Document dQj4pjJkVy0poM9aryZRjbyeq

LTD 48- 50 November 1 , 19^3 ETHYL CORPORATION Research Laboratories Detroit, Michigan MISCIBILITY AND HEALTH HAZARD OF VITOL FLUID,COMPONENTS PURPOSE (1) To determine the temperature and dilution at which TEL (tetraethyllead) begins to separate from aqueous alcohol solutions initially containing 5 cc. TEL/gai. (2) To determine the emulsion stability of Vitol Fluid and the TEL content of the internal and continuous phases. SUMMARY The separation temperatures of TEL, 62-Mix, and 1.0-T "Ethyl5* Antiknock Compounds from various Vitol-like water-alcohol solutions were determined. The separation temperatures of 62-Mix fluid, at a concentration of 5 cc. TEL/gal., from aqueous solutions containing 85 vol. $ methanol, ethanol, and isopropanol were -60 , -7>, and -30C., respectively} as the concentration of water in creased, the TEL separation temperature rose rapidly. Aqueous solutions containing 8 5$ alcohol and 5 cc. TSL/gal. as TEL, 62-Mix, or 1.0-T aviation fluid were diluted with water at room temperature until a phase separation occurred. Separation of TEL begins at the following alcohol concentrations: 68.2$ methanol, 50.6$ ethanol, and 3^*9$ isopropanol. Vitol Fluid prepared according to the present formula of the Thompson Vita-Meter Corporation is a murky, yellow emulsion. Filtration of two samples through filter paper removed the internal or dispersed phase, yielding a clear, yellow filtrate of reduced TEL concentration. On standing or centrifugation, the Internal phases separated as light brown lower layers containing 10 to 12 $ TEL. Altogether, it appears that the TEL In Vitol Fluid may be so (Continued) ' ' K* 0020568 easily concentrated in the course of handling that this anti knock fluid constitutes a much more serious health hazard than leaded gasoline of equal TEL content. INTRODUCTION It has long been recognized that the addition of alcohol to motor fuels reduces knock an? gives generally better performance. However, for several reasons alcohol has not come into wide-spread commercial use. The Thompson Vita-Meter Corporation has experimented with solutions of water in alcohols, and has recently developed an injeeticu device designated the Vita-Meter. This device is d e signed tc inject the so-called Vitol Fluid into the carburetor when the manifold pressure falls below a certain value. The present Vitol Fluid is an alcohol-'water mixture containing ,:Ethyl" Anti knock Compound and a rust inhibitor, such as Penala 2210, in the following proportions: 85 parts methanol, 15 parts water, 1/ 8 part rust inhibitor, 3/8 part kerosene, and 3 cc. TEL/gal. as 62-Mix fluid. Since the Thompson Vita-Meter Corporation, is new market ing the Vita-Meter and Vitol Fluid, it is desirable that this Laboratory evaluate this method of increasing octane number. The present work is particularly concerned vrith possible health hazards resulting from the use of Vitol Fluidj current experiments on the storage stability and the air evaporation of the fluid will be reported in subsequent LTD's. EXPERIMENTAL Separation of TEI, from Alcohol-Nater Solutions As an introduction to the study of Vitol Fluid, a study was first made of the solubility and separation temperatures of TEL from various alcohol-water mixtures. The clouding or initial freezing points of various mixtures of 'water and alcohols containing 3 cc. TEL/jtal. as straight TEL, 62- Mix, or 1.0-T aviation fluid, are presented;in Table I. As the con-, centration of water increases,the TEL separation temperature rises rapidly. .- '-fVkW TABLE I Separation of Leaded Alcohol-Water Solutions Separation temperature, C., for solution containing 5 cc. Alcohol ____ Kind Voi. fo _'J_ ritr TEL/gal. as 62-Mix 1.0-T Mix Methanol Ethanol Isopropanol 35 35 85 -40 -60 -63 -74 -75 -54(a) -- -50 (a) -2 6 (a) Methanol Ethanol Isopropanol 75 75 75 -2 -7 1(a) -57(a) -5 6 (a) -- 25 -5 6 (a) -2 1(a) Methanol Ethanol Isopropanol 50 50 50 -- -- 25 25 -- 25 25 -- -2 1(a) -16 (a) (a) Separated phase fsras solid. Dilution of Vltol-Type Fluids The extent to which 8 5$ alcohol solutions containing p c c . TEL/gal. as TEL, 62-Mix, or 1.0-T aviation fluid can be diluted with water before a second phase separates was also determined. These data, obtained by titrating 25-tnl. samples with water, and comparable data, supplied by the Thompson Vita-Meter Corporation, are given in Table I I, TABLE II - Separation of Vitol-Type Fluid on Dilution with Water Alcohol (8 5 vol. %) TEL Added As Concentration, alcohol Ethyl Data Thompson Data Methane! tt S TEL 62-Mix l.O-T Mir Ethanol fl TEL 62-Mix 1.0-T Mix Isopropanol . TEL H 62-Mix tl 1.0-T Mix 69.5 68.2 6 9 .8 51.2 50.6 52.2 36.5 34.9 35.3 . 73.5 --- 55.1 --- 38.5 - These data show that, of the three alcohols tested, isopropanol is the most effective xclth respect to solubilizing TEL in water and that methanol is the least effective. - 0020570 --4. In the tests in which 62-Mix fluid was used, separation occurred at 6 8 .2 , 5 0 .6 , and 34.9/ alcohol, in methanol, ethanol, and isopropanol solutions, respectively. These values are from 3 .6 to 5 .3/ lower than the corresponding values reported by Thompson Vita-Meter Corporation, which represents a greater discrepancy than would be expected. Perhaps the Thompson data show the minimum alcohol content of alcohol-water systems it v/hich 3 cc. TEL/gal. of the antiknock compound is soluble, whereas the data obtained at this Laboratory represent the mini mum alcohol content at which the antiknock compound added at 3 cc. TEL/gal. to an 85/ alcohol solution remains in solution when the entire system is diluted with water. Study of Present Vitol Formula A 1-gal. sample of Vitol Fluid was prepared according to the directions furnished by the Thompson Vita-Meter Corporation, except that No. 9 oil (refined kerosene) was used instead of ordinary kerosene. The resulting Vitol Fluid was a murky, yellow liquid having a density, d3j, of 0.8428. Analysis indicated that it contained 3*23 g. Pb/gal., or 3.06 cc. TEL/gal. On standing, a small amount of a lower layer separated from the sample. This was surprising since the Thompson Vita-Meter Corporation reported that Vitol Fluid is an emulsion that is completely stable either on standing or on centrifugation. Subsequently, a sample of commercial Vitol Fluid received from the Thompson Vita-Meter Corporation also separated into two.distinct phases on standing or centrifugation. In contrast, a sample prepared at this Laboratory containing only 1 cc. TEL/gal. did not separate when subjected to either treatment. Two methods were used to study the TEL distribution between the two liquid phases of the Vitol solution. The first method was to filter a 20 0 -ml. sample through three thicknesses of filter paper. This treatment removed the internal phase yielding a clear yellow solution as the filtrate. Analysis then showed that approximately 12/ of the TEL was removed in the internal phase. Anal: Vitol solution, 3*23 g. Pb/gal.; filtrate, 2.84 g. Pb/gal. In the second method a 300-ral. sample of Vitol Fluid was centrifuged at 1800 r.p.ra. for 30 min. The bulk of the material remained as a murky yellottf liquid. However, approximately 0.15 g. of a light brovm liquid separated as a lower layer. On analysis this lower layer was found to contain 7.5/ lead, or 11.?/ TEL. 0020571 Similarly, the TEL distribution in a sample of commercial Vitol Plaid received from the Thompson Vita-Meter Corporation was investigated as follows. A 2-gal. sample of the material (contain ing 2.87 g. Pb/gal.) ivas allowed to stand for three days, during which time part of the internal phase coalesced into larger drop lets which vrere concentrated at the bottom of the container. The upper layer, a murky yellox* liquid was removed. A 500-ml. portion was clarified by filtration through three thicknesses of filter paper; the filtrate contained 2.43 g. Pb/gal. (2.30 cc. TEL/gal.). The lower layer, consisting of a high concentration of the sus pended phase as droplets, x?as transferred to a 10 0 -ml. tube and centrifuged for 2 hr. at lSOO r.p.m. A 10.0-ml. quantity of clear yellow oil separated, of which 9 .0 ml. (7 .3 g.) x*as isolated. This material analyzed 6.46 x*t. f lead. The information relative to the TEL distribution is summarized in Table III. TABLE III ~ TEL Distribution in Vitol Fluid Vitol Fluid cr Pb/gal. cc . TEL/gal. Laboratory Blend 3.23 3-0 6 Commercial Sample 2.8 7 2 .72 Continuous Phase g. Pb/gal. cc. TEL/gal. 2.84 2 .6 8 2.43 2.30 Internal Phase Wt. f> Pb Wt. fo TEL g. Pb in phase/gal. (a) Wt. of phase, g./gal. (b) Vol. of phase, cc./gal. (c) fo of total TEL in phase (b) 7.47 n.r 0 .39 5.2 2 6 .2 12 .1 (a) Determined by difference. (b) Calculated values. (c) Assuming a density of 0.84. 6.46 10 .' 0.44 6.8l 8.1 15.5 KE' 0020572 - 6. The TEL distribution data for the two samples are in reasonably close agreement, showing that from 12 to 15$ of the TEL is in the internal phase, and that the TEL content of this phase is high enough, approximately 11$, to be quite hazardous. Reference: Notebooks 1,592 and 1 16 Distribution: G. . Eeste (2) G. Edgar R. A. Kehoe Work by: M . C . Almen R. D. Closson S . 0. Rue Report by: R. D. Closson RDC:gm 0020573