Document ZB7aKzxmO8q3R4EvEXzrdmoVZ

/ INTER-OFFICE CORRESPONDENCE Et h y l Ga s o l in e Co r p o r a t io n Re s e a r c h La b o r a t o r ie s 72 3 Ea s t Mil w a u k e e Av e n u e De t r o it , Mic h ig a n June 26, 1939 Dr. Robert A. Kehoe Dear Bob: I am sending you herewith a copy of our report LTD $39-27 out at the suggestion of Dr. Lachie to get some idea of the amount and nature of the sludge formed in Ethyl Gasoline. Somewhat to our surprise the sludge formation was decidedly small and most of it remained in the gasoline. Insofar as this work is significant, I would say that we would not expect much lead sludge in Ethyl Gasoline storage tanks unless the tank has been spiked. Your comments will be appreciated. Very sincerely yours, ;&w TTEi;Aid ON lb Ti5KL CAJCLI.-E LTD (< 39--27 f. J. fykstra 256-XP-2 Approved by 6-14-39 i'UfXVOiii To study the formation and nature of sludge produced in Lthyl gasoline during its storage in vented mild steel tanks. ION:-'P' i ,, v'vu* wi;WU Seventeen months storage of Lthyl gasoline (containing 3,12 gai. ?b/gal. added as 70-45 Lthyl fluid) in a 55 gallon vented* half-filled steel drum produced a decomposition of 3.1; of the original tetraethyl lead with 74,5 of the decomposed tetraethyl lead soluole in the gasoline arid the remaining 2(5;- present in the sludge. 0 . f/ y 25 gas. (dry basis) sludge had formed* of whien only 3^ was lead and the reminder v/&3 rust, dali of tie lead in the sludge was organic and the ether half inorganic lead compounds. /% , Kuat was found in a depression on the- bottom of the drum but the sides were free of rust. Only traces of water had condensed in the drum. ethyl gasoline was made by mixing 235 co. fed "44s' (70-45) fthyl fluid with 50 gallons of Shite Led Crown winter grade gasoline in the blending tanks for forty minutea. This gasoline was then pumped into a new gasoline-rinsed 55 /palIon mild steel drum. The filled drum iry'upright position and with/bungs moderately tight was left in the storage shed aw the kilwaukeo laboratory from January 7* 1938 until February 10,1938. The drum 'was then sent out to tho fight-mile laboratory whore it was stored outside in the open in an upright position from February 10*1538 to way 31, 1332, Approximately 22 gal. of gasoline was removed and a small copper tube vent pipe installed on February 10,1938. Tho drum was shaken at irregular intervals, usually daily. Samples of the gasoline were removed for lead analysis at the end of 1,4, -7,10 arid 17 months. iho last three samples were also ex tracted with -di^Cii to determine the amount of lead alkyl halides in the gasoline. About 22 gallons of gasoline ws loft at tho end of the exper iment . It was removed and the sludge and rust were rubbed loose and rinsed out with gasoline and 2;, niij.Oh. All of the gasoline was filtered and tile sludge wnich 'was collected was then dried in a vacuum dessicator, weighed and analysed. Tne 2,' t'd&Qjl rinse was also analyzed ior lend to determine approximately the amount o; sludge which uui not been removed from the drum but from which the hii^Oh had extracted the organic lead. ? / f\E' 0022259 N22446.01 RESULTS: Lead Content of Gasoline - */f.al. Time - Ho. Total Pb Pb sol. in 29;i ITii^OH 0 3.12 1 3.20 4 3.27 7 3.70 0.049 10 3,84 0.051 17 4.46 0 .094 Sludge Analysis Total sludge (calc'd, from Kli^OH rinse) Sludge removed from drum (dry basis) 25 gm. 7.6b 1; Analysis of dried sludge Total lead Soluble in SH^Ao solution Soluble in 2'% PJI/.OIi solution 3 ,01> X a 9O/0 1.72# - Steel Drum Inspection There was little water in the residue taken froa t he drum. The residue or sludge consisted mostly of scaly places of rust, which had been scraped from the bottom of the drum. The sides of the drum ''-'ora in perfect condition, the only rust being in the depression in the bottom of the drum. C, Tr\V TV': Q T TT ;otal load concentration in the gasoline increased 'from 3.12 to 4,43 gn. pb/gal. because of the evaporation of the lighter ends from the gasoline. The lead alkyl compounds (bromides, chlorides, carbonates and hydroxides), soluble in the gasoline but extractiole by the NH4OH, increased steadily until they reached 2/S- of the total lend due to the reaction of tetraethyl lead -with the halogen carriers in the Ethyl fluid (ethylene dibromide and ethylene dichloride) and their decomposition products. The sludge, consisting mostly of rust, contained 3,;i Pb, about half of which was inorganic and the ether half organic lead compounds, insoluble in gasoline ((Et^Pb^CQg, etc.), Since neither ammonium acetate nor ammonium hydroxide are perfect solvents for inorganic and organic lead compounds, respectively, they probably give only an approximation. It is interesting to note that of t he 3.1/S of the original tetraethyl lead which had decomposed, 74>v of the product was soluble in gasoline and 26?S was found in the sludge. 0022,260 Breathing of the drum, due to alternate heating and cooling, introduced sufficient water to rust the bottom of the drum moderately. The heating and cooling were accentuated because the drum was painted black on the outside and exposed to sunlight for part of the day. It was well ventilated by means of a copper tube. In view of j>revious com plaints, it is interesting to note the absence of rust on the sides of the drum exposed to air aoove the gasoline. F. J. Dykstra 6-14-39 K? 0022261 3- O/ ? NCOS NO!NO 1N30H1S *H.L AG Al3AlsniDVl HIO ON!HG3N!ON2 iO 1031100 \G OGAO-*:-* IV I ; 1^ :-- c L:Ki 'ii;:- i ;; * r 0 J L: i; : -r .......... 1 - . ; . -;;; | :: : ,,.;i ; j , ;. 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