Kinetics and Thermo by Amarendra Vijay

Thermodynamics and Kinetics
Amrendra Vijay
Department of Chemistry
IIT Madras, Chennai 600 036
Lecture 01
August 04, 2006
why Thermodynamics ?
Broadly speaking, there are two approaches of Science:

Holistic: This approach, also known as Phenomenology, is easy to
understand and utilize in practice. Here, we attempt to rationalize our

observations, using a few physically meaningful variables and formulate
universal Laws. These phenomenological Laws have predictive power,
limited to the range of their validity. Classical Thermodynamics has
grown out of this approach and its utility today is pervasive.
Reductionism: Here, we attempt to determine Laws, governing the
ultimate constituents of matter (for example, electrons) and we hope

these Laws will eventually help to rationalize everything we observe
around us and beyond. This is the Holy Grail of Science. Emergence of
what we call Quantum Mechanics is a fine example of Reductionism.
Laws of reductionism, as we know today, are, unfortunately, too
complicated to use and hence its utility is limited for the world at large.
Present Status: Axiomatically, phenomenological Laws (Classical
Thermodynamics) are derivable from the Laws of reductionism
(Quantum Mechanics), but synthesis of such a knowledge (Quantum
Thermodynamics) is not yet complete.
August 04, 2006
Thermodynamics
Basic concepts and the First Law
Suggested Reading: Physical Chemistry
--- P.W. Atkins
Chapters 2 and 3
or --- D.A. McQuarrie
Chapter 19
or --- Any other author
and --- Ask Professors at IITM
August 04, 2006
System and Surroundings
A thermodynamic system is the content of a

geometrical volume of macroscopic size.
System
Boundary
Examples
A piece of matter, a sample of gas,
chemical reactions in a vessel,
a sample of human population etc.
For molecular applications

Surroundings
August 04, 2006
size < 10 6 cm : microscopic

size > 1 cm
: macroscopic
4
Thermodynamic Variables
Thermodynamic variables are quantities of a macroscopic

system, which can be measured experimentally.
Examples: Pressure, P; Volume, V; Energy, E; Temperature,
T; magnetic field, H and so forth.
Types: (a) Extensive: The value of an extensive variable
depends on the size of the system; that is, total = sum of

parts. For example, Mass, Volume etc. (b) Intensive: The
value of an intensive variable does not depend on system size.
For example, pressure, temperature etc. Note, an extensive
variable can be converted into an intensive variable, if we
scale (say, divide) the extensive variable by the size of the
thermodynamic system.
August 04, 2006
Thermodynamic States
A thermodynamic state is specified by a

set of values of all thermodynamic
variables (temperature, susceptibility,
pressure etc) necessary for the description
of the macroscopic system.
Example: A sample of gas enclosed in a

box at constant temperature and volume.
Here, thermodynamic variables are the
temperature and the volume.
August 04, 2006
Thermodynamic Equilibrium
A thermodynamic equilibrium prevails

when the thermodynamic state
(characterized by thermodynamic
variables, like temperature, pressure etc)
does not change with time. And we say,
the system is in thermodynamic
equilibrium.
August 04, 2006
Equation of State
This is a functional relation among thermodynamic

variables for a system in equilibrium.
f (P, V , T ) = 0
(a function of thermodynamic variables)
Example: For an ideal gas,
f ( P, V , T ) (PV nRT ) = 0
Equation of state is assumed to be known, as a part

of the specification of the thermodynamic system.
August 04, 2006
Thermodynamic Transformation
This is a change of thermodynamic state of the

system. If the initial state is in equilibrium, a
transformation can be brought only by changing
external conditions of the system (like, heating the
system applying external pressure and so forth.
Quasi-adiabatic transformation: Here, the

external conditions change so slowly that at any
moment the system is approximately in equilibrium.
Reversible Transformation: The transformation,
here, retraces its history in time, when the external

condition retraces its history in time.
August 04, 2006
Types of Thermodynamic systems
Three types:
Energy
1. Open system:
Surroundings
Surroundings
Matter
system
Energy
2. Closed system:
Surroundings
Surroundings
Matter
system
Energy
3. Isolated system: Surroundings

August 04, 2006
Surroundings
Matter
system
10
Energy
Energy is the capacity to do work. In

thermodynamics, the total energy of a system is
called the internal energy.
When the work is done on a system, the capacity of

the system to do work increases and we say, the
energy of the system has increased.
When the work is done by the system, the capacity

of the system to do work decreases and we say,
the energy of the system has reduced.
August 04, 2006
11
Heat and Work
Disordered, random or Thermal motion
Organized motion
Heat is the transfer of energy between the system and the

surroundings that makes use of the thermal motion.
Work is the transfer of energy that between the system and

the surrounding that makes use of the organized motion.
August 04, 2006
12
Differentiation
Consider the Taylor series expansion of function of 1 variable:

f ( x ) = [ f (x )]x = x0
1 2 f
1 3 f
f
2
3
+ ( x x0 ) + 2 ( x x0 ) + 3 ( x x0 ) +
2! x x = x
3! x x = x
x x = x0
0
0
Notice, [ f / x ]x = x0 is independent of x and it is valid for all x,

independent of x0 we choose to fix. If ( x x 0 ) = dx is very small,
then we may truncate the series as follows:
m
f
f (x ) [ f (x0 )] = (x x0 )
x x = x0
f
dx
df =
x x = x0
As we deal with a truncated series, we may as well like to

modify [ m f / x m ]x = x0 as we change x. That is, we make [ m f / x m ]x = x0
dependent on x, and write as follows:
August 04, 2006
f
df = dx
x
In thermodynamics, these partial derivatives

define various thermodynamic variables
of our interest.
13
Differentiation
Consider the Taylor series expansion of an N-variable function:

N
f
(xm y m )
f (x1 , x 2, L x N ) = [ f (x1 , x 2, L x N )]x = y +
k
k
m =1 x m x = y
k
1 2 f
+
x
m =1 k =1
m k x
N
(xm y m )
k
Neglect
+ LL
= yk
f
( xm y m )
f ( x1 L x N ) f ( y1 L y N ) =
m =1 xm x = y
m
m
N
f
( xm y m )
f =
m =1 xm x = y
m
m
N
f
df =
dxm
m =1 xm x = y
m
m
N
for an
infinitesimal
change
f
f
f
dx3 for three variables.
dx 2 +
dx1 +
df =
x 2
x1
x3
f
f
dx3 if x2 is constant.
df =
dx1 +
August 04, 2006
x1 x
x3 x
2
14
Integration
Consider,
g (x ) =
y max
dy f (x,y )
ymax
y min
final
E =
dE
initial
ymin
If the value of E does not depend on the path we choose for
integration and depends only on the initial and the final state,
E is called a state function and dE is called an exact differential.
If the value of E does depend on the path we choose for
integration, then E is called a path function and dE is called an

inexact differential.
August 04, 2006
15
First Law of Thermodynamics

energy transfered work done
Change in
+
=
as heat
on a system
Internal Energy
144
42444
3 14243
1442443
q
In thermodynamics, the total energy of a system is called its

internal energy. This is a state function. Only the change in
internal energy involved in a thermodynamic transformation is
of any physical significance.
For an isolated system, q = 0 and w = 0. Hence, the change in
internal energy is zero; that is, the energy is conserved.
By convention, if w > 0 and q > 0 we say the energy is
transferred to the system as work or heat. If w < 0 and q < 0,
we say the energy is lost from the system.
August 04, 2006
16
Computation of Work
Work done by the system to move an object a

distance dZ, against the external force, F:
dW = - F dZ (negative sign means: if the system
does the work, its internal energy decreases.)
Force is pressure, P, per unit area, A, and hence,

dW = - P A dZ = - P dV (volume) w = P dV
If the external pressure is zero, then w = 0. That
is, no work is done. Example: Free expansion of a
gas in a vacuum.
For an ideal gas, P = n R T/V
V2
V1
Vfinal
w = nRT
August 04, 2006
dV
Vfinal
=
nRT
ln
V
Vinitial
Vinitial
17
Internal Energy, U
Consider an ideal gas, for which the equation of state is,

P=nRT/V. That is, a thermodynamic state of an ideal gas is
characterized by three thermodynamic variables (pressure, P,
(temperature, T, and the volume, V); but, only two variables
are independent, as the third one (for examples, P) can be
expressed in terms of other two (volume, V and temperature,
T). This means, the internal energy, U of an ideal gas may be
considered as a function of any two thermodynamic variables,
appearing in the equation of state. Hence, we have:
U
U
U U(V, T ) dU =
dV +
dT
V
T
Remember, this equation retains only first two term of an

infinite Taylor series, and hence this is only an approximation.
August 04, 2006
18
Internal Energy
(Heat Capacity)
U
U
dU =
dV +
dT
V
T
Reference:
If V is constant, then dV = 0
U
dU =
dT = C v dT
T V
1
424
3
Cv
For a finite change,
U
U
Cv =
= Limit
T V T 0 T V
Heat Capacity at constant volume
U = C v T
What is the physical significance of specific heat ? Should this

be temperature dependent or temperature independent ?
August 04, 2006
19
Ref : U = C v T
Heat Capacity
continued
At constant volume, the internal energy of a system is

proportional to the temperature; that is, internal energy
increases when T is raised.
Heat capacity is an extensive quantity. To make it an

intensive one, we divide it by number of moles and call it
molar heat capacity. If we divide it by the mass of the
substance (in gram), it is called Specific Heat.
A large Heat Capacity implies: if we heat a system, the

increase in temperature will be very small --- that is, the
system has a large capacity for Heat.
August 04, 2006
20
Internal Energy
(Internal Pressure)
Reference: dU = U dV + U dT
If T is constant, then dT = 0.
U
dU =
dV = T dV
V T
12
3
T
Internal Pressure
For a perfect gas, the internal pressure is zero.
August 04, 2006
21
U(V, T ) U(P, T )
Internal Energy
What if we consider internal the internal energy of an ideal gas

to be function of temperature, T, and pressure, P ?
U
U
dV
+
dT dU = T dV + C V dT
T
V
Recall: dU =
Internal Pressure
Divide by dT and impose the condition of constant pressure,
V
U
=
+ CV = T V + CV
T
T P
T P
Internal Pressure
Heat Capacity
1 V
where, =
V T P
Expansion Coefficient
For a perfect gas, the internal pressure is zero and hence,
August 04, 2006
U
U
C
=
=
V
T V
T P
22
Enthalpy, H
It is a state function, defined as H = U + P V, where U is the

internal energy of the system, P is the pressure and V is the
volume.
Physical Significance: Let us make a small change in the state

of the system: (H + H ) = (U + U ) + (P + P )(V + V )
and neglect P V term. We then obtain:
H = U + P V + V P
= q + VP
From the first law, if the system

is in mechanical equilibrium at
a pressure, P then
q = U W = U + P V
If the heating occurs at constant pressure then, H = q.

That is, the change in Enthalpy is the Heat supplied at constant
pressure, so long as the system does no additional work.
August 04, 2006
23
Enthalpy
Consider Enthalpy, H as a function of the pressure, P and

the temperature, T of the system.
H
H
H H(P, T ) dH =
dT
dP +
T
P
H
=
dH
dT = C P dT
At constant pressure, dP=0 and hence:
T P
12
3
CP
C P is the Heat Capacity at constant pressure.
Because, the change in Enthalpy is the Heat supplied at

constant pressure, we have dH = C P dT = dq. This relation
allows us to design experiment for measuring C P .
August 04, 2006
24
Enthalpy
H
H
dT
dP +
T
P
Reference: H H (P, T ) dH =
At constant temperature, dT=0 and hence,

H
dH =
dP
P
Thus, we can write:

H
dH =
dP + C p dT
August 04, 2006
25
H
Reference : dH =
dP + C p dT
Enthalpy as a function of temperature

H P
H
=
+ CP
Divide by dT and impose constant volume: T

P
T T V
Use Chain relation,

1
T V
P
=
V
P
T V
T
P
P T
H

=
T
H
P T
H
y x z
if z(x, y ), then = 1
x z z y y x
V V
=

T
P
T
P
V
= V

T H
=
= CP
P
T
T
1424
3
H
C P
+ C P = 1
= C P
T
T V
T
1 V
T
=
V P T
T
Isothermal compressibility
CP
to obtain,
=
P H
Joule-Thomson
Coefficient
This says as how enthalpy changes as a function of

temperature, if the volume of the system is held constant.
August 04, 2006
26
Relation between Heat Capacities

U
H
=
=
C
C
and P
Definition: v
T V
T P
U: Internal energy
H: Enthalpy = U + P V

Expansion
[
]
+
C
P
V
C P C V = [U + PV ] C V =
V
Coefficient
T
T
T
P
V
P
= (P + T ) V
=PV
TV
T P
Internal Pressure
C P C V = (P + T ) V
P
P
= T V because, T = T P
T V
T V
For a perfect gas, the internal pressure is zero and

[P V ] = nR (using PV = n R T) C P C V = n R
T
P
August 04, 2006
27
Finally
Read a Physical Chemistry book, or any
book which has a chapter on First Law of
Thermodynamics.
Try to understand some solved problems,
given in the book and solve other
problems given in the book.
In case of difficulty, come and discuss
with me.
August 04, 2006
28
Amrendra Vijay
Lecture 02
August 07, 2006
Preface
Thermodynamic state of a system is specified by the value of a

set of thermodynamic variables. For example, the state of an
ideal gas is specified by pressure, volume and temperature.
Change of one thermodynamic state into another, is called
Thermodynamic transformation. Broadly speaking, there are
three types of transformations:
Induced: External work is required here. For example, we might
heat the system or pass an electric current.
Spontaneous: No external work is required. It happens all by
itself and is usually irreversible.
Rare events: They are due to fluctuations in thermodynamic
variables.
To understand spontaneous processes in nature, the concept of
energy is not sufficient and we require an additional concept
called Entropy.
August 07, 2006
Notations
F2
F1
F2
F1
dF =
dF =
(F)path
(F2 F1 )
if F is a state function
if F is not a state function. Subscript denotes the

name of the path, for example, reversible (rev),
chosen for thermodynamic transformation.
dF is infinitesimal change.
F refers to a finite change.

As integration is essentially a summation process, a
finite change can be thought of as a sequence of
infinitesimal transformations.
we will henceforth use dF and F rather loosely and
the meaning should be clear from the context.
August 07, 2006
Adiabatic Processes
Adiabatic Process: Here, the external
conditions change so slowly that no energy is

transferred as heat, between the system and the
surroundings.
For adiabatic transformations
External conditions
q = 0
System
August 07, 2006
Surroundings
Reversible Processes
Reversible Process: Here, a thermodynamic
transformation is able to retrace its history in

time, when external condition retraces its history
in time.
Surroundings
Pext
Pext
The system is
an Ideal Gas
Pgas , T, V
compression
August 07, 2006
equilibrium
expansion
For a reversible process, (Pext Pgas ) P 0
Adiabatic vs Reversible
Adiabatic processes are reversible. But, not all

reversible processes are adiabatic.
We will get a clear picture of these thermodynamic

transformations, from the notion of Entropy and its
variation with time.
Before we introduce Entropy, we will consider a

number thermodynamic transformations, for the
Ideal Gas. We use ideal gas as an example, because
its Equation of state is simple: PV = nRT.
Remember: (a) For adiabatic process, q = 0

(b) For reversible process, Pext = Psystem
August 07, 2006
Work done for Expansion/Compression of an ideal gas
Situation-1: Temperature remains constant (Isothermal), and

hence only the volume can change from V1 to V2 .
dW = - F dZ = - P A dZ = - P dV
V2
V2
V1
V1
w = Pext dV w rev = Pgas dV
The equation of state for an ideal gas is:
w rev = nRT
V2
V1
dV
= nRT ln (V2 / V1 )
V
Q Pext Pgas ,
for a reversible
transforma
tion.
Pgas V = n R T
[reversible and isothermal]
For compression, for example, V2 < V1 , w rev > 0. The

convention then says: we have done work on the system and
its energy will increase.
August 07, 2006
Work done for Expansion/Compression of an ideal gas
Situation-2: Both Temperature and Volume change,

from (V1 , T1 ) to (V2 , T2 ).
(V1 T1 )
Consider the process to be adiabatic;

that is, q = 0.
(V2 T1 )
(V2 T2 )
Then, the first law says,
dU = dq rev + dw rev dw rev = dU = C V (T ) dT

w rev = C V (T ) dT
T2
August 07, 2006
T1
A relation between volume and

temperature for an ideal gas
Consider an adiabatic transformation; that is, q

So, the first Law says,
= 0.
dU = dq rev + dw rev dw rev = dU C V (T ) dT = PdV
For an ideal gas, P = n R T/V, and hence
dV
dT
(
)
= nR
CV T
T
Assume, the Heat capacity to be Temperature independent.
CV
nR
August 07, 2006
T2
T1
V2 dV
dT
=
V1 V
T
T2
V1
ln = ln
T1
V2
C V /nR
We will use this for studying

Entropy change in a Carnot Engine.
V1
T2 = T1
V2
nR/C V
9
Adiabatic Process for ideal gases
Consider the following thermodynamic transformation.

To go from Blue to Red, we have three different pathways:
P (P1 V1 T1 )
(P1 V2 T3 )
A
(P2 V2 T1 )
C
Direct path, A
Path B + Path C
Path D + path E
(P3 V2 T2 )
We will now compute the change in internal energy, change in

work done and change in heat, using the first law and other
ideas we developed in the first lecture.
August 07, 2006
For ideal gases, we know: dU = C V (T ) dT
10
Adiabatic process for ideal
Temperature does not change.

Hence, the change in energy,
dU = C V (T ) dT = 0
(P1 V1 T1 ) (P2 V2 T1 )
gases Path A
(P1 V1 T1 )
(P2 V2 T1 )
From the first law then, we have,
dU = dq rev + dw rev 0 = dq rev + dw rev dq rev = dw rev
We already know the reversible work done for ideal gases,
Hence,
August 07, 2006
w rev
V2
= nRT1 ln
V1
V2
Reversible work done : w rev = nRT1 ln

V1
V2
Change in heat : q rev = nRT1 ln

V1
Change in internal energy : U = 0
11
Adiabatic process
As we consider only adiabatic processes.

we have, (q rev )B = 0
P
Temperature changes from T1 T2
(U )B =
(P1 V1 T1 ) (P3 V2 T2 ) (P2 V2 T1 )

for ideal gases Path B+C
T2
T1
(P1 V1 T1 )
C V (T ) dT
C
(P3 V2 T2 )
Then, from the first law, (w rev )B = (U )B

V
Path C has no volume change, so the work, (w rev )C = 0
T
But the temperature changes from T2 T1. (U ) = 1 C (T ) dT
C
T2 V
Then, from the first law, (q rev )C = (U )C
For total, add contributions from path B and C. Hence,
Reversible work: W rev
T2
T1
C V (T ) dT
Heat Change: q rev =

August 07, 2006
Change in energy : U =
T2
T1
T1
T2
C V (T ) dT
C V (T ) dT + C V (T ) dT = 0
T1
T2
12
Adiabatic process for
T3
T1
(P1 V1 T1 )
(P1 V2 T3 )
E
(P2 V2 T1 )
Pressure is constant, so the reversible work,
(w rev )D = V
C V (T ) dT
V2
In path D, temp. changes from T1 T3
(U )D =
(P1 V1 T1 ) (P1 V2 T3 ) (P2 V2 T1 )

ideal gases Path D+E
P1 dV = P1 (V2 V1 )
( )
( )
T3
Then, from the first law, q rev D = P1 V2 V1 + T C V dT

1
In path E, volume is constant. So, the reversible work, w rev E
T1
T
T
.
Temperature changes from 3
1 U
E = T C V T dT
3
Then, from the first law, q rev E = U E
( )
= 0.
For total, add contributions from path D and E. Hence,
Reversible work :(w rev )Total = P1 (V2 V1 ) heat Change: (q rev )Total = P1 (V2 V1 )
Change in energy : (U )Total
August 07, 2006
= C V (T ) dT +
T
T
T3
T1
C V (T ) dT
13
=0
Resume
For a reversible transformation, we have seen the heat change

and the work done are path functions, whereas the change in
internal energy is a state function. And the First Law is,
dq rev = dU dw rev = C V (T ) dT +
nRT
dV
V
(for an ideal gas )
Question: Why is the reversible heat change, a path function?

Answer: Because the expression for heat change involves both
temperature and volume, and the temperature depends on the

volume, for the ideal gas we have considered. However, if we
divide the heat change by Temperature, the resulting expression
will become a state function, and it is called the ENTROPY, S:
That is, the change in Entropy, dS is:
August 07, 2006
dq rev
dT
dV
dS =
= C V (T )
+nR
T
T
V
14
Entropy
physical motivation
A bouncing ball eventually comes to rest. This is a spontaneous

and irreversible process. Bouncing occurs because of some
ordered motion (upward) on the surface and it stops because
there is no more ordered motion. As this is a natural process,
we say: the nature prefers to go towards a disordered state.
Transfer of energy as Heat makes use

Transfer of energy as work
of disordered, or Thermal motion
makes use of ordered, motion
Entropy is a measure of disorder -- Larger the entropy, higher
the disorder -- Nature thus prefers the direction of large
Entropy.
August 07, 2006
15
Entropy
Let us check if the definition of entropy change, dS = dq rev /T

is consistent with our daily experiences?
Observations: At low temperature, the system has access
to only few states (at T=0, system occupies only the lowest
energy state); that means, the system has less options to
disorder itself. At high temperature, it has access to many
more states and hence more opportunity to disorder itself.
Hence, the Entropy change is proportional to the supply of Heat.
For a fixed amount of Heat supply, a colder system would be

more willing (than a hotter system) to accept Heat, as that will
increase its possibility to disorder --- in other words, its easier
to heat a colder system, as that increases the Entropy.
August 07, 2006
Hence, the Entropy change is inversely

proportional to the Temperature.
16
Entropy
Second Law of Thermodynamics
The Entropy of an isolated system increases in the course of a

spontaneous thermodynamic transformation.
This is also known as the Law of increase of Entropy.
And, there are many more equivalent statements of the second
law of thermodynamics.
Entropy, like Energy, is an extensive property --- that is,
Entropy of 2 gm of ice would be twice as that of 1 gm of ice. To
make it an intensive property, we divide it by the number of
moles and call it molar Entropy.
Entropy, like Energy, is a state function --- that is, the value of
Entropy change is independent of the path of thermodynamic
transformations.
August 07, 2006
17
Entropy
an Example
Entropy change for an isothermal expansion of an ideal gas.
Answer: Isothermal means a constant temperature. From the

first Law we have,
dq rev = dU dw rev
nRT
= C V (T ) dT +
dV
V
Q dS = dq rev /T S =
V2
V1
(for an ideal gas )
V2 dV
V2
dq rev
= n R
= n R ln
V1 V
T
V1
Notice, the change in Entropy is positive.
August 07, 2006
18
A precise statement: Consider the change of Entropy,
dS = (dS)INT + (dS)EXT
(dS)INT :
(dS)EXT :
Entropy change due to changes inside the system

Entropy flow due to interaction with the exterior
Second Law:
(dS)INT
is never negative. More precisely,
(dS)INT = 0
(dS)INT > 0
Reversible Process
Irreversible Process
For an isolated system: There is no flow of entropy, and hence
dS = (dS)INT 0
August 07, 2006
19
Entropy
Suppose, we enclose a system, I, inside a larger system II, so

that the global system containing both I and II is isolated. And,
in both parts, I and II, some irreversible process may take
place. The second Law would be,
dS = dSI + dSII 0
What we postulate, is:
(dS )
I
INT
( )
> 0, dSII
INT
(dS )
I
INT
0 and
< 0 with d SI + SII
(dS ) 0
) > 0 is excluded.
II
INT
That is, absorption of Entropy in one part, compensated by a

sufficient production in another part of the system is illegal.
Thus, in every macroscopic region of the system the Entropy
production due to the irreversible processes is positive.
August 07, 2006
20
Entropy production due to Heat flow
Consider two systems , I and II, maintained respectively at

temperatures T I and T II . For the whole system, we have:
( )
(dq )
(dq )
(dq )
I
dq
dS = dSI + dSII
INT
: Heat received by system I from system II
EXT
:Heat supplied to system I from the outside
II
( )
INT
:Heat received by system II from system I = dq I
EXT
:Heat supplied to system II from the outside
II
Hence, the total dS =
August 07, 2006
(dq )
I
EXT
I
(
dq )
+
II
EXT
II
+(
EXT
1
1
dq INT I II = (dS)EXT + (dS)INT
T T
I
This change results from the irreversible heat flow

inside the system, and is postulated to be positive.
21
Ref: (ds )INT = (dq I )INT I II is positive.

T T
In fact,
1
(dq )
I
INT
>0
1
1
when I II > 0
T T
(dq )
I
INT
<0
1
1
when I II < 0
T T
And, the entropy production can be zero, only when T I = T II .

That is, when the thermal equilibrium is reached.
Entropy production per unit time,
dq I 1
1
ds
I II > 0
=
dt INT dt INT T T
Thus, the direction of heat flow is determined by the sign of

the function, 1 1
I II .
T T
August 07, 2006
22
Amrendra Vijay
Lecture 03
Aug. 08, 2006
Recap
First Law:
nRT
(
)
dq rev = dU dw rev = C V T dT +
dV (for an ideal gas )
V
Entropy:
dq rev
dT
dV
(
)
dS =
= CV T
+nR
T
T
V
Example: Isothermal expansion (from volume V1 to V2 ) of an

ideal gas. Isothermal mean constant temperature, and at
constant temperature the change in internal energy of for an
ideal gas is zero.
Q dS = dq rev /T S =
V2
V1
Aug. 08, 2006
V2 dV
V
dq rev
= n R
= n R ln 2
V1 V
T
V1
Second Law of Thermodynamics: A precise statement
Consider the change of Entropy,
dS = (dS)INT + (dS)EXT
(dS)INT :
(dS)EXT :
Entropy change due to changes inside the system

Entropy flow due to interaction with the exterior
Second Law says:
(dS)INT is never negative. More precisely,
(dS)INT = 0
(dS)INT > 0
Reversible Process
Corollary: For an isolated system, there is no flow of entropy

and hence,
Aug. 08, 2006
dS = (dS)INT 0
Entropy
Suppose, we enclose a system, I, inside a larger system II, so

that the global system containing both I and II is isolated. And,
in both parts, I and II, some irreversible process may take
place. The second Law would read,
dS = dS + dS 0
I
I
I
I
As we know, dS = (dS )INT + (dS )EXT and what we actually postulate
in the second Law, is:
(dS ) 0
(dS ) > 0, (dS )
I
INT
II
INT
II
INT
and
(dS )
II
INT
< 0 with d SI + SII > 0 is excluded.
That is, absorption of Entropy in one part, compensated by a

sufficient production in another part of the system is illegal.
Thus, in every macroscopic region of the system the Entropy
production due to the irreversible processes is positive.
Aug. 08, 2006
Consider two systems , I and II, maintained respectively at

temperatures T I and T II . For the whole system, we have:
dS = dSI + dSII
Define:
( )
(dq )
(dq )
(dq )
I
dq
INT
: Heat received by system I from system II
EXT
:Heat supplied to system I from the outside
II
:Heat received by system II from system I = dq I
EXT
:Heat supplied to system II from the outside
II
Hence, the total dS =

Aug. 08, 2006
( )
INT
(dq )
I
EXT
I
(
dq )
+
II
EXT
II
+(
EXT
1 =
1
dq INT I II (dS)EXT + (dS)INT
T T
I
This change results from the irreversible heat flow

inside the system, and is postulated to be positive.
Ref: (ds )INT = (dq I )INT I II is positive.

T T
In fact,
1
(dq )
I
INT
>0
1
1
when I II > 0
T T
(dq )
I
INT
<0
1
1
when I II < 0
T T
And, the entropy production can be zero, only when T I = T II .

That is, when the thermal equilibrium is reached.
Entropy production per unit time,
dq I 1
1
ds
I II > 0
=
dt INT dt INT T T
Thus, the direction of heat flow is determined by the sign of

the function, 1 1
I II .
T T
Aug. 08, 2006
Heat Reservoir
Definition: A Heat reservoir is a system so

large that the gain or loss of any finite
amount of Heat does not change its
Temperature.
Aug. 08, 2006
Kelvin Statement: There exists no thermodynamic

transformation whose sole effect is to extract a
quantity of Heat from a Heat reservoir and to
convert it completely into work.
Clausius Statement: There exists no thermodynamic

quantity of Heat from a colder reservoir and to
deliver it to a hotter reservoir.
Aug. 08, 2006
If Kelvin is false
Clausius is also false.
Proof: Suppose, Kelvin is false.
That means we can extract heat from a reservoir a temperature,

T1 and convert it entirely into work, with no other effect.
Next, we can convert this work into Heat.
Next, we can deliver this Heat to another heat reservoir at a
Temperature, T2 (T2 > T1 ) with no other effect.
The net result is: we have taken heat from a colder reservoir to
a hotter reservoir, with no effect.
Hence, Clausius is false.
Similarly, If Clausius is false
Aug. 08, 2006
Kelvin is also false.

9
Carnot Engine
Definition: A Carnot engine consists of any substance that is

made to go through the Reversible Cyclic thermodynamic
transformation, as shown in the diagram
T1
ab is isothermal, T2 is const and during

which the system absorbs Heat q 2 .
cd is isothermal, T1 is const and during
which the system rejects Heat q1.
T2
a
q2
absorb
bc and da are adiabatics
reject
T2 > T1
Aug. 08, 2006
q1
In a cyclic transformation, the temp.

does not change, so the change in
Internal energy is zero. Hence, the
work done by the system in one cycle
would be (from the first law):
W = q 2 q1
Infinitesimal Carnot engine, if transformations are infinitesimal.
10
Carnot Engine
Ref: For one Carnot cycle, the work done by

the system is:
W = q 2 q1
Efficiency of an Engine: It is defined as,
W
q1
=
= 1
q2
q2
Aug. 08, 2006
11
Carnot Engine and Refrigerator

If W > 0, then q1 > 0 and q 2 > 0.
Show that:
Proof:
q1 = 0 means the system absorbs q 2 heat and rejects nothing; that is, it
converts q 2 entirely into work. This violates Kelvin statement, and hence,
q 1 0.
Suppose, q1 < 0 : This means the engine absorbs q 2 from the reservoir at T2
and q1 from the reservoir at T1 .
The net amount of Heat converted to work, by the engine, therefore is
q 2 + ( q1 ), which is equal to q 2 + q1 because q1 is assumed negative.
We can next convert this work into Heat and then deliver it to the
reservoir at T2 , with no other effect.
The net effect is the transfer of a positive amount of Heat q1 from the
reservoir at T1 to the reservoir at T2 . But, T2 > T1 by assumption. Hence,
this violates the Clausius statement. Thus, q1 > 0, and hence W > 0.
Similarly, we can prove: If W < 0, then q1 < 0 and q 2 < 0. Here, the
Carnot engine operates in reverse and becomes a refrigerator.
Aug. 08, 2006
12
Carnots Theorem
Theorem: No Engine operating between two given

temperatures is more efficient than a Carnot engine.
Proof: Recall, for one carnot cycle, the work done is: W = q 2 q1
Consider a Carnot engine (C) and an arbitrary engine (X), operating

between the heat reservoirs at T2 and T1 (T2 > T1 ).
Work done is:
Let
q C2 N X
= C
X
q2 N
W C = q C2 q1C
W X = q X2 q1X
Integers (ratio of integers can approximate a

Floating point number, to any accuracy we desire)
Operate X engine N X cycles forward and C engine N C cycles in

reverse. At the end of the operation we have:
Aug. 08, 2006
(q 2 )total = N X q X2 N C q C2 = 0 (by the definition of integers)

X
X
C
C
X X
C C
W
=
N
W
N
W
total
(q1 )total = N q1 N q1
Wtotal = (q 2 )total (q1 )total = (q1 )total
13
Carnots Theorem
q C2 N X
= C
X
q2 N
(q1 )total = N X q1X N C q1C
Wtotal = (q1 )total
We would face a violation of the Kelvin statement,

unless we have W 0 and this implies (q1 )total 0.
total
X
In other words,
N
(q1 )total = N X q1X N C q1C 0 C q1X q1C 0
N
C
X
C
X
q
q C2 X
q
q
q
C
1
1
1
1
X q1 q1 0 X C 0 1 C 1 X
q2
q2 q2
q2
q 2 QED
Efficiency of a Efficiency of an
Carnot engine arbitrary engine
Corollary: All Carnot engines operating between two given

temperatures have the same efficiency.
Aug. 08, 2006
14
Absolute Temperature

This gives a definition of a scale of temperature called --- The
Absolute Scale. We define as follows:
The efficiency of a Carnot engine operating between two
reservoirs of respective absolute temperatures 1 and 2 is
1
= 1
2
Also,
Q = 1
q1
q2
q1 1
=
q2 2
Since 0 1, the absolute temperature of any reservoir is

always greater than zero.
Aug. 08, 2006
15
Clausius Theorem
Theorem: In any cyclic transformation throughout which the

temperature is defined, the following inequality holds.
dq
T 0
where the integral extends over one cycle of the transformation.
and the equality holds if the cyclic transformation is reversible.
Proof: Divide the cyclic transformation into N infinitesimal steps
and for each step the temperature is assumed constant.
Imagine, at each step the system is brought in contact with
heat reservoirs at temperatures, T1 , T2 , L , TN .
Let q m be the amount of heat absorbed by the system during
th
the m step, from the heat reservoir of temperature Tm .
N
q m and N will recover the theorem.
We need to prove

Aug. 08, 2006
0
m =1 m
We have essentially discretized the integral.
16
Clausius Theorem
Construct a set of N Carnot engines,
C1 , C 2 ,L C N
such that
1. Operates between Tm and TO (TO Tm , for all m)

(O )
2. Absorbs amount of heat q m

3. Rejects amount of heat
Cm
from TO
q m to Tm
q (mO ) TO
qm
(O )
=
=
q
T
m
O
From the definition of temperature scale, q
T
Tm
m
m
The net result of one complete cycle:
N
N
q m is the amount of heat absorbed from the
(O )
q total = q m = TO
reservoir at TO and converted entirely into
m =1
m =1 Tm
work, with no other effect.
Clausius says: this is impossible unless we have,
q total 0
Aug. 08, 2006
(q m / Tm ) 0
m =1
QED
17
Clausius Theorem
N
We have already seen, (q m / Tm ) 0 for a cyclic transformation.

m =1
If the cyclic transformation is reversible, we reverse it.

The line of arguments remains the same and we arrive at the
same inequality, except the signs of heat, q m are reversed.
That is,
N
(q m / Tm ) 0
m =1
Hence, we finally obtain (q m / Tm ) = 0 for reversible cyclic

m =1
transformations.
dq
Corollary: For a reversible transformation, the integral
is
T
independent of the path of transformations and depends only
on the initial and the final states of the transformation.
Aug. 08, 2006
Hence, the Entropy is a state function.
18
Amrendra Vijay
Lecture 04
Aug. 11, 2006
Ref: Statistical Mechanics, by Ryogo Kubo
Entropy
R
E
S
E
R
V
O
I
R
Consider a model showing a irreversible process (Heat Flow):
TI
(d q )
(d q )
int
ext
(
d q)
(dS) =
T
I
ext
ext
TII
(d q )
II
II
contact
ext
dS = (dS)int + (dS)ext
(
d q)
+
II
(dS)int
ext
TII
Entropy flow from the outside
1 1
= d q int
TII TI
( )
I
R
E
S
E
R
V
O
I
R
Entropy production inside the system
I or II are always internally at equilibrium, but they are not

mutually in equilibrium. And, thermodynamically we postulate:
(dS)int is never negative. (dS) = 0
Aug. 11, 2006
INT
(dS)INT > 0
Reversible Process
Kelvin Statement: There exists no thermodynamic

quantity of Heat from a Heat reservoir and to
convert it completely into work.
Clausius Statement: There exists no thermodynamic

quantity of Heat from a colder reservoir and to
deliver it to a hotter reservoir.
Aug. 11, 2006
Ref: Statistical Mechanics, by Kerson Huang (chapters 1 and 2)
Carnot Engine
Definition: A Carnot engine consists of any substance that is

made to go through the Reversible Cyclic thermodynamic
transformation, as shown in the diagram
T1
ab is isothermal, T2 is const and during

which the system absorbs Heat q 2 .
cd is isothermal, T1 is const and during
which the system rejects Heat q1.
T2
a
q2
absorb
bc and da are adiabatics
reject
T2 > T1
Aug. 11, 2006
q1
In a cyclic transformation, the temp.

does not change, so the change in
Internal energy is zero. Hence, the
work done by the system in one cycle
would be (from the first law):
W = q 2 q1
Infinitesimal Carnot engine, if transformations are infinitesimal.
Carnots Theorem
Theorem: No Engine operating between two given

temperatures is more efficient than a Carnot engine.
Proof:
Consider a Carnot engine (C) and an arbitrary engine (X), operating

between the heat reservoirs at T2 and T1 (T2 > T1 ). In one forward cycle,
C
X
C
X
C/X engine takes q 2 /q 2 amount of Heat and rejects q1 /q1 Heat.
q C2 N X
Let us define two integers such that, X = C
q2 N
(this can be done to any

accuracy we like, as long as
integers are large enough)
Operate X engine N X cycles forward and C engine N C cycles in reverse.

At the end of the operation, the total Heat taken by both machines, is
(q 2 )total = N X q X2 N Cq C2
=0
(by the definition of integers)
This implies, the total work done by both machines,

Aug. 11, 2006
Wtotal 0
(a la Kelvin)
Carnots theorem
The total Heat rejected by both machines:
(q1 )total = N X q1X N C q1C
So, the total work done by both machines is also,
Wtotal = (q 2 )total (q1 )total = (q1 )total
Recall, for one Carnot cycle,

the work done is: W = q 2 q1
But, we have already seen Wtotal 0. Hence, (q1 )total 0.

Use:
C
X
N q N q 0
X
X
1
C
1
q1
q1
1 X
C
q2
q2
Efficiency of a Efficiency of an
Carnot engine arbitrary engine
QED
q C2 N X
= C
X
q2 N

Aug. 11, 2006
Temperature Scale
To fix a Scale, we need (1) a uniform distribution of

points, and (2) either lowest or the highest point of
the scale.
Highest Point
OR
Aug. 11, 2006
Lowest Point
Temperature Scale
Consider a series of Carnot engines, all performing the same

amount of work, W ---- such that, the Heat rejected by any
Carnot engine is absorbed by the next one.
W
q n+2
Carnot
Engine
W
q n +1
Carnot
Engine
W
qn
Carnot
Engine
W
q n 1
q n +1 q n = W
Carnot
Engine
q n 2
W
W
Now, we have a set of equidistant points. To set a Temperature

Scale, let us define: Tn +1 Tn = x W (x : arbitrary constant)
Aug. 11, 2006
For example, we may choose: x W = 1 Kelvin
Temperature Scale
To fix the lowest highest point of our Scale, let us define the
efficiency of a Carnot Engine, operating between two reservoirs
of temperatures, Tn and Tn +1 (Tn +1 > Tn ) as,
Tn
n +1 = 1
Tn +1
Q 0 1 The absolute temperature of any reservoir is
always greater than Zero. It fixes the lower limit.
Thus, the Temperature scale is now fully defined !
A relation between q and T: Recall, the efficiency was originally

defined as
Wn +1
qn
q
T
n +1 =
= 1
n = n = x x is independent of n
q n +1
q n +1
q n +1 Tn +1
Aug. 11, 2006
Clausius Theorem
Theorem: In any cyclic transformation,

throughout which the temperature is
defined, the following inequality holds.
dq
T 0
where the integral extends over one cycle
of the transformation. And, the equality
holds if the cyclic transformation is
reversible.
Aug. 11, 2006
10
dq
T 0
Clausius Theorem
Proof strategy: Divide the cyclic transformation into N
Let q m be the amount of heat absorbed by the system during

the m th step, from the heat reservoir of temperature Tm .
small steps and for each step, the temperature, we assume,

is constant. That is, at each step, the system is thought to
have been brought in contact with heat reservoirs at
temperatures, T1 , T2 , L , TN .
qm
0
m =1 Tm
N
Then, we need to prove:
And, we will recover the original theorem in the limit N
Aug. 11, 2006
NB: We have essentially discretized the integral --- that is, we

have written the cyclic transformation, as a sum of N
infinitesimal cyclic transformations (e.g, Carnot engines). 11
Clausius Theorem
Proof: Construct a set of N Carnot engines, C1 , C 2 , L C N such that C m

2. Absorbs amount of heat q (mO ) from TO
qm
to Tm
q (mO ) TO
=
From the definition of temperature scale,
q m Tm
q (mO ) = TO
qm
Tm

is the amount of heat absorbed from the
N
N
q
m
q total = q (mO ) = TO
m =1
m =1 Tm
q total 0
Aug. 11, 2006
(q m / Tm ) 0
m =1
QED
12
Clausius Theorem
N
We have already seen, (q m / Tm ) 0 for a cyclic transformation.

m =1
If the cyclic transformation is reversible, we reverse it.

The line of arguments remains the same and we arrive at the
same inequality, except the signs of heat, q m are reversed.
N
That is,
(q m / Tm ) 0
m =1
Hence, we finally obtain (q m / Tm ) = 0 for reversible cyclic

m =1
transformations.
dq rev
Corollary: For a reversible transformation, the integral
is
T
independent of the path of transformations and depends only
on the initial and the final states of the transformation.
Aug. 11, 2006
dq rev
13
Hence, T which is called the Entropy, is a state function.
Proof of the Corollary -
Entropy is a state function

I
Consider two reversible paths:

/
Path II is reverse of the path II.
II
For reversible transformations, we have:
dq rev
T =0
dq rev
dq rev
I T + II/ T = 0
dq rev
dq rev
=0
I T
II T
That is:
That is, the difference of Entropy, computed along two different

paths is zero --- so, its path independent. Hence, Entropy is a
state function.
QED
Aug. 11, 2006
14
Entropy
Reference point.
Define Entropy:
A
dq rev
S(A ) =
T
Ref
Ref is some arbitrary

thermodynamic state
Ref
So, the change in Entropy:

A
dq rev
dq rev
S(A ) S(B) =

=
T
T
Ref
Ref
Ref
dq rev
dq rev
dq
+
= rev
T
T
T
Ref
A
Thus, the entropy is defined only up to an arbitrary additive constant,

so long as the state A is accessible from the Ref state, through a
reversible transformation. If not so, we would need the Third Law of
thermodynamics to fix the absolute value of the constant --- and hence,
the Absolute value of Entropy.
Aug. 11, 2006
15
Entropy
Properties
B
dq
A T S(B) S(A ) irreversible
For an arbitrary transformation:
Proof: For reversible transformations,

its obvious by definition.
Consider the cyclic transformation, made

up of (1) Irreversible, plus (2) reverse of
Reversible. From Clausius theorem:
dq
dq
dq
dq
0
IRR T REV T
IRR T REV T
A
reversible
dq
S(B) S(A )
IRR T
QED
Entropy of a thermally isolated system never decreases. This

is because dq is zero, S(B) S(A ) 0. Equals zero for reversible.
That means, for a thermally isolated system, the equilibrium
state is the state of maximum entropy.
Aug. 11, 2006
16
Thermodynamic Relations
dq = dU + PdV
Recall the first law:
And, assuming the internal energy being a function of volume

and temperature,
U
dU = C V dT +
dV
V T
Heat capacity
So,
dS =
Internal pressure
dq
dT 1 U
= CV
+
+
P
dV
T
T T V T
Using this, we can derive several important thermodynamic

relations --- and much more.
Aug. 11, 2006
17
Rules:
df = g(x,y)dx + h(x,y)dy is an exact differential, if
g h
=
y x x y
Given an exact differential, identify all

the variables. This relation then allows
us to obtain a host of useful relations,
(for example, Maxwells relations).
Let x, y and z are quantities satisfying a functional relation,

f(x,y,z)=0. Let w be a function of any two of x, y, z then
x y
x
=
y w z w z w
Aug. 11, 2006
x y
=
y z x z
x y z
= 1
y z z x x y
18
Derivation of TdS equations:
dq
dT 1 U
+
P
+
dS =
= CV
dV
T V T
T
T
Ref:
dS is an exact differential and RHS is a function of V and T, so
C V = 1 U + P

T
T
V
V
T
V T T
U
Use the definition, C V =
, differentiate and rearrange.
T V
U
P
U
P
+
=
P
T
T
=

V T
T V
V T
T V
For ideal gas, P=nRT/V and hence, U = T nR P = 0.

V
V T
Hence, the internal pressure of of an ideal gas is zero,
Aug. 11, 2006
19
and we already knew it !!!
TdS Equations
Recall: dS = C V
dT 1 U
+
+
P
dV
T T V T
U
P
+P=T
V T
T V
P
TdS = C V dT + T dV
T V
Similarly, we can show:
TdS =
V
C P dT T
dP
T P
We can also write TdS equations, purely in terms of

experimental observables:
Aug. 11, 2006
20
TdS Equations
Define: =
1 V
V T P
1 V
V P T
1 V
S =
V P S
T =
with exptal observables

Coefficient of thermal expansion
Isothermal compressibility
adiabatic compressibility
We can then show:

1
1
V V
T V
P
=

=

=
T
T P P T
T V
V P P T
P
Q TdS = C V dT + T dV TdS = C V dT + T dV
T
T V
Aug. 11, 2006
Similarly, TdS = C P dT TVdP
21
Entropy of Phase Transition
Normal transition temperature: This is the temperature at which

two phases are in equilibrium at 1 atmosphere pressure. For
example: Liquid water and vapur at 100 degree C.
Solution: (1) At the transition point, there is an equilibrium and
hence any transfer of heat between two phases is reversible. (2)
The pressure is constant by definition, and at constant pressure,
the change is Heat at constant pressure is the definition of
Enthalpy. Therefore,
(S)Transition
(
H )Transition
=
TTransition
(H )Transition < 0 (exothermic, e.g., freezing)

(H )Transition > 0 (endothermic, e.g., melting )
Troutons rule: Standard entropy of vaporization is amost the

same for a wide range of liquids, and the value is 85 J/(K mol).
Aug. 11, 2006
22
Entropy as a function Temperature

dq
ds =
T
Recall:
If only temperature changes, then we can directly integrate:

T2
dq rev
S(T2 ) = S(T1 ) +
T
T1
If we fix the pressure, then at constant P,
dq rev = C P (T ) dT.
T2
dT
S(T2 ) = S(T1 ) + C P (T )
T
T1
If the heat capacity is independent of Temperature:

T2
Aug. 11, 2006
T2
dT
S(T2 ) = S(T1 ) + C P
= S(T1 ) + C P ln
T
T1
T1
23
Amrendra Vijay
Lecture 05
August 14, 2006
Happy Independence Day
August 14, 2006
Syllabus --- Equilibrium Thermodynamics
Basic Concepts
The Second Law of Thermodynamics; Entropy; Clausius
Inequality.
Entropy Changes for reversible and irreversible processes.
Third Law of Thermodynamics and Absolute Entropy
Definition of Free Energy and Spontaneity; Maxwells Relations;
Free Energy and Chemical Equilibria; Gibbs-Helmholtz and
vant Hoff Equations.
Thermodynamic properties from EMF measurements; Nernst
Equation
Phase Equilibria: Clausius-Clapeyron equation; phase rule
Phase diagrams: One component systems
Eutectic systems
August 14, 2006
References
Physical Chemistry Through

Problems
--- S.K. Dogra and S. Dogra
August 14, 2006
Reference:
Statistical Mechanics by Kerson Huang
Recap
We proved Clausius Inequality:
dq
T 0
We then defined Entropy as: S(A ) =
dq rev
T
Ref
Assuming there is a
continuous path of
transformation from
Ref to A.
We then observed Entropy is defined only up to an arbitrary

additive constant:
B
dq rev
dq rev
dq rev

=
+
S(B) S(A ) =
T
T
T
Ref
Ref
Ref
Ref
dq rev
dq
= rev
T
T
A
That is, S is an exact differential.
This implies: Even though, we defined Entropy only for a

reversible transformation, but we can correctly compute the
change in Entropy of a system by choosing any arbitrary path !
August 14, 2006
What is the implication ?
Change of Entropy
Consider: One mole of an ideal gas expands

isothermally from volume V1 to V2 by two different
routes:
1. Reversible Isothermal Expansion
2. Irreversible Free Expansion
We will compare the change of Entropy of the gas

and of the surroundings, computed by both routes.
August 14, 2006
Entropy Change:
Reversible Isothermal Expansion
Model:
Reservoir, T
Piston
gas
Spring
P
T constant line
Work done
August 14, 2006
V1
V2
Entropy Change:
Computation: Temperature is constant, so the change in

Internal Energy for ideal gas will be zero. The First law then
says: the amount of heat absorbed, q is equal to the work
done, W.
V2
W = RT ln
q
V1
Hence, the change in Entropy of the gas is:
(S)gas = q = R ln V2
T
V1
But, the reservoir has supplied the heat and so the change in
Entropy of Reservoir will be:
August 14, 2006
(S)Reservoir
q
V2
=
= R ln
T
V1
Entropy Change:
So, the total change in Entropy is Zero:
(S)Total = (S)Gas + (S)Reservoir
V2
V2
= R ln
R ln
=0
V1
V1
Question: Where did the work done, W = RT ln V2 by the gas go ?

V1
Answer: Well, the work gets stored in the spring (spring gets
compressed) connected to the piston, which can be used to
compress the gas back, by reversing the transformation.
August 14, 2006
Entropy Change:
Irreversible Free Expansion
Model:
Before
After
Water Bath, T constant

Gas occupies volume,
August 14, 2006
V1
Water Bath, T constant

Gas occupies volume, V2
Joules free-expansion experiment
10
Entropy Change:
Computation: First of all, no heat was supplied by the

Reservoir, and hence the change in Entropy for the Reservoir
would be zero here.
(S)Reservoir = 0
But. the initial and the final states are the same, and the
Entropy has turned out to be a state function, and therefore
the change in Entropy for the gas here will be the same as that
we found for Reversible Thermal Expansion. That is:
(S)gas
V2
= R ln
V1
So the total change in Entropy here is:
(S)Total = (S)Gas + (S)Reservoir

August 14, 2006
V2
= R ln
V1
11
Entropy Change:
(S)Reservoir
T
V1
q
V
=
= R ln 2
T
V1
(S)Total = 0
W = RT ln
V2
V1
Gets stored
in the Spring
Comparison
T
V1
(S)Reservoir = 0
(S)Total
V2
= R ln
V1
W = T (S)Total Gets wasted
We henceforth say: Irreversibility is wasteful, and is marked by

an increase of Entropy of the total system under consideration.
For this reason, the Entropy may be viewed as a measure of the
unavailability of useful energy.
August 14, 2006
12
Entropy as a function Temperature

dq
ds =
T
Recall:
If only temperature changes, then we can directly integrate:

T2
dq rev
S(T2 ) = S(T1 ) +
T
T1
If we fix the pressure, then at constant P,
dq rev = C P (T ) dT.
T2
dT
S(T2 ) = S(T1 ) + C P (T )
T
T1
If the heat capacity is independent of Temperature:

T2
August 14, 2006
T2
dT
S(T2 ) = S(T1 ) + C P
= S(T1 ) + C P ln
T
T1
T1
13
(From Atkins)
Standard State
Definition: The standard state of a substance at a specified

Temperature is its pure form at one bar pressure.
Conventionally, the Temperature at which thermodynamic data

are reported is 298.15 K (Kelvin) = 25 degree C (Centigrade).
Reason: Frequently, we are interested in computing the change

in thermodynamic quantities, like Enthalpy, in which the initial
and the final substances are in their standard state.
Example: (1) The standard state of liquid ethanol at 200 K is

pure liquid ethanol at 200 K temperature and 1 bar pressure.
-2
5
Units: 1 N m = 1 Pa; 10 Pa = 1 bar (1 atm)
August 14, 2006
14
Entropy of Phase Transition
Normal transition temperature: This is the

temperature at which two phases are in equilibrium
at 1 atmosphere pressure. For example: Liquid water
and vapor at 100 degree C.
Solution: (1) At the transition point, there is an
equilibrium and hence any transfer of heat between
two phases is reversible. (2) The pressure is constant
by definition, and at constant pressure, the change in
Heat at constant pressure is the definition of
Enthalpy. Therefore,
(S)Transition
August 14, 2006
(
H )Transition
=
TTransition
(H )Transition < 0 (exothermic, e.g., freezing )

(H )Transition > 0 (endothermic, e.g., melting )
15
Troutons Rule
Standard entropy of vaporization is almost the same for a wide

range of liquids, and the value is 87.822 J K 1mol 1.
Q (S)Transition
(H )Transition
=
TTransition
(S)Vaporization =
(H )Vaporization
TBoiling-Point
85 J K -1mol1
This rule allows us to compute either the Heat of Vaporization

or the Boiling Point of a liquid approximately.
The rule is less valid for liquids, in which molecules are

expected to be arranged in an orderly manner (probably due to
strong intra-molecular interactions) and a great change of
disorder is expected to occur when the liquid evaporates.
August 14, 2006
16
Troutons Rule
Example: The normal boiling point of Chloroform is 61.5C.
Calculate the molar heat of vaporization, from Troutons rule.
Answer:
(H )Vaporization
85 J K -1mol 1
Q (S)Vaporization =
TBoiling-Point
(H )Vaporization = 85 J K -1mol 1 TBoiling-Point
(85J K
August 14, 2006
mol 1 (273 + 61.5)K
17
Example
Calculate the increase in the Entropy if one mole of Krypton is

heated from 27C to 227C at constant volume and at pressure
(the molar heat capacity at constant volume is 1.5 R and
1
1
R=8.314 J K mol).
At constant volume:
(
T2
273 + 27 )K
1
1
S = n C V ln = (1mol) 1.5 8.314 J K mol ln
(273 + 227 )K
T1
At constant pressure:
(
T2
273 + 27 )K
1
1
S = n C P ln = (1mol) [1.5 + 1.0] 8.314 J K mol ln
(273 + 227 )K
T1
August 14, 2006
18
Example
One mole of the ideal gas at 3 atm and 300 K is expanded (1)
isothermally to double its initial volume against an external
pressure of 1.5 atm, (2) isothermally and reversibly to twice its
original volume. Calculate the work done.
(1)
W = Pext V = Pext (V2 V1 )
(2)
nRT
and V1 =
P
2V1
V2
1
1
W = n RT ln = (1mol) 8.314JK mol (300K )ln

V1
V1
August 14, 2006
19
Example
A reversible Carnot cycle does work equivalent to 150 kJ per

cycle. If the heat supplied by cycle is 225 kJ at 227 degree C
per cycle, calculate (1) the temperature at which the heat is
rejected, and (2) the thermal efficiency of the engine.
(1) Thermal Efficiency:
(2)
work (W )
150 kJ 2
=
=
=
heat absorbed (q 2 ) 225 kJ 3
T1
Q = 1
T2
August 14, 2006
2
T1 = (1 )T2 = 1 (227 + 273)K
3
20
Thermodynamic Potentials
Helmholtz Free Energy, A:
Gibbs Free Energy, G:
A = UTS
G = A + P V Enthalpy
G = U TS + P V = H TS
Internal Energy
Entropy
Temperature
Note: We introduce these potentials to rationalize the direction

of natural processes, by focusing our attention only to the
system. In contrast, if we use the concept of Entropy, we also
need to take into account the changes taking place in the
surroundings
August 14, 2006
21
Potentials
---
Physical Meaning
Helmholtz Free Energy, A: Consider an arbitrary Isothermal

transformation from state A to state B. Clausius theorem says:
B
dq
A T S(B) S(A )
Because Temperature, T is constant, we have:
q
S q T S
T
S = S(B) S(A )
q : Heat absorbed
during the transformation
From the First Law we know, q = dU + W
U + W TS
August 14, 2006
and hence,
W (U TS)
W A
A: Helmholtz Free Energy
22
Potentials
---
Physical Meaning
Ref: For an arbitrary isothermal transformation.
W A
Physical Meaning: For an arbitrary isothermal transformation,

the change of the Helmholtz Free Energy is the negative of the
maximum possible work done by the system.
Corollary: If W=0 then ---- For a mechanically isolated system

kept at constant temperature, the Helmholtz Free Energy never
increases.
August 14, 2006
23
Third Law of Thermodynamics
Recall: (1) From Clausius inequality, we deduced that the
Entropy of a substance can be determined up to an arbitrary

constant, and (2) the definition of Entropy depends on the
existence of a reversible transformation, joining an arbitrary
reference state and the state A.
But, a reversible transformation, required for the definition may

not actually exist, for some particular system. If that is the case
then Second Law does not determine the difference in Entropy
of two states uniquely.
Then, the Third Law comes to our rescue in the form Nernst
rule.
August 14, 2006
24
Nernst Rule
Rule: The entropy of a system at absolute zero temperature is

a universal constant, which may be taken to be zero.
Observations: (1) The rule is valid for any system, (2) It
states that S = 0 for T=0, irrespective of the values of any

other thermodynamic parameters, S depends upon. Hence, it
makes the Entropy of any state of any system unique.
August 14, 2006
25
Amrendra Vijay
Lecture 06
August 18, 2006
Entropy
Question: Why do we need a reversible path, for the defintion of

Entropy ?
Answer: Recall,
dq = dU + PdV
U
= C V dT +
dV + PdV
V T
Heat is a path function. And, to convert it into a state function,

we needed to multiply it by an integration factor. It turns out
that 1/T is an integration factor for dq REV and no integration
factor exists for dq IRR . We had then obtained:
dS =
August 18, 2006
dq REV
dT 1 U
= CV
+
+
P
dV
T
T T V T
dq
T 0
Clausius Inequality
Recall, the definition efficiency,
= 1
q1
q2
= 1
q1
q2
(0 1)
of an engine,
If we wish to follow the

Sign Convention explicitly.
q1C T1
=
Recall the definition of temperature,
C
q 2 T2
X
q
q1C
1
T
1
And, Carnot theorem: C 1 C = 1

X

X
q
T
q
2
2
2
q1X T1 But, q X is the heat rejected,

q1X
T1
1
X
1 1 X
T2 and hence it carries a
q2
q2
T2
negative sign.
q1X T1
X
q 2 T2
August 18, 2006
q1X q X2
0
+
T1 T2
for one Carnot Engine

3
QED
Clausius Theorem
Proof: Construct a set of N Carnot engines, C1 , C 2 , L C N such that C m

2. Absorbs amount of heat q (mO ) from TO
qm
to Tm
q (mO ) TO
=
From the definition of temperature scale,
q m Tm
q (mO ) = TO
qm
Tm

is the amount of heat absorbed from the
N
N
q
m
q total = q (mO ) = TO
m =1
m =1 Tm
How ?
August 18, 2006
(q m / Tm ) 0
m =1
q total 0
QED
Explanation
Recall: A Carnot engine is a reversible cyclic transformation.

Arbitrary
Cyclic
Transformation
Infinitesimal
Carnot Engine
qm
q (mO )
Total Heat injected in the complete process is: q total =

August 18, 2006
q(
m =1
O)
m
5
Criteria of equilibrium
algorithm
How do we, in general, determine whether a thermodynamic

system is in equilibrium or a thermodynamic transformation is
irreversible ?
Answer:
Select a thermodynamic function, F and find its natural

variables, X and Y.
Natural variables, X and Y, will allow us to write an inequality
of the following type: dF
dF X,Y 0
X, Y 0 OR
( )
( )
This inequality will allow us to differentiate an irreversible

process from a reversible process and also determine whether
the system is in equilibrium --- and hence the direction of
natural processes.
August 18, 2006
We will henceforth obtain the Maxwells relations.
Criteria of Equilibrium
B
q
S = SB SA = dS
T
A
A
q
We can also write as, dS
T
irreversible
Entropy:
Spontaneous and Irreversible Processes:
q
Reversible Processes: dS =
T q
Impossible Processes:
dS <
T
Entropy
B
q
dS >
T
If the system is isolated then we have,
reversible
q = 0
Spontaneous and Irreversible Processes:

Reversible Processes:
August 18, 2006
Impossible Processes:
dS > 0
dS = 0
dS < 0
Entropy
q
dS
T
Natural Variables: Reference:
If we consider only the Pressure-Volume work then from the

first Law we have,
q = dU + P dV
q = dU
q = 0
(Volume, V constant)
(If the system is isolated, U constant)
At constant U and V,
(dS)U,V 0
U and V are called natural

Variables of S
We then say: In a spontaneous process in an isolated system,
the Entropy increases to a maximum. That is, for a system at
constant U and V, the natural (spontaneous) process is in the
direction of increasing Entropy.
August 18, 2006
Clausius Inequality:
Q q = dU + PdV
q
dS
T
Internal Energy
q TdS 0
dU + PdV TdS 0
At constant Volume, V and Entropy, S, we have

Here, V and S are natural variables for U
Thus, for a system at constant volume and Entropy:

If the change is spontaneous: dU
If the change is reversible: dU = 0
dU 0
<0
Thus, for a conservative system, the stable state is the one of

lowest energy --- that is, if the system is in the lowest energy
state at constant V and S, any change would increase the
energy and such changes will not be spontaneous.
August 18, 2006
Thermodynamic Potentials
Helmholtz Free Energy, A:
Gibbs Free Energy, G:
A = UTS
G = A + P V Enthalpy
Internal Energy
Entropy
Temperature
Note: We introduce these potentials to rationalize (easily) the

direction of natural processes, taking place in the laboratory
conditions (in the laboratory, we control the temperature,
pressure, volume and so forth).
August 18, 2006
10
Helmholtz Free Energy, A

A = UTS
Definition:
For a given thermodynamic transformation, the change in

Helmholtz Free Energy is:
A = U T S S T
If Temperature is constant then A = U T S
August 18, 2006
11
Helmholtz
Recall: For an arbitrary transformation, Clausius Theorem is:

B
dq
A T S
Helmholtz Free Energy, A: Consider an arbitrary Isothermal

(constant Temperature) transformation from state A to state B.
q
S
T
S = S(B) S(A )
q T S
q : Heat absorbed
during the transformation
From the first Law: q = dU + W
U + W TS
August 18, 2006
W A
Change in Helmholtz Free

Energy, at constant temp.
W (U TS)
W = A,
if the transformation
12
is reversible.
Helmholtz
W A
Physical Meaning: For an isothermal (constant temperature)

transformation, the change of the Helmholtz Free energy is the
negative of the maximum possible work done by the system.
August 18, 2006
13
Helmholtz
W A
Situation: If the system is mechanically isolated then, W=0.

And hence,
(Criteria of equilibrium)
A0
Theorem: For a mechanically isolated (constant volume)

system, kept at constant temperature, the Helmholtz Free
Energy never increases.
Corollary: For a mechanically isolated system, kept at constant

temperature, the state of equilibrium is the state of minimum
Helmholtz free energy.
We henceforth determine the direction of natural processes.
Here, V and T are natural variables for A
August 18, 2006
14
dq = dU + PdV
Helmholtz
A = UTS
Useful Relations: We will first attempt to write the

change of Helmholtz Free Energy in terms of its
natural variables, V and T:
A = U T S S T = P V S T
ENERGY
HEAT
A
P =
V T
WORK
A
S =
T V
That implies:
That is, if the function A(V,T) is known, the Pressure

and the Entropy can be calculated.
August 18, 2006
15
Helmholtz
Example:
P1 V1
P2 V2
Question: Release the piston and allow it to slide freely. What

would be the equilibrium position ?
Answer: Equilibrium corresponds to the state of minimum
Helmholtz Free Energy. By minimum we mean, the first
variation of the function is zero. That is: A = 0
A
A
dV1 +
dV2
A =
V1 T
V2 T
V1 + V2 = V (constant)
dV1 + dV2 = 0 dV1 = dV2
A A

dV1 A = A P1 = P2
0 =
V V
V1 T V2 T
1 T 2 T
August 18, 2006
So the equilibrium position is the situation when

the pressure is the same in both vessels.
16
Gibbs Free Energy, G

G =A+PV
Definition:
Change in Gibbs Free Energy:
G = A + P V + V P
If Pressure is constant then
August 18, 2006
G = A + P V
17
Gibbs
From Helmholtz Free Energy, if Temperature is constant then
W A (we have already seen this)

If Pressure is constant then W = P V. And hence,
P V A P
+43
A 0 G 0
1V
42
G for P = Constant
Theorem: For a system at constant Temperature and Pressure,

the Gibbs Free Energy never increases.
Corollary: The state of equilibrium is the state of minimum
Gibbs Free Energy.
We henceforth determine the direction of natural processes.
August 18, 2006
Here, P and T are natural variables for G
18
G = U TS + P V
Gibbs
Useful Relations: We will first write the Change of Gibbs
Free Energy in terms of its natural variables, P and T:
G = U T S S T + P V + V P
ENERGY HEAT
WORK
G = S T + V P
G
S =
T P
August 18, 2006
G
V=
P T
19
Other Relations
Definition of Enthalpy:
Change of Enthalpy:
Enthalpy, H
H=U+PV
H = U + P V + V P
ENERGY
WORK
= T S + V P
HEAT
S and P are natural variables for Enthalpy.
H
T=
S P
August 18, 2006
H
V=
P S
20
Maxwells Relations
V
U
S
T
G
A, G, H and U are flanked by their natural variables. For

example, A is a function of V and T --- A(V,T).
Derivative with respect to one argument, keeping other fixed, is
obtained by going along the diagonal line. If it goes against the
direction of the arrow, it picks up a negative sign. For example,
August 18, 2006
= S
T V
A
= P
V T
G
=V
P T
21


rule.
August 18, 2006
22
Nernst Rule

Observations:
1. The rule is valid for any system.
2. It states that S = 0 for T=0, irrespective of the values of
any other thermodynamic parameters, S depends upon.
Hence, it makes the Entropy of any state of any system unique.

August 18, 2006
23
Nernst Rule
Implications
Any Heat Capacity of a system must vanish at absolute zero.

Proof:
dq REV
dT 1 U
= CV
+
Ref : dS =
+ P dV
T
T T V T
dT
At constant Volume, dV=0 and hence: dS = C V
T
TA
T
A
If TA is very close to 0,
dT TA 0
dT
SA = C V (T )
= C V (TA )
C V (T ) is expected to be
T
T
0
0
constant in the
T
A
= C V (TA ) ln
Temperature range.
1203
infinity at TA 0
Q SA 0 as TA 0, we must then have C V (TA ) 0

August 18, 2006
This has been verified experiementally.
QED
24
Nernst Rule
Implications
All transformations at absolute zero are adiabatic.
Proof: For reversible transformation,
Q (q )REV = T S
q 0 as T 0
August 18, 2006
25
Nernst Rule
Implications
At absolute zero, the coefficient of thermal expansion of

any substance vanishes.
Proof:
August 18, 2006
26
Amrendra Vijay
Lecture 07
August 21, 2006
Criteria for Irreversibility
Clausius Inequality:
B
dq
S SB SA dS
T
A
A
q
dS
T
This is the most general statement on irreversibility. Other

inequalities (for example, using Gibbs energy of Helmholtz
energy) were motivated by our convenience and laboratory
conditions.
Message: Given a particular problem, try first to identify
variables which remain constant. This will give clue on natural
variables and hence appropriate thermodynamic functions, and
corresponding inequality. Use this inequality to predict if the
process is irreversible (spontaneous/natural) or not.
August 21, 2006
Suggested Reading:
Statistical Mechanics by K. Huang, Chapter 1.
August 21, 2006


rule.
August 21, 2006
Suggested Reading: Statistical Mechanics by K. Huang, Chapter 1.
Nernst Rule

Observations:
1. The rule is valid for any system.
2. It states that S = 0 for T=0, irrespective of the values of
any other thermodynamic parameters, S may depend upon.
Hence, it makes the Entropy of any state of any system unique.

August 21, 2006
Nernst Rule
Implications
Any Heat Capacity of a system must vanish at absolute zero.

Proof:
dq REV
dT 1 U
= CV
+
Ref : dS =
+ P dV
T
T T V T
dT
At constant Volume, dV=0 and hence: dS = C V
T
TA
T
A
If TA is very close to 0,
dT TA 0
dT
SA = C V (T )
= C V (TA )
C V (T ) is expected to be
T
T
0
0
constant in the
T
A
= C V (TA ) ln
Temperature range.
1203
infinity at TA 0
Q SA 0 as TA 0, we must then have C V (TA ) 0

August 21, 2006
This has been verified experimentally.
QED
Nernst Rule
Implications
All transformations at absolute zero are adiabatic.
Proof: For reversible transformation,
Q (q )REV = T S
q 0 as T 0
August 21, 2006
Nernst Rule
Implications
At absolute zero, the coefficient of thermal expansion of

any substance vanishes.
Proof:
Refer to Statistical Mechanics by Kerson Huang (pp.)
In case of difficulty, please contact me.
August 21, 2006
Gibbs Free Energy, as a function of Temperature and Pressure.
August 21, 2006
Suggested Reading
Physical Chemistry by R.A. Alberty and R.J. Silbey

Chapters 3 and 4
Practice examples and problems
(particularly the solved ones !)
If you dont find this book, you may borrow from

me and make a xerox copy.
August 21, 2006
10
Ref: G = A + PV = U TS + P V = H TS
Recall: For Gibbs Free Energy, Pressure and Temperature are

natural variables, and therefore
G = S T + V P
H
G G
=
T
T P T
Effect of Temperature
GH
=
T
1
H
1
G + G

= 2
T T P
T
T T
G
H
2
T
T
T
Hence,
= S
T P
(G/T )
=H
(1/T ) P
Alternatively,
Gibbs-Helmholtz Equation
August 21, 2006
Thus, if we know the Enthalpy of the system, we can

predict how G/T varies with Temperature, T.
11
Gibbs-Helmholtz Equation
G
H
Q
= 2
T
T T P
(G/T )
Q
=H
(1/T ) P
G
H

= 2
T
T T P
(G/T )
= H
(1/T ) P
We have written the equation using (G/T) in stead of simply G

for future convenience [in particular, the equilibrium constant
of a chemical reaction is related to (G/T)].
G-H equation is most useful when it is applied to study changes
of physical states and chemical reactions, at constant pressure.
We can determine G at another temperature, if it is known at
one temperature and H is known.
August 21, 2006
12
Effect of Pressure
G = S T + V P
dG = S dT + V dP
Recall,
At constant T,
can integrated directly, if volume
is known as a function of Pressure, at constant T. Then,
dG = V dP
P2
G 2 G1 = V dP
dG = V dP
P1
P2
G 2 = G1 + V dP
P1
In certain circumstances, we can simplify this equation further.
August 21, 2006
13
P2
G 2 = G1 + V dP
Effect of Pressure
P1
Case-I: IF the Volume is independent of Pressure then

P2
G 2 = G1 + V dP
G 2 = G1 + V(P2 P1 )
P1
If we choose the state 1 as the standard state, then the Gibbs

Free Energy is:
G =G +V PP
0
G 0 is Gibbs free energy when the pressure is

equal to the standard state pressure.
August 21, 2006
This is okay for liquid and solid but not for gases.
14
P2
dP
G 2 = G1 + nRT
P
P1
PV = nRT
P2
G 2 = G1 + nRT ln
P1
In terms of standard state, we have:
P
G = G + nRT ln 0
P
0
Effect of Pressure
P1
Case-II: Ideal Gases, for which we know the equation of state.

P2
G 2 = G1 + V dP
is the Gibbs energy when the

pressure is equal to the standard
state pressure 0 .
Thus, the molar Gibbs energy of an ideal gas depends

logarithmically on the Pressure
August 21, 2006
15
Open Systems
Partial Molar Quantities: Chemical Potential

Thermodynamics of (Ideal Gas) Mixtures
Concept of Activity
Reference: Physical Chemistry by Alberty and Silbey
(pages: 122-134)
August 21, 2006
16
Open System
General Consideration
Recall, an open system is the one that allows exchange of

matter (beside energy) with its surroundings.
We will consider a system containing N different species

(molecules, electrons, atoms and so forth).
n1 , n 2 , L , n N
of moles.
where
n j is the amount of jth species, in terms
A given thermodynamic quantity will be a function of {n j ; j = 1, N}

beside the natural variables.
Example: Internal Energy,
August 21, 2006
U(S, V, n1 , n 2 , L , n N )
17
Open System
partial molar quantities
Consider a thermodynamic quantity, F.
f ,
,
{
natural variables
n1 , n 2 , L , n N
142
4 43
4
no.of moles of species in the system
N
f
f
f
df =
d +
d +
dn i
,n1Ln N
i =1 n i ,, n
, n1Ln N
j
Change in f
per mole of
species i added.
August 21, 2006
is the Partial Molar Quantity

n i ,, n j For example: partial molar volume,
Partial molar Free Energy (Chemical

Potential) and so forth.
What good does it do ?
18
Partial Molar Quantity
N
f
f
f
Definition: df =
d +
d +
dn i
,n1Ln N
i =1 n i ,, n
, n1Ln N
j
Assume natural variables are constant, then we have:
(df ),
=
dn i
i =1 n i ,, n
j
N
(df ), = f i dn i
i =1
upon Integration
N
f = n i fi
i =1
Thus the function f may be calculated, if partial molar fs are

known.
This is important, for it shows how to calculate
a thermodynamic property by simply adding up
August 21, 2006
19
contributions from the individual components.
Partial Molar --
Ex: Internal Energy
Consider the Internal Energy, U. Its natural variables are

Volume (V) and Entropy (S) and hence:
N
U
U
U
dU =
dS +
dV +
dn i
S V,n1Ln N
V S,n1Ln N
i =1 n i S, V, n
j ( i )
N
dU = TdS PdV + i dn i
i =1
i =
n i S, V,n j( i )
Chemical Potential
of species i. OR,
Partial Molar
Internal Energy.
So, the Chemical potential of a component of a homogeneous

mixture is equal to the rate of change of the internal energy,
with respect to the amount of that species, at constant Entropy
and Volume.
August 21, 2006 To define Chemical Potential, we could also use
20
other thermodynamic functions, like Gibbs Energy.
Chemical Potential
Using Gibbs Free Energy:

N
dG = S dT + VdP + i dn i
i =1
i =
n i P,T, n j( i )
Using Helmholtz Free Energy:

N
dA = S dT PdV + i dn i
i =1
other definitions
i =
n i V,T, n j( i )
Using Enthalpy:
N
dH = TdS + VdP + i dn i
August 21, 2006
i =1
i =
n i P,S, n j( i )
21
dG = S dT + VdP + i dn i
Gibbs
Additivity Relation
i =1
If P, T, and the relative proportion of the components are held

constant then,
N
dG = i dn i
i =1
Integrate
G = ni i
i =1
Gibbs Free Energy of a system is the sum of

the contributions of the various components.
This relation allows us to compute Gibbs energy of mixture.

If a system contains a single substance (N=1) then,
G=n
August 21, 2006
G
=
n
Thus, for a pure substance, the

Chemical Potential is equal to the
Gibbs Free Energy per mole.
Chemical Potential = Partial Molar Gibbs Free Energy
22
Thermodynamics of an Ideal Mixture
Reference: Phys. Chem. by Alberty and Silbey, pp 130-132.

Recall: Gibbs Free Energy as a function of pressure, for an
ideal gas is,
0
is the Gibbs energy when the
G
P
G = G 0 + nRT ln 0
P
pressure is equal to the standard

state pressure P 0.
Since molar Gibbs energy is nothing but the chemical potential,
Pi
i = + RT ln 0
P
Partial pressure of the species i
0
i
Pi = y i P
y i = mole fraction
P = Total Pressure
We will then add contributions from all species, and finally

obtain the change in Gibbs Energy and Entropy on mixing.
August 21, 2006
(G )mixing = nRT yi ln(yi )

i =1
and so forth.
23
Activity
Recall: Molar Gibbs free energy as a function of Pressure, for

an ideal gas is:
Pi
i = + RT ln 0
P
0
i
Pi : Partial Pressure of species i.

P 0 : Standard State Pressure
If we insist the chemical potential of a real substance to have

the exactly same form as that of an ideal gas, then
i = i0 + RT ln (a i )
a i : activity of species i in the mixture.
Read: Alberty and Silbey, pp. 133.

August 21, 2006
24
Amrendra Vijay
Lecture 08
August 22, 2006
Chemical Equilibrium
Suggested Reading:
Physical Chemistry by R.A. Albery and R.J. Silbey
Keywords:
Chapter 5
Fugacity and Activity.

Chemical equilibrium, Extent of reaction.
Reaction Gibbs Energy is the change of Gibbs energy
as a function of the Extent of reaction, .
Reaction Gibbs energy in terms of activity.
Equilibrium Constant, K.
Thermodynamics of a gas phase reaction.
vant Hoff Equation --- K as a function of Temperature.
Relation between K and the Extent of reaction, .
August 22, 2006
Activity and Fugacity
Recall: Molar Gibbs free energy as a function of Pressure, for

an ideal gas is:
Pi
i = + RT ln 0
P
0
i
Pi = P
i
yi = 1
i

Pi = y i P
y i = mole fraction
P = Total Pressure
For a real gases, we assume the same form as that of ideal

gases and hence we introduce a new quantity, Fugacity:
fi
i = + RT ln 0
P
0
i
Lim
August 22, 2006
P 0
f i : Fugacity of species i.
As pressure approaches zero, real gases

f
= 1 approach the behavior of ideal gases.
P
Read: Alberty and Silbey, pp. 120 and 133.
Activity and Fugacity
More generally, we can write the Chemical Potential as:
i = i0 + RT ln (a i )
Pi
P0
ai =
fi
P0
For an ideal gas
For a real gas

f i : Fugacity of species i.
If i = i then
unity.
August 22, 2006
a i : activity of species i in the mixture.
a i = 1. That is: Activity for the reference state is

4
Definitions
Consider an arbitrary reaction:
a A + b B d C + d D
Products
Reactants
c C + d D a A b B = 0
So, a general chemical reaction may be written as follows:

N
i =1
August 22, 2006
Ai = 0
Reactants or Products
Stoichiometric ve for reactants
Number
5
+ ve for products
Definitions
Usually, we study chemical reactions at constant Pressure, P,

and Temperature, T, and hence we will consider the Gibbs Free
Energy, G, as the criterion of equilibrium. In our discussion, we
will consider reactions, taking place in the single phase.
Recall: The change in Gibbs energy at constant P and T, is

N
(dG )T,P = i dn i
i =1
We need to compute this

before discussing the
equilibrium property of a
Chemical Reaction.
August 22, 2006
N : No. of species involved

in the reaction.
i :
dn i :
Chemical Potential of species i

Differential Change in the
amount of species i
6
Proposition: When a chemical reaction takes place, the changes

in the amount of species involved, are proportional to their
Stoichiometric numbers,
That is:
(n
(
i n
ni n
0
i
0
i
i .
i
= i
n i0 :
Initial amount of species i
ni :
Amount of species I, after

some time.
Proportionality constant, also

called the extent of reaction.
dn i = i d
August 22, 2006
Substitute this in the expression

for the change in Gibbs energy.
Reaction Gibbs Energy
We have:
(dG )T,P = i dn i
i =1
(dG )T, P = i i d
dn i = i d
Reaction Gibbs Energy
i =1
N
G
= i i

T, P i =1
(G )R = i i
i =1
Reaction Gibbs energy is the change in Gibbs energy when the

extent of reaction changes by one mole. The unit is Joule/mole.
August 22, 2006
Equilibrium Behavior
(G )R
N
G
= i i

T, P i =1
When a chemical reaction happens, the Gibbs energy decreases

and the reaction continues till the Gibbs energy reaches its
minimum value.
At equilibrium, at constant T and P,

Gibbs energy is minimum and hence,
(G )R
G
= 0

T, P
eq
i ieq = 0
i =1
August 22, 2006
This is a general condition and

applies to all chemical equilibria.
N
G
(G )R = i i
T, P i =1
Reaction Gibbs Energy in terms of activity
We know: For a general substance, the chemical potential is

given as:
i = i0 + RT ln (a i )
(G )R = i + RT ln a i
i =1
0
i
) =
N
i =1
Reaction Gibbs energy

for the standard state
(G )R = (G )
0
R
August 22, 2006

N
+ RT ln (a i ) i
i =1
a i : activity of species i.
+ RT ln (a i )
0
i
(G )0R
i =1
i
N
ln (a i )
i =1
Product of N terms
10
Example
Reaction Gibbs Energy in terms of activity
Recall: Reaction Gibbs Energy is,
Consider the reaction:
(G )R
August 22, 2006
= (G )
0
R
(G )R
= (G )
1
3
N 2 + H 2 = NH 3
2
2
a NH3
+ RT ln
1/2
a H2
a N 2
0
R

N
+ RT ln (a i ) i
i =1
3/2
( ) ( )
(G )R
(G )R
>0
Forward reaction is not spontaneous.
=0
(G )R
Reactants and Products are at equilibrium

at the specified activities.
<0
Forward reaction is spontaneous.
11
Equilibrium Constant
Recall: Reaction Gibbs Energy is, (G ) = (G )0 + RT ln (a ) i

i
R
R
i =1
We can then also write this as,
(G )R
= (G ) + RT ln (Q )
0
R
Q = (a i )
i =1
If Reactants and Products are in equilibrium then

And hence,
(G )
0
R
= RT ln (K )
(G )R
= 0.

N
K = (a i ) i
i =1
equilibrium
August 22, 2006
12
features
Equilibrium Constant, K, has been defined as follows:
(G )
0
R
= RT ln (K )
K is a function of only Temperature and is dimensionless.
The magnitude of K depends on the way we write the chemical

reactions, because of the Stoichiometric numbers entering into
the final equations. Hence, the value of an equilibrium constant
must be accompanied by a balanced chemical reaction.
August 22, 2006
13
Equilibrium Constant for a gas
WE have already defined activity of a species i as:
Pi
P0
ai =
fi
P0
For an ideal gas
For a real gas
(G ) = RT ln (K )
0
R
(Pi )eq
K = 0
i =1
P
N
August 22, 2006
i
N
K = (a i )
i =1
equilibrium
N (f i ) i
eq
= 0
i =1 P
For an ideal gas
For a real gas

14
Equilibrium constant for a gas
features
For an ideal gas, K is a function of only temperature.

But, for a real gas, K is a function of P and T because fugacity is
not, in general, equal to the partial pressure of the species i.
Meaning of
(G )
0
R
= RT ln (K )
0
(
)
G
R refers to:
Unmixed reactants in their standard state Going

To unmixed products in their standard state.
(G )0R
does not refer to: Mixed reactants Going To Equilibrium

product.
August 22, 2006
Mixing is important and we will see its

implication in the next few slides.
15
Thermodynamics of a gas phase reaction
Experimental Observation: Gas phase reactions never to a full

completion. Why?
Consider the following schematic reaction:
A(gas ) B(gas )
Gibbs energy of the reaction mixture:
In the beginning of reaction,

= 0 and n A = 1 mole.
August 22, 2006
: Extent of reaction
G = nA A + nB B
substitute
n A = 1
nB =
16
Gibbs energy of the reaction mixture becomes:
G = (1 ) A + B
We now need an expression for A and B .
PA
A = + RT ln 0
P
yA P
0
= A + RT ln 0
P
0
A
yA :
Mole Fraction
P : Total Pressure at equilibrium
P
P
0
= + RT ln(y A ) + RT ln 0 = A + RT ln (1 ) + RT ln 0
P
P
0
A
Similarly,
August 22, 2006
P
B = + RT ln ( ) + RT ln 0
P
0
B
We now substitute A and B in the expression for G.
17
G = (1 ) A + B
We have:
P
A = + RT ln(1 ) + RT ln 0
P
0
A
P
B = + RT ln ( ) + RT ln 0
P
P
0
0
0
G = A A B + RT ln 0 + RT[(1 ) ln(1 ) + ln ]
P
0
B
Gibbs Free Energy of mixing

mole of A with mole of B.
(1 )
(G )
0
P
G = + RT ln 0 + G 0
P
0
A
August 22, 2006
0
A
0
B
mixing
mixing
18
Analysis:
P
G = + RT ln 0 + G 0
P
0
A
(G )
0
mixing
0
A
0
B
mixing
= RT[(1 ) ln (1 ) + ln ]
= 0, for = 1 or 0.
P
G = + RT ln 0 for = 0.
P
0
A
P
G = + RT ln 0 for = 1.
P
0
B
August 22, 2006
In the next slide, we see a plot of G as a function of
19
Analysis:
P
0A + RT ln 0
P
P
0B + RT ln 0
P
A
0
eq
B
1
Mixing term is responsible for the minimum of Gibbs energy.

The minimum occurs, even as 1 mole of A (reactant) is still
available in the reaction mixture.
Hence, the gas phase chemical reaction never goes to a full
completion.
August 22, 2006
20
Equilibrium Constant as a function of Temperature
Recall: The Gibbs-Helmholtz Equation
G
H
= 2
T
T T P
(G/T )
(1/T ) = H
We can specialize this equation for chemical equilibrium, by

substituting equilibrium values of relevant quantities.
(G )
0
R
= RT ln (K )
(H )

(
)
ln
K
=
RT
P
T
0
R
2
August 22, 2006
Enthalpy of reaction
in the standard state
(
H )R
ln(K ) =
R
(1 / T )
P
vant Hoff Equation
21
(H )R

(
)
ln
K
=
vant Hoff Equation:

2
T
RT
P
0
K as a function of T
approximations
Case-I: Enthalpy of reaction is independent of Temperature. We

can then integrate the vant Hoff equation as follows:
(
H ) dT
d ln(K ) = R T 2
K2
0 T2
R
K1
T1
K 2 (H ) [T2 T1 ]
=
ln
R T1 T2
K1
0
R
Read pp. 159-160 of Alberty and Silbey.

Read pp. 156 of Alberty and Silbey for effect of Pressure on K
and a simple discussion on Le Chateliers Principle.
August 22, 2006
22
Determination of Equilibrium Constant, K
Here, we will establish an explicit computational relation

between equilibrium constant, K, of a reaction and the extent of
reaction, .
Consider a gas phase reaction of type:
A 2B
n 0 (A ) : Initial amount of A, at a given P and T.
/ : Equilibrium Extent of Reaction.

n 0 (A ) / : Amount of A at equilibrium.
Since the equilibrium composition is independent of the size of the
system, we may as well divide everything by n 0 (A ) and obtain a
dimensionless Extent of Reaction.
August 22, 2006
23
Definitions:
A 2B
1 : Initial amount of A, at a given P and T.
n 0 (A )
Equilibrium Extent of Reaction.
1 : Amount of A at equilibrium.
August 22, 2006
24
Computations:
Equilibrium
Mole Fraction
(Pi )eq
K = 0
i =1
P
August 22, 2006
Total is
2 1+
2
1+
1
1
1+
For an ideal gas, we will use,
2B
0
Initial Amount
Equilibrium Amount
Remember
Exponent i is positive
for product and negative
for reactants.
Equilibrium partial pressure, (Pi )eq = Equilibrium mole fraction

TIMES total Pressure, P
25
(Pi )eq
K = 0
i =1
P
Ref:
A 2B
(
P /P ) [y (P/P )]
=
K =
(P /P ) [y (P/P )]
0 2
On substitution and simplification,
P 4 2
K= 0
P 1 2
August 22, 2006
1
yA =
1+
2
yB =
1+
pressure
P : Total
at equilibrium
This is the required relation

Between K and .
26
Determination of Extent of Reaction,
Extent of reaction is easily obtained by measuring the density of

the partially dissociated gas.
Total amount
in the begining
Initial Volume
1
Total amount
Equilibrium Volume
at equilibrium
2
V:
1+
V :
Relation-1:
1+ 1
=
V2
V1
Density at
Equilibrium
August 22, 2006
1
V1
=
1 + V2
Density in
the begining
Extent of reaction
(dimensionless)
See slide no. 25

27
Relation-2: Start with mass m of ideal gas A.
m RT M : Molar mass of A
Initial Volume, V1 =
1
M1 P
m RT M 2 = M A y A + M B y B
Equilibrium Volume
V2 =
at constant P and T,
M2 P
Average molar mass of the
V1 M 2
Partially dissociated gas A,
=
V2 M1
defined by
1
V1
Relation-1:
=
1 + V2
1
M1
Hence:
=
1+ M2
Thus, for an ideal gas, we can compute the extent of reaction,

from the molar mass of reactants and products,
August 22, 2006
28
use this
to compute the equilibrium constant, K.
Amrendra Vijay
Lecture 09
August 25, 2006
(G )R
A Clarification
Recall:
(G )R
(G )
0
R
i =1
Ai = 0
(G )R
= (G ) + RT ln(Q )

N
+ RT ln (a i ) i
i =1
Q = (a i ) i : Reaction Quotient
i =1
0
R
= RT ln (K )
= (G )
0
R

T, P

N
K = (a i ) i
: Equilibrium Constant
i =1
equilibrium
Observation: Equilibrium constant will depend upon the

Stoichiometric numbers,
i
Algorithm: First, we fix the number of moles for which we wish
to compute the reaction Gibbs energy. Then, we accordingly
balance the chemical reaction --- this will fix the Stoichiometric
numbers, i uniquely. Next, we compute the reaction Gibbs
energy and other quantities.
August 25, 2006
Equilibrium Constant as a function of Temperature
Recall: The Gibbs-Helmholtz Equation
G
H
= 2
T
T T P
(G/T )
(1/T ) = H
We can specialize this equation for chemical equilibrium, by

substituting equilibrium values of relevant quantities.
(G )
0
R
= RT ln (K )
(H )

(
)
ln
K
=
RT
P
T
0
R
2
August 25, 2006
Enthalpy of reaction
in the standard state
(
H )R
ln(K ) =
R
(1 / T )
P
vant Hoff Equation
(H )R

(
)
ln
K
=
vant Hoff Equation:

2
T
RT
P
0
K as a function of T
approximations
Case-I: Enthalpy of reaction is independent of Temperature. We

can then integrate the vant Hoff equation as follows:
(
H ) dT
d ln(K ) = R T 2
K2
0 T2
R
K1
T1
K 2 (H ) [T2 T1 ]
=
ln
R T1 T2
K1
0
R
Read pp. 159-160 of Alberty and Silbey.

Read pp. 156 of Alberty and Silbey for effect of Pressure on K
and a simple discussion on Le Chateliers Principle.
August 25, 2006
Here, we will establish an explicit computational relation

between equilibrium constant, K, of a reaction and the extent of
reaction, .
Consider a gas phase reaction of type:
A 2B
n 0 (A ) : Initial amount of A, at a given P and T.
/ : Equilibrium Extent of Reaction.

n 0 (A ) / : Amount of A at equilibrium.
Since the equilibrium composition is independent of the size of the
system, we may as well divide everything by n 0 (A ) and obtain a
dimensionless Extent of Reaction.
August 25, 2006
Ref: Alberty and Silbey pp. 150-152.
Definitions:
A 2B
1 : Initial amount of A, at a given P and T.
n 0 (A )
Equilibrium Extent of Reaction.
1 : Amount of A at equilibrium.
August 25, 2006
Computations:
Equilibrium
Mole Fraction
(Pi )eq
K = 0
i =1
P
August 25, 2006
Total is
2 1+
2
1+
1
1
1+
For an ideal gas, we will use,
2B
0
Initial Amount
Equilibrium Amount
Remember
Exponent i is positive
for product and negative
for reactants.
Equilibrium partial pressure, (Pi )eq = Equilibrium mole fraction

TIMES total Pressure, P
(Pi )eq
K = 0
i =1
P
Ref:
A 2B
(
P /P ) [y (P/P )]
=
K =
(P /P ) [y (P/P )]
0 2
On substitution and simplification,
P 4 2
K= 0
P 1 2
August 25, 2006
1
yA =
1+
2
yB =
1+
pressure
P : Total
at equilibrium
This is the required relation

Between K and .
Extent of reaction is easily obtained by measuring the density of

the partially dissociated gas.
Total amount
in the begining
Initial Volume
1
Total amount
Equilibrium Volume
at equilibrium
2
V:
1+
V :
Relation-1:
1+ 1
=
V2
V1
Density at
Equilibrium
August 25, 2006
1
V1
=
1 + V2
Density in
the begining
Extent of reaction
(dimensionless)
9
Relation-2: Start with mass m of ideal gas A.
m RT M : Molar mass of A
Initial Volume, V1 =
1
M1 P
m RT M 2 = M A y A + M B y B
Equilibrium Volume
V2 =
at constant P and T,
M2 P
Average molar mass of the
V1 M 2
Partially dissociated gas A.
=
V2 M1
Q Relation-1 was
1
V1
=
1 + V2
1
M1
Hence:
=
1+ M2
Thus, for an ideal gas, we can compute the extent of reaction,

from the molar mass of reactants and products,
August 25, 2006
10
use this
to compute the equilibrium constant, K.
Electrochemical Equilibrium
Reactions in Electrochemical Cell
Suggested Reading
Physical Chemistry --- Alberty and Silbey
Chapter 08 (in particular, pp.238-243)
Physical Chemistry --- Atkins
Chapter 10 (in particular, pp 262-273)
Objective: Nernst Equation
August 25, 2006
11
Recap
To study chemical equilibrium, we introduced the concept of

the Extent of reaction
and defined the reaction Gibbs energy
as the derivative of Gibbs energy as a function of
at
constant Temperature and Pressure.
N
G
(G )R
= i i
T, P i =1
The reaction Gibbs energy is zero at equilibrium and hence we

obtained: N
This is a general condition and
i ieq = 0
applies to all chemical equilibria.
i =1
How does this modify for Electrochemical reactions in equilibrium ?

Ans: As we will see now, everything remains the same, except that
the definition of Chemical Potential changes (this is because the
August 25, 2006
electrical work also has to be taken into account). 12
First Law
Recall the First Law:
non-expansive work
dU = q PdV
Work due to expansion
Work other than Pressure-Volume work is called the nonexpansive work. In the presence of non-expansive work, the
first law modifies as follows:
dU = q PdV + non - expansive works
For example, when a small charge dQ is moved through an

electric potential difference , the work done on the charge is:
(dw )electrical = dQ
And, the first Law becomes:

The term
August 25, 2006
dQ
dU = q PdV + dQ
then carries over to all other thermodynamic

13
quantities, like Gibbs energy and so forth.
dG = SdT + VdP + i dn i
i =1
Gibbs Energy
in the presence of electrical work
Work done on the charge dQ, due to potential difference,
(dw )electrical = dQ
Now, if ions with charge number z i are transferred, the

differential charge dQ can be expressed in terms of the
differential amount dn i of ion i by
dQ = z i F dn i
F: Faraday Constant
(dw )electrical = z i F dn i
i =1
)(
= 6.022 10 23 mol 1 1.602 10 19 C

= 96485 C mol 1
So, the Gibbs energy modifies to

N
i =1
i =1
i =1
dG = SdT + VdP + i dn i + Zi F dn i dG = SdT + VdP + ( i ) =0 + Zi F dn i

August 25, 2006
dG = SdT + VdP + i dn i
i =1
with, i = ( i ) =0 + Zi F
14
dG = SdT + VdP + i dn i with,
Contd
i =1
Gibbs Energy
in the presence of electrical work
At constant Pressure and Temperature, the reaction Gibbs

N
energy is then, (dG ) = dn
i i
= ( ) + Z F
T, P
i
i =1
i = ( i ) =0 + Zi F
i =0
As we have done earlier, we introduce the concept of the Extent

of Reaction and define Reaction Gibbs Energy as the
derivative of Gibbs energy, G with respect to at constant
Pressure and Temperature.
(G )R
N
G
= i i
=
T, P i =1
i : Stoichiometric Number
G
= 0
At the reaction equilibrium, (G )R =
T, P
And hence,
August 25, 2006
i =1
i = 0
i ( i ) =0 + Zi F = 0
i =1
This is the general condition, we will use now.
15
Electrochemical Cell
An electrochemical cell consists of:

Two electrodes (metallic conductor), in contact with
an electrolyte ---- an ionic conductor
(solutions, a liquid or a solid)
Types:
Electrolytic Cell: In this cell, a non-spontaneous reaction is
driven by an external source of current.
Galvanic Cell: It produces electricity as a result of
spontaneous reaction occurring inside the cell.
August 25, 2006
16
Galvanic Cell
Convention:
Electrons
Anode
Reduction/oxidation on the right/left.
Cathode
-ve
+ve
spontaneous Reaction
Rd1 Ox1 + ne
Rd1 Ox1 + ne
Oxidation
Reduction
Zn(s ) Zn 2+ + 2e
August 25, 2006
Cu
2+
Cu 2+ (aq ) + 2e Cu (s )
(aq ) + Zn(s ) Cu (s ) + Zn (aq )

2+
17
Galvanic Cell
operation
Potentiometer
( )
(+ )
V<E
August 25, 2006
( )
(+ )
V=E
The cell discharges

spontaneously.
Galvanic Cell.
V: applied potential
difference.
Current through the

Cell is zero.
Cell at Equilibrium.
( )
(+ )
V>E
Cell reaction in the
reverse direction.
Electrolytic Cell.
E: Electromotive force of the Galvanic Cell
18
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction
an example
Consider the following cell:
Pt Left | H 2 (g ) | HCl(m ) | AgCl(s ) | Ag(s ) | Pt Right
Reduction occurs on the right electrode:
Oxidation occurs on the left electrode:
So, the cell reaction is:
2AgCl(s ) + 2e (Pt Right ) 2Ag(s ) + 2Cl (m )
H 2 (g ) = 2H + (m ) + 2e (Pt Left )
H 2 (g ) + 2AgCl(s ) + 2e (Pt Right )
August 25, 2006
2H + (m ) + 2Ag(s ) + 2Cl (m ) + 2e (Pt Left )
19
Cell Reaction
contd
The cell reaction was:
[( ) + Z F ] = 0
[124(H4+ )4+4
2 (Ag ) + 2 (Cl ) 2F Left ] [ (H 2 ) + 2 (AgCl) 2F Right ] = 0
44
424444444
3 144444244444
3
We now use the equilibrium condition:
i =1
Product
or,
i =0
Reactant
( )
( )
2F( Right Left ) = 2 H + + 2 (Ag ) + 2 Cl (H 2 ) 2 (AgCl)
or,
( )
() is the chemical potential

August 25, 2006
( )
2FE = 2 H + + 2 (Ag ) + 2 Cl (H 2 ) 2 (AgCl)
where, E = ( Right Left )
Electromotive force (EMF) of the Cell
20
Cell Reaction
Thus, for the reaction

we have
( )
contd
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
( )
2FE = 2 H + + 2 Cl + 2 (Ag ) (H 2 ) 2 (AgCl)

Chemical Potential

EMF of the Cell
So, in general:
N
nFE = i i
i =1
August 25, 2006
or,
nFE = (G )R
No of electrons
transferred
Reaction Gibbs Energy, for the

Cell Reaction as written above.
21
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction
Reference:
N
nFE = i i = (G )R
i =1
observations
If the right hand electrode is more positive than the left one, the
EMF of the cell, E, is positive. If E is positive then the reaction
Gibbs energy,(G )R for the cell reaction is negative --- that is
cell reaction, as written, is spontaneous, at constant P and T.
Now that, we have connected the Reaction Gibbs Energy for the
cell reaction, to the EMF (electromotive force) of the cell, we can
now use the full machinery of thermodynamics to compute other
thermodynamics quantities from EMF via Reaction Gibbs energy.
Let us then connect the EMF to the activities of reacting species
via the Chemical Potential. We will then obtain what is popularly
known as the Nernst Equation.
August 25, 2006
22
nFE = i i = (G )R
i =1
Nernst Equation
Recall the Chemical Potential:

So, we have
N
i =1
i =1
i = i0 + RT ln (a i )
nFE = i i = i + RT ln (a i ) = i + RT i ln(a i )
0
i
= nFE + RT ln [ai ] i
i =1
i =1
0
i
i =1
E 0 : Standard EMF
of the Cell.
RT N

E = E
ln [a i ] i Nernst Equation
nF i =1
August 25, 2006
23
RT N

E=E
ln [a i ] i
nF i =1
Nernst Equation
At 25 degree Centigrade, the Nernst equation becomes:
E=E
(
8.314JK mol )(298.15K )
ln [a ]
n (96485 C mol )
-1
(
0.02569 V ) N
ln [a ]
i =1
Equilibrium constant
or, E = E
i =1 i
for the cell reaction
n
RT
0
At equilibrium, E=0 and then, 0 = E
ln K
nF
0
observations
K=e
n F E 0 / RT
And this implies:
So, the measurement of EMF will allow us to compute and

hence discuss various thermodynamics properties.
August 25, 2006
24
Amrendra Vijay
Lecture 10
August 28, 2006
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction
an example
Consider the following cell:
Reduction occurs on the right electrode:
Oxidation occurs on the left electrode:
So, the cell reaction is:
2AgCl(s ) + 2e (Pt Right ) 2Ag(s ) + 2Cl (m )
H 2 (g ) = 2H + (m ) + 2e (Pt Left )
August 28, 2006
Cell Reaction
contd
The cell reaction was:
[( ) + Z F ] = 0
[124(H4+ )4+4
2 (Ag ) + 2 (Cl ) 2F Left ] [ (H 2 ) + 2 (AgCl) 2F Right ] = 0
44
424444444
3 144444244444
3
We now use the equilibrium condition:
i =1
Product
or,
i =0
Reactant
( )
( )
2F( Right Left ) = 2 H + + 2 (Ag ) + 2 Cl (H 2 ) 2 (AgCl)
or,
( )
() is the chemical potential

August 28, 2006
( )
2FE = 2 H + + 2 (Ag ) + 2 Cl (H 2 ) 2 (AgCl)
Electromotive force (EMF) of the Cell
Cell Reaction
Thus, for the reaction

we have
( )
contd
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
( )
2FE = 2 H + + 2 Cl + 2 (Ag ) (H 2 ) 2 (AgCl)

Chemical Potential

EMF of the Cell
So, in general:
N
nFE = i i
i =1
August 28, 2006
or,
nFE = (G )R
No of electrons
transferred
Reaction Gibbs Energy, for the

Cell Reaction as written above.
4
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction
Reference:
N
nFE = i i = (G )R
i =1
observations
If the right hand electrode is more positive than the left one, the
EMF of the cell, E, is positive. If E is positive then the reaction
Gibbs energy,(G )R for the cell reaction is negative --- that is
cell reaction, as written, is spontaneous, at constant P and T.
Now that, we have connected the Reaction Gibbs Energy for the
cell reaction, to the EMF (electromotive force) of the cell, we can
now use the full machinery of thermodynamics to compute other
thermodynamics quantities from EMF via Reaction Gibbs energy.
Let us then connect the EMF to the activities of reacting species
via the Chemical Potential. We will then obtain what is popularly
known as the Nernst Equation.
August 28, 2006
nFE = i i = (G )R
i =1
Nernst Equation
Recall the Chemical Potential:

So, we have
N
i =1
i =1
i = i0 + RT ln (a i )
nFE = i i = i + RT ln (a i ) = i + RT i ln(a i )
0
i
= nFE + RT ln [ai ] i
i =1
i =1
0
i
i =1
E 0 : Standard EMF
of the Cell.
RT N

E = E
ln [a i ] i Nernst Equation
nF i =1
August 28, 2006
RT N

E=E
ln [a i ] i
nF i =1
Nernst Equation
At 25 degree Centigrade, the Nernst equation becomes:
E=E
(
8.314JK mol )(298.15K )
ln [a ]
n (96485 C mol )
-1
(
0.02569 V ) N
ln [a ]
i =1
Equilibrium constant
or, E = E
i =1 i
for the cell reaction
n
RT
0
At equilibrium, E=0 and then, 0 = E
ln K
nF
0
observations
K=e
n F E 0 / RT
And this implies:
So, the measurement of EMF will allow us to compute and

hence discuss various thermodynamics properties.
August 28, 2006
Phase Equilibrium
Suggested Reading
Alberty and Silbey, pp. 179-190.

HW: practice solved examples, 6.1 to 6.6.
OR,
Atkins, pp. 135-149.
Syllabus:
Phase equilibria: Clausius Clapeyron equation;

phase rule. Phase diagram: one component systems. Eutectic
systems.
August 28, 2006
Phase Equilibrium
Definitions
Phase: It is a form of matter, uniform throughout in chemical

composition and physical state.
Example: (1) solid, liquid or gas phase of substance
(2) various solid phases, like white and black
allotropes of phosphorous, etc.
Phase Transition: Conversion of one phase of the matter into

another, occurring at characteristic values of thermodynamic
variables (like, pressure, temperature and so forth).
Ex: At 1 atm pressure, ice is the stable phase of water below 0 K.
Metastable Phase: Thermodynamically unstable phase, that

persists because the transition to a stable phase is hindered due
to kinetic constraints.
August 28, 2006
Example: Diamond is a metastable phase of Carbon
Phase Equilibrium
thermodynamic criterion
If a system contains several phases, isolated from each other

then the internal energy/entropy etc of the system is simply
the sum of internal energies/entropies of the separate phases.
If there is an exchange of heat/matter between phases or if the

volume of one phase can be changes at the expense of other,
then there are certain relations between the thermodynamic
properties of different phases at equilibrium. And, we say --that equilibrium introduces constraints. Here, we will study
these constraints.
August 28, 2006
phase
phase
T , , V
T , , V
10
Phase Equilibrium
Example-1: Consider a system with two phases, and , and

the whole system is isolated. Now, an infinitesimal amount of
heat, q is transferred from phase to phase such that the
volumes of the phases do not change.
phase
+ q
phase
If the system is to be at equilibrium then the total entropy must

not change --- that is, the decrease in entropy of phase is
balanced by the increase in entropy of phase.
August 28, 2006
dS + dS = 0
11
dU = q + PdV = TdS + PdV
dS + dS = 0
Example-1 contd
As the volume of individual phase does not change,

Then, from the first Law:
dU = T dS
dV = 0.
dU = T dS
The system is also isolated (that means total dU is zero) and

hence the change in internal energy of one phase must be
compensated by the change in internal energy of the other
phase. That is:
dU + dU = 0
T dS + T dS = 0
dS = dS
Conclusion: Temperatures of the two
phases must be the same at equilibrium.
August 28, 2006
T = T
12
dA = SdT PdV
Phase Equilibrium
Example-2: Let the total system be at constant temperature and

reduce the volume of phase by an infinitesimal amount dV
and increase the volume of phase by the same amount.
phase
phase
As we are at constant temperature and volume. the Helmholtz

free energy of the total system must not change. That means,
the change in Helmholtz energy of one phase must be
compensated by the corresponding change in the other phase, if
the system is to remain in equilibrium. And hence,
dA + dA = 0 P dV + P dV = 0
August 28, 2006
P = P
Conclusion: Pressure of the two phases

must be the same at equilibrium.
13
dG = i dn i
i
Phase Equilibrium
Example-3: Let us assume the total system is at constant

pressure and temperature. And, we transfer an infinitesimal
amount dn i of species i from the phase to the phase
(assuming the species i existed in both phases).
As we are at constant T and P, the Gibbs energy of the total

system must not change. That means, the change in Gibbs
energy of one phase must be compensated by the
corresponding change in Gibbs energy of the other phase, if the
system is to remain in equilibrium. And hence,
dG + dG = 0 i dn i + i dn i = 0
i = i
Conclusion: The chemical potential of a species

must be the same in two phases,
August 28, 2006
that are in equilibrium.
14
Example-3 continued .
Suppose phases and are not in equilibrium and we transfer

a small amount dn i of species i from phase to phase, in the
direction of approaching equilibrium at constant P and T. So, the
total change in Gibbs energy would be negative. That is:
dG + dG < 0 i dn i + i dn i < 0
i > i
Positive
Conclusion: A Substance will pass spontaneously from the
phase where it has the higher chemical potential
to the phase where it has the lower chemical
potential.
August 28, 2006
15
dG = SdT + VdP
Phase Change as a function of T, at fixed P.
At constant pressure, the molar Gibbs energy (also called the

Chemical Potential) as a function of temperature is:

= Sm
T P
= Sm T
Sm :
Molar Entropy is
Positive for all
substances.
as the temperature is raised, the chemical potential decreases.
It is also known,
Sm (solid ) < Sm (liquid ) < Sm (gas ).

Gas
Solid
Solid
State
August 28, 2006
Hence,
Liquid
State
Liquid
Gaseous State
16
Phase Change

= Sm = Sm T
T P
.vs. T
We have thus seen, the slope of

graph is steeper for
the gas than the liquid and the slope for the liquid is steeper
than that for the solid.
When we bring a phase transition, what we are doing is actually

modifying the relative values of the chemical potentials of the
phases ---- and the easiest way of doing this is by changing the
temperature of the sample.
August 28, 2006
17
Phase Diagram
an example
Consider a gas, with P,V and T as thermodynamic variables.
1:
2:
3:
4:
Solid
transition temperature
vapor pressure
triple point
critical point
Liquid
phase boundary
2
3
Vapor
August 28, 2006
18
Some Definitions
Vapor Pressure: The pressure at which liquid and gas are in

equilibrium.
Transition temperature: Temperature at which two phases are in
equilibrium, and the Gibbs energy is minimized at the prevailing
pressure.
Melting Point: At a given (fixed) pressure, the temperature at
which the solid and the liquid phases co-exist. This is same as
the Freezing point.
Triple point: Point at which the three phases (solid, liquid and
gas) simultaneously co-exist in equilibrium. This point is unique.
Triple point for water occurs at 273.16 K and 611 Pa.
Normal means 1 atm and standard means 1 bar pressure.
August 28, 2006
19
Definition
Critical Point: Consider a liquid
continued
vapor transition.
The condition of free vaporization is called Boiling and The

temperature at which the vapor pressure of liquid is equal
to the external pressure, is called the Boiling Point.
If the vessel is closed (not a free vaporization) and if we keep
heating the liquid , there comes a point when the density of
liquid equals the density of vapor and the surface between two
phases (liquid and vapor) disappears. The temperature at
which this happens is called the Critical Temperature and the
corresponding vapor pressure is called Critical Pressure.
At and above the critical temperature, only a single uniform
phase called Super Critical Fluid (SCF) exists.
August 28, 2006
20
The Clapeyron Equation
preliminary
(
Consider a one component system with two phases and in

equilibrium --- that is, the pressure, temperature and chemical
potential of the two phases must be the same.
phase
phase
T , , V
T , , V
If the temperature and pressure are both changed in such a way

that the chemical potentials for the two phases remain equal,
then the two phases will continue to co-exist. The corresponding
pressure versus temperature plot is called the Coexistence curve
and the necessary equation for dP/dT was derived by
Clapeyron and its called The Clapeyron Equation.
August 28, 2006
21
dG = SdT + VdP
derivation
For a change of pressure and temperature along the coexistence

curve, we have the following condition:
d = d
S dT + V dP = S dT + V dP
Molar
entropy
phase
Molar
volume
dP S S S
H
=
=
=
dT V V V TV
August 28, 2006
phase
Molar
enthalpy
22
The Clausius Clapeyron Equation
dP
H
=
dT TV
This is an approximation to the Clapeyron equation, particularly

useful for studying the vaporization and sublimation process.
Approximations: (1) The vapor obeys the ideal gas law, and (2)
the molar volume of the liquid, being much less than the molar
volume of the gas, can be neglected.
(H )vaporization = (H )vaporization = P (H )
dP
dP 1
dT
=
vaporization
= (H )vap. 2
dT T (Vgas Vliquid )
TVgas
RT 2
P R
T
If we assume the enthalpy of vaporization to be independent of

temperature and integrate the equation from (P1 , T1 ) to (P2 , T2 ) :
August 28, 2006
P2 (H )vap.
ln =
P1
R
1 1

T1 T2
23
Amrendra Vijay
Lecture 11
August 29, 2006
Phase Diagram
an example
Consider a gas, with P,V and T as thermodynamic variables.
1:
2:
3:
4:
Solid
transition temperature
vapor pressure
triple point
critical point
Liquid
phase boundary
2
3
Vapor
August 29, 2006
Some Definitions
Vapor Pressure: The pressure at which liquid and gas are in

equilibrium.
Transition temperature: Temperature at which two phases are in
equilibrium, and the Gibbs energy is minimized at the prevailing
pressure.
Melting Point: At a given (fixed) pressure, the temperature at
which the solid and the liquid phases co-exist. This is same as
the Freezing point.
Triple point: Point at which the three phases (solid, liquid and
gas) simultaneously co-exist in equilibrium. This point is unique.
Triple point for water occurs at 273.16 K and 611 Pa.
Normal means 1 atm and standard means 1 bar pressure.
August 29, 2006
Definition
Critical Point: Consider a liquid
continued
vapor transition.
The condition of free vaporization is called Boiling and the

temperature at which the vapor pressure of liquid is equal
to the external pressure, is called the Boiling Point.
If the vessel is closed (not a free vaporization) and if we keep
heating the liquid , there comes a point when the density of
liquid equals the density of vapor and the surface between two
phases (liquid and vapor) disappears. The temperature at
which this happens is called the Critical Temperature and the
corresponding vapor pressure is called Critical Pressure.
At and above the critical temperature, only a single uniform
phase called Super Critical Fluid (SCF) exists.
August 29, 2006
Phase Rule
Phase rule expresses the following relation:
Number of
degrees of
freedom
August 29, 2006
Temperature
and Pressure
Number of
Components
present in
system
Number of
Phases
present in
system
In the following, we will define F, C and P.
Number of Phases
Definition of Phase: Form of matter, that is uniform in chemical

composition as well as physical state.
Examples:
A gas
A crystal
Two totally miscible liquids
A solution of NaCl in water
P=1
{ P=2
CaCO (s ) CaO(s ) + CO (g ) { P=3
An alloy of two metals, if the

metals are immiscible
August 29, 2006
Number of Components, C
Constituents: A species present in the system. For example,

A mixture of methyl alcohol and water has two constituents
+
A solution of NaCl has two constituents, Na and Cl
Components: A minimum number of independent species,

necessary to define the composition of all the phases present in
the system.
No. of components
Examples:
August 29, 2006
Pure Water:
Equality holds if
No. of constituents there is no
chemical reaction.
C=1, as we need only the species

H 2 O to specify its composition.
CaCO 3 (s ) CaO(s ) + CO 2 (g )
C=2
Degrees of Freedom
Definition: Number of intensive variables that can be

changed independently without disturbing the
number of phases in equilibrium.
August 29, 2006
Phase Diagram
Example:
one component system, C=1

QF = 2 + C P F = 3 P
phase
phase
phase
Four phases in
equilibrium, F=-1.
(Impossible!)
phase
one phase
(F=2)
phase
Three phases
in equilibrium
(F=0)
Two phases
in equilibrium (F=1)
August 29, 2006
preliminary
(
Consider a one component system with two phases and in

equilibrium --- that is, the pressure, temperature and chemical
potential of the two phases must be the same.
phase
phase
T, , P
T, , P
If the temperature and pressure are both changed in such a way

that the chemical potentials for the two phases remain equal,
then the two phases will continue to co-exist. The corresponding
pressure versus temperature plot is called the coexistence curve
and the necessary equation for dP/dT is called The Clapeyron
Equation.
August 29, 2006
10
dG = SdT + VdP
derivation
For a change of pressure and temperature along the coexistence

curve, we have the following condition:
d = d
S dT + V dP = S dT + V dP
Molar
entropy
Molar
volume
S S
dP
S
H
=
=
=
dT V V V TV
August 29, 2006
phase
phase
T
coexistence
curve
Molar
enthalpy
11
(
H )melting
dP
For solid-liquid boundary,
=
dT T (V )melting
Read: Atkins, pp. 145
integration
Observation: The enthalpy of melting is positive (He-3 is an

exception) and the volume change is usually positive. Hence,
the slope, dP is steep and usually positive.
dT
Approximation: If we assume the change in molar enthalpy and

the change in molar volume, are constant and integrate the
Clapeyron Eq. from P , T to P , T , we will obtain:
(
H )
dP = (V )
P2
P1
melting
melting
T2
dT
T T
1
) (
P2
(
H )
=P +
(V )
melting
melting
T2
ln
T1
If T1 and T2 are close then the logarithm can be approximated as,
August 29, 2006
T2 T1 T2 T1
T2

ln = ln1 +
T1
T1
T1
12
The Clausius Clapeyron Equation
dP
H
=
dT TV
This is an approximation to the Clapeyron equation, particularly

useful for studying the vaporization and sublimation process.
Approximations: (1) The vapor obeys the ideal gas law, and (2)
the molar volume of the liquid, being much less than the molar
volume of the gas, can be neglected.
(H )vaporization = (H )vaporization = P (H )
dP
dP 1
dT
=
vaporization
= (H )vap. 2
dT T (Vgas Vliquid )
TVgas
RT 2
P R
T
If we assume the enthalpy of vaporization to be independent of

temperature and integrate the equation from (P1 , T1 ) to (P2 , T2 ) :
August 29, 2006
P2 (H )vap.
ln =
P1
R
1 1

T1 T2
13
Q. 11 of Home Assignment
QF = 2 + C P F = 4 P
If either Temp or pressure is fixed, F = 3 P
Phase Diagram
two component system, C=2
Here, we will study an example of two component systems,

consisting of Solid and Liquid phases.
If we consider only two phases at a time, then the maximum

number of degrees of freedom here will be 2, which we choose
to be (1) Temperature, and (2) composition of the mixture.
The invariant point on the phase diagram here is called the

Eutectic Point, and the corresponding mixture is called the
Eutectic Mixture.
Knowledge of the Temperature-Composition diagram of the solid

mixtures, is important for designing industrial processes, in
particular for semiconductors and Liquid Crystal Display.
August 29, 2006
Read: Alberty and Silbey, pp. 218-219.
14
F = 3 P
Cooling curve for the mixture of Cd and Bi.
Two Component System

350
Eutectic
Composition
40% Cd 100% Cd
0% Cd 20% Cd
80% Cd
Eutectic Point
(3 phases)
300
Liquid
(one phase)
250
t (C )
200
Bi crystallizes
Bi + Liquid
(2 phases)
Eutectic
Temp.
100
August 29, 2006
Bi(s) + Cd(s)
time
0
Both Cd and Bi crystallize
at the same time
Cd + Liquid
(2 phases)
(2 phases)
40
100
weight percent Cd 15
Thermodynamics
The End
Thanks for your patience !
In the end is my beginning ...
August 29, 2006
T.S. Eliot
Nobel Prize (Literature, 1948)
16

Kinetics and Thermo by Amarendra Vijay

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Kinetics and Thermo by Amarendra Vijay

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Thermodynamics and Kinetics

Broadly speaking, there are two approaches of Science:

understand and utilize in practice. Here, we attempt to rationalize our

Reductionism: Here, we attempt to determine Laws, governing the

ultimate constituents of matter (for example, electrons) and we hope

System and Surroundings

A thermodynamic system is the content of a

For molecular applications

size < 10 6 cm : microscopic

Thermodynamic variables are quantities of a macroscopic

Examples: Pressure, P; Volume, V; Energy, E; Temperature,

T; magnetic field, H and so forth.

Types: (a) Extensive: The value of an extensive variable

depends on the size of the system; that is, total = sum of

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A thermodynamic state is specified by a

Example: A sample of gas enclosed in a

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A thermodynamic equilibrium prevails

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This is a functional relation among thermodynamic

(a function of thermodynamic variables)

Example: For an ideal gas,

Equation of state is assumed to be known, as a part

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This is a change of thermodynamic state of the

Quasi-adiabatic transformation: Here, the

Reversible Transformation: The transformation,

here, retraces its history in time, when the external

Types of Thermodynamic systems

3. Isolated system: Surroundings

Energy is the capacity to do work. In

When the work is done on a system, the capacity of

When the work is done by the system, the capacity

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Heat and Work

Disordered, random or Thermal motion

Heat is the transfer of energy between the system and the

Work is the transfer of energy that between the system and

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Consider the Taylor series expansion of function of 1 variable:

Notice, [ f / x ]x = x0 is independent of x and it is valid for all x,

As we deal with a truncated series, we may as well like to

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In thermodynamics, these partial derivatives

Consider the Taylor series expansion of an N-variable function:

If the value of E does not depend on the path we choose for

If the value of E does depend on the path we choose for

integration, then E is called a path function and dE is called an

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First Law of Thermodynamics

In thermodynamics, the total energy of a system is called its

Work done by the system to move an object a

does the work, its internal energy decreases.)

Force is pressure, P, per unit area, A, and hence,

Consider an ideal gas, for which the equation of state is,

Remember, this equation retains only first two term of an

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For a finite change,

Heat Capacity at constant volume

What is the physical significance of specific heat ? Should this

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At constant volume, the internal energy of a system is

Heat capacity is an extensive quantity. To make it an