book reviews Someone has finally written down what everyone has to know ta work effectively and sdely with air-sensitive compounds. There can be little question but that this book will he a. classic for some time to come, as was Stock's hook. The hook is really excellent in every respect. There is certainly a p e s t need for this hook and I highly recommend i t ta every synthetic inorganic and organometallic chemist. Shriver's comments and evaluations of equipment sueh as dry boxes and techniques sueh as Schlenk tube operations could only have been made by an expert. Finally, this book gets down to the nitty-gritty concerning the exact details of construction of msjor and minor pieces of apparatus needed in the manipulation of air-sensitive comoounds. Instead of
inorganic and organometallic chemistry by writing such s. finebook. I have recommended to all of my gradus t e students that they buy this book, study it, and use it as their laboratory bible in tho operations and handling of air-sensitive systems. E. C. Asnnv Georgia Institute of Technology Atlanta, Georgia
lon-Selective Electrodes Edited by Richard A. Durst, Institute for Materials Research, National Bureau of Standards, Washington, D.C. NBS Publicat,ion, 1969. (For sale by the Superintendent of Documents, U.S. Government Printing Office.) xxii 452 pp. Figs. and tables. 15.5 X 23.5 em. 83.60.
+
The development of ion-selective electrode potentiometry has occorred largely during the past five years, although the archetypal iion-selective electrode, the pHresponsive gla3s electrode, has been with 11s for over sixty v e ~ r s . R ~ D O I of ~ Sion electrodes for various ions other than hydrogen and sodiom became commercially available only in 1966. Today there are electrodes for about twenty different anions or cations on the market. The present volume, the proceedings of s. January 1969 ~ymposinmsponsored by the National Bureau of Standards, is the first thorough general review of ion-selective electrodes to appear. Roughly equal coverage is given to discussion of the nature of ion-selective electrodes and to their application to various problems. There is some overlap, perticolarly in the discussion of the flouride electrode. There are very few serious errors. Literature coverage is complete through 1968 and there are some references to papers in early 1969.
A722 1 Journol of Chemicol Education
The introductory chapter by G. Eisenman provides a concise summary of the thmry of ion-selective electrode potentials and a. good description of glasses and macrocyclic antibiotics as cation exchangers. The mathematical develapment is left to appendices, where i t can be ignored by the faint of heart. J. Ross's chapter discusses the materials used as ion exchangers in most of the commercially available electrodes and includes clear drawings of the physical arrangement of such electrodes. There is a. eoad disous-
scribes heterogeneous membrane electrodes. These have proven, for the most part., les? sat,isfactory than other types and are not widely used in this country. Dr. Covington has also contributed aehapter on reference electrodes. Various electrodes are described in addibion to the familiar calomel and silver-silver chloride electrodes, and the problems of liquid junction potential, temperature hysteresis, and temperature dependence are discussed in detail. J. Butler and R. Bates discuss the problems associated with making Betivity measurements with available electrodes. Dr. Butler describes equilibrium const,ant and activity coefficient studies possible with ion-selective electrodes, while Dr. Bates addresses h i m d f to the problem of defining activity coefficients for various ions. This problem is a formidable one, largely because ionic strength variations usually accompany changes in ion activity. As Dr. Bates point,s out, changes in ionic strengt,h change not only activity coefficients, but also liquid junction potentials, and the latter may vary more than they do in routine pH measurements. Two chapters, by R. Khuri and by E. Moore describe bio-medical applications. Dr. Khuri gives s general review of the field, while Dr. Moore describes in detail applications of the calcium ion electrode. The utility of ion selective electrodes in medicine is clear even to the lavman. I t he a welcome advance. The remaining chapters by G. Rechnitz, T. Light, and R. Durst summarise appliescations to problems more familiar to chemists. Dr. Itechnitz touches upon the question of electrode response time, which can be quite long, and discusses in detail studies of equilibrium constants and rate constants for some precipitation and com~ l e xformation reactions. Dr. Light describes the use of potentiometry for control and monitoring of industrial processes. Relatively little has been done, but such applications look qnite promising. Dr. Durst provides a general survey of analytioal applications. That ion-selective electrodes are of interest thronghoot the scientific and technical world is demanstrated by Durst's collectian of references from workers in agriculture, biology, medicine, geology, oceanography, and several branches of chemistry. I n summsry, the book is an up to date and readable summsry of an important growing area. of analytical chemistry. I t is highly recommended to anyone whose
interests include the chemistry of aqueous solutions.
MICHAEL D. MORRIS University o j Michigan Ann A~bor,Michigan
Physical Chemidry Problems and Solutions Leonard C. Labmttz, Stern College for Women, Yeshiva. University, New Yark, and John S. AmUs, City College of the City University of New York. Academic Press, Inc., New Yark, 1969. x 524 pp. Figs. and tables. 15.5 X 23 om. Softbound. $7.50.
+
The first part of this hook contains the problemstatementsaf 590problems. The second part consists of rather complete solntians to the problems. The solutions proceed from a statement of a familiar formula with any derivation or rearrangement for the particular case to numerical expressions and .calculated results. The book does not contain m y text material other than the problems and solutions. The problems are arranged in 16 chept,ers by subject matt,ef, and they are further subdivided into Seotions I, 11, and I11 of graded difficulty. The authors intend the book far advanced undergraduates and graduate students. This estimate of difficultyis reasonable: usually Section I problems are of appropriate difficulty for second or third year undergraduate courses, while the problems in Sections I1 and 111compare in difficulty to those found in texts for graduate or advanced undergraduate students. The coverage of thermodynamics and it8 applications is most complete covering 9 of the 16 chapters. The section on gases cont,ains a number of problems on nonideal equations of state, and the later chapters a n thermodynamic functions place a heavy stress on calculations taking non-ideal behavior into account. A number of very good thought questions are included on frequently misunderstood topics such as entropy change, reversibility, ete. Some problems which require derivations are rather inventive and give good practicein the use of partial differentials. The treatment of kinetics covers many interesting applications of measurements on reacting systems, but it relies on trial and error methods to determine reaction order even though graphical methods such as the Powell d o t make these methods unnecessary. T'he problems deriving rate laws from mechanisms are quite inventive, but there is not much emphasis on predicting mechanisms to fit rate laws. The problems on quantum chemistry emphasize basic principles rather well in the use of operators and the standard systems such as the particle in a box. The application of quantum mechanics to the interpretation of spectra and molecular wave functions is not well covered. With its numerous literature references the book does represent a significant effort t o bring a collection of rather advanced (Continued on page A724)
book reviews problems into the hands of students. It may exceed the needs of students in introductory courses, but i t may be an excellent review source for advanced students. GEORGE L. HARDGROVE JR. St. Olaf College North,field, Minnesota 56057
Quantum Mechanics of Molecular Rate Processes
R. D. Iminr, Ohio State University. Oxford University Press, London, 1969. xi 335 pp. Fig. 13 X 23.3 cm. $14.40.
+
The significance of quantum mechanics for chemixtry is that in principle it gives the solution to almost every chemical problem. However, in practice, the situation is, as 1)irac sbsted in 1929, "The underlying physical laws necessary for the mnthematici~l theory of s. large part of physic? and the whole of chemistry we thus completely known, and the difficulty is only tbe exact application of these laws leads to equations much too complicated to be solvable." Due to the mathematical diffimlty, the quantum-mechanical theory of rate processes has only recently been suffioiently developed and fundamenial qnxntnm mechanical treatments have been carried out for only certain simple reactions. Neverthelesz, the importance of qnant,um mechanical treatrnentz for chemical reaction rates is well known by now. In dealing with chemical rate processes, t,he very simple hard-sphere collision theory of react,ions was widely used a t one time, but. was soon found to he unsabisfactory. In the 1930's t,he development of nbsolute reaction r8t.e theory represented s very important achievement. However, crossed molecular beam and infrared chemiluminescenee experiments have recently been developed to such an extent that i t is now possible t,o obtsin det,aiIed information shout reaction mechanisms, e.g., one csn measure t,he energy and angular distributions of the prodricts. Such results cannot be intepreted by t,he absolute reaction rate theory. These experiments have led to t,he formulation of alt,ernat,ivet,heories which are more nseful and treat rnoleculm collisions in a much more realistic way than had previowly been possible. This book is written to survey these alternative theories whieh have been developed in the last few years. In the first part of the book, the neces sclry quantum mechanical concepts are introduced in terms of a discussion of physical "at,tributes2' and their a v e r q e values as measured in an ensemble of identical, noninteracting systems. The concepts of a state and its representation by s n amplitude and the spectral representation of operators are discussed as tools designed for the evaluation of average values of attributes. The equations of motion for the average values and Green's operator for
A724 / Journal o f Chemical Education
the Schr6dinger equation are also briefly described. The second part of the book is devoted to the quanta1 collision theory. The Lippmen-Schwinger equation in stationary collision theory is inbaduced. This equstion for structureless particles (potential scattering theory) is discussed and solved for the case of separable intersctions. Concepts of scattering amplitude and cross-section are introduced and evaluated exactly for separable inter&* tions and, in general, to the lowest order in the interaction (the Born tapproximatian). The method of partial-wave analysis is described and applied to scattering by a central potential. The equations for relative motion during a collision of molecules with internal structure m e derived. Application to rotational excitation and the Born approximation are also discussed. After the introductory discussion of collision theory, the author presents the operator formulation of collision theory and introduces the concept of the S matrix and the techniques nsed in the bheory of seattering by two and by several potentials. The discussion is extended to cover react,ive collisions. The author also treats the formulation of collision theory from a time-dependent point of view. The technique of t,ime ordering is used to reintruduee the wtwe operator that transforms the wavefunction for the svstem., -in the absence of interaction, to the actual wavefunction. The m e of symmetry in collisions, in particular, time-revernal invariance and its consequences in the form of t,he reciprocit,y and the microscopic reversibility theorem is also discussed. The applicabion and extension of the collision theory are considered in Part 3. After introducing the partitioning technique, the author uses i t in various aspects of molecular encounters. This technique is also applied to the operator formulation of callision theory. Various models in collision theory, whieh are designed to replace an exact solution for the dynamics of the collision, are described. The theory of unimolecular reactions i q discussed. The author concludes the book with a formal disoussion of time-correlation funetions and their application in the study of the linear response of s. system to an external pertmbrttion. The Liouville operator, which enables one to employ the ~artitioninetechniaue in the solution of
treatment is elegant. However, for a book of this type one should expect a more critical and analytical discussion on varinus theories and methods, not just a, restatement or reformulation. Besides, some topics are treated in quite a. terse style. They may not be intelligible to the reader with only a. conventional introductory undergraduate quantum mechanics course, as the author assumed for this book (see the preface). Ilespite these minor shortoomings, I still highly recommend this book to readers with strong quantum mechanical background and rwearch workers in the fields of theoretical chemistry and chemical kinetics because the present book does give a. logical and rigorous description of the quantum me-
last few years.
Ynn KANGPAN Boston College Chestnut Hill, Mess. 02167
Enzymic Calalyrir
John Westley, University of Chicago. Harper and Row, Publishers, New York, 1969. xiii 206 pp. Figs. and tables. 15.5 X 23.5 em. Softbound. $5.95.
+
According t o its author, this book is directed as an aid t o "graduate students in biochemistry and dlied fields who combine a curiosity about enzyme mechanisms with some background in organic chemistry and biochemistry, and a t least an introduction t o physical chemistry." In reality, its audience would seem t o be restricted t o those well versed in physical organic chemistry. Anyone who would pick up this book with the idea of casually reading i t for general information on enzyme eat& ysis and mechanisms would be in for s. rude awakening. But for those who are oriented toward the interface of physical organic chemistry and biochemistry, the book does a thorounh and commendable iob. I t is broken-down into four parts. Part I, Fundamental8 of Enzymology, goes into both the chemiiitsy of proteins and the behavior of catalysed reactions in general. Part 11, The Farms of Enzyme Mechanisms, deals primarily with the kinetic analysis of two-substrate reactions. Past 111, The Particulars of Ensyme Mechanisms, is devoted to methods of determining rate constants for individual reactions and for identifying the particular enzymic groups involved in catalysis. I n the latter vein, Chapter 14 is devoted t o Identification of Specific Groups: Use of pH Variation and "Group-Specific" Reagents. I t appears t o this reviewer that the author must have decided a t the last minute t o throw in the sections on groupspecific reagents because it was the "in" thing to do, and that he should have either left them out entirely or devoted more time t o them. Part IV, Metabolic Control a t the Ensyme Level, deals primarily with "allosteric" enzyme svstems. The author's coverage of this very interesting and emerging area is minimal, and this reviewer believes that more time might also have beenspent on this topic. Although the scope of this book was intended t o reach a general audience, its usefulness would seem t o be as a reference work for someone actively involved in the area. Each of the chapters is well documented with both general references and numerous specific references. Thus, the book could be used t.o advantage in a graduate course devoted t o enzyme catalysis and mechanisms.
C. L. Bonoms, JR. College of Wooster Woostw, Ohio (Continued a page A726)
