MAXWELLS THERMODYNAMIC

RELATIONSHIPS AND THEIR APPLICATIONS

Submitted By
Sarvpreet Kaur
Associate Professor
Department of Physics
GCG-11, Chandigarh
James Clerk Maxwell (1831-1879)
Born in Edinburgh,
Scotland
Physicist well-known
for his work in
electromagnetism and
field theory
Also known for his
work in
thermodynamics and
kinetic theory of gases
http://en.wikipedia.org/wiki/James_Clerk
_Maxwell
Why Use Maxwell Relations?
Certain variables in
thermodynamics are hard to
measure experimentally
such as entropy
Some variables like
Pressure, Temperature are
easily measureable
Maxwell relations provide a
way to exchange variables
Maxwell relations derived by the method
based on Thermodynamic Potentials
Why are thermodynamic potentials useful
Thermodynamic potentials give the complete knowledge about any
thermodynamic system at equilibrium
e.g. U=U(T,V) does not give complete knowledge of the system
and
requires in addition
P=P(T,V) equation of state
U=U(T,V) and P=P(T,V) complete knowledge of equilibrium properties
However
U(T,V) is not a thermodynamic potential
We are going to show: U=U(S,V)
complete knowledge of equilibrium
properties
U(S,V): thermodynamic potential
The thermodynamic potential U=U(S,V)
Now Consider first law in differential notation
W d Q d dU =
inexact differentials
W d
Q d
expressed by exact differentials
PdV W d
TdS Q d
=
=
2
nd
law
PdV TdS dU =
Note: exact refers here to the
coordinate differentials dS and dV.
TdS and PdV are inexact
So dU is an exact potental.
By Legendre transformation
from (S,V)
to
(T,V): PdV TdS dU =
PdV SdT ) TS ( d =
PdV SdT ) TS U ( d =
F : =
Helmholtz free energy
(T,P):
PdV SdT dF = VdP ) PV ( d SdT + =
VdP SdT ) PV F ( d + = +
G : =
Gibbs free energy
TS H PV TS U PV F G = + = + =
( ) VdP TdS PV d dU + = +
( ) VdP PV d TdS dU + =
easy check:
( ) PdV VdP PdV VdP VdP PV d = + = +
Product
rule
( ) VdP TdS PV U d + = +
=:H (enthalpy)
H=H(S,P) is a thermodynamic potential
VdP TdS dH + =
Enthalpy
Using these exact differentials we derive maxwells relations .
VdP TdS dH + = Enthalpy
VdP SdT PV F d dG + = + = ) ( Function s Gibb'
PdV SdT TS U d dF = = ) ( Energy Free Helmholtz
PdV TdS dU = Energy Internal
Now dU, dF, dG and dH are exact differentials e.g
Maxwells Thermodynamic Relations
V S
S
P
V
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
V T
T
P
V
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
P S
S
V
P
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
P T
T
V
P
S
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
Deriving Maxwell Relations Using
thermodynamic Potentials
First, start with a known equation of
state such as that of internal energy
Next, take the total derivative of
with respect to the natural
variables. For example, the
natural of internal energy are
entropy and volume.
dV
V
U
dS
S
U
dU
S V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
Deriving Maxwell Relations Continued
T
S
U
V
=
|
.
|

\
|
c
c
P
V
U
S
=
|
.
|

\
|
c
c
Now that we have the total derivative with
respect to its natural variables, we can refer
back to the original equation of state and
define, in this example, T and P.
dV
V
U
dS
S
U
dU
S V
|
.
|

\
|
c
c
+
|
.
|

\
|
c
c
=
Deriving Maxwell Relations Continued
We must now take into account a
rule in partial derivatives
When taking the partial derivative
again, we can set both sides equal
and thus, we have derived a
Maxwell Relation
Similarily using dF,dG and dH other Maxwell
Relations are
Mnemonic Device for Obtaining Maxwell
Relations
T
V
P
S
Write T,V,S,P in a clockwise manner by Remembering the line
TV Special Programme..
Four relations are obtained by starting either from T or S Clockwise or anticlockwise
direction. A negative Sign must appear in the resulting equation
Using Maxwell Relations
Maxwell Relations can be derived from basic equations
of state, and by using Maxwell Relations, working
equations can be derived and used when dealing with
experimental data.
The Four Maxwell relations have a very wide range
of applications . They apply to all kind of substances
(solids,liquids,gases)under all type of conditions of
Pressure, volume and temperature. Before Discussing applications
We define some thermodynamic terms e.g
Application of Maxwells Relations
1. Cooling Produced By Adiabatic Expansion of Any Substance
i)
Specific Heat at Constant Volume
Specific Heat at Constant Pressure
ii)
p
P
T
U
C
|
.
|

\
|
c
c
=
v
v
|
.
|

\
|
c
c
=
T
U
C
iii) Pressure and Volume Coffecient of Expansion
1. Cooling Produced By Adiabatic Expansion of Any Substance
In adiabatic process entropy S remains constant. Therefore by considering
the Thermodynamic relation
V
S
S
p
V
T
|
.
|

\
|
c
c
=
|
.
|

\
|
c
c
v
mC
Tp
T
|
= A
We can prove
Most of the substances expand on heating , they have +ve beta value. Will be ve
i.e all the substances will cool down. A few substances like rubber have ve beta value.
They will get heat up..
T A
2. Adiabatic Compression of A Substance
By considering the Thermodynamic relation
p
S
S
V
p
T
|
.
|

\
|
c
c
=
|
|
.
|

\
|
c
c
p
C
TV
T
o
= A
We can prove
Above result shows that if is +ve, then adiabatic increase in pressure
causes the temprature to rise.
o
** Similarily using other maxwells equations we can explain the stretching
of wires and thin films
19
3. Change of internal energy with Volume,
Using the third Maxwells relation
T v
T v
s P
v T
u P
T P
v T
c c
| | | |
=
| |
c c
\ . \ .
c c
| | | |
=
| |
c c
\ . \ .
Since
20
For Vander Waals / real gases
This result helps to show that the internal energy of an ideal gas does not depend
upon specific volume. This is known as Joules Law.
RT b V
V
a
p = + ) )(
2
(
( )
V
V
a
T
V
U
A =
c
c
2
For Ideal Gas
Thus Vander Waals gas expands isothermally as its
internal energy increases.
21
Other relations for the specific heats are given below.
where | is the volume expansivity and o is the isothermal compressibility, defined as
4. C
p
C
v
= R for ideal gases.
22
The difference C
p
C
v
is equal to R for ideal gases and to zero for incom-pressible
substances (v = constant).
5. Variation of C
v
with specific volume.
For an ideal gas
5. Variation of C
v
of an ideal gas does not depend upon specific volume.
23
Therefore, the specific heat at constant volume of an ideal gas is independent of
specific volume.
For Vander Waals gas also it is independent of volume.
6. Change of state and clapeyrons equation
In ordinary phase transition of matter(solid phase to liquid phase,
liquid to vapour, and solid to vapour) take place under constant
Temperature and pressure. During the transition a certain amount of
heat, known as latent heat must be supplied to the substance for a change
Of phase. During this change temperature remains constant. Therefore
using maxwell relation
( ) ( )
V
T
p
T
V
S
c
c
=
c
c
have We heat, latent the L, U using =
( )
) (
i f
V V T
L
V
T
p

=
c
c
This equation is known as Clausius-Clapeyrons latent heat
Equation.
Thank You