Chapter 6.

The solution of thermodynamic problems:

With U, A, H and G in hand we have potentials as a functions of whichever variable pair
we want: S and V, to T and P. Additional Legendre transforms will provide us with
further potentials in case we have other variables (such as surface area A, length L,
magnetic moment M, etc.).
Thermodynamic problems always involve computing a variable of interest. It may be a
derivative if it is an intensive variable, or even a second derivative. (Higher derivatives
are rarely of interest.)
G
Example: 1st order ones like = V or 2nd order ones like
P T

2G V
2 = = V
P T P T

The solution procedure is thus:

1. Select the derivative or variable to be computed;
2. Select the potential representation that makes it easiest, or corresponds to
variables you already have in hand.
3. Manipulate the thermodynamic derivative you know to get the one you want.
Easy as 1-2-3!
We now turn to two methods to manipulate the thermodynamic derivations:
Tool 1 Maxwell relations: (useful if two variables are NOT conjugate, e.g. T and V as
opposed to T and S)
z
z
2 z
2 z
If z = z(x, y) dz = dx + dy; but
=
x y
xy yx
y x
z
z
=
y x y x y x
Maxwells relations must hold true if z is a state function, as we saw in chapter 1. They
basically state that the cross-second derivatives of a function must be identical.

Example:
S
V
dG = SdT + VdP + dn =
= V or
P T ,n T P,n

n P,T P n,T
All four of the quantities in parenthesis are second derivatives of G. We can verify the
second line above for an ideal gas:

RT
nRT RT
RT ln P =
and =
=
=
P n,T P
n P ,T n P
P
P
Note: As discussed in chapter 7, only three second derivatives not involving n i are
independent; many sets can be chosen; the conventional one is , , and cP, all defined at
constant T or P (Gibbs ensemble). You can preview them at the begining of chapter 7 if
you wish.
Tool 2 Jacobi determinants: In order to reduce thermodynamic formulas to a minimal
number of derivatives (e.g. , , cP), the Jacobi determinants can be used in addition to
the Maxwell relations. The idea is that you can reduce ANY derivative or variable you
want to functions of T, P, n (if working in the Gibbs ensemble, other combinations
otherwise) and second derivatives , , and cP (others in different ensembles).
The Jacobi determinant is defined as

x

u
y
(x, y,...z)
det u
(u,v,...w)

z

u

x

v
y

v

z

v

x
...
w
...

z
...
w
...

Jacobians are useful for any variables transformation (u, v, w) (x, y, z). Any
thermodynamic derivative can be expressed as follows:

(x, v...w)
v
v
x
=
because
= 0, = 1, etc. in the above determinant will leave

u v...w (u, v...w)
u
v
only the desired derivative when the determinant is multiplied out.
Derivatives can then be manipulated by using the Jacobian identities:
i)

(x, y,...z)
(y, x,...z)
(x, y,...z)
=
=
(row or column permuation of determinant)
(u,v,...w)
(u,v,...w)
(v,u,...w)

ii)

x x r
(x, y,...z) (y, x,...z) (r,s,...t)
=

ex : r s u
y y s
(u,v,...w) (r,s,...t) (v,u,...w)
r s u
x x
= u r
y y
u v

iii)

(x, y,...z)
1
=
(u,v,...w) (u,v,...w)
(x, y,...z)

Proof : det(M 1 ) =

r x r x s x r x s
+
,
+
v = r u s u r v s v
s y r y s y r y s
+
,
+
v r u s u r v s v

1
det(M)

This concludes all the formal thermodynamic tools: From S > 0 (postulate 2), to the
Euler formula, Legendre transforms, and finally Maxwell relations and Jacobians, you
have all the problem-solving tools thermodynamics has to offer to tackle equilibrium
problems.
Armed with the Maxwell and Jacobian relations, we can reduce any expression to , ,
and cP (plus concentration or other derivatives, depending on the extensive variables of
the system). Let us do a few examples:
1) Heat capacity at constant volume in terms of heat capacity at constant pressure
dq
T S
cv =
dT V n T V

( )
( )
T (S, V ) ( T, P )
=
n ( T, P ) ( T, V )
T (S, V )
=
nV ( T, P )
=

T S, V
n T, V

S V
T S V

nV T P P T P T T P

nc p / T

= cp

VT 2
n

-V

cp cv

Going through the rationale for each step:

Step 1: is is there a Maxwell relation? NO: S & T are conjugate variables, so use a
Jacobian
Step 2: we want P held constant in the Jacobian, not V, so split the Jacobian by chain rule
Step 3: Flip columns in the second Jacobian and evaluate P/V|T, the isothermal
compressibility
Step 4: Can we use Maxwell or Jacobians? NO: time to multiply out the determinant
Step 5: We know three of the derivatives in terms of second derivatives of the Gibbs free
energy. The missing one, S/P|T = ? can be obtained using Maxwell: ? = -V/T|P, just
the isobaric expansion coefficient.
Step 6: Collect everything and note that V, T, n and are all positive, as is 2, so cv must
always be smaller than cP. This should make intuitive sense: if I keep a system at
constant pressure and put heat in it, it will also expand, losing some of the heat as work.
Thus the temperature wont go up as much, so the heat capacity is bigger at constant
pressure.

2) Change in enthalpy at const. P:

nc p
H
H S
S
=
=
T
=
T
= nc p
T
S T
T
T
P,n
P,n
P,n
P,n
T

n dq =
T0

dH =

T0

( T)
nc ( T ) dT = H ( T ) H
p

T0

H (0)

Thus dH = ncPdT. We derived this earlier by waving hands and using dqrev, but here it is,
formally.
3) Isentropic quasistatic expansion (S = const,, so dq rev / T = dS = 0 ). Do the homework
problem before you check out the solution below!
This describes the pressure-temperature relationship in a molecular beam, where no heat
can flow into the expanding gas, so its temperature must drop as the pressure drops.
What happens is that at the nozzle of the molecular beam, collisions preferentially eject
particles forward, preserving their average kinetic energy, but making a stream of
particles with a narrower relative velocity distribution. The relevant derivative is T/P|S,
which looks a bit odd at first, but we are fully equipped to handle derivatives at constant
entropy:

(0 = dS = dq

rev

/T

T
dT = dP
P S

S

T,S
T,S P,T
S,T
P T
1
=
=

=
S
P,S
P,T P,S
P,T S, P
T
T, P
P

( )
( )

( ) ( )
( ) ( )

( )
( ) ( )
( )

S
V
For the numerator, =
= V by Maxwell. Note that just because S is
P T T P
constrained to be held constant in (T/P)S does not mean that S/P = 0!
nc
S
VT
For the denominator = p

dT =
dP
T
nc
T
p

For an ideal monatomic gas, =

1 nR
5
=
, and c p = R
T PV
2

so we can write explicitly

2/5

T P
dT 2 dP

=
or = after integrating. Temperature drops in a
T 5 P
T0 P0
molecular beam, but not as dramatically as the pressure.
3) Heat capacity in terms of energy:
dq
T S
c v = = T > 0, n > 0.
dT V n T V

(
(

)
)

(
(

) (
) (

)
)

S, V
S, V U, V S U
S
1 U
=
=
=
=
T

U V T V T T V
T, V
U, V T, V
V
T 1 U
1 U

=
n T T V n T V
Again, we showed this before by invoking dqrev when discussing Legendre transforms
from energy to enthalpy. 1) and 3) are just the formal way of deriving it using Maxwells
relations and Jacobians.
=