Rate constants for the reaction of OH radicals with n-propyl, n-butyl, iso-butyl and tert-butyl vinyl ethers

摘要

Rate constants for the reaction of OH radicals with n-propyl vinyl ether (PVE, CH3CH2CH2OCH = CH2) n-butyl vinyl ether (BVE, CH3CH2CH2CH2OCH = CHA iso-butyl vinyl ether (IBVE, (CH3)(2)CHCH2OCH = CH2) and tert-butyl vinyl ether (TBVE, (CH3)(3)COCH = CH2) have been measured in the temperature and pressure ranges 232-373 K and 30-300 Torr using the pulsed laser photolysis-laser-induced fluorescence method, and at 298K and 760 Torr using the relative method. The obtained results are k(1) = (9.3 +/- 0.6) x 10(-12) exp[(708 +/- 20)/T], k(2) = (1.5 +/- 0.2) x 10(-11) exp[(572 +/- 42)/T], k(3) = (1.6 +/- 0.1) x 10(-11) exp[(567 +/- 20)/T], k(4) = (1.7 +/- 0.2) x 10(-11) exp[(549 +/- 25)/T] cm(3) molecule(-1) s(-1). The values at 298 K are k(1) = (1.0 +/- 0.1) x 10(-10), k(2) = (1.0 +/- 0.1) x 10(-10), k(3) = (1.1 +0.1) x 10(-10), k(4) = (1.1 +0.1) x 10(-10)cm(3) molecule(-1) s(-1). The deduced tropospheric lifetimes of these ethers for reaction with OH are of the order of 1 h and they are comparable to those for reaction with ozone. (c) 2006 Elsevier Ltd. All rights reserved.