Kinetic analysis of ethyl iodide pyrolysis based on shock tube measurements

Abstract

The optimization of a kinetic mechanism of the pyrolysis of ethyl iodide was carried out based on data obtained from reflected shock wave experiments with H-ARAS and I-ARAS detection. The analysis took into account also the measurements of Michael et al. (Chem. Phys. Lett. 2000, 319, 99-106) and Vasileiadis and Benson (Int. J. Chem. Kinet. 1997, 29, 915-925) of the reaction H2 + I = H + HI. The following Arrhenius parameters were determined for the temperature range 950-1400 K and the pressure range 1-2 bar: C 2H5I → C2H5 + I: log 10(A) = 13.53, E/R = 24,472 K; C2H5I → C2H4 + HI: log10(A) = 13.67, E/R = 27,168 K; H + HI → H2 + I: log10(A) = 13.82, E/R = 491 K; C 2H5I + H →C2H5 + HI: log 10(A) = 15.00, E/R = 2593 K (the units of A are cm3, mol, s). The joint covariance matrix of the optimized Arrhenius parameters was also determined. This covariance matrix was converted to the temperature-dependent uncertainty parameters f of the rate coefficients and also to the temperature-dependent correlation coefficients between pairs of rate coefficients. Each fitted rate coefficient was determined with much lower uncertainty compared to the estimated uncertainty of the data available in the literature. © 2013 Wiley Periodicals, Inc.