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Maxwells relations

Maxwell's relations are a set of equations


in thermodynamics which are derivable from
the symmetry of second derivatives and
from the definitions of the thermodynamic
potentials.
T
p

V S
S V
T
V

S
S
p

V T T V
S
V

T p
p T

James Clerk
Maxwell

The four most common Maxwell


relations are the equalities of the
second derivatives of each of the four
thermodynamic potentials, with
respect to their thermal natural
variable (temperature T; or entropy S)
and their mechanical natural variable
(pressure p; or volume V):

The potentials as functions of their


natural thermal and mechanical
variables are the internal energy U(S,
V), enthalpy H(S, P), Helmholtz free
energy F(T, V) and Gibbs free
energy G(T, P). The thermodynamic
square can be used as a mnemonic to
recall and derive these relations.

Flow chart showing the paths between the Maxwell relations.


P:pressure, T: temperature, V: volume, S: entropy, : coefficient of thermal
expansion, : compressibility, CV: heat capacity at constant volume, CP:heat capacity at constant
pressure.

How we get the equations?

Example 1:
The Maxwell relation based on G can be derived as follows.
G SdT Vdp

hence

G
S

T p

G
G
dG
dT

dp

T p
p T

and

G
V

2G 2G

hence we have following Maxwell relation:

S
V

p T T p

T
p

V S
S V

T
V

S
p

dF SdT pdV

S
p

V T T V

dG SdT VdP

S
V

dU TdS pdV
dH TdS Vdp

The Maxwells relations relate a partial differential that corresponds to


something that can be easily measured to a partial differential that
cannot.
V

T p

For example,
describe how the volume changes as the
temperature while keeping the pressure fixed.
This is related to a quantity called the isobaric expansivity and is a
quantity that can easily imagine being something one could measure in
a laboratory.
S

For
, this term is much more mysterious and it is not obvious how
a change of entropy with pressure at constant temperature could
actually be measured.

Heat capacities, CV and Cp:


CV
S

T
T V
S

Cp

Expansivities and compressibilities


1 V
p

V T p

isobaric expansivity

1 V
S

V T S

adiabatic expansivity

1 V
T

V p T

isothermal compressibility

1 V
S

V p S

adiabatic compressibility

Example 2:
Find expressions for
, and .

and

in terms of ,

Q
S
CV

T V
T V

Define and

Q
S
Cp

T p
T p
Q
S
Cp

T p
T p

Now,

S
S
S
C p

T p
p T
p T

Using the Maxwells relations,

V
2V
C p

T
2

p p

2 p
CV
V T
2

Example 3:
By considering = (, ), show that

C p CV VT 2p T .

Considering = , allows to write down as


S
S
dS
dT

dV

Differentiating this equation with respect to T at constant p,


S
S
S V

dT

T p T V
V T T p

The first two terms can be replaced by and respectively,


while use of a Maxwells relation and a partial differential identity,
S
p
p V

V T T V
V T T p

Hence,
C p CV

VT 2p
T

Example 4:
Find the entropy of 1 mole of ideal gas.
For one mole of ideal gas = . Consider the entropy as a
function of volume and temperature ,

= (, )
S
S
dS
dT

dV
T V
V T

CV
p
dT
dV
T
T V
R
p

The ideal gas for 1 mole, = ,

T V V

dS

CV
R
dT
dV
T
V

If is not a function of temperature, so


S CV lnT RlnV constant

The entropy of an ideal gas increases with increasing temperature


and increasing volume.

Question 1:
Find the ratio of the isothermal and adiabatic compressibilities.