BOOK
REVIEWS
pH Measurement and Tiimtion
G. Mattock, with a chapter by G. Rose Taylm, Electronic Instruments, Ltd., Richmond, Surrey, England. The MacMillan Co., New York, 1961. xiv 406 pp. Figs. and tables. 14.5 X 22 cm. $14.50.
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The measurement of the pH of a solution has become such a simple task since the advent of the glass electrode and the electronic pH meter that one tends to lase sight of the theoretical and experimental limitations of the results that are obtained. This book seeks to make the reader aware of the limitations and fundamentals of pH measurement and serve as a practical textbook for technologists in the chemical industry. I t is generdly successful in these aims. The hook treats theoretical prinoiplea and definitions involved in pH measurement, pH measuring and reference electrodes, instrumentation, laboratory and industrial measurements, and aqueous, non-aqueous and automatio acid-base titrations. The author is most successful when he is discussing the pmctical aaspects of pH measurements. Although some of this material has been presented elsewhere, the discussion of the operation and construction of the various measuring and reference eketrodes is very useful. The explanation of "poisoning" of the hydrogen electrode is very clear, as is the discussion of such infrequently-mentioned topios
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as speed of response, resistance measurement and insulation of the glass elee trode. A brief section on reference elee trodes for non-aqueous media is also included. The chapter on the effects of temperature variation on pH measurements discusswr not only changes in the "slope factor" (2.303RTlF) but also the zero shift due to tempert~ture differences between the standardieation buffer and the test solution, temperature hysteresis, and other effects, and is, to this reviewer's knowledge, the most complete treatment of its kind available. The chapter by G. Ross Taylor on pH measuring instruments presents a lucid explanation of the principles of operation of various pH meters and a classification of moat of the pH meters currently in use. The book is much weaker when diacussing theory. The initial discussion of electrolyte solutions, although hasically correct, is too cursory to be of help to a person not already familiar with this material. The same is true of the theoretical treatment of acid-base titration curves. Fortunately these topics have been discussed adequately in other texts. The chapter on acid-base titrations includes, however, a valuable review of the various methods of plotting experimental data in location of the equivalence point in difficult titrations. Although the practical aspects of non-aqueous titrations (solvents, titrants, standardization procedures, endpoint detection, applications) are well
in This Issue
G. Mattock, &h a chapter by G. Ross Taylw, pH Measurement and Titration J . G. Kirkwood and Irwm Oppenheim, Chemical Thermodynamics E. Cartmell and G. W . A. Fowles, Valency and Molecular Structure E. A. Moelw?m-Hughes,Physical Chemistry S . H. Pinner, A Practical Course in Polymer Chemistry Francis J . C. Rossotti and Hazel Rossotti, The Determination of Stability Constants and Other Equilibrium Constants in Solution Stig Vabel, The Identification of Organic Compounds: A Manual of Qualitative and Quantitative Methods A1 Stellerrnark, Quantitative Organie Microanalysis K1al-e S. Mmkley, editor, Fatty Acids: Their Chemistry, Properties, Production and Uses. Part 2 H n r y Guerlac, Lavoisier: The Crucial Year J. H. de Boer et al., editors, Reactivity of Solids J. L. Moilliet, B. Collie, and W . Black, Surface Activity J . T. Davies and E. K . Rideal, Interfacial Phenomena Committee of the National Science Teachers Association, Quality Science for Secondary Schools Eugene Garfield, An Algorithm for Translating Chemical Names to Molecular Formulas Robert F . Gould, editor, Searching the Chemical Literature
described, no mention is made of the theory of these titrations, such as that given by Kolthoff and Bruckenstein for titrations in glacial acetic acid. The hook is well documented with literature references, with some in 1960. Some minor errors are present, hut they do not detract from the usefulness of the book. Generally the hook contains such a wealth of information and detail on apparatus and technique that it is highly recommended as a handbook for workers interested in pH measurement. Unfortunately the price of the book is 80 high in comparison to its size and mechanical conformation that its distribution will probably be somewhat limited.
ALLEN J . BARD University of Tezas Austin
Chemical Thermodynamics
J . G. Kirkwood, late of Yale University, New Haven, Connecticut, and I ~ w i nOppenheirn, Magsachusetts Institute of Technology, Cambridge. M e Graw-Hill Book Co., Inc., New York, 1961. ix 261 pp. Figs. and tables. 16 X 23.5 cm. $8.75.
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This hook is an unusual and most valuable addition to the textbook lib erature in thia field. Within the very modest hulk of a scant 250 pages, it manages not only to treat, with adequate detail, eseentially all the topics usually covered, but also eome, like the Thermodynamics of Surfaces, Electric and Magnetic Fields, and Gravitational and Centrifugal Fields which, though of considerable importance, are often neglected. I t achieves this economy by an admirable conciseness and clarity and the avoidance of circumlocutions, fuzziness, and irrelevant details. The necessary concepts are introduced with precision and meminglulnesa and the discussion is vigorous and closely reasoned. Yet, there is no stinting on needed verbal explanations and relevant details and applications are presented fully. A very helpful and welcome feature is the introduction of each chapter by a short, descriptive paragraph giving the contents of the chapter and placing it aithin the general framework. This reviewer especially welcomes the book's concentration on the macroscopic aspects and the almost complete omission of statistical mechanical ideas; it is his opinion that only thus can the power and unity of the subject be demonstrated and conceptud confusion avoided. A noteworthy feature is the thorough discussion of the Second Law in terms of Camtbbdory's principle. At several points the reader will find it necessary to refer to the eources for additional details or derivations and explanations that are only sketchily indicated; a brief mathematical appendix, while helpful, would not in itself be adequate for the average student in mastering the more difficult mathematical points. Volume 39, Number 7, July 1962
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The book seeme to be ideally suited for eraduate course of use as a textbook in a ~, thermodynanicr for phyrirul rhemwrry studeuts or for self-ytdy I,J persons seriously interested irr the furdamenrnl aspects of the subject. ~
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E. M. LOEBL Polytechnic Institute of Bmoklyn Bmoklyn, New Y w k
Volency and Molecular Structure
E. Cartmell and G. W . A. Fowles, both of the University of Southzmpton, England. 2nd ed. Academic Press, 294 pp. Ine., New York, 1961. xii Figs. and tables. 14.5 X 22 om. $7.
This need is not often recognized in American textbooks, where material is normally either stated dogmatically, developed fully, or not mentioned a t all. Prospective authors might be well advised to study the approach taken in this book, to see if it cannot be applied in other areas, so that students may gain an intuitive erasn of the direction of m.. swrrh rogrthtr with e m w ind~mtio~r as to t r ~ ~ t n l r nCRIl t s he whew more IIIOTOUY~ found. The book is likely to he of use in Senior "Advanced Topics" or "Seminar" courses, and as a book to keep near at hand for seniors, graduate students, and teachers.
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crystal field theory, valeneebond theory of metals, miorowave spectroscopy, EPR and NMR spectroscopy, mscromolecules, and optical rotatory dispersion are not mentioned or are very inadequately treated. The second edition (1961) differs from the first (1957) in only minor ways. Despite its general failure to incorporate adequately the developments of the last two decades the book will be a valuable referenee work for tboae desiring a, clear, sound, easily read introduction to the foundations of a variety of topics and will be particularly useful to graduate students and workers in the field of physical cbemistry. It is a remarkable achievement for 0 . T. BENFEY a single author and represents a unity of Earlham College viewpoint unattainable in compilations Richmond,Indiana of chapters written by different authors. Printing and binding are excellent, it is remarkably free from errors and the price is reasonable for a text of 1333 pages. ~~~
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The authors are to be commended for bringing this useful summary of valence Physical Chemistry theories and applieations upto-date, within five years of its original publication (of. review of 1956 edition, ~ a l Js O U R N A ~ E. A. Moelwy12-Hughes, University of Cambridge, Cambridge, England. 2nd 34, 52 119571). ed. Pergamon Press, New Yark, 1961. Part I on Quantum Theory and Atomic 1333 pp. Figs. and tables. 17 X vii Structure is essentidly unchanged. Part 25 cm. $17.50. I1 dealing with the Quantum Theory of Valeucy bas been rearranged to put The author has provided an unusually greater emphasis on molecular orbital detailed and comprehensive treatment of treatment, this approach now heing physical chemistry written with skill and developed before the valence bond method, care. Experimental and theoretical founThe word resonance is now relegated to the dations are considered side by side and end of the valence bond discussion, mathematities is used extensively. The mainly to emphasize the misconceptions subjects are largely developed in a eonengendered by the term, whereas in the ventional manner as is fitting in a text. first edition the mechaniod resonance Some exeellent problems are included with analogy was used as a device for introeach ehapter. ducing this approach. The change is The book begins with ehapters on welcome. kinetic-molecular theory, quantum meSome recent data have been included in chanics, thermodynamics and st&tisticel Part I1 such as Kolos and Roothaan's mechanics and these theoretical methods (1960) computer solution of a fifty-term are used freely in the remainder of the function for the energy and bond length of book. There fallows a discussion of the hydrogen molecule: atomic structure, two chapters on maleeular structure based largely on specD(~v) R(H) troscopy, and a series of chapters an the Experimental 4.7466 074116 states of matter--gaseous, crystalline, Calculated 4.7467 0.74127 metallie, liquid, dissolved, ionie, and The forty-page expansion of this edition interfacial. The book closes with chaptern over the first occurs largely in Part 111, on homogeneous and heterogeneous equiThe Application of the Principles of libria and on kinetics of gaseous, heteroChemical Bonding. The major innovageneous, photoehemiod, and solution tion is the extensive treatment of ligand reactions. Much material not ordinarily field theory and its more important available in textbooks, such as a chapter achievements in the chemistry of coon intermolecular energy, is included. A multitude of useful tables and graphs ordination compounds. The very useful increase the value of the book as a refgeneralizations of Gillespie and Nyholm erence work. (1957) regarding the geometrical dietribution of electron paim and the relative Although intended for a text in British significance of lone pair and bonding pair universities it does not seem likely to be repulsions are used extensively. Part I11 very useful as such in the U.S.A., since has also been made more useful by numthere is too much material and the level is erous tabulations of available hybrid too advanced far our undergraduate orbitals, geometries resulting from them courses. It might be more useful for and examples. courses a t the graduate level but those The book is "mainly intended for tend to be broken up and covered one first-year honors students" of the British topic a t a time, and this would rarely be a first choice aa a text for s. course in any University system. It does not fit easily into the American pattern, heing too particulm topic. advanced for introductory college inOn the debit side it must be noted that organic courses hut not mathematically coverage of the literature beyond 1940 rigorous enough for graduate school uee. is very sketchy and one eould scarcely It attempts to give the student a "feel" count on the referenees even for an introfor the rightness of a solution when it duction to the recent literature. Tables cannot be solved fully, so that "the reader of data are often ouhf-date. Many subjects such as molecular structure and may accept the results without feeling chemical binding, moleoular orbital theory, that the procedure is quite arbitrary."
MAXT. ROQERLI Michigan State Univewity E. Lansing
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Journal of Chemicol Education
A Practical Course in Polymer Chemistry
S. H . Pinner, Borough Polytechnic, London, England. Pergamon Press, 156 pp. he., New York, 1961. xv Figs. and tables. 14.5 X 22 cm. $4.50.
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This slim volume provides carefully detailed instructions far 41 introductory laboratory experiments involving the synthesis and analysis of polymers. These experiments were specifically designed to furnish praetieal experience required of candidates for the graduateship examinstion given by the British Plastics Institute. Nevertheless, those beginning palymer work in industry or in universities should find this book a useful source of procedures. The experiments fall under three broad beadings: .monomer preparation and the modification and degradation of polymers (12 experiments), polymerization reactions (21 experiments), and polymer evaluation (8experiments). The polymeri~ationsection includes examples of bulk, solution, suspension, and emulsion polymerization, copolymerieetion, redax and ionic polymerization, and polycondensation. Most of the samples prepared are tested to ascertain the quality of the nroduet. r - ~ The instructions are concisely presented in the following format: purpose, r e aetion, special equipment, materials, and total time required,,procedure, and report. The Introduction meludes a list of the general equipment required. There are 22 line drawings, most of which illustrate details of experimental setups. Two appendices furnish praotieal snggestions concerning osmotic pressure and viscosity measurements for more advanced workers. These draw upon the author's eonsiderable experienoe, and will be of value to those in industrial and academic laboratories. The reviewer's only disappointment was to find osmotic pressure treated in terms of the Flory-Huggins ~~~~~~~
