Oxidation of alkyl sulfides by aqueous peroxymonosulfate

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Abstract

The kinetics and mechanism of the oxidation of the alkyl sulfides dimethyl sulfide (DMS) and diethyl sulfide (DES) by peroxymonosulfate (HSO5-) in aqueous solution were studied as a function of pH, temperature, and ionic strength. The rate law was found to be -d[R2S]/dt = k1[R2S][HSO5-] + k2[R2S][SO52-], where k1(DMS) = 0.13 ± 0.09 M-1 s-1, k2(DMS) = 29.8 ± 0.08 M-1 s-1, k1(DES) = 0.29 ± 0.01 M-1 s-1, and k2(DES) = 11.1 ± 1.0 M-1 s-1 (25 °C; ionic strength, 0.2 M). The activation parameters for DMS and DES, respectively, are ΔHk1 = 51.3 ± 0.5 and 40.7 ± 5.9 kJ mol-1, ΔS‡k1 = -87.0 ± 0.1 and -119 ± 20 J K-1 mol-1, ΔH‡k2 = 43.5 ± 1.9 and 18.5 ± 3.3 kJ mol-1, and ΔS‡k2 = -70 ± 7 and -164 ± 18 J K-1 mol-1. Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, and diethyl sulfone were identified as reaction products. A comparison of the relative rates of oxidation of DMS and DES by HSO5-, H2O2, and O3 shows that HSO5- may be a more important aqueous sink for the alkyl sulfides than H2O2. O3 is, however, likely to be the dominant aqueous oxidant under conditions that could be expected in remote marine clouds.

Original languageEnglish (US)
Pages (from-to)527-532
Number of pages6
JournalEnvironmental Science and Technology
Volume26
Issue number3
StatePublished - 1992

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Sulfides
sulfide
oxidation
Oxidation
Ionic strength
Sulfones
Dimethyl Sulfoxide
Reaction products
Oxidants
Chemical activation
diethyl sulfide
dimethyl sulfide
peroxymonosulfate
Kinetics
Dimethyl sulfoxide
oxidant
aqueous solution
Temperature

ASJC Scopus subject areas

  • Environmental Engineering
  • Environmental Science(all)
  • Environmental Chemistry

Cite this

Oxidation of alkyl sulfides by aqueous peroxymonosulfate. / Betterton, Eric.

In: Environmental Science and Technology, Vol. 26, No. 3, 1992, p. 527-532.

Research output: Contribution to journalArticle

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title = "Oxidation of alkyl sulfides by aqueous peroxymonosulfate",
abstract = "The kinetics and mechanism of the oxidation of the alkyl sulfides dimethyl sulfide (DMS) and diethyl sulfide (DES) by peroxymonosulfate (HSO5-) in aqueous solution were studied as a function of pH, temperature, and ionic strength. The rate law was found to be -d[R2S]/dt = k1[R2S][HSO5-] + k2[R2S][SO52-], where k1(DMS) = 0.13 ± 0.09 M-1 s-1, k2(DMS) = 29.8 ± 0.08 M-1 s-1, k1(DES) = 0.29 ± 0.01 M-1 s-1, and k2(DES) = 11.1 ± 1.0 M-1 s-1 (25 °C; ionic strength, 0.2 M). The activation parameters for DMS and DES, respectively, are ΔH‡k1 = 51.3 ± 0.5 and 40.7 ± 5.9 kJ mol-1, ΔS‡k1 = -87.0 ± 0.1 and -119 ± 20 J K-1 mol-1, ΔH‡k2 = 43.5 ± 1.9 and 18.5 ± 3.3 kJ mol-1, and ΔS‡k2 = -70 ± 7 and -164 ± 18 J K-1 mol-1. Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, and diethyl sulfone were identified as reaction products. A comparison of the relative rates of oxidation of DMS and DES by HSO5-, H2O2, and O3 shows that HSO5- may be a more important aqueous sink for the alkyl sulfides than H2O2. O3 is, however, likely to be the dominant aqueous oxidant under conditions that could be expected in remote marine clouds.",
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N2 - The kinetics and mechanism of the oxidation of the alkyl sulfides dimethyl sulfide (DMS) and diethyl sulfide (DES) by peroxymonosulfate (HSO5-) in aqueous solution were studied as a function of pH, temperature, and ionic strength. The rate law was found to be -d[R2S]/dt = k1[R2S][HSO5-] + k2[R2S][SO52-], where k1(DMS) = 0.13 ± 0.09 M-1 s-1, k2(DMS) = 29.8 ± 0.08 M-1 s-1, k1(DES) = 0.29 ± 0.01 M-1 s-1, and k2(DES) = 11.1 ± 1.0 M-1 s-1 (25 °C; ionic strength, 0.2 M). The activation parameters for DMS and DES, respectively, are ΔH‡k1 = 51.3 ± 0.5 and 40.7 ± 5.9 kJ mol-1, ΔS‡k1 = -87.0 ± 0.1 and -119 ± 20 J K-1 mol-1, ΔH‡k2 = 43.5 ± 1.9 and 18.5 ± 3.3 kJ mol-1, and ΔS‡k2 = -70 ± 7 and -164 ± 18 J K-1 mol-1. Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, and diethyl sulfone were identified as reaction products. A comparison of the relative rates of oxidation of DMS and DES by HSO5-, H2O2, and O3 shows that HSO5- may be a more important aqueous sink for the alkyl sulfides than H2O2. O3 is, however, likely to be the dominant aqueous oxidant under conditions that could be expected in remote marine clouds.

AB - The kinetics and mechanism of the oxidation of the alkyl sulfides dimethyl sulfide (DMS) and diethyl sulfide (DES) by peroxymonosulfate (HSO5-) in aqueous solution were studied as a function of pH, temperature, and ionic strength. The rate law was found to be -d[R2S]/dt = k1[R2S][HSO5-] + k2[R2S][SO52-], where k1(DMS) = 0.13 ± 0.09 M-1 s-1, k2(DMS) = 29.8 ± 0.08 M-1 s-1, k1(DES) = 0.29 ± 0.01 M-1 s-1, and k2(DES) = 11.1 ± 1.0 M-1 s-1 (25 °C; ionic strength, 0.2 M). The activation parameters for DMS and DES, respectively, are ΔH‡k1 = 51.3 ± 0.5 and 40.7 ± 5.9 kJ mol-1, ΔS‡k1 = -87.0 ± 0.1 and -119 ± 20 J K-1 mol-1, ΔH‡k2 = 43.5 ± 1.9 and 18.5 ± 3.3 kJ mol-1, and ΔS‡k2 = -70 ± 7 and -164 ± 18 J K-1 mol-1. Dimethyl sulfoxide, dimethyl sulfone, diethyl sulfoxide, and diethyl sulfone were identified as reaction products. A comparison of the relative rates of oxidation of DMS and DES by HSO5-, H2O2, and O3 shows that HSO5- may be a more important aqueous sink for the alkyl sulfides than H2O2. O3 is, however, likely to be the dominant aqueous oxidant under conditions that could be expected in remote marine clouds.

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