ATMOSPHERIC CHEMISTRY OF DI-TERT-BUTYL ETHER - RATES AND PRODUCTS OF THE REACTIONS WITH CHLORINE ATOMS, HYDROXYL RADICALS, AND NITRATE RADICALS

The rate constants for the gas-phase reactions of di-tert-butyl ether (DTBE) with chlorine atoms, hydroxyl radicals, and nitrate radicals ha ve been determined in relative rate experiments using FTIR spectroscop y. Values of k((DTBE+Cl)) = (1.4 +/- 0.2) X 10(-10), k((DTBE+OH)) = (3 .7 +/- 0.7) X 10(-12), and k((DTBE+NO3)) = (2.8 +/- 0.9) X 10(-16) cm( 3) molecule(-1) s(-1) were obtained. Tert-butyl acetate was identified as the major product of both Cl atom and OH radical initiated oxidati on of DTBE in air in the presence of NOx. The molar tert-butyl acetate yield was 0.85 +/- 0.11 in the Cl atom experiments and 0.84 +/- 0.11 in OH radical experiments. As part of this work the rate constant for reaction of Cl atoms with tert-butyl acetate at 295 K was determined t o be (1.6 +/- 0.3) X 10(-11) cm(3) molecule(-1) s(-1). The stated erro r are two standard deviations (2 sigma). (C) 1996 John Wiley & Sons, I nc.