Kinetic and Mechanistic Study of the Thermal Decomposition of Ethyl Nitrate

Abstract

Thermal decomposition of ethyl nitrate (ENT; CH3CH2ONO2) has been studied in a low-pressure flow reactor combined with a quadrupole mass spectrometer. The rate constant of the nitrate decomposition was measured as a function of pressure (1–12.5 Torr of helium) and temperature in the range 464–673 K using two different approaches: from kinetics of ENT loss and those of the formation of the reaction product (CH3 radical). The fit of the observed falloff curves with two-parameter expression provided the following low- and high-pressure limits for the rate constant of ENT decomposition: k0 = 1.0 × 10−4 exp(−16,400/T) cm3 molecule−1 s−1 and k∞ = 1.08 × 1016 exp(−19,860/T) s−1, respectively, which allow to reproduce (via above expression and with 20% uncertainty) all the experimental data obtained for k1 in the temperature and pressure range of the study. It was observed that the initial step of the thermal decomposition of ethyl nitrate is O–NO2 bond cleavage leading to formation of NO2 and CH3CH2O radical, which rapidly decomposes to form CH3 and formaldehyde as final products. The yields of NO2, CH3, and formaldehyde upon decomposition of ethyl nitrate were measured to be near unity. In addition, the kinetic data were used to determine the O–NO2 bond dissociation energy in ENT: 38.3 ± 2.0 kcal mol−1.