎𝑡𝑖𝑜𝑛)
Cathodic Reaction: 𝐶𝑢+2 𝑎𝑞 + 2𝑒 = 𝐶𝑢 𝑆 (𝑅𝑒𝑑𝑢𝑐𝑡𝑖𝑜𝑛)

86
Schematic of Daniel Cell
 LECTURE-30
Electrolytes: Electrolytes are ionic liquids or solids and classified as follows

Classification of Electrolytes

Examples of current carrying

Sl. No. Electrolytes
Ions

1 Aqueous Solutions 𝑁𝑎+ , 𝐻 + , 𝐶𝑙 − 𝑒𝑡𝑐

2 Molten Salts 𝑁𝑎+ , 𝐾 + , 𝐶𝑑 + , 𝐶𝑙 − , 𝐹 − 𝑒𝑡𝑐

3 Molten Slags 𝐶𝑎+2 , 𝑀𝑛2+ 𝑒𝑡𝑐

4 Solid Oxide Electrolytes 𝑂2−

5 Other Solid Electrolytes 𝑁𝑎+ , 𝐴𝑔+ , 𝐹 − , 𝐿𝑖 + 𝑒𝑡𝑐

87
Continued…
 Aqueous solutions constitute the electrolytes in the Daniel cell. For example if
we have considered aq. ZnSO4 solution, then add up some amount of H2SO4 to
improve its electrical conductivity. Due to high mobility H+, it will carry major
fraction of current. The reaction at cathode, primarily discharge of Zn2+ ions
and deposition of Zn.
 Similarly by taking molten salts at high temperature may consists of NaCl, KCl
and CdCl2. But only Cd2+ will participate in electrochemical reaction.
 Generally, for aqueous solutions as electrolyte, the electrochemical cell
operated at room temperature.
 For molten salts, it is about (400-900) 0C.
 For molten slag case, it is about (1000-1500) 0C.

88
Continued…
Solid Electrolyte:
 In case of solid electrolytes, the operated temperature generally very high and
it depends upon the nature of electrolytes.
 Out of many, Zirconia (ZrO2) is well known solid electrolyte. It is a high
temperature ceramic material.
 Zirconia is stable at high temperature but it undergoes some phase
transformation during heating and cooling. Due to which there thermal
stresses developed and that may be cause failure in service.
 To remove these chances, there are various oxides such as CaO, MgO and Y2O3
added and as a result melting point of ZrO2 get increased to approximately
2400 0C.

89
Continued…

Schematic of solid-state electrolyte used battery and compared with conventional

battery
Ref: https://chargedevs.com/newswire/japanese-researchers-use-superionic-conductors-
as-electrolytes-for-solid-state-batteries/
90
Continued…
 Let us consider the example of ZrO2-CaO solid solution.
 In pure ZrO2, Zr4+ ions occupy cationic sites and O2- ions occupy anionic sites.
So after the addition of CaO to ZrO2, some of Ca2+ replace the Zr2+ from the
cationic sites and allows the movement of O2- ions.
 Since Ca2+ and Zr4+ are almost immobile around above (700-800)0C. Thus the
cell operated at high temperature.
 Besides ZrO2-CaO solid electrolytes, other important solid electrolytes are
ZrO2-Y2O3, ThO2-Y2O3, CaF2 doped with YF3 etc.

91
Continued…
THERMODYNAMIC OF REVERSIBLE GALVANIC CELLS:
Some electrical cell can be made to behave either as a Galvanic cell or as
an electrolytic cell.
Example: Daniel Cell.
• If external DC source connected to the cell having imposed voltage (Vext), that
opposes that of the Daniel Cell voltage (Vcell). Then depending on magnitude of
Vext and Vcell, we have two conditions

Condition-1: 𝑉𝑒𝑥𝑡 < 𝑉𝑐𝑒𝑙𝑙 𝐶𝑒𝑙𝑙 𝑏𝑒𝑕𝑎𝑣𝑒𝑠 𝑎𝑠 𝐺𝑎𝑙𝑣𝑎𝑛𝑖𝑐 𝑐𝑒𝑙𝑙

Cell reaction: 𝑍𝑛 𝑆 + 𝐶𝑢𝑆𝑂4 𝑎𝑞 = 𝑍𝑛𝑆𝑂4 𝑎𝑞 + 𝐶𝑢 𝑆

Condition-2: 𝑉𝑒𝑥𝑡 > 𝑉𝑐𝑒𝑙𝑙 𝐶𝑒𝑙𝑙 𝑏𝑒𝑕𝑎𝑣𝑒𝑠 𝑎𝑠 𝑒𝑙𝑒𝑐𝑟𝑜𝑙𝑦𝑡𝑖𝑐 𝑐𝑒𝑙𝑙

Cell reaction: 𝐶𝑢 𝑆 + 𝑍𝑛𝑆𝑂4 𝑎𝑞 = 𝐶𝑢𝑆𝑂4 𝑎𝑞 + 𝑍𝑛(𝑆)
92
Continued…
 In an electrolytic cell, chemical reaction occurs only if current allowed to flow
through the cell. But if no current flow i. e. circuit becomes open then at that
time voltage is known as emf or electromotive force of the Galvanic cell.

 Reversible Galvanic cell possible if and only

• Use of a voltmeter of very high resistance makes current flow negligible.
• Impose voltage from external source, 𝑉𝑒𝑥𝑡 ≅ 𝑉𝑐𝑒𝑙𝑙 i. e. emf of the cell and as a
result current flow is negligible.

93
Continued…
RELATION BETWEEN CELL EMF (E) AND FREE ENERGY OF CELL REACTION (∆𝑮)
From a reversible process
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 − 𝛿𝑊 ′ (322)
[Where, W’ – Work done other than work done against pressure]
At constant P and T,
𝑑𝐺 = −𝛿𝑊 ′ (323)
In case of a reversible Galvanic cell,
𝛿𝑊 ′ = 𝐸𝛿𝑞 (324)

𝑆𝑖𝑛𝑐𝑒 𝑊 = 𝑉𝐼𝑡 = 𝐸𝑞 𝛿𝑊 = 𝐸𝛿𝑞

[Where, E – Cell Emf

𝛿𝑞 − Infinitesimal quantity of electric charge transformed
across the cell due to the chemical reaction in the cell. ]
94
Continued…
Again from the Faraday’s law of electrolysis,
𝛿𝑞 = 𝑍𝐹𝑑𝑛 (325)

𝑆𝑖𝑛𝑐𝑒 𝐹𝑟𝑎𝑑𝑎𝑦 ′ 𝑠 𝑙𝑎𝑤, 𝑤𝑒 𝑘𝑛𝑜𝑤 𝑡𝑕𝑎𝑡

𝐹×𝑊 𝑊
𝐼×𝑡 = 𝑞 = 𝑍𝐹 = 𝑍𝐹𝑛
𝐴 𝐴
𝑍
𝛿𝑞 = 𝑍𝐹𝑑𝑛
[Where, n – Number of moles]
Putting equation (325) in the equation (324), the equation becomes
𝛿𝑊 ′ = 𝐸 × 𝑍𝐹𝑑𝑛 = 𝑍𝐹𝐸𝑑𝑛 (326)
Again putting the equation (326) in equation (323), the equation becomes
𝑑𝐺 = −𝛿𝑊 ′ = −𝑍𝐹𝐸𝑑𝑛 (327)
95
Continued…
So for 1 mol of the above equation (327) becomes

𝑑𝐺 = −𝑍𝐹𝐸 ∆𝐺 = −𝑍𝐹𝐸 (328)

Similarly, at standard state equation (327) becomes
𝑑𝐺 0 = −𝑍𝐹𝐸 0 ∆𝐺 0 = −𝑍𝐹𝐸 0 (329)

Since we know
∆𝐺 = ∆𝐺 0 + 𝑅𝑇 ln 𝐽 (330)
Now using equation (328) and (329) in the equation (330), we will get
−𝑍𝐹𝐸 = −𝑍𝐹𝐸 0 + 𝑅𝑇 ln 𝐽 (331)
𝑅𝑇
− 𝐸 = −𝐸 0 + ln 𝐽 (332)
𝑍𝐹

𝑅𝑇
𝐸 = 𝐸0 − ln 𝐽 (333)
𝑍𝐹
96
Continued…
The above equation (333) is known as Nernst’s equation and it can be written as
2.303𝑅𝑇
𝐸 = 𝐸0 − log 𝐽 (334)
𝑍𝐹

Sign Convention for EMF:

𝑍𝑛 𝑆 /𝑍𝑛𝑆𝑂4 𝑎𝑞 //𝐶𝑢𝑆𝑂4 𝑎𝑞 /𝐶𝑢(𝑆)

𝑆𝑎𝑡 𝑆𝑎𝑡

• Single vertical lines separate electrode from electrolyte. Double vertical

lines represented the porous diaphragm.
• If the reaction proceeds spontaneously from left to right, then the sign of
the E will be positive and for reverse case right to left, sign of E is negative.

97
 QUIZ TEST-6
Q.1 –In metallurgical processes, what type of reactions are more preferably
happened and why, explain with the help of supportive examples.
Q.2 –How the boundary and phase controlling mechanisms affect the overall
rate of reaction?
Q.3 –For mass loss analysis, which type of thermal analysis technique is
preferred?
Q.4–Write the combined expression for 1st and 2nd Faraday’s laws of electrolysis.
Q.5 –Why Zirconia is the more preferred solid electrolyte in contrast to other
available solid electrolytes?
Assignment-2
Briefly discuss the applications of thermal analysis techniques’ in specific to
“metallurgical processes”.
98
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