Thermodynamics, A Rigorous, Postulatory Approach
S. H. Chue, University of Malaya, Kuala Lumpur, Malaysia. John Wiley & Sons, New York, 1977. Figs. and tables. 15.5 X 23.6 em. xii 274 pp. $27.50.
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The author's intention is to "introduce a text a t the undergraduate level while retaining the rigor of Hatsopoulos' and Keenan's presentation" which "demands a level of sophistication generally higher than that possessed by undergraduate students." By presenting a generalized, unified approach to thermodynamics, both texts are intended for students of physics, chemistry, and engineering. Unlike the Hatsopoulos and Keenan (HK) text, the material here could becavered in one semester. Chapter 1,"Fundamental Concepts," hegins with definitions of systems, snrroundings, paths, and properties. In discussing work the author states that the convention of taking work done by the system to be positive "is now universal." Alas, if only this were true. Four new texts on physical chemistry alone use the oooosite convention. Althoueh the drawing of the apparatus nor literature reference thereto is given. Heat and work are correctly described as boundary interactions, hut immediately after stating that they are not forms of energy the (SI) units are given as joules. Adiabatic and diathermal walls are defined in a brief discussion of bringingsystems into equilibrium. Expansion work by the ideal gas is covered in an example. The symbols for C,/C,, heat "flow"and mass are introduced without definition. None of the
-Revie
ah:we discussions are supported hy illustrations. In Chapter 2, "Basic Postulates in Classical Thermodynamics and Their Consequences," the author's statement of the first law is that over a cycle Q = W for a system. The law of energy conservation then follows from this. The discussion is brief but clear. considerine lhnt m >ex;mplei o r illuatratirm are ared. The w n p < an I,? said 4 the development of the srrtmd Inrv.Thiilendinnturally t u a d i i cussion of temperature scales in which the Ramsey scale is mentioned, but there is nothing in the text as to the nature of this scale. A brief discussion of thermometry fallows, also devoid of data, illustrations, or references. The discussion an entropy is goad up to the encounter with absolute values a t which point the reader is left to wonder what sort af system might have zero entropy a t absolute zero. Ta begin Chapter 3, "Thermodynamics of One Component Systems," the state functions are derived for a simde svstem. The lirst of the two captioned figures in the entire text appears here, but no reference is made to it in the text nor is there an explanation of the labels used in the figure. It appears that the relevant discussion was omitted. A numher of Maxwell's relations are derived, some of which are used in Chapter 7. The Clausius and Clausius-Clapeyron equations are derived and applications are mentioned. Following very closely the treatment by HK, the first law is nicelygenerdized to cover w e n systems in Chapter 4, "Extension to Flow Processes: Thermodynamics of Open Systems." In deriving equations appropriate to steady flow conditions the author switches to Newtonian fluxion notation, e.g., for dmldt, without explanation or definition of
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the symbols. Application of the second law to open systems also closely follows HK even to the point of introducing a function a, the meaning of which is clearly defined by HK but can only he inferred by the reader of this text. The usual expresiions for the temperature .md ur preriure dependence of intrmal m ergy, enthalpy, and entropy are derived in succinct fashion for the ideal gas and extended in less than a page to real gases. Thus begins Chapter 5, "Properties of Ideal Substances." The extension to the ideal liquid and solid. defined as beine incomoressible. is hrirf and to the p i n t . 1.nir 12 n disruii~onof tatdrr oi the thermodynamic pn.pertles of saturated steam, although none are given nor are sources mentioned. Temperature-entropy and pressure-enthalpy diagrams are discussed in the examples. Chapter 6, "Direct and Reversed Heat Engines," appropriately begins with comments on the thermodynamic diagrams, illustrated with p-V and T-S diagrams, each of which shows only the liquid-vapor coexistence "dame." That this is the ease is very difficult to ascertain, especially for the p-V diagram, since coexistence domes are not discussed until the next chapter. The section "Vapor Power Cycles" covers the Carnot and Rankine cycles and their efficiency limitations from practical and theoretical viewpoints. Other cycles of interest, including the Otto, Diesel, and Brayton cycles are similarly treated in the following section, "Gas Power Cycles." Vapor and gas refrigeration cycles conclude this, the longest (49 pp.) and most profusely illustrated (39 figs.), chapter. A one component phase diagram is the hasis for introducing Chapter 7, "Properties of Real Substanees."It is not mentioned that since d p l d T < 0 for the solid-liquid eqnilibrium line the diagram is characteristic of very few substances, e.g. HzO. Following a discussion of state equations for dense gases and the law of corresponding states is a useful section on "Developing Thermodynamic Properties from Experimental Data." After treating the Phase Rule and partial molal properties, equilibrium in terms of chemical potentials is discussed in Chapter 8, "Thermodynamics of Multi component (Continued on page A286)
wed in this IsSue
S. H. Chue, Thermodynamics, A Rigorous, Postulatory Approach
Mary H. Saterstrom, Editor, Educators Guide to Free Science Materials. Nineteenth Edition John Creedy, A Laboratory Manual for Schools and Colleges Wilma E. Rollins, Using the Metric System Morris Freifelder, Editor, Catalytic Hydrogenation in Organic Synthesis Procedures and Commentary W. Carruthers, Editor, Some Modern Methods of Organic Synthesis Hntonrd Alper, Editor, Transition Metal Organometallics in Organic Synthesis. Vol. I1 Chris A. Clausen I I I , and Guy Mattson, Principles of Industrial Chemistry A. J. Melue~er,Editor, Resonance Raman Spectroscopy as an Analytical Tool R. J Abraham and P Loftus, Proton and Carbon-13 nmr Spectroscopy W. Klyne and J. Ruchingham, Atlas of Stereachemistry-Absolute Configurations of Organic Molecules. 2nd Edition. Vols. 1-2
Reuiewer Thomas C. Ehlert Stanley T. Marcus
A285 A286
Bill Nickels Donald D. Marshall Walter J. Gender
A286 A286 A288
Sheltan Bank Michael F. Farona W. Conard Fernelius Robert L. Carter Michael Barfield Richard S. Glass
A288 A288 A288 A290 A290 A290
Volume 56, Number 9, September 1979 / A285
Systems." Following this are derivations of the temperature and pressure dependences of fugacity and a description of a method of obtaining fugacity values from compressibility data fnr gases. In order to avoid problems when dealing with non-ideal vapors, the ideal solution is defined in Chapter 9, "Properties of Ideal Solutions," as a solution in which each constituent's partial mold volume is the same as its molar volume a t the same temperature and pressure. The other properties of the ideal solution are then derived. Raoult's law and, ultimately, Henry's law appear as consequences of the above definition of the ideal solution and of ideal behavior by the vapor. Boiling point elevation and osmotic pressure equations are then derived. Freezing point depression is ignored. In dealing with nonideal behavior in both vapor and condensed phase solutions, the author uses the expressions "solutions involving coexisting phases" and "two phase solutions" whieh are very confusing since a solution is a single phase. Actlvity and the activity coefficient are covered in a page and a half. No indication is given as t o how activity may he measured. Chapter 10, "Thermodynamics of Reacting Svstems." heeins with a descriotion of the
through membranes permeable to single species. This is illustrated by an uncaptioned figure to which no reference is made. Extent ~ 1 1 'reaction is used without defining or explaining the symbolism. Tables of AH?, AG? rw iC.-" HH".,..l/T datn are absent and ,-, sources thereof are not mentioned. The discussion of equilibrium is good. Topics covered in Chapter 11, "Thermodynamics of Special Systems,"-"Thermal Radiation" in which the Stefan-Boltzmann equation is derived, but Planek's radiation equation is not. "Fuel Cells" in which electric wrrk and Lhermadynamicpropertiesofcells are discussed, "Surface Effects" in which the IWvin-Helmholtz equation is derived and "Thermodynamics of General Systems"-are lreated in one page plus a table which is an excellent summary of the work possible in simple systems. The treatment of fuels is, a t nine pages, the longest and is quite pracL i d In Chapter 12, "Introduction to Thermodynamics of lrreversihle Processes," the transport equations are stated, followed by I he discussion of weakly coupled flows with application to heat and current in thermorlectric circuits, including the Seebeck, Peltier, and Kelvin e f f e c k "Direct Energy Conversion," the last topic in the chapter, includes an argument for using thermoelectric generation on the hasis of efficiency. Althcmgh the treatment is indeed postulatory, and aside Rom the too frequent use of undefined terms, rigomus, there are genuine reasons tn hesitate to use this book in a graduate or undergraduate class. An exlrrrnely terse treatment such as this one needs the help of illustrations. Yet they are larking in key plaeesas discussed above; only lwci of the figures have captions, figure la~~
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A286 / Journal of Chemical Education
fact, there is but one literature citation in the text. The total absence of references to historically significant papers, data tables, and present day applications is dismaying and would d a c e a ereat burden u ~ o nthe in-
are found only in the examples and problems, the clear majority af which are derivations. momas C. Ehlen Marquene Univmity Milwaukee. W153233
' "Principles of General Thermodynamics," by G. N. HatsopOUlo~and J. H. Keenan. J. Wiley and Sons, Inc.. 1966. Educators Gulde to Free Science Materials. Nineteenth Edition
Edited by Mary H. Saterstrorn, Edueators Proeress Service. Inc.. Randoloh. WI., 1977. Figs. & tables. 21 x 21 Em: rrxix 419pp. $11.95.
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This annual publication lists currently available free films, filmstrips, slides, transparencies, audiotapes, videotapes, scripts, transcriptions, and printed science materials. More than half of the 1658 items are films and a third are printed materials. All items are fully annotated and eross-indexed according to title, subject, source, and availability. There are, in addition, source and availability indices for Australia and Canada. Although the largest source is the federal government, there are hundreds of other sources. such as universities. industrv. .. and state governments. In addition to the annotated lists of materials, there are instructions and suggestions regarding ordering, a philosophical essay entitled "Children Learning Science" by Professor dahn W. Renner, and eight teacher-prepared units of study which show how the materialscan besuccessfully used a t the elementary, junior, and senior high school levels. As might he expected, most of the materials appear to he designed for use a t the elementary and secondary school levels, with perhaps a fourth of the items suitable for college students. It seems to me that elementsryand secondary school libraries definitely should subscribe to this Guide. At the universitv level. lecture demonstrators in
Stanley T. Marcus c o m a University Ithaca. NY 14853
A Laboratory Manual for Schools and Colleges J o h n Creedy, Heinemann Educational Books, lnc., London, 1978. Figs. and tables. 25 X 19 cm. iii 248 pp. $25.00.
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To distinguish this hook from a laboratory manual used by students, the hook might better be called a "laboratory handhook."
structional equipment, animal care, greenhouse management, laboratory solutions, electronics, hand tools, and power tools. Vendors of specific laboratory equipment are also mentioned. Unfortunately, because the author is British, most are in England. The sixty-page chapter on laboratory solutions is the longest in the 248~pagebook. Recipes are included for buffer solutions, indicators, analytical solutions, and often used chemistry, biochemistry, and biology solutiuns. Of the four solutions, this general chemistry instructor recently prepared, only one had a reported recipe. Subjects are discussed a t a hasic level; depth and detail are absent. Specialized chemistry handbooks are not replaced by this reference. Untrained laboratory assistants, skilled technicians, and profe&ional scientists are the author's expected users of this manual. The book would verv heloful for scientists educated in one discipline and working in other disciplines. Scientists educated and working in the same discipline would better use the specialized handbooks from their particular disciplines.
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Bill Nickels Schoolcraft Coliqe Livonia, MI 48152
Using the Metrlc System
Wilma E. Rollins, J. Weston Waleh, Pub., 1978. Figs. & tables. 28X 22.5 cm. 1 69 pp. $3.25.
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This book appears to he written for students who are early teenagers, in high school or younger. There is no scientific emphasis, use of powers of ten, nor use of dimensional nnalv*~;. The txilnlplr< n r p usuall) 01 thr ntmscwnrlfic wriety mrl largely restricwd T I , thv use ,i r,rei~xwfrom mllli- rhroueh - kilw including deka- and heetu-. In the first two chapters, the author presents an interesting history of the earliest measurements followed by the English system nf measurement. The number of problems or exercises included is far more than necessary to justify going to the metric system. There are almost no examples illustrating how these problems are salved. The last four chapters are devoted t o the metric system using approximately the same format as the first two chapters. Unfortunately, the number of errors in these chapters (including the answers to the problems) increased significantly. Little reference is made to the current metric standards. The gram is incorrectly defined as ".. .the mass occupied Ihy 1 cubic centimeter of water." The day is defined as ". . . the length of time for one revolution of the earth around the sun." Cwwersions within the metric system are dnne exclusively by moving the decimal point, completely neglecting the use of powers af ten. When converting between the metric system and the English system, the use of significant figures was for the most part
