Thermodynamics and Statistical Mechanics. - ACS Publications

Beatty Research Institute, Royal Cancer Hospital,. London, England. Academic Press, Inc., Publishers,. 111 Fifth Avenue, New York 3, N. Y. 1956, ix + ...
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in induced carcinogenesis aiid spontaneous tumorigenesis, could not be patent protected, does not seem warranted. of t h e lipids of tumors, and lipids in t h e tunlor-host relatioiiAlso t h e expression t h a t C-dihydrotoxiferine probably ship by Frances L. Haven and W. R . Bloor, who have contains the yohiinbine skeleton is not justified. T h e contributed so much t o this field. T h e material i.eviewed present volume gives a good survey of Bayer’s interests a n d for this reason is worth studying. Its physical appearance should stimulate greater efforts in this area and is likely t o have an increased audience because of interest in the cardiois very good and t h e printing is excellent. vascular diseases. T h e remaining two chapters r-present CIBA PHARMACEUTICAL PRODUCTS specialized aspects of carcinogenesis. A. Lacassazne and 556 MORRISAVESUE,SUXMIT,N.J. E SCHLITTLER associates summarize t h e results of studies, largely from their laboratories, on T h e Relation between Carcinogenic Activity and t h e Physical a n d Chemical Properties of Angular Benzacridines. T h e carcinogenic activities of a Advances i n Cancer Research. Volume I V , Edited By considerable number of benzacridines are conveniently JESSE P. GREENSTEIS, National Cancer Institute, summarized in a lengthy table. Other tables present reSational Institutes of Health, U. S.Public Health Service, lationships of carcinogenicity with physical properties and Bethesda, Maryland, and ALEXANDER HADDOW, Chester are discussed in t h e text. T h e Hormonal Genesis of B e a t t y Research Institute, Royal Cancer Hospital, Mammary Cancer by 0. hliihlbock is a good survel- in this London, England. Academic Press, Inc., Publishers, complex area. Studies in r a t s and mice are discus:ed with 111 Fifth Avenue, New York 3, K. Y. 1956. ix 4- 416 emphasis on t h e hormonal influence as one of a nunibcr of pp. 16 X 23.5 cm. Price, $10.00. factors involved in mammary cancer. Volume IV of Advances in Cancer Research 11.1s been ’L’olume IT.’ of t h e series Advances in Cancer Research built with t h e high quality of scientific and physicd workreflects quite well the editors’ awareness of timely topics and of appropriate authors for their review. This volume suc- manship observed in earlier volumes. Very few typographical errors were noted. On page 42 the formula for tliioccssfully continues the pattern, established in earliervolumes, guanine is mislabeled as a pyrimidine. On page 105 iii of achievement of t h e objectives of the editors as stated in Case 21 i t would seem t h a t t h e dose for urethaii is misstated introductions t o t h e first two volumes. This is t h e reflection or possibly urethan was inadvertently written in place of of t h e “steady a n d inevitable march of t h e tidesof our knowlmyleran. T h e essential author and subject indexes are edge and increasing understanding” in cancer research and provided. A brief check of the latter indicated i.hat an provision of a “recurring stimulus t o the work ahead” in increase in its usefulness, through added cross indexing, addition t o providing a n annual chronicle of progress. Though t h e selections in t h e present volume are timely, might reasonably be requested. This volume merits a place in t h e library of t h e serious informative, and useful from the viewpoint of t h e cancer cancer investigator and will provide chemists and cthers a research investigator, they may as a whole be of less interest good introduction t o a number of important areas of cancer t o chemists t h a n preceding volumes; however, there are a research. This may also be anticipated from future \olumes number of chapters in Volume I V t h a t will make its reading of the series ..\dvances in Cancer Research if we are t o judge well worth while for chemists whether actively participating from t h e first four volumes. or merely interested in cancer research. T h e chapter, .idvances in Chemotherapy of Cancer in M a n , by Sidney SLOAN-KETTERIXG ISSTITUTE FOR CANCER RESEARCII Farber a n d associates, presents problems in clinical studies, 410 EAST68TH STREET C . CHESTERSTOCK surveys the cheniotherapy of acute leukemia, and reviews SEW YORK21, NEWYORK selected chemotherapeutic agents. I t is so written t h a t it can serve a s a n introduction t o clinical cancer chemotherapy as well a s being useful for experienced investigators. T h e chapter furnishes a convenient bibliography of general Thermodynamics and Statistical Mechanics. B y A. H references in addition t o those specifically used in the text. 11~r~so.v. F.R.S. Cambridge Universitv Press. 3% East This reviewer with his prejudices differs on t h e historical 495 pp. 57th Stieet, New York 22,-?j. Y. lS5f. xv aspects of a few of t h e text references. T h e second chapter 18 X 26.5 cm. Price, $9.50. of t h e book, T h e Use of Myleran a n d Similar -4gents in Chronic Leukemias, by D. A . G. Galton, also is concerned This beautifully presented and printed book . b y the with clinical studies with particular emphasis on a limited distinguished author of “The Theory of Metals” is in many ways a rather peculiar hybrid of thermodynamics and statisgroup of chemotherapeutic agents. Like the first chapter this one provides valuable information for t h e clinical tical mechanics, intended, says t h e author in his Preface, investigator and for others some insight on problems in mainly for theoretical physicists, while t h e notice on the clinical chemotherapy investigations. jacket announces as additional possible audience “those T h e chapter, T h e Employment of Methods of Inhibition experimental physicists and physical chemists who wish t o A4nalysis in t h e Normal and Tumor-Bearing Mammalian enter more deeply t h a n is customary into t h e fundamental Organism by Abraham Goldin, presents much of this principles of t h e subject.” How well the author may have investigator’s studies and ideas on t h e application t o experi- succeeded in his appeal t o t h e theoretical physicist will mental cancer chemotherapy of the principle of inhibition probably b e made clear in the reviews which will appear in analysis previously developed in microbiological studies. physics journals. A s far a s the physical chemist is concerned, T h e author suggests t h a t a more detailed study of the whether he considers himself a s theoretical or experimental, tumor-host relationships in the responses t o various toxic the usefulness of this book is very debatable. drugs m a p indicate ways in which the chemotherapy of T h e book begins with a 3-page List of Iniportant S y n b o l s , cancer can be improved. T h e two chapters, Some Recent Units and Physical Constants. Chapter 1 treats “The Work on Tumor Immunity by P. A . Corer and Inductive Classical Development of Therniodynaniics and the First Tissue Interaction in Development by Clifford Grobstein Law.” T h e presentation is highly condensed and contains are important contributions t o this volume. A discussion none of the applications of importance t o the physical of aspects of tumor immunity is most timely in view of the chemist. Guggenheim’s “Zeroth Law” is ignored. Chapupsurge in interest in this subject. T h e mutual relevance of ter 2 is devoted t o “The Classical Development of T1 ermostudies of inductive tissue interaction and of carcinogenesis dynamics and T h e Second Law.” n’hat is presen:ed as is apparent if one assumes “ t h a t involved in embryonic Carnot’s theorem is the following statement: “Tlieri: exist induction are the origins of reactions and materials which two functions of the state S and T , where T is a positive form t h e basis of stability of structure and function of t h e function of t h e empirical temperature e only, such tliat, in adult and also t h a t similar processes may be operating in a n y infinitesimal quasi-static change of a body or system newly developed subsystems of the adult and t h a t they m a y of bodies, dQ = T d S . ” Even for theoretical physicists be involved in reverse in the adult when adult stability of several better presentations of the second law immec iately structure breaks down or is disrupted.” These two chapters come in mind. T h e chapter finishes with four brief pages will pose a problem for most chemists because of their lack on t h e thermodynamics of a perfect gas. In Chapter 3 t h e of familiarity with the language used. T h e more venture- thermodynamic functions are introduced, Helmholtz ’ free some chemists reading these chapters will a t least be reenergy being called free energy at constant volums and warded with a better idea of lhc coiiiplesitics of biological Gibbs’ free energy or free enthalpy being callcd free energy phenomena. a t constant pressure. This chapter iiiclutlrs a treatment of Lipids ill Cltiicer is a cliapter presciitiiig a review of lipids cquilibrium and its stability it1 t h e case of honiogeneot s sys-

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terns. Chapter 4 deals with “The Axiomatic Foundation of Thermodynamics,” a subject which usually does not concern or interest t h e physical chemist. T h e only references given at t h e end of this chapter are t o a 1921 paper of 11.Born and t o t h e 1909 and 1925 papers of Carathkodory whose presentation a very recent paper by Landsbcrg ( l h ~Moderiz . Phys., 28, 363 (1956)) claims t o have improved. With Chapter 5 “the logical order of development is broken in order t o derive t h e fundamental formulae of statistical mechanics.” This “inelegance,” as t h e author designates this procedure, is handled in 46 concentrated pages which assume t h a t the reader is familiar with quantum meclianics. Chapter 6, in 51 equally concentrated pages, presents ‘‘Some Xpplicatioris of Statistical hlechanics” (Specific H e a t of Gases-Crystalline Solids-Systems Obeying Fermi-Dirac a n d Einstein-Bose Statistics-Radiation). Chapter 7 offers a treatment of t h e Third Law basecl largely on t h e w-ork and t h e ideas of F. Simon. Chapter 8 gives in 50 pages a thorough treatment of imperfect gases. Chapter 9 handles “The Heterogeneous Equilibrium of a Single Substance” a n d includes an interesting arid detailed study of the properties of helium. T h e very substantial Chapter 10 on “Electric a n d Magnetic Phenomena” (75 pages) ~ o u l dalone constitute a useful reference work o n topics which texts of chemical thermodynamics usually do iiot touch: force and energy relations in a n electrostatic cal mechanics of polar substances, ferroeleetricity, statistical mechanics of paramagnetic bodies; ferroinagiietism, antiferromagnetism, superconductivity. Chapter 11 on “Gas Mixtures and Chemical Reactions” is a condensed treatment of what mould constitute t h e major portion of a book on chemical thermodynamics. Section 11.411 entitled “The affinity as defined b y ne Doiider” denotes incomplete comprehension of the method and coxitaiiis statements indicating similar incomplete comprchension of other procedures (compare this section XTith t h e preceding one, 11.41). Interestingly enough De Donder’s iriethod is used in section 11.423 t o calculate t h e conditions required for t h e maximum extent of a reaction. Chapter 12 on “Solutions” may be sufficient t o initiate tlicorctical physicists t o t h e subject, b u t is far too incomplete t o be regarded as useful t o physical chemists. T h e same remark applies t o Chapter 13 on “Solutions of Electrolytes and Electrochemical Systems.” Chapter 14 is entitled “Further Topics in Solids” and offers interesting treatments of rubber, superlattices in alloys, and Some exact solutions [if tlie one-dimensional order-disorder problem. .Is a whole i t may be concluded t h a t a book of this type rightfully belongs in a Chemistry Department library, b u t t!iere seems t o be no strong reason t o urge its addition t o the private libraries of physical chemists, although, with the extremely moderate price of $9.50for such a large, beautiful and after all very competcntly written book, the itivestincnt is iiot a t all unattractive.

Vol. 70

chemistry anclniost of t h e remaindcr to aliphatic coiiipounds. Organic compounds of metalloids and non-metals other than nitrogen and sulfur are treated separately. A41though certain of these sections are too brief and out-of-date t o be of interest t o t h e specialist (e.g., silicon chemistry, 3 pages; boron chemistry, 2 pages), t h e sectioii has value iii bringing together for comparison some of t h e chemistry of these elements. A chapter on organometallic compounds of similar size and scope and a separate chapter ou t h e “Grignard reaction” are included. T h e chapter 011 alicyclic compounds deals chiefly with methods of ring closure, expansion and modification. It is particular1)- reconimended for its sections on azulenes, tropolones atid sterols. Twelve pages are devoted t o methods for the modificatiol! of sterol structures without change in ring skeleton. T h e tremendous task of reducing a large part of Bcilsteiii’s Handbook t o two volumes and attempting t o include important recent developments is not a n easy oiie. The author acknowledges his indebtedness t o a host of treatises, monographs and general reviews which i i ~ t d cthis work possible. Even so, t h e integration antl organizatioli ( 1 f thousands of facts and references is not without niajor problems. A few reactions of great breadth such Crafts, Grignard and Diene Synthescs are discu iii separate chapters. T h a t t h e entire ivork coultl riot h v e been so organized seems unfortunate. LIuch d u p l i c a t i i )antl ~~ fragmentation has resulted from tlic classical ~iibdivisio~i into aliphatic, alicyclic and aromatic compcn~tidscoupled with t h e treatment of most series frvni the stsndpoiiit of chemical behavior as well as synthesis. Frequeiitl)-, a reaction is discussed in several places. Thus, o n under chexnical behavior of unsaturated aldeliyc stated t h a t “oxidizing agents even of the mild convert only a small portion of unsaturated aldehytics into the corrcspotiding unsaturated acids.,’,’ Xii illustration, the conversion of “~iiethylethylacrolei~l to “rnetli? lacrylic :tcid,” is giyen with no reference. Iiowcver, 011 p . 957, a general method for t h e preparation of olefinic acids I)>- osidation of t h e corresponding aldehydes is pre=entcd alo~lgwit11 five references from tlie period 1862-1899, and fina!ly a detailed procedure for this oxidation is given on 11. 258. T h e more recent Jvork of Goldberg and Liiistead in which a-metlij-I-P-etl-iylacroleiii is oxidized iri 60%; yield t o t h e corresponding acid is omitted. T h e literature beforc 1925 has been covered more : d e quatel>- than t h a t of recent years. A re soc. chinz. (1905) rather than Organic Syn t h e preparation of P,P-dimethylacrylic acid reaction is one of many examples. Only papers cited in tlie chapter on Aromatic pounds appeared in the last three decades, and of these, lcss than a dozen were in American journals. .Ilthougli the same ratios do not apply t o all chapters, tlie inclusion of cliicstionable work and the omission of recent findiiigs are frequent. Thus, t h e dih~drohalogenation and decarboxylation of I I E P A R T R I E N T OR C H E M I S T R Y dihalo acids, p. 942, does not include the comprehensive A S D CIIEhIICAL ENGISEERISC studies of Farrell and Bachmau, THIS JOURNAL, 57, STASFORD USIVEKSITY r l r e R a E VAS RYSSELEERCIIE 1281 (1935), and the formation of olefiiiic bromides froin the ~ . T A S P O R D .C A I . I F O R S I A corresponding alcohols does not include the iiiotlilications necessary t o prcvent isomerization [Toung a n d I,atic, Tms JOURSAL, 59, 2051 (1937); Cheriiig, Cristol ~tntl Dittiner, ibid., 70, 3314 (1948)] Evexi t h e coiivcrsiori of Organic Synthesis. T~oluiiie I, Open-Chain Saturated simple alcoiiols t o halides ( p p . 11-21) is consitierabl\. outCompounds. Volunie 2. Open-Chain Unsaturated Comof-date from tlie standpoint of rnolccular rearraiigcrlreut pounds. Alicyclic Compounds. Aromatic Compounds. ant1 its prevention. T h e emphasis on the older literature By V h K r K E s MIGKIIICIIIAX, Senior Research Chemist, leutls to crrors of fact, its on p . 116,wlicre it is stated t h a t Central Laboratory, American Cyanainid Company, > icld. of aldehydes by the Bodrous-‘rschiticllibabi~i S y ~ i t l l e Stamford, Connecticut. Reinhold Publishing Corpora- sis do not exceed 2 S ( { . Tlic iiimy excellent preliaralioni tion, 430 Park Avctiuc, A-ew 170rk 22, S. \-. 1957. o f :ill classes of dtlelii-des iii 25-82(!; h-ichls iii tile 1)crimI Voluiiie 1, sxviii 833 111). T-