Mechanisms of inorganic reactions in solution: An ... - ACS Publications

Mechanisms of inorganic reactions in solution: An introduction (Benson, D.) R. Kent Murmann. J. Chem. Educ. , 1970, 47 (4), p A300. DOI: 10.1021/ed047...
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accessible numerical values of free energies and (2) inaccurate information and failure to recqgnize the limitations of this country. These courses are taught at thermodynamics. The book is divided a variety of levels, from that represented into two parts. Section I (Chapters 1 through 5) consists of a review of chemby the more sdvanced freshman chemistry ical thermodynamics as originally formulated by Lewis and Randall. The development of the three laws of thermodynamics is given together with an ed., 1966), currently best-known,' and Phillips and Williams (Oxford, 2 vols. explanation of the usual enthalpy, entropy, and free energy functions. A 1965-66) which provide complimentary views of inorganic chemistry, but these detailed description is given of the equiptexts are obviously too extensive for coverment and methods used to measure age in s single semester, and are probably heat capacities as s. function 01 temtoo sophisticated and detailed for the perature, heats of vaporization and other undergraduilte audience as well. Heslop phase changes, and heats .of reaction. and Robinson (Elsevier, 3rd ed., 1967) and The statistical methods used for calcuDouglas snd MoDaniel (Bleisdell, 1965) lating the heat capacities and entropies me addressed to the undergraduates, and far gases are presented. No equations have hsd a good reception. The recent are derived but detailed explanations text by Sanderson (Reinhold, 1967), based are given as to how they may be used to on his earlier "Chemioal Periodicity," is calculate numerical values. The reviewer idiosyncratic; the one by Sienko, Plane and feels that it it worthwhile to have the Hester (Benjemin, 1965) is s. combination information presented in Chapters 1 4 as it will make the tables in sections I1 of the paperback "Physical Inorganic and 111more readily useable. Chemistry" sewn together with a portion an descriptive material, but the combine Chapter VI discusses methods which tion has not enjoyed the success expected may be used to estimate entropies, heat of this authorship. capacities, heats of formation, and other The text under review is the shortest of thermodynamic properties for compounds those named, and at $8.50 among the least for which no experimental thermodynamic expensive. The page format is the largest studies have been made. Most compounds in the business, and the overall impression of interest in organic research will fall created by the book is pleasing. The outin t,his category. Since changes in approlook is genuinely modern with emphasis on priate thermodynamic quantities deterevidence from physical techniques,'strucmines an equilibrium constant, it seems ture and bonding. Resonance gives way to the reviewer to do no good to guess to MO descriptions, and Gillespie-Nyholm a t their absolute values. Such a proideas are introduced to deal with molecular cedure will almost always give erroneous shape; 6 bonds appear in the chapter on results and this is what the authors wished covalent molecules and again when to avoid. I t would be better at this RelClsz- is mentioned. Organometdic i.s-a n t i a.t.. i d-.. point to drop thermodynamic method - -. compounds of the transition metals and and go over completely to statistical The book contains descript,ionsof a1a1.ge metalloids are included, but Linnett's mechanics. The equilibrium constant number of important reactions and their douhle-quartet approach is ignored. The can be expressed in terms of partition mechanisms, is easy to read, dear and coutelegraphic chapter on experimental functions and appropriate terms then cise. I t contains an adequate selection of methods is, however, too short to be satiscan be cancelled. This requires only references following each chapter and a. list fying. Nuclear chemistry is not treated of books for supplemental reading. Couthst the structure of the compounds be separately. Descriptive chemistry gets known and that one understand a little pled with lectures stressing the experislightly over 50% of the pages. ahout the deviations from the rule of mental approach and stressing alternate Teachers seeking a brief "Introduction constant bond energies. This information interpretations, this book would conto Modern Inorganic Chemistry" written is available to most organic chemists. tribute significantly to a course in inorat a modest level of sophistication, should ganic reaction mechanisms. Chapter VII discusses the application look at this hook. of thermodynamics to industrial problems. R. KENTMURMANN This covers the petroleum industry, d. J. ZUCKERMAN University of Missouri the problem of getting chemicals from Stale University o j New York Columbia, 65801 methane, the synthesis of styrene, acryAlbany, New York 18803 lonitrile, vinyl chloride, methanol, acetic acid, and several others. I t illustrates very well the uses of reliable thermoThe chemical Thermodynamirr of dynamic data. Organic Compounds Mechanisms of Inorganic Reactions The second part of the book, sections in Solution: An Introduction I1 and 111, consists of tables of thermoDaniel R. Shdl, Dow Chemical Co., dynamic data. The functions tabulated Midland, Michigan, Edgar F. WeatD. Bemon, Widnes Technical College, are heat capacity, C,', entropy So, Gibbs rum, Jr., University of Michigan, Englend. MeGraw-Hill Book CO., energy function, (GT' - H d / T , enAnn Arbor, and Gerard C . Sinke, New York, 1969. xii 218 pp. Figs. enthalpy of form* thdpy, H o - HDpm' Dow Chemical Co. John Wiley & and tables. 14 X 21.5 cm. Softbound. tion, AH,', Gibbs energy of formation Sons, Inc., New York, 1969. xvii 85.95. AG," and log If,. The data are furnished 865 pp. Figs. and tables. 16 formme common elements and 39 simple This paperbound hook is an accqunt of X 23.5 cm. $29.95. inorganic compounds (Chapter 8), hydrothe mechanisms of inorganic resctlons in 9). com~ounds of earbans (Chanter The purpose of this book is to provide . homogeneous solution meant for seniors carbon, hydrogen and oxygen (Chapter a comprehensive and systematic treatment and graduate students beginning their lo), nitrogen compounds (Chapter l l ) , of organic chemical thermodynamics. study in this ares. halogen compounds (Chapter 12), and The authors feel thst there are two main I t begins with a brief chapter of sevensulfur compounds (Chapter 13). Each reasons why thermodynamic reasoning teen pages reviewing theory of reaction chapter begins with a summary statement has not been applied to the solution rates, rate laws and mechanism, stationconcerning the st,atus of the patticuler of organic problems as often as it should ary-state approxim&ion, the solvent and (Continued a page A304) he and these we: (1) the lack of easily solvation of ions, and inert and labile com-

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plexes. Undue emphasis is placed on the stationsry-state approximation and the treatment of the other topics is almost limited to a definition of terms nsed later. The other chapters are entitled Substitution Reactions of Metal Complexes, covering octahedral, planar t~nd tetrahedral molecules, Oxidation-Reduction Reactions of Metal Ions, Reactions of Oxoanions, Free Radical Reactions and Protolytic Reactions. For the most pmt a conventional selection of reactions has been presented. In a sense this is a good choice since a deeper knowledge of these reactions is available. However, onemay be left with the impression that inorganic reactions are primarily those of Werner type complexes and simple aquo and 0x0 metalions. A criticism of the presentation, as related to its use as a teaching tool, is the attitude which this reviewer felt would be created in the reader that many of the rate laws and mechanisms described are now essentially correct as stated and need little further investigation. This appears to result from an attempt to simplify and organize and from the less-than-critical approach of the author. Little emphasis has been placed on alternative explanations on the reliability and precisian of the experimental results or on the experimentalprohlems encountered in theinvestigations. I t is a fair question to ask if a need exists far a new book and further if t,his book fulfills those needs. I think there is little doubt that many would find a fresh approach to inorganic mechanisms useful and of help as a teaching tool. Unfort,unately the overlap between this hook and the earlier "Kinetics of Inorganic Reactions" hy A. G. Sykes is considershle. Thus I donbt if t,he need for a di8el-ent viewpoint

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Journol of Chemical Education