At the pmposed level of stt~dent.t,raining, this preciorts space might bc d o t t e d to ot,her chemical topics such as chemical equilihl.iwn ns a ~peeinltopic. The mviewer tl.ensures this book as a refel.ence work and priaes especially t,he exercises contained in it.
would have been well served by the inclusion of atomic absorption spectrophotometry and electron probe mieroanalysir. There is no other volumetric chemistry than Briinsted acid-b~qe; and no diucussion of membrane ("specific-ion") electrodes other than glass. This book may be attacked by some B. A. F ~ l i ~ ~ : n swith orthodox viewpoints. I t omits College of the Holy Cross gravimetry and the techniques of vohtI170rces/er, Mass. 01610 metry on the theory that a modern freshman laboratory provides sufficient groonding in these. I t is not a typical instrumental analysis text (nothing on statistical inorganic Qualitalive Analysis design of experiments, on electronics, or on principles of instrumentation). The level Kichald N. Hahn, Wayne State Univerof presentrttion is low considering the sity, and Prank J . Weleher, Indiana sophisticated aibject matter. Taken on University. 2nd ed. 1). Van Nostrand its own terms, the text is innocent of the Company, Inc., Princeton, New Jersey. first two charges. I t is intended neither 326 pp. Figs. and tables. 15 X viii cu a tradit,ional "quant!' text nor as a 22 cm. 86.40. traditional instrumental analysis text, but a? a sui generis re-thinking of the needs of This second edition is s, considerable mkdergraduste chemists for analytical improvement of the fimt edition (see J. chemistry. The reviewer is in sympathy CHEM.EDUC., 40,442 (1063)). I t is now si with this approach. quite satisfactory text and manna1 for However, given the goal of making qr~alit,ativeanalysis as it is taught in many truly modern instrumental techniques fl.eshmnn chemistry conrses. comprehensible to tmly typical sophaThe treatment of the calcrdation of the mores, a much mare careful job than thik hydrogen ion eoncentralion of sodium book is required. In an undergraduate hicarbonate solutions is still not correct,. text, whet you say is not much more In fact, following the instructicns an the important than how you nay it. M y bot,tam of page 8: and top of page 86 complaints fall into two categories: would lend one to pH of 10.3 for a 1 M (1) outright errors, which may he inevitaNaHCO. snlntion, while it is well known ble in s first edition; and (2) aversimplito be 8.33, and nearly as well known that fications and careless writing. t,he hydlogeu ion molarity of an amphiConsidering the rango and complexity protic ion sol~ttion,snch as bicarbonate, of the topics treated, this reviewer was not is given by klkrfor carbonic acid, rmless able to find a large number of substantive the concentration is very small. errors. A modest collection includes the This is the only f a d t I e m find in the %sert,ion that one cannot mecuure thefugapresent edition, and it does not serionsly city of a real ga?; the definition of the mar the total effect of the book. chemical potential as the free energy per mole (Gln); and the inevitable use of the College of SI. Thomas HrI. reaction as an example of one wibh St. P a d , Alinnesola a simple mechanism, despite evidence to the contrary. Much more serious than the above rather minor mistakes is a chronic unModern Methods of Chemical Analysis willingness to face the difficult problem of truly simplifying or summarizing camR. I,. Pecsok, University of California, plex ideas. The tone of too many of the Las Angeles, and I,. Donald Shields, summaries in this book i hasty ("the Ca1ifonli.z State College, Fullert,on. most efficient boner for any system eonJohn Wiley & Sons, IIIC., New York, sistr of 8. 1:1 ratio of a weak acid or base 480 pp. Figs. and tables. 1968. xvi to it,%conjugate base.") and opaque. Fur 17 X 24.5 em. $O.0>. example, in a two-page explication uf thel.modynamics, tho (2ibb.i free energy The appearance of this book as rs %xt . . a t the sophomore level" cmsos mixed is introduced and "explained" w a. combination oi the (i~ndefined)enthalpy and feelin@. The study, if not the practice, entropy, (Il-'1's). The next sentence of modern analytical chemistry seema to brings in the activity. I t is hard to conbe left by defar~ltto the chemistry majors ceive of a student who is familiar with If who constitute a minority of sophomore and S, but not with G ; or of one unfamiliar chemistry students. Scientists in other with any of those who could make moch fields, more than many chemist*, have of the presentztion given. The magnetic considerable rue for "modern methods of moment, p, appears in the sectibn before chemical snalysis." The present text the one in which i t is identified; the attempts to meet this need, particularly Boltzmsnn distribution is invoked withfor the biochemically inclined. The atout comment or explanation; the eontempt is not entirely snccessful. cepts "ligand field strength" and "conTopics covered include such strangers centration of electrons" are used, in to "quant!' as ext,raet,ian and chromatoquotation marks, without any comment graphy (3 chapt,ers), spectroscopy, ina t d l . I t is not a legitimate simplification cluding nmr (5 chapters), mass speetrothat hits only the high spots of a complex metry, and radiochemistry, in addition concept, but retains in its 1ctngun.g~such to the more traditional olectrochcmistry loaded terms ss ligrtnd field strength, and acid-base equilibria. (aqueous and Entropy, or the Bolt,smann distribution non-aqneous). Fnturc earth and marine seienl.istx, as well ax future biochemists, when these are not relat,ed by the author.
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Jovrnol o f Chemical
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particular course with a particular lebaratory text (the authors' companion vohlme, "Experiments In Modern Methods Of Chemical Analysis"). For example, Chapter 18 is a wholly orthodox, low-level treatment of chemical kinetics, with only the barest clues to its relevance to the rest of the text. However, in the laboratory text this material is applied to an enzyme kinetics experiment. The chapter in the text is there to ilhminate the laboratory, and is not really meant to sband on its own. Otherwise, i t would be difficult to justify its inclusion in a text on chemical analysis. This book, one hopes, begins a new departure in undergraduate texts in analysis; much important infarmstion is correctly presented; but the authors have forfeited the opportunity to write e classic text by their proneness to careless writing. T H O M R. . ~ BLACKBURN Hobart and William Smith Colleges Gaeua, New York 14466
Kinetics in Analylical Chemirlry Hamy l3. Mark, 57.) University of Michigan, Ann Arbor., and Carr.?, A . Rechnitr, State University of New York, Buffalo, with the assistance of Ronald A . Creinke, Universit,y oi Michigan. John Wiley & Sons, Inc., Now York, 1068. x 339 pp. Figs. and tahleq. 16 X 23 cm. 816.!1;.
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This book deals primarily wibh t,he principles underlying the utilization rrf kinetic informat,ian far the solution of analyt.ical problems. Two points of view are emphasized. The first is bhnt kinetic ur reaction-rate meaxnroments can be w e d
or new equilibrium methods. The fil.st two chapters in the book are brief and inl,~.oductory in natrwe. The first presents a one sided view of the advantages of kinetic methods relative to equilibrium melhods, while the necand pvewnts a brief disewsion of t,he more common met,hods f o ~measuring reaction rates. Chapter three presents a cursory t,reabment of t,he applicalion of catalytic react,ions for ynxntitative analyses. Examples discnssed include inorganic oxidation-reduction reactions, enzymatic reactions, and ligand exchange reactions. Chapters four and five contain an extensive listing and discussion of methods developed over the I& two decades for single and multiple component analyses nsing slow organic functional-group reactions. The chapters deal primarily with the mathematical and graphical manipulntion of common rate expressions to yield forms explicit in concentration. The relative merits of bhe different approaches are compared. Chapter six contains a brief discussion of facbors affeet,ing the kinetics of organic reactions along with an extensive tabulation of rate constants for a wide variety of reactions. This (Cmtinued on page A.374)
book reviews collection of rate constants may prove useful as a first step in evaluating the feasabilit,y of a given reaction type for a proposed kinetic method. Chapter seven contains a n extensive mathematical and graphical error analysis for several of the common approaches for differential kinet,ic analyses. A limited number of examples are presented to illustrate the applicability of results of the errnr analysis. The principal theme of Chapter 8 is that a consideration of the dynamic aspects of reactions involved in equilibrium methods can lead to improved analyses. The chapter contains a brief discussion of the hlarcus theory followed by a compilation of kinetic data on a variety of classical inorganic oxidizing and reducing agents as well as the salvaked electron. The chapter contains frequent comment on the mechanistic implicat,ions of reported data. The principal strength of this book is that i t repl.esenta a collecbiolr and discussion of most of the methods which have been pvoposed and developed for differeni,ial kinetic nnslyies using classical organic reactions. The reader with problems which can be solved using the differential kinetic methods will find this infarmet,ian nseful in selecting the experimental appvoaeh l,o follow. The rate constants compiled in Chapters 6 and 8 for a variety of organic and inorganic roaetions, may prove llseful to some readers. I n terms of representing the current s t a t r ~ sof t,he applicat,ion of kinetics to analysis, this book is rather misleading. Dwing the last eight years there have been major advances made in instrumontat,ion for collecting and processing kinotie data. Typical instruments automatically generate digital printout of concentration data wi1,h measorements times as short as ten seconds and with relative errors below 1%. The nut,hors have not included any discusuion of these developments in the book. One area in which the kinetic method is pwving itself as a n analytical tool is in analyaw involving enzymes. A conservative estimate would place the number of practical analyses involving enzymes in the range of hundreds of thonsands per year in the Unit,ed S t a t e alone. Yet this snbject merits only nine pager of text matcrid in this book. Tho introdi~ctory remarks in Chapter 8 in effect eensiwe a large population of analyt,ical chemists (past and present) for failing utilize kinetic informstion to ..Impmvet.oequilibrinm methods. The Ianguage w e d is, in this readers view, rather strong, especially in view of the fact t h a t tho mxt,e~islwhich follows does not contain a single examplo illustrating haw accurnte qnantitalive kinetic data have been u1,ilised lo yield improvements in an ot,herwise faulty eqltiiibriim method. This type of onsupporl.ed criticism of unnamed wo~.kcrsis a lrtnury which should not be indulged in scientific writing. I n summary this book contains useful informnlion pertinent t o (he determination of organic species nsing the so called differential kinetic methudr. However,
A374 / Journal of Chemical Education
alkali meld-smine combinaliom, especially the Birch 2nd Bonkeiev t.educlimw. The various metals, cosolvenla, proton sources and substrates are all mentioned in torn, but,, although this seclim is yllite HARRYL. PARDUE informative, the reviewet. found i t someZ'urdue University what difficult t o cull fmm i t the heat I,afayelle, Indiana 47907 conditions for attacking x given synthetic problem. The remzindev of the chapter, devoted to other reducliolrs with alkali metals and to reduclions with magnesium, Reduction: Techniques and aluminum, iron, tin, zinc, and variow Applirationr in Organic Synthesis metal combinatio~rs,esporislly amalgams, is of nccessit,y more skotchy; yet the Mark N. Rerick, Providence College; literattwo eovemge (over 330 rofwenrer in William Reusch, Michigan State Uniall) is extensive. versity; and Michael Smith, Geigy Tho third chapter (41 pages) deals with Chemical Corp. Edited by Robert I,. the Wolff-Kishner redudion, Clemmensen Augusthe, Sel.on Hall University. Marredoelion, desdforisntion, and miseelcel llekker, Ine., New York, 1968. laneous methods for ~.eductionof kelwes ix 242 pp. Figx. and titble-;. 16 X t o hydrocarbons. The teacher, especially, 23.5 em. 512.7S. will welcome the comparison of the val.iorts modificat,ions of the hydraaine-plrrs-base This, the second volume in a trilogy: reduction pracedme and the chemist "Cstalybic IIydrogenation," "lleduction," confronted with a synthetic pmhlem will and "Oxidation," is s very useful book. appreciate t,he explicit comparison of the Whereas Angostine wrote the fiwt, valnme merits and demerits of the numerons ways himself, he is acting as editor 101. the of reducing C=O t o C I h . This chapter remaining two. "lleduction" contains has over 173 references. three chapters: The Chemistry of hIixed The literature coverage reaches into IIydt.idw by Mark N. Ilerick, I)issolving 1967. The book is attractively printed, Metal lleductians by Michael Smith, and with clear formulas and is quite f m of I)eoxygenation of Carbonyl Compounds misprint,s. The author and subject illby William Ilerach. As indicntcd by the dexes are extensive. One attractive editor, othw topics we1.e not inrloded feature, carried over from the first volume, becswe the reaction in qlrestion wa.; not in is the prinlirrg of short experimental progeneral nse, becanse a recent review giving cednrw in block letters within the text. the synthetic applications was availnhle, Although these instructions are quite or beealtse n realistic cvaluslian of the brief, they do impart a quick impression genwal synt,hetic utility of ,z pilrticular o f t h e convenience or difficulty of a given redocing agent was not availahlo. Acpreparation. t,nally, most, major reduction methods This book is a mnst item for any chem(with the notable exception of the M e e c ical library. Notwithstanding its relawein-Ponndorf-7;erley reduction and simitively high price ( $ X i per page) it is lar hydride transfer reactions) are, in fact,, highly recommended for anyone whose eovorod in this voltme or the first one. work involves organic synt,he~is. Despite The first chapter provides a. very eomthe (delibemte) omission of mechanistic pletc and competent survey of reductions information, the volume is also a wefnl with various alkaryaluminum hydrides, one for the researeh-oriented teacher, with sluminrm hydride and chlorothough here i t must compete with Howe'a aluminum hydrides, with lithium a h "Modern Synthetic Ileactians" and the minom hyd~.ide-boron triflooride comFiesers' reagent,^ in Organic Synthesis" binatiam, with combination of LiAlH, far a limited budget. with metal salts and with pyridine, with The editor and authors are to be eomalkoxyborohydrides and with eombinamended far a job well done; this reviewer t,ions of ~adilrm borohydride with a h is looking forward to the publication of the minom and boron halide? and with metal third volume of the series. salts. These reductions are compared and contrasted with those involving plain Eaxwr L. ELI^ lit,hinm aluminum hydride or sodium IJniuersily q f Notre Dame bornhydride. Considering the fact t,hat Nolre Dame, Indiana 4655fi reduction wit,h these reagents alone has because of certain key omissions, the book is not representative of the cnrrent state of t,his important. aspect of analytical chemistry.
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been the subject of several monographs,
Dr. Ilerick's success in doing the modified hydrides justice in 94 pages deserves high praise. I n t h s e pages will be found mention of the reduct,ion of almost every redl~ciblefunctional group with virtually each one of the many mixed hydrides. If the overburdened organic chemist has forgotten, far example, how best t o reduce a n acid to an aldehyde, a n ester to a n ether, or an alkylcyelohevanone t o the eqoatorial alcohol, he will find the information in this well-organized chapter (with over 300 references). I n the chapter on dissolving met,al reductions (76 pages), the preiwre of space limitation appears more evident,. About half the pages are devoted lo reductions with alkali metnl-ammonia and
Synthetic Methods of Organic Chemistry, Val. 22 (1968 Yearbook)
W . Theilheimer. S. Karger AG., New York, 1968. xxiv 23..j cm. SS.j.i.50.
+ >58 pp.
16 X
The pr~rposeof this book is to serve as upto-date handbook of refercnres to synthetic methods of wgnnic chemi9tl.y. T o achieve this goal, 0!16 shol.t monographs have been abstracted from articles in the literat~re-l5~/f dated 1065, 60% dated 1966, and 2 5 5 , dated IOGi. 111 addition, perhaps three times ns many at1
( C o n l z n e ~ on i pngr A.778)
