186

25. E N T R O P Y P R O D U C T I O N IN THE STEADY STATE

The preceding chapter introduced the notion of the two pivotal functions of steady-state
thermodynamics, the entropy production function, ~, and the energy retention function, T,
without as yet having addressed the underlying issue of the production of entropy in the
steady state. This issue, as stated in the introduction to Chapter 23, is the basic problem of
the thermodynamics of irreversible processes, and thus also of the thermodynamics of
coupled linear steady states. In accordance with w24.7 the present chapter therefore
considers the rate at which entropy is produced in a simultaneous flow of matter and heat.
To do this, we first establish the equations of continuity for the energy, for the matter, and
for the entropy, in a region small enough to be in local equi#brium (Postulate VI). The
continuity equation for the entropy yields the rate of entropy production per unit volume in
the region. Integration over all regions then furnishes the global rate of entropy production,
O. The entropy production function is then obtained simply by dividing O by the volume,
V, since 9 is the rate at which entropy is produced per unit time and unit volume
(cf w22.6).

25.0 Chapter Contents

25.1 The Gibbs Equation for Simultaneous Matter and Heat Flow
25.2 The Continuity Equation for the Energy
25.3 The Continuity Equation for the Matter
25.4 The Continuity Equation for the Entropy
25.5 The Rate of Entropy Production

25.1 The Gibbs Equation for Simultaneous Matter and Heat Flow
The starting point in our presentation of the steady-state thermodynamics of a
simultaneous flow of matter and heat is the Gibbs equation, the differential form of the
fundamental equation. Consider a system consisting of a fluid mixture contained in a vessel
of fixed volume, V The walls of the vessel are diathermal and permeable to the jth matter
species. The Gibbs equation in the entropy representation, Eq.(3.9)2,

1 P #JdNj, (25.1)1

is reduced, in view- of the fixed volume, to

1 v--, #j
(25.1)2

where s = S / N , u = U / N , and cj = N j / N .
25. ENTROPY PRODUCTION IN THE STEADY STATE 187

In the energy representation the Gibbs equation becomes

du = T d s + Z j l . z j d c j . (25.1)3

Equations (25)2 and (25.1)3 are molar forms ofthe Gibbs equation (cf w 14.3).

25.2 The Continuity Equation for the EnergT

We now establish the equation of continuity for the energy. Let R be a region within
the vessel with volume, r and surface, or. We consider this volume to be small enough so
that it is in local equilibrium (Postulate VI). If dv is an elemental volume in R, the total
internal energy in the region is fo u du. The rate at which the internal energy changes in the
region R equals the r a t e at which energy enters or leaves R across its surface, a.
Introducing the energy flux, energy f l o w vectoi; or energy current density, J u , as the
amount of energy crossing unit area in unit time, we have

- -d-~d v = Ju " da (25.2)1

where d a is an elemental vector area of the surface, cr, and the flow vector is defined as
positive for outward flow. Thus, Eq.(25.2 h expresses the fact that the energy within the
region R decreases when the matter flows from the inside to the outside of the region.
Now, by the divergence theorem,

f Jc~ 9da = fo ~7. J u d v , (25.2)2

and, therefore,

-d-~ + V . Yv) d v = O. (25.2)3

But this is true for an arbitrary volume, dr. Consequently, the continuity equation for the
energy becomes

du
d-t- q- ~ ' " J v = O. (25.2)4

The first term on the left represents the increase in the energy in the region R per trait time.
The second term represents the rate of outflow of the energy from the region per unit area
188 U. STEADY-STATE THERMODYNAMICS

of surface in an exchange with the surroundings. According to Eq.(25.2)4 the sum of the
two terms is zero. The equation thus expresses the conservation o f energy (cf. w 2.4).

25.3 The Continuity Equation for the Matter

The amount of the jth species of matter in R is f0cj dv. We introduce the matter
flux, matter flow vector, or matter current density, JN~, of the jth species as the number of
moles of j, Nj, entering or leaving R across unit area of its surface, a, in unit time. Here
also, the flow vector is defined as positive for outward flow. Hence, we have

--
fo--d-( d v = JN.~ " da . (2S.3)1

Again invoking the divergence theorem, the continuity equation for the jth species
of matter results as

dc~
+ g r . J~3 = O. (25.3)2
dt

The first term on the left represents the increase in the matter contained in the region R per
unit time. The second term represents the rate of outflow of matter from the region per unit
area of surface in an exchange with the surroundings. By Eq.(25.3)2 the sum of the two
terms is zero. The equation thus expresses the conservation o f matter.

25.4 The Continuity Equation for the Entropy

We are now ready to calculate the local rate of change of the entropy, i.e., the rate
of entropy production in the local region R. By Eq.(25.1)2

ds_ du ~ #jdcj (25.4)1

dt Tdt z..~j T d t "

Substituting from Eqs. (25.2)4 and (25.3)2 gives

ds ~V #J
dt - T . du + E j - ~ V . dx, . (25.4)2

But, if A is a scalar, and A is a vector, then

~ v . A = v . ( ~ A ) - A- v ~ . (25.4)3

Making use of this identity in both terms on the right hand side of Eq.(25.4)2, and
introducing the entropy flux, entropy flow vector, or entropy current densi~,
25. ENTROPY PRODUCTION IN THE STEADY STATE 189

=
(25.4)4

we obtain

ds (1 #j) ."
+ 9 (,4),

This equation is the equation of continuity for the entropy in the region R. The first
term on the left represents the increase of the entropy per-atilt time. The second term
represents the rate of outflow of the entropy per unit area of surface in an exchange with
the surroundings. The sum of these two terms is not zero. Hence, the entropy in the region
R is not conserved. The right hand side represents the rate of production, generation, or
creation of entropy in ~ e region R per-trait volume in unit time, i.e., the entropy production
function, ~. We thus have

d3
+ V..Is = ~ (25.4)6
dt

where

(25.4)7

is the entropy produced per trait time and unit volume. Since this does not vanish,
Eq.(25.4)6 expresses the non-conservation o f the entropy {cf. w 2.17).

25.5 The Rate of Entropy Production

So far we have examined the situation in a region R of the total volume m a ~ g use
of the postulate of local equilibrium (Postulate VI). The global relations are obtained simply
by integrating over all regions. Integrating Eq.(25.4)5 over unit volume, V, and using the
divergence theorem, we find

d--t s dv + J s 9da = ~ dv = O . (25.5)

The fight hand side of this equation is the rate of entropy production, O. ~ the vessel is
isolated, the second integral on the left hand side vanishes. The first integral is thus seen to
represent the entropy generated within the vessel per unit time, diS~dr. By Eq.(25.4)5 this
vanishes when the gradients of the temperature and of the chemical potentials vanish, i.e., at
equilibrium.