AGH - UNIVERSITY OF SCIENCE AND TECHNOLOGY

FACULTY OF NON-FERROUS METALS

Department of Theoretical Metallurgy and Metallurgical Engineering








Ph.D. THESIS




Title: MINIMIZATION OF ENTROPY GENERATION IN STEADY
STATE PROCESSES OF DIFFUSIONAL HEAT AND MASS
TRANSFER








Author: Mgr Jacek Mikoaj atkowski

Supervisor: Prof. zw. dr hab. in. Zygmunt Kolenda










KRAKW, NOVEMBER 2006

2





























Pozwalam sobie wyrazi serdeczne podzikowanie
Profesorowi Zygmuntowi Kolendzie za cenne rady
i za kierownictwo naukowe mojej pracy doktorskiej


I would like to express my sincere gratitude to
Professor Zygmunt Kolenda, for his guidance
and support during the completion of the thesis.






3
Table of Content


1. Introduction 7

2. Description of the thermodynamics of the non-equilibrium
processes of mass and energy transfer literature overview 8

2.1 Theoretical background 8

2.2 Calculation of entropy production 12

2.3 Examples of phenomenological description 17

2.3.1 Heat conduction and electric current flow 17

2.3.2 Thermal diffusion 19

2.4 Irreversible, stationary process of heat conduction 20

2.5 The principle of minimum entropy production in
stationary states 23

2.6 Principle of entropy production compensation 26

3. Aims of the thesis 29

4. Minimization of entropy production and principle of
entropy production compensation in steady state linear
processes of diffusional mass and energy transfer 33

4.1 Heat conduction in a plane-wall 33

4.2 Diffusional mass transfer 39

5. Entropy production minimization in stationary processes
of heat and electric current flows 42

5.1 Non-linear boundary problem without the
internal heat source 45

5.2 Boundary problem with boundary conditions
of the third kind (Sturm-Liouville boundary
conditions) without internal heat source 45

5.3 Boundary problem with simultaneous heat
and electric current flows 49

5.4 Methods of calculation of additional internal
heat source and entropy generation rate 51
4
6. Methods of solving the boundary problems with
Euler-Lagrange equations 61

6.1 General method of determining the internal heat
source and entropy generation rate 61

7. Solutions for the specific boundary problems 68

7.1 Simultaneous heat and electric current flows 68

7.2 Boundary conditions of the second and third
kinds - heat conduction coefficient
independent of temperature 87

7.3 Boundary conditions of the third kind
(Sturm-Liouville boundary conditions) - heat
conduction coefficient dependent on temperature 92

8. Applications 96

9. Summary 98

Appendix 1 100

References 102






















5
Symbols


A - chemical affinity
A, B - integration constants
C
i
- concentration of i-th component
c
i
- integration constants
d
e
S - entropy exchange with surroundings
d
i
S - entropy production due to irreversibility
D
T
- thermal diffusion coefficient
D
d
- Dufour coefficient
F - Helmholtz free energy
F - thermodynamic force
F - function
G - Gibbs free energy
H - enthalpy
h - heat transfer coefficient
I,i - density of electric current
J - thermodynamic flux
J
k
- mass flux of k-th component
J
q
- heat flux
J
s
- entropy flux
J
u
- internal energy flux
k - thermal conductivity coefficient
k
f
- thermal conductivity coefficient of fluids
L
ik
- phenomenological coefficients
n - normal to the surface
n
i
- number of moles of i-th component
p - pressure

q&
- heat flux

v
q&
- internal heat source

Q
&
- heat flow
Q - heat
s
T
- Soret coefficient
S - entropy of the system
s - specific entropy





6


T - absolute temperature or dimensionless temperature
T
f
- fluid temperature (absolute or dimensionless)
u - specific internal energy
U - internal energy
v - specific volume
V - volume
W - work
X - thermodynamic force
x, y ,z - cartesian coordinates




Greek symbols


- change

i
- chemical potential of i-th component

i
- stoichiometric coefficient

ik
- stoichiometric coefficient of the k-th component for the i-th
chemical reaction
- extent of reaction
- density
- specific electric resistivity
- entropy generation rate (entropy production)
- time
- boundary surface
- function
- electric potential












7
1. Introduction

Progress of the human civilization is intrinsically connected with the use
of energy sources. Methods of harnessing the natural energy resources can be
better or worse, more or less effective, cost-conscious or unlimited. It is rather
obvious that we are trying for those methods to be better, more effective and
cost-cutting. These aims are primarily reached through the development of
scientific research and in the topics discussed in this thesis, through the
applications of methods of non-equilibrium thermodynamics. The main
problem, widely discussed during the last decade, is the issue of diminishing
natural resources, specially the energy resources.

The problem of diminishing energy resources was first discussed in a well
known report Limits of progress (Meadows and others, 1972). The authors of
the report, using various mathematical models, formulated the hypothesis that in
the middle of the 21
st
century there will be a collapse in the development of rich
countries as the result of the overexploitation of the natural resources.
We know well today that those catastrophic predictions have not been
confirmed. In addition to economic problems, we face today the dangers of
excessive pollution and irreversible destruction of the natural environment as the
result of increasing demand for nonrenewable energy resources. Negative
consequences of global warming as an effect of human activity are the prime
example.

Thus, we can ask the question are the dangers of our civilizations
progress real as the effect of diminishing natural resources, especially fuel
resources. This question is based on the premise that non-renewable natural
resources are gone. However, the optimistic is the fact that natural energy
resources can be replaced by other renewable sources of primary energy or
nuclear energy, which at the current progress of technology, could become the
sources of unlimited energy.

Even, considered negative, population growth does not seem to be a threat
since each new human being is born with the ability to be creative. It seems as
well that the accumulated use of energy in the industrial countries allows for the
fast progress in technology which in turn results in a decrease of irrational use of
resources.

The following thesis is about the solutions which lead to the decrease in
the exploitation of natural resources and to limiting the dangers to the natural
environment.


8
2. Description of the thermodynamics of the non-equilibrium processes of
mass and energy transfer literature overview

In this chapter the fundamental terminology of the non-equilibrium
thermodynamic processes has been presented. The expression describing the
entropy production (entropy generation rate) has been derived as the measure
of intensity of the irreversible process. The principle of entropy production
compensation has been discussed as the basis for minimizing entropy
production. The main non-equilibrium processes and their links have also been
discussed.


2.1 Theoretical background

The fundamental relationship resulting from the classical
thermodynamics, known as the Clausius inequality, describes the change of
entropy dS of the thermodynamic system in the form:

Q
dS
T

(2.1)

where Q is the elementary heat exchanged between the system and the
environment and T is the local temperature (relation (2.1) has a local character).
Relation (2.1) can also be written in the form:

0 TdS Q

(2.2)

Inequality sign in (2.1) and (2.2) describes the irreversible processes while the
equality is required for the idealized equilibrium or reversible processes.

Deriving , as done by T. de Donder [2], the term for non-compensated heat

Q TdS Q =

(2.3)
the Second Law of Thermodynamics can be written as:

0 Q


9
As the result of de Donders analysis, non-compensated heat is the
measure of spontaneity of the process which consequently leads to general
definition of chemical affinity A for the spontaneous chemical reaction:


Q
A
d
=


where d = dn
i
/
i
is called the extent of a reaction, dn
i
is the elementary change
in number of moles of the particular component in the reaction while
i
is the
stoichiometric coefficient.
In case when the system is doing only the mechanical work, the formulation of
the First Law of Thermodynamics gives:

Q dU pdV = +

(2.4)

where dU is the elementary change of internal energy, p is the pressure and dV
is the elementary change of volume of the system.

Combining equations (2.3) and (2.4) results in:

dU TdS pdV Q =


Introducing, from the definitions the expressions for:

enthalpy H: H = U + pV

Helmholtz free energy: F = U TS

Gibbs free energy: G = H TS,

we receive the following set of equations:

dU TdS TdV Ad
dH TdS Vdp Ad
dF SdT pdV Ad
dG SdT VdP Ad

=
= +
=
= +

(2.5)

10
Expression (2.3) can be further changed into the expression:

Q Q
dS
T T
= +

(2.6)

From the definitions
e
Q
d S
T
=

and (2.7)

i
Q
d S
T
=

(2.8)

equation (2.6) becomes:

e i
dS d S d S = +

(2.9)
Since

Q
dS
T

then
e
dS d S

(2.10)


which means that always:
d
i
S 0
(2.11)

where: d
i
S > 0 for irreversible processes
d
i
S = 0 for reversible processes

11
From equation (2.6) we can see that
e
Q
d S
T
=
describes the exchange of
entropy between the system and the surroundings and
i
Q
d S
T
= is the entropy
production due to irreversible processes inside the system. In the analysis of
expression for d
i
S, significant role is played by the local formulation of the
Second Law of Thermodynamics. It states that in every microscopic part of the
system in which irreversible processes take place, the entropy production
(entropy generation rate) d
i
S/d, where is the time, must be positive or:


0
i
d S
d
>

(2.12)

It means as well that in a given volume, there can simultaneously take place
processes with positive and negative entropy production but in such a way that
the positive entropy production is greater from the negative production (within
the absolute value), which insures the validity of inequality (2.12).
Differentiating equation (2.9) gives:

e i
d S d S dS
d d d
= +

(2.13)

where dS/d is the entropy rate of change of the system as the result of the
entropy rate of exchange with the surroundings dS
e
/d and the entropy
production (entropy generation rate) is

i
d S
d

=

(2.14)

The general differential equation of the local entropy for any irreversible closed
system is:
s
ds
divJ
d

= +

(2.15)
and
12

( )
s
ds
div J sv
d

= + +

(2.16)

for the open system, where s represents the entropy value per unit volume ,
the density of the substance, J
s
entropy flow (entropy flux) exchanged with
the surroundings and v is the flow velocity.

The most important element, in the analysis of irreversible processes, is the
calculation of entropy production (rate of entropy production). This value
directly describes the level of irreversibility of the given process. It is important
to mention as well that the entropy production is path dependant and should not
be confused with entropy change.

The condition:

0
i
d S
d

=

(2.17)

directly indicates that, for example, the process along two different paths A and
B such that
A B
>

(2.18)


means that path A is more irreversible than path B.


2.2 Calculation of entropy production

The method of calculating the amount of entropy production related to
different irreversible processes, is based on the entropy balance equations. For
example, equation (2.15) yields:

s
ds
J
d

= +
r

(2.19)


13
Neglecting the kinetic energy dissipation and with no external fields, Gibbs
relation:

k k
k
Tds du dn =

(2.20)

where
k
is the specific thermodynamic potential for the k-th component of the
system while dn
k
represents the elementary change of the amount of the k-th
component, leads to:
1
k k
k
n s u
T T

=


(2.21)

Introducing the mole-number balance equation for the amount of the k-th
component,
k
k jk j
j
n
J

= +

r

(2.22)

where
ik
is the stoichiometric coefficient of k-th component for the j-th
chemical reaction and
j
is the rate of the j-th reaction in volume V,

1
j
j
d
V d

=


and the equation of the First Law of Thermodynamics:

0
u
u
J

+ =

r

(2.23)

where J
u
is the internal energy flux, equation (2.21) takes the following form:

,
1
k k
u k jk j
k k j
s
J J
T T T

= +

r r


(2.24)
Introducing from definition,

14
j k jk
k
A =

equation (2.24) becomes,

1
j j
u k k k
u k
k k j
A
J J s
J J
T T T T T

+ = +

r r
r r

(2.25)


where the following property was used for the scalar function g and vector J,

( ) ( )
gJ J g g J = +
r r r


Comparing equation (2.25) with the entropy balance equation (2.19) leads to
the expression:

u k k
s
k
J J
J
T T

r r
r

(2.26)

and the expression for entropy production:

1
0
j j
k
u k
k j
A
J J
T T T

= +

r r

(2.27)

In case of the external electric field with the electric field strength E =
( electric potential) resulting in the flow of electrical current with the current
density I, the following equation is derived

( ) 1
j j
k
u k
k j
A I
J J
T T T T

= + +

r
r r

(2.28)

15
The derived equation (2.28) is the general expression for the entropy production
in which four irreversible processes were taken into account: heat conduction,
mass diffusion, electric current flow and chemical reactions.

Mathematical structure of equations (2.27) and (2.28) indicates that they be both
written in the general form:

k k
k
F J =


(2.29)

where F
k
is called the thermodynamic force and J
k
the thermodynamic flow,
coupled with forces. For the processes discussed above, the forces and flows are
listed in Table 1.

Table 2.1 Forces and flows in entropy generation equations
Irreversible Process Force F
k
Flow J
k
Heat Conduction 1
T

Heat flow J
u
Diffusion
k
T

Diffusion current J
k
Electric current flow
E
T T

=
r

Current density I
Chemical reaction
j
A
T

Reaction rate
1
j
j
d
V d

=


Equations (2.27) and (2.28) play a fundamental role in determining the entropy
production for the processes with known thermodynamic forces and flows. In
general, the amount of entropy production is calculated from the mathematical
models for the processes being considered.

In case of cross effects, for example simultaneous heat conduction and electric
current flow, the entropy production is described, with a good accuracy, by the
linear relationship between flows and thermodynamic forces, in the form:


k kj j
j
J L F =


(2.30)

16
where L
kj
is called phenomenological coefficients, whose values can be found
experimentally.

Substituting equation (2.30) into equation (2.29), the entropy production takes
the quadratic form:
,
0
jk j k
j k
L F F = >

(2.31)

Because of positive sign of entropy production, a matrix L
jk
is said to be positive
definite. This means that the two-dimensional matrix L
jk,

11 12
21 22
L L
L L


is positive definite if the following conditions are satisfied:

L
11
> 0, L
22
> 0 and (L
12
+L
21
)
2
< 4L
11
L
22



In general, for the matrix
11 12 1
21 22 2
1 2
............
...........
:
...........
n
n
n n nn
L L L
L L L
L
L L L
=


there are following conditions:

L
kk
> 0 for k < 1, n >

and all the main minors are positive definite.

In 1931, Lars Onsager introduced the principle of symmetry of matrix L. This
means that for the linearly independent forces and flows, the following relations
hold true:
L
jk
= L
kj

(2.32)

These relations are sometimes known as the Fourth Law of Thermodynamics.
17
2.3 Examples of phenomenological description

In the following sections, the phenomenological description of several
cross effects such as heat conduction and electric current flow as well as thermal
diffusion will be presented in detail.

2.3.1 Heat conduction and electric current flow

This phenomena is known as thermoelectric effect and its general description is
shown in Figure 1.

I



Al Al

Cu Cu J
q

T T+T T T


Seebeck Effect

Peltier Effect

- /T =J
q
/I

Fig. 2.1 Thermoelectric effect

Phenomenological equations are as follows:

1
1
q qq qe
e ee eq
E
J L L
T T
E
I L L
T T

= +



= +


r
r
r
r
(2.33)
where index q and e relate to heat flow and current density.
According to Onsagers principle:

L
qq
> 0 , L
eq
> 0 and L
ee
=L
qe


After rearrangement, equations (2.33) become

18
2
2
1
1
q qq qe
e ee eq
T E
J L L
T x T
E T
I L L
T T x

= +

r
r
r
r
(2.34)
Comparing expression
2
1
qq
T
L
T x

with the Fouriers law leads to the relation:

2
qq
L
k
T
=

(2.35)

which for the known coefficient of heat conduction k, allows
for calculation of L
qq
. In a similar way, another relation can be derived:

ee
T
L

=

(2.36)
where is the specific electric resistance and

0
eq ee
T
L L T
T

(2.37)

where /T is the Seebecks coefficient determined experimentally
similarly to

qe ee
L L =

(2.38)

where
0
q
e
T
J
I
=

=


is the Peltiers coefficient.
19
2.3.2 Thermal Diffusion


The interaction between heat and mass flows produces two effects known
as the Soret effect and the Dufour effect. The equation for entropy production
has the form:
( )
,
1 k
T p
q k
k
J J
T T

=



r

(2.39)


For the two component system, the following relations are obtained:

1 1 1
1 1
2
2 2 1
1
1 1 1
1 11 1
2
2 2 1
1
1
1
1
qq
q q
q
L
n
J T L n
T T n n
L
n
J T L n
T T n n

= +





= +




(2.40)


where n and mean accordingly the number of moles in the substance and the
partial molar volume. This allows to determine the diffusion and heat
conduction coefficients:

1 1 1
1 11
2 2 1
2
1
1
qq
n
D L
T n n
L
k
T

= +



=

(2.41)

From the Onsagers principle,

L
q1
= L
1q


Introducing the general coefficient of thermal diffusion

20
1
2
1
1
q
T
L T
D
T n T

the Soret coefficient becomes:

1
2
1 1 1
q
T
T
L
D
s
D D T n
= =

(2.42)
and the Dufour coefficient is:

1 1 1
1
1 2 2 1
1
1
d q
n
D L
n T n n

= +




(2.43)


The values of coefficient s
T
and D
d
are determined experimentally what allows
for the calculation of phenomenological coefficient L
q1
.

Many examples of the applications of linear thermodynamics for irreversible
processes can be found in literature [2].



2.4 Irreversible, stationary process of heat conduction

An important group of irreversible processes is represented by stationary
states. Stationary state is reached by the system when the imposed
thermodynamic forces are constant (independent of time) and this state is
characterized by the constant entropy production. As an example, stationary
state for heat conduction has been discussed. The schematic diagram (infinite
plane-wall) and the geometry of the process are shown in Figure 2. The heat
flows spontaneously from the source with the higher temperature T
H
to a source
with a lower temperature T
L
. The coefficient of thermal conduction of the plane-
wall is constant.






21
T


H
h

-
L
h


k
T
H

q
J
r



fluid flow
fluid flow kk with temp. T
L
with temp. T
L
T
H


x
0 L

Fig. 2.2 Boundary value problem of the first kind


Since the heat conduction is the only irreversible process, therefore the entropy
production is
1
q
J
T
=
r

(2.44)

If the temperature gradient is only in x direction, the entropy production per unit
length is given by

2
1 1 ( )
( )
( )
q q
T x
x J J
x T x T x

= =




(2.45)
The total entropy production is therefore

0 0
1
( )
L L
i
t q
d S
x dx J dx
d x T

= = =

(2.46)


q
J
r






k = constant
22
In case of the stationary state, 0
T
t

and
q
J
r
is constant. The stationary state
also implies that the total entropy of the system is constant:

0
e i
d S d S dS
d d d
= + =


which means that:
e i
d S d S
d d
=


Integrating equation (2.46) gives

0 0
1
0
( )
L
L
q q q
i
q
C H
J J J
d S
J dx
d x T x T T T

= = = >

so
, ,
i
s out s in
d S
J J
d
=

(2.47)

where J
s
is the entropy flow.



In general:
i
s
d S
div J
d
=

(2.48)

Identical equations describe the mass diffusion while the temperature T is
replaced by the concentration of the k-th component of the substance.







23
2.5 Principle of minimum entropy production for stationary states


The expression

k k
k
F J =


which describes the entropy production for irreversible processes, shows how
different thermodynamic flows J
k
are coupled with the corresponding
thermodynamic forces F
k
.
Let some forces F
k
, (k=1,2,..,m) to be at a fixed nonzero value, while leaving
the remaining forces F
k
, (k=m+1, ..n), free. In stationary state the
thermodynamic flows corresponding to the constrained forces reaching a
nonzero constant (k = 1,2,..m), J
k
=constant, whereas the other flows are equal
to zero, J
k
=0, (k=m+1,..n).
Prigogine [2] has revealed the truthfulness of the following principle:

In a linear regime, the total entropy production in a system subject to flow of
energy and matter, /
i
d S d dV =

reaches a minimum value at the non-

equilibrium stationary state.

Mathematically,

minimum
i
t
V
d S
dV
d

= =

(2.49)

Such a general criterion was first formulated by Lord Rayleigh as the principle
of least dissipation of energy.


Consider, for example, a system with two forces and flows that are coupled. The
total entropy production is:


( )
1 1 2 2
i
t
V
d S
FJ F J dV
d

= = +

24
Let the force F
1
remain at a fixed nonzero value. In addition, in a stationary
state, J
1
=constant 0 and J
2
= 0 .The linear phenomenological relations of
flows and forces give:

1 11 1 12 2
2 21 1 22 2
0
J L F L F
J L F L F
= +
= + =


Using Onsagers reciprocal relations L
21
=L
12
, the total entropy production
becomes:

( )
2 2
11 1 12 1 2 22 2
2
t
V
L F L FF L F dV = + +

In follows from the Prigogines principle that reaches minimum when:

( )
22 2 12 1
2
2 0
V
L F L F dV
F

= + =

(2.50)

where F
2
is the free force.

The entropy production is minimized when the integrand expression in (2.50)
is equal to zero, that is

2 21 1 22 2
0 J L F L F = + =
.

This result can easily be generalized to an arbitrary number of forces and flows.

Consider the boundary problem of the first kind shown in Figure 2.2. For the
one dimensional heat flow, entropy production is given by equation (2.46):

0 0
1
( )
L L
i
t q
d S
x dx J dx
d x T

= = =

Introducing expression:
1
q qq
J L
x T

25
equation (2.46) becomes:
2
0
1
L
qq
L dx
x T

(2.51)
where T=T(x) .

In can be demonstrated that according to calculus of variation, integral (2.51)
reaches minimum when the Euler-Lagrange equation is satisfied:

0
x
d
T dx T



=




(2.52)
where
x
T
T
x

Assuming that [2]

2 2
qq avg
L kT kT =


(2.53)

where T
avg
is the average temperature of the plane-wall, the Euler-Lagrange
equation gives
1
0
qq
d d
L
dx dx T


=




Therefore

1
qq q
d
L J const
dx T

= =



Finally
T
k c o n s t
x

which leads to the Laplace differential equation:

26
2
2
( )
0
d T x
dx
=


In case of 3D the following equation is obtained:

2 2 2
2
( , , ) 0
T T T
T x y z
x y z

= + + =



(2.54)

This classical approach is only valid when the assumption of the average
temperature (equation 2.53) can be accepted. When such an assumption is not
justified, the resulting heat conduction equation takes a different form. This is
discussed in the Chapter 3 - Aims of the Thesis.


2.6 Principle of entropy production compensation

The previous discussions concerning the local formulation of the Second Law of
Thermodynamics can be generalized. Let the thermodynamic system consist of
r subsystems. The additive property of entropy as the function of state results in


1 2 3
....... 0
r
i i i i i
d S d S d S d S d S = + + + +


where d
i
S
k
is the entropy production in the k-th subsystem.
Local formulation of the Second Law of Thermodynamics requires that the
following inequality must be satisfied:

0
k
i
d S

for every k.

The above inequalities are valid for all systems, not only isolated systems,
regardless of the boundary conditions.

Therefore, the local entropy production can be defined as

( , ) 0
i
d S
x
d

=

(2.55)
27
and
( , )
i
V
d S
x dV
d

=


where the local entropy production depends on the Cartesian coordinates x.

It has also been shown that the positive sign of the local entropy production does
not preclude at same place the processes with both positive and negative entropy
production as long as the condition (2.55) is satisfied.

Assuming that the subsystem A is not isolated but it can interact with another
subsystem A , it is obvious that for the isolated system consisting of A and A,
its entropy is
S
*
= S
A
+ S
A

therefore
*
'
0
A A
S S S = +


It can be therefore concluded from the above that if S
A
is decreasing than S
A

must be increasing in such a way that the following inequality is satisfied:

' A A
S S >

(2.56)

Because of the local formulation of the Second Law of Thermodynamics,
inequality (2.55) applies to each smallest part of the system.

Based of the above considerations, one can formulate the principle of entropy
production compensation:

Entropy production for the thermodynamic system can be decreased in only
such a way if the system undergoes coupled processes.

This principle has important practical applications. It also allows to introduce
optimization and direct comparison methods for various solutions to the process.

For example, the process of synthesis, important in the creation of
macromolecules in living organism, can be considered here [6].

glucose + fructose sucrose + H
2
O
(2.57)
28
The changes of entropy in this reaction can be replaced by the analysis of Gibbs
free energy changes G. This change G = + 0.24 eV, which means that,
spontaneous reaction (2.57) is taking place in the wrong direction, from right to
left, which means it leads to decomposition of sucrose.

In order of achieving the preferable direction of the process, the entropy
production compensation principle says that there must be another reaction
taking place in the system, with a negative entropy production (G) so

G + G 0

In living organisms, such a reaction does take place and involves the ADP
(adenosine diphosphate) and ATP (adenosine triphosphate) molecules.

ATP + H
2
O ADP + phosphate

The ATP and ADP molecules play an important role in the process of
metabolism (see [6]).

The change of Gibbs free energy in the above reaction, G = 0.30 eV

Therefore
G + G = - 0.06 eV

The full mechanism of the chemical reactions consists of two component
reactions:

ATP + glucose ADP + glucose 1-phosphate

(glucose 1-phosphate) + fructose sucrose + phosphate


The summary reaction looks as follows:


ATP + glucose + fructose sucrose + ADP + phosphate


The principle described above also applies to the processes of protein synthesis
from amino-acids and DNA, carrying the genetic information.



29
3. Aims of the thesis

The irreversibility of the physical and chemical thermodynamic processes,
taking place in the surrounding Nature, are the reasons for degradation
(dissipation) of all forms of energy, and the measure of this dissipation,
according to the Second Law of Thermodynamics, is the increase of entropy or
entropy production. Qualitatively, this is described by the Gouy-Stodola
theorem [1], which states that the lost available work (destroyed exergy) W is
directly proportional to the entropy increase S for all elements taking part in
the process. Mathematically,

0
W T S =

or
0
W T =
&

(3.1)

where T
0
is the temperature of the environment and is called the entropy
production or rate of entropy generation.
Note: the exergy is the maximum available work to be gained from the system
when the conditions of the surroundings are the frame of reference. More on
exergy, see [7].

The above equations directly indicate that the amount of entropy
production is the measure of degree of irreversibility in the system. The energy
lost, described by the Gouy-Stodola theorem, are not possible to be recovered,
therefore the above law is often called the law of destroyed exergy. The typical
irreversible processes are processes with finite gradient values characterizing the
field potential diffusional flow of energy and matter, processes of friction and
turbulent flow, irreversible chemical reactions.
The Gouy-Stodola theorem concludes that minimization of non-linear losses of
exergy is only possible through the minimization of entropy production.
As already shown in Chapter 2, entropy production is defined by

i
d S
d

=


where d
i
S is the entropy change of the system resulting from the irreversibility
of the process, while is time and the Second Law of Thermodynamics shows
that always and in each place of the thermodynamic system:


30

0


which means that entropy production is path dependant (entropy production is
path dependant and should not be confused with entropy change).

The core of entropy production minimization centers on searching for
methods of conducting the process, so with the known constraints and boundary
conditions, is minimum. The entropy production minimization principle is
fully appreciated in conjunction with the entropy compensation principle, which
appears to be a new, expanded version of Prigogines principle.
It is important to emphasize though the difference between Prigogines
principle and entropy production minimization as two principles are often
understood as equivalent.
Prigogines principle allows to determine the parameters of stationary
process as in Chapter 2.5 where the constant thermodynamic force F
1
gives as
the condition for stationary process the zero value of flow J
2
.
Since, as shown in Chapter 2.1, entropy production is path dependant,
minimum can be reached in various ways which will be explained below.
Entropy production in the one-dimensional process of heat conduction
(k=constant) , when the assumption that T=T
avg
can not be accepted, is

2
2
( )
( )
( )
k dT x
x
T x dx

=




Calculating the classical minimum of this function

2
2
( )
0
( )
d d k dT x
dx dx T x dx

= =







the Euler-Lagrange equation is obtained (Chapter 4.1)

2
2
2
1
0
d T dT
dx T dx

=




The solution T=T(x) of the above equation determines the minimum since

31
2
2
0
d
dx

>


The above short discussion illustrates the new and additional
interpretation of Prigogines principle which should not be consider
equivalent to entropy production minimization principle. It is interesting to see
that Bejan, without explaining, as above, the difference between the two
principles, does not link Prigogines principle with the entropy production
minimization principle [1].

The above principles have been used in this thesis in order to minimize
the entropy production in diffusional flow of matter and heat.

New differential equations were presented, describing the processes of
heat conduction in solids and the equation of diffusional mass transfer has been
obtained. This equation was derived with the use of calculus of variations.
The Euler-Lagrange differential equations were introduced. The in-depth
physical analysis of the additional internal heat source was introduced, as the
element insuring the entropy production minimization. The agreement of the
analysis with the First and Second Laws of Thermodynamics has been shown.

It is very important to emphasize that in this thesis, the classical Prigogines
assumption that

T=T
avg

is not accepted and the entropy production is considered in the most general
form
2
1
2
0
( )
( )
k T dT
dx
T x dx

=



instead of

2
1
2
0
1
( )
avg
dT
k T dx
T dx

=





The major difference resulting from deriving the equation for heat conduction
with the use of Prigogines principle has been demonstrated.
The detailed analysis has been devoted to boundary conditions, including the
32
conditions of Sturm-Liouville type. Equations describe the simple cases when
the physical properties of the system such as the coefficient of heat conduction
or the coefficient of mass diffusion are constant as well as when they are
functions of temperature and substance concentration. The obtained equations
describing the energy and mass transfer are mathematically non-linear due to
the non-linear nature of internal sources of heat and mass. In addition, this non-
linearity is intensified by the nature of physical constants and difussional field
potentials, mentioned above. Finally, the practical applications of the obtained
results have also been discussed.


































33
4. Entropy production minimization and entropy production
compensation principle in stationary, linear processes of diffusional
transfer of mass and energy

In this chapter, the main applications of the entropy minimization
principle and compensation of entropy production have been presented for some
specific processes of mass and energy transfer. The discussion centers on the
stationary processes. Since the mathematical description is similar, the specific
discussion was presented for the processes of heat conduction in solids with the
boundary conditions of the first kind (first boundary problem).


4.1 Heat conduction through a plane-wall

As clear from the previous discussion, entropy production in the process
of heat conduction is given by


term u u
J X =
r r
o

(4.1)

where:

- the thermodynamic force
( )
1
u
i
X grad
T x

=



r

- thermodynamic vector flow ( ) ( )
u i
J k T grad T x =
r



For the one-dimensional steady state heat flow (Figure 4.1), we obtain

2
1 ( )
u
dT x
X
dx T
=
r


( )
( )
u
dT x
J k T
dx
=
r

therefore
2
2
( )
term
k T dT
T dx

=



(4.2)
and
34
2
1
2
0
( )
t
k T dT
dx
T dx

=




















Fig. 4.1 Heat Conduction through a plane-wall



The aim is to look for a such temperature function T=T(x) which ,while
satisfying the boundary conditions, minimizes the entropy production.

The application of calculus of variations (see Appendix 1) leads to Euler-
Lagrange differential equation.

0
x
d d
T dx T

=





where
x
dT
T
dx
=


With the use of (4.2) and assuming that k = const, the above equation becomes

( )
dT
dx
q k T = &
( ) T T x =
T
1
T
2
0 1 x
Boundary Conditions:

x = 0 T(0)=T
1

x = 1 T(1)=T
2


A=1m
2


x < 0 , 1 >

T < T
1
, T
2
>
35
2
2
2
1
0
d T dT
dx T dx

=



(4.3)

whose solution, with the boundary conditions from Figure 4.1., has the form

2
1
1
( )
x
T
T x T
T

=



(4.4)

which describes the temperature distribution along the thickness of the plane-
wall. The entropy production is

2
1
2
0
( ) k T dT
dx
T dx

=




which in combination with the above solution for T(x) gives

2
2
1
ln
t
T
k
T

=



(4.5)



versus the classical solution:

1 2
2 1
1 1
( )
c
t
k T T
T T

=




where it can be easily shown that
c
t t
>


Analysis of the equation (4.3) demonstrates that the expression:

36
2
( )
v
k dT
q x
T dx

=


&

(4.6)

is the additional internal heat source , which must be continuously
removed from the system.

Applying the solution (4.4), the following expression is obtained:

2
2 2
1
1 1
( ) ln 0
x
v
T T
q x kT
T T

= <


&

(4.7)
and after integrating

2
1 2
1
( ) ln 0
v
T
q k T T
T
= < &

(4.8)

Practical method insuring the minimization of requires the removal of heat
from the internal source described by the equation (4.7), for example as the
driving heat in Carnot engines as presented in Fig. 4.2.















Figure 4.2 Physical interpretation of the entropy production minimization


0
1 x
out
q&
( )
v
q x &
Work done
W
rev

Elementary Carnot
cycles
in
q&
37
The quantities q
in
and q
out
can be derived from the relations:
1
1
0
2
1
2
1
2
ln
ln
in
x
out
x
dT T
q k kT
dx T
dT T
q k kT
dx T
=
=
= =
= =
&
&

(4.9)
which shows that
2
1
1
out
in
q T
q T
= <
&
&

(4.10)
and
in out v
q q q = + & & &

(4.11)
Physical interpretation of these results demonstrates that through the
minimization of the production of entropy, generated as the result of the heat
conduction irreversibility, it is possible to perform additional work, as shown in
Fig. 4.2. This work is given by
1
2
0
1
( )
rev v
T
W q dx
T x

=

&
&

and using (4.6)
2
1
2
0
1
( ) ( )
rev
k dT T
W dx
T x dx T x


=

&


where T
2
is the temperature of the surroundings. Using solution (4.7) and
integrating gives
2
1 2
1 2 2
2 1
( ) ln ln
rev
T T
W k T T kT
T T

=


&


38
The above discussion provides some key conclusions about the First and Second
Laws of Thermodynamics.
In the classical boundary problem the following relations are satisfied:
0 0 div q and div s = > & &

Relations (4.5) and (4.7), on the other hand, show that
0 0 div q and div s < = & &

which is a contradiction to both laws of thermodynamics. Explanation comes by
considering equation (4.3) and its second term as the additional internal heat
source q
v
resulting in the entropy production which does not exist in the classical
approach. Substituting (4.8), (4.9) into balance equation (4.11) satisfies the First
Law of Thermodynamics. Integration

1
0
( )
( )
v
q x
dx
T x

&

gives the entropy production
2
2
1
ln 0
t
T
k
T

= >




which satisfies the Second Law of Thermodynamics.

One of many applications of the above discussion, has been presented by Bejan
[1] for the process of minimization of liquid helium boil-off in the cooling
system of the superconducting magnet (Fig. 4.3).
The balance equation for heat flow results in

out in i
i
Q Q Q =

& & &

Minimization of
out
Q
&
leads to the minimization of the helium boil-off rate. The
minimization problem can be formulated as follows:
To determine the optimal distribution of cooling stations (flows
i
Q
&
) which leads
to the minimization of /
out fg
m Q h =
&
& .

39
The detailed solution is presented by Bejan [1].






/
out fg
m Q h =
&
&



















Fig. 4.3 Mechanical support for helium boil-off cooling


4.2 Diffusional transfer of matter

Lets consider the two component perfect solution in which the
concentration of substance dissolved C
1
is much smaller than the concentration
of the solvent C
2
, hence C
1
<<C
2
.The solution undergoes the process of
diffusional transfer of dissolved substance. The entropy production is

1 1
i
V
d S
J X dV
d
=

while for the isothermal transfer,

R Ro oo om m t te em mp pe er ra at tu ur re e, , T T
H H
Q Q
i in n
.
.
Q Q
o ou ut t
.
.
0
/
fg
m Q h =
&
&
h h
f fg g
l la at te en nt t h he ea at t o of f
e ev va ap po or ra at ti io on n
L Li iq qu ui id d h he el li iu um m
t te em mp pe er ra at tu ur re e
4
T
Q Q
i i
.
.
M Me ec ch ha an ni ic ca al l
s su up pp po or rt t
40
1 1
11
1 1
1
X
T
L
J
T

=
=


Using the relation
1 1,0 1
ln RT C = +


and assuming one dimensional flow

1
1
1
RT C
C
=

and hence
1 1
1
R
X C
C
=


and
1 11 1
1
1
J L R C
C
=


from the Ficks Law
1 1
J D C =



which means that
11
1
L R
D
C
=

finally, the entropy production for the stationary flow is

2
1
1 1
1
( )
dC RD
x X J
C dx

= =




and the entropy production for D = constant

41
2
1
1
1 0
1
t
dC
RD dx
C dx

where C
1
=C
1
(x) .

The minimum of this integral

2
1 1
1
1 0 0
1
( ) minimum
dC
x dx dx
C dx

=





is reached for the function C
1
(x) satisfying the Euler-Lagrange equation

1
0
x
d
C dx C



=





where C
x
= dC/dx .

After some rearrangement, the following differential equation is obtained

2
2
1 1
2
1
1
0
2
d C dC
dx C dx

=




which has a general solution

2
1
( ) ( ) C x Ax B = +


Assuming the boundary conditions of the first kind: for x = 0, C
1
= C
1, 0

and for x = 1, C
2
= C
2, 0
, the solution looks as follows:

2
1/ 2 1/ 2 1/ 2
1 1,0 1,0 2,0
( ) ( ) C x C C C x

=



The solutions of several mass transfer processes when the diffusion coefficient
D is the function of concentration, can obtained in the identical way as for the
processes of heat conduction.

42
5. Entropy production minimization in stationary processes of heat
and electric current flows


The topic of this discussion will be the formulation of three boundary value
problems, non-linear in general, with a significant practical importance.

1 - boundary value problem with boundary conditions of the first kind without
internal heat source

2 - boundary value problem with boundary conditions of the third kind (Sturm-
Liouville boundary conditions) without internal heat source

3 - boundary value problem with the simultaneous heat and electric current
flow (Joules heat dissipation as the internal heat source) with the boundary
conditions of the first kind

Numerical calculations were done the given forms of the relations k=k(T) and
= (T) with various boundary conditions of the third kind.


5.1. Non-linear boundary value problem without the internal heat source

The geometry of the system has been presented in Fig. 5.1. In was assumed
that the heat conduction coefficient depends on the temperature.


q&


adiabatically insulated rod

T
1
T
1
T
2


q&

aa


A=1 T
2

A=1

0 1 x 0 1 x

Fig. 5.1 Plane-wall or equivalently adiabatically isolated rod (all variables
are dimensionless)

additional
internal heat
source
ss





k=k(T)
additional internal heat source
v
q&

43
Entropy production minimization

2
1
2
0
( )
t
k T dT
dx
T dx

=




leads to the Euler-Lagrange equation

2
2
2
1 ( )
( ) 0
2
d T dk k T dT
k T
dx dT T dx

+ =



(5.1)

Comparing with the classical approach

2
2
2
( ) 0
d T dk dT
k T
dx dT dx

+ =





equation (5.1) can also be written in the form


2 2
2
2
1 ( )
( ) 0
2
d T dk dT dk k T dT
k T
dx dT dx dT T dx

+ + =



(5.2)


The physical interpretation of (5.2) leads to the conclusion that the additional
internal heat source is

2
1 ( )
( )
2
v
dk k T dT
q x
dT T dx

= +


&


which satisfies the First and Second Laws of Thermodynamics.

As shown by the experimental results, the coefficient of heat conduction
k = k(T) dependence on temperature also depends on many factors. Hence, the
most appropriate method is the approximation in the given temperature interval.
44
In general, in practical cases, the temperature interval is not large and permits
for the approximation [1]
1
1
( )
( )
n
T x
k T k
T

=




(k
1
the value of heat conduction coefficient at temperature T
1
), which is
usually sufficient. An important characteristic is the fact that equation (5.2)
allows to find effective analytical solutions as shown in this thesis.

Finally, the Euler-Lagrange equation (5.1), after dividing by k(T), leads to the
general expression

2
2
2
1 1
0
2 ( )
d T dk dT
dx k T dT T dx


+ =





which can be written as

2
2
2
( ) 0
d T dT
F T
dx dx

+ =



(5.3)
where
1 1
( )
2 ( )
dk
F T
k T dT T
=


In addition to equation (5.3), the boundary value problem must also contain the
boundary conditions. In this case they are:

1
2
( 0)
( 1) .
T x T
T x T
= =
= =

where
1
T and
2
T are known.






45
5.2 Boundary value problem with boundary conditions of the third kind
(Sturm-Liouville boundary conditions) without internal heat source

The uniqueness of a solution to each boundary value problem is achieved
by setting the boundary conditions. From the physical point of view, differential
equation describes the process inside the thermodynamic system while the
boundary conditions set the interaction mechanism of the system with its
surroundings. In case of the one-dimensional systems, the boundary conditions
applied most often can be classified into three groups.

- boundary conditions of the first kind, or Dirichlet conditions, describe the
functional distribution of the thermal field potential (temperature at the
boundary surface) what can be generalized as


( )
i
x
T x T

=


where denotes the boundary surface.

- boundary conditions of the second kind, or Neumann conditions, describe the
case of a given derivative of the field potential in the direction normal to the
boundary surface, what means the following relation is know:


( )
T
f x
n

The solution is then known with the accuracy of the constant.

- boundary conditions of the third kind, or Sturm-Liouville conditions, are given
in the form

( )
f
T
k h T T
n

where k heat conduction coefficient of the solid, n normal to the boundary
surface, h coefficient of heat transfer at the boundary surface, T
f
fluid
temperature, T

- the boundary surface temperature .

It is easy to notice that through the appropriate choice of constants in the third
kind boundary condition, the first and second kinds can be obtained. The
46
derived solutions of the boundary value problems with the Sturm-Liouville
conditions have therefore the most general meaning. Lets consider the transfer
of heat between two fluids separated by the plate (Fig. 5.2)

T

T
0



T
1




fluid 2
T
2

T
0,0

fluid 1
0 1 x

Figure 5.2 Heat flow between two fluids



The boundary value problem is described by the following relations:


- equation of heat transfer through the plane-wall


2
2
2
1
0
d T dT
dx T dx

=




which can be written in the form


2
2
2
( ) 0
d T dT
F T
dx dx

+ =




where
1
( ) F T
T
=




q&

47
the term
2
( )
v
k dT
q x
T dx

=


&


represents the additional internal heat source.


- the Sturm-Liouville boundary conditions

x = 0

Heat transferred to the boundary surface x = 0.


fluid 1

h
1

c o n v e c t i o n
q&

0 x
q
=
&


T
0


T
1

x = 0

0
convection
x
q q
=
= & &



which leads to the following condition:

( )
1 0 1
0 x
dT
h T T k
dx
=
=
(5.4)


where h
1
is the coefficient of heat transfer from fluid 1 to the wall at x = 0.






48
x=1

Heat transferred from the boundary surface x = 1.


fluid 2

h
2



1 x
q
=
&

c o n v e c t i o n
q&

T
0,0
T
2


x = 1

1
convection
x
q q
=
= & &



which leads to the following condition:

( )
2 2 0, 0
1 x
dT
h T T k
dx
=
=
(5.5)

where h
2
is the coefficient of heat transfer from the plate to the fluid 2.

In both boundary conditions, the values of h
1
, h
2
, k, T
0
and T
0,0
are known and
the temperatures T
1
and T
2
are calculated. The solution to the boundary problem
(5.4) and (5.5) describes the temperature field inside the plane-wall.

In is important to mention that the boundary problem presented above is
somewhat simplified where the entropy production at the near the wall at x=0
and x=1 has been assumed to be negligible.

The full mathematical description would requires the introduction of two
additional terms in the expression for entropy production:

-for the near the wall surface at x=0

1
1 1
1
2
2
0
d
f f
f
k d T
d x
d x T





49
-for the near the wall surface at x=1

2
2 2
2
2
2
0
d
f f
f
k d T
d x
d x T





where
1
f
T
and
2
f
T
describe the temperature distribution, correspondingly in
the near the wall regions of fluid 1 (x=0) and fluid 2 (x= 1) with the thickness of
d
1
and d
2
and heat conduction coefficients
1
f
k
and
2
f
k
.
Since the thickness of the near the wall regions, in turbulent flows, is usually in
the neighborhood of few millimeters, the influence of these additional entropy
production can be ignored.

The numerical analysis focuses therefore on the effect of the heat transfer
coefficients h
1
and h
2
on the amount of entropy produced in the plate.

The above discussion goes beyond the established aims of the thesis. However,
the closer analysis demonstrates that including the convection (near the wall)
terms of the entropy production would not be difficult from the methodological
point of view and could be solved with the numerical methods. The simplified
case of the problem discussed above has been presented by Rafois and Ortin [8].




5.3 Boundary value problem with the simultaneous heat and electric
current flow

The boundary value problem, generally non-linear, of the simultaneous
heat and electric current flows with the boundary conditions of the first kind is
being discussed here. The Joules heat is dissipated inside within the system. It
is assumed that the heat conduction coefficient and the electric resistivity are
functions of temperature, k=k(T) and =(T).

The geometry of the system for the adiabatically insulated rod is shown in
Figure 5.3.






50
adiabatically insulated rod surface
T(x=0) = T
1
T(x=1) = T
2



in
q&

out
q&






x = 0 x = 1



Fig.5.3 Geometry of the adiabatically insulated rod surface


Entropy generation rate is

2
2
2
( ) ( )
( )
( ) ( )
k T dT i T
x
T x dx T x

= +




where i is the electric current density

Minimization

2
1 1
2
2
0 0
( ) ( )
( ) minimum
( ) ( )
k T dT i T
x dx dx
T x dx T x

= +







leads to Euler-Lagrange equation

2
2 2
2
1 ( ) 1 ( )
( ) 0
2 ( ) 2 ( )
d T dk T dT i d T
T T
dx k T dT T dx k T dT

+ + =




which can be written in the general form

2
2
1 2
2
( ) ( ) 0
d T d T
F T F T
d x d x

+ + =



additional internal heat source

k=k(T) =(T)
51
where

1
1 ( ) 1
( )
2 ( )
dk T
F T
k T dT T
=


2
2
( )
( ) ( )
2 ( )
i d T
F T T T
k T dT

=




Boundary value problem is completed with the boundary conditions

1
2
( 0)
( 1) .
T x T
T x T
= =
= =

Several special cases have been analyzed by the use of various analytical and
numerical methods. The work has been divided into four following situations:

k
Case #1


k - constant

- constant

Case #2

1
1
n
T
k k
T

=




- constant
Case #3


k-constant

1
1
n
T
T


=



Case#4

1
1
n
T
k k
T

=




o
L T
k
=




5.4 Methods of calculation of additional internal heat sources and
entropy generation rate

The obtained solutions allow to determine the additional (resulting from
the entropy production minimization) internal hear sources and the entropy
generation rate. Particularly, the derivation of the Bernoulli equation from the
Euler-Lagrange equation allows to derive these values. The difficulties that
might be encountered during the calculations result from the non-explicit form
of the solution.

52
1 - k=constant, boundary conditions of the first kind without the internal heat
sources

Boundary value problem is described by:

- Euler-Lagrange equation

2
2
2
1
0
d T dT
dx T dx

=




- boundary conditions

1
2
( 0)
( 1) .
T x T
T x T
= =
= =

where
2
( )
( )
v
k dT
q x
T x dx

=


&



and the total heat source


2
1
,
0
1
( )
( )
v t
dT
q x k dx
T x dx

=

&

Since
2
1
1
( )
x
T
T x T
T

=




and
2 2 2
1
1 1 1
ln ( ) ln
x
T T T dT
T T x
dx T T T

= =




therefore

53
2
2
1
( ) ( ) ln
v
T
q x kT x
T

=


&


and

2
; 1 2
1
( ) ln 0
v t
T
q k T T
T
= < &


Entropy generation rate is

2
2 2
1
1 1
( )
( ) ln
( )
x
v
q x T T
x kT
T x T T

= =


&


and

2
1
2
1 0
( )
ln 0
( )
v
t
q x T
dx k
T x T

= = >

&




2 - k = k(T) , boundary conditions of the first kind without the internal heat
sources

Boundary value problem is described by:

- Euler-Lagrange equation

2
2
2
1 ( )
( ) 0
2
d T dk k T dT
k T
dx dT T dx

+ =


(5.6)

- boundary conditions

1
2
( 0)
( 1) .
T x T
T x T
= =
= =
(5.7)

54
and
2
1 ( )
( )
2
v
dk k T dT
q x
dT T dx

= +


&



and the total amount of the heat source


2
1
,
0
1 ( )
2
v t
dk k T dT
q dx
dT T dx

= +

&


and entropy generation rate connected with heat source becomes

2
1 1 ( )
( )
( ) 2
dk k T dT
x
T x dT T dx

= +



and

2
1
0
1 1 ( )
( ) 2
t
dk k T dT
dx
T x dT T dx

= +

The functional relations for T(x) and dT/dx are determined by solutions to
equations (5.6) and (5.7) after prior calculation of the integration constants,
while F
2
(T) = 0.

The total entropy production is

( )
2
1
2
0
( )
( )
t
k T dT
dx
dx
T x

=



or
( )
2
1
2
( )
( )
T
t
T
k T dT
dT
dx
T x
=



Solution to Eq.(5.6) can be easily obtained by the substitution

55
dT
u
dx
=


which gives
2
2
d T du
u
dx dT
=


and equation (5.6) takes the form

( ) ( ) 0
du
k T F T u
dT
+ =

(5.8)
where
1 ( )
( )
2
dk k T
F T
dT T
=


The solution of (5.8) is

( )
( )
1
F T
dT
k T
dT
u c e
dx

= =


which after simplification gives

1
ln ( ) ln
2
1
k T T
dT
c e
dx
+
=

hence

1
( )
dT
c T k T
dx
=

and

1 1 2
( )
( )
dT
c dx c x c
Tk T
= = +


Finally
56
[ ]
2
1
3
2
( )
T
t
T
k T
dT
T
=



3 - k=constant, boundary conditions of the third kind (Sturm-Liouville
boundary conditions) without the internal heat sources.

Boundary value problem is described by:

- Euler-Lagrange equation

2
2
2
1
0
d T dT
dx T dx

=


(5.9)

- boundary conditions

1 0
0
0
2 0,0
1
1
0 ( )
1 ( )
x
x
x
x
dT
for x k h T T
dx
dT
for x k h T T
dx
=
=
=
=
= =
= =

(5.10)

The general solution has the form

1
3
( )
c x
T x c e =

hence
(5.11)
1
3 1
c x
dT
c c e
dx
=


Substitution of expressions (5.11) into the boundary conditions (5.10) gives

57
1 1
1 3 1 3 1
1 3 2 3 2
c c
kc c hc
kc c e h c e

+ =
=

(5.12)

where
1 1 0 2 2 0,0
and h T h T = =


The values of c
1
and c
3
are numerically determined because of the non-explicit
character of equations (5.12).

The additional internal heat source is


2
( )
( )
v
k dT
q x
T x dx

=


&


and its total value is

2
1
,
0
1
( )
( )
v t
dT
q x k dx
T x dx

=

&


Using equations (5.10) leads to

1
2
3 1
( )
c x
v
q x kc c e =
&


and
1
, 1 3
( ) (1 )
c
v t
q x kc c e =
&



Entropy generation rate is

2
1
( )
( ) 0
( )
v
q x
x kc
T x
= = >
&


and is equal to
t
as div s&
= 0.
58
4 - k = k(T), boundary conditions of the third kind (Sturm-Liouville boundary
conditions) without the internal heat sources.


Boundary value problem is described by:

- Euler-Lagrange equation

2
2
2
1 1
0
2
d T dk dT
dx k dT T dx

+ =



(5.13)


- boundary conditions

1 0
0 0
0
2 0,0
1 1
1
0 ( ) ( )
1 ( ) ( )
x x
x
x x
x
dT
for x k T h T T
dx
dT
for x k T h T T
dx
= =
=
= =
=
= =
= =


(5.14)


After substitution u=dT/dx, equation (5.13) becomes

( ) 0
du
F T u
dT
+ =


while
1 1
( )
2
dk
F T
k dT T
=


which leads to equation

( )
1
F T dT dT
u c e
dx

= =

(5.15)
59

and after the second integration

2
( )
1
F T dT
dT
x c
c e

= +

(5.16)

Equation (5.16) is given in the non-explicit form.

The additional internal heat source is given by:


2
1 ( )
( )
2
v
dk k T dT
q x
dT T dx

= +


&


and

2
1
,
0
1 ( )
( )
2
v t
dk k T dT
q x dx
dT T dx

= +

&



while T(x) and dT/dx are described by equations (5.13) and (5.14). Examples of
the numerical analysis are provided in Chapter 7.

Entropy production at the additional heat source takes the form

2
( ) 1 1 ( )
( )
( ) ( ) 2
v
q x dk k T dT
x
T x T x dT T dx

= = +


&

and

2
1
0
1 1 ( )
( ) 2
t
dk k T dT
dx
T x dT T dx

= +

Total value of the entropy production comes from the definition

60
2
1
2
1
2 2
0
( ) ( )
T
t
T
k T dT k T dT
dx dT
T dx T dx

= =




and is obtained in the same way as in 2.


5 - Simultaneous heat and electric current flows, k = k(T) , = (T)

Boundary value problem is described by:

- Euler-Lagrange equation

2
2
1 2
2
( ) ( ) 0
d T d T
F T F T
d x d x

+ + =



(5.17)

where
1
1 ( ) 1
( )
2 ( )
dk T
F T
k T dT T
=


2
2
( )
( ) ( )
2 ( )
i d T
F T T T
k T dT

=




- boundary conditions

1
2
( 0 )
( 1)
T x T
T x T
= =
= =

(5.18)

It can be easily shown that equation (5.17) can be transformed into the Bernoulli
equation in the form

1
1 2
( ) ( )
du
F T u F T u
dT

+ =

(5.19)
61
where
d T
u
d x
=


The additional internal heat source is

2
2
1 ( )
2 2
v
dk k T dT i d
q T
dT T dx dT

= + +


&


and
1
,
0
( )
v t v
q q x dx =

& &


In general, because of the non-explicit form of the solution, the numerical
calculations must follow.

Energy generation rate at the additional heat source is

2
2
( ) 1 1 ( ) ( )
( ) ( )
( ) ( ) 2 2
v
q x dk T k T dT i d
x T T
T x T x dT T dx dT

= = + + +





&

and

2
1
2
0
1 1 ( ) ( )
( )
( ) 2 2
t
dk T k T dT i d
T T dx
T x dT T dx dT

= + + +

Total value of the entropy production comes from definition

2 2
1 1
1
2
2
( )
T T
t
T T
k T dT i dT
dT dT
T dx T dx

= +





where T(x) and dT/dx are obtained from the solution of Bernoulii equation
(5.19) (see next Chapter 6).

62
6. Methods of solving the boundary problems with Euler-Lagrange
equations

The analysis of the non-linear boundary value problems with internal heat
sources always leads to the non-linear Euler-Lagrange differential equation of
the second order in the form


2
2
1 2
2
( ) ( ) 0
d T d T
F T F T
d x d x

+ + =



(6.1)


In particular, the functions
1
( ) F T and
2
( ) F T have the form:

- heat conduction coefficient k does not depend on temperature,
without the internal heat sources


1 2
1
( ) , ( ) 0 F T F T
T
= =


- heat conduction coefficient k = k(T), without the internal heat
sources

1 2
1 ( ) 1
( ) , ( ) 0
2 ( )
dk T
F T F T
k T dT T
= =


- heat conduction coefficient k = k(T), internal heat source in the
form of Joules heat

1
1 ( ) 1
( )
2 ( )
dk T
F T
k T dT T
=


2
2
( )
( ) ( )
2 ( )
i d T
F T T T
k T dT

=






63
The specific form (6.1) of the Euler-Lagrange equations, when F
1
(T) and F
2
(T)
are both not equal to zero, allows to obtain an analytical solution, usually though
in the non-explicit form.

By substitution
dT
u
dx
=


and differentiating

2
2
d T du du dT du
u
dx dx dT dx dT
= = =


after substituting into (5.19) gives


2
1 2
( ) ( ) 0
du
u F T u F T
dT
+ + =


Finally equation (5.19) becomes

1
1 2
( ) ( )
du
F T u F T u
dT

+ =
(6.2)

Equation (6.2) represents the Bernoulli differential equation which has the
general solution in the non-explicit form:

1 1
2
2 ( ) 2 ( )
2 1
2 ( )
F T dT F T dT dT
e F T e c
dx


= +




(6.3)


Hence

1 1
1
2
2 ( ) 2 ( )
2 1
2 ( )
F T dT F T dT dT
F T e c e
dx




= +





(6.4)


64


and finally in the non-explicit form

1 1
1
2
2 ( ) 2 ( )
2 1 2
2 ( )
F T dT F T dT
F T e c e dT x c

+ = +






(6.5)

The integration constants c
1
and c
2
must be determined from the boundary
conditions, usually numerically.

The derivations presented above as well as the solutions obtained are new in
the literature of entropy production minimization problems.
The above solution has been used in the analysis of the boundary problems
discussed in chapter 5.



6.1. General method of determining the internal heat source and entropy
generation rate

As seen in the relations derived in chapter 5.4, the integration over the x
coordinate, expression for
, v t
q&
and
t
, is very difficult because of the presence
of T(x) and dT/dx, which must be substituted as the functions of x.

The analysis of the equations indicates as well that it is possible to simplify
the calculations by using simple substitutions and the solutions to Bernoullis
equation for / u dT dx = . In the following discussion, as an example, the
calculation method for case 2 will be presented.

- k = k(T) , boundary conditions of the first kind without the internal heat
sources


Expression

2
1
,
0
1 ( )
2
v t
dk k T dT
q dx
dT T dx

= +

&

65

can be rewritten in the form

1
,
0
1 ( )
2
v t
dk k T dT dT
q dx
dT T dx dx

= +

&

hence

2
1
,
1 ( )
2
T
v t
T
dk k T dT
q dT
dT T dx

= +

&

(6.6)
By substitution

( )
dT
u T
dx
= =

(6.7)


the integration of (6.6) becomes much easier, as dT/dx is the indirect function of
x (as T=T(x)). Substituting (6.7) into (6.6) yields

2
1
,
1 ( )
( )
2
T
v t
T
dk k T
q T dT
dT T

= +

&



In the identical way, the calculation for the entropy production resulting from
the additional heat source can be simplified by transforming expression

2
1 1
0 0
1 1 ( )
( ) ( ) 2
v
t
q dk k T dT
dx dx
T x T x dT T dx

= = +



&


into

2
1
1 1 ( )
( ) 2
T
t
T
dk k T dT
dT
T x dT T dx

= +

66
using, as before,
( )
dT
u T
dx
= =


The calculations can be done in the same way as for other boundary problems
without the internal heat sources.

Total value of the entropy production comes from definition

2
1
2
( )
T
t
T
k T dT
dT
T dx
=

(6.8)

and the solution is identical as in 2.

For the problem of simultaneous heat and electric current flows, the above
analysis requires modification.


Entropy production describing additional heat source becomes

2
1
2
0
1 1 1
( )
( ) 2 ( ) 2 ( )
t
dk dT i d
T T dx
T x k T dT T dx k T dT

= + + +

which can be written in the form of two integrals


2
1
1
1
2
0
1 1 1
( ) 2 ( )
1
( )
2
T
t
T
dk dT
dT
T x k T dT T dx
d dT
i T T dT
dT dx

= +





+ +

Transformation above allows, as before, for solving the Bernoulli equation for

67
( )
dT
u T
dx
= =


which after substituting into expression for
t
leads to the direct expression


2 2
1 1
1
2
2
( )
T T
t
T T
k T dT i dT
dT dT
T dx T dx

= +





The method described above is the new concept in literature dealing with
entropy production minimization, calculation of the internal heat sources and
entropy production
t
. The most important feature of this method is that it can
be applied to any mathematical relationship for k=k(T) and =(T) as the
solution of the governing differential equation is given in the general form.


























68
7. Solutions for the specific boundary value problems


7.1 Simultaneous heat and electric current flows

All the calculations below originate from the general solution (6.4) which
can be easily rearranged into


1
1
2 ( )
2
2
2 ( )
2 ( ( )
F T dT
F T dT
F T e dT
dT
dx
e

=





(7.1)

Case#1

The values for k, are both constant

General equation

( ) 0
2
'
1
2
1
' '
2
2
=

+
dT
d
T
k
i
T
T dT
dk
k
T

is simplified to the form

( )
2 1
'' ' 0 T T
T
+ =

(7.2)
where
2
2
''
d T
T
dx
=


'
dT
T
dx
=


2
2
i
k

=

69
which according to (7.1) has the solution for F
1
(T)= - 1/T and F
2
(T)= in the
form:


( )
1
2
2
2
2
1
1
2
2
1
2 ( )( )
2
2
1
dT
T
dT
T
dT
e dT
dT
T
T c T
dx
e
T

= = =

(7.3)
Hence

2
1
2
dT
dx
T c T
=

(7.4)

which after the substitution

1
1
1
2
w c T
c
=

gives

2
1
2
1
1
2
1
2
dw
dx
c
w
c
=

after integration

1
1 2
1
1
sin (1 2 ) 2 ( ) c T x c
c

= +


an explicit solution becomes

1 2
1
1 sin 2 ( )
( )
2
c x c
T x
c

+ +

=

(7.5)
70
Applying boundary conditions, two algebraic equations are obtained which
allow to find the integration constants c
1
and c
2


1 1 1 2
1 2 sin 2 ( ) c T c c

=


and

1 2 1 2
1 2 sin 2 (1 ) c T c c

= +




The graphs of T (x) vs. x are shown in Fig. 7.1.



Fig. 7.1 The graph of T(x) vs. x for different values of boundary
temperatures when k=constant and =constant


Local entropy production (x) can also be calculated according to

2
2
2
( )
( ) ( )
k dT i
x
T x dx T x

= +




71
it is assumed that
2
= 1
2
i
K
k

=

Therefore

[ ]
2
1
2
4
2
( )
( )
( )
k T c T
k
x
T x
T x

= +


and
1
4
( ) 2
( )
k
x kc
T x

=



The graph of local entropy production (x) vs. x is shown in Fig. 7.2.





Fig. 7.2 The graph of local entropy production (x) vs. x for different
values of boundary temperatures when k=constant and =constant

72

The total entropy production
t
can also be calculated according to:

1 1
1
0 0
2
( ) 2
( )
t
x dx k c
T x


= =




Assuming k = 20 W/mK , the following numerical values for total entropy
production are obtained and shown in Table 7.1.

Table 7.1
Boundary
Temperatures
T
1
=0.4
T
2
=0.1
T
1
=0.8
T
2
=0.5
T
1
=1.0
T
2
=0.6
T
1
=1.0
T
2
=0.7
Total
Entropy
Production

t

(W/K)

226.4


63.6

54.8

48.4


The internal heat source

2
2
1
( )
2 2
v
dk k dT i d
q x T
dT T dx dT

= + +


&


can also be calculated and when k=constant and =constant:

2
2
( )
2
v
k dT i
q x
T dx


=


&


substituting for (dT/dx)
2
from Eq. 7.3 gives

2
2
1 1
( ) 2 ( 3 2
2
v
k i
q x T cT k kcT
T

= = +

&

and
73
1 2
( ) 3 1 sin 2 ( )
v
q x k k c x c


= + + +


&

Finally

{ }
1 1
, 1 2
0 0
( ) 2 sin 2 ( )
v t v
q q x dx k c x c dx

= = + +


& &



Assuming again k = 20 W/mK , the following numerical values for the total heat
source are calculated and presented in Table 7.2.

Table 7.2
Boundary
Temperatures
T
1
=0.4
T
2
=0.1
T
1
=0.8
T
2
=0.5
T
1
=1.0
T
2
=0.6
T
1
=1.0
T
2
=0.7
Total Heat
Source
, v t
q
&

(W)

-31

-24.6


-25.4


-24.2






Case #2


Conditions:
n
T
T
k k

=
1
1 and = constant


General equation

( ) 0
2
'
1
2
1
' '
2
2
=

+
dT
d
T
k
i
T
T dT
dk
k
T

becomes
74
2
2 1
'' ( ') 0
2
n
n
T T
T T

+ + =

(7.6)
where
2
1
1
2
n
i T
k

=



which according to equation (7.1) has the solution for


1
2 1
( )
2
n
F T
T

=

and
2
( )
n
F T
T

=



in the form:


2 1
2
2
2
2
1
2 1 2 1
2
2
2
2
2 (1 )
n
dT
T
n
n
n
n n n
dT
T
e dT
T dT
dT c T
T
T
dx T T
e

= = =

(7.7)


Hence
1
2
1
2
1
n
T dT
dx
c T

(7.8)




75



Table 7.3 below is the summary of the integrals obtained and the solutions for
different values of n.


Table 7.3
n integral solution

-2
2
1
2
( )
dT
dx
T T c T
=

2
1
2
2
2 ( )
T c T
x c
T


= +


-1
1
2
1
dT
dx
T c T
=

1
2
1
1 1
ln 2 ( )
1 1
c T
x c
c T


= +
+


0
2
1
2
dT
dx
T cT
=

1 2
1
1 sin 2 ( )
( )
2
c x c
T x
c

+ +

=

Same as in case#1, k, constant
1
1
2
1
dT
dx
c T
=

1
2
1
2 1
2 ( )
c T
x c
c

= +

k-linear, - constant
2
1 / 2
1
2
1
T dT
dx
c T
=

1
1 1
2
3/ 2
1 1
sin ( ) 1
2 ( )
cT T cT
x c
c c

= +


3
1
2
1
T dT
dx
c T
=

( )
1
1 2
2
1
2 2
1 2 ( )
3
cT
cT x c
c

+
= +









76



The total entropy production can be determined with the described earlier


2 2
1 1
2
1 1
2
2
0 0
2
2
( ) ( )
( ) ( ) 1
t
T T
T T
k T dT i T
dx dx
T dx T
k T dT i T
dT dT
dT T dx T
dx

= + =



= +








(7.9)


Applying this method in Case#2 yields



2 2
1 1
2 2
1 1
1 1
2
1
1
2
1 2
1
2
3
3
2
2
1
2
1
1
1
2 (1
1
2 (1 )
2
1
2 1
n
T T
t n
T T
n
n
T T n
n
T T
T
k c T
T
i
dT
T
c T
T T
T
k i T
T c T dT dT
T
c T

= + =

= +

which provides a general expression which can be calculated numerically for the
specific boundary conditions.





77
In the section below, a specific solution for n=1 (k-linear function of
temperature, constant, same as Case#4) is examined. Solution

1
2
1
2 1
2 ( )
c T
x c
c

= +

results in
2 2
1 2
1
1
1 ( )
2
( )
c x c
T x
c
+
=

(7.10)
or
2 2
1 1 2 1 2
1
1 1 1
( )
2 2
T x c x c c x c c
c
= +


which produces the following graphs for the specific boundary temperatures,
represented in Fig.7.1.



Fig. 7.3 Graph of T(x) versus x for n=1 and for different values of
boundary temperatures when k=linear and =constant

78
The local entropy production can be calculated according to:


2
2
2
( )
( )
( ) ( )
k T dT i
x
T x dx T x

= +





which in this case becomes

( )
1
2
1 1 1
1 1
2
1 1
2 1 2 1
( ) 2 1
k
T
i k k T
x c T c
T T T T T T



= + = +




as
2
2 1
1
1
2
n
i T
K
k

= =

and

T
1
=1 (dimensionless temperature)


the following expression is obtained:


1
1
1
2 2
( )
( )
k
x c
T T x

=





which is represented graphically in Fig 7.2.







79


Fig.7.4 Graph of local entropy production (x) versus x for n=1 and for
different values of boundary temperatures when k=linear and
=constant


The total entropy production
t
can also be calculated according to:

1 1
1
1
1 0 0
2 2
( )
( )
t
k
x dx c dx
T T x

= =




Assuming k
1
= 20 W/mK , the following numerical values for total entropy
production are obtained and shown in Table 7.4.

Table 7.4
Boundary
Temperatures
T
1
=1.0
T
2
=0.1
T
1
=1.0
T
2
=0.3
Total
Entropy
Production

t

(W/K)

139.2

82


80
The internal heat source

2
2
1 ( )
( )
2 2
v
dk k T dT i d
q x T
dT T dx dT

= + +


&



can also be calculated, giving

[ ]
2
1 1
1
1 1
1
( ) 2 (1
2 2
v
k k i
q x cT
T T

= +


&

or

[ ]
1 1
1
1 1
3
( ) 1
v
k k
q x cT
T T

= &

and finally

2 2
1
1 2
1
3
( ) 1 ( ) 0
2
v
k
q x c x c
T

= + + <


&


therefore

1 1
2 2
1
, 1 2
1 0 0
3
( ) 1 ( )
2
v t v
k
q q x dx c x c dx
T

= = + +



& &


Assuming k
1
= 20 W/mK , the following numerical values for the total heat
source are calculated and presented in Table 7.5.

Table 7.5
Boundary
Temperatures
T
1
=1.0
T
2
=0.1
T
1
=1.0
T
2
=0.3
Total Heat
Source
, v t
q
&

(W)

-46.4

-37.0


81

Case#3


Conditions:

k= constant and
n
T
T

=
1
1


General equation


( ) 0
2
'
1
2
1
' '
2
2
=

+
dT
d
T
k
i
T
T dT
dk
k
T

becomes
2
1
'' ( ') ( ) 0 T T g T
T
+ =

(7.11)
where
2
1
1
( ) (1 )
2
n
n
i
g T n T and
kT

= =


which according to (7.1) has the solution for


1
1
( ) F T
T
=


and

2
( ) (1 )
n
F T n T =



in the form:
82
1
2
2ln
2
2ln 1
2
2
2
2 2
1
1
2 1
1
2
2 ( (1 ) 2 ( (1 )
1
2 ( (1 )
2 ( 1)
1 1
2 ( 1)
1
2 ( 1)
1
dT
n n T T
T
dT
T
n
n
n
n
n T e n T e
dT
dx e
e
n T dT
n T dT
T
T T
T
n c
n
T T n c
T

= = =





= = =

+

= = +

Hence:
1
1
( 1)
n
dT
T T n c

=
+

1 2
1
2
( 1)
n
dT
dx
T n c T

+
= =
+



(7.12)

Note: In case of n=1 (k-constant, linear), the above integral solution can not
be used as F
2
= 0 and equation
2
1
'' ( ') ( ) 0 T T g T
T
+ =

becomes
2
1
'' ( ') 0 T T
T
=


the substitution u=dT/dx leads to the known solution

2
1
1
x
T
T T
T

=



83
Table 7.6 is the summary of the integrals obtained and the solutions for different
values of n.

Table 7.6
n integral solution

-2

3
1
2
1 3
T dT
dx
c T
=

1 3 / 2
1
2
1
2sin ( 3 )
2 ( )
3 3
c T
x c
c

= +

-1

2
1
2
1 2
dT
dx
cT
=

( )
1
1 2
1
1
sin 2 2 ( )
2
cT x c
c

= +

0

2
1
2
dT
dx
T cT
=

1 2
1
1 sin 2 ( )
( )
2
c x c
T x
c

+ +

=

same as in Case#1, k, constant
2

1
2
dT
dx
T T c
=
+



1
2
1
ln 2 ( )
1
T c
x c
T c

+
= +
+ +

3

2
1
2
2
dT
dx
T T c
=
+



2
1 1
2
1
2 2
1
ln 2 ( )
2
c T c
x c
T
c


+ +

= +



















84
The total entropy can be determined with the use of the method described in
Case#2 (equation 7.7)
2 2
1 1
2 2
1 1
2
1
1
1 1 1
2
1
1
1
2 2
1
1
1
1
1
1
2 ( 1)
1
( 1)
( 1)
2
2
( 1)
n
T T n
t
n
T T
T T n
n
n
n
T T
T
i
kT T n c T
dT dT
T T
T T n c
T n c
i T
k dT dT
T
T
T n c

+

= +
+
+
= +
+





Case #4


Conditions:
n
T
T
k k

=
1
1
,
k
T L
0
=
(Wiedemann-Franz Law)
General equation

( ) 0
2
'
1
2
1
' '
2
2
=

+
dT
d
T
k
i
T
T dT
dk
k
T

becomes
2
2 1
'' ( ') ( ) 0
2
n
T T g T
T

+ + =

(7.13)
where
1
2 2
1 2
0 1
2
( )
2
n
n
i L T
g T n T and
k

= =

which according to (7.1) has the solution for

1
2 1
( )
2
n
F T
T

=

and
85
1 2
2
( )
n
F T n T

=


in the form:

( 2) 1
2
1 2 1 2 ( 2) ln
2
2
( 2) 1 ( 2) ln
2
2
1 2 2 1
1
2 2 2
1 1
2 2 2
2 ( 2 (
2
2 ( 2 (
2 2 1
n
dT
n n n T
T
n n T
dT
T
n
n n n
n n n
n n
n n
n T e dT n T e dT
dT
dx e
e
T
n c
n T T dT n T dT
n
T T T
T nc ncT
T T

= = =



+




= = = =


= =



Hence:
1
1
2
1
n
n
T dT
dx
nc T

(7.14)


Note: In case of n=0 (k-constant, linear), the above integral solution can not
be used as F
2
= 0 and equation

2
1
'' ( ') ( ) 0 T T g T
T
+ =

becomes
2
1
'' ( ') 0 T T
T
=



the substitution u=dT/dx leads to the known solution

2
1
1
x
T
T T
T

=



86
Table 7.7 is the summary of the integrals obtained and the solutions for different
values of n.

Table 7.7
n integral solution
1

1
2
1
dT
dx
cT
=

1
2
1
2 1
2 ( )
c T
x c
c

= +

same as in case #2 (for n=1) k-linear, -constant
2

2
1
2
1 2
TdT
dx
c T
=

2
2
1
1
1 1
2 ( )
2
2
T x c
c
c
= +


3

2
3
1
2
1 3
T dT
dx
c T
=

3
1 2
1
2
1 3 2 ( )
9
c T x c
c
= +




The total entropy production can be determined with the use of the method
described in Case#2


2 2
1 1
2 2
1 1
1 1
2
1
0
2 1
1
1
1
1
2
1
0 1 1
1
1
1
2 (1 )
1
2 (1 )
1
2
2
1
n
n
T T
t n n
n
T T
n
T T n
n
n
n
T T
T
k ncT
T
i L T
dT dT
T T
ncT
T
T k
T T
ncT
i L T k dT
dT
T T
k
T ncT

= + =

= +

87
7.2 Boundary conditions of the second and third kinds - heat conduction
coefficient independent of temperature


Case#1 Boundary conditions of the second kind (gradient at x=0)

2
2
2
1
0
d T dT
dx T dx

=




2
0 constant
1 (1)
dT
x
dx
x T T
= = =
= =

the solution is
1
3
( )
c x
T x c e =


The graph of T(x) vs. x for dT/dx = -1 and different values of T
2
is shown in Fig.
7.5.



Fig.7.5 Graph of T(x) versus x for dT/dx = -1 and for different values of T
2
.

88
Local entropy production

( )
1
1
2
2
2
3 1 1 t
2 2
3
( ) constant =
( )
c x
c x
k dT k
x c c e kc
T x dx
c e


= = = =






Assuming, as before k = 20 W/mK , the following numerical values for total
entropy production are obtained and shown in Table 7.8.

Table 7.8
Boundary
value at x=1
T
2
=0.1 T
2
=0.2 T
2
=0.5 T
2
=0.8 T
2
=1.0
Total Entropy
Production

t

(W/K)

60.9

35.2

14.5

8.5

6.4



Case#2 - Boundary conditions of the second kind (gradient at x = 1)

2
2
2
1
0
d T dT
T dx dx

=




1
1
0 ( 0)
1
x T x T
dT
x
dx

= = =
= =

the solution is
1
3
( )
c x
T x c e =



The graph of T(x) vs. x for different values of
1
and for T
1
=1.0

is shown in Fig.
7.6.

In addition, local entropy production

( )
1
1
2
2
2
3 1 1 t
2 2
3
( ) constant =
( )
c x
c x
k dT k
x c c e kc
T x dx
c e


= = = =






89


Fig.7.6 Graph of T(x) versus x for different values of dT/dx and for T
1
=1.0



Case#3 - Boundary conditions of the third kind (Sturm-Liouville boundary
conditions).

2
2
2
1
0
d T dT
dx T dx

=




0 1 0 0
1 2 1 0,0
0 ( )
1 ( )
x x
x x
dT
x k h T T
dx
dT
x k h T T
dk
= =
= =
= =
= =


or
0 1 0 1 0 1
1 2 1 2 0,0 2
x x
x x
dT
k h T hT
dx
dT
k h T h T
dk

= =
= =
+ = =
= =


90
which in combination with the solution


x c
e c x T
1
3
) ( =


results in the following equation for constant c
1
:

1
1 2
1 1 1 2
( )
c
h kc e kc h

=
+


where
1
3
1 1
c
h k c

Taking
T
0
=1.3 , T
0,0
=0.85 (dimensionless temperatures)
h
1
=h
2
=20, 200, 2000 W/m
2
K
k = 20 W/mK

1
= h
1
T
0
= 26, 260, 2600 W/m
2
K

2
= -h
2
T
0,0
= -17, -170, -1700 W/m
2
K

results in the following graph of T(x) vs. x as shown in Fig.7.7.



Fig.7.7 Graph of T(x) vs. x for different values of heat transfer coefficient
h and for T
0,0
=0.85
91
Similarly, taking
T
0
=1.3 , T
0,0
=0.05
h
1
=h
2
=20, 200, 2000 W/m
2
K
k = 20 W/mK

1
= h
1
T
0
= 26, 260, 2600 W/m
2
K

2
= -h
2
T
0,0
= -1, -10, -100 W/m
2
K

the graphs presented in Fig. 7.8 are produced.




Fig.7.8 Graph of T(x) vs. x for different values of heat transfer coefficient
h and for T
0,0
=0.05



Local entropy production, as in the previous cases is given by

( )
1
1
2
2
2
3 1 1 t
2 2
3
( ) constant =
( )
c x
c x
k dT k
x c c e kc
T x dx
c e


= = = =








92
7.3 Boundary conditions of the third kind (Sturm-Liouville boundary
conditions) - heat conduction coefficient dependent on temperature

( )
2 1 1
'' ' 0
2
dk
T T
k dT T

+ =



with
n
T
T
k k

=
1
1

becomes
2
2 1
'' ( ') 0
n
T T
n T

+ =

(7.15)

Sturm-Liouville boundary conditions are described by the system of two
equations:

1 0 1 0 0
2 1 2 0,0
1
0 ( )
1 ( )
x x
x
x
dT
x k h T T
dx
dT
x k h T T
dk
= =
=
=
= =
= =

Thus
1 0 1 0 1 0 1
2 1 2 1 2 0,0 2
x x
x x
dT
k hT hT
dx
dT
k h T h T
dk

= =
= =
+ = =
= =


(7.16)

It can be easily shown that the solution of equation (7.13) is

2
( )
n
T Ax B = +

(7.17)

which when substituted into Sturm-Liouville boundary conditions (7.14) gives:

93
( ) ( )
2 2
1
1 1 1
2 2
1
2 2 2
2
2
n n
n n
A
k B h B
n
A
k A B h A B
n

+ =



+ + =



taking
T
0
=1.3 , T
0,0
=0.05
h
1
=h
2
=20 W/m
2
K
k = 20 W/mK

1
= h
1
T
0
= 26 W/m
2
K

2
= -h
2
T
0,0
= -1 W/m
2
K
and using
[ ] [ ]
2
2 /
1 1
2 / 1
1
2 / 1 2 /
1
2 2
2
( ) ,
,
2
2
,
( )
n
n
n
n n
T Ax B
n h B
A
k B
Ak
A B h A B
nB

+
= +


=

+ + =

(7.18)

produces the following graph of T(x) vs. x for different values of n.



Fig.7.9 Graph of T(x) vs. x for different values of n
94
The total entropy production is calculated in the following way:

( )
( )
( )
( )
2
2
2( 1)
2
2
1
2 2
2
1
2
1
1
2
( )
'
2
n
t
n
n
n
A
Ax B
k Ax B
k T
n
T
T T
Ax B
k A
T n

+

+

= =
+

=



Since
n 2 2
1
T ( (0) ) A B B = + =

then
2
1
4
t
k A
n B

=





Equations (7.16) can be expressed as the function of ratio R=k/h in order to see
how the values of k and h influence the solution. For k=20W/mK and R=k/h,
values of total entropy production (W/K) for different values of n and R are
shown in Table 7.9.

Table 7.9
h
n R
1
20
2
10
5
4
10
2
20
1
100
0.2
-5
11.8 31.7 87 16.1 2.5 1.9
-4
10.3 24.9 47 10.6 3.9 3.0
-3
8.8 19.7 34 19.8 9.0 5.9
-2
9.4 22.9 63 118 177 80.9
-1
13.9 34 101 218 459 2368
0
0.043 0.17 1.03 3.9 14.0 103
1
0.010 0.035 0.162 0.43 0.92 2.4
2
0.013 0.047 0.226 0.63 1.4 4.0
3
0.014 0.051 0.266 0.80 2.0 6.3
4
0.014 0.053 0.291 0.97 3.1 5.0
5
0.014 0.053 0.309 1.21 3.2 3.2



95
It is easy to see that for n=0, different solution is obtained and the different
method of entropy production calculation is required.

Using the solution
2
1
1
( )
x
T
T x T
T

=




the following equations are obtained:

2
1 0 1
1
2
2 2 0 , 0
1
l n ( )
l n ( )
T
k T h T T
T
T
k T h T T
T
=
=

(7.19)

Dividing the two equations by each other produces the following expression

2 0,0
2
1 0 1
T T
T
T T T

and
1 0,0
2
1 0
2
TT
T
T T
=

Substituting the above expression for T
2
into first of equations (7.17) gives

0,0
1 0 1
1 0
-kT ln ( )
2
T
h T T
T T

=

which can be solved numerically for T
1
.

Using k=20 W/mK, T
0
= 1.3 and T
0,0
= 0.05

gives T
1
=0.70773 and T
2
=0.30648

and
2
2
2
2
0.30648
ln 20 ln 14.0 /
0.70773
t
T
k W K
T

= = =




96
8. Applications

As stated by Bejan [1]: Entropy Production Minimization is the method of
thermodynamic optimization of real systems that owe their thermodynamic
imperfections to heat transfer, fluid flow, and mass transfer irreversibilities.
The method combines at the most fundamental level the basic principles of
thermodynamics, heat and mass transfer and fluid mechanics and because of its
interdisciplinary character, EGM is distinct from each of these classical
disciplines.

The above statement indicates the possibility of some significant practical
applications. This is indeed a case. The wide overview of the applications is
presented by Bejan [1].

One of the first applications has been the determination of the units of
heat exchanger when the entropy production is minimized in the system as the
result of two irreversible processes flow with friction and heat transfer
between two fluids across the finite temperature difference. Entropy production
minimization allows to determine the optimal pipe diameter of the heat
exchanger. These topics are well supported in literature (see Bejan [1], Chapter
4 and 5).

Another application involves problems with Insulation Systems both in
powers plants and in refrigeration plants (Chapter 6).
The entropy production minimization method has also been used in the analysis
of energy and exergy storage.

An important application is also represented by the optimization of
thermodynamic cycles in the contemporary power plants systems. The analysis
is focused on the role of heat exchangers and the optimal combustion
temperature. Bejan has shown that the maximum power of the electric power
plant means the entropy production minimization.

An important range of applications is also reflected in the solar-thermal
power generation, particularly in finding an optimal temperature of the solar
collector which is working under non-isothermal conditions with the decreasing
fluid temperature as the result of decreasing in time amount of sunshine.

Many important applications are also related to the problems of
refrigeration which can be solved by designing an optimal system of heat
exchangers and by selecting appropriate circulation parameters.


97
In addition to Bejans achievements, it is important to mention the
application of the entropy production minimization method in describing the
formation of the dissipative structures in life processes (see for example the
work of Kirkaldy [12] concerning the thermodynamic explanation of human
brain activity).

Large attention should also be paid to the work describing the metabolic
processes or the diffusional coupling of the substances flow in sodium and
potassium ions pumps across the organisms single cell membranes [12].

The solutions, achieved in this thesis , of the entropy production problems
in the processes of heat transfer with various boundary conditions , represent the
theoretical basis of the entropy production minimization problems.






























98
9. Summary


In the thesis, the applications of entropy production minimization method
have been presented, in the stationary processes of heat conduction in solids and
diffusional mass transfer.

It has been shown that these processes are described by the similar
differential equations and boundary conditions and hence their methods of
solving are, in principle, identical.

It has been established that the well known differential equations of
Laplace and Poisson are the approximations resulting from assuming the
average temperature across the entire region of the thermodynamic system. This
has been demonstrated by the in depth analysis of the entropy production
minimization according to Prigogines procedure. The general approach with
calculus of variations allows to derive a full differential equation for the heat
transfer.

For example, when the heat conduction coefficient is constant, the calculus of
variations approach leads to equation

2
2
2
1
0
d T dT
dx T dx

=



(9.1)
while the classical equation is
2
2
0
d T
dx
=


in the one-dimensional system or

2
2 2
2 2 2
2 2 2
1
0
T T T T T T
dx dy dz T x y z



+ + + + =






and
2 2 2
2
2 2 2
( , , ) 0
T T T
T x y z
dx dy dz

+ + = =


for the 3-D ortho-cartesian geometry.
99
The detailed interpretation of the second term in equation (9.1) has been
presented as well as its agreement with the First and Second Laws of
Thermodynamics.

The boundary value problems have been formulated for all three kinds of
boundary conditions including the most general conditions of Sturm-Liouville.

The discussion has also focused on the method of solving general non-linear
Euler-Lagrange equations. It has been demonstrated that the non-linear
boundary problems, for any heat conduction coefficient with internal heat
source, lead to the differential equation for heat transfer which can be further
rearranged into the Bernoulli differential equation. This transformation permits
to obtain, in spite of its non-linearity, an analytical solution which is often given
in the non-explicit form.

This is definitely a new contribution to the boundary problems with the entropy
production minimization. The possible uses of the solution methods have been
demonstrated by various numerical calculations.

Another important achievement of this thesis is the demonstration of the method
allowing for the calculation of the additional internal heat source and the
entropy production rate in case of the non-explicit solutions.

Finally, it has been explained that there is no direct link between Prigogines
minimum entropy production in stationary processes and the entropy production
minimization methodology. This derives from the important statement that the
entropy production is path dependent and it can not be linked to the concept of
entropy as the function of state.















100
Appendix 1

Principles of Calculus of Variations

Calculus of Variations is concerned with finding the function y(x) such that the
definite integral of the functional dependent on y(x) would reach the minimum.
In case of one independent variable x and one dependent variable y(x), the
problem reduces to finding the minimum of the integral:

2
1
x
( , , ) minimum
x
x
F x y y dx
(A.1)

where y
x
= dy/dx. The integral limits are set and each dependent variable y(x
1
)
and y(x
2
) have a set value.
It can be shown [11] that the necessary condition for integral (A.1) to have a
minimum, it must satisfy the following differential equation:

0
x
F d F
y dx y


=




(A.2)

known as the Euler-Lagrange equation.

In case of more independent variables, the problem focuses on finding the
function u=u(x, y, z), such that the integral

2 2 2
1 1 1
,
( , , , , , )
x y z
x y z
x y z
F x y z u u u u dxdydz



reaches the extreme value.
In this case, the necessary condition for the minimum is met if the following
Euler-Lagrange equation is satisfied:

0
x y z
F F F F
u x u y u z u

=


(A.3)

101
If, in addition to function u(x,y,z), there are other dependent functions, then the
necessary condition becomes a system of Euler-Lagrange equations.

In practical applications, quite often, the problems arise in which the specific
integral is expected to reach the extreme value while the additional conditions
must be satisfied described as the integrals containing the same variables in the
same domain of independent variables. This type problems are solved with the
method of Langrange multipliers. One searches for the minimum of the integral


V
F d V


with the additional conditions

1 1 2 2 3 3
, , ,.........., ,
n n
V V V V
FdV c FdV c FdV c FdV c = = = =



where dV represents the volume element of the multidimensional space and
c
1
,c
2
,..,c
n
are the known constants. The solution is determined by finding the
minimum of the integral

V
K d V


where
1 1 2 2
........
n n
k F F F F = + + + +
.

The necessary condition for the minimum is met if the following Euler-
Lagrange equation is satisfied (for one independent variable):

0
x
K d K
y dx y


=





The unknown values of
i
( i = 1,2,3,..,n) are found from the additional
conditions. If the function F includes the derivatives of higher orders, the
additional terms are included in the Euler-Lagrange equations.



102
References


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2. Kondepudi, D. and Prigogine, I. ; Modern Thermodynamics , John Wiley
and Sons, Chichester, 1998

3. Guminski, K. ; Termodynamika procesow nieodwracalnych , PWN,
Warszawa, 1962

4. Bujakiewicz-Koronska, R.; Przemiany materii i informacji w strukturach
dyssypatywnych , Rozprawa doktorska, Wydzial Fizyki i Techniki Jdrowej
AGH, Krakow, 1997

5. Bejan, A. ; Heat Transfer , John Wiley and Sons, New York, 1993

6. Reif, F.; Statistical Physics , McGraw Hill Book Company, New York,
Berkeley Physics Course Vol.5, 1965

7. Szargut, J. ; Exergy Method, WIT Press, Southhampton, 2005

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11. Martin Becker ; The Principles and Applications of Variational Methods,
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12. Kirkaldy, J.S. ; The Thermodynamics description of heterogeneous
dissipative systems by variational methods, Part III, Can.J.Phys. 42, 1964,
1437-46 and Part II, 38, 1960, 1356-66