PARTIAL DIFFERENTIATION
Although the Helmholtz potential has other uses, in this context it has simply
provided a means for a quick derivation of the Maxwell relation. The other
Maxwell relations can be derived similarly by using two other potentials, the
enthalpy,H=U+PV,andtheGibbs free energy,G=U+PV−ST(see
exercise 5.25).
5.12 Differentiation of integrals
We conclude this chapter with a discussion of the differentiation of integrals. Let
us consider the indefinite integral (cf. equation (2.30))
F(x, t)=
∫
f(x, t)dt,
from which it follows immediately that
∂F(x, t)
∂t
=f(x, t).
Assuming that the second partial derivatives ofF(x, t) are continuous, we have
∂^2 F(x, t)
∂t∂x
=
∂^2 F(x, t)
∂x∂t
,
and so we can write
∂
∂t
[
∂F(x, t)
∂x
]
=
∂
∂x
[
∂F(x, t)
∂t
]
=
∂f(x, t)
∂x
.
Integrating this equation with respect totthen gives
∂F(x, t)
∂x
=
∫
∂f(x, t)
∂x
dt. (5.46)
Now consider the definite integral
I(x)=
∫t=v
t=u
f(x, t)dt
=F(x, v)−F(x, u),
whereuandvare constants. Differentiating this integral with respect tox,and
using (5.46), we see that
dI(x)
dx
=
∂F(x, v)
∂x
−
∂F(x, u)
∂x
=
∫v
∂f(x, t)
∂x
dt−
∫u
∂f(x, t)
∂x
dt
=
∫v
u
∂f(x, t)
∂x
dt.
This isLeibnitz’ rulefor differentiating integrals, and basically it states that for