Detergents from Kerosene ALKYL SULFATES A. R. PADGETTI WITH ED. F. DEGERING Purdue University, Lafayette, Ind.
Sodium alkyl sulfates have been prepared from kerosene and have been compared with similar commercial compounds of known structure by means of a foam test and an interfacial tension test. The sodium alkyl sulfates have been prepared from all of the straight-chain dodecanols and similarly tested. The sodium alkyl sulfates have progressively less effect on the interfacial tension values and have lower foam values as the sulfate group is moved from the first to the sixth carbon atom of the chain. The derivatives obtained from kerosene have slightly less effect on the interfacial tension values and have lower foam values than similar compounds with a terminal polar group.
HE ready availability of organic raw material in the form of petroleum has long been a challenge to the synthetic organic chemist. The huge increase in the consumption of gasoline in this country in recent years has resulted in a great waste of some of the other less readily usable fractions of petroleum. Although processes have been developed rapidly to convert the lighter and heavier fractions to products boiling in the gasoline range, the increased cost of gasoline manufacture from these fractions makes them less desirable to the industry than fractions already boiling in the desired range; for this reason synthetic organic chemistry has been concerned more with the conversion of lighter and heavier fractions to other commercially valuable products than with the conversion of the gasoline fraction. For a number of years research has been in progress a t Purdue University upon the utilization of natural gas as a raw material in the chemical industry (20-24). More recently attention has been focused upon the heavier fractions, such as kerosene, which have a limited commercial value as such. The preparation and utilization of the chlorination products of kerosene appeared to offer possibilities, since it seemed probable that chlorination might be carried out to yield high proportions of desired chlorides by the application of postulates developed in chlorination work a t Purdue upon lower hydrocarbon fractions (21-23). The preparation of detergents was undertaken as a possible outlet for the chlorination products. Since it is the general consensus that the anion-active detergents are more satisfactory than the cation-active, the sodium alkyl sulfates were first investigated and are considered in this report (6, 16, 18, 19). I n a later paper the detergent amines will be discussed as examples of the cation-active type. The discovery of the value of the metallic alkyl sulfates as detergents was made almost simultaneously by Bertsch of H. Th. Bohme A.-G. ( 2 , 28) and Schrauth of Deutsche Hydrierwerke A,-G. (37), and both must receive credit for the development of relatively inexpensive methods of production. The chief source of information concerning the metallic alkyl sulfates is the patent literature, although a number of excellent general reviews of their preparation, properties, and
uses are available (7, 13, 28, 30, 36). The essence of the patents is that alcohols, made chiefly by reduction of esters of fatty acids, are sulfated with chlorosulfonic acid, fuming sulfuric acid, or sulfur trioxide, and the products are neutralized with caustic. The early patents dealt almost exclusively with the sulfation of primary alcohols, but more recently a number of patents have been issued upon the sulfation of secondary (8, 11, 17, 26, 27) and tertiary (25) alcohols. The sulfation procedure in the two latter cases is somewhat vague. A process for obtaining good yields of sodium alkyl sulfates from primary alcohols does not necessarily give correspondingly good yields from secondary and tertiary alcohols.
T
1 Preaent
Chlorination of Kerosene The alcohols most commonly used for the preparation of the metallic alkyl sulfates have been prepared in the past by the reduction of fatty acids or their esters. This procedure yielded primary alcohols. Chlorination of hydrocarbons, the procedure contemplated as a starting point in the preparation of detergents from kerosene, yields a large quantity of secondary and tertiary chlorides as well as primary chlorides. Hydrolysis of the secondary and tertiary chlorides does not yield the alcohols heretofore considered most desirable (15) ; and for the preparation of detergent amines and sodium alkyl sulfates from chlorides from kerosene, it was thus considered preferable to have as large a proportion as possible of the primary monochlorides. It is evident from the experiments of Hass and co-workers (21-23) that, in order to get the best yields of primary monochlorides, liquid-phase chlorination a t as high a temperature as possible without decomposition of the products is desirable. The hydrocarbon should be in considerable excess in the reaction zone. Bielouss and Gardner (3, 17) showed that over 90 per cent of the chlorine which they substituted into petroleum boiling over 200" C. was removed as hydrogen chloride, either with or without the aid of a catalyst, upon heating a t 190-230" C. for several hours; and Mabery (31) chlorinated a t 70" C. with little apparent decomposition. Therefore it appeared that a reaction temperature near 100' C. would be suitable.
address, Humble Oil and Refining Company, Baytown, Texas.
204
INDUSTRIAL A N D ENGINEERING CHEMISTRY
FEBRUARY, 1940
205
,--
The kerosene utilized was obtained from the Standard Oil Company (Indiana) and was recommended as high in normal paraffin hydrocarbon content. A true boiling distillation curve is shown in Figure 1. The wide boiling range of kerosene makes chlorination impractical without some modification because of the difficulty of separating the chlorinated products from the unchlorinated portion. The noticeable flattening of the true boiling point distillation curve in the regions where the successive normal paraffin hydrocarbons would be expected to boil suggests the possibility of separating narrow-boiling distillates which would contain relatively
:-I1476
I
8 1.460 1 cl
1.450 /
I
' t
!!
\-
i
PER CENT OF CHLOWDES
XTILLID
FIGURE 2
10 PO PER
30
iwr
40 i l 60 OF KEROSEYE
introduced below the surface of the kerosene a t a relatively slow rate for a half hour until the induction period was over, then faster for an hour. The rate was SO regulated that one fourth to one third of the kerosene was chlorinated. Air was then bloivn through the solution for about 15 minutes in order to remove most of the hydrogen chloride. The product was fractionated and the fraction boiling a t 120-135" C. (1 5 mm.) was collected as monochlorides. The yield was 80-90 per cent of the chlorinated kerosene. Figure 2 shows distillation and refractive index curves for the product.
70 50 90 DISTLLEC
FIGURE1
large amounts of each of these compounds. That these would not be pure is apparent when the possibility of the presence of isomeric paraffins and of naphthenes, aromatics, and nitrogen and sulfur compounds is considered (4, 14). A 5" C. boiling range was finally selected as sufficiently narrow to allow adequate separation of the chlorides by fractional distillation. The distillation was performed in a batch column [1.5 inches (3.8 cm.) in diameter and 5 feet (1.52 meters) long] filled with glass helices and operated a t the rate of about 2 ml. of distillate per minute with a reflux ratio of 15 to 1. Three complete. fractionations were made a t 15 mm. pressure. All compounds tested were prepared from the 95-100" C. fraction because this corresponds in boiling range to dodecane, from which all of the known compounds which were later prepared and tested for comparative purposes may be considered as derived. The chlorination procedure was essentially that of Pelouze and Cahours (32) and of hlabery (Sf),except that no purification of the kerosene other than fractionation was attempted. The kerosene (95-100" C. a t 15 mm.) mas placed in a flask immersed in a boiling water bath. Chlorine was
OF CHLORIDES
.u
B. p..
Sp. gr.
c.
2 14-2 16 0.768-0.78520
Monoohlorides B. p. C. 230-5O Sp. gr. 0.891920 Analysis Carbon, % 69.93 Hydrogen, yo 11.81 Chlorine, yo 17.93 Mol. wt., grama 200 a From Pennsylvania petroleum.
242-53b 0.896020 70.79 11.46 18.20
....
b
196-200 0.77820
214-221 0.779-0.78327
... ...
242-245
246-259 0.877-0.89627
:1:
... ... ...
... ...
........ ........
........ ........
From Canadian petroleum.
q F IT'DROLY5'S
LXTR4CT OISTILLLD
FIGURE3
Pelouze and Theoretical Cahours This Research for C12Hd21
Mabery
95
PER CENT
TABLE I . PHYSICAL CONSTANTS AND ANALYSIS OF MONOCHLORIDES FROM KEROSENE Kerosene
bLCCHOL5 PRODXLD BY HYDROLYSIS OF CHLORIDES
125
70.42 12.23 17.36 204
The identity of the monochlorides was established by comparison with the monochlorides of Mabery (Sf) and of Pelouze and Cahours (32). Their constants, the constants of the product obtained in this laboratory, and the analysis of Mabery, which agrees rather closely with that of Pelouze and Cahours, are shown in Table I. All boiling points were calculated to 760 mm.
Alcohols from Chlorides from Kerosene Hydrolysis of the chlorides to the alcohols was carried out by a procedure similar to that used by the Sharples Solvents Corporation in the preparation of pentanols from the chlorides (1,9, 38). Oleic acid was dissolved in a mixture of
206
INDUSTRIAL AND ENGINEERIKG CHEMISTRY
VOL. 32, NO. 2
acid sulfates were then neutralized with sodium bicarbonate. The yield was approximately 55 per cent of the theoretical. I90
Preparation of n-Dodecanols In order to furnish a basis for interpreting interfacial tension and foam tests, all of the straight-chain dodecanols were obtained and converted to the corresponding sodium alkyl sulfates. 1-Dodecanol was purchased from the Eastman Kodak Company. The 2-, 3-, 4-, 5-, and 6-dodecanols were prepared in this laboratory from the appropriate aldehyde and alkyl halide by the Grignard reaction.
I80 170
r'
160
0
3
3 150
TABLE11. PREPARATION OF DODECANOLS Boiling Range Cf Product
G
0
k y
Compound Prepared 2-Dodecanol 2-Dodecanol 3-Dodecanol 4-Dodecanol 5-Dodecanol 6-Dodecanol
140 130
Aldehyde Used Acetddeh d e Undecanar Decanal Nonanal Octanal Heptanal
Halide L-sed Decyl bromide Methyl iodide Ethvliodide Propyl iodide Butyl iodide Amyl chloride
O
C. (9 MI&.,
Yield,, %
121-125 126-127.5 119-123 116-120 11'3121 120-122
93.3 43 5 49.4 63.8 65.3
'
83:O
I20 110
2
4
6 8 MINUTES
10
12
14
FIGURE 4
The 2-, 3-, and 6-dodecanols had been prepared before (6, 33, 8.4, but no mention was found in the literature of 4and 5-dodecanols. The method of Pickard and Kenyon (33) for the preparation of 3-dodecanol by the Grignard reaction was used for all of the secondary alcohols because it seemed the most suitable of those available. The more detailed directions for the preparation of methylisopropylcarbinol ( l a ) are easily adapted to the higher alcohols by substituting the appropriate halide and aldehyde. All reagents mere fractionated in a modified Podbielniak column, and only the portion distilling within a 2" range was used. The product in each case was also fractionated in a modified Podbielniak column, and the portion of the product distilling within a 2" range was refractionated. That part which showed a constant refractive index was then taken as the pure dodecanol. Refractive index was measured with an Abbe refractometer. Tables I1 and I11 give a resume of the preparation and some of the constants of these alcohols. All of the fractionation curves show a flat portion corresponding in every case to the alcohol which would be obtained by reduction of the aldehyde used. In the 6- and 5-dodecanols this impurity is not serious. I n the 4- and 3-dodecanols (when the long-chain aldehydes are used) this impurity cuts down the yield enormously, besides making the separation of a pure product difficult. The 2-dodecanol (Table 111) cannot be obtained pure from undecanal because 1-undecanol boils a t about the same temperature. It was necessary in this case to use the long-chain halide to obtain the pure product. This procedure is recommended when a choice is to be made,
eodium hydroxide, water, and n-amyl alcohol. This contained slightly in excess of one mole of sodium oleate and one mole of sodium hydroxide per estimated mole of chlorides of kerosene. The chlorides from kerosene were stirred into this paste, and the mixture was heated slowly in a steel autoclave to 160-170" C. under 130-150 pounds per square inch (9.1-10.5 kg. per sq. cm.) pressure. These conditions were maintained for 9 hours, after which the autoclave was allowed to cool overnight. A large amount of salt was found to have crystallized. The remaining material was a jellylike mass, Since steam was found impractical for the separation of the alcohol from this mixture, the amyl alcohol was distilled off as long as water was still present, and the remaining alcohols were then extracted from the soap by means of acetone in which the soap was only slightly soluble. These alcohols were fractionated in a modified Podbielniak column, and the portion distilling a t 125-140" C. (15 mm.) was collected as the desired alcohols. The yield was only 30 per cent, since a large part of the chlorides formed unsaturates. A typical distillation curve is shown in Figure 3. The flat portion a t 50-55' C. represents amyl alcohol, and that at 95-100" C. unsaturates. Attempts to use acetone instead of amyl alcohol as a part of the reaction paste proved unsucCONSTAXTS OF DODECANOLS TABLE111. PHYSICAL cessful. Smaller amounts than the molecular Boiling Refractive Index Point, Freezing Point. amounts of sodium oleate apparently led to in(25' C.) C. (9 Mm.) C. This This This complete hydrolysis, since the products were less re- Litera- re- Litera- reSp. Gr., viscous than the earlier product, and the reaction Compound Literature search ture eearch ture search Literature with chlorosulfonic acid left almost half of the 1-Dodecanol 1.4415 1.4424 133 133 23.6 24 0.8312(25° c.) alcohol fraction unreacted. 18-18 . . .. 125 5 129
c.
Sodium Alkyl Sulfates from Kerosene The alcohols from kerosene were converted to the alkyl acid sulfates by treatment with chlorosulfonic acid according to a method described in detail in a later portion of this paper. The alkyl
...
d-2-Dodecanol dl-3-Dodecanol 2-3-Dodecanol dl-4-Dodecanol dl-5-Dodecanol dl-6-Dodecanol
1.4421
..,. .... .... .... ....
127
. ..
123 124 119
123
1.4390 1,4388 ... 1.4386 119
120 121 120
1.4402
..
...
...
...
25
- 10 ,.. ... .. .
30
29
18.7 12
.... ..
... ...
o.s369(;11:)
0.82ii(d3:)
.... .... ....
FEBRUARY, 1940
INDUSTRIAL AND ENGIKEERING CHEMISTRY
since a more easily purified product is obtained by the use of the lower molecular weight aldehyde and higher halide. The dl-2-dodecanol of Pickard and Kenyon (34) was obviously impure, and probably contained some of the ketone from which it was made. The dl-2-dodecanol prepared in this laboratory compares favorably with the carefully purified d-2-dodecanol of Pickard and Kenyon. The same criticism may be applied to the melting point of the dl-3-dodecanol as compared with that of the I-3-dodecanol alone, although the product of this laboratory was not obtained pure enough to give the melting point reported by them
Preparation of Sodium Alkyl Sulfates Sodium lauryl sulfate was prepared by the procedure mentioned in the patents of Bertsch (9). Lauryl alcohol, dissolved in absolute ethyl ether, was treated with chlorosulfonic acid a t 30-40" C. Some air was bubbled through the solution to remove most of the hydrogen chloride, and the mixture mas neutralized with an excess of anhydrous sodium carbonate. The product mas filtered, washed once with ether, and dried, and the sodium lauryl sulfate was extracted with absolute alcohol. The yield was 84 per cent. The same procedure did not yield the corresponding product with 6-dodecanol. Refluxing the ether, the use of isopropyl ether, chloroform, or carbon tetrachloride as solvent, and the preparation of the sulfate by adding the alcohol to an ether solution of the chlorosulfonic acid, all gave equally poor results. The preparation of the sodium alcoholate and treatment with chlorosulfonic acid finally yielded a product that was water-soluble, but the experiment could not be duplicated with the alcohols from kerosene. It was then discovered that if the ether solution were neutralized immediately after the reaction by the introduction of an excess of aqueous sodium carbonate before an
207
attempt was made to distill off the ether or neutralize the sulfate with solid sodium carbonate, the product was completely soluble in water, and the solution had the properties of a solution of sodium alkyl sulfate. The sodium sec-dodecyl sulfates were not isolated as such in the procedure as finally adopted, since foam tests and drop number determinations are only qualitative a t best, but all of the solutions to be tested were prepared in exactly the same manner. Comparative evaluation was thus obtained. The procedure finally adopted was as follows: a 3.5-gram portion of chlorosulfonic acid (2.0 ml., 0.03 mole) dissolved in 50 ml. of anhydrous ethyl ether is placed in a 500-ml. threeneck flask equipped with a stirrer, a dropping funnel, and a reflux condenser. A 4.15-gram portion (5.0 ml., 0.022 mole) of the desired dodecanol in 10 ml. of anhydrous ether is introduced from the dropping funnel a t such a rate that the ether refluxes gently. Seven grams (0.083 mole) of sodium bicarbonate in 70 ml. of water are added a t such a rate that the refluxing does not become too vigorous. The two layers are allowed t o separate, and the ether is distilled from the upper layer. Any residue is dissolved in the loller layer, which is then heated on the steam bath for about 5 minutes to expel most of the ether still present. The solution is then made just acid to methyl orange with 2.0 N sulfuric acid, then just basic to phenolphthalein with 2.0 N sodium hydroxide solution. This yields a slightly basic solution of the sodium alkyl sulfate containing certain amounts of sodium sulfate, sodium chloride, and sodium carbonate. Any unreacted alcohol is found in the ether layer and can be separated a t the time of evaporation of the ether layer to dryness. Five-milliliter portions of 1-, 2-, 3-, 4-,5-, and 6-dodecanols and the alcohols of kerosene yielded 0, 0, 0.3, 0.5, 0, 0, and 2.3 ml. of insoluble residue, respectively, when treated by this method. When 10-ml. portions of 1-, 2-, 3-, 4-, 5-, and 6-dodecanols were used with twice the amount of chlorosulfonic acid, but the ether was evaporated before neutralization n-ith sodium bicarbonate solution, the insoluble residues were 0, 7.6, 7.1, 8.7, 8.4, and 8.7 ml., respectively
Comparative Tests 8.20
A washing test is unquestionably the best and probably the x SODIUM 5-DODECYL SULFATE Q SODIUM 4- DODECYL SULFATE v SODIUM 3-DODECYL SULFATE 6 SODIUM 2- DODECYL SULFATE
a
I
60
I
I
I
100
140
180
RATE OF FLOW, SECONDS
FIGURE 5
I
220
PER
I
1
260
300
50 DROPS
only satisfactory method of evaluating detergents, but the cost of satisfactory equipment for such a test is very high (29, 35). Tests finally adopted to replace the washing test, are adaptations of the foam test and the interfacial tension or drop number test. No attempt is made to correlate these vvitfi a washing test. It is possible, since the compounds tested are all of the same chemical class, that the tests used are true measures of the relative detergent value of the compounds, but this is not claimed a t present. The sodium alkyl sulfates from kerosene were compared with the alcohol extract from a commercial detergent known to contain sodium alkyl sulfates, arid with the sodium alkyl sulfates prepared from the severnl dodecanol3 by means of these tests. The foam test !vas carried out in a manner worked out more or less arbitrarily in this laboratory (IO). d tube 93 inchei, long and 3.6 inches inside diameter (236.2 and 9.14 em.) was equipped a t one end with a sintered glass plate which caused compressed air forced through it to form small bubbles in the liquid above. Two hundred milliliters of a 0.2 per cent solu-. tion by weight of the detergent to be tested mas placed in this tube, and foam was produced a t such a rate by means of' compressed air that the tube filled in 5 to 6 minutes. When the tube was full, the air was turned off and the height of the liquid level in mm. was read each minute for 15 minutes. The results were plotted with the liquid level as the ordinate and time as the abscissa in each case. I n all comparative
208
INDUSTRIAL AND ENGINEERING CHEMISTRY
tests the solutions were allowed to stand the same length of time before the tests were made. Sodium lauryl sulfate and the alcohol extract from “Dreft”, a commercial product, were chosen as standards. The curve for each appears in Figure 4. In every case the curve is the average of two or more determinations. These solutions, with the exception of the alcohol extract from “Dreft”, contain some salts, and they were prepared to contain 0.2 per cent of the detergent by a suitable dilution of the solutions originally prepared. For example, the solution containing sodium 5-dodecyl sulfate was diluted to 250 ml., and 38.9 ml. of this solution were diluted to 500 ml. to yield a solution of the desired concentration. The interfacial tension test, as finally adopted, measured the number of milliliters of a 0.2 per cent solution by weight of the desired detergent per 50 drops of solution when the solution was allowed to drop from a buret, the tip of which was immersed in benzene. The rate of dropping was varied, and the number of milliliters per 50 drops was plotted against the rate of dropping. Figure 5 shows the comparison. Pure water is included in this figure.
Summary and Conclusions 1. Kerosene boiling a t 95-100” C. (15 mm.) was chlorinated to yield 80-90 per cent of the monochlorides. The chlorides were changed to alcohols with a yield of about 30 per cent, the remainder of the chlorides forming unsaturates. The alcohols were converted to the corresponding sodium alkyl sulfates. 2. The 2-, 3-, 4-, 5-, and 6-dodecanols were prepared (the 4- and 5-dodecanols probably for the first time), and the corresponding sodium alkyl sulfates were obtained from them. Sodium lauryl sulfate was prepared from I-dodecanol. 3. The sodium alkyl sulfates were compared by means of a foam test and an interfacial tension test. The tests indicate that the foam value and the ability to lower the interfacial tension for a given chain decreases progressively from a maximum for the primary to a minimum for a symmetrical secondary sodium alkyl sulfate. 4. The sodium alkyl sulfates obtained from kerosene appear inferior to similar compounds with a terminal polar group when measured by these tests.
Acknowledgment This research was sponsored by The Mathieson Alkali Works, Inc., under the general supervision of H. B. Hass.
Literature Cited (1) Ayres, E. E., Jr., U. S. Patent 1,869,928 (Aug. 2, 1932); Canadian Patent 278,537 (March 13, 1928). (2) Bertsch, Heinrich (to American Hyalsol Corp.), U. 9. Patents 1,968,793-7 (July 31, 1934); Canadian Patent 356,113 (Feb. 25, 1936). (3) Bielouss, E., U. S. Patent 1,384,423 (July 12, 1921).
VOL. 32, NO. 2
(4) Blair. C. M., and Henze, H. R., J . Am. Chem. SOC.,54, 1098 (1932). (5) Bouveault, L., and Locquinn, RenQ, Compt. rend., 140, 1700 (1905); Bull. soc. chim., [3] 35, 644, 648 (1907). (6) Boxser, H., Melliand Teztile M o n t h l y , 4, 380-4 ( (1932). (7) Briscoe, M., Dyer, Jan. 22, 1932, 83; Chem. Trade J., 90, 76 (1932); I n d . Chemist, 8, 67 (1932). (8) Carbide and Carbon Chemicals Corp., British Patents 446,084 (April 23, 1936), 456,214 (Nov. 4, 1936); French Patenta 782.835 (June 12, 1935), 786,734 (Sept. 9, 1935), 789,406 (Oct. 29, 1935), 799,037 (May 30, 1936). (9) Clark, L. H., IND.ENG.CHEM.,22, 439-43 (1930). (10) Degering, E . F., Ibid., 24, 181 (1932). (11) Deutsche Hydrierwerke A.-G., German Patent 535,853 (March 28, 1929). (12) Drake, N. L., and Cooke, G. B., OW. Syntheses, 12, 48 (1932). (13) Duncan, R. A., IXD.ENG.CHEM.,26, 24 (1934). (14) Eliis, Carleton, “Chemistry of Petroleum Derivatives”, pp. 33-5 (1934). (15) Ibid., pp. 711-43. (16) Evans, J. G., J . SOC.Dyers Colourists, 51, 233-40 (1935). (17) Gardner, H. A., and Bielouss, E., U. S.Patent 1,384,447 (July 12, 1921); J . ISD.ENG.CHEM.,14, 619 (1922). (18) Gotte, E., Kolloid-Z., 64, 327-31, 331-5 (1933). (19) Gotte, E., and Kling, W., Ibid., 64, 222-7 (1933). (20) Hass, H. B., Hodge, E. B., and Vanderbilt, B. M., IND.ENQ. CHEM.,28, 339-44 (1936). (21) Hass. H. B., McBee, E . T., and Hatch, L. F., Ibid., 29, 1335-8 (1937). (22) Hass, H. B., McBee, E. T., Hinds, G. E., and Gluesenkamp, E. W., Ibid., 28, 1178 (1936). (23) Hass, H. B., McBee, E. T., and Weber, P., Ibid., 27, 1190-5 (1935); 28, 333-9 (1936). (24) Hass, H. B., and Marshall, J. R., Ibid., 23, 352-3 (1931). (25) Henkel & Cie., G. m. b. H., British Patent 424,891 (Feb. 26, 1935). Henkel & Cie., G. m. b. H., French Patent 778,373 (March 15, 1935). I. G. Farbenindustrie Akt.-Ges., Ibid., 716,604 (May 6, 1931). 751,652 (Sept. 7, 1933); British Patents 354,992 (July 25, 1930), 392,636 (May 25, 1933), 407,187 (March 15, 1934). Killeffer, D. H., IND.ENQ. CHEM.,25, 138 (1933). Kind, Klepzig’s Teztil-Z., 41, 171 (1938). Lindner, K., Seifensieder-Ztg., 61, 470, 491, 833, 856 (1934); 62, 257-8, 277-8, 299-300 (1935). Mabery, Proc. Am. A m d . Arts Sci., 32, 121-76 (1897); Am. Chem. J . , 19, 419 (1897). Pelouze and Cahows, Compt. rend., 57, 62 (1863), 54, 1241 (1862), 56, 505 (1863); J. pralct. Chem., 88, 314 (1863), 89, 359 (1863), 91, 98 (1864); Ann. chim. phys., [4] 1, 1 (1864). Pickard, R. H., and Kenyon, J . , J . Chem. SOC.,99,55,70 (1911); 101, 627, 638 (1912); 103, 1957 (1913). Ibid., 103, 1934, 1935, 1948, 1954, (1913). Rhodes, F. H., and Brainard, S.W., ISD.ENQ.CHEM..,21, 60-8 (1929). Schrauth, W., chem.-Ztg., 55, 3, 17-18 (1931) ; Seifemieder-Ztg., 58, 61-3 (1931). Schrauth, W. (to Deutsche Hydrierwerke A.-G.), German Patent 542,048 (March 10, 1928) : British Patents 307,709 (March 19. 1928). 355.484 (AuR. . - 3, 1929); French Patent 671,065 (March 8; 1929). Sharples Solvents Corp., private communication to H. B. Hass.
PRESENTED before the Division of Industrial and Engineering Chemistry a t the 97th Meeting of the American Chemical Society, Baltimore, Md. This paper is a portion of an abstract of a thesis submitted t o the faculty of Purdue University by A. R. Padgett in partial fulfillment of the requirements for the degree of doctor of philosophy, June, 1937.
