Resource Pa pers-lI Prepared under the sponsorship of The Advisory Council on College Chemistry
Harvard University Cambridge, Massachusetts
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In 1943 a paper in THIS JOURNAL' began: "The teachmg of thermodynamics in a beginning course in physical chemistry is a very difficult task, but it is becoming a necessity." Perhaps even in 1943 the author might better have written not "is becoming" hut rather "has become"; certainly today the proposition is no longer open to doubt. Yet the above statement can easily be converted into a proposition of lively current interest, by changing just one word: The teaching of thermodynamics in a beginning course in college chemistry is s. very difficult task, but it is becoming a necessity.
This survey is conducted with a view to meeting the necessity, by ameliorating the difficulties of that task. Thermodynamics is an immense subject, with a correspondinglyimmense literature. A resource survey of manageable size becomes possible only when one has severely limited the area of thermodynamics to be surveyed. The operative limitation in the present case is a restriction to those aspects of thermodynamics likely to be of most concern to students in, and teachers of, introductory college chemistry courses. Acting on this restriction one can, for example, exclude consideration of the extraordinary phenomena of lowtemperature physics, the complexities of phenomena around the critical point, the thermodynamics of fields (electromagnetic and otherwise), and a variety of other thermodynamic topics of interest primarily to the physicist. Probably one can also exclude detailed consideration of the complexities of non-ideal systems (e.g., fugacities, activities, and the lice), as well as a multitude of other topics (e.g., extended treatment of the relations of partial molal quantities) likely to he better treated a t a more advanced level. Statistical thermodynamics has been regarded as fallmg under this last head and, for the most part, is represented here only by relatively qualitative considerations that may usefully supplement an elementary presentation of classical thermodynamics. Due to these omissions, teachers and students in standard junior-year courses in physical chemistry will find the present survey incomplete: nevertheless, i t is believed that the large majority of the items cited hereafter have substantial relevance to such courses. At the most elementary level, modern chemical thermodynamics is a comparatively ancient subject-
WOOD,S. E., J. CHEM.EDUC., 20,80 (1943).
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having undergone little fundamental change since the monumental work of Lewis and Randall some 40 years ago. Thus any of a variety of excellent standard texts can and do offer the entire substance of the subject in well worked-out forms. What is likely to be most helpful, then, is not a catalog of recent research papers on advanced points in thermodynamic theory but, on the contrary, papers that help us to make a more effective presentation of the basic subject and/or a more effective illustration of its manifold chemical applications. Thus a large fraction of the following bibliography is made up of those modest publications that do no more than offersimple presentations of difficult points: these are the papers most likely to help the novice chemist (and his teacher when, as is now often the case, thermodynamics is taught by one not himself professionally concerned with that subject). Pursuing this line, one looks primarily for methods of presentation less demanding of mathematical sophistication than, say, the highly formal and abstract approach of CarathBodory. Similarly, one looks for simple experiments that can be made effectively with the unsophisticated equipment likely to be (or to become) available in the laboratory of the freshman chemistry course-or within the scope of the demonstration facilities available in such a course. In the following tabulation of sources, the symbol "pb." following the name of the publisher of a book
signifies that that work is available in an inexpensive paperback edition. For full addresses of publishers, consult the Annual Book List appearing in the September, 1964, issue of J. CHEM.EDUC. Standard abbreviations of journal titles have been used throughout this resource letter with two notable exceptions. Since a majority of the cited references are to just two journals, it has seemed worthwhile to abbreviate the title of the JOURNAL OF CHEMICAL EDUCATION as JCE, and the title of the American Journal of Physics as AJP. The numbered references are considered those most likely to he useful; many additional supplementary references have been incorporated in the text. General Sources Textbooks
Treatments of chemical thermodynamics expressly prepared for, and accessible to, college freshmen include the following-listed in estimated order of increasing difficulty (and comprehensiveness). (1) BROWN, T. L., "General Chemistry," Merrill, 1963. Makes minimal uuse of calculus; very simple and, perhaps, occasionally oversimplified. (2) ANDREWS,D. H., AND KOKES, R. J., "Fundamental Chemistry," Wiley, 1962. Ineorporetes extensive treatment of thermodynamics in a. full freshman text; somewhat awkward notation characterizing first edition will be replaced in the second. -~~~ (3) MAHAN,B. H., "Elementary Chemical Thermodynamics, Benjamin pb., 1963. (4) NASH,L. K., "Elements of Chemical Thermodynamics," Addison-Wesley ph., 1962. (5) FERMI,E., "Thermodynamics," (1936), Dover pb., 1956. lacks chemical orienConcise, lucid.. ~enetratina-but . tiltion. (6) KLOTB,I. M., "Introduction to Chemical Thermodynamics," Benjamin pb., 1964. Presumably not intended primarily for freshmen, but accessible to those who have had mme calculus. Uses great care in explaining difficult points.
References (5) and (6) make extensive use of partial differential formulations, which are adequately explained in a preliminary chapter of (6). The other four texts cited require only the most elementary calculus, the operations of which are explained in separate sections in references (2) and (4). For an exposition of elementary calculus-through exponentials and partial differentials-accessible to the bright freshman without previous training in calculus, see: (7) DANELS,F. D., "Mathematical Preparation for Pbysical Chemistry," (1928), McGraw-Hill pb., 1956.
With no more mathematics than is provided in reference (7), one may deepen his understanding by reading any of several excellent texts written a t a more advanced level. Reference (6) is quite suitable in this connection, as are also the following: (8) CALDIN,E. F., "An Introduction to Chemical Thermcdynamics," Oxford Univ. Press, 1958. OBem a remarkably clear and thoughtful appraisal of many questions that arise when one thinks of them* dynamics as more than s. ctllculational device. (9) WALL, F. T., "Chemical Thermodynamics," Freeman, 1958. - -~
ical applications. K., "Principles of Chemical Equilibrium, Cam(11) DENBIGH, bridge University Press pb., 1955. A sunerb advanced text combinina a careful treatment of findamentals with a strong chemical orientation. Comorehensive (includes an introduction to statistical mechanics); clo~elyreasoned hut lucid. Presupposes some elementary understanding of thermodynamics.
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These specialized monographs on thermodynamics are probably to be preferred to the treatments of that subject to be found in general-purpose physical chemistry texts, excellent though these often are. One notes in passing that the text by Glasstone and Lewis and the text by Barrow (which is otherwise notable for its early introduction of statistical considewtions in thermodynamic arguments) are elementary enough to be accessible to freshmen; that the texts by Daniels and Alberty and by Sheehau offer clear standard treatments; that Castellan's text is notable for its extended verbal explications of thermodynamic formulas, as well as for its lengthy treatment of the phase rule; and that Moore's text remains the standard of comparison though not always the easiest to comprehend. For full specifications of these texts, consult p. A700 of the above-noted Annual Book List. For a brief "Manual of Physico-Chemical Symbols and Terminology" recommended by the IUPAC, see J. A. CHRISTIANSBN, J . Am. Chem. Sac., 82,5517 (1960). History and Philosophy
A full listing of materials on the history and philosophy of thermodynamics is not among the objectives of this survey. A few readily available sources of information on particular points are listed under the correspondins t o ~ i c s : the teacher for student) who wishes to gain some'feeling for the general historical and philosophical foundations of thermodynamics will be well advised to consult the following:
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(12) BnmGMAN, P. W., "The Nature of Thermodynamican (1941), Harper pb., 1961. Operational analysis of the concepts af thermadynamics, conducted by the most eminent exponent of such analysis. E.,"Identity and Reality" (1930), Dover ph., (13) MEYERSON, 1962. A distinguished philosopher who began as a. chemist conducts (in chanters 5 and 8)a searchine exnloration detail. (14) MERZ,J . T., "A History of European Thought in the Nineteenth Century," vol. 2, Blackwood, Edinburgh, 1912. Chapter 7, "On the Physical View of Nature," oBen a valuable perspective on the history of thermodynamics, and contains in its footnotes a wealth of bibliographic citations. E., Physiw. Today, 14, 32 (Feb. 1961). (15) MENDOZA, A sketch for the history of early thermodynamics, oontaining a brief account of the work of the French cdoloricists: Litplace, Poisson, Delaroche and BBrard. For s. fuller account of their work see T. S. XUHN, Isis, 49, 132 (1958).
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A painstaking development of classical thermodynamics, incorporating several chaptem on the rudiments of statistical mechanics. M. W., "Heat and Thermodynrtmics," 4th ed., (10) ZEMANSKY, MeGraw-Hill, 1957.
Experiments and Data
A goodly proportion of the thermodynamic experiments traditionally associated with the junior-year course in physical chemistry can be reworked for use Vol. 42, Number 2, February 1965
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in the freshman courses now taking shape. Descriptions of many specific experiments of this sort will be noted under the corresponding topics, but three general collections containing numerous thermodynamic experiments are noted here: (16) DANIELS, F., ET AL, "Experimental Physical Chemistry," 5th ed., McGraw-Hill, 1956. Has a very long history of popularity. C. W., ,'Experiments in (17) SHOEMAKER, D. Y., AND GARLAND, Physical Chemistry," McGraw-Hill, 1962. The most sophisticated of recent manuals, containing also a great deal of background material on the baeic theories involved. (18) JAMES,A. M., "Practicsl Physical Chemistry," Churchill, London, 1961. Thoueh - not well known to American readers, this manual contains brief descriptions of a very large number of experiments, thermodynamic and otherwise.
Beyond the data obtainable through experiments like those described in the foregoing, one often finds need for comprehensive tables of thermodynamic data of the highest accuracy. For sources of up-to-theminute values, consult the Bulletin of Thermodynamics and Thermochemistry, but the following standard tabulations will meet almost all needs. (19) LATIMER, W. M., "Oxidation Potentials," 2nd ed., Prentiee-Hall, 1952. Still an enormously serviceable compilation of data, particularly as regards the thermodynamics of aqueous solutions. (20) Rossr~r, F. D., ET AL, "Selected Values of Chemical Thermodynamic Properties" (Circular 500 of the National Bureau of Standards), US. Government Printing Ofice, Washington, D. C., 1952. Probably the mast often cited, the most widely available, and the mcst generally useful compilation of thermodynamic data. (21) ROSSINI,F. D., ET AL, "Selected Values of Physical and Thermodynamic Properties of Hydrocarbons and R s lated Materials," Cmnegie Press, Pittsburgh, Pa., 1953. (22) KELLEY,K. K., "High Temperature Heat-Content, HeatCapacity, and Entropy Data. for the Elements snd Inoreanic Com~ounds,"US. Bureau of Mines Bulletin 584 ' (1960). (23) KELLEY,K. K., AND KING,E. G., "Entropies of the Elements and Inorganic Compounds," US.Bureau of Mines Bulletin 592 (1961). Values a t 298.15' K. (24) STULL,D. R., ET AL, "JANAF Interim Thermochemicd Tables," Dow Chemical Co., Midland, Mich., 1960 and Inter. Reflection of a continuing endeavor and, as such, not the easiest of compilstions to use. (25) Qurm, L. L. (ed.) "The Chemistry and Metallurgy of Miscellaneous Materials: Thermodynamics," McGrawHill 1950. In addition to a wealth of tabulated thermodynamic data, contains some interesting analyses of them. (26) KusAscHEws~r, O., AND EVANS,E. L., "Metallurgical Thermochemistry," 3rd. ed., Pergamon, 1958. The First Principle of Thermodynamics
For a careful and complete examination of all the concepts appertaining t o the first principle, see reference (10). Temperature, Heat, and Work
For some historical introduction to the concepts of heat and temperature, see: (27) ROLLER,D. E., '
