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Plenum:
New York, 1998. xxxvii + 769 pp. 15.7 x 23.5 cm.
Hardbound: ISBN 0-306-45554-4, $95.00. Paperback: ISBN
0-306-45555-2, $49.50.
The first edition of Modern
Electrochemistry, a two-volume set published in 1970, is familiar as a classic work to
those who teach and practice electrochemistry. The second
edition of Volume 1 here reviewed is a worthy successor,
containing nearly all the original material, updated with the results
of two and one-half decades of additional research, as well as
a large amount of new material.
For those unfamiliar with the original work, this is
not a treatment of applied analytical methods such as
classical polarography and cyclic voltammetry. Rather, it seeks to
gather together the most current thought regarding the
theoretical underpinnings of all electrochemical phenomena. As such
it is more appropriately regarded as a textbook in physical
rather than analytical electrochemistry. Investigators seeking
descriptions of the latest tricks for lowering the detection limits
of their favorite techniques should look elsewhere. The
second edition of Volume 1, like the original, is devoted to a study
of ionics, the physical electrochemistry of
solutions- primarily, but not exclusively, those prepared with water. The
original Volume 2 is a treatment of electrodics, the physical
chemistry of heterogeneous phenomena observed at the
solution-electrode interface.
This book begins with a brief survey of
electrochemistry, a virtually complete revision of the original reflecting
modern concerns. Chapter 2 describes the physical nature of
solvents, particularly water, and ion-solvent interactions, and
contains a detailed analysis of the properties of solvents and ions
at the atomic level. This chapter is also a significant rewrite
of the original, including all the material on ion-solvent
interactions, solvation number and dielectric constant, plus
additional treatments of the thermodynamics of hydration,
modern theories based on simulation, and phenomena relating
to biological systems. Ion-ion interactions with
particular attention to activity coefficients are dealt with in the
third chapter, including a critical analysis of the
Debye-Hückel theory and a multitude of improvements thereupon.
The content is similar to that of the original edition, again
with the addition of some modern theories based upon
computational methods, including simulation. Chapter 4 covers
ion transport, focusing almost exclusively on the
processes of diffusion and electrostatic migration. Added in the
second edition is an updated version of material on proton
transport found in Chapter 5 of the original. The remainder of
the original Chapter 5, regarding proton transfer
reactions, appears to have been eliminated from the second edition. Volume
1 concludes with a new Chapter 5, which incorporates
the material from Chapter 6 of the first edition on ionic
liquids, including properties and models of transport phenomena
in pure molten salts and mixtures of salts. Descriptions
of current models based on simulation and a short
treatment of room-temperature liquid electrolytes are added.
The authors claim to have prepared this work as a
textbook for undergraduates. A sizable collection of problems
has been included at the end of each chapter, with a few
"micro research" problems that reward a somewhat greater
amount of effort with a significant result. Although the authors
have done an admirable job of beginning each idea at a very
basic level and building from there, the buildup is quite rapid
as textbooks go and liberally sprinkled with mathematics
and its attendant condensation of information, so the reading
is challenging. Additionally, the authors are not bashful
about invoking the calculus when it is appropriate. On
the basis of the level of treatment and the sheer volume of
material, this volume would be most appropriate as a
textbook for an advanced course (post physical chemistry) in
physical electrochemistry. It seems eminently suitable as a source
of supplemental reading for students in a variety of
upper-level courses, including physical chemistry. As a reference for
the practicing electrochemist it shines because of its thorough
coverage of the discipline, its excellent index, and its
easy-to-use system of paragraph headings, each of which
includes sufficient detail to enable the researcher to confidently
identify the relevant portion of text.
In view of the challenge presented in reading this text,
I (who consider myself an applied analytical chemist)
confess significant surprise in finding that the volume is
relatively difficult to put down. The authors have managed to
include more than their fair share of the "So that's why that
happens!" factor.
Assuming that the successor to Volume 2 of this
work reflects revision similar to that of Volume 1, this set is a
must-have for any technical college or university library,
especially if it was not acquired in its original edition. While its
utility as an undergraduate textbook appears limited in view of
its rigor and the frequency with which advanced courses
devoted to electrochemistry are offered at the undergraduate level,
it will certainly provide an intellectual treat for the
motivated student with the patience to absorb it.
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