d Kinetics Equilibria O - k H Q U EN and JAMES P. HSU UNlVERSlTY OF WISCONSIN, M A D I S O N , WIS.
A
CLASSIFICATION is given herewith of the significant papers on chemical kinetics and themadynamics which appeared principally during 1948. Because of the vast scope of these two basic fields of science no attempt was made to present a critical analysis of these contributions. 1.
APPLIED CHEMICAL KINETICS
BOOKS
The book by Ames (1) presents a modern treatment of dielectric constants and activity coefficients related to the rates of chemical change in solutions. The last three chapters deal with chain reactions, homogeneous catalysis, and heterogeneous reactions. GENERAL THEORY
The Eyring theory of reaction rates has been Penner (19, 80)to the rate processes of fusion and Hirschfelder (14) discusses the limitations in the assumption of equilibrium of reactants with the activated complex in the Eyring theory. The Polanyi-Hinshelwood hypothesis of unimolecular reactions is given extended mathematical treatment by Barrer (3). Energies involved in bond rupture of hydrocarbon are presented by Ger6 (11). Djerassi (8) gives extensive tables of experimental data of the Wohl-Zi presents a mechanism classification f tracers in establishing mechanisms Hammel, and Taylor (18) in the methane and deuteromethane (methane-d) on a silica-alumina cracking catalyst. A similar study was made by Aman, Farkas, and Farkas (8) on the catalytic hydrogen exchange reactions in hydrocarbons on palladium and nickel catalysts. General methods of applying kinetic data to industrial problems have been advanced by Wilhelm, Johnson, Wynkoop, and Collier (86) to the calculation of temperature distributions in fixed bed catalytic converters. Gordon (IS) gives an interpretat,ion of kinetic data when obtained from adiabatic operation. I n the mathematical solution of complex problems in chemical kinetics, Wood, Crank, and Twigg (27) apply the differential analyzer t o the rate equations involved in the catqlytic oxidation of ethylene. Chien (6) presents a kinetic analysis of irreversible consecutive reactions. Simonetta (23) gives the distribution laws of products where a process proceeds by a chain of successive reactions. Russian technical periodicals stress the importance of the theory and application of chemical kinetics, as well as the devel-
on the dissociation on tungsten atoms.
Progress in the field of
catalysis in the Soviet Union is reviewed by Treszczunowicz (94), with twenty-one references. An equivalent velocity constant for adiabatic reactions related to their isothermal value is developed by Goldman (19). The paper by Epstein (10)on “A Classification of Chemical Reactions in Connection with the mum Conditions of Technological Procunusual industrial importance. A number of important industrial reactions are cited, such as the oxidation of nitric oxide in the presence of water, the water gas reaction, and the ammonia synthesis. Kinetics in the solid state have been advanced by Pruna, Fauire, and Chaudron (81) by studies of the induction period in the transformatioh of aragonite into calcite. A comprehensive treatment of reactions in the solid state with the phenomena of phase boundary processes, formation of nuclei, and diffusional ented by Cohn (7). introduced in kinetic studies by time-temperature lags in starting the reaction are discussed by Horton (15). DIFFUSIONAL EFFECTS
Levich (31-33) presents a series of three papers on the effect of diffusion in heterogeneous reactions. Two significant papers appear on the effect of chemical reactions in the absorption of gases by liquid by Pozin (35), and by van Krevelen and Hoftijzer
are reviewed by Jungers (8#9). The film concept applied to mass and heat transfer in reaction rates is discussed by Missenard (34). The effect of diffusion on reaction rates in liquid solutions is demonstrated by Williams and LaMer (38). Rates of adsorption in granular beds are discussed by Amundson (28). CATALYSTS
A significant paper dealing with the structure of the catalyst surface is presented by Sips ( 4 7 ) with mathematical treatment. Methods are described which make i t possible to calculate the distribution of adsorption energies a t various sites on the catalyst. Another fundamental paper deals with the relation of catalysis to the phase diagram of salt pairs by Schwab and Karatzas (45). Problems dealing with the poisoning and deactivation of catalysts are given by Roginskii (48, 43), by Savage (44) for a platinum catalyst, and by Maxted (41) on the general problems of shielding the catalyst from poisoning. The preparation and properties of specific catalysts are included in the following papers: improving the Fischer-Tropsch catalyst by Teichner (49); nickel catalysts produced by the reduction of salts in liquid ammonia by Watt and Davis (60); supported oxides of manganese by Selwood, Moore, Ellis, and Wethington (46); preparation of alumina gels by Abe (39); structure and activity of chromium-aluminum oxides by Eischens and Selwood (40); and activation of alumina by Taylor (48). 1825
1826
INDUSTRIAL A N D ENGINEERING CHEMISTRY
ACETYLATION
Acetylation of benzoquinone and toluoquinone is discussed by Mackenzie and Winter (68) and acetylation of methyl alcohol by Beretta and Janelli (61 DEHYDROGENATION
Comprehensive researches on the kinetics of dehydrogenation of n-butenes to butadiene for primary and secondary reactions are formulated by Beckberger and Watson (65). Other studies without formulations include: pilot plant dehydrogenation of butane by Hachmuth and Hanson (56); catalytic dehydrogenation of ethyl benzene by Wenner and Dybdal (59); on reactor design for the manufacture of butene by catalytic reforming by Burton, Chiswell, Claussen, Huey, and Senger (64); on the effect of operating variables on methylamine production by Egly and Smith (55); and a description of the Phillips butane dehydrogenation process by Hanson and Hays ( 6 7 ) . The U. S. Bureau of Mines Technical Paper by Orchin, Reggel, Friedel, and Woolfolk (68) reports a t length on the extensive investigations dealing with the catalytic dehydrogenation of coal with formation of five- and six-member ring compounds. HALOGENATION
The kinetics of the thermal chlorination of benzyl chloride is reported by Scheraga and Hobbs (6.8). Brown and Whalley (60) discuss the mechanism of the fluorination of organic compounds with anhydrous hydrogen fluoride. Rate equations for the vapor phase reaction between trichlorobromomethane and bromine are given by Davidson and Sullivan (61). The displacement reaction of triphenylmethyl halides in benzene solution is shown by Swain (63) to follow a termolecular mechanism.
Vol. 41, No. 9
hydrolysis and ethanolysis of certain allyl chloride derivatives are given by Andrews and Kepner (80). IONIC REACTIONS
Reaction rates are formulated by McCabe and Warner (91) for the reaction of ethylene halohydrin with hydroxyl ions in water and mixed solvents. In liquid phase catalysis Taube (96, 96) studied the catalytic effect of the manganic ion in the reaction of bromine with oxalic acid. Kinetic studies on the decomposition of chloral hydrate by sodium hydroxide in aqueous solutions are reported by Gustafson and Johnson (86). The decomposition of hydrogen peroxide as catalyzed by ferric salts is reported by Andersen (86). Kinetic studies on alpha bromo acids are given by Saito (99). Other ionic reactions reported include: aliphatic tert-d-chloroethyl amines in dilute aqueous solution by Cohen, Van Artsdalen, and Harris (83); interaction of manganic ion and oxalate by Taube (96, 9 6 ) ; ethylene chlorohydrin with hydroxyl or alkoxy1 ions in mixed solvents by Stevens, McCabe, and Warner (94); chlorate-bromide reactions in acid solution with arsenious acid as a catalyst by Grieger ( 8 5 ) ; reaction of thiosulfate ion with ethyl, propyl, and isopropyl bromides by Crowell and Hammett (84); activation energy in the decomposition of ozone catalyzed by the cobaltous ion by Hill (88); and formation and dissociation of ferrous phenanthiolene by Lee, Kolthoff, and Leussing (90). Juda and Carron (89) report the equilibrium and velocity constants of the sodium-hydrogen exchange in carbonaceous exchangers in contact with chloride solutions. The acid binding properties of long chain aliphatic amines are described without kinetic data by Smith and Page (93), and similarly the use of ion exchange resins for separation of basic amino acids by Hems, Page, and Walker (87).
HYDRATION
The hydration of ethylene oxide was studied by Lichtenstein and Twigg (64) in neutral and in alkaline solutions and a t different temperatures and concentrations, HYDROGENATION
Among kinetic investigations involving hydrogenation, the following reactions are reported: production of hydrogen sulfide pyrites by Clark and Spettle (67, 68); catalytic formation of methane by hydrogenation of ethane by Kemball and Taylor ( 7 0 ) ; atomic hydrogen with oxygen-containing organic compounds by Trost, Darwent, and Steacie (78); atomic hydrogen with paraffin hydrocarbons by Trost and Steacie (79); atomic hydrogen with acetylene by Tollefson and LeRoy ( 7 7 ) ; methane synthesis by hydrogenation of carbon monoxide by Akers and White (66); catalytic hydrogenation of the benzene nucleus by Bmith and Meriwether ( 7 4 ) ; and catalytic hydrogenation of furans and substituted furans by Smith and Fuzek ( 7 3 ) . The limitations in applying kinetic data of homogeneous reactions to those catalyzed are discussed by Fuzek and Smith (69). The protection of the catalyst in the hydrogenation of carbon monoxide is presented by Braude, Shurmovskagg, and Bruns (66).
Prigogine ( 7 2 ) presents rate studies on the hydrogenation of benzene to cyclohexane. A comprehensive account of the extensive Bureau of Mines experiments on the production of synthetic liquid fuels from the hydrogenation of carbon monoxide is reported by Storch, Anderson, Hofer, Hawk, Anderson, and Golumbic (76). A study of the fluidization of an iron Fischer-Tropsch catalyst is reported by Leva, Grummer, Weintraub, and Storch ( 7 1 ) . A discussion of the development of this process in Germany since 1938 is given by Storch ( 7 6 ) . HYDROLYSIS
The kinetic equations for the hydrolysis of ethyl thioacetate in aqueous acetone are given by Schaefgen ( 8 1 ) . The rates of
OXIDATION
In the third symposium on Combustion and Flame and Explosion Phenomena held in Madison, Wis., in September 1948, significant progress was reported on the mechanism of the oxidation of hydrogen in accounting for the complex explosion limits of oxygen-hydrogen mixtures. Lewis and Von Elbe (111) reported on the mechanism of chain initiation in the thermal reaction between hydrogen and oxygen, and Badin (100,101) on atomic hydrogen-molecular oxygen reactions. In this same symposium Whittingham (190, 121) reported on the oxidation of sulfur dioxide; Gordon (106) on the reaction between hydrazine and hydrogen peroxide in the liquid phase; Appleby and Avery ( 9 7 ) on the kinetics and mechanism of the reaction between n-butane and oxygen at high butane-oxygen ratios; and Badin (99) on the oxidation of metal alkyls and related compounds. The mechanisms of several elementary reactions in flames were postulated by Griffing and Laidler (107). The corrosion of metals in atmospheres containing sulfur dioxide and the catalytic oxidation of sulfur dioxide on metal surfaces are presented by Tolley (114-116) in a series of papers. A study of the oxidation of sulfur dioxide near the critical point is reported by Toriumi et aE. ( 117). The Bureau of Mines report by Wender and Orchin (119) gives a critical review of oxosgnthesis in the production of alcohols from olefins, carbon monoxide, and hydrogen. Miscellaneousoxidation systems of recent study are the following: wall effects in the oxidation of boron triethyl vapor by Brokaw, Badin, and Pease (104); the slow oxidation of ethane by Chirkov and Entrelis (105); the oxidation of acetaldehyde in the gas phase by Maims and Emanuel (113); the oxidation of uranium tetrachloride by Wazer and John (118); the catalytic reaction of hydrogen and oxygen on the plane faces of a single crystal of copper by Leidheiser and Gwathmey (110); the oxidation of glucose by periodate by Hughes and Neve11 (109); and the reaction of carbon absorbents with oxygen by Loebenstein, Gleysteen, and Dietz (112).
September 1949
INDUSTRIAL AND ENGINEERING CHEMlSTRY
A mechanism for the combustion of carbon in a fuel bed is given by Arthur, Bangham, and Thring (98),and Bridger and Appleton (103)report on the inhibition of the combustion of carbon and carbon monoxide caused by the presence of small amounts of chlorine compounds. Heiple and Sullivan (108)app combustion of fuel oils with app lenberg (1.2.2)explains the influence of reaction interface surface in the combustion of gaseous fuels. I n the sixth of a series of kinetic studies on the chemistry of rubber and related materials, Bolland (102) reports on the benzoyl peroxide oxidation of ethyl linoleate. PHOTOCHEMICAL REACTIONS
On June 27, 1947, a symposium was held at Notre Dame on “Radiation Chemistry and Photochemistry.” Here Hirschfelder (127) reported on chemical reactions produced by ionization processes; Glockler (1.26) on controlled electron reactions; Hipple (1.26) on the spontaneous dissociation of ions; and Eltenton (18.4)on the detection of free radic spectrometer. The photochemical reaction between iodine and hydrogen peroxide in aqueous solutions was investigated by Bennett and Griffith (1.23) and was found to involve primary produotion of iodine atoms followed by a chain breaking step. POLYMERIZATION
The phenomena of inhibition, retardation, and copolymerization are studied by Melville and Watson (131)in the thermal and peroxide-catalyzed polymerization of styrene and methyl methacrylate. The kinetics of styrene polymerization in emulsions is studied by Smith (132) in liquid phase reactions. Dats on the kinetics of the polymerization of propylene with aluminum bromide-hydrogen bromide catalyst are given by Kidder (128) with evaluation of velocity and th constants. Matheson, Auer, Bevilaequa, and Hart (180)give rate constants in the free radical polymerization of methyl methacrylate. In the polymerization of styrene Kolthoff and Bovey (129) describe the effect of retarders and inhibitors. REDUCTION
Woodward and Glover (186)report on the determination of molybdenum oxide catalyst activities in the reduction of phenol to benzene and correlations with x-ray examinations. Rate equations are given for the reaction betweea methane and carbon dioxide by Rossi ($34)from data of Chipman (183)and Rossini (1%). SYNTHETIC FUELS
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1827
Rates of decofnposition of explosives are reported for pentaerythritol tetranitrate, nitroglycerol, ethyl diamine, dinitrile, ammonium nitrate, ethylene dinitramine, tetryl and trinitrotoluene by Robertson (143-1.46). The interaction of trinitrotoluene with ammonium nitrate was investigated by Copp and Ubbelohde (140). The kinetics of the decomposition of alkyl peroxides is given as a first order reaction by Raley, Rust, and Vaughan (149). The dissociation of tert-butyl benzoate was followed by Altschul and Herbert (137) by measuring the change in vapor pressure of isobutene over dioxane. The status of catalytic cracking is reviewed by Sittig (147) with an extensive list of references. Equations for catalytic cracking are evaluated by Frost (141). A study of the operating variables in Thermofor catalytic cracking is presented with graphical correlations by Bednars, Luntz, and Bland (138). The thermal decomposition of propane was traced by the use of isotopic carbon in the molecule by Stevenson, Wagner, Buck, and Otvos (148). MISCELLANEOUS REACTIONS
“he mechanism of formation of diethyl ether using the heavy oxygen isotope as a tracer element was shown by Lauder and Green (166)to be due to the oxygen bond in the ester and not in the alcohol. The kinetics of neutraliaation of nitroethane with ammonia and methylamine is recorded by Pearson (166). An attempt to apply kingtics to metallurgical reactions is made by Yap (169) in the oxidation of silicon, manganese, and carbon in the acid refining of steel. The rate of dissolution of aluminum in sodium hydroxide solutions is reported by Streicher (168). The kinetic and thermodynamic properties in the disproportionation of chlorosilanes are evaluated by Zemany and Price (160). The variables controlling the kinetics of the conversion of fumarose to I-malate were studied by Scott and Powell (167). Equilibria and rate studies were conducted by Evans and Workurst (164)in the reaction between arsenic trichloride and monophenylchloroarsineand in the disproportioning of diphenylchloroarsine to triphenylchloroersine. A correlation of reactor performance in the alcohol-butadiene process is presented by Coull and Bishop (163).
BIBLIOGFAPHY ON CHEMICAL KINETICS BOOKS
(1) Ames, E. S., “Kinetics of Chemical Change in Solution,” New York, Maomillan Go., 1949. GENERAL THEORY
The extensive investigations of the U. 5. Bureau of Mines in the production of liquid fuels were authorized by the Synthetic Liquid Fuel Act of April 5, 1944, and current findings are given in Reports of Investigation 4456, 4457, and 4458 for the year 1948. These deal with the pro shale, and agricultural residue. a bimonthly publication which opments of the synthetic li references to synthetic fuels will be found under the classificatipn of hydrogenation, THERMAL DECOMPOSITION AND CRACKING
In the thermal decompositions kinetic data are reported for the following systems: methyl ethyl ketone in the gaseous phase by Waring and Mutter (26B); isopropyl chl Choppin and Compere (139);silver oxalate by and disilane and trisilane by Stokland (149). Kinetic data are obtained by infrared measurements in the thermal decomposition of ethylene oxide in a pape Steger, Manner, Salley, and Williams (146). Measurements of the C-H bond energy in the pyrolysis of toluene and xylenes are reported by Szwarc (160). t
(2) Aman, J., Farkas, L., and Farkas, A., J . Am. Chem. SOC., 70, 727 (1948). (3) Barrer, R. M.,Trans. Faraday floc., 44,399(1948). (4) Bogolyvbov,N.,J . C h m . Phys. (U.S.S.R.), 20,264(1946). (6) Bruns, B.P.,Ibid., 21, 1011 (1947). J. Am. C h m . SOC.,70,2256(1948). (6) Chien, J. Y., (7) Cohn, G . , Chem. Revs.,42, [3]527 (1948). (8) Djerassi, C.,ZbU..43, [2]271 (1948). (9) Eley, D.D.,Trans. Farday SOC.,44,216(1948). (10) Epstein, D. A., J . A p p l h d C h m . (U.S.S.R.), 19,1125 (1946). (11) Gerb, L.,J . Chem. Phya., 16, 1011 (1948). (12) Goldman, I.,J.Phys. Chem. (U.S.S.R.),21,1293(1947). (13) Gordon, M., Trans. Faradau SOC.,44,196 (1948). (14) Hirschfelder. J. O.,J . Chem. Phys., 16, 22 (1948). (15) Horton, W.S.,J.Phys. d? Colloid C h m . , 52-11,1129(1948). (16) Ivanovskagg, T..and Mochan, I., J . Phys. Chem. (U.S.S.R.), 22, 439 (1948). (17) Kobzer, N.I.,Ibid., 21, 1413 (1947). (18)Parravano,QG, Hammel, E. F., and Taylor, H. S., J . Am. Chem., 52-11,949 (1948). (20) Ibid., p. 1262. (21) Prune, M.,Fauire, R., and Chaudron, G., Compt. rend., 227, a90 8).. - - - 11 -9 -4_-, (22) PsheshetskiY, S. Y.,and Rubinshtein, R. N., J . Phys. Chem. (U.S.S.R.), 21, 659 (1947). (23) Simonetta,M.,Rend. kt. lombardo sei., 78, No. 1,307 (1946).
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INDUSTRIAL AND E N G INEERING CHEMISTRY
1828
(24) Treszczanowicz, E., f'raarfiyd Chem., 27, 43 (1948). (25) Vvendenskii, A. A., J . Gen. Chem. (U.S.S.R.), 17,1573 (1947). (26) Wilhelm, R. H., Johnson, W. C., Wynkoop, R., and Collier, D. W., Chem. Eng. Progress, 44, 105 (1948). (27) Wood, A. M., Crank, J., and Twigg, C . H., Trans. Faradag SOC., 44, 256 (1948). DIFFUSIONAL EFFECTS (28) Amundson, N. R., J . Phys. & Colloid Chem., 52-11,1153 (1948). (29) Jungers, J. C., SOC.roy. beige ing. et ind., Sir. 23. Mbm., 6, 14 (1948). (30) Krevelen, D. W. van, and Hoftijzer, P. J., Chem. Eng. P r o p Tess, 44, 529 (1948). (31) Levich,V., J . Phys. Chem. (U.S.S.R.), 22, 575 (1948). (32) Ibid., p. 711. (33) Ibid., p. 721. (34) Missenard, A., Chalezw ind., 29, 220 (1948). (35) Pozln, M . E., J . Applied Chem. (U.S.S.E.),19, 1201 (1946). (36) Ta'icke, E . ,Angew. Chem., B19,57 (1947). (37) M7icke,E., and Voigt, U., Ibid., p. 94. (38) Williams, B., and LaMer, V. K., J . Am.. Chem. SOC.,70, 717 (1048).
Vol. 41, No. 9
(70) Kemball, C., and Taylor, 11. d., Ibid., p. 345. (71) Leva, M., Grummer, M., Weintraub, M., and Storch, H. EI., Chem. Eng Progress, 44,707 (1948). (72) Prigogine, I., Outer, P., and Herbo, C., J . Phus. & Colloid Chem., 52, 321 (1948). (73) Smith, H. 4., and Fueek, J . F., Ibid., p. 415. (74) Smith, H. A., arid Meriwether, H. T., J . Am. Chem. Soc.. 70, 413 (1948). (75) Storch, H. H . , Chem. Eng. Progress, 44,469 (1048). (76) St,orch, H. € Anderson, I., R. B., Hofer, L. J. E., Hawk, C. O., Anderson, H. C., and G.olurnbic, N., U. S. BUT.i l l i n ~ s Tech. Paper 709 (1948). (77) Tollefson, E. L., and LcRoy, D. J., J . Chem. Ph?/s., 16, 1057 (1948). (78) Trost, W.R.. Darnrent, B. D., and Stewie, E. W. R..Ihid. p. 353. (79) Troat,, W. R., and Rteacie. E. W. R., Ibid., p. 361. HYDROLYSIS (80) Andrews, L. L.,and Kepner, R. E., J . d m . Chem. Soc., 70, 3456 (1948). (81) Schaefgen, J. R,, Ihid., p. 1308.
CATALYSTS (39) Abe, S., B d l . Inst. Phys. C'hern. Research (Tokyo), 21, 424 (1942). (40) Eischens, R. P., and Sclwoad, P. W., J . Am. Chem. SOC.,70, 2271 (1948). (41) Maxted, E. R., J . SOC.Chem. Ind. (London),67, 93 (1948). (42) Roginskii, S. Z., J . Phys. Cham, (U.S.S.E.),21, 1143 (1948). (43) Ibid., 22, 669 (1948). (44) Savage, R. €I., J . Chem. Phya., 16. 237 (1948). (45) Schwab, G. M., and Karatma, A., J . P h g s . & Colloid Chem., 52-11, 1053 (1948). (46) Belwood, P. W., Moore, T.E., Ellis, M., and Wethington, K., J . Am. Chem. SOC.,71,693 (1949). (47) Sips, R.. J . Chem. Phys., 16,490 (1948). (48) Taylor, R. J., J . SOC.Chem. I n d . (London),68, 23 (1949). (49) Teichner, S., Compt. rend., 227,478 (1948). (60) Vat&,G. W., and Davis, 11. D., J . Am. CKem. SOC.,70, 3753 (1948). ACETYLATION (51) Beretta, U., and Janelli, L., Atii. ctccad. Nazl. Lencei, Classe sci. fis.,mat. e nat., 2,197 (1947). (52) Mackenzie, H. A. E., and Winter, E. R. S., Trans. Faraday Soc., 44, 159 (1945). DEHYDROGENATION (53) Beckberger, L. H., and Watson, K. M., Chem. Eng. Progress, 44, 229 (1948). (54) Burton, A. A., Chiswell, E. B., Claussen, W. H., Huey, C. S., and Senger, J. F., Ibid., p. 195. Egly, R. S., and Smith, E. E., Ibid., p. 357. Hachmuth, K., and Hanson, G. €I.,Ibid., p. 421. Hanson, G. H., and Hays, H. L., Ibid., p. 431.
Orchin, M., Reggel, L., Friedel, R. A., and Woolfolk, E. O., U.S . BUT.Mines, Tech. Paper 708 (1948). (59) Wenner, R. R., and Dvbdal, E. C., Chem. Eng. Progress, 44, 275 (1948).
HALOGENATION
(60) Brown, J. H., and Whalley, W. H., J . SOC.Chein. Ind. (London),
67,331 (1948). (61) Davidson, B. N., and Sullivan, J.. J . Chem. Phys., 17, 176 (1949). (02) Scheraga, H. A., and .Hobbs. SI. E., J . Am. Chem. Snc., 70, 3015 (1948). (63) Swain, C. G., Ibid., p. 1119. HYDRATION (64) Lichtenstein, H. J., and Twiyg, G . H., Trans. Faraday SOC., 44, 906 (1948). HYDROGENATION (65) Akers, W. W., and White, R. R., Chem. Eng. Progress, 44, 553 f1948).
Braude: G., Shurmovskagg, N., and Bruns, B.. J . Phys. Chem.,
(U.S.S.R.), 22, 483 (1948).
Clark, L. M., and Spettle, H. M., J . SOC.Chem. Ind. (London), 67, 6 (1948).
Ibid., p. 9. Fueek, J. F., and Smith, 13. A., J . Am. Chem. SOC.,70, 3743 (1948).
ONlC REACTION§ (82) Andersen, W. S., Acta Cltem. S c a d . , 2, 1 (1948). (83) Cohen, B., Van Artsdalen, E. R., and Harris, J., .1. Am. Chem. Soc., 70, 281 (1948). (84) Crowell, F. i.,and Hammett, L. P., Ibid.,p. 3444. (85) Grieger, P. F.,Ihid., p. 3045. (86) Gustafson, C., and Joh.nson, M., Acta Chem. Qcand., 2, 42 (1948). (87) Hems, B. A., Page, 5. E., and Walker, "J. G., J . Soc. Chem. I n d . (London), 67, '77 (1948). (88) Hill, G. R., J . Am. Chem. Xoc., 70, 1306 (1948). (89) Juda, H., and C a n o n , M . , l b i d . , p. 3295. (90) Lee, T . S., Nolthoff, I. M., and Leusuing, D. L., I b i d . , g. 3595. (91) McCabe, C . I,.,and Warner, J. C., Ihid., p. 4031. (92) Saito, E., Bzkz2. SOC. chim. F'rance. 1948, p. 465. (93) Smith, E. L., and Page, J. E., J . 9oc. Chem. Ind., 67, 48 (1948). (94) Stevens, J. E., lMcCabe, C. L., and Warner, J. C., J . Am. Chem. Soc.. 71, 2449 (1949). (95) Taube, H.. Ibid., 70, 1216 (1948). (96) Ibid., 70, 3928 (1948), OXIDATION (97) Appleby, W. G., uiJ h c e i > , W. II., Third Symposium on COrfibustiori and E lame and Explosion Phenomena, Univ. of Wisrorisin (1948). (98) Arthur, J. R., Bangham, D. E.,and Thring, M . W., J . Am. Chem. Soc., 71,1 (1940). (99) Badin, E. J., Third Symposium on Combustion and Flame and Explosion Phenomena, Univ. of Wisconsin, 110 (1948). (100) Ibid., p. 113. (101) Badin, E. J., J.Am. C'hem. Soc., 70, 3651 (1948). (102) Bolland, J. L., T r 0 7 ~ dFaraday . Soc ,44, 069 (1948). (103) Bridger, G. H., a d Appleton, R . .T. Soc. Chem.Irkd. (London), 67,445 (1948). (104) Brokaw, R. S., Badiri, E .J , m d Pease, R. N.,J. Am. Chem. SOC.. 70.1921 (1948). (105) Chirkov, k. M,; and Entrelis, 8. G., J . Phys. Chem., 22, 930 (1948). (106) Gordon, A. S., Third Symposium on Combustion and Flame and Explosion Phenomena, Univ. of Wisconsin, 147 (1948). (107) Griffing, V. F., and Laidler, K. J., Ibid., p. 128. (108) Heiple, H. R., and Sullivan, W. A., Trans. Am. Soc. Mech. Engrs., 70, 343 (1948). (109) Hughes, G., and Nevell, T. P., Trans. Faraday SOC.,44, 941 (1948). (110) Leidheiser, H., Jr., and Gwathmey, A. T., J . Am. Chem. SOC., 70, 1200 (1948). (11 1) Lewis, B., and Von Elbe, G., Third Symposium on Combustion,
Univ. of Wisconsin, 145 (1948). (112) Loebenstein. W. V.. Glevsteen, L. F.,and Dietz, V. R., J . Kesearch Natl. Bur. Standards, 42 (1949). (113) Maizus, Z. K., and Emanuel, N. M., Bull. acad. sci., U R 8.8 , classe sci. chim., 1948, p. 182. (114) Tolley, G., J . XOC.Chem. I n d . (London),67,369 (1948). f115) Ibid., p. 401. (116) /hid., p. 404. (117) Toiiumi, T., Kawaksmi, T., Sakai, J., Ogawa, D., and Aauma, F., J . Soc. Chem. I n d . ( J a p a n ) ,49, 1 (1946). (118) Wazer, J. V., and John, G., J . Am Chrm Soc , 70, 1207 (1948) (119) Wender, J., and Orchin, M., 1 J . R E711 Mqwru, R c p t s . Invent. 4270 1114%
September 1949
INDUSTRJAL A N D ENGINEERING CHEMISTRY
(120) Whittingham, G., Third Symposiurh On Cornbaatioh )and Flame and Explosion, Univ. of Wisconsin, 136 (1948). (121) Whittingham, G.,T r a m . Faraday SOC.,44,141 (1948). (122) Wohlenberg, W. J., Trana.’Am. SOC.Meoh. Engrs., 70, 143 (1948). PHOTOCHEMICAL REACTIONS
(123) Bennett, J. G.,and Gri5th, R. O., T r a m Faraday SOC., 44, 471 (1948). (124) Eltenton, G. C., J . Phys. & Colloid Chem., 52-1,463(1948). (125) Glookler, G.,Ibtd., p. 451. (126) Hipple, J. A.,Ibid., p. 466. (127) Hirschfelder, J. O.,Ibid., p. 447. POLYMERIZATION
(128) Fontana, C. M., and Kidder, G. A., J . Am. Chem. SOC.,70. 3745 (1948)., (129) I(uIthoff, I. M.,and Bovey, F. A.,Ibid., p. 791. (130) Matheson, M. S.,Auer, E. E., Bevilaequa, E. B., and Hart, E. J.,J . Am. Chem. SOC.,71,497(1949). (131) Melville, H. W., and Watson, W. F., Trans. Faraday Soc., 44, 886 (1948). (132) Smith, W.V.,J. Am. Chem. SOC..70,3695 (1948). REDUCTION
(133) Chipman, J., IND. ENG.CHEM.,24, 1013 (1932). (134) Rossi, C.,Gazz. chim. ital., 77,222(1947). (138) Rossini, F. D., Bur. Standards J . Research, 7,329 (1931). (136) Woodward, L. A., and Glover, A. T., Trans. Faraday SOC., 44, 608 (1948). THERMAL DECOMPOSITION AND CRACKING
(137) Altschul, R., and Herbert, J., J . Am. Chem. SOC.,70, 361 (1948). (138) Bednars; C.,Luntz, D.M., and Bland, R. E., Chem. Eng.Progress, 44, 293 (1948). (139) Choppin, A. R., and Compere, E. R., J . Am. Chem. Soc., 70, 3797 (1948). (140) CORR. _ _ J. L.,and Ubbelohde, A. R., Trans. Faradau SOC.,44, 646 (1948). Frost, A. V., Vestnik, Moskov Univ., 1946,No. 314,p. 111-D. Raley, J. H.,Rust, F. F., and Vrtughan, W. E., J . Am, Chem. Soc., 70,88 (1948). Robertson, A. J . B., Trans. Faraday SOC.,44,677(1948). Ibid., p. 977. Robertson, A. J. B., J . SOC.Chem. I n d . (London), 67, 221 (1948). (146) Simard, G.L., Steger, J., Mariner, T., Salley, D. J., and Williams, V . Z., J . Chem. Phys., 16,836(1948). Petroleum Processing, 4,No. 3,274 (1949). (147) Sittig, M., (148) Stevenson, D.P.,Wagner, C. P., Buck, O., and Otvos, J. W., J . Chem. Phys., 16,993(1948). 44,645(1948). (149) Stokland, K.,Trans. Faraday SOC., (150) szwarc, M., J. Chem. Phys., 16, 128 (1948). (151) Tompkins, F. C.,Trana. Faraday Soc., 44,206 (1948). (152) Waring, C. E.,and Mutter, W . E., J . Am. Chem. SOC.,70, 4073 (1948). MISCELLANEOUS REACTIONS
(153) Coull, J., and Bishop, C. A., Chem. Eng. Progress, 44, 443 (1948). (154) Evans, A. G.,and Workurst, E., Trans. Faraday SOC.,44, 189 (1948). (156) Lauder, I.,and Green, J. H., Ibid., p. 808. (156) Pearson, P.G., J. Am. Chem. SOC.,70,204(1948). (157) Scott, E. M., and Powell, R., Ibid., p. 1104. (158) Streicher, M.A., J . Electrochem. Soe., 93,285 (1948). (159) Yap, C.P.,Trans. Am. SOC.Metals, 40,83(1948). (160) Zemany, P.D.,and Price, F. P., J . Am. Chem. SOC.,70,4222 (1948).
II. THERMODYNAMICS AND EQUILIBRIA Two important symposia were held during the year, one in Portland, Ore., on the “Thermodynamics and Molecular Structure of Solutions,” under the auspices of the and Inorganic Chemistry of the AMERICAN September 13and 14,1948, as reported in the February 1949 issue of Chemical Reviews, and the other in Atlantic City, N. J., under the auspices of the American Society of Mechanical Engineers, as reported in the transactions of tthat society in the August issue (1948).
1829
BOOKS
New books in the field of thermodynamics include a “Table of Properties of Gases” by Geyer and Bruges (1) and “Thermodynamic Charts for Combustion Processes” by Hottel, Williams, and Satterfield (9). GENERAL THEORY
The most significant contributions to thermodynamic theory were presented at the Portland symposium with papers by Scatchard (83) on “Equilibrium in Nonelectrolyte Mixtures”; by Hildebrand (77) on “A Critique of the Theory of Solubility of Nonelectrolytes”; by Parlin and Eyring (78) on “Binary Solutions of Imperfect Liquids”; by Latimer (39) on “The Dielectric Constants of Hydrogen-Bonded Substances”; by Rice (89) on “Critical Phenomena in Binary Liquid Systems”; by Young and B l a h (1.37) on “The Variation in the Properties of Electrolytic Solutions with Degrees of Dissociation”; by Beattie (6) on “The Computation of the Thermodynamic Properties of Real Gasas and Mixtures of Real Gases”; by Hough and Sage ( 9 4 ) on “Volumetric Behavior in Several Gaseous Hydrocarbon Systems”; by Hirschfelder, Bird, and Spotz (64)on “The Transport Propertiw of Gases and Gaseous Mixtures”; and by Redlich and Kwong (81) on “The Thermodynamics of Solutions.” I n the A.S.M.E. symposium the physical and thermodynamic properties of twelve gases-hydrogen, helium, argon, mercury, nitrogen, oxygen, carbon menoxide, water, carbon dioxide, ammonia, methane, and ethane, and in addition air-are reviewed by Keyes (53);Hersberg (93)presented a paper on the determination of molecular constants from spectroscopic data; Gratch ($1) and Keyes (34)on vapor pressures, specific volumes, and PVT data; and Johnston and White (93)on a summary of the experimental determinations of the Joule-Thomson effect. The transport properties of dynamic viscosity and thermal condustivity are given by Hawkins (63). Another paper of general theoretical value describes a statistical cooperative system based on the quasi-chemical method by Guggenheim (3). A system for rapid thermodynamic transformation is graphicall represented by Prim (6) as a modification of Koenig’s square. A summary of thermodynamic principles and relations is reviewed by Parkington ( 4 ) . GENERAL PROPERTIES
The Bureau of Standards (138) has continued to distribute loose sheets on thermodynamic properties as fast as accumulated. General thermodynamic properties of various pure substances are presented by Prengle, Greenhaus, and York (48) for nbutane; by Organick and Studhalter (@), and by Oliver, Eaton, and Huffman (46)for benzene; by West (69)for hydrogen sulfide; by Smith (64)for methyl alcohol; by McCready (41) for the sodium silicates; by Pace and Aston ( 4 7 ) on hexafluoroethane; by Gordon and Giauque (90)on ethyl chloride; by Huffman, Eaton, and Oliver (%’7), and by Beckett, Freeman, and Pitzer ( 7 ) on cyclopentene and cyclohexane; by Woolley (60) on molecular oxygen; and by Woolley, Scott, and Brickwedde (61) on the isotopes of hydrogen. The basic theoretical concepts on the calculation of thermodynamic functions from spectroscopic data are summarized by Reis (60)and Cherkezoff (11) with application to numerical problems. Heat capacity data on halogen derivative and acyclic hydrocarbons are reported by Xurbatov (38); on carbonyl chloride by Giauque and Jones (19); on calcium borates by Kelley, Todd, and Shomate (39); on calcium oxide and barium oxide by King, Torgeson, and Cook (36);and on vanadium chlorides by King (36). Crawford and Parr (14)present new constants for the heat capacity equations of gases at zero pressure from vibrational frequencies. Kravchenko (37)presents a survey of the melting points of organic crystals as related to the number of carbon atoms in homologous series.
1830
INDUSTRIAL A N D E N G I N E E R I N G C H E M I S T R Y
A relationship between heats of fusion and molecular structure is given by Liittringhaus (40). Vapor pressure data are reported by Small, Small, and Cowley (65)for some high boiling esters used as plasticizers; and by Brewer, Gilles, and Jenkins (IO) for graphite. A theory of vapor pressures of liquids based on van der Waal’s equations of state is derived by Wall (55). Weiner (58) gives an equation for the vapor pressure temperature relationships of branched paraffin hydrocarbons. Vapor pressure data are given for methyl sulfoxide by Douglas (16). An equation for the entropy of an ion in the crystal state is given by Kapustinskii and Yatsimirskii (30) and the calculation of such entropies by Gapon (18). Standard entropies and heats of formation for chlorinated ethylene and ethane are reported by Tatevskii and Frost (90). A theory for the heat of formation of salts as related to the radii of ions is given by Yatsimirskii ( 6 2 ) . Experimental data on the heat of formation of tungstic oxide are reported by Huff, Squitieri, and Snyder (26); and on solid solution of sodium chloride-sodium bromide by Fineman and Wallace ( 1 6 ) . An important discussion of recent works on heat of formation and chemical thermodynamic properties is given by Rossini ( 5 1 ) as one of the series of papers of the A.S.M.E. symposium mentioned above. The heats of combustion of some organic nitrogen compounds are given by Salley and Gray (62); of 2-2-bis-4hydroxyphenylpropane by Hubbard, Knowlton, and Huffman ( 2 6 ) . The various methods of reporting the heats of combustion of fuels are discussed by Fiock, Jessup, and Ruegg ( 1 7 ) and by Christie (la. A group contribution method for predicting free energies of formation of gaseous organic compounds is given by Bremner and Thomas (9). The Joule-Thomson effect is given for ethylene gas by de Groot and M. Geldermans ( 2 2 ) and a summary of experimental determination of this property by Johnston and White ( 2 9 ) . PVT data for oxygen are presented by Meyers (4.2)together with an equation of state and convenient charts. Two reviews of the PVT data of twelve gases by Gratch ( 2 1 ) and Keyes ( 3 4 ) appear in the A.S.M.E. symposium. Compressibility factors for gaseous mixtures are given by Redlich and Kwong (49). together with an equation of state and calculation of fugacities. The volumetric behavior of several hydrocarbon gaseous mixtures is reported by Hough and Sage ( $ 4 ) and with application of the Benedict equation of state. The prediction of PVT properties of gases from critical data by Joffe (88) is again presented. Beattie (6) presented the computation of thermodynamic properties of real gases and their mixtures. The generalized compressibility chart for gas is discussed by Obert (44). The relation of the physical properties of the isomeric alkanes t o molecular structure are forrnulated by Weiner ( 6 7 ) . The gaps in data for physical constants of hydrocarbons are pointed out by Corbin, Alexander, and Egloff (IS). The thermodynamic function of free radicals such as appear in rocket propellant gases are presented in the range of 2000° to 4000°K. by Ward ( 6 6 ) . An extensive treatiae is given by Kauzniann (31) on the glassy state a t low temperatures. TRANSPORT PROPERTIES
The most significant contribution to the theory and correlation of the transport properties of gases is given by Hirschfelder, Bird, and Spotz (64)based on intermolecular forces and covering the properties of viscosity, self-diffusion, and thermal diffusion with remarkable accuracy for simple gases and complex gaseous mixtures. A theoretical discussion with experimental data is reported on the viscosity of solutions and suspensions in a series of articles by Vond (66,67). The theory of gaseous self-diffusion i s reported by Pollard and Present (65).
Vol. 41, No. 9
HELIUM AND ITS ISOTOPES
Extensive papers have been prepared on the properties and separation of helium and its isotopes by Andrew and Smythe (68); on the concentration of helium 3 by Clusius-Dickel columns by hlcInteir, Aldrich, and Kier (74) by thermal diffusion; on vapor-liquid equilibria by Fairbank, Lane, Aldrich, and Nier (70); and on separation processes by Daunt, Probst, and Smith ( 6 9 ) . The effect of helium 3 on the vapor pressure of liquid helium is given by Fairbank, Reynolds, Lane, McInteir, Aldrich, and Nier ( 7 1 ) . Some thermodynamic properties of the systems are given by Stout ( 7 6 ) . Vapor-liquid equilibria o f helium isotope solutions are given by London and Rice (73) and Lane, Fairbank, Aldrich, and Xier (72). THEORY O F SOLUTIONS
A theory for the thermodynamic properties of imperfect liquids based on intermolecular forces and the random distribution of molecules is presented by Parlin and Eyring ( 7 8 ) . Rice (88) describes the critical phenomena of binary liquid solutions. Extensive theoretical treatment of equilibria in nonelectrolyte mixtures is discussed by Scatchard (83). A critique of the theory of the solubility of nonelectrolytes is given by Hildebrand ( 7 7 ) . An analytical treatment of multicomponent systems is presented at length by Dah1 ( 7 6 ) . A general theory regarding the thermodynamics of nonelectrolyte solutions is presented by Redlich and E s t e r (79, 80). The theory of corresponding states is applied to estimation of critical densities and related properties of liquids by Benson (8). CHEMICAL EQUILIBRIA
Chemical equilibria are reported for the reaction of chlorine substituted ethylene and ethane by Tatevskii and Frost (90). Five methods of measuring the dissociation of the hydroxyl radical are given by Edse (84). Chemical equilibria between ammonia and hydrogen selenide are given experimentally by blikus and Poss (89). In the combustion of fuel comprehensive thermodynamic charts have been prepared in book form by Hottel, Williams, and Satterfield ( 2 , 86), with extensive application to turbocompressors, compression-ignition cycles, Otto cycle, rockets, and ramjets. Another book by Geyer and Bruges ( 1 )in applied therrnodynamics presents ready methods of solving complex problems of internal combustion engines including effects of chemical dissociation and equilibrium by means of the new tables of thermodynamic functions. The energy-temperature relations in the combustion of fuels are discussed by Kleinschmidt ( 8 7 ) . The method of calculating the equilibrium composition of complex gaseous products in the combustion of fuels is given by Fehling and Leser (85)- A simplified procedure of computing equilibrium composition in complex gaseous systems by use of punched cards is described by Krieger and White (88). The concept of the hydrogen potential in the reaction of metals by steam is presented by Zapffe (91). VAPOR-LIQUID EQUILIBRIA
Vapor-liquid equilibria are reported for methylene dichloride and 1,2-dichloroelhane water systems by .Davies, Jrtgger, and Whalley (98). The deviations of vaporization equilibrium constants from true equilibrium constants in hydrocarbon systems has been attempted by Hadden ( 9 3 ) with special consideration of the deviations caused by components of low molecular weight. Low-temperature vapor-liquid equilibria of the common components of natural gas are given by Stutzman and Brown ( 9 7 ) . Redlich and Kister (79, 80,96) present a series of papers on the thermodynamics of solutions; in Part IV vapor-liquid equilibria are determined from measurements of total pressures. A general discussion of vapor-liquid equilibrium relations is given by Kay
(94).
September 1949
INDUSTRIAL AND ENGINEERING CHEMISTRY
GAS-SOLID EOUlLlBRlA
Specific systems for the adsorption of gases are given by Crawford and Tompkins (100)for sulfur dioxide, ammonia, carbon dioxide, and nitrous oxide on crystals of barium flu Differential and integral heats of adsorption of nitrogen on activated charcoal are given by Perren (109). The separation of ethyl chlorohydrin by adsorption is presented by Sulzbacher and Pariser (118). Equilibria in iron-carbon-silicon and iron-carbon-manganese alloys in the presence of hydrogen and methane are studied by Smith (117). The Brunauer, Emmett, and Teller (BET) equation is applied to the adsorption and pore size measurements on charcoal in an extensive paper by Emmett (103)and by Halsey (107)to adsorption on nonuniform surfaces. The thermodyn from solutions is presented by Fu, Hansen, 106). Pierce and Smith (110,111) present data on the variation of differential and integral heats of adsorption with the mass adsorbed per unit mass of adsorbent, decreasing gradually after the f i s t layer, but not quite reaching the heat of liquefaction with increased coverage. The relation of molecular configuration to adsorption was investigated by Volman and Andrews (119) by studying the adsorption of the cis and trans isomers of dichloroethylene on activated carbon. A statistical method of treating the adsorption of vapors after the method of Fowler and Guggenheim is presented by Dole (109). In the third of a series of papers on physical adsorption, Ross and Lecoy (116) present an equation of state for adsorption for adsorbed gases a t high pressures similar to the van der Waal’s equation. In the fourth paper Ross (114) presents a modification of the Brunauer, Emmett, and Teller equation. Cook (99) also reviews the applications of the Brunauer, Emmett, and Teller equation.
fluorine on tungsten by Metlay and Mimball (108); nitrogen on crystals by Reyerson and Wertz (113);a on glass by Davis and D e Witt (101). Savage and Brown (116) discuss the adsorption of gases on carbon dust, and Armbruster (98) the adsorption of gases on a plane surface of stainless iron-chromium-nickel alloys. LIQUID-LIQUID SYSTEMS
The partition coefficients of formaldehyde between water and organic solvents are given by Johnson and Piret (191). The selective extraction of ethyl chlorohydrin from aqueous solutions is described by Weizmann (129). Other systems studied by Weizmann and Bergmann (123)are for the adsorption of acetone, butyl alcohol, and 2,a-butylene glycol from dilute solutions. SOLID-LIQUID SYSTEMS
The effect of surface agents on the properties of the solidliquid interface is shown by Lomas (126)with applications to dispersion and wetting. The activity coefficients of calcium carbonate in melts of alkali carbonates are studied by Flood, Forland, and Roald (194). AQUEOUS SOLUTIONS
Equilibrium conversions in the system potassium chloridepotassium sulfate-calcium sulfate-water are presented by Abel and Fanto (196)with estimations of activity coefficients.
The variation of the properties of electrolytic solutions with degree of dissociation is reviewed by Young and Blatz (137)‘
1831
Specific systems are studied such as the activity coefficients of lead chloride in aqueous solutions by Garrels and Gucker (199); the partial mold volume of acetic acid in sodium acetate and sodium ohloride solutions by Wirth (136); the thermochemistry of sodium carbonate and its solutions by Kobe and molal expansibilities of potassium de, and lanthanum chloride by Jones, sodium chloride-methanol-water systems by Butler and Gordon (198); aqueous solutions of potassium hydroxide by Akerlof and Bender (297); the reaction of ferrous and ferric ions with 1,lO-phenanthroline by Lee, Kolthoff, and Leussing (139);and equilibrium in saturated solutions of calcium chloride-magnesium chloride-potassium chloride-water by Lightfoot and Prutton (188). Stokes and Robinson (136) discuss the modified Debye-Hiickel equation to relatively dilute solutions in calculating ionic hydration and activities in solutions of electrolytes.
BIBLIOGRAPHY O N THERMODYNAMICS AND EQUILIBRIA BOOKS
E. W.,and Bruges, E. A., “T&bles of Properties of Gases,” New York, Longmans, Green and Co., 1948. (2) Hottel, H.C.. Williams, G . C., and Satterfield, C. N., “Thermodynamic Charta for Combustion Processes,” New York, John Wiiey & Sons, 1949. (1) Geyer,
GENERAL THEORY
(3) Gugaenheim, E. A., Trans. Faraday Soc., 44, 1007 (1948). (4) Parkington, J. R.,Scientia (Milan),81,85 (1947). (5) Prins, J. A.,J. Chem. Phys., 16,66 (1948). GENERAL PROPERTIES
(6) Beattie, J. A.,Chem. Rev., 44,[I] 141 (1949). (7)Beckett, C. W., Freeman, N. K., and Pitzer, K. S., J. A m . Chem. SOC..70, 4227 (1948). (8) Benson, S., J . Phys. & Colbid Chem., 52-11,1060 (1948). ~ (9) Bremner, J. G. M., and Thomas, G. D., Trans. F U T U &SOC., 44,230 (1948). (10) Brewer, L.,Gilles, P. W., and Jenkins, F. A., J . Chem. Phys., 16,797 (1948). (11, Cherkezoff, N. V., Rev. inst. franc. pdtrole et Ann. cmbuatiles liquuides, I, 33 (1946). (12) Christie, A. G . , Tram. A m . SOC.Mech. Engrs., 60, 819 (1948). (13) Corbin, N.,Alexander, M., and Edoff, G., J. Phgs. & Colloid Chem., 52,387 (1948). (14) Crawford, B. L.,Jr., and Parr, R. G.. J . Chem. Phws.. 16. 233 (1948). (16) Douglas, T. B . , J . A n . Chem. SOC.,70,2001 (1948).
(20) Gordon, J., and Giauque, W. F.,Ibid., p, 1606. (21) Gratch, S.,Trans. A m . Soc. Mech. Engrs., 60,631 (1948). (22) Groot, S. R. de, and Geldermans, M.,Physica, 13 (Wniv.of Amstordam), 2638 (1947). ms,B., Trans.A m . SOC.Mech. Engrs.,
B. H . , Chem. Revs.,44,193 (1949). (25) Hubbard, W.N., Knowlton, J. W., and Huffman, J.A m . Chem. SOC.,70,3259 (1948). (26) Huff, G., Squitieri. E., and Snyder, P. E., Ibid., p. 3380. Eaton, M., and Oliver, G . D., Ibid., p. 2911. (27) Huffman, H.M., (28) Joffe.J., Chem. Eng. Progress, 45,160 (1948). Mech. Engre., (29) Johnston, H.L.,and White. D., Trans. A m . SOC. 60, 651 (1948). (30) Kapustinskii. A. F., and Yatsimirskii, K. B., J. Phys. C h m . (U.9.S.R.),22, 1271 (1948). (31) Kauzmann, Walter. Chem. Revs.,43, [2] 219 (1948). (32) Kelley, K.K..Todd, S. S., and Shomate, C. H., J. A n . C h m . Soc., 70,1350 (1948). (33) Keyes, F.G., Trane. A m . SOC.Mech. Engrs., 60,621 (1948). (34) Ibid., p. 641. J. Am. Chem. Soc., 70,2154 (1948). (36) Xing, E.G., (36) King, E.G., Torgeson, D. R., and Cook, 0. A.,Ibid., p. 2160. (37) Kravchenko, V. M..J . Applied Chem. (U.S.S.R.), 19, 241 (1946).
I N D U S T R I A L A N D ENGINEERING CHEMISTRY Kulbatov, V-. P., J . Gem Chem. (U.S.S.R.), 18,372 (1948). Latimer, W., Chem. Revs.,44, 59 (1949). Ltittringhaus, A., Rngeu. Cham., A59,228 (1947). MoCready, N. W., J . Phys. & Colloid Chem., 52-11, 1277 (1948). Meyers, C. H., J. Research Natl. Bur. Standards, 40, [6] 457 ( 1948). Miller, J. G., Trans. Am. SOC. Mech. Engrs.. 60, 645 (1948). Obert, E. F.. IND. END.CHEM.,40,2185 (1948). Oliver, G. D., Eaton, M.,and Huffman, H. M., J . Am. Chem. SOC.,70, 1502 (1948). Organlck, E. D., and Studhalter, W. R., Chem. Eng. Progress, 44, 847 (1948). Pace, E. L., and Acton, J. G., J. Am. Chem. SOC.,70, 566 (1948). Prengle, H. W., Greenhaus, L. B., and York, R., Chem. Eng. Progress, 44, 863 (1948). Redlich, O., and Kwong, J. N. S., C!wn. Revs., 44, [I] 233 (1949). Reis, T., Rev. inst. franc. pBbrole et A.~wL.combustites Zz'quides, 1, 33 (1946). Rossini, F. D., l'rans. Am. SOC.Mech. Engrs., 60,625 (1948). Salley, D. J., and Gray, J. B., J . Am. Chem. Soc., 70, 2650 (1948). Small, P. A , , Sniall. K. W., arid Cowlcy, P., Trans. Faraday Soc., 44, 810 (1948). Smith, J. M., Chem. Enn. P ~ o y r a s a44, , 521 (1948). Wall, F'. T., J . Chem. Phgs., 16,508 (1948). Ward, J. J., Third Symposium on Combustion and Flame and Explosion Phenomena, Univ. of Wisconsin (1948). Weiner, H., J . Phys. Chem., 52-11, 1082 (1948). Weiner, H., J. Phys. & Colloid Chem., 51, 425 (1948). West, J. R.,Chem. Eng. Progress, 44, 287 (1948). Woolley, H. W., J . Research Natl. Bur. Standards, 40, 163-8 (1948). Woolley, H. W., Scott, It. R.. and Brickwedde, F. G., Ibid., 41, [5] 379 (1948). Yatsiniirskii, K. B., Bull A.cad. Sci., U.S.S.R., Classe Sci. Chim., 1947, p. 453. TRANSPORT PROPERTIES
(63) Hawkins, G. A., Trans. Am. Soc. Mech. Erkgrs., 60, 655 (1948). (64) Hirschfelder, J. O., Bird, R. B.,and Spots, E. L., Chem. Revs., 44, [ l ] 205 (1949). (65) Pollard, W. G., and Present, R, D., Phys. Rev., 73, [7] 762 (1948). (66) Vond, V,. J. Phys. (I% Colloid Chem.. 52,277 (1948). (67) Ibid., p. 3214. HELIUM A N D ITS lSOTOPES
(68) Andrew. A., and Smythe, 117. R., Phys. Rev., 74, [4] 496 (1948). (69) Daunt, J. G., Probst, R. E., and Smith, S. R., Ibid., p. 495. (70) Fairbank, H. A.. Lane, C. T., Aldrich, L. T., and Nier, A. O., Ibid., 73, [7] 729 (1948). (71) Fairbank, H. A,, Reynolds, C. A., Lane, C. T., McInteir, B. B., Aldrich, L. T., and Nier, A. O., Ibid., 74, [3] 345 (1948). (72) Lane, C. T., Fairbank, H. A., Aldrich, L. T.,and Nier, A. O., Ibid., 75, [ l ] 46 (1949). (73) London, F., and Rice, 0. K., Ibzd., 73, [ l o ] 1188 (1948). (74) McInteir, B. B., Aldrich, 'L. T., and Nier, A. O., Ibid., 74, [SI 947 (1948). (75) Stout, J. W., Ibid., 74, [5] 605 (1945). THEORY OF SOLUTIONS
(76) (77) (78) (79) (80) (81) (82) (83)
Dahl, L. A., J . Phys. & Colloid Chem.. 52,698 (1948). Hildebrand, J. H.. Chem. Revs., 44, [ l ] 37 (1949). Parlin, R. B., and Eyring, I€.,Ibid., p. 47. Redlich, O., and Kister, A. T., IND.ENG.CHEM., 40, 341 (1948). Ibid., p. 345. Redlich. O., and Kwong, J . N. S., Chem. Revs., 44, [I] 233 (1949). Rice, 0. K., Ibid., p. 69. Scatchard, G., Ibid., p. 7.
CHEMICAL EQUILIBRIA
(84) Edse, R., Third Symposium on Combustion, Univ. of Wis-
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ronqin (194R). - - ..__ - -.-. ,
(85) Fehling, H. R., and Leser, T., Ibid. (86) Hottel, H. C., Williams, G. C., and Satterfield, C. N., Trans. Am. SOC.Mech. Engrs., 60, 667 (1948). (87) Xleinschmidt, R. V., Ibid., p. 821. (88) Krieger, F. J., and White, 117. B., J . Chem. Phys., 16. 258 (1948). (89) Mikus, F. F., and Poss, F. J., J . Am. Chem. SOC.,71, 129 (1949).
Vd. 45, No.
(90) Tatevukii, V. &I., and 1 r o n t , I V , L esknik, Mwkow Univ 3, 65-83 (1947). (91) Zapffe, C. A., T r a m . .4ni. Sot. Metale, 4@, 81.5 (IW8)
9
,
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(92) Davies, W., Jagger, J. B , and Whalley, H. K , .F. Snc Chern. Ind. (London), 68,26 (1949). (93) Hadden. S. T., Chem Eng. Progress, &,37 (1948). (94) Kay, W. B., IXD.ENG.CHEM., 40, 1459 (1948). (95) Landsberg, V. der, I n d . chim. belge, 2, 37 (1948). (96) Redlich, O., and Kister, A. T.,J. Am. Chem. Soc., 71,505 (19W). (97) Stutsman, La F., and Brown, G. M.,Gkem. Brig. Progress, 45, 139 (1949). GAS-SOLID EOUlLlBRlA
(98) Armbluster, M. E., J . A m . Chem. ~ O O C 70, ., I734 (2948). (99) Cook, M. A., Ibid., p. 2925. (100) Crawford, V. A., and Tompkins, F. Trans. Faraday Sm., 44, 698 (1948). (101) Davis, R. T., and De Witt, T. W., J . d m . G'hem. SOC., 70, 1135 (1948). (102) Dole, iM.,J . Chem. P h w . , 16, 16 (1948). (103) Emmett, P. H., Chem. Revs., 43,69 (1948). (104) Frey, H. J., and -Moore, W. J., J . Ana. Chem. Soc., 70, 3644 (1948). (105) Fu, Y.,Hansen, R. S.. and Bartell, F. E., J . Phgs. & Colloid Chem., 52, 374 (1948). (106) Ibid., p. 574. (107) Halsey, G., J. Chem. P'hys., 16, 931 (1945). (108) Metlay, M., and Kimball, G. E.. Ibid., p. 779. (109) Perren, J., Compt. rend., 226,492 (1948). (110) Pierce, C., and Smith, R. N., J . Php8. S Colloid Chem., 52 (7)+ 1111 (1945). (111) Ibid., p. 1115. (112) Razoak, R. I., and Salem, A. S.,Ibid., p. 1208. (113) Reyerson, L. €I., m d Wertz, J. E.,I M . , 53,234 (1949))). (114) Ross, S., Ibid., p. 383. (115) Ross, S., and Leooy, C. H., Ibid., p. 906. (116) Savage, R. H., and Brown, C., J. Ana Cheita. Soc., 70, 2362 (1948). (117) Smith, R. P., Ibid., p 2724. (118) Bulsbaoher, M., and Paritier, X.,J. soc. Chen. Ind. (London), 67, 205 (1948). (119) Volman, D. €I., and AndIews, L. J., J . Am. Chem. SOC.,70. 457 (1948). (120) Wig, E. O., and Juhola, -4.J., Ibid., 71, 561 (1949)
e.,
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(121) Johnson, H. G., and Piret, E. I,., IKD.END.CHEM.,40, 743 (1948). (122) Weizmann, C. H., J . Soc. Chem. Ind. (London), 67, 203 (1948). (123) Weirmann, C. H., Bergmann, E., Sulzbacher, -M., and Pariser, E. R., Ibid., p. 225. SOLID-LIQUID EQUILIBRIA
(124) Flood, H., Borland. H. F., and Roald, R., J. -4m. Chem. SOC.. 71, 572 (1949). (125) Lomas, H., J. SOC.Chem. l a d . (London),68, 37 (1949). AQUEOUS SOLUTIONS
(126) Abel, E., and Fanto, J. .M., Trans. Faraday SOC.,44,97 (1948). (127) AkerIof, G. C., and Bender, P., J. Am. Chem. Soc., 70, 2366 (1948). (128) Butler, J. P., and Gordon, A . R., Ibid., p. 2276. (129) Garrels, R. M., and Gucker, F. T., Jr., Chem. Revs., 44, [ I ] 117 (1949). (130) Jones, G., Taylor, E. F., and Vogel, 1%.C., J. -4m.Chem. SOC., 70, 966 (1948). (131) Kobe, K. A., and Sheehy, T. M., 1x11. ENG.CHCX., 40. 99 (1948). (132) Lee, T. S., Kolthoff, I. AM.,and Leussing, D. L.,
