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Book Review Lsungsmittel-Effekte in der organischen Chemie (Solvent Effects in Organic Chemistry). By Chr. Reichardt. Volume 4 of УChemische TaschenbcherФ edited by W. Foerst and H

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hydrogen sulfide, and hydrogen cyanide. This is followed by a
section on aprotic solvents such as sulfur dioxide, halogens
and interhalogen compounds, mercury bromide, dinitrogen
tetroxide, and other ionizing solvents. A brief account is also
given of halogen compounds of semi-metals and organic
solvents, particularly amines.
Each section begins with data for the physical properties of
the solvent discussed. The acid-base theory occupies a central position. The Arrhenius theory, expanded as “solvent
theory”, which assigns particular importance to the ions of
the solvent itself, can be used in the most general way t o
display analogies t o the aquo system, provided that the solvent undergoes even minimal self-dissociation. A special section is devoted t o treatment of the relevant acid-base theories
as a group, their utility being discussed with special reference
to the general applicability of the ionotropy theory.
A great number of reactions is discussed in this book, showing again and again how their course can be influenced by
varying the solvent used. For instance, different solubilities
of reactants in water and in ammonia can reverse the direction of a reaction; and the proton affinities of the solvent
molecule or of the ions derived from it can decide, for example, whether a reaction leads t o salt-formation or t o solvolysis. A chapter on solutions of alkali metals in liquid ammonia gives a very nice, short review of the present state of
research in this field.
The book can give the advanced student an insight into the
topic of water-like solvents, should he be unable t o attend a
special lecture course on the subject, and it is certainly apposite for this purpose. The authors have thoroughly thought
out the way t o cover the wide field; they have doubtless put
the recently published comprehensive book on reactions in
liquid ammonia t o good use. This masterly exposition of
water-like solvents is also to be warmly recommended to all
scientists working in related fields who spurn a too detailed
bibliography.
The publishing program for the Chemische Taschenbucher,
which has appeared meanwhile, lists a number of interesting subjects, mainly from theoretical chemistry but also from
preparative chemistry, with a long series of authors who are
recognized experts. The series will doubtless direct the attention of scientists to the most varied fields of chemistry as
well as t o borderline areas.
R.Juza [NB 810 IE]
Losungsmittel-Effekte in der organischen Chemie (Solvent
Effects in Organic Chemistry). By Chr. Reichardt. Volume
4 of “Chemische Taschenbiicher”, edited by W. Foersr and
H . Griinewald. Verlag Chemie GmbH, Weinheim/Bergstr.
1969. 1st Edit., 180 pp., 23 figures, 22 tables, D M 16.-.
The use of solvents in chemical reactions and for the spectral
examination of substances has become so commonplace that
the role of the solvent is often overlooked. The reaction
equations deduced from experiments are usually presented
with no mention of the solvent, so that the young chemist
usually has to acquire a knowledge of solvent effects by
purely empirical means. In the past few decades, many series
of experiments have been carried out and theoretical ideas
presented on the (often dramatic) effects of the solvent, but
these have rarely been treated from the same point of view.
This shortcoming is made good by Chr. Reichardr with his
introduction to the field.
The book deals first with the types of interaction that occur
between solvents and solutes, clearly showing e.g. the difference between ionization and dissociation, and including
hydrophobic interaction and selective solvation (18 pages).
After a discussion of various principles for the classification
of solvents (11 pages), their effect on chemical equilibria
(acid-base, keto-enol) is explained (1 1 pages). The important
and manifold solvent effects in chemical reactions, which
should be familiar to every chemist to enable him t o plan his
experiments, are discussed at length (49 pages). Here. as
elsewhere, instructive examples, often supported by tables,
Angew. Chem. internat. Edit.
/ Vol. 8 (1969) J N o . 6
are used to show how the effect of the solvent on the reaction
path and rate as well as on the steric course depends on the
polarity and charge of the reactants and on the reaction type.
23 pages are devoted t o the effect of the solvent on electronic
spectra (solvatochromism) and on IR, N MR, and EPR spectra.
The final chapter (27 pages) describes the empirical solvent
polarity parameters, which are particularly useful in practice
for the choice of solvents. An appendix presents hints on the
use of organic solvents for spectroscopic and preparative
purposes. A selected bibliography for further reading is found
at the end of each chapter.
The text is written critically and informatively. The author
avoids simplifications, but presents rules that have proved
useful in sectors of this extremely complex field. The treatment
leaves little t o be desired, apart from a distinction between
contact and solvent-separated ion pairs, as well as a detailed
discussion of the resonance-solvatochromism problem. The
print and formulas are easily legible. Since the book will undoubtedly see considerable use, it would probably benefit
S. Hiinig [ N B 820 IE]
from a more durable cover.
Ullmanns Encyklopadie der technischen Chemie, Bd. 212 :
Betriebsuberwachung mit Dokumentation und Patentrecht
(Ullmann’s Encyclopedia of Technical Chemistry, Vol 2;2:
Process Control, and Documentation and Patent Law).
Chief editor: W. Foerst. Editor: Heriha Buchholz-Meisenheimer. Urban und Schwarzenberg, Miinchen-Berlin-Wien
1968. 1st Edit., viii + 677 pp.. 547 illustrations, D M 160.-.
The new Ullmann volume is a self-contained work, extracted
from the alphabetically arranged Encyclopedia “1 and independent thereof. A self-coherent important complex of
themes is considered under the following headings: Control
Techniques (132 pp.). Measuring Processes in Industry (121
pp.), Pure Air Conservation (91 pp.), Calculation by Computer, An Introduction to Programming (60 pp.), Waste
Water (57 pp.). Documentation (39 pp). Industrial Toxicology (34 pp.), Patent and Trademark Law (31 pp.), Safety in
the works (26 pp.), Statistical Methods of Planning and Evaluation of Experiments (25 pp.), Non-destructive Testing of
Materials (20 pp.), Dust Explosions and their Prevention
(9 pp.), Waste Disposal (9 pp.).
The chapter on measuring techniques deals not only with
methods for measurement of temperature, pressure, and
quantities, but also with modern analytical procedures. The
sections on transducers and analog-digital converters are
worthy of note. The chapter on control techniques gives, in
49 pages, an elementary and instructive introduction with
information that is intelligible to the user and in general sufficient for him. A second section on this subject, “Mathemathical Methods” (49 pp.) goes deeper into the matter. The
chapter on “Calculation by Computer” is also written in such
an elementary way that the non-expert can by himself extract
the details required for use of this new method of thinking.
The chapter on “Statistical Methods in the Planning and
Evaluation of Experiments” provides deeper insight into what
was previously called determination of error. The methods
of variance and regression analysis are briefly developed,
these being particularly valuable for control and optimization
of complicated processes. In such cases it is often necessary
to determine by purely empirical means the relation between
objectives (yield, economics, quality of a product) and factors
of influence thereon (pressure, temperature, throughput, concentrations of reactants, etc.), so that it becomes a matter of
determining the relations with the minimum number of single
measurements. This chapter is well written but requires concentrated reading.
The section o n “Patent Rights” is especially timely because
important changes in patent law became operative between
January 1st and October lst, 1968. In contrast t o the previous
patent law, which in chemistry permitted only the patenting
[ll Cf. Angew. Chem. 80, 8 5 5 (1968); Angew. Chem. internat
Edit. 7, 834 (1968).
465
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