Thermodynamic potentials
Thermodynamic potentials are state functions that, together with the corresponding equa-
tions of state, describe the equilibrium behavior of a system as a function of so-called
natural variables. The natural variables are a set of appropriate variables that allow to
compute other state functions by partial differentiation of the thermodynamic potentials.
m
X
X
dU = T dS + Fi dqi + j dNj , (5.1)
i=1 j=1
where {F, q} denote the set of conjugate intensive and extensive variables that characterize
a system. For instance, for a gas
{F, q} {P, V },
39
40 CHAPTER 5. THERMODYNAMIC POTENTIALS
" #1
2U
CV = T ,
S 2 V,N
2U P 1
= =
V 2 S,N V S,N V kS
" #1
1 2U
kS = . (5.2)
V V 2 S,N
Maxwell relations
A Maxwell relation follows from the differentiability of U :
U U
=
V S S V
T P
= (Maxwell relation). (5.3)
V S S V
Example: monoatomic ideal gas. The behavior of a monoatomic ideal gas obeys the
following relations:
P V = nRT,
5.1. INTERNAL ENERGY U 41
3
U = nRT,
2
3
CV = nR.
2
Let us use this information and derive an expression for U in terms of its natural variables:
dU + P dV dT dV
dS = = CV + nR ,
T T V
T V
S(T, V ) = CV ln + nR ln + S0
T V
0 0
U V
= CV ln + nR ln + S0 ,
U0 V0
S S0 U nR V
= ln + ln . (5.4)
CV U0 CV V0
Since
nR = CP CV
nR CP CV 5 2
= =1= 1= ,
CV CV 3 3
we can write eq. (5.4) as
CnR
SS0 U V V
e CV
= ,
U0 V0
from which
1
V0 SS0
U (S, V ) = U0 e CV
(5.5)
V
follows. Eq. (5.5) is the fundamental equation for the ideal gas, with U (S, V ) as the
thermodynamic potential and S, V as independent natural variables.
Corollary: the natural variables for U are S and V , which means that if the function
U (S, V ) is known for a given system we can obtain all the thermodynamic properties of
the system through the differentiation of U (S, V ).
U = U (T, V, N ) (5.6)
U is not an appropriate thermodynamic potential any more since from the first derivatives
of eq. (5.6),
U
= CV
T V
and
U P
=T P,
V T T V
42 CHAPTER 5. THERMODYNAMIC POTENTIALS
1 1 1X
dS = dU + P dV i dN ,
T T T j=1
Independent variables x, y, z S, V, N
V
Dependent variables Fx = ,... Maxwell relations:
x
U
obtained differentiating P = ,...
V S
A thermodynamic potential for a system with variable number of particles should depend
on {, N } as well as a thermal variable and a mechanical variable, which can be (for a
gas):
P Enthalpy H(S, P ) S
T Free energy F (T, V ) V
d
(f ux) = x.
du
We define
df
g(u) = f (x) ux = f (x) x
dx
as the Legendre transformation of f (x).
In
dF = dU d(T S) = dU SdT T dS
we substitute dU from eq. (5.1) and get
X
dF = SdT P dV + j dNj .
j=1
The natural variables of the free energy are {T, V, N }. The dependent variables are
obtained out of the first derivatives:
F F
S = , P = thermal state equations
T V,N V T
and
S P
= Maxwell relation.
V T T V
5.4 Enthalpy
Enthalpy
H = H(S, P, N )
is obtained when we substitute the variable V by P in U (S, V, N ):
H = U + PV .
The total differential of H is derived as follows.
U
H =U V ,
V S,N
| {z }
P
dH = dU + d(P V ) = dU + V dP + P dV
X
= T dS P dV + j dNj + V dP + P dV
j=1
X
dH = T dS + V dP + j dNj .
j=1
The natural variables of the enthalpy are {S, P, N }. Out of the first order derivatives we
obtain
H
T = ,
S P,N
H
V = ,
P S,N
and the Maxwell relation
T V
= .
P S,N S P,N
5.5. GIBBS ENTHALPY 45
G = U TS + PV .
The total differential of the Gibbs enthalpy:
dG = dU T dS SdT + P dV + V dP,
X
dG =
T dS PdV
+ j dNj SdT +
T dS
PdV
+ V dP,
j=1
P
dG = SdT + V dP + j=1 j dNj .
Out of the first derivatives of G, we obtain
G
S= ,
T P,N
G
V = ,
P T,N
and the Maxwell relation
S V
=
P T,N T P,N
S, dS: extensive
j : intensive
P: intensive
V, dV : extensive
It follows then that dF , dG, and dH, i.e., F , G, and H are all extensive state properties,
and the following homogeneity relations should be fulfilled:
F (T, V, N ) = F (T, V, N ),
H(S, P, N ) = H(S, P, N ),
G(T, P, N ) = G(T, P, N ). (5.8)
Let us now use the extensivity of G. If we differentiate eq. (5.8) with respect to and
set = 1:
d
G(T, P, N ) = G(T, P, N )|=1
d !
X G
= Nj ,
j=1
(Nj ) T,P,Ni6=j
=1
we obtain:
X
G(T, P, N ) = j Nj Gibbs-Duhem relation. (5.9)
j=1
G(T, P, N ) = N .
G = U T S + P V,
can be written in very simple forms for the various exchanges between the system and its
environment by using various thermodynamic potentials. The thermodynamic potentials
allow for the description of the development of a system towards equilibrium state itself.
Depending on a specific experimental situation, an adequate potential is to be used.
dU = 0 (Q = 0),
dV = 0,
dN = 0.
dS 0
dS = 0 in equilibrium.
U = const,
V = const,
N = const,
The wall is movable and allows exchange of energy and particles. V1 , V2 , U1 , U2 , N1 , and
N2 are variable but must obey the following constraints:
S = S(U1 , V1 , N1 ) + S(U2 , V2 , N2 ) = S1 + S2 .
5.8. EQUILIBRIUM CONDITIONS 49
Both systems will interchange particles and energy until equilibrium is attained. In the
equilibrium state
0 = dS = dS1 + dS2
( )
S1 S2
= dU1
U1 V1 ,N1 U2 V2 ,N2
( )
S1 S2
+ dV1
V1 U1 ,N1 V2 U2 ,N2
( )
S1 S2
+ dN1
N1 U1 ,V1 N2 U2 ,V2
1 1 P1 P2
= dU1 + dV1
T T2 T1 T2
1
1 2
+ + dN1 .
T1 T2
Since U1 , V1 , and N1 are independent variables, each curly bracket {} has to be zero.
Therefore,
T1 = T2 = T ; P1 = P2 = P ; 1 = 2 = .
T dS dU,
if
T = const,
then
T dS = d(T S) d(U T S) 0 .
50 CHAPTER 5. THERMODYNAMIC POTENTIALS
The latter expression tells us that in this case the free energy F ,
F = U T S,
dF 0
dF = 0 in equilibrium
T = const,
V = const,
N = const,
the free energy decreases and reaches a minimum at equilibrium.
0 = dF = dF1 + dF2
( )
F1 F2
= dV1
V1 N1 ,T V2 N2 ,T
( )
F1 F2
+ dN1
N1 V1 ,T N2 V2 ,T
= {P1 + P2 } dV1 + {1 2 } dN1 . (5.11)
5.8. EQUILIBRIUM CONDITIONS 51
From eq. (5.11) follows that, since V1 and N1 are independent variables,
P1 = P2 = P,
1 = 2 = .
In a closed system with constant volume V in contact with a heat bath at constant
temperature T , the equilibrium state is characterized by the same pressure
and chemical potential everywhere.
One more example: closed system in a heat reservoir at constant pressure P (will be
worked out in the exercises).
dT = 0, dNj = 0, dP = 0
dG 0,
dG = 0 in equilibrium.
The Gibbs energy decreases in an irreversible process under the above conditions
and reaches its minimum at equilibrium. In this case, the equilibrium state is
characterized by the same chemical potential everywhere.
52 CHAPTER 5. THERMODYNAMIC POTENTIALS