Kinetics of the reactions of hydroxyl radicals (OH) and of chlorine atoms (Cl) with methylethylether over the temperature range 274-345 K

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

“…In the SAR method, the calculation of the overall rate constant is based on the estimation of 9 CH 3 , 9 CH 2 9 and ϾCH 9 group rate constants. For example, for DME, F(O) ϭ k exp /(2 ϫ k prim ) ϭ 1.30 ϫ 10 Ϫ10 / (2 ϫ 3.32 ϫ 10 Ϫ11 ) ϭ The rate constants for the Cl reactions are from this work and references [7,8,18]; those for the OH reactions are from reference [19,20]. These parameters deduced from the existing kinetic database for alkanes are the following at 298 K [17]: k prim ϭ 3.32 ϫ 10 Ϫ11 , k sec ϭ 8.34 ϫ 10 Ϫ11 , k tert ϭ 6.09 ϫ 10 Ϫ11 (in units of cm 3 molecule Ϫ1 s Ϫ1 ), F( 9 CH 3 ) ϭ 1.00, and F( 9 CH 2 9 ) ϭ F(ϾCH 9 ) ϭ F(ϾCϽ) ϭ 0.79.…”

“…For Cl ϩ ether reactions, in addition to our data, we have added those of Wallington et al [7] for DME, MTBE, and DEE with Cl because of the disagreement with our values. We have also added the data for CH 3 OC 2 H 5 (MEE) from Starkey et al [18] and for (C 5 H 11 ) 2 O (DpenE) from Nelson et al [8]. The rate constants for the reactions of OH with DME, DEE, DPE, DBE, DIPE, MTBE, and ETBE are taken from references [19,20].…”

Atmospheric Degradation of Volatile Organic Compounds

“…9,16 No reaction with O 3 is expected 46 and no photolysis occurs. Rate constants have been measured for the reactions of OH radicals with 15 ethers, 16,29,30,38,43,205,[236][237][238][239][240][241] and Table 1 lists the roomtemperature rate constants and temperature-dependent parameters for dimethyl ether, diethyl ether, methyl tert-butyl ether (MTBE), ethyl tert-butyl ether (ETBE), and tert-amyl methyl ether (TAME). Rate constants have been measured at temperatures down to ∼230 K for several of these ethers, including those listed in Table 1.…”

Atmospheric Chemistry of CH3CH2OCH3: Kinetics and Mechanism of Reactions with Cl Atoms and OH Radicals

“…The kinetics and atmospheric oxidation mechanisms of the symmetric short n-chain ethers, dimethyl ether, CH 3 OCH 3 , and diethyl ether, CH 3 CH 2 OCH 2 CH 3 , have been the subject of numerous studies in the past [1,2,[4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19][20][21]. By contrast, only one kinetic study of methyl ethyl ether (CH 3 CH 2 OCH 3 ), by Starkey et al [22], exists in the literature. No study of the end products of the atmospheric oxidation of CH 3 CH 2 OCH 3 exists.…”