SRI CHAITANYA EDUCATIONAL INSTITUTIONS, AP

RAMAN BHAVAN :: VISAKHAPATNAM

Thermodynamic relations
Gibbs Function and Helmholtz Function
Gibbs equation is
dU Tds PdV

The enthalpy H can be differentiated,

dH dU PdV VdP
Combining the two results in
dH TdS PdV
The coefficients T and v are partial derivative of h(s,P),

T
S P

V
s

Since V > 0, an isentropic increase in pressure will result in an increase in enthalpy.

Similarly, using the Gibbs function
G H TS

dG VdP SdT
Consequently,

V
P T

S
P

Note:
1. The decrease in Helmholtz function of a system sets an upper limit to the work done in any process
between two equilibrium states at the same temperature during which the system exchanges heat only
with a single reservoir at this temperature. Since the decrease in the Helmholtz potential represents the
potential to do work by the system, it is also a thermodynamic potential.
2. The decrease in Gibbs function of a system sets an upper limit to the work, exclusive of pdv work
in any process between two states at the same temperature and pressure, provided the system
exchanges heat only with a single reservoir at this temperature and that the surroundings are at a
constant pressure equal to that in the end states of the pressure.
The maximum work is done when the process is isothermal isobaric. Gibbs function is also called
Chemical Potential.
Maxwells relations:

 T
P

[From equation du Tds PdV ]
V s S v
T V

[From equation dH Tds VdP]
s P
P s
P S

[From equation dA Pdv SdT ]
T v V T
V
S

[From equation dG VdP SdT ]
T P P T
The internal energy
u = u(T,v)
For a simple compressible substance,

U
dv
V T

dU Cv dT

dS

Cv
1 U
dT

T
T V

P dv

Taking entropy as a function of temperature and volume,

Cv
S

T v T

Using thrid Maxwell's relation,

P
S P
1 U

T
P

P From this we obtain

T v
V T T v T V T

V T
This important equation expresses the dependence of the internal energy on the volume at fixed
temperature solely in terms of measurable T, P and v. This is helpful in construction of tables for u in
terms of measured T, P and v.

For a perfect gas,

Pv = RT

R
P

T v V

T
T

R
P PP0
V

This implies that, for a perfect gas, internal energy is independent of density and depends only on T.

dS

Cv
P
dT
dv
T
T v

Similarly it can be shown using Fourth Maxwells relation that

dS

CP
V
dT
dP
T
T P

Using the above two equations and solving for dP,

dP

CP Cv
(P / T ) v
dT
dv
T (V / T ) P
U / T P

Considering P as a function of T and v, we see that

CP Cv
P

T (v / T ) P T v

Two thermodynamic properties can be defined at this stage,

1 V
1 V

v T P
V P T

is called the isobaric compressibility and is called the isothermal compressibility.

From calculus, it can be shown that,Therefore,

C P Cv

T V / P P

V / P T

Thermodynamic Relations Involving Entropy

(a) Entropy as a function of T and P:Consider s= s (T,P)
Then the differential in change in the entropy,

dT
T p

dS

dP
T

Tds CpdT VTdP

(b) Entropy as a function of T and v:ds

Cv

dT dv
T

Tds CvdT

T
dv

Thermodynamic relations involving Enthalpy and Internal energy

dh CpdT (v Tv )dP

JOULE THOMSONS COEFFICIENT

JT

1
1

(Tv v)
v(T 1)
Cp
Cp

ENTROPY CHANGE OF DIFFERENT PROCESS

PROCESS

Isothermal reversible
process

Isothermal reversible
compression

ENTROPY OF SYSTEM

T2
v
nR l n 2
T1
v1
(+ve)

S nCV l n

v2
v1
(-ve)

ENROPY OF
SURROUNDINGS

S nR l n

( - ve)
nR l n

nR l n

v2
v1

ENTROY OF
UNIVERSE

v2
v1

(+ve)

Adiabatic reversible
expansion

Increase in Entropy due to

volume increase will be
compensated by decrease
in temperature
(0)

Adiabatic reversible
compression

v2
v1

P2 v2 v1
T
(-ve)

+ve

v2
v1

P2 v2 v1
T
(+ve)

+ve

T2
v
nR l n 2
T1
v1
(+ve)

+ve

T2
v
nR l n 2
T1
v1
(+ve)

+ve

Isothermal irreversible
expansion

S nR l n

Isothermal irreversible
compression

S nR l n

(+ve)

(-ve)

Adiabatic irreversible
compression

S nCV l n

Adiabatic irreversible
expansion

S nCV l n

Isothermal free
expansion

S nR l n

v2
v1

+ve

Adiabatic free expansion

S nR l n

v2
v1

+ve