Reaction of oxygen atoms with methyl and ethyl nitrates

Abstract

The reaction of oxygen atoms with methyl nitrate and with ethyl nitrate have been studied in a discharge–flow system at temperatures between 294 and 473 K. The initial attack involves abstraction of a hydrogen atom for which the rate expressions are shown to be 1.5 × 10¹⁰ exp (–22.0 ± 1.0 kJ mol^–1/RT) dm³ mol^–1 s^–1 and 2.6 × 10¹⁰ exp (–21.6 ± 2.6 kJ mol^–1/RT) dm³ mol^–1 s^–1 respectively. The activation energy for hydrogen abstraction is not reduced by the fact that the initially formed radical ruptures exothermically to yield an aldehyde plus nitrogen dioxide.