Kinetics and Thermo by Amarendra Vijay PDF

Thermodynamics and Kinetics
Amrendra Vijay
Department of Chemistry
IIT Madras, Chennai 600 036
Lecture 01
August 04, 2006 1
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 2

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 3

System and Surroundings
A thermodynamic system is the content of a
geometrical volume of macroscopic size.
Examples
A piece of matter, a sample of gas,
chemical reactions in a vessel,
Boundary
System a sample of human population etc.
For molecular applications

Surroundings size < 10 −6 cm : microscopic
size > 1 cm : macroscopic
August 04, 2006 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 5

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 6

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 7

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 8

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 9
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 Surroundings

Matter system
August 04, 2006 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 ⎤ 1 ⎡∂2 f ⎤ 1 ⎡ ∂3 f ⎤
f ( x ) = [ f (x )]x = x0 + ⎢ ⎥ ( x − x0 ) + ⎢ 2 ⎥ ( x − x0 ) + ⎢ 3 ⎥ ( x − x0 ) +
2 3
L ∞
⎣ ∂x ⎦ x = x0 2! ⎣ ∂x ⎦ x = x
0
3! ⎣ ∂x ⎦ x = x
0
Notice, [∂ f / ∂x ]x = x0 is independent of x and it is valid for all x,

m m

independent of x0 we choose to fix. If ( x − x 0 ) = dx is very small,
then we may truncate the series as follows:
⎡ ∂f ⎤ ⎡ ∂f ⎤
f (x ) − [ f (x0 )] = ⎢ ⎥ (x − x0 ) ⇒ df = ⎢ ⎥ dx
⎣ ∂x ⎦ x = x0 ⎣ ∂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:
⎛ ∂f ⎞ In thermodynamics, these partial derivatives
df = ⎜ ⎟ dx
August 04, 2006 ⎝ ∂x ⎠ define various thermodynamic variables 13
of our interest.
Differentiation
Consider the Taylor series expansion of an N-variable function:
⎡ ∂f ⎤
f (x1 , x 2, L x N ) = [ f (x1 , x 2, L x N )]x = y + ∑ ⎢
N
⎥ (xm − y m )
m =1 ⎣ ∂x m ⎦ x = y
k k
k k
N N
1⎡ ∂2 f ⎤ Neglect
+ ∑∑ ⎢ ⎥ (xm − y m ) 2
+ LL
m =1 k =1 2 ∂x ∂
⎣ m k ⎦x
x = yk
k
N
⎡ ∂f ⎤
⇒ f ( x1 L x N ) − f ( y1 L y N ) = ∑ ⎢ ⎥ ( xm − y m )
m =1 ⎣ ∂xm ⎦ x = y
m m
N
⎡ ∂f ⎤ ⎡ ∂f ⎤N for an
⇒ ∆f = ∑ ⎢ ⎥ ( xm − y m ) ⇒ df = ∑ ⎢ ⎥ dxm infinitesimal
m =1 ⎣ ∂xm ⎦ x = y m =1 ⎣ ∂xm ⎦ x = y change
m m m m
⎛ ∂f ⎞ ⎛ ∂f ⎞ ⎛ ∂f ⎞
df = ⎜⎜ ⎟⎟ dx1 + ⎜⎜ ⎟⎟ dx 2 + ⎜⎜ ⎟⎟ dx3 for three variables.
⎝ ∂x1 ⎠ ⎝ ∂x 2 ⎠ ⎝ ∂x3 ⎠
⎛ ∂f ⎞ ⎛ ∂f ⎞
August 04, 2006
⎜
df = ⎜ ⎟
⎟ dx1 + ⎜⎜ ⎟⎟ dx3 if x2 is constant. 14
⎝ ∂x1 ⎠ x 2
⎝ ∂x3 ⎠ x 2
Integration
y max
Consider,
g (x ) = ∫ dy f (x,y )
• ymax
y min
↑
final y
∆E = ∫ dE ymin
initial
x→
• 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 w ∆U
• 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
V2
V1
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
Vfinal
dV ⎛ Vfinal ⎞
⇒ w = − nRT ∫
Vinitial
V
= − nRT ln ⎜ ⎟
⎝ Vinitial ⎠
August 04, 2006 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 ⎞
Reference: dU = ⎜ ⎟ dV + ⎜ ⎟ dT
⎝ ∂V ⎠ ⎝ ∂T ⎠
If V is constant, then dV = 0 ⎛ ∂U ⎞
⇒ dU = ⎜ ⎟ dT = C v dT
⎝1∂T ⎠ V
424 3
Cv
Heat Capacity at constant volume

For a finite change,
⎛ ∂U ⎞ ⎛ ∆U ⎞
Cv = ⎜ ⎟ = ⎜ Limit ⎟ ⇒ ∆U = C v ∆T
⎝ ∂T ⎠ V ⎝ ∆T →0 ∆T ⎠ V
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
⎝ ∂V ⎠ ⎝ ∂T ⎠
If T is constant, then dT = 0.
⎛ ∂U ⎞
⇒ dU = ⎜ ⎟ dV = Π T dV
⎝1∂2
V ⎠T
3
ΠT
Internal Pressure
For a perfect gas, the internal pressure is zero.
August 04, 2006 21

Internal Energy U(V, T ) → U(P, T )
What if we consider internal the internal energy of an ideal gas

to be function of temperature, T, and pressure, P ?
⎛ ∂U ⎞ ⎛ ∂U ⎞
Recall: dU = ⎜ ⎟ dV + ⎜ ⎟ dT ⇒ dU = Π T dV + C V dT
⎝ ∂V ⎠ ⎝ ∂T ⎠
Internal Pressure Heat Capacity
Divide by dT and impose the condition of constant pressure,

⎛ ∂U ⎞ ⎛ ∂V ⎞ 1 ⎛ ∂V ⎞
⎜ ⎟ = Π T ⎜ ⎟ + CV = α Π T V + CV where, α = ⎜ ⎟
⎝ ∂T ⎠ P ⎝ ∂T ⎠ P V ⎝ ∂T ⎠ P
Internal Pressure Expansion Coefficient
For a perfect gas, the internal pressure is zero and hence,

⎛ ∂U ⎞ ⎛ ∂U ⎞
⎜ ⎟ = C V = ⎜ ⎟
⎝ ∂T ⎠ P ⎝ ∂T ⎠ V
August 04, 2006 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:
From the first law, if the system
∆H = ∆U + P ∆V + V ∆P is in mechanical equilibrium at
a pressure, P then
= ∆q + V∆P
∆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 = ⎜ ⎟ dP + ⎜ ⎟ dT
⎝ ∂P ⎠ ⎝ ∂T ⎠
⎛ ∂H ⎞
At constant pressure, dP=0 and hence: dH = ⎜ ⎟ dT = C P dT
⎝1∂2
T ⎠P
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
Reference: H ≡ H (P, T ) ⇒ dH = ⎜
⎛ ∂H ⎞ ⎛ ∂H ⎞
⎟ dP + ⎜ ⎟ dT
⎝ ∂P ⎠ ⎝ ∂T ⎠
At constant temperature, dT=0 and hence,
⎛ ∂H ⎞
dH = ⎜ ⎟ dP
⎝ ∂P ⎠T
Thus, we can write:
⎛ ∂H ⎞
dH = ⎜ ⎟ dP + C p dT
⎝ ∂P ⎠T
August 04, 2006 25

⎛ ∂H ⎞
Reference : dH = ⎜ ⎟ dP + C p dT
⎝ ∂P ⎠T
Enthalpy as a function of temperature

⎛ ∂H ⎞ ⎛ ∂H ⎞ ⎛ ∂P ⎞
⎜ ⎟
Divide by dT and impose constant volume: ⎝ ∂T ⎠
= ⎜ ⎟ ⎜ ⎟ + CP
V ⎝ ∂P ⎠ T ⎝ ∂T ⎠ V
⎛ ∂y ⎞ ⎛ ∂x ⎞ ⎛ ∂z ⎞
Use Chain relation, if z(x, y ), then ⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ = −1 to obtain,
⎝ ∂x ⎠ z ⎝ ∂z ⎠ y ⎝ ∂y ⎠ x
−1 −1 −1 −1 1 ⎛ ∂V ⎞
⎛ ∂P ⎞ ⎡⎛ ∂T ⎞ ⎤ ⎡⎛ ∂V ⎞ ⎤ ⎡⎛ ∂V ⎞ ⎤ ⎡⎛ ∂V ⎞ ⎤ ⎡⎛ ∂V ⎞ ⎤ α Tκ = − ⎜ ⎟
⎜ ⎟ = − ⎢⎜ ⎟ ⎥ ⎢⎜ ⎟ ⎥ = − ⎢⎜ ⎟ ⎥ ⎢⎜ ⎟ ⎥ = α V ⎢⎜ ⎟ ⎥ = V ⎝ ∂P ⎠ T
⎝ ∂T ⎠ V ⎣⎝ ∂V ⎠ P⎦ ⎣⎝ ∂P ⎠T ⎦ ⎣⎝ ∂T ⎠ P ⎦⎣⎝ ∂P ⎠T ⎦ ⎣⎝ ∂P ⎠T ⎦ κT
−1 −1
Isothermal compressibility
⎛ ∂H ⎞ ⎡⎛ ∂P ⎞ ⎤ ⎡⎛ ∂T ⎞ ⎤ ⎡⎛ ∂T ⎞ ⎤ ⎡⎛ ∂H ⎞ ⎤
⎜ ⎟ = − ⎢⎜ ⎟ ⎥ ⎢⎜ ⎟ ⎥ = − ⎢⎜ ⎟ ⎥ ⎢⎜ ⎟ ⎥ = − µ CP
⎝ ∂P ⎠ T ⎣⎝ ∂T ⎠ H⎦ ⎣⎝ ∂H ⎠P ⎦ ⎣⎝ ∂P ⎠ H⎦ ⎣⎝ ∂T ⎠P ⎦ ⎛ ∂T ⎞ Joule-Thomson
1424 3 µ=⎜ ⎟
⎝ ∂P ⎠ H Coefficient
CP
⎛ ∂H ⎞ α ⎛ αµ ⎞
∴⎜ ⎟ = −µ C P + C P = ⎜⎜1 − ⎟⎟ C P
⎝ ∂T ⎠ V κT ⎝ κT ⎠
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 ⎞ U: Internal energy
C =
Definition: v ⎜ =
⎟ and P ⎜
C ⎟
⎝ ∂T ⎠ V ⎝ ∂T ⎠ P H: Enthalpy = U + P V
⎛ ∂ ⎞ ⎛ ∂U ⎞ ⎛ ∂ ⎞
C P − C V = ⎜ [U + PV ]⎟ − C V = ⎜ [ ] Expansion
⎟ − C V + ⎜ P V ⎟ Coefficient
⎝ ∂T ⎠P ⎝ ∂T ⎠P ⎝ ∂T ⎠P
⎛ ∂V ⎞
= α (P + Π T ) V α ΠTV P ⎜ ⎟ =αPV
⎝ ∂T ⎠ P
Internal Pressure
∴ C P − C V = α (P + Π T ) V
⎛ ∂P ⎞ ⎛ ∂P ⎞
= α T V ⎜ ⎟ because, Π 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
August 04, 2006
⎠P 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 1
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 2
Notations
(F2 − F1 )
F2
∫ F1
dF = ∆F ≡ if F is a state function
if F is not a state function. Subscript denotes the

(∆F)path
F2
∫
F1
dF = 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 3

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 4

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 equilibrium expansion
For a reversible process, (Pext − Pgas ) ≡ ∆P → 0

August 07, 2006 5
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 6
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 ⎛Q Pext ≈ Pgas , ⎞
⎜ ⎟
V2 V2 ⎜ for a reversible ⎟
w = − ∫ Pext dV ⇒ w rev = − ∫ Pgas dV ⎜
transforma tion.
⎟
V1 V1 ⎝ ⎠
The equation of state for an ideal gas is: Pgas V = n R T
dV
= − nRT ln (V2 / V1 )
V2
⇒ w rev = − nRT ∫ [reversible and isothermal]
V1 V
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 7
Work done for Expansion/Compression of an ideal gas
Situation-2: Both Temperature and Volume change,
from (V1 , T1 ) to (V2 , T2 ).
(V1 T1 ) (V2 T1 )
Consider the process to be adiabatic;

that is, ∆q = 0.
(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
T1
August 07, 2006 8
A relation between volume and
temperature for an ideal gas
Consider an adiabatic transformation; that is, ∆q = 0.
So, the first Law says,
dU = dq rev + dw rev ⇒ dw rev = dU ⇒ C V (T ) dT = −PdV
For an ideal gas, P = n R T/V, and hence

dT dV
(
CV T ) = −nR
T V
Assume, the Heat capacity to be Temperature independent.
CV T2 dT V2 dV
∴
nR ∫
T1 T
=−∫
V1 V
We will use this for studying
Entropy change in a Carnot Engine.
C V /nR nR/C V
⎛ V1 ⎞ ⎛ T2 ⎞ ⎛ V1 ⎞
ln⎜ ⎟ = ln⎜⎜ ⎟⎟
⎜ ⎟ ⇒ T2 = T1 ⎜⎜ ⎟⎟
⎝ V2 ⎠ ⎝ T1 ⎠ ⎝ V2 ⎠
August 07, 2006 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 ) D
(P1 V2 T3 )
A E • Direct path, A
• Path B + Path C
(P2 V2 T1 )
B • Path D + path E
C
(P3 V2 T2 )
V→
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
(P1 V1 T1 ) → (P2 V2 T1 )
Adiabatic process for ideal gases Path A
↑
Temperature does not change. P (P1 V1 T1 )
Hence, the change in energy,
∴ dU = C V (T ) dT = 0 A
(P2 V2 T1 )
From the first law then, we have,

V→
dU = dq rev + dw rev ⇒ 0 = dq rev + dw rev ⇒ dq rev = −dw rev
We already know the reversible work done for ideal gases,
⎛ V2 ⎞
∆w rev = − nRT1 ln⎜⎜ ⎟⎟
Hence, ⎝ V1 ⎠ ⎛ V2 ⎞
• Reversible work done : ∆w rev = − nRT1 ln ⎜⎜ ⎟⎟
⎝ V1 ⎠
⎛ V2 ⎞
• Change in heat : ∆q rev = nRT1 ln ⎜⎜ ⎟⎟
⎝ V1 ⎠
August 07, 2006
• Change in internal energy : ∆U = 0 11
(P1 V1 T1 ) → (P3 V2 T2 ) → (P2 V2 T1 )
Adiabatic process for ideal gases Path B+C
As we consider only adiabatic processes. (P1 V1 T1 )
we have, (∆q rev )B = 0 ↑
P
Temperature changes from T1 → T2
B
∴ (∆U )B = C V (T ) dT
T2
∫
T1
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
But the temperature changes from T2 → T1. ⇒ (∆U ) = 1 C (T ) dT
T

C ∫T2 V
Then, from the first law, (∆q rev )C = (∆U )C
For total, add contributions from path B and C. Hence,
C V (T ) dT
T2
• Reversible work: ∆W rev = ∫
T1
C V (T ) dT
T1
• Heat Change: ∆q rev = ∫T2
August 07, 2006 12
C V (T ) dT + ∫ C V (T ) dT = 0
T2 T1
• Change in energy : ∆U = ∫ T1 T2
(P1 V1 T1 ) → (P1 V2 T3 ) → (P2 V2 T1 )
Adiabatic process for ideal gases Path D+E
↑
In path D, temp. changes from T1 → T3 P (P1 V1 T1 ) D
∴ (∆U )D = C V (T ) dT
T3 (P1 V2 T3 )
∫T1 E
Pressure is constant, so the reversible work, (P2 V2 T1 )
(∆w rev )D = − ∫V P1 dV = −P1 (V2 − V1 ) V→

V2
( ) ( ) ∫
1 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 ( ) = 0.
( ) ( )
T1

Temperature changes from 3 T → T1 ∴ ∆U
(
.
Then, from the first law, ∆q rev E = ∆U E )
E = T C V T dT
( )
3
∫
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 = ∫ C V (T ) dT + ∫ C V (T ) dT

August 07, 2006 T3 T1 13
=0
T 1 T 3
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,
nRT
dq rev = dU − dw rev = C V (T ) dT + dV (for an ideal gas )
V
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:
dq rev dT dV
August 07, 2006 dS = = C V (T ) +nR 14
T T V
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, it’s easier
to heat a colder system, as that increases the Entropy.
August 07, 2006 • Hence, the Entropy change is inversely 16
proportional to the Temperature.

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,
nRT
dq rev = dU − dw rev = C V (T ) dT + dV (for an ideal gas )
V
V2 dq rev V2 dV ⎛ V2 ⎞
Q dS = dq rev /T ⇒ ∆S = ∫ = n R∫ = n R ln⎜⎜ ⎟⎟
V1 T V1 V
⎝ V1 ⎠
• Notice, the change in Entropy is positive.
August 07, 2006 18

Second Law of Thermodynamics
A precise statement: Consider the change of Entropy,
dS = (dS)INT + (dS)EXT
• (dS)INT : Entropy change due to changes inside the system
• (dS)EXT : Entropy flow due to interaction with the exterior
Second Law: (dS)INT is never negative. More precisely,

(dS)INT = 0 ↔ Reversible Process
(dS)INT > 0 ↔ 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 and (dS ) ≥ 0
II
INT
(dS ) I
INT ( )
> 0, dSII 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.
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:
dS = dSI + dSII
( )
• dq
I
INT : Heat received by system I from system II
• (dq )
I
EXT :Heat supplied to system I from the outside
• (dq ) ( )
II
INT :Heat received by system II from system I = − dq I EXT
• (dq )
II
EXT :Heat supplied to system II from the outside
(dq )
I
+
(dq )
II
+( I
)
⎡1 1 ⎤
dq INT ⎢ I − II ⎥ = (dS)EXT + (dS)INT
Hence, the total dS =
EXT EXT
I II
T T ⎣T T ⎦
August 07, 2006 This change results from the irreversible heat flow 21
inside the system, and is postulated to be positive.
Ref: (ds )INT = (dq I )INT ⎡⎢ I − II ⎤⎥ is positive.
1 1

⎣T T ⎦
In fact,
(dq ) I
INT >0
⎡1 1 ⎤
when ⎢ I − II ⎥ > 0 (dq )
I
INT <0
⎡1 1 ⎤
when ⎢ I − II ⎥ < 0
⎣T T ⎦ ⎣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,
⎛ ds ⎞ ⎛ dq I ⎞ ⎡ 1 1 ⎤
⎜ ⎟ = ⎜⎜ ⎟⎟ ⎢ 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 1
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.
V2 dq rev V2 dV ⎛V ⎞
Q dS = dq rev /T ⇒ ∆S = ∫ = n R∫ = n R ln⎜⎜ 2 ⎟⎟
V1 T V1 V
⎝ V1 ⎠
Aug. 08, 2006 2
Second Law of Thermodynamics: A precise statement
Consider the change of Entropy,
dS = (dS)INT + (dS)EXT
• (dS)INT : Entropy change due to changes inside the system
• (dS)EXT : Entropy flow due to interaction with the exterior
Second Law says: (dS)INT is never negative. More precisely,

(dS)INT = 0 ↔ Reversible Process
(dS)INT > 0 ↔ Irreversible Process
Corollary: For an isolated system, there is no flow of entropy
and hence,
dS = (dS)INT ≥ 0
Aug. 08, 2006 3
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 II
As we know, dS = (dS )INT + (dS )EXT and what we actually postulate

I I I

in the second Law, is:
(dS ) ≥ 0
I
INT and (dS )
II
INT ≥0
(dS ) > 0, (dS )

I
INT
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 4
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
I
INT : Heat received by system I from system II
• (dq )
I
EXT :Heat supplied to system I from the outside
• (dq ) ( )
II
INT :Heat received by system II from system I = − dq I EXT
• (dq )
II
EXT :Heat supplied to system II from the outside
(dq )
I
+
(dq )
II
+( I
)
⎡1 1 ⎤=
dq INT ⎢ I − II ⎥ (dS)EXT + (dS)INT
Hence, the total dS =
EXT EXT
I II
T T ⎣T T ⎦
Aug. 08, 2006 This change results from the irreversible heat flow 5
inside the system, and is postulated to be positive.

Ref: (ds )INT = (dq I )INT ⎡⎢ I − II ⎤⎥ is positive.
1 1

⎣T T ⎦
In fact,
(dq ) I
INT >0
⎡1 1 ⎤
when ⎢ I − II ⎥ > 0 (dq )
I
INT <0
⎡1 1 ⎤
when ⎢ I − II ⎥ < 0
⎣T T ⎦ ⎣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,
⎛ ds ⎞ ⎛ dq I ⎞ ⎡ 1 1 ⎤
⎜ ⎟ = ⎜⎜ ⎟⎟ ⎢ 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 6
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 7

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 8

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 ⇒ Kelvin is also false.

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

reject does not change, so the change in
q1 Internal energy is zero. Hence, the
T2 > T1 ↓ c work done by the system in one cycle
d
would be (from the first law):
V→ W = q 2 − q1
Aug. 08, 2006 10
Infinitesimal Carnot engine, if transformations are infinitesimal.

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
η= = 1−
q2 q2
Aug. 08, 2006 11

Carnot Engine and Refrigerator
Show that: If W > 0, then q1 > 0 and q 2 > 0.
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
Carnot’s 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: W C = q C2 − q1C W X = q X2 − q1X

q C2 N X
• Let X
= C Integers (ratio of integers can approximate a
q2 N 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:
(q 2 )total = N X q X2 − N C q C2 = 0 (by the definition of integers)
(q1 )total = N q1 − N q1 = −
X X C C
X X C C Wtotal N W N W
⇒ Wtotal = (q 2 )total − (q1 )total = −(q1 )total
Aug. 08, 2006 13
Carnot’s Theorem
q C2 N X
X
= C (q1 )total = N X q1X − N C q1C Wtotal = −(q1 )total
q2 N
We would face a violation of the Kelvin statement,

unless we have W ≤ 0 and this implies (q1 )total ≥ 0.
total
In other words,
X
N
(q1 )total = N X q1X − N C q1C ≥ 0 ⇒ C q1X − q1C ≥ 0
N
q C2 X q X
q C
⎛ q C
⎞ ⎛ q X
⎞
1 1 ⎜
⇒ X q1 − q1 ≥ 0 ⇒ X − C ≥ 0 ⇒ ⎜1 − C ⎟ ≥ ⎜⎜1 − X ⎟⎟
C 1
⎟ 1
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
θ
reservoirs of respective absolute temperatures 1 and 2 is θ
Also,
θ1
η = 1− Q η = 1−
q1
⇒
q1 θ1
=
θ2 q2 q2 θ 2
Since 0 ≤ η ≤ 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 .
We need to prove
N
⎛ q m ⎞ and N → ∞ will recover the theorem.
⎜ ⎟∑⎜ T ⎟≤0
m =1 ⎝ m ⎠
Aug. 08, 2006 16
We have essentially discretized the integral.

Clausius Theorem
Construct a set of N Carnot engines, C1 , C 2 ,L C N such that Cm
1. Operates between Tm and TO (TO ≥ Tm , for all m)
(O )
2. Absorbs amount of heat q m from TO
3. Rejects amount of heat q m to Tm

q (mO ) TO (O ) qm
From the definition of temperature scale, q
= ⇒ q m = TO
m Tm Tm
The net result of one complete cycle:
N N
q m is the amount of heat absorbed from the
q total = ∑ q m = TO ∑
(O )
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

N
Aug. 08, 2006 ⇒ ∑ (q m / Tm ) ≤ 0 QED
17
m =1
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
N
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 1
Ref: Statistical Mechanics, by Ryogo Kubo
Entropy
Consider a model showing a irreversible process (Heat Flow):
TI TII R
R
(d q ) (d q )
I
E
S
I
ext
int
(d q )II
ext
E
S
I II
E
E contact
R R
V dS = (dS)int + (dS)ext V
O
I (dS) = (d q)
I
ext
+
(d q)
II
ext
(dS)int ( ) ⎡1 1⎤
= d q int ⎢ − ⎥
I
O
I
ext
R
T I TII ⎣ TII TI ⎦ R
Entropy flow from the outside 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 ↔
INT Reversible Process
(dS)INT > 0
Aug. 11, 2006 2
↔ Irreversible 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 3

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
T2 • ab is isothermal, T2 is const and during
which the system absorbs Heat q 2 .
T1 a • cd is isothermal, T1 is const and during
q2 which the system rejects Heat q1.
↑ ↓ b • bc and da are adiabatics
P absorb
In a cyclic transformation, the temp.

reject does not change, so the change in
q1 Internal energy is zero. Hence, the
T2 > T1 ↓ c work done by the system in one cycle
d
would be (from the first law):
V→ W = q 2 − q1
Aug. 11, 2006 4
Infinitesimal Carnot engine, if transformations are infinitesimal.

Carnot’s 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 (this can be done to any

• Let us define two integers such that, X = C accuracy we like, as long as
q2 N 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)
5
Carnot’s 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
q1 X
⎛ q1 ⎞
⇒ N q −N q ≥0
X X
1
C C
1
⎜
⇒⎜ 1 − ⎟
C ⎟ ≥ ⎜⎜1 − X ⎟⎟ q C2 N X
⎝ q2 ⎠ ⎝ q2 ⎠ QED X
= C
Efficiency of a Efficiency of an q2 N
Carnot engine arbitrary engine

Aug. 11, 2006 6
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 7
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 W W W
q n +1 − q n = W
q n+2 q n +1 qn q n −1 q n −2
Carnot Carnot Carnot Carnot
Engine Engine Engine Engine
W
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)
For example, we may choose: x W = 1 Kelvin

Aug. 11, 2006 8
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
η n +1 = 1 −
Tn +1
Q 0 ≤ η ≤ 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
η 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 9
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
Clausius Theorem ∫ T ≤0
Proof strategy: Divide the cyclic transformation into N
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 .
Let q m be the amount of heat absorbed by the system during

the m th step, from the heat reservoir of temperature Tm .
N
⎛ qm ⎞
Then, we need to prove: ∑ ⎜⎜ ⎟⎟ ≤ 0
m =1 ⎝ Tm ⎠
And, we will recover the original theorem in the limit N → ∞
NB: We have essentially discretized the integral --- that is, we

have written the cyclic transformation, as a sum of N
Aug. 11, 2006 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
3. Rejects amount of heat qm to Tm

q (mO ) TO qm
From the definition of temperature scale, = ⇒ q (mO ) = TO
q m Tm Tm
N N is the amount of heat absorbed from the
q
∑
m =1
∑
q total = q (mO ) = TO
m =1 Tm
m reservoir at TO and converted entirely into

N
⇒ ∑ (q m / Tm ) ≤ 0
Aug. 11, 2006 m =1 12
QED
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
N
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
Consider two reversible paths: I
/
Path II is reverse of the path II. II
For reversible transformations, we have:

dq rev
∫ T =0
dq rev dq rev dq rev dq rev
That is: ∫I T + ∫II/ T = 0 ⇒∫
I T
−∫
II T
=0
That is, the difference of Entropy, computed along two different

paths is zero --- so, it’s path independent. Hence, Entropy is a
state function.
QED
Aug. 11, 2006 14

Entropy Reference point.
Define Entropy:
A Ref A
dq rev
S(A ) = ∫
Ref is some arbitrary
thermodynamic state
Ref
T
So, the change in Entropy:

A B Ref A B
dq rev dq rev dq rev dq rev dq
∴ S(A ) − S(B) = ∫ − ∫ = ∫ + ∫ = ∫ rev
Ref
T Ref
T B
T Ref
T A
T
• 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
For an arbitrary transformation: dq
∫A T ≤ S(B) − S(A ) irreversible

Proof: • For reversible transformations,

it’s obvious by definition. B
• Consider the cyclic transformation, made A
up of (1) Irreversible, plus (2) reverse of reversible
Reversible. From Clausius’ theorem:
dq dq dq dq dq
∫IRR T ∫REV T
− ≤ 0 ⇒ ∫IRR T ∫REV T
≤ ⇒∫
IRR T
≤ S(B) − S(A )
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
Recall the first law: dq = dU + PdV
And, assuming the internal energy being a function of volume

and temperature, ⎛ ∂U ⎞
dU = C V dT + ⎜ ⎟ dV
⎝ ∂V ⎠ T
Heat capacity Internal pressure
So,
dq dT 1 ⎡⎛ ∂U ⎞ ⎤
dS = = 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 ⎞ Given an exact differential, identify all

⎜⎜ ⎟⎟ = ⎜ ⎟ the variables. This relation then allows
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y us to obtain a host of useful relations,
(for example, Maxwell’s 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
−1
⎛ ∂x ⎞ ⎛ ∂y ⎞ ⎛ ∂x ⎞ ⎛ ∂x ⎞ ⎧⎛ ∂y ⎞ ⎫
⎜⎜ ⎟⎟ ⎜ ⎟ = ⎜ ⎟ ⎜⎜ ⎟⎟ = ⎨⎜ ⎟ ⎬
⎝ ∂y ⎠ w ⎝ ∂z ⎠ w ⎝ ∂z ⎠ w ⎝ ∂y ⎠ z ⎩⎝ ∂x ⎠ z ⎭
⎛ ∂x ⎞ ⎛ ∂y ⎞ ⎛ ∂z ⎞
⎜⎜ ⎟⎟ ⎜ ⎟ ⎜ ⎟ = −1
Aug. 11, 2006 ⎝ ∂y ⎠ z ⎝ ∂z ⎠ x ⎝ ∂x ⎠ y 18
Derivation of TdS equations:
Ref: dq dT 1 ⎡⎛ ∂U ⎞ ⎤
dS = = CV + ⎢⎜ ⎟ + P ⎥ dV
T T T ⎣⎝ ∂V ⎠ T ⎦
dS is an exact differential and RHS is a function of V and T, so
⎛ ∂ ⎞ ⎧ C V ⎫ = ⎛⎜ ∂ ⎞⎟ ⎧ 1 ⎡⎛⎜ ∂U ⎞⎟ + P ⎤ ⎫
⎜ ⎟ ⎨ ⎬ ⎨ ⎢ ⎥⎬
⎝ ∂V ⎠ T ⎩ T ⎭ ∂T
⎝ ⎠ V ⎩ ⎣⎝T ∂V ⎠T ⎦⎭
⎛ ∂U ⎞
Use the definition, C V = ⎜ ⎟ , differentiate and rearrange.
⎝ ∂T ⎠ V
⎛ ∂U ⎞ ⎛ ∂P ⎞ ⎛ ∂U ⎞ ⎛ ∂P ⎞
⎜ ⎟ = T ⎜ ⎟ − P ⇒ ⎜ ⎟ + P = T ⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V ⎝ ∂V ⎠ T ⎝ ∂T ⎠ V
For ideal gas, P=nRT/V and hence, ⎛⎜ ∂U ⎞⎟ = T nR − P = 0.

⎝ ∂V ⎠ T V
Hence, the internal pressure of of an ideal gas is zero,
Aug. 11, 2006
and we already knew it !!! 19
TdS Equations
dT 1 ⎡⎛ ∂U ⎞ ⎤ ⎛ ∂U ⎞ ⎛ ∂P ⎞
Recall: dS = C V + ⎢⎜ ⎟ + P ⎥ dV ⎜ ⎟ +P=T⎜ ⎟
T T ⎣⎝ ∂V ⎠ T ⎦ ⎝ ∂V ⎠ T ⎝ ∂T ⎠ V
⎛ ∂P ⎞
⇒ TdS = C V dT + T⎜ ⎟ dV
⎝ ∂T ⎠ V
Similarly, we can show:
⎛ ∂V ⎞
TdS = 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 with exptal observables
1 ⎛ ∂V ⎞
Define: α = ⎜ ⎟ Coefficient of thermal expansion
V ⎝ ∂T ⎠ P
1 ⎛ ∂V ⎞ Isothermal compressibility
κT = − ⎜ ⎟
V ⎝ ∂P ⎠ T
1 ⎛ ∂V ⎞ adiabatic compressibility
κS = − ⎜ ⎟
V ⎝ ∂P ⎠S
We can then show: −1 −1

⎛ ∂P ⎞ ⎡⎛ ∂T ⎞ ⎛ ∂V ⎞ ⎤ ⎡
⎛ ∂V ⎞ ⎛ ∂V ⎞ ⎤ α
⎜ ⎟ = − ⎢⎜ ⎟ ⎜ ⎟ ⎥ = −⎜ ⎟ ⎢⎜ ⎟ ⎥ =
⎝ ∂T ⎠ V ⎣⎝ ∂V ⎠ P ⎝ ∂P ⎠ T ⎦ ⎝ ∂T ⎠ P ⎣⎝ ∂P ⎠ T ⎦ κT
⎛ ∂P ⎞
Q TdS = C V dT + T⎜ ⎟ dV ⇒ TdS = C V dT + αT dV
⎝ ∂T ⎠ V κT
Similarly, TdS = C P dT − αTVdP

Aug. 11, 2006 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 (∆H )Transition < 0 (exothermic, e.g., freezing)
(∆H )Transition > 0 (endothermic, e.g., melting )
TTransition
Trouton’s 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
Recall: ds =
T
If only temperature changes, then we can directly integrate:
T2
dq rev
S(T2 ) = S(T1 ) + ∫
T1
T
If we fix the pressure, then at constant P, dq rev = C P (T ) dT.
T2
dT
S(T2 ) = S(T1 ) + ∫ C P (T )
T1
T
If the heat capacity is independent of Temperature:
T2
dT ⎛ T2 ⎞
S(T2 ) = S(T1 ) + C P ∫ = S(T1 ) + C P ln⎜⎜ ⎟⎟
Aug. 11, 2006
T1
T ⎝ T1 ⎠ 23
Amrendra Vijay
Lecture 05
August 14, 2006 1
Happy Independence Day
August 14, 2006 2

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; Maxwell’s Relations;
Free Energy and Chemical Equilibria; Gibbs-Helmholtz and
van’t 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 3
References
• Physical Chemistry Through

Problems
--- S.K. Dogra and S. Dogra
August 14, 2006 4

Reference: Statistical Mechanics by Kerson Huang
Recap …
dq
We proved Clausius Inequality: ∫ T ≤0
Assuming there is a
A
dq rev continuous path of
We then defined Entropy as: S(A ) = ∫ T transformation from
Ref Ref to A.
We then observed Entropy is defined only up to an arbitrary
additive constant:
B A B Ref B
dq rev dq rev dq rev dq rev dq
S(B) − S(A ) = ∫ − ∫ = ∫ + ∫ = ∫ rev
Ref
T Ref
T Ref
T A
T A
T
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 5
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 6

Entropy Change: Reversible Isothermal Expansion
Model:
Reservoir, T
Piston
gas
Spring
↑
P
T constant line
Work done
August 14, 2006 V1 V2 V→ 7

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:
∆q V2
(∆S)Reservoir =− = − R ln
August 14, 2006 T V1 8
So, the total change in Entropy is Zero:
V2 V2
(∆S)Total = (∆S)Gas + (∆S)Reservoir = 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 9

Entropy Change: Irreversible Free Expansion
Model:
Before After
Water Bath, T constant Water Bath, T constant
Gas occupies volume, V1 Gas occupies volume, V2
August 14, 2006 10

Joule’s free-expansion experiment
Entropy Change: Irreversible Free Expansion
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:
V2
(∆S)gas = R ln
V1
So the total change in Entropy here is:
V2
(∆S)Total = (∆S)Gas + (∆S)Reservoir = R ln
August 14, 2006 V1 11
Entropy Change: Comparison
Reversible Isothermal Expansion Irreversible Free Expansion
(∆S)gas = ∆q = R ln V2 (∆S)gas = ∆q = R ln V2
T V1 T V1
∆q V
(∆S)Reservoir =− = − R ln 2 (∆S)Reservoir = 0
T V1
V2
∴ (∆S)Total = 0 (∆S)Total = R ln
V1
V2 Gets stored
W = RT ln W = T (∆S)Total Gets wasted
V1 in the Spring
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
Recall: ds =
T
If only temperature changes, then we can directly integrate:
T2
dq rev
S(T2 ) = S(T1 ) + ∫
T1
T
If we fix the pressure, then at constant P, dq rev = C P (T ) dT.
T2
dT
S(T2 ) = S(T1 ) + ∫ C P (T )
T1
T
If the heat capacity is independent of Temperature:
T2
dT ⎛ T2 ⎞
S(T2 ) = S(T1 ) + C P ∫ = S(T1 ) + C P ln⎜⎜ ⎟⎟
August 14, 2006
T1
T ⎝ 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.
Units: 1 N m = 1 Pa; 10 Pa = 1 bar (1 atm)
-2 5

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 =
(∆H )Transition (∆H )Transition < 0 (exothermic, e.g., freezing )
(∆H )Transition > 0 (endothermic, e.g., melting )
August 14, 2006
TTransition 15
Trouton’s 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.
(∆H )Transition (∆H )Vaporization

Q (∆S)Transition = ∴ (∆S)Vaporization = ≈ 85 J K -1mol−1
TTransition TBoiling-Point
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

Trouton’s Rule
Example: The normal boiling point of Chloroform is 61.5°C.
Calculate the molar heat of vaporization, from Trouton’s rule.
Answer:
(∆H )Vaporization
Q (∆S)Vaporization = ≈ 85 J K -1mol −1
TBoiling-Point
⇒ (∆H )Vaporization = 85 J K -1mol −1 × TBoiling-Point
(85J K −1
)
mol −1 × (273 + 61.5)K
August 14, 2006 17

Example
Calculate the increase in the Entropy if one mole of Krypton is
heated from 27°C to 227°C 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
(
∆S = n C V ln = (1mol) 1.5 × 8.314 J K mol ln
−1 −1
) (273 + 27 )K
T1 (273 + 227 )K
At constant pressure:
T2
( )
∆S = n C P ln = (1mol) [1.5 + 1.0]× 8.314 J K mol ln
−1 −1 (273 + 27 )K
T1 (273 + 227 )K
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)
nRT
W = Pext ∆V = Pext (V2 − V1 ) and V1 =
P
(2)

⎛ V2 ⎞ ⎛ 2V1 ⎞
(
W = n RT ln⎜⎜ ⎟⎟ = (1mol) 8.314JK mol (300K )ln⎜⎜
−1 −1
) ⎟⎟
⎝ 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:
work (W ) 150 kJ 2
η= = =
heat absorbed (q 2 ) 225 kJ 3
(2)
T1 ⎛ 2⎞
Q η = 1− ∴ T1 = (1 − η)T2 = ⎜1 − ⎟(227 + 273)K
T2 ⎝ 3⎠
August 14, 2006 20

Thermodynamic Potentials
Helmholtz Free Energy, A:
A = U−TS Entropy
Gibbs Free Energy, G:

G = A + P V Enthalpy
⇒ G = U − TS + P V = H − TS
Internal Energy 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 ) ∆S = S(B) − S(A )
Because Temperature, T is constant, we have:

∆q ∆q : Heat absorbed
≤ ∆S ⇒ ∆q ≤ T ∆S
T during the transformation
From the First Law we know, ∆q = dU + W and hence,
∆U + W ≤ T∆S ⇒ W ≤ −(∆U − T∆S)

August 14, 2006
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 1
Entropy
Question: Why do we need a reversible path, for the defintion of
Entropy ?
⎛ ∂U ⎞
Answer: Recall, dq = dU + PdV = 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:
dq REV dT 1 ⎡⎛ ∂U ⎞ ⎤
dS = = CV + ⎢⎜ ⎟ + P ⎥ dV
T T T ⎣⎝ ∂V ⎠ T ⎦
August 18, 2006 2

dq
Clausius Inequality ∫ T ≤0
Recall, the definition efficiency, (0 ≤ η ≤ 1) of an engine,
q1 q1
η = 1− η = 1− If we wish to follow the
q2 q2 Sign Convention explicitly.
q1C T1
Recall the definition of temperature, C
=
q 2 T2
⎛ q1C T ⎞ ⎛ q X
⎞
⎜ 1 ⎟ ⎜ ≡ 1− ⎟
≥ ⎜
1
And, Carnot theorem: η C ≡ 1 − C = 1 − η X ⎟
⎜ q T ⎟ X
q
⎝ 2 2
⎠ ⎝ 2 ⎠
⎛ T1 ⎞ q1X q1X T1 But, q X is the heat rejected,

⇒ ⎜⎜1 − ⎟⎟ ≥ 1− X ⇒ X ≥ 1
⎝ T2 ⎠ q2 q2 T2 and hence it carries a

negative sign.
q1X T1 q1X q X2
⇒− X ≥ ⇒0≥ + for one Carnot Engine
August 18, 2006 q 2 T2 T1 T2 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
3. Rejects amount of heat qm to Tm

q (mO ) TO qm
From the definition of temperature scale, = ⇒ q (mO ) = TO
q m Tm Tm
N N is the amount of heat absorbed from the
q
∑
m =1
∑
q total = q (mO ) = TO
m =1 Tm
m reservoir at TO and converted entirely into
How ?
N
⇒ ∑ (q m / Tm ) ≤ 0
August 18, 2006 m =1 4
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 = ∑ q(

m =1
O)
m
August 18, 2006 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 ( )
X, Y ≤ 0 OR
( )
dF X,Y ≥ 0
• 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 6
We will henceforth obtain the Maxwell’s relations.

Criteria of Equilibrium Entropy
B B
δq irreversible
Entropy: ∆S = SB − SA = ∫ dS ≥ ∫
T
A
δq A
A B
We can also write as, dS ≥
T reversible
δq
• Spontaneous and Irreversible Processes: dS >
δq T
• Reversible Processes: dS =
T δq
• Impossible Processes: dS <
T
If the system is isolated then we have, δq = 0
• Spontaneous and Irreversible Processes: dS > 0
• Reversible Processes: dS = 0
August 18, 2006 7
• Impossible Processes: dS < 0

Criteria of Equilibrium Entropy
Natural Variables: Reference: δq
dS ≥
T
If we consider only the Pressure-Volume work then from the
first Law we have,
δq = dU + P dV
δq = dU (Volume, V constant)
δq = 0 (If the system is isolated, U constant)
At constant U and V, (dS)U,V ≥ 0U 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 8

Criteria of Equilibrium Internal Energy
δq
Clausius Inequality: dS ≥ ⇒ δq − TdS ≤ 0
T
Q δq = dU + PdV ∴ dU + PdV − TdS ≤ 0
At constant Volume, V and Entropy, S, we have
Here, V and S are natural variables for U
dU ≤ 0
Thus, for a system at constant volume and Entropy:
• If the change is spontaneous: dU <0

• If the change is reversible: dU = 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 9
Thermodynamic Potentials
Helmholtz Free Energy, A:
A = U−TS Entropy
Gibbs Free Energy, G: G = A + P V Enthalpy

⇒ G = U − TS + P V = H − TS
Internal Energy 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
Definition: A = U−TS
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 ∆S = S(B) − S(A )
Helmholtz Free Energy, A: Consider an arbitrary Isothermal

(constant Temperature) transformation from state A to state B.
δq δq : Heat absorbed
≤ ∆S ⇒ δq ≤ T ∆S during the transformation
T
Change in Helmholtz Free
From the first Law: δq = dU + W Energy, at constant temp.
⇒ ∆U + W ≤ T∆S ⇒ W ≤ −(∆U − T∆S)
August 18, 2006 W ≤ −∆ A W = −∆ A, if the transformation

is reversible.
12
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,
∆A≤0 (Criteria of equilibrium)
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 = U−TS
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 WORK
⎛ ∂A ⎞ ⎛ ∂A ⎞
That implies: P = −⎜ ⎟ S = −⎜ ⎟
⎝ ∂V ⎠ T ⎝ ∂T ⎠ V
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: δA = 0
V1 + V2 = V (constant)
⎛ ∂A ⎞ ⎛ ∂A ⎞
δA = ⎜⎜ ⎟⎟ dV1 + ⎜⎜ ⎟⎟ dV2 ⇒ dV1 + dV2 = 0 ⇒ dV1 = −dV2
⎝ ∂V1 ⎠ T ⎝ ∂V2 ⎠ T
⎡⎛ ∂A ⎞ ⎛ ∂A ⎞ ⎤ ⎛ ⎞ ⎛ ⎞
∴ 0 = ⎢⎜⎜ ⎟⎟ − ⎜⎜ ⎟⎟ ⎥ dV1 ⇒ ⎜ ∂A ⎟ = ⎜ ∂A ⎟ ⇒ P1 = P2
⎢⎣⎝ ∂V1 ⎠ T ⎝ ∂V2 ⎠ T ⎥⎦ ⎜ ∂V ⎟ ⎜ ∂V ⎟
⎝ 1 ⎠T ⎝ 2 ⎠T
August 18, 2006 So the equilibrium position is the situation when 16
the pressure is the same in both vessels.

Gibbs Free Energy, G
Definition: G =A+PV
⇒ G = U − TS + P V = H − TS
Change in Gibbs Free Energy:
∆G = ∆A + P ∆V + V ∆P
If Pressure is constant then ∆G = ∆A + P ∆V
August 18, 2006 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 1∆V42 +43
∆ A ≤ 0 ∴ ∆G ≤ 0
∆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

Gibbs G = U − TS + P V
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 ⎞ ⎛ ∂G ⎞
S = −⎜ ⎟ V=⎜ ⎟
⎝ ∂T ⎠ P ⎝ ∂P ⎠ T
August 18, 2006 19

Other Relations Enthalpy, H
Definition of Enthalpy: H=U+PV
Change of Enthalpy: ∆H = ∆U + P ∆V + V ∆P
ENERGY WORK
= T ∆S + V ∆P
HEAT
S and P are natural variables for Enthalpy.
⎛ ∂H ⎞ ⎛ ∂H ⎞
T=⎜ ⎟ V=⎜ ⎟
⎝ ∂S ⎠ P ⎝ ∂P ⎠S
August 18, 2006 20

Maxwell’s Relations
V A T
U G
S H P
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,
⎛ ∂A ⎞ ⎛ ∂A ⎞ ⎛ ∂G ⎞
⎜ ⎟ = −S ⎜ ⎟ = −P ⎜ ⎟ =V
August 18, 2006
⎝ ∂T ⎠ V ⎝ ∂V ⎠ T ⎝ ∂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 ⎞ ⎤
Ref : dS = = CV + ⎢⎜ ⎟ + P ⎥ dV
T T T ⎣⎝ ∂V ⎠ T ⎦
dT
At constant Volume, dV=0 and hence: dS = C V
T
If TA is very close to 0,
TA T
dT TA →0 A
dT
∴ SA = ∫ C V (T ) = C V (TA ) ∫ C V (T ) is expected to be
T T
0 0 constant in the
⎡ A⎤
T
= C V (TA ) ln ⎢ ⎥ Temperature range.
1⎣203⎦
infinity at TA →0
Q SA → 0 as TA → 0, we must then have C V (TA ) → 0

August 18, 2006
QED 24
This has been verified experiementally.

All transformations at absolute zero are adiabatic.
Proof: For reversible transformation,
Q (δq )REV = T ∆S
∴ δq → 0 as T → 0
August 18, 2006 25

At absolute zero, the coefficient of thermal expansion of
any substance vanishes.
Proof:
August 18, 2006 26

Amrendra Vijay
Lecture 07
August 21, 2006 1
Criteria for Irreversibility
Clausius Inequality:
B
dq
B
δq
∆S ≡ SB − SA ≡ ∫ dS ≥ ∫ dS ≥
A A
T 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 2
Suggested Reading:
Statistical Mechanics by K. Huang, Chapter 1.
August 21, 2006 3


rule.
August 21, 2006 4
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 5

Any Heat Capacity of a system must vanish at absolute zero.
Proof: dq REV dT 1 ⎡⎛ ∂U ⎞ ⎤
Ref : dS = = CV + ⎢⎜ ⎟ + P ⎥ dV
T T T ⎣⎝ ∂V ⎠ T ⎦
dT
At constant Volume, dV=0 and hence: dS = C V
T
If TA is very close to 0,
TA T
dT TA →0 A
dT
∴ SA = ∫ C V (T ) = C V (TA ) ∫ C V (T ) is expected to be
T T
0 0 constant in the
⎡ A⎤
T
= C V (TA ) ln ⎢ ⎥ Temperature range.
1⎣203⎦
infinity at TA →0
Q SA → 0 as TA → 0, we must then have C V (TA ) → 0

August 21, 2006
QED 6
This has been verified experimentally.

All transformations at absolute zero are adiabatic.
Proof: For reversible transformation,
Q (δq )REV = T ∆S
∴ δq → 0 as T → 0
August 21, 2006 7

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 8

Gibbs Free Energy, as a function of Temperature and Pressure.
August 21, 2006 9

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 don’t 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
Gibbs Free Energy, G Effect of Temperature
Recall: For Gibbs Free Energy, Pressure and Temperature are
natural variables, and therefore
⎛ ∂G ⎞ G−H
∆G = −S ∆T + V ∆P ⇒⎜ ⎟ = −S =
⎝ ∂T ⎠ P T
⎛ ∂G ⎞ G H 1⎛ ∂ ⎞ ∂ ⎛1⎞ H
∴⎜ ⎟ − =− ⇒ ⎜ G⎟ + G ⎜ ⎟=− 2
⎝ ∂T ⎠ P T T T ⎝ ∂T ⎠ P ∂T ⎝ T ⎠ T
⎛ ∂ ⎡G ⎤⎞ H ⎡ ∂ (G/T ) ⎤
Hence, ⎜⎜ ⎟ = − Alternatively, ⎢ =H

⎢⎣ T ⎥⎦ ⎟ ⎥
∂ ⎣ ∂ (1/T ) ⎦ P
2
⎝ T ⎠P T
Gibbs-Helmholtz Equation
Thus, if we know the Enthalpy of the system, we can

August 21, 2006 predict how G/T varies with Temperature, T. 11
Gibbs-Helmholtz Equation
⎛ ∂ ⎡G ⎤⎞ H ⎛ ∂ ⎡ ∆G ⎤ ⎞ ∆H
Q ⎜⎜ ⎢ ⎥ ⎟⎟ = − 2 ⇒ ⎜⎜ ⎢ ⎥ ⎟⎟ = − 2
⎝ ∂T ⎣ T ⎦ ⎠ P T ⎝ ∂T ⎣ T ⎦ ⎠ P T
⎡ ∂ (G/T ) ⎤ ⎡ ∂ (∆G/T ) ⎤
Q⎢ ⎥ =H ⇒⎢ ⎥ = ∆H
⎣ ∂ (1/T ) ⎦ P ⎣ ∂ (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
Gibbs Free Energy, G Effect of Pressure
Recall, ∆G = −S ∆T + V ∆P dG = −S dT + V dP
At constant T, dG = V dP can integrated directly, if volume
is known as a function of Pressure, at constant T. Then,
2 2 P2
∫ dG = ∫ V dP ⇒ G 2 − G1 = ∫ V dP
1 1 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
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 P−P
0
( 0
)
G 0 is Gibbs free energy when the pressure is
equal to the standard state pressure.
August 21, 2006 14

This is okay for liquid and solid but not for gases.
P2
G 2 = G1 + ∫ V dP
P1
Case-II: Ideal Gases, for which we know the equation of state.

PV = nRT
P2
dP P2
∴ G 2 = G1 + nRT ∫ ∴ G 2 = G1 + nRT ln
P1
P P1
In terms of standard state, we have:
0
⎛ P⎞ G is the Gibbs energy when the
G = G + nRT ln⎜ 0 ⎟
0
pressure is equal to the standard
⎝P ⎠ state pressure 0 .
P
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 where n j is the amount of jth species, in terms

of moles.
A given thermodynamic quantity will be a function of {n j ; j = 1, N}

beside the natural variables.
Example: Internal Energy, U(S, V, n1 , n 2 , L , n N )

August 21, 2006 17
Open System partial molar quantities
Consider a thermodynamic quantity, F.
⎛ ⎞
f ⎜ α, β, n1 , n 2 , L , n N ⎟
⎜ { 142 4 43 4 ⎟
⎝ natural variables no.of moles of species in the system ⎠
⎛ ∂f ⎞ ⎛ ∂f ⎞ N
⎛ ∂f ⎞
∴ df = ⎜ ⎟ dα + ⎜⎜ ⎟⎟ dβ + ∑ ⎜⎜ ⎟⎟ dn i
⎝ ∂α ⎠β,n1Ln N ⎝ ∂β ⎠ α, n1Ln N i =1 ⎝ ∂n i ⎠ α,β, n
j
⎛ ∂f ⎞
⎜⎜ ⎟⎟ is the Partial Molar Quantity
Change in f ⎝ ∂n i ⎠ α,β, n j For example: partial molar volume,
per mole of Partial molar Free Energy (Chemical
species i added. Potential) and so forth.
August 21, 2006 18
What good does it do ?

Partial Molar Quantity
⎛ ∂f ⎞ ⎛ ∂f ⎞ N
⎛ ∂f ⎞
Definition: df = ⎜ ⎟ dα + ⎜⎜ ⎟⎟ dβ + ∑ ⎜⎜ ⎟⎟ dn i
⎝ ∂α ⎠β,n1Ln N ⎝ ∂β ⎠ α, n1Ln N i =1 ⎝ ∂n i ⎠ α,β, n
j
Assume natural variables are constant, then we have:

N
⎛ ∂f ⎞ N
(df )α,β = ∑ ⎜⎜ ⎟⎟ dn i ⇒ (df )α,β = ∑ f i dn i
i =1 ⎝ ∂n i ⎠ α,β, n i =1
j
upon Integration
N
f = ∑ n i fi
i =1
Thus the function f may be calculated, if partial molar f’s are

known.
This is important, for it shows how to calculate
August 21, 2006
a thermodynamic property by simply adding up 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:
⎛ ∂U ⎞ ⎛ ∂U ⎞ N
⎛ ∂U ⎞
dU = ⎜ ⎟ dS + ⎜ ⎟ dV + ∑ ⎜⎜ ⎟⎟ dn i
⎝ ∂S ⎠ V,n1Ln N ⎝ ∂V ⎠S,n1Ln N i =1 ⎝ ∂n i ⎠ S, V, n
j ( ≠i )
N
⎛ ∂U ⎞ Chemical Potential
⇒ dU = TdS − PdV + ∑ µ i dn i µ i = ⎜⎜ ⎟⎟ of species i. OR,
i =1
⎝ ∂n i ⎠S, V,n j( ≠i ) 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 other definitions
Using Gibbs Free Energy:
N ⎛ ∂G ⎞
dG = −S dT + VdP + ∑ µ i dn i µ i = ⎜⎜ ⎟⎟
i =1
⎝ ∂n i ⎠ P,T, n j( ≠i )
Using Helmholtz Free Energy:
N
⎛ ∂A ⎞
dA = −S dT − PdV + ∑ µ i dn i µ i = ⎜⎜ ⎟⎟
i =1 ⎝ ∂n i ⎠ V,T, n j( ≠i )
Using Enthalpy:
N ⎛ ∂H ⎞
dH = TdS + VdP + ∑ µ i dn i µ i = ⎜⎜ ⎟⎟
i =1 ⎝ ∂n i ⎠ P,S, n j( ≠i )
August 21, 2006 21
N
dG = −S dT + VdP + ∑ µ i dn i
Gibbs
i =1
Additivity Relation
If P, T, and the relative proportion of the components are held
constant then,
N Integrate N
dG = ∑ µ i dn i ⇒ G = ∑ ni µi
i =1 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 Thus, for a pure substance, the

G=nµ ⇒µ = Chemical Potential is equal to the
n Gibbs Free Energy per mole.
August 21, 2006 22
Chemical Potential = Partial Molar Gibbs Free Energy
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
G is the Gibbs energy when the
⎛ P⎞
G = G 0 + nRT ln⎜ 0 ⎟ pressure is equal to the standard
⎝P ⎠ state pressure P 0.
Since molar Gibbs energy is nothing but the chemical potential,
⎛ Pi ⎞ Partial pressure of the species i

µ i = µ + RT ln⎜ 0 ⎟
0
i y i = mole fraction
⎝P ⎠ Pi = y i P 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 N 23
(∆G )mixing = nRT ∑ yi ln(yi ) and so forth.
i =1
Activity
Recall: Molar Gibbs free energy as a function of Pressure, for
an ideal gas is:
⎛ Pi ⎞ Pi : Partial Pressure of species i.
µ i = µ + RT ln⎜ 0 ⎟
0
i
⎝P ⎠ 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
µ i = µ 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 1
Chemical Equilibrium
Suggested Reading:
Physical Chemistry by R.A. Albery and R.J. Silbey
Chapter 5
Keywords:
• 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, ξ.
• Reaction Gibbs energy in terms of activity.
• Equilibrium Constant, K.
• Thermodynamics of a gas phase reaction.
• van’t Hoff Equation --- K as a function of Temperature.
• Relation between K and the Extent of reaction, ξ.
August 22, 2006 2

Activity and Fugacity
Recall: Molar Gibbs free energy as a function of Pressure, for
an ideal gas is:
⎛ Pi ⎞ Pi : Partial Pressure of species i.
µ i = µ + RT ln⎜ 0 ⎟
0
i
⎝P ⎠ P 0 : Standard State Pressure
y i = mole fraction
∑ Pi = P ∑ yi = 1
i
Pi = y i P P = Total Pressure
i
For a real gases, we assume the same form as that of ideal

gases and hence we introduce a new quantity, Fugacity:
⎛ fi ⎞ f i : Fugacity of species i.
µ i = µ + RT ln⎜ 0 ⎟
0
i
⎝P ⎠
f As pressure approaches zero, real gases
Lim = 1 approach the behavior of ideal gases.
August 22, 2006
P →0 P 3
Read: Alberty and Silbey, pp. 120 and 133.

Activity and Fugacity
More generally, we can write the Chemical Potential as:
µ i = µ i0 + RT ln (a i ) a i : activity of species i in the mixture.
⎧ Pi
⎪ P0 For an ideal gas Pi : Partial Pressure of species i.
⎪
ai = ⎨ P 0 : Standard State Pressure
⎪ fi For a real gas f i : Fugacity of species i.
⎪ P0
⎩
If µ i = µ i then a i = 1. That is: Activity for the reference state is

0

unity.
August 22, 2006 4
Chemical Equilibrium Definitions
Consider an arbitrary reaction:
νa A + νb B → νd C + νd D
Reactants Products
⇒ νc C + νd D − νa A − νb B = 0
So, a general chemical reaction may be written as follows:
N
∑ν
i =1
i Ai = 0
Reactants or Products
Stoichiometric ⎧− ve for reactants
Number ⎨
August 22, 2006
⎩ + ve for products 5
Chemical Equilibrium 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 = ∑ µ i dn i N : No. of species involved
in the reaction.
i =1
µi : Chemical Potential of species i
We need to compute this
before discussing the dn i : Differential Change in the
equilibrium property of a amount of species i
Chemical Reaction.
August 22, 2006 6
Chemical Equilibrium
Proposition: When a chemical reaction takes place, the changes
in the amount of species involved, are proportional to their
Stoichiometric numbers, That is:νi .
(n i −n
0
i ) ∝ νi n i0 : Initial amount of species i
ni : Amount of species I, after

some time.
(
⇒ ni − n 0
i ) = ξ νi ξ: Proportionality constant, also
called the extent of reaction.
⇒ dn i = ν i dξ
Substitute this in the expression
August 22, 2006
for the change in Gibbs energy. 7
Reaction Gibbs Energy
N
We have:
(dG )T,P = ∑ µ i dn i dn i = ν i dξ
i =1
N
∴ (dG )T, P = ∑ µ i ν i dξ Reaction Gibbs Energy
i =1
⎛ ∂G ⎞ N N
⇒ ⎜⎜ ⎟⎟ = ∑ µ i ν i ⇒ (∆G )R = ∑ µ i ν i
⎝ ∂ξ ⎠ T, P i =1 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 8

⎛ ∂G ⎞ N
(∆G )R ≡ ⎜⎜ ⎟⎟ = ∑ µ i ν i
⎝ ∂ξ ⎠ T, P i =1
Equilibrium Behavior
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,

G
Gibbs energy is minimum and hence,
⎛ ∂G ⎞
(∆G )R ≡ ⎜⎜ ⎟⎟ = 0
⎝ ∂ξ ⎠ T, P ξ eq ξ→
N
⇒ ∑ ν i µ ieq = 0
i =1
This is a general condition and
August 22, 2006
applies to all chemical equilibria. 9
⎛ ∂G ⎞ N
(∆G )R ≡ ⎜⎜ ⎟⎟ = ∑ µ i ν i
⎝ ∂ξ ⎠ T, P i =1
Reaction Gibbs Energy in terms of activity
We know: For a general substance, the chemical potential is
given as:
µ i = µ i0 + RT ln (a i )
( ) = ∑ν
N N N
⇒ (∆G )R = ∑ ν i µ + RT ln a i µ + RT ∑ ln (a i )
0 0 νi
i i i
i =1 i =1 i =1
Reaction Gibbs energy ⎡N νi ⎤

for the standard state (∆G )0R ln ⎢Π(a i ) ⎥
⎣i =1 ⎦
⎡N ν ⎤
∴ (∆G )R = (∆G ) + RT ln ⎢Π(a i ) i ⎥
0
R Product of N terms
⎣i =1 ⎦
August 22, 2006 a i : activity of species i. 10
Reaction Gibbs Energy in terms of activity Example
⎡N ν ⎤
Recall: Reaction Gibbs Energy is, (∆G )R = (∆G )
0
R + RT ln ⎢Π(a i ) i ⎥
⎣i =1 ⎦
1 3
Consider the reaction: N 2 + H 2 = NH 3
2 2
⎡ a NH3 ⎤
(∆G )R = (∆G )
0
+ RT ln ⎢ 3/2 ⎥
R
( ) ( )
⎢⎣ a N 2
1/2
a H2 ⎥⎦
(∆G )R >0 Forward reaction is not spontaneous.
(∆G )R =0 Reactants and Products are at equilibrium

at the specified activities.
August 22, 2006 (∆G )R <0 Forward reaction is spontaneous. 11
Equilibrium Constant
Recall: Reaction Gibbs Energy is, (∆G ) = (∆G )0 + RT ln ⎡Π(a )ν i ⎤
N

R R ⎢ i ⎥
⎣i =1 ⎦
We can then also write this as,
N
(∆G )R = (∆G ) + RT ln (Q )
0
R
Q = Π(a i )
i =1
νi
If Reactants and Products are in equilibrium then (∆G )R = 0.

And hence,
⎡N ν ⎤
(∆G )
0
R = − RT ln (K ) K = ⎢Π(a i ) i ⎥
⎣i =1 ⎦ equilibrium
Equilibrium Constant
August 22, 2006 12
Equilibrium Constant 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 For an ideal gas
⎪
ai = ⎨
⎪ fi For a real gas
⎪ P0
⎩
⎡N νi ⎤
∴ (∆G ) = − RT ln (K ) K = ⎢Π(a i ) ⎥
0
R
⎡ N ⎛ (f i ) ⎞ ν i ⎤
= ⎢Π⎜⎜ 0 ⎟⎟ ⎥
eq
For a real gas
⎛ (Pi )eq ⎞ ⎢⎣i =1⎝ P ⎠ ⎥⎦
νi
N
K = Π⎜⎜ 0 ⎟⎟ For an ideal gas
i =1
⎝ P ⎠
August 22, 2006 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 )

(∆G )0
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 15
implication in the next few slides.
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: G = nA µA + nB µB
substitute
• In the beginning of reaction,
ξ = 0 and n A = 1 mole. ⎧n A = 1 − ξ
⎨
August 22, 2006
ξ : Extent of reaction ⎩ nB = ξ 16
Gibbs energy of the reaction mixture becomes:
G = (1 − ξ ) µ A + ξ µ B
We now need an expression for µ A and µ B .
⎛ PA ⎞
µ A = µ + RT ln⎜ 0 ⎟
0
A yA : Mole Fraction
⎝P ⎠
⎛ yA P ⎞
= µ A + RT ln⎜ 0 ⎟
0
P : Total Pressure at equilibrium
⎝ P ⎠
⎛ P⎞ ⎛ P⎞
= µ + RT ln(y A ) + RT ln⎜ 0 ⎟ = µ A + RT ln (1 − ξ ) + RT ln⎜ 0 ⎟
0
A
0
⎝P ⎠ ⎝P ⎠
⎛ P⎞
Similarly, µ B = µ + RT ln (ξ ) + RT ln⎜ 0 ⎟
0
B
⎝P ⎠
We now substitute µ A and µ B in the expression for G.
August 22, 2006 17
We have: G = (1 − ξ ) µ A + ξ µ B
⎛ P⎞
µ A = µ + RT ln(1 − ξ ) + RT ln⎜ 0 ⎟
0
A
⎝P ⎠
⎛ P⎞
µ B = µ + RT ln (ξ ) + RT ln⎜ 0 ⎟
0
B
⎝P ⎠
( )
⎛ P⎞
∴ G = µ A − ξ µ A − µ B + RT ln⎜ 0 ⎟ + RT[(1 − ξ ) ln(1 − ξ ) + ξ lnξ ]
0 0 0
⎝P ⎠
Gibbs Free Energy of mixing
mole of A with ξ mole of B.
(1− ξ )
(∆G ) 0
mixing
0
A ( 0
A
⎛ P⎞
0
B )
⇒ G = µ − ξ µ − µ + RT ln⎜ 0 ⎟ + ∆G 0 ( )
mixing
August 22, 2006 ⎝P ⎠ 18
( ⎛ P⎞
) ( )
Analysis:
G = µ − ξ µ − µ + RT ln⎜ 0 ⎟ + ∆G 0
0
A
0
A
0
B mixing
⎝P ⎠
(∆G )0
mixing = RT[(1 − ξ ) ln (1 − ξ ) + ξ lnξ ]
= 0, for ξ = 1 or 0.
⎛ P⎞
G = µ + RT ln⎜ 0 ⎟ for ξ = 0.
0
A
⎝P ⎠
⎛ P⎞
G = µ + RT ln⎜ 0 ⎟ for ξ = 1.
0
B
⎝P ⎠
August 22, 2006 19
In the next slide, we see a plot of G as a function of ξ.

Analysis:
⎛ P⎞
µ 0A + RT ln⎜ 0 ⎟
⎝P ⎠
↑ ⎛ P⎞
µ 0B + RT ln⎜ 0 ⎟
G ⎝P ⎠
A B
0 ξ→ ξ eq 1
Mixing term is responsible for the minimum of Gibbs energy.
( )
The minimum occurs, even as 1− ξ 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 ⎡ ∂ (∆G/T ) ⎤
⎜⎜ ⎢ ⎥ ⎟⎟ = − 2 ⎢ ∂ (1/T ) ⎥ = ∆H
⎝ ∂T ⎣ T ⎦ ⎠ P T ⎣ ⎦P
We can specialize this equation for chemical equilibrium, by
substituting equilibrium values of relevant quantities.
(∆G ) 0
R = −RT ln (K ) Enthalpy of reaction
in the standard state
⎛ ∂ ⎞ (∆H ) 0
⎛ ∂ ⎞
ln(K )⎟⎟ = −
(∆H )R
0
⎜ ln (K ) ⎟ = R
⎜⎜
⎝ ∂T ⎝ ∂ (1 / T )
2
⎠P RT ⎠P R
August 22, 2006

van’t Hoff Equation
21
⎛ ∂
( ) ⎞
=
(∆H )R
0
van’t Hoff Equation: ⎜ ln K ⎟

⎝ ∂T ⎠P RT 2
K as a function of T approximations
Case-I: Enthalpy of reaction is independent of Temperature. We
can then integrate the van’t Hoff equation as follows:
K2
(∆H ) dT
0 T2
⎛ K 2 ⎞ (∆H ) [T2 − T1 ]
0
∫ d ln(K ) = R ∫ T 2 ⇒ ln⎜⎜ ⎟⎟ =
R R
K1 T1 ⎝ K1 ⎠ R T1 T2
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 Chatelier’s 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, ξ.
Consider a gas phase reaction of type: A → 2B

n 0 (A ) : Initial amount of A, at a given P and T.
ξ / : Equilibrium Extent of Reaction.
n 0 (A ) − ξ / : 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.
/
ξ
ξ≡ : Equilibrium Extent of Reaction.
n 0 (A )
1 − ξ : Amount of A at equilibrium.
August 22, 2006 24

Computations: A → 2B
• Initial Amount 1 0
Total is
• Equilibrium Amount 1− ξ 2ξ 1+ ξ
• Equilibrium 1− ξ 2ξ
Mole Fraction
1+ ξ 1+ ξ
For an ideal gas, we will use,
⎛ (Pi )eq ⎞
νi Remember
N
K = Π⎜⎜ 0 ⎟⎟ Exponent ν i is positive
⎝ P ⎠
i =1 for product and negative
for reactants.
August 22, 2006
Equilibrium partial pressure, (Pi )eq = Equilibrium mole fraction 25
TIMES total Pressure, P

⎛ (Pi )eq ⎞ A → 2B
νi
Ref: N
K = Π⎜⎜ 0 ⎟⎟
i =1
⎝ P ⎠
1− ξ
(P /P ) [y (P/P )] 0 2 yA =
0 2
∴K = = B B 1+ ξ
(P /P ) [y (P/P )]
A
0
A
0
2ξ
yB =
On substitution and simplification, 1+ ξ
P : Total pressure
P 4ξ 2 at equilibrium
K= 0
P 1− ξ2
August 22, 2006
This is the required relation 26
Between K and ξ.
Determination of Extent of Reaction, ξ
Extent of reaction is easily obtained by measuring the density of
the partially dissociated gas.
Total amount
V:
Initial Volume in the begining 1
1
Total amount
2 V :Equilibrium Volume at equilibrium 1+ ξ
1+ ξ 1 1 V1
Relation-1: = =
V2 V1 1 + ξ V2
Extent of reaction
Density at Density in See slide no. 25
(dimensionless)
Equilibrium the begining
August 22, 2006 27
Relation-2: Start with mass m of ideal gas A.
m RT M : Molar mass of A
Initial Volume, V1 = 1
M1 P
Equilibrium Volume m RT M 2 = M A y A + M B y B
at constant P and T,
V2 =
M2 P
V1 M 2 Average molar mass of the
∴ = Partially dissociated gas A,
V2 M1 defined by
1 V1 1 M1
Relation-1: = Hence: =
1 + ξ V2 1+ ξ M2
Thus, for an ideal gas, we can compute the extent of reaction, ξ,
August 22, 2006
from the molar mass of reactants and products, 28
ξ
use this to compute the equilibrium constant, K.
Amrendra Vijay
Lecture 09
August 25, 2006 1
⎛ ∂G ⎞
(∆G )R ≡ ⎜⎜ ⎟⎟
⎝ ∂ξ ⎠ T, P
A Clarification
N
Recall:
∑ν ⎡N ν ⎤

i Ai = 0 (∆G )R = (∆G )
0
R + RT ln ⎢Π(a i ) i ⎥
i =1 ⎣i =1 ⎦
(∆G )R = (∆G ) + RT ln(Q )
N
Q = Π(a i ) i : Reaction Quotient
0 ν
R i =1
⎡N ν ⎤
(∆G ) 0
R = − RT ln (K ) K = ⎢Π(a i ) i ⎥ : Equilibrium Constant
Observation: Equilibrium constant will depend upon the
Stoichiometric numbers, i ν.
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
ν
numbers, i uniquely. Next, we compute the reaction Gibbs
energy and other quantities.
August 25, 2006 2

Equilibrium Constant as a function of Temperature
Recall: The Gibbs-Helmholtz Equation
⎛ ∂ ⎡ ∆G ⎤ ⎞ ∆H ⎡ ∂ (∆G/T ) ⎤
⎜⎜ ⎢ ⎥ ⎟⎟ = − 2 ⎢ ∂ (1/T ) ⎥ = ∆H
⎝ ∂T ⎣ T ⎦ ⎠ P T ⎣ ⎦P
We can specialize this equation for chemical equilibrium, by
substituting equilibrium values of relevant quantities.
(∆G ) 0
R = −RT ln (K ) Enthalpy of reaction
in the standard state
⎛ ∂ ⎞ (∆H ) 0
⎛ ∂ ⎞
ln(K )⎟⎟ = −
(∆H )R
0
⎜ ln (K ) ⎟ = R
⎜⎜
⎝ ∂T ⎝ ∂ (1 / T )
2
⎠P RT ⎠P R
August 25, 2006

van’t Hoff Equation
3
⎛ ∂
( ) ⎞
=
(∆H )R
0
van’t Hoff Equation: ⎜ ln K ⎟

⎝ ∂T ⎠P RT 2
K as a function of T approximations
Case-I: Enthalpy of reaction is independent of Temperature. We
can then integrate the van’t Hoff equation as follows:
K2
(∆H ) dT
0 T2
⎛ K 2 ⎞ (∆H ) [T2 − T1 ]
0
∫ d ln(K ) = R ∫ T 2 ⇒ ln⎜⎜ ⎟⎟ =
R R
K1 T1 ⎝ K1 ⎠ R T1 T2
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 Chatelier’s Principle.
August 25, 2006 4

Here, we will establish an explicit computational relation
between equilibrium constant, K, of a reaction and the extent of
reaction, ξ.
Consider a gas phase reaction of type: A → 2B

n 0 (A ) : Initial amount of A, at a given P and T.
ξ / : Equilibrium Extent of Reaction.
n 0 (A ) − ξ / : 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 5
Ref: Alberty and Silbey pp. 150-152.

Definitions: A → 2B
1 : Initial amount of A, at a given P and T.
/
ξ
ξ≡ : Equilibrium Extent of Reaction.
n 0 (A )
1 − ξ : Amount of A at equilibrium.
August 25, 2006 6

Computations: A → 2B
• Initial Amount 1 0
Total is
• Equilibrium Amount 1− ξ 2ξ 1+ ξ
• Equilibrium 1− ξ 2ξ
Mole Fraction
1+ ξ 1+ ξ
For an ideal gas, we will use,
⎛ (Pi )eq ⎞
νi Remember
N
K = Π⎜⎜ 0 ⎟⎟ Exponent ν i is positive
⎝ P ⎠
i =1 for product and negative
for reactants.
August 25, 2006
Equilibrium partial pressure, (Pi )eq = Equilibrium mole fraction 7
TIMES total Pressure, P

⎛ (Pi )eq ⎞ A → 2B
νi
Ref: N
K = Π⎜⎜ 0 ⎟⎟
i =1
⎝ P ⎠
1− ξ
(P /P ) [y (P/P )] 0 2 yA =
0 2
∴K = = B B 1+ ξ
(P /P ) [y (P/P )]
A
0
A
0
2ξ
yB =
On substitution and simplification, 1+ ξ
P : Total pressure
P 4ξ 2 at equilibrium
K= 0
P 1− ξ2
August 25, 2006
This is the required relation 8
Between K and ξ.
Extent of reaction is easily obtained by measuring the density of
the partially dissociated gas.
Total amount
V:
Initial Volume in the begining 1
1
Total amount
2 V :Equilibrium Volume at equilibrium 1+ ξ
1+ ξ 1 1 V1
Relation-1: = ∴ =
V2 V1 1 + ξ V2
Extent of reaction
Density at Density in
(dimensionless)
Equilibrium the begining
August 25, 2006 9
Relation-2: Start with mass m of ideal gas A.
m RT M : Molar mass of A
Initial Volume, V1 = 1
M1 P
Equilibrium Volume m RT M 2 = M A y A + M B y B
at constant P and T,
V2 =
M2 P
V1 M 2 Average molar mass of the
∴ = Partially dissociated gas A.
V2 M1
1 V1 1 M1
Q Relation-1 was = Hence: =
1 + ξ V2 1+ ξ M2
Thus, for an ideal gas, we can compute the extent of reaction, ξ,
August 25, 2006
from the molar mass of reactants and products, 10
ξ
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
Chemical Equilibrium Recap …
To study chemical equilibrium, we introduced the concept of
the Extent of reaction ξ and defined the reaction Gibbs energy
as the derivative of Gibbs energy as a function of ξ
at
constant Temperature and Pressure. ⎛ ∂G ⎞ N
(∆G )R ≡ ⎜⎜ ⎟⎟ = ∑ µ i ν i
⎝ ∂ξ ⎠ T, P i =1
The reaction Gibbs energy is zero at equilibrium and hence we
obtained: N This is a general condition and
∑
i =1
ν i µ ieq = 0
applies to all chemical equilibria.
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 non-expansive work
Recall the First Law: dU = δq − PdV
Work due to expansion
Work other than Pressure-Volume work is called the non-
expansive work. In the presence of non-expansive work, the
first law modifies as follows:
dU = δq − PdV + non - expansive works
For example, when a small charge dQ is moved through an
electric potential difference φ, the work done on the charge is:
(dw )electrical = φ dQ
And, the first Law becomes: dU = δq − PdV + φ dQ
The term φ dQ then carries over to all other thermodynamic
August 25, 2006 quantities, like Gibbs energy and so forth. 13
N
dG = −SdT + VdP + ∑ µ i dn i
i =1
Gibbs Energy in the presence of electrical work

Work done on the charge dQ, due to potential difference, φ,
(dw )electrical = φ 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
N
⇒ (dw )electrical = ∑ z i F φ dn i
( )(
= 6.022 × 10 23 mol −1 1.602 ×10 −19 C )
i =1 = 96485 C mol −1
So, the Gibbs energy modifies to
[ ]
N N N
dG = −SdT + VdP + ∑ µ i dn i + ∑ Zi F φ dn i ⇒ dG = −SdT + VdP + ∑ (µ i )φ =0 + Zi F φ dn i
i =1 i =1 i =1
with, µ i = (µ i )φ =0 + Zi F φ
N
⇒ dG = −SdT + VdP + ∑ µ i dn i
August 25, 2006 14
i =1
N
dG = −SdT + VdP + ∑ µ i dn i with, µ i = (µ i )φ =0 + Zi F φ
Contd … i =1
Gibbs Energy in the presence of electrical work

At constant Pressure and Temperature, the reaction Gibbs
N
energy is then, (dG ) = µ dn
T, P ∑ i i µ = (µ ) + Z F φ i i φ =0 i
i =1
As we have done earlier, we introduce the concept of the Extent

of Reaction ξ and define Reaction Gibbs Energy as the
derivative of Gibbs energy, G with respect to ξ at constant
Pressure and Temperature.
⎛ ∂G ⎞ N
(∆G )R = ⎜⎜ ⎟⎟ = ∑ ν i µ i ν i : Stoichiometric Number
⎝ ∂ξ ⎠ T, P i =1
⎛ ∂G ⎞
At the reaction equilibrium, (∆G )R = ⎜⎜ ⎟⎟ = 0
⎝ ∂ξ ⎠ T, P
[ ]
N
And hence,
⇒ ∑ν i (µ i )φ =0 + Zi F φ = 0
N

∑ν
i =1
i µi = 0
August 25, 2006 i =1 15
This is the general condition, we will use now.
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 Reduction/oxidation on the right/left.
Anode Cathode
-ve +ve
spontaneous Reaction
Rd1 → Ox1 + ne − Rd1 → Ox1 + ne −

Oxidation Reduction
Zn(s ) → Zn 2+ + 2e − Cu 2+ (aq ) + 2e − → Cu (s )
(aq ) + Zn(s ) → Cu (s ) + Zn (aq )

August 25, 2006 17
2+ 2+
Cu
Galvanic Cell operation
Potentiometer
V: applied potential
difference.
V V V
(− ) (− ) (+ ) (− ) (+ )
(+ )
V<E V=E V>E

The cell discharges Current through the Cell reaction in the
spontaneously. Cell is zero. reverse direction.
Galvanic Cell. Cell at Equilibrium. Electrolytic Cell.
August 25, 2006 18
E: Electromotive force of the Galvanic Cell

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:
2AgCl(s ) + 2e − (Pt Right ) → 2Ag(s ) + 2Cl − (m )

Oxidation occurs on the left electrode:
H 2 (g ) = 2H + (m ) + 2e − (Pt Left )
So, the cell reaction is:
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:
→

H 2 (g ) + 2AgCl(s ) + 2e − (Pt Right )

2H + (m ) + 2Ag(s ) + 2Cl − (m ) + 2e − (Pt Left )
∑ν [(µ ) + Z F φ] = 0
N
We now use the equilibrium condition: i i φ =0 i
i =1
[12µ4(H4+ )4+4
2µ (Ag ) + 2µ (Cl − ) − 2Fφ Left ] − [µ (H 2 ) + 2µ (AgCl) − 2Fφ Right ] = 0
44 424444444 3 144444244444 3
Product Reactant
or, ( ) ( )
− 2F(φ Right − φ Left ) = 2µ H + + 2µ (Ag ) + 2µ Cl − − µ (H 2 ) − 2µ (AgCl)
or, ( ) ( )
− 2FE = 2µ H + + 2µ (Ag ) + 2µ Cl − − µ (H 2 ) − 2µ (AgCl)
µ (∗) is the chemical potential

where, E = (φ Right − φ Left )
August 25, 2006 20
Electromotive force (EMF) of the Cell

Thus, for the reaction H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
we have
( ) ( )
− 2FE = 2µ H + + 2µ Cl − + 2µ (Ag ) − µ (H 2 ) − 2µ (AgCl)
Chemical Potential
So, in general: EMF of the Cell

N
− nFE = ∑ ν i µ i or, − nFE = (∆G )R
i =1
Reaction Gibbs Energy, for the

Cell Reaction as written above.
No of electrons
August 25, 2006
transferred 21
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction observations …

Reference: Pt Left | H 2 (g ) | HCl(m ) | AgCl(s ) | Ag(s ) | Pt Right

N
− nFE = ∑ ν i µ i = (∆G )R
i =1
• 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
N
− nFE = ∑ ν i µ i = (∆G )R
i =1
Nernst Equation
Recall the Chemical Potential: µ i = µ i0 + RT ln (a i )
So, we have
[ ]
N N N N
− nFE = ∑ ν i µ i = ∑ ν i µ + RT ln (a i ) = ∑ ν i µ + RT ∑ ν i ln(a i )
0
i
0
i
i =1 i =1 i =1 i =1
⎛ ν ⎞
= −nFE + RT ln⎜ Π[ai ] i ⎟
N
0
E 0 : Standard EMF
⎝ i =1 ⎠ of the Cell.
RT ⎛ N ν ⎞
∴E = E − ln⎜ Π[a i ] i ⎟ Nernst Equation
0
nF ⎝ i =1 ⎠
August 25, 2006 23

RT ⎛ N ν ⎞
E=E − ln⎜ Π[a i ] i ⎟
0
nF ⎝ i =1 ⎠
Nernst Equation observations
At 25 degree Centigrade, the Nernst equation becomes:
E=E 0
−
(8.314JK mol )(298.15K ) ⎛
−1 −1
ln⎜ Π[a ]
N
νi ⎞
⎟
n (96485 C mol ) -1 i
⎝ i =1 ⎠
or, E = E 0
−
(0.02569 V ) ⎛ N⎞
ln Π[a ]
νEquilibrium constant
⎜ i =1 i ⎟ i
for the cell reaction
n ⎝ ⎠
RT
At equilibrium, E=0 and then, 0 = E −
0
ln K
nF
n F E 0 / RT
And this implies:
K=e
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 1
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:
2AgCl(s ) + 2e − (Pt Right ) → 2Ag(s ) + 2Cl − (m )

Oxidation occurs on the left electrode:
H 2 (g ) = 2H + (m ) + 2e − (Pt Left )
So, the cell reaction is:
H 2 (g ) + 2AgCl(s ) + 2e − (Pt Right ) →

August 28, 2006
2H + (m ) + 2Ag(s ) + 2Cl − (m ) + 2e − (Pt Left ) 2
The cell reaction was:
→

H 2 (g ) + 2AgCl(s ) + 2e − (Pt Right )

2H + (m ) + 2Ag(s ) + 2Cl − (m ) + 2e − (Pt Left )
∑ν [(µ ) + Z F φ] = 0
N
We now use the equilibrium condition: i i φ =0 i
i =1
[12µ4(H4+ )4+4
2µ (Ag ) + 2µ (Cl − ) − 2Fφ Left ] − [µ (H 2 ) + 2µ (AgCl) − 2Fφ Right ] = 0
44 424444444 3 144444244444 3
Product Reactant
or, ( ) ( )
− 2F(φ Right − φ Left ) = 2µ H + + 2µ (Ag ) + 2µ Cl − − µ (H 2 ) − 2µ (AgCl)
or, ( ) ( )
− 2FE = 2µ H + + 2µ (Ag ) + 2µ Cl − − µ (H 2 ) − 2µ (AgCl)
µ (∗) is the chemical potential

August 28, 2006 3
Electromotive force (EMF) of the Cell

Thus, for the reaction H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
we have
( ) ( )
− 2FE = 2µ H + + 2µ Cl − + 2µ (Ag ) − µ (H 2 ) − 2µ (AgCl)
Chemical Potential
So, in general: EMF of the Cell

N
− nFE = ∑ ν i µ i or, − nFE = (∆G )R
i =1
Reaction Gibbs Energy, for the

Cell Reaction as written above.
No of electrons
August 28, 2006
transferred 4
H 2 (g ) + 2AgCl(s ) = 2HCl(m ) + 2Ag(s )
Cell Reaction observations …

Reference: Pt Left | H 2 (g ) | HCl(m ) | AgCl(s ) | Ag(s ) | Pt Right

N
− nFE = ∑ ν i µ i = (∆G )R
i =1
• 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 5
N
− nFE = ∑ ν i µ i = (∆G )R
i =1
Nernst Equation
Recall the Chemical Potential: µ i = µ i0 + RT ln (a i )
So, we have
[ ]
N N N N
− nFE = ∑ ν i µ i = ∑ ν i µ + RT ln (a i ) = ∑ ν i µ + RT ∑ ν i ln(a i )
0
i
0
i
i =1 i =1 i =1 i =1
⎛ ν ⎞
= −nFE + RT ln⎜ Π[ai ] i ⎟
N
0
E 0 : Standard EMF
⎝ i =1 ⎠ of the Cell.
RT ⎛ N ν ⎞
∴E = E − ln⎜ Π[a i ] i ⎟ Nernst Equation
0
nF ⎝ i =1 ⎠
August 28, 2006 6

RT ⎛ N ν ⎞
E=E − ln⎜ Π[a i ] i ⎟
0
nF ⎝ i =1 ⎠
Nernst Equation observations
At 25 degree Centigrade, the Nernst equation becomes:
E=E 0
−
(8.314JK mol )(298.15K ) ⎛
−1 −1
ln⎜ Π[a ]
N
νi ⎞
⎟
n (96485 C mol ) -1 i
⎝ i =1 ⎠
or, E = E 0
−
(0.02569 V ) ⎛ N⎞
ln Π[a ]
νEquilibrium constant
⎜ i =1 i ⎟ i
for the cell reaction
n ⎝ ⎠
RT
At equilibrium, E=0 and then, 0 = E −
0
ln K
nF
n F E 0 / RT
And this implies:
K=e
So, the measurement of EMF will allow us to compute and
hence discuss various thermodynamics properties.
August 28, 2006 7
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 8

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 9
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.
α − phase β − phase
Tα , µ α , Vα Tβ , µ β , Vβ
August 28, 2006 10
Example-1: Consider a system with two phases, α and β, and
the whole system is isolated. Now, an infinitesimal amount of
heat, δq is transferred from phase α to phase β such that the
volumes of the phases do not change.
α − phase − δq + δq β − phase
If the system is to be at equilibrium then the total entropy must

not change --- that is, the decrease in entropy of α phase is
balanced by the increase in entropy of β phase.
August 28, 2006

dSα + dSβ = 0 11
dSα + dSβ = 0 dU = δq + PdV = TdS + PdV
Example-1 contd…
As the volume of individual phase does not change, dVα = 0.
Then, from the first Law:
dU α = Tα dSα dU β = Tα dSβ
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 α + dU β = 0 ⇒ Tα dSα + Tβ dSβ = 0
dSα = −dSβ
Conclusion: Temperatures of the two
Tα = Tβ
phases must be the same at equilibrium.
August 28, 2006 12

dA = −SdT − PdV
Example-2: Let the total system be at constant temperature and
reduce the volume of α phase by an infinitesimal amount dV
and increase the volume of β phase by the same amount.
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 α + dA β = 0 ⇒ − Pα dV + Pβ dV = 0 ⇒ Pα = Pβ
Conclusion: Pressure of the two phases
must be the same at equilibrium.
August 28, 2006 13
dG = ∑ µ i dn i
i

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 α phase to the β 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 α + dG β = 0 ⇒ −µ iα dn i + µ iβ dn i = 0 ⇒ µ iα = µ iβ
Conclusion: The chemical potential of a species

August 28, 2006
must be the same in two phases, 14
that are in equilibrium.
Example-3 continued ….
Suppose phases α and β are not in equilibrium and we transfer
a small amount dn i of species i from α phase to β 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 α + dG β < 0 ⇒ −µ iα dn i + µ iβ dn i < 0 ⇒ µ iα > µ iβ
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:
⎛ ∂µ ⎞ Molar Entropy is
⎜ ⎟ = −Sm ⇒ ∆µ = −Sm ∆T Sm : Positive for all
⎝ ∂T ⎠ P substances.
∴ as the temperature is raised, the chemical potential decreases.

It is also known, Sm (solid ) < Sm (liquid ) < Sm (gas ). Hence,
Gas
↑
Solid
µ
Solid Liquid Liquid
State State
August 28, 2006 Gaseous State 16
T→
⎛ ∂µ ⎞
⎜ ⎟ = −Sm ⇒ ∆µ = −Sm ∆T
⎝ ∂T ⎠ P
Phase Change
We have thus seen, the slope of µ .vs. T 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: transition temperature
2: vapor pressure
↑ Solid 3: triple point
4: critical point
P
Liquid
2 phase boundary
3
Vapor
August 28, 2006

1 T→ 4 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 continued …
Critical Point: Consider a liquid → 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 α and β in )
equilibrium --- that is, the pressure, temperature and chemical
potential of the two phases must be the same.
Tα , µ α , Vα Tβ , µ β , Vβ
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 it’s called The Clapeyron Equation.
August 28, 2006 21
dG = −SdT + VdP
The Clapeyron Equation derivation
For a change of pressure and temperature along the coexistence
curve, we have the following condition:
dµ α = dµ β ↑
P α phase µ α = µβ
⇒ − Sα dT + Vα dP = − Sβ dT + Vβ dP β phase
Molar Molar T→
entropy volume
Molar
dP Sβ − Sα ∆ S ∆H
⇒ = = = enthalpy
dT Vβ − Vα ∆V T∆V
August 28, 2006 22
dP ∆H
=
dT T∆V
The Clausius – Clapeyron Equation
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.
dP (∆H )vaporization = (∆H )vaporization = P (∆H )

= (∆H )vap. 2
= dP 1 dT
dT T (Vgas − Vliquid ) TVgas RT 2
vaporization ⇒
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 ) :
P2 (∆H )vap. ⎡1 1 ⎤
ln = ⎢ − ⎥
P1 R ⎣ T1 T2 ⎦
August 28, 2006 23
Amrendra Vijay
Lecture 11
August 29, 2006 1
Phase Diagram an example
Consider a gas, with P,V and T as thermodynamic variables.
1: transition temperature
2: vapor pressure
↑ Solid 3: triple point
4: critical point
P
Liquid
2 phase boundary
3
Vapor
August 29, 2006

1 T→ 4 2
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 3

Definition continued …
Critical Point: Consider a liquid → 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 4
Phase Rule
Phase rule expresses the following relation:
Number of Temperature Number of Number of

degrees of and Pressure Components Phases
freedom present in present in
system system
August 29, 2006 In the following, we will define F, C and P. 5

Number of Phases
Definition of Phase: Form of matter, that is uniform in chemical
composition as well as physical state.
{
Examples: • A gas
P=1

• A crystal
• Two totally miscible liquids
• A solution of NaCl in water
{ P=2
• An alloy of two metals, if the
metals are immiscible
CaCO (s ) → CaO(s ) + CO (g ) { P=3

3 2
August 29, 2006 6

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.
Equality holds if
No. of components ≤ No. of constituents there is no
chemical reaction.
Examples: • Pure Water: C=1, as we need only the species

H 2 O to specify its composition.
August 29, 2006 CaCO 3 (s ) → CaO(s ) + CO 2 (g ) C=2 7

Degrees of Freedom
Definition: Number of intensive variables that can be

changed independently without disturbing the
number of phases in equilibrium.
August 29, 2006 8

Phase Diagram one component system, C=1
Example: QF = 2 + C − P ⇒ F = 3− P
↑ phase ε Four phases in

P phase γ equilibrium, F=-1.
phase α (Impossible!)
phase β
one phase phase δ
(F=2)
Three phases
in equilibrium
Two phases (F=0)
in equilibrium (F=1)
August 29, 2006 9
T→
The Clapeyron Equation preliminary
(
Consider a one component system with two phases α and β in )
equilibrium --- that is, the pressure, temperature and chemical
potential of the two phases must be the same.
T, µ, P T, µ, 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
The Clapeyron Equation derivation
For a change of pressure and temperature along the coexistence
curve, we have the following condition:
dµ α = dµ β ↑
P α phase µ α = µβ
⇒ − Sα dT + Vα dP = − Sβ dT + Vβ dP β phase
Molar Molar T→
entropy volume coexistence
curve
Molar
dP Sβ − Sα
∆S ∆H
⇒ = = = enthalpy
dT Vβ − Vα ∆V T∆V
August 29, 2006 11
Read: Atkins, pp. 145
For solid-liquid boundary,
dP
=
(∆H )melting
dT T (∆V )melting
The Clapeyron Equation 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
( 1 1 ) (
Clapeyron Eq. from P , T to P , T , we will obtain:
2 2 )
P2
(∆H ) T2
dT (∆H ) ⎛ T2 ⎞
∫ dP = (∆V ) ∫T T ln⎜⎜ ⎟⎟
melting
melting
⇒ P2 =P +
P1 melting 1
(∆V )
1
melting ⎝ T1 ⎠
If T1 and T2 are close then the logarithm can be approximated as,

⎛ T2 ⎞ ⎛ T2 − T1 ⎞ T2 − T1
ln⎜⎜ ⎟⎟ = ln⎜⎜1 + ⎟⎟ ≈
⎝ T1 ⎠ T1 ⎠ T1
August 29, 2006 12
⎝
dP ∆H
=
dT T∆V
The Clausius – Clapeyron Equation
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.
dP (∆H )vaporization = (∆H )vaporization = P (∆H )

= (∆H )vap. 2
= dP 1 dT
dT T (Vgas − Vliquid ) TVgas RT 2
vaporization ⇒
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 ) :
P2 (∆H )vap. ⎡1 1 ⎤
ln = ⎢ − ⎥
P1 R ⎣ T1 T2 ⎦
August 29, 2006 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 14
Read: Alberty and Silbey, pp. 218-219.

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

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Thermodynamics and Kinetics

August 04, 2006 2

August 04, 2006 3

System a sample of human population etc.

For molecular applications

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

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

August 04, 2006 5

 Example: A sample of gas enclosed in a

August 04, 2006 6

August 04, 2006 7

f (P, V , T ) = 0 (a function of thermodynamic variables)

 Example: For an ideal gas,

August 04, 2006 8

1. Open system: Surroundings Surroundings

2. Closed system: Surroundings Surroundings

3. Isolated system: Surroundings Surroundings

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

 When the work is done by the system, the capacity

Disordered, random or Thermal motion Organized motion

 Heat is the transfer of energy between the system and the

 Work is the transfer of energy that between the system and

August 04, 2006 12

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

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

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

• For an isolated system, q = 0 and w = 0. Hence, the change in

• By convention, if w > 0 and q > 0 we say the energy is

 If the external pressure is zero, then w = 0. That

Heat Capacity at constant volume

August 04, 2006 19

Heat Capacity continued…

 Heat capacity is an extensive quantity. To make it an

 A large Heat Capacity implies: if we heat a system, the

August 04, 2006 20

 For a perfect gas, the internal pressure is zero.

August 04, 2006 21

 What if we consider internal the internal energy of an ideal gas

 Divide by dT and impose the condition of constant pressure,

 For a perfect gas, the internal pressure is zero and hence,

C P is the Heat Capacity at constant pressure.

August 04, 2006 24

 At constant temperature, dT=0 and hence,

 Thus, we can write:

August 04, 2006 25

Enthalpy as a function of temperature

August 04, 2006 26

 For a perfect gas, the internal pressure is zero and

August 04, 2006 28

if F is not a state function. Subscript denotes the

August 07, 2006 3

August 07, 2006 Surroundings 4

For a reversible process, (Pext − Pgas ) ≡ ∆P → 0

 We will get a clear picture of these thermodynamic

 Before we introduce Entropy, we will consider a

 Remember: (a) For adiabatic process, ∆q = 0

 For compression, for example, V2 < V1 , ⇒ w rev > 0. The

 Consider the process to be adiabatic;

 Then, the first law says,

 For an ideal gas, P = n R T/V, and hence

 From the first law then, we have,

(∆w rev )D = − ∫V P1 dV = −P1 (V2 − V1 ) V→

• Change in energy : (∆U )Total = ∫ C V (T ) dT + ∫ C V (T ) dT

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

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

Example: A sample of gas enclosed in a

Example: For an ideal gas,

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

When the work is done by the system, the capacity

Heat is the transfer of energy between the system and the

Work is the transfer of energy that between the system and

If the external pressure is zero, then w = 0. That

Heat capacity is an extensive quantity. To make it an

A large Heat Capacity implies: if we heat a system, the

For a perfect gas, the internal pressure is zero.

What if we consider internal the internal energy of an ideal gas

Divide by dT and impose the condition of constant pressure,

For a perfect gas, the internal pressure is zero and hence,

At constant temperature, dT=0 and hence,

Thus, we can write:

For a perfect gas, the internal pressure is zero and

We will get a clear picture of these thermodynamic

Before we introduce Entropy, we will consider a

Remember: (a) For adiabatic process, ∆q = 0

For compression, for example, V2 < V1 , ⇒ w rev > 0. The

Consider the process to be adiabatic;

Then, the first law says,

For an ideal gas, P = n R T/V, and hence

From the first law then, we have,

For a fixed amount of Heat supply, a colder system would be

The Entropy of an isolated system increases in the course of a

Second Law: (dS)INT is never negative. More precisely,

Thus, the direction of heat flow is determined by the sign of

Second Law says: (dS)INT is never negative. More precisely,

Thus, the direction of heat flow is determined by the sign of

Definition: A Heat reservoir is a system so

Kelvin Statement: There exists no thermodynamic

Clausius Statement: There exists no thermodynamic

Similarly, If Clausius is false ⇒ Kelvin is also false.

Efficiency of an Engine: It is defined as,

We would face a violation of the Kelvin statement,

Corollary: All Carnot engines operating between two given

Since 0 ≤ η ≤ 1, the absolute temperature of any reservoir is

Clausius says: this is impossible unless we have, q total ≤ 0

If the cyclic transformation is reversible, we reverse it.

Hence, we finally obtain ∑ (q m / Tm ) = 0 for reversible cyclic

I or II are always internally at equilibrium, but they are not

Kelvin Statement: There exists no thermodynamic

Clausius Statement: There exists no thermodynamic

Corollary: All Carnot engines operating between two given

A relation between q and T: Recall, the efficiency was originally

Let q m be the amount of heat absorbed by the system during

And, we will recover the original theorem in the limit N → ∞

Clausius says: this is impossible unless we have, q total ≤ 0

If the cyclic transformation is reversible, we reverse it.

Hence, we finally obtain ∑ (q m / Tm ) = 0 for reversible cyclic

For reversible transformations, we have:

That is, the difference of Entropy, computed along two different

So, the change in Entropy:

Proof: • For reversible transformations,

And, assuming the internal energy being a function of volume

Using this, we can derive several important thermodynamic

Let x, y and z are quantities satisfying a functional relation,