Thermodynamics - American Chemical Society

of inorganic substances, particularly the rare earths and their compounds, was especially noticeable in the ther- modynamic literature reviewed in 196...
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Thermodynamics by J. M. Smith, Northwestern University, Evanston, Iil.

1 More reports of thermodynamics work in the Soviet-bloc nations were noticeable in 1960

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National Bureau of Standards published its machine computation procedure for establishing equilibrium compositions of chemical species T H E STRONG INTEREST in properties of inorganic substances, particularly the rare earths and their compounds, was especially noticeable in the thermodynamic literature reviewed in 1960. This has stimulated development and review of experimental methods for high temperature studies. The emphasis on fuel-cell work appears to be shifting from exploratory studies to development-type activity, with attention focused on increasing capacity and efficiency. The amount of experimental work on P-V-T relations for multicomponent systems is increasing each year. Sufficient data are accumulating to evaluate methods of combining constants in reliable equations of state. Similarly, more and more data are appearing on vapor-liquid equilibria for multicomponent systems. Some new theoretical methods of attacking vapor-liquid equilibria problems appeared. Developments in the theories of liquids are beginning to be applied to problems in engineering thermodynamics. This review extends from the latter part of 1959 up to about November 1960, for both the condensed and complete version.

38, 47, 66, 73). Obert’s new book (66) presents the basic concepts of thermodynamics to students new in the field. The Hall and Ibele book (32) is a sound treatment of engineering thermodynamics from a broad viewpoint, although the emphasis is directed toward mechanical engineering topics. From the textbooks (42, 47, 64, 82) coming from Russia and its satellites it would appear that attention is being directed toward the practical and problem-solving applications of engineering thermodynamics. The chemical thermodynamicist from the Technische Hoogeschool in Delft, Schaeffer, has published a basic book (78) on the energy and equilibrium aspects of chemical processes. I n addition there have appeared three books (49, 72, 80) on general chemical thermodynamics. An advanced book on irreversible processes was written by Eisenschitz (25):and Guggenheim and his colleagues (37) published a comprehensive treatment of chemical physics and physical chemistry which includes much thermodynamics. A readable text (33) introducing the subject of statistical thermodynamics has also appeared.

General A symposium on fuel cells, introduced in a general report by Moos (67), is evidence of the growing research effort in this field. Other articles in the symposium include discussion of electrode kinetics, the hydrogen-oxygen cell, and high temperature and high pressure operation. Investigations of the thermoelectric power of various thermocouples (83) and the Peletier cooling effect (75) have also appeared. A detailed study of the Hs-air fuel cell, by Gorin and Recht (30), showed that the polarization which limited the operating current density was minimized by using silver gauze and nickel electrodes. With these electrodes, operation a t 750” C. and current densities u p to 125 ma. per sq. cm. without polarization was possible. The internal resistance of the cells, which also limits power output, was believed to be due to high contact resistance between the electrodes and the matrix and between the metal conductors and the electrodes. Pressurized, double-porosity electrodes should give improved results. Among the reviews of the literature published during the year were the pre-

Books During the review period, publications ranging from general treatments of entropy (27) and energy (57) to the third edition of Dreisbach’s book (22) appeared in the thermodynamics literature. Three additional books (8, 74, 86) on thermodynamic properties were published. The manuscript by Bockris and others (8) emphasized vapor pressure, liquid density, and chemical reaction equilibria data at high temperatures. Timmermans’ book (86), the third volume of a series, is concerned with properties of binary solutions. There were seven texts written from a n engineering viewpoint (72, 27, 32,

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vious thermodynamics review (I/EC, May 1960, p. 451) and the chapter on thermochemistry and thermodynamic properties of substances (55). Miller (60) published a literature survey containing 162 references on the experimental verification of the Onsager equations of irreversible thermodynamics. Among the general articles was an analysis (23) of the fundamental constants of physics and chemistry. I t is indicated that recent measurements show a need to revise the values of some of the constants agreed upon in 1955. T o locate the source of deviation from nonideal solution behavior, Musil (63) has proposed two activity coefficients, one related to the heat of mixing and the second related to the entropy of mixing. In a similar effort, Maron (57) has proposed that the free energy of mixing is the sum of the following three contributions: the effect of dilution, the effect of interaction between like molecules, and the effect of interaction between unlike molecules. The thermodynamic behavior of substances in the critical region was studied by Rusanov (76), xvho was specifically concerned with the shape of the phase separation curves in the critical region for ternary systems. In another study (48),careful measurements were made of the enthalpy of COZ in the critical region. The results extrapolated to very large values of the specific heat a t the critical point. Schmidt (79) found appreciable differences between the density of the gas and liquid phases for COZa t point where the meniscus disappears. By allowing for surface tension effects, equations have been developed by Rusanov (77) for the composition of phases in equilibrium where the interface is a curved surface. Equations of State and P-V-TData The need for improved equations of state for mixtures continues to en-

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courage efforts in this area. Data for COQ-argon were measured up to 1000 atm. a t 50" C. ( 7 ) . Kay's pseudocritical point rule predicted the data well; the average deviation was 2.27,. In another experimental study (45), data were obtained a t 90' K. for 13 binary gas mixtures. Rules for combination of pure component data to predict the results for mixtures were examined, but no general conclusions were reached. The methane-nitrogen system was studied (26) for 10 to 1500 atm. and -280' to 200' F. Second virial coefficients were determined for binary mixtures of trichloromethane, diethylamine, methyl formate, methyl acetate, and ethyl acetate at 50' to 95O C. (50). The results were used to predict the degree of dimerization of the esters and to shed light on the hydrogen bonding with trichloromethane. The Benedict-RubinWebb equation of state was found (24) to predict accurately the P-V- T behavior of SOZ-COQhydrocarbon mixtures to 3000 p.s.i.a. over the temperature range 40' to 460' F. The volumetric behavior of pure components continued to receive attention, both theoretical and experimental. Bottomley (70) suggested a n experimental approach in which the volume is measured of sample gas which has the same pressure as a known quantity of nitrogen a t the same temperature. By this method it is claimed that very accurate virial coefficients can be obtained since the only measurements necessary are temperature and volume difference. In another new experimental method (87) an unballasted piezometer of constant capacity is used. The mass of gas in the piezometer is determined by adsorbing the qas - in an adsorbent in a separate container. The method appeared to give accurate results with COz using activated carbon as adsorbent. In a three-part study (19, 20),Doo-

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little and coworkers reported extensive studies on the volume of liquid n-alkanes as a function of pressure and temperature. The first part describes the experimental equipment which gives results for n-heptane indicating an accuracy of three parts in 10,000. The second part summarizes the experimental data for n-alkanes of 7, 9, 11, 13, 17, 20, 30, and 40 carbon atoms from 20' to 300' C. and 0 to 4000 kg. per sq. cm. pressure. The data are correlated very well with the Huddleston equation [Trans. Faraday SOL.33, 97 (1937)] which relates the pressure, P: to the volume at P and the volume at a very low pressure, both a t the same temperature. The equation contains two constants which are temperature dependent. I n the third part, the Huddleston constants are related empirically to the temperature, so that the result is an equation for evaluating the volume a t any pressure and temperature. 'The standard percentage error of the equation, when compared with the data, was 0.2%. S e w reduced equations of state for pure gases include a modified Eucken equation (68) and a three-constant expression (74) which fits the critical isotherms within 1% for GO*, xenon, and the light normal paraffins. A new third parameter was chosen by Bloomer and Peck ( 7 ) to improve the generalized compressibility factor chart. The new parameter is based upon the slope of the critical isometric at reduced temperature Tr = 1.4 and may be estimated from the ratio of the critical temperature to the normal boiling point. The results are of about the sameaccuracy as the correlation of Lydersen and others (Univ. Wisconsin. Eng. Expt. Sta., Rept. S o . 4, 1955) using the compressibility factor a t the critical point as the third parameter. The Pitzer correlation [ J . Am. Chern. SOL.77, 3427 (1955)l was preferred by Hooper and Joffe (37) using a third parameter related to the slope of the vapor pressure curve. The possibility of adding a fourth parameter to handle dipole and other effects was discussed. New P-TI-T data (76) for benzene and cyclohexane do not fit with virial coefficients determined from the LennardJones potential energy function. Rather the results suggest a 28-7 repulsionattraction potential function.

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More than 35 new references on vapor pressure measurements appeared in the literature during the year. A summary (49) reported all the published information on the sublimation pressure of organic compounds. A new vapor pressure equation for alkyl aromatics ( 9 )

an contains parameters which are related to the structure of the hydrocarbon, An equation of the form:

was found (5) to fit data well for water, methanol, benzene, SOZ,COZ,NHs, and mercury. The expression contains three constants, c, d, and D . A more elaborate (and more accurate) equation, proposed by Martin and coworkers (5G), has six constants and fits water data with a maximum deviation of 0.4%. Vapor pressure measurement at low pressures were discussed by Klumb and Luckert (44). The molecular beam and radiometer methods were recommended, the latter for the range from l o v 3 to 10-6 mm. of mercury. I n one of the few measurements of its kind, De Nevers and Martin (77) reported constant volume heat capacities for propylene and perfluorocyclobutane at pressures u p to 800 p.s.i.a. The results were compared with computed values based upon zero-pressure heat capacities and the Benedict-RubinWebb and the Martin-Hou equations of state. Both equations gave equally good results, the maximum deviations being about 6.7'%. General Thermodynamic Properties

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The Purdue University conference on thermodynamic and transport properties in 1959 contained numerous reports on general thermodynamic properties (enthalpy, entropy, and free energy). These are included in the 40 references on the subject of general properties given in the complete version of this review (see coupon). Many of the reports in this classification present properties in the ideal gas state a t 1 atm. pressure, although some, such as the contribution on nitrogen (58), covered a wide range of pressures. The compilation of heat capacity and entropy data for inorganic substances at high temperatures (originally presented as U. S. Bur. Mines Bull. No. 476, 1949) has been revised and expanded (43). There appeared (77) in the Russian literature in 1960 a comprehensive tabulation and summary of the thermodynamic properties of air extending from 0.001 to 1000 atm. pressure and 1000* to 12,000" K. This contribution is illustrative of the increased number of Russian studies published during the year. The articles covered a wide range of thermodynamic subjects but were concentrated in the proprrty area. Thermodynamic properties were evaluated by Wachman and coworkers (88) for equilibrium mixtures containing oxygen, carbon, argon, and nitrogen. The conditions included were

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4000' to 10,000' K. and 0.1 to 100 atm. for the following chemical species: N, 0 , A, C, N2, 0 2 , Cz, NO, GO, CN, and C3. The application of his earlier work, on using Z , as a third parameter in generalized correlations of properties, I n this was extended by Lydersen. instance (53) charts were presented for the effect of pressure on the heat capacity and enthalpy of gases with ZL value of Z, (compressibility factor at the critical point) equal to 0.27, Approximately 25 references on heats of mixing were found, including enthalpy-concentration diagrams for ureawater ( 4 ) and NH4NOo-water(67). Lu, in a more general study (52), analyzed data for the effect of temperature on the heat of mixing. Phase Equilibria Phase equilibria continues to be one of the most extensively studied subjects in chemical and chemical engineering thermodynamics, with a total of about 150 investigations reported during the period of the review. The interest in obtaining data on multicomponent systems is increasing; about 30 of the 90 reports on vapor-liquid equilibria were for systems of more than two components. The number of studies on solid-liquid equilibria also increased, with more than 15 investigations noted in the complete version of this review. A more accurate computational method has been proposed (75) for evaluating individual activity coefficients from total pressure and vapor density measurements for binary systems. Also for two-component cases, Yamada and coworkers (89) have developed a theoretical equation for predicting activity coefficients. The approach is based upon Guggenheim's concept of the zeroth approximation and reduces to the Margules two-suffix equations under certain conditions. The rigorous form of the Gibbs-Duhem equation was applied to test the consistency of experimental data by Adler and coworkers ( 2 ) . Particular attention was devoted to the case where the temperature of the mixture is above the critical temperature of one of the components. In another theoretical study, Bellemans (6) proposed equations for the excess free energy. From these expressions, it is possible to obtain activity coefficients from the dew point pressure us. composition curve at constant 1:emperature. The method appears to have merit for fluids with a simple molecular structure. The problem of predicting phase equilibrium constants ( K values) for hydrocarbon systems, without taking composition variations completely into

account. continues to attract attrntion ( 7 7 , 63. 70). A new approach (70) is based upon assuming that the liquid phase is a regular solution of the Hildebrand form-that is, the entropy is equal to that of an ideal solution. With this approach, the effect of liquid composition on K values can be expressed in terms of solubility parameters. The method is compared with data for mixtures of the light hydrocarbons with aromatic, naphthenic, and paraffin oils and shows an average deviation of 13%. Measurement of K values was made by Motard and Organick (62) for mixtures of Hz, CHI, and C3H8 from -250' to 0" F. and 500 to 1500 p.s.i.a. Comparison with computed results based upon the Benedict-Rubin-Webb equation of state was not good. However, if the constants, originally based upon pure component data and arbitrary combination rules, were adjusted, a better fit was obtained. N j d t (65) and Kogan and Safronon (46) proposed approximate and empirical methods for predicting phase equilibrium in ternary systems from similar data on the constituent binaries. Vapor-liquid equilibria were studied by Gerster and coworkers (29) for mixtures of n- and isopentane with 33 different third components. Two reports (78, 8 7 ) of a similar nature relate the solubility of gases in liquids to liquid composition. Himmelblau and Arends (35) correlated the solubility of inert gases in water at high pressures and temperatures. The use of experimental enthalpy and vapor pressure information to obtain vapor-liquid phase composition data was utilized by McCracken and coworkers (54) for alcohol-hydrocarbon systems up to the critical pressure. The method is based upon observing the intersections of dewpoint and bubble point enthalpy curves corresponding to different compositions. The many contributions to the literature on azeotropy include that of Terry and coworkers (85), who worked with amyl alcohol-hydrocarbon systems and Swietoslawski (84),with quaternary mixtures of HzO, CzHsOH, Cd36, and methylcyclohexane. Chemical Equilibria Over 80 articles appeared on free energy and enthalpy for chemical reactions. Most of the studies presented heats of formation, or combustion, of specific compounds. Two (28, 36) offered simplified procedures for evaluating the equilibrium composition from equilibrium-constant information. The National Bureau of Standards experimental equipment and procedures VOL. 53, NO. 4

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for measuring heats of combustion were described in detail by Jessup (39). The machine computation procedures used by NBS for establishing equilibrium compositions and thermodynamic properties were presented by Hilsenrath and others (34). Chipman and coworkers (73) have reviewed experimental methods for studying chemical reaction and phase equilibria a t high temperatures in a summary article containing 93 references. T w o reports offered correlations for estimating heats of formation from structure, one for metal halides (3) and one for alkyldienes (59) in the gas phase.

literature Cited ( I ) Abraham, W. H., Bennett, C. O., A.1.Ch.E. Journal 6, 257 (1960). (2) Adler, S. B., Friend, L., others, Ibid., 6, 104 (1960). (3) Anderson, H. W.,Bromley, L. A., J . Phys. Chem. 63, 1115 (1959). (4) Banerjee, S. C., Coraiswamy, L. K., Brzt. Chem. Em. 5. 269 (1960). (5) Barkhuyson,=F.’H. C.: Chem. Weekblad 55, 509 (1959). (6) Bellemans, A , , Bull. soc. chzm. belges 68, 355 (1959). T., Peck, R. E., A.I.Ch.E. (7) Bloomer, 0. Journal 6, 240 (1960). (8) Bockris, J. O’M., White, J. L., Mackenzie, J. D., eds., “Physical Chemi-

cal Measurements at High Temperatures,” Academic Press, New York, 1959. (9) Bond, D. L.. Thodos, G.. J . Chem. Eng. 1

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Data 5,’289 (1960). (IO) Bottomley, G. A,, Australian J . Chem. 13. 311 11960). (11) ’Cajan‘der, ‘B. C., Hipkin, H. G., Lenoir, J. M., J . Chem. Eng. Data 5, 251 (1960).

,’. -“Thermodynamics,” ,-

., Averbach,

‘m~ 9, Paper rmophysical Gosudarst. Izdatel, Moscow: 1959. (15) Christian, S. D., Neparko, E., Affsprung, H. E., J . Phjs. Chem. 64, 442 (1 960). (16) David, H. G.?Harnan, S. D., Thomas, R. B., Australian J . Chem. 12, 309 (1959). (17) DeNevers, N., Martin, J. J., A.1.Ch.E. Journal 6, 43 (1960). (18) Deno, N. C., Berkheimer, J . Chem. Eng. Dada 5 , 1 (1 960). (19) Doolittle, A. K., Doolittle, D. B., A.I.Ch.E. Journal 6, 153, 157 (1960). (20) Doolittle, ,4. K., Simon, I., Cornish, R. M., Ibid., 6 , 150 (1960). (21) Doolittle, J. S., “Thermodynamics

for Engineers,” International Text Book Co., Scranton, Pa., 1959. (22) Dreisbach, R. R., “Pressure-VolumeTemperature Relationships of Organic Compounds,” 3rd ed., Handbook Publishers, Inc., Sandusky, Ohio, 1960. (23) DuMond, J. Mi. iM., Ann. Phys. ( N . Y . ) 7, 365 (1959). (24) Eakin, B. E., Ellington, R. T., Thermodynamic Transport Properties Gases, Liquids, Solids, Papers Symposium, Lafayette, Ind., p. 195 (1959). (25) Eisenschitz, R., “Statistical Theory of Irreversible Processes,” Oxford Univ. Press, New York, 1960.

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others, Thermodynamic Transport Properties Gases, Liquids, Solids, Papers Symposium, Lafayette, Ind., p. 102

(19591. (27) Fait, J. D., ‘(Entropie,” 2nd ed., D. B. Center, Hilversum, The Netherlands, 1959. (28) Fliszar, S.,Arch. Sci. (Geneva) 12, 124 11959). (29) G&ster, J. .4., Gorton, J. A., Eklund, R . B., J . Chem. Eng. Data 5, 423 (1960). (30) Gorin, E., Recht, H. I,., Chem. Eng. Progr. 55, 51 (1959). (31) Guggenheim, E. -4., Mayer, J. E., Tompkins, F. C., eds., “The International Encyclopedia of Physical Chem-

istry and Chemical Physics,” Pergamon Press, New York, 1960. (32) Hall, N. A., Ibele, W. E., “Engineering Thermodynamics,” Prentice-Hall, Englewood Cliffs, h-. J., 1960. (33) Hill, T. L., “An Introduction to Statistical Thermodynamics,” AddisonWesley Publishing Co., Reading, Mass., 1960. (34) Hilsenrath, J., Kleim, M., Sumida, D. Y . , Thermodynamic Transport Prop-

erties Gases, Liquids, Solids, Papers Symposium, Lafayette, Ind., p. 416 (1 C)$C)I \-’-’,. (35) Himmelblau, D. M., Arends, E.,

Chem.-Ingr.-Tech. 31, 791 (1959). (36) ,Hoffman, R . F., Boudart, M., Ind. chzm. belpe, Subbl. 1. 298 (1959). (37) ~ool;k;, 6: D.’, JO&, J.: J . Cizem. Eng. Data 5, 155 (1960). 138) Jante, A , , “Thermodvnamik,” B. G. ‘ Teubner; Leipzig, 1959. ’ (39) Jessup, R. S., Natl. Bur. Standards (U. S.),Monograph 7, 1960. (40) Jones. A. H.. J . Chem. Enp. Data 5. u ‘ i 9 6 (1960). (41) , . Jones, J. B., Hawkins, G. A . , “Ensineerin.; Thermodvnamics.” Wilev. , * Ne\y York, 7 960. (42) . , Kalcik, J.. ”Technicka termody-

namika.’ ‘Saki. Ceskoslovenskeacademie ved., Prague, 1960. (43) Kelley, K . K., U. S. Bur. Mines Bull.

No. 584.’1960. (44) Klumb, H., Luckert, J.: VakuumTech. 8, 62 (1959). (45) Knobler, C . M., Beenakker, J. J. M., ’ Knaap, H.’F. P., &pica 25, 909 (1959): (46) Kogan, V. B., Safronov, V. M., Zhur. Fir. Khim. 33, 1353 (1959). (47) Kondukov, N. B., “Brief Course in ’

Technical Thermodynamics,” Minister. Vyssh. i Sred. Spets. Obrazovaniya, Moscow, 1960. (48) Koppel, L. B., Smith, J. M., J . Chem. Eng. Data 5 , 437 (1960). (49) Kortum, G.: “Einfuhrung in

die Chemische Thermodynamik,” 3rd ed., Vandenhoeck and R., Gottingen, 1959. (50) Lambert, J. D., Clarke, J. S., others, Proc. Roy. Sac. (London) A249, 414 (1959). (51) Lazarev, P. P., “Energy, Its Sources on the Earth and Its Origin,” Izdatel, Moscow. 1959. (52) Lu, B. C. Y., Can. J . Chem. Eng. 37, 193 (19591. (53) Lydersen, A., Dechema Monogl-ajli. 32, 39 (1959). (54) McCracken, P. G., Storvick, T. S., Smith. J. M.. J . Chem. Ene. Data 5. 130 (i96oj. (55) McCullough, J. P., Ann. Rev. Phys. Chem. 11, 1 (1960). (56) Martin, J. J., Kapoor, R. M., Shinn, R. D., Dechema Monograph. 32, 46 (1959). (57) Maron, S. H., J. Polyrn~r.Sci. 38, 329 (1959).

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(58) Martinek,

F., Thermodynamics Transport Properties Gases, Liquids, Solids, Papers Symposium, Lafayette, Ind., p. 130 (1959). (59) Maslov, P. G., Maslov, Y. P., Zhur.

Priklad. Khim.33, 134 (1960). (60) Miller, D. G., Chem. *Revs. 60, 15 11960). ( 6 i ) Mbos, A. M., IND.END.CHEM. 52, 291 (1960). (62) Motard, R. L.: Organick, E. I., A.1.Ch.E. Journal 6 , 39 (1960). (63) Musil, A., Monatsh. 90, 488 (1959). (64) Novikov, I. I., Zaitsev, V. M.,

“Problem Book in Technical Thermodynamics,” Izdatel, Moscow, 1959. (65) Npvlt, J., Chem. prz2mysL 9, 579 (1959). (66) Obqrt, E. F., “Concepts of Thermodvnamics.” McGraw-Hill. New York,

1960. (67) Othmer, D. F., Frohlich, G. J., A.I.CI1.E. Journal 6. 210 (1960). (68) Planck, R., Bre,instoff-‘War~e-Kra~t12, 302 (1960). (69) Plit, I. G., Zhur. Przklad. Khim. 32, 2405 (1959). (70) Prausnitz, J. M., Edmister, W. C., Chao, K. C.. A.1.Ch.E. Journal 6, 214 (1960). (71) Predvoditelev, A. S., “‘Thermodynamic Functions for ,4ir from 100012,000’K. and 0.001 to 1000 Atmospheres,” Izdatel Akad. h-auk S. S. S. R., Moscow, 1960. (72) Reid, C. E.? “Principles of Chemical ’

Thermodynamics,” Reinhold, New York,

1960. (73) Roberts, J. K., “Heat and Thermo-

dynamics,”

Interscience,

New York,

1960. (74) Rombusch, U. K., Thermodynamic

Transport Properties Gases, Liquids, Solids, Papers Symposium, Lafayette, Ind., p. 205 (1959). (75) Rosi, F. D., hbeles, B., Jensen, R. V., Ann. Reu. Phys. Clzeni. 10, 191 (1959). (76) Rusanov, A . I.: Vestnik Leninpad Unzv. 13, No. 4, Ser. Fiz. z Khim. No. 1, 84 (1958). (77) Rusanov, A . I., Vestnik Leningrad Univ. 14, Ser. Fiz. i Khim. KO. ’3, 71 (1959). (78) Schaffer, F. E. C., Toepassingen, van de, “Thermodynamica op chemische Processes,” 2nd ed., Waltman, Delft, The Netherlands, 1960. (79) Schmidt, E.: Chrm.-1ngr.-Tech. 32, 230’ (1960). (80) Shireby, D., “.A Digest of Elementary

Chemical Thermodynamics,” Pitman, London, 1959. (81) Skau, E. L., Bailey, A . V., J . Phyyr. Chem. 63, 2047 (1959). (82) Stefanowski, Bohdan,

“Termodynamika technicma,” Panstwowe Wydawn. Naukowe, \,Varsaw, 1959. (83) Stoneburner; D. F.? Yang, L., Derge, G., Trans. A m . Inst. Mining, M e t . , Petrol. Engrs. 215, 879 (1959). (84) Swietoslawski, X., Zieborak, K., Galska-Krajewska, A.: Bull. acad. polon. xi.? ser. sci., c h i n . , geol. et geograph. 7, 43 (1959). (85) Terry, T. D., Kepncr, R. E., Webb, A. D., J . CIz~rn.Eng. Data 5, 403 (1960). (86) Timmermans, J., “The Physico-

Chemical Constants of Binary Systems in Concentrated Solutions,” Vol. 111, Irterscience, New York, 1960. (87) Vukalovich, M. P., .4ltunin: V. V., Tejloenergetika 6, 58 (1959). (88) Wachman, H. Y . , Linevsky, M. J., Lyon, R . F., J . Chem. En,.. Data 5, 456 (1 960). (89) Yamada, I., Yoshida, T., others: Kagaku Kogaku 23, 630 (1959).