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Original Title: Maxwells Relations Third Law

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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

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):

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.

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.

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

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

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.

CV

S

T

T V

S

Cp

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

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 .

S

S

dS

dT

dV

S

S

S V

dT

T p T V

V T T p

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

T V V

dS

CV

R

dT

dV

T

V

S CV lnT RlnV constant

and increasing volume.

Question 1:

Find the ratio of the isothermal and adiabatic compressibilities.

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