Reviews of Books Chemical Industries/21. Catalysis and Surface Science. Ed. by H. Heinemann and G. A. Somorjai. (Marcel Dekker, New York, 1985). Pp. xi + 435. Price $90. This is a particularly good book; one that actually exceeds the advertiser’s blurb on the back cover. It is, as they say, a comprehensive survey of industrially important areas of catalysis and is tackled from a multi-disciplinary point of view which will render it almost essential reading to chemical technologists, catalytic scientists and materials scientists. Not only does it cover the technology and science of catalysis, commercial aspects and future commercial trends are also considered. (The book was compiled from the papers presented at the 2nd Berkeley Catalysis and Surface Science Conference held in January 1984 and it is surprising to see how the techno-commercial prognostications of the early 80s have been buffetted by the recent slump in oil prices.) Although the book purports to treat five subjects: Chemicals from Methanol, Hydrotreating of Hydrocarbons, Catalyst Preparation, Monomers and Polymers and Photocatalysis and Photo- voltaics, the main thrust of the book is on the Hydrotreating of Hydrocarbons.Ostensibly this topic is covered in only four articles, but one of the papers on catalyst preparation relates to preparative techniques for the production of hydrotreating catalysts. [In the opinion of this reviewer this latter article was somewhat disappointing since virtually no correlation was obtained between the preparative method used, the nature of the surface of the catalyst so derived, as determined by surface analysis techniques (e.g.XPS, SEM, TEM and EDX), and catalyst activity.] Two particularly good articles relating to the fundamental science of hydrodesulphurization were contributed by Chianelli and by Topsare and Clausen. In these articles the uniquely different line of investigation that the different authors take is reflected in the fact that Chianelli references Topsare’s work only once in his 34 references, while Topsare affords Chianelli the same number in his 64 references. The Technology of Hydrotreating in general is well reviewed by Dautzenberg and De Deken in an article following those of Chianelli and Topsare. The earlier section of the book on Chemicals from Methanol is less profound than the section on Hydrotreating and the article by Wender degenerates almost to a catalogue of what might be possible in the future.The other particularly strong section of the book is on Monomers and Polymers. Articles by Kaeding et af. on Mobil Zeolite Catalysts for Monomers and by Chien on A Fundamental Study of High Activity Catalyst for Olefin Polymerisation are substantial reviews on their respective subjects. These are followed, as in the format in the Hydrotreating section, by an article on Olefin Polymerization Catalysis Technology by Hsieh which is also of a high standard. The book finishes with articles on Hydrogen Evolving Solar Cells by Heller, The Catalysed Photodissociation of Water by Somorjai et af. and again by their possible future technological application in an article by Wald on The Present Status of Industrial Production and Use of Photovoltaic and Photocatalytic Solar Energy Conversion Devices.The interest in the use of solid cells derived from the oil crisis in 1973 and to an extent the commercial considerations which stimulated this research appear somewhat to have been overtaken by time. They are, nevertheless, extremely good articles. Overall, therefore, I would thoroughly recommend this book as being of keen and abiding interest to both industrial and academic scientists. PhD students in chemistry and chemical engineering will also find much of interest in it, but at $90 (€60) a copy, it may well be out of their reach. K. C. Waugh Received 9th September, 1986 Experimental Physical Chemistry.By G. P. Matthews. (Clarendon Press, Oxford, 1985). Pp. xxvii + 495. Price €30. G. P. Matthews has written a highly structured book which appears to be the companion experimental text to the established physical chemistry text by P. W. Atkins. The broad division of physical chemistry into three familiar parts : equilibrium, structure and change precedes subdivision into 8 topic sections and thence to some 59 individual experiments. Of these, 8 are 32233224 Reviews of Books claimed to be original, whilst the remaining 51 have been ‘gleaned’ from contemporary experimental courses in numerous chemistry departments. In this way Dr Matthews approaches the laudable aim of producing a book that relates to current courses in physical chemistry, whilst, at the same time, ensuring the security of future editions.Following a brief introductory paragraph, each experiment is set out under eight uniform sub-headings : theory, apparatus, procedure, calculation, results, comment, technical notes and references. Although the theoretical sections vary in quality, each gives ample background to the experiment so that it can be both tackled and appreciated by students who have yet to cover the topic in lectures. In this respect the book is considerably better than some experimental texts that are available. Suggestions are made concerning the student level to which each experiment is applicable, and in this way the book covers a complete undergraduate course apart from project work. There is no doubt that Dr Matthews has selected experiments that cover a wide range of both classical and modern physicochemical topics.However, it is disappointing that surface chemistry is represented only by experiments on the surface tension of liquid oxygen and the physisorption of 1,2-dichlorotetrafluoroethane on charcoal, whilst heterogeneous catalysis and colloid chemistry are not represented at all. Seven of the experiments necessitate the use of a computer and Dr Matthews offers to supply programs for these-an act of generosity that he may come to regret! Any teacher with the responsibility of organising undergraduate courses in practical physical chemistry will want a copy of this well produced book. For them the price of &30 is not unreasonable and could justifiably be met from departmental funds, but it is certainly sufficient to preclude the adoption of this hard-back edition as an essential undergraduate text. R.Rudham Received 1st September, 1986 Advances in Polymer Science 68/69. Cationic Ring-opening Polymerization. Part 11: Synthetic Applications. By S. Penczek, P. Kubisa and K. Matyjaszewski. (Springer-Verlag, Berlin, 1985). Pp. xviii+317. Price DM 188. This volume contains a truly comprehensive review of cationic ring-opening polymerisation. An outstanding feature is the effort which is made to resolve uncertainties and conflicting views by critical analysis, and where necessary reanalysis, of published data. Throughout the treatment is authoritative, reflecting the extensive experience which the authors have in this field. The task of synthesising a polymer in a particular molar-mass range is much simplified if the propagating chains are not subject to either termination or transfer reactions.Of the systems under review only a few can be considered to fall into this class of so-called ‘living systems’. The latter would be some of the cyclic ethers, iminoethers, amines and acetals. It is explained in the text why various groups of monomers show other types of more complex behaviour and how this must be taken into account if certain polymers are to be obtained in acceptable yields by the synthetic chemist. On these lines there is a particularly useful discussion regarding the formation of macrocyclic rings versus linear chains. The material is organised in a logical fashion. A short introductory first chapter is followed by a thorough treatment of the thermodynamics of ring-opening polymerisation in chap.2. Peculiarities of cationic ring-opening polymerisations are considered together with the basic parameters that need to be taken into account in choosing the preparation conditions for some particular homopolymers and copolymers. In chap. 3 there is a unified treatment of the thermodynamics and kinetics of macrocyclisation. The probability of cyclisation depends on such factors as ring size, the presence of substituent groups, chain flexibility and the nucleophilicity of the heterochain. The Jacobson-Stockmayer theory is naturally considered first, this being an equilibrium theory which may be used to relate the distribution of cyclic oligomers to the conformational probability of ring closure.In many cases, however, this simple theory is inadequate and the discussion of experimental results emphasises the need to recognise factors which can lead to kinetic control of cyclisation. Chap, 4-14 inclusive give accounts of the polymerisation of various types of monomers: cyclic ethers (including oxiranes, oxetanes, oxolanes, acetals and bicyclic compounds), lactones, cyclic sulphides, cyclic amines, lactams, cyclic iminoethers, siloxanes and cyclic phosphorus-containingReviews of Books 3225 compounds. A wealth of information is presented in these chapters in an interesting and easily digestible form. Some applications of the polymers are also mentioned, along with relevant trade names when commercial products are involved.The book contains 15 chapters, and the final chapter is devoted to copolymerisation. Some of the explanations put forward in the final chapter will be much studied by workers in the field. Included in the treatment is a critical examination of schemes used to interpret statistical copolymerisation. The effect of a reversible propagation stage is considered and it is shown how many of the reactivity ratios reported in the literature were determined using an oversimplified scheme. Finally, consideration is given to the formation of block, alternating and graft copolymers. The authors have carried out what was undoubtedly a difficult task with distinction. Their overall treatment of the subject will be found stimulating by specialists in the field, whilst the blend of theoretical and practical discussion will be much appreciated by synthetic polymer chemists in general.The book is an important addition to the polymer literature and polymer chemists will certainly wish to see it included in their library. C. Price Received 18th September, 1986 Specialist Periodical Reports. Spectroscopic Properties of Inorganic and Organometallic Compounds. Vol. 18. Ed. G. Davidson and E. A. V. Ebsworth. (Royal Society of Chemistry, London, 1985). Pp. xiv+466. Price E95, $171. When receiving this book to review, I was reminded of the critic who, being sent a copy of the telephone directory, remarked that it had too many characters and no discernible plot. The n.m.r. chapter of the present volume has 2792 references. To deal with these in 108 pages of text can only be achieved by resorting to telegrammatic brevity which, combined with the camera-ready typeface now required by Specialist Periodical Reports, makes for a very heavy read.Other chapters deal with vibrational spectra, including those of coordinated ligands, Mossbauer, n.q.r. and rotational spectra, covering the literature in a most comprehensive way up to late 1984. There can be little doubt about the completeness of all these surveys and the authors should be complimented on their assiduity and speed of working. Nevertheless, if such surveys are to be undertaken by people, and not computer-aided retrieval systems, I would have liked to see some commentary signalling the most important developments in each topic and evaluating their significance for the future.Probably, this is too much to ask of busy professionals, but it would make such compilations as the present one more valuable and fun to read. P. Day Received 20th August, 1986 Cambridge Solid State Science Series. Modern Techniques of Surface Science. By D. P. Woodruff and T. A. Delchar. (Cambridge University Press, Cambridge, 1986). Pp. x+453. Price &50, $89.50. This book provides a comprehensive account of experimental developments over the last tfvo decades in the field of surface science. It is difficult to find a surface-sensitive technique that has not been covered and any newcomer to the field will find the book a good source of information on both the principles on which they are based and the kind of information that is likely to emerge from each of them.There are nine chapters, the first is a very brief account of some background information on surfaces and adsorption. This is then followed by chapters dealing in turn with surface crystallography and diffraction; electron spectroscopies ; desorption studies ; field electron and field ion emissions; work function studies, scattering techniques and lastly with vibrational spectroscopies. The book is both well written and produced and I have no doubt that any undergraduate or recent graduate student will find it both readable and a very useful reference book. Although I enjoyed the scholarly approach, where I think it does fall down is the dkjb uu flavour that it has for the more senior researcher. A perhaps obvious example is the chapter on Desorption Spectroscopies which, in various guises, has been on the scene for nearly 30 years with significant contributions made by Ehrlich and Redhead in the 1950s and early 1960s.Over the last decade3226 Reviews of Books there have been numerous books (and series of books) devoted to the subject of surface science embracing both the chemists’ and physicists’ approach. The subject has been treated so well at so many different levels that it would indeed be difficult for any author of a new book, written for the recent graduate, to bring a different slant or perspective to the subject at this stage. In this sense I sympathise with any potential author in a field which has, and rightly so, attracted so much attention over the last decade.Perhaps a book devoted to the impact of the newer experimental techniques on heterogeneous catalysis would be appropriate. M. W. Roberts Received 12th September, 1986 Modelling of Oxidation Processes. By N. M. Emanuel and D. Gal. (Akademiai Kiado, Budapest, 1986). Pp. 436. Price E33. This book traces principles and practices that may be adopted in order to establish a quantitative kinetic interpretation of a complex chain reaction system when mathematical modelling is brought to bear on experimental data. There is approximately equal emphasis on experimental kinetic and computational aspects. This is a timely and appropriate topic in the context of current developments of ‘expert’ systems. The subject for this case study is liquid-phase oxidation, with exclusive reference to the oxidation of ethylbenzene. Every kinetic aspect is presented and discussed in depth.Following an introduction to the main aims, the book opens with an extensive, modern account of experimental methods that have been adopted for the study of liquid-phase reactions. Kinetic features that emerge are illustrated in general terms. The theme then changes to general considerations of the components of a kinetic network to explain a complex chain reaction, now illustrated by ethylbenzene oxidation and expressing all possible elementary reaction modes for it, as perceived by logical deduction. Some preliminary pruning of the scheme is possible on the basis of kinetic knowledge, and is exploited here, but the advice is that, in general, only thermochemical considerations should be invoked as constraints on the multiplicity of the scheme.The authors use a matrix representation for compilation of the ‘possible mechanism’. The heart of the text follows in the next two chapters. These sections constitute a masterly, quantitative account of kinetic deductions from experimental measurements : the different subsets of reactions that comprise the overall kinetic network to explain the experimental features of ethylbenzene oxidation are discussed. The general description of the ‘possible mechanism ’ and the experimental kinetics are brought together in chap. 6 in order to reduce the elementary kinetic model to its most manageable proportions. Validation by numerical simulation is incorporated at this stage and the section closes with the derivation of a ‘main contributory mechanism’ that is capable of explaining the principal features of ethylbenzene oxidation.The penultimate chapter comprises a supplementary discussion of homogeneous and heterogeneous catalysis of this oxidation and how these aspects are incorporated in the numerical analysis. The book closes on a technological note of industrial applications. The combination of experimental data with mathematical analysis and numerical interpretations has, in the last decade, afforded insight into complex kinetic interactions that had been inaccessible hitherto. The computational foundation is presented in a way that would be of particular interest to the computer modeller developing ‘expert’ systems to provide the basis for interpreting general reaction mechanisms.The authors do not address the formal mathematical routes of sensitivity analysis now widely adopted to interpret specific kinetic mechanisms. Above all, this is an authoritative account of liquid-phase oxidation, as befits its most distinguished authorship. Perhaps its greatest strength lies in the lucid and definitive interpreta- tion of experimental, kinetic studies. I can commend it on this account to kineticists who wish to enhance their awareness of the present status of understanding of liquid-phase oxidation. J. F. Griffiths Receiued 8th October, 1986Reviews of Books 3227 Combustion of Polymer Materials. By R. M. Aseeva and G. E. Zaikov. (Hanser, Munich, 1985). Pp. xvi + 389. The authors believe that this book differs from others on the same subject inasmuch as it places emphasis on the general characteristics and principles of polymer combustion. A brief introduction explains that the impetus for research in this area comes largely from the need to develop less-flammable polymeric materials.Chap. 1 first gives a general account of combustion and then goes on to consider theories of the ignition and self-ignition of polymers. Chap. 2 deals with the roles of heat and mass transfer and with the factors affecting the rates at which polymeric materials burn. Chap. 3 is concerned with the chemistry of polymer combustion and considers separately pyrolytic breakdown in the condensed phase, diffusion flames and the formation of smoke; it also deals, in general terms, with the mechanism of action of flame retardants and smoke suppressants.A useful Addendum contains an account of work on the effects of oxygen on polymer decomposition. Chap. 4 describes some of the principal experimental methods used to study the combustion of organic polymers. It deals, in particular, with the determination of rates of combustion, of temperature and product profiles in flames and of smoke and toxic gas formation, as well as with modelling techniques. Chap. 5 considers principally the design and synthesis of thermally stable polymers and the use of flame retardants, fillers and fireproof coatings to reduce the flammability of some of the commoner polymeric materials. The literature references have a strong leaning towards research carried out in the U.S.S.R.and this is valuable since it draws the attention of authors elsewhere to work which might otherwise remain largely unnoticed. It is a pity, however, that the great majority of the references are to research completed by the early 1970s, and that more recent work receives rather scant attention. All in all, however, this book makes interesting reading and has the virtue of stressing the importance of physical, as well as chemical, factors in the combustion of organic polymers. C. F. Cullis Received 25th October, 1986 Annual Reports on the Progress of Chemistry. Volume 82. Section C, Physical Chemistry. Senior Reporter M. C. R. Symons. (Royal Society of Chemistry, London, 1986). Pp. xii + 324. Price E52.50, El3 (members), $102. Never a day goes by but one hears the term ‘information technology’.I think it must be what they call a ‘buzz-word’. I don’t know what it is and, while I have often heard it talked about with erudite-sounding solemnity by such august collections of scholars as the Board of the Faculty of Pure Science and the Senate of my University, I have never yet been able to get a colleague to define it to my satisfaction. I therefore suspect that there is a lot of humbug about it. On the other hand, in my state of blissful ignorance I am completely free to fantasise about it. Thus, it seems to me we are approaching the time when everybody will be an expert at fiddling about with data on computers, but nobody will actually be able to do anything practical; then will come the time when no more computers (or anything else for that matter) are being developed and built, shortly after which all the existing computers will wear out; and that will be that, a singularity in the history of mankind from which we will have to start our pursuit of knowledge and understanding all over again.In contrast to the foregoing liverish hyperbole, I do adore books. For me they are an essence of civilised society; they are the supreme repository of human experience and knowledge and I would not wish to live in a world where they did not exist. Of course, writing a review of a Section of Annual Reports I must have no pretensions to literary criticism, for I do not think they can properly be described as literature. However, this book is a mine of information so I suggest that Annual Reports are representative of a primitive form of information technology.Clearly it is a form of which, at least in principle, I approve. When Annual Reports was reorganised in 1979, and Professor Symons took over the editorship of the newly autonomous Physical Chemistry issue, he asserted that his policy would be to have articles of two sorts : (a) those covering broad areas of mainstream physical chemistry, which would appear at fairly regular intervals and ( b ) reviews of specific topics currently of importance, hopefully of interest to a wide audience of chemists. The authors of one of the articles in this volume begin by defining their report to be in the second category. The report is on Conduction Electron3228 Reviews of Books Spin Resonance in Metallic Systems (Edmonds, Harrison and Edwards) and in my view it succeeds very well: the technique, the systems and representative results are set out in a readable and understandable way.It is interesting that this article has the lowest indigestibility factor, i.e. reference/page ratio, (IF), of any in the book; its value is 1.51. In contrast, the highest IF, 9.34, is achieved by Webb, writing about Nuclear Magnetic Resonance. To be fair, Webb does concentrate on physical applications of n.m.r., he includes useful diagrams illustrating the experiments which can now be performed and he concludes with a glossary of acronyms: thus, in spite of the initial impression of high-density jargon, I felt that the article does give a good feeling for what has been happening in the field. Given my own interests, it is perhaps not surprising that, of the other reports, I particularly enjoyed Matrix Isolation (Perutz, IF = 4.6) and Physical Aspects of Photochemistry (Osborne, IF = 3.19). I found Reactions of Silicon Intermediates (Davidson, IF = 5.80) a bit specialised but 1 felt that each of the three remaining articles covered areas which I really ought to know more about and that they formed suitable bases from which further study could be pursued. These articles are, Isobaric Heat Capacites (Blandamer, Burgess and Scott), Physical Chemistry of Solids (Rao, Rao and Gopalakrishnan), and Electronic Processes in Thin Films and Novel Conductors (Rosseinsky); they all have IF in the range 7.76-7.82. Of course, these are personal views and a different reviewer, with different prejudices and preoccupations, would comment differently. However, I am sure that he would agree with me that there is much of interest here. If one of the Reports is on your special field of interest then you really should not pass it by, but quite apart from that I think it would be time well spent for any physical chemist to browse through this book. It gives stimulating impression of what is happening in a wide range of areas, and it is good for us all to once in a while lift our heads above the battlements of our entrenched research positions and have a look around. N . M. Atherton Received 6th November, 1986