Thermodynamics

Session 12
Internal energy changes:
The internal energy changes can be expressed in terms measurable quantities such as heat
capacities, pressure, volume and temperature. We can use Maxwells relations to get
these expressions.
The following are fundamental property relations.
We have derived the following relations.
Let us derive the expression for internal energy in terms C
P
and C
V
.
Replace dS in terms of C
V
,
dp
T
V
dT
T
C
dS
p
P

d
d

dV
T
p
dT
T
C
dS
V
V

d
d
+
dV
) p / V (
) T / V (
dT
T
C
dS
T
p
V
d d
d d

1
V
T
T
p
p
V
p V
T

d
d

d
d

d
d
pdV TdS dU
pdV dV
) p / V (
) T / V (
dT
T
C
T dU
T
p
V

d d
d d

dV p
) p / V (
) T / V (
T dT C dU
T
p
V
]

+
d d
d d

pdV TdS dU
Vdp TdS dH +
SdT pdV dA
SdT Vdp dG
Internal energy change in terms of C
p
:
Replace dS in terms of C
p
,
Enthalpy changes:
Starting from
in the same way we can get,
We can use these expressions and find the changes in enthalpy. These equations are
applicable for any gas. P-V-T relations used should be for the gas for which you are
determining the changes.
Use these relations and derive the expressions for dH and dU for ideal gas.
Effect of p, V and T on U, H and S:
This is one of the Maxwells relations which gives the effect of pressure on entropy at
constant temperature.
This equation derived earlier gives the effect of temperature on entropy at constant
pressure.
pdV TdS dU
pdV dp
T
V
dT
T
C
T dU
p
P

d
d

d
d
pdV dp
T
V
T dT C dU
p
P
Vdp TdS dH +
dp
T
V
T V dT C dH
p
P

d
d
+
p
T
T
V
p
S

d
d

d
d
T
C
T
S
P
p

d
d
At constant volume,
Or
This gives the effect of temperature on internal energy at constant volume.
At constant temperature, since dT is zero,
This gives the effect of volume of internal energy at constant temperature.
Similarly from
we can get,
At constant pressure,
At constant temperature,
These expressions give the effect of temperature and pressure on enthalpy.
Relationship between the heat capacities:
The heat capacities are related by the following expression.
which can also be written as
using the cyclic relation of partial derivatives of p, V and T.
dV
) p / V (
) T / V (
T Vdp dT C dU
T
p
V
]

d d
d d
+
V
C
dT
dU

V
V
C
T
U

d
d

+
d d
d d

d
d
p
) p / V (
) T / V (
T
V
U
T
p
T
dp
T
V
T V dT C dH
p
P

d
d
+
P
p
C
T
H

d
d
p
T
T
V
T V
p
H

d
d

d
d
V p
V P
T
p
T
V
T C C

d
d

d
d

T
2
p
V P
V
p
T
V
T C C

d
d

d
d

are called Volume expansivity and isothermal Compressibility. The difference between
heat capacities is written in terms of these as
Effect of pressure and volume on heat capacities:
These are given by the following equations.
T
p
V
V
1

d
d

;
T
V
V
1
p

d
d

VT
C C
2
V P

p
2
2
T
P
T
V
T
p
C

d
d

d
d
T
p
2
2
T
P
V
p
T
V
T
V
C

d
d

d
d

d
d
V
2
2
T
V
T
p
T
V
C

d
d

d
d
T
p
2
2
T
V
p
V
T
p
T
p
C

d
d

d
d

d
d