52670-37-8Relevant academic research and scientific papers
The Dimethylhydroxysulfuranyl Radical
Merenyi, Gabor,Lind, Johan,Engman, Lars
, p. 8875 - 8881 (1996)
By use of pulse radiolysis the one-electron reduction potentials, E0(DMS(.+)/DMS) and E0(DMS(.+)/DMS) and E0((DMS)2(.+)/2DMS) (dimethyl sulfide, DMS) were determined to be 1.66 +/- 0.03 and 1.40 +/- 0.02 V vs NHE, respectively.DMS(.+) was found to be in equilibrium with DMSOH(.) with a pKa = 10.2.The conditional equilibrium constant for the reaction DMSOH(.) + DMS ->//-1.DMSOH(.) reacts with O2 with a rate constant of 2E8 M-1 s-1, independent of pH (11-14).From this and other observations, we estimate the pKa for deprotonation of DMSOH(.) to exceed 17.From spectral and kinetic data, the maximum lifetime of the radical (DMS)2OH(.) was predicted to be 10 ns.The stability of DMS-X(.) (X = OH, I, Br, Cl) in aqueous solution was shown to correlate with the one-electron reduction potential of X(.).Comparison of gaseous and aqueous behavior of DMS-OH(.) reveals that aqueous solvation strongly stabilizes the S-O bond against dissociation into DMS and OH(.).The Gibbs free energy of solvation of DMSOH(.) was calculated to be -12 +/- 3 kcal/mol, an unusually large value for a neutral species.
Rate coefficients for the gas-phase reaction of OH radicals with dimethyl sulfide: Temperature and O2 partial pressure dependence
Albu, Mihaela,Barnes, Ian,Becker, Karl H.,Patroescu-Klotz, Iulia,Mocanu, Raluca,Benter, Thorsten
, p. 728 - 736 (2008/02/07)
Rate coefficients for the gas-phase reaction of hydroxyl (OH) radicals with dimethyl sulfide (CH3SCH3, DMS) have been determined using a relative rate technique. The experiments were performed under different conditions of temperature (250-299 K) and O2 partial pressure (～0 Torr O2-380 Torr O2), at a total pressure of 760 Torr bath gas (N2 + O2), in a 336 l reaction chamber, using long path in situ Fourier transform (FTIR) absorption spectroscopy to monitor the disappearance rates of DMS and the reference compounds (ethene, propene and 2-methylpropene). OH was produced by the photolysis of H2O 2. The following Arrhenius expressions adequately describe the rate coefficients as a function of temperature (units are cm3 molecule-1 s-1): k = (1.56 ± 0.20) × 10 -12 exp[(369 ± 27)/T], for ～0 Torr O2; (1.31 ± 0.08) × 10-14 exp[(1910 ± 69)/T], for 155 Torr O2; (5.18 ± 0.71) × 10-14 exp[(1587 ± 24)/T], for 380 Torr O2. The results are compared with previous investigations. the Owner Societies 2006.
