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Book Review Analytical Chemistry of Ruthenium. By T. D. Avtokratova

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ids, cardenolides, or bufadienolides, and n o natural bile
acid is included. Even the choice of chromophoric systems is
not as complete as is to be expected in a book with claims of
this sort [there is, for instance, no 15-ketone or 9(11)-ene-12one]. However, for the types that are described (170 in the
infrared and 101 in the ultraviolet section) there are extensive
data concerning band assignments and, above all, the small
but significant shifts dueto additional substituents;itisjust such
data which are of particular value in structure determination.
For the ultraviolet spectra half-widths are given in each case
in addition to E; these are particularly important for narrow
bands; unfortunately there is no indication that both E and
the half-width are dependent on slit width, though their
product is almost independent thereof.
The N M R spectra were measured on a 40 Mc instrument
and thus d o not show the quality that one has become accustomed to in recent years. Thus the tables contain only the
chemical shifts, and spin-spin splitting is hardly ever described. On the other hand, the very valuable section on dipole
moments of steroids is rich in tables and practical instructions. In cases where several polar groups are present the experimental dipole moment is always compared with the calculated value and a n estimate of the conformation is attempted; for conjugated 3-ketones this is, however, discussed only
for the twist form and for one of the two possible half-chair
forms of ring A. Collection of data of this sort is a novelty in
the steroid field and will induce many to carry out dipolemoment measurements.
Each chapter has a theoretical introduction on techniques;
but these introductions often leave much to be desired. For
instance, configuration is often confused with conformation,
and in the correlation table for infrared bands, which is very
clear in other respects, the chromophores are denoted only
by numbers. In the ultraviolet section it is noted that polar
solvents usually cause a bathochromic shift of the bands, but
without indicating that just the opposite is true for n-n*
bands. Remarkably, Woadward’s rules for dienes and unsaturated ketones are mentioned only in one short sentence,
and are there erroneously assigned to the longest-wavelength
ultraviolet bands whereas for enones they are valid only for
the short-wavelength K bands. In the N M R section, which was
originally written in English, there are uncorrect translations (“integral” values instead of “ganzzahlig”, “Feldkonstanz of 10-8 gauss” instead of “Homogenitat of 1 : lo*”,
etc.), and it is claimed, for instance, that a keto group does
not influence the position of the signal of a neighbouring CH2
group except with 11-ketones. The region given for the 12methylene signal of the latter is in general not the correct one
- it is correct only for compounds having an oxygen-rich side
chain. The existence of long-distance couplings for a-bonds
is denied, and there is no reference to Shoolery’s rule or the
Karplus equation, to Ziircher’s tables of the positions of
methyl signals, or the types of spin-spin splitting.
The relation between specific rotation and configuration is
regarded as too complex; yet, on the basis of Klyne’s and
Barton’s work (not Djerassi’s, as stated), many configuraiotns
can be determined by the method of molecular rotation differences (which, like the concept of molecular rotation, is not
mentioned). It is unusual that hardly any literature is cited
- neither review, nor handbook, nor original paper. Therefore it is very difficult for the user of the atlas to compare its
data with those from other laboratories.
If these and other drawbacks could have been avoided, this
atlas would have served also as a very good introduction into
methods of instrumental analysis. The criticisms of the textual material should not, however, be held to diminish the
great value that steroid chemists will find in the tables, which
have been constructed with great care from extensive factual
material, and in the rules deduced therefrom. Production of
the book and reproduction of the illustrations are excellent,
which indeed should be expected in view of the price, which
unfortunately will be a severe hindrance to wide distribution.
G . Snatzke
[NB 453/306 IE]
686
Chemische Veranderungen von Stoffen durch energiereiche
Strahlung. (Chemical Changes of Materials by EnergyRich Radiation). By E. Rexer and L. Wuckel. VEB Deutscher Verlan fur Grundstoffindustrie. Leipzig 1965. 1st
Edit., 275 pp., 74 figs., 78 tables, bound. MDN 32.(ca. $ 8.00).
This book about radiation chemistry has the usual weakness
of most of its predecessors in that, while it reviews a mass of
material about the behavior of substances under the influence of ionizing radiation, it usually leaves open the
question “Why?” This question is not answered by the
many reaction sequences, whose necessity is not evident to
the reader because details of experimental methods and
methods of investigation are missing. The treatment covers
gases, water, aqueous solutions, organic compounds, and
polymers.
The introduction into the fundamentals of radiation chemistry is truly unfortunate. Kinetics, mass spectrometry, electron
spin resonance, excited molecules, and the like are mentioned
only incidentally. This part, written in phraseology that is
often imprecise, contains also notable omissions and errors,
e.g.: 1 curie is seen as the activity of 1 g of Ra in equilibirum
with its decomposition products (p.33 , the output of a
cobalt source is wrongly calculated since the fact that each
6OCo atom emits two y-quabta is neglected (p. 36), data
about mass absorption coefficients would be useful (p. 40),
figure 3.2 contains an unexplained parameter (p. 49), the
colour of F centers
a function of the lattice constants and
not the same as the absorption of the free metal atoms
(p. 67), and the names of Franck and Rahinowitch d o not
appear in the discussion of the cage effect (p. 125). The
description of radiation damage to solid bodies seems to
have been derived from the secondary literature and is
superfluous since crystalline inorganic and organic materials
are not treated in the main section; here the omissions
abound: for instance, only the least probable of the disoider
models, that of Brinkman, is described; the problematics of
disorder are not discussed at all (p. 79).
The book cannot serve as an introduction to radiation
chemistry, and citation of the literature is, of course, incomplete. The production is satisfactory.
Horst Miiller
[NB 4801334 IE]
Analytical Chemistry of Ruthenium. By T. D . Avtokratova.
Series: “Analytical Chemistry of Elements”. Academy of
Sciences of the U.S.S.R., Moscow 1962. English translation: lsrael Program for Scientific Translations, Jerusalem 1963. 224 pp., 36 figs., 54 tables, 13 analytical schemes,
$ 14.00
This book is the first of the translations of a series of new
Russian monographs. The occurrence, properties, and use
of ruthenium and its compounds are reported in an introductory chapter (use as pen points is omitted). Chapter 2 treats
qualitative detection (20 pages). Here the expert will be
especially pleased with the tables of color reactions with
organic reagents that include the limits of detection, and the
table of qualitative microreactions where those for the
other five platinum metals are also listed In chapter 3 methods of determining ruthenium are described, arranged as
gravimetry, titrimetric analysis, potentiometry, and spectrophotometry. Electrochemical methods including polarography, ultraviolet, and X-ray spectral analysis, as well as
radiochemical methods, complete a rich section.
Chapter 4 contains methods of separation, much space being
devoted to methods involving distillation of the tetroxide.
The determination of ruthenium in raw materials, concentrates, osmiridium, slurries, slags, etc., is described in
chapter 5; the text is completed by 13 schemes for separation.
An appendix treats ruthenium fluoride and the preparation
of some ruthenium compounds.
Citation of the literature, with 784 references, appears
complete up to 1960. In some cases the evaluation could
Angew. Chern. internat. Edit. 1 Vol. 5 (1966)
1 No. 7
have been more critical. In addition to the analytical methods,
this book contains much non-analytical information about
the chemistry of ruthenium. The subject index is too short
and makes reference to a n individual item difficult. Those
interested in platinum and nuclear chemistry will welcome
H.-L. Grirhe [NB 476aj329 IE]
this monograph.
Analytical Chemistry of Molybdenum. By A . I. Busev. Series:
“Analytical Chemistry of Elements”. Academy of Sciences
of the U.S.S.R., Moscow 1962. English translation: Tsrael
Proqram for Scientific Translations, Jerusalem 1964. 1st
Edit., vi + 247 pp., numerous ngs., J 15.25.
This book forms part of a series of about SO volumes being
published under the title “Analytical Chemistry of Elements”
by the Institute of Geochemistry and Analytical Chemistry
of the Academy of Sciences, Moscow. The volumes all
follow the same design in respect of content and presentation.
The present monograph begins with a discussion of the
properties of molybdenum and its compounds, and continues with a description of the chemical reactions that are
of importance for analysis of the metal. Physical, physicochemical, and chemical methods of analysis, and their use
for determination of molybdenum in ores, semi-finished
materials, and end products (metal, oxides, salts, and compounds), are treated in detail.
The presentation is particularly valuable because the practical
importance of individual methods is indicated, which
prevents the book from being a n uncritical collection. The
analyst will be able to obtain much useful information.
H. Braun [NB 476bj330 IE]
High Resolution Spectra of Inorganic and Related Compounds.
Inorganic Spectra with Indexes and Binders. Published
by Sadtler Research Lab., Inc., PhiladelphiaiPa. 1965.
1st Edit., $160.00.
A card index of vibration spectra of “inorganic” compounds
fills a gap in present documentation and can be expected to
arouse the critical interest of chemists working in this field.
The first part of the collection, for which yearly supplements
are foreseen as for the older “organic” series, is now available
either as single sheets (format 2 1 . 5 ~ 2 8cmz), printed on one
side and contained in two strong ring binders, or as 16 mm
microfilm. An edition o n punched cards, which would have
many advantages, is, however, not announced.
The 600 infrared spectra illustrated include coordination
compounds such as K3[Fe(CN)6], (NH&[PtC14], and
[Ni(NH&]CIz, as well as classical inorganic compounds
such as LiF, NH4N03, AlC13, SiOz, P4S1o. CdC03, and
PbCr04. Their choice and arrangement is apparently according to receipt and origin of the material. This has the
consequence that many classes of compounds such as halogens, boron hydrides, and simple metal(0) complexes are
not considered here at all, whereas on the other hand spectra
are given for borates (MB03) of indium, scandium, yttrium,
and lanthanum and for 20 complexes of 2,4-pentanedione.
The purity of the substances is described summarily as
> 98 %.
The compounds characterized by vibration spectra in these
two volumes are recorded together in three indexes, placed
at the beginning: a n alphabetical index ,‘a molecular formula
index, and - unnecessarily in view of the lack of order in the
arrangement - according to the spectrum number. Issue of
an index arranged according to functional groups is planned.
The vibration spectra were measured using capillary films,
discs, and/or NujoljHostaflon suspensions between 4000
and 200 cm-1 (2.5 to SO I*) with a grating spectrograph and
are reproduced linear in wave number. Thus a high degree
of accuracy is obtained for the short-wave region which,
however, is in many cases free from lines for inorganic
Angew. Chem. internat. Edit.
Yol. 5 (1966) 1 No. 7
compounds that contain no water of crystallization. Wave
numbers of maxima and assignments of significant bands
are not indicated.
The sheets contain the vibration spectrum (format 8x 25 cmz),
the firm’s imprint (format 2x13 cm*), and the spectrum
number, then the name, composition, formula weight, and
sometimes a schematic structural formula of the substance,
the origin cf the sample, and the method of measurement.
Physical data such as melting point, boiling point, refractive
index, and density are given incompletely or not at all;
criteria of purity and literature references are totally lacking.
As to detail, a very heterogeneous picture is presented by
different sizes and kind of type, even sometimes handwriting,
in different positions on the individual sheets. Like other
alums (e.g. Y 51 S and Y 73 S), sodium aluminum sulfate
dodecahydrate (Y 173 S ) has the simple formula weight, as
given correctly in the molecular formula index. On the
other hand, the molecular formula index does not include
the water of crystallization of ammonium cobalt hexahydrate
that is given o n the spectral sheet Y 208 S. It is proved that
in nickel bis(biacety1 dioxime) (Y 266 S) coordination is to
the nitrogen atoms and not to oxygen. In the reviewer’s copy
spectrum Y 370 S is missing.
In conclusion it must be stated that the present collection
does close the documentation gap mentioned above but that
many improvements could be effected. Its utility would in
particular be raised by classification of the spectra, by a
wider choice of substances, and, in view of the blank reverse
pages, by the additions mentioned above.
H. Bock
[NB 481/335 IE]
Biology Data Book. Edited by P . L. Altman and D . S. Dittmer.
Federation of American Societies for Experimental Biology,
Washington, D.C., 1964.2nd Edit., 633 pp., numerous figs.,
$ lo.--.
In this book are collected data of particular concern to biologists. He who is interested in the pulse frequency of the bat,
the expectation of life of the crocodile, or the number of eggs
in herring roe, or who is looking for an authoritative comparison of the most poisonous snakes, the highest trees, or the
fastest spread of organisms, can occupy himself contentedly
with this book for many hours and find in the process a host
of the most interesting facts fr?m toxicology, ecology, and the
inexhaustible reservoir of the biological collector’s treasure.
Here are presented to the biochemist most valuable data about
the foods essential for every species and genus, about hormones, antibiotics, and antimetabolites, about enzymes and
their properties. All in all, however, this industrious book is
biological. Even the chapter headings will show, that
unless he has wide-ranging biological interests, the chemist
will find more satisfaction for his lexical curiosity than directly useful information.
The 155 tables concern the following physiological areas:
genetics, cytology, reproduction, development, and morphogenesis; food, nutrition, and metabolism; breathing, life cyle,
and blood; biological control, habitat, and adaptation. They
are all compiled from the original papers by experts in the
field, and contain very exhaustive references. However, as
these references disclose, there has been little culling from the
most modern literature, for the book is described as an abbreviated and improved version of the “Handbook of Biological Data” of 1956. It is questionable whether the citation
of sources, obviously wanted by many readers, need have
been quite so extensive. The scholastic was given a scientific
alibi by quotation of older authorities. In such quotations the
compilers are, however, too easily satisfied by a complicated
chemical word - they d o not explain it. For instance, among
the physical properties of compounds there are none of the
more modern characteristics, for the hexoses and pentoses no
strucural formulae, for acids and bases no p K values (there
are a few of these, but in reference to buffers).
687
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