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Book Review Chemical Equilibria in Solution. Dependence of Rate and Equilibrium Constants on Temperature and Pressure. (Physical Chemistry Series). By M. J. Blandamer

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bene complexes is examined in detail and illustrated by a
multitude of well selected examples. Catalytic and noncatalytic processes are explained with equally great care,
and even enantioselective methods are not neglected.
The two concluding chapters deal with “organometallic”
strategies for the synthesis of natural products and
heterocycles, providing striking illustrations, in the context of specific synthetic problems, of the usefulness
of the methods previously introduced. Here, if not
earlier, it also becomes evident that “habitual retrosynthetic thinking” must be thrown overboard if one really
wants to use the opportunities of transition metal chemistry.
The text is written in a concentrated but very readable
style, and is interlarded with valuable information and references. Preparative aspects clearly dominate throughout the
book, but are always complemented and connected by mechanistic considerations. The scope and limitations of the individual methods generally become clearly evident, which is of
great interest for potential “users”.
The impressive wealth of material is backed up by more
than 2000 literature references, which are grouped (sorted by
chapters) at the end of the book. The literature is continuously covered up to 1988, and partly even up to 1990. It
should be mentioned that the appealing quality of the
book is also reflected in its appearance (binding. paper,
printing, harmony of typesetting and formula diagrams).
The book is also provided with an extensive subject index,
which. together with the well structured table of contents,
facilitates quick orientation even during the search for single
A safety bibliography warns of potential risks associated
with the handling of organometallic reagents. However,
there is a possibility of an immediate danger of a different
kind to the reader of the book, insofar as some misunderstandings could occur. Some readers, especially those not
completely well versed in stereochemistry, could possibly be
misled by the fact that a clear distinction is not always made
between absolute and relative configuration. For instance,
not all racemic target compounds are indicated as such, and
the diagrammatic representation of stereochemical details
(particularly of z-complexes) in many structural formulas
could certainly be improved. But these are more or less
minor matters: on the whole, the formula diagrams are clearly arranged, and also the number of misprints and other
mistakes is small.
Of course, one is tempted to rate the book as overexpensive. However, if one takes into account the excellent quality
of its appearance and contents, the enormous wealth of upto-date, well selected, and conscientiously processed information on almost 600 pages, the price seems reasonable. To
the publisher one could make an appeal to also provide a
cheaper paperback edition, which would enable a larger circle of private individuals (e.g., students! !) to buy this important work.
To summarize, this generally excellent book entirely fulfills its intention, and is well worth its (high) price. On the
back cover is the claim: “This book stands as an invaluable
reference work as well as a source for initiating the design of
new organometallic procedures, and as such will be of great
value to organic chemists and research workers in both universities and industry”. I can only agree with this statement
and I hope this book will be well received by a wide readership.
Hans-Giinther Schmalz
Institut fur Organische Chemie
der Universitiit Frankfurt/M. (FRG)
Chemical Equilibria in Solution. Dependence of Rate and
Equilibrium Constants on Temperature and Pressure.
(Physical Chemistry Series). By M . J. Blandamer. Ellis
Horwood/Prentice Hall, Chichester, 1992. 144 pp., hardcover $68.50.--ISBN 0-13-131 731-8
This monograph (142 pages) uses a thermodynamics
theme to provide arrays of suitable equations which can be
used to analyze data from solution equilibrium and kinetics
experiments in which pressure or temperature, or both, are
varied. It does not purport to, and does not discuss experimental methods or provide interpretative discussion of activation parameters derived from the various treatments. A
pleasing feature, and one making for easier reading, is the
separation of sets of equations from the narrative.
The author presents a literature survey in addition to contributions from his group, and successfully manages, almost
without fault, the unenviable task of providing an orderly
and consistent set of symbols throughout. References are
cited for each subsection of a chapter, a convenient approach. However, the lack of lists of chapter-end references
or of a cumulative reference list could be bothersome for
some. There is an index of essential terms and named equations.
Chapters 1. 2, and 3 develop standard thermodynamics i n
terms of symbolism and application to solution chemistry
into the repertoire of needs for the heart of the book (Chapters 4-6). Of these latter chapters. the first examines methods for treatment of pressure dependence results, while
Chapters 5 and 6 consider, at length, methods for treating
equilibrium and kinetics temperature dependence results. In
the seventh and final chapter the dependence of equilibrium
composition and rate constants on temperature and pressure
is covered. The reader is given a lucid account of recent
contributions to characterization of the isochoric condition
and to calculations of isochoric activation parameters.
Overall the writing style is direct. There are some minor
errors, such as missing words, for example in the first sentence of Section 4.14, and in the second sentence o f the first
complete paragraph of page 91, a missing letter as in pentaamminecobalt(r1I) (p. 69), and occasional confusing use of
units; in this latter category an enthalpy change A,H“ is
given in J m o l - ’ on page 102, and in kJmol-’ on page 105,
and the volume parameter A,V“ is expressed iii cm3mol-’
on page 71 but is given (erroneously) as -35.9 m3mol-’ on
page 66. The Tait equation, introduced in Chapter 1 and
used again on page 72, contains lower case c, but when it is
applied in the context of the Benson-Berson approach
(pp. 73-74) a capital C appears.
Given that the author is a renowned thermodynamics expert one might expect that only other thermodynamics specialists will be attracted to this book. This would not be an
accurate assessment. since the book can appeal in total, or in
selected parts, to chemists and other scientists who have an
undergraduate or more advanced knowledge of physical
chemistry. It is likely that it could form part of the recommended reading for a graduate student lecture course on
solution thermodynamics. The promotional material on the
back cover cites among others “researchers in medicinal
chemistry and medically related subjects. . .” as potential
readers. While the broad appeal of the text can be lauded, it
is not clear why these groups were selected.
Because of its focus only on development of thermodynamics equations for treatment of data, there is. at times. a
sense of lack of connection with actual chemical equilibria
and various chemical reactions. This is a disappointing aspect, and for some experimentalists could have the effect of
reducing the scope of use of the book. An emphasis could
have been placed on the limitations which are not so much
a lack of will or skill to tit data, but of suitable instrumentation. time, or amenable reacting systems. Obtaining data of
sufficient quality to justify pursuit of calculation of the pressure and temperature derivatives of A V * and A H * respectively is seldom possible. Again, although this would have
broadened the purpose of the book, it would have benefited
from the inclusion of a section devoted to interpretation of
derived parameters, and explaining how this contributes to
understanding the chemical processes being studied. However, all the treatments experimentalists require are collected
together here in one convenient source with each method
easily accessible and referenced. This alone merits a place for
this book in chemistry libraries and in the personal collections of thermodynamicists and kineticists.
Colin D.Hubbard
Department of Chemistry
University of New Hampshire
Durham, N H (USA)
Materials’ Science and Technology. A Comprehensive Treatment. Series editors: R. W Cahn, P. Huusen, and E. J.
Kuinzer. VCH Verlagsgesellschaft, Weinheim/VCH Publishers. New York.
Volume 3 A: Electronic and Magnetic Properties of Metals
and Ceramics (Part[). Edited by K. H. J. Buschow, 1991.
XIV. 641 pp.. hardcover D M 430.00.--ISBN 3-527268 16-2/0-89573-691-8
Volume 4: Electronic Structure and Properties of Semiconductors. Edited by W. Sciztoter, 1991. XVI, 603 pp., hardcover DM 430.00. - ISBN 3-527-2681 7-0/0-89573-692-6
Volume 7: Constitution and Properties of Steels. Edited by
F: B . Pickering, 1992. XVI, 824pp., hardcover
DM 430.00. --ISBN 3-527-26820-010-89573-695-0
Volume 15: Processing of Metals and Alloys. Edited by R. W
Cuim, 1991. XIV, 628 pp., hardcover D M 430.00.--ISBN
The new IS-volume series “Materials Science and Technology” covers the properties. manufacture, and processing
of materials, and their specific areas of use. It brings together
the know-how of chemists, physicists, and engineers, and
shows how fundamental research and applications-orientated research can be made to interact most effectively and
The first volume to appear, in 1991, was Volume 5, “Phase
Transformations in Materials”, and has already been reviewed in the context of the series as a whole (Angew. Ciiem.
1992, 104, 245; Atipw.. Clzem. Int. Ed. Engf. 1991,30, 1521).
U p to now Volumes 2A, 3 A, 4. 5A. 7,9,14, and 15 have been
published, and four of these (3 A, 4. 7, 15) are reviewed here.
During the planning of Volume 3 (“Electronic and Magnetic Properties of Metals and Ceramics”) it already became
clear that it would hardly be possible to treat all the necessary aspects and phenomena of this subject in a single volume, and it was decided to have two volumes. The second of
these (Vol. 3 B) has not yet appeared, but the chapter titles
have already been given as: “Magnetic Properties of Spinel
Ferrite”; “Electronic Properties of Liquid, Amorphous, and
Quasicrystalline Alloys”; “Invar Alloys” ; “Magnetic
Recording Materials”; “Hydrogen in Pure Metals and Solid
Solutions”; “Ternary Hydrides” ; “Soft Magnetic Metallic
Materials” ; “Permanent Magnet Materials”; ”Magnetostrictive Materials”.
The first chapter of Volume 3 A deals with the calculation
of electronic structures. The ability to perform such calculations for the highly complex systems of interest to materials
science has come with the availability of very fast computers.
Chapter 2 is concerned with the magnetooptical properties
of metals, alloys, and compounds. After an introduction to
the fundamentals (theory and measurement techniques),
some special materials are described and their properties
discussed (alloys and compounds of 3 d metals. materials
based on lanthanoids and actinoids, and mixed 3d-4f and
3d-5f compounds). Chapter 3 is devoted to electron transport properties of “normal” metals, including the behavior
of electrons in magnetic fields, electrical resistivity, the Hall
effect. thermoelectric power, etc. Chapter 4 covers superconductivity, with discussions of the Bardeen-Cooper~4chrieffer (BCS) and Ginzburg-Landau (GL) theories; the oxide
high-temperature superconductors are also described, of
course. In Chapter 5 the focus of interest turns to the magnetic properties of metallic systems, then Chapter 6 deals
with ultrathin films and superlattices (epitaxy). The book
concludes with Chapter 7 on Fermi surfaces in strongly coupled electronic systems. This, like Chapter I , treats the topic
in a fundamental way, and includes instructive comparisons
of experimental results with band structure calculations.
Volume 4 (“Electronic Structure and Properties of Semiconductors”) presents the basic concepts of modern semiconductor physics. starting from the fundamentals of ideal
semiconductors and continuing through the physics of defects and heterostructures (artificial semiconductors) to
amorphous semiconducting systems. Chapter 1 (“Band Theory Applied to Semiconductors”) and Chapter 2 (“Optical
Properties and Charge Transport”) are of an introductory
nature. They cover the basic theory needed to understand the
formation of energy bands in solids with three-dimensional
structures and structures of lower dimensionality and in
amorphous materials, the investigation of band structures by
measuring intrinsic optical properties. charge transport, and
nonlinear optics. Chapter 3 deals with the simplest types of
point defects, the intrinsic defects that occur in crystal structures where some atoms have changed their positions or are
missing altogether; essentially one is concerned here with
vacancies, interstitial sites, and sites at which anions or
cations have been changed (“antisites”). As examples of different types the chapter discusses silicon (an elemental semiconductor), ZnSe (a 11-VI semiconductor), and GaAs (a
111-V semiconductor). In Chapter 4 (“Deep Centers in Semiconductors”) the discussion moves on from intrinsic defects
to doped materials (e.g.. with nitrogen and transition metals
as dopants in silicon or compound semiconductors, chalcogens in silicon, and DX centers--in which D represents a
donor and X an unknown effect--in the mixed crystal system A1,Ga -,As). Silicon and gallium arsenide are nowadays the most important semiconducting materials used in
the manufacture of electronic and optoelectronic components, and Chapter 5 (“Equilibria, Nonequilibria, Diffusion,
and Precipitation”) is concerned particularly with these materials and the behavior of their point defects (whether intrinsic or produced by doping). Moving on from point defects, Chapters 6 (“Disiocations”) and 7 (“Grain Boundaries
in Semiconductors”) deal with these more extended types of
defects and their effects on the physical properties of semiconductor materials, from both the phenomenological and
theoretical standpoints. Newer manufacturing techniques,
including the now highly developed methods of epitaxial
growth, make it possible to produce artificial materials and
components with special properties that depend on the presence and concentration of interhces. Chapter 8 gives the
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