Professional Documents
Culture Documents
Thermodynamic potentials
Thermodynamic potentials are state functions that, together with the corresponding equations 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.
5.1
Internal energy U
m
X
Fi dqi +
i=1
j dNj ,
(5.1)
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 },
for a magnetic system
{F, q} {B, M}.
In (5.1), N is the number of particles in the system (an extensive variable); the index j
(j = 1, . . . , ) denotes different sets of particles that may constitute the system.
Chemical potential (an intensive variable): is defined as the energy needed to add a
particle to a thermally and mechanically isolated system.
The last term in eq. (5.1), dN , is needed if the number of particles in the system is not
kept constant, i.e. if particles enter or leave the system.
For a gas, eq. (5.1) is written as
dU = T dS P dV +
X
j=1
39
j dNj ,
40
2
S V,N
S V,N
T V,N
CV
2U
V 2
CV = T
=
S,N
P
V
"
1
kS =
V
2U
S 2
=
S,N
"
V,N
1
V kS
2U
V 2
S,N
#1
#1
(5.2)
Maxwell relations
A Maxwell relation follows from the differentiability of U :
U
U
V S
S V
P
T
=
(Maxwell relation).
V S
S V
(5.3)
Example: monoatomic ideal gas. The behavior of a monoatomic ideal gas obeys the
following relations:
P V = nRT,
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:
dS =
dT
dV
dU + P dV
= CV
+ nR
,
T
T
V
Since
T
V
S(T, V ) = CV ln
+ nR ln
+ S0
T
V
0
0
V
U
+ nR ln
+ S0 ,
= CV ln
U0
V0
U
V
nR
S S0
= ln
ln
+
.
CV
U0
CV
V0
(5.4)
nR = CP CV
CP CV
5
2
nR
=
=1= 1= ,
CV
CV
3
3
SS0
CV
from which
U
U0
U (S, V ) = U0
V0
V
V
V0
CnR
V
1
SS0
CV
(5.5)
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 ).
On the contrary, in the equation of state
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
V
=T
T
P
T
P,
V
42
1
1X
1
i dN ,
dS = dU + P dV
T
T
T j=1
Potential
V (x, y, z)
U (S, V, N )
x, y, z
S, V, N
Independent variables
Dependent variables
Fx =
V
,...
x
obtained differentiating
5.2
Maxwell relations:
U
,...
P =
V S
Legendre transformation
thermal:
mechanical:
S (extensive)
T (intensive)
V (extensive) P (intensive)
43
Extensive variables
Enthalpy H(S, P )
Gibbs enthalpy
G(T, P )
Internal energy
U (S, V )
df
dx = udx.
dx
d
(f ux) = x.
du
We define
g(u) = f (x) ux = f (x) x
df
dx
5.3
Free energy.
44
In
dF = dU d(T S) = dU SdT T dS
we substitute dU from eq. (5.1) and get
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
, P =
thermal state equations
S =
T V,N
V T
and
5.4
S
V
=
T
P
T
Maxwell relation.
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
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
T
P
=
S,N
V
S
.
P,N
45
5.5
Gibbs enthalpy
G = U TS + PV .
dG =
T dS
P
dV
+
SdT +
j dNj
T dS
P
dV
+ V dP,
j=1
dG = SdT + V dP +
j=1
j dNj .
5.6
S
P
=
T,N
V
T
P,N
Homogeneity relations
The thermodynamic potentials vary as extensive state properties if the volume and number of particles vary by a factor , i.e.,
V V
U U.
(5.7)
Nj Nj
The property (5.7) is a true one only if we neglect interactions between particles as
well as surface effects.
Since dU is extensive and T is intensive, from
dU = T dS P dV +
X
j=1
j dNj
46
extensive
intensive
intensive
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 )|=1
d
X
G
G(T, P, N ) =
=
j=1
(Nj )
Nj
T,P,Ni6=j
,
=1
we obtain:
G(T, P, N ) =
j Nj
Gibbs-Duhem relation.
(5.9)
j=1
5.7
j=1
j Nj = 0 .
In a system that interchanges particles with a reservoir, the chemical potential is constant
and the number of particles changes accordingly. In order to describe such a system,
we introduce the grand canonical potential (T, V, ), where the natural variable N is
replaced by :
(T, V, ) = F (T, V, N ) N .
47
d = SdT P dV N d .
S=
,
T V,
P =
,
V T,
.
N =
T,V
Since G = N and G = F + P V ,
= F N = F G = P V,
from which follows
= P
V
5.8
Equilibrium conditions
j dNj ,
(5.10)
j=1
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.
Let us now consider several examples.
48
5.8.1
Isolated system
In an isolated system
dU = 0 (Q = 0),
dV = 0,
dN = 0.
Then, according to eq. (5.10),
dS 0
dS = 0 in equilibrium.
In all irreversible processes, under the conditions
U = const,
V = const,
N = const,
the entropy increases and is maximum in the stationary equilibrium. S evolves to
a maximum under conditions of fixed U , V , N . This is an extremum principle.
Consider two isolated systems 1 and 2 separated by a wall (Fig. 5.1).
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:
U = U1 + U2 = const
dU1 = dU2 ,
V = V1 + V2 = const
dV1 = dV2 ,
N = N1 + N2 = const
dN1 = dN2 .
49
Both systems will interchange particles and energy until equilibrium is attained. In the
equilibrium state
0 = dS = dS1 + dS2
)
(
S2
S1
dU1
=
U1 V1 ,N1
U2 V2 ,N2
(
)
S1
S2
+
dV1
V1 U1 ,N1
V2 U2 ,N2
)
(
S2
S1
dN1
+
N1 U1 ,V1
N2 U2 ,V2
1
P1 P2
1
=
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 = .
In an isolated system in equilibrium everywhere there is the same temperature,
pressure and chemical potential.
5.8.2
We consider now a closed system in a reservoir without work interchange. Such a system
has the following features according to the attributes that we gave it:
closed
in a reservoir
without work interchange
Nj = const
T = const
V = const
dNj = 0,
dT = 0,
dV = 0.
d(U T S) 0 .
50
The latter expression tells us that in this case the free energy F ,
F = U T S,
is the appropriate potential.
dF 0
dF = 0 in equilibrium
In all irreversible processes, under the conditions
T = const,
V = const,
N = const,
the free energy decreases and reaches a minimum at equilibrium.
Consider a composite system in a heat reservoir at temperature T (Fig. 5.2), whose
particles can pass through the wall.
dV1 = dV2 ,
N = N1 + N2 = const
dN1 = dN2 ,
F = F (T, V1 , N1 ) + F (T, V2 , N2 ) = F1 + F2 .
In equilibium,
0 = dF = dF1 + dF2
)
(
F2
F1
dV1
=
V1 N1 ,T
V2 N2 ,T
)
(
F2
F1
dN1
+
N1 V1 ,T
N2 V2 ,T
= {P1 + P2 } dV1 + {1 2 } dN1 .
(5.11)
51
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
5.9
Potential
Natural
independent
variables
S, V , N
Entropy
S
U, V , N
T
V
=
S
S
V
T, V , N
S, P , N
H
T =
S P,N
H
V =
P S,N
H
=
N S,P
T
P
T, P, N
P
S
S
1
=
T
U V,N
P
S
=
T
V U,N
S
=
T
N U,N
Gibbs enthalpy
G = H T S = N
F
S=
T V,N
F
P =
V
T,N
F
=
N T,V
Enthalpy
H = U + PV
Maxwell relations
and others
Free energy
F = U TS
U
T =
S
V,N
U
P =
V
S,N
U
=
N S,V
Internal energy
U
Conjugated
dependent
variables
G
S=
P,N
T
G
V =
P T,N
G
=
N T,P
P
=
T
T
V
F
2
U = T
T T
V
=
T
T P
G
H = T 2
T T
S
P
=
S
V
S
Potential
Natural
independent
variables
Grand canonical
potential
T, V ,
= F N = P V
Chemical potential
=
G
N
Conjugated
dependent
variables
T
P
S=
T V,
P =
V
T,
N =
T,V
S
=
s=
N
T
P
V
=
v=
N
P T
53
Maxwell relations
and others