BOOK REVIEW
ELECTROCHEMISTRY
By PHILIP
Prentice-Hall,
This is a textbook designed to introduce electrochemistry to
the previously uninitiated. As the author states in the Preface,
breadth has been sought at the expense of depth. The book
consists of 6 chapters plus a number of appendices. Chapter 1
(63 pp.) has the title “Electrochemicnl Potenrials” but it does
not contain what one may expect from the heading. After a
short introduction presenting Galvanic cells, electrochemical
thermodynamics is developed up to some practical impact
such as “Latimer” and potential-pH diagrams. The way an
electrode potential can be measured is then illustrated to-
gether with a description of the commonest reference and
ion-selective electrodes. After a brief account of the analytical
applications of potentiometry, the most known batteries and
fuel cells are described.
Chapter 2 (54 pp.) is entitled “The Electri$ed Interface”.
After a discussion of the Poisson-Boltzmann equation lead-
ing to the Gouy-Chapman theory, a few concepts of double
layer interaction are applied to colloid stability. The classic
electrokinetic phenomena are then described, followed by a
few glances at electrocapillary and capacitance curves. The
chapter ends with a rather detailed treatment of the
Debey-Hiickel theory. Although finding the D-H theory in a
chapter on interfaces is rather unusual, it emphasizes the
close conceptual relationship of this theory to the G-C
double layer approach.
Chapter 3 (45 pp.) deals with “Electrolytic Conductnnce”. It
describes the classic phenomenology and related quantities,
including applications to determine dissociation constants,
charge number of ions, and concentrations (chemical anal-
ysis). After a short discussion of the relation between diffus-
ion and mobility, membrane and liquid junction potentials
are dealt with in a classic fashion.
Chapter 4 (79 pp.) discusses “ Yoltammetry of Reversible
Syste;ns”. After a discussion of diffusion-dependent quanti-
ties, and a brief survey of experimental variables (choice of
solvent, electrolyte, reference and “indicator” electrodes, em),
a number of experimental techniques (explicitly defined as
“electroanalytical” methods) is described including poten-
tiometric titration, chronoamperometry, chronopotentiome-
try, LPS and cyclic voltammetry (also at microelectrodes),
polarography and its variations, rotating disk and ring-disk
electrode. Examples of electrode potential+lectronic struc-
ture correlations, determination of stability constants and
electroanalysis are given as applications.
Chapter 5 (100 pp.) is devoted to “Electrode Kinetics”. It
starts with an introductory account of the transfer coefficient,
of Frumkin’s effect and of the classic derivation of
current-overpotential curves; multistep mechanisms are then
illustrated by means of a couple of practical cases. After a
discussion of irreversibility in voltammetry, faradaic impe-
dance is described, followed by some general mechanistic
principles for reactions initiated by oxidation or reduction at
an electrode. Typical mechanisms known as CE, EC, EC’
(cat.) and ECE are discussed in relation to their diagnostic
implications for the various techniques described in the
preceding chapter.
1489
H. RIEGER
1987, f17.95.
The final chapter (6) (55 pp.) deals with “Electrolysis”.
There is a pot-pourri of examples, from the analytical appli-
cations to a few cases of electrosynthesis (eg Kolbe reaction),
to finish with a short description of industrially developed
processes: electroplating, anodization, Al, Cl,, adiponitrile,
lead tetraalkyls, and a few minor inorganic and organic
processes. The chapter ends with 11 pages devoted to cor-
rosion and its prevention.
In the Preface, the author maintains that electrochemistry
is really a branch of physical chemistry and that electro-
chemists have tended to retreat into analytical chemistry (out
of the great tradition established by the work of Arrhenius,
Ostwald and Van’t Hoff) in the 1950s as physical chemistry
was captured by chemical physicists. However, during the
last 30 years electrochemistry has not lived only on analytical
chemistry, but has grown also by developing the (up to then
underdeveloped) physical and quantum mechanical aspects.
This book does not reflect such conceptual advances, thus
offering a concept of electrochemistry which recalls an atti-
tude more generally diffuse a few years ago, although the level
of the treatment is modern and updated, in the best tradition
of electoanalytical chemistry.
The above comment is not intended to be a criticism
(electroanalytical chemistry is a modem reality); it takes note
of a fact. Admittedly, the impact of electrochemistry on the
everyday life means electrolysis, conductance, batteries and
electroanalysis, but a textbook should not only inform but
also form. Thus, the risk is that electrochemistry may appear
as a mere methodology without a specific content. The
electrode is dealt with as a reservoir of electrons without any
surface structure and even without any specific chemical
identity. The “electrified interface” (although the term is
modern) is pictured as it was envisaged at the time Grahame
started to think about it. The various “potentials” (chemical,
inner, outer, surface) are not mentioned. Adsorption is not
dealt with in any detail. Despite the title of Chapter 1,
electrochemical potentials are encountered for the first time
on p. 158 (although the reader may not be sure of that
because the symbol used is the same as that of the chemical
potential and the quantity is not termed as it should be), and
later on only on p. 168. In short, surface electrochemistry in
this volume is still to come.
Despite the above remarks prompted by my “physical”
conception of modern electrochemistry, I have enjoyed rea-
ding this book and am sure that the way it is written has
many valuable merits from the tutorial point of view. The
part on experimental techniques is interestingly developed
for a book directed to uninitiated. Although emphasis is
essentially placed on organic and metallorganic mechanisms,
this part fills the gap, as a rule found in textbooks, between
concepts and experiments. Another pleasant feature is the
inclusion in the chapters of various examples (calculations or
practical cases) related to the topic being discussed, usually
taken from the literature. This offers another way offilling the
gap between “what is written and how it is carried out”.
There are about 65 “examples” distributed over the six
 Book Review
chapters. Moreover, at the end of each chapter there are
several unsolved problems, not only asking for numerical
calculations, but also for the derivation of equations.
The book is rich in references. Besides specific references at
the end of each chapter, Appendix 1 lists co 85 entries
grouped into Introductory Texts, More Advanced Texts,
Monographs, Electroanalytical Methods, Organic Electro-
synthesis, Experimental Methods, Technological Appli-
cations (here the absence of Kuhn’s book is surprising),
Handbooks and Compilations, and Review Series.
The other Appendices (50 pp.) are devoted to: (Appendix 2)
Symbols and Units, a very commendable initiative especially
from the educational point of view (but why such an empha-
sis in the preface on the important difference between mol l- ’
and mol mm3?. IUPAC gives no special preference to mul-
tiples and sub-multiples); (Appendix 3) compilations of data:
standard and formal potentials, including a number of
biochemical reactions, conductivities and solvent properties,
including potential windows for electrochemical stability on
Pt and Hg (typical electroanalytical electrodes); (Appendix 4)
Laplace transform methods; (Appendix 5) digital simulation
methods; (Appendix 6) RDE methods; (Appendix 7) answers
to selected problems. In closure, there are an index of the
names cited in the text, and a subject index.
A few final remarks. Biographical notes are reported for
the most outstanding pioneers of electrochemistry. This is an
interesting initiative which offers a particular view of the
links between a scientist and the discipline in which he is
renowned. Incidentally, we can thus learn that Luggin was
not a scientist who invented the famous capillary, but the
glassblower who realized the idea. What a lucky laboratory!
(However, in order to keep a distance, Luggin is not listed in
the index of names).
The book is well printed, and it is interesting to learn that it
was produced by the author using a word-processing system
and a Laser printer. Practically no misprints have been left in
the text, which is highly commendable in such circumstances.
The only regret is that with a small additional effort all
physical quantities (and not only some of them, whose logic
of selection escapes me, and the physical constants) could
have been printed in italics as recommended by IUPAC.
In conclusion, although from my personal point of view as
a teacher I would not adopt this book as the one and only
basis for an electrochemistry course, it will certainly be a very
precious teaching aid because of the valuable didactic ap-
proach, of the wealth of information on techniques, mechan-
isms and their identification, and of its large supply of
examples, problems and references linking theory with
practice.
SERGIO TRASA-I-H