Statistical Molecular

Thermodynamics
Christopher J. Cramer

Video 8.4

Maxwell Relations from G

 Working With Gibbs Free Energy
G = U − TS + PV

differentiate dG = dU − TdS − SdT + PdV + VdP

using dU = TdS – PdV dG = − SdT + VdP

compare with the formal ⎛ ∂G ⎞ ⎛ ∂G ⎞

derivative of G = G(P,T):
dG = ⎜ ⎟ dT + ⎜ ⎟ dP
⎝ ∂T ⎠ P ⎝ ∂P ⎠T

⎛ ∂G ⎞ ⎛ ∂G ⎞
Thus ⎜ ⎟ = − S and ⎜ ⎟ = V
⎝ ∂T ⎠ P ⎝ ∂P ⎠T
 Equating Key Cross Derivatives
⎛ ∂G ⎞ ⎛ ∂G ⎞
⎜ ⎟ = V and ⎜ ⎟ = −S
⎝ ∂P ⎠T ⎝ ∂T ⎠ P

∂ ⎛ ∂G ⎞ ∂ ⎛ ∂G ⎞ equality of mixed
As ⎜ ⎟ = ⎜ ⎟ partial derivatives
∂T ⎝ ∂P ⎠ ∂P ⎝ ∂T ⎠
€ €
⎛ ∂G ⎞ ∂ ⎛ ∂G ⎞ ⎛ ∂V ⎞
⎜ ⎟ = V ⎜ ⎟ = ⎜ ⎟
⎝ ∂P ⎠T ∂T ⎝ ∂P ⎠ ⎝ ∂T ⎠ P
€
⎛ ∂G ⎞ ∂ ⎛ ∂G ⎞ ⎛ ∂S ⎞ James Clerk Maxwell
⎜ ⎟ = −S ⎜ ⎟ = −⎜ ⎟
⎝ ∂T ⎠ P ∂P ⎝ ∂T ⎠ ⎝ ∂P ⎠T
€ ⎛ ∂V ⎞ ⎛ ∂S ⎞
⎜ ⎟ = −⎜ ⎟
Another of many Maxwell relations ⎝ ∂T ⎠ P ⎝ ∂P ⎠T
€
 Utility of The Maxwell Relation
⎛ ∂V ⎞ ⎛ ∂S ⎞ From this Maxwell relation we can see how S
⎜ ⎟ = −⎜ ⎟
⎝ ∂T ⎠ P ⎝ ∂P ⎠T changes with P given an equation of state

P2 ⎛ ∂V ⎞ Note that T is held

Integrate at constant T:
ΔS = − ∫ P1
⎜ ⎟ dP
⎝ ∂T ⎠ P
constant during
integration over P

Get P dependence of S from P-V-T data.

Example: Ideal€gas
⎛ ∂V ⎞ nR P2 dP P2
⎜ ⎟ = ΔS = −nR ∫ P = −nRln (isothermal)
⎝ ∂T ⎠ P P 1 P P1

€
€
 Entropy of Ethane Again
If P1 is chosen to be so small that a gas behaves ideally (P  0),
⎛ ∂V ⎞
P2
ΔS = S (T,P2 ) − S id
(P → 0) = − ∫ P id ⎜ ⎟ dP (constant T)
⎝ ∂T ⎠ P
S(Pid → 0) [246.45 J • mol−1 • K −1 at 1 bar (from Q!)]

Ethane at 400 K
For real gases, i.e.,
€ those having no readily
€ available, analytical
P2 ⎛ ∂V ⎞ equation of state, this
S (T,P ) = S(Pid → 0) − ∫ P id ⎜⎝ ∂T ⎟⎠ dP requires data for how
P
volume varies with
temperature over a full
range of pressures
€
 Enthalpy Dependence on P
⎛ ∂G ⎞ ⎛ ∂H ⎞ ⎛ ∂S ⎞
Differentiating G = H – TS wrt P : ⎜ ⎟ = ⎜ ⎟ − T⎜ ⎟ (isothermal)
⎝ ∂P ⎠T ⎝ ∂P ⎠T ⎝ ∂P ⎠T
⎛ ∂V ⎞ ⎛ ∂S ⎞ ⎛ ∂G ⎞
using ⎜ ⎟ = −⎜ ⎟ and ⎜ ⎟ = V
⎝ ∂T ⎠ P ⎝ ∂P ⎠T ⎝ ∂P ⎠T ⎛ ∂H ⎞ ⎛ ∂V ⎞
Maxwell previously ⎜ ⎟ = V − T⎜ ⎟
relation derived
€ ⎝ ∂P ⎠T ⎝ ∂T ⎠ P
€ €
H id
(P → 0) [17.87 kJ • mol −1
(from Q!)]
P2 ⎡ ⎛ ∂V ⎞ ⎤ For real gases, i.e., those
H (T,P ) = H id
(P → 0) + ∫ P id ⎢V − T⎜€ ⎟ ⎥dP having no readily available,
⎣ ⎝ ∂T ⎠ P ⎦
€ analytical equation of state,
this again requires data for
how volume varies with
€ temperature over a full
Ethane at 400 K
range of pressures
 Pressure Dependence of G
⎛ ∂G ⎞ P2
⎜ ⎟ = V
⎝ ∂P ⎠T integrate
ΔG = ∫ P1
VdP (constant T)

Ideal gas example, V = nRT/P :

€ P2 1 P2
€ ∫P
ΔG = nRT dP = nRT ln (constant T)
1 P P1

Compare this to a previous result V2 P2

for an ideal gas at constant T: ΔS = nRln = −nRln
V1 P1
€
As expected, ΔG = ΔH –TΔS is equal simply to –TΔS
since ΔH = 0 at constant T for an ideal gas
€