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Book Review Electrochemistry. Principles Methods and Applications. By C. M. A. Brett and A. M. O

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Pleasure in Principles
Principles of Electrochemistry. By J.
Korytu, J. Dvorak and L. Kuvan. Wiley, Chichester, 1993. 486 pp., paperback f 24.95.-ISBN 0-471-93838-6
Electrochemistry. Principles, Methods, and Applications. By C. M . A .
Brett a n d A . M . 0. Brett. O x f o r d
University Press, O x f o r d , 1993.
427 pp., paperback f 25.00.-1SBN 0-19-855388-9
Electrochemistry has been transformed
into an interdisciplinary science during
the last few decades. It encompasses such
widely different fields as the characterization of complex electrode processes, applications in synthesis, energy technology,
and sensors. and the extensive areas of
materials research and the biosciences.
Publishers are therefore aiming to reach a
wide readership by offering up-to-date
textbooks at affordable prices. Two recent
examples are the books reviewed here,
which stress different aspects of the subject. Principles OJ‘ Electrochemistry, written by three well-known authors of the
Czech school, is mainly a survey of the
thermodynamics of electrolyte solutions
and electrode equilibria and of electrode
kinetics. In contrast the second book,
Electrochcmistr~c,belongs to the tradition
of the English-speaking school of textbooks, and emphasizes electrochemical
methodology and applications in sensor
This difference in emphasis of the two
textbooks is easily seen from a summary
of their contents. The book by Koryta
et al. begins with an introduction to the
theory of electrolytes, dealing with ionsolvent interactions, acid-base equilibria, polyelectrolytes and ampholytes,
and the classical Debye-Hiickel theory of
This section contains hook reviews and a list of
new hooks received by Iheeditor. Book reviews are
written by invitation from the editor. Suggestions
for books to be reviewed and’for book reviewers
are welcome. Publishers should send brochures or
(better) hooks to Dr. Ralf Baumann, Redaktion
Angewandte Chemie. Postfdch 10 11 61, D-69451
Weinheim. Federal Republic of Germany. The editor reserves the right of selecting which books will
be reviewcd. Uninvited books not chosen for
review will not he returned.
interactions between ions. The second
chapter discusses transport processes.
with the main emphasis on the conductivity phenomena associated with ion migration. Chapter 3 contains an introduction
to the thermodynamics of electrode equilibria. As well as explaining basic concepts
such as electromotive force and the voltaic
(electrochemical) and electric potentials.
this chapter describes practical applications, including the determination of p H
values and measurements of activity coefficients and dissociation constants. Chapter 4 briefly discusses the properties of the
electrical double layer, including the classical Gouy- Chapman- Stern theory
and the more recently developed “jelly”
The last two chapters are mainly devoted to modern developments in electrochemistry. As well as an introduction to
electrode kinetics these chapters include
brief descriptions of some important electrochemical methods. The recently developed ultramicroelectrode is mentioned, as
also are in-situ methods that allow simultaneous measurements of spectroscopic
data and electrical quantities. Other aspects touched on include homogeneous
processes, electrocatalysis, deposition and
separation of metals, and the broad field
of bioelectrochemistry. Due attention is
also given to the electrochemistry of conducting polymers.
Despite the inclusion of recent results
such as these, a detailed study of the book
leaves one with the impression that the
view of electrochemistry presented here is
that of the older generation of electrochemists. with a strong emphasis on thermodynamic principles. The reader wishing to approach the subject by this
conventional route will find that the new
third edition of “Koryta” is a reliable
guide and tutor.
The Bretts’ textbook begins with a description of the thermodynamics of electrochemical cells. This is followed in
Chapter 2 by a discussion of the electrode/
electrolyte boundary, introducing the
theory of the electrical double layer. The
kinetics of heterogeneous and homogeneous charge transfer and transport processes are then treated in concisely written
chapters. The second, more extensive,
part of the book consists of six chapters
devoted to methods for investigating electrochemical processes. Modern measurement techniques, ranging from the widely
used method of cyclic voltammetry to the
various impedance methods, are treated
at considerable length. Further chapters
describe the many in-situ and ex-situ
methods that have considerably extended
the electrochemist’s armory of experimental capabilities in recent years. such as the
quartz microbalance and spectroscopic
In the third and last part of the book the
authors describe modern applications of
electrochemistry in basic research and in
industry. Important topics include sensors based on ion-selective electrodes or
amperometric detectors, modified electrodes, and corrosion phenomena.
Bioelectrochemical phenomena are also
discussed, as well as industrial processes
such as electrosynthesis and metals deposition, and processes involving the conversion and storage of energy. Lastly there is
an appendix containing some important
mathematical relationships used for solving partial differential equations. diagrams of equivalent circuits, and basic
principles of digital simulation methods.
As in Koryta’s book, a comprehensive
bibliography is provided to enable the
reader to study topics in greater depth.
With its emphasis on modern techniques of electrochemistry, the Bretts’
book is certainly well suited to meet the
wide-ranging needs of readers wishing to
apply such methods in chemistry, physics,
bioscience, and materials science. Despite
the mathematical complexity of the theoretical concepts, the presentation is clear
and understandable, enabling both beginners and interdisciplinary scientists to
quickly build up a knowledge of methods
relevant to their needs. They will be greatly helped in this by the practical advice
about electrode materials, cell construction, and instrumentation.
To summarize, both these new paperbacks on electrochemistry offer sound
and reliable introductions to this wellestablished field of physical chemistry.
Readers who are mainly interested in the
thermodynamic fundamentals, including
the properties of electrolyte solutions,
should use the book by Koryta et al. For
all those readers who wish to learn about
the methods of electrochemistry and how
to apply them, the book by Brett and
Brett will prove a reliable guide.
Jiirgen Heinze
Institut fur Physikalische Chemie
dzr Universitat Freiburg (FRG)
Organic Photochemistry. Principles
and Applications. By J Kagan. Academic Press, London, 1993. 234 pp.,
hardcover E 40.00.-ISBN
Anyone hoping to find here an up-todate textbook of organic photochemistry
will be disappointed. In the first place, this
is not a book oriented towards teaching,
as is already evident from the statement in
the preface that “the order of topics ... is
totally arbitrary”. Secondly, many important principles and applications of photochemistry have either been simply left out
o r have received inadequate treatment with
an underemphasis that is difficult to understand. The author’s comment that “old
and well-established reactions and processes are described without references” is not
a justification for neglecting a number of
fundamental points. This apparently very
subjectively-based book consists of two
main parts, dealing with photochemical
and photobiological aspects. respectively.
The first chapter introduces principles
and mechanistic models of photochemical
and photophysical processes; with only 25
pages it is too short. Some important principles, such as the first law of photochemistry, the Kasha rule, and the FranckCondon principle, are mentioned but are
not explained in the usual way. The mechanisms involved in the decay of electronically excited states are described in more
detail, with a surprisingly large amount of
space devoted to the quenching of photooxidation reactions. Chapter 2 gives a
brief outline of experimental methods;
only four literature references are given,
two of which are useless. Thus the reader
may safely skip over the first two chapters, if necessary referring instead to other
standard textbooks. Chapters 3 and 4 give
a rough idea of the photochemistry of the
C C and CO double bonds. A few synthetic applications are described (limited to
intramolecular reactions), and the di-rcmethane rearrangement is mentioned. The
mechanism given for this is probably incorrect; in any case, the work of H. Zimmerman is not discussed or even cited. On
the other hand the author cites Doering’s
synthesis of bullvalene-not very consistent. Ten pages are devoted to the chemistry of the photoexcited carbonyl group;
however, the Paterno-Buchi reaction receives less than a page. What is the reader
supposed to make of a statement such as
“Fortunately, the reaction is usually rather
selective”? Chapter 5 on fragmentations
describes some interesting and topical applications. The author puts a much greater
emphasis on oxidation processes, which
are discussed in Chapter 6, “Photochemistry with Oxygen”. Unfortunately though,
the description of the electronic states of
molecular oxygen is limited to only four
lines; here the interested reader will need to
refer to the up-to-date reviews by Frimer
and Ando. An appropriate amount of
space is devoted to the generation, detection, and reactivity of singlet oxygen. The
author also discusses the properties of other reactive species that can be generated
photochemically, such as superoxide anion, atomic oxygen, S,. and SO. Reference is also made to the possible biological
activity of singlet oxygen, anticipating a
topic treated in the second part of the
book. In Chapter 7, on photoelectron
transfer (PET) processes, the author manages to treat this subject without mentioning any of the names Marcus, Rehm, or
Weller. Some up-to-date applications of
PET processes in organic synthesis are described, giving some indication of the potential of this important class of reactions.
For readers who already have a good
knowledge of the repertoire of organic
photochemistry. Chapter 8 on *‘Synthetic
Applications” offers a wealth of information about interesting applications, from
which they will pick up lots of useful ideas.
However, it was not necessary to mention
the synthesis of a triquinane by Cossy,
Belotti, and Pete twice, first under 6.E-unsaturated carbonyl compounds (8.14)
then again under photochemical reductions (8.20).
In contrast to the above highly critical
comments on the first part of the book. the
second part. beginning with Chapter 9, can
be emphatically recommended for the interested photochemist. Here the author’s
own research interests become dominant,
and this improves the quality and the
thoroughness of the discussions. The ways
in which photochemistry interacts with
biochemistry. biology, and medicine are
well illustrated in Chapters 9-1 1 respectively, which describe important and highly topical developments in these fields. After an introduction to the photochemistry
of amino acids and nucleic acids, the ways
in which light radiation interacts with
D N A are described (photochemically induced chain breaking, production of pho-
VCH Vwlugsgesell.~chaflmhH, 0-69451 Wrlnhe.rm, 1994
toadducts, photoaffinity labeling, etc.) .
The important role of photooxidation processes in biochemical reactions is also mentioned and clearly explained. Under the
heading “Photochemistry and Biology”
the phototoxic effects of compounds which
act as sensitizing agents are described.
Those processes that can be described as
“photochemistry without light” are also
included in the discussion. There is also a
very competent and informative discussion
on light-induced changes to the human
skin and their harmful consequences.
Chapter 11 describes the medical applications of photochemical reactions that are
continuing to grow in importance (PUVA
therapy, photodynamic therapy, photosensitized inactivation of viruses). This and
the preceding two chapters undoubtedly
form the main strength of the book. It
ends, in Chapter 12, with a brief outline of
some applications of photochemical processes (more or less arbitrarily chosen).
This rather personal foray into photochemistry by Kagan has certainly not
turned out to be a student textbook or a
work of reference; instead it is a wideranging and not very orderly collection of
various aspects of organic photochemistry. Many readers interested in the subject will find it a source of useful ideas.
Axel G. Griesheck
Institut fur Organische Chemie
der Universitat Wurzburg (FRG)
Life During a Golden Age of Peptide
Chemistry: The Concept and Development of Solid-Phase Peptide Synthesis. (Series : Profiles, Pathways,
and D r e a m s . Series editor: J. I . Seeman.) By B. Mevrifield. American
Chemical Society, Washington, DC,
1993. XXI, 297 pp., hardcover
$24.95.-ISBN 0-8412-1842-9
Bruce Merrifield’s 1984 Nobel chemistry prize “for his development of
methodology for chemical synthesis on a
solid matrix” is unusual in that it was
awarded for work conceived and singlehandedly achieved within 44 months. On
May 26, 1959, Merrifield recorded the basic concept in his laboratory notebook
(reproduced on p. 56): “There is a need
for a rapid, quantitative, automatic
method for synthesis of long chain peptides. A possible approach may be the use
of chromatographic columns where the
peptide is attached to the polymeric packing and added to by an activated amino
acid, followed by removal of the protecting group and with repetition of the process until the desired peptide is built up.
0570-0833/94~1919-1990$ 10.00+.25;0
Angrn. Chem. I n t . Ed. EngI. 1994, 33. N o . I Y
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