Reference electrodes: Theory and practice (Ives, David J. G.; Janz

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BOOK REVIEWS

striven t o maintain functional balance hetween theory and experiment, since "all reference electrodes must. be examined All told, this reviewer considers Wallfrom bothmechanisticand thermodynanic work in this second edition has produced viewpoints. They must, in the limit, be an excellent yet inexpensive book, nicely regarded as working electrodes a t which trimmed to the objectives of the specialbalanced processes maintain s. dynamic ized group for whieh i t is designed. equilibrium which the act of use in measWILLIAM H. JONES urement must not significantly disturb; Emory University . . . these processes. . .are themselves of Atlanta, Georgia great intrinsic interest." Twelve chapters cover theory, the hydrogen electrode ("the best electrode of all, Reference Electrodes: Theory and Pmccapable of the highest degree of rep*+ tice dueihility"), mercury-mercury ( I ) salt, Edited by David J. G. Ives, Birbeck silver-silver halide, glass, quinhydrane, College, London, England, and George oxide and sulfide, sulfate, and membrane J . Janz, Rensselaer Polytechnic Inelectrodes, nonaqueous reference, biostitute, Troy, New York. Academic logical, ttnd fused-salt electrodes. 651 Press, Inc., New York, 1961. xi Ever since Theodore William Richards pp. Figs. and tables. 16.5 X 23.5 em. of Harvard, in his classic study of the $20. thermal electromotive forces of the calomel electrode (2.physik. Chem., 24,39 (1897)) "ReferenceEleotrodes,"edited by D.J. G. described the behavior of some of his Ives of Birkheck College, London, and G. calomels as "lobenswerte," electrochemists . I . Jane of R.P.I., includes as en-authors, have been on the look-out for "praisetogether with t h e editors, R. G. Bates of worthy" and "unpraiseworthy" electrodes. the National Bureau of Standards, D. B. The present volume, in an admirable blend Cater and I. A. Silver of Cambridge, G. J. of theory and experimental details, enHills of Imperial College, R. W. Laity of deavors t o give sufficient information 80 Princeton, and F. R. Smith of Mullard that the user will be able to prepare only Research Laboratories, of Salfords, Red"praiseworthy" electrodes. In a treatise hill, Surrey, England. as comprehensive as this one, one might The authors state they have long felt the regret that the thermal emf's of the refneed of a book covering "critical and re* erence electrodes, which werealready being sonably exhaustive accounts, with full studied by Richards in the aforementioned bibliographies, of the experimental methpaper of 1897, and which have received ods by whieh the most reliable reference (Cmtinued n page 4 1 3 6 ) electrodes may be set up." They have

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Journal of Chemical Education

BOOK REVIEWS considerable attention in recent years, receive hut a scant mention in Chapter 12. The book, intended for honors graduate students and research workers i n specialised fields, has been well pulled together by the editors so that i t reads as a connected text, while each chapter can stand alone as an authoritative treatise on one particular electrode type. The presentation of text and figures is pleasing throughout. On page 65, the ratio of the physical to chemical atomic =-eights should be amended to read 1.000276.

NMR and EPR Spectroscopy

The NMR-EPR Staff of Van'an Associates, Pslo Alto, California. Pergamon Press, Inc., New York, 1960. viii 288 pp. Figs. and tables. 16 X 23.5 cm. $12.

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This volume is the product of the Third Annual Varian Workshop, held 1959, on nuclear and Octoher 19-23, electron paramagnetic resonance, and is a collection of papers presented by the staff of Varian Associates. One cannot resist commenting categorically that an over-dl attractive feature of the hook is its description of the present status of the equipment AND^^; J. D E B ~ T A U N E fields of NMR and EPR-the design, operating fundamentals, and apBoston College plications in physics and chemistry. Chestnut Hill,Mass.

The book is understandably terse in detailed development of resonsnee and electronic theory. Consequently, to the neophyte who is seeking mathematical and theoretical completeness, the material, though effectively concise, might appear somewhat abstruse. A general impression is that since the papers were each contributed rather independently, there is some repetition, and a t times an ineamplete precursory discussion is followed in a. later paper by a fuller development. The structure of the book is divided into three major areas: Introduction, High Resolution NMR Spectroscopy, and E P R Spectroscopy. Part I is an excellent qualitative and enlightening introductory commentary on thc physical principles of resonance, and why the NMR and E P R spectrometers are such ingenious devices for the detection of resonance. The dipolemagnetic field interaction, relaxation times, the chemical shift and coupling constants are equally well presented. As a matter of organization, there seem to he two maverick papers, the first (No. 18, P a r t 111) on Theory of E P R Spectra, which should more properly find itself in P a r t I, where the introductions are made, and No. 10, Analysis of High Resolution NMR Spectra, which should come near the beginning of Part 11. Part 11, containing ten papers, is devoted to high resolution S M R . Papers of special mention are NMR for the Physical Chemist, wherein a fairly detailed discussion is offered on the t,heory of fast, slow, and intermediate oxchange reactions of protons treated according to McConnell's method. Special techniques such as electric shims to improve field homogeneity, magnetic field modulation, and an NMR integrating system are each described in separate papers. Part I11 on E P R spectroscopy contains nine papers, only one of which deals specifically with the instrumentation of EPR. The remaining eight papers describe some very intriguing aspects of E P R application including biological and photochemical uses. One of the areas of E P R application in which much progress is yet to he made is that of color center systems. Once the atom, ion, or electron is locilliaed in a crystal, specific and reasonably long range interactmns between the electron or nucleus and lattice can arise which are extremely complicated to untangle. This problem is outlined in a paper entitled Paramagnetic Response of Color Centers. Other papers discuss theory of E P R spectra, paramagnetic ions in crystals, and dynamic polarization in liquids. The hook concludes with a. unique paper of four pages which discusses s. Color Center "Workshop" Experiment. This demonstration experiment involved several experimental vvariahles (temperature, microwave power level, and field modulation frequency and amplitude) and the principles of color center resonance. This book is recommended to anyone actively working in the field of NMR or EPR. It is also recommended to those seeking an idea of what is going on in the field currently-what some of the tech(Catinued on page A138)

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