J. CHEM. SOC. FARADAY TRANS., 1994, 90(14), 2155-2157 Electrode Kinetics for Chemists, Chemical Engineers and Materials Scientists. By E. Gileadi. VCH Wein- heim, 1993. Pp. xviii + 597. Price DM 189, f65 (hardcover). ISBN 3-527-89561-2. Gileadi writes with enthusiasm and in a very clear and read- able style which makes this book a pleasure to read. The book concentrates on the explanation of the phenomena rather than providing extensive derivations of the various models and equations and, as a result, the mathematical content is kept to a reasonable minimum. The main emphasis of the text is on the electrode surface and on reactions at the electrode surface. Thus there are extended discussions of the adsorption of species at electrode surfaces and the mecha- nisms and kinetics of inner sphere electrode reactions, such as the hydrogen evolution reaction.His treatment of these topics is sound. Where the text is very weak is in the dis- cussion of outer sphere electron transfer and of coupled homogeneous kinetics, a topic which is not mentioned at all. Also omitted are the whole collection of electroanalytical applications and techniques. The text is broadly divided between general considerations and fundamental concepts, techniques and applications. The techniques are focussed on those applicable to the measure- ment of the kinetics of electrode reactions, particularly those involving adsorbed intermediates. Thus fast transient mea-surements, coulostatic pulse techniques, sweep voltammetry and electrochemical impedance are all discussed.The applica- tions are directed towards the areas of batteries, fuel cells, electroplating and corrosion. These are discussed with authority and enthusiasm, and again the emphasis is on the role of adsorbed intermediates present on the electrode surface. In summary this is an attractive book and one which could profitably be read by those interested in the field of electro- catalysis and elect rochemis try postgraduate students. The treatment should be accessible to those with a background in materials science and in chemistry. The book has much less to offer as a first text in modern electrochemistry because of its narrow view of the subject, or for those interested in elec- troanalytical applications or in electrochemical reactions coup,led with homogeneous chemical processes.P. N.Bartlett Received 1st February, 1994 Advances in Photochemistry. Volume 18. Ed. by D. H. Volman, G. S.Hammond and D. C. Neckers. Wiley- Interscience, New York, 1993. Pp. ix + 406. Price f103.00.ISBN 0-471-59133-5. This latest volume in the Advances in Photochemistry series comprises four independent contributions on time-resolved FTIR emission spectroscopy, the effects of molecular entrap- ment on photochemical reactions, scale-up of photochemical reactions and the photochemistry of xanthene dyes. The con- tributions are of good to excellent quality with applications for both academic and industrial laboratories. Individuals will find only certain parts of interest, but overall the volume should appeal to a wide audience. The major section by far is the 167 page contribution from V.Ramamurthy, R. G. Weiss and G. S. Hammond entitled ‘A model for the influence of organised media on photo- chemical reactions ’. They collate a large amount of informa- tion on the effects of organised environments on trapped molecules, considering host materials ranging from individual organic molecules such as the cyclodextrins through micelles, LB films and liquid crystals to inorganic materials (silica, clays and zeolites). The effect of the host structure is con- sidered systematically in terms of the nature of reaction cavi- ties and the consequences of enclosure on reactions (mostly photoinduced) of trapped species.The authors then focus on Norrish I1 reactions of ketones, first discussing the processes in general then considering the effect upon them of inclusion of the ketone in various types of constraining host material. The latter half of this chapter will be of interest mostly to photochemists, while the first half is also a good general introduction to the nature and effects of constraining media on chemical reactivity. The other three sections are all of roughly half the length of the above. G. Hancock and D. E. Heard have written an interesting chapter on time-resolved emission studies using FTIR instru- mentation. This section should appeal to photochemists who are willing to construct their own instrumentation, or to hack commercial spectrometers.After a description of the basics of FTIR measurements Hancock and Heard consider and compare stop-scan and continuous scan modes of data col- lection, then review applications of time-resolved IR emission measurements. Photodissociation is considered first, followed by pulse laser-induced bimolecular reactions and finally kinetic studies of vibrational state changes during photo- chemical reactions. Industrial chemists may find useful the chapter on upscal- ing of photochemical reactions by A. M. Braun, L. Jakob, E. Oliveros and C. A. 0.do Nasciemento. This is a clear, well written guide to reactor design, scale-up of processes and modelling of reactor behaviour. Reactor designs, reaction media and safety requirements are introduced, followed by consideration of available light sources and the implications of the source properties on reactor design.Qualitative scale- up parameters are mentioned, followed by a discussion on mathematical modelling of reactor behaviour. TiO, photo- catalysed oxidative treatment of wastewaters is used as an example in the analysis of reactor performance. Finally, D. C. Neckers and 0.M. Valdes-Aguilera provide a chapter which is ‘straight’ photochemistry, considering the photochemical reactions of some of the many xanthene dyes. Fluorescein, Eosin, Rose Bengal and a new series of hydroxy- fluorones are discussed, with a brief history of each followed by a survey of applications. The use of Eosin as a photoinitia-tor in polymerisation of acrylates is discussed in some detail, and the properties and photoreactions of Rose Bengal receive considerable attention.The wide range of applications for the xanthenes (from polymer chemistry to insect control), mostly relying on photoinduced redox reactions, makes this an inter- esting and at times amusing read. The volume is a useful addition to the series and is well produced. D. Crowther Received 1st February, 1994 Scanning Tunnelling Microscopy and Spectroscopy : Theory, Techniques and Applications. Ed. by D. A. Bonnell. VCH, New York, 1993.Pp. xiv + 436. Price DM 196.00, f80.00. ISBN 3-527-27920-2. Given the spectacular advances in the development of the STM and related methods, there is no doubt a market for a book on this topic.The approach here has been to assemble a multi-author text, with chapters grouped under the head- ings of ‘Fundamentals.. .’, ‘Structure of sample and tip surfaces’ and ‘Related techniques and applications’. The strength of the book is the coverage of issues other than the high-profile application of topological imaging: the dangers of interpreting ‘images’ as topography are frequently flagged and well demonstrated; the detailed chapter on tun- nelling spectroscopy was particularly well done; inclusion of a chapter on surface thermodynamics and structure, includ- ing ‘traditional’ approaches to their study, gave perspective; there was detailed discussion of the importance of the elec-tronic, as well as morphological, structure of the tip.Sur- prisingly, only one author discussed the question of whether the small sampled areas are representative: perhaps the prac- titioners are better judges of this. As an interested outsider, I often question the nature of the relationship between the raw data and the exquisite pro- cessed images commonly presented. Chapter 7 includes figures making this comparison directly. This is typical of the commendable approach taken by the authors in confronting the difficult issues. As one interested in applications of the STM, I naturally found that section most interesting. The tabulation of electrochemically-based systems studied to date was very good: comprehensive but not obtrusive.The chapter on biological applications has an excellent exposition of the forces involved, with particular reference to the imaging of large, soft (biological) molecules. In presentational terms, a book on the STM has the benefit of a wealth of spectacular illustrative material. In terms of the text, there was an annoying number of unnecessary minor typographical errors. The dramatic rate of progress that creates the need for such a book also limits its life. With the exception of the last two chapters, the references run up to 1990. This must limit the value of the book for those working at the forefront of this area. Nevertheless, this is a useful book for those con- sidering entering the area and provides a very good snapshot of the field at the end of 1990.A. R. Hillman Received 18th February, 1994 ~ ~ Surfactant Science Series Volume 50. Fluorinated Surfactants. Synthesis, Properties and Applications. Ed. by Erik Kissa. Marcel Dekker, New York, 1993. Pp. vii + 469. Price $165.00. ISBN 0-8247-901 1-1. The author writes at the beginning of his preface: ‘fluorinated surfactants are truly the super surfactants’. Thus, the pub- lication of Vol. 50 of the Surfactant Science Series dedicated to the synthesis, properties and applications of fluorinated surfactants (FS) is fully justified by the widespread evolution of this subject over the last years. The work could be read and re-read with new information on each occasion because it is a coherent and stimulating handbook in this field of aca- demic and industrial research.For people in the field of colloid chemistry it is undoubtedly very important and is probably the most useful book to have appeared in the FS field to date. After a brief introductory chapter on the title compounds, grouped according on their different charge and structure and summarised in detailed tables, nine additional chapters follow with a comprehensive and exhaustive review of the properties of FS, of their analysis and use, including environ- mental and toxicological aspects. Each chapter is authori- tative and, usually, well organised with updated citations (over 2000 in total; many referenced papers and patents have been published in 1992). It contains concise explanations of the treated chemico-physical concepts and quantities so that J.CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 the author’s intention to write a stand-alone book is widely satisfied. The second chapter, on chemical synthesis, is very detailed as most of the preparation procedures are reported, although yield data are only seldom given. A list of the commercial products together with their manufacturers could be of help to the reader, as well as a list of the abbreviations used for compounds quoted in the whole text. The physical and chemical properties of FS are treated in Chapter 3 with many figures and tables. Four further chap- ters follow on typical surface and aggregation properties. These are the core of the book, where the surface tension and the adsorption at the liquid/vapour, liquidfliquid, and liquid/ solid boundaries are dealt with in terms of the current theo- ries (Chapters 4 and 5).The behaviour of FS in solution and their self-assembled phases is presented in Chapters 6 and 7. The presentation of the theories tends to be rather long and there is some overlap among these chapters. The many tables (with the complement of figures) on surface tension data in both water and organic liquids, on solubilities, Krafft points and critical micelle concentrations, and on the effect of pressure, temperature and additives, are an indispensable source for each worker engaged in this field. In particular I wish to mention here the reference the author makes (in Chapter 5) to the preparation and characterisation of mono- and multi-layer films of FS, for their novelty and foreseeable applications in many fields.This is strictly related to the structure of micelles and mesophases discussed in Chapter 7 on the basis of proposed models for the micellization process in pure and mixed surfactants and of the results obtained with many experimental techniques, included scattering and magnetic resonance spectroscopies. It is a pity that the space dedicated to the literature on both mesophases and micro- emulsions and to the use of physical techniques for structural and dynamical characterisation is not so wide as it would deserve, and that the very recent applications of EPR spec- troscopy in micellar and lamellar FS systems did not find any place in this chapter.The applications and the analysis of FS are reviewed in Chapters 8 and 9 with particular emphasis on their applied and industrial aspects. The alphabetical list of applications starts with Adhesives and Antiflogging and ends with Wetting agents, through Coatings, Cosmetics, Emulsions, Fire-fightings, Metal finishing, Photography, Repellancy, etc. The enormous number of referenced patents in this chapter gives clear evidence of the industrial interest. The analytical methods for FS characterisation are con- sidered, in perhaps too much detail, in Chapter 9. This chapter does not seem to be in the proper location. Most of the quoted techniques are indeed presented here and they would perhaps have been more fruitful to have presented these in the previous chapters.The inclusion of tables with comparisons of data from different sources could be very sig- nificant. The final chapter deals with toxicology and environmental aspects of FS and this is the best conclusion for such an exhaustive handbook. The toxicological and physiological properties of FS are fully considered. The author proves to be an expert on this topic in particular. An enthusiastic approach is given to the use of fluorinated compounds and emulsions as oxygen carriers in blood substitutes and to their bio-compatibility, with a clear and convincing indication of the future perspective. Although minor points and a few typographical errors remained, I must recommend this book, which is clearly written throughout with an enormous number of diagrams and tables that are generally well chosen and clear.Dr. Kissa gives in his work a complete account of his personal interest J. CHEM. SOC. FARADAY TRANS., 1994, VOL. 90 in this field without being biased towards his own particular interests; this is a positive sign as it occurs rarely in the liter- ature. G. Martini Received 4th March, 1994 Advances in Chemical Physics. Volume LXXXIII. Ed. by 1. Prigogine and S.A. Rice. Wiley, New York, 1993. PP. ix + 744. Price f136. ISBN 0-471-54018-8. This series has a well deserved reputation for the high level of expertise of its contributors, and the present volume main- tains that reputation.There are seven articles of varying lengths, each covering a fairly narrow area, but in consider- able detail. The topics chosen are spread across the field of chemical physics and do not appear to have any particular connection with each other. The article by Gina et a/. summarises their own recent theoretical work on geometric Berry phases. A model system is considered consisting of a ring of nuclei which can undergo Pseudo-rotation, represented by an elliptical distortion, the axes of which rotate. There is also a Jahn-Teller coupling of this distortion to the electronic quantum states of the mol- ecule. They then propose an experiment in which the mol- ecule is subjected to a pair of pulses separated by a time-delay.The initial pulse causes an excitation to an upper Jahn-Teller state, the phase of the electronic component of the wave function of this state then developing in time according to an expression which includes the so-called geo- metric contribution. Interference between this ‘developed’ excited wave function and the delayed pulse will then give information on the rate of geometric phase (Berry phase) development. Numerical evaluations of various possible out- comes to the experiment are discussed. Lee and Albrecht deal with the conservation of global energy in non-linear radiation/matter processes. In particular, they discuss the apparent breakdown of energy conservation in some so-called ‘passive’ processes (of which the most important spectroscopically are CARS and CSRS).No problem arises for ‘active’ (or direct) processes or for those ‘passive’ (or indirect) processes not involving resonance between field and material: conservation of energy is found, as has been previously realised. However, for resonant passive’ processes, previously thought to involve constancy of field energy but changing energy of the material, the present treatment exposes a coupling between radiation and matter by means of an in-phase component of the induced electrical polarisation. When this is taken into account the paradox is resolved and energy conservation survives. The arguments are carefully formulated, mainly in terms of Per-turbation theory. The chapter by Polimeno and Freed on ‘A many-body sto- chastic approach to rotational motions in liquids’ starts with a very informative introduction to the field, but particularly to Langevin and Fokker-Planck type treatments.The authors take as a model a solute molecule in a cage made UP of its nearest neighbour solvent molecules, which is in turn subjected to the influence of a fluctuating ‘field’ arising from the remaining molecules. The presence of the two kinds of neighbours leads to a biexponential decay of correlations. Results are presented for four different realisations of this approach and these are compared with the results of molecu- lar dynamics simulations (which can be regarded as exact evaluations for the molecular parameter values introduced). Agreement with molecular dynamics is claimed for various orientational correlation functions up to the maximum times for which molecular dynamics is feasible.The Fokker-Planck methods have the advantage of retaining their usefulness upto very much longer times. An interesting discussion of some of the new high-temperature superconductors by Burdett follows. This article concentrates on the crystal structures of Some of the families of cuprates which show superconductivity in Some of their members. In particular the way in which the ligand environ- ments of the CU ion varies with the composition of the solid, and how that, in turn, affects the energy levels of the d electrons and ultimately their localisation or delocalisation is discussed in detail. In this way a rationalisation of the switch from insUlatOr to metal is accounted for with a good deal of Success.The author does not delve into attempts to predict whether and when superconductivity might be found. The nearest he goes to this is some exploration of the connection between the CU-0 distance and electron localisation, cating that strong electron-phonon coupling would in Some cases be expected. COffeY et a/. give a detailed account of the relaxation of sinde-domain ferromagnetic particles, the latter being suffi-ciently small that the stable state of each is for a single domain to occupy the whole of the particle. The radius below which single domain magnetic particles are stable is of the order of 100 A. TWOtypes of magnetic relaxation are recog- nised: one which arises from motion of the whole particle (Debye relaxation), and the other which is caused by move- ment of the magnetic dipole with respect to the particle (Nee1 relaxation).The article largely ignores the case where the two processes are of comparable importance. The Debye- and Neel-dominated cases are, however, discussed in detail in terms of both Langevin and Fokker-Planck equations. The article by Hurtubise and Freed examines the nature and properties of effective Hamiltonian and other effective operators. In general, effective operators fail to conserve com- mutation relations between arbitrarily chosen pairs of oper- ators, although some definitions preserve the commutation rules between the Hamiltonian operator and an arbitrary operator and/or that between an arbitrary operator and any constant of motion.Other advantages and disadvantages of various choices of effective operator are also discussed. The volume is completed by a discussion of melting and liquid structure in two dimensions by Glaser and Clark. There is a good introduction, which dwells particularly on the theory of melting first proposed by Kosterlitz and Thou- less and subsequently developed by others. This is followed by much shorter discussions of several other theories, such as defect-mediated and grain boundary theories. The main thrust is contained in the following sections: those on com- puter simulation studies of melting, with a careful analysis of the onset of positional and bond-orientational disorder. In parallel with this is a section on studies on random Packing of hard discs. Insight obtained from the simulations is then used to develop a tiling model for melting, use being made of the dense random packing results. The last three sections draw heavily on work by the authors themselves. Readers may find the conclusions drawn to be heretical, but they are certainly interesting. The authors favour geometric (taking account of varying bond lengths), as distinct from toPologi- cal, defects as the main driving force for melting. In Particu- lar, the condensation of these geometric defects is regarded as the Source of the cooperative aspect Of melting. Some measure of topological constraint seems to be necessary in order to avoid the extremes of loss of the transition, on the one hand, or loss of all long-range interactions between the defects, on the other. Finally, the authors Put forward the provocative general conclusion that there is no real qualit- ative difference between two- and three-dimensional melting. Receioed 1st March, 1994N.G. Parsonage