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

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Molecules, spectroscopy, kinetics, environment, & general theory, 1997-07, Vol.101 (30), p.5489-5493
• Main Authors: Le Calvé, Stéphane, Le Bras, Georges, Mellouki, Abdelwahid
• Format: Article
• Language: English
• Subjects: Analytical chemistry; Chemical Sciences; Ocean, Atmosphere; or physical chemistry; Sciences of the Universe; Theoretical and
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp970554x

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 cm3 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 cm3 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.