Classical Thermodynamics

CHM102

1
Quantum Chemistry: Dr. Saurav Pal
Molecular properties
Spectroscopy: Dr. Pankaj Mandal

Kinetics
Macroscopic
p p properties
p
Thermodynamics

2
Thermodynamics: “Heat”
Heat + “Study
Study of motion”
motion Heat Transfer

 Themodynamics: Heat, work, energy

Wide Applications:

1. Energy change associated to all chemical and physical processes.

2. Mutual transformation of different kinds of energy.

3. reaction.
3 To predict the direction and extent of chemical reaction

Birth:
3
Industrial revolution (late 18th, early 19th century)
4
 Thermodynamics

Basically is based on four laws.

These laws
Th l are nott formulated,
f l t d rather
th these
th are generalization
li ti
deduced from our long experience in nature.

Classical thermodynamics… is the only

physical theory of universal content which
I am convinced that, within the
applicability of its basic concepts, will
never be
b overthrown.”
h ”
Albert Einstein
5
 Classical Thermodynamics:

Describes macroscopic properties of the systems.

Entirely Empirical

 Based on 4 Laws:

0th Law
L ⇒ Defines
D fi T
Temperature
t (T)

1st Law ⇒ Law of conservation of energy

energy. It tells that system may
exchange energy with its surroundings strictly by heat flow or
gy ((U))
work. Defines Internal Energy

2nd Law ⇒ Defines Entropy (S)

3rd Law ⇒ Gives Numerical Value to Entropy

 Systems
• A system is part of the universe chosen for observation,
separately from the rest of the universe.
universe
• The system plus surroundings comprise a universe.
• The boundary between a system and its surroundings is the
system wall.
• If heat cannot pass through the system wall,
wall it is termed an
adiabatic wall, and the system is said to be thermally isolated
or thermallyy insulated.
• If heat can pass through the wall, it is termed a diathermal
wall.
• Two systems connected by a diathermal wall are said to be in
thermal contact.
7
 Isolated Closed and Open Systems
Isolated,
• An isolated system cannot exchange mass or energy with its
surroundings.
di
• The wall of an isolated system
y must be adiabatic.

• A closed system
y can exchange
g energy,
gy, but not mass,, with
its surroundings.
• The energy exchange may be mechanical (associated with a
volume change) or thermal (associated with heat transfer
through a diathermal wall).

• An open
p system
y can exchange
g both mass and energy
gy with
its surroundings. 8
Open System

9
 Closed System

Isolated System Isolated System 10

 Isolated, Closed and Open Systems

Isolated Closed Open

S t
System S t
System System
Neither energy
Energy, but not Both energy and
nor mass can be
mass can be
b mass can be
exchanged.
exchanged. exchanged. 11
 Properties of a System

Thermodynamic variables which are experimentally

measurable. Such variables are macroscopic properties
such as P,
P V,
V T,
T m,
m composition,
composition viscosity etc
etc.

Thermodynamic
y variables

Intensive variables extensive variables

T, P, density, specific gravity, Volume, energy, enthalpy,
surface tension,
Entropy, free energy, mass
specific heat capacity, dielectric
constant.
Depends on the mass
Does not depend
p upon
p mass of of the system.
the system
12
 States of a system
How do we define a State of a System?

Macroscopic
p state of a system
y can be specified
p by
y
thermodynamic variables which are experimentally
measurable

• Composition – mass of each chemical species that is

present in the system
system.

•p
pressure (p or P),
), volume ((V),
), Temperature
p ((T),
), density,
y,
etc.

• field
fi ld strength,
t th if magnetic/electrical
ti / l t i l fifield
ld actt on th
the
system

• gravitational field 13
 Equilibrium States

1. Co
Composition
pos t o remains
e a s fixed
ed a
and
d de
definite.
te

2. Temp. at all parts of the system is the same.

3. No unbalanced forces between different parts

of the system or between system and surroundings.
surroundings

System at equilibrium must have definite P, T, and composition

14
 Processes

A process refers to the change of a system from one equilibrium

state to another
another.

Isothermal (T)

Adiabatic (no heat exchange between system and surroundings).

Isobaric (p)
(p),

( )
Isochoric (V)

Cyclic
15
 Reversible Process:

• Change must occur in successive stages of infinitesimal quantities

• Infinite duration
• Changes of the thermodynamic quantities in the different stages will be the
same as in the forward direction but opposite in sign wrt forward
direction

Irreversible Process:

• Real / Spontaneous
• Occurs suddenly or spontaneously without the restriction of
occurring in successive stages of infinitesimal quantities.
ot remain
• Not e a in tthe e virtual
tua equ b u during
equilibrium du g the
t e transition.
t a sto
• The work (w) in the forward and backward processes would
be unequal.
16
State function: Those thermodynamic properties depends on the state of the
system, not on the path through which it has been brought in
that state. Potential energy, Internal energy, entropy,
enthalpy.

Path function: Those thermodynamic properties depends on the path

through which it has been brought in that state.
(Heat, work).

17
 Mathematical formulation of State function (TUTORIAL 1):
1. If any thermodynamic property or function, z = f(x,y) depends
on the initial and final values of thermodynamic variables, then the
change of zz, ii.e.,
e dz is a perfect differential
differential,

2 In that case,
2. case it will follow the following mathematical relationship
relationship,

3. If Z = f(x,y) depends on the initial and final values of

thermodynamic variables, then also ∮dz= 0

18
 Concept of Heat and work
Joule s experiment
Joule's W = JQ

W = work expended in the

production of heat or
obtained from heat

Heat  Work

Both heat and work represents energy in transit

transit.

Work involved in a process , heat change involved during

a process depend
d d on the
h pathh off transformation.
f i

 Work and heat are the two methods by which energy is exchanged
between system and surroundings.
19
 Sign Convention of heat and work:

Work:
The work done by the system is defined to be nagative (-).
 The work done on the system – the external work of
mechanics – is positive (+).

Heat:
The heat absorbed by the system is defined to be positive (+)
(+).
 The given out by the system is negative (-).

20
U = Uf – Ui Measurable 21
 (TUTORIAL-1)
Concept of Internal energy:

Internal Energy, U. is the total energy within a system.

U is the internal energy of the body (due to molecular motions
and intermolecular interactions)

• Extensive property.
• State
S ffunction,
i independent
i d d off path.
h
• For cyclic process,
dU is a perfect or exact differential
22
Thermal Equilibrium and Zero’th Law of Thermodynamics

23
 First Law of Thermodynamics:

Energy cannot be destroyed, it can be transformed to

one form to another
another. (Law of conservation of energy)
energy).

K E 0,
K.E.= 0 P E = maximum
P.E. i

K.E.= maximum, P.E. = 0

 Energy
gy is conserved
24
 1st law of Thermodynamics

The first law for a closed system or a fixed mass may be expressed
as:

net energy transfer to (or from)

the system as heat and work = net increase (or decrease) in the
total energy of the system

q+ w = U
25
Moving Boundary Work

26
How the pressure of a cylinder can be changed?

27
 Equation of state for Ideal and Real gas

Ideal gas: PV = nRT

Real gas: van der Waal

Waal’s
s equation

 n 2a 
 P  2 V  nb   nRT N·b

 V 

28
 TUTORIAL 2
Work and heat change associated in Isothermal Reversible
and irreversible expansion

(b) Irreversible process:

Wirr = Pext (V2 – V1)

29
 TUTORIAL 3
Adiabatic process in an Ideal Gas
• Since dQ = 0 for an adiabatic process,
dU = – P dV andd dU = CV dT,
dT so that
th t dT = – (P/CV) dV .
• For an ideal g
gas, PV = nRT,
so that P dV +V dP = nR dT = – (nRP/CV) dV.
Hence V dP + P (1 +nR/CV) dV = 0
0.
Thus, CV dP/P + (CV + nR) dV/V = 0.
For an ideal gas, CP – CV = nR.
so that CV dP/P + CP dV/V = 0,0 or dP/P + γ dV/V = 0.
0
• Integration gives ln P + γ ln V = constant, so that
PVγ = constant.
t t
30
 Adiabatic process in an Ideal Gas
• Work done in a reversible adiabatic process

For a reversible adiabatic process, PVγ = K.

• Since the process is reversible, W = -CV∆T =Cv(T1-T2) ,
For 1 mole of gas , T=PV/R
so that Wadi = = Cv[P1V1/R-P2V2/R]

= Cv/R[P1V1-P2V2]

 W = 1/(γ –1) [P2V2 – P1V1].

• For an monatomic gas
gas, γ = 5/3
5/3, so that
W = –(3/2)] [P2V2 – P1V1].

31
 Reversible Processes for an Ideal Gas
Adiabatic Isothermal Isobaric Isochoric
process process process process

PVγ = K T constant P constant V constant

γ = CP/CV
W = – [1/(γ –1)] W = nRT ln(V2 /V1) W = P V W=0
.[P2V2 – P1V1]
∆U = CV ∆T ∆U = 0 ∆U = CV ∆T ∆U = CV ∆T

PV = nRT, U = ncVT, cP – cV = R, γ = cP/cV.

Monatomic ideal gas cV = (3/2)R, γ = 5/3.
32
O
O
C
C

5
O
FF

120
Thermal insulation
0
100
4
0
3 80
0
2 60
0
1
40
0
20
0
1
0
0
2
0 20
3

Valve
0 40
4
0 60
5
0

A
B
T1, Vm,1, P1

Stirrer
1. No change in temperature was detected,

dq = 0

2. As expansion is taking place against zero pressure,

d = 0,
dw 0

As a result
result, dU = 0

U = f(V
f(V,T)
T)  U   T   U 
     
 V T  V  U  T V
 T 
   0,
 V U
 U 
Hence ,    0
 V T 34
  U 
   0 (VALID ffor Ideal
Id l gas only)
l )
 V T
 U   U 
   0  V  = a/v2 (VALID for REAL gas only)
 V T  T

Actually the gas in A warmed up slightly and the one which had
expanded into B was somewhat cooler and when thermal
equilibrium
q was finally
y established the g
gas was at a slightly
g y
different temperature from that before the expansion.

 Because the system used by Joule had a very large heat

capacity compared with the heat capacity of air, the small change
of temperature that took place was not observed
observed.
35
 Concept of Enthalpy and heat Capacities

 Prove that,, H = q
qP

 Prove that, CP - CV = R (for one mole of Ideal gas)

36
 Joule-Thompson Effect

A gas passes through a POROUS PLUG from

a region
i where
h it is
i att high
hi h pressure to
t a region
i
where it is at lower pressure. The gas expands,
and the temperature of the gas can be lowered.
This is an important tool in low temperature
physics.

37
Joule-Thompson Apparatus

38
39
40
41
 Background
The objective of this experiment is to quantitatively
measure the non-ideality of gases using the Joule-
Th
Thomson coefficient
ffi i t andd relating
l ti it tto the
th coefficients
ffi i t off
equations for non-ideality.

For an ideal gas, the internal energy is only a function

of the absolute temperature
p so in an isothermal
process ∆U = 0. The same is true for the enthalpy for
such a process: ∆H = 0.

Thus:
 H   H 
    0
 V T  P T

These are non-zero for a real gas.

 Suppose the volume V1 under a constant pressure P1 is
allowed to pass through porous plug from region of the left to
right where the constant low pressure is P2. The net volume
change in the right side of the chamber is V2.

The workk done

Th d on th
the lleft
ft side
id iis: w1 = P1V1.
The work done on the right side is:W2 = -P2V2.
The total work done is then:
w = P1V1 - P2V2 (1)

Since the process is adiabatic, the total change in U,

U = W
U = U2 − U1 = P1V1 - P2V2 (2) H1 = H2 ,
U2 + P2V2 = U1 + P1V1 (3)
  H 
 
 T   P T 1  H 
        JT
 P  H  H  C P  P T
 
 T  P

Later we can show

 T  1   V  
    JT  T   V 
 P  H C P   T  P 
 P

T
 In an adiabatic throttle process, the gas pressure is reduced (P2<P1),
and thus
 If   ( T )  0 the temperature of the gas is reduced,T2<T1 , which
J T

H
P
produces a cooling effect;

 If J T  ( T ) H  0 ,the temperature of the gas is raised, T2>T1,

which producesP a heating effect;

T
 If  J T ( )H  0 , the temperature of the gas has no change, i.e.,
P 45
T2=T1
46
S d llaw off Th
Second d i
Thermodynamics

47
 Second Law of Thermodynamics

Hot Reservoir, TH
QH
W
E i
Engine
QC

Q W Cold Reservoir, TC
Is it possible?
It is impossible for a system to undergo a cyclic process whose sole effects
are the flow of heat into the system from a heat reservoir and the performance
of an equivalent amount of work by the system on the surroundings.
-------Kelvin-plank statement

48
 Kelvin statement (1851)

No process can completely convert heat into work; i.e. it

is impossible to build a “perfect” heat engine.

Efficiency = work done/heat absorbed

Hot Reservoir, TH = W/QH

QH = QH- QC/QH
W
Engine
QC Later we will show,
W = QH*T/TH
Cold Reservoir, TC

49
 Heat Engine

A heat
h t engine
i iis a cyclic
li process th
thatt absorbs
b b h heatt ffrom
a heat bath and converts it into work. We shall see that
i th
in the cyclic
li process th
the engine
i also
l di dissipates
i t some
heat to a heat bath at a lower temperature.

Hot Reservoir,, TH Hot Reservoir,, TH

QH QH
W W
Engine Engine
QC QC = 0

Cold Reservoir, TC Cold Reservoir, TC

Real engine. QH = QC + W Impossible engine. QH = W
50
 Q1 = Q2 + W

• It is impossible for a system to undergo a cyclic process whose sole

effects are the flow of heat into the system from a cold reservoir and the
flow of an equal amount of heat out of the system into a hot reservoir.
• -------Clausius statement

Refrigeration engine takes away heat from the colder reservoir

to hot reservoir with the help of external electrical work
51
 Carnot engine or Carnot cycle

1 Th
1. i mustt operate
The engine t in
i complete
l t cycles
l tto exclude
l d any
work involved in its own change.

2. T
2 To obtain
bt i maximum
i workk iin a cycle
l off operations,
ti every step
t
should be carried out in a reversible fashion.

52
 Carnot Cycle
Pressure

a
• Q1
Step -I
b
Step -IV
IV • T1
Q=0
Q=0
• Step -III
Step -II
d
Q2 •c T2
Volume
 Step 1 a-b (Isothermal Reversible Expansion):

The gas enclosed in a cyclinder fitted with frictionless

Piston. To start with cylinder containing the gas is kept in a
large thermostat at higher temp. T1 (source), and suppose the
volume of the gas be V1.

V1 V2

As temperature remains constant

As, constant, hence the change in
Internal energy (U = 0).
Hence,, U = q + W

Heat absorbed by the system = (-) of work done by the system

The
e heat
eat absorbed
abso bed by tthe
e gas, Q1 = RTln(V
( 2//V1)
= work done by the gas 54
= w1
 Step 2 (Adiabatic Reversible Expansion):

The cyclinder is taken out from the thermostat and kept in a

thermally insulated enclosure. The gas is allowed to expand
further from volume V2 to V3 adiabatically and reverasibly until
the temperature falls down to that of the sink T2.

The heat absorbed by the gas = nil

The work done by the gas, w2 = Cv (T2 – T1) (T1 > T2)

55
 Step 3 (Isothermal Reversible Compression):

The cylinder is then placed in a thermostat at lower temp. T2

((sink),
) and the g
gas is compressed
p isothermally
y and reversibly
y
from V3 to V4.
V3 V4

Th workk done
The d on the
th gas, w3= (-)RT
( )RT2ln(V
l (V4/V3) (as
( V4 < V3)

The heat given out by the gas, Q2 = - w3

( 4/V3)
= RT2ln(V

56
 Step 4 (Adiabatic Reversible Compression):

The cyclinder is taken out from the thermostat and kept in a

thermally insulated enclosure. The gas is allowed to compress
reversibly to its volume V1 and its original temperature T1 is
attained.

The heat absorbed by the gas = nil

The work done on the gas, w4 = Cv (T1 – T2)

57
 Carnot Engine

1. Calculate total work involved in all these steps:

2 Net heat absorbed :

2.

3. Efficiencyy of the engine:

g

TH = Temperature
p of the source

TL = Temperature of the sink

Efficiency of any heat engine does not depend

on the working substance,
substance rather depends on the temperature
of the source and sink 58
Second law of Thermodynamics

C
1. Concept off time-arrow

2 Concept
2. C off entropy.

59
63
The total energy is dispersed into random thermal motion of the
64
particles in the system.
65
• The thermodynamic property of a system that is related to its
degree of randomness or disorder is called entropy (S).
(S)

• E
Entropy
t i a measure off the
is th extent
t t to
t which
hi h energy is
i
dispersed.

• The entropy S and the entropy change ∆S=S2-S1 are state

functions.
functions

The entropy
• Th t S has
h a unique
i value,
l once th
the pressure P,
P
temperature T and the composition n of the system are
specified, S = S(P,T,n).

• The entropy is an extensive property,

property i.e.
i e increases with the
amount of matter in the system. 66
Entropy Criteria in different Processes

67
Change in the extent to which energy is dispersed depends on
how much energy is transferred as heat.

In case of closed system:

68
Combination of first and 2nd law:

dS =

70
Entropy Criteria in different Processes

67
Change in the extent to which energy is dispersed depends on
how much energy is transferred as heat.

In case of closed system:

68
Entropy is state function?

69
Combination of first and 2nd law:

dS =

70
 Entropy change due to Phase Transition

At the transition temperature, any transfer of energy as heat

between system and its surroundings is reversible because the
two phases in the system are in equilibrium

71
Entropy of Mixing

72
 Calculate entropy change in several processes
for ideal gas. (Tutorial
(Tutorial-----))

Isothermal
sot e a C Changes:
a ges
(a) Reversible
(b) Irreversible process

Adiabatic
Adi b ti Changes:
Ch
(a) Reversible
(b) Irreversible process

73
 Clausius Inequality: ds ≥ dq/T
Assume reversible and irreversible paths between two states.

R
Reversible
ibl path
th produces
d more workk than
th irreversible
i ibl path,
th

is /dwrev/ ≥ /dw/.
That is, /dw/ Because dw and dwrev are negative when
energy leaves the system as work, this expression is same as
- dwrev ≥ dw, and hence, dw –dwrev ≥ 0

dU is the same for both the paths.

dU = dq + dw = dqrev + dwrev
dqrev–dq = dw - dwrev ≥ 0
dqrev/T ≥ dq/T

dS ≥ dq/T 74
If N be the total number of distinguishable molecules in a
system, and N1, N2, N3……. etc. be number of molecules
distributed in different energy levels, then the number of
microstates corresponding to the given distribution is called
Thermodyamic Probability,

SS= klnW
klnW

1
Let us a take a sample containing 16 distinguishable molecules,
sharing a total energy of 16 E and quantum states differing
by unit E
E.

0
W=1 W=8.9  10⁵ W=1.44  10⁷

Number of microstates increases with increase in the randomness
in the distribution of the molecules. Hence, entropy increases. 

S= klnW
Third LAW  of Thermodynamics
W =1 W >1
S= klnW = 0 S= klnW  0
Vapour cycle Refrigeration 
Magnetic refrigeration
Energy levels of Paramagnetic Substance in Absence and 
Presence of Magnetic Field:
g
Total: 191.05
Corollary of the Third LAW of Thermodynamics

Absolute zero ????

Concept of Helmholtz work Function and Gibbs Free energy
Helmholtz work Function A
 Why it is called  free energy or available energy?
G = H – TS
If a system undergoes reversible change
dG = dH – d(TS)
= d(U + PV) – d(TS)
= dU + d(PV) – TdS – SdT
= dU + VdP + PdV – TdS – SdT
At constant external P & Isothermal condition
dG = dU + PextdV – TdS
P,T

= dU + PextdV – dq
= -(dW) + PextdV
= -(dWP-V + dWnonP-V ) + PextdV
= -(PdV
(PdV + dWnonP-V ) + PextdV
= - dWnonP-V
-dGP,T
P T = dWnonP-V
It is the amount of work required for any external
use exclusive of the expansion work. This work may be electrical
work for pushing electron through a circuit or work required for
transmitting nerve impulse.
Isothermal processes can occur in any kind of 
system, including highly structured machines, 
and even living cells. 

Surroundings act as heat sink in most of the 
Surroundings act as heat sink in most of the
cases.
 Example of constant T and Pressure  Reaction
Most reactions of an acid and base mixed together to form a
salt are exothermic. If a strongly acidic solution is rapidly
poured into a strongly
p g y basic solution in a beaker (g
(glass cup)
p)
that is wrapped with thermal insulation, the heat generated
cannot escape, and the resulting system of solution plus salt
( i h dissovled
(either di l d or precipitaed)
i i d) heats
h up. This
Thi is
i not an
isothermal process. But if the thermal insulation is removed
from the beaker of basic solution,
solution and the beaker is set into a
large tub of water, and the temperature of the basic solution is
allowed to equilibrate with the water bath (come to the same
temperature), and the acid solution is added slowly, then the
heat of reaction will have time to move through the beaker
glass
l wallll into
i t the
th large
l b th off water,
bath t and d the
th temperature
t t off
the solution in the beaker will remain at the temperature of the
bath as the acid is slowly poured into the beaker and the acid
and base react. This is an isothermal process.
Problem: How much energy is available for sustaining
muscular
l andd nervous activity
i i from
f the
h combustion
b i off 1
mol of glucose molecules under standard conditions at
37 °C (blood temperature)? The standard entropy of
reaction is +259.1 JK-1 mol-1. ΔrH = -2808 kJ mol-1

Method: The available energy gy from the reaction is

equal to the change in standard Gibbs energy for the
reaction (ΔrG). To calculate this quantity, it is legitimate
to ignore the temperature dependence of the reaction
enthalpy to obtain ΔrH, and to substitute the data into
enthalpy,

rG  r H  TrS
Answer: Because the standard reaction enthalpy is
-2808 kJ mol-1, it follows that the standard reaction
Gibbs energy
gy is
 r G   2808kJmol 1  (310K )  (259.1JK 1mol 1 )
 2888kJmol 1
Therefore, Wadd,max = -2888
2888 kJ.mol-1 for the combustion
dd
of 1 mol glucose molecules, and the reaction can use
2888 kJ for external work.
work
To place this results in perspective, consider that a
person of mass 70 kg needs to do 2.12 1 kJ of work to climb
vertically through 3 m; then at least how much amount
off glucose
l i needed
is d d to
t complete
l t the
th task?
t k?
Gibbs Free Energy
Gibbs Free Energy
gy
1. If G is negative, the 
g ,
forward reaction is 
spontaneous.
p
2. If G is 0, the system is 
at equilibrium.
at equilibrium.
3. If G is positive, the 
reaction is spontaneous
reaction is spontaneous 
in the reverse direction.
 Free Energy and Equilibrium
Free Energy and Equilibrium
Remember from above:
If G is 0, the system is at equilibrium.

So G must be related to the equilibrium constant, 
q ,
K. The standard free energy, G°, is directly 
linked to Keq by: 
27
Masters Equations of Chemical Thermodynamics

A closed system (constant
composition, and only p‐V work)

28
α

29
The "cyclic relation" (sometimes called Euler's chain relation) is a calculus identity which is very 
useful in thermodynamics. This relation can appear in several different forms all of which are 
equivalent. The form that we will find most useful is,

30
Maxwell’s Relation:

Imp

Imp

31
 Maxwell Relation for G 
The Gibbs function (or free energy) is defined as
G = U 
G  U – TS 
TS + PV
PV
 dG = dU – TdS – SdT + PdV + Vdp .
dU = TdS – PdV,
so that dG = – SdT + VdP ; i.e. G = G(T,P).

so that S
so that S = – (G/T)P and V = (G/P)
and V (G/P)T...

2G/TP 
G/TP = 2G/PT,
so that (S/P)T =  –(V/T)P .

Note that Maxwell’s relation equates (S/P)T , a theoretical
q antit to (V/T)P = α
quantity, to (V/T) α V , both of
both of which may be measured.
hi h ma be meas red
32
Maxwell’s Relations

33
34
35
Now you should be able to show that,

36
 closed system, only p‐V work

Does not apply
pp y

• When composition is changing due to exchange of matter 
with surroundings (open system)

• Irreversible chemical reaction

• Irreversible inter‐phase transport of matter
38
39
40
 Physical Significance of Chemical potential

 Chemical potential as measure of a general tendency of substances to transform, 
and as central concept of chemical dynamics
and as central concept of chemical dynamics.

It reflects the potential of a substance to undergo physical 
Change or chemical change.
Change or chemical change.

In thermodynamics, chemical potential, also known as 
partial molar free energy, is a form of potential energy 
that can be absorbed or released during a chemical reaction.

41
 Phase Transition

 Map showing conditions of T
and p at which various phases
and p at which various phases
are thermodynamically stable.

 At any point on the phase
boundaries, the phases are in
, p
dynamic equilibrium.

Water and ice are in equilibrium at 00C and 1 atm.
Water and vapour are in equilibrium at 100 at 1 atm.

G = 0 at phase transition temp at 1 atm.
42
43
Effect of pressure and temperature on Phase Equilibrium

44
At point a, 
µα = µβ (as system exists in equilibrium at point a)
Or
(We can write with respect to partial molar quantity.  G bar means per mole)

Now imagine  you move to point b, where new equilibrium will be established.
g y p , q

At point b,

µα + dµα = µβ + dµβ

As µα = µβ , hence, 
dµα =  dµβ or

Clausius Clapeyron equation

q p p
This equation dictates how the pressure variation leads to temperature
variation or vice versa in order to achieve new equilibrium condition.
45
 Phase Transition

 Map showing conditions of T
and p at which various phases
and p at which various phases
are thermodynamically stable.

 At any point on the phase
boundaries, the phases are in
, p
dynamic equilibrium.

Water and ice are in equilibrium at 00C and 1 atm.
Water and vapour are in equilibrium at 100 at 1 atm.

G = 0 at phase transition temp at 1 atm.
46