The pyrolysis of 2-methyl-2-nitrosopropane

Abstract

The pyrolysis of 2-methyl-2-nitrosopropane has been studied in a static system over the temperature range 1 40-220'. From a consideration of the products and their distribution with time it is shown that a considerable number of elementary reactions participate in the pyrolysis. The significance of these results for mechanisms of nitric oxide-inhibited pyrolyses is discussed.NITRIC OXIDE has been used as an inhibitor of gaseous free-radical chain reactions for more than thirty years.It has generally been accepted1 that the primary reaction is removal of the free-radicals R by reaction (1) to form a nitroso-alkane R + NO _t RNO(1) There are, however, differences of opinion concerning the fate of the nitroso-alkane. It has been suggested that primary and secondary nitroso-alkanes isomerise to the oxime and some direct studies of the reactions of oximes2-5 have been carried out. Other reactions suggested for nitroso-alkanes include :Apart from one study of the thermal decomposition of nitrosomethane at low pressure in a flow system and an i.r. examination of the same reaction in a static system 7 no direct study of the gas reactions of nitrosoalkanes has been reported although many workers have reported on the direct reaction of free radicals with nitric oxide. It was therefore decided to make a direct study of the pyrolysis of 2-methyl-2-nitrosopropane, the simplest tertiary alkyl-nitroso-compound. Pyrolysis of such a nitroso-alkane cannot involve isomerisation to the oxime and hence might be expected to be simpler than for a primary or secondary nitroso-alkane.

Very‐low‐pressure pyrolysis of nitroso‐ and pentafluoronitrosobenzene CNO bond dissociation energies

“…Recently we have shown [3] that the decomposition of nitrosoisobutane could be successfully studied using the very-low-pressure pyrolysis (VLPP) technique, while conventional high-pressure static pyrolysis gave products too complicated for quantitative understanding of the system [4]. '[n this paper we wish to report the absolute rate constants for the thermal decomposition of nitroso-and pentafluoronitrosobenzene.…”

Reaction of di‐tert‐butylnitroxide radicals

“…The reaction at high conversion does not follow a simple kinetic law due possibly to the secondary reactions of 2-methyl-2-nitrosopropane, which decomposes at the temperatures employed in the present work [14]. This is also clearly shown by the decrease in the absorbance at 675 nm observed at long reaction times (see Fig.…”