KINETICS OF OH RADICAL REACTIONS WITH A SERIES OF ETHERS

The rate constants for the reactions of OH with dimethyl ether ((k1)), diethyl ether ((k2)), di-n-propyl ether (k(3)), di-isopropyl ether (k (4)), and di-n-butyl ether (k5) have been measured over the temperatur e range 230-372 K using the pulsed laser photolysis-laser induced fluo rescence (PLP-LIF) technique. The temperature dependence of k(1), k(4) , can be expressed in the Arrhenius plots form: k(1) = (6.30 +/- 0.10) x 10(-12) exp[-(234 +/- 34)/T] and k(4) = (4.13 +/- 0.10) x 10(-12) e xp[(274 +/- 26)/T]. The Arrhenius plots for k(2), k(3), and k(5), were curved and they were fitted to the three parameter expressions: k(2) = (1.02 +/- 0.08) x 10(-17)T(2) exp[(797 +/- 24)/T], k(5) = (1.84 +/- 0.23) x 10(-17)T2 exp[(767 +/- 34)/T], and k(5) = (6.29 +/- 0.74) X 10 -T-18(2) exp[(1164 +/- 34)/T]. The values at 298 K are (2.82 +/- 0.21) x 10(-12), (1.36 +/- 0.11) x 10 (-11), (2.17 +/- 0.16) x 10(-11), (1. 02 +/- 0.10) x 10(-11), and (2.69 +/- 0.22) x 10(-11) for k(1), k(2), k(3), k(4), and k(5), respectively, (in cm(3) molecule(-1) s(-1)). The se results are compared to the literature data. (C) 1995 John Wiley an d Sons, Inc.