Reviews of Books Viscosity and Diffusion. A Predictive Treatment. By JOEL. H. HILDEBRAND. (Wiley-Interscience, N.Y., 1977). Pp. xivf109. Price f.7.15/ 9612.00. The sub-title of this book is important. It is certainly not a general review of viscosity and diffusivity, but a predictive treatment based on the author’s own ideas. Strictly, it is not a book at all but a collection of thirteen papers, most written with collaborators, which have appeared in a variety ofjournals from 1971 up to the present time, with a foreword by Joseph Hirschfelder and a vintage preface by Joel Hildebrand himself. The papers are reproduced in their original format and are uncorrected. They show how Hildebrand’s basic ideas on these subjects have evolved as new evidence, much of which has come from his own laboratory, has accumulated.W e are thus allowed to see Hildebrand’s mind at work. One main theme is the evidence for the relationship between the molar volume (V) and the fluidity (+), namely + = B(V/Vo-l), proposed in the first paper. Vo is, by definition, the molar volume at which the fluidity becomes zero, and B is related (paper 3) to energy absorption in collisions involving a transfer of momentum. In metals (paper 11) and in simple liquids like carbon tetra- chloride, Vo is close to the molar volume (V,) of the solid, but in other cases this is not so. Hildebrand has developed simple and convincing physical explanations both for such differences and for failures of the simple fluidity equation near the melting point for liquids with bulky molecules, and also in the critical region where the mode of momentum transfer must change. Papers 3, 6, 10 and 12 show the development of Hildebrand‘s ideas on contributions to the overall viscosity in this critical region in a very interesting way.Diffusion forms another theme. If the diffusion coefficient of a dilute solute in a given solvent is proportional to the solvent fluidity, and if this fluidity obeys the Hildebrand equation given above, then D should vary linearly with temperature and become zero at the temperature when V = VO. Evidence, based mainly on diffusion coefficients of gases in liquids, is produced to show that this is so for some, though not for all (cf. paper 8) liquids, and activation models which require that In D is linear in 1/T are consequently rejected. It must be said that Hildebrand is not alone in rejecting activation models, though it may appear so from these papers.An allied question is the relationship of solute size to diffusion coefficient for a series of solutes in dilute solution in the same solvent at a given temperature. Conventional wisdom, based on the Stokes-Einstein hydrodynamic model, would require the product of D and the molecular radius (Q) to be constant. Hildebrand begins here by suggesting that D V% [that is, essentially (Do2), where V is a corresponding states molar volume for the solute], should be constant. Corrections to this are needed in any case for quantum gases, but paper 8 shows how further evidence caused him to modify his original view. For non- quantum gases, D @, where Vo is derived from fluidity measurements on the liquid solute, is shown to be linearly related to the “ configurational entropy ”, a quantity derived from solubility data and discussed in detail in paper 7.This correlation is a typical example of Hildebrand’s insight into relationships between different phenomena, insight based, as always, on clear and physically sensible principles. The reader seeking a balanced view of viscosity and diffusion will not find it here. Instead he will be stimulated by new ideas and insights on well-worked topics. Like them or not, they cannot be ignored or forgotten, and it is chastening to realise that the principal author of these fascinating papers was publishing important scientific work before most of us were born.He has, indeed, now passed his 95th birthday. This little book does nothing to diminish the author’s great reputation and shows that age has not greatly withered Joel Hildebrand’s capacity to produce new and interesting ideas . H. J. V. TYRRELL Received 5th September, 1977 Characterisation of Metal and Polymer Surfaces. Ed. LIENG-HUANG LEE. (Academic Press, N.Y., 1977). Vol. 1, Metal Surfaces. Pp. xiv+515. Price $26.50/E18.80. ISBN: 0 12 442101 6. Vol. 2, Polymer Surfaces. Pp. xii+465. Price $24.00/E17.50. ISBN: 0 12 442102 4. These two volumes are a collection of papers, plus brief discussions, presented at a Symposium on Advances in Characterisation of Metal and Polymer Surfaces to celebrate the 100th year of the 30273028 REVIEWS OF BOOKS American Chemical Society.If we take it that characterisation of a surface requires that the chemical constitution, atomic architecture and topography, and electronic and vibrational states of the few outermost atomic layers of the solid be known, then volume 1 shows that for metal surfaces a great deal of progress towards this goal has been achieved, while volume 2 shows that for polymers there is still a long way to go. Volume 1, metal surfaces, consists of eighteen papers divided into five parts, preceded by a useful general paper giving the historical background to the main modern experimental techniques of surface science. The first part starts with a first class paper on the use of the field ion microscope as an atom probe; followed by two papers on the application of Mossbauer spectroscopy to surface problems (corrosion and catalysis).Part I1 begins with a most stimulating paper on low energy electrons as a probe of solid surfaces, silicon and aluminium are used to illustrate the various energy loss mechanisms considered. There then follows a brief, but useful, resume of the use and limitations of X-ray fluorescence electron probe microanalysis. There are two further papers, one devoted to a most workman-like review of Auger electron spectroscopy (AES), especially as a tool for determining surface composition; and the other demonstrating the use of AES to the study of the nature of the passive a m formed on nickel and Inconal X-750 (the results, however, do not allow a decision to be made between rival film formation mechanisms).Part I11 consists of four papers on low energy electron diffraction (LEED). The first paper is an introduction to the subject and an up-to-date statement of the " state-of-the-art ". The subsequent papers are all theoretical in nature and address themselves to the pressing problem of surface structure determinations. One is left with the impres- sion that success is very close, but that the cost in computer time may prove, for a while yet, to be somewhat restrictive. Part IV has three contributions on microspot secondary ion mass spectrometry (SIMS) as a surface (and depth) analytical tool. The first paper deals with the fundamentals of the method and gives two interesting examples of its application: namely, the corrosion of steel cables by sea salt and the incorporation of foreign ions during anodic oxidation of InSb surfaces.The next papers using variations of the basic method report on yet other applications to the solution of industrial problems. Finally, part V has a paper on the use of X-ray photoelectron spectroscopy (XPS) to the study of polymer adhesion to metals, the fluoridation of enamel, and chemical changes on the surface of a hydrogenation catalyst. Then follows an extensive review paper on the application of ultraviolet photoelectron spectroscopy (UPS) to the study of chemisorption on metals. Systems such as: benzene and pyridine on MoS2, CO on Ni, Pt and Ir, CzH4 and C2H2 on Ir(100), HZ on W(lOO), 0 2 on Cc-Fe(lOO), are used to illuminate the arguments. A paper on organic reactions at the surface of magnetic pigments using XPS methods follows.The last paper is concerned with molecular spectroscopy by inelastic electron tunnelling. This is really a method for investigating very thin films rather than a surface region. The quality of the papers in this volume is, on average, high and it is gratifying to see that some success is being achieved in the application of surface characterisation methods to industrial problems. Research workers in the field will find this to be a valuable collection. Volume 2, polymer surfaces, has eighteen papers in four parts. Part I has six papers devoted to X P S investigations of a wide variety of polymer systems. The authors, to different degrees, apply themselves to the problem of determining whether the XPS data are typical of the bulk or are special to the surface.Surface oxidation and transfer of material after contact are among other problems considered. The first paper gives a good " front-line " introduction to XPS and polymers. The next paper is concerned with the effect of sputter etching on polymer surface composition, especially as to its usefulness, or otherwise, in obtaining composition versus depth data. There then follow two papers on surface chemical effects on cotton and wool respectively. The flth paper is concerned with using XPS to follow polymer synthesis and polymer modification using RF induced plasmas (argon). This contribution should also be of interest to those engaged in the study of inorganic amorphous solids. The last contribution is about polymer surfaces for biomedical applications.This is undoubtedly an important area in which problems such as the compatibility of a polymer with blood (clotting) are considered: the surface concentration of various functional groups is shown to be important, and amenable to XPS investigation. Part I1 is restricted to infrared (i.r.) and laser Raman spectroscopy, and starts with a review by N. J. Harrick on transmission and reflection i.r. spectroscopy. Particular emphasis is laid upon interpretation of spectra obtained under different experimental conditions. The article is recommended to almost any experimentalist working in the field of i.r. The next contribution is about the use of reflection-absorption i.r. spectroscopy to follow the oxidation of poly (1-butene) on Au and Cu surfaces.The final paper of the section is concerned with the applications of laser Raman spectroscopy to various polymer problems (bulk not surface). The power of the method as a solid state spectroscopy is impressive, but it is not nearly so elegant when applied to surface problems. Part 111 contains five papers on the use of microscopy in the examination of polymers and is about the correlation of large scale structure and various physical properties such as wetability. The final section consists of four papers on,REVIEWS OF BOOKS 3029 respectively, the characterisation of latices, the surface area of latices, the evaporation rates of polymers and finally the radiation (0.3 to 7p) absorption of various polymers. There should be much here for the polymer chemist, but the surface scientist will find that there is more challenge than knowledge when it comes to surface properties.Mmo GREEN Received 9th November, 1977 Ion Exchange and Solvent Extraction: A Series of Advances: Volume 7. Ed. J. A. MARINSKY and Y. MARCUS. (Marcel Dekker, N.Y., 1977). Pp. xvi+294. Price SFr 106. Each volume in this series contains a collection of specialist topics written by acknowledged experts in the particular field. This volume is devoted entirely to solid ion exchange materials and contains five chapters. The fist two chapters deal with the structure and properties of ion exchange materials and in methods of assessing mass transfer rates and performance. An excellent chapter is included on spectroscopic studies of adsorbed species in both inorganic zeolites and organic ion exchange resins.The use of clays and other naturaIly occurring materials in the processing of natural water systems is reviewed in chapter four. Finally, the book contains a lucid account of a novel method of water treatment involving thermal regeneration of organic ion exchange resins. There has been little fundamental treatment of the chemical reaction finetics and mass transfer rates in ion exchange polymers. The presentation of work performed by Gabriella Schmuckler and Shimon Goldstein is therefore timely, since there is currently considerable interest in complex ion exchange reactions, particularly those involving chemical interactions such as chelation. The concept of a shell-progressive mechanism is appealing when one observes specific interactions between ionic complexes and the reactive sites.The theory developed for the electrophilic substitutions carried out on the solid polymer during chemical reaction has here been adapted to encompass other mass transfer situations. The treatment is a valuable addition to our knowledge of ion exchange kinetics. The importance of polymer matrix structure on ion exchange resin performance has long been realised. This is stressed by Davankov, Rogozhin and Tsyurupa in chapter two. It is particularly useful to read of the extensive work performed in the U.S.S.R. The authors have reviewed the field in some detail and have cited 164 references, of which the vast majority originate in the U.S.S.R. Polymer scientists interested in resin synthesis will find this chapter revealing and a valuable precis of a wide and ever developing topic. Carla Heitner-Wirguin is to be congratulated on the chapter entitled " Spectroscopic Studies of Ion Exchangers ".This review mentions the many experimental techniques that have been used, e.g. near infrared, visible and ultraviolet spectra, infrared spectra, Raman spectra as well as n.m.r., e.s.r. and Mossbauer methods. An interpretation of results obtained in zeolites as well as in organic ion exchange resins is shown in detail. Much of the chapter is devoted to the analysis of complex forming species sorbed on cation and anion resins as well as on recently developed chelating resins. The elucidation of the ionic complex structure within the resin phase is at the heart of many theoretical and practical problems in ion exchange and the systematic way in which the topic is treated will undoubtedly codirm this review as a landmark in ion exchans chemistry. Michael Reddy provides a readable account of the ion exchange behaviour of clays and other naturally occurring materials in natural water systems. The theory of selectivity and equilibria is presented and supported with considerable experimental evidence.It is important to appreciate the value of accurate selectivity calculation in low concentration waters. The " Sirotherm " process is already well known and represents one of the major development projects in water treatment to emerge in the last ten years. The entire background to this ingenious process is described by Bolto and Weiss in chapter five.It is a concise account of the theory and operation of the process and will be of interest to all workers in the field of water treatment. This book continues to maintain the very high standard of the entire series. It is an invaluable collection of specialist topics and I can recommend this text to all research workers and practitioners in ion exchange. M. STREAT Received 29th November, 1977 Contact Catalysis. Ed. Z . G. SZANO and D. KALLO. (Elsevier, Amsterdam, Oxford, New York 1976.) Vol. 1, pp. 540. Vol. 2, pp. 480. Price $96.25. These two volumes represent a completely revised edition of the Hungarian Kontakt Katalyizis. Recent results and their applications up to 1970, with additional references up to 1975, are included;3030 REVIEWS OF BOOKS this publication must be regarded as a major contribution on heterogeneous catalysis, being a text for university graduates and also a reference oook for industrial scientists. Most of the authors of this collaborative effort are members of the Hungarian Academy of Sciences and well-known to most workers in this field in Europe and America.Volume 1 provides the theoretical and funda- mental aspects of the solid-state chemistry and physics of bulk metals and semiconductors in a fairly rigorous and mathematical treatment. A chapter on the electronic properties of surfaces, however, might well have been more fully treated since these do represent the most important features in catalytic reactions. The thermodynamics, kinetics and mechanism of adsorption precedes two contributions of con- siderable merit concerned with (i) the structure and activity of metal and semiconductors, including supported and insulator catalysts; and (ii) the kinetics of surface reactions including a section on heat and mass transfer and the design of laboratory reactions.Volume 2 comprises a comprehensive and detailed account of catalyst technology. The pre- paration, modification and classification of catalysts and the technological principles relating to choice, operation and economic aspects are most competently presented. The physical examination by small-angle X-ray scattering, LEED, Auger and electron microscopy is reviewed at length; and measurements of adsorption parameters, the application of infrared and electron paramagnetic spectroscopy are also included.The final part of about 100 pages deals with the practical realization of catalytic processes, including the design of reactors and their optimization. The organization and presentation of material in this volume is excellent; it provides the more academic scientist with a balanced account of the problems and complexity of industrial processes and the technologist with examples of the value and applications of fundamental research in assisting him in unravelling the many factors that contribute to the efficiency of industrial catalytic processes. The price may deter the personal purchase of this set of volumes, but no library catering for scientists engaged in catalytic research should be without a copy. F. C .TOMPKINS Received 13th December, 1977 Microemulsions: Theory and Practice. Ed. L. M. Prince. (Academic Press, N.Y., 1977). Pp. xii+ 179. Price E8 .50/$12.00. Although microemulsions have been used in a wide variety of technologies, ranging from detergency to pharmacy, for several decades, they have only relatively recently been the subject of intensive academic study-largely through the impetus given by tertiary oil recovery research programmes. Some controversy has developed as to the exact thermodynamic description of these systems. The argument has essentially revolved around the question: are microemulsions thermo- dynamically stable or not? This book attempts to set forth clearly the different points of view, and chapters by the main protagonists are included. The book is, however, primarily intended as an introductory text to the subject and to this end it fills a gap in the literature. Numerous articles on microemulsions have appeared in review journals or as chapters in other texts, but this is the first text exclusively devoted to the subject. In the opening chapter the editor discusses the variety of uses to which microemulsions have been put, followed by a somewhat cursory guide to the general techniques used in the field. Topics covered in subsequent chapters include : commercial history, formulation, mixed film theory, micro- emulsions and micellar solutions, microemulsions and tertiary oil recovery. The reviewer found the chapter on formulation by Shinoda and Kunieda particularly worthwhile. In summary this is a very useful, practical book, reasonably priced, which both industrial, as well as academic, practitioners will lind a worthwhile addition to their bookshelves. B. VINCENT Received 20th December, 1977