Lecture 13: Method of thermodynamic potentials.

Maxwell Relations.
1 Introduction
The fact that a small amount of heat Q, which is not a dierential itself, can be written in the
dierential form Q = TdS has important consequences and is the cornerstone of a method of
thermodynamic potentials. We shall need two mathematical theorems. Consider a function of
two variables f(x, y). The rst theorem tells us that the dierential change of f can be written
as
df = Adx +Bdy,
where
A =
f
x
|
y
B =
f
y
|
x
.
The second theorem states that
A
y
|
x
=
B
x
|
y
,
which simply expresses the fact that the mixed derivatives do not depend on the order of
dierentiation,

2
f
xy
=

2
f
yx
.
Equipped with this simple math, let us have a look at the equation which is a combination
of the rst and second laws
TdS = dU +PdV.
Note that it involves only total dierentials (in contrast to the rst law Q = dU +W where
Q and W are not dierentials of any functions). This innocent fact leads to important
implications which we are about to consider.
1
2 Internal energy as a thermodynamic potential. The
rst Maxwell relation
Let us write our equation in the form
dU = TdS PdV.
Recall that the systems we consider in this course are two-coordinate systems, i.e. their state is
completely specied by any two thermodynamic coordinates. Suppose we choose as independent
variables entropy and volume. Then in the above equation U = U(S, V ), T = T(S, V ), and
P = P(S, V ). Comparing the equation dU = TdS PdV with the rst mathematical theorem
df =

f
x

y
dx +

f
y

x
dy
gives the relations
T =
U
S
|
V
, P =
U
V
|
s
,
while the second theorem gives
T
V
|
s
=
P
S
|
v
.
This last expression is called the rst Maxwell relation.
These results are obtained considering the internal energy U as a function of S and V ,
U(S, V ). It is common to express it saying that the internal energy U is a thermodynamic
potential in variables S and V . The term potential is used in analogy with mechanics:
thermodynamic parameters (forces) T and P can be obtained by taking derivatives of the
potential U(S, V ). Let us also note, that according to the formula dU = TdS PdV , U can
be dened as heat the system gets in an isochoric (V = const) process.
3 Enthalpy and Second Maxwell relation
What if we use another pair of variables, say S and P. In this case we would like to transform
our basic relation
dU = TdS PdV
in such a way that it would contain a dierential dP instead of dV . It can be done easily as
follows:
dU = TdS PdV = TdS PdV V dP +V dP = TdS (PdV +V dP) +V dP.
2
The combination in brackets is the perfect dierential,
PdV +V dP = d(PV ).
Then the previous formula can be re-arranged
d(U +PV ) = TdS +V dP.
The function H = U + PV considered as a function of S and P is called enthalpy. We can
write
dH = TdS +V dP,
and therefore
T =
H
S
|
P
, V =
H
P
|
S
and
T
P
|
S
=
V
S
|
p
,
which is the second Maxwell relation.
Enthalpy H(S, P) as a function of S and P is a function of state. According to the denition
dH = TdS +V dP = Q+V dP
enthalpy equals to heat which a system obtains or releases in an isobaric reversible process.
4 Free energy and third Maxwell relation
Every new pair of variable gives us a new Maxwell relation. We have already used the pairs
S, V and S, P. Let us try the pair V, T. Again, one has to modify our relation
dU = TdS PdV
to make it contain dT instead of dS:
dU = TdS PdV = (TdS +SdT) SdT PdV.
Noting that TdS +SdT = d(TS), one obtains
d(U TS) = SdT PdV.
The function
F(T, V ) = U TS
3
is called the free energy (sometimes Helmholtz free energy). In new notation our result takes
the form
dF = SdT PdV,
which gives
S =
F
T
|
V
, P =
F
V
|
T
,
and
S
V
|
T
=
P
T
|
V
,
which is the third Maxwell relation.
5 Gibbs energy and Fourth Maxwell relation
Now our variables are P and T. It is convenient to start from the formula for enthalpy
dH = TdS +V dP
rewriting it as follows
dH = (TdS +SdT) SdT +V dP = d(TS) SdT +V dP.
Introducing the function
G(P, T) = H TS
called Gibbs energy (or Gibbs free energy), the result can be rewritten in the form
dG = V dP SdT,
which gives
V =
G
P
|
T
, S =
G
T
|
P
,
and
V
T
|
P
=
S
P
|
T
.
which is the fourth Maxwell relation.
4
6 Comments
As was shown above, one can nd thermodynamic parameters of a system just dierentiating a
thermodynamic potential. Let us show that actually one can nd all relevant thermodynamic
parameters, namely
S, P, U, C
v
, C
p
,
if one knows explicitly a thermodynamic potential, say free energy F(T, V ). Indeed, we have
seen that
S =
F
T
|
V
, P =
F
V
|
T
.
Next, for the internal energy one obtains
U = F +TS = F T
F
T
|
V
.
Next, the heat capacity C
V
can be calculated as follows
C
V
=
U
T
|
V
=

T

F T
F
T
|
V

= T

2
F
T
2
|
V
.
A little longer calculations are needed to get C
P
. According to the general formula for heat
capacity (see Lecture 5)
C
P
= C
V
+

P +
U
V
|
T

V
T
|
P
.
Here C
V
, P and U are already found. What remains to be found is the derivative
V
T
|
P
. It can
be obtained as follows. Considering P as a function of T and V , and can write
dP =
P
T
|
V
dT +
P
V
|
T
dV.
For an isobaric process dP = 0, and the above expression gives
V
T
|
P
=
P
T
|
V
P
V
|
T
=

2
F
TV

2
F
V
2
|
T
.
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