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Book Review Statistical Mechanics of the Liquid Surface. By C. A. Croxton

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[ I ] T h i s problem was a major topic of discussion at three international conferences
(Reading 1973. Oxford 1976, Ann Arbor 1979) on “The Chemistry and Uses of
Molybdenum”: cf. also [Z].
[2] a) G. P. Haight. D. R . Bosfon in P. C. H. Mitchell: Proceedings of the First International Conference on the Chemistry and Uses of Molybdenum, Climax Molybdenum Company, London 1973, p. 48; b) M. Ardon. A. Pernick in P. C. H.
Mirchell. A . Seaman: Proceedings of the Second International Conference on
the Chemistry and Uses of Molybdenum, Climax Molybdenum Company, London 1976, p. 206; J. Less-Common Met. 54, 233 (1977); c) E. I . Slfefei. Prog.
Inorg. Chem. 22, 1 (1977); d) M. Lamache. J. Less-Common Met. 39, 179
(1975); e) F. A . Coflon, G. Wrlkinsonr Advanced Inorganic Chemistry. 4th Ed.,
Wiley-Interscience, New York 1980; A . Bino. F. A . Cotton. 2. Dori. J. Am.
Chem. SOC. 100, 5252 (1978).
131 Th. Ramasami, R. S. Taylor. A . G. Sykes. J. Am. Chem. SOC.97,5918 (1975); M.
Ardon. A. Bino, G. Yahoo. ibid. 98, 2338 (1976).
141 M.Ardon. A. Pernick, J. Am. Chem. SOC.95,6871 (1973).
I51 S. P. Cramer, H. B. Gray. 2. Dori. A. Bino. J. Am. Chem. SOC. 101, 2770
161 A. M d l e r . R. Josles. F A. Cotlon. Angew. Chem. 92,921 (1980); Angew. Chem.
Int. Ed. Engl. 19, 875 (1980).
I71 Space group P 2 J c ; Z = 4 ; a = 13.662(2), b=8.193(1), c= 15.355(2), +94.21( I)’;
3615 observed reflections (Syntex PZ,); R=0.037.
(81 R . Manes, K. Mennemann. 2. Anorg. Allg. Chem. 437, 175 (1977).
191 Note added upon supplementation: Recently published results on isotopic exon Mo‘”-containing solutions, which contain
change reactions (‘‘0/‘’0)
NCS -,also point to a trinuclear species; R. K. Murmann, M. E. Sheiton. J. Am.
Chem. SOC. 102, 3984 (1980).
Comprehensive Biochemistry. Edited by M . Florkin (deceased), A . Neuberger and L. L. M . van Deenen. Vol. 19,
Part B 1 : Protein Metabolism. Elsevier Publishing Company, Amsterdam 1980. xx, 528 pages, 64 figs., bound,
Dfl. 168.00.
This volume of “Comprehensive Biochemistry”“’ begins
with a disarming declaration: “The Editors were faced
with alternative possibilities: one either tried to deal with
the major topic in a comprehensive manner, but this would
have meant almost unavoidably a degree of superficiality
which was unacceptable.. .”. They therefore decided to
give progress reports on somewhat randomly chosen but
particularly topical areas of protein metabolism.
I n their chapter, V . M . Pain and M . J . Clernens manage
to summarize the present knowledge of the many components that take part in the protein synthesis machinery of
the eukaryotic cell, to describe the mechanisms of their interactions, and to give the most important aspects of the
regulation of translation. With the inclusion of more than
500 references u p to 1979 and building-on on a corresponding chapter in Volume 24 (1977), this has obviously
succeeded well. Just how long this information will remain
new in the rapidly evolving field is a question that occurs
time and again when using the whole work, which is evidently considered to be a long-term investment.
The sections by P. J. Garlick and D . J. Millward are devoted to the turnover of plasma proteins and enzymes in
the flowing equilibrium of continuous synthesis and degradation in various tissues and in the whole organism.
The first of these authors concentrated more on the regulation of the rates of these reactions in vivo and on the contribution this makes to the total nitrogen balance of an animal, the second on the various courses of degradation in
the muscles and liver. In these painstaking and well coordinated articles, too, more than 500 publications have been
worked into a clearly arranged and readable general presentation.
Protein metabolism and protein structure are closely entwined subjects. A . J . Bailey and D . J . Etherington were
evidently of the opinion that our knowledge of general
structural chemistry and of the metabolism of collagen and
elastin has now reached such a state that it deserved a really detailed presentation, and convinced the sympathetic
editors to allocate to them almost one-third of the book for
I*] Cf. Angew. Chem.
Int. Ed. Engl. 17, 873 (1978)
a thorough review. In spite of dealing with more than 800
references, they still regard this review as not exhaustive.
The main emphasis is placed on connective tissue biosynthesis during growth and on the mechanisms of degradation, thus providing more than just a basis for this research
field equally important to medicine and the food industry.
K . B. M . Reid offers a stimulating and understandable
resume to the complement system, a proteolytic cascade
system of a special kind. This complex defensive mechanism of higher organisms has many molecular special features, so that this chapter, too, will only be a snapshot from
the year 1979.
With its extensive literature reviews and sensible presentation by the authors, who mostly come from the close circle of one of the editors, this topical book will undoubtedly prove a useful new publication for users in the fields
of chemistry, biochemistry, pharmacology, and medicine.
This major volume supplements a field always deliberately
neglected in the main work, which has thus perhaps not always become “more comprehensible” but certainly “more
comprehensive”, in spite of the editors’ reservations.
L. Jaenicke [NB 540 IE]
Statistical Mechanics of the Liquid Surface. By C. A. Croxton. John Wiley and Sons, Chichester 1980. xi, 345
pages, bound, f 25.00.
Our understanding of the equilibrium properties of
atomic fluids has increased so much in recent years with
the help of statistical mechanics that a transition to complex systems appears to be realistic. The particular questions here are whether the principles of statistical mechanics can also be applied to the inhomogeneous region of the
liquid-gas interface, and if the familiar thermodynamic
concepts such as pressure, density, and chemical potential
can be extended to the phase interface. Since many properties of the liquid surface are excess-quantities, which record the change in the liquid’s properties on transition to
the surface, and consequently require knowledge of the
properties of the liquid, a statistical-mechanical description is difficult. Two quantities characterize the liquid-gaseous region: the density profile, which describes the
change in density perpendicularly to the liquid surface,
going from the density of the liquid to the density of its vapor, and the anisotropic pair distribution function, which
gives the probability of finding a second particle at a defiAngen, Chem. I n / . Ed. EngI
20 I I Y H I ) No. 5
nite distance from a selected reference particle. In contrast
to the liquid-and this is decisive-this pair distribution
function is still dependent on the distance of the selected
particle from the liquid surface.
In the present work, the author-who has already written several books o n the theory of the liquid state-gives
the first resume of the statistical-mechanical theories of the
liquid surface. The relationships between the thermodynamic parameters of the liquid surface, among them surface tension, and the density profile and the anisotropic
pair distribution function are shown very clearly in the
first chapter. Since these functions are necessary for the
determination of thermodynamic quantities, the second
chapter-occupying almost one-fifth of the book-is devoted to the calculation of the density profile and the anisotropic pair distribution function for spherically-symmetric particles. O n the one hand, a quasi-thermodynamic approximation is used, which means that in the transition
zone between the liquid and the vapor the chemical potential and pressure must be constant to ensure thermodynamic and mechanical stability of the liquid surface. O n
the other hand, well-known integral equations from liquidstate theory, e. g . the Born-Green-Yvon equation, are used.
The presentation is in places very compact and presupposes that the reader is well aquainted with the theories of
the liquid state, e. g . with perturbation theory and the associated mathematical formalism, so that original literature
may have to be consulted. However, this is facilitated by
the wealth of literature citations.
The technique described in this chapter is then extended
to liquid surfaces of nonspherical systems. I n systems of
this kind, the density profile is additionally dependent o n
the orientation of the molecules relative to the phase interface, and the resulting expressions are correspondingly
complicated. With the aid of the perturbation theory, in
which anisotropic interaction is interpreted as a perturbation of spherical interaction, relationships are derived for
the surface tension, free energy, etc.; owing to the complexity of the expressions, the author cannot reproduce
each calculation step and must refer to the original literature. The effects of dipole and quadrupole interactions on
the density profile are discussed. In two-component systems the way in which the surface tension and the density
profile depend on the composition of the mixture poses a
new problem. In a n infinitely sharp surface the component
with the lower surface tension accumulates at the interface.
In reality, according to theory, this anomaly is determined
by the mean density of the liquid at the surface, also called
surface adsorption, the density profile and the interaction
between the particles. The way in which such density profiles can be calculated for linear molecules is also discussed in detail in Chapter 4.
Following the general theoretical part, the second part
of the book is devoted to specific systems, and firstly to the
surfaces of liquid metals which are formally two-component systems of mobile cations and conducting electrons.
For the simplest model the density profiles of the cations
and electrons are calculated, from these the surface tension
and surface energy and their temperature variations, and
thus the essential characteristics of the liquid metal surfaces. Detailed refinements of the models are then discussed. A chapter is added on the surface of quantum liquids, whose experimentally determined surface tension
can be interpreted with quantized capillary waves known
as “ripplones” or “surfones”. A formal quantum-mechanical description shows that the surface tension is the excess
quantity of an impulse current. The characteristic feature
Angew. C‘heni In[. Ed. Engl. 20 (1981) No. 5
for water-Chapter 7-is the appearance of surface polarization. This polarization, as well as the surface tension, is
calculated in detail. The result shows that the water molecules on the liquid surface are arranged with the protons
facing outward.
The statistical-mechanical treatment of the conformational change of a polymeric o n transition from bulk liquid
to the surface is still far from being fully developed. The
suppression of one degree of freedom at the phase interface implies a greater spread of the molecule on the surface. The effect o f polymers on surface tension is shown
within the framework of the Prigogine-Marechal theory,
and the distribution of the polymer segments o n the surface is deduced. The book then turns to liquid crystals.
After a brief survey of the theory the excess quantity of
free energy and the corresponding surface tension are calculated for perpendicular and parallel orientations of the
As practically no experimental work has been done on
the determination of the density profile, computer simulation has a special relevance as a test for statistical-mechanical theories. Accordingly, in the penultimate chapter the
techniques needed for the simulation of an inhomogeneous region are compared with those for the simulation of
homogeneous liquids, and the results are discussed. The
rapid development in the statistical mechanics of liquid
surfaces is illustrated in the final chapter.
To summarize, the book gives a very clear presentation
of the statistical-mechanical theory of the liquid surface. It
contains many derivations and can therefore be used as an
introduction to this field, assuming that the reader is familiar with the principles of statistical mechanics and with the
theory of the liquid state. It gives an excellent review of the
present state of the research and thus greatly facilitates access to the original literature. Unconditionally recommended.
Helmut BertagnoNi [NB 538 IE]
Personal Computers in Chemistry. Edited by P. Lykos. John
Wiley & Sons, Chichester 1981. xi, 262 pp., bound, L
14.57.- ISBN 0-471-08508- 1
Drug Design. Vol. 10. Medicinal Chemistry. Edited by E. J .
Ariens. Academic Press, New York 1980. xi, 432 pp.,
bound, $ 49.50.--ISBN 0-12-060310-1
Analytical Chemistry. Vol. 2. Basic Analytical Chemistry.
By L. Pataki and E. Zapp. Pergamon Press, New York
1980. xiii, 463 pp., bound, $ 55.00.--ISBN 0-08-0238505
Alternative Energy Sources. Part A and B. By J. T. Manussah. Academic Press, New York 1981. xi, 922 pp.,
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Chromatographic Methods. Recent Advances in Capillary
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and R. E. Kaiser. Huthig Verlag, Heidelberg 1981. 592
pp., bound, DM 75.00.-ISBN 3-7785-0711-7
General and Synthetic Methods. Vol. 4. Senior Reporter: G.
Puttenden. The Royal Society of Chemistry, London
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Chromatographic Methods. Theory and Mathematics of
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Treatment of Domestic and Industrial Wastewaters in Large
Plants. Proceedings of a conference held in Vienna, Austria, September 1979. Edited by S . H. Jenkins. Pergamon
Press, Oxford 1981. 773 pp., bound, f: 40.00.-ISBN 008-026033-0
Fundamentals of Chemistry. By J. E. Brady and J . R . Holum. John Wiley & Sons, Chichester 1981. xvii, 797 pp.,
bound, E 13.75.--ISBN 0-471-05816-5
Recent Advances in the Chemistry of p-Lactam Antibiotics.
Edited by G . Z. Gregory. The Royal Society of Chemistry, London 1981. ix, 378 pp., bound, E 16.00.-ISBN 085186-815-0
Methoden. Band 1 und 2. By D. Jarsen, W.
Klingelholler, and E. Schonduoe. Edition Cantor, Aulendorf 1981. Vol. 1 : 193 pp.; Vol. 2: 278 pp., bound, together DM 175.00.--ISBN 387-193-059-8
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Trace Element Analytical Chemistry in Medicine and Biology. By P. Bratter and P. Schramel. De Gruyter, Berlin
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Wissenschaftliche Verlagsgesellschaft, Stuttgart 1981.
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Reqsrered iiames. rradetsorks, err used in this jotmial, euen a.~rho~~r
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Angew. Chem. I n t . Ed. Engl 20 (1981) No. 5
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