Metal Ions in Aqueous Solution
BOOK
REVIEWS
Physical Inorganic Chemistry
Michell J . Sienko and Robert A. Plane, hoth of Cornell University, Ithaea, New York. Physical Inorganic Chemistry Series, edited by R. A. Plane and M . J . Sienko. W . A. Benjamin, Inc., 166 pp. Figs. New York, 1963. ix and tables. 16 X 23.5 cm. Cloth, $7; paperbound, $3.95.
+
This is the first volume of the Physical Inorganic Chemistry series. The authors indicate that it ~houldserve as a bridge between inorganic chemistry and calculus, elementary physics, and physical chemistry. The book covers five topics: atomic structure, molecular structure, solid state, liquids and solutions, rtnd chemical reactions. I t is suggested as a textbook for a senior course in inorganic chemistry. I t is also ppoesible to use thii book and some, or all, of the other volumes of this series as course material in a more advanced sequence in inorganic chemistry. This approach is not only novel but aLso of great help to the instructor, since it gves him a much wider choice in the selection of course material. For the student, however, it may be rather difficult to understand many of the statements and approaches in some of the chapters (particularly in Chapter 1) unless he has had a
-Reviewed
in this Issue
John P . Hunt, Washington State University, Pullman. Physical Inorganic Chemistry Serieq edited by Robert A. Plane and Michell J . Siako. W . A. Beniamin. Ine.. New York. 1963. xi iza F&S. and t&s. 16 x 23.5 cm. $5.50.
+
ip.
This hook is intended to be an introduction to research in the area of aqueous solution for curious and skillful inveatigators, as well as a supplementary text for very rigorous two (or better three) semesan advanced inorganic chemistry sequence. ter course in physical chemistry. I t is Dr. Hunt attempts to cover this vast practically impossible to give the student field in seven chapters, with a total of 124 a full understanding of one electron wave p a g e e a n impossible task. The first function, the Hartree-Foch method, chapter compares the chemical properties Slater's Rules, spectrpoecapic states, magof gaseous and aqueous ions. Thia leads netic properties, and electronic spectra in him in Chapter 2 into a discussion of the just 24 pages. thermodynamics of ion hydration, hydraSimilar comments can he made on the tion enthalpies, and entropies. The danother four chapters which are, however, a gers inherent in using single ion values are hit better in this respect. pointed out. Chapter 3 pertains to the I t must be realized that it is extremely structure of water and ionic solutions. difficult, if not impossible, to present a I t includes a discussion and evaluation of self-coneistent picture of five such topics the various models for calculating hydrain about 150 pages. However, the hook tion enthalpies of ions. Crystal Field is written in the lucid style for which effects are discussed briefly. Chapter 4 Sienko and Plane have hecome so well describes hydrolysis and related pheknown. Several of the chapters contain nomena; hoth anionic and cationic spetables which have been compiled from the cies are discussed briefly. In Chapter 5 literature and wbieh should be valuahle the suthor elahorates an the basic confor quick references. Each chapter a180 wpts of ~quiliklriairlvuiving vornplex iom has a list of supplementary references nml nmlrvulee. (:ltupter ti review rather which will be of great help. hricfly swle of the ti~eoretiraland experiThis book will be controversial because mental aspects of ratio and mechanisms. for the physical chemist it lacka rigor, hut Substitution, aquation, and exchange rethis reviewer has found it of great use in action of some complexes are discussed. an undergraduate inorganic chemistry Chapter 7 pertains to electron transfer recome. actious and their mechanism. Each chapter has an excellent set of HANSB. JONASSEN references which, as the author mentions, Tulane University are often essential to a complete underNew Orleans, Lozlisiana standing of 8. particular topic. The hook is very Lucidly written although in many cases some of the necessary details are missing. This hook is recommended for undergraduates interested in thk field.
HANSB. JONASSEN Tulone University New Orleans, Lrmisiana
Michell J . Siako and Robert A. Plane, Physical Inorganic Chemistry John P . Hunt, Metal Ions in Aqueous Solution William N. Lipscomb, Boron Hydrides WiUiam L . Jolly, The Inorganic Chemistry of Nitrogen Gilbert W . Castellan, Phyaied Chemistry D. F. Eggera, Jr., el al., Physical Chemistry Kenneth B . Fiberg, Physical Organic Chemistry Robed M. Silverstein and G. Clayton Basaler, Spectrometric Identification of Organic Compounds Hertha v a Deehend, Justus von Liehig in eigenen Zeugnissen und solchen seiner Zeitgenossen, George T . Rado and Harry Suhl, editors, Magnetism: A Treatise on Modern Theory and Materials. Volumes 1 rtnd 3
576
/
lournol of Chemical Fducofion
Boron Hydrides
Williarn N . Lipscomb, Hamard Univenity. Physical Inorganic Chemistry Series, edited by Robed A. Plane and MizheU J . Sienko. W. A. Benjamin, 275 pp. Inc., New York, 1963. ix Figs. and tables. 16 X 23.5 cm. $14.
+
Professor W. N. Lipscomh's book, "Boron Hydrides," is another volume in the Physical Inorganic Chemistry series, m d it is excellent. It is quite fitting that it was published on the thirtieth anniversary of Professor Alfred Storch's hook on horon hydrides. Professor Storch's and Professor Lipscomb's hooks both describe the pioneering work of their authors and both are milestones in this field.
texts of the level of Maron and Prutton, "Physical Chemidry" and Daniels, el al. The text opens with faur chapters (70 pages) on the physical properties of gases and the kinetic theory of gases. Some derivations, e.g., pressure of a gas, are covered using average molecular speeds, and then the Maxwell distribution function is presented and a variety of averages and properties are derived from this. A short chapter on the bulk properties of solids and liquids is then followed by a dethis area. velopment of the laws of thermodynamics, The first chapter is the best summary of overing 110 pages, which NnS through the molecular structures of neutral and conditions for equilibrium and properties ionic boron hydrides, boron halides, of the free energy functions. This deborohydrides and carboranes ever written. velopment follows an outline somewhat Chapter 2 describes the three types of similar to that of the first eight chap"three center bond" for the more open ters of Klotz, "Chemical Thermodyboron hydrides. I t also includes the namics!' The discussion is begun with a topological theory of boron hydrides careful consideration of the concept of developed by the author. Chapter 3 contemperature and the definition of temtinues in detail the applic&m of the perature scdeles with the use of the "zeroth molecular orbital theory to the structure law!' The treatment of the first law, and relative stabilities of the various which probably introduces and applies the molecular conformations of the boron bulk of the mathematical apparatus and hydrides. Chapter 4 discwe8 the nuapproach of thermodynamics as well as the clear magnetic resonance studies reported thermochemicd applications, takes about for these compounds; advantages and 50 pages of this block of material. After pitfalls of these studies are clearly pointed this general treatment follow four chapters out. (120 pages) on the applietttions of thermoThe last chapter summarizes and atHNO.)~ dynamics to systems of variable composi-",. tempts to systematize the chemistry of the The style of writing, however, is exceltion, phase equilibria, and ideal solutions various boron hydrides. Much of this is and colligative ~ r o ~ e r t i eof s solutions. lent and easily understandable. The in concise tabular form. illustrations are well done, and the paper, This is done with full use of the chemical The book includes 339 recent references, type, and binding are of high quality. potential and its properties in the derive some from 1963, and references to eleven tians. Two chapters on equilibria in nonreview articles written in the last ten HANSB. JONASSEN ideal systems and in electrochemical cells, years. Two appendixes are attached; Tulane University with a later chapter on electrical conducthe first one on "three center bond" New Orleans, Louisiana tion, mostly of electrolyte solutions, prostructures of the boron hydride ions; the vide 80 pages of material on electrochemsecond on "spherical coordination for istry. Quantum theory is treated in three boron hydride models." chapters on the structure of matter, modThe book is a joy to read as Profeasor Physical Chemistry ern theory of the atom, and the covalent Lipscomb's enthusiasm for this topic bond. An argument is presented for the permeates it from cover to cover. This Gilbert W. Cmaslellan, Catholic UniverSchrBdinger equation and the formalism volume is a must for the bookshelves of all sity of America, Washington, D. C. of modern quantum mechanics is suminorganic chemists. Addison-Wesley Publishing Co., Inc., marized. The problems of the free par1964. xv f Readimg, Massachusetts, HANSB. JONASSEN ticle and the particle in a. one dimensional 717 pp. Figs. and tables. 1 7 x 2 4 cm. Tulane Universily box with infinite walls are solved care$12.50. N m Orleans. Louisiana fully, and the results of the one electron hydrogen atom problem are presented and The author seta the stage for his text in used in the usual "aufbau" discussion of the preface with the comment that "rather electronic configurations of polyelectronic than attempt an encyclopedic coverage of The Inorganic Chemistry of Nitrogen atom. A description of chemical bonding the subject and include a paragraph on anin the valence bond and molecular orbital most anything, I have tried to cover Wdliam L. Jolly, University of Caliapproaches precedes a qualitative disousfundamentals and some applications in fornia, Berkeley. Physical Inorganic sion of the hondimg of the first row eledepth," and with a discussion of his aims Chemistry Series, edited by Robert A. ments in t e r m of hybrid orbitals and to cover topics with s. fair amount of Plane and Michell J. Siako. W. A. sigma and pi honding. Solutions for the mathematical rigor, which is held in most Benjamin, Inc., New York, 1964. xi energy levels of the rigid rotor and harcases to make the subject simpler than the 124 pp. Figs. and tables. 16 X monic oscillator are given with a very incomplete "simplified" derivations fre23.5 em. $5.75. brief oonsideration of molecular spectra. quently encountered in physical chemistry Chapters of approximately 20-page length texts. This is done with elementary The folloving topics are covered in the are found on the structure of solids and cdculua including use of partial derive first six chapters of this book: unique liquids, statistical thermodynamics, surtives; interludes on the uses and manipfeatures of nitrogen, elementary nitrogen, face phenomena, and tranaport properties. ulations of partial derivatives are added ammonia, nitrogen halogen compounds, An 80-page, three-chapter unit, discussing where appropriate. the hydronitrogens and hydroxylamine, various aspects of chemical kinetics, conThe choice of topiea and relative emand the nitrogen oxides and oxyacid. cludes the book. Sufficient, hut not exphasis would make this text most approThe next four chapters cover the comcessive, time is spent on the integration of priate for a two-semester course in physical pounds of nitrogen with sulfur, phospho~imnle rate laws. The Lindemann mechchemistry in which the bulk of time is r ~ rous, carbon, and boron. The final aniwl fur a unimolrrulxr rrartion is formspent on "classical" topics with short chapter discusses the thermodynamics of ul~r~ i~dan e m m p l ~ ui a irwdel far a reactreatments of quantum theory with its nitrogen compounds. rim mechanism, und s trearmeut of mnlriapplications and a moderate amount of The author points out that the chemical step chain reactions includes the hydrogentime allotted to topics of statistical meand physical properties of nitrogen combromine reaction and the Rice-Herefeld chanics. For such a course this would be pounds vary widely and that a large mechanism for the decomposition of the reviewer's choice of the texts available number of strueturea has been established ethane as the principal examples. The far a degree of sophistication, rigor, and for them. He emphasizes throughout the chapter on the theoretical aspects of understanding higher than that found in hook that most nitrogen compounds are
In the last ten years Professor Lipscomh's brilliant X-ray diffraction studies have established not only the structures of the simple boron hydrides discussed by Profemor Starch, these have also been extended to the much more complex neutral and ionic boron hydride species only recently discovered. Their topological and moleculsr orbital treatment of th-
unstable with respect to their elements and that in all these basic reactions which are favored thermodynamirally proceed at a rate which is negligible. This m t urally makes this field of great interest to scientists to whom numerous pmblems are pointed out which need to be studied. At the end of each chapter a few general references are listed. These, however, are so general, that in many cases they are of limited usefulness to the reader whose appetite has been whetted by the material in the chapter. One of the prime purposes of this series as indicated by the editors was to create a series of inexpensive monographs which could be used as supplementary text in advanced treatments of inorganic chemistry in which a physical chemical approach was strong. I t was also hoped that these volumes could be used as reference books which would elearly point out meas in which research would be fruitful and would contribute to the accumulation of fundamental knowledge. Unfortunately this volume is not inexpensive (a. paperback edition would he welcome). I t is also too short to serve as a good reference book. A few emom have crept in (for example: Fig. 6-1 is not the phase diagram of H20-
+
~~~~
~
~~
~~
~
Volume 41, Number 10, October 1964
/
577
