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. © 1994 John Wiley & Sons, Inc.