Rate coefficients and mechanisms of the reaction of Cl-atoms with a series of unsaturated hydrocarbons under atmospheric conditions

  • Orlando J
  • Tyndall G
  • Apel E
 et al. 
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Abstract

Rate coeffs. and/or mechanistic information are provided for the reaction of Cl-atoms with a no. of unsatd. species, including isoprene, methacrolein (MACR), Me vinyl ketone (MVK), 1,3-butadiene, trans-2-butene, and 1-butene. The following Cl-atom rate coeffs. were obtained at 298 K near 1 atm total pressure: k(isoprene) = (4.3 ± 0.6) × 10-10 cm3 mol.-1 s-1 (independent of pressure from 6.2 to 760 torr); k(MVK) = (2.2 ± 0.3) × 10-10 cm3 mol.-1 s-1; k(MACR) = (2.4 ± 0.3) × 10-10 cm3 mol.-1 s-1; k(trans-2-butene) = (4.0 ± 0.5) × 10-10 cm3 mol.-1 s-1; k(1-butene) = (3.0 ± 0.4) × 10-10 cm3 mol.-1 s-1. Products obsd. in the Cl-atom-initiated oxidn. of the unsatd. species at 298 K in 1 atm air are as follows (with % molar yields in parentheses): CH2O (9.5 ± 1.0%), HCOCl (5.1 ± 0.7%), and 1-chloro-3-methyl-3-buten-2-one (CMBO, not quantified) from isoprene; chloroacetaldehyde (75 ± 8%), CO2 (58 ± 5%), CH2O (47 ± 7%), MeOH (8%), HCOCl (7 ± 1%), and peracetic acid (6%) from MVK; CO (52 ± 4%), chloroacetone (42 ± 5%), CO2 (23 ± 2%), CH2O (18 ± 2%), and HCOCl (5%) from MACR; CH2O (7 ± 1%), HCOCl (3%), acrolein (≈3%), and 4-chlorocrotonaldehyde (CCA, not quantified) from 1,3-butadiene; CH3CHO (22 ± 3%), CO2 (13 ± 2%), 3-chloro-2-butanone (13 ± 4%), CH2O (7.6 ± 1.1%), and MeOH (1.8 ± 0.6%) from trans-2-butene; and chloroacetaldehyde (20 ± 3%), CH2O (7 ± 1%), CO2 (4 ± 1%),. And HCOCl (4 ± 1%) from 1-butene. Product yields from both trans-2-butene and 1-butene are O2-dependent. In the case of trans-2-butene, the obsd. O2-dependence is the result of a competition between unimol. decompn. of the CH3CH(Cl)-CH(O·)-Me radical and its reaction with O2, with kdecomp/kO2 = (1.6 ± 0.4) × 1019 mol cm-3. The activation energy for decompn. is estd. at 11.5 ± 1.5 kcal mol-1. The variation of the product yields with O2 in the case of 1-butene results from similar competitive reaction pathways for the two β-chlorobutoxy radicals involved in the oxidn., ClCH2CH(O·)Et and ·OCH2CHClEt. [on SciFinder(R)]

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Authors

  • John J. Orlando

  • Geoffrey S. Tyndall

  • Eric C. Apel

  • Daniel D. Riemer

  • Suzanne E. Paulson

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