Chemical Systems: Energetics, Dynamics, Structure(Campell

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book reviews Editor: W. F. KIEFFER CQlege of Woorter

W-ter,

Chemical Systems: Energetics, Dynamics. Structure

J . A . Campbell, Harvey Mudd College, Claremont, California. W. H. Freeman and Co., San Francisco, 1970. xiv + 1111 pp. Figs. and tables. 19.5 X 26 em. $12.50. "Chemical Systems" is 8. carefully structured approach to responsibly teaching introductory chemistry to science students. The main premise is that content should be introduced in the manner of scientific problem solving: present observations first, make what you can of them using existing theory and common .sense, then develop sufficient additional theory to accomodate what remains unexplained. Put the expanded theory to the test of predicting the p r o p erties of other system, compare with observed behavior, and iterate the process throughout the course. The ideal result is that the student in addition to learning chemistry gains an enhanced appreciation for the reasoning process by which complex scientific problems have been solved in the past, and thereby develops the sbility and confidence to approach unsolved problems independently. The openkg chapter, Conservation and Change, illustrates the approach very well. At the outset a variety of interesting chemical reactions are presented. To discuss them the author develops atomic symbology and introduces chemical equations. To describe the other

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observations (evolution of heat, light, change of phase) AH and AS are qualitatively explained and rationalized into the free energy equation. By the end of the chapter, students are guessing the signs of AG's for chemical equations and predicting if the reaction will go ss written. The predictions can he tested against observations made during classroom demonstration of the reactions (facilitated by instructions collected in the Teacher's Guide) or by comparison with reported data. Other observations on the system, such as a wlor change, key up the introduction of additional theory. The hook contains forty chapters, some twenty to twenty five of which can be covered in the standard two semester course. The chapters are grouped into seven parts: Energy, Atoms and Molecules (12 chaps.), Chemical Bonds (5), Dynamic Equilibria (3), Rates and Mechanisms (5), Thermodynamics (5), Structure and Change (5), and Reaction Chemistry (5). Basic material in each chapter is presented under red section headings and advanced materid under black section headings or in smaller type. An extensive set of numerical problem of. graded difficulty follows each chapter and extends the material considerably. For these a sturdy grounding in dimensional analysis is absolutely essential (Estimate the number of molecular layers lost by an automobile tire per revolution). The Teacher's Guide contains fully worked out solutions to each problem. A valuable selected bibliography of chemical educsi

-Reviewed in this Issue J . A . Campbell, Chemical Systems: Energetics, Dynamics, Structure Arnold Thaekray, Atoms and Powers: An Essay on Newtonian Matter-Theory and the Development of Chemistry Jaek E. Fermndez, Modern Chemical Science R. T . Sanderson, Chemical Bonds and Bond Energy Joel H. Hildebrand, John M . Prawnitr, and Robert L. Scott, Regular and Related Solutions: The Solubility of Gases, Liquids, and Solids Hans Netter, Theoretical Biochemistry N . Amand, J . S. Bindm, andS. Rangamthan, Art in Organicsynthesis Herbert A . Sober, editor, Handbook of Biochemistry: Selected Data for Molecular Biology R. Alan Jones, An Introduction to Gss-Liquid Chromatography K.Yamauuchi, Dataof Natural Products. Vol. I . . Soectral C. Simpson, Laboratory Instruments and Techniques Series: Gas Chromatography A. Wilson, Laboratory Instruments and Techniques Series: pH Meters H. Lipson andH. Steeple, Interpretation of X-Ray Powder Diffraction Patterns A . Rabemu, editor, Problems of Nonstoiohiametry S. Sourkajan, Reverse Osmosis New Volumes in Continuing Series

A560 / Journal o f Chemical Education

tion articles on the topics covered of each chapter is given in an appendix. The overall presentation achieves an excellent balance between chemical theory and descriptive chemistry, interleaving the two throughout each part. Most major chemical concepts are introduced qudit%tively in an early chapter in the context of some application, then given a complete treatment in a later chapter. This is espeoizlly well done in Chapter 5, The Chemical Elements, wherein the theory of atomic energy levels is woven into practical information on occurrence and preparation of the elements. Lewis structures are introduced a t the end of Chapter 5, but extensive discussion of bonding theory is postponed until Chapters 14-17, after spectroscopic evidence for the existence of molecules has been presented. Molecular geometry and related properties are clearly developed before valence bond and molecular orbital theory. With this approach, seemingly arbitrary concepts like atomic orbital hybridization can be considered in much better perspective. Including a substantial quantity of advanced mrtterisl makes the hook appear more formidable than it rtotuelly teaches, since the essence of the spproach can be developed on the basis of the red sections plus selective inclusion of advanced topics. At thi! same time the presence of the advanced material is very valuable since it is readily avdilable to highly motivated students fa. soecial advantaee and encourages browsing in areas not covered in clsss. In this form the text can also serve as a. secondary reference for advanced courses, giving maximum value for the student dollar. The level of presentation is uniformly high. Many sections require several readings for adequate comprehension and the student is carefully advised of this in the preface. His persistence will he well rewarded with an experience in introductory chemistry highly relevant to a research career in the physics1 and life sciences. Davro L. BEVERIDGE Hunter College of the City Lrniuwsity of New York New York, N . Y . lWBl

Atoms and Powers: An Essay on Newtonian Matter-Theory and the Development of Chemistry

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Arnold Thackray, University of Pennsylvania, Philadelphia. Harvard University Press, Cambridge, iMass., 1970. 326 pp. Figs., tables, and hihxxii liography. 15 X 23 cm. $12.

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This is a fascinating h o ~ k ! It is written gracefully and elegantly and is a jewel in the Harvrtrd Monographs in the History of Science edited by a. committee chaired by I. Bernard Cohen. I t traces the development of chemistry from Newton to the radical break with Newtonian chemistry

occasioned by Dalton, yet i t is as much a. book on intellectual history as i t is a history of chemistry. ~ e w t o ndid a n astonishing amount of chemistry and developed notions of chemical affinities related to his concepts of attractive forces. H e believed these affinities could he quantified and explained 'by mathematical lsws. He attempted firmly to reconcile God, force, and brute matter. Central to his concerns was to develop a form of atomism free from all taint of materialism and atheism. He also mmaged to do an astonishing amount of chemistry even while he believed firmly in t,ransmutation and the matterless nature of the universe. By the mid-eighteenth century, chemistry had already established its identity and prafessionslization. I t had its own teaching and research chairs in universities. Of the three Newtonian beliefs in matter-theory, short-and-long-rsnge forces, inertially homogeneous matter with complex internal structure, and the imponderable repulsive-fluid ether, only the last survived. Boscovich, in particular, thought of elements as points possessing only inertia and relative acceleriltions. He argued in elaborate mathematical terms that a t infinitely small distances the "force-curve" tends to infinite repulsion. One of the more interesting of the science-society phenomena of that time, carried on to some extent in modern England, was the popular science lecturing tradition. The English cofiee houses were hosts to thesepopulsr science lectures and they were widely accepted by the English public. Many scientists of that time were able to make their livings through this tradition. Priestley's work toward the end of the eighteenth century was received with great antagonism. His chemistry was believed to be "materialism pure and simple" end "materialism must terminate in atheism." I t was into the environment in whioh theological belief conditioned acceptance of work in chemistry, that John Dalton introduced his own work. His intelleotusl development was strongly conditioned by his Quaker pietistic and conservative theology. His education, contrary to popular belief, was quite sophisticated. His work and thinking was fundamentally anti-physicalist and antiNewtonian and because it was predictive, it was able to end the century-long tradition in Newtonian chemistry. His lew of partial pressure (1793) came a t a time when i t was believed that there were allpervasive chemical forces. His atomic theory and atomic weights (180.5) aroused no interest when first published. This is not surprising because i t took Dalton several years to see the consequences of his own work, a. phenomenon found frequently in the history of science. By 1810 Dalton recognized i d l y the implications of his work and others were quick to see its implications. This book describes in detail the theological, national, and social backgrounds of chemical theory. I t details the. reduetionist effortsby Newton and his followers. While most of the chemists discussed are English, continental chemists with their

differentbackgrounds are part of the thesis of this book. Their science is modified by their own intellectual and social milieu. From this development it becomes clew that Dalton did indeed engineer a chemical paradigm.

discussions which include good physical analogies. A fine selection of references a t the end of each chapter includes original sources and reviews from papular journels which are useful and desirable as teaching aids. In the preface, the author states his LEO SCHUBERT primary objective: to convey to the nonThe American Univmity sciencestudent an appreciation "of the real Washington, D. C . nature of chemistry as a science in s state of intellectual m d happy turmoil". I t is the opinion of this reviewer that he succeeds moderately well with this lively presentation.

Modern Chemical kienee

Jack E. Fernandez, University of South Florida. The Macmillan Co., New 288 pp. Figs. and York, 1971. xii tables. 24 X 16 cm. $8.95.

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This textbook is written for a one semester (one term if same material is deleted) survey course in chemistry for nonscience msjors. As such, no mathemstical material beyond the level of average high school preparation is presented. The book is one of several newly published, or about to be published, texts which are concerned more with telling the story about chemistry than with providing a detailed and rigorous account of chemical principles. Much of the general presentation is set on an historical foundation. T h e material covered and the style should be attractive to students not professionally interested in science, although this text does not distinguish itself from other offerings in this ares. It is refreshing, however, to know there is so much current interest in exposing the non-professional student to textual material shout chemistry and chemical technology that is relevant to his casual involvement in science. The most noticeable deficiencies in this reviewer's opinion are related to (1) the ordering of chapters, (2) the paucity of problems, and (3) the uneven level of sophistication in some of the dkcussion. It is strongly felt that in a text of this general type every effort should be made to promote continuity in the subject matter. I n this case, a reorganization of chapters would serve to accomplish such s. continuity. For example, a grouping of chapters 6, 9, 13, 11, 12, 15, and 16, in that order, might provide a more unified approach to organic chemistry and its applications. I n general, the problem sets are disappointing, both because there are so few questions in each, and because many of the questions are not up to the standard of the discussions in the text. The third critioism refers to the author's tendency in a few places to lapse into complex terminology and discussion, for example, Chapters 6 and 11. I n addition, on occagion, important concepts, such as that of the mole (p. 173) are introduced in footnotes without adequate development. Very few technical or typographical errors are apparent throughout the book (one such error occurs on page 142, equation two). The strength of this book as a text lies in bold attempts, and frequent suecesses, a t exposing the nonscience oriented student to some truly exciting advances in chemistry and technology. This is gene r d y accomplished in very readable

LEONARD D. SPICI,:R Uniuersily of Utah Sall I,& City, 8411.9

Chemical Bonds and Bond Energy

R. T . Sanderson, Arizona State University, Tempe. Academic Press, New York, 1971. ix 222 pp. Figs. and tables. 23.5 X 16 cm. $11.50.

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Professor Sanderson's approach to bond energies is highly original. While most chemists will not agree with all his o m ventions on electronegativity, charge distribution, covdmt radii, and super single bonds, his challenge to the more f r e q u e d y adopled conventions does serve a useful pnrpose. The range of comnounds for which Sanderson is able to

is truly impressive. On the other hand there are cases such as BHzCO(g), HBe(g), CCldg), and K&c) where the discrepancy between calculatedand exoerimentalvxlues is greater than 10 kcal mole.? Far from ignoring these, the author gives them full discussion. Professors involved in teaching inorganic chemistry may find the types of explanations for observed phenomena in this book useful as models for what can be done with bond energies. Unfortunately i t is not easy to learn how to calculate bond energies from this book. For example, partial charges calculated by Sanderson's methods are used, but the application of these methods in this book does not extend beyond diatomic molecules. I found it necessary to refer to his earlier publications in order to fallow the ealculsLions presented here. Similarly the discussion of the distinctions between the three homonuclear bond energies for N, 0,F and similar elements is spread over a number of chapters. Thus a substantial amount of study is required before one can follow the calculetions. For this reason I would hesitate to refer undergraduate students to this book. The most unique f e ~ t u r eof Sanderson's calculations is the use of experimental bond lengths. This procedure automatically gives a lower bond energy for alonger bond: for example, 105 kcal mole-' s t 1.03 in OH compared to 112 kcal mulecl a t 0.96 A in 11.0. This use of bond lengths also provides a useful way of edculsting the "resonance energy" in

Volume 48, Number 9, September 7977

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book reviews molecules like benzene and anthracene, or 'even in graphite. Sanderson's methods of allowing for increming hond energy with increasing eleetronegetivity difference are 'certainly applicable over a larger range than is Pauling's equation in AxZ. There is a good discussion of the "half hond postulate" for PCls, interhalogen compounds, and xenon fluorides on pages 96-9 and 104. There are many good ideas in this hook, hut i t is difficult to dig them out, and even more difficult to evaluate the significance of the various ideas independent of the rest of Sandenon's conventions. REEDA. HOWALD Montana State University Boreman. Mont. 69715

Many readers will appreciate Professor Hildehrand's introductory remarks regarding the proper role of mathematies in the development of physical theory. He cautions against using mathemati- as a. substitute for thought and promises not to build "imposing mathemat,ical superstructures upon foundations of ill-defined parameters and concepts." Regular solution theory is built close to the ground; its developers are lucid in proceeding from the simnle maximum-randomness entroov

Joel H. Hildebranrl, John M. Prausnilr, hoth of University of California, Berkeley, and Robert L. Scott, University of California, Los Angeles. Van Nastrand Reinhold Co., New York, 1970. ix 228 pp. Figs. and tables. 23.6 X 15.7 om. 810.95.

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"Regular and Related Solutions" is a welcome extension of the classic monographs, "Salrtbility of Nonelectrolytes" and "Regular Solutions" by Hildehrand and Scott,. The hook will he a valuable addition to the library of chemists and engineers who require a, working knowledge of the thermodynamics of liquid mixtures. The development of the regular solution concept and the solubility parameter equations is retraced from the beginning, and newer applications and extensions are incorporated into a very readable whale. Much of the material is new, including expanded sections on solutions of gases, polar solutions, and free energy calculations. The regular solution and solubility parameter theories have found extensive application in numerous fields of science and engineering in the prediction and correlation of properties of nonpolar mixtures. One indication of the utility of the development provided in the earlier hooks is the frequency with which the work is cited; during recent years, the two monographs have been cited more than a thousand times in major research journals in diverse fields. "Regular and Related Solotians" does not pretend to he comprehensive in tree& ing alternative theories of liquids and solutions. The authors make clear their aversion to lattice models as a point of departure for predicting thermodynamic properties of liquids and liquid mixtures. Little attention is given to the molecular and statistical thermodynamic theories of nonpolar liquids which have been developed by other schools.

A562 / Journol of Chemical Education

N . Arnand and J . S . Bindra, Central Drug Research Institute, Lucknow, and S . Ranganathan, Indian Institute of Technology, Kanpur, India. HoldenDay, Inc., Ssn Francisco, 1970. xiv 414 pp. Figs. and tables. 23.5 X 16 cm. $9.95.

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Rather than a. text on standard methods or organic synthesis, here is a hook of which the avowed purpose is to illustrate the art of combining standard,. and some not so standard, synthetic methods to of nonelectrolyte mixtures solve complex synthetic problems. SHERRILD. CHRISTIAN Whereas the exciting discoveries in organic University of Oklahoma chemistry during the twentieth century Norman. Oklahoma 73069 lie in the successful explanation of chemical and physical properties by electronic and steric factors, the great achievements of oreanic chemists in this centurv have been

At first sight, this hook appesrs to be a momentous work in the area of biophysical chemistry. Further examination reveals i t to be much less than first meets the eye. The work ir an English translation of the German edition first published by Professor Netter in 19.58. A check of the references indicates that very little new material was added to bring the hook up to date. The references to original articles show very few after 1960. In fact, a spot check indicated that there were numerically more pre-1925 referenres than there are post-I958 references. An indication of how far behiid the times the book is: the section on structural analysis by X-rays (pp. 408-17) has 1956 as the date of its most recent reference. I t does not mention a t all the tremendous advances that have been made in the area. of protein structure determination. Along the same line, the section on eneyme kinetics (pp. 623-89) does not even mention the ares, of allosteric enzymes. No one can hold that every book that comes out should cover these topics, but any newly ~ublished book which supposedly coven "theoretical hiochemistry" should a t Least make an attempt to hring its coverage up to date. To this reviewer, it seems rather questionable whether there is s. need for newly books which ere "years behind the times," especially in an area which changes so rapidly as molecular biology. Another disadvantage is that this book is very difficult to read because of its cold and mathematical style. This may p03sihly he the result of translation. Finally, the most discouraging thing shout the book is its price, $40. This would seem to put i t out of the reach of most private purchasers even if it were a book of unquestionable merit, which i t is not.

ural products ranging in complexity from steroids to nucleic acids. Because of the length and scope of such schemes, very few of them are described in textbooks, and their many steps may he detailed through several journal articles. This hook brings together a substantial number of the more elegant and more important syntheses of divers natural products and other interesting species in outline form. The general problem and the major challenges me discussed tersely in each synthesis. Steps involving ingenious applications of stereospecificity, rearrangement, or positional selectivity are indicated. Occasional hints of mechanism are provided, although the authors make no attempt to explain every reaction. The synthetic steps are given in outline form, with stereoformulas where appropriate. Such diverse orohlems as the synthesis of neoclassical aromatics (e.g., f&racenes and cyclic (CO),'- anions) and thesynthesis of rihonuelease and ribonucleotides are included. Compounds synthesized are presented in alphabetical order of generlc names. References to original works include key references to prototypes of unusual reactions as well as to the original descriptions of the syntheses. Although one might quibble about the selection of examples, each one chosen offers some uncommon yet generally usable spplication of reactions, such as the reduction-rearrangementcombined cycliaetion of a hett+formyl-delta-lactone to a. fnrobenzofurm in the synthesis of aflotoxin BI. This book should delight hoth the synthetic organic chemist surveying the achievements of his art and t,he advanced tescher seeking important examples of the illustrstiaons of modern principles. To the organic chemist familiar enough with the structures named, t,he hook c a n also serve s s a quick reference for methods of preparing particular strnctuml systems. However, the most conspicuous utility of "Art in Organic Synthesis" is t.he basis of s. graduate course in the art of organic synthesis.

C. L. BORDERS, JR. The College of Wooster Wooster, Ohio

L. OLIVERSMITH Valparaiw University Valparaiso, Indiana

Theoretical Biochemistry

Regular and Related Solutions: The Solubility of Garar, Liquids, and Solids

Art in Organic Synthesis

Hans Netlw, Institute for Physiological Chemistry, Kid. John Wiley & Sons, 928 pp. Inc., New York, 1970. xx Figs. and tables. 26.5 X 17 em. $39.50.

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Handbook of Biochemistry: Selected Data for Molecular Biology

Edited by Herbert A. Sober, National Institutes of Health. 2nd ed. The Chemical Ruhher Co.. Cleveland. Ohio. 1722 pp.' Tables. 27.2 x 1970. xi 19.5 cm. $33.50.

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This handbook contains a. very useful compilrttion of dats which should be useful to every practicing biochemist as well as to those only indirectly involved in the area. Section A is devoted to abbreviations and nomenclature of biochemical compounds. Section B is devoted to Amino Acids. Not only does it contain data on the physical properties of these

on gas-liquid chromatography and ion exchange chromotography, to mention some areas of coverage. Section C covers Peptides and Proteins on a level comparable to the coverage of amino acids. Section D is devoted to Carbohydrates, Section E to Lipids, and Section F to Steroids. Purines, Pyrimidines, Nucleotides, snd Oligonucleotides are covered in Section G, and Section His devoted toNucleic Acids. There are also sections on Genetics and Biology (Section I), Physical and Chemical Dats (Section J), and a final one entitled Miscellaneous which covers many topics which do not conveniently fit into any of the earlier sections. A very useful feature of the handbook is that the tables of dats. nearly always make reference to the original literature. All in all, it is a very admirable collection of biochemicsl data and would make a very useful addition to any biochemical library or laboratory. C. L. BORDERS, JR. The College of Wooster Wooster. Ohio

An Introduction to Gadiquid Chromatography

R. Alan Jones, School of Chemical Sciences, University of East Anglia, Norwich, England. Academic Press, 202 pp. Inc., New York, 1970. xi Figs. and tables. 23.8 X 15.7 cm.

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This book is properly advertised as providing "a basic introduction to the practice of gwliquid chromatography for organic chemists." I t is indeed limited to GLC, and the practice is emphasized rather than the theory. As such, it is a useful contribution to the GLC literature. The coverage is quite broad; special techniques like programmed temperature and preparative scale GC are appropriately treated briefly. I t is also "intended to be used aa a For this handbook or reference.. purpose nearly one-third of the book is devoted to tables of stationary phases,

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instruments, and operational problems. Despite this emphasis, the hook will not serve as a useful laboratory manual or reference due to a lack of specific instructions. Far the chemist who is beginning lab work or setting up a chramatograph, a far mare useful book would be the one by McNab and Bonelli ("Basic Gas Chromatography," Varian Aerograph Co., Walnut Creek, Calif., 1969). The latter contains less theory but more explicit instructions. In some. respects the books are complementary. Both are introductory. The hertrt of Jones' book should be Chapter 3, Principles of Operation, in which one is told how to approach an unknown sample. It is too short (20 pp.), and the attempted combination of theoretical principles and practical suggestions lack the clarity necessary in an elementary monograph. The basic theory is also treated in about 20 pages which is inadequate for the depth presented. By comparison, an equal number of pages is devoted to ancillary- techniques used for qualitative analysis (ir, nmr, ms; etc.). This seems to be out of proportion. There are no examples of typical andyseses and few actual chrromatogrh-ms. The comparison of packed and capillary columns is weak. There are about 160 references which is an adequate number for a book of this sine and scope but some important ones have been over-looked. The figures are good (about one-half are taken from other publications), and there are separate author and subject indexes which increase the usefulness of the book. Even though there are a few mistakes (e.g., Figure 7%) and a few misleading statements in the hook, it does provide a great deal of information which will be helpful to the chemist seeking an introduction to GLC.

JAMES M. MILLER Drew University Madison, New Jersey

Labordory Instrumentsand Techniques Series: Gar Chromatography

C . Simpson, University of Sussex. Barnes & Noble. Inc.. New York. 1970. 717 pp. Figs.' and' tables. 22.5 X 14.5 em. $8. The theory and techniques of gas chromatography have been the subject of numerous books that have appeared in the past five years. For this reason, any additional hook that is published must meet a fairly high standard. Any new book shoud be well-written, cover new developments in the area, and ohviously, add something pew to the existing literature. The authors of this volume have compiled 8. book which is not hard to read. It is meant to be a practical book, and in this vein, it is somewhat similar to that published by Varian Aerograph on "Practical Gas Chromatography." It do& include a, compilation of the commercially availilahle instruments, complete with the type of detector employed. Some of the newer ancillary techniques have been included in a short chapter. It covers some theoretical concepts as well as giving many practical cconsiderstions. I suspect that this hook will find its chief use among persons who wish to introduce students to the field of gas chromatography by giving them an overnight reading assignment. I am not sure this volume will prove more useful than the monographs previously published in this field. T. R. WILLIAMS College of Wooster Wooster, Ohio 44691

Laboratory Instrumentsand Techniques Series: pH Meters

A. Wilson, Unilever Research. Barnes and Noble, Inc., New York, 1970. 119 pp. Figs. and tables. 22.5 X 14.5 cm. $6.50.

Spectral Data of Natural Products. Vol. I

K . Yarnag~chi,Torii and Co., Ltd., Nihonbashi, Tokyo, Japan. Elsevier Publishing Co., New York, 1970. v 765 pp. Figs. and tables. 26.5 x 19 cm. $56.

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This is the first of 8, proposed twovolume set to provide a systematic colleetion of the data on the structures of natural products. The basis for classifioation is structural type. Information won by all spectroscopic methods is included: uv, ir, nmr, ord, cd, ms, and X-ray andysis. About 6000 compounds are classified into 20 erouos bv structural tvoe. Included present volume covers compounds known by 1963. This should be a monumental help to workers in the field of natural products. WPK

In the recent years, there has been a renaissance in the use of pH meters as a result of the increased development of specific ion electrodes. The newly published book by A. Wilson is presumably designed to bring the reader up to date on the increased use of pH meters so that one may pick the proper instrument for 8. particular problem. It is my opinion that the author has ~roduced an adequate international listing of pH meters, but has barely scratched the surface and not responded to the new developments in this field. Granted, there are small sections dealing with pH measurements in biological systems such as blood and gastric fluids, hut the t r e a h e n t is simply cursory. The author also spent a very short amount of space dealing with the very important area of specificion electrodes. The subject has been introduced, b u t s treatment which is only three pages leaves the reader with an empty feeling.

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believe, is that its presence emphasizes the fact t h a t . structures can sometimes be determined from powder data. A set of 25 problems and their solutions Much of the material in the first half of have been added a t the end of the hook. the book is a. repeat of the past literature. Since the solutions are presented in some This material is not substantially better detail, the value of the book as a text is than any of the earlier treatments of the certainly increased by this addition. subject. For the price of the book, $6.50, Both authors are well known and highly one might be just as well off purchasing a regarded crystallogmphem, so it is not copy of Bates' earlier work, and reading surprising that the book, in general, the instrumentation section of THIS reveals intimate knowledge of the subject. JOURNAL since the treatment of new liters, It is particularly regrettable, therefore, ture is minimal. The book does have that a number of statements appear in the pictures of different types of electrodes introductory sections which could mislead and simplified diagrams of pH meters, the beginner. Some examples follow: but I am not sure these two items are Item: "When the vectors defining the worth the total priceof the book. lattice and its unit cell are the three This hook wouldprobably only be used shortest that can be drawn from the by a petson who wants a quick "on-critical origin. then the lattice is B primitive summary of relative merits of different lattice and the unit cell is primitive. . .." commercial pH meters. The unit cell in this case would be primiTHEODOERR. WILLIAMS tive (one of many primitive possibilities) College of Wooster hut the lattice need not be. Woosler, Ohio 44691 Item: "A tetragonal lattice may, for example, have a = b=c accidentally, but it does not have the four triad axes which are characteristic of a cube and does not, therefore, have cubic symmetly." In this case the lattice does have cubic symmetry, but the structure based on t h k lattice might not, in which event the crystal ~ymmetrywould be lower than cubic. I t is necessary to distinguish between lattice and structure. Interpretation of X-Ray Powder Item: In the table on Bravais lattices Diffraction Patterns it is not pointed out that in the trigonal H . Lipson and H.Steeple, University of system two lattice types are possible, P Manchester Institute of Science and and R. Only R is listed. In the same Technology, England. St. Martin's table, the more common b axis unique 335 pp. Press, New York, 1968. viii convention is used for the monoclinic Figs. and tables. 15.5 X 23.5 em. system and the lattice types are listed as $15. P and A, B, C. However, for this convention the B lattice type, i f it is listed at This hook is a revised and enlarged all, should be listed with P, since it is edition of the pdwder diffraction part of equivalent to it, not with A and C, which "The Interpretation of X-Ray Difare equivalent to each other but not to B. fraction Photographs,'' by Henry, Lipson, Typographical errors are for the most and Wooster (HLW). Much of the text part not too troublesome and probably no and many of the tables and figures are more frequent than should be expected unchanged, though the larger print and for a new edition. An unfortunate the use of white space and holdface type omission is an index reference to the give a mare modern appearance to the table of multiplicities. newer version. Since about nine years I t should he pointed out that the hook is have elapsed between the second edition of not an in-depth treatise, nor is it inHLW and the current book, it ha3 been tended to be. For instance, "preferred possible to add some new materialorientation" is mentioned twice, but the roughly 20% of the references are post effects of preferred orientation and how to 1960. However, much of the enlarge cope with these effects in intensity mes, ment has been for the purpose of creating 6 self-contained book. Revisions of the surements are not discussed s t all. In other portions of HLW are to appear as contrast, Klug and Alexander devote companion volumes. about forty pages to this topic in their The introductory chapters on lattices book "X-Ray Diffraction Procedures." and symmetry, geometry of diffraction, Overdl, this reviewer's impression is and X-rays, are followed by chapters on that for the person who owns a text on recording and measuring powder patterns, X-ray diffraction procedures which ininterpretation (indexing), determination cludes s, fairly extensive section on of cell dimensions, measurement and powder diffraction, particularly if it is cslculation of intensities, line broadening, HLW, there k not much need to purchase and identification, Also included is s. this new volume. For the person who is chapter on the determination of crystal beginning a library in the field, and esstructures. Lipson is a co-author (with pecially if his interests are likely to be Cochran) of a pioneering book on crystal limited to powders, the book's reasonable structure determination, which, even coverage and updated list of ,references though it is about 400 pages long, is demake it well worth considering. scribed in the preface to the third edition (1966) as an "introductory account." The chief value of the 22 page chapter appearing in Lipson and Steeple's book, I

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Journal of Chemiml Education

Problems of Nonstoichiometry

Edited by A. Rabenau, Philips Forchungslabaratorium, Aachen, Germany. American Elsevier Publishing Company, Inc., New York, 1970. viii 292 pp. Figs. and tables. 23.5 X 16 cm. $17.25.

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Chemists have generally been not very ~ ~ active in the consideration of nonntoichiometry in chemical compounds, perhaps because the present method of teaching chemical combination requires the use of small whole number relationships between the combining elements, as shown in the law of constant proportions. This concept k of course fwldamental to classical chemical quantitative analysis, being dependent on exact weight relationships between the combining elements, and when carried to its logical extreme by T . W. Richards some fifty years ago led ta exact values for atomic weight relationships. However, in the 1930's point defect theory studies initiated by Schottky gave to present day understanding of the smell deviations from stoichiometry essential to semiconductors, but usually not d e tectable by classical quantitative analytical methods. Now a new era of research in nonstoichiometry has begun, snd in the first chapter of this booE, J . S. Anderson speaks of the "chemioally interesting, grossly nonstoichiometric compounds," toward the understanding of which the current research described in this and six fallowing chapters is directed. Each chapter is written by a person currently active in a. articular field. There is. in addition ta ~~~~

theory from nearly stoichiometric compounds to compounds showing large variations in ratios of the combining elements. The remaining five'chapters consider more specialized topics: spinels (H. Jagodsinski), solid-state exchange (E. F. Bertaut and co-workers), surface layers (J. Benard), sintering (P. J. L. Reijhen), and Mossbauer spectroscopy (N. N. Greenwood). Each chapter includes complete introductions to each topic with references to general and review articles for additional study so that a student with physical chemistry background should be able to follow the general principles of the research. The editor has not attempted to be comprehensive in coverage of gross nonstoichiometry and indeed it is evident that rapid development makes suoh comprehensive coverage impossible. Nevertheless, this volume is an excellent introduction to current r e search for chemists in general and an essential reference volume for workers in the various specialized fields of researoh desoribed. For example, the reader interested in the overall approach to nonstoichiometry will find interesting comparisons of the two general approaches. The crystallographic school attempts to resolve nonstoichiametric phases by more careful heat treatment and crystallographic work, an outstanaing example of this being the resolution of oxygen deficient titania into the

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series of Ti.Onn-L phases by the work of Magneli. The other school views the nonstoichiometric ~ h a s eto he due to rnnrlon~dcfect.~afier ihe Sehotlky-N'nm~er modrl, however, perhaps clustered or in micnrdomairlq wthi~rihc phase. These approaches are not as sharply separated as might be inferred from the above, far example, it is pointed out that the same compound may he stoichiometric a t low temperatures, while still subject to point equilibria defects, and grossly non-stoiohiomctric a t high temperatures. In this connection, the discussion af copper-sulphur compounds by Jemnin is incomplete in neglecting the crystallographic work of Kullerud and coworkers at the Carnegie Geophysical Laboratory, especially since their conclusions are quite different from the defect model proposed by Rau, which is presented. The typography and general editing, including complete indexing, is excellent. I t is unfortunate that the price will prohably restrict distribution of the volume to readers specifically interested in the special fields covered.

lose acetate membranes," to the method of reverse osmosis. The basic method used in preparing these membranes is to incorporate a watersoluble additive in the film casting solution, and then to leach out the additive from the membrane with water. Examination of the membrane with an electron microscope shows the membrane to consist of s. dense surface layer, and a spongy, porous mass underneath. The surface layer shows pore size of 100 A or less, whereas the spongy mass underneath has poresof 1000A in Size. Sanrirajan believes that reverse osmosis is "applicable for the separation, wncentration, and fractionation of inorganic or organic (ionic or non-ionic) substances in aqueous or non-aqueous solutions in the liquid or gaseous phase. . .Detailed studies.. .have established beyond doubt the general applicability of the reverse osmosis separation technique!, Data on the overall performance of the 5000 gallon-per-day reverse osmosis plant for desalinizing brackish water a t Coalinga, Calif., are given. The plant is "the first practical installation of its kind [to experience in reverse osmosis give] DAVIDDINGLEDY enginee~ing." The feed water in this State University College installation was about 750 ppm total Fredonia, Nnu York 14063 solids, the concentrated brine came out with 1673 ppm total solids, and the desalinized water 34 ppm total solids. Total production during the period June 4, 1965 to June 4, 1967 was 3,863,000 gallons at an average desalination ratio of 15.4, with the plant avdable for use 98.7% of the time.

S. Sourirajan, National Research Council of Canada, Ottawa. Academic Press, 580 pp. Ine., New York, 1970. xiii Figs. and tables. 25.5 X 16 cm. $25.

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J. A. SCHUFLE New Mezico Highlands University Las Vegas, New Mezieo 87701

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Potentially the cheapest method for extracting pure water from sea water is believed to be one in which the salt is "filtered" away from the water by a membrane of very small pore size, a pmces8 sometimes referred to as "reverse osmosis!' To quote from Chapter 1, General Applicability of the Technique: "In spite of rapid advances which are being made with respect to this application, the process is still a t its very early stages of development. The basic principles involved are still controversial, and no currently available theory on the mechanism of the

no simple diagram to explain how ;he process works, such as K. S. Spiegler gives in his book on "Salt-Water Pnrification," is given in Sourirajan's hook. The first diagram, a n page 3, is entitled Schematic Representation of Preferential SorptionCapillary Flow Mechanism, thus jumping immediately into a detailed analysis of recent theories about the method. The specialist will find the book useful as a review of the engineering developments in the field of ultrafiltration. For example, the author discusses treatment of waste waters and sewage by reverse osmosis. Considerable attention is given throughout the hook lo application of the memhrsnes developed by the author which he calls "Loeb-Sourirajrtn type porous celluVolume 48, Number 9, September 1971

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