Pyrolysis of Ethyl Iodide as Hydrogen Atom Source: Kinetics and Mechanism in the Temperature Range 950–1200 K

Abstract

Abstract Ethyl iodide is a well known H atom precursor in shock tube experiments. In the present work, we study peculiarities, when C2H5I is used under conditions, where its decomposition is not longer fast compared to consecutive bimolecular reactions. On the basis of shock tube experiments with detection of H and I atoms by resonance absorption spectrometry, accompanied by quantum chemical (CCSD(T)/6-311G//CCSD/6-311G) and statistical rate theory calculations, we propose a small mechanism (5 reactions, 7 species) and kinetic data, which allow an adequate description of C2H5I pyrolysis as a H atom source down to temperatures between 950 and 1200 K at pressures ranging from 1 to 4 bar: C2H5I→C2H5 + I (1), k 1 = 9.9 × 1012 exp(−23200 K/T) s−1; C2H5 + M→C 2H4 + H + M (2), k 2 = 1.7 × 10−6 exp(−16800 KT) cm3 s−1 [D. L. Baulch et al., J. Phys. Chem. Ref. Data 34 (2005) 757]; C2H5I→C2H4 + HI (3), k 3 = 1.7 × 1013 exp(−26680 KT) s−1; H + HI→H2 + I (4), k 4 = 7.9 × 10−11 exp(−330 KT) cm3 s−1 [D. L. Baulch et al., J. Phys. Chem. Ref. Data 10(Suppl. 1) (1981) 1]; C2H5I + H→C2H5 + HI (5), k 5 = 7.0 × 10−9 exp(−3940 KT) cm3 s−1. The latter bimolecular abstraction step turned out crucial for an adaquate d escription of the hydrogen atom concentration-time profiles in the above mentioned temperature and pressure range for initial concentrations [C2H5I]0 > 2 × 1013 cm−3 corresponding to mole fractions > 1 ppm.