dynamic physical chemistry: a textbook of thermodynamics, equilibria, and kinetics (rose, j.)

1
experiments are included on column and on the part of research-minded students. Nevertheless, questions raised in alert minds by many of these interesting experiments will lead to additional study. The general impression of the manual is that of careful, competent writing baaed upon wide experience in the field. WILLIAM C. OELKE Grinnell College Clinnell. Iowa Dynamic Physical Chemistry: A Text- book of Thermodynamics, Equilibria, and Kinetics J. Rose, Birkenhead Technical College, England. John Wiley 8- Sons, Inc., New York, 1961. xii + 1218 pp. Figs. and tables. 14.5 X 22 cm. $11.50. The avowed purpose of this volume is to he a text and reference for persons with an elementary knowledge of the subject and some mathematical understanding. It is to be intermediate between single volume treatises and hooks "written by experts for experts." Although the production by one man of a hook of this length on such a range of topics is no small feat (and one which the author has performed moder- ately well), this reviewer cannot escape the conclusion that the possession of two or three separate volumes selected from ones already in print by different authors would better meet the need for an ad- vanced text or referenee than this book. The first two laws of thermodynamics are presented in a standard manner using Cilrnot cycles. The approach through CarathQodory's principle is given in a bit less than three pages near the end of this section, hut it seems that considerably more thought and space could and should be devoted to this elegant approach if it is to he discussed at all, The CarathBo- dory treatment is cited by the author as a special feature of the hook. The like amount of time devoted to irreversible thermodynamics appears to be too short to be of significant help to a person not already familiar with the material. The sections an statistid therma- dynamics are also 8. hit frustrating in terms of an incomplete or diffuse discussion of fundamental points. The Bolt~mann equation derivation is started (equation 8.2) midstream, and after deriving the mean kinetic energy of an ideal gas molecule to be 3/28, where 0 is the usual undetermined multiplier, thia energy was asserted to be 3/2 kT. This assertion is not obvious, and unless an explicit connection is made with experiment the argument would appear to be a bit circu- lar. The term "phase space" is used on p. 259 without previous or future ex- planations. These and other such objec- tions might seem unimportant in consider- ing a condensed summary work if the author had not spent one hundred and forty pages in discussing many aspects and cases of phase rule studies. Value judgments made by the reviewer favor a reapportionment of effort. A book such as the one by Aston and Fritz, "Statistical Mechanics and Thermodynamics" (Wiley, 19591, would be a preferred substitute to the first fourteen ohapters of this hook. It would he presumed that the methods of solving problems in chemical equilibria would have been thoroughly covered in the texts used to give the reader his "elementary knowledge of the subject." Books on reaotion kinetic6 such as the ones by Frost and Peamon and by Trot- man-Dickenson provide coverages of chemioal kinetics whieh the reviewer thinks would be preferable to the non- specialist interested in reaction rates from an experimental or theoretical point of view. It is true that there are topics not discussed in the three alternate hooks cited as preferenoes. Separate mono- graphs or review articles would have to be consulted for the materid covered in this text on solid state and photochemical reactions, radiochemicd kinetics, and properties of high temperature reacting' systems; hence these parts are useful to have disoussed in one volume. JOHN P. CAESICK Yale University Mew Hauen. Connecticut Molecular Orbital Theory for Organic Chemists Andrew St~eitwieser, Jr., University of California, Berkeley. John Wiley & Sons, Ino., New York, 1961. xii + 489 pp. Figs. and tables. 15.5 X 23.5 cm. $14.50. As the author states in the Preface, in this book he tries to do three things: teach Hiickel theory, survey the literature, and present interpretations (some new) of various phenomena in organic ehem- istry. In the opinion of this reviewer the author has done an excellent joh with all three. The teaching part is gentle without being undignified. Moreover, one does not get the feeling that rigor, or a. po- tentiality far rigor, is being subverted in the cause of simplicity. Topics covered include s. matrix algebraic viewpoint, factoring of the secular equation using group representation theory, and various accepted refinements of Hiickel theory on the one-electron level. The survey of the literature throughout is broad and balanced. One can see that the author has put in a lot of hard work. The applications to organic chemistry are likewise broad and balanced. A final major section of the book on wactions is the same size as the preceding section which deals with the better known properties of molecules. Among the less usual topics covered in the section on reactions are radical reactions and four center reactions. Two of the less usual topics in the section on properties of molecules are electron spin resonances and ionization potentials. The author states that "neither reso- nance theory nor its parent VB theory is suited for general quantitative or semi- quantitative ealeulations and carrela- tions." The holding of such an opinion has not prevented the author from writing a fine book on molecular orbital theory (it may have helped). Still, the opinion itself represents to thia reviewer a state of affairs in organic chemistry in which it may be said that the pendulum has now swung the other way. WILLIAM T. SIMPSON University of Waskingla Seattle Tutorial Questions in Organic Chemistry P. 8. Ongley, College of Technology, Birmingham, England. University of London Press, Ltd., London, 1959. xii f 276 pp. 14.5 X 22 em. $2.94. Questions of three general types, and their answem, constitute the major portion of this hook, which is intended to serve as an aid to a student reviewing for an organic examination. Problems are given on preparations, organio reactions, and identification from behavior. Forty prob- lems of the third type were selected tst random and solved by the reviewer. Four contained errors serious enough to cause difficulty. In three, there was faulty reference to compounds in the succession of reactions, but the intent was clear from the answers. In another, an incorrect moleoular formule. was given, with a corresponding pentavalent carhon atom in the answer. The answer section would have been easier to use if the head- ing of each page had given the page num- ber of the corresponding questions. Two of the three appendices are of little value. The first, a list of trivial names with formulas, serves no purpose whieh could not be met better hy the index of any good organio text. The second, on nomenclature, is poorly done. For ex- ample, the prefix "n" is said to be needed in IUPAC nomenclature for chains up to six carbons in length. Thus the compound which ~ o u l d be called 3-hexanone hy Chemical Abstracts and by American chemists is given as n-hexan-3-one. The position of the looant is British usage; either position is acceptable. Also, hy- bridization of trivial and IUPAC systems is frequently given in this book in ways which are generally avoided by Americans, hut which are sometimes used in England. Examples are hotylene-1 instead of a-butylene or l-hutene, isobutene in- stead of isohutylene or 2-methylpropene, and isoprapanol instead of isopropyl alcohol or 2-propanol. 4 tmical example of a nrong and misleading statement is this quotation from the section on nomenclature of carboxylic acids. "The lover acids have trivial names; the higher, systematic; and the intermediate, both trivial and systematic." As a matter of fact, the lower acids also have IUPAC names, and many of the higher acids hrwe trivial names. On the next page the names methanoic acid and ethanaic acid are used, and elsewhere in the book one finds stearic acid, etc. The last appendix is a list of several (Continued on page A604)

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Page 1: Dynamic physical chemistry: A textbook of thermodynamics, equilibria, and kinetics (Rose, J.)

experiments are included on column and

on the part of research-minded students. Nevertheless, questions raised in alert minds by many of these interesting experiments will lead to additional study. The general impression of the manual is that of careful, competent writing baaed upon wide experience in the field.

WILLIAM C. OELKE Grinnell College

Clinnell. Iowa

Dynamic Physical Chemistry: A Text- book of Thermodynamics, Equilibria, and Kinetics

J . Rose, Birkenhead Technical College, England. John Wiley 8- Sons, Inc., New York, 1961. xii + 1218 pp. Figs. and tables. 14.5 X 22 cm. $11.50.

The avowed purpose of this volume is to he a text and reference for persons with an elementary knowledge of the subject and some mathematical understanding. It is to be intermediate between single volume treatises and hooks "written by experts for experts." Although the production by one man of a hook of this length on such a range of topics is no small feat (and one which the author has performed moder- ately well), this reviewer cannot escape the conclusion that the possession of two or three separate volumes selected from ones already in print by different authors would better meet the need for an ad- vanced text or referenee than this book. The first two laws of thermodynamics are presented in a standard manner using Cilrnot cycles. The approach through CarathQodory's principle is given in a bit less than three pages near the end of this section, hut it seems that considerably more thought and space could and should be devoted to this elegant approach if i t is to he discussed a t all, The CarathBo- dory treatment is cited by the author as a special feature of the hook. The like amount of time devoted to irreversible thermodynamics appears to be too short to be of significant help to a person not already familiar with the material.

The sections an s ta t i s t id therma- dynamics are also 8. hit frustrating in terms of an incomplete or diffuse discussion of fundamental points. The Bolt~mann equation derivation is started (equation 8.2) midstream, and after deriving the mean kinetic energy of an ideal gas molecule to be 3/28, where 0 is the usual undetermined multiplier, thia energy was asserted to be 3/2 kT. This assertion is not obvious, and unless an explicit connection is made with experiment the argument would appear to be a bit circu- lar. The term "phase space" is used on p. 259 without previous or future ex- planations. These and other such objec- tions might seem unimportant in consider- ing a condensed summary work if the author had not spent one hundred and forty pages in discussing many aspects and cases of phase rule studies. Value

judgments made by the reviewer favor a reapportionment of effort. A book such as the one by Aston and Fritz, "Statistical Mechanics and Thermodynamics" (Wiley, 19591, would be a preferred substitute to the first fourteen ohapters of this hook. It would he presumed that the methods of solving problems in chemical equilibria would have been thoroughly covered in the texts used to give the reader his "elementary knowledge of the subject."

Books on reaotion kinetic6 such as the ones by Frost and Peamon and by Trot- man-Dickenson provide coverages of chemioal kinetics whieh the reviewer thinks would be preferable to the non- specialist interested in reaction rates from an experimental or theoretical point of view. It is true that there are topics not discussed in the three alternate hooks cited as preferenoes. Separate mono- graphs or review articles would have to be consulted for the materid covered in this text on solid state and photochemical reactions, radiochemicd kinetics, and properties of high temperature reacting' systems; hence these parts are useful to have disoussed in one volume.

JOHN P. CAESICK Yale University

Mew Hauen. Connecticut

Molecular Orbital Theory for Organic Chemists

Andrew St~eitwieser, Jr., University of California, Berkeley. John Wiley & Sons, Ino., New York, 1961. xii + 489 pp. Figs. and tables. 15.5 X 23.5 cm. $14.50.

As the author states in the Preface, in this book he tries to do three things: teach Hiickel theory, survey the literature, and present interpretations (some new) of various phenomena in organic ehem- istry. In the opinion of this reviewer the author has done an excellent joh with all three.

The teaching part is gentle without being undignified. Moreover, one does not get the feeling that rigor, or a. po- tentiality far rigor, is being subverted in the cause of simplicity. Topics covered include s. matrix algebraic viewpoint, factoring of the secular equation using group representation theory, and various accepted refinements of Hiickel theory on the one-electron level.

The survey of the literature throughout is broad and balanced. One can see that the author has put in a lot of hard work.

The applications to organic chemistry are likewise broad and balanced. A final major section of the book on wactions is the same size as the preceding section which deals with the better known properties of molecules. Among the less usual topics covered in the section on reactions are radical reactions and four center reactions. Two of the less usual topics in the section on properties of molecules are electron spin resonances and ionization potentials.

The author states that "neither reso- nance theory nor its parent VB theory is suited for general quantitative or semi-

quantitative ealeulations and carrela- tions." The holding of such an opinion has not prevented the author from writing a fine book on molecular orbital theory (it may have helped). Still, the opinion itself represents to thia reviewer a state of affairs in organic chemistry in which it may be said that the pendulum has now swung the other way.

WILLIAM T. SIMPSON University of Waskingla

Seattle

Tutorial Questions in Organic Chemistry

P. 8. Ongley, College of Technology, Birmingham, England. University of London Press, Ltd., London, 1959. xii f 276 pp. 14.5 X 22 em. $2.94.

Questions of three general types, and their answem, constitute the major portion of this hook, which is intended to serve as an aid to a student reviewing for an organic examination. Problems are given on preparations, organio reactions, and identification from behavior. Forty prob- lems of the third type were selected tst random and solved by the reviewer. Four contained errors serious enough to cause difficulty. In three, there was faulty reference to compounds in the succession of reactions, but the intent was clear from the answers. In another, an incorrect moleoular formule. was given, with a corresponding pentavalent carhon atom in the answer. The answer section would have been easier to use if the head- ing of each page had given the page num- ber of the corresponding questions.

Two of the three appendices are of little value. The first, a list of trivial names with formulas, serves no purpose whieh could not be met better hy the index of any good organio text. The second, on nomenclature, is poorly done. For ex- ample, the prefix "n" is said to be needed in IUPAC nomenclature for chains up to six carbons in length. Thus the compound which ~ o u l d be called 3-hexanone hy Chemical Abstracts and by American chemists is given as n-hexan-3-one. The position of the looant is British usage; either position is acceptable. Also, hy- bridization of trivial and IUPAC systems is frequently given in this book in ways which are generally avoided by Americans, hut which are sometimes used in England. Examples are hotylene-1 instead of a-butylene or l-hutene, isobutene in- stead of isohutylene or 2-methylpropene, and isoprapanol instead of isopropyl alcohol or 2-propanol.

4 tmical example of a nrong and misleading statement is this quotation from the section on nomenclature of carboxylic acids. "The lover acids have trivial names; the higher, systematic; and the intermediate, both trivial and systematic." A s a matter of fact, the lower acids also have IUPAC names, and many of the higher acids hrwe trivial names. On the next page the names methanoic acid and ethanaic acid are used, and elsewhere in the book one finds stearic acid, etc.

The last appendix is a list of several

(Continued on page A604)