Document rBogjM9LpYem1872kMnjvBGkG

ETHYL CORPORATION RESEARCH LABORATORIES 1600 WEST EIGHT MILE ROAD FERNDALE 20 DETROIT, M ICHIGAN c c : H. J . Gibson J . B. Macauley R. K.Scales J . S . Wintringham D r. R o b e rt A. Xehoe College of Medicine U niversity of C incinnati Eden Avenue C in c in n a ti 1 9 , Ohio September 2, 1948 Dear D r. Kehoe ; - 1. Air Evaporation of V itol We h a v e c o m p l e t e d a n i n v e s t i g a t i o n o f t h e a i r - e v a p o r a t i o n c h a r a c t e r i s t i c s of V ito l f l u i d , as sug g ested a t th e m eeting w ith th e Thompson people in C le v e la n d on A p r i l 2 0 . Our f i n d i n g s a r e s u f f i c i e n t l y d i f f e r e n t from w h at we ex p e c t e d t h a t I am t r a n s m i t t i n g our d a t a t o yo u now i n t h e fo rm o f t h i s memorandum, r a t h e r t h a n w a i t u n t i l t h e f o r m a l LTD r e p o r t i s i s s u e d . F u r t h e r m o r e , we w e r e n o t i f i e d b y H r . Van H a r t e s v e l d t t h a t y o u had g iv e n p r o v i s i o n a l a p p ro v a l t o p ro ceed w i t h th e Columbus p rogram , and o u r i n f o r m a t io n may have a b e a r i n g on t h a t d e c is io n . You w i l l r e c a l l t h a t D r. .Roush o f t h e Thompson P r o d u c t s r e p o r t e d p r e l i m i n a r y r e s u l t s i n d i c a t i n g t h a t t h e v o l a t i l i t y o f TEL i n V i t a l was a b o u t o n e f o u r t h t h a t o f TEL i n g a s o l i n e . Our r e s u l t s i n d i c a t e t h a t a v e r y d i f f e r e n t s i t u a tion ex ists. We h a v e e v a p o r a t e d s a m p le s o f V i t o l b y i n t r o d u c i n g n i t r o g e n t h r o u g h a s i n t e r e d d i s c , so t h a t n e a r - e q u i l i b r i u m c o n d i t i o n s e x i s t . The e f f l u e n t v a p o rs , c o n s i s t i n g o f n i t r o g e n , m e t h a n o l, w a t e r and t h e com ponents o f t h e A n tik n o c k Coispound *vere s c ru b b e d th r o u g h an i o d i n e s o l u t i o n , and th e s c r u b b e r s o l u t i o n s a n a ly z e d fo r le a d . This procedure d u p lic a te s t h a t used fo r TEL-heptane so lu tio n s as d e sc rib e d i n o u r r e p o r t LTD 4 6 - 4 7 , a c o p y o f w h i c h y o u r e c e i v e d a t t h e t i m e i t was i s s u e d . W it h g a s o l i n e , we fo u n d t h a t v e r y l i t t l e o f t h e TEL e v a p o r a t e d u n t i l a b o u t 9 Of o f th e f u e l was e v a p o r a t e d . C o n s e q u e n tly d a n g e ro u s TEL c o n c e n t r a t i o n s i n t h e a i r do n o t e x is t during most o f the e v a p o ra tiv e p ro ce ss, nor would th e vapor space in a p a r t l y f i l l e d c o n t a i n e r c o n t a i n h i g h c o n c e n t r a t i o n s . On t h e o t h e r h a n d t h e r e s i d u a l l i q u i d g a s o l i n e becomes, h i g h e r i n TEL c o n t e n t . The d a t a w h ic h we h a v e o b t a i n e d a r e p r e s e n t e d i n th e f o ll o w i n g t a b l e and in th e a tta c h e d g rap h s. Under these co n d itio n s o f e v ap o ratio n , vapors from V ito l f lu id w ill c o n ta in betw een 9000 and 1 2 ,5 0 0 J ig . P b /c u . f t . o f a i r u n t i l e s s e n t ia l ly a l l t h e TEL h a s e v a p o r a t e d . An a l m o s t s t r a i g h t --l i n e r e l a t i o n s h i p e x i s t s b e tw e e n t h e amount o f l e a d a n d V i t o l e v a p o r a t e d -- 2% o f t h e TEL f o r e v e r y 1% o f t h e l i q u i d . C a l c u l a t i o n s show t h a t e v a p o r a t i o n o f p u r e TEL u n d e r s i m i l a r c o n d i t i o n s w o u ld p r o duce a c o n c e n tra tio n o f 130,000 ,ug. P b /c u . f t . o f a i r . The e v a p o ra tio n c h a ra c te r i s t i c s o f V i t o l a r e , t h e r e f o r e , e q u i v a l e n t t o t h o s e ofV lO fo TEL s o l u t i o n . HE 0020661 D r. Xehoe S ep t. 2. 1948 2 A IR EVAPORATION OF VITOL FLUID M D ''ETHYL" AVIATION GASOLINE Run 1 V itol F ra ctio n , w t. % of samnle 53 30 10 7 Wt, % E vaporated, cum ulative Fuel Lead 53 83 93 Res . 97.2 98.2 98.8 - C o n cen tratio n of lead in a ir, M g ./cu , f t . / 9500 ; " 200 30 - C o n cen tratio n o f TEL i n r e s i d u e m l.TEL/gal. 0.19 .26 .54 - 2 V itol 5 5" 5 11 74 5 10 15 26 Res. 11.8 21.4 35.2 61.2 - , 12,500 12,400 13,000 12,100 - 2.82 ` 2.64 2.33 1.62 - 3 V itol 4 G aso lin e 6 11 10 73 0 40 40 10 5 3 6 17 27 Res . 0 40 80 90 95 98 10.7 32.0 49.8 - 0 (0.5) 2.1 5.4 13.0 35.5 9200 9200 9100 - 130 160 480 1250 3130 8540 2.58 2.25 1.88 - 4.5 7.45 22.0 42.5 78.5 145.0 Run 1 . V ito l f l u i d , la b o ra to ry p re p a r a tio n , no c o rro s io n i n h i b i t o r , 3.03 ml. TSL/gal. Run 2 . V i t o l f l u i d , l a b o r a t o r y p r e p a r a t i o n , no c o r r o s i o n i n h i b i t o r , 3.03 m l. TEL/gal. Run 3 . V ito l f l u i d , com m ercial g ra d e , 2 .7 2 m l. T S L /g al. Run 4 . A v i a t i o n g a s o l i n e , CRC-28R, 4 . 5 m l . T E L / g a l . , d a t a f r o m LTD 4 4 - 5 7 . These r e s u l t s , s tr i k in g as th ey may seem, are in q u a lita tiv e agreem ent w ith th e laws o f p h y sic a l ch em istry : as systems approach im m is c ib ility the p a r t i a l p ressu res of th e i r components in c re a se co n sid erab ly and approach the vapor p ressu res o f th e pure compounds, a s t a t e w hich i s reached when the components become im m iscible, The e x p e r i m e n t s w h i c h we c o n d u c t e d w e re n o t d e s i g n e d to d u p l i c a t e th e surface evaporation experienced in a liq u id s p ill, but w ith th is reserv atio n in mind, the fo llo w in g p ic tu r e o f th e r e l a t i v e e f f e c ts of V ito l and le a d e d g a so lin e s p ills can be drawn. In the f i r s t place, the evaporation of V ito l w ill, from th e s t a r t , i n t r o d u c e c o n s i d e r a b l y g r e a t e r q u a n t i t i e s o f TEL i n t o t h e a t m o s p h e r e , b u i l d i n g up t h e TEL c o n c e n t r a t i o n much f a s t e r t h a n i s t h e c a s e w i t h g a s o l i n e . I n a confined space a re a l hazard w ill e x i s t , For example, (1) i f one g a llo n of V ito l is allow ed to evaporate to th e 50/ poinm, e ith e r as th e r e s u l t o f a s p i l l or from s to r a g e i n a n open c o n t a i n e r , i n t o a room o f 1000 c u . f t . , 2 .9 g . ,of Pb w i l l be i n t r o d u c e d i n t o t h e a t m o s p h e r e , o r 2 , 9 0 0 ^ g . ? b / c u . f t . On t h e o t h e r h a n d , u n d e r th e same c irc u m s ta n c e s , th e r e Would be o n ly 0.048 g . Pb, or 4 8 /* g .P b /c u . f t . r e su ltin g from ev ap o ratio n -o f a sim ila r q u a n tity .o f a v ia tio n g a so lin e . These fig u re s D r . Ke ho e S e p t . 2 , 194-8 3. a r e SI and 0 .5 t i m e s , r e s p e c t i v e l y , th e maximum a ll o w a b l e c o n c e n t r a t i o n f o r 2 0 - minute ex p o su re. (2) The heel rem aining i n a sto ra g e ta n k c o n ta in in g V ito l or g a s o li n e f u r n i s h e s a n o th e r i n t e r e s t i n g c o m p a ris o n . With V i t o l we c a n e x p e c t about 10,000 /ug.Pb/cu. f t . o f vapor space in the ta n k , no m atter what the siz e o f t h e h e e l i n r e l a t i o n t o t h e t a n k . W ith g a s o l i n e e v e n i f 805? o f t h e h e e l e v a p o r a t ed i n to th e v a p o r s p a c e , th e r e would be l e s s t h a n 500 / g .F b /c u . f t . in th e ta n k atm osphere, and to b rin g about th is c o n d itio n th e liq u id hold-up in th e tan k would have to be on th e o rd e r o f 0.2/? o f th e ta n k volum e, or sa y 20 g a l. in a 1 0 ,0 0 0 - g a l. ta n k w hich would be u n u s u a lly lo w , (3 ) S t i l l a n o th e r c o n d it io n , 'which may e x i s t in p r a c t i c e , i s th e b u ild -u p o f a h ig h lea d (TEL) c o n c e n tra tio n under th e sem i- enclosed hood of an autom obile from the, ev ap o ratio n o f V ito l from th e sto rag e ca n n is- t e r . A mechanic m ight be su b je c ted to a high c o n c e n tra tio n v ery r e a d ily from t h is source. : ........ On t h e o t h e r s i d e o f t h e p i c t u r e , ou r e x p e r i m e n t s show t h a t e v a p o r a t i o n o f V i t o l i s a v e r y e f f i c i e n t m ea n s o f e l i m i n a t i n g TEL f r o m t h e r e s i d u e , t h e o p p o s i t e p i c t u r e from w hat o c c u rs i n th e c a s e o f g a s o l i n e . I n c i d e n t a l l y , we have s a t i s f i e d o u r s e l v e s t h a t a lth o u g h th e w a t e r c o n te n t o f th e r e s i d u a l f l u i d i n c r e a s e s , t h e T3L is removed s u f f i c i e n tl y r a p id ly th a t no se p a ra tio n occurs due t o e v a p o ra tio n . I f w a t e r I s a d d e d , h o w e v e r , s u c h a s i n w a s h i n g f o r i n s t a n c e , TEL w i l l , o f c o u r s e , separate im m ediately. Thus, from c e r t a i n sta n d p o in ts V ito l p re s e n ts more o f a h azard th a n gaso l i n e , a n d fro m o t h e r s l e s s . C e r t a i n l y t h e s i t u a t i o n i s d i f f e r e n t , ,-ve w i l l b e v e r y In te re s te d in le a rn in g your re a c tio n to th e se r e s u l ts , and what recommendations you w i l l make c o n c e r n in g t h e s t o r a g e , h a n d li n g an d u s e o f t h i s p r o d u c t b a s e d on t h e s e observations. . 2 . F u rth e r Work The r e s u l t s r e c o r d e d above have seemed s u f f i c i e n t l y p r o v o c a t i v e to w a r r a n t f u r t h e r 'w o rk . Vie p l a n t o c a r r y o u t t h e f o l l o w i n g p r o g r a m , t o b e c o m p l e t e d i n a b o u t two months : 1 ) D e t e r m in e e v a p o r a t i o n c h a r a c t e r i s t i c s o f V i t o l f l u i d c o n t a i n g Q% 5% w a t e r . I f we a r e a t p r e s e n t d e a l i n g w i t h b o r d e r l i n e i n u n i s c i b i l i t y , t h e s e e x p e r i ments should p o in t i t out. 2 ) D e te rm in e a c c u r a t e l y t h e p a r t i t i o n f u n c t i o n o f TEL b e t w e e n t h e a l c o h o l w ater and dispersed in h ib ito r phases. P relim inary experim ents in d icate the in h ib ito r c o n ta in s a p p re c ia b le , perhaps dangerous, c o n c e n tra tio n s o f TEL. 3) Determine th e s e p a r a b ility of th e i n h i b i t o r p h a se . A lthough Thompson i n s i s t s t h e e m u l s i o n i s p e r m a n e n t , we a r e s t i l l s k e p t i c a l . We h a v e o b s e r v e d a g glom eration o f in h ib ito r d ro p le ts , se p a ra tio n on c e n trifu g in g and a co n c en tra tio n g rad ien t in commercial V ito l. In view of (2 ) above, th is p o in t needs c l a r i f i c a t i o n . We s h a l l k e e p y o u a d v i s e d o f o u r p r o g r e s s , a n d s e n d y o u a c o p y o f our fin is h e d r e n o r t on the work to d a te . We w o u ld b e i n t e r e s t e d i n t h e r e s u l t s o f y o u r t o x i c i t y s t u d i e s a n d i n le a rn in g th e d e ta ils of your recommendation to Thompson. . 0020663 AVery t r u l y y o u rs, 0, OJJU5---- . f } f I t }? *---: L-* Dv'-ii i * L a b o r a t o r y v L . t o i o u n S - L a b o r a t o r y V i / s o l r ;u a o S h u E i p o o n ?&'o d , V !i i i . g . T1 - > .... , . . Q u an tity j I o f Fuel ano 2EL IS1api'Gtc., j i ............ ........- J layl origli ovap. SL-Wuothanol 40 s o ! c<* Por cent o f fu o l svaporateci RZ 0020664 x 2 ~ C oncentration cf 'i'EL i n i . n c v o p o r n t o d P o r t i o n of vivol flu ii.. . O \s i\ V\ \ a lira 1 - L aboratory V ito! 0 Enti 2 - L a b o r a t o r y V i t a l t\ fina 3 I 've: ;; >'; P r e , 'vi.t o i 't \ xftorrpson ??.vod, V i t o l Gl \ ' \i % V iV \ \ ? t i \ ) [ i i ticrograas lea lOC.OOO ICyOOO Sun 2 Jiin 1 L ab o ratcry Yito'l Sun 3 " Thompson VAtol 1 , COO - p> 3O a. LOO JOadsd a so liaio LI D 44- 67 ' ti ! 10 1 L-. 0 Toado lirrh 4 m:lcrograrns/cu, ft* i. 20 40 60 Woigh p o r con* ev ap o rato d 80 F ig. 3 " Comparieon of Load i i r t o r E v a p o ratlo n o' Y ito l F lu id and Loado! G asolina. 100 K 0020666