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Book Review Modern Hot Atom Chemistry and its Applications. By T. Tominaga and E. Tachikawa

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60” only causes a reduction of the CCC interorbital angle
to 102.6”. Irrespective of whether the CCC bond angle is
reduced or widened, the hybrid orbitals of all three hydrocarbons apparently have a strong tendency to retain the
ideal tetrahedral angle as far as this is energetically possible, and to limit the orbital following to a minimum. This
behavior, at least for saturated hydrocarbons, appears to
be valid in general.
As we have found, the CCC coupling constants of aliphatic hydrocarbons can be represented well by the linear
relationship (using the data of nine symmetric hydrocarbons).
‘Jcc = 658.sl.s~- 7.9
If the scc data of Table 1 determined from the ‘JCHvalues
oia the sum rule[2b1are inserted into this equation, ‘Jcc values of 13.2 for 1, 33.5 for 2, and 33.2 for 3 result. The
(only slight) deviations of these data from the experimental
ones (Table 1) provide a measure for the non-contact contributions to the ‘Jcc Hence, in 1, 2, and 3 the ‘3C-’3C
coupling actually arises almost completely from the Fermi
contact mechanism.
Received: May 15, 1981 [Z 195 IE]
revised: July 28, 1982
German version: Angew. Chem. 94 (1982) 873
CAS Registry numbers:
1, 75-19-4; 2, 110-82-7; 3,74-98-6
I. Kowalewski, Prog. Nucl. Magn. Reson. Specrrosc. 11 (1977) 1.
a) N. Muller, D. E. Pritchard, J. Chem. Phys. 31 (1959) 1471: b) Th. Forster, Z. Phys. Chem. 8 4 3 (1939) 58.
W. A. Bingel, W. Liittke, Angew. Chem. 93 (1981) 944; Angew. Chem. Inr.
Ed. Engl. 20 (1981) 899.
M. D. Newton: Strained Organic Molecules, in H. F. Schaefer: Applications of Electronic Structure Theory. Plenum, New York 1977, p. 242.
P. Coppens, Angew. Chem. 89 (1977) 3 3 ; Angew. Chem. In<. Ed. Engl. 16
(1977) 32.
BOOK R E V I E W S
Modern Hot Atom Chemistry and its Applications. By T.
Tominaga and E. Tachikawa, Inorganic Chemistry Concepts 5 . Springer-Verlag, Berlin 1981. viii, 154 pp., bound
DM 98.00.
The chemistry of hot atoms is dead, long live hot atom
chemistry, in its modern and applied version, of course, at
least that is what the title of the book suggests. On a closer
inspection, however, the reader will inevitably come to the
conclusion that the term “modern” means the beginning of
the seventies and that the applications seem modest. This
is not the fault of the authors. Already by the end of the
sixties hot atom chemistry was no longer an individual and
uniform field of endeavour, and what appeared to have a
future has meanwhile been substantially taken over by
physical chemistry, chemistry of the solid state, radiation
biology, or radiolabelling chemistry.
One would certainly expect something new on experimental techniques, and it is precisely here that the book is
disappointing. A modern book on hot atom Chemistry
(HAC) should, for example, devote more than two pages
to atomic and molecular beam techniques. Equally disappointing is the treatment of radiochemical separation techniques of the stable labelled molecules which are formed
as a final manifestation of a nuclear recoil process. The
Angew. Chem. Inr. Ed. Engl. 21 (1982) No. I 1
chromatography has remained at the 1965 level; there is no
mention of more sophisticated techniques, such as highperformance liquid chromatography.
The core of the book is the chapter “Characteristics of
Hot Atom Reactions”. On the whole, the parts on the reactions of hot tritium, halogen, carbon, silicon, germanium,
and phosphorus atoms are didactically clear and coherent.
A comparison with the reactions of the corresponding
thermal atoms would have been useful here, especially as
many thermochemical, photochemical, and radiation
chemical investigations have now been published, which
clearly show the similarities and the differences between
the reactions of hot and thermal atoms. The part on “Solid
Phase Hot Atom Reactions” is also too short.
In the chapter “Application ofHot Atom Chemistry and
Related Topics” the emphasis is obviously on the related
topics, since it is difficult to force subjects such as laser
isotope separation or NEET (Nuclear Excitation by Electron Transition) into the HAC category. With this broadening of the concept of HAC in mind, it is difficult to see
why muonium chemistry is discussed but positronium
chemistry is not. Naturally, there are also HAC problems
in energy research, but they play a minor role, and the examples confirm this. However, better choices could have
813
been made, particularly in the case of nuclear fusion. On
the whole, the authors’ aim to demonstrate the many-sided
relationships of HAC with other research sectors is certainly praiseworthy, and has substantially been achieved.
The importance of HAC is made obvious in topics such as
the unimolecular decomposition of highly excited products, the study of the selectivity and reactivity of unsolvated decay ions, processes for rapid labelling with shortlived radionuclides, the chemical consequences of the radioactive decay and the Auger effect in biomolecules as
the starting point for entry into novel areas of selective radiation biology. But all this is touched on only briefly, as if
to give the reader no more than a taste. Few will quite get
their money’s worth (DM 98!), if any, hot atom chemists
themselves. Either the book has come out five years too
late or it is much too superficial.
Gerhard Stocklin
[NB 563 IE]
Elektrochemie (Electrochemistry) I1 (taschentext [pocket
text] 42) by C. H . Hamann and W. Vielstich, Verlag
Chemie, Weinheim 1981. xv, 428 pp., bound, DM
52.00.
A second volume on the subject of electrochemistry has
now appeared in the “taschentext” series, building on Volume I (ionics, electrochemical thermodynamics) which appeared six years ago[’]. The extensive subjects of electrochemical kinetics and applied electrochemistry are now
dealt with, each of them taking up about as much space as
the whole of the first volume.
At the center of the kinetic treatment of electrode processes is, naturally, the current-voltage curve. The influence
of the types of overvoltage on the course of this curve is
discussed in detail. Not only simple metal electrodes but
also mixed electrodes, semiconductor electrodes, and illuminated semiconductor electrodes are considered.
The chapter on electrochemical measurement techniques
leads to the classical steady-state and nonsteady-state
methods, the authors obviously being concerned to give a
concentrated account of the theoretical foundations. Nonelectrochemical techniques for surface analysis are also
discussed, including such areas of topical interest as field
desorption mass spectroscopy.
Among others, the processes at the hydrogen and oxygen electrodes are discussed as specific examples of electrode processes. The oxygen anode is considered somewhat
too briefly; reference should perhaps have been made to a
possible third mechanism of redox catalysis (decomposition of electrochemically formed oxides).
In the second part of the volume electrochemical syntheses, galvanic cells, and electrochemical surface techniques are discussed in extensive detail and the reader is
acquainted with some modern developments. However, in
the chapter on chlorine-alkali electrolysis one would like
to find a somewhat more detailed account of the technical
prerequisites for the vigorous development that set in 15
years ago with the advent of activated titanium anodes
(Beer) and perfluorinated ion-exchange membranes, acknowledged perhaps in footnotes. The Monsanto process
for the electrosynthesis of adiponitrile has for technical
reasons been carried out in undivided cells since the end of
the sixties, as has now become known through Danly’s
[*] See Angew. Chem. Int. Ed. Engl. 15 (1976) 447
874
publications. Unfortunately, there is no mention of Baizer,
the man who initiated this innovation.
In connection with a possible future hydrogen economy
the electrolysis of water and the hydrogen/oxygen fuel cell
are discussed in detail. The possibilities of secondary cells
are outlined. These sections are particularly well arranged.
The authors’ wish to present not only an accurate but
also a clear account of the individual fields can be considered as largely achieved, and the few blemishes present
hardly affect this over-all impression. (Thus, on p. 15-and
then again on p. 39-it is expressly emphasized that the
transfer reaction of electrons can be described as a quantum-mechanical tunnelling process. In spite of this, the
Butler-Volmer equation on pp. 16-21 is derived precisely
on this example with the aid of the Arrhenius equation.)
In spite of the necessary brevity, in most cases the authors succeed in formulating the problems precisely. On
the whole, a readable and reliable account of electrochemistry has thus been achieved, which leads directly to the
present situation in areas that are very much in a state of
flux. The arrangement of the volume, and particularly the
figures, is good. The book can be safely recommended to
anyone who wishes to become acquainted with modern
electrochemistry, and this also applies to the university level, although many students could be put off by the relatively high price.
Fritz Beck [NB 564 IE]
Heterocyclic Compounds. Vol. 32, Part 2: Quinolines.
Edited by G. Jones. John Wiley & Sons, Chichester 1982.
xii, 685 pp., bound, L 70.00.--ISBN 0-471-28055-0
Benzodiazepines. A Handbook. Basic Data, Analytical
Methods, Pharmacokinetics and Comprehensive Literature. By H . Schiitz. Springer-Verlag, Berlin 1982. xii, 439
pp., bound, DM 198.00.-ISBN 3-540-11270-7
Synergetik. Eine Einfiihrung. By H . Haken. Springer-Verlag, Berlin 1982. xiv, 382 pp., bound, DM 69.00.--ISBN
3-540-11050-X
Cyclodextrins and Their Inclusion Complexes. By J. Szejtli.
Akademiai Kiado, Budapest 1982. 296 pp., bound, DM
67.50.--ISBN 963-05-2850-9
Vibrations at Surfaces. Edited by R . Caudano, J.-M. Cilles,
and A . A . Lucas. Plenum Press, New York 1982. xii, 585
pp., bound, $ 69.50.-ISBN 0-306-40824-4
Fundamentals of General, Organic and Biological Chemistry. 2nd Edition. By J. R . Holum. John Wiley & Sons,
Chichester 1982. xvii, 717 pp., bound, L 19.20.-ISBN 047 1-06314-2
Angew. Chem. Inr. Ed. Engl. 21 (1982) No. I1
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