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) x 10(-13) exp[-(461 +/- 70)/T], k(2) = (5.66 +/- 1.10) x 10(-13) exp[(134 +/- 53)/T], k(3) = (1.65 +/- 0.45) x 10(-12) exp[(42 +/- 78)/T], k(4) = (3.63 +/- 1.08) x 10(-12) exp[(15 +/- 88)/T], and k(5) = (3.59 +/- 0.98) x 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.