These conditions should give : free oil-active, wt.%, less than 3.5; salt-active, wt.yo, less than 0.25; and color, R C D , approximately 0.25 for blend A-4 and 0.35 for blend D-4. \\'it11 the blend A-4 and D-4 alcohol ethoxylates, the salt levels are usually very low. T h e colors reported were measured immediately after neutralization. T h e colors usually improve to a colorless or almost colorless solution on standing in the presence of light. E t h e r Sulfate Neutralization. A study was made to determine the relationship between concentrations of active, ethyl alcohol, and water and the viscosity of the slurry. Figure 6 shows the regions of slurry properties with different active and ethyl alcohol concentrations. When neutralizing on a large scale, the proper mixture of caustic: water. and alcohol must be introduced in such a manner that the conditions during processing are ahvays in the fluid region sho\vn in Figure 6 . T h e neutralization temperature must be kept belox 90" F. to minimize alcohol evaporation. Since the neutralized mixture is fluid and does not foam
with agitation. the selection of agitation equipment does not present a problem. A buffer (0.1 \vt.% Na2C03 and 0.1 ~ 1 . t . 7citric ~ acid) is usually added to the neutralized slurry to prevent pH drift to the acid side. literature Cited
(1) Carlson. E. J., Flint, G., Gilbert, E. E.: Nychka. H. R.. Ind. Eng. Chem. 50, 276 (1958). (2) Gilbert, E. E.. Chem. Rev. 62, 549 (1962). ( 3 ) Gilbert. E. E., Veldhuis, B.. J . Am. 021 Chemists' Soc. 36, 208 11960).
(4)' Lobo, P. A , . Vernon, L. N.. .4shton. A . T.. Chem. En?. Progr 58, No. 5, 85 (1962). (5) Lohr, J . \I.., J . Am. OdChemzsts' SOL. 35, 532 (1958). (6) Silvis. S. J.. Ballestra. M.. Ibzd.. 40, 618 (1963). RECEIVED for review September 24. 1964 ACCEPTED January 18. 1965 Division of Industrial and Engineering Chemistry, 148th Meeting; ACS, Chicago. 111.. September 1964.
DETERGENCY AND BIODEGRADABILITY
OF ALCOHOL-BASED sec-SULFATES J .
R . L I V I N G S T O N , J R . ,
R O B E R T D R O G I N , A N D
Chemicals Research Dimion, Esso Research and Engineering
R . J . K E L L Y
eo.,Linden, S . J .
Sodium alkyl sulfates were prepared by the sulfation of linear sec-alcohols.
The sulfates were prepared
from discrete carbon number alcohols and evaluated individually for foaming ability and cotton detergency. The effect of molecular weight on foaming and cotton detergency will b e discussed. At the optimum molecular weight, the sulfates were equivalent to or better than tetrapropyl benzene sulfonate in foaming and cotton detergency, Individual sulfates were also evaluated for wetting power, biodegradability, and hydrolytic stability. The sulfates were as biodegradable and almost as hydrolytically stable as primary fatty sulfates.
see-sulfates as surfactants have been known for many years (8).they have not achieved a significant commercial success, with the exception of Teepol, which has been sold in Europe. This failure has been attributed to the poor quality of starting materials availa'ble. T h e availability of high purity, linear feedstocks and the need for biologically soft surfactants have resulted in a renewed interest in sec-sulfate s. Most of the sec-sulfates made in the past have been prepared by the direct sulfation of a n olefin. Olefins varying in complexity from squalene, a highly unsaturated hydrocarbon occurring in shark liver oil. to 1-hexadecene have been sulfated and their sulfates examined for surface active properties (8). Linear a-olefins. \vhich are now attaining commercial status, have recently been re-examined as intermediates for making rec-sulfates. Sulfates of these olefins are reported to be predominantly the 2-isomer ( 3 ) and are said to be comparable in performance with the now Lvidely used tetrapropylene-based alkylbenzene sulfonate (.4BS) as surfactants (7). T h e authors' interest has been in alkyl sulfates prepared by the sulfation of linear sec-alcohols xvhich have a random distribution of the hydroxyl group along the chain. T h e hydroxyl group is positioned randomly along the chain in the alcohols used in this study. hlthough both the alcohol-based and
A
28
LTHOUGH
l&EC PRODUCT RESEARCH A N D DEVELOPMENT
a-olefin-based compounds are see-sulfates. one might expect that these materials kvould have different performance characteristics, since the literature indicates significant differences in the performance of specific isomers. For instance, Dreger and coworkers ( 4 ) synthesized discrete isomeric see-sulfates and found that the internal isomers, although better foamers and wetting agents, were inferior in cotton detergency to the isomers in which the sulfate group was near the end of the chain. In the work reported here, the effect of molecular \\eight on foaming, cotton detergency. and \vetting po\ver of secsulfates made from random! isomeric linear see-alcohols was determined. Included in this study is a comparison of their foaming power and cotton detergency with those for ABS and for see-sulfates made by the direct sulfation of linear a-olefins, and of the wetting ability for the alcohol-based and olefinbased sec-sulfates Lvith that for a \vetting agent. sodium dioctyl sulfosuccinate? and for .4BS. T h e comparative biodegradability of sec-sulfates. "linear" alkylbenzene sulfonate (LAS): and lauryl alcohol sulfate was also determined. Experimental
Sulfation of sec-Alcohols-General Procedure. Chlorosulfonic acid, 1 mole, was added slowly with stirring to 200 grams of anhydrous ethyl ether maintained at 0' to 5' C.
After addition was complete, 1 mole of sec-alcohol in 400 grams of anhydrous ethyl ether was added to the chlorosulfonic acid-ether complex a t 0" to 5 " C. over a 10-minute period. T h e mixture was stirred and purged with nitrogen for a n additional 35 minutes. b>- which time all of the hydrogen chloride had been removed. 'The mixture was poured onto 507, sodium hydroxide solution (1 mole of N a O H ) and 300 grams of ice. T h e 507, sodium hydroxide solution was added to effect complete neutralization (to p H 10). T h e mixture was diluted \vith 800 ml. of isopropyl alcohol and 500 mi. of water and extracted with t\vo 500-ml. portions of petroleum ether to remove unsulfated oil. T h e alcohol-water layer was stripped of solvents on a short path still and, finally, on a rotary evaporator. T h e residue \vas dried in a vacuum oven at 40' C.? and a sample \vas titrated \vith standard cetyl trimethyl ammonium bromide. Sulfation of Linear a-Olefins. a-Olefin, 1 mole. \vas added to a n equal volume of hexane, and the solution was agitated vigorously and cooled to 0" to 15" C. Concentrated, 96yc. sulfuric acid. 2 moles. was added over a 5-minute period to the olefin-hexane solution maintained at 0' to 15" C. T h e reaction mixture was held at 0 to 5 ' C. for a n additional 5 minutes and then poured onto ice containing sufficient sodium hydroxide to neutralize the entire mixture. Isopropyl alcohol was added to give a 507, alcohol solution. which was heated to 50' C. T w o phases appeared. T h e lower, aqueous layer was dra\vn off and discarded, and sufficient water was added to the upper alcohol layer to make it 507, with respect to alcohol. T h e 507, alcohol solution was extracted twice with pentane, and then isopropyl alcohol added to mak? it 85yG with respect to alcohol. T h e alcohol solution was gently refluxed for one hour and filtered while hot to remove sodium sulfate. T h e deoiled. desalted alcohol solution of sec-sulfate was evaporated, and the residue was carefully dried in a vacuum oven at 40' C. Isomeric Distribution of sec-Octadecyl-Sulfate. T h e random distribution of the alcohol-based sulfates was determined hy a n improvement (2) on a method by Asinger ( 7 ) . secOctadecyl sulfate, 36 grams. was mixed thoroughly with 58 grams of sodium methylate in a 250-ml., round-bottomed flask. T h e reactants \vere fused a t 240' C. under vacuum for 4 hours. and the distillate. 21 grams, was collected. ,4 stream of oxygen containing approximately 37, ozone by \\.eight \vas passed through a solution containing 7.5 grams of the above distillate in 50 ml. of carbon tetrachloride at -10' C.. until no more ozone was consumed. T h e carbon tetrachloride \\-as removed from the ozonide on a rotary evaporator. T h e ozonide was dissolved in 50 ml. of n-pentane. and this solution \vas added drop\vis? into a rapidly stirred suspension of 50 grams of silver oxide in 10 ml. of 10% sodium hydroxide solution maintained at 90' C. T h e mixture was then refluxed foi 6 hours. Approximately 100 ml. of concentrated nitric acid, 707,. was slo\vly added at 60' C.. and the clear solution was stirred for 2 hours a t 60' C. T h e resultant carboxylic acids were extracted with pentane and treated with aqueous potassium hydroxide solution. .4cidification of the basic aqueous layer u i t h concentrated hydrochloric acid-follo\t.ed by pentane extraction and subsequent evaporation-gave 4.2 grams of carboxylic acids. T h e acids were converted to the methyl esters and analyzed by gas chromatography on a 5-foot. 207,. 20M-carbo\vax column. Table I summarizes the data. T h e isomeric distribution of sulfate group on the octadecyl chain was calculated in the usual manner from the distribution of acid carbon numbers. This shelved that the original alcohol used to prepare the sulfate had a random distribution of hydroxyl group along the chain.
Table I.
Gas Chromatographic Determination of Methyl Esters of Oxidized Desulfate Hydroxyl Group Carbon .Vo
Acid Carbon h,
Mole
15 13 14 14 12 10
10 11 12 13 14 15 16 17 18"
5 6
7 6 8 2 0 8 0 6 3 5 0
a Determined by gas chromatography followed by time-oj-Jight mass spectrometry.
Discussion
Foaming Ability. T h e foaming ability of the sec-sulfates was determined in a manual dishwashing test. In this test, conventional dinner plates are soiled with molten Crisco. allowed to age for one hour, and then washed in a detergent bath at 120 ' F. T h e concentration of unformulated surfactant used in this study was 0.03 Ivt. yc. T h e point at lvhich onl>50yc of the surface of the wash liquid remains covered \vith foam is defined as the end point. T h e results are reported in terms of the number of dishes \vashed. Foaming ability is directly proportional to the number of dishes Lvashed. T h e results of our comparisons are summarized in Figure 1. T h e optimum range of carbon numbers for foaming ability of both the alcohol and a-olefin based sec-sulfates is 15 to 17. T h e foaming ability in the optimum range of both types of sulfates is esscntially identical in soft and hard \cater. Differences in foaming ability of the tivo types of sulfates appear a t both ends of the molecular weight range. In soft water. the (214 olefin-based sulfate is superior to the C I 4alcoholbased sulfate. However. at the CIS level. the alcohol-based sulfate seems to have the advantage over the olefin-based sulfate. As the response of the sulfates to formulation has not been measured. it is not known whether they are equivalent to ABS and LAS in foaming ability. T h e results of this preliminarv
WATER HARDNESS 35 P P ~
25
I
l
l
1
WATER HARONESS 255 ppm I
25
20
20
15
15
10
10
0 Y 8
W
E 0 LL
m
5
1
LEGEND ALCOHOL BASED SEC-SULFATES
5
a-OLEFIN-EASE SEC-SULFATES
I2
14
16
18
LEGEND ALCOHOL BASED =-SULFATES
5
0-OLEFIN-BASED SEC-SULFATES
1
I
I
1
12
14
16
18
AVERAGE CARBON NUMBER
Figure 1.
Foaming ability of sec-alkylsulfates
Manual dishwashing, 120'
VOL. 4
F., Unformulated, 0.03 wt.% NO. 1
MARCH
1965
29
Alcohol- and olefin-based sec-alkyl sulfates, ABS, and LAS were compared in this study. ABS )vas included in each set of comparisons to serve as an internal standard and as a base of reference. Changes in LR level of standard. from run to run, are not unusual in this test. These changes are attributed principally to the difference in the lots of soiled cloth used. T h e results of the cotton detergency comparisons on discrete carbon number sulfates based on sec-alcohols are summarized in Table 11. Alcohol-based sec-sulfates in the molecular weight range of C16to CI8 are optimum for cotton laundering application. In this range the sec-sulfates are equivalent to or better than ABS in performance. T h e lower molecular Lveight (C13 to Clj) are inferior to ABS. ABS and the alcohol-based
work are encouraging, however, and give incentive to d o formulation work, since in the CIS to Cli range, the unforrnulated sulfates are equivalent to, or outperform. ABS and L.4S as foamers. Cotton Laundering. Cotton laundering comparisons were made with a Terg-0-Tometer a t 120' and 140" F. using Vnited States Testing Co. soiled cloth and 0.2 weight 76 heavy duty formulated detergent. Eight swatches were washed in each test. T h e angle of rotation for the agitator was 350', and the rate of agitation was set a t 100 cycles per minute. T h e cleaning ability of the detergent is reported in terms of lR, the difference in per cent reflectance between the washed cloth and the original soiled cloth. T h e greater the increase in per cent reflectance, the more efficient is the cleaning agent.
Table II.
Comparison of Cotton Detergency of Alcohol-Based rec-Alkyl Sulfatesa
Expressed as Increase in Per Cent Reflectance ( A R ) *
Temp..l2OoF.(49"C.) Temp.,140"F.(6O0C.)
Surfactantc ABS C I Sulfate ~ Water Hardness, P . P . M . 35 255 35 255 35 255 35 255 5 . 1 0 5 . 0 0 6 . 7 5 6 . 0 0 6 . 7 5 6 . 1 5 4 75 2 . 7 0 5.75 4.50 7.00 6.00 6.40 5.45 4.75 2.80
CIS Sulfate
C i 3 Sulfate
35 255 3.80 2.75 3.05 2.35
LSD 95Cod
C I Sulfate ~
C I Sulfate ~
35 255 6 . 1 0 4.50 7 . 1 5 4.95
0.48
CISSulfate 35 6.20 6.90
ABS
255 4.45 5.00
35 255 6.25 4.60 5.50 3.65
0.90
0 Terg-0-Tometer Test. c '.S. Testing Co. cloth at 0.2 zet. 5 detergent. Rate of agitation-700 cyclesper minute, an angle of 350" rotation. Value Surfactants formulated reported is the mean of two replicates. Eight replicate swatches (4l/4 X 4 inches) rcere rcashed in each of the t w o replicate tests. in a heacy duty formulation containing 20% actice, 3 4 5 sodium sulfate, 40% sodium tripolyphosphate, 57, sodium metasilicate: and 7 7, carboxymethyl
cellulose,
d
Least signi3cant difference at the 95% confidence level calculated f r o m LSD
Table 111.
=
(.\/2)(t)(s)
4
Comparison of Cotton Detergency of Olefin-Based rec-Alkyl Sulfates with Alkyl Benzene Sulfonatesa
Expressed as Increase in Per Cent Reflectance ( A i ? ) * SurfactantC
CISSulfate
Sulfate
LAS
ABS
W a t e r Hardness. P.P.M.
Temp., 1 2 0 ' F . (49" C . ) Temp.. 1 4 0 ° F . (60" C . ) LSD 95';'cd
255 4.45 4.20
35 4.95 6 15
35 6.90 7 15
255 6 20 6.80
255 5.45 6.05
35 6.50 6.95
35 6.55 7.00
255 5.55 6.10
1.12
Rate of agitatzon--100 cyclesper minute, an angle of 350" rotation. * Valut. a Terg-0-Tometer T e s t , c'. S. Testing Co. cloth at 0.2 w t . y c detergent. Surfactants formulated in a rtported is the mean of t w o replicates. Eight replicate swatches (4l/4X 4 inches) were Lcashed in each of the two replicate tests. heazly duty formulation containing 20% actioe, 34Tc sodium sulfate, 40% sodium tripolyphosphate, 5 5 sodium metasilxate, and 7% carboxymethyl ceilulose. d
Least signifcant diference at the Q5ycconjdence leime1 calculated f r o m LSD
Table IV.
0.25
0.5
c 1 3
Cl5
7.5 24.2
0
3 2.3 4
12
11.6 7.0 7 9 9 26
180+ 19 4 14 22 25 39
6 Insol.
12 32
30 180+
0-Olefin-based sec-sulfate 4 Insol.
c1t
c 1 6
30
I&EC
0.063
2.5 6.9
, . .
CIS
0.725
0 4.1
5
C I:
'
0 2.1
3
C16
.\/n
0.037
0.015
22.8 180+
180+
Wetting T i m e , Seconds
0 0
C14
(.\/z)(t)(s)
Draves-Clarkson Wetting Test on sec-Alkyl Sulfates Concn. o f Surfactant. Wt. %
Surfactant
Sodium Dioctylsulfosuccinate ABS Alcohol-based sec-sulfate
=
-
3
.
PRODUCT RESEARCH A N D DEVELOPMENT
180+ 45 107 92 168 180+
18Of 180+ 180+ 180+
LAURVLALCOHOL SULFATE
DAYS
Figure 2.
Comparative biodegradability Research biodegradation test
DAYS
in
Esso
Figure 3.
Analyses b y methylene blue technlque
sec-sulfates are adversely affected by hard water to a significant and comparable degree. At the elevated temperature (140' F.) the sec-sulfates show a definite advantage over ABS. Comparison \vas also made \vith a C 1 4 and Cle a-olefin based .rpc-sulfate. a "linear" alkyl benzene sulfonate and ABS. T h e results are summarized in Table 111. O u r tests show that C,6 sa.-sulfate. ABS and LAS are equivalent in cotton detergent); performance. A s in the case of the ClQ alcohol-based .r~c-siilfatethe C1, olefin-based sulfate is inferior to both the C16sec-sulfate and ABS. I'hr relative performance of the C18 alcohol-based set-sulfate to ABS (Table 11) and that of the CIS a-olefin based sec-sulfate to ABS ('Table 111) indicated that these malerials are equivalent. Wetting Ability. T h e \vetting ahility of the C13through C I b sulfatrs derived from linear set-alcohols vias measured by the Dravrs-Clarkson \vetting test (,5). 'l'he results are slimmarizcd in Table I V , For comparison. the \vetting ability of rodium dioctyl sulfosuccinate. a !vetting agent. a commercial :\HS. and C , , and CIAsec-sulfates based on olefins was also drtrrmined. '1he !vetting ability of the alcohol-based sec-sulfate reaches a peak a t C,; Lvhere it is superior to ABS but not quite as good as sodium dioct);l sulfosuccinate. I n the range of Clb to C17 the ret.-sulfate5 are equal to or better than .4BS. T h e alcoholbawd ter-sulfates are superior in wetting ability to the olefinbased sulfates. Hydrolytic Stability. T h e hydrolytic instability of secondary siilfater has been frequently given as a reason for their failurc to achieve commercial success as a general purpose drtergent. Solutions, 1.2%. of the C I 4 .Cis. and C I Salcoholbased sdfatrs \vere prepared in deionized ivater and allo\vc d to rtand at ambient temperatures for 14 months. Since acid i j producrd in the hydrolysis of sulfates. pH drift toxrard acidity is ail indication of hydrolytic instability. 'I'hr, results in Table V correspond to the formation of about
Comparative biodegradability Research biodegradation test
in Esso
Based upon chemical oxygen demand analyses
mole % of acid, for the C14 and Cl8 sec-sulfates, a negligible amount. For some reason unknown to us, the C16 sulfate hydrolyzed to a higher, but still negligible degree. A corresponding amount of free alcohol is produced, but this should have no deleterious effect on the product since several per cent of free alcohol is intentionally allowed to remain in alkyl sulfates. Thermal Stability. Commercial spray drying of a surfactant subjects the surfactant to a stream of hot air for a short time. During the initial stage of the drying operation, water freely evaporates from the particle and maintains the particle temperature below 100' C. When partially dry? however. the water content of the outside of the bead is low relative to the insidr. and thus the skin temperature of the bead may rise well above 100' C . Unfortunately, no information is available regarding the actual maximum skin temperature reached. T h e absolute thermal stability requirement of a surfactant to be spray dried, therefore, cannot be defined. In order to assess the thermal stability of set-sulfates. their stability has been measured by thermogravimetric analysis (TGA) relative to primary sulfates which can be spray dried commercially. A sample of C13 set-alcohol-based sulfate was heated in a nitrogen atmosphere a t a rate of 6' C. per minute and the weight loss measured. 'The first sign of decomposition
Table V.
Hydrolytic Stability of Alcohol-Based sec-Sulfates at Ambient Conditions, 1.2% Solution Start of
pH----
A f t e r 14
Compound
10.4 10.2 10.6
C I stc-sulfate ~ Clbsec-sulfate C , , sec-sulfate
VOL. 4
NO. 1
9 2
76 9 3
MARCH 1965
31
by weight loss took place a t 120' C., but the rate of weight loss did not become high (about 47, per minute) until the temperature reached about 145' C . T h e weight loss of the same sample using vacuum T G A gave substantially the same results. A slow rate of weight loss began at 100' C. and 0.35 mm. of H g while heating was maintained at 6' C. per minute. T h e rate of weight loss began to be significant at 140' C . indicating decomposition. T h e maximum rate of Xreight loss \vas reached a t 160' C. and was about ljYC per minute. A sample of lauryl alcohol (primary) sulfate was also analyzed by TGA. At atmospheric pressure decomposition started at 190' C. Decomposition of the primary sulfate began a t 200' C. under vacuum. These data indicate that the sec-sulfate is not as thermally stable as the primary sulfate. Unfortunately, one cannot tell from this simple test brhether sec- sulfates will be sufficiently stable for commercial use. This can probably be determined only by a test in a commercial-type spray dryer. Biodegradation. Lnder the conditions of the Esso Research biodegradation test ( 6 ) , the sec-sulfates based on linear alcohols degrade as rapidly and completely as the easily degraded surfactant, lauryl alcohol sulfate (dentifrice grade). Figures 2 and 3 summarize the results of the test. This procedure is a modified die-away test in which small, measured amounts of bacteria, obtained from a municipal sewage treating plant, are added to a n aqueous solution containing inorganic buffers, trace metal nutrients, and the surfactant under test. T h e standard methylene blue analysis is used to follow the disappearance of the surface active properties of the test sample. Since no appreciable organic material, except the surfactant to be tested. is added to the solutions, the undegraded residual soluble organic material derived from the surfactant may be estimated by a standard chemical oxygen demand procedure. This C O D test is thought to be a more exacting criterion for the true biodegradability of a surfactant since it measures not just the "foam potential" but the "pollution potential'' of the surfactant. T h e test is normally carried out for a period of 21 days. ABS is essentially undegraded in this period of time as measured both by the methylene blue technique and the chemical oxygen demand technique. A chemically pure, idealized linear alkylbenzene sulfonate, 2-phenyldodecane sulfonate: degrades completely by the methylene blue analysis, but chemical oxygen demand analysis shoLvs that about 207' of the organic material is undegraded at the end of the test. A larger proportion of undegraded residue is observed for the best LAS which \vas obtainable. In contrast to all of the alkylbenzene sulfonates, the alkyl sulfates degraded rapidly and until no surfactant and only about
32
I&EC PRODUCT RESEARCH A N D DEVELOPMENT
5y0 organic material remained. These results show clearly that linear sec-sulfates are as highly biodegradable as primary sulfates. Conclusions
Sulfates based on sec-alcohols exhibited sufficiently desirable properties in the preliminary screening tests to warrent further investigation as to their possibilities for future commercialization. In preliminary foaming ability studies: the sulfates in the C l j to C1; range lvere equivalent to their olefin-based analogs, to a .'linear" alkylbenzene sulfonate: and to tetrapropylene-based alkylbenzene sulfonate. In preliminary cotton detergency studies, both the alcohol-based and olefin-based sec-sulfates in the C i s to C l j range performed as well as or better than both the branched and "linear" alkylbenzene sulfonates. T h e alcohol-based sulfates have good \retting power and appear to have sufficient hydrolytic' stability. They are less thermally stable than primary sulfates. but there still is a good possibility that they can be spray dried. An outstanding property of the sec-sulfates is their rapid and complete biodegradeability. Acknowledgment
T h e authors thank Esso Research and Engineering Co. for permission to publish this paper. They also acknowledge the efforts of J F. Johnson for his constructive criticism of the manuscript and the assistance of F. S. Osmer and R. J. Brojanowski. w.ho performed many of the experiments. literature Cited
(1) Asinger, F., Geiseler, G., Eckoldt. H., Ber. 89, 1037 (1956). (2) Brois, S.J., Esso Research and Engineering Co., Linden. N. J., private communication, 1961. (3) Clippinger. E., ISD. ESG. CHEM.PROD.RES. DEVELOP. 3, 3 (1964). (4) Dreger. E. E., Keim. G. J.. Miles. G. D.! Shedlovsky. L., Ross, J.; Ind. Eng. Chem. 7, 610 (1944). (5) Harris, J. C.! "Detergency Evaluation and Testing," p. 40, Interscience, New York. 1954. (6) Konecky. M. S., Kelly, R. J., Symons. J. M.. McCarty, P. L., 36th Annual Meeting it-ater Pollution Control Federation, Seattle. \l'ashington. October 1963. (7) Oronite Division, California Chemical Co.; "Alpha-Olefins." 1963. (8) Schwartz, A. M.. Perry. J. \ V . , "Surface Active Agents-Their Chemistry and Technology." Vol. I, p. 66. Interscience, New York. 1959. RECEIVED for review September 24, 1964 ACCEPTED January 2 5 , 1965 DiL ision of Industrial & Engineering Chemistry, 148th Meeting, ACS. Chicago, Ill., September 1964.
