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FT-IR kinetic and product study of the OH radical and Cl-atom–initiated oxidation of dibasic esters

✍ Scribed by Fabrizia Cavalli; Ian Barnes; Karl Heinz Becker


Publisher
John Wiley and Sons
Year
2001
Tongue
English
Weight
238 KB
Volume
33
Category
Article
ISSN
0538-8066

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✦ Synopsis


Using a relative kinetic technique, rate coefficients have been measured, at 296 Ϯ 2 K and 740 Torr total pressure of synthetic air, for the gas-phase reaction of OH radicals with the dibasic esters dimethyl succinate

The rate coefficients obtained were (in units of cm 3 molecule Ϫ1 s Ϫ1 ): dimethyl succinate (1.89 Ϯ 0.26) ϫ 10 Ϫ12 ; dimethyl glutarate (2.13 Ϯ 0.28) ϫ 10 Ϫ12 ; and dimethyl adipate (3.64 Ϯ 0.66) ϫ 10 Ϫ12 . Rate coefficients have been also measured for the reaction of chlorine atoms with the three dibasic esters; the rate coefficients obtained were (in units of cm 3 molecule Ϫ1 s Ϫ1 ): dimethyl succinate (6.79 Ϯ 0.93) ϫ 10 Ϫ12 ; dimethyl glutarate (1.90 Ϯ 0.33) ϫ 10 Ϫ11 ; and dimethyl adipate (6.08 Ϯ 0.86) ϫ 10 Ϫ11 . Dibasic esters are industrial solvents, and their increased use will lead to their possible release into the atmosphere, where they may contribute to the formation of photochemical air pollution in urban and regional areas. Consequently, the products formed from the oxidation of dimethyl succinate have been investigated in a 405-L Pyrex glass reactor using Cl-atom-initiated oxidation as a surrogate for the OH radical. The products observed using in situ Fourier transform infrared (FT-IR) absorption spectroscopy and their fractional molar yields were: succinic formic anhydride (0.341 Ϯ 0.068), monomethyl succinate (0.447 Ϯ 0.111), carbon monoxide (0.307 Ϯ 0.061), dimethyl oxaloacetate (0.176 Ϯ 0.044), and methoxy formylperoxynitrate (0.032-0.084). These products account for 82.4 Ϯ 16.4% C of the total reaction products. Although there are large uncertainties in the quantification of monomethyl succinate and dimethyl oxaloacetate, the product study allows the elucidation of an oxidation mechanism for dimethyl succinate.


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