book reviews Chemicol Equilibrium
Carl J . Nynan and Randall E . Hamn, both of Washington State University, Pullman. Topics in Modern Chemistry Series. Raytheon Education Co., 285 Columbus Ave., Boston, Massachusetts, 1968. ix 177 pp. Figs. and tables. 14 X 21 cm. Softhound. $1.95.
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This hrief monograph is designed as a supplement for 8, general chemistry course in which the teacher desires to present t,he subject of chemical equilibrium mare rigorously than the treatment in a. typical general chemistry textbook. An introduction to chemical kinetics and thermodynamics provides the basis for the presentation of the concept of equilibrium. After a. general discussion of the subject the following types of equilibria are h a t e d in some detail: acid-base, complex ions, solubility and oxidat,ion-reduction. The method of charge balance and mass balance is used in solving for equilibrium concent,rations. Log concent,ration versus pH diagrams are used extensively in the chapter on homogeneous equilibria. The plots and illustmtions given thmughaut the book are very helpful in clarifying the subject matter. Much of the book is mathematical in its aporoach. Problems are given at the end bi each chapter in order to provide drill for the reader. The answers to these problems appear in the appendix. The treatment of the subject matter is thorough and ~roeeedsfrom the simple to the more complex. I n addition to it,s usefulness as a supplement in a general chemistry course, the book is excellent for self-study for anyone who wishes to sharpen his understanding of the fnndamentals of chemical equilibrinm.
EUGENE C. JEXEL Hope College Holland, Michigan Experiments in Physical Organic Chemistry
Neil S . Isaacs, University of Reading, England. hIacmi1la.n Co., New York, 1960. xii 323 pp. Figs. and tables. 16 X 24 cm. $9.95. (Canada, $11.)
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This text introduces both principles and pract,iee of physical organic chemistry with interesting and important lahoratory experiments. Instrumental methods such as glpc and esr, nmr, ir, and uv spectroscopy are freely used as tools for studying basic principles of organic chemistry. Experiment 1, for example, deals with measurement of the relative reactivities of benzene and toluene in electrophilic substitution reactions and calculation of partial rate factors. Some of the many topics covered are: Hammett rho-sigma. linear free energy treat,ments, determination of kinetic order, deuterium isotope eflect,s, cryoscopie evidence for formation of carbonium ions in sulfuric acid, kinetic in^ and product evidence for neighbor group heats of reaction,
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kinetic and thermodynamic control of a reaction, properties of the naphthalene anion radical, and asymmetric indoction. The section of this laboratory text on chemical prepsratians contains synthetic procedures of ~tnusual and current interest. For example, syntheses of !3,!3dimethylstyrene by the Wittig reaction, preparation of A1,%ctalone-2 from o y c b hexanone by condensation of the pyrrolidine enamine with methyl vinyl ketone, and preparation of dichloronarcarene fmm cyclohexene and dichlorocarbene, and of tryptycene from beneyne and anthracene are included. Each topic has a deer and concise development of the theory behind the ex~ e r i m e n t references , to the original literature, and supplementa~yproblems. This book deserves serious considerntion as a manual for advanced laboratory courses and s*i a reference text on experimental methods in ~hysicalorganic chemist~y. STANLEY G. SMITH University of Illinois Urbana A Brief Introduction to Quantitative Chemical Analysis
Robert B. Fischer, California State College, Domingues Hills, and Dennis G. Peters, Indiana University, Bloomington. W. B. Saunders, Co., Philadelphia, 1969. xii 537 pp. Figs. and tables. 16 X 24.5 cm. $9.25. iCansda. $10.)
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This book is an %bridged version of the third edition of "Quantitative Chemical 46,A196 (1969)). Analysis" (THISJOURNAL, It is significant to note that this new version was essentially prepared by deleting sentences, paragraphs and pages and not (with only a few exceptions) by condensing any of the material in the parent edition. Nearly 350 pages of subject matt,er have been removed; yet the aame basic format of chapter and material presentation has been retained. Examples of reductions in material include the following: two chapters on electrochemical methods of snaiysis (135 pages) have been merged into one such chapter (43 pages); material in a separate chapter on acidbase reactions in nonaqueous solvents (38 pages) is now shortened to 7 pages and included in the chapter on acid-base titrations; chapter on chemical equilibrium shortened bv 24 pages: chapter on separations shortened by5'page;. spacedoes not permit the listing of topics that have been omitted, hut as stated in the Preface, "many of the discussions here are less rigorous and some of the advanced and specialized topics have either been eliminated altogether or reduced t o hrief descriptive statements." I n excess of 30 figures and tables have been omitted, a3 has an excellent table in the appendix on Standard and Formal Potentials for HalfReactions. The abridged text contains 5 fewer laboratory experiments (4 titrimetric, 1 colorimetric). The remaining 27 experiments are identical wit,h those found in the parent edition. The questions and problems a t the end of each chapter are reduced somewhat. in number (Calinued on page A136)
b00k reviews from those in the expanded version. The answer8 to the numerical problems are given. An adequate index is included. The passage on potentiomet,ric titrations has been moved from the materid on electrochemical methods t,o the chapter on oxidation-reduot,ion methods. In conjunction wit,h this move a "figure" error ocn~rred. A glass membrane electrode is shown instead of the stated satomted calomel electrode. The parent, edition was somewhat of a departure from a traditional quantitative analysis text-both by the types and depth of matter included. The authors in their desire to produce a. less rigorous text have accomplished their goal; however, in so doing have created a text, that has last much of its earlier citement" or advantages. Both texts are adequate for s. one-semester quantitative analysis course, with the expanded version still not suitable for a separate tev instrumental-type eourse. With this last point in mind a11d the difference in price being only a few dollsrs, the reviewer prefers the parent edition. The tional subject matter providesmuch better of the material and allows the instructor greater versatility in planning his course.
Ion Exchonge ond Solvent Extrodion of Metmi complexes
Y. Alarczu, and A . S. Kertes, Hebrew Univemity of Jerusalem, Israel. Interscience Publishers (a division of John Wiley & Sons, Inc.), New York, 1969. ix + 1037 pp. Figs. and tables. 16 x 23.5 em. $44.9.5.
A rigorous and detailed examination of the thermodynamics of metal complex formation provides the leitmotif for this massive, mholal.ly contribution of two Israeli seientifit,~in which the complementary techniques of solvent extraction and ion exchange are described. Marcus and Kert,es, themselves active researchers in these fields, provide a firm foundation for the thermodynamic aspects ,of t.he two important separation techniques in the first quarter of their hook where, in three chapters, the t,hermodynamics of aqueous and non-aqueous eleotrolgte solutions are presented. Thorny prohlemn snch as the quantitative consideration of concentrated and mixed electrolyte aqlleous salutiona as well as mixed solvent and aggregation (including micelle formation) in organic solvents are presented and dealt with in a competent, "present state of the art" approach. The mathematical appamtufi for dealing with complex formation equilibria with particr~lar emphasis on the delicate decisions required to distinguish hebween true complex formatiall and J. M. PAPPENHAGEN"lreachemu~" activity effectsis presented. Kenym College After a chapter dealing with ion exGambier,Ohio changers, ttheir swelling and sorption
equilibria, as well a5 exchange phenomeua occurring in concentrated solutions and mired solvents, there follows twin chapters dealing with the many ramifications of the use of cation and anion exchange to determine the equilibrium constants of metal complex formation. The use of solvent extraction in stndying metal complex equilibria receives a similar treatment. The authors organize extraction systems inio the following categories and devote a chapter to each: Extraction by (1) compound formation (chelates, acidic organophosphorus compounds, salts of earboxylic and sulfonic phosacids), (2) solvation (carbon-r phorus-bonded oxygen-donor solvents, (3) ion-pair formation (use of quaternary ammonium, phosphonium, and xrsoninm salts), and (4) syuergism (mixed ligand systems). The hook is well organized and each of the twelve chapters has a detailed summary of the viewpoint and the content of the text material. There are occasional examplea of the need far better integration of the material in various sections of the hook. For example, after a, fourpage exposition on the nature and use of the solubility parameter the aothars repudiate the validity of its u w with "polar" substances. Later in the text, however, solubility parameter considerations are freely employed. Again, in the section on dithisone they espouse the outmoded and incorrect Fischer stmcture of primary chelates (involving only nitrogen-metal bonding) despite their
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