PHYSICAL CHEMISTRY IN BRIEF

(Wang) #1
CHAP. 3: FUNDAMENTALS OF THERMODYNAMICS [CONTENTS] 84

By comparing (3.33) and (3.37) we obtain


(
∂U
∂S

)

V

=T ,

(
∂U
∂V

)

S

=−p. (3.38)

In a similar way we obtain forH=f(S, p),F=f(T, V),G=f(T, p)


(
∂H
∂S

)

p

= T ,

(
∂H
∂p

)

S

= V , (3.39)

(
∂F
∂T

)

V

= −S ,

(
∂F
∂V

)

T

= −p , (3.40)
(
∂G
∂T

)

p

= −S ,

(
∂G
∂p

)

T

= V. (3.41)

3.4.3 Maxwell relations


By applying the equalities of mixed derivatives (3.26) to the Gibbs equations (3.33) through
(3.36), i.e. to the total differentials of the functionsU,H,F,G, we obtain the so-called Maxwell
relations
(
∂T
∂V


)

S

= −

(
∂p
∂S

)

V

, (3.42)

(
∂T
∂p

)

S

=

(
∂V
∂S

)

p

, (3.43)

(
∂p
∂T

)

V

=

(
∂S
∂V

)

T

, (3.44)

(
∂V
∂T

)

p

= −

(
∂S
∂p

)

T

. (3.45)

Maxwell relations, in particular (3.44) and (3.45), rank among the major thermodynamic rela-
tions. They are used to derive many other equations.

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