3.

7 Equilibrium Conditions 95

Because of dH D 0 and dp < 0, the entropy thus increases:

V
dS D  dp > 0 :
T

3.7 Equilibrium Conditions

The thermodynamic potentials, as functions of their natural variables, are character-

ized, in particular, by the fact that, by keeping certain variables constant and varying
others, one can very easily recognize in which manner energy is exchanged with the
surroundings. As an example, let us take the internal energy U of a gas:

dU D T dS  p dV H) 1: S D const W dU D p dV (work)
2: V D const W dU D T dS (heat)

The
basic relation of thermodynamics

X
m ˛
X
T dS  ıQ D dU  Fi dqi  j dNj
iD1 jD1

can be brought into especially simple forms by the use of the thermodynamic
potentials for the different contacts of the system and its surroundings. The
potentials convey the possibility to describe the evolution of a thermodynamic
system towards equilibrium and the equilibrium state itself. The various potentials
are thereby suited to different experimental situations. Let us consider the most
important special cases.

3.7.1 Isolated Systems

This situation we have already discussed in connection with the second law of
thermodynamics (Sect. 2.7). Isolated systems are defined by:

dU D 0 .ıQ D 0/ I dqi D 0 I dNj D 0 : (3.69)

96 3 Thermodynamic Potentials

Fig. 3.8 An outwardly isolated system with an intermediate wall permeable to particles and
energy

This means:

dS  0 ;
dS D 0 in the equilibrium. (3.70)

So long as real irreversible processes run in isolated systems, these always behave
such that the entropy thereby increases. The entropy is maximal in the stationary
equilibrium!
As long as we take only the equilibrium value of the entropy S D S.U; q; N/ as a
basis, we cannot draw further conclusions beyond (3.70) since by assumption U, q
and N are constant. We therefore create now in the form of a gedanken-experiment,
a simple non-equilibrium situation from which further information can be derived.
Let the outwardly isolated system .U D const; V D const; Nj D const/ be
decomposed by a wall into two parts. For simplicity, we assume that the gas in the
chambers consists only of one single type of particles .˛ D 1/. The generalization
to more than one type will pose no difficulty.
Let the wall be movable and permeable with respect to energy and particles!
V1 , V2 as well as U1 , U2 and N1 , N2 are thus still variable, but with the boundary
conditions (Fig. 3.8):

U D U1 C U2 D const I V D V1 C V2 D const I N D N1 C N2 D const :

The total entropy is additive:

S D S .U1 ; V1 ; N1 / C S .U2 ; V2 ; N2 / D S1 C S2 :

Since U, V, N are constant, we have:

dU1 D dU2 ; dV1 D dV2 ; dN1 D dN2 :

The two partial systems will react until the equilibrium condition (3.70) is fulfilled:

0 D dS D dS1 C dS2
(    )
@S1 @S2
D  dU1
@U1 V1 ; N1 @U2 V2 ; N2
3.7 Equilibrium Conditions 97

(    )
@S1 @S2
C  dV1
@V1 U1 ; N 1 @V2 U2 ; N 2
(    )
@S1 @S2
C  dN1
@N1 U1 ; V 1 @N2 U2 ; V 2
   
1 1 p1 p2
D  dU1 C  dV1
T1 T2 T1 T2
 
1 2
C  C dN1 : (3.71)
T1 T2

U1 , V1 and N1 are independent state variables so that each of the brackets must
separately vanish. The equilibrium is therefore characterized by

T1 D T2 D T I p1 D p2 D p I 1 D 2 D  : (3.72)

We can proceed in the gedanken-experiment with the subdivision in order to come

eventually asymptotically to the statement that
all points in an isolated system in equilibrium have the same temperature, the same
pressure and the same chemical potential!

3.7.2 Closed System in a Heat Bath Without Exchange of Work

That means in detail:

closed H) Nj D const ” dNj D 0 ;

in a heat bath H) T D const ” dT D 0 ;
without exchange of work H) qi  const ” dqi D 0 :

The basic relation then reads:

T dS  dU ; T D const H) T dS D d.T S/ H) d.U  T S/ 0:

This leads to the important result:

dF 0;
F D 0 in the equilibrium. (3.73)

For all irreversible processes which are possible under the given boundary
conditions,
T D const ; q D const ; N D const ,
the free energy always decreases. F is minimal at equilibrium.
98 3 Thermodynamic Potentials

Fig. 3.9 System in a heat

bath with a dividing wall V1 , N1 , V2 , N2 ,
permeable to particles T T

HB(T )

To get further statements we perform a similar gedanken-experiment as was done in

the last section for isolated systems, and that again for gas, as an example.
The system is subdivided by a wall which is freely movable and permeable to
particles. The heat bath ensures a constant temperature in both chambers (Fig. 3.9).

V D V1 C V2 D const H) dV1 D dV2 ;

N D N1 C N2 D const H) dN1 D dN2 ;
F D F .T; V1 ; N1 / C F .T; V2 ; N2 / D F1 C F2 :

At equilibrium we have:

0 D dF D dF1 C dF2
(    )
@F1 @F2
D  dV1
@V1 N1 ; T @V2 N2 ; T
(    )
@F1 @F2
C  dN1
@N1 V1 ; T @N2 V2 ; T
D fp1 C p2 g dV1 C f1  2 g dN1 :

Since V1 and N1 are independent variables, it follows necessarily:

p1 D p2 D p I 1 D 2 D  : (3.74)

From this gedanken-experiment we can learn that in a closed system (gas), whose
volume V is constant and which is in thermal contact with a heat bath, at
equilibrium, the pressure and the chemical potential have the same values at all
points in the system.
3.7 Equilibrium Conditions 99

3.7.3 Closed System in a Heat Bath with Constant Forces

That imposes the following preconditions:

dT D 0 ; dNj D 0 ; dFi D 0 (3.75)

(Gas: T D const, N D const, p D const). The basic relation now reads:

!
X
m X
m
T dS D d.T S/  dU  Fi dqi D dU  d Fi q i
iD1 iD1
!
X
m
H) d U Fi q i  T S 0:
iD1

This means:

dG 0;
dG D 0 in the equilibrium. (3.76)

The free enthalpy (Gibb’s potential) G always decreases during all irreversible
processes which take place under the above boundary conditions. At equilibrium
G is minimal!
The same gedanken-experiment as in the last section with the additional precon-
dition p D const in each chamber will now be performed with several types of
particles (Fig. 3.10). The boundary conditions

.1/ .2/ .1/ .2/

Nj C Nj D Nj D const 8 j ” dNj D dNj

lead with
   
G D G T; p; N.1/ C G T; p; N.2/ D G1 C G2

N (1) N (2)
p,T p,T

HB(T )

Fig. 3.10 System in a heat bath of the temperature T with a dividing wall permeable to particles,
being bordered to the right and to the left by movable pistons which take care for a constant pressure
p in the chambers
100 3 Thermodynamic Potentials

to the following expression:

2 3
˛
! !
X 6 @G1 @G2 7 .1/
dG D 4 .1/
 .2/ 5 dNj
jD1 @Nj .1/
T; F; Ni; i ¤ j
@Nj .2/
T; F; Ni; i ¤ j

˛ n
X o
.1/ .2/ .1/ Š
D j  j dNj D0:
jD1

This means that at equilibrium the chemical potential

.1/ .2/
j D j D j (3.77)

assumes the same value everywhere in the system.

3.7.4 Extremal Properties of U and H

The equilibrium conditions derived so far are the in practice important ones. It is of
course possible also to derive formally the conditions for U and H, which, however,
are rather unwieldy because of the precondition to keep the entropy S constant.
1) Closed system of constant entropy without performance of work
This means:

dNj D 0 ; dS D 0 ; dqi D 0 .ıW D 0/ : (3.78)

The basic relation in this case yields:

dU 0;
U D 0 in the equilibrium. (3.79)

For all processes, which can take place under the conditions (3.78), the internal
energy U will never increase. It is minimal at equilibrium.
2) Closed system of constant entropy and with constant forces
With the boundary conditions

dNj D 0 ; dS D 0 ; dFi D 0 (3.80)

3.8 The Third Law of Thermodynamics (Nernst’s Heat Theorem) 101

the basic relation reads:

!
X
m X
m
0  dU  Fi dqi D d U  Fi q i :
iD1 iD1

The consequence is:

dH 0;
dH D 0 in the equilibrium. (3.81)

H decreases under the boundary conditions (3.80) for all processes, which can take
place, and is minimal at equilibrium!

3.8 The Third Law of Thermodynamics (Nernst’s Heat

Theorem)

With the aid of the second law of thermodynamics we have introduced in Sect. 2.7
the fundamental state quantity entropy, which we could define, however, only
except for an additive constant. Therefore, only entropy-differences between two
points of the state space are unique, provided that they can be connected by a
reversible state change. This, however, can not at all be taken for granted.
The equation of state, e.g. f .T; p; V/ D 0 for a gas, defines a state plane in
the . p; V; T/-space. If both the states A and B are on the same connected sheet of
the state plane, then they can always be linked by a reversible path (Fig. 3.11). If,
however, the state plane consists of two or more unconnected sheets (metastable
phases, mixture of different substances, or something like that) then it is possible
that such a reversible path does not exist. Then the undetermined constant prevents
the direct comparison of the entropies in the states A and B.
The theorem of Nernst makes a statement about the behavior of the entropy for
T ! 0 and abolishes therewith, at least partially, the mentioned indefiniteness.
The theorem must be considered here as an empirical matter of fact, which can
theoretically be reasoned only in the framework of Statistical Mechanics (Vol. 8).
Assertion 3.8.1 (Third Law of Thermodynamics) The entropy of a thermody-
namic system is at T D 0 a universal constant which can be chosen to be zero. That

Fig. 3.11 Path from state A

to state B on a connected
sheet of the state plane
f .T; p; V/ D 0