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Book Review KirkOthmer Encyclopedia of Chemical Technology. Vol. 1 A to Alkaloids. Vol. 2 Alkanolamines to Antibiotics (Glycopeptides). 4th Edition. (Series editor J. J. Kroschwik.) Edited by M. Howe-Grant

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[l I] In addition to the values of E, and A E listed in Table 1 for 1 and its monoand disubstituted derivatives the following quantities (in kcalmol- ‘) were
obtained (at MP4/6-311g(2d,p)jjMP2/6-31g(d) level): I 31.7 (a,), -27.3
(A€); N-1 26.2. 55.5; 1,3-N2-1 29.1, 90.0; P-1 9.3, - 3.2; 1,3-P2-1
- 17.3.
18.3 1.2.3-N3-1-135.3 ( A E ) ; N,-1 -188.5; 1,2,3-P3-I-29.4; P,-1
- 39.5. These values are in good accord with the results of the more
involved MCSCF calculations (see Table 1). The calculations were conducted with the GAUSSIAN 90 set of programs (M. J. Frisch, M. HeadGordon, G. W. Trucks, J. B. Foresman, H. B. Schlegel, K. Raghavachari,
M. A. Robb, J. S. Binkley, C. Gonzaler, D. J. Defrees, F. J. Fox, R. A.
Whiteside, R . Seeger, C. F. Melius. J. Baker, R. L. Martin, L. R. Kahn,
J. J. P Stewart. S. Topiol, J. A. Pople, Gaussian Inc., Pittsburgh, PA,
1990).
~
~
~
[12] We have computed the IR spectra of 1 and its mono- and disubstituted
derivatives, as they have the best prospects for experimental verification.
The vibrational analyses were performed within the harmonic approximation at MP2/6-31G* level. Details of the computed spectra are available on
request and we will comment on them only briefly here. For example. an
inversion center in 1 and its 1.3-heteroderivatives simplifies the expected
IR spectra. For 1 seven IR-active bands [12a] and for 1,3-P2-1six 1R-active
bands [12b] are predicted. For P-l the situation is more complicated since
it has no inversion center. Here all 15 vibrations are IR-active. a) For 1
these values are in excellent agreement with experiment [I] (values in
cm-’): 559 ( b 3 J , 750 ( b 2 J ,1081 (blu), 1293 ( b 2 J ,1619 ( b , ” ) ,3281 (b2”),
3300 (/I,“). b)For 1,3-P2-1(values in cm- I): 275 (u,), 581 ( b J . 672 (UJ. 946
( b J , 1168 (bJ, 3267 (bJ.
BOOKS
Book Reviews
Kirk/Othmer Encyclopedia of Chemical Technology. Vol. 1 :
A to Alkaloids. Vol. 2: Alkanolamines to Antibiotics (Glycopeptides). 4th Edition. (Series editor: J. J. Kroschwik.)
Edited by M . Howe-Grant. Wiley, Chichester. Vol. 1 :
1991. XXII, 1087 pp., hardcover E 135.00.--ISBN 0-47152669-X; Vol. 2: 1992. XXVIII, 1018 pp., hardcover
,f 135.00.--ISBN 0-471-52670-3
In September 1991 a new edition of “Kirk/Othmer” started to appear from the publishers John Wiley and Sons. The
fourth edition of this standard Encyclopedia of Chemical
Technology will consist of 27 volumes (25 on topics in alphabetical order, together with a supplementary volume and a
keyword index), which is one more than in the third edition.
Up to now Volumes 1 and 2 have appeared. The rest are to
follow at three-monthly intervals, so that the entire work
should be completed by the end of 1998.
Volume 1 (33 articles) extends from “Ablative Materials”
to “Alkaloids”, and Volume 2 (27 articles) from “Alkanolamines” to “Antibiotics”. Scanning through the articles
it is evident that the new Kirk/Othmer continues the excellent tradition of earlier editions. The contributions have
again been written by acknowledged experts, and despite this
(or perhaps because of it) they can be understood even by the
interested non-specialist. The literature citations are carefully chosen and very up-to-date; some of the articles even cite
sources as recent as 1991.
Angen. Chem. Inr. Ed. Engi. 1993. 32. N o 4
8 VCH
The choice of topics reflects recent progress in science and
technology. For example, separate articles are now dedicated to key technologies such as “Advanced Ceramics” (for
electronic and engineering components), to developing fields
with high growth potential such as “Antiaging Agents”, and
to technologies that have increased in importance such as
“Aeration” (in biotechnology and effluent treatment). On
the other hand product areas that have stagnated or become
less important (e.g., acetylene, anthraquinone derivatives)
have now been relegated to subsections. Other articles have
been revised and updated. A high standard of treatment has
been maintained throughout. This applies not only to bulk
commodity products but also to products in the middle or at
the end of the value-added chain. Thus, on the one hand new
developments in large-scale processes such as the production
of cyclohexanol by addition of water to cyclohexene, or of
adipic acid from butadiene as a cheap feedstock, and on the
other hand advances in specialized areas, for example the
synthesis of special amines such as tevt-butylamine, where
the Ritter reaction is being replaced by the more environmentally acceptable direct catalytic amination of isobutene,
are treated with equal thoroughness.
The articles that are concerned not with products but with
basic science (e.g., absorption and adsorption), with working
techniques (e.g., analytical methods), or with environmental
topics (e.g., atmospheric pollution) also reflect the latest
knowledge. For example, in the article on “Air Pollution”
we find not only data from measurements in 1990 and values
for the ozone-depleting potential and greenhouse-effect potential of important atmospheric pollutants, but also an informative section on “Indoor Air Pollution”, which puts this
topic into perspective without playing down the risks.
Whereas in “Ullmann” the topics of a more fundamental
nature are treated in a separate series, in the new Kirk/Othmer these are integrated into the main volumes.
Unlike previous editions this new edition consistently
uses SI units in the tables and figures (although in the text the
American units are occasionally added in parentheses-not
surprisingly, some conversion errors have crept in here, but
on the whole these are comparatively rare).
Some of the articles contain many abbreviations, which
can be rather troublesome. Headings such as “UOP MRUORU Processes” (Vol. 1, p. 593) convey hardly anything to
the reader who wants to find information quickly. On encountering a sentence such as “The related simple design
concepts of WES, WUB, and LUB for constant-pattern adsorption are discussed later” (VoI. 1, p. 540, “Adsorption
Dynamics”), the reader who is new to the subject but wants
to find out more will be deterred rather than encouraged to
read on, especially as the meaning of WES, WUB, and LUB
can only be discovered by first turning back to page 51 7 (for
Verlugsgesellschaft mbH, W-6940 Weinheim. 1993
0570-0X33/93/0404-0~19
$ 10.00+ .25/0
619
LUB) then further on (!) to page 564 (for WES and WUB).
On the other hand, in cases where abbreviations are listed at
the end of an article, when one no longer needs them, it is
simply a waste of space (e.g., “IARC”, Vol. 1, p. 310, and
“ADI”, Vol. 2, p. 578.
In the articles concerned with products one finds that the
information given in the section “Economic Aspects” in
each case varies greatly in the amount of detail and sometimes in quality. For example, under “Ammonia”, “Adipic
Acid”, and “Acrylonitrile” one finds a considerable amount
of information about production capacities, consumption,
and market growth, not only for the USA but also for Europe and Asia. In contrast, under “Anthraquinones” (Vol. 2,
p. 81 1 ) the section “Economic Aspects” gives only one quantitative item, the price. Under “Alkyl Phenols” (Vol. 2,
p. 128) the “Economic Aspects” amount to no more than a
breakdown of the production costs, and under “Amino
Resins and Plastics” (Vol. 2, p. 635) they consist essentially
of a list of manufacturers occupying nearly half a page. Here
the work could certainly have been improved by some systematization and unification of treatment, like that found in
the corresponding sections of “Ullmann”.
However, despite the few shortcomings the new Kirk/Othmer, like its predecessors, is a work of reference in the top
rank worldwide, and it is essential to every scientific and
technical library as a complementary work to “Ullmann”.
Friedbert Nees
BASF Aktiengesellschaft
Ludwigshafen (FRG)
Computational Chemistry. Structure, Interactions and Reactivity. (Series: Studies in Physical and Theoretical Chemistry.) Edited by S. Fvaga. Elsevier, Amsterdam, 1992.
Part A : XXXII, 744 pp., Part B: XIX, 661 pp., hardcover
HF1995.00.-ISBN 0-444-88512-9
This two-volume work of altogether more than 1400 pages
is the result of the efforts of 111 authors. More than half of
these are Spanish; moreover, the make-up of nationalities in
the rest is significant, as it is dominated by countries such as
Argentina, Cuba, and Mexico. Thus the work is in effect a
literary demonstration by the Hispanic countries. The editor
has exercised little, if any, control over the authors, and has
also succumbed to the temptation of assuming that one can
never have too much content and variety. It therefore comes
as no surprise to find that the majority of the 52 chapters
have turned out to be neither “computational” nor “chemistry”. It is not possible here, nor even necessary, to describe
in detail and evaluate all the chapters. Instead this review will
offer some general comments on the contributions, will identify those chapters that are in the nature of a general
overview of a particular topic, and will discuss the extent to
which they present results relating to theories that are
described.
Unfortunately a good many of the authors seem unable
(or unwilling) to present review articles of general interest
such as one expects to find in a book of this kind. These
authors assume that their own work and very individual
views will be of interest to the reader, and they give numerous references to their own publications. For example, in the
report on excited states of simple molecules it is not clear
why one should want to systematically calculate the excited
states of molecules with two, three, and four atoms. Who is
interested in this apart from the author? What is sadly missing here is a review of the current situation in theoretical
620
$3 VCH ~~rlujisjiesells~huf~
n7hH. W-6940 Weinhc,.rm,1993
photochemistry. Another example is the article on configurational interaction, which is in fact very well written, but
leaves one at the end wondering what it all adds up to. What
are the capabilities and limitations of the computational
methods described? To discuss such methods without including the sets of basis functions is like having a vessel without
a bottom. Moreover, the article fails to give any experimental results, and without these one cannot evaluate the theories. ?‘he authors of a chapter on basis sets have even managed to discuss the topic entirely in verbal terms, giving
neither basis sets nor any results derived from them. One also
feels regret for what is missing in the chapter on molecular
integrals based on Slater functions, in which the final climax
is a closely printed list of pointless integral formulas. A chapter entitled “Geometries, Energies and Molecular Properties” includes, in addition to the properties mentioned here,
calculations of dipole and quadrupole moments, field gradients, and electron densities for many molecules such as W,O,
NH,, CH,, C,H,, etc., with six basis sets in each case. However, the 19 enormous tables amount to nothing more than
a large occupational therapy exercise, as the discussion of the
basis set dependence at the Hartree-Fock level, without taking into account electron correlations, has long since ceased
to be of interest to anyone. Regrettably, this antiquated article is not an isolated example; to conclude these adverse
comments the prize for this must go to Cuba for the contribution on “Approximate Methods for Polyatomic Systems”,
in which a whole group of authors introduces the reader to
the basic equations of the elementary Hartree-Fock theory
and to the NDO approximation-and this in 1992!
The transition from the barren wastes to the more worthwhile contributions is smooth. A chapter on photoelectron
spectroscopy contains not only an up-to-date account of the
theory but also many examples, in which different methods
of calculation are compared with each other and with experimental results. The literature on this topic is extensively
reviewed. In this respect one should also mention the article
by Moccia which is an introduction to calculations on multiphoton processes, including a detailed account of the theory
and of methods of calculation together with results. Leaving
the area of spectroscopy the reader’s attention may be
caught, for example, by a chapter on solvent effects in reacting systems. The theories of the self-consistent reaction field
are clearly described, but unfortunately their applications
are only indicated sketchily. This situation could quickly
change, as these methods are already included in the latest
versions of readily available program packages. The reader
concerned with applications will also certainly appreciate the
analysis of the concepts of basicity and acidity using reliable
ab-initio calculations. This excellent article is hidden away
under the rather uninformative title “Organic Molecules”.
The chapter by Smeyers on “Non-Rigid Molecules” meets
the criteria for a good and easily understandable review article. The applications described are mainly to calculations
on IR spectra of systems with internal rotation. The contribution by Strausz et al. on the Wolff rearrangement of r-diazoketones is worth mentioning as a classic example of the
application of modern ah-initio methods of calculation to a
chemical problem. Ventura gives an excellent review of
chemical reactivity. with a pithy discussion in which formulas are kept to a minimum; the aspects covered range from
the energy hypersurface through modern quantum chemical
methods of calculation to reaction dynamics, concluding
with kinetics and thermodynamics. The concise style continues in the section on applications, without leaving out any of
the essentials. The examples chosen range from gas phase
reactions to enzyme reactions. This very informative review,
0~7(1-0833~93/0404-11620
S 10.00 + . 3 l U
Anjitw. Clrern. In!. Ed. EnjiI. 1993, 32. No. 4
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