September 25, 2001

Reading: Chapter V
Homework: 5.2, 5.4, 5.6, 5.8, 5.10, 5.11, 5.12.
More examples of use of Maxwells equations:
Gibbs-Helmholtz equation:
Consider a process at constant pressure and composition.
dG = SdT + VdP
dG
= S
dT
G = H TS = H + T
So,

H = G T

dG
dT

G

S =
T P

dG
dT

Since,
d G
G 1 dG
= 2 +
dT T
T dT
T
Then,
T 2

d
dT

dG
G
=H
= G T
dT
T

So,
G
d
d G
T
H = T 2
=
dT T
1
d
T
Similarly, for a constant volume process
A = U TS
dA
A =U +T
dT

A

S =
T V

Since
d A
A 1 dA
= 2 +
dT T
T dT
T
d A
dA
T 2
=U
= A T
dT T
dT

(1)

 A
d
d A
T
So,
U = T 2
=
dT T
1
d
T
For a constant entropy process,

(2)

H = U + PV
dH
H =U + P
dP

H

V =
P S

H
d
d H
P
U = P 2
=
dP P
1
d
P

(3)

Also, for a constant entropy process,

U = H PV
dU
U = H +V
dV

U

P =
V S

U
d
d U
V
H = V 2
=
dV V
1
d
V

(4)

Equations (1) through (4) are referred to as Gibbs-Helmholtz equations.

Application to ideal gas:

dU = TdS PdV
U
V

= P

T S
T S
For an ideal gas, entropy remains constant during an adiabatic-reversible process
(S=constant), then
PV =constant, or TV 1 =constant
Differentiating TV 1 =constant with respect to T,
V
V 1 + T ( 1)V 2
=0
T S

i.e.,

V
V

=
( 1)T
T S

So,

PV
R
R
3
U
V
=
=
= R = CV

= P
=
T S
T S ( 1)T 1 5 3 1 2
This is expected become for ideal gas U is only a function of T.

S
U
Also,
= CV
= T
T V
T V
This is because
C dT
q
dS = V = V
T
T
Similarly,
C dT
q
dS = P = P ,
T
T

C
S
,
= V
T
T V

C
S

= P
T
T P
R
U
S
V

= T
P
= C P P = C P R = CV
P
T P
T P
T P

So, for an ideal gas,

U
U
U

= T
=
= CV
T S
T V T P
Now, take a look at enthalpy,
dH = TdS + VdP

H
S

= T
= CP
T P
T P
Also,

R
H
S
P

= T
+V
= CV + V = CV + R
V
T V
T V
T V
So, for an ideal gas,
H

= CV + R = C P
T V
H
H
i.e.,

=
= CP
T P T V

General Relationship between differentiations of U and H

In general,
dH = TdS + VdP

H
S

= T
= CP
T P
T P
P
P
S
H

= CV + V
+V
= T

T V
T V
T V
T V
Now,

P T V
= 1

T V V P P T
So,

T V

T V

T P
=
=

P T
V
= CV +

Thus, in general,
H
H

T P T V
For a constant pressure process,
H = C P dT .
But, for a constant volume process,
V
H = C P dT +
dT .

The changes of H in the two processes are different in general, but the same for ideal gas.
Now, take a look at U:

dU = TdS PdV
U

T
U

S
V

P
= C P PV
= T
T P
P
T P

S
= CV
= T
V
T V

U
V

= P

T S
T S

 V T S
Since,


= 1
T S S V V T
Then,
S

V
T V

=
S
T S

V T
Also,
C
S

= V
T
T V

S
P

=
= , Maxwells equation
V T T V
Thus,

and

C
V

= V ,
T
T S
PCV
V
U
=

= P
T
T S
T S

Therefore, in general,
U
U
U

T P T V T S