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Metallurgical Engineering
Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
MT – 2102 Credit:04
Instructors:
Dr. C. K. Behera
and
Metallurgical Thermodynamics
Mr. J. K. Singh
Marks Distribution
D E P A R T M E NT O F
Metallurgical Engineering
Institute of Technology Banaras Hindu University
Sessional Test - I 15
Sessional Test - II 15
Assignments / Attdn. 10
End Semester 60
Metallurgical Thermodynamics
Grading System
D E P A R T M E NT O F
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S 90 -100
A 80-89
B 70-79
C 60-69
D 50-59
E 40-49
F < 40
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D E P A R T M E NT O F
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Course Content Institute of Technology Banaras Hindu University
Basic Principles
Extensive and intensive properties, thermodynamic systems and processes. First Law of
Thermodynamics, enthalpy, Hess’ Law, heat capacity, Kirchhoff’s law. Second Law of
Thermodynamics, entropy, entropy change in gases, significance of sign change of entropy.
Trouton’s and Richard’s rules. Driving force of a chemical reaction, combined statement of first and
second laws of thermodynamics, Helmholtz and Gibbs free energies. Ellingham diagram,
Equilibrium constants, van’t Hoff’s isotherm, Le Chatelier principle. Clausius-Clapeyron equation.
Maxwell’s equations, Third Law of Thermodynamics.
Solution Thermodynamics
Solution, mixture and compound. Raoult’s law: activity, ideal solution, standard state. Partial
molar quantities, Gibbs-Duhem equation, chemical potential, fugacity, activity and equilibrium
constant. Free energy of mixing, excess and integral quantities. Regular solutions, -function.
Dilute solutions: Henry’s and Sievert’s laws. Alternative standard states. Gibbs-Duhem integration
Statistical concept of entropy. Elements of Gibbs Phase Rule and its applications.
Experimental Techniques
Determination of thermodynamic quantities by different techniques, viz. calorimetry, chemical
equilibria, vapour pressure and electrochemical: aqueous, fused and solid electrolytes; formation,
concentration and displacement cells.
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Suggested Reading D E P A R T M E NT O F
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Metallurgical Thermodynamics
Scope, Basic Concepts and D E P A R T M E NT O F
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Definitions Institute of Technology Banaras Hindu University
Thermodynamics is that branch of science which deals with the study of the
transfer and conversion of energy from one form into other and its
conversion to work.
It deals with only conventional forms of energies like electrical, mechanical,
chemical. etc.
The non-conventional energy like nuclear energy related to atomic and sub-
atomic particle forms has to be dealt separately because in that case all
matter would have to be considered as per the famous Einstein’s equation :
E = mC2 .
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Scope, Basic Concepts and D E P A R T M E NT O F
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Definitions Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Scope, Basic Concepts and D E P A R T M E NT O F
Metallurgical Engineering
Definitions Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Scope, Basic Concepts and D E P A R T M E NT O F
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Definitions Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Energy
D E P A R T M E NT O F
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Metallurgical Thermodynamics
Scope,
SystemBasic
and Concepts and
Surrounding D E P A R T M E NT O F
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Definitions Institute of Technology Banaras Hindu University
Any portion of the universe selected for consideration is known as the system
or thermodynamic system.
For example a live animate body like tree and human being are not system. All
inanimate aggregates are called systems as they have their fixed chemistry
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Classification of D E P A R T M E NT O F
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thermodynamic systems
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Thermodynamic Systems
Single Multi
Homogeneous
component component
Heterogeneous
Isolated Open
Closed
Heterogeneous
Neither Both
Homogeneous
Heterogeneous
Homogeneous
matter nor matter Can
energy is and exchange
exchanged energy energy
with exchange not the
surrounding occurs matter
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Homogeneous and D E P A R T M E NT O F
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Heterogeneous system
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D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
All other variables whose values get fixed with the specification of
independent state variables are referred to as dependent state
variables.
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Extensive and Intensive D E P A R T M E NT O F
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State properties Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Extensive and Intensive D E P A R T M E NT O F
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State properties Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
Path and State Functions D E P A R T M E NT O F
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D E P A R T M E NT O F
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Properties of State Function
D E P A R T M E NT O F
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Relationship among D E P A R T M E NT O F
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state variables
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Z Z
dZ dX dY
X Y Y X
And
Y Y
dY dX dZ
X Z Z X
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Relationship among D E P A R T M E NT O F
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state variables
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state variables
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Similarly, Y 1
Z 1
X Z X and
Y X Y X
Z Z
Y
Finally after substitution we can write
Z Y X
1
Y X X Z Z Y
similarly
X Y Z
1
Y Z Z X X Y
The above two expressions correlate the partial differentials of three state
variables w.r.t one another and are popularly called reciprocity theorem.
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D E P A R T M E NT O F
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Reversible and D E P A R T M E NT O F
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Irreversible Processes
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Reversible and D E P A R T M E NT O F
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Irreversible Processes
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Experimental Evidence D E P A R T M E NT O F
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Leading to First Law
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• For number of
thermodynamic cycle each
consisting of number of
processes
W i
4.184
q i
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Experimental Evidence D E P A R T M E NT O F
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Metallurgical Thermodynamics
Experimental Evidence D E P A R T M E NT O F
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Metallurgical Thermodynamics
Experimental Evidence D E P A R T M E NT O F
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know that q and W cannot be equal we can consider two distinct cases:
ii) q > W: The heat is partly retained by the system itself and partly
returned to the surrounding in the form of work done.
In both the cases system acts as a reservoir of energy. This stored energy
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Internal Energy D E P A R T M E NT O F
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It consists of
macroscopic kinetic energy due to motion of the system as a
whole.
potential energy of the system due to its position in the force
field.
kinetic energy of atoms and molecules in the form of
translation, rotation and vibration.
energy of interaction amongst atoms and molecules
columbic energy of interaction amongst electrons and nucleii
in atoms
energy contents of the electrons and nucleii of atoms
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Internal Energy D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Internal energy in terms D E P A R T M E NT O F
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of Partial Derivatives
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Internal energy in terms D E P A R T M E NT O F
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of Partial Derivatives
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Enthalpy
D E P A R T M E NT O F
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dV P V II V I
II II
w PdV P
I I
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Enthalpy
D E P A R T M E NT O F
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Hence the above two partial differentials are equal proving thereby that
the equation for dH is an exact differential equation and thus leading to
the conclusion that H is a function of state.
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Enthalpy
D E P A R T M E NT O F
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Metallurgical Thermodynamics
Enthalpy
D E P A R T M E NT O F
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H U
0
P T P T
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Internal Energy Vs Enthalpy
D E P A R T M E NT O F
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Internal energy is all that energy stored in the system. But, What does
enthalpy mean? This can best illustrated by the example of calcination of
calcium carbonate.
CaCO3 = CaO + CO2
The enthalpy change of the process will be equal to invested
bond energy to break the bond between CaO and CO2 or internal energy
provided both CaO and CO2 are solids.
However if CO2 is allowed to form gas then breaking of one mole of CaCo3
nearly 22.4 ltrs. of CO2 will be formed. The expansion in volume will take
place.
In this process of expansion the system will do work equivalent to ∫ PdV as
mechanical work on the surrounding.
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Internal Energy Vs Enthalpy
D E P A R T M E NT O F
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Heat Capacity
D E P A R T M E NT O F
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Heat Capacity
D E P A R T M E NT O F
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q U
CV
T V T V
Since at constant volume δq = dU.
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Heat Capacity
D E P A R T M E NT O F
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q H
C P
T P T P
Since at constant pressure δq = dH. Further we can write
dH = CP dT
T2
Or H T2 H T1 T1
C P dT
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D E P A R T M E NT O F
H U U PV U
C P CV
T P T V T V T V
U U V
P
T P T V T P
And we know U U
dU dV dT
V T T V
differentiating w.r.t T at constant P we get
U U V U
T P V T T P T V
Metallurgical Thermodynamics
D E P A R T M E NT O F
U
Putting the value of we get
T P
U V V V U
C P CV P P
V T T P T P T P V T
V
C P CV P
T P
RT
For ideal gas V
P
So C P – CV = R
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Application of First law D E P A R T M E NT O F
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to Thermodynamic Processes Institute of Technology Banaras Hindu University
With the help of the first law, one is able to calculate the changes
taking place in internal energy and enthalpy of a system during a
thermodynamic process.
Processes which are frequently studied and to which this law will
be applied include: i) Isothermal process ii) Adiabatic process iii)
polytropic processes.
In all these cases working substance of the system shall be
considered to be an ideal gas
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Application of First law D E P A R T M E NT O F
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to Thermodynamic Processes Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Application of First law D E P A R T M E NT O F
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to Thermodynamic Processes Institute of Technology Banaras Hindu University
If Vf < Vi i.e. for compression of gas q is negative i.e. the system will impart
heat to the surroundings at the same time absorbing mechanical energy from
them in the form of mechanical work done on it.
The change in enthalpy of the system will be:
H H f H i U ( Pf V f PiVi )
R (T f Ti ) 0
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Application of First law D E P A R T M E NT O F
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to Thermodynamic Processes Institute of Technology Banaras Hindu University
ii) Adiabatic Process: There is no exchange of heat between the system and
surrounding i. e. δq = 0. Hence first law takes the form
dU = - δW = - P dV
Or dU = CV dT = - P dV
This indicate that system will perform work at the cost
of its internal energy and therefore the lowering of
temperature of the system will result.
dT CV T f Ti
Tf
Adiabatic work done (w) CV Ti
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D E P A R T M E NT O F
Or T V 1 Const Or P V Const
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D E P A R T M E NT O F
P V Const
As for such process.
This on integration lead to the expression
Pi Vi Vi
1
H 1
1 V f
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D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
P V n const.
PiVi Vi
n 1
1
n 1 V f
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D E P A R T M E NT O F
Pf V f PV C P V Pf V f
CV i i V i i 1
R R R PiVi
CV Pi Vi V i
n 1
1
R V f
From the first law heat exchanged q is obtained as
C n 1 R Pi Vi V
n 1
q V i 1
R n 1 V f
For n = γ; q = 0 obtained from the above expression which is true for adiabatic
process.
Metallurgical Thermodynamics
D E P A R T M E NT O F
CV R Pi Vi Vi
n 1
H
1
R V f
Or
C P Pi Vi Vi
n 1
H 1
R V f
Above equation show that for n = 1 i.e. isothermal process with ideal gas ,
both
change in internal energy and enthalpy
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Thermodynamics
Summary of Thermodynamic D E P A R T M E NT O F
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Processes
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D E P A R T M E NT O F
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Hess’s Law D E P A R T M E NT O F
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It states that the total heat exchanged in a given chemical reaction, which may take place
under constant pressure, volume or temperature is the same irrespective of the fact
whether it is made to take place over a path involving formation of number of
intermediate products or over the one involving the formation of final product from the
reactant directly in one stage.
ΔH =ΔH1+ΔH2+ΔHx+ΔHy
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Hess’s Law D E P A R T M E NT O F
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Variation of heat Capacity D E P A R T M E NT O F
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with Temperature
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Variation of heat Capacity D E P A R T M E NT O F
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with Temperature
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Variation of Enthalpy D E P A R T M E NT O F
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with Temperature
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Enthalpy change
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Metallurgical Thermodynamics
Classification of D E P A R T M E NT O F
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Enthalpy change
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Classification of D E P A R T M E NT O F
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Enthalpy change
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a b T c T dT
T
2
H T H 298
298
a T 298 T 298 c
b
2
2 2 1
T 1
298
A T B T 2 C T 1 D
Where A, B, C and D are lumped parameters and functions
of empirical constants a, b, c
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Classification of D E P A R T M E NT O F
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Enthalpy change
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Metallurgical Thermodynamics
Classification of D E P A R T M E NT O F
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Enthalpy change
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Enthalpy change
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Classification of D E P A R T M E NT O F
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Enthalpy change
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Some comments:
• For calculation of enthalpy change, reactions, dissolutions and
phase transformations has been assumed to occur
isothermally. Since enthalpy is a state property, it depends
only on initial and final states and not the path.
• For a reversible isothermal process, the temperature remains
constant all through. If the process is not reversible, then
temperature at the beginning and end of a process would be
same. In between, temperature can vary significantly.
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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Kirchoff’s Law D E P A R T M E NT O F
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Utility:
It allows us to calculate the enthalpy changes at various
temperatures, provided the enthalpy is known at some other
temperature, and the heat capacity of the reactants and
products are known in the range of temperatures under
consideration.
Derivation:
Consider a chemical reaction at temperature T1 whose enthalpy
change is ΔH1. Calculate the enthalpy change ΔH2 at
temperature T2.
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Kirchoff’s Law D E P A R T M E NT O F
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Metallurgical Thermodynamics
Kirchoff’s Law D E P A R T M E NT O F
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T2
H 2
T1
C Px C P dT
y
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Kirchoff’s Law D E P A R T M E NT O F
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According to Hess’s law the heats absorbed during the two ways of
producing z must be the same since the initial conditions of the
reactants and final conditions of the products are in each case the
same. T2
T2
H 2
T1
C Px C P dT
y = H1
T1
C Pz dT
Or
H 2 H 1
T2
T1
C Pz
C Px C Py dT
T2
Or H 2 H 1 T1
C P dT
Or T2
H 2 H 1 T1
C P dT
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Kirchoff’s Law D E P A R T M E NT O F
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Since all the terms are known in the right hand of the equation, ΔH2
can be calculated. We know
T2
H 2 H 1 T1
C P dT
H
Or C P
T P
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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Enthalpy change:
H (a → c) = U (a→c) + (Pc Vc – Pa Va)
= - 9.13 + n R (Tc – Ta)
= - 9.13 + 4.09 x 8.3144 x (119 - 298)
= - 9.13 - 6.0870 kJ = - 15.2170 kJ
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
1000
H 1000 H 298 C
298
p .dT
1000
= 117800 + ∫(
298
7.06 6.88 x10 3
) T + 9.52 x105 T 2
)dT
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D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
The reaction is
1 3
N 2 g H 2 g NH 3 g H 298
0
11030 cal / mol
2 2
1 3
C p C p , NH C p N 2 C p H 2
3 2 2
= -7.457 + 7.38 x 10-3T – 1.409 x 10-6T2
298
ΔH 273 = ΔH 298 - ∫ ΔC dT
273
p
298
-11030 - ∫(
273
7.457 + 7.38 x 10 3 T 1.409 x10 6 T 2 ) dT
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
1000
ΔH 1000 = ΔH 298 + ∫ ΔC dT
p
298
1000
= -11030 + ∫(
298
7.7457 + 7.38 x10 3 T 1.409 x10 6 T 3 ) dT
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D E P A R T M E NT O F
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Problem- 4 Institute of Technology Banaras Hindu University
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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CT-I D E P A R T M E NT O F
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Solution
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ΔH1123 = ΔH 298 + ∫ ΔC
298
p1 dT - ΔH tr + ∫ ΔC
1033
p2 dT
1 3
ΔC p1 = C p ,Feo - C p ,Fe,mag - C p ,O 2 = 3.9 -4.42 ×10 T -0.47 ×105 T 2
2
1 3
ΔC p 2 = C p ,Feo -C p ,Fe,nonmag - C p ,O 2 = -0.92 +1.5 ×10 T -0.47 ×105 T 2
2
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CT-I D E P A R T M E NT O F
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Solution
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dT = ( ∂∂TP ) V dP + ( ∂∂VT ) P dV
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CT-I D E P A R T M E NT O F
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Solution
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( )
∂M
∂P v = ∂2U
∂P∂V + 1 -( ∂T
) ( )
∂S
∂P v ∂V p -T ∂ 2S
∂P∂V -( ∂S
) ( )
∂T
∂P v ∂V p -S ( ∂ 2T
∂P∂V )
( )
∂N
∂V P = ∂2U
∂P∂V + 1 -( ∂T
) ( )
∂S
∂ P v ∂V p -T ∂ 2S
∂P∂V -( ∂S
) ( )
∂T
∂P v ∂V p -S ( ∂ 2T
∂P∂V )
So G is a function of state
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CT-I D E P A R T M E NT O F
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Solution
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(b)
dH = TdS + VdP
[
dH = T ( ∂P
∂S
]
) v + V dP + T( ∂V∂S ) P dV
= MdP + NdV
( ) = ( ) ( ) + T( ) + 1
∂M
∂V P
∂T ∂S
∂V P ∂P V
∂ 2S
∂P∂V
( ∂P ) V = ( ∂P ) V ( ∂V ) P + T ( ∂P∂V )
∂N ∂T ∂S ∂ S 2
Metallurgical Thermodynamics
Second law of D E P A R T M E NT O F
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Thermodynamics Institute of Technology Banaras Hindu University
Introduction
System which are away from equilibrium, upon initiation, shall
move towards equilibrium and such processes are referred to as
natural or spontaneous or irreversible processes.
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Second law of D E P A R T M E NT O F
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Thermodynamics Institute of Technology Banaras Hindu University
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Similarly heat can not flow from a colder to a hotter body unless
aided by the surroundings in the form of compressor energy as in
the refrigerator.
But in chemical processes it is not readily possible to assess as to
what is a natural or unnatural process. This can only be evaluated
from the equilibrium state of the system.
The knowledge of equilibrium CO / CO2 ratio in contact with Fe
or FeO can only guide us as to how to prevent oxidation of iron or
effect reduction of iron oxide by providing a suitable CO / CO2
gas mixture as surroundings.
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Heat Engines Institute of Technology Banaras Hindu University
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Efficiency of a heat engine Institute of Technology Banaras Hindu University
Definition:
HOT
work done per cycle
efficiency
heat input per cycle
Q1
W
Q1
Engine W
•Because engine returns to
original state at the end of each
cycle, U(cycle) = 0, so W = Q2
Q1 - Q2
•Thus: Q 1 Q 2 1 Q 2
Q1 Q1 COLD
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Efficiency of a heat engine Institute of Technology Banaras Hindu University
BUT………….
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Both processes
opposite are perfectly COLD HOT
Q
OK according to First
Law (energy
conservation)
WARM WARM
COLDER HOTTER
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Rudolf Clausius (1822-1888)
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How to design a “perfect” D E P A R T M E NT O F
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Sadi Carnot (1796-1832)
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The Carnot Cycle (I): D E P A R T M E NT O F
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P Q1
a
b
b
T1
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The Carnot Cycle (II): D E P A R T M E NT O F
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P
a
b b Piston
T1
c
T2 c
V
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The Carnot Cycle (III): D E P A R T M E NT O F
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P
a d
b
T1
d c
T2 c Piston
V
Q2
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The Carnot Cycle (IV): D E P A R T M E NT O F
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Gas
Gas isis compressed
compressed Gas
adiabatically
adiabatically,, temperature
temperature
rises
rises from
from TT22to
to TT11and
andthe the
piston
piston isis returned
returnedto to its
its
original
original position.
position. Work done
The work a
isdone
the shaded
per cyclearea.
is the shaded
area.
d Piston
P
a
b
W T1
d c
T2
V
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Efficiency of ideal gas D E P A R T M E NT O F
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P Q1
Q1 Q 2 Q2 a
1
Q1 Q1 b
W T1
d c
T2
V
Q2
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Isothermal expansion D E P A R T M E NT O F
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P Q1
a
b
T1
Va Vb V
Vb
Q1 Wab nRT1 ln
Va
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Isothermal compression D E P A R T M E NT O F
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P
a
b
T1
d c
T2
V
Q2
Vc
Q 2 Wcd nRT 2 ln
Vd
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Efficiency of ideal gas D E P A R T M E NT O F
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V
Q1 nRT 2 ln c
P Q Vd
a 1 2 1
Q1 Vb
b nRT1 ln
T1
Va
W
d c
T2
V
Q2
T1V b 1 T 2Vc 1
(1) T2
V b Vc 1
1 1
(1) (2) T1
T1V a T 2Vd (2) V a Vd
Q1 Q 2
T1 T 2
Adiabatic processes
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So……..
For all Carnot Cycles, the following results hold:
Tc
1
Th
Qc Q h Qc Q h Conservation
0
Tc T h Tc T h of “Q/T”
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The expression
Qc Q h Qc Q h
0
Tc T h Tc T h
Was derived from expressions for efficiency, where
only the magnitude of the heat input/output matters.
If we now adopt the convention that heat input is
positive, and heat output is negative we have:
Qc Q h
0
Tc T h
dQ
In other words
cycle
T
0
For any reversible cycle:
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D E P A R T M E NT O F
dQrev
dS
T
Reversible cycle
For whole cycle:
dQ rev B
S
T
cycle
0 P
path1
B A
dQrev dQ rev
A
T
path 1 B
T
path 2
0 A
path2
V
B B
dQ rev dQ rev
A
T
path 1 A
T
path 2
Entropy change is
path independent
→ entropy is a
thermodynamic
function of state
S BA (path 1) S BA (path 2) S B S A
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Irreversible processes
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Qc Tc Qc Tc
c 1 1 irrev 1 1
Qh rev Th Qh irrev Th
Qc Tc Qc Tc Qc Qh
Qh irrev Th Q h irrev Th Tc irrev Th
Qh Qc
0
T h irrev T c irrev
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Irreversible processes
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dQirrev
cycle
T
0 For irreversible cycle
Irreversible cycle
Path 1 B ( irrev ) A( rev )
B
dQirrev dQ rev
(irreversible)
P 0
T T
Path 2 A( irrev ) B ( rev )
(reversible)
B ( irrev ) B (rev )
dQirrev dQ rev
A
A( irrev )
T
A( rev )
T
V
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Irreversible processes
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dQ irrev
dS
General Case T
dQ
dS
T
Equality holds for reversible change, inequality holds for irreversible change
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“Entropy statement” D E P A R T M E NT O F
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dS 0
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What is an “isolated system”
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Entropy changes: a summary D E P A R T M E NT O F
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Dependence of entropy D E P A R T M E NT O F
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Volume dependency D E P A R T M E NT O F
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q rev 1
We know; dS
T
dU d PV
T
U U
dU dT dV
and T V V T
1 U 1 U
So dS dT P dV
T T V T V T
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So we can write
1 U P
dS dT dV
T T V T V
In case of gas one can directly integrate the above expression to calculate
the change in entropy during a process.
However, in case of solid and liquids, the equation of state is not known
P
and T can also not be determined experimentally. Hence in such cases
V
P V P
.
T V T P V T
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We know:
q rev 1 P 1
dS dU dV dU P dV
T T T T
From the definition of the enthalpy, one can get
Therefore, dH dU P dV VdP
1 V
dS dH dP
T T
H H
dH dT dP
T P P T
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1 H V
V
T P T P T P
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Relationship between CP&CV D E P A R T M E NT O F
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P V P
.
T V T P V T
1 V 1 V
V T P V P T
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U
• Elimination of V T from the above equation leads to the relation
P V
C P C V T
T V T P
• Or
2 V T
CP CV
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S1 p1 Change S2 p2
v1 T1 v2 T2
Ideal gas
dq/T = Cv .dT/T + R dV/V = dS
T2 v2
S = S2 –S1 = dT dv
Cv ∫ +R ∫
T1
T v1
v
On integration S = Cv ln T+2 R ln v2
T1 v1
Entropy change can be calculated when temperature and volume
change take place on heating an ideal gas
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S = Cv ln (T2/T1) + R ln (T2p1/T1p2)
= Cv ln (T2/T1) + R ln (T2/T1 )+ R ln (p1/p2 )
Or S = Cp ln (T2/T1 )– R ln p2/p1
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As the system absorbs heat, its entropy will increase e.g. with
melting and boiling.
T2
S= S2 – S1 = Cpd ln T
T1
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Significance of sign of entropy D E P A R T M E NT O F
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change of a process in closed system
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• T1 – T2 is the measure of
irreversibility of this process.
This also denote the how much
heat will flow Insulation
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T1 > T2 ; Sirr > 0 (+ve) : The entropy change of a real process is greater
than zero(+ve).
T1 = T2 ; Srev = 0 (zero): Dynamic equilibrium exists between two vessels
and there is no heat transfer.
T1 < T2 ; Sirr < 0 (-ve). : Entropy change is negative and the process
proceeds in the reverse direction.
Sign of entropy change shows the direction of flow of heat energy.
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Entropy changes associated D E P A R T M E NT O F
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with phase transformation
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TV
H 0
S 0tr tr
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Tm C 0P s H 0m Tb C 0P l
S0T S0298 298 T
dT
Tm
Tm T
dT
H 0V T C g
0
P
dT
TV Tb T
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Entropy changes in D E P A R T M E NT O F
S S
0
T
0
AB (at T) S (at T) S (at T) S
0
C
0
A
0
BC (at T)
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S0T2 S0T1 S
product
0
T2 S0T1 S
Re ac tan t
0
T2 S0T1
T2 C P product T2 C P reac tan t
S 0
T1 dT dT
T1 T T1 T
CP T2
S 0
T1 dT
T1 T
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q rev
dS for an infinitesimal, isothermal reversible process.
T
Entropy is times arrow i. e. a fundamental indicator of
time.
Entropy has the relationship with heat not available for
work.
Entropy is a measure of disorder of a system.
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Combined statement of D E P A R T M E NT O F
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first and second law Institute of Technology Banaras Hindu University
If a system is capable of doing only mechanical work the first law equation can be put
as:
dU = δq – P dV. It is not exact differential. Holds true for the reversible processes.
The second law for the reversible process gives
dS = δq rev / T or δq = T dS
The two laws therefore can lead to
dU = TdS – P dV or TdS = dU + PdV
This is the combined statement of first and second law.
It includes only those terms which are state functions only and
hence is exact differential equation.
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Is this driving force or potential the same under all conditions of the system or
it varies from condition to condition of the system ?
Heat flow s from higher to lower temperature. The flow is possible due to
higher thermal potential.
Also higher electrical voltage is driving the electrons under the influence of
electrical potential as voltage.
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So far the internal energy, enthalpy and entropy have been evolved as
energy parameters but it is not yet known as to whether these act as
potential in driving a particular process?
It must be noted that for natural process the system moves from lower
to a higher entropy level hence entropy can not be considered as a
driving force.
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Can internal energy and enthalpy qualify as potentials capable of driving the
process towards equilibrium if already at higher levels ?
If internal energy and enthalpy are potential terms then changes in them will have
to be zero at equilibrium and these will have to decrease for natural changes and
increase for unnatural changes.
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U U
dU dS dV
S V V S
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We know: dU = TdS – P dV
On comparison this leads to
U and U
T P
S V V S
By specifying U as function of S and V it is possible to evaluate T and
P thereby describing the system fully.
By describing U as a function of any other two variables, it is not
possible to describe the system fully.
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Potentials under constant pressure D E P A R T M E NT O F
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H H
T and V
S P P S
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A A
S and P
T V V T
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Again dG = dH – T dS – SdT
On putting dH = dU + P dV + V dP
dG = dU + P dV + VdP – T dS – SdT
Putting in this dU + P dV = T dS
dG = T dS + V dP – T dS – S dT
= V dP – S dT
At constant temperature when dT = 0 ; dG = V dP
Or dG
V
d P T
Since G is a state function any change in G can be
represented as G = U – T S + (P V)
= - Wrev + (P V)
The change of Gibbs free energy during a process is equal and opposite in sign to the
net reversible work obtainable from the process occurring under isothermal condition
when corrected for change in volume under isobaric condition.
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(dU)S, V = 0 (U)S, V = 0
(dH)S, P = 0 (H)S, P = 0
(dA)T, V = 0 (A)T, V = 0
(dG)T, P = 0 (G)T, P = 0
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of a Chemical Reaction
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The Driving Force D E P A R T M E NT O F
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The Driving Force D E P A R T M E NT O F
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The Driving Force D E P A R T M E NT O F
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The Driving Force D E P A R T M E NT O F
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The Driving Force D E P A R T M E NT O F
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The Driving Force D E P A R T M E NT O F
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we can say that (H – T S) must always be –ve for a reaction to proceed
spontaneously in order that the total entropy change of the system and
surroundings can be +ve, when the reaction proceeds.
We should examine the factor (H – T S) for the above three reactions in
question. For the reduction of ZnO by C at 25 0C
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The Driving Force D E P A R T M E NT O F
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Thermodynamic Mnemonic Square D E P A R T M E NT O F
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S H P
The other four primary functions namely V, T, P, S are placed at the four corners in such a way
that each thermodynamic potential is surrounded by the condition under which it acts
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This coefficients are taken to be positive if arrow points away from the
variable and negative if it points towards the variable.
dG = - S dT + V dP
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Negative sign on the right hand side of the equation is put if the arrows
are placed unsymmetrically with respect to vertical axis drawn from
centre of the square on rotation.
T P
V S S V
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Standard state of free energy D E P A R T M E NT O F
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Some thermodynamic D E P A R T M E NT O F
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relationships
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By definition G = H – TS = U + PV –TS
differentiating dG =dU + PdV + VdP – TdS – S.dT (1)
Assuming a reversible process involving work due only to
expansion at constant pressure
According to First Law: dU = dq – PdV and from Second
Law: dq = TdS
dU = TdS – PdV (2)
From (1) and (2) we get dG = (TdS – PdV) + PdV + VdP –
TdS – SdT
or dG = VdP – SdT (3)
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Some thermodynamic D E P A R T M E NT O F
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relationships
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Some thermodynamic D E P A R T M E NT O F
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dG A S A .dT and dG B S B dT
d ( G B -G A ) = (S B - SA ) dT
but G = GB – GA and S = SB – SA and so that d (G) = -S.dT
G G
T S on substitution G H TS H
P
T P ,T
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G 0T H 0T T S 0T
0 T
0 T
C P
or G 0T H 298
298 C P dT T S298 298 T dT
It must be remembered that if any transformation
takes place between 298 and T K in reactants and
products must be introduced in the above equation.
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Fugacity D E P A R T M E NT O F
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contd……
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If the gas is not ideal then the relation of molar free energy and
logarithm of pressure is not linear.
A function is invented which when used in place of pressure gives a
linear relationship.
This function is called ‘Fugacity ( f )’ is partially defined as
dG = RT dln f
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f fi
a 0 or a i 0
f fi
So we can write
G G 0 RT ln a Or G i G i0 RT ln a i
The standard state of a substance are generally chosen as the pure solid
or liquid form of the substance at 1 atm pressure and temperature under
consideration or as the gases at 1 atm pressure at the temperature under
consideration.
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G q G Q r G R l G L m G M
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The standard free energy change can be written as Institute of Technology Banaras Hindu University
0 0 0 0
G q G r G l G m G
0
Q R L M
0
G G q G G Q r G G R
0
Q
0
R
l G
0
L
GL m G 0
M GM
Or
G 0 G q RT ln a Q r RT ln a R
l RT ln a L m RT ln a M
Or a qQ a rR
G 0 G RT ln RT ln J
a a
l
L
m
M
The parameterMetallurgical
J is called activity quotient
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Or G G 0 RT ln J
K
Q R
a a
l
L
m
M
At equilibrium G = 0,
G 0 RT ln J at eq. RT ln K
J
Or G RT ln
K
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G
S
T P
G
0r G H T S H T
T P
Deviding bothsides by T 2 we obtain
G H 1 G
T 2
T 2
T T P
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1 G G H
or 2 2
T T P T T
G T H
or 2
T P T
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G T H
T2 2 H
1 T
T
P
This is the alternative form of Gibbs – Helmholtz Equation .
We can write Gibbs – Helmholtz Equation for a process as
G T H
T P T2 Utility
Evaluation of enthalpy of reaction from
free energy change.
G T Evaluation of free energy change from
H
1 calorimetric data.
T
P
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G 0T H 0T
T
T2 d T
H 1
or G 0T T 2 0 2 C P d T d T
T T
H
T 2 0 2 a b T c T 2 d T d T
1
T T
H a b c
T 20 3 dT
T T 2 T
b 2 c 1
H 0 a T ln T T IT
2 2 T
Where H 0 and I are int egration cons tan t. These are det er min ed
from the knowledge of either G 0 at two temperatur es or G 0 and
H 0 at one temperatur e.
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Trouton’s and D E P A R T M E NT O F
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Rechard’s Rules Institute of Technology Banaras Hindu University
HV
87 J / K
TV
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Problem Institute of Technology Banaras Hindu University
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2 2 V2 V2
q rev d U P dV P R
S
1
T
1
T
V1
T
dV
V1
V
dV
V 24.62
R ln 2 8.314 ln 19.14 J / K
V1 2.462
q rev
b) dS 0 as q rev 0 for adiabatic process
T
3 P V 1 2.462
c) P2 1 atm., C V R , T2 2 2 30 K
2 R 0.08207
2 2 2 T2
q rev d U P dV dU CV
S
1
T
1
T
1
T
T1
T
dT
T 3 30
C V ln 2 8.314 ln 28.71 J / K
T1 2 300
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Problem Institute of Technology Banaras Hindu University
1336
29.69 12360
1250
23.68 5.19 10 3
T
1250
T
dT
1336
1336
T
dT
9.327 J K 1
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ii) SSurrounding
Both the initial and final state of the system have been assumed to be at 1250 K.
This is possible only if the surroundin g is at 1250 K and it has inf inite heat capacity.
Surrroundi ng absorbs heat released during freezing reversibly at 1250 K. Hence
q H System
SSurrounding
T T
1336 1250
H System H 2 H 1 C P ( l) d T H
0
m C P (s) d T
1250 1336
1336 1250
23.68 5.19 10
3
29.69 d T 12360 T dT
1250 1336
12460 J
H System 12460 Suniverse is positive since
SSurrounding 9.967 J K 1
T 1250 the process is irreversible.
SUniverse 9.327 9.967 0.64 J K 1
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Problem
one gram of liquid ThO2 at 2900 0C is mixed with 5 gm of ThO2
at 3400 0C adiabatically. a) what is the final temperature
b) What is the entropy change of the system and surrounding
Combined c) is the process spontaneous? Assume CP to be
Independent
Solution
of temperature.
a ) Heat released by hotter body heat absorbed by colder body
m C P d T Hot m C P d T cold
5 C P Tf 3173 1 C P 3673 Tf
Tf 3589 K
Tf
dT
entropy change of cold body ( SC ) C P T
TC
Tf
dT
entropy change of hot body ( SH ) 5 C P T
TH
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Problem
Calculate the standard entropy change of the following reaction
at 1000 K.
Pb (l) + 0.5 O2(g) = PbO (s)
and also calculate the entropy change of the Universe.
Given: Tm, Pb = 600K, H0m, Pb = 4812 J mol-1, H0PbO,298 = -219 kJ
S298, PbO = 67.78 J K-1, S298, Pb = 64.85 J K-1, S298, O2 = 205.09 J K-1
CP, PbO(s) = 44.35 + 16.74x10-3 T J K-1mol-1
CP,Pb(s) = 23.55 + 9.75X10-3 T J K-1mol-1
CP,Pb(l) = 32.43 – 3.09X10-3 T J K-1mol-1
CP,O2 = 29.96 + 4.184X10-3 T - 1.67x 105 T-2 J K-1mol-1
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Solution
The Pr oblem physically consists of evaluation
S1000
0
for the reaction
1
Pb (l) O 2 (g ) PbO (s) ................(1)
2
from S0298 and C P values for the reaction
1
Pb (s) O 2 (g) PbO (s) .................(2)
2
1 0
S0298 S0298, PbO S0298, Pb S298, O 2
2
1
67.78 64.85 205.09 99.615 J K 1
2
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17.72 10 3
H 3.05 600 298
0
298
2
600 2 2982
1 1
0.836 10 5 4812 5.811000 600
600 298
4.89 10 3
2
10002 600 2 0.836 10 5
1
1000
1
600
219 10 3 9 21.10 2402.79 141.20 4812 2324 1564.80 55.73
218.244 kJ
Assu min g that the surr ounding is at 1000 K having l arg e heat capacity.
H1000
0
218.244
Ssurrounding 218 J K 1
T 1000
SUniverse SSystem SSurrounding
99.079 218 119 J K 1
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Problem Institute of Technology Banaras Hindu University
From the data given for different phases involved, calculate the
change in entropy of one mole of manganese when it is heated
from 298 K to 1873 K under one atmospheric pressure.
(CP)-Mn = 5.7 + 3.4 x 10-3 T – 0.4 x 105 T – 2 cal / deg/ mol
(CP)-Mn = 8.3 + 0.73 x 10-3 T cal / deg/ mol
(CP )γ-Mn = 10.70 cal / deg/ mol
(CP )δ-Mn = 11.3 cal / deg/ mol
(CP )Mn, l = 11.0 cal / deg/ mol
Transformation Temperature / K Latent heat in Cal / mol.
Mn 990
Mn 1360
Mn 1410
Mn 1517
l Mn
990
C P Mn 535
1360
C P Mn 525
S
298
T
dT
990
990
T
dT
1360
1410
C P Mn 430
1517
C P Mn
1360
T
dT
1410 1410 T
dT
3500
1873
C P l Mn
dT
1517 1517 T
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1517 1873
11.3 11
0.3049
1410
T
dT 2.3071
1517
T
dT
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Problem
Using the following values, calculate the standard free energy change per
mole of the metal at 1000 K for the reduction of molybdic oxide and chromic
oxide by hydrogen:
G 1000
0
, Cr2 O 3 ( s ) 205.5 kcal / mol.
G 1000
0
, MoO 3 ( s ) 120.0 kcal / mol.
G 1000
0
, H 2 O ( g ) 45.5 kcal / mol.
Solution
3
2 Cr O 2 Cr2 O 3 ; G1000
0
205.5 kcal / mol.
2
3
Mo O 2 MoO 3 ; G1000
0
120.0 kcal / mol
2
1
H 2 O 2 H 2 O; G1000
0
45.5 kcal / mol
2
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G 0
3 45.5 205.5
34.5 kcal / mol.
1000
2
MoO 3 3 H 2 Mo 3 H 2 O
G1000
0
3 45.5 120 16.5 kcal / mol.
sin ce the free energy change for the reduction of chromium
oxide is ve , it can not be reduced by hydrogen at this
temperature. But, molybdenum can be reduced at this
temperature as the free energy change is ve.
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Problem
The standard heat of formation of solid HgO at 298 K is – 21.56
kcal / mol. The standard entropies of solid HgO, liquid Hg and
O2 at 298 K are 17.5, 18.5 and 49.0 cal /deg/mol, respectively.
Assuming that H0 and S0 are independent of temperature,
calculate the temperature at which solid HgO will dissociate
into liquid Hg and O2.
Solution
H 0298, HgO (s ) 21.56 kcal / mol
S0298, HgO (s ) 17.5 cal / deg/ mol /
S0298, Hg ( l ) 18.5 cal / deg/ mol /
S0298, O 2 ( g ) 49 cal / deg/ mol /
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Solution:
3
WO3(s) = W(s) + O2 ( g ), G 201500 10.2 T log T 91.7 T cals
0
1 2
H2 + O 2 ( g ) H 2 O ( g ) , G 0
58900 13.1T cals.
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
a) i) G 0 at 4000 K G4000
24800 10. x 400 log 400 52.4 x 400 14460 cals.
ii) G 0 at 700 0 K ΔG 0700 = 5122 cals.
iii) G 0 at1000 0 K ΔG1000
0
= 3000 cals.
G 0
G 0 RT
G RT ln K i.e. ln K
0
or K e
RT
K400= 1.26x10-8
K700= 2.5x10-2
K1000= 0.22
3
b) p H 2O
K
pH
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
p H 2O
= K14003 = ( 1.253 x 10-8 )
1 3
= 2.472 x 10-3
pH2
p H 2O + pH2 = 1
p H 2 (0.00247+1) = 1
1
pH2 = = 0.9975 atm.
1.002472
and ∴p H 2O = 0.002466atm
% moisture = 0.24 %
At 700K, K700 = 2.317x10-3
p H 2O
= ( 2.5 x 10-2 )
1 3
= 0.296
pH2
Metallurgical Thermodynamics
D E P A R T M E NT O F
p H 2 (0.296 +1) = 1
1
pH2 = = 0.7716 and p H 2O = 0.2283
1.132
∴% H 2 O at 700K = 22.83%
at 1000K K1000 = 0.22
p H 2O
= ( 0.22) 1 3 = 0.6067
p H2
1
pH2 = = 0.6223
1.6067
pH2O= 0.3776
% H2O at 1000K = 37.76 %
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution
Equation under question Ni + H2O = NiO(s) +H2
ΔG 0r = ΔG10 - ΔG 02
= 450 + 10.45 T cals.
Metallurgical Thermodynamics
D E P A R T M E NT O F
from 1 & 2 :
1
or p H 2O 0.99585
0.0041669 p H 2O + p H 2O = 1 1.0041669
p H 2 0.00415 Hence maximum tolerable partial pressure of
moisture is 0.99585 atm
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution:
G0 = -RTlnK = -4.575 x 1125 log K = -5147
5147
log K = = 1.000 K = 10
4.575 x1125
K for the above reaction is
p CO 2 a Ni a Ni 1 a NiO
K= .
p CO a NiO
p CO 2
= = 10
p CO
In the given atmosphere p CO 2 i.e J/K is <1 so no oxidation of nickel
=3= J
p CO
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
p H 2O
K 240 i.e. p H 2O 240 p H 2
pH2
p H 2O 95
given : = = 19 = J J/K <1 rxn in forward direction
p H 2will take
So no oxidation 5 place
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Problem
Calculate the standard enthalpy and entropy changes at 298 K
for the reaction
2 Cu (s) + ½ O2 = Cu2O (s)
G0 = - 40500 -3.92 T log T + 29.5 T cal / mol
Solution
G 0 40500 3.92 0.4343 T ln T 29.5 T
40500 1.702 T ln T 29.5 T
G 0 40500
1.702 ln T 29.5
T T
Differentiating,
G 0 T
40500 1.702
T T 2
T
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Problem
Enthalpy of the solid platinum at any temperature is given by
the expression:
H T H 298 5.8 T 0.64 10 3 T 2 1785 cal / mol.
Derive an expression for the change in free energy when one
mole of platinum is heated from 298 K to any temperature T K.
Solution
According to G H equation of any system at
temperature T.
G HT
2 dT C
T T
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Thus
GT
H
298
2
5. 8
0.64 10 3
1785
2
dT C
T T T T
G H 1785
or T 298 5.8 ln T 0.64 103 T C
T T
or G T H 298 1785 5.8 T ln T 0.64 103 T 2 C T
G 298 H 298 1785 5.85 298 ln 298 0.64 103 2982 298 C
Calculate (1) the elevation of the boiling point of zinc when the external pressure
is 2 atm. and (ii) the depression of the freezong point when the external
pressure is 50 atm. The latent heat of vaporization of zinc is 27.3 kcal/g atom
and the normal temperature of boiling is 907 0C. The corresponding heat of
fusion is 1.74 kcal/gatom and the normal temperature of fusion is 419.5 0C.
The density of solid zinc is 7.0 g/cc and that of liquid zinc is 6.48 g/ce at 1
atm. pressure.
Solution
Using the Clausius-Clapeyron equation for this problem we have dP S e
dT V
dP Le
where v g is the volume of 1gatom of zinc vapourand v l is the volumeof 1g atom of
dT T e v g vl )
liquid
To zinc this problem we have also to know the values of the volume of 1
solve
gatom of zinc in the vapour and liquid states. The volume occupied by 1 gatom
of a perfect gas at STD in 22400 cc.
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49 × 692.5
= (10.089 - 9.34) × 0.024212
1740
49 × 692.5
= × 0.75× 0.024212
1740
= 0.354 K Ans
Metallurgical Thermodynamics
D E P A R T M E NT O F
The latent heat of vaporization of zinc is 27.3 k cal/mole at the boiling point of
9070C. Find the vapour pressure over pure zinc at 8500C.
Solution:
for l g transformation we have
dP Le Le RT
e e v g . vl ; v
dT T v g vl T v g P
dP LP
p 1 1 atm., T1 1180 K , p 2 ? , T2 1123K
dT RT 2
dP L 1 p2 L T2 T1
P R T2 or ln
p1
R
T1T2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Statement
It states that if an equilibrium in a system is upset,
the system will tend to react in a direction that will
reestablish the equilibrium.
Factors
i) Concentration of reactant and product
ii) Pressure
iii) Temperature
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Effect of concentration D E P A R T M E NT O F
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If the reactant is removed, the equilibrium will shift towards reactant and
same is true for the product.
This shift of equilibrium may be used to advantage in some commercial
processes since continuous removal of product will drive the reaction to
completion. This is more easily achieved if one of the product is a gas e.g.
CaCO3 = CaO + CO2
In the lime kiln removal of CO2 in an air current drives the reaction
towards right.
Other example is the production of magnesium:
2 MgO(s) + Si(s) = 2Mg (g) + SiO2(s)
At the temperature employed the magnesium vapour can be evacuated.
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Endothermic reaction:
ZnO + C = Zn + CO H = +349 kJ
Increase in temperature will again shift the equilibrium in the
direction which absorbs heat
i. e. to the right in this case.
Endothermic reactions are therefore, favoured by high temperatures.
Metallurgical Thermodynamics
Clausius-Clapeyron Equation
D E P A R T M E NT O F
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There is a natural tendency for the molecule to pass from solid into liquid
or vice versa.
The number of atoms passing at any time from one state to other will
depend on the temperature and pressure.
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GA GA GB GB
. dT . dP T . dT P . dP
T P P T P T
S A dT v A dP S B dT v B dP
Or
vB v A dP S B S A dT
Or
v . dP S . dT
Or
dP S H tr
as S
Or dT V Ttr
dP H tr
d T Ttr v B v A
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Or dP H tr
Clausius – Clapeyron
dT Ttr v Equation
If v is +ve as is normally in the case of melting and Htr will be +ve quantity i. e as
the pressure increases the transition temperature should also increase. In other
words the equilibrium melting point shall increase with pressure and vice versa.
However, for ice – water system v is – ve and hence (dP / dT) is –ve and which is
fully exploited in the game of skating on ice wherein the skate pressure increase
shall decrease the melting point of ice and hence help skating by providing fluid for
lubrication.
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Contd….
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P2 HV 1 1
or ln
P1 R T2 T1
This equation can be used to calculate the vapour pressure at
any temperature if the vapour pressure at another temperature
and heat of vapourization are known.
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D E P A R T M E NT O F
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d ln P HS
dT R T2
Where Hs is the heat of sublimation
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d T Tf v liq v solid
Applying C – C equation to so solid liquid equilibria
dP Hf
d T Tf v liq v solid dP Hf
Hf is the molar heat of fusion, vliq and vsolid are the
molar volumes of liquid and solid respectively.
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dP H tr d T Ttr v v
d T Ttr v v dP H tr
Where Htr is the molar heat of transition, v and
v are the molar volume of the indicated forms of
solid measured at Ttr.
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Ellingham Diagram D E P A R T M E NT O F
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Features of Ellingham diagram D E P A R T M E NT O F
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2x 2
M O2 g M x Oy
y y
Where the values of x and y will depend on the specific
compound. M and M x O y are general symbols for metal
and metal oxides, respectively.
Specific examples are
2 Ni O 2 (g ) 2 NiO
4 2
Al O 2 (g) Al 2 O3
3 3
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The entropy changes of various such metal oxidation process are expected to
be substantially of the same value. Therefore, the most of the oxide lines
slope upwards and parallel to each other.
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4) The intercept of the straight line with the ordinate at absolute zero gives
approximately the value of H0, since from the equation G0 = H0 - T S0
when T = 0, G0 = H0
5) since G0 must have a negative value for the reaction to take place, it can be seen
from this plot that all metals shown below the negative areas of G0 are oxidized
spontaneously by oxygen while those above are not e. g. gold
6) When a line touches the positive regions of G0 this means beyond that
temperature no further oxidation can take place or the oxide formed in that
region is unstable or oxides will start decomposing when G0 = 0. i. e Ag2O will
decompose at 15000C.
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D E P A R T M E NT O F
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7) The stability of an oxide is directly related to its - G0 values; less stable
oxides have a small - G0 and more stable oxides have a high - G0 value.
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11) The line for the reaction 2 C + O2 = 2CO runs downwards i.e. it has a negative
slope, this is due to the large increase in entropy: two volume of gaseous CO are
formed from one volume of oxygen gas. In this case G0 become more negative
as the temperature increases.
12) That the line for CO formation runs downward is of great importance in
pyrometallurgy. It enables almost all the metal – metal oxide lines meet C – CO
lines at high temperature. This makes most the oxides unstable beyond point of
intersection. This is called reversion of stability. This means that reduction of
most metal oxides by carbon is possible at high temperature.
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13) Carbon monoxide can reduce all oxides above the CO2 lines. For example at
7000C NiO can be reduced by CO
2 CO + O2 = 2 CO2 G0 = - 95 kcal.
2 Ni + O2 = 2 NiO G0 = - 75 kcal.
2CO + 2NiO = 2Ni + 2CO2 G0 = - 20 kcal.
14) All oxides above H2O lines can be reduced by H2 e.g at 7000C
2 H 2 + O 2 = 2 H 2O G0 = - 92 kcal.
2 Co + O2 = 2 CoO G0 = - 75 kcal.
2CoO + 2 H2 = 2Co+ 2 H2O G0 = - 17 kcal.
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D E P A R T M E NT O F
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Disadvantages of Ellingham diagram D E P A R T M E NT O F
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1) The diagram is applicable only for the substances present in their standard
states. But practically activity may not be unity.
2) Compound whose formation lines are represented in the diagram are
assumed to be stoichiometric only which often is not true.
3) The information regarding rate of the reaction can not be obtained.
4) The diagram do not show the condition under which the reaction tend to
occur.
5) Where oxide formation lines in the diagram are close together accurate
measurement and subsequent calculation is difficult.
6) The possibility of formation of intermetallic compound between reactants
and products is ignored
Metallurgical Thermodynamics
D E P A R T M E NT O F
If any one of the constituents of the reaction is not present in its standard state
is called non-standard state condition.
The activity of that substance will be less than one.
It can be best illustrated by the reduction MgO by silicon.
2 MgO(s) + Si(s) = 2 Mg(g) + SiO2(s)
G01473 = + 272 kJ
So there appears to be very little chance of using silicon as a reducing agent to
produce magnesium from magnesia.
Metallurgical Thermodynamics
D E P A R T M E NT O F
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From the van’t Hoff isotherm, the actual free energy change of the this
reaction is given by
p 2
Mg . a SiO 2
G G R T ln 2
0
a MgO . a Si
If pMg and aSiO2 can be lowered sufficiently, G can be made negative even
though G0 is positive.
PMg is lowered by working at a pressure of 10 – 4 atm.
aSiO2 is lowered by adding sufficient CaO to form orthosilicate (2 CaO. SiO 2). A
basic slag would give aSiO2 < 0.001.
Metallurgical Thermodynamics
D E P A R T M E NT O F
T
CV
S
0
T
dT S0, V Where S0, P, and S0,V are the
integration constant.
Metallurgical Thermodynamics
D E P A R T M E NT O F
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These equations also state that for calculation of absolute value of entropy of
any substance, these constants should be known.
In order to evaluate the constant, Nernst analyzed the low temperature data
on free energy and enthalpy of chemical reactions.
The analysis lead to the formulation of first, the Nernst heat theorem and later
the third law of thermodynamics.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
Experimental verification D E P A R T M E NT O F
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of the third law
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Third law is not so obvious as first and second law; hence it is required to
describe some of the evidence by which it was established.
The so called direct verification of the third law involves the application of the
second law, namely the principle that the entropy of the system is a function of
state and the net entropy change experienced by a system undergoing a cycle is
therefore zero.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Qr 541
S II 1.85 EU
Tr 292
0
S III
292
C P ( white) d ln T 11.04 EU
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
GHTS
G H S
T S
T P T P T P
G H
As we know S and C P
T P T P
S
we can write C P T
T P
S Prove that CV is zero
as is finite , at T 0 C P 0
T P at absolute zero
Metallurgical Thermodynamics
D E P A R T M E NT O F
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1 V
V T P
according to max well' s equation
V S
T P P T
S
as T 0 , S 0 so 0
P T 0
V
0 0
T P
Metallurgical Thermodynamics
D E P A R T M E NT O F
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where SI is the entropy change during isothermal expansion and SIII is the entropy
change during isothermal compression.
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D E P A R T M E NT O F
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But this not true as both heat exchange and temperature for
this is finite non-zero and positive.
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Third law also helps in the calculation of free energy during the
chemical reaction from the calorimetric data obtained in the
form of enthalpy of a reaction as a function of temperature. We
know G = H – T S
T T
C P
S d T and H H 0 C P d T
0
T 0
Metallurgical Thermodynamics
D E P A R T M E NT O F
we know Metallurgical Engineering
G = G0 + RT ln K Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution Metallurgical Engineering
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G0 = - R T ln K
Or – 318 000 = - 8.316 x 1273 ln K
Or K = 1.11 x 1013 = (P2CO . PTiCl4) / (aTiO2 . a2C . P2Cl2)
Assuming TiO2 and carbon as pure solid aTiO2 = 1= aC
From the stoichiometry of the reaction production of one mole
of TiCl4 leads to the production of 2 moles of CO i.e.
PCO = 2 PTiCl4
Making all the substitution
P3TiCl4 / P2Cl2 = 0.275 x 1013 i.e PTiCl4 >> PCl2
So as a first approximation let us take PTiCl4= PT = 1atm. Then
we get PCl2 = 6 x 10 -7 atm. This is truly negligible. Therefore,
the thermodynamic utilization of Cl2 is 100%.
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D E P A R T M E NT O F
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Problem Institute of Technology Banaras Hindu University
Solution
In equilibrium with pure iron the reaction is:
Fe (s) + H2O(g) = FeO(g) + H2(g)
For which: K = (aFeO . PH2) / (aFe . PH2O)
Metallurgical Thermodynamics
Fe and FeO are in their standard state (aFe = 1 = aFeO) D E P A R T M E NT O F
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K = (PH2 / PH2O)Fe, Pure Institute of Technology Banaras Hindu University
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D E P A R T M E NT O F
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Problem Institute of Technology Banaras Hindu University
Solution
i)For the reaction: 2 Cr (s) + 3 H2O(g) = Cr2O3(s) + 3 H2
G01000K = - 68250 cal = - R T ln K
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Problem
i. At what temps will carbon reduce a) SnO2(s) b) Cr2O3 (s) and c) SiO2(s)?
ii. Steam blown through hot coke gives rise to the fuel gas mixture called water gas
(CO+H2): C + H2O = CO + H2. calculate the temperature the coke must be
maintained for the reaction to be feasible?
iii. At what temperature the Ag2O just begin to decompose at one atmospheric
pressure?
iv. In what temperature range can hydrogen be used to reduce SnO2 to Sn?
v. Deduce the standard free energy change for the reduction of Al 2O3 by Mg at
1000 0C.
vi. Explain the reasons for the change in slope of the following lines:
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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Problem
Calculate the vapour pressure of liquid silver at its melting
point, 960 0C, making use of Trouton’s rule. Boiling point of
silver is 2210 0C.
Solution: According to Trouton ' s rule
H V
87 J / K
Tb
Hence H V 87 2483 216.021 kJ / mol.
We know for the liquid vapour equilibria
H V
ln p C
RT
C can be evaluated by the condition P 1 at T 2483 K
C comes out to be 10.46.
H V
So ln p 10.46
RT
216021
or ln p 10.46 2.459 10 5 atm
8.314 (960 273)
Metallurgical Thermodynamics
Problem D E P A R T M E NT O F
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The equilibrium vapour pressure in atm. of a solid is given by the
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H S RT
2
2.8310 Metallurgical Engineering
(300 273)
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1.987 573
2
2.7399 10 7
2.8310 3
1846.085 cal.
Heat of sub lim ation is 1846.085 cal. at 573 K
Problem
Calculate the melting point of ice under a pressure of 2 atm.
From the following data.
Density of water at 00C = 1.0 gm /cc
Density of ice at 00C = 0.9174 gm /cc
Latent heat of fusion of ice = 80 cal / gm
Assume that the above data to be independent of temperature
and pressure and also that the ice melts at 0 0C under 1 atm.
Pressure.
Metallurgical Thermodynamics
Solution D E P A R T M E NT O F
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molecularweight 18Institute of Technology Banaras Hindu University
ln T
18 19.62 PC
80 18 41.293
2.7 10 5 P C
From the given condition T 273 K, P 1 atm
5
So ln 273 2.7 10 1 Thermodynamics
Metallurgical C or C 5.6095
For the calculation of melting po int of ice at
Metallurgical Engineering
D E P A R T M E NT O F
Metallurgical Thermodynamics
molecular wt. 56
Molar volume of solid iron Metallurgical
7.124 cc / mol
D E P A R T M E NT O F
Engineering
density 7.86 Institute of Technology Banaras Hindu University
molecular wt. 56
Molar volume of liquid iron 7.4172 cc / mol
density 7.55
1 cal 41.293 c.c atm
we know for the solis liquid equilibria
d T Vl Vs 7.4172 7.1246 1808 3.88 10 3 deg ree / atm.
Tm
dP H m 3300 41.293
Problem
Rhombic sulphure transform to monoclinic sulphure at 368.5
K. with an enthalpy changes of 96 cal / mol. test the validity of
the third law of thermodynamics for this transition from the
following data:
i) CP of the rhombic sulphure at 15 K = 0.3 cal/deg/mol
ii) Area under the curve drawn between (Cp / T ) and T for rhombic sulphure
between T = 15 K to 368.5 K is 8.71 cal/deg/mol.
Metallurgical Thermodynamics
D E P A R T M E NT O F
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III
K
0
I
0 IV
0 100
% reacted
Metallurgical Thermodynamics
D E P A R T M E NT O F
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15 368.5
CP CP
0
T
dT
15
T
dT
368.5
1 3 15 CP
aT 0
3 15
T
dT
368.5
1 CP
CP 0
15
dT
3 15 T
Metallurgical Thermodynamics
D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
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368.5
1 CP
CP 0
15
dT
3 15 T
368.5
1 CP
C P 15 dT
3 15 T
1
0.3 8.71 8.81 cal / deg / mole
3
H tr 96
SII 0.2605
Ttr 368.5
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Statistical Thermodynamics:
It deals with the interpretation and derivation of thermodynamic
properties based on the properties of the particles constituting
the system and their distribution in the system.
Elementary Statistical Concepts
Microstates: In a gaseous system, each particle shall have
three position coordinates namely x, y, and z and three velocity
coordinates vx, vy, and vz. If at any instant one is able to specify
value of all these six coordinates for each of the particle
constituting the system, such a complete specification is said to
define the microstate of the system.
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D E P A R T M E NT O F
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• A set which defines all the possible microstates of a Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
D E P A R T M E NT O F
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These eight microstates can be grouped into the following four
macrostates:
I. All the three particles lie in compartment I – only one No.1 microstates
corresponds to this macrostates.
II. Two particles present in compartment I and only one in compartment II:
three microstates namely 2, 3, 4 correspond to this macrostates.
III. one particle present in compartment I and two in compartment II: three
microstates namely 5, 6, 7 correspond to this macrostates.
IV. All the three particles present in compartment II corresponds to Microstate
no.8
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D E P A R T M E NT O F
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In actual practice a system consists of a large no. of particles and hence for every
macrostates there are large no. of microstates and no. of such macrostates are also
large. For the calculation microstates for a macrostates, one uses the technique of
permutation and combination.
Next, how to calculate the no. of microstates or maximum no. of possible
arrangement of particles in a system.
This can be illustrated by an example: let us consider first where we have, say,
eight object numbered 1 through 8 and four boxes.
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D E P A R T M E NT O F
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Let us attempt to answer the question: in how many different waysBanaras
canHindu
these
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objects are placed in these boxes assuming that each box is large enough to contain
the all of the objects.
We may put object labeled 1 in any of the four boxes. Similarly, since each event is
independent we may do likewise for the object 2 etc.
The total no of ways of putting object 1 is four . The total no of ways of putting
object 2 is four, etc up through object 8.
The total no of ways of arranging all the balls is therefore 48.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
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Metallurgical Thermodynamics
Thus we need to calculate how many ways we have of arranging
Metallurgical two objects in box
D E P A R T M E NT O F
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1 two of the remaining six in box 2 and two of the remaining four in
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etc.
The first step is to calculate the no of ways of picking two objects out of eight for
box 1. This is done by combination of N objects taken n at a time i.e 8C2 = 8! / (2!
6!).
We have six objects left. So no. of ways of putting two object out of remaining six in
box 2 is 6C2 = 6! / (2! 4!).
Similarly for box 3 we have four objects left and
4 C2 = 4! / (2! 4!) and so on..
Now we are ready to answer: the total no of ways putting two balls in each box is
(W)
W = 8C2 x 6C2 x 4C2 x 2C2 = N! = 8! = 2520
n1!n2!n3!n4! (2!)4
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D E P A R T M E NT O F
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What is the probability of achieving the macrostate inInstitute
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D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
Differenti antion with respect to WB gives
D E P A R T M E NT O F
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(W A .WB ) 2
(W A .WB )
or
2 f (W ) f (W )
W. 0
(W ) 2
(W )
A general solution to the sec ond order diff . eq. is
f (W ) C1 ln W C 2
Thus
for a perfect CS1 =ln
S crystal W =
0 forW Cget2 C = 0
1, we 2
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The entropy change during this process is D E P A R T M E NT O F
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Pf
Pf
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R
S S f S i dP R ln
Pi
P Pi
In this process of throttling Pi Pf / 2
Therefore S f the
Let us calculate S iW in
R ln
the2initial and final state
N!
Wf
( N / 2) ! ( N / 2) !
N!
Wi 1
N!
According to sterling approximation i.e ln N ! N ln N N
S f Si C1 ln W f ln Wi ;
N N N
N ln N N ln
2 2 2 R
or ln 2 C1 C1 K
N N N N
ln
2 2 2
putting the value of C1 we get S Thermodynamics
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D E P A R T M E NT O F
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Entropy of Mixing for a Binary Solution Institute of Technology Banaras Hindu University
Component A Component B
(N0 –n) atoms n atoms
Sm
Solution
N0 atoms
In 1 mole of solution
there are N0 lattice sites
Sm = SA,B – SA – SB (Avogadro's no.)
Or Sm Metallurgical
= K (ln W Thermodynamics
– ln W – ln W )
WA,B is the no.of ways of arranging (N0 – n) A atoms andMetallurgical
n DBE Patoms on N0 sites so
A R T M E NT O F
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N 0!
W A, B
0 n)!
Since, in purenmetal
! ( Nthe atoms are indistinguishable so
WA = WB= 1. Thus
N 0!
S m K ln
n ! ( N 0 n)!
entropy of mixing
Applying sterling approximat ion
of ideal solution
n n N n N0
S m N 0 K ln 0 ln
N
0 N 0 N 0 N 0 n
N0 n n
as x A and x B
N0 N0
So S m R x A Metallurgical ln x B
ln x A x BThermodynamics
THERMODYNAMICS D E P A R T M E NT O F
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OF SOLUTIONS
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
and xA + xB = 1
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
pA
1 0 xB
pA
pA pB
0
1 x B x A and 0 x B
pA pB
i.e. p A p 0A .x A or ( p A x A )
and p B p B0 .x B or ( p B x B )
A solution which obeys Raoult’s law is called an
ideal solution.
A A B B 1
A A B B
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
a A A .x A
where γA is a fraction greater or less than unity for a positive or negative
deviation, respectively is called Raoultian activity coefficient.
For a pure substance: xA = 1 and γA = 1, so that we have unit activity of the
substance A which is said to be in its ‘standard state’
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
2. Positive deviation: When the net attractive force between the substances
A and B is less than between A-A and B-B, then the solution of A and B
exhibits positive deviation from Raoult’s law. In this case the Raoultian
activity coefficient is always greater than unity except when approaching
the concentration of xA 1 Pb and Zn liquid solutions show such
behaviour at temperature above 1071K. The heat of solution in systems
showing positive deviation is endothermic. In general a solution, A-B
exhibiting positive deviation has
1
A B {( A A ( B B))}
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
3. Negative deviations occur when the attractive force between the two
components A and B is higher than between A-A and B-B. For example
Mg-Bi system shows such a behaviour. Negative deviations generally
indicate a tendency for compound formation (Mg3Bi2). The heat of
solution for systems exhibiting negative deviatias is usually exothermic.
Occasionally both negative and positive deviations from Raoult’s law
occur in the same binary system. An outstanding example of this
behaviour is found in the Zn-Sb, Cd-Bi and Cd-Sb systems. In general in
case of negative deviation in the system, A-B we have
1
A B A A B B
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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In dealing with solutions, one of the first questions which naturally arises is
how to express molar quantities of a substance in solution when two liquids
are mixed, the total volume of the solution is, in general, not equal to the sum
of the individual volumes before mixing, this reflects the difference of the
interatomic forces in the pure substance and in the solution.
Metallurgical Thermodynamics
PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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Q
Q (1)
n1 n2 n3 ..........
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PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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Metallurgical Thermodynamics
PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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n1Q1 n 2 Q2 ...........
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PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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Q x1Q1 x 2 Q2 (5)
Q n1Q1 n 2 Q2 (6)
Metallurgical Thermodynamics
PARTIAL MOLAR D E P A R T M E NT O F
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QUANTITIES
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Metallurgical Thermodynamics
Method of obtaining partial D E P A R T M E NT O F
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molar quantities from molar quantities Institute of Technology Banaras Hindu University
dQ dQ
Q2 Q x1 Q 1 x 2 (12)
dx2 dx2
Similarly,
dQ
Q1 Q 1 x1 (12a)
dx1
Metallurgical Thermodynamics
D E P A R T M E NT O F
dQ CH CF y y1
A E C ( slope 2 )
dx 2 1 x2 x 2 x1
0
dQ
Q2 Q (1 x 2 )
Q1 dx 2
CH CF
↑ Q2 CF (1 x 2 ).
1 x2
Q G
B CF CH CF CH
D F
dQ AG AD y y
H ( slope 2 1 )
dx1 1 x1 x2 x1
dQ
Q1 Q (1 x1 )
dx1
1 x2 2 AG AD
AD (1 x1 ).
1 x1
AD AG AD AG
Metallurgical Thermodynamics
Method of obtaining one partial D E P A R T M E NT O F
molar quantities
Metallurgical Thermodynamics
Method of obtaining one partial D E P A R T M E NT O F
molar quantities
If the input in the calculation is the functional relationship
between ⎯ and x2, then
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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Metallurgical Thermodynamics
Obtaining Molar property D E P A R T M E NT O F
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Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
H = - 7100 x (1-x)
H
H Zn H 1 x Zn .
x Zn
H H d
7100 x1 x
x Zn x dx
=
d
dx
7100 x x 2 7100 1 2 x
= 1 x 7100 x 71001 2 x
7100 1 x x 1 2 x 7100 1 x 1 x 7100 1 x
2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Methanol =0.3 mole fraction
Water=0.7 mole fraction
V=0.3 x38.36x10-6+0.7x17.765x10-6
=24.025x10-6 m3/mol
For 2 m3 solution
2
6
83.246 10 mol
3
24.025 10
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
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d G1 2
54 x1 70 x1 16
dx1
d G2 2
54 x1 16 x1
dx1
G D equation
d G1 d G2
x1 (1 x1 ) 0
dx1 dx1
2 2
x1 ( 54 x1 70 x1 16 ) ( 1 x1 )( 54 x1 16 x1 ) 0
It satisfies the GD equation, the above equation is consistent.
Metallurgical Thermodynamics
The Free Energy Change due to D E P A R T M E NT O F
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the Formation of a solution Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
The Free Energy Change due to D E P A R T M E NT O F
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the Formation of a solution
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Metallurgical Thermodynamics
The Free Energy Change due to D E P A R T M E NT O F
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the Formation of a solution
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Metallurgical Thermodynamics
The Free Energy Change due to D E P A R T M E NT O F
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the Formation of a solution
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G M n A G A n B G B n A G A0 n B G B0 n A G A G A0 n B G B G B0
= n A ΔG AM + n BΔG BM
= RT (nA ln aA + nB ln aB)
Metallurgical Thermodynamics
Properties of Raoultian D E P A R T M E NT O F
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Ideal solution
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Gi G 0i
V i Vi 0
P
T ,Comp P T ,Comp
(G i G 0i )
P
V
i Vi
0
T ,Comp
∂ ΔG i M M
= Δ Vi
∂P T ,Comp
Metallurgical Thermodynamics
Properties of Raoultian D E P A R T M E NT O F
Metallurgical Engineering
Ideal solution
Institute of Technology Banaras Hindu University
M ,id
for an ideal solution, G i RT ln xi
= n A ΔVAM + n BΔVB M = 0
M ,id M ,id
V M ,id
x A V A xB V B 0 or ΔV M,id = 0
Metallurgical Thermodynamics
Properties of Raoultian D E P A R T M E NT O F
Metallurgical Engineering
Ideal solution
Institute of Technology Banaras Hindu University
Gi / T -
Hi
T P , comp T 2
For the pure component
∂ ( G i 0 / T) Hi o
P , comp = -
∂T T2
G i G 0i
T
H i H i0
T T2
P ,Comp
Metallurgical Thermodynamics
Properties of Raoultian D E P A R T M E NT O F
Metallurgical Engineering
Ideal solution
Institute of Technology Banaras Hindu University
G iM
T M
H i
2
T T
P ,Comp
M
H i is the partial Molar heat of solution (mixing) of i
M ,id
In an ideal solution, G i RT ln xi
R ln xi
M ,id
H i
T P ,Comp T 2
M ,id
or H i 0
Integral molar heat of mixing, H M ,id x H M
A
,id M ,id
xB H B 0
A
H M ,id 0
Metallurgical Thermodynamics
Properties of Raoultian D E P A R T M E NT O F
Metallurgical Engineering
Ideal solution
Institute of Technology Banaras Hindu University
G M RT x A ln a A x B ln a B
G M RT x A ln A xB ln B RT x A ln x A xB ln xB
G XS G M ,id
Metallurgical Thermodynamics
D E P A R T M E NT O F
Vi
M
G M
i
P
T , Comp
ln ai
RT
P
ln a A ln a B
V M
RT x A xB
P P
Metallurgical Thermodynamics
D E P A R T M E NT O F
Si
M
G M
i
T P , Comp
ln ai
RT R ln ai
P
Integral molar entropy of mixing
M M
S M
x A S A xB S B
ln a A ln a B
S M RT x A xB R x A ln a A x B ln a B
T T
Metallurgical Thermodynamics
D E P A R T M E NT O F
R ln ai
M
H i
T2 T P ,Comp
M ln ai
H i RT 2
T P ,Comp
Metallurgical Thermodynamics
D E P A R T M E NT O F
M M
H M
xA H A xB H B
ln a A ln a B
H M
RT x A
2
xB P , comp
T T
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
0
By similar comparison 1of co-efficients
1
of the power series, Margules further
demonstrated that the variation of the γ’s can be represented by the quadratic
terms only, when
2 2
Metallurgical Thermodynamics
D E P A R T M E NT O F
α is independent of composition
which indicates that Tl – Sn
system follows regular solution
model.
Metallurgical Thermodynamics
D E P A R T M E NT O F
ΔG XS = ΔG M ,R - ΔG M ,id
Metallurgical Thermodynamics
D E P A R T M E NT O F
it may be shown as G XS
S XS
T p
ΔGxs = ΔHxs - TΔSxs = (ΔHM,R – ΔHM,id ) – T (ΔSM,R – ΔSM,id )
= ΔHM,R (as ΔHM,id =0 and ΔSM,R = ΔSM,id )
ΔGxs = ΔHM,R
ΔG XS = ΔG M ,R - ΔG M ,id
RT x A ln a A xB ln aB RT x A ln x A xB ln xB
RT x A ln A xB ln B H M , R
XS XS
xA G A xB G B
M M
G A
XS
RT ln A H A and G B
XS
RT ln B H B
Metallurgical Thermodynamics
D E P A R T M E NT O F
G XS RT x A ln A xB ln B
RT x A xB2 xB x A2
RT x A xB x A xB
= RT α x A x B
Hence for regular solution
G XS H M RT x A xB
x A xB where
RT
This means GXS for a regular solution is independent of
temperature
Metallurgical Thermodynamics
D E P A R T M E NT O F
ln A at temperatureT2 T1
ln A at temperatureT1 T2
Metallurgical Thermodynamics
D E P A R T M E NT O F
ln A at temperature T2 T1
; dividing by (1 x A ) 2 we get
ln A at temperature T1 T2
ln A
at T2 (T2 ) T1
(1 x A ) 2
T
1 (T1 ) T2
ln A T2
at T1 or 1T1 2T2
(1 x A ) 2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Vi
M
G M
i
P T , Comp
ln ai
RT
P T ,omp
Integral molar volume of mixing
M M
V M
x A V A x B V B
ln a A ln aB
V M
RT x A xB
P P T ,omp
Metallurgical Thermodynamics
D E P A R T M E NT O F
S M R x A ln x A xB ln xB
Metallurgical Thermodynamics
D E P A R T M E NT O F
H M RT x A ln A xB ln B
Metallurgical Thermodynamics
Regular solution behaviour: D E P A R T M E NT O F
Metallurgical Engineering
Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Thermodynamic properties D E P A R T M E NT O F
Metallurgical Engineering
of Solutions
Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
Thermodynamic properties D E P A R T M E NT O F
Metallurgical Engineering
of Solutions
Institute of Technology Banaras Hindu University
Q x . Q
k K
Q XS
Q M Q M ,id
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
GIBBS – DUHEM INTEGRATION Institute of Technology Banaras Hindu University
Xi dQ 0,i
Q is any extensive property.
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION – D E P A R T M E NT O F
Metallurgical Engineering
METHOD -I Institute of Technology Banaras Hindu University
x A d ln a A x B d ln a B 0 (2)
xB
or d ln a A = d ln a B (3)
xA
xA xA
xB
ln a A | x A x A d ln aB
x
x A 1 A
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION D E P A R T M E NT O F
Metallurgical Engineering
METHOD -I Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION – D E P A R T M E NT O F
Metallurgical Engineering
METHOD -II Institute of Technology Banaras Hindu University
(4)
Eq.(4) Eq.(2)
(5)
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
GIBBS – DUHEM INTEGRATION Institute of Technology Banaras Hindu University
xB
as xB 1, a A 1, ln B 0 but
xA
xB
as xB 0, aB 0, B is finite and ln B is also finite for 0
xA
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION – D E P A R T M E NT O F
Metallurgical Engineering
METHOD -III Institute of Technology Banaras Hindu University
xB
substituting this into d ln A d ln B
xA
xB xB 2
d ln A 2 B x A dx A .x A .d B 2 x B B .dx A x B x A d B
xA xA
On integration
x A xA B at x A x A
ln A
x A 1
2 xB B dx A x
B at x A 1
x d B
B A ( A)
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION – D E P A R T M E NT O F
Metallurgical Engineering
METHOD -III Institute of Technology Banaras Hindu University
(A)
Metallurgical Thermodynamics
GIBBS – DUHEM INTEGRATION – D E P A R T M E NT O F
Metallurgical Engineering
METHOD -III Institute of Technology Banaras Hindu University
Thus ln at xA=xA is obtained as – xBxAB minus the area under the plot of
B vs xA from xA=xA to xA = 1. Since B is everywhere finite, this
integration does not involve a tail to infinity.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
xCd xCd
1 - xCd
xCd
2
1.74 xCd - 0.90 xCd dxCd
xCd 1
xCd xCd
Cd
(1 - x ) 1.74 xCd - 0 .90 xCd dxCd
2
xCd 1
Metallurgical Thermodynamics
D E P A R T M E NT O F
xCd 0.3
= [ - 1.74x Cd + 1.32x 2
Cd - 0.3 x 3 0.3
Cd 1
]
= -1.74(0.3-0.1) + 1.32 (0.09-1)-0.3 (0.027-1)
ln γ Cd = 1.218 - 1.201+ 0.292 = 0.309
Cd 1.362
a Cd = γ Cd .x Cd = 1.362 × 0.3 = 0.4086 Ans.
Metallurgical Thermodynamics
D E P A R T M E NT O F
xCd xCd
xZn
(b) ln Cd
xCd
xCd
d ln Zn
xCd xCd
1 - xCd
xCd
2
1.74 xCd - 0.90 xCd dxCd
xCd 1
xCd xCd
Cd
(1 - x ) 1 .74 xCd - 0 .90 xCd dxCd
2
xCd 1
1 - xCd (1.74 - 0.9 xCd )dxCd (1.74 - 2.64 xCd 0.9 xCd
2
)dxCd
xCd xCd
2
( -1.74 2.64 xCd - 0. 90 xCd ) dxCd
xCd 1
Metallurgical Thermodynamics
D E P A R T M E NT O F
2 3 x Cd= x Cd
[-1.74x CD +1.32x Cd - 0.3 x ] Cd x Cd=1
= 0.3x 3Zn + x 2Zn (-0.9+ 1.32) + x Zn (0.9 - 2.64 + 1.74) - 0.3 + 1.32 - 1.74 + 0.72
x
xCd 1
Zn (1.74 - 0.9 xCd ).dxZn 1.74 x
xZn 0
Zn dxZn - 0.9 xZn (1 - xZn ) dxZn
3
x
0.84 x Zn dxZn 0.9 xZn
2
dxZn [0.42 xZn ]0 [0.90. Zn ]0xZn 0.42 xZn
2 xZn 2
0.3 xZn
3
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
x Bi d ln γ Bi + x Pb d ln γ Pb = 0
on integration we get
ln Pb at x Bi x Bi
xPb ln Pb 0.74(1 x Pb ) 2
ln Bi -
ln Pb at x Bi 1
xBi
d ln Pb
d ln Pb 1.48(1 x Pb )dx Pb
xPb
1.481 - xPb dxPb
1 - xPb
Metallurgical Thermodynamics
D E P A R T M E NT O F
x Bi 2 x Pb (1 x Bi )
x
1.48 x
x Bi 1
Pb dxPb -1.48
2
Pb
x Pb 0
= - 0.74(1-xBi)2
Metallurgical Thermodynamics
D E P A R T M E NT O F
ln γ Pb ln γ Bi
( b ) α Pb = α Bi = =
x Bi 2 x Pb 2
Metallurgical Thermodynamics
D E P A R T M E NT O F
at 746 K
ln γ Pb = αx Bi 2 = -0.74x 2Bi
ln γ Bi = αx Pb 2 = -0.74 x 2Pb
G XS H M RT x Pb ln Pb xbI ln Bi
= RT xAxB
= - 1.987 746 0.74 0.4 0.6
= -263.3 cal/mole. Ans.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Engineering
Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
D E P A R T M E NT O F
G M RT x Pb ln a Pb x Bi ln a Bi
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
1750 3500
ln Zn (1 xZn ) , d ln Zn -
2
(1 - x Zn ) dx Zn
RT RT
appropriate form of the Gibbs-Duhem equation.
x Al d ln Al x Zn d ln Zn 0
xZn
ln Al .d ln Zn
x x
x Al
Al Al
xZn 3500
x Al 1
1 xZn RT
(1 x Zn ) dx Zn
x Al x Al 2
3500 3500 xZn xZn (1 x Al )
RT
x Al 1
x Al dxZn .
RT 2 xZn 0
1750
(1 x Al ) 2
RT
Metallurgical Thermodynamics
D E P A R T M E NT O F
H M G XS RTx Al x Zn
1750 xZn = 0.4, xAl = 0.6
RT . 0.6 0.4
RT
= 1750 0.24 = 420 cal/gatom Ans.
Metallurgical Thermodynamics
D E P A R T M E NT O F
(iii) G M RT ( x Al ln a Al x Zn .a Zn )
Metallurgical Thermodynamics
D E P A R T M E NT O F
Zn ( 780) 1.50146
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution:
By third method of integration calculate Ni
xNi 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9
aNi 0.067 0.137 0.208 0.287 0.376 0.492 0.620 0.776 0.89
γNi 0.67 0.685 0.69 0.72 0.75 0.82 0.986 0.96 0.99
(1-xNi)2 0.81 0.64 0.49 0.36 0.25 0.16 0.09 0.04 0.01
Ni -0.49 -0.59 -0.75 -0.92 -1.14 -1.24 -1.35 -1.07 -1.01
Making use of function we have
x Fe x Fe
ln Fe Ni .xFe x Ni
x Fe 1
Ni .dxFe
[ Ni xFe x Ni Ni dxFe ]
= - (-0.92 0.6 0.4 – 0.08) = 0.301 i.e. γNi = 1.35, aFe = 0.6 1.35 = 0.81
Metallurgical Thermodynamics
D E P A R T M E NT O F
M
G RT ln a Ni 8.314 1873ln(0.287) 19438J / mole.
Ni
M
G Fei RT ln aFei 8.314 1873 ln(0.81) 3281 J / mole.
G M ( xNi G Ni xFe G Fe ) 0.4 (19438) 0.6(3281) 9744J / mole.
= 758 J/mole
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
ln Zn ln Cu
Zn Cu 1.929
(1 x Zn ) 2
(1 xCu ) 2
H M G XS RT ( xZn ln Zn xCu ln Cu )
T = 1200 K , xCu = 0.4, xZn = 0.6
ln Zn 1.929 xCu
2
1.929 0.4 2 0.30864
Metallurgical Thermodynamics
D E P A R T M E NT O F
ln Cu 1.929 xZn
2
1.929 x 0.6 2 0.6944
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
G M ,id RT ( xZn ln xZn xCu ln xCu ) 1.987 1300 (0.6 ln 0.6 0.4 ln 0.4)
1738.5 cal / mol.
Metallurgical Thermodynamics
D E P A R T M E NT O F
M M
Difference in change in free energy = G Zn (1300) - G (1200)
Zn
=RT ln aZn(1300) – RT ln aZn (1200)
=1.987 (1300 ln 0.4513 – 1200 ln 0.4406)
=1.987 (-1034.31 + 984.54) = -98.9 cal/mol. Ans.
Metallurgical Thermodynamics
Dilute Solution – D E P A R T M E NT O F
Metallurgical Engineering
Henry’s Law
Institute of Technology Banaras Hindu University
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
p A x A
i.e. p A kx A (1)
pA k
dividing by p 0A we have 0
0 .x A i.e.a A const x A or a A x A
pA pA
The constant is equal to the slope of the curve at zero concentration of
A, designated by A0 (activity coefficient of the solute A at infinite
dilution).
a A A0 . x A
Like Raoult’s law, Henry’s law is valid within a concentration range
where the extent varies from one system to another, but it is valid only
at low concentration.
Metallurgical Thermodynamics
D E P A R T M E NT O F
aA
xA
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
K
xN 2 ( so lub ility ) p N 2 k p N 2
k
Metallurgical Thermodynamics
D E P A R T M E NT O F
a 2
N ( inFe ) (kx N ) 2
K
pN 2 pN 2
K
or x N (inFe) ( so lub ility) pN2 k ' pN2
k
Metallurgical Thermodynamics
Solubility of Gases – D E P A R T M E NT O F
Metallurgical Engineering
Sievert’s law
Institute of Technology Banaras Hindu University
Since all the common diatomic gases N2, O2, H2 etc. dissolve
atomically in metals, the general expression for solubility is
given as:
S k pN2
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution:
According to Sieverts law: S k pO2 i.e. 3.3 k 1 k 3.3
Metallurgical Thermodynamics
D E P A R T M E NT O F
a) Show whether these observations agree with Sievert’s law for the
solubility of oxygen in metals.
b) How much oxygen does 100g of silver absorb at 10750C from air?
c) What pressure of air corresponds to one atm of O2 with respect to the
solubility of oxygen in silver at 10750C.
Metallurgical Thermodynamics
D E P A R T M E NT O F
solubility
Sievert ' s cons tan t k s
pO2
81.5
kS 7.2037
128
156.9
ks 7.1025
488
193.6
ks 7.0226
760
247.8
kS 7.1444
1203
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
5
N 2O5 ( g ) N 2 ( g ) O2 ( g ) 2 N 5 O
2
N2 gas : O2 gas
1 mol : (5/2) mols
2 mol : 5 mols.
2 vol : 5 vol.
2 5
p N 2 atm and pO2 atm
7 7
S N K N p N 2 0.04 K N 1 K N 0.04
S N' (dissociated N 2 O5 ) K N p
2
0.04 0.02138% Ans.
7
Metallurgical Thermodynamics
D E P A R T M E NT O F
SO K O p
0.23 K O 1
K O 0.23
S O (dissociated N 2O5 ) 0.23 5 0.19439%
7
Metallurgical Thermodynamics
D E P A R T M E NT O F
aA
A0 as x A 0
xA
where a A is the activity of A w.r.t Roultian
s tan dard state and 0
A is
If the solute obeys Henry’s law over the Henery
a finite ' s law
concentration cons
range, thentan t
a A A0 . x A
Metallurgical Thermodynamics
D E P A R T M E NT O F
h A = 1 = γ 0A at x A = 1 .
This is the henerian s tan dard state and
h A is the henerian activity
Having defined the Henrian standard state, the activity of A in
solution with respect to the Henrian standard state is given by:
hA f A . x A
where f A is the henerian activity coefficient
Metallurgical Thermodynamics
D E P A R T M E NT O F
a A x A . A A
hA x A . f A f A x A cons tan t
aA 0
A
hA x A cons tan t
Metallurgical Thermodynamics
D E P A R T M E NT O F
The free energy change accompanying the transfer of one mole of solute A
from pure substance standard state (Raoultian standard state) to Henerian
standard state, that is:
A (in the Raoultian standard state) → A( in the Henerian standard state)
is given by
G A0 ( R H ) G 0A ( H ) G 0A ( R )
The partial molar free energy of the solute at constant concentration is
independent of standard state. The value of ΔGA0 remains unchanged if
is added and is subtracted from the right hand side of the above
G A (R)
equation G A(H )
G A0 ( R H ) G 0A ( H ) G 0A ( R ) G A ( R ) G A ( H )
G A ( R ) G 0A ( R ) G A ( H ) G 0A ( H )
Metallurgical Thermodynamics
D E P A R T M E NT O F
But G A G A0 R T ln a A
a
Hence, G A0 ( R H ) RT ln A
hA x A cons tan t
RT ln A0
Metallurgical Thermodynamics
D E P A R T M E NT O F
aA
1 as wt.% A 0
wt.% A
or a A wt.% A wt .% A 0
Metallurgical Thermodynamics
D E P A R T M E NT O F
hA (1wt %) wt.% A
Metallurgical Thermodynamics
D E P A R T M E NT O F
aA x A . A
hA(1wt %) f A(1wt %) .wt % A cons tan t composition
In the range of composition in which the solute obeys Henry’s Law,
fA(1wt%) =1 and γA = γA0 , therefore,
aA xA.
A
0
hA(1wt %) wt % A cons tan t composition
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
The free energy change accompanying the transfer of one mole of solute
A from pure substance standard state (Raoultian standard state) to 1 wt.%
standard state, that is:
A (in the Raoultian standard state) → A( in the 1 wt.% standard state)
is given by
aA
G ( R 1 wt. %) RT ln
0
A
h
A (1Wt.%) x A const
MB
RT ln RT ln
0
A
100.M A
Metallurgical Thermodynamics
D E P A R T M E NT O F
100.M A
MB
RT ln
100.M A
Metallurgical Thermodynamics
D E P A R T M E NT O F
Calculate the free energy change when the standard state of manganese is
transferred from pure liquid state to infinitely dilute wt% solution of
manganese in iron at 16270C melting point of Mn =12450C, at wt of Mn =
54.94, Fe = 55.85. Assume ideal behaviour of the solution.
Solution:
T = 1627 + 273 = 1900, MMn = 54.94, MFe = 55.85 Mn 1 (ideal )
0
55.85
8.314 1900 ln 1
100 54.94
72455 J / mol
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
wt % Si
atom% si 0.01 28.09
wt % Si 100 wt % Si
28.09 55.85
wt% Si = 0.50
Si (pure, 1) Si (1wt% in Fe)
0
M 0
Si .55.85
GSi ( R 1 wt %) RT ln
0 Si Fe
RT ln 39360
100M Si 100 28.07
Si 0.00128
0
Metallurgical Thermodynamics
D E P A R T M E NT O F
Metallurgical Thermodynamics
D E P A R T M E NT O F
wt % Si
0r 0.01 28.09
wt % Si (100 wt % Si )
28.09 55.85
or wt % Si 0.50
Metallurgical Thermodynamics
D E P A R T M E NT O F
0
The Raoultian activity coefficient of Al at infinite dilution, Al in
liquid Fe-Al alloys is reported to be 0.063 at 16000C. Calculate the
standard free energy of formation of Al2O3(s) at 16000C for each of the
three standard states for solution of Al in Fe.
MAl = 26.98 and MFe = 55.85
given 1. 2 Al(l) + 3/2O2(g) = Al2O3(s) G0 = -1682927 – 323.24TJ
2. 2 Al(l, H) + 3/2O2(g) = Al2O3(s)
3. 2 Al(l, wt %) + 3/2O2(g) = Al2O3(s)
Metallurgical Thermodynamics
D E P A R T M E NT O F
(1) 3
2 Al (l ) O2 ( g ) Al2O3 ( s ) (1)
2
G0 = -1082927 +323.24 1873 = -1077498.5 J
3
2 Al (l , H ) O2 ( g ) Al2O3 ( s) (2)
2
Al (l ) Al (l , H ) (3)
Metallurgical Thermodynamics
D E P A R T M E NT O F
G(0R ) 2 RT ln Al0
= -1077498 – 2 8.314 1873 ln (0.063)
= -1077498 – (-86102) = -991396 J.
3
2 Al (l ,1wt %) O2 ( g ) Al2O3 ( s ) ( 4)
2
Al (l ) Al (l ,1wt %) (5)
Total fre energy change for the reaction (4) = G(01wt %) G(0R ) 2G(0R 1wt %)
Al0 M Fe
G 0
(R) 2 RT ln
100 M Al
Metallurgical Thermodynamics
D E P A R T M E NT O F
0.063 55.85
= -1077498 – 2 8.314 1873 ln
100 26 .98
= -1077498 – 2 8.314 1873(-6.6422)
= -1077498+206866.8
= -870631J Ans.
Metallurgical Thermodynamics
D E P A R T M E NT O F
Solution:
Metallurgical Thermodynamics
D E P A R T M E NT O F
The general equation for the free energy change of a system with temperature
and pressure dG = VdP – SdT, does not take into account any variation in free
energy due to concentration changes.
We know G G (T , P, n1 , n2 , ....)
From the fundamentals of partial differentiation we have
∂G '
= S'.dT + V' dP + ∑ dn i
∂n i T , P , n1 ....
except n i
Metallurgical Thermodynamics
D E P A R T M E NT O F
G
i
n
i Except1 ni
T , P , n .....
is an intensive variable
This gives a new sets of fundamental equations for the open systems.
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Physical Meaning of D E P A R T M E NT O F
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Chemical potential
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G
G A A for a large quantity of solution
n A P ,T , n B
G
G A A for one mole of solution
n A P ,T , n B
Chemical potential of either 1 g mol or 1 g atom of a substance dissolved
in a solution of definite concentration is the partial molar free energy. Thus
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Equality of chemical potential D E P A R T M E NT O F
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Equality of chemical potential D E P A R T M E NT O F
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Hence,
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Equality of chemical potential D E P A R T M E NT O F
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D E P A R T M E NT O F
Phase(P)
A phase is defined as any homogeneous and physically distinct part of a
system which is separated from other part of the system by a bounding
surface. For example, at 273.15K, three phases ice, water and water vapour
can exist in equilibrium. When ice exists in more than one crystalline
form, each form will represent a separate phase because it is clearly
distinguishable from each other.
Components(C)
The number of components in a system at equilibrium is the smallest
number of independently variable constituents by means of which the
composition of each phase present can be expressed directly or in the form
of a chemical equation.
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D E P A R T M E NT O F
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D E P A R T M E NT O F
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D E P A R T M E NT O F
The water system for example consists of one component, viz., H2O each
of the phases in equilibrium i.e. solid, liquid and vapour may be regarded
as being made of this component only.
Degrees of freedom(F)
The number of degrees of freedom is the number of variable factors, such
as temperature, pressure and concentration that need to be fixed in order
that the condition of a system at equilibrium may be completely defined
when referring to its equilibrium phase diagrams.
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Derivation of the Phase D E P A R T M E NT O F
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Rule Equation
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Metallurgical Thermodynamics
Derivation of the Phase D E P A R T M E NT O F
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Rule Equation
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Metallurgical Thermodynamics
Derivation of the Phase D E P A R T M E NT O F
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Rule Equation
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Application of phase rule D E P A R T M E NT O F
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Application of phase rule D E P A R T M E NT O F
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Two components D E P A R T M E NT O F
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Eutectic system
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Phase rule in Reactive D E P A R T M E NT O F
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Components
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Phase rule in Reactive D E P A R T M E NT O F
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Components
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Application of Phase rule D E P A R T M E NT O F
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in Reactive Components
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Problem:
A system is composed of a solid phase CaCO3, a solid phase CaO,
and a gas phase CO2 . The following equilibrium occurs:
CaCO3(s) = CaO(s) + CO2(g)
How many components are there and what are the degrees of
freedom?
Solution:
Species: CaCO3(s) , CaO(s), CO2(g) : N =3, Phases : two solid and a gas phase P
= 3. No. of independent reaction equilibria r = 1. There is no
stoichiometric or special constraints.
So s = 0 and t = 0
C = N-r-s = 3-1-0= 2
F = C-P+2-t = 2-3+2-0 = 1
Either temperature or pressure must be specified.
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Application of Phase rule D E P A R T M E NT O F
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in Reactive Components
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Problem:
A pure solid NH4Cl is introduced into an evacuated chamber. It is
then allowed to decompose and equilibrium has been established by
following reaction:
NH4Cl(s) = NH3(g) + HCl(g)
Calculate the number of components and degrees of freedom.
Solution:
N = 3 (NH4Cl(s) , NH3(g) , HCl(g))
P = 1 solid (NH4Cl(s) ) + 1 gases (NH3(g) + HCl(g ) = 2
r=1
s = 1 as P NH3(g) = P HCl(g)
t=0
C = N – r – s = 3 – 1 -1 = 1
F = C – P + 2 – t = 1 -2 + 2 – 0 = 1
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Application of Phase rule D E P A R T M E NT O F
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in Reactive Components
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Problem:
Show that the system in which the reaction
Mn(s) + 2/3 AlCl3(g, 1atm) = MnCl2(l) + 2/3 Al (l)
is at equilibrium is invariant.
Solution:
N = 4 (Mn(s), AlCl3(g), MnCl2(l), Al (l))
P = 1 solid (Mn) + 2 liquids(MnCl2(l)and Al (l)) + 1 gas (AlCl3(g)) = 4
r=1
s=0
t = 1 (1 atm of AlCl3(g))
C = N –r – s = 4 – 1 – 0 = 3
F=C–P+2–t=3–4+2–1=0
This is an invariant system
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Application of Phase rule D E P A R T M E NT O F
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in Reactive Components
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Problem:
Consider reduction of FeO with CO under standard
conditions i.e. P = 1 atm.
FeO(s) + CO(g) = Fe(s) + CO2(g).
Calculate the number of components and degrees of freedom.
Solution:
In this system we have P = 3 (i.e. two solids FeO and Fe
and a gaseous phase CO+CO2) and N = 4, r = 1, s = 0 and
t = 1 (PCO + PCO2 =1 atm)
C = N –r –s = 4 -1 -0 = 3
F = C - P + 2-t = 3 – 3 + 2 -1 = 1
Thus the above system has only one degree of freedom,
either temperature or pressure.
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Phase Diagram
D E P A R T M E NT O F
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Solid Solution
D E P A R T M E NT O F
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Solid Solution
D E P A R T M E NT O F
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Types of Solid Solubility
D E P A R T M E NT O F
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Phase Diagram
D E P A R T M E NT O F
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Solidus
The phase boundary between solid and two phase region.
Liquidus
The phase boundary between liquid and two phase
region.
Solvus
The solid state phase boundary between terminal solid
solution and two phase region.
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Single – Component System –
Variation of Free energy with
D E P A R T M E NT O F
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Temperature
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G( s )
S ( s )
T P
G(l )
S (l )
T P
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Single – Component System –
Variation of Free energy with
D E P A R T M E NT O F
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Temperature
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G
S
T P
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Single – Component System –
Variation of Free energy with
D E P A R T M E NT O F
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Pressure
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G( l )
V( l )
P T
G( s )
V( s )
P T
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Variation of Free energies of
solid liquid and vapour H2O with
D E P A R T M E NT O F
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Binary Phase Diagrams
D E P A R T M E NT O F
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Isomorphous system
D E P A R T M E NT O F
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Eutectic system
D E P A R T M E NT O F
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Experimental Determination of D E P A R T M E NT O F
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Liquidus and Solidus– Cooling Curve Method Institute of Technology Banaras Hindu University
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Experimental Determination of D E P A R T M E NT O F
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Liqidus and Solidus– Cooling Curve Method Institute of Technology Banaras Hindu University
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Experimental Determination of D E P A R T M E NT O F
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Solvus– Cooling Curve Method
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Experimental Determination of D E P A R T M E NT O F
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Solvus– Cooling Curve Method
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Free energy – Composition D E P A R T M E NT O F
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Diagram
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Free – Energy Composition D E P A R T M E NT O F
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Diagram for Binary Systems Institute of Technology Banaras Hindu University
Isomorphous
System
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Free – Energy Composition D E P A R T M E NT O F
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Diagram for Binary Systems Institute of Technology Banaras Hindu University
Eutectic System
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D E P A R T M E NT O F
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