1916
KRAMER
VOL.32
The Oxidation of Paraffins in Sulfuric Acid G. M. KRAMER Central Basic Research Laboratory, ESSOResearch and Engineering Company, Linden, New Jersey Received September f39, 1966 Branched paraffins have been found to undergo moderately long-chain reactions in concentrated sulfuric acid after an induction period during which oxidation occurs. The chain lengths decrease as conversion proceeds. The small amount of oxidation observed is attributed essentially entirely to the initial reaction of the paraffin and not to secondary reactions of product olefins.
Carbonium ion theory provides a convenient basis Results and Discussion for the discussion of an enormous range of reactions. In Table I are summarized the extent of oxidation The behavior of branched paraffins in concentrated and conversion observed for a series of oxidation exsulfuric acid in particular has been the subject of periments under pseudo-adiabatic (A) and pseudonumerous investigations which lend themselves readily (B) conditions. isothermal to this theory. Still, little quantitative information is available dealing with the initiation process by which TABLEI the ions form and its relation to observed reactivity. OXIDATION AND CONVERSION OF BRANCHED, In a previous paper,' and in agreement with ~ t h e r s , ~ , ~ SATURATED IN 98.5y0 SULFURIC ACID HYDROCARBONS it has been noted that 2,3,4-trimethylpentane reacts Condn, 2 min in sulfuric acid after an induction period during which Pseudo-adiabatic, Pseudo-isothermal, -T = 27.5 f 2'7 - T 21 f 2'sulfur dioxide is formed. The reaction follows a secSO,, Convn, 801, Convn, ond-order dependence on acidity which can be raCompound P P ~ ' %* ppm % tionalized by assuming that a steady-state carbonium 3-Methylpentane 17
