摘要:

Review of Books Polymer Chemistry, An Introduction. By RAYMOND B. SEYMOUR and CHARLES E. CARRAHER JR. (Marcel Dekker, New York and Basel, 1981). Pp. xvi+564. Price SFr 80. This new undergraduate textbook has been written as the successor to Seymour’s ‘Introduc- tion to Polymer Chemistry’ (1971) and is designed to meet the current American Chemical Society guidelines for an introductory course in the subject. In sixteen chapters it covers an extensive range of topics from polymer structure and rheology to polymer processing, and the industrial synthesis of reactants and intermediates for polymer manufacture. Each chapter ends with a summary, a glossary of terms used, a bibliography and a page or two of questions on the material covered. Most of the latter are very pertinent: some diverting (Q.How would you synthesize pip-pip? A. Add carbon disulphide to piperidine at room temperature); and one is an undisguised academic commercial (Q. What percentage of polymer science students receive jobs offers after graduation? A. Approximately 100 percent). The appendices include a 34-page guide to the brand-names of polymer products, and a list of sources of practical demonstrations and laboratory exercises. Applications and industrial practice receive considerable emphasis. With various exceptions the level of treatment of the more theoretical aspects is below that of a U.K. degree course, and tends to be uneven. For example, the Norrish-Trommsdorff autoacceleration is not very clearly explained or illustrated; the concepts of ceiling-temperature and polymerization thermodynamics are not set out fully; and the account of the basis of stereoregularity could prove difficult to grasp.Partly this arises from the authors’ method of briefly introducing a concept and of developing it further in a later section. Only a few potentially misleading statements were noticed, e.g. (p. 304) ‘ . . .relatively stable macroradicals are produced in the emulsion process.. . ’. Apart from some reservations of this type the book is a very good and up-to-date introductory text. It contains a great amount of information, will give new students an insight into the nature and content of much modern polymer chemistry, and should stimulate interest through its frequent references to applications in materials technology. Received 5th April, 1982 K.E. WEALE The 180-Exchange Method in Zeolite Chemistry: Synthesis, Characterization and Dealumination of High Silica Zeolites. By ROLAND VON BALLMOOS. (Salle und Sauerlinder, Frankfurt am Main and Aarau, 1981). Pp. viii+235. Price DM 45. The strange combination of the title and the sub-title introduces an element of uncertainty in identifying the aim of this book. This ambiguity extends through the contents, variously described as ‘progress report ’ and ‘ thesis ’ by the author himself. Unfortunate consequences are numerous redundant equations and arguments, and a general lack of cohesiveness in the development of the subject. The study of dealumination on zeolites whose framework geometry is dictated by the presence and dispositions of SiO, and A10, tetrahedra is of some industrial importance.Removal of A1 from the framework can doctor the number and nature of active sites in these materials. This book primarily deals with two aluminosilicates. Mordenite and ZSMS, both of which are highly siliceous, and the experiments outlined are less likely to be influenced by non-framework cations. Although the dealumination reaction outlined here usually involves partial breakdown of the frameworks of most zeolites, it is shown to behave rather well on high-silica materials, to enable 180-tracer exchange and analysis to be effective in probing the mechanisms. The success of the tracer technique in identifying domains of occluded ‘gel’ is noteworthy. There are some disconcerting omissions like the information on change of framework due to twinning in ZSM 5 and other dealumination reactions, including gas-phase replacement with SiCl,, which3704 REVIEW OF BOOKS are known to preserve the framework intact.I must point out that active workers in the field more conversant with the ‘style of patent literature’ may find some useful hints. S. RAMDAS Received 5th April, 1982 Catalysis and Chemical Processes. Ed. by R. PEARCE and W. R. PATTERSON. (Leonard Hill, Catalysis. Science and Technology. Volume 1. Ed. by J. R. ANDERSON and M. BOUDART. At a first glance, these two recently published books on Industrial Catalysis show a striking similarity. They are both multi-authored works which deal with a spectrum of related topics in the chemistry and engineering of catalytic processes.A more careful study reveals that although the subject matter is similar in both cases, the approaches and the scope of the two volumes are significantly different, and they will probably appeal to different audiences. The work by Pearce and Patterson is a well integrated, logically oriented presentation of some current ideas of catalysis and catalytic processes. It provides the reader with a good perspective on the present state of industrial catalysis and in some respects, it is the natural updating of the I.C.I. Catalyst Handbook, which has been so widely used over the past decade. The first two parts of the book (6 chapters) deal with some basic general principles and factual information on the role and assessment of catalytic processes with reference to specific industrially important process steps.The topics dealt with are extremely broad and vary from economics to reactor design to general aspects of the production of feedstocks from oil, coal and natural gas. The treatment is necessarily brief and somewhat superficial; nevertheless, although these chapters will have little to offer to experts in the field, they provide a suitable introduction to students or to chemists and engineers working in related areas. The last part of the book examines in more detail the present status as well as future trends in synthetic route planning for organic materials. This is accomplished, first, by overall descriptive analyses of the currently known alternative routes to several important products and comparison of the advantages offered by each route.This is followed by a more fundamental detailed inspection of possible catalytic mechanisms for important synthetic routes. The bulk of the discussion centres on several aspects of the synthesis of hydrocarbons and higher oxygenated species from lower molecular weight compounds and is developed within the general context of building carbonsarbon bonds. Included are a summary of current ideas on the mechanisms for Fischer-Tropsch synthesis, disproportionation, oligomerisation and polymerisation. Both homogeneous and heterogeneous catalytic routes are presented and compared, but no attempt is made to deal with the quantitative aspects of the syntheses (control of molecular weight distributions, product distributions, etc). There follow shorter reviews in the same vein, of well established partial oxidation reactions on both metals and metal oxides and some discussion of hydrogenation catalysis.The final chapters deal with a token treatment of enzyme catalysis and speciality chemical synthesis, which are probably too brief to be of general value to the reader. On balance, the editors have assembled a cogent, readable account of the evolution of industrial catalysis to its present state and some indications as to how its influence is likely to be felt in the coming decade. Its primary value will undoubtedly be for newcomers in the general field of industrial chemistry or for those who are about to branch out into a different specific application of catalysis to industrial processes. The volume by Anderson and Boudart is the first in a projected series on industrial catalysis which attempts to achieve similar objectives to those of Pearce and Patterson.The pathway, however, is very different; it is much more of an encyclopaedic approach to the subject in which the contributions are assembled in a near-random order and each chapter is essentially an independent review, not unlike those in the Chemical Society’s Specialist Periodical Reports on Catalysis. Such a format clearly provides scope for a much deeper exposition on each of the subjects in question, but sacrifices any semblance of continuity of presentation within the Glasgow, 1981). Pp. xix+ 348. Price E25. (Springer Verlag, Berlin, 1981). Pp. 309. Price DM 142.REVIEW OF BOOKS 3705 volume.In fact, because the individual chapters are well written, complete and filled with up-to-date information, the lack of continuity between chapters is not a serious problem. The first chapter is a general history of industrial catalysis which deals with material similar to that in the first half of Pearce and Patterson, but very much in outline form. It makes interesting reading and would serve the uninitiated as a very good introductory guide to the subject. The second chapter is an equally good guide for those who have had little or no experience in the area of catalytic reaction engineering. It is a highly selective but certainly adequate treatment of simple ideal reactors and is followed by a presentation of the most important features of heat and mass transfer resistances in catalytic systems.The presentation illustrates the most relevant points only, and avoids complications which are usually of secondary importance. The remaining three chapters address themselves to specific catalytic processes. The most comprehensive chapter deals with the many aspects of nitrogen fixation, including adsorption, complexing and reaction; the major emphasis, quite naturally, is related to the synthesis of ammonia. There is a detailed discussion of the current understanding of commercial ammonia catalysts and the role played by the various promoters included in the their formulation. Proposed kinetic expressions are reviewed, although most of these have been available in the literature for some time. The chapter concludes with surface studies of ammonia synthesis catalysts and a summary of metal-nitrogen complexes in solution.The review on Fischer-Tropsch synthesis will be a great source of information for those who seek detailed plant operating data. After a long introduction which describes the overall process, the author gives details of preparation of many types of catalysts which have been used commercially. He then presents comparative industrial-plant and pilot-plant data for varying catalyst formulation and plant operating conditions. Many important results are presented including selectivity, product distribution, activity and catalyst life. The discussion of possible mechanisms for the synthesis is quite brief, but this is perhaps less important in the light of recent reviews of this topic which have appeared in the literature over the past year.The final chapter is a rather more brief treatment of hydrocarbon reforming reactions, specifically the characterisation and mechanisms of platinum/alumina catalysts plus those bimetallic catalysts with iridium or rhenium. Significant numbers of Mossbauer spectra and X-ray data on different catalysts are included. On the whole, the book contains a useful set of in-depth reviews on specific areas of applied catalysis. The editors give us no idea of the number of volumes they have planned for the series. If they can maintain the level of treatment in subsequent volumes, they will have assembled something approaching an encylopedia of industrial catalysis. L. S. KERSI-ENBAUM Received 7th April, 1982 Chemical Kinetics and Reaction Mechanisms.By JAMES H. ESPENSON. (McGraw-Hill, New York, 1981). Pp. x+218. Price f17.50. The author states that this text is based upon a one-term course (at Iowa State University) for graduate students from all disciplines of chemistry. However, since extensive prior exposure to kinetics is not assumed it is suggested that this book could be used as an undergraduate text. It is only as the latter that it could expect to find many purchasers in this country. The first four chapters deal with the bread-and-butter aspects of formal kinetics covering reactions of simple kinetic form, more complex reactions (reversible and concurrent) and consecutive reactions and those involving reaction intermediates. The treatment is quite conventional though wherever possible real reactions are used rather than the usual (and very dull) A + B etc.Commendable attention is paid to such aspects as the use of physical properties to follow concentration changes and such topics as exchange reactions and the use of small perturbation methods (more usually discussed only as a fast reaction technique). Chap. 5 deals in under 20 pages with the methods by which reaction mechanisms are deduced and this reviewer felt that the average student would find it very hard going. Of course, if he3706 REVIEW OF BOOKS then did the 10 pages of problems he would be well away but he would be a remarkable student indeed if he could, just on the basis of what he had read here. Chap. 6 deals with Energetics- thus the effect of temperature on a chemical reaction is only considered quantitatively when more than half way through the book! Chap.7 deals with Chain Reactions in a curiously unbalanced way-9 pages on stationary chains, less than one on branching chains and then nearly 4 pages on oscillating reactions. It really is difficult to understand why the hydrogen- oxygen reaction (arguably the most studied reaction in the entire history of gas kinetics and displaying numerous interesting and important features) warrants only about one fifth of the space devoted to the cerium(1v)-catalysed oxidation of malonic acid by bromate ions (the oscillating reaction). Chap. 8 polishes off Collision Theory, Activated Complex Theory and the Kinetics of Unimolecular Gas-phase Reactions in 13 rather confusing pages.It is difficult to see why the last topic is placed in this chapter and the treatment is poor and contains errors. Chap. 9 deals with reactions in solution and chap. 10 with reactions at extreme rates (i.e. fast). This latter chapter is too brief to deal with any technique in detail but might whet the appetite of some students and thus encourage them to look elsewhere. The final chapter, entitled Extrakinetic Probes of Mechanism, is something of a hodge-podge encompassing such topics as Linear Free-energy Correlations, The Marcus Relation for Electron Transfer, Acid-Base Catalysis and Isotope Effects. Throughout, as one has come to expect in American texts, there are numerous problems which in general look very good but do tend to be difficult, and the average student might give up pretty quickly; perhaps the encouragement of a few easy ones would have been better psychologically.While there are many good features to this little book, the balance is far from ideal and it will probably be of most use located in the undergraduate section of the library where odd parts of chapters can be consulted. Indeed at the price it is unlikely that it will be found anywhere else. H. M. FREY Received 16th April, 1982 Comprehensive Treatise of Electrochemistry, Volume 4. Electrochemical Materials Science. Ed. by J. O’M. BOCKRIS, B. E. CONWAY, E. YEAGER, R. E. WHITE. (Plenum Press, New York, 1981). Pp. xxii+616. Price $55. In the General Preface to the whole treatise the editors’ objective is stated to be ‘a mature statement about the present position in.. . a new interdisciplinary field’ i.e. electrochemistry. Volume 4 should, perhaps be judged with that in mind. Some materials scientists will be surprised, perhaps a little disappointed, to find that the editors are mainly concerned with the degradation of materials. Thus, the book commences with a clear account of the thermodynamics of corrosion by van Muylder. This is long enough and sufficiently well documented to be a useful contemporary supplement to established monographs, albeit the reader is left with some sense of dtjh-vu. In the real world the punter needs more than a knowledge of breeding to survive, and so it is reasonable that thermodynamics is followed by kinetics (W. H. Smyrl), a chapter that has again to compete with many well established and more extensive treatments.The third chapter, on the study of the passivation process by electrode impedance analysis (by I. Epelboin, C. Gabrielli, M. Keddam and H. Takenouti) is particularly valuable and timely in view of recent advances in instrumentation that are enabling a wide diagnostic application of the technique to complex situations. Then more passivation (N. Sato and G. Okamoto) and on to the kinetics of the growth of oxides, an unavoidably very selective review by M. J. Dignam. Practical corrosion inhibition is dealt with very briefly by R. N. Parkins, who concentrates on steel. The chapter exemplifies the difficulties, at present, in relating experience in the field with the performances of inhibitors under the better control of laboratory experiments; it does not, to my mind, reflect the consequences of the growing realisation of need for less toxic inhibitors; and it is tantalizinglyREVIEW OF BOOKS 3707 curt regarding synergism.G.P. Cherepanov gives an interesting account of stress corrosion cracking, i.e. electrochemical stress corrosion and hydrogen embrittlement ; the references are, however, fairly old. Electrochemical aspects of hydrogen in metals are surveyed by P. K. Subramanyan who, again, refers disappointingly to rather elderly literature at a time when the usefulness of hydrogen-in-metal studies has stimulated a number of important international meetings. It is good that the topic of triboelectrochemistry (V. Guruswamy and J.O’M. Bockris) should rate a mention, although the science, like this chapter, is embryonic. Finally there is a solid chapter on non-metallic materials (by J.P. Randin). This deals with carbon, carbide, sulphide, phosphide and boride electrodes and with transition-metal oxide electrodes ; there are 338 references. It does not cover a number of oxides, e.g. TiO,, MnO,, RuO,, with wide applications and it does not deal with photoeffects. The editors emphasize their concern to present the modern view rather than the most recent situation, so the book has something of a testamentary quality; where it might have excited it becomes over-brief and fragmentary. Nevertheless it is a convenient compendium and useful addition to the series. J. P. G. FARR Received 5th April, 1982 Polymer Latices and Their Applications.Ed. by K. 0. CALVERT. (Applied Science Publishers, London, 198 1). Pp. xi + 262. Price E18.00. Insofar as readers of this journal are interested in the subject of polymer latices, they will probably tend to regard latices as model colloids rather than as representing an interesting and important physical form in which polymeric substances can be obtained and applied industrially. It therefore has to be emphasised at the outset of this review that the concern of this book is exclusively with latices as industrial materials. As such, this book is to be warmly welcomed as giving an authoritative, broad, up-to-date survey of the subject. A book of this kind is especially welcome as there has been a dearth of publications in this area. It has been written by a team of fifteen authors, thirteen of whom are drawn from leading industrial latex companies in the United Kingdom, and two of whom are from the Malaysian Rubber Producers’ Research Association.This team has been led by Mr K. 0. Calvert, who is himself a well known contributor to the more technical aspects of latex science and technology. The first chapter of this book gives a general introduction to the subject of polymer latices. Matters surveyed briefly include types of latices, properties of latices, applications of latices, handling of latices and compounding of latices. The two following chapters deal respectively with natural and synthetic latices. The fourth chapter surveys latex specifications and test methods. Then comes a succession of chapters which deal with the various applications of polymer latices.The application areas covered are carpets, binders, adhesives, paints, dipping processes, moulded latex foam and ‘diverse’ applications. In the latter category are included applications such as latex thread, rubberised hair, latex casting processes, leatherboard manufacture, applications in admixture with cement and with bitumen, and applications to tyre-cord dipping. The concern is exclusively with aqueous latices. As a broad survey of aqueous polymer latices and their industrial applications, this book will no doubt be valuable and can be commended. However, the present reviewer suspects that many readers of this journal will find the book less than entirely satisfactory for several reasons.In the first place, there is an almost complete absence of discussion of the fundamental principles of either the technological or the physiochemical aspects of the subject. Readers of this journal are likely to find that the approach adopted by the authors is excessively empirical and discursive for their taste. In the second place, the treatment is often rather superficial. Expecially is this the case in the chapter which deals with the production of synthetic latices by emulsion polymerisation. Whilst it is true that the information given in the book itself can usefully be supplemented by following up the references which are cited, it is likely that most readers of this journal would have preferred more detailed treatment to have been given in the book itself; this would have been possible without lengthening the book unduly, had a less discursive style been adopted. A third aspect of this book which will probably disappoint readers of this journal3 708 REVIEW OF BOOKS is the absence of any reference to possible new and potentially significant applications for polymer latices.Novel applications may well be found in at least two directions, namely, those which exploit the large polymer-aqueous-phase specific surface area of latices, and those which exploit the electrical dissymmetry which is present at the interface between polymer and aqueous phase in the case of electrostatically stabilised latices. No reference is made in this book to the efforts which have so far been made to exploit for medical purposes the adsorptive and binding potentialities of the large area of polymer-aqueous-phase interface in latices.Nor is there any mention of possible catalytic applications of this large interfacial area. So far, catalytic applictions have been confined to those which rely essentially upon enhancement of the counter-ion concentration in regions of the electrical double layer which are near to the polymer surface. However, it is at least possible that the adsorptive capacity of the interface may also be useful in catalytic applications. Some discussion of possibilities such as these would have been welcome. D. C. BLACKLEY Received 14th April, 1982 Shock Waves in Chemistry. Ed. by ASSA LIFSHITZ. (Marcel Dekker, New York, 1981). Pp. ix + 390. Price SFr 182. After a somewhat hesitant start, the use of shock waves to study chemical and physical processes at high temperatures has become an accepted technique and reliable kinetic data can be obtained in this way.Several books have been written, notably by Bradley and by Gaydon and Hurle, which describe not only the underlying principles and the experimental procedures but also give some account of the early results obtained using shock waves to provide high temperatures for short, well defined times in the reactant gases. Inevitably, these books have become rather dated. This new book, edited by Lifshitz, is rather different. It is a collection of self-contained review articles on various aspects of shock waves. The first (by Khandelwal and Skinner) is concerned with hydrocarbon oxidation, and the next (by Tsang) describes the results obtained using the comparative rate technique which he has pioneered.Both these articles include extensive lists of references and represent useful summaries of the present situation. Boyd and Burns have contributed a chapter on dissociation-recombination reactions, while Kiefer describes the laser-schlieren method which he has done so much to develop. There is another chapter by an acknowledged expert, Just, on atomic resonance absorption spectrometry. Under shock-tube conditions it is very seldom that the concentrations of radicals and other species reach a steady state, and so the classical Bodenstein steady-state approximation cannot be used. Instead, it is necessary to integrate the differential equations describing the time-variation of species concentration, and Gardiner, Walker and Wakefield have provided a useful guide to the computational procedures available in this and other aspects of shock-tube work. In addition to these contributions there is another by Bar-Nun on Chemical Aspects of Shock Waves in Planetary Atmospheres which, although interesting in itself, fits rather uneasily with its companions. As is inevitable in a book of this type the standard and style of the chapters varies and there is some overlapping material; none of this, however. represents a serious drawback. What is more difficult to understand is the audience for whom the book is intended. Each chapter is a useful and interesting review which will appeal to a fairly restricted readership, but, in the opinion of this reviewer, the whole volume lacks coherence. The time-honoured phrase ‘should be on the shelves of every library’ probably applies, though the price, over &50 at the current exchange rate, must cause all university librarians to flinch in these days of U.G.C. cuts. There is still room for the definitive up-to-date book to be written on shock waves in chemistry. J. A. BARNARD Received 5th April, 1982

ISSN:0300-9599    

DOI:10.1039/F19827803703

出版商:RSC    

年代:1982

数据来源: RSC