Fundamentals of physical chemistry

the authors have recognized this fallacy, one wonders why such an approaoh cannot at this level be eliminated. In ionic equilibria the hydronium ion o...
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Fundamentals of Physical Chemistry

H . D. Crockjwd and Samuel B . Knight, Professors of Chemistry, University of North Carolina. John Wiley & Sons, Inc., New York, 1959. xvii 463 pp. Figs. and tables. 15 X 22 em. $6.95.

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This text is a revision of one published earlier by the authors, "Fundamental I'rinciples of Physical Chemistry for Premedical Students" (J. CHEM.EDUC., 27,695 (1950)). The new edition is more attractive, with a new oover design (blue replacing the familiar Wiley red), higher quality paper, and type which is easier to read. The illustrations have been improved, and several have been added, including some: from the physical chemistry lab text by the senior author and J. W. Nowell. There have been minor changes in the selection of problems. None of the chapters of the previous edition have been deleted. The chapter on radiochemistry has undergone major revision, with more advanced material replacing most' of the elementary principles covered in the previous edition. Three new chapters on thermndynamics have been added, increasing the length of the text by a, hundred pages. As with most such texts deeigned for students of premedicine, biology, eta., if one assumes the usual me-reouisites uf g c n w ~ lc l ~ c m i ~ r:,mi ~ y qu.di~.ttiwand q w m i l n t i \ r :~~:Jv.~is, rot~iicbrdtly rqw~

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titive material might have been omitted. Revision of the chapter on radiochemistry is an improvement, hut the material on ionic equilibria. and colorimetry, to cite specific examples, continues to be of questiomhle value as it stands. Acidbase equilibrium is discussed from the classical standpoint, with virtually no attempt to introduce the simplifying eoncepts of the Bydnsted-Lowry theory in explaining hydrolysis, etc. Material on the solubility of sparingly soluble salts is restrioted to instances where no hydrolysis of the ions occurs, and no mention is made of complex ion formation, The authors have iemoved a -serious deficiency of the previous edition by the addition of the section on thermodynamics. I t is unfortunate that their effort has not met with more success. The section often gives the impression of being s, patchwork of isolated facts, lsoking the necessary continuity for such a complex topic. This reviewer considers that the material is also presented out of order. It follows chemical equilibrium and emf, probably the two topics of the text where the application of thermodynamics is most needed to give an intelligent approaoh. If the student is to appreciate thermodynamics he must use it as a tool. There are several instances in the text where confusion may arise. Discussions of Dalton's law and methods of expressing solution composition are carried out

without the adoption of any symbol for mol fraction, but during the description of steam distillation the familiar symbol ' 8 ,, x appears without delinition. The same symbol is used two pages later in a statement of Raoult's law in such a manner that the student msv wonder whether i t is t o be identified with the condensed or vapor phase. In the discussion of free energy (pp. 298-9) a 1 malal solution of AgCl is considered. A word concerning the hypothetical nature of such a system would be useful here, especially since the authors have previously shown (p. 192) that AgCl is a sparingly soluble salt. Some items of personal preference are of interest. The authors continue to separate the material on ionic redox systems from the chapt,er on emf proper, introducing s. lack of oontinuity to these two aspects of the same phenomenon. Equilibrium constants are first considered in relation to reaction rates despite the well documented evidence that such an approach is generally not valid. While the authors have recognized this fallacy, one wonders why such an approaoh cannot a t this level be eliminated. I n ionic equilibria the hydronium ion of the previous edit,ion has been replaced by H'. Typographical errors are few: h has slipped in for y in equation 3-5 with reference to surface tension; units of the second order rate constant of example 17-3 are devoid of concentration units; the uuits of Table 1 8 2 disagree with those of Figs. 18-3 and 1&4. This newer edition will undoubtedly, like its predecessor, be widely adopted. The fact that this is probably one of the most acceptable texts in this field, along with that of Brey (J. CHEMEDUC., 35, 530 (1958)) in the reviewer's opinion, is ample evidence of the need for a, better selection of texts in the field. Students are capable of handling a more mature approach to the subieot.

E. L.HERIC University qi Georgia Alhens The Determination of Moleculat Structure

P . J. Whealley. Oxford University

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263 pp. Press, New York, 1959. vi Figs. and tables, 14.5 X 22 cm. $5.60. "The book is designed t o give an introductory survey of the main physico-chemical methods that have been devised for the determination of molecular structures.'' The author has eminently succeeded in this gigantic undertaking. The book is not intended to he a, detailed treatise on any or all of the various methods, but to provide the advanced undergraduate and graduate student with an acquaintance and moderate understanding of the methods, their theoretical hbasis, their soope and limitations, and their reliability. Experimental techniques are discussed only briefly, and long mathematical derivations have been omitted; the reader is asked to accept their results. The book begins with a chapter of symmetry in which the basic principles of symmetry operations are discussed and developed into the paint-groups. Hermann-

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