Chemistry 433

Lecture 17
Maxwell Relations

NC State University

Thermodynamicstatefunctions
expressedindifferentialform
d i diff
i lf
Wehaveseenthattheinternalenergyis
We
have seen that the internal energy is
conservedanddependsonmechanical(dw)and
thermal(dq)energy.Giventhatpressurevolume
( q)
gy
p
workdonebythesystemisdw=PdVandthatthe
entropychangecanbeexpressedasdS=dq/T(i.e.dq
=TdS)wecanexpresstheinternalenergyas
dU=TdS pdV
ByatransformationofvariableswedefineH=U+PV
ordH=d(U+PV)=dU+PdV+VdP.Therefore,
dH=TdS+VdP
Thesetwoexpressionsareknownastotalderivatives.

Thetotalderivative
Thetotalderivativepermitsmorethanone
variable to change at one time. We can write
variabletochangeatonetime.Wecanwrite
thestatefunctionsUandHinthefollowing
formtomakeitclearerwhatthevariable
dependenciesare:
U
U
dU =

whichimpliesthat

dS +

V
dS + H
P
P

S
dH = H
S
T = U
S
T = H
S

dV

dP
S

, P = U
V S
, V = H
P S

Definition of an exact differential

Definitionofanexactdifferential
Inthegeneralcasewecanwriteatotalderivativeas:
g
dF =Fxdx +Fydy
or
dF = F dx + F dy
x y
y x
Ifthetotalderivativeisanexactdifferentialthenthe
secondderivativesofbothtermsinthedifferentialare
equal.l
Fy
Fx
F
F
=
=
Fyx =
=
= Fxy
y
yx xy x

Secondderivativesofthe
internalenergyfunction
Thedifferentialformoftheinternalenergyis:
Th
diff
ti l f
f th i t
l
i
dU =TdS PdV
Usingthedefinitionswedeterminedabove:
T = U
S
S

, P = U
V
V

Thesecondderivativescanbewrittenas:
T = U = U = P
V VS SV
S

Secondderivativesofthe
enthalpyfunction
Thedifferentialformoftheenthalpyis:
Th
diff
ti l f
f th
th l i
dH =TdS +VdP
Usingthedefinitionswedeterminedabove:
T = H
S

,V =
P

H
P

Th
Thesecondderivativescanbewrittenas:
d d i ti
b
itt
T = H = H = V
P PS SP S

SecondderivativesoftheGibbs
freeenergyfunction
ThedifferentialformoftheGibbsenergyis:
Th
diff
ti l f
f th Gibb
i
dG =VdP SdT
Usingthedefinitionswedeterminedabove:
V = G
P

, S
S=
T

G
T

Th
Thesecondderivativescanbewrittenas:
d d i ti
b
itt
S = G = G = V

PT

TP

Secondderivativesofthe
Helmholtzfreeenergyfunction
ThedifferentialformoftheGibbsenergyis:
Th
diff
ti l f
f th Gibb
i
dA = PdV SdT
Usingthedefinitionswedeterminedabove:
P = A
V

, S
S=
T

A
T

Th
Thesecondderivativescanbewrittenas:
d d i ti
b
itt
P =

A = A = S
TV VT
V

Summary of Maxwell Relations

SummaryofMaxwellRelations
FForeachofthefourstatefunctionsU,H,A
h f th f
t t f ti
U H A
andGwecanderiveacorrespondingMaxwell
relation:
U
A
T = P
V
S

P = S
T V

G
T = V
P S

S = V