Mechanism of Gum Formation in Cracked Gasoline Formation of Peroxide, Aldehyde, and Acid in Storage CG. Daven, C.D. Lowney, Jn,, J.C. Monnrut, an Gusti Eetor Universal Oil Products Company, Chicago, 1. HIE reactions which ceeur ‘when oradkel gasoline ie Stored in contact with The fist evi- that bas been dezected isthe formation of per~ osidis products. From coe ‘mercial standpoint, atleast, the final step in deterioration is the fonmatinotgum. Besidesthese two products, aldehydic and faci products have been #0 ported. No one has coselasvely Shown’ what relationships exist between the peroxides, alde- hytles, and acids formed and iat part they play in the gu forming process Smith snd Cock (9) obtained evidence of aldehydes in. aged tracked gesolines and considered them primarily: responsible Tor the formation of gum. Story, Provine, and Beanet® (10) detected peroxides, acids, and aldehydes in gasoline which ‘was being evsporated in a copper dish and in fasoline exposed to sunlight. ‘They came to the eonelusion that "the products of the oxidation appear to_be prindpally peroxides, with acids as the eble! end product, aking up the gum.” Yule fand Wilson (12) showed that the peroxide method whic Story, Provine, end Bennett used determined only a small part of the totsl peroxides in the gasoline. Brooks (1) Stated that. peroxides, aldehydes, leobols, and ketenes “could easily be detected in samples of eracked gasoline ‘becom slightly oxidized.” Ho reposted the mn of formaldehyde, acetaldehycie, propionaide- hhyde, and butyraldehyde in old gasoline. The aldehydes formed, he bebeved, by the reaction of peroxides with olefins (Pailestajew's resction, 7) and opposed the couclusion cf Smith and Cocke that aldohydse are intermediato in gum for mation, as be found that addition of eldshydes to gasoline being evaporated did not inorease the amount of gum formed. ‘Brooks considered that gum was largely a mixtare of per oxides, although the gum formed after a loag period of storage ccntaized aside substancer. ‘Wagner and Hyman (11) also reported aldehydes, acids, fund peroxides in old gasoline ard, while they confirmed the finding of Brocks that addition of simple sliphatic aldehydes to gasoline did not inerease its tendency to form gum, they found that erotonaldehydlo did accolarste gumming. "They origins. on peroxide, Sormation. Earlier work has shown thal peronide, alde- Iryde, and acid can te deteced in cracked gasoline as i deteriorates ard forme gum. In this study the rate of fermation of substances of these four classes has teen followed in gasolires of several Some were wurefiaed, sume. refined, tnd some contained inhibitors tion has been stadied daring siorage fora year. Peroxide can be selected early in. the slorage period when no aldehyde or acid and prac ically no gun io presen!. The rate of perozide Jormalica accelerates with time. igins 10 appear somewhal laler and increases ‘more gradually than perozide. Acid formation begins Ail laler, and acid concentration in. creases mare siouly than Bra! of wither aldehyde Gum begins lo oppeer in rather large amount ax ss90n as considerable peroride has formed and before any large development of aldehyde or acid. The curve of gum content vs. time is similar in shape lo the perorie curve, and the conclusion seems juslifiable that gum formation is closely related to te concentration of peroride, and that aldehyde and acid are products of secondary reactions rather than infermediates in gum also reported the odar of seri= loin in gaeoline oxidized undor pressure. They postulated actions giving rise to perasids, which they considered the essen tial catalysts in gum formation. Yeleand Wilson (12) questioned thie mechanism, pointi hata sample of gammy gasoline which had been washed with The deteriora: ‘would not contain peracis, has just as great an effect in uocoler= ‘ting gum formation in freshly cracked gascline as if it ad not bbean washed, ‘Marites and Doss (9) stated that “the process of gumming. ‘appease to! be intinted by the phunary formation of organic perorides. .. .and the products Of oxidation other than per~ oxides—natcely, aldeliydes, Re tones, aida, ate.—wers found to hhave no accelerating effect on the gum rate” Aldehyde be Hoffert and Claxion (6) have reported that aged Denzole containing umatarated hydro- "Ties waer studies we langaty untae in nature. Tne preeat investigation, the rater of formation of peroid,alihyt, ned aed gum Saree eral hates Ss torsira ible number ‘amples of guline in tome. Prom thse mite some ea‘ the median by ‘wileb gstine dtaiocaton and gum forns may te obiained Metsops oF ANatats Peroxides vere determined by the thiocyanate methed of ‘Yule and Wilson (12). Tn considering the values reported, it should be borne in mind dat, f determined by a method ts- {ng potansium iodide, the peroside concentrations would Ihave been considerably higher. ‘This was shown in tbe worke cf Yule and Wileon, and has been confirmed inthis laboratory. Aldehydes were determined by theamount of eclorimparted to a special Schiff reagent. ‘The usual Schiff reegent, a water eclution of rosaniline hydrochloride deoolorized with sillur dioside, emultifes badly if shaken with gasoline Emuulsifieation was avoiied by adding aleokol to the reageut. ‘The concentration of sulfur dioxide was variod until the de- sired sensitivity was obtained. The solution adopted had the following, composition: