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Book Review Solvent Mixtures Properties and Selective Solvation. By Yizhak Marcus

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Angewandte
Chemie
editor of electrochemical journals. This
monograph, with its at first sight vague
but intriguing title, is based on a series of
lectures given in Oxford in 1998, which
the author has collected together and
edited. On reading the subtitle “Principles
and Illustration of Voltammetric and
Related Techniques” our curiosity about
the contents is answered. In this book, on
the basis of his wide-ranging knowledge
and experience of the many variants and
derivatives of voltammetry, which is now
probably the most popular and versatile
of electrochemical measurement techniques, the author presents a survey of the
fundamentals and applications.
As is appropriate in a book where the
style of presentation is based on the
lecture format, Bond begins with an overview of the fundamentals of electrochemistry. However, this introduction turns out
on closer examination to be not so much a
systematic treatment as a colorful mixture, which brings together such widely
different aspects as reaction volumes,
thermodynamics versus kinetics, fuel
cells, and the lead – acid accumulator.
Leaving aside one-s surprise on finding
this random collection of topics, it must be
pointed out that there is already no
shortage of introductions to electrochemistry, which vary in length and amount of
detail to suit every taste, and some are
perhaps even better than this one.
Chapter 2 presents, at least according to its long and all-embracing title,
the principles of all kinds of electrochemical and related measurement procedures. Not surprisingly, however, the
main emphasis is on cyclic voltammetry,
which is introduced by a discussion of
the experimental aspects then followed
by some theoretical considerations, and
lastly touching briefly on different
models and mathematical treatments.
Next there is a remarkably brief and
highly subjective view of spectroelectrochemistry, followed by some more special cases of cyclic voltammetry. This
chapter ends, rather unexpectedly, with
some considerations about scanning
probe microscopic methods and the
quartz microbalance. Both these methods are presented as means of obtaining
information at the molecular level,
which seems a highly over-optimistic
claim in the latter case.
There is practically nothing in the
book about numerical simulation methAngew. Chem. Int. Ed. 2003, 42, 2934 – 2936
ods, which can be performed with various commercial software packages that
differ in their quality and detailed
capabilities. By consulting the index
the patient reader can find references
which lead, after a little searching, to a
figure that actually shows a set of
simulated
voltammograms.
Their
alleged convincing similarity to the
experimental observations is not easy
to see, because the calculated and
experimental curves are presented,
inexplicably, in two separate figures.
However, this treatment certainly does
not adequately reflect the importance
and capabilities of simulation.
The two following chapters are
devoted to detailed discussions of the
electrochemistry of polyoxometallates
and to coupled chemical – electrochemical processes. The book ends with
chapters on the use of cyclic voltammetry to study microparticles adhering to
the electrodes, and on “metalloproteinvoltammetry” (an interesting coining of
a new word).
There remains the question: what is
the purpose of and justification for this
book? It is certainly appropriate that a
systematic introductory lecture, or a
series of lectures devoted to an indepth treatment of a related special
topic, should be carefully extended and
edited for publication in book form,
provided that it is likely to serve a real
need. However, that does not mean that
any lecture, after a gap of several years,
can be made into a book, especially if it
consists of a highly individual and subjective selection of topics. Before writing such a book one should consider
such questions as who the readers are
likely to be, and make a sober assessment of their needs. The book may
perhaps be useful to scientists with a
special interest in certain topics within
it, if they happen to come across it. To
benefit from it they will have to endure
the long, whimsical, and confusing chapter titles, and must not be put off by the
rather useless running page headings.
The book is of little value as a textbook,
reference source, collection of methods,
or anything else. I regret that I cannot
recommend libraries to buy it.
Rodolf Holze
Institut fr Chemie
Universitt Chemnitz (Germany)
www.angewandte.org
Solvent Mixtures
Properties and
Selective Solvation. By Yizhak
Marcus. Marcel
Dekker, New York
2002. 258 pp.,
hardcover
$ 150.00.—ISBN
0-8247-0837-7
Most of the chemistry developed by
modern industries and laboratories is
conducted in solution, and the properties of the medium used, whether a pure
or a mixed solvent, is known to significantly influence the physical and chemical processes involved. The fact that the
physical properties of pure solvents
remain fixed under given experimental
conditions, whereas solvent mixtures
readily lend themselves to alteration of
their properties simply by changing their
composition, has led to a steadily
increasing use of the latter.
Thus, solvent mixtures are currently
used to accomplish both the dissolution
of solutes that are only sparingly soluble
in their pure components (an approach
widely used by the pharmaceutical
industry) and the opposite function,
the insolubilization and subsequent
recrystallization of solutes, a strategy
widely employed in the purification of
synthetic products. Solvent mixtures are
also used in both normal and reversedphase liquid chromatography, with a
view to facilitating the separation of
the different solutes present in a given
solution.
The choice of an appropriate solvent
mixture and the modulation of its properties can be facilitated by an accurate
knowledge of its physical, chemical, and
thermodynamic behavior, and that is the
focus of this book by Marcus. In fact, the
book can be considered both as an
introduction to the patterns governing
the behavior of solvent mixtures and as
a rationalization in the light of the
preferential solvation model. It consists
of six chapters: 1. Introduction; 2. Properties of Binary Solvent Mixtures; 3. The
Structure of Solvent Mixtures; 4. Preferential Solvation in Binary Solvent
5 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
2935
Books
Mixtures; 5. Preferential Solvation of
Solutes; 6. Multicomponent Solvent
Mixtures.
Throughout the book Marcus places
special emphasis on the preferential
solvation model, which distinguishes
the behavior of a solvent mixture from
that of a pure solvent. The concept is
introduced by dividing the solvation
process into a series of hypothetical
elementary steps, of which those potentially involving the preferential phenomenon are given special emphasis.
Also, the best way to describe the
composition of a solvent mixture is
discussed.
Almost half of the book is devoted
to describing the physical, chemical, and
thermodynamic properties of binary
solvent mixtures, the structure of which
is subsequently examined in detail in the
light of experimental results (from diffraction and spectroscopic measurements) and theoretical models (simulation). Of special value are the tabulated
data for a selection of typical binary
2936
solvents, which are listed together with
their literature sources. The author also
provides mathematical expressions for
some mixture properties, so that the
reader can predict such properties for
other mixtures for which no experimental measurements are available. This
makes the book additionally useful.
The second half of the book is
primarily concerned with the analysis
of mixture properties in the light of the
preferential solvation model. Thus,
Chapter 4 examines the behavior of
the mixture components, and Chapter 5
discusses the changes caused by the
presence of a neutral or ionic solute in
the mixture. Both chapters discuss the
use of chemical probes, and underscore
the conceptual difficulty encountered in
applying the preferential solvation
model in conjunction with chemical
probes for solvent mixtures. In this
respect, some readers will be surprised
to find that there are no references to
chemical probe experiments which have
provided evidence contradicting some
5 2003 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.angewandte.org
of the hypotheses on which the preferential solvation model relies; without
them, the view of the topic is somewhat
incomplete.
The book ends with a generalization
to mixtures of more than two solvents,
with special emphasis on the behavior of
ternary mixtures.
With the above-mentioned exception concerning results that do not
support the preferential solvation
model, the literature references provide
good coverage of published work on the
topic up to 2001. For such a complex
subject, Marcus provides an accurate,
yet straightforward description that
makes the book a useful tool which is
therefore highly recommended for those
with an interest in the behavior and use
of solvent mixtures.
Javier Catalán
Departamento de Qu?mica
F?sica Aplicada
Universidad Autónoma de Madrid (Spain)
Angew. Chem. Int. Ed. 2003, 42, 2934 – 2936
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