INDUSTRIAL AND ENGINEERING CHEMISTRY
1698
(53) McBee, E. T., and Devany, L. W., Ibid., 2,473,161(June 14, 1949). (54)Ibid., 2,473,162(June 14,1949). (55) McBee, E.T.,Lindgren, V. V., and Ligett, W. B., Ibid., 2,488,216 (Nov. 15,1949). (56) Ibid., 2,489,969(Nov. 29,1949). (57)Ibid., 2,489,970(Nov. 29,1949). (58) hlcBee, E.T., Robb, R. M., and Ligett, W. B., Ibid., 2,493,007 (Jan. 3, 1950). (59)Ibid., 2,493,008(Jan. 3,1950). (60) McBee, E.T.,Sanford, R. A., and Graham, P. J., J . Am. Chem. SOC.,72,1651-2 (1950). (61) Mahler, P., U.S.Patent 2,484,042(Oct. 11, 1949). (62) Miller, C. B., and Bratton, F. H., Ibid., 2,478,201 (Aug. 9, 19491. (63)Ibid., 2,k78,932(Aug. 16,1949). (64) Miller, W.T.,Jr., Fager, E. W., and Griswald, P. H., J . Am. Chetn. SOC., 72,705-7(1950). (65) Musgrave, W.K.R., and Smith, F., J . Chem. Soc., 1949,30216. (66)Ibid.. 1949,3026-8. (67) Nagy, D. E.,and Kaiser, D. W., U. S. Patent 2,498,217(Feb. ii, 1950). (68) Newton, T. W., and Rollefson, G. K., J . Chem. Phys., 17,71825 (1949). (69) Norris, M. D., and MoCrecken, J. H., U. S. Patent 2,503,290 (April 11, 1950). (70) Ibid., 2,504,083(April 11, 1950). (71)Ibid., 2,504,084(April 11,1950). (72) Novotny, E.E.,and Vogelsang, G. K., Ibid., 2,490,462(Dec. 6, 1949).
(73) Park, J. D., Sharrah, M. L., and Lacher, J. R., J . Am. Chem. SOC.,71,2337-9 (1949). (74) Patat, F., and Weidlich, P., H e h . Chim. Acta, 32, 783-94 (1949). (75) Plump, R. E., U. S. Patent 2,478,008(Aug. 2,1949). (76) Price, D., and Sgrules, F. J., Ibid., 2,481,036(Sept. 6,1949). (77) Pudovik, A. N., Zhur. Obschel Khim., 19,1174-92 (1949). (78) Rust, F. F.,Vaughan, W. E., and Wheatcroft, R. W., U. S. Patent 2,501,966(March 28,19.50).
WILLIAM J. TAPP,
Vol. 42, No. 9
(79) Sarsfield, N. F.,Ibid., 2,473,911(June 21,1949). (80) Schwabe, K., Schmidt, H., and Kuhneman, R., Angew. Chem., 61,48-6 (1949). (81) Sconce, J. S.,Rosenberg, D. S., and Johnson, A. W., U. S. Patent 2,492,941(Dec. 27,1949). (82)Sharpe, A. G., J . Chem. SOC.,1949,2901-2. (83) Simons, J. H.,U. 5. Patent 2,490,099(Dec. 6,1949). (84)Ibid., 2,500,388(March 14,1950). (85) Simons, J. H., Pearlson, W. H., and James, W. R., Ibid., 2,494,064 (Jan. 10,1950). (86) Steiner, H., and Watson, H. R., Discussions Faraduy SOC.,1947, NO.2,88-97. (87) Stormon, D. B., U. S. Patent2,499,120(Feb. 28,1950). y biopufm., Univ. nacl. mayor (88) Suarez, D. V., Rev. facultad fm. S a n Marc08 ( L i m a , Peru), 10, 323-32 (1948). (89) Tess, R. W.,Kearne, G. W., and Yale, H. L., U. 9. Patent 2.490.386 [Dec. 6. 1949). (90) Tew’ksbury,d. I., and Hae’ndler,H. M., J . Am. Chem. Soc., 71, 23357 (1949). (91) Thompson, J., and Emeleus, H. J., J. Chem. Soc., 1949,3080. (92) Thurman, P. J., and Downing, J., U. S. Patent 2,480,982(Sept. 6, 1949). (93) Tome, E. B.,and Dickey, J. B., Ibid., 2,500,218(March 14, 1950). (94) U. S. Bur. Census, Inorgpic Chemicals, U. S. Production Series M19A-30. (95)U. S. Office of Naval Research, London Branch, Tech. Rept. OANAB-52-49 (1949). (96) U.S.Tariff Commission, Chemical Division, Series 62-67. (97) Walker, J. F.,U. S.Patent 2,463,227(March 1, 1949). (98) Webb, 0.A,, Brit. Patent 625,940(July 6,1949). (99)Whitaker, G. C.,U.S. Patent 2,506,438(May 2,1950). (100) Wilson, M. J. G., and Howland, A. H., Fuel, 28,No. 6,127-35 (1949). (101)Wood, 8. R., U. S. Patent 2,484,061(Oct. 11, 1949). (102)Young, J. A., and Tarrant, P., J . Am. Chem. SOC.,71,2432-3 (1949). (103)Ibid., 72,1860-1 (1950). RECEIVED June 21,1950
CARBIDE AND CARBON CHEMICALS DIVISION,
UNION CARBIDE AND CARBON CORPORATION, SOUTH CHARLESTON, W. VA.
OST of the reactions of water with other molecules can be divided into two classes: hydration and hydrolysis. The scope of each of these, although defined in an earlier review (116),may be redescribed here. Hydration involves the reaction of water with a given compound in which the reaction product contains both reactants in a single compound. Hydrolysis, by contrast, is the reaction of water with a compound to yield two or more products, no one of which contains all of the components of both reactants. These definitions have been used as a basis for classifying the reactions that are described below. The following discussion covers developments during the past two years; in some instances, however, earlier developments whose general availability has been delayed and which were deemed to be of some importance have also been included. Although both fields are older industrially than most of organic chemistry, publication of new discoveries in these fields is extremely unusual. For that reason it is believed that only biennial review is justified. HYDRATION In the industrial aspects of hydration the manufacture of alcohols reprepents by far the major commercial application. The
number of bulk and fine chemicals which may be obtained from alcohols by substitution, oxidation, and dehydrogenation reactions followed by subsequent reactions of the products obtained has been described in a number of publications. Until the recent development of the carbonylation of olefins with carbon monoxide, essentially all of the commercially available alcohols of two to ten carbon atoms were derived by hydration of the corresponding olefins. Even with the introduction of the Oxo synthesis on a manufacturing scale, the major production of alcohols is achieved by a hydration process. Developments in the field of olefin hydration have been concerned with improvements in catalysts, processing conditions, and reaction equipment. By contrast, the hydration of acetylene and substituted acetylenes has received little attention; many of the new developments of products from acetylene, such as the enormous developments by Reppe and his coworkers, have involved the addition of water as only one of several reactants. OLEFINS
Judging from the number of patents relating to the hydration of olefins, particularly ethylene and propl,lene, the majority of
September 1950
I N D U S T R I A L A N D E N G I N E E R I N G CHEMISTRY
the developments in reaction conditions and equipment is related to the liquid phase process involving sulfuric acid. An increasing interest is being shown, however, in catalysts other than those employed in this well established process; other catalysts for the liquid phase have been reported, and a number of solid oatalyste for vapor phase hydration are described in the patent literature. In an interesting article Aries (10 ) haa discussed both the vapor phase and the sulfuric acid hydration processes, considering the thermodynamics, the economics, and the inherent advantages and disadvantages of each. Efforta have been made to devise liquid phase processes which tend to favor higher conversion of olefin to alcohol, thereby minimizing recycle of unreacted gas, and a t the same time avoiding the use of corrosive sulfuric acid under pressure. A number of patents assigned to the Phillips Petroleum Campany (29, 30,63) have involved the use of hydrofluoria acid either in anhydrous form or in aqueous solutions varying from 30 to 70 weight % contained acid. Another patent (68)to the eane assignee haa been granted in which a mixture of aqueous hydrofluoric acid and boron trifluoride waa claimed as the catalyst. The mole ratios of contained acid to olefin for the aqueous hydrofluoric acid proceases were of the order of 5: 1 to 10:1 and presumably involved formation of an alkyl fluoride aa an unieolated intermediate which was hydrolyzed immediately and not as a successive operation. The use of anhydrous hydrofluoric acid in comparable mole ratios resulted in the formation of alkyl fluorides which were isolated and could be hydrolyzed in turn to the desired alcohol by means of dilute acid. In addition to the w e of boron trifluoride, which was claimed (68)as a promoter for the acid catalyst, other metallic fluorides also were described as functioning in a similar capacity. In each instance hydrofluoric acid bas been ascribed as suitable for use with olefins containing two to five carbons. A study has been made by Ciapetta and Elpatrick (36)of the liquid phase hydration of isobutylene, in which the rates of reaction were measured in the presence of perchloric, trichloroacetic, and ptoluenesulfonic acida aa catalyst. Using a dilatometric method of measurement, the reaction was found to be firat order and dependent upon the olefin concentration. A recent patent issued to Romage (101) described a number of catalysts for the hydration of ethylene by means of sulfurous acid, introduced as sulfur dioxide and water. The process, in the presence of silver sulfate a8 catalyst, claimed the intermediate formation of ethyl sulfite a t 300' F. and 500 pounds per square inch gage followed by hydrolysis of the ester a t a lower pressure; sulfur dioxide could be recycled to the reactor. Ultraviolet light, sodium bisulfite, and calcium bisulfite were also described as serving as catalysts for the reaction. Developments in the field of vapor phase hydration of olefins have produced a variety in the types and kinds of catdysts used. Robinson (100) in a process patent for the manufacture of ethyl alcohol has described the use of 20% sulfuric acid a t 450"F. and pressures of 2500 pounds per square inch absolute to yield a mixture of alcohol and ether; following the hydration, the contained ether was hydrolyzed over activated alumina a t 700' F. with sufficient quantities of water to prevent dehydration of the ethyl alcohol formed. An over-all 25% conversion of ethylene to alcohol and ethyl ether with a 68% conversion of 80% of the ethyl ether to alcohol in the second step has been claimed. A number of suitable catalysts for the initial hydration were mentioned: metal phosphates, phosphoric acid on diatomaceous earth, aqueous hydrofluoric acid, and phosphoric acid, with a preference for solid catalyst. Tungsten oxide, WPO, has been claimed by Reynolds and Grudgings (99) as a catalyst for the hydration of propylene, and the propylene conversion under 250atmospheres(hydrogen added) at 270" C. was stated to be 14.6%. The catalyst was prepared through reduction of WOCor ammonium tungstate in pelleted form by heating in ethyl alcohol vapor at approximately 250' C. for 18 hours a t atmospheric pressure. A catalyst of similar activ-
1699
Alcohol Refining Still
ity was said to be prepared by precipitation of tungstic oxide on alumina or silica gel, followed by a reduction procedure identical with that used for pelleted oxide catalyst. The only novelty apparent, in view of similar catalysts mentioned earlier (116)' appears to be in the extreme pressure, 32 tons per square inch, used in manufacture of the catalyst pellets. A patent has been issued to Kreps and Nachod (79)for the use of an ion exchange catalyst for the hydration of iso-olefins, of four to twelve carbons, to yield tertiary alcohols. The catalyst was prepared by treating the sodium salt of sulfonated coal with hydrochloric acid follovTed by a water wash. Sixty-one per cent conversion per pass was reported with isobutylene at 219' F., 400 pounds per q u a r e inch gage, and 1.14 volume/volume/hour space velocity. Two other vapor phase catalysts, which have been the subject of a patent issued to Carter (U),are said to be suitable for the conversion of ethylene to ethyl alcohol and ethyl ether, acetylene to acetic anhydride, and carbon bisulfide to carbon dioxide and hydrogen sulfide. A catalyst suitable for use in the range 400 'to 600"C. may be made by incorporating a mixture of strontium hydroxide, potassium carbonate, ferric oxide, and charcoal a t 37, 11,4,and 30%, respectively, in 18% aqueous tar emulsion; the mixture is briquetted, dried in an oven, and calcined a t 800O C. A comparable catalyst may be prepared for use below 400" C.from magnesium oxide, potassium carbonate, f e r ric oxide, and charcoal. Two additional vapor phase hydration catalysts should be mentioned: a synthetic lithium spinel (Ill),from which the lithium oxide may be leached to give an acidic catalyst, and a silica catalyst impregnated with sulfuric acid (66). In a novel process, the
1700
INDUSTRIAL A N D ENGINEERING CHEMISTRY
latter catalyst was prepared by passing sulfur trioxide over 4- to 8-mesh silica containing water of gelation, with the resultant formation of sulfuric acid in situ; any excess acid above 23% was removed by aeration with nitrogen. In spite of the number of patents khat have been issued over a period of several years for vapor phase hydration of ethylene, the first commercial production utilizing this process was reported in 1949 ( 9 ) . The manufacture of ethyl alcohol by the Shell Chemical Company a t Houston, Tex., was stated to be accomplished by the interaetion of steam and ethylene a t a pressure just under 1000 pounds per square inch using a phosphoric acid catalyst. Most current process patents for the hydration of olefins have been concerned primarily with liquid phase procedures, although that outlined by Robinson (100) is presumed to be adaptable to either liquid or vapor phase operation, Interesting data are cited by Frey ( 5 3 )in the use of aqueous hydrofluoric acid for batchwise hydration reactions of ethylene, propylene, isobutylene (2methyl propene), and 2-butene. Under optimum conditions yields of 39% ethyl alcohol, 50% isopropyl alcohol, 38% 2-butanol, and 65% tert-butyl alcohol (2-methyl-2-propanol) were obtained with the use of 20 to 50% acid at acid to olefin mole ratios of 3.1: 1 to 7.7:l. As would be anticipated, isobutylene was the olefin most readily hydrated and this was accomplished under relatively mild conditions. In a process similar to that cited above, Cade (29) has devised a hydration of ethylene as an intermediate step in the alkylation of paraffins with olefins. Ethylene was reacted with 30 to 60% hydrofluoric acid at 200' to 500 ' F. and 500 to lo00 pounds per square inch pressure a t acid to ethylene mole ratios of 6: 1 to 20: 1. The ethyl alcohol-acid mixture obtained was then fed to the alkylation stage. Morrell and Robey have been granted a patent (87')on a threestage process for the manufacture of ethyl alcohol from ethylene and sulfuric acid. The first stage required absorption of gas rich in ethylene in concentrated acid a t 60" to 100"C. and 300 to 500 pounds per square inch gage pressure, followed by a second absorption, by the acid reaction mixture a t a somewhat higher temperature, of ethylene preferably of relatively high purity. The final stage was hydrolysis of the ethyl sulfate to form ethyl alcohol. In a similar process described by Bannon and Morrell(19) a skpwise method was used to minimize the formation of ether and ensure essentially complete hydrolysis of ethyl sulfate. In the process, the hydrolysis was conducted as three operations, each of which was designed to further the hydrolysis. In another patent (82) sulfuric acid was used for the absorption of olefins to yield a mixture of alkyl sulfates and alkyl sulfuric acids derived from two-, three-, and four-carbon molecules. The mixture obtained was used either,for the production of ethers by reaction with added aleohols or for manufacture of alcohols by hydrolysis. Hunter (66)has claimed improved efficiency in the hydration of ethylene and propylene by removing the alcohol formed in the hydrolysis phase under reduced pressure and accomplishing concomitantly concentration of the sulfuric acid. Improvements in the hydration of propylene, in the presence of sulfuric acid, have been claimed by aFrench concern (118,119). The principal claims to novelty are those of equipment design and not in the chemistry involved. Additional improvements are claimed also by Schneider and Mistretta (106)for the sulfuric acid hydration of propylene a t elevated temperatures and pressures, in which the hydrolysis step was conducted also a t elevated temperatures and under pressure. Improved yields were claimed for isopropyl alcohol, and sec-butyl alcohol (2-butanol) was described as being prepared in the same fashion. The use of sulfuric acid for higher olefins has received little attention, and only one patent (43) has been mentioned here in which, by improvements in process control and operating temperature, higher quality tert-butyl alcohol from isobutylene was reported. Katuno (72)has information, which has only recently become available, although published several years ago, on the effect of temperalure and acid concentration on the yields of tert-butyl alcohol from iso-
Vol. 42, No. 9
butylene. Optimum conditions with 67% acid a t 20' C. resulted in 96% conversion to alcohol. Hunt (64) has described the conversion of isoprene, by a combination dimerization and hydration, to geraniol by the addition of water to the diene in the presence of chloroacetic acid catalyst; other strongly acidic organic acids were reported to be equally satisfactory. Camphor has been prepared (107) by heating p cymene with water in alcohol as a solvent in the presence of a mercury compound or fatty acid salt. Among the catalysts claimed are mercurous chloride or oxide, mercuric chloride or oxide, and sodium or potassium stearate, palmitate, or oleate. The hydration of gum turpentine (18) to yield 40% terpene alcohols, 15.9% monocyclic terpene hydrocarbons, and 4oy0 turpentine recovery was accomplished using sulfamic acid as catalyst. By the same process a- and @-pineneyielded 70 and 72%, respectively, of the corresponding alcohols. Data also were given for a mixed catalyst consisting of equal parts by weight of sulfuric and sulfamic acids in the hydration of turpentine and also the pinenes; an improved yield of terpene alcohols was obtained. MISCELLANEOUS
Two novel processes yielding glycols as the major products have been patented recently. Hatch and Evans (60) have received a patent on the manufacture of 1,3-propanediol in 65.5% yield by the reaction of acrolein with dilute sulfuric acid followed by hydrogenation over Raney nickel. Propanol and 2-hydrorymethyl-1,5-pentanediol were obtained as by-products in varying amounts depending upon the reaction conditions. The simultaneous reaction of water and formaldehyde with olefins to yield 1,3-glycols has been established by Hamblet and McAlevy (59). The reaction was performed at 400 to 1000 atmospheres' pressuro at 100" to 200" C . in the presence of catalysts such as hydrated boron trifluoride, sulfuric acid, methyl formate, and sulfuric acid. Thus propylene was successfully converted to 1,3-propanediol with minimum production of formals as by-products. A number of papers have been published upon the hydration of acetylenes and substituted acetylenes; by far the majority of these reports were by Russian authors. Among the catalysts listed for hydration are those reported by Carter (91)and also a mixture of cupric chloride and biguanide hydrochloride (114). Several authors (62, 89, 124) have described the use of mercuric salts alone and with sulfuric acid, and Nazarov (88) has studied the addition of water to a substituted acetylene in the presence of sulfuric, hydrochloric, phosphoric, and acetic acids. In fact, an entire series of papers (55, 7'9, 90, 91) has reported extensive investigations concerning catalysts, mechanisms, and reaction conditions for acetylene-water reactions, and Treibz ( 1 f 7 ) has reviewed the reactions of vinylacetylene including those involved in hydration. By definition (116) the addition of water to epoxy compounds has been classified as a hydration reaction. One very interesting article describes investigations on the vapor phase hydration of ethylene oxide by Cartmell and others (32). The following were found to be optimum reaction conditions: 170' C. converter temperature, 1.8 seconds' contact time, a steam to oxide mole ratio of approximately 15; with silver oxide catalyst, a yield of 80% was obtained. Below 110"C. yields were negligible, and at about 200" C . , an aldehydic product predominated. A t the preferred conditions, ethylene oxide, ethylene glycol, and diethylene glycol were obtained, and yield values over a fresh catalyst increased to a maximum during the first 4 hours of catalyst life. Data have been given on catalyst preparation, activity, and regeneration and theories advanced for the reaction mechanism. Additional information has been presented concerning various catalypts, including phosphoric acid on silica, thoria on alumina, thoria on silica, and silver on alumina, silica, and thoria. None of these was found to be of particular value in the hydration reaction; nearly all influenced the formation of aldehydic products. Effective catalysts were prepared eithcr by the decomposition of silver osa-
September 1950
INDUSTRIAL AND ENGINEERING CHEMISTRY
1701
late impregnated on alumina or by precipitation of the oxide, impregnated as the nitrate, by means of dilute sodium hydroxide. Another ether hydration reaction which has been patented recently ( 7 1 ) is the introduction of water into substituted 2,Sdihydrofurans. From these compounds, malealdehyde or its derivatives were obtained in approximately 38% yields in the presence of traces of strong organic acids or the common mineral acids.
HYDROLYSIS The variety of organic compounds which are cleaved by water is immeasurably greater than that to which water may be added. In the majority of classes of such compounds, however, the magnitude of the operations involving hydrolysis as the principal feature is smaller than those of hydration. Exceptions to this, of course, are the soap and wood pulping processes which are conducted upon tonnage quantities. SILICON COMPOUNDS
During the period covered by this review, certainly the largest single class of products is the silicon compounds. No attempt has been made to cover this particular phase of hydrolysis exhaustively, but the number of publications during the past two years has been voluminous and informative. It is of interest to note that the period of prolific investigation has begun to subside and that the reports of new hydrolytic studies during the immediately past few months have been infrequent. Polymeric organio silicon compounds resulting from hydrolytic reactions have been obtained principally by the replacement either of alkoxy1 (or aryloxy]) or of halogen groups bonded to the silicon. Recently Hellstrijm (68)has reported the synthesis of polyethylsilicates by the simultaneous reaction of silicon tetrachloride, ethyl alcohol, and water to yield hexaethoxy disiloxane and higher esters. Products of low molecular weight were obtained also by Daudt (41) and by McCusker and Greene (8.9)in the reaction of alkoxy substituted silanes. The latter paper compared the relative rates of hydrolysis of a number of substituted silanes in the presence of alkaline and acid catalysts and the effect of substituents which were replaced. A review (97) has appeared in which the hydrolysis of tetraethyl orthosilicate has been discussed thoroughly, including rates of hydrolysis, solvents, and industrial applications of the silicic acids obtained. Acidic catalysts for hydrolysis of alkoxysilanes predominate in industrial applications leading to polymeric products. Dilute aqueous hydrochloric acid has been used by Albright and Wilson, Ltd. (6); mutual solvents have been described by Hyde (66, 68, 70)and-in other patents assigned to the Corning Glass Works (39, I,%?). Among the solvents used were ethyl alcohol and dioxane. Both sulfuric acid in ethyl alcohol and 85% sulfuric acid have been cited by McGregor and Warrick (84) in describing a controlled polymerization. One British patent (68)has been granted in which dilute sulfuric acid was claimed as a catalyst, and another patent (98) has been issued in which sulfuric, phosphoric, or boric acid was described as catalyst. In both patents the acids were specified as catalyst for the formation of polymers. In contrast, only two reports were noted describing other than acid catalysts. In one article (108) the hydrolysis of tetraethyl
Alcoholic Refining Still orthosilicate was catalyzed by 5% magnesium chloride to yield a “modified ester.” In the other (4S),products having certain desired properties were obtained with Bpecifia reagent concentrations by the partial hydrolysis of diethoxydimethylsilane under neutral or slightly alkaline conditions. The hydrolysis of substituted silicon halides to yield linear, cyclic, two-dimensional, and three-dimensional polymers has been studied in great detail, and comprehensive reviews have been published. Interesting data have appeared recently on industrial applications such as the use of alcohol, dioxane, acetic acid, acetone, and acetaldehyde, mentioned as mutual solvents for hydrolysis reactions in two patents (88, 67). Rate studies have been reported by Swain and others (116), in which the effects of pH and ring substitution in triphenyl fluorosilanes upon the hydrolysis have been compared with analogous triphenylmethyl halides. Two papers by Anderson (7,60)have been published in which hydrolysis rates of aryl and alkyl silicon isocyanates, similar in character to the halides, have been compared with the corresponding halogen compounds. Andrianov and Breitman (8)have conducted an extensive study of the hydrolysis of phenyl trichlorosilane and diphenyl dichlorosilane by the action of moist air on solutions of these compounds singly and together in chlorobenzene solution. Data have been reported on the effect of hydrolysis temperature, reaction time, and action of acidic catalysts upon the nature of the polymeric products obtained. A preparation of mixed aromatic or aliphatic silicone polymers was described by Rust (rod), in which the product waa prepared by hydrolysis of the mixed chlorosilanes obtained h their synthesis from silicon tetrachloride and Grignard reagent.
1702
INDUSTRIAL AND ENGINEERING CHEMISTRY
Catalysts for the hydrolysis of halogenated silanes include bases, acids, and salts. Bowman (20) and others described the use of aqueous sodium hydroxide solution with Cellosolve as a mutual solvent; alkalies in dioxane have been reported (69); and a British patent (109) has been issued to cover the use of hydroxides of metals in both of the first two groups of the periodic table. One process has been patented ( 2 3 )in which aqueous hydrochloric acid mixed with organic solvents was used as the catalyst; the process has been designed to permit recovery of the hydrochloric acid. Concentrated sulfuric acid has been mentioned also @E?), although its principal function is to serve as a condensing agent to promote additional polymerization. After examination of three patents issued to the British Thompson-Houston Co., Ltd. (24-26), it is difficult to imagine that any readily available inorganic salts could fail to function in a catalytic fashion to some extent. Claims have been made that higher polymers resulted and that superior products were obtained by the use of the various salts cited; among theee were chlorides, sulfates, nitrates, and carbonates of nearly all the alkali and alkaline earth metals, c o p per, iron, mangantse, cobalt, zinc, and tin. Some interesting derived products have been obtained in the hydrolysis of chlorosilanes containing substituents capable of further reaction, as in polymers from 1,2-dichlorovinyl trichlorosilane ( 4 ) which may be polymerized further by means of the vinyl side chains. Three different reports have appeared (27, 46, 113) in which chlorosilanes substituted with chloromethyl groups, as chloromethyl dimethyl chlorosilane, yielded polymers upon hydrolysis which were then treated with alkaline reagents. Depending upon the reaction conditions, polysilanols or higher polymers, formed by cross linking of polysilanols, were isolated. Extensive information has been published by Miner and others (86) on the hydrolysis products from aminosilanes with data upon the effect of heat treatment and its effect upon the character of the resinous product. Rosnati (102) also has published results obtained in the study of a number of aminosilanes, and found them generally more resistant to hydrolysis in alkaline solutions than in neutral or alkaline media. Thermodynamic data which can be of some value in the field have been reported (97) for the silicion-hydrogen bond under conditions of alkaline cleavage. HALOGEN COMPOUNDS
Studies concerning the mechanism of hydrolysis of aliphatic halides have been published over a period of several years, and these data have proved of value in industrial applications. Additional data have been reported recently by Brown and Fletcher (28) on the effect of structure upon the rates of hydrolysis of tertiary aliphatic halides. Yield data and optimum reaction conditions for the hydrolysis of isopropyl chloride with aqueous sodium hydroxide under pressure have been given by Russian authors (92); a maximum yield of 28% was obtained at 175 O C. with minimum by-product formation of propylene. Ross (103) has published interesting information upon rates of hydrolysis of Nmono- and N,Ndi(2-haloethyl) aromatic amines and the effect of various ring substituents upon these reactions. ABwould be expected, electron-releasing groups in the position para to the amino group induced more rapid hydrolysis. Mixtures of alcohols containing seventeen and eighteen carbon atoms have been made by alkaline hydrolysis of the corresponding benzoate esters (46). The esters were prepared by reaction of sodium benzoate-benzoic acid with chlorinated hydrocarbons obtained from kerosene. Two publications have been concerned with the vapor phase hydrolysis of chlorobenzene to phenol. Work published by Freidlin and others (61)was concerned with cupric chloride catalyst supported on titania and on stannic oxide; both were found to be unsatisfactory with low conversion to phenol and high yields of benzene and hydrogen chloride. Balandin (11) found that a catalyst containing 0.2% cupric chloride and 6% copper on silica gel gave yields of over 30% phenol per pass under optimum
Vol. 42, No. 9
conditions. Although copper itself was not a catalyst for the reaction, yields were double when copper was present. This effect was attributed to replacement, by the metallic copper, of cupric salt lost by volatilization, thereby allowing full catalyst activity at higher temperatures. Phosphoric acid, magnesium chloride, and chromic chloride were found to be effective catalyst poisons. Preparation of unsaturated alcohols by hydrolysis of the corresponding halides has been claimed in two patents issued to the Shell Development Company. In the first of these (2)allyl chloride monomer, dimer, or trimer has been reported to give a 97% yield of the corresponding alcohol after treatment with potassium hydroxide in mixed ethyl alcohol-water solution. The second patent (121) is concerned with the conversion of allyl and homologous chlorides to the alcohol by continuous liquid phase hydrolysis over cuprous chloride catalyst in the presence of hydrochloride acid. With allyl chloride at 80" C. in a tube packed with glass rings, yields of 60% allyl alcohol, 7,3% diallyl ether, and 22% unreacted chloride were reported. The volume of permanent antifreeze sold annually is sufficient indication of the commercial interest in the hydrolysis of ethylene dichloride or of ethylene chlorohydrin. An interesting review of commercially attractive methods for the manufacture of ethylene glycol from ethylene has been published by Sherwood (110). Data have been given for process equipment and a fiow sheet was shown for the successive conversion of the olefin to chlorohydrin, oxide, and glycol; a yield of 70% glycol, based on olefin, was eatimated. Zimakov (125) has reported the vapor phase hydrolysis of ethylene dichloride over a lead oxide catalyst to yield ethylene oxide via ethylene chlorohydrin as a presumed intermediate. Some additional data were given regarding cupric oxide, lead carbonate, and soda-lime as catalysts; the yields reported were not impressive. Bradlow and VanderWerf (21 ) have studied rates of acid-catalyzed hydrolysis of a-halogenated pyridines, and Pesez (94, 96) has presented data on hydrolysis of chloroform and bromoform in a number of solvents, and solvent effect on hydrolysis of the chlorine in DDT. General preparation of polyhydric alcohols by hydrolysis of the corresponding halides has been described in a French patent (112) with no specific catalyst claimed, but methanol or ethyl alcohol was added to ensure reaction with hydrogen chloride. Ethylene dichloride has been converted to sodium chloroethanesulfonic acid by the action of sodium sulfite and water (81)at superatmospheric pressure a t 100' C. and with an alcoho lpresent to act as a mutual solvent. Included in the field of ester hydrolyses is the manufacture of soap. No attempt has been made to cover this field.in any detail, but two items of interest have been noted. The first is a British patent (47)for a liquid phase noncatalytic process for the hydrolysis of fatg and oils at elevated temperatures and pressures; the second is an interesting article by Barnebey (14)on plant design for a continuous process for fat hydrolysis t o give a product of high purity and excellent yield a t an economical cost. Salmi (105) has studied the effect of structure upon reaction rates in the hydrolysis of esters and has presented a detailed discussion of the effects observed. Difficulties observed in achieving any extensive polymerization of allyl alcohol have been overcome, at least in part, by polymerization of allyl esters. Two processes for the manufacture of allyl alcohol have been described in patents, assigned to the Shell Development Company, wherein allyl esters were polymerized and the resulting polymer8 hydrolyzed to polyallyl alcohol. Polyallyl acetate ( 4 ) was hydrolyzed by a solution of sodium hydroxide in aqueous methanol; polyallyl borate (18 ) was hydrolyzed without any added catalyst. Gresham (66) has received a series of patents for hydrolysis of propiolactone and other lactones to yield p-substituted carboxylic acids by reaction of a number of organic and inorganic reagents in aqueous solution, Thus among the examples cited sodium cyanide gave p-cyanopropionic acid; sodium acetate, 8-acetoxy propionic acid; and eodiuni sulfide, 8-mercaptopropionic acid, all as
September 1950
1103
INDUSTRIAL A N D ENGINEERING CHEMISTRY
sodium salts prior to acidification. Hydrolysis of esters also has been used in salvage operations a.a in recovery of terephthalic acid (61)from polymer waste scraps from the polymerization of the acid with glycols; nitric acid was used to catalyze the reaction. Pentaerythritol (49)also has been recovered in 70% yield by treatment of the tetranitrate (PETN) with aqueous sodium sulfide a t 60" to 75 O C. Although the reaction of nitriles with water to yield amides, by the definitions used here, is a hydration reaction, the reaction may, and often does, continue to the formation of a carboxylic acid. Thus, it has been discussed aa part of the section of hydrolysis reactions. Acid and alkaline catalysts have been used for the hydrolysis of nitriles. A pantothenic acid intermediate has been prepared from 1,3-dihydroxy-2,2-dimethylbutyronitrile by treatment with aqueous sodium carbonate (6); trichloroacetamide has been made by the reaction of trichloroacetonitrile with concentrated hydrochloric acid (16);and 2,2,4-trichlorobutyramide haa been prepared by hydrolysis of the trichlorobutyronitrile by means of cold concentrated sulfuric acid (16). Christian and Exon (34) have described a series of @-alkoxypropionitriles and the effect of alkaline and acidic catalyzed hydrolyses. In general, acidic catalysts yielded the corresponding acids; basic catalysts gave complex mixtures, probably through the formation of acrylonitrile. Hydrochloric acid has been found to catalyze the complete hydrolysis of cyanogen chloride (IN),and Galat (64)has used Amberlite resin IRA-400 to catalyze the formation of nicotinamide from nicotinonitrile. Two interesting processes for the production of substituted amides from nitriles have been reported recently. The reaction of nitriles, water, and either a tertiary olefin, tertiary alcohol, or ester of a tertiary alcohol in the presence of sulfuric acid a t 300 to 400 pounds per square inch gage and 90' to 100"C. has been described (67)as giving excellent yields of the monosubstituted amide; the production of N-tettbutyI-~-hydroxyamide from hydroxyacetonitrile and isobutylene WBB cited. Mahan (86) has used a silica-alumina catalyst for the reaction of nitriles with amines and water to yield mono- and disubstituted amides. The reaction of acetonitrile, diethylamine, and water at 480. to 550OF.and IO00 pounds per square inch gage gave 37.3% yield of N,N-diethylacetamide per pass with an ultimate yield of 95% by recycling unreacted materials. The hydrolysis of ethers has been described in two patents discussed earlier in this review in connection with the hydration of olefins. Carnell(30) has described in some detail the use of dilute hydrofluoric acid for the hydrolysis of alkyl ethers. Bohme and Sell (17) have investigated, in great detail, the hydrolysis of both halogenated ethers and thio ethers. Rates of reaction were measured, and theories were propounded to cxplain the data obtained. The hydrolysis of diallyl ether to give 29% conversion to allyl alcohol in 4 hours has been reported by Cheney and others (83); cupric sulfate on alumina was used as a catalyst for the vapor phase process. A number of unclassified hydrolyses have been noted and presented as a miscellaneous group. The hydrolysis of aldol-type condensation products from acetone has been used by Pines and Ipatieff (96)as a means of obtaining purified isophorone. A mixture containing isophorone, phorone, and mesityl oxide upon treatment with a large excess of either aqueous ferric or ammonium chloride solution, under pressure at temperatures to 350' C., gave isophorone and acetone. A similar process to yield acetone and isophorone from condensation products boiling higher than the cyclic ketone has been described (183),in which the mixture is treated in the vapor phase over activated alumina with a large excess of steam. Polyallyl formal has been prepared from the monomer and then hydrolyzed with dilute hydrochloric acid to yield polyallyl alcohol (8). This method has been used as a means of obtaining the polyalcohol as a polymer of high molecular weight. Hydrolysis of aniline to yield phenol has been investigated
thoroughly by Patat (93),who has reported extensive data on the reaction of the amine in the liquid phase above the critical temperature in the presence of ammonium dihydrogen phosphate. In a British patent, Cross (40)hau described the hydrolysis of a number of aromatic amines with steam at 450" to 550" C. in the presence of activated alumina catalyst. Kratzl(76-78) has presented information of considerable interest on the hydrolysis of l i ~ o m l f u r i cacids and the quantities of vanillin that may be obtained. A large number of hydrolytic reactions were reported in which compounds aimilar to components of the lignosulfuric acids were subjected to hydrolyses. The use of a number of acids including sulfurous, lignosulfurk, formic, and acetic acids in prehydrolysis of wood pulp and optimum temperatures haa been studied by Lslutsch (#), and optimum sulfuric acid concentrations in the hydrolysis of cellulose to hydrocellulose have been determined by Abadic (I). A number of catalysts, including bleaching earth, activated carbon, ion exchange resin, and sulfuric acid esters of alcohols have been claimed as being desirable in the hydrolysis of carbohydrates (74). Controlled sulfonation and hydrolysis of a mixture containing indene, aromatic, and nonaromatic hydrocarbons have been reported, in B British patent (48), to give mesitylene and pseudocumene aa products. Rates of hydrolysie of carbaoolesulfonic acid in the presence of various acid catalysts have been studied by Russian workers (N), who reported 81% yield of carbazole with 45% sulfuric acid at atmospheric pressure. Intereating data were cited by Kortschak and Payne (76) to show that 70% hydrolysis of Amberlite resin IR-4B, after exhaustion with hydrochloric acid, oould be achieved with water alone, indicating that the ion exchange activity of the resin was due to adsorption.
LITERATURE CITED (1) Abadic, F. A., CompLrend., 226,153841 (1948). (2) Adelaon, D. E., and Gray, H. F., Jr. (to Shell Development Co.), U. S. Patent 2,426,913 (Sept. 2, 1947). (3) Zbid.,2,455,722 (Dec. 7, 1948). (4) Agre, C. L., J. Am. C h m . SOC.,71,3004 (1949). (5) Albright and Wilson, Ltd., and Taylor, A. Brit. Patent 607,811 (Seqt. 0, 1948). (0) Amerioan Cyanamid Co., Zbid., 597,648 (Jan. 30,1948). (7) Anderson, H, lL,J. Am. C h n . Soc., 70,1220-2 (1948). (8) Andrianov, K.A., and Breitman, B. M., J. Gtn. C h . (u.8. S.R.), 17, 1522-7 (1947). (9) Anon., Chem. Eng., 56, No. 8, 109 (1949). (IO) Aries, R. S., Can, C h n . P~ocessZnds.,32, 1004-7 (1947). (11) Balandin, A. A., Lebedeva, A. I., and Fridman, G. A., Bull. a d . sCi. U.R.B.S., cluaae soi. chim., 1947,515-22. (12) Ballard, 8. A, (to Shell Development Co.), U. 8. Patent 2,431,224 (Nov. 18, 1947). (13) Bannon, L. A.. and Morrell, C,E. (to Standard Oil Develop ment Co.), Zbial., 2,474,568 (June 2S,1949). (14) Barnebey, H. L., J. Am, Oil Chemhts' Soc., 25,QS-9 (1948). Bauer. 0. W.. and Teter. J. W. (to Sinclnir Refining CO.), (15) . . U. S . Patent 2,429,791 (Oct. 28,1947). ( 1 0 ) Ibid., 2,443,291 (June 15, 1948). (17) Biihme, H., and Sell, K., C h m . Bm., 81,12340 (19a). (18) Borglin, J. N. (to Hercules Powder Co.), U. 8. Patent 2,432,656 (Dec. 16,1947). (19) Borodkin, V. F., and Malk'ova, T. V., Zhw. FrikloJ. Khdm. ( J . Applied Chcm.), 21, 1032-6 (1948). (20) Bowman, A,, Evana, E. M., Mylee, J. R., Payman, L. C.,
a,,
and Imperial Chemical Industries, Ltd., Brit. Patent 613,048 (Dec. 1, 1948). Bradlow, H. L., and VanderWerf, C. A., J. OTO.Chmt., 14, 609-16 (1949).
British Thompson-Houston Co., Ltd., Brit. Patent 686,189 (March 11, 1947). Zbid., 590,736 (July 28, 1947). Zbid., 591,221 (Aug, 12.1947). Zbid., 592,450 (Sept. 18, 1947). Zbid., 594,485 (Nov. 12, 1947). Zbid*,611,495 (Oot. 29, 1948). Brown, H. C., and Fletcher, R. S., J. Am. Chem. &e.,
71,
1845-54 (1949).
Cade, G. N. (to Phillips Petroleum Co.), U. 9. Patant 2,431,658 (Dec. 2, 1947). Camell, P. H. (to Phillips Petroleum:Co.), Zbid., 2,430,388 (Nov. 8, 1947).
INDUSTRIAL AND ENGINEERING CHEMISTRY
Lautsch, W., Cellulosechem., 21,148-51 (1943). L’atat franqais, Brit. Patent 605,973(Aug. 4,1948). Luderman, C. G.(to Texaco Development Corp.), U. 8. Patent 2,428,119(Sept. 30,1947). McCusker, P. A., and Greene, C. E., J. Am. Chem. SOC.,70,
Carter, A. G. (to American Magnesium Metals Corp.), Zbid., 2,470,688(May 17, 1949). CartmeU, R. R., Galloway, J. R., Olsen, R. W., and Smith, J. M., IND.ENG.CEEM.,40,389-92 (1948). Cheney, H. A., Dagley, R., Jr., and McAllister, S. H. (to Shell Development Co.), U. 9. Patent 2,434,394(Jan. 13,
2807-8 (1948).
1948),
MaGregor, R. R.,and Warrick, E. L. (to Corning Glass Works). U.S.Patent 2,452,254(Oct. 26,1948). Mahan, J. E. (to Phillips Petroleum Co.), Zbid., 2,476,500 (July 19, 1949). Miner, C. S.,Jr., Bryan, L. A,, Holysz, R. P., Jr., and Pedlow, G. W., Jr., IND. ENG.CHEM.,39, 1368-71 (1947). Morrell, C. E., and Robey, R. F. (to Standard Oil Development Co.), U. s. Patent 2,474,588(Jan. 28,1949). Nazarov, I. N., et al., Bull. a&. sci. U.R.S.S. Classe, sci. chim.,
Christian, R. V., Jr., and Hixon, R. M., J. Am. Chem. SOC., 70,1333-6 (1948).
Ciapetta, F. G. (to Atlantic Refining Co.), U. S. Patent 2,434,833 (Jan. 20,1948). Ciapetta, F. G., and Kilpatrick, M., J. Am. Chem. SOC., 70,639-46 (1948).
Cogan, H. D., and Setterstrom, C. A,, IND.ENQ.CHEM., 39,1364-8 (1947). Corning Glass Works, Brit. Patent 603,076 (June 9,1948). Zbid,, 611,700(Nov. 2, 1948). Cross, C. A. (to Imperial Chemical Industries, Led.), U. S. Patent 2,438,694(March 30, 1948). Daudt, W. H. (to Corning Glass Works), Zbid., 2,451,664 (Oct. 19,1948). Dow Chemical Co., Brit. Patent 618,459 (Feb. 22,1949). Draeger, A. A. (to Standard Oil Development Co.), U. S. Patent 2,456,260(Dec. 14,1948). Edelson, D. E., and Gray, H.F., Jr. (to Shell Development Co.), Ibid., 2,467,105(April 12,1949). Eitleman, M. A. (to Allied Chemical and Dye Corp.), Zbid., 2,428,450(Oct. 7, 1947). Elliot, J. R., and Krieble, R. H. (to General Electric Co.), Ibid., 2,457,539(Dec. 28,1948). Emery Industries, Inc., Brit. Patent 594,141 (Nov. 4,1947). Fidler, F. A., Dean, R. A., and Anglo-Iranian Oil Co., Ltd., Ibid., 594,983 (Nov. 24, 1947). Fischer, H., Angew. Chem., A60,334(1948). Forbes, G. S.. and Anderson, H. H., J . Am. Chem. SOC.,70, 1222-3 (1948). Freidlin, L. Kh., Balandin, A. A., Lebedeva, A. I., and Fridman. G. A.. Zmest. akad. Nauk S.S.S.R. Otdel. Khim. Nauk, 1946,439-4’6. Frey, F. E. (to Phillips Petroleum Co,), U. S. Patent 2,457,882 (Jan. 4, 1949). Ibid., 2,484,702(Oct. 11, 1949). Galat, A., J. Am. Chem. SOC.,70,3945 (1948). Goguadze, V. P., and Rukhadze, I. S., Bull. Acad. Sci. Geor&n S.S.R., 7,345-51 (1946). Gresham, T. L.. et al. (to B. F. Goodrich Co.), U. S. Patents 2,449,987, 2,449,988, 2,449,989, 2,449,990, 2,449,991, 2,449,992, 2,449,993, 2,449,996(Sept. 28, 1948). Gresham, W. F., and Grigsby, W. E. (to E. I. du Pone de Nemours & Co.), Zbid.,2,457,660(Dec. 28,1948). Hackford, J. E., Shaw, C., and Smith, W. E., Brit. Patent 591,149 (Aug. 8, 1947). Hamblet, C. H., and McAlevy, A. (to E. I. du Pont de Nemours & Co.), Zbid., 590,571 (July 22, 1947). Hatch, L. F., and Evans, T. W. (to Shell Development Co.), U. S. Patent 2,434,110(Jan. 6,1948).
1946,529-40;1947,51-62,205-12,277-87,353-61,647-55.
Nazarov, I. N., et al., Zzvest. Akad. Nauk S.S.S.R. Otdel. Khim. Nauk, 1949,No. 1, 184-9,293-8. Nazarov, I. N., el al., Zhur. Obshchel Khim. ( J . Gen. Chem., U.S.S.R.), 18,665-74,675-80,681-5,896-902.911-16,13327 (1948). Ibid., 18,1077-82,1083-9(1948). Nekrasov, A. S., and Nagatkina, A. A., Bull. a&. sci. U.R.S.S. Classes&. tech., 1947,803-4. Patat, F., Monatsh., 77,352-75 (1947). Pesez, M.. Ann. pharm. franc., 5, 165-7 (1947). Zbid., 5,167-70(1947).
Pines, H., and Ipatieff, V. N. (to Universal Oil Products Co.), U. 9. Patent 2,465,475(March 29,1949). Price, F. P., J. Am. Chem. SOC.,69,2600-4(1947). Revertex, Ltd., and Campbell, A. H., Brit. Patent 609,324 (Sept. 29, 1948). Reynolds, P. W., Grudgings, D. M., and Imperial Chemical Industries, Ltd., Zbid., 622,937(May 10,1949). Robinson, 5. P. (to Phillipa Petroleum Corp.), U. S. Patent 2,486,980(Nov. 1, 1949). Romage, A. S. (to Maxwell, A. A. F.), Zbid., 2,472,618(June 7, 1949).
Rosnati, L.,Uazz. chim. ital., 78,516-28 (1948). ROSS,W. C. J., J. C h . SOC., 1949,183-91. Rust, J. B., and MacKenzie, C. A. (to Montclair Research Corp.), U. S. Patent 2,426,121(Aug. 19,1947). Salmi, E. J., and Leimu, R., Suomen Xemestilehti, 20B, 43-8 (1947).
Schneider, H. G.,and Mistretta, V. F. (to Standard Oil Development Co.), U. s. Patent 2,473,224(June 14,1949). Schwartz, F., Swed. Patent 118,286(March 11, 1947). Shaw, C., Brit. Patent 574,548(Jan. 10,1946). Shaw, C., Smith, W. E., and Emblem, H. G., Zbid., 606,301 (Aug. 11,1948). Sherwood, P. W., Petroleum Rejiner, 28,NO.7,120-4 (1949). Smith, A. E., and Beech, 0. A. (to Shell Development Co.). U. 5. Patent 2,474,440(June 28, 1949). Soci6t6 belge de l’azote et des products chimiques du Marly, French Patent 861,835(Feb. 18, 1941). Speicer, J. L., J. Am. Chem. SOC.,71,273-4 (1949). Sugino, K., Aiya, Y., and Ariga, K., J. SOC.Chem. Znd. Japan,
Heath, R. L., and Imperial Chemical Industries, Ltd., Brit. Patent 610,135 (Oct. 12,1948). Heilbron, I. M., and Jones, E. R. H., Zbid., 611,072 (Oct. 25, 1948).
Hellstrom, H., Svensk. Kem. Tid., 60, 223-7 (1948). Hunt, M., U. S. Patent 2,460,291(Feb. 1, 1949). Hunter, W., Brit. Patent 606,608(Aug. 17,1948). Hyde, J. F. (to Corning Glass Works), U. S. Patent 2,449,940 (Sept. 21, 1948). Ibid., 2,456,783(Dec. 21, 1948). Zbid., 2,458,944(Jan. 11, 1949). Zbid., 2,460,457(Feb. 1, 1949). Zbid,, 2,462,640(Feb. 22, 1949).
Jones, D. G., and Imperial Chemical Industries, Ltd., Brit. Patent 603,422 (June 15,1948). Katuno, M., J . SOC.C h a . Znd. Japan, 44,903-7 (1941). Klebanskii, A. L.,and Titov, V. D., J . Applied Chem. (US.S.R.), 20,1005-12 (1947).
Kool, C. hl. H., vanwesten, H. A., and Hartstra, L. (to N.V.W.A. Scholten’s Chemische Fabrieken), Dutch Patent 60,860(March 15,1948). Kortschak, H. P., and Payne, J. H., J. Am. Chem. Soc., 70, 3139-40 (1948).
Kratzl. I(.. M a a t s h . . 78.173-4 (1948). . . Zbid., pp. 392405. Kratzl. K., and Khautz, I., Ibid.. 78,376-91,406-10 (1948). Kreps, S. I., and Nachod, F. C. (to Atlantic Refining Co.), U. S. Patent 2,477,380(July 26, 1949). I
.
Vol. 42, No. 9
46,573-6 (1943).
Swain, C. G., Esteve, R. M., Jr., and Jones, R. H., J. Am. Chem. SOC.,71,965-71(1949).
Tapp, W. J., IND. ENQ.CHEM.,40,1619-23 (1940). Treibz, A., Angew. Chem., A60,289-97 (1948). (118) Usines de Melle, Brit. Patent 614,165(Dec. 10, 1948). (119) Uaines de Melle, French Patent 871,565 (April 30. 1942). (120) Vancleave, A. B.,and Mitton, H. E., Can. J . Research, 25B, 1
430-9 (1947). (121) Van deGriendt, G. H., and Peters, L. M. (to Shell Develop ment Co.), U. S. Patent 2,475,364(July 5. 1949). (122) Warrick, E. L. (to Corning Glass Works), Brit. Patent 607,253 (Aug. 27,1948). (123) Winkler, D. L. E., %ab, W. J., and Ballard, 8. A. (to Shell Development Co.), U.S. Patent 2,434,631(Jan. 13,1948). (124) Yur’ev, Yu. K.,Korobitsyna, I. K., and Brige, E. K., Doklady Acad. Naulc S.S.S.R., 62,645-7 (1948). (125) Zimakov, P. V., Zbid., 50,219-22 (1945). RECEIVED June 7, 1950.
