Mass spectrometry of organic compounds - ACS Publications

schule, Braunschweig; Carl Djermsi,. Stanford University; and Dudley H. Williams, University Chemical Labora- tory, Cambridge University. Holden-. Day...
0 downloads 0 Views 2MB Size
book reviews jected three-volume series of "text-monographs" a n the thermal properties of ma& ter for modern, one-year introductory physical chemistry courses. "Thermodynamics and Statistics" has many excellent scientific and heuristic features. These are lucidly presented, in a style sometimes epigrammatic, sometimes chatty, but always unobtrusive and nicely suited to the purpose a t hand. The presentation is controlled and balanced, but never rigid. General derivations alternate with numerous interesting and illuminating specific examples. Important paints-the Second Law, Boltzmlann's distribution, chemical equilibrium, and Gihbs' paradox-are discussed from several points of view. Mathematics and well-designed figures re-enforce effectively the printed text. The book's physical layout expertly reflects the general plan of the work. Clear identification of important results and generous repetition of important equations add t o the pleasure and ease with which the book can be studied. An outstanding feature of the book is the large number of topics covered, comfortably, in depth, in relatively brief compass. In five chapters (Mathematical Background, The First Law, The Second Law, The Molecular Interpretation of Entropy, and The Free Energies and Their Application to Chemical Reactions Involving Gases) the author presents most of the high points of classical and statistical thermodynamics. Solutions are not covered in the present volume. I noticed no errors and would question, only, the practice in this country of suggesting that, unlike thermal and hydrostatic equilibrium, there am two conditions for chemical equilibrium, depending on whether the volume and temperature or the pressure and temperature of the system are held constant, when, in fact, far a system in thermal and hvdrostatie equilibrium with its wrnmndir~gs,I he r-i~psof rhnngr of the Helrnhnlr, a d G i l h rnergics with respcrr ro rlre dcgrcc of ndvat.ccnwnt of u chemical change in the system are equal. I s it not misleading, also, to represent this quantity, which has the units "calories per male," and the different quantity G (some final state) - G (some initial state), which has the units "calories," by the same symbol, AGf This question is not intended as a criticism peculiar to the present volume. Most wrlters on chemical thermodynamics, the reviewer included, have allowed the symbol "A" to assume two functions, without comment. Two special sections of relatively advanced-and optional, hut valuable-material not found in other texts a t this level are a n eighteen-page discussion near the beginning of the book on sound and shock waves and 8 section of similar length near the end on the development of classical and quantum statistics. Both sections are well-supplied-as are other sections of the hook-with graded, carefdly integrated exercises and problems. Altogether, the book contains over two hundred problems. These alone are worth the price of the book. Much useful information and many interesting ideas are

A438

/

Journal o f Chemical Education

packed into them. They are intellectually challenging yet algebraically usually relatively simple. Hints and answers are often given. Thus, the hook should find good use, not only in regular classroom courses but, also, in seminars and programs of independent study. Throughout, the author encourages the reader to develop an intuitive feeling for, as well as manip~dativefacility with, the equations of classical and statistical thermodynamics. Motivations, explanations, and justifications are sprinkled liberally through the text. Several strategically placed, carefully written passages on the genetic development of thermodynamics serve to stimulate the imagination while reason rests, momentarily. This hook should delight many students-and teaohers-f physical ehemistry. HENRYA. BENT Universitg of Minnesota Minneapolis

Mass Spectrometry of Olganic Compounds

Herbert Budrikiewicz, Technische Hachschule, Braunschweig; Carl Djermsi, Stanford University; and Dudley H. Williams, University Chemical Laboratory, Cambridge University. HoldenDay, Inc., San Francisco, August 1967. xv 690 pp. Figs. and tables. 19.5 X 26 cm. $17.95.

+

"This hook brings together in remarkably clear and concise form essentially everything that is known about the ways in which organio molecules break up under electron impact. The material is presented in the language of the organic chemist. I t is carefully organized around functional groups for easy reference, and the pieces are tied together by numerous beautiful examples in which a well-defined reaction sequence is shown to operate in many classes of compounds containing similar controlling structural elements." The preceding paragraph is quoted from a review (S. Meyerson, Chem Eng. News, August 10, 1964, p. 54) of "Interpretation of Mass Spectra, of Organic Compounds," by the authors of the present volume, to which i t is every bit as applicable. The authors started out to revise the earlier book hut quickly discovered, in view of the huge growth of the literature in three and a half " v e m ., that revision meant nearlv total rewriting. Hence the change in title. This hook is the result of a remarkable feat of compilation and organization of results from a highly active field of research %Imost up to the very date of publication. The authors are in a particularly good position to ~ e r f a r mthis task hv virtue of direct. pipelines, largely througg their students and their students' students, to a substantial proportion of all the laboratories in the world with active programs in the field. A 4Bpage introduction defines in clear, simple language the state of the art: the questions involved in predicting spectra from structures and inferring structural features from spectra; useful, broad gen(Continued on page A440)

book reviews el.aliantions; experimental techniques for pmbing the underlying chemistry. This introduction furnishes a conceptual framework on which to hang the snccecding chapters, gives the hook unity, and helps place the subject matter in context as a branch of physical organic chemistry. One gets the impression that the authors have considwed carefully the comments and criticisms of reviewers of the earlier book. The result is not perfect, but one does not find in it a, great deal to criticize. A number of statement,s have been para-

"The relevant literatrlre is spread aver so many different jonrnals." Surely they deserve a t least 8. mild chiding on this scare. I know of no group that has published in as many and as widely scattered journals as the Stanford group, even if one makes sllowances for collaboration with its alumni and others located in laboratories all over the world.

phrased from the literature in such a way as to convey an incorreot or misleading impressirx-passibly a. result of the pressure of the authors' self-imposed early deadline. The language idiosyncrasy that struck memost forcibly is the use of numerous synonyms to avoid using the same word repeatedly, e. g., "loss," "expulsion," "elimination," or "abstraction" of a neubral particle. Repeated use of sword that says exnctly what is iniended is not necessarily bad and, in fact, the use of many different wards to convey the same sense can he quite distracting. I n the preface, in defining the need for such n book, the ant,hors comment that

SEYMOUR EYERSO SON American Oil Cornpang $500 New York Avenue Whiling, Indiana 46394

Chelate* in Analytical Chemistry. Volume 1

Edit,ed by H. A . Flaschka, Georgia.Instit,nte of Technology, and A . J. Barnard, J7.,J. T. Baker Chemical Co. Marcel lhkker, Inc., New York, May, 1967. xii 418 pp. Figs. and tables. 16 X 23.5 cm. %18.75.

+

,

A440

/

Journol of Chemicol Education

The point of view of this new series, as expressed b y the editors in the Intraduction, is that ehelatiou is a "prominent chemical principle" which can serve "to unify a large area of analyt,ical chemistry." The editors stato flirther: "No grand scheme has been devised. Instead, an &tempt will nsoally be made to treat dissimilar topics within n single voh~me.. . . Same overlap of information from one article to another may occur, (but) it is hoped that as the number of valnmes in this series increases, a comprehensive treatment of chelating agents and chelates in analytical chemist,ry will he approached -at least asympt,otically." Volume I does present a diverse collection of topics, each treated with competence. Aft,er a. hrief history of analytical methods based on complex formation (including complexes wit,h monodent,at,e ligands, not generally treat,ed in this series), by F. SaabadvAry and M. T. Beck, there follow seven monographs ranging in length from 26 to 01 pages, with an average of one page of references per 10 pages of t,ext. The volume has a deliberate international flavor-of the eight sections, the authors of four are irom Csechodovakia, with Anstrin, Germany, I-Tungsry, and t,he USA each represented by one section. The v d ~ ~ mhas e ovwall ant,hor and subject indexes, and c~~mnletive indexes are planned. T'ery few errors were ionnd. Fonr specialized topics are t,xeated with relative completeness: Xylenol Orange m ~ d Methylthymol Blne, by B. BndE8inskjr, adds a new dimension to the use of these reagents as metallochromic indicat,om in ehelometric titrations: reactions with fifty different, met,al ions are t,t.eat,ed, with an amazing correlation between calc~daled and ohserved optimum pH values for complex format,ion. Chelating Ian-Exchange Resins, by E. Blasins and B. Brosio, deals with the prohlem of synt,hesiaing varioils types of chelate resins, with a detailed discnssion of the synthesis and properties of t,hree such (Continued on page A442)