Rate constants for the gas‐phase reactions of alkanes with Cl atoms at 296 ± 2 K

Abstract

AbstractRate constants for the gas‐phase reactions of the Cl atom with a series of alkanes have been determined at 296 ± 2 K using a relative rate method. Using a rate constant for the Cl atom reaction with n‐butane of 1.94 × 10−10 cm3 molecule−1 s−1, the rate constants obtained (in units of 10−11 cm3 molecule−1 s−1) were: 2‐methylpentane, 25.0 ± 0.8; 3‐methylpentane, 24.8 ± 0.6; cyclohexane, 30.8 ± 1.2; cyclohexane‐d12, 25.6 ± 0.8; 2,4‐dimethylpentane, 25.6 ± 1.2; 2,2,3‐trimethylbutane, 17.9 ± 0.7; methylcyclohexane, 34.7 ± 1.2; n‐octane, 40.5 ± 1.2; 2,2,4‐trimethylpentane, 23.1 ± 0.8; 2,2,3,3‐tetramethylbutane, 15.6 ± 0.9; n‐nonane, 42.9 ± 1.2; n‐decane, 48.7 ± 1.8; and cis‐bicyclo[4.4.0]decane, 43.1 ± 0.8, where the indicated errors are two least‐squares standard deviations and do not include the uncertainties in the n‐butane rate constant. These data have been combined with rate constants obtained previously for ten C2C7 alkanes and this entire data set has been used to develop an estimation method allowing the room temperature rate constants for the reactions of the Cl atom with alkanes to be calculated. © 1995 John Wiley & Sons, Inc.