Observation of adducts in the reaction of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) using cavity ring-down spectroscopy

Shinichi Enami; Satoshi Hashimoto; Masahiro Kawasaki; Yukio Nakano; Takashi Ishiwata; Kenichi Tonokura; Timothy J Wallington

doi:10.1021/jp047297y

Observation of adducts in the reaction of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) using cavity ring-down spectroscopy

J Phys Chem A. 2005 Mar 3;109(8):1587-93. doi: 10.1021/jp047297y.

Authors

Shinichi Enami¹, Satoshi Hashimoto, Masahiro Kawasaki, Yukio Nakano, Takashi Ishiwata, Kenichi Tonokura, Timothy J Wallington

Affiliation

¹ Department of Molecular Engineering and Graduate School of Global Environmental Studies, Kyoto University, Kyoto 615-8510, Japan.

PMID: 16833481
DOI: 10.1021/jp047297y

Abstract

The reactions of Cl atoms with XCH2I (X = H, CH3, Cl, Br, I) have been studied using cavity ring-down spectroscopy in 25-125 Torr total pressure of N2 diluent at 250 K. Formation of the XCH2I-Cl adduct is the dominant channel in all reactions. The visible absorption spectrum of the XCH2I-Cl adduct was recorded at 405-632 nm. Absorption cross-sections at 435 nm are as follows (in units of 10(-18) cm2 molecule(-1)): 12 for CH3I, 21 for CH3CH2I, 3.7 for CH2ICl, 7.1 for CH2IBr, and 3.7 for CH2I2. Rate constants for the reaction of Cl with CH3I were determined from rise profiles of the CH3I-Cl adduct. k(Cl + CH3I) increases from (0.4 +/- 0.1) x 10(-11) at 25 Torr to (2.0 +/- 0.3) x 10(-11) cm3 molecule(-1) s(-1) at 125 Torr of N2 diluent. There is no discernible reaction of the CH3I-Cl adduct with 5-10 Torr of O2. Evidence for the formation of an adduct following the reaction of Cl atoms with CF3I and CH3Br was sought but not found. Absorption attributable to the formation of the XCH2I-Cl adduct following the reaction of Cl atoms with XCH2I (X = H, CH3, Br, I) was measured as a function of temperature over the range 250-320 K.