Molybdate/Peroxide Oxidation of Mustard in Microemulsions

Abstract

Environmentally friendly and noncorrosive methods to decontaminate the blister agent mustard (HD) bis(2-chloroethyl) sulfide are currently being developed. HD may be rendered nonvesicant by oxidation to the corresponding sulfoxide. In microemulsions, the mildly basic molybdate/peroxide oxidant system rapidly oxidizes HD initially to the sulfoxide. Secondary oxidation to the sulfone does occur, but this reaction is about 2 orders of magnitude slower. A microemulsion found to be stable at low temperature was identified, enabling the decontamination of HD at -30 °C. The mild basicity of such solutions also affords the peroxyhydrolysis (OOH -) of nerve agents GD and VX.

Kinetics of the Oxidation of Methyl Phenyl Sulfide by Hydrogen Peroxide in the Presence of Hydrocarbonate Anion

“…In weakly alkaline media they can act as a mild oxidant in the un-ionized form [1,4] and as an effective α-nucleophile in the form of the HO 2 − anion [5]. The problem of the low solubility of organic substrates, important for the development of green technologies, is solved by conducting the nucleophilic oxidation reactions in aqueous solutions of surfactants (micellar catalysis) [6][7][8] and also in microemulsions [9,10] and water-alcohol mixtures [1, 4,8,11]. In oxidation processes hydrogen peroxide is usually activated by various acids, transforming it into highly reactive peroxy acids.…”

DECON GREEN (Trademark) Development and Chemical Biological Agent Efficacy Testing

“…In 1998, Prof Clifford A. Buntont had suggested using molybdate as a peroxide activator for HD oxidation, although the need for an alternative activator that could function at the higher pH needed for the VX reaction did not become apparent until 1999. Wagner et al 8 did find that molybdate, as an activator, was about two orders of magnitude more powerful than bicarbonate for the oxidation of HD and, just as important, that molybdate had no deleterious effect on the reaction of VX. At the same time, trial oxidations using molybdate were successfully carried out in microemulsions consisting of propylene carbonate (oil phase) and TritonE X-100 (surfactant).…”

Ionic Liquids as Solvent, Catalyst Support Chemical Agent Decontamination and Detoxification

“…The presence of a thickener in the poison adds constraints to the conception of an efficient decontamination medium. [53][54][55][56][57] The choice of mustard gas analogue will be critical: indeed, the model must present a lipophilicity near that of yperite, and must also allow similar solubilization of the polymer (Paraloid K125). The rheology and the behavior of the couple polymer/model substrate must be as near as possible to those of the thickened mustard gas.…”