RATES OF REACTION BETWEEN THE NITRATE RADICAL AND SOME ALIPHATIC ETHERS

Rate coefficients for the reaction of NO3 with dimethyl ether, diethyl ether, di-n-propyl ether, and methyl t-butyl ether (MTBE) have been determined. Absolute rates were measured at temperatures between 258 and 373 K using the fast flow-discharge technique. Relative rate experiments were also made at 295 K in a reactor equipped with White optics and using FTIR spectroscopy to follow the reactions. The measured rate coefficients (in units of 10(-15) cm3 molecule-1 s-1) at 295 K are: 0.26 +/- 0.11, 2.80 +/- 0.23, 6.49 +/- 0.65, and 0.64 +/- 0.06 for dimethyl ether, diethyl ether, di-n-propyl ether, and methyl t-butyl ether, respectively. The corresponding activation energies are 21.0 +/- 5.0, 17.2 +/- 4.0, 15.5 +/- 2.1, and 20.1 +/- 1.7 kJ mole-1. The error limits correspond to the 95%-confidence interval. (C) 1994 John Wiley & Sons, Inc.