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Veterans at Risk: The Health Effects of Mustard Gas and Lewisite
So-called Levinstein mustard gas as manufactured on a large-scale contains 69.3 percent sulfur mustard new and 71.5 percent after aging. To this day, no one knows exactly what is in this material, but physiological tests have disclosed no appreciable difference between it and the highly purified material used in chemical studies. Sulfur mustard is a heavy, somewhat oily liquid that is clear or straw colored when pure but dark when crude. Its molecular weight is 159.08, boiling point 215°C-217°C, freezing point 14.45°C, specific gravity 1.27. It is sparingly soluble in water but very soluble in organic solvents, animal oils, and fats. It is stable for weeks at room temperature, slowly hydrolyzed by water, and destroyed by strong oxidizing agents.
Studies on the mechanism and kinetics of the hydrolysis of sulfur mustard have shown that the first step in this reaction is the formation of a transient cyclic sulfonium cation, which then reacts quickly with water to form 2-chloroethyl-2-hydroxysulfide and a hydrogen ion. The reaction sequence is repeated to give dithioglycol (5-5):
To ensure pure first-order kinetics, sulfur mustard is predissolved in a polar organic solvent, and its concentration is kept low in solution so that the rate of the reverse reactions become negligible compared to kw. The overall reaction—the formation of dithioglycol and 2 HCl—can be described as a quasi-monomolecular process with first-order kinetics. The rate constant for the hydrolysis of sulfur mustard, as determined by acid production, is markedly dependent on temperature and the presence of chloride ion, which retards the hydrolysis rate without altering the reaction products. The retardation of hydrolysis by added chloride is consistent with the reversibility of the activation step to cyclic sulfonium ion. The rate of hydrolysis is not pH dependent and is not altered by metal ions.
At greater substrate concentrations in the absence of an organic solvent, however, the reaction is more complex, since both dissolution and reaction take place simultaneously and the initial product from the reaction with water accumulates in the aqueous phase and reacts with the sulfonium cation to form a dimeric sulfonium cation (5-6):