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Rate constant for the reaction of Cl with CHCl3

✍ Scribed by Karen M. Brahan; Arlene D. Hewitt; Gwen D. Boone; Scott A. Hewitt

Publisher: John Wiley and Sons
Year: 1996
Tongue: English
Weight: 551 KB
Volume: 28
Category: Article
ISSN: 0538-8066
DOI: 10.1002/(sici)1097-4601(1996)28:6<397::aid-kin1>3.0.co;2-q

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✦ Synopsis

The rate constant for the reaction of CI with CHCI, was measured relative to the CI reaction with Cti, and CH,CI using long path FTIR. The measured rate constant at 298 K and 1 atm total pressure was ( I 21 ? 0 13) X 10-"cm3 molecule-'s-' ( 2 ~1 , about 60%larger than the currently recommended value (although within the large error bars) The implications of the CI * CHCI, reaction for relative rate studies, chloromethane reactivity, and tropospheric chemistry are discussed. 0 1996 lohn Wiley &Sons, Inc

Introduction

Chloroform, CHCI, , comprises approximately 1 % of the organic chlorine in the troposphere [ 11. The main sources of atmospheric CHCl, are oceans, industry, and termites 12-41, The only significant sink for CHCI, i \ thought to be reaction with OH, leading to a lifetime of 0.5-0.8 years [1,4]. The OH-induced oxidation of CHCl, has been estimated to be the largest source of phosgene, CCI,O, in the troposphere [5,6]:

(2)

(3)

During our relative rate studies of the reaction of C1 with CO [7], we attempted to verify the accuracy of our relative rate constant measurements by determining the rate constant for the reaction of C1 with CHCI, relative to the reaction of C1 with CH,. Our

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