Inorganic qualitative analysis: A short course for introductory chemistry

Inorganic qualitative analysis: A short course for introductory chemistry (Hahn, Richard B.; Welcher, Frank J.) W. D. Larson. J. Chem. Educ. , 1963, 4...
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layman when they write for the beginning student. Ryschkewitsch's aim is to pr* vide the student not only with information but with a measure of intellectual stimulation. The evidence for the constitution of the atom provided by electrolysis, radioactive decay and t,he bombardment of metal foil with charged helium atoms is quickly s u c veyed in the first chapter, and the periodic arrangement of the elements by atomic numbers is presented. The second chapter deals with the electronic structures of atoms. The first point developed is the difficultyin accounb ing for the fact that electrons are held t o atoms by using simple electrostatic theory; next, the quantum nature of electromagnetic radistion; then, logically, to the conclusion that the energies of the atoms themselves have distinct values. This brings the reader up to 1913, one of the most important dates in the present century. Then come Heisenberg's Uucertainty Principle, de Broglie's mrttterwaves, and the full application of the mathematical theory of waves to the description of electrons in atoms by Heisenberg and Schraedinger. The ooncept of the orbital, replacing theideaof a strictly d e h e d orbit for an electron, is introduced next, along with the idea of four quantum numbers and Pauli's Exclusion Principle. A summary of the electron configurations of neutral isolated atoms is presented in the format of a periodic table. Each chapter in this book is substautially longer than the one preceding it. The t,l>irdchapter deals with ionic bonding and discusses such topics as ionization potential, electron affinity, dependence of crystal geometry on ion siaos and ion charges, and the Born-Haber cyole. The fourth and last chapter devotes 47 pages to covalent bonding. The topics discussed in the first half of the chapter include orbital overlap, the octet rule and its limitations, electron pair donation, odd electron molecules, multiple bonding, formal charge, dipole moments, and electrouegativity. These are discussed quite dearly and should be understandable to competent and interested first-year 001lege students. The concluding 22 pages are devoted to molecular geometry. Bond lengths, bond angles and covalent radii are discussed, with meaningful examples; and i t is shown how molecular geometries are accounted for from a consideration of electrostatic repulsions of electron pairs. The necessitv for the concent of hvbridization is explained and the sigma and pi bonding in ethylene are described. Resonance structures, electron delocalization, and the attendant increase in stability are the concluding topics. Ryschkewitseh writes well and he includes useful diagrams and tables. A well-chosen list of selected readings is added as an appendix. In spite of its small size the book is cs.refully indexed. I t is a valuable supplement for a. student whose introductory text does not adequately or systematically discuss the correlation of structure with properties.

P. EBLIN LAWRENCE Ohio University Athens 442

!Journal

of Chemical Education

Entropy: The Significance of the Concept of Entropy a n d Its Applications in Science and Technology

J. D. Fast, Technical University, Eindhoven, MoGrrtw-Hill Book Co., 313 pp. Inc., New York, 1962. vii Figs. and tables. 16 X 23.5 cm. $10.75.

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This is a. nice book. I t is well written; the viewpoint is mature; it is rich in examples; and throughout, the pace and level of presentation are well suited to the author's purpose, which is "to reach all those students and researchers to whom thermodynamics and statistical mechanics seem a little frightening, although a certain knowledge of these subjects is indiepensable to them." Science students that possess an ordinary knowledge of calculus and a normal interest in their subject should find this an enjoyable book to study. Beyond that, students with a particular bent toward physical chemistry, or metallurgy, or the solid state, mrty find in i t a deep source of understanding and, stemming from this, an inner sshisfaction and inspiration t o explore further in these areas the applications of thermodynamics and statistical mechanics. The book is an introduction to both disoiplines and also to quantum mechanics. The baok is divided into six chapters of sppraximately equal length. It opens, after a brief general introduction, with a conventional, but readable discussion of classical, Clausius-Kelviu-type "black box" thermodynamics. Internal energy and entropy are introduced through a discussion of thermodynamic systems, state^. and variables. exact and inexact differentials, reversible and irreversible changes, and Carnot's cycle. The second chapter, The Strttistical Significance of the Entropy Concept, nioely illustrates how to blend mathematical logic with apt examples to achieve a treatment that is both humane and robust. Dr. Fast treats large numbers and most probable states clearly and in some detail without getting bogged down in mathematical details. Included, also, is a disoussion of Einstein's Solid (and the The third chapter, Applications of the Cuncept of Entropy, mrty strike many teachers in this country-although not necessarily their students-as the least conventional chapter in the book. Not to be found is a discussiou of Maxwell's relations, the Gibbs-Helmholtz equation, the Clausius-Clapeyran equation, calligative properties, the phsse rule, or partial mold quantities. Instead, the examples chosen-the author says, "mare or less a t random," although there is to them a unity this statement does not reflect-include the following: the "free enthalpy" (G-H-TS), chemical equilibrium (illustrated chiefly by the reactions of oxygen with met& and carbon); paramagnetism and low temperatures (an unusually clear discussion of adiabatic demagnetization); interstitial &oms in body-centered cubic metals (probably

the most autharative section of the baok); substitutiond alloys and ferromagnetism; vacancies and diffusion in solids; elasticity of rubber; solutions of polymers; black body radiation; and fuel cells and heat pumps. The fourth chapter, Quantum Mechanics and Statistics, contains brief, but lucid, discussions of the uncertainty principle, the wave equation, and the statistics of Fermi-Dirac, Bose-Einstein, and Maxwell-Boltemann. Appropriately, the particle in a box is treated in cansiderable detail. The chapter closes with nine pages on electrons in solids. The last two chapters, The Entropy of Monatomic Gases and The Entropy of Diatomic Gases, contain more modern physical chemistry than one might suspect from their titles. Teachers and students dike should find these two chapters pmticularly useful for their well-worked out numerical examples. Cover to cover, this carefully written book nioely illustrates the view that while a study of broad theories, such as statistical mechanics, which apply to many phenomena, is indeed often profitable, it is sometimes equally profitable and probably mare in keeping with the general character of a growing science to focus attention a t times upon a phenomenon, such as entropy, to which many theories apply. "Entropy" could probably be used in some schools in a beginning physical chemistry course, if not as a text (it contains no problems), then as a reference or supplemental reading. Graduate students reviewing for examinations in physical chemistry should 6nd it very useful; there is much in it they should know. HENRY A. BENT Uniuei.sity of Minnesota .Ilinnmpolis

Inorganic Qualitative Analyrir: Short Course for Introductory Chemistry

A

Richard B . Hahn, Wayne State University, Detroit, Michigan, and Frank J. Welcher, Indiana University, Bloomington. D. Van Nostrand Co., Inc., 304 pp. Figs. New York, 1963. ix and tables. 14.5 X 21.5 cm. $4.95.

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The authors state that this book was designed especially for courses in general chemistry which include qualitative analysis as the laboratory portion of the second semester. Their objectives are (1) to acquaint the student with the properties of common inorganic substances; (2) t o apply this knowledge in the development of a system of inorganic qualitative analysis; (3) to study chemical equilibrium as i t is applied to qualitative analysis; and (4) to teach useful laboratory techniques. The book is divided into two parts: Theory and Laboratory. Part One consists of six chapters which cover the nature of qualitative analysis, solutions and colloids, and ohemical equilibrium. Part Two presents some preliminary

experiments, some discussions on the properties of the ions, and detailed procedures. The theoretical part is short of what many readers will want. For example, the rate of a chemical rereaction is stated to be proportional to the molarity "of each of the reactants raised t o a power equal to the number of molecules or ions of that substance appearing in the balanced equation for that reaction." This statement nmy be correct, but to lead beginning students to believe that molecularity and order are always the same is hard to justify. Another example is found in the discussion of the computation of the hydrogen io3 conoentration of NaHCOa solutions. It isinferred that the hydrogen ion concentration of NaHCOa solution is computed solely from the hydrolysis of HCOI- instead of considering the sum of the hydrolysis and the ionieation of HCO1as an aeid, or the disproportionation of HCOa- t o give [ H + ] =Other errors were not discovered, but many of the discussions are cursory. Part Two contains satisfactory procedures far analysis of the conventional groups, but no experiments t o make the student familiar with the properties of the individual ions precede the use of flowsheet type of procedures. In Part Two there are some equations which are erroneous. On p. 214 there appears the "equation" MnB+

OH+ 02+Mn02

On p. 222, the authors say the blue substance formed in the vanishing blue test is HzCrOs. This material was shown not to exist thirty years ago although some salts of the acid are known. The hlue substance is probably CrOs in which the oxidation state is +6. On the same page the startling "equation" 4HzCrOa

-

4Crs+

+ 1302 + 6H10

appears without apology. Part Two contains auestionable orocedures for saturating solutions with hydrogen sulfide. The reviewer seriously questions whether the authors have acromplished their stated objectives in an outstanding way in contrastto comparable texts. Only use will tell.

W. D. LARSON College of St. Thomas St. Pad, Minnesota

Spectroscopy. Volume 1. Atomic, Microwave. and Radio-Frequency Spectroscopy

S. Walker and H . Straw, both of the College of Technology, Leicester, England. The Macmillan Co., New York 1962. xix 267 pp. Figs. and tables 16 X 25.5 cm. 59.

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Spectroscopy. Volume 2, Ultra-Violet, Visible, Infra-Red. and Roman Spectroscopy

xvi

+ 386 pp.

$12

This subject is covered in two volumes whioh are designed t o be independent.

The volumes are directed t o the beginning research worker who wishes a comprehensive view of the field and to spectroscopists having specialized experience end desiring information on branches of spectroscopy outside of this specialty. The authors are physical chemists and their treatment is largely directed to chemical rather than physical applications. Volume 1 discusses atomic, molecular, and microwave spectra, as well as, electron spin and nuclear magnetic resonance. Molecular spectroscopy is not discussed in detail in this volume since i t constitutes the m a o r subject of Volume 2. Volume 2 contains chapters on molecular spectra including infrared, Raman and electronic and concludes with short chapters on phosphorescence, fluorescence, flames, and astrophysics, as well as applications of spectroscopic data in calculating force constants, dissaoiation energies, thermodynamic functions, etc. Almost every subject is illustrated by t ~ nexperimental example and a brief description of the pertinent instrumentation. Topics are treated very concisely but in considerable detail particularly with respect to spectral analysis. The classical approach is followed with results from quantum theory introduoed as necessary. A minimum of theory is presented even in the appendices which give bare outlines of quantum mechanical treatments of such subjects as intensities, selection rules etc. At the end of each chapter, references to more advanced treatises are given but the references do not include same recent works of which the reviewer is aware. There are few errors of commission, the most obvious omission is the absence of any treatment of refleetian spectroscopy. There are few typogrs,phicd errors, the terminology used is generally rigorous, and mathematical symbols conform t o general current practices. "Spectroscopy" in these volumes is understood to involve only electromagnetic radiation; ~ubjectssuch as mass spectroscopy are omitted. The volumes are not highly mathematical and require no more than a knowledge of the calculus. Spectra are considered primarily from the energy level paint of view and extensive use is made of energy level diagrams. Considerable space is devoted to questions of coupling between orbital momentum and electron and nuclear spins. These sections are clearly written and well illustrated. The authors' attempt to show the correlations between the different branches of speetroscopy is quitesuecessful. These are not textbooks and they will probably be unintelligible to the reader without previous background in spectroscopy. They represent an intermediate level treatment of practical spectroscopy. Their use for supplemental and reference reading is to he recommended. Someone preparing for serious work in spectroscopy will require more information than is to be found in these volumes. However, anyone conversant with the subject matter ss described here should he able to read current research papers in spectroscopy with considerable understanding. C. E. W ~ r n Nalional Bureau of Standards Washington, D. C.

Organic Syntheses.

Volume 42, 1962

Virgil Boekelheide, editor-in-chief. John Wiley and Sons, Inc., New York, 1962. 118 pp. 15.5 X 23.5 cm. $4.25. ix

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This latest volume of the series is once again a useful compilation of an array of organic reactions. The syntheses, 35 in number, range from the preparation of dlene, a valuable chemical intermediate, t o [2.21 paracyclophane, a compound of unusud geometry. The preparation of several cam~oundswhich can be used far specific areincluded: among these are 3@-acetoxyetienic aeid (resolution of alcohols), 2,4,5,7-tetranitrofluorenone (characterization of hydrocarbons), thiobeneoylthioglycolie acid (thiobenmylating agent), and N-iadasuceinirnide (iodination of en01 acetates). Among the useful chemical intermediates whose syntheses are presented are tetrolic acid, 2-cyelopentenone, 2-cyclopentene-1,4dione, ethylene sulfide and 2-norbornanone. I n general the syntheses require standard equipment and are not of the multistep, low yield variety. Twenty-four are scaled to give twenty or more grams of final product. The informative fourth section under each synthesis entitled Merits of Preparation now seems t o be firmly established after appeaing in some of the Volume 40 preparations and in all of those in Volume 41. LEROYW. HAYNES College of Wooster Wooster, Ohio

Principles of Radioisotope Methodology

Grafton D. Chase, Philadelphia College of Pharmacy and Science, and Joseph L. Rabinouritz, University of Pennsylvania, Philadelphia 2nd. ed. Burgess Publishing Ca., Minneapolis, Minnesota, 371 pp. Figs. and 1962. viii tables. 22 X 28.5 em. $6.

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This revision of an earlier text by Chase is a considerably enlarged and greatly improved volume. As the title suggests, its main concern is with radioisotope laboratory techniques rather than with theoretical principles. However, most of the experiments are introduced with a brief treatment of the related theory and the detail is about as complete as could be expected in a volume of this type. More extensive use of diagrams, charts, and illustrations add to the attractiveness of this new edition. The clarity of the earlier work has been maintained, perhaps even somewhat improved. Each chapter of the text contains a lecture outline and study guide, an introductory statement of principles, laboratory directions, and in most cases, references t o the journal literature relating to the experiments. An unusually comprehensive group of detection instruments and methods is discussed. These include: electroscopes, electrometers (with consideration of the vibrating reed electrometer), proportional, Geiger, windowless flow, neutron, scintilla-

Volume 40, Number 8, August 1963

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443