The kinetics of the reactions of chlorine atoms with acrylates have been studied by the

relative kinetic method. While there are a few studies in the literature of OH radical

reactions with unsaturated esters there are almost no data concerning their Cl-initiated

degradation. In this work, we report rate coefficients and preliminary product results for the

reactions of Cl with CH2=CHC(O)OCH3 (k1), CH2=C(CH3)C(O)OCH3 (k2) and

CH2=C(CH3)C(O)O(CH2)3CH3 (k3).

The experiments were performed over the temperature range 283-313K at atmospheric

CH2=C(CH3)C(O)O(CH2)3CH3 (k3).

The experiments were performed over the temperature range 283-313K at atmospheric

The experiments were performed over the temperature range 283-313K at atmospheric

pressure in a large volume photoreactor using in situ FTIR analysis to monitor the decay of

the organics and the reference compounds.

The following Arrhenius expressions (in units of cm3 molecule-1 s-1) have been obtained: k1

CH2=C(CH3)C(O)O(CH2)3CH3 (k3).

The experiments were performed over the temperature range 283-313K at atmospheric

The experiments were performed over the temperature range 283-313K at atmospheric

pressure in a large volume photoreactor using in situ FTIR analysis to monitor the decay of

the organics and the reference compounds.

The following Arrhenius expressions (in units of cm3 molecule-1 s-1) have been obtained: k1

The experiments were performed over the temperature range 283-313K at atmospheric

pressure in a large volume photoreactor using in situ FTIR analysis to monitor the decay of

the organics and the reference compounds.

The following Arrhenius expressions (in units of cm3 molecule-1 s-1) have been obtained: k1

= (0.59 ± 0.11) × 10-11 exp[(1.097 ± 0.098) × 103 / RT], k2 = (3.77 ± 1.12) × 10-11 exp[-

(16.68 ± 1.54) × 103 / RT], k3 = (1.34 ± 1.04) × 10-11 exp[-(19.59 ± 3.21) × 103 / RT]. The

negative temperature dependencies of the three reactions supports that addition of Cl to the

(16.68 ± 1.54) × 103 / RT], k3 = (1.34 ± 1.04) × 10-11 exp[-(19.59 ± 3.21) × 103 / RT]. The

negative temperature dependencies of the three reactions supports that addition of Cl to the

negative temperature dependencies of the three reactions supports that addition of Cl to the

double bond is the main reaction pathway for each reaction.

This is further supported by the currently ongoing product analyses. The observed products

are in line with the preferential addition of Cl to the less substituted carbon atom of the

double bond followed by decomposition of the 1,2-hydroxyalcoxy radicals formed.

Reaction mechanisms will be presented for the Cl initiated oxidation which can be used to

construct mechanisms for the analogue more atmospherically important OH radical

reactions.

(16.68 ± 1.54) × 103 / RT], k3 = (1.34 ± 1.04) × 10-11 exp[-(19.59 ± 3.21) × 103 / RT]. The

negative temperature dependencies of the three reactions supports that addition of Cl to the

negative temperature dependencies of the three reactions supports that addition of Cl to the

double bond is the main reaction pathway for each reaction.

This is further supported by the currently ongoing product analyses. The observed products

are in line with the preferential addition of Cl to the less substituted carbon atom of the

double bond followed by decomposition of the 1,2-hydroxyalcoxy radicals formed.

Reaction mechanisms will be presented for the Cl initiated oxidation which can be used to

construct mechanisms for the analogue more atmospherically important OH radical

reactions.

negative temperature dependencies of the three reactions supports that addition of Cl to the

double bond is the main reaction pathway for each reaction.

This is further supported by the currently ongoing product analyses. The observed products

are in line with the preferential addition of Cl to the less substituted carbon atom of the

double bond followed by decomposition of the 1,2-hydroxyalcoxy radicals formed.

Reaction mechanisms will be presented for the Cl initiated oxidation which can be used to

construct mechanisms for the analogue more atmospherically important OH radical

reactions.