Due to the increasing usage of combustion as an effective treatment process for the disposal of hazardous organic wastes, including chlorinated hydrocarbons (CHC), kinetic modeling of the combustion of CHCs is a rapidly growing field of study. The kinetics of the reaction CH3CHCl + O2 ⇔ CH3CHClO2 - products (1) has been studied at temperatures 296-839 K and He densities of (3-49) × 1016 molecules cm-3 by laser photolysis/photoionization mass spectrometry. Rate constants were determined in time resolved experiments as a function of temperature and bath gas density. At low temperatures (298-400 K) the rate constants are in the falloff region under the conditions of the experiments. Relaxation to equilibrium in the addition step of the reaction was monitored within the temperature range 520-590 K. Equilibrium constants were determined as a function of temperature and used to obtain the enthalpy and entropy of the addition step of the reaction (1). At high temperatures (750-839 K) the reaction rate constant is independent of both pressure and temperature within the uncertainty of the experimental data and equal to (1.2 ± 0.4) × 10-14 cm3 molecule-1 s-1. Vinyl chloride (C2H3Cl) was detected as a major product of reaction 1 at T = 800 K.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry