The Cl-initiated oxidation of CH(3)C(O)OCH=CH (2), CH (3)C(O)OCH (2)CH=CH (2), and CH (2)=CHC(O)O(CH (2)) (3)CH (3) in the troposphere.
OBJECTIVE
Unsaturated esters are emitted to the atmosphere from biogenic and anthropogenic sources, including those from the polymer industry. Little information exists concerning the atmospheric degradation of unsaturated esters, which are mainly initiated by OH radicals. Limited information is available on the degradation of alkenes by Cl atoms and almost no data exists for the reactions of unsaturated esters with Cl atoms. This data is necessary to assess the impact of such reactions in maritime environments where, under circumstances, OH radical- and Cl atom-initiated oxidation of the compounds can be important. Rate coefficients for the reactions of chlorine atoms with vinyl acetate, allyl acetate, and n-butyl acrylate have been determined at 298 +/- 3 K and atmospheric pressure. The kinetic data have been used in combination with that for structurally similar compounds to infer the kinetic contributions from the possible reaction channels to the overall reaction rate.


METHODS
The decay of the organics was followed using in situ Fourier transform infrared spectroscopy and the rate coefficients were determined using a relative kinetic method and different hydrocarbon reference compounds.


RESULTS
The following room temperature rate coefficients (in cm(3) molecule(-1) s(-1)) were obtained: k (1) (Cl + CH(3)C(O)OCH=CH(2)) = (2.68 +/- 0.91) x 10(-10), k (2) (Cl + CH(3)C(O)OCH(2)CH=CH(2)) = (1.30 +/- 0.45) x 10(-10), and k (3) (Cl + CH(2)=CHC(O)O(CH(2))(3)CH(3)) = (2.50 +/- 0.78) x 10(-10), where the uncertainties are a combination of the 2sigma statistical errors from linear regression analyses and a contribution to cover uncertainties in the rate coefficients of the reference hydrocarbons.


CONCLUSIONS
This is the first kinetic study of the title reactions under atmospheric conditions. The kinetic data were analyzed in terms of reactivity trends and used to estimate the atmospheric lifetimes of the esters and assess their potential importance in the marine atmosphere.


CONCLUSIONS
Although reaction with OH radicals is the major atmospheric sink for the unsaturated esters studied, reaction with Cl atoms can compete in the early morning hours in coastal areas where the Cl concentration can reach peak values as high as 1 x 10(5) atoms cm(-3). The calculated residence times show that the chemistry of unsaturated esters will impact air quality locally near their emission sources.


CONCLUSIONS
The reactions need to be studied over the range of temperatures and pressures generally encountered in the marine atmosphere. In addition, product studies should also be performed as a function of temperature since this will allow degradation mechanisms to be derived, which are representative for the wide range of conditions occurring in marine environments. Inclusion of the kinetic and product data in tropospheric numerical models will allow an assessment of potential environmental impacts of the esters for different marine pollution scenarios.
Blanco
María B
MB
Instituto de Investigaciones en Fisicoquímica de Córdoba (I.N.F.I.Q.C.), Dpto. de Fisicoquímica, Facultad de Ciencias Químicas, Universidad Nacional de Córdoba, Ciudad Universitaria, 5000, Córdoba, Argentina.
Bejan
Iustinian
I
Barnes
Ian
I
Wiesen
Peter
P
Teruel
Mariano A
MA
D000393:Air Pollutants / Q000737:chemistry*; D001274:Atmospheric Pressure; D002713:Chlorine / Q000737:chemistry*; D004952:Esters / Q000737:chemistry*; D010084:Oxidation-Reduction; D013696:Temperature
D000393:Air Pollutants; D004952:Esters; D002713:Chlorine