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Non equilibrium Thermodynamics for Engineers 1st
Edition S Kjelstrup Digital Instant Download
Author(s): S Kjelstrup, D Bedeaux, E Johannessen, J Gross
ISBN(s): 9789814322157, 9814322156
Edition: 1
File Details: PDF, 3.62 MB
Year: 2010
Language: english
EPIOPTICS-10
This page intentionally left blank
THE SCIENCE AND CULTURE SERIES — PHYSICS
EPIOPTICS-10
Proceedings of the 43rd Course of the
International School of Solid State Physics
Erice, Italy 19 — 26 July 2008
Editors
Antonio Cricenti
Series Editor
A. Zichichi
World Scientific
NEW JERSEY • LONDON • SINGAPORE • BEIJING • SHANGHAI • HONG KONG • TA I P E I • CHENNAI
Published by
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UK office: 57 Shelton Street, Covent Garden, London WC2H 9HE
British Library Cataloguing-in-Publication Data

A catalogue record for this book is available from the British Library.
NON-EQUILIBRIUM THERMODYNAMICS FOR ENGINEERS

Copyright © 2010 by World Scientific Publishing Co. Pte. Ltd.
All rights reserved. This book, or parts thereof, may not be reproduced in any form or by any means,
electronic or mechanical, including photocopying, recording or any information storage and retrieval
system now known or to be invented, without written permission from the Publisher.
For photocopying of material in this volume, please pay a copying fee through the Copyright
Clearance Center, Inc., 222 Rosewood Drive, Danvers, MA 01923, USA. In this case permission to
photocopy is not required from the publisher.
ISBN-13 978-981-4322-15-7
ISBN-10 981-4322-15-6
Printed in Singapore.
Julia - Non-Equilibrium thermodyanics.pmd 1 5/3/2010, 5:18 PM

PREFACE
This special volume contains the Proceedings of the 10th Epioptics Workshop,
held at the Ettore Majorana Foundation and Centre for Scientific Culture, Erice,
Sicily, from June 19 to 26, 2008. This was the 10th Workshop in the Epioptics
series and the 43rd of the International School of Solid State Physics. Antonio
Cricenti from CNR Istituto di Struttura della Materia and Theo Rasing from the
University of Njimegen, were the Directors of the Workshop. The Advisory
Committee of the Workshop included Y. Borensztein from U. Paris VII (F),
R. Del Sole from U. Roma II Tor Vergata (1), D. Aspnes from NCSU (USA),
O. Hunderi from U. Trondheim (N), J. McGilp from Trinity College Dublin
(Eire), W. Richter from TU Berlin (D), N. Tolk from Vanderbilt University
(USA), and P. Weightman from Liverpool University (UK). Fifty scientists from
sixteen countries attended the Workshop.
The Workshop brought together researchers from universities and research
institutes who work in the fields of (semiconductor) surface science, epitaxial
growth, materials deposition and optical diagnostics relevant to (semiconductor)
materials and structures of interest for present and anticipated (spin) electronic
devices. The Workshop was aimed at assessing the capabilities of state-of-the-
art optical techniques in elucidating the fundamental electronic and structural
properties of semiconductor and metal surfaces, interfaces, thin layers, and layer
structures, and assessing the usefulness of these techniques for optimization of
high quality multilayer samples through feedback control during materials
growth and processing. Particular emphasis was dedicated to the theory of non-
linear optics and to dynamical processes through the use of pump-probe
techniques together with the search for new optical sources. Some new
applications of Scanning Probe Microscopy to Material science and biological
samples, dried and in vivo, with the use of different laser sources were also
presented. Materials of particular interest were silicon, semiconductor-metal
interfaces, semiconductor and magnetic multi-layers and III-V compound
semiconductors. As well as the notes collected in this Volume, the Workshop
v
vi
combined tutorial aspects pr~per to a School with some of the most advanced
topics in the field, which better characterized the Workshop.
I wish to thank Prof. A. Zichichi, President of the Ettore Majorana
Foundation and Centre for Scientific Culture (EMFCSC), the Italian National
Research Council (CNR) and the Sicilian Regional Government. I wish to thank
Prof. G. Benedek, Director of the International School of Solid State Physics of
the EMFCSC. Our thanks are also due to the Director for Administration and
Organizational Affairs, Ms. F. Ruggiu and all the staff of the Centre for their
excellent work.
Antonio Cricenti
Preface
To meet the entropy challenge, is probably more central than the

issue of provision of sufficient power to the world. The entropy
production, not the energy used, can measure our wastes and
the efficiency of work, or the limit of our activity. This book
introduces non-equilibrium thermodynamics to engineers, and
discusses how the theory can be useful for typical engineering
problems.
The book has been written on the basis of many years of teaching
at the Norwegian University of Science and Technology, Trond-
heim, Norway, and the Technical University of Delft, Delft, The
Netherlands. Early versions of the book have been used at short
courses at the International Center of Thermodynamics, Istan-
bul, Chalmers Technical University, Gothenburg, Helsinki Tech-
nical University and Pennsylvania State University.
It can be used in the Bachelor or Master study programs af-

ter a basic course in thermodynamics, or for self study in the
industry. The book requires knowledge of basic thermodynam-
ics corresponding to that given by Smith, van Ness and Abbott,
Introduction to chemical engineering, or Moran and Shapiro,
Fundamentals of Engineering Thermodynamics.
To facilitate learning, exercises for the topics of the book and

viii Preface
solutions to these, are available on the NTNU homepage.1 Eight

DVD lectures are likewise available there or from The Technical
University of Delft.2
Financial support from the Research Council of Norway is ac-

knowledged. The authors are grateful to Statoil ASA for the
cover picture from Mongstad.
The authors welcome comments and suggestions that can

improve future editions.
Trondheim and Stuttgart, March 2010
Signe Kjelstrup Dick Bedeaux

signe.kjelstrup@chem.ntnu.no dick.bedeaux@chem.ntnu.no
Eivind Johannessen Joachim Gross

eijoh@statoil.com gross@itt.uni-stuttgart.de
1
http://www.chem.ntnu.no/nonequilibrium-thermodynamics/
2
http://collegerama.tudelft.nl/mediasite/Catalog/?cid=0cbe1b45-
06c6-4d03-a692-92a6dad4711d
Contents
Preface vii
1 Scope 1
2 Why non-equilibrium thermodynamics? 7

2.1 Simple flux equations . . . . . . . . . . . . . . . . 8
2.2 Flux equations in non-equilibrium thermodynamics 11
2.3 The lost work of an industrial plant . . . . . . . . 13
2.4 The second law efficiency . . . . . . . . . . . . . . 19
2.5 Consistent thermodynamic models . . . . . . . . 21
3 The entropy production of one-dimensional trans-

port processes 23
3.1 Balance equations . . . . . . . . . . . . . . . . . . 25
3.2 Entropy production . . . . . . . . . . . . . . . . . 27
3.3 Examples . . . . . . . . . . . . . . . . . . . . . . 33
3.4 The frame of reference for fluxes . . . . . . . . . 41
4 Flux equations and transport coefficients 45

4.1 Linear flux-force relations . . . . . . . . . . . . . 46
4.2 Transport of heat and mass . . . . . . . . . . . . 49
4.3 Transport of heat and charge . . . . . . . . . . . 58
4.4 Transport of mass and charge . . . . . . . . . . . 63
4.4.1 The mobility model . . . . . . . . . . . . . 69
4.5 Transport of volume and charge . . . . . . . . . . 70
x Contents
4.6 Concluding remarks . . . . . . . . . . . . . . . . . 73
5 Non-isothermal multi-component diffusion 75

5.1 Isothermal diffusion . . . . . . . . . . . . . . . . . 76
5.1.1 Prigogine’s theorem applied . . . . . . . . 77
5.1.2 Diffusion in the solvent frame of reference 78
5.1.3 Maxwell-Stefan equations . . . . . . . . . 81
5.1.4 Changing a frame of reference . . . . . . . 84
5.2 Maxwell-Stefan equations generalized . . . . . . . 87
6 Systems with shear flow 93

6.1 Balance equations . . . . . . . . . . . . . . . . . . 94
6.1.1 Component balances . . . . . . . . . . . . 95
6.1.2 Momentum balance . . . . . . . . . . . . . 95
6.1.3 Internal energy balance . . . . . . . . . . . 96
6.2 Entropy production . . . . . . . . . . . . . . . . . 98
6.3 Stationary pipe flow . . . . . . . . . . . . . . . . 104
6.3.1 The measurable heat flux . . . . . . . . . 106
6.4 The plug flow reactor . . . . . . . . . . . . . . . . 107
7 Chemical reactions 109

7.1 The Gibbs energy change of a chemical reaction . 112
7.2 The reaction path . . . . . . . . . . . . . . . . . . 116
7.2.1 The chemical potential . . . . . . . . . . . 117
7.2.2 The entropy production . . . . . . . . . . 119
7.3 A rate equation with a thermodynamic basis . . . 119
7.4 The law of mass action . . . . . . . . . . . . . . . 122
7.5 The entropy production on the mesoscopic scale . 124
8 The lost work in the aluminum electrolysis 129

8.1 The aluminum electrolysis cell . . . . . . . . . . 130
8.2 The thermodynamic efficiency . . . . . . . . . . . 132
Contents xi
8.3 A simplified cell model . . . . . . . . . . . . . . . 135

8.4 Lost work due to charge transfer . . . . . . . . . . 137
8.4.1 The bulk electrolyte . . . . . . . . . . . . 137
8.4.2 The diffusion layer at the cathode . . . . 137
8.4.3 The electrode surfaces . . . . . . . . . . . 138
8.4.4 The bulk anode and cathode . . . . . . . . 139
8.5 Lost work by excess carbon consumption . . . . . 139
8.6 Lost work due to heat transport through the walls 140
8.6.1 Conduction across the walls . . . . . . . . 141
8.6.2 Surface radiation and convection . . . . . 142
8.7 A map of the lost work . . . . . . . . . . . . . . . 143
9 The state of minimum entropy production and

optimal control theory 147
9.1 Isothermal expansion of an ideal gas . . . . . . . 148
9.1.1 Expansion work . . . . . . . . . . . . . . . 150
9.1.3 The optimization idea . . . . . . . . . . . 153
9.2 Optimal control theory . . . . . . . . . . . . . . . 158
9.3 Heat exchange . . . . . . . . . . . . . . . . . . . . 163
9.3.2 The work production by a heat exchanger 168
9.3.3 Optimal control theory and heat exchange 171
10 The state of minimum entropy production in

selected process units 177
10.1 The plug flow reactor . . . . . . . . . . . . . . . . 178
10.1.2 Optimal control theory and plug flow re-
actors . . . . . . . . . . . . . . . . . . . . 184
10.1.3 A highway in state space . . . . . . . . . . 185
10.1.4 Reactor design . . . . . . . . . . . . . . . 191
10.2 Distillation columns . . . . . . . . . . . . . . . . . 192
xii Contents

10.2.2 Column design . . . . . . . . . . . . . . . 203
Appendix A 207
A.1 Balance equations for mass, charge, momentum
and energy . . . . . . . . . . . . . . . . . . . . . . 207
A.1.1 Mass balance . . . . . . . . . . . . . . . . 208
A.1.2 Momentum balance . . . . . . . . . . . . . 210
A.1.3 Total energy balance . . . . . . . . . . . . 213
A.1.4 Kinetic energy balance . . . . . . . . . . . 214
A.1.5 Potential energy balance . . . . . . . . . . 215
A.1.6 Balance of the electric field energy . . . . 215
A.1.7 Internal energy balance . . . . . . . . . . . 215
A.1.8 Entropy balance . . . . . . . . . . . . . . . 217
A.2 Partial molar thermodynamic properties . . . . . 219
A.3 The chemical potential and its reference states . . 222
A.3.1 The equation of state as a basis . . . . . . 223
A.3.2 The excess Gibbs energy as a basis . . . . 224
A.3.3 Henry’s law as a basis . . . . . . . . . . . 226
A.4 Driving forces and equilibrium constants . . . . . 227
A.4.1 The ideal gas reference state . . . . . . . . 228
A.4.2 The pure liquid reference state . . . . . . . 229
Bibliography 231
List of Symbols 245
Index 251
About the authors 259

Chapter 1
Scope
The aim of this book is to present the essence of non-equilibrium

thermodynamics for engineers. The field was established in 1931
and developed during the forties and fifties for transport in ho-
mogeneous phases. Applications of the theory are now increas-
ing. Some perspectives on the applications are given after a brief
introduction.
Non-equilibrium thermodynamics describes transport processes

in systems that are not in global equilibrium. The field resulted
from efforts of many scientists to find a more explicit formula-
tion of the second law of thermodynamics. This started already
in 1856 with Thomson’s studies of thermoelectricity, see [1]. On-
sager is, however, counted as the founder of the field with his
papers from 1931 [2, 3], see also [4], because these put earlier
research by Thomson, Boltzmann, Nernst, Duhem, Jauman and
Einstein into a systematic framework. Onsager was given the
Nobel prize in chemistry in 1968 for this work.
The second law is reformulated in terms of the entropy pro-

duction σ. In Onsager’s formulation, the entropy production is
2 Chapter 1. Scope
given by the product sum of so-called conjugate fluxes, Ji , and

forces, Xi , in the system. The second law then becomes
X
σ= Ji Xi ≥ 0 (1.1)
i
where σ is larger than or equal to zero. Each flux is taken to be

a linear combination of all forces,
X
Ji = Lij Xj (1.2)
j
and the reciprocal relations
Lji = Lij (1.3)
apply. They now bear Onsager’s name.
In order to use the theory, one first has to identify a complete

set of extensive independent variables, αi . The resulting conju-
gate fluxes and forces are Ji = dαi /dt and Xi = (∂S/∂αi )αj6=i ,
respectively. Here t is the time and S is the entropy of the sys-
tem. The three equations above contain then all information on
the non-equilibrium behavior of the system.
Following Onsager, a consistent theory of non-equilibrium pro-

cesses in continuous systems was set up in the forties by Meixner
[5–8] and Prigogine [9]. They calculated the entropy production
for a number of physical problems. Prigogine received the Nobel
price for his work on dissipative structures in systems that are
not in equilibrium in 1977, and Mitchell the year after for his
application of the driving force concept to transport processes
in biology [10].
The most general description of non-equilibrium thermodynam-

ics is still the 1962 monograph of de Groot and Mazur [11]
reprinted in 1985 [12]. Haase’s book [13] also reprinted [14],
contains many results for electrochemical systems and systems
Chapter 1. Scope 3
with temperature gradients. Katchalsky and Curran developed

the theory for biophysical systems [15]. Their analysis was car-
ried further by Caplan and Essig [16]. Førland and coworkers
gave various applications in electrochemistry and biology, and
they treated frost heave [17,18]. Their book presented the theory
in a way suitable for chemists. Newer books on equilibrium ther-
modynamics or statistical thermodynamics often include chap-
ters on non-equilibrium thermodynamics, see e.g. [19]. In 1998,
Kondepudi and Prigogine [20] presented an integrated approach
of basic equilibrium and non-equilibrium thermodynamics. Jou
et al. [21] published the second edition of their book on ex-
tended non-equilibrium thermodynamics and Öttinger gave a
non-equilibrium description of the nonlinear regime [22].
Non-equilibrium thermodynamics is constantly being applied in

new contexts. Fitts gave an early presentation of viscous phe-
nomena [23]. Kuiken [24] has written the most general treatment
of multicomponent diffusion and rheology of colloidal systems.
Rubi and coworkers [25–27] used the internal molecular degrees
of freedom to explore the development within a system. We
are now able to deal with chemical reactions within the frame-
work of non-equilibrium thermodynamics [12] and shall do so
in Chapter 7. Bedeaux and Mazur [28] extended the theory
to quantum mechanical systems. Kjelstrup and Bedeaux [29]
wrote a book dealing with transports into and across surfaces.
All these efforts broaden the scope of the theory.
Chemical and mechanical engineering needs theories of trans-

port in systems with gradients in pressure, concentration, and
temperature, see Denbigh [30, 31]. In isotropic systems there
is no coupling between tensorial (viscous) and vectorial (diffu-
sional) phenomena, so the two classes can usually be dealt with
separately [12]. We concentrate on isotropic systems here.
4 Chapter 1. Scope
Simple vectorial transport laws have long worked well in engi-

neering, but there is now an increased effort to be more pre-
cise. The need for more accurate flux equations in modeling [32]
increases the need for non-equilibrium thermodynamics. The
books by Taylor and Krishna [32], Cussler [33] and Demirel [34],
which present Maxwell-Stefan’s formulation of the flux equa-
tions, are important books in this context. Krishna and Wes-
selingh [35] and Kuiken [24] have shown that the coefficients
in the Maxwell-Stefan equations are relatively well-behaved, by
analyzing an impressive amount of experimental data.
Non-equilibrium thermodynamics is necessary for a precise de-

scription of all systems that exchange heat, mass and charge.
There is a need in mechanical and chemical engineering to design
systems that waste less work [36–38]. Fossil energy sources, as
long as they last, lead to waste that may harm the environment.
Better and more efficient use of energy resources is therefore
central. It is then not good enough to only optimize the first
law efficiency. The second law has to be taken into account.
The entropy production σ can be seen as a measure for the non-
sustainability of a technical process. Through non-equilibrium
thermodynamics, one can develop methods to improve the sec-
ond law efficiency. One purpose of the book is to present such
methods.
The process industry may, in a not too distant future, have to

give annual reports not only on the products that they produce,
but also on their annual lost exergy or entropy production. Some
energy companies are making an effort in this direction already.
The public sector can enhance this development, by giving bene-
fits to those who limit their entropy production, or increase their
energy efficiency. And the engineering community can develop
tools to accomplish the task. The present book should be seen
in this context. Efforts in other fields, like control theory [39],
are also made. This book as well as the references cited above,
Chapter 1. Scope 5
gives instruments that are needed to understand the nature of

the entropy production and can therefore help to avoid it.
We give in Chapter 2 the characteristics of non-equilibrium ther-

modynamics and explain why it is an important field. In Chap-
ter 3, we show how to derive the entropy production for systems
with diffusion and conduction. The derivations follow de Groot
and Mazur [12] and Førland, Førland and Kjelstrup [18]. Chap-
ter 4 presents examples of flux equations for coupled transport
of heat, mass and charge. Chapter 6 deals with shear flow and 7
with chemical reactions. Examples are used to show how the dif-
ferent processes are coupled. In Chapter 8 we estimate the lost
work in an industrial process, the Hall-Heroult process for alu-
minum electrolysis. The entropy production by charge transfer
and by heat transfer are both large. In Chapter 9, we describe
a method to minimize the entropy production in process equip-
ment. The method is described in detail for ideal gas expansion
and energy efficient heat exchange in this Chapter. Its applica-
tion to chemical reactors and distillation columns is illustrated
in Chapter 10.
This page intentionally left blank
Chapter 2
Why non-equilibrium
thermodynamics?
This chapter explains in more detail what non-equilibrium ther-

modynamics is, and how it adds to engineering fields.
The most common industrial and living systems are those that
transport heat, mass, charge, and volume, in the presence or
absence of a chemical reaction. The process industry, the elec-
trochemical industry, biological systems, as well as laboratory
experiments; all are systems that are out of equilibrium. Equi-
librium thermodynamics is then not sufficient. There are six
main reasons why non-equilibrium thermodynamics theory [12,
13, 18, 29] is needed. The theory
• gives an accurate description of coupled transport pro-

cesses.
• gives the same systematic basis to all transport processes.
• can be used to define experiments.

8 Chapter 2. Why non-equilibrium thermodynamics?
• quantifies produced entropy, lost work or lost exergy.

• gives an entropy balance to use in thermodynamic model-
ing.
• can be used to optimize the energy efficiency.
These statements will be illustrated briefly in this Chapter, and

more in-depth in the rest of the book.
The design of systems which waste less energy, is becoming in-

creasingly more important [37]. We show in the end of this
Chapter how entropy production of an industrial plant is related
to the lost work in the plant. Non-equilibrium thermodynam-
ics is the only theory that can be used to assess in detail the
second law efficiency, or how valuable (energy) resources are ex-
ploited. It is the aim of this book to contribute especially to
this issue. Chapter 10 develops rules for energy efficient designs
in engineering practice.
2.1 Simple flux equations

Accurate expressions for the fluxes are required in engineering.
In order to see immediately what non-equilibrium thermody-
namics can add to the modeling of real systems, we compare
simple flux equations to flux equations given by non-equilibrium
thermodynamics in the following two sections.
The simplest descriptions of heat-, mass-, charge- and volume

transport are the equations of Fourier, Fick, Ohm, Darcy and
Newton. Fourier’s law expresses the measurable heat flux in
terms of the temperature gradient by:
dT
Jq0 = −λ (2.1)
dx
where λ is the thermal conductivity, T is the absolute temper-
ature, and x is the direction of transport. Fick’s law gives the
2.1 Simple flux equations 9
mass flux of one of the components in terms of the gradient of

its molar concentration c:
dc
J = −D (2.2)
dx
where D is the diffusion coefficient. Ohm’s law gives the electric
current in terms of the gradient of the electric potential:
dφ
j = −κ (2.3)
dx
where κ is the electrical conductivity, and φ is the electric po-
tential. Darcy’s law says that the volume flow Jv in a tube is
proportional to the pressure gradient dp/dx via the coefficient
Lp :
dp
Jv = −Lp (2.4)
dx
And, a laminar flow in the x-direction with velocity v = (vx , 0, 0)
and velocity component vx = vx (y) obeys Newton’s law of fric-
tion:
∂vx
Πxy = −η (2.5)
∂y
where Πxy is the viscous pressure tensor, and the proportionality
constant, η, is the shear viscosity.
The fluxes in Eqs. (2.1)-(2.5) are all caused by one gradient, or

one driving force (see next Section). Fick’s law, for instance, says
that there is no mass flux if there is no concentration gradient.
We know from experiments that a temperature gradient and an
electric potential gradient also can give rise to a mass flux. To
neglect such effects can have severe consequences. When used
at interfaces, such assumptions can even be in conflict with the
laws of thermodynamics [29, 40].
Non-equilibrium thermodynamics generalizes equations (2.1)-

(2.5) by taking all driving forces into account. The theory gives
a common basis to all simple transport equations, and show how

they are connected. The basis is the second law of thermody-
namics as expressed through (1.1)-(1.3). This means that the
hydrodynamics of viscous fluids, the theory of diffusion, heat
conduction, and chemical reaction, all have a common system-
atic basis [12]. One purpose of the book is to give this.
Exercise 2.1.1 In a stationary state there is no accumulation

of internal energy, mass or charge. This means that the heat,
molar, and electric fluxes are independent of position. The deriva-
tive of the above equations with respect to x are then zero. For
the first equation, we have:
d dT
λ =0 (2.6)
dx dx
Equations like these can be used to calculate the temperature,

concentration, electric potential and pressure as a function of
the position, when their values on the boundaries of the system
and λ, D, κ, Lp and η are known.
Calculate the temperature as a function of position between two

walls separated by 10 cm. The walls are kept at constant tem-
perature, 5 and 25 o C, respectively. Assume that the thermal
conductivity is constant.
• Solution: According to Eq. (2.6) d2 T /dx2 = 0. The gen-

eral solution of this equation is T (x) = a + bx. The con-
stants a and b follow from the boundary condition. We
have T (0) = 278 K and T (10) = 298 K. It follows that
T (x) = (278 + 2x/cm) K.
2.2 Flux equations in non-equilibrium thermodynamics 11
2.2 Flux equations in non-equilibrium thermo-

dynamics
Many natural and man-made processes are not adequately de-
scribed by the simple flux equations given above. There are,
for instance, always large fluxes of mass and heat that accom-
pany charge transport in batteries and electrolysis cells. The
resulting local cooling in electrolysis cells may lead to unwanted
freezing of electrolyte. Electrical energy is frequently used to
transport mass in biological systems. Large temperature gradi-
ents across space ships have been used to supply electric power
to the ships. Salt concentration differences between river water
and sea water can be used to generate electric power. Pure wa-
ter can be generated from salt water by application of pressure
gradients. In all these more or less randomly chosen examples,
one needs transport equations that describe coupling between
various fluxes. The flux equations (2.1)-(2.5) become then too
simple.
Non-equilibrium thermodynamics prescribes coupling among

fluxes. Coupling means that transport of mass will take place in
a system, not only when the gradient in the chemical potential
is different from zero, but also when there are gradients in tem-
perature or electric potential. Coupling between fluxes describes
precisely the phenomena mentioned above.
For example, in a bulk system with transport of heat, mass, and

electric charge, we shall learn in Chapters 3 and 4 that the linear
relations for the fluxes (2.1)-(2.3) take the form

d 1 1 dµT 1 dφ
Jq0 = Lqq + Lqµ − + Lqφ − (2.7)
dx T T dx T dx

d 1 1 dµT 1 dφ
J = Lµq + Lµµ − + Lµφ − (2.8)
dx T T dx T dx

d 1 1 dµT 1 dφ
j = Lφq + Lφµ − + Lφφ − (2.9)
dx T T dx T dx
The forces of transport conjugate to the fluxes Jq0 , J and j are the
thermal force d (1/T ) /dx, the chemical force [− (1/T ) (dµT /dx)],
and the electrical force [− (1/T ) (dφ/dx)], respectively. The sub-
script T of the chemical potential, µT , indicates that the deriva-
tive should be taken keeping the temperature constant. We
return to this point in Section 3.2.
The L-coefficients are so-called phenomenological coefficients, or

Onsager coefficients, as we shall call them. They must be mea-
sured. The Onsager coefficients on the diagonal of the matrix
can be related to λ, D, and κ. They are called main coefficients.
The off-diagonal L-coefficients describe the coupling between the
fluxes. They are called coupling coefficients. Another common
name is cross coefficients. According to Onsager, we have here
three reciprocal relations or Onsager relations for the coupling
coefficients:
Lµq = Lµq , Lqφ = Lφq , Lφµ = Lµφ (2.10)
The Onsager relations simplify the system. They reduce the

number of independent coefficients from nine to six. Coupling
coefficients are small in some cases but large in others. We shall
see that large coupling coefficients lead to a small entropy pro-
duction. If it is difficult to measure Lij , we can rather measure
Lji . To measure both, gives a good control.
We shall see in Chapters 3, 6 and 7 how the conjugate forces can

be found in a systematic manner. In Chapter 4 we shall learn
how to write equations like the ones above. The importance
of some coupling coefficients will be discussed. The exercise
below show that knowledge of non-equilibrium thermodynamics
is useful for interpretating experiments.
2.3 The lost work of an industrial plant 13
Exercise 2.2.1 Find the electric current in terms of the electric

field E = −dφ/dx, using Eqs. (2.7)-(2.9), in a system where
there is no transport of heat and mass, Jq0 = 0, J = 0.
Solution: It follows from Eqs. (2.7) and (2.8) that
Lqq dT dµT Lµq dT dµT

+ Lqµ = Lqφ E and + Lµµ = Lµφ E
T dx dx T dx dx
Solving these equations, using the Onsager relations, one finds
1 dT Lqφ Lµµ − Lµφ Lqµ dµT Lqq Lµφ − Lµq Lqφ

= 2
E and = E
T dx Lqq Lµµ − Lqµ dx Lqq Lµµ − L2qµ
Substitution into Eq. (2.9) then gives

E Lqφ Lµµ − Lµφ Lqµ Lqq Lµφ − Lµq Lqφ
j= Lφφ − Lφq − Lφµ
T Lqq Lµµ − L2qµ Lqq Lµµ − L2qµ
The exercise shows that the electric conductivity that is nor-

mally measured, as the ratio of measured values of j and E,
is not given by Lφφ /T as one might have thought considering
Eq. (2.9). The coupling coefficients lead to temperature and
chemical potential gradients, which affect the electric current.
The measured electric conductivity is the combination of the
conductivity of a pure homogeneous conductor, found at zero
chemical potential gradient and temperature gradients, minus
additional terms. The combination of coefficients is an effective
conductivity, or stationary state conductivity.
2.3 The lost work of an industrial plant

We shall see here why a second law analysis is important for the
process industry. The industrial plant is a system, in which the
materials undergo transformations. Materials are taken in and
Figure 2.1: A schematic illustration of thermodynamic variables

that are essential for the lost work in an industrial plant.
are leaving the plant at the conditions of the environment, see

Fig. 2.1.
The environment is therefore the reference state for the thermo-

dynamic analysis. It has constant pressure, p0 (1 bar) and con-
stant temperature, T0 (for instance 298 K). We consider changes
that take place during the time interval ∆t. The first law of ther-
modynamics gives the change in internal energy of the process
∆U = Uout − Uin :
∆U = q − p0 ∆V + w (2.11)
Here q is the heat delivered to the materials. The total work de-
livered to the system is decomposed in two parts; with −p0 ∆V as
the work done on the system by volume expansion, ∆V , against
the pressure of the environment, p0 , and w as the additional
work done on the materials.
We consider first processes for which work is needed, so that

w > 0. The minimum work needed to perform a process, was
defined as the least amount of energy that must be supplied,
when at the conclusion of the process, the only parts which
have undergone any change are the process materials and the
environment [30]. To see that this is so, we first replace q by the
heat delivered to the environment, q0 = −q:
∆U = −q0 − p0 ∆V + w (2.12)
In the classical formulation of the second law, we have
∆S + ∆S0 ≥ 0 (2.13)
where ∆S is the entropy change of the process materials and
∆S0 is the entropy change in the environment. The total entropy
change is positive. For a completely reversible process the sum
of the entropy changes is zero. For an irreversible process, the
sum can be used to define the average total entropy production,
dSirr /dt, in the time interval ∆t of a stationary process, as

dSirr
∆t ≡ ∆S + ∆S0 (2.14)
dt
Assuming always that the environment behaves reversibly, the

entropy change in the surroundings is ∆S0 = q0 /T0 . By intro-
ducing q0 into the expression for the entropy production, and
combining the result with the first law, we obtain

dSirr
w = T0 ∆t + ∆U + p0 ∆V − T0 ∆S (2.15)
dt
The left hand side of this equation is the work that is needed
to accomplish the process with a particular value of the entropy
production, (dSirr /dt). Since (dSirr /dt) ≥ 0, the least work re-
quirement is
wideal = ∆U + p0 ∆V − T0 ∆S ≡ E (2.16)
This is the work requirement for a completely reversible process.

The equation defines the exergy, E, of the material [37,41]. The
exergy of the environment at p0 , T0 (the reference state) is set to
zero. We see that exergy analysis uses the classical formulation
of the second law. It calculates the ideal work and the lost work
(see below) from values at the system boundaries. Another word
for exergy is availability [42]. It is an important supplement to
non-equilibrium thermodynamics.
For processes that produce work, w and wideal are negative as

defined above. Correspondingly, the signs of ∆U, ∆V, and ∆S
are such that the system can perform work. The ideal work
wideal is minus the maximum work that can be obtained in the
time interval ∆t. This is the work performed by the system if
the process is completely reversible. By comparing Eqs. (2.15)
and (2.16), we see that T0 (dSirr /dt) ∆t is the additional quantity
of work that must be used in the actual process, compared to
the work in an ideal reversible process. Thus T0 (dSirr /dt) ∆t is
the so-called non-compensated heat of Clausius. By comparing
Eqs. (2.15) and (2.16), we see that T0 (dSirr /dt) ∆t is the work
that is lost in the actual process, compared to the available
work produced in an ideal (reversible) process. So, the lost work
relative to the surroundings is:
dSirr
wlost = w − wideal = T0 ( )∆t (2.17)
dt
This is the Gouy-Stodola theorem [43]. Equations (2.16, 2.17)

are central in the field that bears the name exergy analysis. In
exergy analysis, the lost work is calculated from knowledge of w
and wideal in Eq. (2.17).
In non-equilibrium thermodynamics we calculate the lost work

from the entropy production. The entropy production is be
found by integrating the local entropy production, σ, over the
volume of the system

Z
dSirr
= σdV (2.18)
dt
Non-equilibrium thermodynamics provide an explicit expression

for σ of Eq. (1.1) from Eq. (1.2). The local resolution of dSirr /dt
in terms of σ is beyond the scope of exergy analysis, where only a
balance around the outside of a process (unit) is conducted. The
explicit expression of σ can be used to understand the origin of
the entropy production or the lost work. At stationary state, the
entropy production in a volume element is equal to the entropy
flow into the surroundings of the element, see Section 2.5, and
Chapter 3, Eq. (3.1). In Chapters 9 and 10 we show how the local
resolution of irreversibilities can be used to optimize process
units, by minimization of the entropy production.
Exercise 2.3.1 A cylinder of a combustion engine contains 600

cm3 of air at a pressure of 10 bar and a temperature of 1200 K,
just before the exhaust valve opens (before the expansion starts).
Determine the maximum available work (the exergy) of the air.
Assume that air consists of ideal gases. The molar weight of
air is Mair = 28 g/mol. The temperature and pressure of the
surroundings are T0 = 300 K, p0 = 1 bar.
• Solution: The maximum available work per kg of gas is
|wideal | = u (T, p) − u (T0 , p0 ) + p0 [v (T, p) − v (T0 , p0 )]

− T0 [s (T, p) − s (T0 , p0 )]
where the subscript 0 refers to values of the internal energy,

the specific volume and the entropy of the air in the engine
at the temperature and pressure of the surroundings. The
thermodynamic functions were tabulated, see for instance
Moran and Shapiro [44]
u (T, p) − u (T0 , p0 ) =719.3 kJ/kg

T0 [s (T, p) − s (T0 , p0 )] =

R p0
T0 s(T, p0 ) − s(T0 , p0 ) + ln =237.9 kJ/kg
Mair p

R T T0
p0 [v (T, p) − v (T0 , p0 )] = − = − 53.5 kJ/kg
Mair p p0
This results in
|wideal | = 427.9 kJ/kg
for the maximum available work. Most of this work is

normally not converted into useful work. The lost work is
often significant in processes with chemical reactions, cf.
Chapter 7.
Exercise 2.3.2 A heat reservoir has a temperature-independent

heat capacity at constant volume CV . The temperature of the
environment is T0 = 300 K. Determine the maximum available
work (the exergy) of the heat reservoir when it has temperatures
T = 400, 4000 and 40000 K. The volume of the reservoir is
constant, V = V0 .
• Solution: The maximum available work is
|wideal | = U (T, V0 ) − U (T0 , V0 ) − T0 [S (T, V0 ) − S (T0 , V0 )]
We have:
U (T, V0 ) − U (T0 , V0 ) = CV (T − T0 )
and
T
S (T, V0 ) − S (T0 , V0 ) = CV ln
T0
2.4 The second law efficiency 19
This results in

T
|wideal | = CV (T − T0 ) − T0 ln
T0
for the maximum available work. By introducing T = 400,
4000 and 40000 K and T0 = 300 K, |wideal | = 13.7 K CV ,
2923 K CV and 38232 K CV where CV has unit J, respec-
tively. The entropy contribution becomes negligible for
(T − T0 ) T0 . The relative contribution of the entropy
to the ideal work is larger, the lower is the temperature.
We can thus expect larger losses of work at temperatures
around T0 .
2.4 The second law efficiency

In a work consuming process w > wideal , see Section 2.3. The
second law efficiency is then:
wideal wlost
ηII ≡ = 1− (2.19)
w w
This efficiency is also called the thermodynamic efficiency or the
exergy efficiency. It includes wlost . In a work producing process
w < wideal and
|w| wlost
ηII ≡ =1− (2.20)
|wideal | |wideal |
The exergy destruction coefficient is ξ ≡ 1 − ηII . The defini-
tions of ηII in work (exergy) consuming or producing processes
have values that vary between zero and one. An ideal reversible
machine has ηII = 1, while a real machine has normally an effi-
ciency far from one. A fuel cell, which is considered to be rather
efficient, has typically ηII = 0.6. The efficiency refers to an
unattainable reversible limit. An alternative practical limit is
therefore proposed in Section 9.2; the state of minimum entropy
production [45].
The Carnot-process played an important role in the definition

of the entropy by Clausius. The process starts with a volume of
gas at pressure pA and temperature Th . The system, in contact
with a hot thermal reservoir with temperature Th , is expanded
isothermally to a pressure pB . Subsequently it is expanded adi-
abatically (qBC = 0) until it has the temperature Tc of a cold
thermal reservoir. The pressure has then been changed to pC .
The next step is to compress the system in contact with the cold
reservoir at constant temperature to a pressure pD . Finally, the
system is compressed adiabatically (qDA = 0) to the original
pressure pA and temperature Th . The system has now returned
to its original state, but an amount of heat qAB has been taken
from the hot bath and converted into work wideal and heat |qCD |
added to the cold bath.
In the reversible cycle of the Carnot process, the entropy pro-

duction is zero, and the second law efficiency is unity. Stirling
machines are examples of nearly reversible machines.
The first law efficiency [46] of a process is defined as

w
ηI = (2.21)
q
where q is the heat added to the process. For the Carnot pro-
cess, this efficiency depends only on the temperatures of the two
reservoirs
wideal qAB + qCD Th − Tc
ηI ≡ = = (2.22)
qAB qAB Th
where Th and Tc are the temperatures of the hot and cold reser-
voirs, respectively. The first law efficiency is only close to unity
if Th Tc .
In a combustion process, the heat available for work is the en-

thalpy of reaction, giving q = ∆r H and w = ηI ∆r H. This is no
measure of how well the machine operates in terms of frictional
2.5 Consistent thermodynamic models 21
and other losses. Such information can only be obtained from

the second law efficiency, which measures how far the system is
from reversible operation.
Exercise 2.4.1 A saline power plant produces electric power

from the mixing of sea water and river water to brackish wa-
ter, at one bar and temperature T0 = 300 K. One way to do this
is by reverse electrodialysis, see Fig.4.3. Discuss the second law
efficiency of this plant.
• Solution: The ideal electric work obtainable from an elec-

trochemical cell is given by Nernst’s equation wideal =
F E = −∆G [46]. Here ∆G is the Gibbs energy differ-
ence of the mixing process, E is the ideal cell potential
and F is Faraday’s constant. We refer to one faraday of
electrons transferred. The cell delivers in reality a smaller
voltage, E 0 , due to its resistance and the concentration
gradients inside the cell. The difference between E and E 0
is the lost work. The second law efficiency is
E0
ηII =
E
The enthalpy of mixing ∆H is negligibly small for the
mixing process. The ratio −∆G/∆H obtained from ηI is
therefore clearly not a good measure of the plant’s perfor-
mance.
2.5 Consistent thermodynamic models

We refer to a thermodynamic model as a set of thermodynamic
and transport relations (equation of state, system variables etc.,
and flux-force equations) that are needed to solve the balance
equations of the system. General balance equations are given in
the Appendix A.1.
Non-equilibrium thermodynamics offers possibilities to test the

model for consistency. We mentioned a first test in Section 2.2.
Two independent experiments can be done to find the coefficients
Lij and Lji . According to Onsager, these should be identical.
A second possibility is to use the entropy balance to evaluate

the consistency of the thermodynamic model. The local en-
tropy production can be calculated from Eq. (1.1) using the flux
equations, Eq. (1.2), or alternatively, from the entropy balance
2.24. By integrating the local entropy production, σ, we obtain
the total value: Z
dSirr
= σdV (2.23)
dt
At stationary state, we also have from Eq.(3.1):
dSirr
= − Jsi − Jso Ω (2.24)
dt
where Jsi is the entropy flux into the volume, Jso the entropy
flux out of the volume and Ω is the surface area through which
the fluxes enter or leave the volume. The entropy balance is a
governing equation. Examples of entropy balances are given for
heat exchangers, chemical reactors and distillation columns in
Tables 9.1 and 10.3.
While dSirr/dt depends on Lij and the local values of the ther-
modynamic variables, the entropy fluxes Jsi and Jso can be calcu-
lated without knowledge of Lij . When the entropy production
from Eq. (2.24) agrees with the one found from Eq. (2.23), the
model is consistent with the second law of thermodynamics.
Through such analyses one may reveal inconsistencies in as-

sumptions that are made, either in thermodynamic relations or
in choice of parameters [47, 48]. Verification of assumptions is
essential for model improvements. Examples of consistency con-
trols are given in Chapter 9 and 10, Exercises 9.3.1 and 10.1.1.
Chapter 3
The entropy production of

one-dimensional transport
processes
We derive the entropy production for a volume element of a

homogeneous phase where diffusion, conduction, and chemical
reaction can take place along the x-axis. The system is in me-
chanical equilibrium. Equivalent pairs of conjugate fluxes and
forces are derived.
The second law of thermodynamics, Eq. (2.13), says that the

entropy change of a system plus its surroundings is positive for
irreversible processes and zero for reversible processes. This for-
mulation of the law gives the direction of a process; it does not
give its rate. Non-equilibrium thermodynamics assumes that
the Gibbs equation remains valid locally. We shall see that the
second law, as expressed by Eq. (1.1), results from Gibbs equa-
tion. Rates of processes as introduced through Eq. (1.2) will
then have a thermodynamic basis.
24 Chapter 3. One-dimensional transport processes
In this Chapter we shall consider systems where the transport

processes are one-dimensional. They take place in the x-direction
only. Such systems are essential in many industrial applications,
where diffusion, conduction and chemical reaction take place.
The change in the entropy in a volume element is the result

of a flow of entropy into and out of a volume element, and of
the entropy production inside. The rate of change in the local
entropy density is
∂s ∂
= − Js + σ (3.1)
∂t ∂x
where s is the entropy density per unit of volume, Js is the en-
tropy flux and σ the entropy production per unit of volume. By
integrating Eq. (3.1) for stationary state conditions, we obtain
Eq. (2.24). We shall now find an explicit expression for σ by
combining:
• mass balances,
• the first law of thermodynamics,
• the local form of Gibbs’ equation.
We shall see that σ can be written as the sum of the products of

thermodynamic forces and fluxes in the system. These are the
so-called conjugate fluxes and forces. The fluxes are used in sub-
sequent Chapters to describe transports. The importance of σ
for determination and minimization of lost work, see Eq. (2.17),
shall be dealt with in Chapters 8, 9 and 10.
Consider a volume element between x and x + dx of a container

with an electroneutral homogeneous phase, see Fig. 3.1. The
volume element does not move with respect to the walls of the
container. It has a sufficient number of particles to give a sta-
tistical basis for thermodynamic calculations. We assume local
equilibrium in the element. Its state is given by the temperature
3.1 Balance equations 25
Figure 3.1: A volume element of a homogeneous phase with

transport along the x−axis. J i and J o indicate fluxes that en-
ter and leave the element. The element is in local equilibrium.
indicates one of the fluxes.
T (x), the pressure p (x), and the chemical potentials µi (x). The
system is in mechanical equilibrium. This means that the sys-
tem has no acceleration. The pressure in a homogeneous phase
is then constant.
The assumption of local equilibrium is basic to irreversible ther-

modynamics. It has been tested using non-equilibrium molecu-
lar dynamics and found valid for very large temperature gradi-
ents [49]. Our aim is to find σ in Eq. (3.1). The symbol list in
the front of the book gives the dimensions in the equations that
follow.
3.1 Balance equations

The balance equations for the components of the system in the
volume element are
∂cj ∂
= − Jj + νj r for j = 1, ..., n (3.2)
∂t ∂x
where Jj are the component fluxes, all directed along the x-axis,
νj are the stoichiometric constants in a chemical reaction, r is
26 Chapter 3. One-dimensional transport processes
its rate in the volume element. The reaction Gibbs energy1 is

X
∆r G = νj µj (3.3)
j
Exercise 3.1.1 Derive Eq. (3.1) by considering changes in a

fixed volume element.
• Solution: The change of entropy is equal to the entropy

flux into the volume element minus the flux out of the vol-
ume element, plus the increase in the entropy production.
One has therefore
dS
= −Ω[Js (x + dx) − Js (x)] + V σ
dt
By using again that the cross section is equal to the volume
divided by dx, we obtain in the limit of small dx
dS [Js (x + dx) − Js (x)] dJs (x)

= −V + V σ = −V +Vσ
dt dx dx
By dividing this equation left and right by the volume, one
obtains Eq. (3.1).
The conservation equation for charge is
∂z ∂
=− j (3.4)
∂t ∂x
where z is the charge density. The systems that we consider, can
all be described as electroneutral. It follows that ∂j/∂x = 0 so
that the electric current, j, is constant throughout the system.
1
The driving force of the chemical reaction was called the affinity, A, by
De Donder, with A = −∆r G, see e.g. [21].
3.2 Entropy production 27
According to the first law of thermodynamics, the change in

internal energy is the net heat plus the work added to the system.
For a change in the internal energy density u = U/V per unit
of time, we have for a volume element:
∂u ∂
= − Jq + Ej (3.5)
∂t ∂x
where Jq is the energy flux. In most of the cases in the book we
shall use the definition
n
X
Jq = Jq0 + H j Jj (3.6)
j=1
The energy flux is here the sum of the measurable heat flux Jq0 (x)
and the enthalpy flux carried by the component fluxes, Jj , where
Hj are the partial molar enthalpies. This definition has lead to
the name “total heat flux” which we shall use for this quantity
throughout the book. For other definitions, see Appendix A.1.
The product Ej in Eq. (3.5) is the electric power added to the

volume element. The electric field is often replaced by minus
the gradient of the electric potential:
∂φ
E=− (3.7)
∂x
The first law is illustrated in Fig. 3.2. Appendix A.1 gives a
discussion of the relation between Eq. (3.5), the first law and
the definition of the total heat flux.
3.2 Entropy production

The balance equations shall be combined with the Gibbs equa-
tion n
X
dU = T dS − pdV + µj dNj (3.8)
j=1
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our interests, and consider our position, but that of the whole
of Afghanistan. We therefore send these eighteen persons
from among our Maliks, Mullahs, and Elders, with our
petitions to your Highness’s presence. We are at present
engaged in a jehad on the Samana range, and we request
that your Highness will be pleased to do what is for our good
and benefit; and, by the grace of God, we will act up to your
Highness’s instructions, because we leave the conduct and
management of our affairs in the hands of your Highness in
every respect. We have used our endeavours with our
tribesmen to do service to your Highness. This is the time to
gain the object of your Highness. All the Moslems are now at
the disposal of your Highness in the shape of regular troops,
artillery and money. If the British prove victorious, they will
ruin the Moslems. The services to be done on this side may
be left to us by your Highness. We hope that after the perusal
of our petition your Highness will favour us with a reply.
Dated 7 Rabi-us-Sani, 1315 (September 7, 1897).
This prayer of the Afridis had not reached Kabul, when a further
letter, September 6, was sent to the Amir from the Government of
India, anticipating Afghan assistance in catching the Hadda Mullah
should he escape into the Kunar valley. Meanwhile, the aspect of the
precise relations existing between Kabul and the revolting tribesmen,
and disclosed by this deputation from the Afridi jirga was not very
much improved when, on September 10, Abdur Rahman, in
acknowledging the letter of August 30, wrote:
... I have ordered the local officers to keep watch on
Afghan subjects to the best of their ability, and prevent them
from joining Mullah Hadda.... No tribesmen from my
territories can do such an act in an open manner. Some of
them, however, have great faith in Mullah Hadda, and it is
possible that they may have joined him during the night,
travelling like thieves by unfrequented roads. How is it
possible to keep watch on thieves during nights along such an
extensive frontier?... My kind friend, such an arrangement
could only be possible by posting about 10,000 soldiers on all
the mountain tops and at all the fords in that district. Then
they will be able to execute properly such an arrangement,
otherwise how would it be possible to stop the people who
are familiar with the country? If the well-known roads be
guarded against them, they can owing to their knowledge of
the country find paths over mountains and through desert
tracts to cross the frontier. As far as possible, however, the
local officials have been watching and will watch any open
movements of the tribesmen.
As regards the dead and the wounded whom your
Excellency writes that the tribesmen carried away with them
after the fight at Shabkaddar, I beg to state that, if they have
brought back their dead secretly, they have already, according
to their custom, buried them, and now no trace can be
obtained of them. As to the wounded, if questions be asked
they explain that they are always engaged in tribal feuds,
with one another, and they often kill and wound one another,
and that the wounded men have received their wounds in
such tribal feuds; and, as the witnesses belong to the people
concerned, it is difficult to prove anything contrary to what
they allege....
As regards the camels which the Waziri thieves stole from
the troops in Dawar, and brought to Khost where they sold
them to the inhabitants, I have to state that Sirdar Sherindil
Khan has ordered the owners of the camels to keep them
safe. If your Excellency considers it necessary that the camels
should be taken back from them, then, as the inhabitants of
Khost have bought the camels from the Waziri thieves, the
price current in the country should be given to them and the
camels taken back, so that the people of Khost may not suffer
loss...!
The air of truculent triumph which pervaded this communication
elicited no rebuke. Naturally enough a government, which made no
effective preparation to protect the native guards of British posts in
their hour of need, would hesitate to take exception at the twist of a
Persian phrase. Two days later, September 12, the same strain of
insolence, coupled with many amiable sentiments, could be detected
in the reply to the Viceroy’s letter of September 6. With remarkable
effrontery Abdur Rahman expressed the fear that collisions might
occur in the Kunar valley between the Afghan and British forces, if
the pursuit of Hadda Mullah were pushed too far in that direction.
Events, culminating with the fall of Saraghari fort on September
12, were making it incumbent to administer sharp punishment to the
Afridis; and the Tirah field force, 60,000 strong, was concentrated at
Kohat under Lieutenant-General Sir William Lockhart for this
purpose. Concerned at the dislocation of border affairs, at the loss of
revenue attendant upon the closing of the Khyber, and deriving an
inspiration from the magnitude of the force which was collecting for
service with General Lockhart, the Amir himself from this time
became less obstructive, withdrawing his own troops from outlying
posts, refusing to harbour armed fugitives and turning a very cold
shoulder to those who invoked his aid. In consequence of this
change of front he refused to permit the Afridi elders to come to
Kabul, detaining them in Jelalabad while he posted in public in the
capital on September 23, the following reply:
I have perused your petitions, all of which were with one
object. I now write to you in reply that it is eighteen years
since I came to Kabul, and you know yourselves that I went
to Rawal Pindi (in April 1885) by the Khyber route. In
consideration of my friendship with the British Government I
had gone to their country as their guest, and on my way I
found many of your tribesmen on both sides of the pass, who
made salaams to me. If what you state now is true, why did
you not tell me at that time about the matter, so that I might
have conferred with H.E. the Viceroy about it? Some years
after this when the boundary was being laid down, Sir
Mortimer Durand passed through the Khyber and came to
Kabul. All the frontier tribesmen knew of this, and saw the
Mission with their own eyes. Why did not then your Mullahs,
and Maliks, and Elders come to me when Sir Mortimer Durand
came with authority to settle the boundary, so that I could
have discussed the matter with him? At that time you all
remained silent, and silence indicates consent. I do not know
on what account now a breach has taken place between you
and the English. But after you have fought with them, and
displeased them, you inform me.
I have entered into an alliance with the British Government
in regard to matters of State, and up to the present time no
breach of the agreement has occurred from the side of the
British, notwithstanding that they are Christians. We are
Moslems and followers of the religion of the Prophet, and also
of the four Kalifs of the Prophet. How can we then commit a
breach of an agreement? What do you say about the verse in
the Koran—Fulfil your promise; to fulfil your promise is the
first duty of a Moslem. God, on the day when the first
promise was taken, asked all the creatures whether he was
their God or not. They said, “Yes, you are our God and our
Creator.” Therefore, on the day of the resurrection the first
question will be about the observance of agreements. Infidels
and Moslems will thus be distinguished by this test. You will
thus see that the matter of the agreement is of great
importance. I will never, without cause or occasion, swerve
from an agreement, because the English, up to the present
time, have in no way departed from the line of boundary laid
down in the map they have agreed upon with me. Then why
should I do so? To do so will be far from justice. I cannot, at
the instance of a few interested people, bring ignominy on
myself and my people.
What you have done with your own hands you must now
carry on your own backs. I have nothing to do with you. You
are the best judge of your affairs. Now that you have got into
trouble (literally, spoiled the matter) you want me to help
you. You have allowed the time when matters might have
been ameliorated to slip by. Now I cannot say or do anything.
I have sent back from Jelalabad the Maliks you had deputed
to me. I gave them each a lungi and ten rupees for their road
expenses, and I did not trouble them to come to Kabul.
In spite of the Amir’s attitude towards the Afridi deputation on
September 23, and his emphatic denial of the complicity of Ghulam
Haidar in his letter to the Viceroy on August 18, evidence of Afghan
participation was again unpleasantly prominent, negotiations for
peace with certain of the tribal factions being complicated by the
acts of the Afghan commander-in-chief. On one occasion, September
1, when the Hadda Mullah had been compelled to disperse an
Afghan lashkar by specific orders from the Amir, Ghulam Haidar had
sent the fakir encouraging messages, a present of five British rifles,
cartridges and a horse. Five weeks later Major Deane, political agent
in the Dir-Swat-Chitral country, complained on October 8 that two
mule-loads of ammunition sent by Umra Khan from Kabul had
passed through Ghulam Haidar’s camp at Asmar; while a few days
previously Sir Bindon Blood had reported from Panj-kora, September
28:
The jirga told the native political assistant that the Sipah
Salar had encouraged them to attack the troops, promising
ammunition as well as compensation in kind for any loss of
grain....
Again, when the Mahmunds finally submitted, dreading Kabul
reprisals for their surrender they begged to be protected from Abdur
Rahman and Ghulam Haidar. Although these were merely the under-
currents of the situation as it appeared at the outset of the Tirah
campaign in 1897, by the close of those operations in 1898
tribesmen of all denominations of fanatical obstinacy were alluding
to the encouragement which they had received from the Sipah Salar
and Abdur Rahman. Over the singular propensity for blundering
which distinguished the elect in these two years and the protracted
misfortunes attending Anglo-Indian arms during the long series of
minor wars which concluded with the Tirah, it is permissible at
length to draw the veil. In any case, the Tirah, no less a stage in the
course of Anglo-Afghan history than were the earlier occurrences, is
of fading interest in this little survey; the trend of affairs passes,
almost with relief, to consideration of the happier prospect which the
advent of a new Viceroy, Lord Curzon of Kedleston, January 1899,
inaugurated for India itself and of the more encouraging note
introduced into Imperial relations with the spheres beyond its
borders.
jamrud fort
CHAPTER XVII
ANGLO-AFGHAN RELATIONS—continued
Upon the conclusion of the Tirah campaign the forward policy ceased
to be measured by the virulence of Anglo-Afghan amenities.
Relations between Kabul and Calcutta were dominated by the
pleasant impressions of his guest which Abdur Rahman had
gathered when, as the Honourable George Nathaniel Curzon, M.P.,
the incoming Viceroy had visited Kabul in 1894. With much care this
distinguished student had made an elaborate examination of border
politics, presenting the results of his diligence in a series of scholarly
and exhaustive studies of Russia in Central Asia, Persia and the
Persian Question, The Pamirs and the Source of the Oxus, and A
Recent Journey in Afghanistan. By reason of these journeys across
Asiatic Russia, the Pamirs, Afghanistan and Persia, and through his
remarkable opportunities for observation, unrivalled powers of
assimilation, grasp of subject, luminosity of judgment and lucidity of
expression, Mr. George Curzon was without a peer as an authority on
frontier problems. When this brilliant and indefatigable mind was
called to India as Lord Curzon of Kedleston, the methods by which
the forward policy had been regulated in the closing decade of the
nineteenth century had broken down, the labour of reconstruction
reverting to a man who at least was the foremost expert of his time.
Modifications were now essential; and Lord Curzon at once put into
execution a number of important reforms in the economic and
military control of the north-west frontier. The regular garrison in
Chitral was lessened by one third. The soldiers in Lower Swat and
the Malakand were reduced from 3550 men to one battalion and a
half of native infantry and a small detachment of cavalry, while
regular troops were withdrawn from the Gilgit Agency. Similarly,
communication with Malakand was strengthened by constructing a
railway, 2 feet 6 inches in breadth from Nowshera to Dargai, to
which four companies were posted, while a very large cantonment
was created at Nowshera. In the Khyber the regular establishment,
3700 strong, was replaced by two battalions (1250 in all) of the
reorganised and enlarged Khyber Rifles, with an increased number
of British officers and an improved scale of pay. The costly and
extensive fortifications which at one time it was proposed to build in
the pass, and at its further extremity, were abandoned in favour of a
cheaper and improved scheme of defences, constructed to meet the
requirements of the Afridi garrison. The plan of laying either the bed
of a railway or a railway itself up the Khyber pass was displaced by
the extension of the existing north-west railway from Peshawar to
Jamrud, a distance of 10 miles.
jamrud fort, khyber pass
Between Peshawar and Kohat, the amiable co-operation of the

pass tribes was secured in the peaceable construction of the long
desired cart-road through the Kohat pass, and a military road
through the Mullagori country in the Khyber region, serving as a safe
alternative road to that by way of Ali Masjid, was undertaken. At the
same time a narrow gauge line, linking Thall viâ Kohat with
Kushalgarh upon the Indus and now converted to broad gauge, was
projected; while, at a later date Nushki was joined up with Quetta.
The finishing touch to an almost perfect system of frontier
communications may be found in the preparations recently made for
carrying the line along the left bank of the Kabul river to Dakka.
South of Kohat the Samana Rifles, a force of tribal militia 450
strong under British officers and recruited from the Orakzai
tribesmen, was furnished as an extra battalion to the border military
police, and the strength of the regular garrisons, maintained on the
Samana range, reduced from 1700 to 600 men. In the Kurram valley,
the Kurram militia were reorganised in two battalions (1250 strong)
under British officers. In Waziristan, two battalions of Waziristan
militia, 800 strong, were raised, the one for the Tochi valley or
Northern Waziristan, the other for the Gomul valley or Southern
Waziristan, thus releasing the services of 4000 regulars. These
changes were rendered possible by the organisation and training of
border police, militia and levies, the total strength of which is 10,000
men. The risk of entrusting to these irregulars the garrisoning of
advanced posts was provided against by maintaining flying columns
at Peshawar, Kohat, Bannu and Dera Ismail Khan, and minimised by
the marked improvement of road and railway communication with all
strategic centres in the North-West Province. While the financial
saving was great, efficiency was increased because regiments were
no longer split up into detachments. The number of regulars serving
beyond the administrative frontier was reduced from 10,200 in 1899
to 5000, while supporting garrisons were increased from 22,000 in
1899 to 24,000.
caravansary at dakka
When the Viceroy of India was satisfied that these measures were
destined to reap their complement of success he supplemented his
experiments in frontier management by their concluding phase. On
August 27, 1900, after eighteen months’ patient inquiry and constant
observation, he drew up a Minute advocating the separation of the
administration of the north-west frontier from the control of the
Punjab Government. These proposals were supported by the
signatures of his colleagues in a covering despatch on September
13. Following the lines of Lord Lytton’s celebrated Minute upon the
creation of a distinct Trans-Indus District, April 22, 1877, Lord
Curzon embodied in one of the most brilliant pieces of analysis ever
placed before the Imperial Government a temperate and lucid
exposition of the existing order of frontier administration. The
acceptance of the views enunciated in this Minute was notified by
the Secretary of State for India, Lord George Hamilton, on December
20, 1900, but it was not until November 9, 1901, that the
establishment of the new territory under the name of the North-
West Frontier Province was proclaimed.
While Lord Curzon during the first three years of his régime—
January 1899 to November 1901—was occupied with repairing the
fabric of Indian frontier administration, Afghanistan, in the early
spring of 1900, became the cause of an exchange of diplomatic
notes between the late Lord Salisbury as Secretary of State for
Foreign Affairs and the late Russian Ambassador to Great Britain, M.
de Staal, acting under the orders of the Russian Minister for Foreign
Affairs, Count Mouravieff. In a communication dated February 6,
1900, M. de Staal informed the Foreign Office that the Russian
Government were proposing that direct relations should be
established between Russia and Afghanistan with regard to frontier
matters; but that such relations should have no political character as
the Russian Government intended to maintain their former
engagements and would continue to consider Afghanistan outside
the sphere of Russian influence. An immediate reply to this request
was vouchsafed in which it was stated that, having regard to the
understanding by which Afghanistan is outside the sphere of Russian
influence,
... it would be impossible for the British Government to
take into consideration any change in existing arrangements
or to frame proposals to be brought before the Amir without
more precise explanation in regard to the method which the
Russian Government would desire to see adopted for the
exchange of such communications between the frontier
officials, the limitations to be placed on them and the means
of ensuring that those limitations would be observed.
To this intimation no reply at the moment was preferred by the
Russian authorities, and the study of Anglo-Afghan relations shifts
once more to the dominions of the Amir. Throughout the period in
which Lord Curzon was so engrossed with the machinery of frontier
and administrative reforms Abdur Rahman had not been in any way
an idle ruler. In spite of his failing powers, with great energy and
determination, he had concentrated his efforts upon the completion
of his life’s work. With that accomplished, assured of the good-will of
the Government of India shortly after Lord Curzon’s arrival in 1899
by the release of the munitions of war which had been detained
through the outbreak of the Tirah troubles, he turned his hand to
matters of more domestic concern. Satisfied with the improvements
in his military establishment, content with the reforms which he had
introduced in the administrative economy of his state, and having
established its independence by elaborate artifices, he again sought
the preservation of his line. In an effort to prepare his people for the
acceptance and accession of Habib Ullah Khan at his demise he had,
in 1891, delegated to this son authority to hold the public Durbars in
Kabul. At the same time he had reserved to himself the control of
foreign affairs, manifesting in this direction a keen appreciation of
the value to the position of India which underlay the situation of
Afghanistan. Menaced by growing physical infirmity and with strange
premonition of his approaching end, at a special Durbar in the
autumn of 1900 he informed the assembled nobles and high officials
of his inability to cope with the increasing volume of affairs.
Thereupon, amid a scene of singular pathos, the old Amir indicated
that his son, Habib Ullah, would be given a still larger measure of
authority.
A few months later, in May of 1901, a more emphatic warning of
the grave state of the Amir’s health was received. Intelligence came
through from Kabul to Peshawar that Abdur Rahman was no longer
able to walk, and that he was not expected to live through the
approaching winter. Incapacitated by a combination of Bright’s
disease and gout as he was, the mental faculties of the ruler of
Afghanistan were nevertheless unimpaired, and throughout the
closing year of his life he applied them constantly to the
improvement of his country. Interested in the South African War and
grasping the salient lessons of our unreadiness, the Amir laid out
much money in 1900-1901 upon a scheme of mobilisation; while in
May 1901 he secured permission to import from Germany some
thirty howitzers and field guns. At the same time, and without
informing the Government of India, he ordered a large number of
castings for big guns, an order which was subsequently repudiated
by Habib Ullah. In August 1901 he personally directed the
preparations for the suppression of the threatened disaffection in
Khost, besides attending to the rising of the Tagis of Hariob on the
Peiwar in September. These events were the last affairs of a
prominent description to which Abdur Rahman was able to apply
himself. Even while engaged in the business attending the Tagis
operations his Highness began to show signs of decline and, on
September 20, he was seized with a stroke of paralysis which
disabled his right side.
His native physicians had prepared a compound of rare medicines
costing several thousand rupees; but, as the paralytic seizure was
kept strictly secret in the palace, this concoction was not in
readiness and, when offered to the Amir, he could not take it. On
September 28 his Highness, feeling his end approaching, summoned
his sons, the nobles, the principal civil and military officers and the
chief raises of Kabul, Hindu and Mahommedan. One son only,
Mahommed Afzul Khan, a boy of thirteen, was absent. He was with
his mother at Balkh, that lady belonging to the Saids of Balkh. When
all had assembled the Amir by look acknowledged their homage and
then addressed them in a feeble, but distinct voice, saying:
You know when a king becomes old and infirm and near
his end he always desires to nominate a successor. I wish to
have my successor settled now. Consider among yourselves
whom you believe fit to succeed me.
The listeners were affected to tears by this speech. They declared
that the Shahzada Habib Ullah, who had managed the state affairs
so well for eight years, was the ruler whom they desired. On this the
dying Amir indicated that a sword with a belt set with precious
stones should be handed to Habib Ullah, together with a big volume
containing his will and instructions for the future management of the
state. He then ordered Nasr Ullah Khan to gird his brother with the
sword, and dismissed the audience. Abdur Rahman had always the
presentiment that he would die in the same year as our lamented
sovereign Queen Victoria; and, after this assemblage, his condition
became rapidly worse and he died on October 1. The news was kept
secret until the morning of the 3rd, when, his precautions against
disturbance having been completed, Habib Ullah himself made it
public. Later in the day, on October 3, at a special Durbar Habib
Ullah was formally accepted as Amir, whereupon he issued the
following proclamation to the high officers of state:
His Excellency is informed of the demise of my august
father, the light of religion and the kingdom (may his abode
be in Paradise) who (as the verse runs “Death is the end of all
and not a moment’s delay is possible when it draws nigh”)
welcomed the invitation of God, and took his way to Paradise.
His Excellency is now given a detailed account of what
happened. His late Highness had been frequently unwell; but
notwithstanding his chequered health he was not for a
moment found lacking in the conduct of his kingly duties,
until the light of his life was put down. He breathed his last
on Thursday night dated 19th Jamadi-ul-Sani at Kala Bagh,
his summer residence. He gave his soul to the Creator of the
Universe (truly all things tend towards God). On Friday 19th
rumours got abroad and the news was communicated to the
capital for the information of officials. The people of the
country, subjects as well as military, came together to convey
condolence, one and all. Beyond the possibility of doubt they
considered the monarch was their kind father and their
gracious ruler. The people of the territories of Herat,
Kandahar and Turkestan, etc., who were present in the
metropolis, attended the exalted Court and My Presence (who
am the slave of God) and praised the Almighty. Great was the
concourse and so large the number of those who witnessed
the Fateha[44] that it is known to God and to God alone. All of
them followed the service with sincerity of heart and purity of
mind. Then they took the oath of allegiance with praises to
Omnipotent God. They said as follows: “We desire to make
your Highness our king so that we may not live in an
uncivilised state. We wish you to acknowledge our oath of
allegiance; and we beg your Highness to take the
management of all the affairs of state and that of our nation;
and we ask you to discharge your duties night and day like
his Highness the deceased ruler of ours and to give us rest
and repose.”
After the close of the speech and prayer I too with the
Throne’s usual kindness and munificence accepted their oath
of allegiance and request; and I have given them such entire
satisfaction as lies in my power. On that very day all of our
brothers took their oath of allegiance and after them all the
members of the House Royal and persons of the noble
families of Mahommed Zai and other tribes, saids, priests,
gentry and all officials of state, civil and military, took the
oath; and I too for my reign and time acknowledged the oath.
Then all offered up their prayers for the late monarch (may
his abode be in Paradise) and gave thanks to God for my
reign. After the dismissal and breaking up of all the aforesaid
proceedings the officials of state, civil as well as military, and
all those who could afford and spare time from matters
temporal took their road to Kala Bagh and, together with
those who were already present, joined the funeral
procession of the late ruler (Light of the Country and
Religion). The blessed corpse of that august and potent king,
according to his will, was carried to the royal cemetery with
great pomp and honour; and he was interred in the ground
and placed in the place which is the real and ultimate abode
for man. That august and potent monarch, that king of
pleasing and praiseworthy manners, expired and sank in the
depth of the kindness of God (may his abode be in Heaven).
His Excellency is now informed of all that has happened.
He is given an account for his full information; and a separate
report is despatched to His Excellency the Viceroy of India on
account of the alliance that exists between us.
A second Durbar was held on the 6th, when the commander-in-
chief, the principal military officers, the tribal chiefs then in Kabul,
the leading nobles and the chief mullahs renewed publicly their
agreement, made with the late Amir in the autumn of 1900,
regarding the succession of Habib Ullah. With the Koran before them
they affixed their seals to an oath which ran as follows:
We, all military officers, together with the army, all Afghan
tribal chiefs, sirdars, mullahs and other followers of Islam in
Afghanistan, do swear by the Koran to accept Amir Habib
Ullah as our King of Islam.
Habib Ullah replied:
You have appointed me as your king and I accept the
office. Please God I will be always a follower of the religion of
Mahomet the Prophet of God (may peace be on him) and I
will be guardian of the Mussalmans of Afghanistan who will
obey me as King of Islam.
The thousands of people assembled on the occasion of this
Durbar solemnly removed their turbans, loudly acclaiming Habib
Ullah as their new ruler. The leading Hindus of Kabul, headed by
Dewan Harinjan, afterwards presented their agreement to the Amir,
who graciously accepted it with the assurance that they should
continue to live in peace and quietude, and promising a reduction of
the taxes hitherto levied on their community. In Kabul on October 8,
yet another Durbar was held, whereat Sirdar Nasr Ullah Khan
brought the Koran, the sword and the flag belonging to the late
Amir. Habib Ullah rose on the approach of his brother. Placing the
Koran upon his head and fastening the sword round his waist, he
raised the flag and took the oath to rule Afghanistan as a true
Mahommedan. He said his brothers, the whole army and the people
had appointed him king. He accepted the office and publicly asked
God to pardon all his sins. The Amir then declared that he confirmed
his brother, Nasr Ullah Khan, in the offices which he had held under
the late Amir, at the same time appointing Omar Khan to take
charge of the Revenue Department and Amin Ullah Khan to preside
over the Judicial Department.
Simultaneously with these announcements several acts of
clemency and generosity were proclaimed. In each of the important
centres prisoners, confined for minor offences, were released; while
various sums of money for charitable distribution, in all aggregating
one lakh of rupees, were remitted to the local authorities. Kabul
naturally came in for especial marks of grace. The trading
community was advised of the remission of the more oppressive
taxes, and certain guilds were notified that Treasury grants would be
made to them. Five hundred prisoners in the capital province were
also set at liberty. In a general way, since Abdur Rahman’s scheme
of taking one able-bodied man in eight for military service had given
rise to discontent, Habib Ullah advanced the pay of all ranks in the
Regular and Irregular establishments. The pay of the cavalry was
increased from twenty rupees to twenty-five rupees per month, the
infantry from eight rupees to ten rupees per month, and the levies
from six rupees to eight rupees per month. The officers enjoyed a
proportionate increment. These evidences of consideration secured
the tranquillity of the people at a change of ruler, although the
perspicacity of the late Amir, in arranging matrimonial alliances for
Habib Ullah with the leading families in the army and priesthood,
had already secured the allegiance to his successor of these two
important factors in the state. The accession, therefore, was
undisturbed; and, while couriers bore the news far and wide to
officials, the issue of a fresh coinage, bearing the impression in
Turkish characters “Amir Habib Ullah Khan, Amir of Kabul, the Seeker
of God’s Help,” carried conviction in the market-place. At the same
time in India, October 14, was observed as an official Day of
Mourning, and Habib Ullah was informed that a Mahommedan
deputation, charged with the condolences of the Government of
India and the personal greetings of the Viceroy, would immediately
set out for Kabul. A few days later Habib Ullah’s preoccupation with
the affairs of state passed from the civil to the spiritual side, when
the new ruler of Afghanistan gave an ominous sign of that bigotry
which has since distinguished him. For the first time in the country’s
history the head of the state publicly performed the priestly
functions in celebrating the Id at the Idgah Mosque. The chief priest
of Kabul immediately proclaimed Habib Ullah to be the successor of
Mahommed, whereupon the Amir of Afghanistan delivered an
address inspired throughout by a spirit of intolerant ecclesiasticism.
Among other things, he laid down that a fine not exceeding ten
Kabuli rupees would be inflicted on all who did not offer prayers
night and morning in the mosques. A register of the daily attendance
of all individuals in the various quarters was to be kept; and a “box
of justice” set up in each into which secret reports, upon any who
neglected their religious duties, could be dropped.
grounds of palace occupied by the dane mission
The visitation of Providence upon Abdur Rahman could hardly

have come at a more inopportune moment. Although the peace of
the Indian frontier in 1901 was disturbed only by the Mahsud-Waziri
operations, resulting from the legacy of hate which our activities on
the Waziristan border during Lord Elgin’s administration had
bequeathed to Lord Curzon, the action of Russia in the previous year
in respect of Russo-Afghan relations had made it quite clear that the
harmony of Mid-Asia was involved in the disastrous failure of British
arms in the Transvaal. Nothing had ever been more probable than
that an irruption of disorder throughout Afghanistan would attend
the death of the late Amir. It was upon this contingency that, in the
past, much thought and no little speculation had turned. Even if
historical parallels were ignored, there were so many claimants to
the accession in the field that the wiseacres of the chancelleries
throughout the world had freely prophesied the decease of Abdur
Rahman to be the signal for a general mêlée in Asia, in which Russia
and Great Britain would support the rival factions. The Russians, no
less than ourselves, shared these premonitions; and, when the
precarious condition of Abdur Rahman’s health became actually
alarming in the spring of 1901, there was a wealth of suggestion in
the silent preparation which took place along the Russo-Afghan and
Indo-Afghan borders. Under the watchful ægis of Lord Curzon no
sign of the apprehensions to which the death of Abdur Rahman gave
rise in the mind of the Government of India was permitted to
become public. While the first indication of a recrudescence of
Russian activity along the Afghan border had been given nearly two
years before, a fresh fillip to the situation was imparted by the
sudden departure for the Afghan frontier of the Russian Minister of
War, General Kuropatkin, who quitted St. Petersburg immediately
after the receipt of the tidings of the Amir’s demise. Almost the
earliest act of the former Governor-General of Asiatic Russia upon
his arrival in Trans-Caspia was to release from imprisonment at Merv,
on October 19, 1901, six Afghans who had been charged with
espionage. Summoning them to his presence, he gave them the
following message of good-will to the new Amir:
A misfortune has befallen Afghanistan. The Amir Abdur
Rahman is dead and Habib Ullah, one of his sons, has
ascended the throne. We Russians have always considered
ourselves friends of Afghanistan and we wish to remain so in
the present change of Government. Therefore, in setting you
at liberty, I command you to report yourselves to your nearest
chieftain and to repeat to him the words you have heard from
the Russian Minister of War.
While General Kuropatkin moved from Merv to Tashkent, where
he was engaged in an inspection of the garrison, besides taking part
in the ceremonies attendant upon the turning of the first sod of the
Tashkent division of the Orenburg-Tashkent Railway, the Government
of India replied to his act of overt insolence by entrusting to the
chief of the Mahommedan Mission, which left Peshawar for Kabul on
November 20, 1901, an invitation for his Highness the Amir of
Afghanistan to visit India. In spite of certain pre-occupation, General
Kuropatkin, during his visit to Central Asia, found time to devote
considerable attention to Abdur Rahman’s successor. Before
December 11, when the deputation of Indian Mahommedans quitted
Kabul for their own homes, Habib Ullah received from the Governor
of Mazar-i-Sharif an intimation that the Governor of Tashkent would
send towards the close of the winter 1901-02 a deputation of
Mahommedan officials from Russian Turkestan to participate in the
Nauroz festival on March 21 at Kabul. Accompanying the escort were
to be several batteries of field guns with supplies of ammunition,
intended as a gift to his Highness in commemoration of his
accession.
The significance of these circumstances was not lost upon Habib
Ullah, whose perception would indeed have been dim if the
antagonism of Anglo-Russian interests at the Court of Kabul had
escaped his notice. An inkling of his attitude towards foreign affairs
had been given when, in the very early days of his reign, he had
ordered his people to observe Abdur Rahman’s prohibition against
any use of the Quetta-Chaman extension between the first station
on the southern side of the Khwaja Amran tunnel and the terminus
at its northern extremity. In view of this, more than ordinary interest
attached to the pronouncement which, it was anticipated, Habib
Ullah would make to the members of the Indian Mission of
Condolence.
At their first reception Habib Ullah’s attitude hardly commended
itself to the pleasure of his guests. Inquiring what were the
intentions of the Government of India in respect of his father’s
subsidy, the invitation from the Viceroy was handed to him. After
expressing satisfaction at the compliment which had been paid to
him and alluding to the difficulty of accepting the invitation for some
time, he hinted that the obligations contracted by Abdur Rahman
were not binding upon himself. Finally, he threw the delegates a
crumb of comfort in the assurance that he would follow in the
footsteps of his lamented father. At a later date, in full Durbar and
attended by the Mission, he expounded his policy, reiterating his
intention to respect Abdur Rahman’s prejudices in regard to the
introduction of telegraphs, the construction of railways, the
reorganisation of the army, the appointment of a European British
agent to Kabul and the adoption of Western customs—even the use
of foreign medicines was banned. Schools for instruction in the
Persian and Arabic languages, and the Mahommedan faith, would be
opened, but the country would be jealously guarded against every
form of external aggression.
For reasons which did not transpire, but which would not be
difficult to determine, the visit of a Mahommedan deputation from
Russian Turkestan did not take place. Meanwhile, astonishment at
the promulgation of the recent ordinances had barely subsided when
Habib Ullah began to press attentions upon his former tutor and
pestilential frontier fanatic, Najib-ud-Din, the Mullah of Hadda, this
action at once introducing into the arena of Anglo-Afghan relations a
disquieting figure. Ostensibly with a view to honouring his former
teacher, Habib Ullah detached certain disciples from the mullah’s
entourage for a Mahommedan crusade in Kafiristan, increased his
sacerdotal powers by placing a large section of the frontier within his
religious jurisdiction, ordered a new mosque to be built for him and
invited him to participate in the Installation ceremonies at the
Nauroz, presenting him with the gift of an elephant and howdah for
the journey. Invitations to the Nauroz celebrations were issued to
other leading spirits in the frontier disturbances of 1897, including
the notorious Mullah Powindah from Waziristan, the troublesome
fire-eater Mullah Said Akbar from Tirah and the Safi Mullah.
Following so closely upon the semi-contemptuous rejection of the
representations which the Government of India had made through
the deputation of Indian Mahommedans, Habib Ullah’s predilection
for the society of men who had already incurred the displeasure of
the Government of India made manifest the fact that the impulse of
bigotry was stronger in him than the dictates of policy. The late Amir
was accustomed to use the mullahs to consolidate his own authority
and to interpose a fretful hedge of fanaticism between his kingdom
and the outside world. But he knew also how to curb their insolence
when occasion required, and he made them all—kazis, imams and
muftis—servants of the state. This adroitness in professing a militant
orthodoxy and in securing at the same time the supremacy of the
state over the church in Afghanistan, has been described as one of
the most remarkable proofs of Abdur Rahman’s political genius.
Habib Ullah’s action in immersing himself in religious affairs so
soon as he had ascended the throne, belonged to a different
category. It gave rise to misgivings with regard to his capacity to
hold the helm of state with the same firmness and clearness of
vision as had enabled his father to descry the various shoals ahead.
In any case since it boded no good to the peace of the frontier, it
drew down upon the Amir a polite but unmistakable remonstrance.
The effect of this was not lost upon the throne; and when the aged
mullah pleaded, in excuse of his inability to attend the Nauroz, the
difficulties of a journey across the hills in March, the point was
conceded by his late pupil. Moreover, the Amir’s attitude at the
Nauroz was circumspect and remarkable only for a very colourless
exposition of the divine character of the shariat, the strict fulfilment
of which he enjoined upon all good Mahommedans. Five days after
the celebration of the Nauroz, however, the summons to the Hadda
Mullah was repeated, but the Amir’s reception of this distinguished
prelate was sufficiently cool to disarm criticism.
Administrative and domestic difficulties beset Habib Ullah at an
early date in his career as Amir of Afghanistan. Before the summer
of 1902 had waned the discovery of a palace intrigue with extensive
ramifications induced him, at a Durbar on June 8, to order the re-
establishment of the Secret Intelligence Branch in Kabul, the reports
from which were to be presented to him each morning. At the same
time, in an interesting attempt to temper despotism with justice, he
ordained that an influential rais from each tribe should be associated
with each local governor to assist in the disposal of tribal cases.
More important matters were to come before a Council of State in
Tribal Affairs, which he now proceeded to create. It was composed
of leading members of various tribes; and weekly meetings were to
take place in Kabul under his own presidency. Almost the first matter
to engage the consideration of this body was, in August 1903, a joint
protest from the Ghilzais, Duranis and Suliman Khels against the
application of Abdur Rahman’s scheme of calling up one man in
eight for military service. In preference to this measure the objectors
propounded the suggestion that musketry instructors should be
appointed to all large villages. Acceptance of any modification of
Abdur Rahman’s plan was deferred until the return of Nasr Ullah
Khan from a tour of inspection of the military conditions of the state,
which the Amir had projected.
As these events were occurring at Kabul, it became evident in
Europe, that although Russia had not returned to the charge in
respect of her communication to the Foreign Office on February 6,
1900, she had not abandoned the purpose which she had in view. In
the middle of August 1902 the Russian authorities, in defiance of
their treaty limitations, twice secretly addressed the Afghan
Government, concealing this grave breach of their obligations
towards us by an impudent agitation in the press for liberty of direct
communication with Afghanistan. On August 31, the mouthpiece of
the Russian Foreign Office, the Novoe Vremya, contained the
following startling observation:
... The necessity for closer intercourse has so increased
that it is impossible longer to observe the conditions of the
1873 Agreement. The Russian Government have notified
England that the effort of two years ago to enter into direct
relations with Afghanistan continues. We cannot, therefore,
consider ourselves bound by any obligations whatsoever on
the question of having direct relations with Afghanistan on
any subject that might interest us. By virtue of the proximity
of the two countries, the development of intercourse between
the local populations which goes on every year will
undoubtedly call for the adoption of measures for the
establishment of normal relations with Afghanistan as being
the only ones possible with a neighbouring state. Upon the
progress of events generally and the civilising effects over the
local populations of Russian influence will depend alone the
time when such measures will be adopted....
Four days later, on September 4, the St. Petersburg Bourse
Gazette, a paper in close relation with the Finance Ministry, said:
... The question which is ripe for settlement and will not
brook delay is the question of Russian diplomatic
representation at Kabul. Now that the Russian outposts have
been pushed to the Afghan frontier, it is unreasonable that
Kabul should remain inaccessible....
A message from the governor of Russian Turkestan to the
governor of Afghan Turkestan, requesting that direct commercial
intercourse might be established across the Oxus, had already been
delivered when the initiatory efforts of the Novoe Vremya and the St.
Petersburg Bourse Gazette were seconded by the Viedomosti and
the Moscow Bourse Gazette. While the Russian press debated the
character of their obligations to us in respect of Afghanistan, the
emissary of the Russian Government, Sikandur Khan, a Turcoman
from Ali Yurt, proceeded to Kabul. Nearly two months elapsed before
tidings of the arrival of Sikandur Khan at Kabul on September 4,
reached India. Proof of Russia’s proceedings was then incontestable
since, on September 5, at a State Durbar which had been specially
summoned, Habib Ullah read a letter from the Russian Government
to the following effect:
... In the opinion of the Russian Government the time has
now come for closer commercial relationship between
Afghanistan and Russia. The Afghans have nothing to fear
from Russian aggression, since the friendliness existing
between England and Russia would be endangered if further
annexations were made by the Government of the Tsar in the
direction of Badakshan and Wakhan. This fact in itself
becomes a permanent guarantee of peace. In these
circumstances it is an act of folly to continue the attitude of
suspicion and concealed hostility that now exists between the
Afghan and Russian commanders of frontier posts. The
Russian Government, therefore, invites the Amir to throw
open to Russian caravans the trade routes between Khushk
and Herat and Khushk and Kabul. The Russian Government in
return will allow Afghan traders to enter freely and traverse
without restrictions Russian territory. The matter has already
been laid before the British Government, but this letter is
addressed personally to the Amir of Afghanistan because a
favourable answer from the Afghan Government would
greatly strengthen the Russian case....
When the reading of this document was finished the Amir asked
for the opinion of the Durbar, the temper of its members being
illustrated by Ali Yar Khan, who said:
“Let this Turki dog who carries messages for infidels be beaten on
the head with shoes till his hair falls off. That ought to be our answer
to the Russians.”
The Amir, greatly displeased at this remark, observed that, if
there were any shoebeating, it would be for him who suggested the
maltreatment of the messenger. Subsequently fifty rupees were
given to the Russian courier. After some public discussion the Durbar
dispersed, the Amir ordering the State Secretary to acknowledge
receipt of the Russian communication, and to say that, while he was
willing to discuss the matter, the interchange of views must in future
be made through the Government of India in accordance with the
precedent established by his father, the Amir Abdur Rahman. The
Russian proceedings not unnaturally attracted the attention of
Parliament; and on October 21, Lord George Hamilton acquainted
the British public for the first time with the receipt of the proposal
which had been transmitted by the Russian Embassy to the Foreign
Office nearly three years before. The correctness of the Amir’s reply
was in striking contrast with the impropriety of the Russian
communication, the despatch of which had transgressed the limits of
diplomatic etiquette. As far back as 1868-69, Prince Gortchakoff had
assured Lord Clarendon that the Russian Government regarded
Afghanistan as completely outside her sphere of influence. That
engagement had been re-affirmed in 1875; extended, according to
the statement made by M. de Giers to Mr. Kennedy on October 2,
1883, to include abstention from the transmission of letters of
ceremony, and constantly renewed in personal conversation upon a
variety of occasions since the original was enacted.
This action of Russia on the waters of the Oxus had drawn
attention to the vague, uncertain state of the relations subsisting
between Kabul and Calcutta. As matters stood all former agreements
between India and Afghanistan had automatically terminated with
the death of Abdur Rahman; and it remained for the succeeding
Amir to adjust the situation by calling upon the Government of India
to renew the arrangements by which Afghanistan had become a
subsidised and protected state of India. Although twelve months had
passed since the decease of the late Amir and many opportunities
had been accorded him, Habib Ullah had given no indication of any
desire to enter into any undertaking with the Government of India.
Nevertheless he credited himself quite wrongfully each month with
the accretions of his subsidy and the balance of his father’s monies
which were lying, by the particular arrangement of the late Amir, at
the Treasury in India. There is, to the onlooker, the greater piquancy
in this regular remittance to India of debit cheques against the
Treasury, since Habib Ullah, from the outset of his reign, had
exhibited a most imperfect loyalty. The patronage which he extended
to the Hadda Mullah had already brought one rebuke upon him; its
continuation, in the face of such remonstrance, disclosed no sense of
responsibility to the Government of India. Again his procrastination
in dealing with the Viceroy’s invitation to a conference obviously
qualified those amiable expressions of regard for Lord Curzon which
Habib Ullah was at such pains to profess.
takht-i-rawan
Since his accession, in marked contrast with the policy of his

father, he had received numerous deputations from the Afridi zone,
including one from the most predatory of all the clans south of the
Khyber, the Zakka Khels, whose hostility to the British Government
has always been a prominent feature of the frontier. The good
impression, created in September, when he had invited the Hadda
Mullah to return finally to his own country, placing a takht-i-rawan at
his disposal for the journey, was ruined by this foolish dalliance with
Afridi tribes from within the Durand border. At the moment, taking
time by the forelock, Habib Ullah was anxious to raise an Afridi
bodyguard, composed of men upon whose personal loyalty absolute
reliance could be placed in case of an émeute in the palace.
Knowledge of this fact acted as a spur to the more disorderly border-
elements, who wished to separate the Afridis, as a tribe, from the
control of the Indian Government. Embodying their several schemes
in one, they put forward a plan which was presented to Habib Ullah
by Khawas Khan, an Afridi malik, who, in 1897, had fled before the
avenging arm of the Indian Government to Kabul. This worthy, now
entirely dependent upon the benevolence of the Amir’s Government,
urged his protector to raise an Afridi contingent, to which project
Habib Ullah was foolish enough to assent. Robes of honour were
issued to the tribal chiefs and a rate of pay, double the amount
allowed to the Afghan soldiery, with a month’s advance, was
promised to all recruits. Two thousand Afridis came forward in the
first week, 500 of whom after receiving their rewards at once
deserted. The success of this new departure appeared to be
assured, when the corps was disbanded on account of the hostility
which was displayed by the Afghans themselves to the scheme, the
men being permitted to retain the clothing, modern breech-loading
rifles and ammunition with which they had been supplied. The
moving influence in this salutary change of mind on the part of
Habib Ullah had been that of Nasr Ullah Khan; and it was with the
greater regret that, in a little time, the Amir of Afghanistan was
found to have broken away from the more masterful will of his
brother to toy once again with the questionable ministrations of the
Hadda Mullah. Early in November this holy, but tiresome, prelate
wrote and persuaded Habib Ullah to hold a special Durbar in order to
accept from the hands of the mullahs the title of Siraj-ul-Millat wa
ud-Din—“The Lamp of The Congregation and The Faith.” In view of
this it was generally felt that the happiest augury for the peace of
the Indo-Afghan border, at the end of 1902, was the death of the
Hadda Mullah on December 23, when the Afghan Government
devoted a sum of 30,000 rupees towards the funeral obsequies of
their sainted protégé.
The removal of the obstacles in the way of any cordial
understanding between Russia and Great Britain in respect of
Afghanistan was not assisted when, on January 14, 1903, the
Foreign Office in St. Petersburg issued, in reference to the
declaration made by Lord George Hamilton, the following
communique:
As regards Russia’s relations with Afghanistan, it is
necessary to declare that Russia addressed no request of any
sort to the British Cabinet, but simply notified it of her desire
and purpose to enter into direct relations with Afghanistan in
the future.
No further declarations were made on this subject.
If language is to have any meaning at all in diplomacy, as in
ordinary life, this utterance can only be characterised as one of the
most flagrant perversions of truth that have ever disgraced the
history of even Russian politics. Quite rightly the request of February
6, 1900, had been interpreted as a veiled demand for the right to
establish a Russian representative at Kabul. The proposal admits of
being supported by the plausible contention that such an agency
would be a convenient means of settling disputes and avoiding
collisions on the Russo-Afghan border. It must not be forgotten that
it was over almost an identical question—the reception of the
Stolietoff Mission by Shir Ali—that Great Britain fought the Second
Afghan War; and it can hardly be denied that, if the concession
demanded by the Note of 1900 were granted, the result would be to
set up an influence in Kabul hostile in spirit to our own and from the
first day of its existence there devoted to the sapping of our
position.
Great inconvenience of course attaches to a system by which the
smallest detail in the adjustment of any difficulty along the Russo-
Afghan frontier must be referred for settlement from the Oxus to
Tashkent, from Tashkent to St. Petersburg, from St. Petersburg to
London, from London to the Government of India, and from the
Viceroy’s Council to Kabul where, after much delay, the same
process is repeated over the return journey. Unfortunately, the
maintenance of such a cumbersome procedure is essential to the
harmony of Anglo-Afghan relations since, although Russia professes
to require facilities for frontier intercourse in commercial matters
alone, similar protestations reduced Manchuria to the level of a
Russian protected State until Japan intervened. Great Britain does
not wish to embark upon a campaign in Central Asia and there need
be no war so long as Russia, observing the pledges which she has
given, tempers her desires with discretion. But continuation of the
mischievous interference in Persia and Afghanistan, which has
distinguished her actions hitherto, is a menace to the world’s peace,
as the indulgent nature of the British Government has now been
pushed to the limit of its endurance.
So far as Anglo-Afghan relations were concerned the New Year of
1903 held out little prospect of improvement. Possibly the mass of
business, associated with Habib Ullah’s installation as Siraj-ul-Millat
wa ud-Din, early in April, did prevent the Amir of Afghanistan from
visiting India in the spring of this year. But, aside from the
irregularity of the Amir’s behaviour, the incident of April 6, when
Lieutenant-Colonel A. C. Yate, commanding the 24th Baluchistan
Infantry Regiment and stationed at Chaman, was arrested by Afghan
officials for an innocent trespass beyond the Indo-Afghan border and
removed to the fort at Baldak Spin, may be regarded as throwing
light upon the precise quality of the bonds of amity which were
uniting the two countries. Again, serious exception could be taken at
the manner in which the Amirs of Afghanistan were employing the
permission to import munitions of war which had been granted by
the Government of India. The arrival of the thirty Krupp guns,
acquired by Abdur Rahman on the eve of his death, had revealed
the presence of a large number of castings for heavy ordnance
which had been secretly obtained from Essen by the late Amir. A
small army of carts and camels, lent by the Government of India,
carried the thirty guns from Peshawar to Jelalabad, whence forty
elephants, sent by Habib Ullah for the purpose, bore them to Kabul.
Very properly transport was denied to that part of the purchase
which disclosed Abdur Rahman’s strange dereliction of his treaty
rights. Moreover, it was not difficult for Habib Ullah to recognise the
irregularity of his father’s procedure, the immediate consequence of
which was the repudiation of the order by the son. Unhappily, before
this particular incident could be considered to have closed an
immense consignment of rifle cartridges, numbering several millions
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British Library Cataloguing-in-Publication Data

NON-EQUILIBRIUM THERMODYNAMICS FOR ENGINEERS

Julia - Non-Equilibrium thermodyanics.pmd 1 5/3/2010, 5:18 PM

To meet the entropy challenge, is probably more central than the

It can be used in the Bachelor or Master study programs af-

To facilitate learning, exercises for the topics of the book and

solutions to these, are available on the NTNU homepage.1 Eight

Financial support from the Research Council of Norway is ac-

The authors welcome comments and suggestions that can

Trondheim and Stuttgart, March 2010

Signe Kjelstrup Dick Bedeaux

Eivind Johannessen Joachim Gross

2 Why non-equilibrium thermodynamics? 7

3 The entropy production of one-dimensional trans-

4 Flux equations and transport coefficients 45

4.6 Concluding remarks . . . . . . . . . . . . . . . . . 73

5 Non-isothermal multi-component diffusion 75

6 Systems with shear flow 93

7 Chemical reactions 109

8 The lost work in the aluminum electrolysis 129

8.3 A simplified cell model . . . . . . . . . . . . . . . 135

9 The state of minimum entropy production and

10 The state of minimum entropy production in

10.2.1 The entropy production . . . . . . . . . . 195

List of Symbols 245

About the authors 259

The aim of this book is to present the essence of non-equilibrium

Non-equilibrium thermodynamics describes transport processes

The second law is reformulated in terms of the entropy pro-

given by the product sum of so-called conjugate fluxes, Ji , and

where σ is larger than or equal to zero. Each flux is taken to be

and the reciprocal relations

Lji = Lij (1.3)

apply. They now bear Onsager’s name.

In order to use the theory, one first has to identify a complete

Following Onsager, a consistent theory of non-equilibrium pro-

The most general description of non-equilibrium thermodynam-

with temperature gradients. Katchalsky and Curran developed

Non-equilibrium thermodynamics is constantly being applied in

Chemical and mechanical engineering needs theories of trans-

Simple vectorial transport laws have long worked well in engi-

Non-equilibrium thermodynamics is necessary for a precise de-

The process industry may, in a not too distant future, have to

gives instruments that are needed to understand the nature of

We give in Chapter 2 the characteristics of non-equilibrium ther-

This chapter explains in more detail what non-equilibrium ther-

• gives an accurate description of coupled transport pro-

• gives the same systematic basis to all transport processes.