Theoretical study on the gas phase reaction of allyl chloride with hydroxyl radical

Abstract

The reaction of allyl chloride with the hydroxyl radical has been investigated on a sound theoretical basis. This is the first time to gain a conclusive insight into the reaction mechanism and kinetics for important pathways in detail. The reaction mechanism confirms that OH addition to the C=C double bond forms the chemically activated adducts, IM1 (CH2CHOHCH2Cl) and IM2 (CH2OHCHCH2Cl) via low barriers, and direct H-abstraction paths may also occur. Variational transition state model and multichannel RRKM theory are employed to calculate the temperature-, pressure-dependent rate constants. The calculated rate constants are in good agreement with the experimental data. At 100 Torr with He as bath gas, IM6 formed by collisional stabilization is the major products in the temperature range 200-600 K; the production of CH2CHCHCl via hydrogen abstractions becomes dominant at high temperatures (600-3000 K).

Theoretical Study on the Reactions of (CF3)2CFOCH3 + OH/Cl and Reaction of (CF3)2CFOCHO with Cl Atom

“…The T 1 values of all species in our system are smaller than 0.045, indicating that multireference character in CCSD(T) wave function is not a problem. 36 All the electronic structures are carried out with Gaussian 09 program package. 37 The initial PES information, including optimized geometries, energies, and frequencies along the MEPs as determined from IRC theory, are prepared for dynamic calculations.…”

Temperature dependence of rate coefficients for the gas phase reaction of OH with 3-chloropropene. A theoretical and experimental study

“…Grosjean 5 has proposed that the reaction releases Cl atoms and leads to carbonyl compounds as reported by Zhang et al. 6 and Tuazon et al 7 To the best of our knowledge, the reaction of OH with 3-chloropropene has been investigated by a limited number of groups. Edney et al 8,9 and Tuazon et al 7 used the relative rate method to determine the rate coefficient value at room temperature in N 2 as bath gas.…”

“…[14][15][16] . In particular, Zhang et al 6 have computationally investigated the gas phase reaction of OH radical with 3-Chloropropene to products at 100 Torr and between 200-600 K temperature range. They have considered two addition and four hydrogen abstraction pathways.…”

“…Taking into account the experimental and theoretical results of Tuazon et al 7 and Zhang et al 6 , we have considered in this work that at temperatures lower than 600 K the rate limiting step of the reaction [1] is determined by a mechanism composed by OH addition to double bond and the β-H atom abstraction parallel reactions, according to the following general scheme:…”

“…Reaction [1] (involving the elementary reactions [2][3][4][5][6][7][8] and the further splitting explained in the discussion section) has been described at Density Functional Theory (DFT) level, 18 adopting the M06-2X functional 19 along with the aug-cc-pVTZ basis sets…”