Introduction to Chemical Thermodynamics (Everdell, M. H.) - Journal

Introduction to Chemical Thermodynamics (Everdell, M. H.). Frank C. Andrews. J. Chem. Educ. , 1966, 43 (11), p A1014. DOI: 10.1021/ed043pA1014...
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BOOK REVIEWS sented. This is altogether an outstsnding book which can be highly recommended. ERNESTM. LOEBL Polytechnic Institute of Brookl~n Brooklyn, New York Introduction to Chemical Thermodynamics

IM.H . Euerdell, University of Aston in Birmingham, England. W. W. Norton and Co., Inc., New York, 1965. xxviii 436 pp. Figs. and tables. 16 X 24 em. 88.75.

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One could justify a. new textbook in the overworked x m a of the rhemical thermodynamics if i t offered an improved treatment of the fundament& and s. more easily understood and organized approach to standard applications. I n addition, a reference baok mieht be useful if it eon-

poor classroom text became of weak treatment of the fundamentals, imprecise wordiug, and loose organization. It might have some use &8 a reference because of its strong orientation toward chemical problems. The baok is designed to be a thermodynamics and statistical mechanics text st the senior or first-year graduate level. It starts by presenting the four tbermodynamic laws and extended treatments of their applications. I t then treats elementary statistical thermodynamics with rtpplicat,ion to ideal gases. Chapters follow on phase equilibria, electrolyte solutions, electrochemioal cells, and caloulation of activit,y coefficients. A strong bias t,oward chemical applications is present throughout,; fur example, the treatment of the third law and sbsolute entropy calculations is ext,ensive. Great effort is made to motivate t,he reader by telling him in advance how useful new cuncept,s will prove to he. The reviewer now paraphrases or quotes a few ideas or sbtements he dislikes, so the reader call form his own opinion. Hopefully, the quotes are not too distorted from the intention of the author. The concept of energy is taken to be intnitive, and the first law is stated, "energy can neither be created nor dest,myed." The concept af heat is also taken to be intuitive, somethiug which most thermodynamics writers have avoided, at least since Bridgman's analysis of t,he problem. Work is called a "movement against a resistance," and heat and work so defined are stated to he the only ways one body can give energy to another (What about matter flow?) The discussion of the experimental basis of the absolnt,e temperature scale is out of date. Also, the important statement that a reversible process can occur "only if the system concerned and the surroundings are in equilibrium and remain so throughout the process" seems likely to confuse students.

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B O O K REVIEWS The second laa. is stated, "No substance can he caused t o undergo a cyclic s e k of operations unless a t least one operation involves the absorption of heat, and at least one operation involves the rejection of heat." Not only is this statement clearly false in itself, but many qwles cor~ldbe imagined which conform to it and still violate the second law! Fnrthermore, much is made of equations like d S = qinev/T dSirrevaud dS.,&, = qi,,,/T, which hopelessly confuse the fact that entropy is n state function defined by d S = 6qdT. The statistical mechanics section is based on the Boltzmmn expression, S = k 111 W, the utility of which is a matter of taste. The symhol tab,is given to the particle partition f~mrtion,which is an mncommon choice. This reviewer is forced to conclude that

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cal thermodynamir~"is more nearly true of the hook than of thermodynamics itself.

FRANKC. A N D R E ~ S Universiff, of Wisconsin Madison

Adsorption from Solutions of Non-Electrolytes

3. J . Kipling, University of Hull, England. Academic Press, Inc., New York, 1965. xii 328 pp. Figs. and tables. 16 X 23.5 cm. 512.

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This research monograph is the only one of its kind, a t least in the Western World, so far as the reviewer is swnre. It is an essential part of the personal library of every surface and colloid chemist. Despite some serions shortcomings it is well orgitniaed and eminenbly readable. The coverage appears ta he virtually con~plete in both time and international scope. I t mmut have been a gargantoan task to assemble the material, and all who read it deeply regret the untimely death of its author making it impossible for him to receive directly the honor due him for its preparstiao. After a brief informatory introduction and a second chapter summarizing esperimental techniques of adsorption me* surement there follow ten chapters giving the types of results found for (3) the liquid solid interface, (4) adsorption by solids from completely miscible liquids over the full composition range, (5) the same but for partially miscible liquids s t eompositions where a single liquid phase exists, ( 6 ) adsorption of gases from solution onto solids, (7) adsorption of solids from solution, (8) adsor~tionof polymers, (9) adsorption in multicomponent systems, (10) competitive adsorption (a theme (Catinued on page A1018)

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involved also in former chapters), (11) admrption a t the liquid-vapor interface, (12) adsorption s t the liquid-liquid interface. Of these Chapter 3 sets the stage for the monograph. Dr. Kipling points out emphatically that experiment measures a weight of adsorbent, a quantity of solution (s), an initial and a final composition, and lliat is all (apart from s quwtionahle surface area of adsorbent and, of course, pressure and temperature). H e designhtes the result a t mnstant tenqmature ''a composite isotherm." I t s resolution into individual isotherms mnst involve some assumption any one of which is difficult to justify. H e prefers the $implest-that the adsorbed layer is monomolecular and all subsequent layem have the composition of the bulk solntion. Even so, it becomes necessary to deduce a number for the area available to each adsorbed species, to choose whether or not. it r i l l he taken to remain constant at all compositions, to distinguish chemisorption from physirnl adsorption (not very hard in general), and finally (related to .wea/n~olecule)to choose an orientation for the (several in some cases) adsorbed species. These chnices are needed to resolve the ron~poniteisot,herm into individual ones, and is only the heginning since the object is to proponxi an adequate theory for the results. Many will object to one or another detail for a specific system. Let him who can do it better cast the finst &me. However, there are many details of format which make serious study difficult. Often symbols under graphs do not match those on the graph itself. Sometimes lines are d r a m a t the ordinate value corresponding to monoleyer coverage without refe~ence tn the source, and with preferential adsorption per gram and not per unit area plotted. References to lengthy books do not indicate the pertinent. page, ete. I n the opinion of this reviewer, Dr. Kipling has not been sufficient1 skepticnl of Lhe hypothesis of monola>-er coverage, I ~ ofT the hypothesis of Gem Sehay t,hat a linear composite isoiherm indicstes a n t~daorbedmanolsyer of constant eomposition which can be extrapolated to the cwdinntes corresponding to each mole fraction being unity to find the number of molecules of each species (in a two cornponent liquid adsorbate) needed hy the surbent for a complete monolayer. I n :tdditiou, the mobility or lark of it far adsorbed molecules end their lateral inter:action in the adsoybed etnte seems not to have been considered adequately. The crit,ical reader who hns dealt extensively with some small part of the general topic cannot help hut b e startled at how much is yet unknown. The last five chapters deal respectively >\.ith (13) kinetics of adsorption from the liquid phase, (14) thermodynamics of this itdsorption, (15) brief comparison and contrast with adsorption of electrolytes, (16) adsorption columns, and (17) ad(Continued a page AIOZO)

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BOOK REVIEWS sorption from solution as a tool in measurement of surface area. By contrast with the others, all but Chapter 14 give the impression of hasty writing. The thermodynamic treatment is soond, although this reviewer prefers Everett's definition of surface excess to the more uwnl Gihhs'. Also Dr. Kipling tends (don't we all?) to incorporate a discussion of models and statistical treatment into the chapter labeled "Thermodynamic?!' G. N. Lewis seems right in asserting that thermodynamics is a useful formalism a d nuthing more. It is a pleasure to end this review with a commendation of the exeell~nreof the three indenw,systems, authors, subjectseven though i t seems necessary to mourn the absenre of a short succinct summary for each chapter. The final words are "Buy it today" (for research and reference). Mnwonr~J. \-OLD Uniuercilg qf Southern Calijornia Lo6 Angeles

KekulL und seine Benrolformel: Vier Vorlrige

R. Wizinger-Aust, Basel, J. B . Gillis, Ghent, B. Helferich, Bonn, and C . Wursler, Ludwigshafen/Rhein. Berlag Chemie, GMBA, Weinhe~m/Bergstrasse, West Germany, 1966. 93 pp. Plates. 16 X 24 cm. 10 marks (about laZ.50).

The centenmy of the annom~cementof the Kekul6 hexagonal formulation of benzene was suitably observed a t Bonn in September, 1965, by the C:esellschaft Deutscher Chemiker a t its nst.ionsl meeting. The four invited lerturers were authorities on the life of KekulB and the consequences of his theory, conceived while he was professor a t Ghent and more fully developed a t Bonn, where he spent the last period of his career. The respective leotorw bear the titles: August Kekul6, Leben und Werk; Leben und Wirkeu von Kekul6 in Gent; Zur Geschichte der Chemie in Bonn: Die heutige Bedeutung der Benzolchemie. Their text? have been gathered into the present volume together with a prefatory word by Richard Kuhn (Heidelberg). Numerons wellchosen and beautifully reproduced photographs, drawings, etc., add much to the interest and attractiveness of this fine volume. The lectures themselves are full of meaty information and are a joy t o read. Teachers, students, and lovers af the history of our scienceshould he grateful for this opportunity to acquire a t a modest price this fine souvenir of a great milestone in the advanceof organic chemistry.

RALPHE. OESPER University of Cincinnati Cincinnati, Ohio