Rate constants for the gas-phase reactions of Cl atoms with a series of ethers

The laser photolysis-resonance fluorescence technique has been used to dete rmine the absolute rate coefficient for the Cl atom reaction with a series of ethers, at room temperature (298 +/- 2) K and in the pressure range 15-6 0 Torr. The rate coefficients obtained (in units of cm(3) molecule(-1) s(-1 )) are dimethyl ether (1.3 +/- 0.2) x 10(-10), diethyl ether (2.5 +/- 0.3) x 10(-10), di-n-propyl ether (3.6 +/- 0.4) x 10(-10), di-n-butyl ether (4.5 +/- 0.5) x 10(-10), di-isopropyl ether (1.6 +/- 0.2) x 10(-10), methyl ter t-butyl ether (1.4 +/- 0.2) x 10(-10), and ethyl tert-butyl ether (1.5 +/- 0.2) x 10(-10). The results are discussed in terms of structure-reactivity relationship. (C) 2000 John Wiley & Sons. Inc.