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An Introduction
to Electrochemical
Engineering
An Introduction
to Electrochemical
Engineering
By
All rights for this book reserved. No part of this book may be reproduced,
stored in a retrieval system, or transmitted, in any form or by any means,
electronic, mechanical, photocopying, recording or otherwise, without
the prior permission of the copyright owner.
Foreword .................................................................................................... x
Part 1: Fundamentals
Chapter Seven........................................................................................... 96
The Perfectly Stirred Electrochemical Tank Reactor
7.1. Analysis of the perfectly stirred electrochemical tank reactor
(PSETR)
7.2. Cascades of PSETR
7.3. The PSETR operating in batch conditions
7.4. The semi – batch PSETR
7.5. PSETR with electrolyte recycling
7.6. PSETR with simultaneous chemical reaction
7.7. Parallel reactions on a PSETR
Since the early days of the 20th century, when chlor-alkali industry and
metal electrowinning were, with lead-acid and Leclanché batteries, almost
the only economically significant electrochemical processes, a dramatic
change has taken place.
We hope that the present book, whose content has evolved from the quite
traditional view our course had in the late 90’s to its present form, will help
to improve undergraduate curricula in chemical engineering and, also, be a
valuable asset for graduate courses in other engineering branches.
PART 1
FUNDAMENTALS
CHAPTER ONE
INTRODUCTION
These reactions might take place in several steps but in all cases, as shown
in Figure 1.1, electron transfer is produced when the involved species
collide with enough energy to overcome the activation barrier.
Introduction 3
Figure 1.1: Schematic representation of the reduction of an Fe+3 ion and the
oxidation of Cu+ ion.
Figures 1.2a and 1.2b schematically show the way in which electron transfer
between reagents takes place in both cases.
4 Chapter One
Faraday´s law indicates that the number of electrodes that flow through the
circuit per unit time is proportional to the reaction rate and, hence, we have:
ௗಲ ூ
ൌ (1.7)
ௗ௧ జ࣠ כ
In the first case, the transformation of reactants into products results in the
production of electrical energy:
In the second case, electrical energy must be applied in order to obtain the
products:
2 H2O + I. ǻȌ = 2 H2 + O2 (1.9)
The energy balance of the process is, thus, the core problem to be solved by
the engineer and, on a first analysis, the following contributions can be
identified for a process occurring at a given current value:
The purpose of this book is to provide the reader with the basic knowledge
required to understand the main factors that impact on the different
contributions shown in Eqn. (1.10) and apply it to some cases of practical
interest.
CHAPTER TWO
2.1. Introduction
In order to sustain an electric current through a piece of matter an electric
potential difference must be applied. The relationship between electric
current and potential is given by Ohm’s law:
In order to give an idea of the importance of this fact, Table 2.1 shows some
typical current values for several industrial processes.
Table 2.1: Typical current values in industrial cells for some important
industrial processes.
With these current values, applying equation 2.1 and assuming that electric
energy is provided at a cost of 0.02 US$/kWh, Table 2.2 shows the cost per
kilogram of product, for three electrolyte resistance values.
The Electrolyte Resistance 9
Table 2.2: Energy cost in US$ per kilogram due to electrolyte resistance.
with units ࣭.cm-1 where ࣭ = Siemens = ȍ-1. Table 2.3 shows resistivity and
conductivity values for several electronic and ionic conductors.
A careful look at data of Table 2.4 indicates that conductivity increases with
concentration and therefore one might assume that in a first, coarse,
approximation the conductivity of a mixture of ionic compounds should be
the sum of the conductivity of each component of the mixture. Thus, if we
The Electrolyte Resistance 11
ߢ ൎ ߢଵ ߢଶ ߢଷ (2.4)
of a mixture. Hence, the idea is to look for a method that allow to express
conductivity of a solution in such a way that its dependence with
concentration be described by means of general equations in which the
individual contribution of each ion can be identified.
has been customary where, for a solution of the ionic compound ܣಲ ܤಳ ,
݊ ൌ ݊ ݖ ൌ െ݊ ݖ , is the number of equivalents in a mole of electrolyte,
݊ and ݊ indicate the stoichiometric number of cations and anions in the
electrolyte molecule, and ݖ and ݖ their charge. Ȧ units are, then, ࣭.cm2.eq-
1
.
From the obtained experimental data Kohlrausch showed that, for a binary
ionic compound, the electrolyte equivalent conductance at infinite dilution
could be described as the sum of two independent contributions, one from
the cation and other from the anion:
The Electrolyte Resistance 13
and thus, recording the ߣ values for the different ions, it is possible to
obtain the equivalent conductance at infinite dilution of any ionic
compound. Table 2.5 shows the equivalent conductance at infinite dilution
for some of the most usual ions in aqueous solution.
ሬԦ
ࡲ
ሬvԦ୨ ൌ (2.10)
గೕ ఔ
where ࡲሬԦ is the applied force, ݎ the effective ionic radius and ߥ the solution
viscosity.
Defining ionic mobility, ݑ , as the velocity attained by the ion under unit
force:
ሬሬሬሬԦห
ห௩ ണ
ݑ = ሬԦห
(2.11)
หࡲ
ሬሬሬԦ ൌ ݖ . ࡱ
ࡲ ሬሬሬԦ ൌ ݖ ൫െࢺࢸ
ሬሬሬሬሬሬԦ൯ (2.12)
where ࡱሬሬሬԦ is the electric field, the electrical mobility of an ion, ݑᇱ , is defined
as the velocity attained by the ion under a unit electric field:
ሬሬሬሬԦห
ห௩ ണ ሬሬሬሬԦห
ห௩ ണ
ݑᇱ ൌ ሬሬԦ ห
ൌ ሬሬሬሬሬሬԦ ห
(2.13)
หࡱ ห ࢺࢸ
Ionic electrical mobility clearly has a direct link with ionic equivalent
conductance as can be seen if a volume element with unit length and cross-
sectional area, containing a solution of the ionic compound ܣ ܤ with
concentration c is considered. In this volume the ionic total charge for each
species is:
ܫൌ ߢ. ߂ߖ ൌ ߢ. 1ܸ (2.15)
࣠.ݑᇱ = ߣ (2.18)
and
࣠.ݑᇱ = ߣ (2.19)
In the general case it can be shown that in a solution with several ionic
components with concentrations and charges ci and zi, the transport number
for each species is:
,
ห௭ೕ ห.ೕ .௨ೕ
߬ = σ , (2.22)
ሺ|௭ |. .௨ ሻ
where A and B are constants, and ࣣ is the solution ionic force defined by:
ଵ
ࣣ ൌ σ ܿ ݖଶ (2.24)
ଶ
where ܿ is the molar concentration of species i, ݖ its charge, and the sum
is carried over all ionic components. Obviously, Kohlrausch´s equation is a
particular case of Eqn. (2.24) for 1 – 1 electrolytes.
Thus, when an acid molecule dissociates in water, the H+ ion forms the
species H3O+ that, by the conductive mechanism originally suggested by
Grotthuss (Grotthuss, 1806), schematically shown in Figure 2.4, explains
the observed value for the ionic conductance of the H+ ion.
In the case of molten salts, the solvent is formed by ions and, so, it is
convenient to compare specific conductivities. Table 2.7 shows some
experimental values obtained for different molten salts compared to a KCl
4 M solution.
References
Debye, Peter and Hückel, Erich. 1923. "Zur Theorie der Elektrolyte. I.
Gefrierpunktserniedrigung und verwandte Erscheinungen”
Physikalische Zeitschrif 185-203
Fuoss, Raymond and Onsager, Lars. 1957. “Conductance of Unassociated
Electrolytes” J. Phys. Chem. 668-682
Fuoss, Raymond and Onsager, Lars. 1958. “The Kinetic Term in
Electrolytic Conductance” J. Phys. Chem. 1339-1340
Grotthuss, Christian. 1806. “Sur la decomposition de l´eau et des corps
qu´elle tient en dissolution à l´aide de l´électricité galvanique” Annales
de Chimie. 54-73
Kohlrausch, Friedrich and Grotrian, Otto. 1874. “Das elektrische
Leitungsvermögen der Cholr-Alkalien und alkalischen Erden, sowie der
Salpetersäure in wässerigen Lösungen”. Göttingen Nachrichten. 405-
418
Onsager, Lars. 1927. “Zur Theorie der Elektrolyte. II” Physikalische
Zeitschrift. 277-298
Bibliography
MacInnes, Duncan. 1939. The Principles of Electrochemistry. New York.
Reinhold Publishing Corporation.
Robinson, R and Stokes, R.1970. Electrolyte Solutions. 2nd edition. London.
Butterworths
CHAPTER THREE
THERMODYNAMICS OF
ELECTRODE REACTIONS
Eqn. (3.1) explicitly shows that all the independent variables that describe
the change of internal energy of a system are extensive parameters and
further analysis leads to Gibbs’ equilibrium conditions:
By the same token, Eqn. (3.3) indicates that a system that is at constant
internal energy and constant extensive parameters is at equilibrium if and
only if any change of the intensive parameters leads to a decrease of entropy
(irreversible change) or to the conservation of its value (reversible change).
Thus, if the system volume, V, is the first extensive work variable, the first
thermodynamic potential, enthalpy, H, is defined as:
24 Chapter Three
డ డு డி
ߤ ൌ ൬ ൰ ൌ ൬ ൰ = ൬ ൰ =
డೖ డೖ డೖ
ௌ,ௐೕ ,ಯೖ ௌ,,ௐೕಯభ ,ಯೖ ்,ௐೕ ,ಯೖ
డ
൬ ൰ (3.10)
డೖ
்,,ௐೕಯభ ,ಯೖ
ሺߜܪሻௌ,,ௐೕಯభ, 0 (3.11)
with
Consequently,
and the system will transfer the necessary number of moles of species i from
one phase to the other, until equilibrium is attained, and Eqn. (3.22) is
satisfied.
In such a system the electric potential difference ߖ(1) - ߖ(ȟ) can be measured,
since both phases are identical. This measurement must be carried out under
thermodynamic equilibrium conditions, which means that electrical current
should be zero. This can be accomplished by means of a potentiometric
circuit as shown in Figure 3.2
28 Chapter Three
Figure 3.2: Potentiometric circuit for measuring the galvanic cell potential difference.
For a galvanic cell that operates adiabatically and at constant volume Eqn.
(3.1) yields:
כሺఈሻ ሺఈሻ
ܷ݀ ൌ σ,ఈ ߤ . ݀݊ (3.25)
When a galvanic cell works adiabatically and at constant pressure Eqn. (3.7)
gives:
Thermodynamics of Electrode Reactions 29
כሺఈሻ ሺఈሻ
݀ ܪൌ σ,ఈ ߤ . ݀݊ (3.26)
Hence, if the electrochemical reaction associated with the galvanic cell is:
where ܽ is the activity of species i and ߤ ሺܶ, ܲሻ is its chemical potential at
a given standard state. The equilibrium constant of reaction (3.29), K,
verifies:
This equation, which gives the electromotive force of the galvanic cell as a
function of reactants and products concentrations, was originally formulated
by Nernst.
Where ǻࣰ is the molar volume change associated with reaction (3.29).
Usually, and except in the case that the system works at very high pressures,
ǻࣰ is significant only if gaseous components are involved. Thus, in a
reaction involving k gaseous components with partial pressure ܲ it comes
that:
Thermodynamics of Electrode Reactions 31
ோ்
߂ࣰ ൌ σ ݒ (3.39)
ೖ
is considered, we have that for unit activity of both ions at 298 K the
electromotive force, in terms of decimal logarithms, is:
ଵ ಹమ మ
ȟȲ ൌ ȟȲ ୭ 0.059ܸ log ቀ మ ቁ (3.43)
ଶ
ഔ
ோ் ೂషభ …
߂Ȳ௧, ൌ ߂Ȳ – ݈݊ሾ ഔ ഔ ሿ (3.46)
జ࣠ כ ಲభ మ …
with:
ܯሃ݈ܥܯሃ݈ܰܽܥሺܽݍሻ
where two interphases exist, one between metal M and the sparingly soluble
salt MCl and the other between the solid salt MCl and a NaCl solution, direct
experimental measurement of the electrode potential, which is the electric
potential difference ߖM – ߖS between M and the solution, would require
that one of the probes of the measuring instrument gets in contact with metal
M and the other with the solution. Now, as mentioned before, two new
interphases would appear, each one with a particular electric potential
difference, which impede direct experimental determination of ߖM – ߖS.
LA MORAL Y EL ARTE