Introduction to statistical mechanics - Journal of Chemical Education

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JOURNAL O F CHEMICAL EDUCATION

170 example, the reader is constantly presented with exceptions to and defects in the exclusively heteropolar approach to the properties of molecules and crystals, whereas a more unified treatment which admits the concept of covalence would aid materially in avoiding these confusions. The many figures are well drawn, but could be better labeledin most of the drawings of orystal structures there is no identification of the various kinds of atoms present. Very few typographical errors seem to have slipped in, although on p. 8, a reference to Table V should be changed to Table VI, and on p. 9, the element astatine is called astatium. JERRY DONOAUE

PRINCIPLES OF ORGANIC CHEMISTRY

John Leo Abernethy, Associate Professor of Chemistry, The Univel.sitv of South Carolina. Columbia. South Carolina. W. B. Saunders Company, Philadelphia, Pennsylvania, 1949. viii 317 pp. 21 tables. 14 X 22 cm. $4.

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THISbook is designed to be used as a worldng text by students enrolledin the conventional one-semester course. The task which an author faces in writing such a book is an imphsing one; he must abbreviate the formal aspects of the subjeot without simultaneously emasculating it and at the same time must allow room for the inclusion of that descriptive material which will retain the interest of those students pursuing their major work in biology, bacteriology, home economics, dentistry, and veterinary medicine. One does not rely exclusively on a text for the maintenance of interest to he sure, but a text still fills an important need of the American undergraduate student. At the present time fewer than five texts designed to be wed in a one-semester course are available. Professor Abernethy employs the conventional approach to the subject. Sixteen chapters are devoted to the aliphatic series, two to aromatic compounds, and one chapter each to heterocyolic compounds, dyes, the Grignard reaction, and oxidation-reduction reactions. Proper emphasis is given to nomenclature. Equations involving structural formulas are used lavishly and a number of illustrations are inoluded. A number of problems for home assignment are given in each chapter. As with all textbooks it is an easy matter to find portions of the presentation which do not meet with the approval of the critic. Your reviewer believes, however, that a sound evaluation of a new text can come only after the book has been used in actual classroom work. Our examination of this new text leads us to conclude that its use is well worth a trial. EDWARD R. ATKINSON UW~VERBITT 06. NEWHAMPBBIBB Dnnnm. New H*la~samE

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CALIIORNIA INBTITOTE OP TECBNOGO(IY PA~ADENA. CALTFOBN~&

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the Weimarn method for making oalloidd sulfur by dissolving sulfur in hat alcohol, and pouring into excess water. Pages 494-6, experiments with iron oxide supported on silica. gel. The gel is made by stirring 1volume of 2 N water glms into 2 volumes of 1 N BSOc then adding 1 volume of 1 molar F&O4 as the gel forms. This is used to catalyze SOs 0.; and, after that, CO steam H* CO* illustrating the removal of CO from producer and water gas in the ammonia synthesis. Also, steam HZ which will passed over red-hot wood charcoal gives CO darken ammoniacal silver nitrate, or form H$ upon being passed through sulfur. Pages 558-604 contain "a supplement of some sixty experiments most of which deal with more advanced work." The 0~over hopcalite. A titles of the experiments follow. CO wet asbestos plug for generating steam to be passed over (a) iron or (b) charcoal. An asbestos plug moistened with concentrated HISO, or HNOs the heated acids passed over pumice which decomposes them to give oxygen. Reduction of KMnO, by cold alkali gives green KsMnO,; by warm alkali gives brown MnO,; by cold acid gives white Mn(0H)s. HNOi reduced with zinc plus sulfuric acid to hydroxylamine. Action of permanganate; dichromate, and ferric ion on HI, HBr, and HCI. Action of 0.5 N KC1 and KI with 4 N HNO1, 8 N HNO., and acidified NaNOn to compare oxidizing aotion of the halogens. Flotation experiments with sand, red lead, oil, and wrtter; slso, with copper powder, sand, acidified water, and cottonseed oil containing a AgNOr. little kerosene. Hydrolysis of PbCI'; and of borax The Mattuck electrolytic cell. Action of marble with HCI in water and in toluene. Electroplating of Ni and Cr. Osmotic pressure thimble using gelatinsupported on a porous pot. Phenol acting as a semipermeable membrane between water and a concentrated Ce(N03)s solution. Methyl violet with oxalio, tartaric, acetic, and hydroohloric aoid solutions. Color changes upon diluting weakly aoid solutions containing methyl violet, phenolphthalein, and methyl orange. The green ethyl tetrsr borate flame test. The Marsh and the Gutzeit tests for arsenic. The preparation of KBr08, of KIO1, and of HCIO. Gas-volume ratios by counting bubbles. Methods for cleaning mercury with (a) acid permanganate, (b) aqueous mercurous nitrate. Anhydrite desiccant. The diffusion of BIZ from an aqueous to a nonaqueous solvent. HZ+ Izover platinized asbestos. Time reactions include (a) the influence of dilution on the decomposition of tbiosulfurio acid, and on the iodine clock reaotion, (b) the effect of temperature on the thermolysis of NH4N02, and the oxidation of HI. Heat of solution:of HCI and of NaNO.. 2N01 equilibrium by changing pressure. Shifting the NzO. The common ion effect for (a)silver acetate, (b) salt precipitated from saturated solution, ( c ) cadmium sulfide. Formation of the most insoluble phase; of the most unionized phase. Fifteen reactions encountered in routine qualitative sulfide analysis. Partition of Bra between water and a nonaqueous solvent; the immiscibility of ether and brine; ether extraction of methyl red from water. The above list covers all titles of the new experiments in this third edition. Teachers who already own the second edition may either work out the details suggested in the above titles, or acquire a new edition. All other teachers of general chemistry cannot afford to be without thisvaluable guide.

LECTURE EXPERNEWTS IN CHEMISTRY

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G. Fowles, Latymer Upper School, London. The BlaListan Company, Philadelphia. Third edition with supplement, 1947. xvi 612pp. 158figs. 14 X 22 cm. $7.

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EXCEPTING for the following experiments, the first 556 pages (547 experiments) of edition 3 are identical with edition 2 (J. CHEM.EDUC.,14,550 (1937)). Page 90 describes filling a rnbber balloon from footbellows previously filled with hydrogen. Page 182, detecting the decomposition of ammonia passed over hot CuO by counting the bubbles arising in water. Page 242, hydrogen peroxide reducing lead dioxide plus nitric acid. Page 298, phmphine formed by adding yellow phosphom to ainc in sulfuric acid. Page 409, a note on the distinctive color of gas cylinders, wherein we learn that oxygen tanks in England sle black, not green. Page 453, preparation of silica gel. Page 493,

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INTRODUCTION TO STATISTICAL MECHANICS

G. S. Rushbrooke, Senior Lecturer in Theoretical Physics in the Universitv of Oxford. Enaland. Oxford Universitv Press. Amen 334 pp: 47 f&. House, iondon, ~ngiand; 1949. eii 11 tables. 14 X 23 em. $5.50.

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T m author explicitly restricts himself to equilibrium theory. He excludes reaction rate theory from consideration because it

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"is still very much in process of development." He develops the three statistical methods based on the microcanonical ensemble, canonical ensemble, and grand-canonical ensemble. His statistical treatment is based on quantized energy levels and an the assumption that each unique state of a system has the same a prioe probability as does any other state of equal energy. The theory for systems obeying classical mechanics is then obtained as an extension of the results for quantized systems. Liouville's theorems are by passed along with the usual considerations of the ergodic hypothesis. Thermodynamic relations are in part taken for grant.edwith justification appearing, however, in appendixes. Rushbrooke illustrates his theoretical development with relatively few examples but these are well done. The treatment of specific heats of gases and the properties of certain types of liquid solutions are interestingly carried through. This is a good beginning book in statistical mechanics which leaves much out but does well the part which is treated. It should prove interesting to a wide circle of readers. HENRY EYRING

U~r~~sm OFrUPAX r SALT Lnae CITY,U ~ d a

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INORGANIC QUANTITATIVE ANALYSIS

C m l l Wardlaw Griffin, Professor of Chemistry, Vessar College, Ponghkeepsie, New York. The Blakiston Company, Philadelphia, Pennsylvania, 1949. xiv 368 pp. 4 3 figs. 25 tables. 15 X 23 cm. $4.50.

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T m s textbook has been written for a one-year course in quantitative analysis including the usual theory and laboratory work. The principal sections are: General Operations; Accuracy Precision, Errors; Balance; Volumetric Apparatus; Acidimetry; Oxidstion-Reduction; Gravimetric Analysis; Volumetric Precipitation Methods; Potentiometric Titrations; Electroanalysis; 0-2 o ",..":-..*-.. ""r"Lrr,rruLJ.

The chief virtue of this book lies in its conversational stvle which should appeal especially to the slower student who (as difficulty in working out the development of ideas by himself. At the same time, this conversational style is also the chief fault of this book. At times the more important and less important ideas are not easily distinguished whicb is likely to make studying, especidly reviewing, difficult. Some important points are omitted or relegated to notes in the experimental procedures: A discussion of displacement titrations, such as the titration of NaCN with a.strong acid is omitted. Principles of gravimetric separations are not discussed in detail. The influence of acidity or oomplexing on oxidation potentials is mentioned only briefly in a few praoedures. Inasmuch as the majority of physical chemistry textbooks use the Lewis convention of signs for the oxidation-reduction potentials, it is to be regretted that not more textbooks in quantitative analysis follow the same convention. Unfortunately this book also uses the convention which assigns the more positive potential to the stronger oxidizing agent. Students are likely to be confused by the v a k t y of terms zpplied for "oxidation number;" "valence," "valence number," "oxidation number," "oxidation state," and "charge" are used interchangeably even in the same sentence (pp. 153, 154, and 155). The rules for balancing equations by oxidation numbers are not given. On p. 165 the statement that "since ZnO is a solid its concentration is constant" is indeed misleading. On p. 185 the reduced form of diphenylamine sulfonate is said to be green in color, which is likelv to ousele students since the indicator solution is C O ~ O ~ P R R .A d i ~ c l l ~ sof i ~t,he n irreversible oxidation of diohenvla-

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a calcium chloride tube charged with a desiccant is recommended to protect the standard permanganate solution in a syphon bottle; this reviewer can see reason for a dust filter, but certainly not for s. desiccant. In the discussion of permangamte methods for the

determination of iron in iron ore on p. 187 the statement is made that "in cases where hydrochloric acid has been employed to bring a sample into solution, the solution must he evaporated with sulfuric acid in order to expel the hydrochloric acid before titrating with permanganate," yet the Zimermaun-Reinhardt method is given on p. 191 which makes removal of hydroohlorio acid unnecessary. On p. 194 one of the chief advantages of silver reductors over Jones' reductors is omitted, namely, the possibility of using hydrochloric acid solutions. This reviewer fails to see why the author concludes on p. 224 that the formation of precipitates in gravimetric analysis constitutes an "irreversible chemical reaction." On p. 275 Brunck is the only name mentioned in connection with dimethylglyoxime as precipitant for nickel even though Tschugaeff published his work in 1905, two years earlier than Brunck (1907). Numerous problems are given at the end of most chapters and they appear to be easefully selected and well-worded. In the earlier sections up to acidimetry many sample problems are worked out in great detail, in fact, this reviewer feels that there are too few problems which necessitate more than recognition of the "type" and substitution. This criticism is not valid for sections beyond acidimetry. Numerous drawings and graphs are scattered throughout the book. In the case of illustrations of laboratory equipment the equipment dealers who supplied the cuts have been credited, but the manufacturers have not been mentioned. Five-place logarithm tables (without interpolation tables) and tables of ionization constants, solubility products, formula weights, and specific gravities of acids and ammonia are given in an appendix. The book appears to be free from typographical errors. The nrintinn is well done oresentine a ulessant annearance even of pages Gled with formuias. ~he'bindingappeagto be sturdy. On the whole this book does not offer much that is novel. The chief deviation from customary treatment consists of placing the section on volumetric precipitation methods following those on

cussing

precipitations. ARNO HEYN

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THE PRACTICE OF RESEARCH IN THE CHEMICAL INDUSTRIES

R. H. Griffith, Senior Research Chemist, .North Thames Gas Board, London, England. Oxford University Press, London, England, 1949. vii I84 pp. 14 X 22 om. $3.25.

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WRITTEN by an administrator who is also an authority ou contact catalysis, this hook reflecta the English scene in research at a time when the pound has tumbled on one side of the Atlantic and the industrial laboratory has risen to unprecedented heights on the other. I t is compounded of a mass of fact and detail evidently gathered from personal experience and of opinions culled from speeches, Nature editorials and Amerioan writings. Sir Henry Tisard and Dr. Mees are the authorities most often quoted. The eontents cover everything to do with research, packed into 170 closely printed pages. Beginning with an estimate of the cost of doing research, the distribution between the various functions of the lahoratotory will strike the reader as suitable, but the totals fall short by a decimal point of the expenditures to whicb we are now becoming accustomed. The next chapters show that Dr. Griffith places the selection and quality of the staff in greater esteem than the physical design of the laboratory; with which we can heartily concur. The space devoted to laboratory construction looms unduly large, and one is both astounded and delighted with such injunctions a s . . ."moveable platforms about 3 feet square with steps and hand rail are of general value.. ." Considerable emphasis is placed on the costing of research and the assessments of probable profit^, direct and hidden, for presenta-