Indian Institute of Technology Roorkee

Spring semester-2017

MTN-102 Metallurgical Thermodynamics and Kinetics

Course Instructor

S.R. Meka

Metallurgical and Materials Engineering Department

most of the contents are from book titled

Introduction to the Thermodynamics of Materials by David R. Gaskell
Equation of State – Ideal Gas
V of a fixed quantity of pure gas has dependence on independent properties T and P

Equilibrium state of existence lie on a surface in P-V-T space

Equation of State – Ideal Gas
Boyle’s law: @ constant T, n Charles law: @ constant P,n

R – universal gas constant

Avogadro’s law: @ constant T, P

V of 1 mole of ideal gas at STP is 22.414 liters

STP: 273.15K and 1 atm
 Thermodynamic Terminologies
Extensive properties
Volume, mass, length, heat capacity

Intensive properties
T, P, density, specific heat capacity, molar volume
For n moles of ideal gas the equation of state

Phase: finite volume of physical system having uniform constant properties

Components: chemical species of fixed composition

- chemical elements and stoichiometric compounds

Phase diagrams: graphical representation of equilibrium states of a system

1 component system (unary), 2 component (binary), 3 component

(ternary), etc.
 Unary phase diagram of water

Melting (solid to liquid), sublimation (solid to vapor) and evaporation (liquid to vapor)
 Binary phase diagrams

We need three axes to represent composition, T and P; 3D diagram

Constant P (usually 1atm) section can be presented as a T vs composition diagram

 Fe-O phase diagram

T (oC)
 Relation between heat and work
Caloric theory: heat consists of a invisible caloric fluid/gas. More caloric gas more temperature

1798 Count Rumford: heat production during boring of cannon at Munich Arsenal

Defense from caloric theory: Caloric content per unit mass depends on total mass of body
Count Rumford: Blunt borer resulted in same heat production at lower content of metal turnings
Defense from caloric theory: Action of air on metal surfaces during boring
1799 Humphrey Davy: Melting of two blocks of ice by rubbing them in vacuum

Experiments by James Joule: performing work in a adiabatically contained water and

measuring T of water

Source: Wikipedia
 Relation between heat and work
Experiments by James Joule: performing work in a adiabatically contained water and
measuring T of water
Methods of work

Increase in T is proportional to amount of work done

Mechanical equivalent of heat: 1 calorie = 4.184 Joules
Calorie: quantity of heat required to increase
the T of 1g of water (@ 1atm pressure) by 1oC
 Internal Energy
• Joules experiments resulted in the following statement;
“ the change of a body inside an adiabatic enclosure from a
given initial state to a given final state involves the same
amount of work by whatever means the process is carried out”

• Need for functions which depends only on the internal state of a body
- Internal Energy U

• Lifting a body of mass m in a gravitational field from height h1 to h2

Work done on the body is only position (H) dependent and independent of path taken by the body
 Internal Energy – 1st law of Thermodynamics

Change in the internal energy between two states in an adiabatic process is equal to work done
work done by a body + ve
work done on a body - ve

Change of state can also be achieved by adding or subtracting the heat into the system

heat flow into the body + ve

heat flow out of the body - ve

Simultaneous changes of amount of work done and the heat flow

 Internal Energy – 1st law of Thermodynamics

Independent of path – state function

Path dependent
pressure

volume constant pressure process

constant volume process

@ constant volume, w = 0

Integration; Enthalpy (H)

 1st law of Thermodynamics; Heat Capacity

constant volume process constant pressure process

1st law of Thermodynamics; Heat Capacity

common sense!

for Ideal Gas;

 1st law of Thermodynamics; Heat Capacity

the work done by the system per degree rise in temperature in expanding
against the constant external pressure acting on the system.

the work done per degree rise in temperature in expanding against the internal
cohesive forces acting between the constituent particles of the substance.
For ideal gas containing non-interacting particles this work is zero.

In real gases the internal pressure contribution is very much smaller in magnitude than
the external pressure contribution; but in liquids and solids, in which the interatomic
forces are considerable, the work done in expanding the system against the external
pressure is insignificant in comparison with the work done against the internal pressure.
 1st law of Thermodynamics
Reversible Adiabatic Processes
In reversible adiabatic process, and gas never leaves the equilibrium state

for ideal gas,

Integration,
 1st law of Thermodynamics
Reversible Isothermal Processes

, then
 Thermodynamic Temperature and Ideal Gas

Gas Thermometer Ideal Gas PV = nRT = NkT k=1.3806×10−23 J K-1

R=8.314 J mol-1 K-1

PV

slope = nR

273.16 0
T (oC) T

Triple point of water is set at 273.16 K

18
Microscopic Interpretation of Ideal Gas Law : Statistical Mechanics
Assumptions:
- 1/3rd of atoms are moving normal to each face
- All atoms are moving with same velocity

F=

P=

P=

PV = =

= kT

T of a ideal gas represents the kinetic energy of atoms

19
 Fist Law of Thermodynamics and Specific Heat

W = F x L = P x A x L =P dV L

Molar specific heat (C):

Amount of heat required to raise the temperature of a I mole of gas by 1K

At constant volume At constant pressure

20
 2nd law of Thermodynamics
Spontaneous or natural or irreversible processes
Can we know the exact values of heat and
work in a spontaneous reaction?
1st law of Thermodynamics

c initial state final state

c2 A isolated system,
ceq dU = 0
c1 B
A B

model system (closed system, dU = 0) spontaneous processes:

contact: 1) DW →DQ at Th
Th = const. →DQ Tl = const. 2) DQ at Th →DQ at Tl
3) DW →DQ at Tl
→DQ →DQ

kg kg DQ change of a new
Sf  Si  variable of state:
DW T entropy
2nd law of Thermodynamics- Reversible and Irreversible Processes
sudden decrease of by
- decrease
- water evaporates spontaneously; its T decreases
- flows from reservoir to cylinder

after 1 mole of water evaporation, if is restored

instantaneously, evaporation and heat flow ceases
i.e., equilibrium reestablishes
work done by the system,
water vapor
= (T) where, is molar volume of water vapor at T
which represents
liquid water
sudden increase of by
after 1 mole of water condensation, if is
Reservoir @ constant T
restored instantaneously, condensation and
heat flow ceases i.e., equilibrium reestablishes
work done on the system,
Permanent change in the external agency
on the system - by the system
equivalent heat has been absorbed by the cylinder
 2nd law of Thermodynamics- Reversible and Irreversible Processes
irreversible process
sudden decrease of by
- decrease
- water evaporates spontaneously; its T decreases
- flows from reservoir to cylinder
water vapor
after 1 mole of water evaporation, if is restored
= (T)
instantaneously, evaporation and heat flow ceases
i.e., equilibrium reestablishes
liquid water
work done by the system,
Reservoir @ constant T where, is molar volume of water vapor at T
which represents
reversible process
is changed only by an sudden increase of by
infinitesimal value, after 1 mole of water condensation, if is
restored instantaneously, condensation and
-Negligible permanent change heat flow ceases i.e., equilibrium reestablishes
in the external agency work done on the system,
on system ≈ by system Permanent change in the external agency
very slow processes on the system - by the system
 2nd law of Thermodynamics- Entropy and reversible heat
Evaporation process
Reversible evaporation – maximum work,
maximum heat,

Irreversible evaporation – less work,

less heat,

is the amount of mechanical energy

which degrades to thermal energy during irreversible process

reversible evaporation irreversible evaporation

as entropy increases
24
 2nd law of Thermodynamics- Entropy and reversible heat
condensation process
Reversible condensation – less work,
less heat,

Irreversible condensation – maximum work,

maximum heat,

is the amount of mechanical energy

which degrades to thermal energy during irreversible process

reversible condensation irreversible condensation

entropy is not created as entropy is created

25
 2nd law of Thermodynamics- Entropy and reversible heat

irreversible evaporation irreversible condensation

as entropy is created as entropy is created

The difference in entropy between the final and initial states is independent of
whether the process is conducted reversibly or irreversibly, i.e., independent of the
path; Entropy is a state function

when the system changes from state A to state B,

change in entropy can be determined only by measurement of heat flow at the

temperature T. Therefore entropy changes can be measured only for reversible processes
26
 2nd law of Thermodynamics- Entropy and reversible heat
- reversible isothermal compression of an ideal gas
as ,

on the gas = flown out of the gas

as , is negative, i.e., work is done on the gas

as , is negative

In reversible process, , therefore

27
 2nd law of Thermodynamics- Entropy and reversible heat

THE REVERSIBLE ADIABATIC EXPANSION OF AN IDEAL GAS

- Change in entropy is zero

- wmax equals the decrease in the internal energy of the gas.
- All states on a PVγ=constant line are states of equal entropy
- A reversible adiabatic process is an isentropic process.

THE IRREVERSIBLE ADIABATIC EXPANSION OF AN IDEAL GAS

-The heat produced by the degradation remains in the gas, and thus the final temperature of
the gas after an irreversible expansion is higher in comparison to the final temperature reached
during reversible expansion.
- Final state of a gas differs from the final state after a reversible expansion from the same
initial to the same final pressure.
 2nd law of Thermodynamics- Heat engines
Heat Engine Efficiency Carnot reversible heat engine

Reservoir of at

pressure
Heat
Work w
Engine

Reservoir of at

volume
1. A to B – reversible isothermal expansion 3. C to D – reversible isothermal compression

2. B to C – reversible adiabatic expansion 4. D to A – reversible adiabatic expansion

 2nd law of Thermodynamics- Heat engines
Efficiency of Carnot Engine
1. A to B – reversible isothermal expansion 3. C to D – reversible isothermal compression

2. B to C – reversible adiabatic expansion 4. D to A – reversible adiabatic expansion

Total work done

for proof, see next slide

( ) ( )
Efficiency
 2nd law of Thermodynamics- Heat engines
Efficiency of Carnot Engine ( ) ( )
Efficiency

B to C – reversible adiabatic expansion

…….(1)

D to A – reversible adiabatic expansion

…….(2)

( )
gives,
( )
 2nd law of Thermodynamics- Carnot Heat engines

Carnot Engine Engine more efficient than Carnot Engine!

efficiency efficiency

Reservoir of at Reservoir of at

Carnot best Work

Work
Engine Engine

Reservoir of at Reservoir of at
 2nd law of Thermodynamics- Carnot Heat engines
Scaled up Carnot Engine

Engine efficient than Carnot Engine! Scaled up and reversed Carnot Engine

Reservoir of atReservoir of at
.5

Carnot 12.5
Work
refrigerator
22.5
Reservoir of atReservoir of at
 2nd law of Thermodynamics- Carnot Heat engines
Carnot engine efficiency

For any reversible cyclic process ABA

and
work done = area ABA
not state functions
area ABA =
into system +ve
pressure

out of system -ve

for very small sized Carnot cycles

- entropy S
volume
 2nd law of Thermodynamics- Entropy
“ The entropy of a system in an adiabatic enclosure can never decrease; it increases
during an irreversible process and remains constant during a reversible process”

Isothermal expansion from state A to state B

1st law of Thermodynamics

Can we know the exact values of and in a spontaneous reaction after defining the path
from A to B?

and in a spontaneous reaction depends on degree of spontaneity/irreversibility

2nd law of Thermodynamics sets a limit on amount of work which can be done by a system
- Sets an upper limit on the value of

Integration between states A and B

 2nd law of Thermodynamics- Entropy
entropy is a state function- the change in the entropy of the system is the same whether the
process is conducted reversibly or irreversibly

Free expansion of a gas What is the limit of irreversibility?

Adiabatic container
Adiabatic container Initial state
with gas
under vacuum

Adiabatic container with gas

final state

Entire work gets degraded into heat

- maximum possible entropy creation
- Limit of irreversibility is free expansion
 2nd law of Thermodynamics- Entropy

2nd law of thermodynamics: statements

- “It is impossible to construct an engine which will work in an complete cycle, and
convert all the heat it absorbs from a reservoir into mechanical work”, i.e. a perpetuum
mobile of second kind cannot exist

- “Heat cannot by itself pass from a colder to a hotter body.” (Clausius)

- “The energy of the universe is a constant. The entropy of the universe approaches a
maximum” (Clausius)

- “The sum of the entropy changes of a system and its exterior can never decrease.”

- “The increase of entropy distinguishes the future from the past: there exists an arrow of
time”

(Kondepudi & Prigogine, Modern Thermodynamics)

 Combined 1st and 2nd laws of Thermodynamics

2nd law of thermodynamics

Irreversibility – entropy

1st law of Thermodynamics

Relation between heat and work

Combination of 1st and 2nd laws

Closed system and change in volume is the only form of work

Characteristic state function for

internal energy:
 Combined 1st and 2nd laws of Thermodynamics

Combination of 1st and 2nd laws

Characteristic state function for

internal energy:

Considering S as dependednt
variable on U and V:

Rearranging (1)
 Combined 1st and 2nd laws of Thermodynamics

At equilibrium;
- for a system of constant and constant , of the system is maximum
- for a system of constant and , of the system is minimum
 Statistical Interpretation of Entropy
Entropy – atomic disorder

Gibbs: Entropy is a measure “degree of mixedup-ness” at the atomic/molecular level,

- Larger value of Entropy means more mixed up of the constituent particles of a system

Melting phenomena: at absorbs , latent heat of melting

increases, @ constant,

Overall during melting at the Tm ,

Melting and freezing at is a reversible process

Spontaneous freezing of a supercooled liquid- irreversible process

Overall ( ) increases
 Statistical Interpretation of Entropy
Spontaneous freezing of a supercooled liquid- irreversible process
Overall ( ) increases
Step 1: cooling of liquid from to

+
L L
@ Reservior at Reservior at

Step 2: freezing of liquid at

liquid metal
reservoir at

.
.
 Statistical Interpretation of Entropy
CONCEPT OF MICROSTATE
three identical particles located on three distinguishable lattice sites A, B, and C
Energy quantization: total
equally spaced levels ground level , the first level , the second level ….

possible (a) (b) (c)

distributions

ABC ABC ABC ABC ABC ABC ABC ABC ABC

microstates within distributions of particles among energy levels in a system of constant energy
 Statistical Interpretation of Entropy
CONCEPT OF MICROSTATE
THE MOST PROBABLE MICROSTATE

probability of observing the system in any one of its ten possible microstates is 1/10

probabilities that the system occurs in distributions a, b and c are 1/10, 3/10 and 6/10

Distribution c is thus the “most probable.”

Macrostate dictates the unique values for U, V, T, n

Microstate dictates the positions and velocities of particles

 Statistical Interpretation of Entropy
Calculating the number of arrangements within a given distribution Ω

( )

( )

( )

For total of particles distribution among the energy levels; in level , in level
and in highest level

The set of numbers which maximizes the value of Ω represents the most probable microstate
 Statistical Interpretation of Entropy

most probable microstate-set of numbers which maximizes the

Ω
Taking log on both sides For larger values of , Stirling’s approx.

Fixed macrostate (i.e., fixed values of U, V and n)

At most probable distribution ,

method of undetermined multipliers

 Statistical Interpretation of Entropy
method of undetermined multipliers is constant having unit reciprocal of energy
after, (1) X , (2) X , sum (1 to 3) is a dimensionless constant

is a energy partition function which depends on

magnitude of β and by the quantization of the energy
 Statistical Interpretation of Entropy
is constant having unit reciprocal of energy

is a energy partition function which

@ particle occupancy in energy depends on magnitude of β and by the
levels decreases exponentially with quantization of the energy
increase in energy of the level

high/lower
low/higher
Energy level

Energy level
@ constant V and n

Number of particles ) Number of particles )

Statistical Interpretation of Entropy
@ very large values of ,
 Statistical Interpretation of Entropy

System of particles in thermal equilibrium with heat bath

 Statistical Interpretation of Entropy

System of particles in thermal equilibrium with heat bath

combined system (particle system + heat bath) state is fixed

particle
Particle
combined system (particle system + heat bath) state is fixed; system
Fixed values for , and

heat bath

For small exchange of energy from heat bath to the particle system at constant , and

is only function of only

For small exchange of energy from heat bath to the particle system at constant
1st law of thermodynamics
are state functions
2nd law of thermodynamics
 Statistical Interpretation of Entropy- Boltzmann’s equation
A and B made of same element
- no. of microstates/complexions

Spontaneous flow of from hot to cold bodies A-Hot B-Cold

- Should increase and net flow ceases at equilibrium

impossible
Maximum of product occurs at equilibrium , i.e.,

At thermal equilibrium (same T for A and B), exchange of between A and B;

At thermal equilibrium (same T for A and B), exchange of between A and B;

Irreversible process: non-equilibrium state to equilibrium state(classical thermodynamics)

less probable state to more probable state
 Statistical Interpretation of Entropy-
configurational and thermal entropies
- no. of microstates/complexions

Thermal entropy: number of ways distribution of (thermal) energy among identical particles
of a closed system can be realized

Configurational entropy: number of ways particles can be distributed in space

: all A atoms are on A-side :

crystal A @ T crystal B @ T
: one A atom on B-side :
A A B B
:
two A atoms on B-side :

: three A atoms on B-side A A B B

:

: four A atoms on B-side :

Spontaneous flow of matter
Total no. of distinguishable arrangements A to B and B to A
 Statistical Interpretation of Entropy-
configurational and thermal entropies
- no. of microstates/complexions

Thermal entropy: number of ways distribution of (thermal) energy among identical particles
of a closed system can be realized

Configurational entropy: number of ways particles can be distributed in space

: all A atoms are on A-side :

crystal A @ T crystal B @ T
: one A atom on B-side :
A A B B
:
two A atoms on B-side :

: three A atoms on B-side A A B B

:

: four A atoms on B-side :

Spontaneous flow of matter
Total no. of distinguishable arrangements A to B and B to A
:
no concentration gradients
 Statistical Interpretation of Entropy-
configurational and thermal entropies
/ Configurational entropy

Initial state-1 Final state-2

crystal A @ T crystal B @ T crystal A @ T crystal B @ T

A A B B Spontaneous A B A B

@ constant
A A B B U, V and n B A B A

closed systems in thermal contact; Ideal mixing;

open chemically identical systems in thermal contact;
 Statistical Interpretation of Entropy-
configurational and thermal entropies

Stirling’s approx.
 Statistical Interpretation of Entropy-
configurational and thermal entropies
Stirling’s approx.

ln  N !
N=2
20
200

N  ln N  N
 Need of convenient auxiliary state functions
Combination of 1st and 2nd laws

U has dependence on independent variables S and V

–S is not easily measurable and controllable although V can be measured and controlled

Experimentalist choice: P and T convenient to define equilibrium at constant T and P

- equation of state at constant P and T

Theoretician choice: V and T fixes the quantization of energy and the partition function
- equation of state at constant T and V

Equation of state should also accommodate the

- change in chemistry of system (chemical reactions)
- work other than PdV (electrical work in a galvanic cell)

Need for state functions which are convenient and compatible with the thermodynamic laws
 convenient auxiliary state functions-Legendary transformations
Combination of 1st and 2nd laws

every point has values of x and y

every point has values of and

slope
legendry transform of

Intercept

is differentiation of
eliminating x and y gives
Convenient auxiliary state functions- Enthalpy
Combination of 1st and 2nd laws

constant S
Convenient auxiliary state functions- Helmoltz Free Energy
Combination of 1st and 2nd laws

constant V
Convenient auxiliary state functions- Gibbs Free Energy

constant P

H
 Characteristic State Functions

Internal energy dU  TdS  pdV

H  U  pV

Enthalpy dH  TdS  Vdp

A  U  TS
Helmholtz Energy / dA   SdT  pdV
Free Energy
G  H  TS
Gibbs Energy /
Free Enthalpy dG   SdT  Vdp
 1st order derivatives of state variables

 U   H 
   T   
 S V  S  p
dU  TdS  pdV
 A   U 
    p  
dH  TdS  Vdp  V T  V S

dA   SdT  pdV  G   A 
   S   
 T p  T V
dG   SdT  Vdp
 H   G 
  V   
 p S  p T
 2nd order derivatives- Maxwell relations
dU  TdS  pdV U = U(S,V)

   U    T   p     U    T   p 
                  
 V  S V  S  V S S
 V  S V  S V  V  S  S V

H = H(S,P)  V   T 
dH  TdS  Vdp    
 S  p  p  S

A = A(T,V)  S   p 
dA   SdT  pdV    
 V T  T V

 V   S 
dG   SdT  Vdp G = G(T,P)      
 T  p  p T
 Equilibrium Criterion

Combination of First & Second Law provides the criteria for equilibrium that

1. In a system of constant internal energy and constant volume(constraint

dU = 0, dV = 0), the entropy has its maximum value, and

2. In a system of constant entropy and constant volume (constraint dS = 0,

dV = 0), the internal energy has its minimum value.
 Equilibrium Criterion- Helmholtz Free Energy
@ constant T and constant V

1st law

2nd law

@ constant V,

- A decreases during a spontaneous process as

- minima in A represents the equilibrium condition
- At equilibrium =0,

closed system @ constant T and V:

the A can only decrease or remain constant
equilibrium is attained when A achieves its minimum value.
 Equilibrium Criterion- Helmholtz Free Energy
Solid vapor equilibrium at constant V and T

( . )

No. of atoms in vapor phase ( )

No. of atoms in vapor phase ( )
 Equilibrium Criterion- Gibbs Free Energy
@ constant T and P

1st law

2nd law

for

- G decreases during a spontaneous process as

- minima in G represents the equilibrium condition
- At equilibrium =0,
 Case of change in composition and size of system
G is a function of T, P, and the numbers of moles of all of the species present in the system

G = G(T,P, ni, nj, nk,….) ni, nj, nk,…are the numbers of moles of the species i, j, k,…

, , … , , … , , … , , …

constant T, P, ni, nj, nk,….represents closed system

Chemical Potential
, , … , , …

G is f(T, P, and composition)

for open systems and closed systems undergoing chemical reactions.
 Case of change in composition and size of system- chemical potential
- Rate of increase of G with the species i added to the system at constant T, P and , ,…
-extensive property

, , …
characteristic state f(T,P, composition)
Similarly,

, , …
characteristic state f(S,V, composition)

, , …

characteristic state f(S,P, composition)

, , …
characteristic state f(T,V, composition)
 Case of change in composition and size of system- chemical potential
- Rate of change of G with the species i added to the system at constant T, P and , ,…
-extensive property

, , …
characteristic state f(T,P, composition)

for reversible change in composition , therefore;

chemical work

mechanical work
 usefulness of 2nd order derivatives- Maxwell’s equations

of an Ideal gas in a closed system

Maxwell’s equations
 T   p 
     
 V  S  S V

 V   T 
   
 S  p  p  S
@ constant V

 S   p 
   
 V T  T V
for ideal gas
 V   S 
     
 T  p  p T
 usefulness of 2nd order derivatives- Maxwell’s equations
of an closed system of constant chemistry
Maxwell’s equations
 T   p 
     
 V  S  S V

 V   T 
   
 S  p  p  S

 S   p 
   
Relation of U to measurable T,V and P  V T  T V
for ideal gas
 V   S 
     
 T  p  p T

of an ideal gas depends on only T and independent on V

Similarly for H,
 Gibbs-Helmholtz Equation

@constant P and chemistry

divide by and rearrange

G-H equation; for system at constant composition and P

can be obtained from the knowledge of as a function of T

can be obtained from the knowledge of as a function of T

 Temperature dependence of characteristic functions
dU   Q  pdV dA   SdT  pdV dH  TdS  Vdp dG   SdT  Vdp

dU d2 A dH d2G
 CV T  CV  Cp T  Cp
dT V 2
dT V dT p dT 2 p

T
H (T )  H0   c p dT
0
T T
S T   S0,p   and S T   S0,V   cTV dT
cp
T
dT
0 0
T T
G T   H0   c p dT  TS0,p  T  Tp dT
c

0 0
T T
A T   U0   cV dT  TS0,V  T 
cV
T
dT
0 0
 Heat Capacities

Some rules of thumb:

Dulong-Petit (1819): The heat capacity of solid elements is equal.

Neumann-Kopp (1831): heat capacity of a solid solution

 Heat Capacities- Theoretical predictions
Dulong-Petit

Einstein (1907): atoms are oscillators vibrating

with a single frequency

Temperature (K)

Debye atoms are oscillators vibrating with

Debye (1912):
Einstein a range of frequencies; interatomic
distance sets a limit on vibration

Al Debye law for low T specific heat

 Heat Capacity
Measured heat capacities are usually expressed as,
valid in a selected range of T

monoclinic − ZrO (298 − 1478K) J/K.mole

tetragonal − ZrO (1478 − 2950K) J/K.mole

Temperature (K) Temperature (K)

 Enthalpy- reference state

Elements in stable modification: Substance H298.15 K in kJ/mol

Sn (white) 0
H298,15 K ≡ 0 J at T  298,15K;
Sn (grey) -2.09
p  10 Pa
5
C(Graphite) 0
C (Diamond) 1.9

@ 298K Mg3Sb2 - 330.76

( ) ( ) ( )

( ) ( )
 Enthalpy- T dependence

( ) ( )
 G and A : T dependence

G = H - TS A = U - TS

Tu  T
H T   H 0   cp dT  DH u     c p dT
with reaction 0  
Tu
→
Tu  T
cp c p
S T   S0, p   T
 
dT  DSu   T dT
0 Tu 
 T dependence of Entropy: 3rd law of thermodynamics

Third law of thermodynamics

Entropy has an absolute value, and the entropy of all substances
which are in complete internal equilibrium is zero at 0 K
Entropy change at constant T and P

DG  DH  T DS  0

H  HI  DH p,T
SE  SI  p,T  E    DS  p,T
T p,T
T

Typical process: melting, evaporation,...

Entropy of melting for pure metals DSm:

DH m
DS  m 
m
Richard’s rule
T

Entropy of evaporation for pure metals DSV:

DH V
DS  b  Trouton rule
V

Entropy change at constant T and P

Phase Equilibrium- One Component System
Variation of G with T @ constant P dG   SdT  Vdp P= constant-1atm
( ) ( ) @ P= 1 atm and T=273K

( )

( → ) ( → )

( → ) ( → )

Variation of G with P @ constant T=273K

P= constant=1atm
Phase Equilibrium- One Component System

THE VARIATION OF G WITH T and P

() ( ) at equilibrium

dG   SdT  Vdp

( ) () → at equilibrium
. ( ) () →

Clapeyron Equation
.
Phase Equilibrium- One Component System
Equilibrium between vapor phase and condensed phase

( ) ( ) at equilibrium

Clapeyron Equation
.

assuming ideal nature for vapor phase

.

. .
Phase Equilibrium- One Component System

Clausius-Clapeyron Equation

If is independent of temperature, i.e., Cp (vapor) = Cp (condensed)

Saturated vapor P increases exponentially with increase in T

Phase Equilibrium- One Component System

Clausius-Clapeyron Equation

If Cp (vapor) ≠ Cp (condensed) but ∆Cp is independent of T

( )

( )

Integration of Clausiaus-Clapeyron equation gives,

Knowing this, one can calculate the

 Phase Equilibrium- One Component System
() ( ) (→ )

Normal (at P= 1 atm) of water = 373K and

Clausius-Clapeyron Equation

( ) (→ )

( )

( )

C can be calculated using = 373K at P= 1 atm.

after inputting the value of R and converting ln to log
Phase Equilibrium- One Component System

() ( )
calculated

Fit to experimental data to an expression

()

experimental

( )

calculated
Phase Equilibrium- One Component System
Equilibrium vapor pressure of several elements
Phase Equilibrium- One Component System

Gibbs phase rule

This will be derived later!

Phase Equilibrium- One Component System
Phase Equilibrium- One Component System
Equilibrium of two phases: G  G  dG   dG 

Projection of coexistence curves on P-T space provides the one component phase diagram
Phase Equilibrium- One Component System

Phase diagram of Fe G vs. T curves for various Fe phases

Clapeyron Equation
.
Phase Equilibrium- One Component System

Schematic Phase diagram of ZrO2

Clapeyron Equation
.