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542 BOOK REVIEWS [Analyst, 1 7 0 1 . 91 Book Reviews STABLE RADICALS. By ANATOLI LEONIDOVICH BUCHACHENKO. Pp. viii + 1SO. New York: Consultants Bureau. 1965. Price $15.00. The appearance of this book is timely, as it gives a fairly comprehensive and up-to-date account of the properties of stable, electrically neutral radicals. The space allotted to different aspects of the subject varies considerably; but this is mainly attributable to gaps in the present state of knowledge rather than to a lack of balanced treatment on the part of the Russian authors. As with most monographs of this type, a revised edition will sooner or later be required, dependent upon the rate a t which the subject is extended. Nevertheless, it will be of great value to chemists concerned with such matters as kinetics of reactions, polymerisation, oxidation - reduction processes and the like.The first chapter is devoted to the general methods used in the detection and investigation of the behaviour of stable radicals, among which electron paramagnetic resonance predominates. This method is described in considerable detail and this chapter could be read with profit even by those spectroscopists to whom the technique is unfamiliar. In the ensuing chapters reference is irequently made to the various derivations discussed in this basic section, and for this reason, if for no other, i t is a pity that no index is provided. Chapters 2 to 4 deal successively with radicals formed with tervalent carbon, monovalent oxygen and bivalent and quadrivalent nitrogen. Chapter 4 contains something of importance to analysts, particularly with respect to the well known diphenylpicrylhydrazyl (DPPH) radical.Mag- netic and electrical properties of stable radicals are treated briefly in Chapter 5, while the last chapter deals with the use of stable radicals in the investigation of chemical reactivity, particularly with respect to oxidation - reduction processes. As in many other connections, chromatography is often enlisted as a valuable purification technique in the isolation and separation of stable radicals. Finally, the book is well produced and the molecular formulae and spectra are clearly printed, while plentiful literature references are given a t the end of each chapter. A word of praise is due to the translators who have produced a most readable, yet clearly expressed text.There are a few trivial and irritating misprints, particularly in the latter part of the book, suggestive of rather casual proof-reading. F. G. ANGELLAugust, 1966; BOOK REVIEWS 543 CELL K. By RODERICK P. KERNAN, D.Sc. Pp. viii + 152. London: Butterworth & Co. (Pub- This little monograph warrants review in these columns only because one of its seven chapters describes the assay of potassium in tissues and body fluids. In fact, it provides a fascinating account of some effects of the evolution of living organisms from primitive creatures that existed millions of years ago when the oceans contained about equal amounts of sodium and potassium. As sea-water now contains about thirty times more sodium than potassium, the latter element must have been absorbed preferentially by living matter.Ingenious mechanisms have evolved whereby most living cells maintain higher concentrations of potassium than the fluids by which they are bathed. With other ions, cellular potassium plays a major part in the electrical properties of resting and active cells; those of nerves and muscles have been well studied on account of the changes in electrical potential and polarisation which take place during nerve conduction and muscle contraction. Cell potassium also plays a major part in many metabolic reactions of the body. This book provides an interesting account which can be read as an academic exercise, and perhaps for pleasure, by all those analysts whose knowledge of physical chemistry and electro- chemistry has remained up to date.lishers) Ltd. 1965. Price 27s. 6d. C. H. GRAY KIRK-OTHMER ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY. Second Edition. Volume 7. Dialysis to Electron-spin Resonance. Edited by HERMAN F. MARK, JOHN J . MCKETTA, Jim., and DONALD F. OTHMER. Executive Editor: ANTHONY STANDEN. Pp. xvi -+ 903. New York, London and Sydney: Interscience Publishers, a division of John Wiley & Sons Inc. 1965. Price j16 18s.; price per volume for subscribers to the complete set of 18 volumes L13. I t has naturally been the policy of the reviews of this series of volumes (see Analyst, 1963, 88, 899, et seq.) to draw special attention to sections of the contents having special reference t o chemical analysis and associated subjects. As a rule these have been part of an individual mono- graph, and as such the)- have been subsidiary to the main subject matter of the monograph.This of course does not detract from their importance; chemical analysis has been described as “the hand-maiden of chemistry.” From time to time, however, as successive volumes appear there have been monographs devoted exclusively to specific branches of chemical analysis. From this point of view the recently published Volume 7 is of special importance, in that it deals with Electroanalytical methods which, together with the following monograph on Electrochemistry, comprise 115 pages. The former monograph starts with a short but succinct theoretical chapter that includes the latest conceptions of the subject, such as chronopotentiometry (the variation of potential with time), a specific name for which is polarography.Then follows one of the main sections which is on potentiometry, both direct and depending on zero faradic currents, i.e., precipitation and oxidation - reduction titrations. The section on apparatus for this work is not developed in detail. This is understandable as “do-it-yourself” apparatus is now seldom used for this type of work; certainly not in this country and probably to an even smaller extent in the Vnited States. I t is more usual to purchase ready made equipment from a reliable manufacturer. The treatment of the subject is sufficient to indicate the principles of such apparatus without descriptions of particular instruments in any detail; nevertheless, some notes on the relative merits of the various makes \iould have been of value to the newcomer in this field.The applications of polarography to both qualitative and quantitative analysis arc fully discussed. Here again the instrumental side, both manual and recording, is dealt with generally rather than in particular. Of special interest in the latter connection are the recent developments in the use of operational amplifiers of the type used in modern analogue-computer circuits; and the use of 3-electrode circuits (also known as potentiostats) to remedy the loss of potential in over- coming the internal resistance of a cell. Another little known technique is amperometric titration, in which a rotating platinum electrode is used. The next main heading is electrolysis methods, more commonly knonm as electro-deposition, although strictly this is a particular instance in which insoluble products are formed. In the monograph, this is described under electro-gravirnetry, and a distinction is made between it and coulometry, i.e ., the measurement of the quantity of electricity which accomplishes the depletion of a sample from a solution by electrolysis.There is a brief reference to the numerous devices that have been described for the integration of current - time curves in controlled-potential544 BOOK REVIEWS [Analyst, 1’01. 91 coulometry. These are of considerable potential importance especially for process control, and they can be chemical, electromechanical or electronic in nature. The final section of this monograph deals with conductance methods (more conimonlJ- known as conductimetry), and the treatment follows the same lines.The Lrery useful type of conductivity cell having electrodes whose distance apart can be varied is not mentioned. There are 99 literature references. The 57-page article on Electrochemistry is purely theoretical, and is best studied in con- junction with the first part of the monograph on Electroanalytical methods. The alphabet has made them neighbours, but unfortunately in the reverse order of the natural sequence. On reading these 2 important articles, one is impressed by the necessity for standardisation of the nomenclature of the subject. This is apparent even from the comments made above in this review. Other monographs based on the ramifications of electrical techniques are ElectrodialS-sis and Electrodecantation (electrogravitational separation), The latter depends upon the stratification phenomena that occur when colloidal dispersions are subjected to an electrical field between vertical membranes, permeable to the electrical current and impermeable to the colloid.Apparently laboratory equipment of this nature can be used for chemical preparatory work, although the principal practical application has been to the concentration of rubber latex. IJnder Electro- dialysis, applications to the removal of salt from water, de-ashing sugar solutions, de-acidification of citrus juices, de-contamination of milk, sulphite pulp and waste recovery are all considered ; the last, however, is as yet of academic interest only.The monograph on Electrolytic Machining Methods provides another example of ambiguity of nomenclature. Many would feel that i t is more correctly described as electrochemical machining, and indeed i t is so listed in the present Encyclopedia, but with an appropriate cross-reference. It is useful to have a record of recent advances in this field, because, although at present the applications are not yet widely used in industry, they appear to have a future especially where stress-free metal objects are involved. The short section on Electrical Testing provides an intro- duction to the subject which otherwise is of limited interest to analysts and, indeed, to chemists. However, electron-spin resonance spectroscopy is an important and sensitive technique for detecting unpaired electrons, and as such has many applications in the analytical field. X ”-page monograph deals with i t clearly and adequately.Previous reviews of this series have commented on the strange situation that self-contained monographs arranged in a purely alphabetical order inevitably produces. In the present volume, for example, the author of the section on Dialysis differs from the author of Electrodialysis; and, moreover, neither monograph makes reference to the other. A further article deals with Diffusion Separation Methods a t some length ; this is related, perhaps somewhat remotely, to Electro- decantation. One comprehensive section on separation methods might have brought all these into their correct relative perspective. However, as Diffusion Separation Methods follows Diffusion (a short, 12-page section), there is sonic argument for combining these two.A somewhat unexpected monograph in a chemical encyclopaedia is Dimensional Analysis, a purely mathematical tool, enabling a set of variables to be reduced to a set of dimensionless products of the variables. Of a similar fringe character is Economic Evaluation, a short but excellent monograph which tells the chemist in simple terms just about as much as he needs to know on the financial evaluation of a proposed course of action. Lkilling Fluicls (20 pages) is another off-track subject. Chemically, it is of some importance in view of the wide variety of chemical substances used in the preparation, maintenance and utilisation of drilling fluids. Examples of their functions are to increase density or viscosity, form seals, reduce filtrate loss, and act as stabilisers, emulsifiers, inhibitors, bactericides, lubricants and flocculants. Xs may be expected a wide variety of chemical substances is involved, although strangely, there is no reference to the latest addition to thc list, namely dextran, which has given promising results in preliminaq- trials in the United States.Lllthough this does not deal with analytical methods, it contains some valuable data on the compositions of various types of processed eggs. Similarly, the monograph on Dry Cleaning lists the operations and chemicals involved. I t also makes some attempt to evaluate dry cleaning performance, a difficult matter when water-soluble soil removal is measured in terms of the removal of sodium chloride, glucose and a water-soluble food dye from rayon. The chemistry of clothes marking, and even “coinop” (self service) dry cleaners are included.In all there are 32 monographs in this volume. Most of those not mentioned above are relatively short, with the exception of Dyes and Dye Intermediates, their applications and evaluation, Food chemists will turn with special interest to the monograph on Eggs.Ahgust, 19661 BOOK REVIEWS 545 followed by Natural Dyes and Reactive Dyes as separate monographs. These 4 dyestuffs mono- graphs total 168 pages. I t is interesting to learn from the monograph on Natural Dyes that logwood is still of great importance, nearly one million pounds’ weight having been consumed in 1964 in the United States alone. Further detailed comments on individual monographs is not possible, but mention should be made of those on Diamines and Diarylamines (31 pages), Diatomite, Diphenyl, Distillation, Diuretics, Driers (including metallic soaps), Drying and Drying Agents, Drying Oil and Elastomers.This volume once again demonstrates the wide scope, up-to-date treatment and high standard of presentation by both authors and publishers, which have characterised the 6 previous issues. Ilespite the claims of an international approach to the subject matter made in the Preface t o I’olume 1 , the list of authors appears to be wholly American, and the bibliographies reflect this trend. I t is only fair to add that this does not appear to detract materially from the value of the subject matter; however, i t does mean that statistics and view-points are not a s widely spread as one might expect in a work of this kind.JIJLIUS GRANT ANALYTISCHE CHEMIE IN DER INDUSTRIELLEN PRAXIS. No. 2. By Prof. WOLFGANG LEITHE. Pp. xvi + 412. Frankfurt: Akademische Verlagsgesellschaft. 1964. Price Dl1 60. Books on analytical chemistry are almost always written purely for specialists or students of the subject, and I find i t interesting that I have now read the third book in 2 years (one each in French, English and German) written to inform the non-specialist about present-day analytical chemistry. This seems to indicate a revival of general interest in a subject that concerns all chemists to some extent. Dr. Leithe has wide experience both as a professor and as head of a large industrial laboratory, and few people are in a better position to appreciate the gap between academic teaching and industrial practice.He writes for the newcomer to industry and starts by indicating the range of industrial analysis. Before going on to describe, very briefly, almost a11 current techniques from gravimetric analysis to differential thermo-analysis, he has about 30 pages on laboratories, their siting and fittings, sampling and samplers, laboratory personnel, costing and the recording of results. To the experienced analyst this is the most interesting section of the book. I t is virtually impossible to describe all analytical techniques in 270 pages, but this is a very good attempt. I would, however, comment on the variable value of the diagrams.The photograph of the piston burette on p. 35 and the sketch of the optics of the Abb6 refractometer on p. 172 tell one nothing unless one is already familiar with the apparatus; on the other hand, the diagram of the infrared spectrophotometer on p. 164 is clarity itself. The next section (pp. 301 to 342) on the analytical needs of certain industries is, in my opinion, too short to be really informative. The book concludes with a section on the analysis of gaseous and liquid effluents (pp. 343 t o 386), and a brief sketch of automatic methods of analysis (pp. 387 to 402). These should give the student an adequate outline of the subjects, but too much space is given to sulphur dioxide. There is a table giving the reagents used in a well known German series of gas-detector tubes for toxic gases.Perhaps I ought to say that unless the reader has a much better knowledge of German than the average modern student, he will need to have a t hand a good German dictionar?-. H. N. ~YILSON ANALYTICAL CHEMISTRY OF BOROS. By Ad. A. NEMODKUK and 2. E(. KARALOVA. Pp. s i i f 236. Jerusalem : Israel Program for Scientific Translations. llistributed in Great Britain and the Commonwealth, South Africa, Eire and Europe by the Oldbourne Press, London. 1965. Price 103s. 6d. Very few analysts have never been asked to determine boron, and when parts, or fractional parts, per million of boron are involved this invariably presents a problem. If the material is a solid, the problem arises of how best to obtain the sample in solution, without loss of boron, in a form suitable for the direct evaluation of boron, or its subsequent isolation as methyl borate, and a recommended procedure for one class of material often fails if i t is applied to another.Difficulties associated in the initid stages of this determination have led to the development of separations based on pyrolysis, chromatography, the use of ion exchangers, the mercury-cathode cell, etc., but methods used in t h e f i d stages of this determination may be described as “variations on the same theme.”546 BOOK REVIEWS [Analyst, 1701. 91 The hrst two chapters of this book describe the fundamental physical and chemical properties of boron and its compounds, and subsequent chapters deal with methods of detection, separation, and determination of the element, including the more important analytical procedures for deter- mining boron in various naturally occurring and industrial materials.Based on information contained in over 1200 Soviet and foreign references up to early 1963, and the authors’ personal experience, published methods are discussed, and comment is made on their respective merits, limitations, sensitivity, accuracy and reproducibility, and methods that have proved more reliable in practice receive special attention. The only adverse comment on this book is that i t does not deal with some of the more recent important developments that show a marked tendency towards the use of procedures for the dived determination of boron a t very low levels in certain selected materials.This, however, is understandable in view of the inevitable delays associated with double publications. The book, which was first published in Moscow in 1964, is a translation of one of a series of about 50 monographs to be published by The Institute of Geochemistry and Analytical Chemistry, U.S.S.R. Already about 10 of this series have been either translated and published in the English language, or are in the course of being translated for publication. Published translations of ten contain irritating, if insignificant, misprints and inconsistencies, but this cannot be said of this book, and all concerned, especially the translator and proof-reader are to be congratulated for presenting such a clearly written English version. -4 publication such as this, that deals in considerable detail with the subject up to the time of its initial publication, is an asset to any analytical laboratory, because it covers, in about the right amount of detail, a wide variety of materials ranging, alphabetically, from animal tissues to zirconium alloys.CHEMISTRY OF ORGANIC SCLFUR COMPOUNDS I N PETROLEUM AND PETROLEUM PRODUCTS. Pro- ceedings of the 3rd Scientific Session, held in Ufa, June 3-8, 1957. General Editor: Prof. K. I>. OBOLENTSEV. Pp. xii - 364. Jerusalem: Israel Program for Scientific Translations. Distributed in Great Britain and the Commonwealth, South Africa, Eire and Europe by Oldbourne Press, London. 1965. Price 90s. In June 1957, a Congress on the Chemistry of Organic Sulphur Compounds was held a t Ufa; the proceedings of the Congress were published in Russia in 1959, edited by Professor R.D. Obolentsev. This work has now been translated by the Israel Programme for Scientific Transla- tions, the translation being the text of this book. ‘The reason for the Congress was the increased availability of high sulphur-content crude oils (e.g., Tuimazy deposits), which prompted Soviet scientists to work out a centrally co-ordinated research programme in this field in order to attempt to solve 2 problems: to develop basically new methods of primary processing of sulphur-containing petroleums ; and to develop existing processing procedures by inclusion of new methods of petroleum distillation causing de-sulphurisation, such that sulphur could be used in other ways. This book gives an account of the proceedings of the fundamental studies carried out up to that time. Divided into 6 parts, the proceedings range over the following aspects of sulphur chem- istry : synthesis, characterisation, and analysis of sulphur-containing organic compounds ; the isolation and composition of organic sulphur products in petroleum ; thermo-catalytic transforma- tions of organic sulphur compounds ; corrosi1Te and tar-forming properties of sulphur crudes ; the utilisation of organic sulphur compounds ; and toxicology of certain sulphur compounds. To the analyst a t first glance there does not appear to be much of interest, but the first two sections are full of analytical procedures, including extensive use of chromatography for separating the vast range of compounds encountered. Details of an oscillographic polarograph for analysis of sulphur compounds is also given. Naturally only Russian research was given a t the conference but reference is made to work in Western Europe and America. The book is relatively free from errors (although in some places benzene is spelt benzine), and the standard of translation is high. The major criticism is that the length of time since the original Russian publication (7 years), causes the book to be only of reference value, because most of the information is now already known to those working in this field. W, T. ELWELL G. NICKLESS

ISSN:0003-2654    

DOI:10.1039/AN9669100542

出版商:RSC    

年代:1966

数据来源: RSC

摘要:

546 BOOK REVIEWS [Analyst, 1701. 91 Errata JLWE (1966) ISSUE, p. 343, 4th line of synopsis. JULY (1966) ISSUE, p. 431, 10th line under Fig. 4. For “for tetramethyl lead and 86 to 89 per cent. for tetrsmcthyl lead” read “for tetraethyl lead and 86 to 89 per cent for tetramethyl lead.” For “of the indicator” read “of the phenol.”

ISSN:0003-2654    

DOI:10.1039/AN9669100546

出版商:RSC    

年代:1966

数据来源: RSC