Topics in current chemistry, volume 86. Spectroscopy - Journal of

Spectroscopy. Fitzgerald B. Bramwell. J. Chem. Educ. , 1982, 59 (9), p A281. DOI: 10.1021/ed059pA281.2. Publication Date: September 1982. Cite this:J...
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Chemistry: A Conceptual Approach, Fourth Edition Charles E. Moriimer, D. Van Nostrand GO., New York, NY, 1979. xiv 815 pp. Figs. and tables. 19 X 23.5 cm. $20.95.

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The contents and organization of the fourth edition of this oouular textbook are similar to those of the third editiun. IIOWPWL some irnprowmenls have been made. The t o p ~ of c hvbridizatiun now fullows the trcatment of molecular geometry, and reaction rates and rate laws arediscussed prior to the collision theory of reaction rates. The list of rules for drawing Lewis structures is the best that I have seen in a general chemistry

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Srwral sections ha\,e hem rwiipd in this cd~tiun,notably thosedcaling uith the I h h r model, the i'nccrtatnty Principle, normnl~ry. hydrated ions, free energy and equilibrium, molecular structure and acid strength, pH measurement and hvdrolvsis. . . Discussions of cunvcrswn facum, s~uichiumetryond t h w mochrmistry have bren rxpandcd. With a few excrptions, SI units arc uscd rhrou:hout the text. Problems a t the end of chapters are now grouped by topic, and the number of prohlems. as well as the number of in-ehauter examples, has been incrensrd Several mu photographs h a w also been included Those who liked the third edition of this textbwk should be very pleased with the new edition Wavne P. Anderson Bloomsburg State College Bloornsburg. PA 17815

Topics in Current Chemistry, Volume 86. Spectroscopy. M. N. R. Ashford. M. T. Macpherson, and J. P. Simons. Springer-Verlag. New York, NY. 1980. 294 pp. Figs. and tables. 17 X 24.5 cm. $77.40. The spectroscopic investigation of photo-, chemical processes in small molecules through the use of vacuum ultraviolet, ultraviolet (uv), and photoelectron spectroscopy (PES), is the central theme of "Topics in Current Chemistry: Spectroscopy, Volume 86." The book is a compilation of four monugraphs which servc as rha~rrers.The text highliphts the interprrtat~onof rxpetimental rcsult.r olnainrd throuah enrlv 1978 on the following suhjeets: (1) p~otocbekistry and spectroscopy of simple polyatomic molecules in the vacuum uv; (2) far uv absorption spectra of organic molecules; (3) PES of orpano-sulfur compounds; (4) PES in small ring hydrocarbons. The first monograph reviews the literature oublished throueh 1978 on uv and vacuum uv spectroscopy of a representative sample of simple polyatomic molecules. Three hundred seventy one references are cited in producing this revi,:w. There is a special emphasis placed on examining differences between intervalency (valence shell) and Rydberg transitions. The second monoeraoh focuses on the ., phmochcm~ralwnsequencrs of thp far uv absurptitm o f s ~ m r ~hydrocarbonsand le sub s t ~ t u t r daminrs The technical base fur this chapter rests upon the results of far uv studies with reference to PES and quantum ~~~

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t.hmretiral cnleulntions. Within this mono~

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graph,differencer lretween Hydbergsnd valence shell transitions are reviewed and possible interpretations of representative spectra are suggested. The representative spectra include relevant sigma-electron spectra (e.g., paraffins, silanes); lone pair spectra (e.g., halides, 0x0 compounds), and pi-electron spectra (e.g., simple olefins, cyano, and carbonyl functional groups.) The third monograph reviews the PES of hydrocarbons containing sulfur bonded to one or two carhon atoms, (ex., sulfides, thiocarhonyls.) The presentation is based on illustrative examples rather than on detailed coverage of the literature. However, there are ample references to more specialized review material. Among the different systems considered are the saturated sulfides, unsaturated sulfides, and thiocarbonyls. Some reference is made to variable temperature PES, a technique useful in examining short-lived species (e.g., pyrolysis intermediates.) There is a useful table a t the end of the chapter which contains PES data for 110 organosulfur compounds, molecular symmetry point groups, vertical ionization energies, tentative orhital assignments, and literature references. The fourth monograph reviews P E S and bonding in small ring hydrocarbons. Special emphasis is placed on specific ring systems as examples rather than on exhaustive coverage of the literature. The examples include cyclopropane rings, cyclobutane rings, systems containing a bicyclobutane moiety, cuhane,

Reviewed in this Issue Charles E. Mortirner, Chemistry: A Conceptual Approach, Fourth Edition M. N. R. Ashford, M. T. Macpherson and J. P. Sirnons, Topics in Current Chemistry, Volume 66. Spectroscopy A. Julg, Lecture Notes in Chemistry, Volume 9. Crystals as Giant Molecules A. G.Gaydon a n d H G. Wolfhard, Flames-Their Structure, Radiation and Tempbrature, Fourth Edition Edward Carberry, Glassblowing: An introduction t o Artistic and Scientific Flameworking Fourth Edition New Volumes in Continuing Series Titles of Interest

Volume 59

Reviewer Wayne P. Anderson Fitzgeraid B. Bramwell

A281 A281

Colin MacKay Richard A. Ashby

A282 A282

Jerry W. Ellis

A282 A284 A286

Number 9

September 1982

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and its derivatives. There is a useful tabulation of PES data for 100 small rine comnounds which is similar in format to the table prehensive coverage of the literature. Each monograph tends to stress representative examples and refen the reader to more specialized reference material. The writing is crisp, well edited, and presents a variety of viewpoints on the interpretation of such spectra. However, only the third and fourth monographs, (which have the same author in common), show continuity in style, content, and level of presentation. This text is desiened to serve as a reference -guide for ad" vancrd spectruac ilpir relearch on the photuchelnistry of smnll mdecules. Fitzgerald B. Bramwell Brwklyn College Brwklyn. NY 11210

Lecture Notes In Chemistry, Volume 9. Crystals as Glant Molecules. A. JulQ, Springer-Verlag. New Yo*, NY, 1978. vii 135 pp. 16.5 X 24 cm. PB $10.50.

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The series "Lecture Notes in Chemistry" of which "Crystals As Giant Molecules" is a part aims a t quick, informal, high level reports of new developments in chemical research and teaching. Such volumes have a potential for being useful to both teachers and students and it is this which the oresent revlew attrmptc to assecs. In this hook. Julg covers material on crystals from a point of view which is h t h different trom and more extrnrively worked out than that usually found in advanced tertIrmku. His overall theme i* that mderular orbital theory provides a useful framework for understanding phenomena associated with crystals just as it does for individual molecules. In developing this framework he makes extensive use of the concept of hybridization. For example he discusses sodium chloride in terms of a cell consisting of one sodium atom and six chlorine atoms with the eight valence electrons contained in four delocalized orbitals constructed from the s and p orbitals of the chlorine atoms and spSd2 hybrids of the sodium. Net charges on Naand C1 turn out to be close to those of the isolated ions. The overall stability of the structure is related to the change in the energy of the isolated cell arising from the proximity of other cells. There are six chaoten. The first reviews mdrc ular orhital theory, including localimd and nonlocalired hmdiny, and hybridized ort,itals fnm aimple rp to rp 'dsf I. Chapter ~

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I1 aoolies .. these considerations to molecular and marnmolerular crystal*, with the relatlon between hyhrid17atiun and structure discussed where pertinent. This material is useful and much of it is comprehensible without a study of Chapter I. The chapter ends with a discussion of cohesive energies. Chanter I11 deals with "Electron Charees and Ionirity in Macromolecular Crystals." Chapter lV, "The Crystal Arrangrmrnt." first discusses the inadequacies of the ratio of ionic radii as an index of crystal structure and then shows how qualitative considerations derived from examination of hybridized orbitals and from simple molecular orbital theory can provide useful insights into many systems. Finally there are two short chapters on "Distortions Caused by the Existence of Faces and the Finite Sizes of Crystals," and "External Shapes of Crystals." This bwk would have been much more useful to the uninitiated in the subject if it had been edited more carefully. Misprints, awkward choices of English words, phrases that do not make sense, and failures to define wnbols, lessen its utility. There are several potentially confusing choices of poor English equivalents to the French. For example, ''Repartition" becomes "repartition" instead of the commonly used "distribution"in discussing electron density; "quadratique" hecomes "quadratic" rather than "tetragonel" with reference to crystal structure; "faible" is consistently rendered as "weak when ''small" is more appropriate. As one of several examples of nonsensical phrasing consider the following from p. 99: ". . . ,na (denotes) the number of atoms situated on a face, but neither on a corner nor on a face.. . ."One of a series of failures to define symbols occurs an p. 66 where the symbol "A" is introduced without definition just after having been used to denote the Madelung constant on the previous page, the symbol r is not defined, nor are the symbols used for ionization potential and electron affinitv. I n theend, thrse flaws are more annoylng than d~sabhng,and so the book can be rec ommended to teachersot phys~caland mor ganic chemistry who are interested in e m ples of the application to crystals of the same quantum chemical concepts which they use in describing molecules. Students who have some background in quantum chemistry, including elementary molecular orbital thwry, and some knowledge of the solid state might also benefit from it. Colin MacKay Haverford College Haverford. PA 19041

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Flames-Their Structure, Radlatlon and Temperature, Fourth Edltlon A. G. Gaydon and H. G. Wolfham: C h a p man 8 Hall Ltd.. U.S. Distribution bv Methuen, New ~ o r k ;NY. 449 pp. ~igs..andtables. $49.95.

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Journal of Chemical Education

This is the fourth edition of the wellknown and respected book concerned with

the physical processes occurring in flames. The fourth edition contains the hulk of the material of the third, with the addition of pertinent material, text, diagrams and references, covering advances in the field from 1969 to 1918, with a few references to work done in 1979. The most thorough revisions relate to the sections of flame propagation, structure of turbulent flames and soot formation. The chapter entitled "The Structure of the Reaction Zone" contains the particularly valuable additions of (1) a detailed discussion of mechanisms of flame propagation in the HzlO~lNzand methanelair flames, with associated kinetic data --.-, (21 the concept of flame stretch,and 1.O the fnrmation of oxides of nitrugen. Ilnfonunawlv, there is noexplicit discussion or reference & work on how the pollution hazard.. NO..-. can be reduced in various combustion processes. A dircusrion of the pnhlrm of scot mluction in the environmrnt is similarly lacking. The application of the laser to the study of flames is described primarily in relation to laser-doppler anemometry (the measurement of localized gas velocities) and the measurement of rotational and vibrational temoeraturr prufiler of flnmw uvrng laser Haman spectroscupy and ('ARS The crmcal evaluation of all methods of temperature measurement, including new work on ionization and electron temperatures, is particularly helpful. To those who use the third edition as a stnndard reference, the fourth edition is highly recomnlended because of its wpalth uf new material, particularly the references. Tu those who are contemplating the purchase of a reference bwk, for personal or student use, again, the fourth edition is highly recommended. The clarity of presentation, the critical discussion of the measurement and nature of the physicd processes occurring in premixed and diffusion type stationary flames, and the large number of references to the original literature, all recommend this book to those venturing into the complex world of flames. Richard A. Ashby The N.S.W. lnstitufe of Technology, P.O. Box 123. Broadway. ~

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Glassblowing: An Introduction to Artistic and Scientific Flameworkino. ", Fourth Edltlon Edward Carbeny, M G L S Publishing. Marshall, MN, 1980. Figs. and tables. 262 pp. 21 X 25.5 cm. $16.95. "Glassblowing," by Edward Carherry, was written as a textbwk for a one-quarter or (Continuedon pags A284