man chemistry sections, competent lahorittory instroction on a rather low st,ndontfamlt,y rat,io would seem essential. (4) The lecture comse which this mnm~al would accompany mast logleally is one that makes rather extensive use of st,lxct,nral, thermodynamic, and kinetic argrt menk I n snmmsry, this hhoratory m a n ~ ~ a l ha? mnrh to recommend its rise in the right lahoratory situation. The avnilability of experiments nnder separate cover should add to its xpplicahility. Most, freshman chemistry instruct~ors, I t,hink, woold certainly find it profitable t o fhmiliarim themielves wit,h its rontents.
book reviews Editor: W . F. KIEFFER Woorter Woorler, Ohio
College of
Composition, Reaction, and Equilibrium: Experiments in Chemistry
Norman C. Craig, Terry S . Carltn, Martin N . Ackermann, Richard C . Schoonmaker, and William B. Renjrow, all of Oherlin College. Addison-Wesley Puhlishine 0 . . Readinn. Massachusetts, 1970. x 341 pp. Fim. and tables. 23.5 X 19 rm. $4.50.
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This attractively-designed lahoratory manual has s. numher of ouhstanding features. The 30 experiments, together with a section on inorganic qualitative analysis, have been carefully chosen and written to illustrate the basic subject matter t,hst has come to he associated with an upper-level freshman chemistry comse for science majors. A standard format is followed for each experiment--sections on theory, procedure, calculations, results, questions, equipment, and notes an preparation. Since all of the st,udent's work is summarized in a. laboratory notebook, the manual does not have the bulky fill-in-theblank appearance of many laboratory manuals. For a lahoratory manual, this hook is rather profusely illustrsted. In addition to customary line drawings, there is a total of about 40 photographs. Most of these photographs should prove quire helpful to t,hestudent in visualizing key operations in the experiment, e.g., the use oi syringes in conducting a g~ phase react,ion; the primitive spectroscope used to obtain the Balmer series; and npparatr~sfor the reduction of ametal oxide, condoct~ancemeasurements, the reaction of chlorine gas with
-Reviewed
is that experiments are avsilahle in any comhinat,ion as separate pamphlets. To this reviewer, tho section on inorganic qualitative analysis would seem particularly useful as il laboratory separate. The experiments were ohvionsly written wit,h a view toward t,heir separate availahilit,y; each experiment is self-contained. An additional advantage of this feature is that the experiments can he assigned in just ahout any order, in groups by srthject matter. I n spite of its outstanding features, I do not believe that this m a n ~ ~ acan l he adopted quite as widely as its authors imply in bheir preface. The siudents who are not likely to he as well fiewed nre t,he average (and, alas, helow-average) s t w dents in large freshman chemistry courses, and for t,he following reasons: (1) A mlmher of the experiments require specialized equipment that must either he pnrchased or const,racted (e.g., neulron howitzer, Landsverk electrometer, infrared spectromete~, and conductance apparst,us). This fact, in tom, may reqrure that several different experiments he in progress a t one time. Such a format may or may not he possible in large lahoratory sect,ions. (2) Although the theory section of each experiment, is developed with care, to ohviate t,he need for a 1;thorator.y lectnre, a number of these discussions start at, t, level that may not he elementary enough for self-study hy average st,udcnts. (3) Because some of t,he appamt,ns and teehniqnes employed are more sophisticated than is traditional in large fresh-
in this Issue
l ~ o r m a nC..C~oio,T p y 8.Corlton, Martin N . Ackermonn, RiehoidC. Schoonmakcr, and William B . Renfiow, Com~osition,Roaofion, and E~eilibriilm:Experimentsin Chemistry . . .A415 James W . Robinaon, UnderprsduateInstrumental Analysis . . .A415 Philip John Duvanl and Beryl Durvant, Introdnotion to Advanced Inorganic Chemistry . . .A416 . . .A416 Robert B. Woodwordsrnd RooldHo6monn. The Conservation of OrbitalSymmetry . . A416 A. J . C . Wilson. Elements of X-ray Crystallography
Gene B. Carpantar. Principles of Crystal Structure Determination A . R . Littlewood, Gas Chromotogrsnhy. Priooiples, Techniques and Applicetioos Charlea K . Monn and Karen K . Bemar, Eleotroehemiosl Resotions in Nonsqueous Systems
. . .A416 .. A 4 1 8
Edwaid L . M c C o 6 e v . Laborhtory Preparstion for ~aoromoleeuiarChemistry
. . .A418 . . .A418
K o r w Nokomolo, Infrsrred Spectra of Inorgenic and Coordination Compounds
. . .A419
E . Emmet Reid. Chemistry Through the Language Barrier Roderiob K . Clayton, Light and Living Matter.
Volume I : The Physical Part
. . .A410 . . .A420
Emil Ploss, editor, Heinr Roo~sn Rur&ge,-~HeiwichSehipwyea. Kevwig~Bunts, Alehimis. . . . A420 Ideologic und Teohnolosie E w s n Mullei, editor, Methoden der Orgsrnischen Chemie. Band 5/1A Hydrookrbons. Al. . .A423 kanes. Cyolaalkanes. Except C~c1opropm.e~ and Cyolobutanes Alan W. Seorcg, David V . Ragone, and Umberto Colombo, editors: Chemiohl and Mechmicsl . . A423 Behavior of Inorganic Mkterisls
RALPHIf. P I : T ~ ~ C C I California State College San Bernnrrlino
Undergraduate Instrumental Analysis
James W . Robinson, Looisiana. State University, Baton Itonge, Louisiana. Mmcel Dekkor, Inc., New York, 1970. 378 pp. Figs. and tables. 17 X xvii 24 cm. $11.50.
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I n the preface the author explains his aims: to mesent a hird's eve view of the
major, and to provide ,z text suibahle for an introductory course for chemistry majors. The first chapter, n survey of concepts of analytical chemistry, roold have been omitted to save space to cover other suhjeets not in the hook. I t is a repet,ilion of the materials generally included in elementary qunntilative ~nnlysis. Besides Chapter 12 (Chromatography), Chapter 13 (Thermonnalysis), and Chnpter 15 (Electrochemistry), the hook denis mainly with spectroscopy; concepta of spectroscopy, nmr, ir, uv, atomic absorption spectmphotamot,ry, and polarimet,ry, flame photometr,~,omission, X-my, nnd mass spectrometry. Throughout t,he hook, the presenla1,ion of both principles and techniques is clear and easy Lo rend, but certain parts may he too brief to he followed by most nonehemistry major students. The rarely used bnlnncing and dihtbion methods of culorimetry (p. 155-6) may he omitted, sud the npplieation of colorimetry to photometric litration should have been included. The yelalive error curve for spect;rophotometry (p. 160, Fig. 8.9) is not qinte tho ssme as that commonly shown in tho liter.zt,ure (see Kolthoff, e t al., "Qnnntit.ntive Chemical Andysia," 4th Ed., p. 970, llacmillan, 1969). The spectrum of benzene (p. 131, Fig. 6.11) is not, for benzene vapor but in 8. solvent such xs ethanol. The melric syslem has been recommended for the wavelengt,h units by IUPAC and t h ~ National Burem of Stmdnrdr; unfortonat,oly it is oat mentioned in this hook. The revieruer has an impressinn that this hook was rushed to the pnhlisber; he foru,d a ereat mnnv erww. most of which could have heen corrected hy cnrcf u l checking. (Continxed on pagc A 4 l f i )
Volume 48, Number 6, June
1971
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A415
book reviews In spite of some shortcomings, this book can be recommended for considers, tion as a text for an instrumental analysis course directed to nonchemistry majors. K. L. CHENQ UniYersity of M i s s m i Kansas City, 64110
Introduction to Advanced Inorganic Chemistry
Philip John Durrant, Selwyn College, Cambridge and Dery1 Dunant, Girton College, Cambridge, and Bedfard College, University of London. 2nd Ed. John Wiley & Sons, Inc., New York, 1250 pp. Figs. and tables. 1970. x 23.4 X 16 em. $22.
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The second edit,ion of this comprebensive inorganic source book has been expanded to make it a. valuable addition for the reference shelf. As was pointed out by the reviewer of the first edition [ J. CHIIM. 40, 169 (1863)1, t,he Durranb have I~DWC., produced an encyclopedic work of great sophistic~tion and originality. The anthots point out in the preface that the style m d arrangement is m~changedfrom t,he first edit,ion, that is, t,he concepts of theoret,ieal chemistry are followed by descriptive chemistry. The first part of the book which is roughly one third of the tots1 presents the theoretical concepts in a sound treatment which is easily followed. Important additions and changes include a, new chapter on group theory and extensive revkion of the chspbers on valency. The Durrants have x very navel approach to group theory which provides the reader with E coherent account of the subject, leading up to the use of the character tables, withont employing matrix notation. The chapter on directed valeney has extensively emplnyed the me of gmop theory in the choice of the correct orbit,alls for byhridizstion by the consideration of their symmet,rypropert,ies. The chapters in the first part of the book are canclnded with a list of books for ft~rther reading and selected reviews. This shonld be most valuable for students of inorganic chemistry and workers, in other fields who want or need more exhaustive t.reatment of s. particular topic. The second part of the hook dealing with the dtscriptive chemistry of the elements is organized in an intermbing and informst,ive manner. The system is based on the hybridization of orbitals from valence bond iheory and is used to rlassify the compounds of each element. Another very positive feature of the meterid on the descriptive chemiat,ry of the elements iu the extensive use of tables to summarize data. These tahles are referenced t o pages in the text which makes for easy access to the material. One cannot review such an extensive work as this is without finding points of concern. The authors have chosen to emphmise the regular elements. Their coverage is thorough. In the authors' discussion of the st,ructure of S4N4a footnote is given with t,he reference omitt,ed.
A416
/
Journal of Chemical Education
reaction course of nrrumed elemeats of symmetry. Inspection of the rorrespnponding electronic state diagram then lends to a designation of the reaction ns symn~etryallowed (ground state of react,nnt rorrelates with ground state of prodnct) or ns symmetry-forbidden (groond state of reactant correlates with an excited state of product). Consideration of such general symmetry-based electronic state dingrams permits the deduction of the Woodward-Hoffmann Rules for symmetryallowed reactions. "A ground state pericyclic change is symmetry-allowed 2). and when the total number of (4q (4r), components is odd!' New words spawned by these studies include conrotatory, disrotatory, suprafacial, antarafacial, pericyclic, cycloreversions, cheletropic, and electrocyclic. An examination of a recent research journal will indicate that these distinctions have been rapidly and widely accepted even though it was but recently realized that distinct modes of concerted reactions could occur. The presentation of molecular orbital diagrams is clarified by the use of color coding for the phases of wave functions (of course, blue = positive). The elegant simplicity of the language and the authoritarian directives make the conclusions deceptively easily reached. An acceptance of the rules without a complete understanding of their basis should he guarded against. The exemplification of the various types of concerted reactions is a major strength of the book. Included are large numbers of references as well as the authors often colorful evaluations of the experimental results. Thet the concertedness of many of the cited examples has not been estabWILLI.LM A. DI.:SKIN lished is not always clearly brought out. Cornell College The absence of an index to the book is an Mount Vcmon, Iowa inconvenience. Alternative theoretical approaches are d l too briefly mentioned. The book is recommended to all those The Conservation of Orbital Symmetry interested in concerted ehemicd reactions. As a text, it should prove to he a useful Robert B . Woodwa~d, Harvard Unf supplement to a senior or first-yea ggrdversity, Cambridge, Mass., and Roald uste course. Those instructors choosing Hoffmann, Cornell University, Ithaca, to present an alternate theoretical apNew Yark. Verlag Chemie Academic proach will still find the hook a weiul Press, Germany, 1970. 177 pp. 21 X source of well-chosen examples. 14.8 cm. $3.50 paperback, $5. hsrdcover. KENNETH L. SICRVIS Universzt?~of Soulhern California An understanding of the basis of stereoLos Anaeles chemical and product control in numerous concerted reactions has developed rapidly within the pmt few years. One of the most readily understood and therefore Elements of X-Ray Crystallography widely accepted theoretical approaches A. J . C. Wikon, University of Birminghas been enunciated by these authors as ham, England. Addison-Wesley, Readthe principle of conservation of orbital ing, Massachusetts, 1970. 256 pp. symmetry. Their central recurring theme 16 X 23 em. 514.95 is that orbital symmetry is conserved in concerted reactions. In this book, which Principles of Crystal Structure originally appeared as a psper [Angew. Determination Chem., Int. Ed. Engl., 8, 781 (1969)l the authors present their treatment of this Gene. B. Carpenter, Brown University, rapidly growing subject. Providence, Rbode Island. W. A. After s. brief summary of the molecular Benjamin, Inc., New York, 1969. xii orbital theory of ehemicd bonding, the 237 pp. Figs. and tables. 16 X rules to be used for the construction of 23.5 cm. $15. correlation diagrams are presented. These A decsde ago, the necessity to teach correlation diagrams, which are analogous X-ray crystal structure analysis in a forto the united atom-separated atom dimal lecture course was dehatahle. The atomic correlation diagrams, may be principles of the crystalline state and drawn for a. concerted reaction occurring diffraction theory, such as periodicity, with the milintainence throughout the
In many cases diagrams are presented which could but do not show the structure, such as with Sb(C204),"-, s. trigonal prism. The treatment of the system of NH8 and HsO infers t h t t species NHIOII exists. But for the most part these are minor points. A more serious objection to the descriptive portion of the book is an almost complete lack of references. Even the continuation of providing a list of selected reviews would have been a vduable addition. But perhaps my most serious concern is the extremely limited coverage of the transition elements. The last twenty years has been a period in which trmsition-metal chemistry and coordinrttion compounds of transition metals have been the topics of research of a large fraction of the inorganic chemists of the world. Although this hook is excellent in many respects it can not claim to cover the entire subject of inorganic chemistry and hilve the limited coverage of complexes of the transition metals. Ligands, such as ditbiolstes, porphyrin and similar species are not discussed. Neither are topics such ae optical activity or the trans effect p r e sented. The coverage is also very sparse on electronic spectre, and magnetic p r o p erties of the transition elements and their compounds. Metal clusters have been treated in less than a hdf-page. With the omissions which have been referred to above, this hook can still be highly recommended. I t is the most comprehensive one available in the last ten years and its organisation provides an excellent volume for reference. A verv positive point, which should be noted, is the excellent index which is provided.
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book reviews
For the majority of papers in Acla Cr~stallographica,Part R, it would seem that the computers will soon be well symmetry, and elementary wave theory, educated enough t o write much of the were included in physical chemistry or text and do R better job than most crystal physics. Crystal structure deterhumans, minations were difficult and the work was This does not mean that crystal struclong and tedious. Therefore the underture determination is now 8, guaranteed standing and use of the mathematics analytical procedure. Experienced crysnecessary to transform diffraction distritallographers are sometimes defeated by butions in reciprocal space to electron apparently simple structures. Since density distributions in real space could soient,ists are ~ermittedto report their he develooed at 8. Dace commensurate with ihr progrev of the grnhntr rrcmr~.h. successes but not their failures, the st* tistics on the current success/fa,ilure ratio Wlwrc S - r s y y wni taught are uncertain. Nevertheless it is true as agraduate course, the primary objective that a. student oan go into a well orwas often to attract students to an area of ganized laboratory and, with luck, descience which, in the opinion of the termine his first crystal structure with teacher, had received inadequate attention considerddy less expenditure of time and at the undergraduate level. effort than is required to read either of The eomm~ters have disru~ted this these introductory texts. There must be balance of learning and research. Success an increasing number of doctoral thesis in crystal structure determination is no examinations where the candidate is longer a guarantee of some minimal level of simultaneously congratulated for ununderstanding. Small computers, supraveling a series of complex structures and plied with manufacturer's software, reprimanded for not demonstrating a very control automatic diffractometers to eolclear understanding of the methods used. lect in few days the experimental data This trend in recent years has not gone which had taken a. few months by the unnoticed. More formal coums in X-ray earlier photographic methods; large oomcrystallography are being offered and out puters are programmed with a variety of of them have come a. number of valuable interpretive methods; progress is montexts. The wise student will browse in all itored by means of the "agreement and select that best suited to his personal index," which tells the investigator when background. "he" has solved the phase problem; the These two books are almost identical in computer then goes into the le& squares size, objective, and contents. Both are refinement routines, finally preparing the written by distinguished scientists in the tables and making the diagrams for puhfield. They present the important elelication in the editorially approved format.
ments, or principles, in an accurate and concise form which is pleasing to the reader, who is himself an expert in the field. They are excellent texts to support B lecture course by a professor who is himself well-experienced. I t is more difficult to judge their effectiveness for self-learning. Fortunately, the provision of problems s t the end of each chapter gives the redly serious reader the opportunity to test for himself whether he h s j obtained a good grasp of the suhject; a grasp, incidentally, which will quickly evaporate if not consolidated by actual practice of the methods. Although they cover the same subject, which is the use of X-ray diffraction to study the structure of crystalline matter, the "elements" are sj seen by a physicist snd the "principles" by a chemist. The claim of crystallography to he a meetingplace of the sciences is well-supported by the fact that this distinction is only a p parent in the finer details of presentation. The "elements" follow the traditional sequence of the X-ray diffractionist, X-rays, powder techniques, symmetry, singlecrystal methods, intensities, stmcture determination, with a final chapter on diffraction by imperfect crystals which reflects the special contribution of the suthor. The "principles" differ in being almost entirely concerned with single crystal structure determination. Again it is the find chapters, on the determination and refinement of atomic parameters, which reflect the background of the au(Catinued m page A W )
Volume 48, Number 6, June 1971
/
A417
book reviews thor's personal research in crystal structure determination.
G. A. JEFFREY Department of Crystallography Uniucrsity of Pillsbul-gh Piitsburgh, Pmnsylmnia Gar Chrornatogmphy, Prlnclples, Techniques and Application
short paragraph. Some of the newer tools for separation such as t,he porous polymers and Halasd's "bmshes" are ment.ioned only in passing or not aL d l . This book is among the best offeld t,oday in providing underdanding of the vilrioos parnmeters operating in gas chromatography in the light, of pmsent theory. While tho book is "addressed to the roniine lrser," it wonld serve ns n poor ope~.ationsl ma~lnnl,since little detail of nct,ud opevation is included.
Soc., 114, 942 (1967)) xlld is not indicst,ive of freeradirnlf~,mmalion. Finnlly, the acid form of nliphst.ir rril.ro compotutds (p. 348) is prodnced in alkaline medium and not in xcid. Formulas in eqnntions 7-(28) and 9-(2) and sperifirnlly 9-52, 10-60 and 10-100 are incorrect,. This book should he in the lihrary of d l individuals inkrested in elerlrochemist,ry; ils acquisition by individuals may he prohibited hy the price.
Electrochemical Reactions in Nonaqueous Systems
Laboratory Preparation for Macromolecular Chemistry
A . B. Littlnuood, University of Newcastle upon Tyne, England. 2nd ed. Academic Press. h e . . New York. 1970. 546 pp. Pigs. and tnbles. ' 16 X xi 23.5 cm. $2230.
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The second edition of "Gas Chromatography" contains a number of significant additions to the first edition, which presented pa4 chrnmatography aq seen in 1962. The general organization has not, been changed, with abont, one-half of the hook dealing wit,h theory as it applies to the design and operation of cohlmns to achieve separet,ion, while nt least onefourih consider^ detector systems and t,he remaining space is devoted to applications of gas chromatography. A detailed presentaiion of parameters affecting retention in t,he liquid phase is given with the applopriate theory. The new edition includes an excellent section on soliltion in polar solvents as well %Q a discussion of solute structure and solubility. Kovats Retention Index, frequently used today, is also covered. The added chapter on ndsorbenta in the serond edition is informative, but the theory discussion is somewhat sketchy. The chapter considering column per-
geometry of columns, the "coupling" eflect, and a good p~esentationof the "nonequilibrium" theory. A detailed description of the preparation of open tube or capillary columns is given. Variations on open tube colomns, such as porous layer and packed capillary columns are also mentioned in some detail. The material dealing with glass beads has been ~lpdated,hut some of the more recently introduced supports, such as porous silica heads, have not been ment,ioned. The relative popularity and use of the various types of detectors is reflected by the amount of discussion devoted to thermal conductivity, flame ionization, electron caoture. 8 ionization. and areon
ing importance of mass spectrometers and infrared for the identification of components separated by x ga4 chromatograph is also indicated in a somewhat limited presentation. A few methods are given for the handling of the large amounts of data, a problem faced by many labomtories. Very little change has been made in the portion of the hook dealing with applice tions of gas chromatography. The author has dealt with general clnsss of compounds rather than preparing a separation handbook. Pesticides are covered in one
A418 / Journal of Chemical Education
C h a h I
