Statistical Molecular

Thermodynamics
Christopher J. Cramer

Video 8.3

Maxwell Relations from A

 Interrelated Thermodynamic Quantities
When you are not able to directly measure a given thermo-
dynamic property, it is very useful to express it in terms of
other properties.
dA = dU − TdS − SdT (general)

for a reversible process dU = TdS − PdV

dA = − PdV − SdT
compare with the formal ⎛ ∂A ⎞ ⎛ ∂A ⎞
derivative of A=A(V,T):
dA = ⎜ ⎟ dV + ⎜ ⎟ dT
⎝ ∂V ⎠T ⎝ ∂T ⎠V
⎛ ∂A ⎞ ⎛ ∂A ⎞
Thus ⎜ ⎟ = − P and ⎜ ⎟ = − S
⎝ ∂V ⎠T ⎝ ∂T ⎠V
 Equating Key Cross Derivatives
⎛ ∂A ⎞ ⎛ ∂A ⎞
⎜ ⎟ = − P and ⎜ ⎟ = − S
⎝ ∂V ⎠T ⎝ ∂T ⎠V
∂ ⎛ ∂A ⎞ ∂ ⎛ ∂A ⎞ equality of mixed
As ⎜ ⎟ = ⎜ ⎟ partial derivatives
∂T ⎝ ∂V ⎠ ∂V ⎝ ∂T ⎠
⎛ ∂A ⎞ ∂ ⎛ ∂A ⎞ ⎛ ∂P ⎞
⎜ ⎟ = −P ⎜ ⎟ = −⎜ ⎟
⎝ ∂V ⎠T ∂T ⎝ ∂V ⎠ ⎝ ∂T ⎠V
€
⎛ ∂A ⎞ ∂ ⎛ ∂A ⎞ ⎛ ∂S ⎞ James Clerk Maxwell
⎜ ⎟ = −S ⎜ ⎟ = −⎜ ⎟
⎝ ∂T ⎠V ∂V ⎝ ∂T ⎠ ⎝ ∂V ⎠T
€ ⎛ ∂P ⎞ ⎛ ∂S ⎞
⎜ ⎟ = ⎜ ⎟
One of many Maxwell relations ⎝ ∂T ⎠V ⎝ ∂V ⎠T
€
 Utility of a Maxwell Relation
⎛ ∂P ⎞ ⎛ ∂S ⎞ From this Maxwell relation we can determine how
⎜ ⎟ = ⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂V ⎠T S changes with V given an equation of state

V2 ⎛ ∂P ⎞ Note that T is held

Integrate at constant T:
ΔS = ∫ V1
⎜ ⎟ dV
⎝ ∂T ⎠V
constant during
integration over V

Get V (or ρ) dependence of S from P-V-T data.

Example: Ideal €
gas
⎛ ∂P ⎞ nR V2 dV V2
⎜ ⎟ = ΔS = nR ∫V = nRln (isothermal)
⎝ ∂T ⎠V V 1 V V1
(a previous result derived another way, cf. Video 6.2)

€
 Entropy of Ethane
If V1 is chosen to be so large that a gas behaves ideally (=Vid),

id V2 ⎛ ∂P ⎞
( )
ΔS = S T ,V2 − S(ρ→0) = ∫ id ⎜ ⎟ dV (constant T )
V ⎝ ∂T ⎠
V

S(Pid → 0) [246.45 J • mol−1 • K −1 at 1 bar (from Q!)]

For real gases, i.e.,
those having no readily
available, analytical
€ Ethane at 400 K
equation of state, this
€
requires data for how
pressure varies with
temperature over a full
V2 ⎛ ∂P ⎞ range of volumes (or
id
S (T,V ) = S(ρ→ 0) + ∫ ⎜ ⎟ dV
V id ⎝ ∂T ⎠ densities, since density
V
is equal to V –1)

€
 Internal Energy of Ethane
⎛ ∂A ⎞ ⎛ ∂U ⎞ ⎛ ∂S ⎞
Differentiating A = U – TS wrt V : ⎜ ⎟ = ⎜ ⎟ − T ⎜ ⎟ (isothermal)
⎝ ∂V ⎠T ⎝ ∂V ⎠T ⎝ ∂V ⎠T
⎛ ∂P ⎞ ⎛ ∂S ⎞ ⎛ ∂A ⎞
using ⎜ ⎟ = ⎜ ⎟ and ⎜ ⎟ = − P
⎝ ∂T ⎠V ⎝ ∂V ⎠T ⎝ ∂V ⎠T ⎛ ∂U ⎞ ⎛ ∂P ⎞
Maxwell previously ⎜ ⎟ = − P + T ⎜ ⎟
relation derived ⎝ ∂V ⎠T ⎝ ∂T ⎠V

U(Pid → 0) [14.55 kJ • mol−1 (from Q!)] For real gases, i.e., those
having no readily available,
V2 ⎡ ⎛ ∂P ⎞ ⎤ analytical equation of state,
U (T,V ) = U id
+ ∫V id ⎢T⎜ ⎟ − P ⎥dV
(ρ→ 0)
⎣ ⎝ ∂T ⎠V ⎦ this again requires data for
€ how pressure varies with
temperature over a full
Ethane at 400 K

range of volumes (although
€ the plot here is over
pressures, which are
obviously readily measured
for each volume)
 Volume Dependence of A
⎛ ∂A ⎞ V2
⎜ ⎟ = − P ΔA = − ∫V PdV (constant T)
⎝ ∂V ⎠T integrate 1

Ideal gas example, P = nRT/V :

V2 1 V2
€ ∫V
ΔA = −nRT dV = −nRT ln (constant T)
1 V V1

Compare this to a previous result V2

for an ideal gas at constant T:
ΔS = nR ln
V1
€
As expected, ΔΑ = ΔU –TΔS is equal simply to –TΔS
since ΔU = 0 at constant T for an ideal gas