A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to study the detailed mechanism for the reaction of OH radicals with deuterated dimethyl sulfide [(CD&S, DMS-d6]. Equilibration of pulsed laser-generated OH with a (CD,),S-OH adduct has been directly observed, thus confirming the existence of this controversial weakly bound species. Elementary rate coefficients for adduct formation and decomposition and, therefore, the equilibrium constant for OH + (CD3)2S -(CD&SOH have been determined as a function of temperature. From the temperature dependence of the equilibrium constant over the relatively narrow temperature range 250-267 K, a 258 K adduct bond strength of 13.0 zk 3.3 kcal mol-' has been obtained (second law method). Altematively, an entropy change calculated using standard statistical mechanical methods and ab initio theory (for determining the (CD3)zS and (CD&SOH structures) has been employed in conjunction with an experimental value for the equilibrium constant at a single temperature to obtain a 258 K adduct bond strength of 10.1 f 1.1 kcal mol-' (third law method). Experiments in the presence of 0 2 confirm the previously reported dependence of the OH + DMS-d6 rate coefficient on the 0 2 partial pressure and are consistent with the previously proposed four-step mechanism involving hydrogen abstraction, addition of OH to the sulfur atom, and adduct decomposition in competition with an adduct + 0 2 reaction [Hynes et al. J. Phys. Chem. 1986, 90, 41481. The rate coefficient for the adduct + 0 2 reaction is found to be (8 f 3)x lo-', cm3 molecule-' s-l independent of pressure (100-700 Torr of N2) and temperature (250-300 K).

A pulsed laser photolysis-pulsed laser-induced fluorescence (PLP-PLIF) system was employed to study the kinetics and mechanisms of reactions (1) OH + h6-DMS --> products and (2) OH + d6-DMS --> products. We report direct observations of the rate coefficients for the formation and dissociation of the h6-OHDMS and d6-OHDMS adducts over the pressure range 50-650 Torr and between 240 and 245 K, together with measurements of the oxygen dependence of the effective rate coefficients for reactions 1 and 2 under similar conditions. The effective rate coefficients increased as a function of O2 concentration reaching their limiting values in each case. The values of the adduct formation rate, obtained from the O2 dependencies, were in excellent agreement with values determined from direct observation of adduct equilibration in N2. OH regeneration is insignificant. The rate coefficients for the formation of the adduct isotopomers showed slight differences in their falloff behavior and do not approach the high-pressure limit in either case. The equilibrium constants obtained show no dependence on isotopomer and are in good agreement with previous work. A "second-law" analysis of the temperature dependence of the equilibrium constant gives an adduct bond strength (DeltaH degrees =-10.9 +/- 1.0 kcal mol(-1)), also in good agreement with previously reported values. Using the entropy calculated from the ab initio vibrational frequencies, we obtain a "third-law" value for the reaction enthalpy at 240 K, DeltaH(240K) degrees = -10.5 kcal mol(-1) in good agreement with the other approach. The rate coefficient for the reactions of the adducts with O2 was obtained from an analysis of the O2 dependence and was determined to be 6.3 +/- 1.2 x 10(-13) cm3 molecule(-1) s(-1), with no dependence on pressure or isotopomer. The pressure and temperature dependence for all of the elementary processes in the initial steps of the dimethylsulfide (DMS) oxidation mechanism have been characterized in the range 238-245 K, allowing the formulation of an expression which can be used to calculate the effective rate coefficient for reaction 1 at any pressure and oxygen concentration. The expression can calculate the effective rate coefficient for reaction 1 to +/- 40% over the range 220-260 K, with the largest errors at the extremes of this range. Gaussian 03 has been used to calculate the structure of the OH-DMS adduct and its deuterated isotopomer. We find similar bound structures for both isotopomers. The calculated enthalpies of formation of the adducts are lower than the experimentally determined values.

A pulsed laser photolysis-pulsed laser induced fluorescence technique has been employed to measure rate coefficients for the OH initiated oxidation of methylethyl sulfide (MES) and diethylsulfide (DES). In the absence of oxygen and at low sulfide concentrations we measure rate coefficients that are independent of pressure and temperature. At high sulfide concentrations and a temperature of 245 K, we observed the equilibration of MESOH and DESOH adducts over the pressure range 100-600 Torr. In the presence of O(2) the observed rate coefficients show a dependence on the O(2) partial pressure. We measured the dependence of the overall rates of oxidation on the partial pressure of O(2) over the temperature range 240-295 K and at 200 and 600 Torr total pressures. All observations are consistent with oxidation proceeding via a two channel oxidation mechanism involving abstraction and addition channels, analogous to that observed in the OH initiated oxidation of dimethylsulfide (DMS). Structures and thermochemistry of the MESOH and DESOH adducts were calculated and all results compared to those for DMS. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations.

A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d(6)), dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O(2) over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O(2) enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C(2)-C(8)) reactions are analyzed. All reactions proceed via a two-channel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O(2). Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O(2). This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

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