Journal of Physical Chemistry A, Vol.103, No.17, 3210-3215, 1999
Absolute reaction rate of chlorine atoms with chloroiodomethane
The reaction of Cl atoms with CH2ClI was studied in the gas phase with the very low pressure reactor (VLPR) technique over the temperature range 273-363 K. The absolute rate constant was found to be k(1) = 3.13 +/- 0.27 x 10(-11) cm(3) molecule(-1) s(-1) (2 sigma uncertainty), independent of temperature. The reaction occurs through iodine atom abstraction leading to CH2Cl and ICI products. The secondary reaction of Cl atoms with ICl as well as the self-reaction of CH2Cl radicals was also occurring, leading to the production of I atoms, Cl-2, CH2=CHCl, and HCl, respectively. Ab initio calculations at the MP2/3-21++G(2d,2p) level of theory suggest that the title reaction may proceed via the intermediate formation of a weakly bound adduct CH2ClI-Cl, with an I-Cl bond strength of 54.8 kJ mol(-1). The enthalpies of formation for CH2ClI and CHClI at 298.15 K were also calculated at the MP2/3-21++G(2d,2p) level of theory to be 13.0 and 212.0 kJ mol(-1), respectively.
Keywords:TEMPERATURE-RANGE;RATE CONSTANTS;METHYL-IODIDE;CL ATOMS;KINETICS;IODOMETHANE;TROPOSPHERE;MECHANISM;RADICALS;CH2ICL