the condensation of oxygen in cold traps).
I would like to imental observations that led to the formulation of quantum
add that substances hazardous to health, such as Na/Pb
alloys (p. 8) or chromic acid (p. 75) should no longer be used
in a modern research laboratory, and should be replaced by
more suitable drying and cleaning agents. Chapter 2 (The
main vacuum line) can be considered the heart of the book.
It contains detailed descriptions of the building and running
of a high-vacuum line. After a short overview, the individual
components of this equipment (pumps, cold-traps, taps,
valves, manometers) are described and compared. The read-
er thereby obtains important advice on which device best
suits each situation. Here too, Plesch succeeds in giving the
reader the experience he has gained from many years of
working with high-vacuum techniques. Even apparently
minor particulars, like the correct greasing of ground glass
connections, are not to be underestimated in practice. Practi-
cal advice of this kind makes the book useful reading mate-
rial for every diploma or PhD research student who needs to
use some form of vacuum technique. After the construction
of the vacuum line the sometimes laborious task of detecting
leaks is discussed. In Chapter 3 (Applications and proce-
dure) countless specialized apparatus and additional pos-
sible applications for high-vacuum techniques are described.
Plesch gives particular attention to the filling and melting of
glass phials. Much of this equipment (burettes, dilatometers,
viscometers, calorimeters, etc.) is useful, but some, in my
view, is a little too exotic (e.g., on page 93, the device for
simultaneous filling of several dilatometers). On the other
hand the section on NMR measurements (p. 96) is a little too
short. Sealing NMR tubes under vacuum should be a routine
operation for any advanced graduate student. However, I
consider the making of NMR tubes (p. 97) a waste of time.
Chapter 4 (Purification, including drying) contains countless
useful tips for practical work. Every synthetic chemist will
daily encounter problems with cleaning and drying reagents
and solvents. A book about potential applications of vacu-
um techniques would therefore be incomplete without advice
on drying glass apparatus (p. 119) as well as degassing and
drying the solvent to be used. Thus, Section 4.6 (What is so
special about drying?) particularly is worth reading atten-
tively. Chapter 5 concludes the book with a few syntheses
and measurements, chosen to show the advantages of the
high-vacuum technique.
In the introduction P . H . Plesch defines the aim of the
book: ”. . .to enable a chemist to assess the possible utility of
high-vacuum techniques for his purposes, to design and
build a high-vacuum system, and to do good chemistry with
it”. The author has succeeded in doing this.
Frank T Edelmann [NB 1178 IE]
Institut fur Anorganische Chemie
der Universitat Gottingen (FRG)
Basic Principles and Techniques of Molecular Quantum Me-
chanics. By R. E. Christoffersen. Springer, Berlin 1990. xiv,
686 pp., hardcover DM 178.00.--ISBN 3-540-96759-1
This book is a comprehensive student text and work of
reference on the theoretical fundamentals of quantum chem-
istry and their practical applications. It differs from other
books on this theme in several respects, including the amount
of space devoted to describing the mathematical basis of
quantum-mechanical methods.
A brief introductory section reminds the reader of some of
the concepts of classical mechanics, and describes the exper-
Angrw. Cliem. In[. Ed. Engl. 30 (1991) No. I t 0 V C H Verlagqeselischufr mbH, W-6940 Wrinheim. 1991
mechanics. This is followed by 140 pages on vector space and
function space, matrix algebra, operator algebra, etc. After
this come several chapters in which the postulates of quan-
tum mechanics are introduced and the usual model problems
are treated (particle in a box, harmonic oscillator, the hydro-
gen atom, etc.). The Hamiltonian operator for molecular
systems is discussed in considerable detail, including the ef-
fects of external magnetic fields as well as relativistic effects.
The final chapter of the book contains an equally detailed
treatment of the approximate methods that are commonly
used in quantum chemistry, such as the closed- and open-
shell Hartree-Fock SCF approximations, perturbation theo-
ry and configuration interaction.
The overall impression is of a sound and competently
written book. Explanations are given of many points that are
not often covered in comparable textbooks; for example,
there are discussions of the Rayleigh-Schrodinger and Bril-
louin-Wigner perturbation theories, of methods of calculat-
ing lower limits for the energy, and of such details as the
origin of the s,p,d. . . nomenclature for atomic orbitals. Nev-
ertheless, there is some doubt as to whether the book entirely
succeeds in the ambitious aim of presenting the complex
mathematical background in a form which is both detailed
and comprehensible to the student. Too often one finds that
proofs and theorems are glossed over, and the reader is re-
ferred, in one of the many footnotes, to the original litera-
ture. Also the mathematics is presented without directly re-
lating it to applications, and one suspects that many students
will consequently feel that this part of the book is an unap-
pealing and barren slog.
It is also regrettable that the discussion of quantum-me-
chanical computational methods is not always completely
up-to-date. New developments such as the use of direct SCF
methods for calculations on large molecules or of natural
atomic orbital basis sets are not described. In the discussion
of the multiconfigurational SCF approach one searches in
vain for a mention of the CASSCF method that is now most
commonly used; also the direct CI methods that have now
become so important are treated rather too briefly. A further
example of the sometimes rather outdated treatment is the
comment by Christoffersen that the diagonalization of a
1000 x 1000 matrix takes several seconds of computation,
whereas fast modern computers can in fact perform
such tasks in fractions of a second. This tendency towards
outdatedness is also reflected in the choice of literature
references, which mostly come from the 1970s and early
1980s.
It is also unfortunate that many printing errors have
found their way into the text, including some that are rather
confusing. For example, “yield” has become “field”, a factor
of 1/2 has been omitted from one formula, and one suddenly
finds that instead of an external force one is dealing with an
“external face”. With monotonous regularity a trial wave-
function becomes a “trail” wave-function, and even the
names of authors in the literature citations do not escape
distortion. A particularly annoying error is a reference to a
figure at the end of Chapter 7, where one looks in vain for it;
it is not until four chapters later that one suddenly comes
across an identical paragraph, this time with the figure.
Blunders such as these could certainly have been avoided
with a little care.
However, if one leaves aside these deficiencies in the prep-
aration, the tendency towards outdatedness in some parts,
and the fact that the planning of the mathematical part is
perhaps not entirely successful, Christoffersen’s book is an
interesting addition to the range of textbooks on theoretical
OS70-0833/9I/111t-l523S S.SO+.ZS/O I523
chemistry, and is to be welcomed especially for its many-
faceted treatment of the subject.
Wolfam Koch [NB 1116 IE]
IBM Deutschland GmbH
Heidelberg Scientific Center
Institute for Supercomputing and Applied Mathematics
Heidelberg (FRG)
Houben-Weyl. Methoden der Organischen Chemie. 4th Edi-
tion, supplementary volumes. Volume E 16a, Parts 1 and
2: Nitrogen Compounds I. Edited by D.Klamann. Thieme,
Stuttgart 1990. Part 1: xxxvi, pp. 1-855; Part 2: xiv,
pp. 856- 1516; hardcover DM 2100.00 (subscription
price: DM 1890.00).-ISBN 3-1 3-218-604-X
The publishing house Thieme continues to press on with
the work of updating the Houben-Weyl volumes written in
the period from the 1950s to the 1980s, by publishing a
supplementary work which takes into account the latest state
of development on methods and the most recent literature.
In these two part volumes on organonitrogen compounds
they have again succeeded in an impressive way.
This work again meets the aim (which has never been
explicitly stated) of not only giving an appropriate experi-
mental procedure for each special case, but also providing
the reader who has not yet become a specialist in a particular
field with an introductory, but nevertheless thoroughly
sound, overview of the possibilities. The reader may look up
a specific method and gain some additional information as a
result, or browse around the special problem of interest, or
again may read a few dozen pages almost in the manner of
a textbook. Each of these types of readers will get good value
from the work, helped by the information-packed and main-
ly well chosen subject matter, although not necessarily by the
arrangement of the contents, which follows an ever more
rigid pattern. The strict adherence to the ten hierarchical
levels of classification sometimes results in an undue empha-
sis on unimportant features, and often separates closely re-
lated topics. For example, the closely similar procedures of
the N-alkylation of hydroxylamine and that of N-alkyl-
hydroxylamines appear in different sections, as also do the
entirely analogous methods used to synthesize mono- and
dihalogenated amines.
The limitation to work published during the last twenty to
thirty years, which is usually applied very consistently, some-
times results in an emphasis on procedures that have been
overrated. Without actually copying “Beilstein” it would
have been useful to keep in mind the system used there, in
which the variety of routes to a class of compounds is shown
under the heading “Bildungsweisen”, whereas under
“Darstellung” the more generally useful and perhaps less
elegant method is chosen. The recommended procedures
should always be rather more generally applicable than the
reactions described in between these. A welcome feature is
the caution that has been applied with regard to mecha-
nisms, avoiding unnecessary embellishments on this theme;
in view of the need for “Houben-Weyl” to remain up-to-date
for decades, speculations of that nature would be likely to
become obsolete more rapidly than the established facts.
The first of the two part volumes contains two very long
chapters on organic hydroxylamine compounds (395 pp.)
and organic hydrazine compounds (435 pp.), together with
much shorter chapters on nitroxyl radicals, nitroxides and
amino-oxides. The considerable length of the chapter on the
hydroxylamines is no doubt due to the many different types
1524 0 VCH Verlagsgesellschafi mbH, W-4940 Weinheim. 1991
of redox reactions of N-0 compounds and the biological
activity shown by many individual compounds. In the case
of the hydrazines the reason for the length is that the alkyl-
hydrazines have made a welcome appearance in the last
few decades; previously these could only be prepared with
great difficulty by laborious alkylation of hydrazine or by
reduction of nitrosamines, whereas they are now accessible
by a variety of interesting reactions, mainly by forming
N-N bonds. The lengths of these two chapters are therefore
justified. However, the lengths of some of the subsections are
not commensurate with the importance of the topics. Addi-
tion reactions of nitrones and olefins occupy 20 pages with
an enormous table, and the (admittedly interesting) criss-
cross cycloaddition of alkenes to hexafluoroacetone is given
a six-page table. Such comprehensive treatments of examples
that are analogous should be left to specialized monographs.
The same also applies to the 16 pages with analogous exam-
ples of Meerwein’s reaction of diazonium salts with alkenes
in Part 2 of the work. On the other hand the work does not
give an up-to-date procedure for preparing solutions of
chloramine; the conventional procedure giving a yield of
30-40% (reproduced here on p. 250) can be improved to
give reproducibly more than 90 ‘YOsimply by adding ammo-
nium chloride ( Z . Anorg. Allg. Chem. 396 (1973) 178).
In the chapter on hydrazines it would have been useful in
a number of cases to indicate how precursors that are not
altogether commonplace can be prepared, for example, when
describing the reduction of alkoxy(alky1)diazene-N-oxides
(p. 463). The usefulness of the method for preparing 1,2-di-
ethylhydrazine by reduction of the azo compound (p. 523)
could be better appreciated if one knew whether it was pos-
sible to make the azo compound by some route other than
the reverse of the reaction described, i.e. by oxidation of di-
ethylhydrazine. The interesting synthesis of arylhydrazines
by acid hydrolysis of arylsydnones cannot give acetic acid as
the secondary cleavage product, as is shown in the formula
on page 793. Also, the preparation of methylhydrazine from
methylamine (p. 426) should not be described as an oxida-
tion.
In Part 2 the long chapter on N-halogenated amines possi-
bly puts too much emphasis on the preparation of pure com-
pounds; it is more important to have straightforward meth-
ods for preparing well-defined solutions for use in further
reactions. This chapter is followed by the subject of C-nitro-
so compounds, which obviously has a great many subdivi-
sions and requires no less than 129 headings in 47 pages of
text. In the description of the nitrosation of arenes it would
have been desirable to show a clear division between those
nitrosation reactions that are useful for synthetic purposes
(e.g. those of phenols) and the nitrosations of simple arenes
such as benzene that have also been investigated. The chap-
ter by J. Goerdeler on ammonium compounds is excellent;
this describes the quaternization of amines of increasing in-
ertness on reaction with alkylating agents of increasing reac-
tivity. A separate chapter is devoted to the hydrazinium
compounds, which have only attained importance in recent
years. This is followed by the classical diazonium com-
pounds; as these have had a career of more than a hundred
years their preparation occupies less space (35 pp.) than their
reactions (49 pp.). Next come chapters on a few special
classes of compounds such as nitrosamines, triazenes and
tetrazenes; the work ends with a chapter on azides.
Finally a few errors and incorrect usages need to be men-
tioned. On page 462 the statement that the pressure falls from
73 694 torr to 60 765 torr is hardly in accord with the preci-
sion of typical pressure measurements in the preparative lab-
oratory. Quoted values such as 101.87 kPa (p. 878) probably
0570-0833~9iIllil-~524$3.50+.2S/0Angew. Chem. Inr. Ed. Engl. 30 (1991) No. i l