Alkyl nitrate formation from the reaction of a series of branched RO₂ radicals with NO as a function of temperature and pressure

Abstract

Alkyl nitrate yields from the NO _x photooxidations of neopentane, 2-methylbutane and 3-methylpentane have been determined over the temperature and pressure ranges 281–323 K and 54–740 torr, respectively. The formation of the alkyl nitrates is attributed to the reaction pathway

$${\text{RO}}_{\text{2}} + {\text{NO}}^{{\text{ }}\underrightarrow {\text{M}}} {\text{ RONO}}_{\text{2}}$$

((1b))

and rate constant ratios k _1b/(k _1a+k _1b) are estimated, where (1a) is the reaction pathway

$${\text{RO}}_{\text{2}} + {\text{NO}} \to {\text{RONO}}_{\text{2}} .$$

((1a))

A method for estimating this rate constant ratio for primary, secondary and tertiary alkyl peroxy radicals is presented.