- Degradation of Sulfur Mustard on KF/Al2O3: The Role of Organic Solvents and Active Species
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Solvent effects on the ability of KF/Al2O3 supports to degrade the warfare agent sulfur mustard (HD) were explored. RP-KF/Al2O3 possessing hydroxide ions and ECUF/KF/Al2O3 holding fluoride
- Fridkin, Gil,Columbus, Ishay,Yehezkel, Lea,Zafrani, Yossi
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- Reactions of 2-Chloroethyl sulfides: III. Mechanism of methanolysis of 2-Chloroethyl sulfides
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The products and kinetics of methanolysis of 2-chloroethyl methyl sulfide, 2-chloroethyl 2-methoxyethyl sulfide, 2,2′-dichlorodiethyl sulfide, and 2-chloroethyl phenyl sulfide (at a concentration of 0.05-0.2 M) were studies by 13C NMR spectroscopy and gas-liquid chromatography. The rate of methanolysis decreases in the following series: methyl > methoxyethyl > 2-chloroethyl > phenyl. The amount of sulfonium dimers among the products decreases in the same series; the rate of dimerization of 2-chloroethyl methyl sulfide exceeds the rate of methanolysis. The reaction of 2-chloroethyl sulfides in methanol with a strong neutral nucleophile, thiourea, is of the second order. The rate constants of this reaction show a correlation with the constants σ* of substituents on the sulfur, which is similar to that found for the hydrolysis. This correlation indicates formation of intermediate ethylenesulfonium ion. Unlike the hydrolysis process, the rate-determining stage in the methanolysis is the reaction of ethylsulfonium ion with the nucleophile rather than ionization of 2-chloroethyl sulfide.
- Fomina,Vishnyakov,Glushkov
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p. 1282 - 1288
(2007/10/03)
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