Temperature Dependence for the Rate Coefficients of the Reactions of the OH Radical with a Series of Formates

The kinetics of the reactions of OH with methyl formate (1), ethyl formate (2), n -propyl formate (3), n -butyl formate (4), and tert -butyl formate (5) were studied using the pulsed laser photolysis−laser-induced fluorescence technique. The obtained results in the temperature range 233−372 K were the following (in cm 3 molecule -1 s -1 ): k 1 = (8.54 ± 1.98) × 10 -13 exp[−(461 ± 70)/ T ], k 2 = (5.66 ± 1.10) × 10 -13 exp[(134 ± 53)/ T ], k 3 = (1.65 ± 0.45) × 10 -12 exp[(42 ± 78)/ T ], k 4 = (3.63 ± 1.08) × 10 -12 exp[(15 ± 88)/ T ], and k 5 = (3.59 ± 0.98) × 10 -12 exp[−(449 ± 82)/ T ]. At room temperature the obtained rate coefficients were the following (in 10 -13 cm 3 molecule -1 s -1 ): k 1 = 1.73 ± 0.21; k 2 = 8.52 ± 0.75; k 3 = 18.0 ± 1.7; k 4 = 35.4 ± 5.2; and k 5 = 7.46 ± 0.91. These results are discussed with respect to literature data and structure−activity relationships.