Study of the reactions of oxygen atoms with hydrogen sulfide, methanethiol, ethanethiol, and methyl sulfide

Abstract

Comparison of the Room Temperature Rate Constants for the Reaction OH + ROH Determined by Different Techniques ku X 10"12 (cm3 mol"1 s"') Reactant This work Lit. value Ref CH3OH 0.64 ± 0.06 0.57 ± 0.06 4°0 .12 ± 0.02 3b 0.90 16c c2h5oh 2.25 ± 0.22 1.8 ± 0.2 4°1 .85 16c i-c3h,oh 3.21 ± 0.32 2.3 ± 0.2 4°2 .8 16c 2-C3H,OH 3.30 ± 0.33 4.3 ± 1.3 5d 2.15 16e 0Relative to the rate constant OH + n-butane, for which a value of 1.4 X 1012 cm3 mol"1 s"1 has been used. b Relative to the rate constant of OH with CO, for which we used the high pressure value of 1.9 X 10" cm3 mol"1 s'1.6 c Liquid phase determination; OH was generated by pulse radiolysis of H,0. Rate constants are mean values reported in ref 16. d The ráte constant was determined at 305 K, relative to the rate constant of OH + isobutene at 305 K, for which a value of 3.05 X 1013 cm3 mol"1 s"1 has been used. error from the secondary reaction 2.As mentioned in the Introduction all the other studies are relative determinations. Our values agree well with those of Campbell et al.4 for CH3OH and C2H5OH, while for l-C3H7OH their value is ~30% lower than ours; they used a rate constant for the reaction of OH + n-butane of 1.4 X 1012 cm3 mol"1 s"1, if the more recent value of 1.65 X 1012 cm3 mol"1 s"1 is used,15 very good agreement is obtained for all alcohols. Our value for 2-C3H7OH is somewhat lower than, but within the wide error limits of

Temperature dependence of rate constants for reaction of oxygen atoms, O(3P), with allene and 1,3-butadiene

“…The room temperature rate constants for 0 + allene and 0 + 1,3-butadiene have been shown (9) to fit adequately into the correlation of k0+,,,,,, vs. the ionization potential of the olefin. Also, the activation energies for reactions [IA] and [IB] are consistent with the correlation between activation energies for 0 + olefin reactions vs. ionization potential of the olefin (19). On the other hand, the pre-exponential factors for 0 + allene and 0 + 1,3-butadiene are somewhat larger (2-3 x lo-'') than those for most of the 0 + olefin reactions (1-1.5 x lo-'', except for tetramethylethylene, for which it is 2.1 x lo-'' cm3 molecule-' s-l) (17), reflecting, perhaps, the number of double bonds.…”

Environmental effects of large igneous province magmatism: a Siberian perspective

“…O + H 2 S. This recommendation is derived from an unweighted least squares fit of the data of Singleton et al [1201] and Whytock et al [1453]. The results of Slagle et al [1208] show very good 1-100…”

“…The uncertainty factor at 298 K has been chosen to encompass the room temperature rate constant values of Slagle et al [1208] and Hollinden et al [595]. Other than the 263 K data point of Whytock et al and the 281 K point of Slagle et al, the main body of rate constant data below 298 K comes from the study of Hollinden et al, which indicates a dramatic change in E/R in this temperature region.…”

“…Such a nonlinearity in the Arrhenius plot might indicate a change in the reaction mechanism from abstraction (as written) to addition. An addition channel (resulting in H atom displacement) has been proposed by Slagle et al [1208], Singleton et al [1201], and Singleton et al [1203]. In the latter two studies, an upper limit of 20% was placed on the displacement channel.…”

A temperature‐dependent kinetics study of the reaction of O(3PJ) with (CH3)2SO

“…A Pyrex, jacketed reaction cell with an internal volume of ∼150 cm 3 was used in all experiments. The cell was maintained at a constant temperature by circulating ethylene glycol from a thermostated bath through the outer jacket.…”