| Abstract: | Using a relative kinetic technique, rate coefficients have been measured, at 296 ± 2 K and 740 Torr total pressure of synthetic air, for the gas‐phase reaction of OH radicals with the dibasic esters dimethyl succinate CH3OC(O)CH2CH2C(O)OCH3], dimethyl glutarate CH3OC(O)CH2CH2CH2C(O)OCH3], and dimethyl adipate CH3OC(O)CH2CH2CH2CH2C(O)OCH3]. The rate coefficients obtained were (in units of cm3 molecule?1 s?1): dimethyl succinate (1.89 ± 0.26) × 10?12; dimethyl glutarate (2.13 ± 0.28) × 10?12; and dimethyl adipate (3.64 ± 0.66) × 10?12. 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 cm3 molecule?1 s?1): dimethyl succinate (6.79 ± 0.93) × 10?12; dimethyl glutarate (1.90 ± 0.33) × 10?11; and dimethyl adipate (6.08 ± 0.86) × 10?11. 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 ± 0.068), monomethyl succinate (0.447 ± 0.111), carbon monoxide (0.307 ± 0.061), dimethyl oxaloacetate (0.176 ± 0.044), and methoxy formylperoxynitrate (0.032–0.084). These products account for 82.4 ± 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. © 2001 John Wiley & Sons, Inc. Int J Chem Kinet 33: 431–439, 2001 |
