Physical chemistry (Berry, RS; Rice, SA; Ross, J.) - ACS Publications

Physical chemistry (Berry, R. S.; Rice, S. A.; Ross, J.) H. H. Carmichael · T. C. Caves · Cite This:J. Chem. Educ.19815810A312. Publication Date (Prin...
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ROOH REVIEWS heavy type and are wisely repeated as necessary rather than being replaced by references to a previous mention of the hazard. The IR and proton NMR spectra of the products are depicted. T1.C is often used, but GLC is not. A number of the experiments use phase transfer catalysis. Some of the syntheses areof common substances such asaspirin, phenacetin, and DEET. There are a couple of isolation experiments-caffeine from tea leaves and eugenol from c l o v e s b u t no experiments on kinetics, polymers, carbohydrates, or amino acids. Questions and exercises are found a t the end of each chapter. Part I11 (161 pp.) coven the qualitative analysis of the main organic functional groups. Several new classification tests utilizing phase-transfer catalysis are employed as is spectroscopic confirmation of structure. Forty-seven pages of derivative tables are in Part Ill. 1 believe the authors should have omitted the IXototization of Primary Amines (p. 542) from their procedures. Carcinogenic nitrosamines, which are not mentioned in the text, might he formed from secondary amine contaminants o r by misapplication of t h e test t o a second a r y amine. Durst and Gokel have written a first rate, modern laharatory text which gives today's safety conscious instructor a large number of experiments to chwse from and allows him to incorporate qualitative organic analysis into the laboratory without requiring purchase of an additional text. Kenneth K. Andersen University of New Hampshire D d m . NH 03824

Modem Molecular Photochemistry Nicholas J. Tuno. Benjamln/Cummings. Menlo Park. CA. 1978.628 pp. Figs. and tables. 17 X 24. $23.95. Fifteen years have elapsed since the publication of Nicholas T u r d s superb "Molecular Photochemistry" (reviewed in J. CHEM. EDUC.,43.A546. (1966)).and a wide variety of fundamental developments have wcurred in the field during that time. "Modern Molecular Phatochemistrv" is a com~letelv . . reworked, yet equally outstanding. text. It 1s greatly expanded and nimed s t the advanced undergraduate or lrcginnmg gmdunte ~ t u . dent. The volume consists of fourteen chapters, of which the first four present a very general overview of the physical models used in the remainder of the book. The concepts of electronic states and potential enerw surfaces are presented in a simplified and nonmathematical fashion for ultimate application in describing bath photophysical processes and photochemical reactions. Presentations emphasize visualization of processes on a qualitative or semi-quantitative level.Thestudent isencouraged to learn the "spirit" of the use of operators, selection rules, and other quantum mechanical concepts rather than to master their rigorous mathematical derivation or application. ~

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Significant aspects of some key topics are deliberately omitted and, on accasion, presentations have been oversimplified in order t o prevent the main points under discussion from being obscured by excessive detail. The diseussiun of a vector model of singlet and triplet spin states (Chapter 2) is a case in point where pictorial clarity is maintained a t the expense of some mathematical accuracy. This approach is later used to great advantage in describing the relationship between perturbations that induce spin state interconversion with the mechanisms of the interconversions themselves. In all caqes like this, references are made to source materials containing more thorough or rigorous treatments of the subject matter. Chapters 5-9 expand upon and effectively utilize this introductory material, presenting detailed descriptions of radiative and radiationlers transitions, extensive discussion of both theoretical and mechanistic aspects of in general, and a comprehensive section on energy transfer. The simplified surface diagrams presented earlier are extensively applied in these chapters. A general framework for understanding photochemical reactions is constructed hased on the nature of n,n*, and n, ' a states and the zwitterionie or diradical states with which they correlate. One outstanding feature of these chapters is the frequent evaluation of order of magnitude estimates of the likelihwd, duration, or strength of an interaction or process, utilizing very simple techniques that students should he readily able to assimilate. A section a n "Kinetic Feasibility" relating A values, E.s, and rate constants is one very useful result of this approach. Also gratifying is thecare with which the order of presentation of the material has been thought out. All termsarecarefuliy defined a t anearly stage to allow subsequent discussion and application to prweed clearly and efficiently. Even relatively difficult topics such as ClDNP are presented concisely and effectively. Of the remaining five chapters, four are devoted to a very comprehensive review of organic photoreactions, and the fifth covers chemilumineseence. Detailed mechanistic information is given with virtually every example related to the general concepts introduced earlier. Frequent and extensive structure-reactivity correlations are presented in tabular form to allow ready comparison of rates of photophysicaland photochemical processes as a function of excited state configuration and energy. Theoverall presentation of the text isvery attractive. The chapters are divided into numerous sections which are listed in the table of contents, making i t almost as useful as the excellent index for finding specific topics. Subsections are concise and the text as a whole is generously illustrated (over 150 figures in the first nine chapters alone). The many charts, graphs, and tables contain an enormous array of data covering all aspects of photochemistry and spectroscopy. Typographical errors are few in number with only two worthy of mention: figure 7.6. p. 210, mislabels e cyclobutene-butadiene r* ra orbital correlation as a' an,and equation 14.49, p. 598. gives the triplet acetone yield from tetrsmethyldioxetane as 0.5% rather than the correct value of 50%. The book lacks problems but contains a number of workedout examples as well as summaries a t the end of each chapter.

Journal of Chemical Education

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As both an up-to-date source book and a teaching text of organic photochemistry, "Modern Molecular Photochemistry" is, quite simply, an indispensable addition to the literature of the field. Neil E. S c h o r e University of Califwnia Davis. CA 95618

Physical Chemistry R. S.Berry. S. A. Rice, and J. Ross. John Wiley 8 Sons. New York. 1980. xvi 1259 pp. Figs. and tables. 26 X 22 cm. $34.95.

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This is bath literally (2.7 kg) and figuratively a weighty tome. The authors have been particularly careful to define terms (a fourteen-page list of symbols is included in the appendix) and to cross reference different sections of the text. The book is divided, roughly: 40% on structure of matter. 40% on thermodynamics, and 20% on physical and chemical kinetics. The prefaeecontainsoutlines of the various orders in which the ehaptersmay be covered to put either quantum mechanics or thermodynamics first. The discussion of atomic structure and quantum mechanics is s t a very high level of mathematical rigor for a physical chemistry textbook. For a student with adequate background and ability in mathematics, the treatment of these suhjectsk superb. Fur instance, the third appendix to Chapter 2 an Rutherford scattering is an extension of the already very rigorous discussion of the Geiger-Marsden experiment The authorsdo not quite slog through theseriessolutionsof the Schr6dinger Equation for the hydrogen atom and the harmonic oscillator, hut they come close. Finally, there is a goad discussion of how a "closed-subshell structure" leads to inertness in some cases but not in others. The authors should be commended for providing physical interpretations and helpful analogies in great abundance. For instance, the gravitational analogy of a hill with many ledges is used to represent quantized energy levels. There is a very intuitive, physical description of the interaction of a hydrogen atom with light of very low frequency, very high frequency, and a t a resonance frequency. Computer-generated perspective plots are used liberally throughout. Most arevery helpful, although the reviewers had trouble understanding the depiction of standing waves in a circular box (Fig. 3.10). and students will have a hard time understanding Fig. 4.8, because the axes are not labeled. (They are described 2 pages earlier.) Thermodynamics is presented in careful detail. Terms are clearly defined, often by example. This is oneof the few texts to state explicitly that the thermodynamic equilibrium constant is a ratio of dimensionless ratios. Thermodynamics is treated from both the macroscopic and microscopic points of view with emphasis on the latter. An entire chapter is devoted to a discussion of ensemblesand the microscopicview ofentropy, but the derivation of the Gibbs-Helmholtz equation is left asan exercise for thestudent, and the closest approximation of the van't (Continued on pnge A314)

Hoff equation appears in a complicated example treating the ammonia synthesis reaction. This example includes effects due t o non-ideal gas behavior and temperature dependence of theenthalpy af reaction. On the other hand, topics such as the electronic specific heat of metals and the thermodynamics effects of the structure of water are discussed in some detail. The third part. Physical and Chemical Kinetics, begins with a lengthy and detailed discussion of collision processes, including a discussion of the probabilities for energy exchange between differentdegres of freedom. Integrated rate laws are covered in two wellwritten naees. . followed immediatelv bv a discussion of potential energy surfaces and the internal energy of product molecules. The discussion of the connection between observed rate law and mechanism follows fifty pages later. In summary, this is a very wide ranging, well.written text that requires considerable mathematical sophistication and ability to interwlate and extra~olateon the oart of the studints. The seven'hundred oroblems indude iew that involve s ~ m p l erahstttutions and many that involve cunsidrrahlc decision making by the student. This book includes many topics not discussed in other physical chemistry texts-mechanical action, thermodynamics of nonequilibrium processes, oscillatory reactions, symmetry rules for chemical reactions, for example-hut it leaves laree eaos .. .. . between its theoretical discussimr and nclunl applirntwns. I t is eertatnly weighted in favor ofchemical physics and ihe mirn~seop~r puint of \.icw, devoting minimum space to the connection between microscopic models and laboratory abservations. The reviewers have two minor quibbles. In discussing the particle in a one-dimensional box. the authors state (on o. 97). that neeative values of n are reieeted because .,would - - ~,~~ -~~~~~ thcv cmrerpond tu thr same energies as the corresponding positwe values of n . Energy d r generacy wcurs frequently in chemistry; the negative ns are rejected here because they correspond to wavefunctions indistinguishahle from those for corresponding positive values of n. Thus, no new states occur. Secondly, a name better than the "thermochemistrv of ohvsical orocesses" could have heen found f& the appitmtm of the lint law of t h e r m d y n a m ~ r ~phnsechangw H. H. Carmichael and T. C. C a v e s N& C a r o l i ~State University Raleigh. NC 27650

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lntroductlon to Macromolecular Chemistrv.. 2nd Edltlon H. Batzer. F. Lohse. John Wiley & Sons, New York. 1979. xiv 297 pp. Figs. and tables. 16 X 23.5 cm. $34.50.

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According to its preface, the text by H. Batzer and F. Lohse, translated from the German edition (1976) by W. Good, is inA314

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of Chemlcal Education

tended for use a t an introductory level, either in asuitable formalcourse, or in an informal reading program. The bonk is divided into three major sections plus a general introduction. The latter (18 pp.) provides a qualitative comparison among the properties of macromolecules, colloids and small molecules, and presents definitions and terms used elsewhere in the book. The major sections involve polymer synthesis (128 pp.). characterization (54 pp.), and processing and physical properties (80 pp.). The treatment throughout is a t a qualitative, introductory level, as might be suitable, for example, in some terminal one-semester undergraduate COUrSe6. The preparation of a number of technically important monomers and polymers is described in the section on synthesis. In general the approach is to present the relevant reactions, with minimal treatment of their mechanistic aspects or of the statistical and kinetic features of polymerization reaction. For example, neither the relations for effects of impuritieson chain length, nor for the gel point in multifunctional condensations are given in the treatment of step growth polymerizations. Similarly, the kinetic chainlength concept is not discussed. and the analytical consequence on chain length of solvent, monomer, and chain transfer reactions is not given in the treatment of radical polymerization. Following a brief discussion of molecular weight distributions, a number of important methods for molecular weightdetermination are introduced in the section on characterization. The underlying physical chemistry is treated lightly. For example, the reason that large second virial coefficients often obtain with polymer solutions is not discussed. The suggested procedure for analysis of data on size exclusion chromatography (GPC) is outdated, and the most useful extrapolation method for osmotic pressure is not given. Nearly a third (Ifi pp.) of the section concerns the viscosity. Nonetheless, the basic relations among the intrinsic viscosity. chain dimensions, and molecular weight are not presented. Rather, several empirical representations of the concentration dependence of thespecifie viscosity aregiven along with a qualitative discussion of the effect of :hain length and solvent on the intrinsic viscosity. The section is mostly concerned pith dilute solutions, but some data on the viscosity of a melt are also presented. With :he latter the dominant role of interchain intanglements is not mentioned. The section on processing and physical sroperties contains 38of the88Tables in the look. and 18 of the 54 Figures. Many of the brmer are used to demonstrate qualitative ,elations among the characteristics of polyners and their d u t i o n s and the physical )roper%iesof the proces~edmaterial. Several echnicslly important methods to process ~olymersare discussed. A brief section on ~hysicaltesting (13 pp.) introduces a few of he important concepts on the viscoelastic )roperties of polymers. Although serious typographical errors are ew in number, equations 8 6 % each contain In error; for example, B in eqn. 84 should ead B/RT. The authors present a bibliography of 32 lntries consisting of texts and reference ources-a number of recent introductory eve1 textsare not included. Original work is nentioned throughout the text, hut this is of

limited use to the student since no references are given.

G. C. Berry CamegiaMellon University Pinsburgh, PA 15213

Prlnclples ot Instrumental Analysis. 2nd Edition D. A. S k c q . D. M. West, Saunders College.. Philadelphia. PA. 1980. iii 769 pp. Figs. and tables. 24.2 X 19.4 cm.

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This textbook is a new edition of that published and reviewed in THIS JOURNAL (p. A362; 1972) nine yearsago. During that time the metamorphosis of instrumental analysis has been great and as a result substantial revisions have heen made in the text. A few chapters have been combined to makemam for six new ones, bringing the total t o twenty-six. New chaptersare two covering an elementary treatment of electronics and computers, one on components of instmments for optical spectroscopy, and chapters on thermal methods, general theory of chromatography and liquid chromatography. No laboratories are included, but these are usually institution specific. As was the first edition, this one is well written and in general student oriented. De. tailed explanations and examples are included t o clear up possibly difficult points. Figures are descriptive and further exnlained in the text. Nowaftereachehapter there isa mare extensive problem set including both computational and conceptual exercises. Special mentinn of the electronics treatment is in order. In two chapters (90 pp.) a t thestartofthe text, theauthorscover DCand AC electrical circuits, transistors, operational amplifiers, microprocessors. and computers in acceptable detail. Students with a general physics background should have little problem with this material; however, it is this reviewer's opinion that because substantial laboratory time is required for proper treatment they are best left out and offered in an elective course. Still, the inclusion of the chapters along with comments throughout the text on how instruments are automated make it complete. The title and the introduction point out that the text is principle oriented and this is so. It is very inclusive of descriptions of how many different instruments function, but only short mention is given to sample preparation, specific applications, and intermethod comparisons. The authors' contention that principles must come beforeappli:ntion is well taken, and with usually only a semester it would seem impossible to teach both. It should he mentioned that same dudication exists between the authors' "Analytical Chemistry" text and this one in the weas of introductory electrochemistry and rpeetroscopy. In summary, "Principles of Instrumental 4nalysis" is a strong text and should be coniidered by those starting or updating their nstrumentation course. Bruce 0.Pollard Marqwrne University

Mikaukee. WI 53233