RATE CONSTANTS FOR REACTIONS OF OH RADICALS WITH A SERIES OF ASYMMETRICAL ETHERS AND TERT-BUTYL ALCOHOL

Absolute rate constants for the reactions of OH radicals with butyl et hyl ether (k(1)), methyl tert-butyl ether (k(2)), ethyl tert-butyl eth er (k(3)), tert-amyl methyl ether (k(4)), and tert-butyl alcohol (k(5) ) have been measured over the temperature range 230-372 K using a puls ed laser photolysis-laser induced fluorescence (PLP-LIF) technique. Th e temperature dependence of k(1) - k(5) when expressed in Arrhenius fo rm gave: k(1) = (6.59 +/- 0.66) X 10(-12) exp[(362 +/- 60)/T], k(2) = (5.03 +/- 0.27) X 10(-12) exp[-(133 +/- 30)/T], k(3) = (4.40 +/- 0.24) X 10(-12) exp[(210 +/- 37)/T], k(4) = (4.7 +/- 0.7) X 10(-12) exp[(82 +/- 85)/T], and k(5) = (2.66 +/- 0.48) X 10(-12) exp[-(270 +/- 130)/T ]. However, the Arrhenius plots for k(1) - k(5) were slightly curved a nd are best fitted by the three parameter fits which are given in the article. The room temperature values of k(1),k(2),k(3),k(4), and k(5) are (2.08 +/- 0.23) X 10(-11), (3.13 +/- 0.36) X 10(-12), (8.80 +/- 0. 50) X 10(-12), (6.28 +/- 0.45) X 10(-12), and (1.08 +/- 0.10) X 10(-12 ), respectively, in cm(3) molecule(-1) s(-1). (C) 1996 John Wiley & So ns, Inc.