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Book Review Photochemistry. By J. Calvert and J. N. Pitts jr

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This series of monographs, which was started by G. Junder
and H. Spandnu and is being carried on by H . Spundau and
C . C . Addison, is to consist of eight volumes on chemistry in
non-aqueous inorganic and organic solvents. The inorganic
solvents discussed include ammonia, sulfur dioxide, dinitrogen tetroxide, a few halides and oxyhalides, and a number
of salt melts, while the organic solvents include the lower
fatty acids and their derivatives, nitrogen bases, alcohols,
ethers, and esters.
The first part of the first volume deals with inorganic and
general chemistry in liquid ammonia. The author has taken
great pains to cover all the literature on inorganic and physical chemistry in liquid ammonia. The resulting article covers
500 printed pages, including a 42-page list of about 2000 references (from 1826) and more than 200 tables, the longest of
which occupies 32 pages.
This passion for completeness is not always to the reader’s
advantage, since all the published values for one quantitative
measurement are often presented on an equal footing and
without discussion, and the reader has to decide which value
is correct. This is not troublesome e.g. in rhe case of the boiling point and the melting point of pure ammonia or its
critical temperature, since the numerous values differ by less
than 1 deg, and the best values can be found in suitable tables
anyway. However, the inclusion of all the values e.g. for
solubilities (Table 86) is confusing. For example, the following values are given fox the solubility of NaCl between
-76.9 and -74.9’C: 0.232, 0.074, 0.28, 0.123, and 0.306 g/
100 g and 0.203 g/lOcJml. A similar situation is found e.g. i n
Table 152 (phase separatlon in metal-NH3 solutions): the
existence of a miscibility gap in Li-NH3 solutions is given as
“not detectabk”, “uncertain”, and “certain” a d in K-NH3
solutions as ‘ not detectable” and ‘‘unCertain ’ (in fact both
systems have ‘ a miscibility gap with an accurately known
critical temperature). Similar lack of clarity is found i n the
subsequent tables o n the metal adducts.
References to other parts of the book are given, not as a page
number containing u p to three digits, which would be easy to
remember and could be found quickly, but as a key number
for the section in question, which may contain up to seven
digits, e.g. 2.9.2.2.2.1.6. (Oxidation of ammonium aiide with
exclusion of solvent molecules as reactants). The key numbers in the supplementary chapter, in which the latest literature is collected do not agree with those of the principal
chapters.
Apart from these and similar failings, however, the book
probably fulfils the purpose expressed in the Preface, i.e. to
be of use to all chemists in the laboratory and in practice.
Owing to its completeness, it can replace all past volumes of
Chemical Abstracts or of Chemisches Zentralblatt for the
chemist who is working with liquid ammonia.
U. Schindewolf
Both books are recommended to a wide circle of readers.
Their aim is to provide information required in order to
understand current publications o n photochemical investigations, and hence to provide the newcomer with a foundation
o n which to base his own investigations.
I n the book by Turro, an eight-page introduction is followed
by four chapters on photophysical processes and problems
(electronic excitation, 11 pages; electronic spectra and electronic excitation states, 48 pages), and the transfer of electronic energy, 45 pages). Four further chapters deal with
photochemical processes and problems (photvreductions and
related reactions, 25 pages; photo-rearrangements and photoisomerization, 32 pages; photo-cycloadditions 30 pages;
photofragmentation and related processes, 21 pages), and a
final chapter (It papes)touches on a number of experimental
aspects. This book is based op a lecture manuscript, and is
naturally selective in character. The fact that the author
belongs t o one of the leading schools of photochemistry
guarantees the significance of the material.
Cnlvert and Pirts have succeeded in producing the standard
work on photochemistry. Every conceivable field apart from
photoblology and photography is covered. The first four
chapters (Irghtand the laws ofphgtochemistry, 22 pages; the
action of Irght on atom5 and reactions photosensitized by
atoms, 90 pages; the action’of light on simple molecules and
their phokxhemistry, 100 pages; the primary photophysical
processes of polyatomic molecules, 112 pages) provide a
fundamental description of photophysical principles. The
fifth chapter (190 pages) presents a colorful review of the
photochemistry of polyatomic molecules, which systematically
embraces all the known classes of photoreactive substances.
Two further chapters (determination of the mechanism of a
photochemical reaction, 83 pages; the experimental methods
of photochemistry, 111 pages) deal with the fundamental
methods used i n the study of reaction mechanisms and with
the detailed procedures used.
The book contains a comprehensive author and subject index
and more than 1500 references.
T o those who wish to buy only one of these books, the reviewer would recommend that by Crrlverf and Pitts.
G. Quinkert
[NB 607 [El
[NB 598 IE]
Molecular Photochemistry. By N . J . Turro. W. A. Beniamin.
Inc., New York-Amsterdam 1965. 1st Edit., xiii, 286
pages, numerous figures, D M 55.-.
Photochemistry. By J . Culvert and J . N . Pitts j r . John Wilev
and Sons, Inc., New York-London:Sydney 1966.1st bait.,
xvii, 899 pages, numerous figures, D M 84.-.
The reviewer can recall the earnest discussions only 10 years
ago on whether a light-induced reaction in the course of a
total synthesis made such a synthesis doubtful as structural
evidence. Photochemistry has now been emancipated, and
chapters on this field a:e now no longer found only in textbooks of physical chemistry, but have recently also earned a
firm place in textbooks of organic chemistry. The preparative
chemist now values light as a cheap reagent; the M O theory,
which should already have been met in basic chemistry reading, provides a structural model that is partly based o n consideration of the primary photophysical processes, and that
offers an explanation of the primary photochemical processes.
720
The further development of photochemistry will open up new
preparative routes; it will add to and improve the model
concepts of the structure and structural changes of mclecules. Accordingly, a steadily growing number of workers
will wish to enter this field and to take part in its development. The two monographs reviewed here may help them to
d o this.
Encyclopedia of Chemical Technology. By R . E. Kirk and D.
F. Othmer. Edited by A . Stunden. Vol. 9: Ferroelectrics to
Foams. Interscience Publishers, a Division of John Wilev &
Sons, Inc., New York-London-Sydney 1966. 2nd Edit.,
xvi, 901 pages, numerous illustrations, bound 338s; subscription price 260s.
Volume 9 of Kirk-Othmer[*l contains 22 articles having an
average length of 41 pages, including fluorine chemistry (341
pages), fertilizers (126 pages), fluidization (47 pages), flavors
and spices (44 pages), fluid mechanics (38 pages), foamed
plastics (37pages), and ferroelectrics (25 pages), as well as
fibers, films, filtration, fish, fire prevention, fluorescent pigments, and foams. The second edition is largely rewritten,
mainly by new authors (of the 60 contributors to this volume,
only 10 were connected with the first edition). The volume
has increased in size to about 900 pages, as opposed to 445
pages in the edition published 15 years ago. The detailed
coverage of new developments is very pleasing, though the
increase in the quantity of material to be included forces the
editorial staff to abbreviate and compress in order that the
required information may still be quickly accessible.
Angew. Chem. internut. Edit. 1 Vol. 6 (1967) 1 No. 8
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