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Hydrolysis of Dimethyl Methylphosphonate (DMMP) in Hot-Compressed Water

Brian R. Pinkard, S. Divakara Shetty, John C. Kramlich, Per G. Reinhall, Igor Novosselov

2020The Journal of Physical Chemistry A22 citationsDOI

Abstract

Dimethyl methylphosphonate (DMMP) is often used as a chemical surrogate for organophosphate nerve agents, as it exhibits similar physiochemical properties while having significantly lower toxicity. Continuous hydrolysis of DMMP in hot-compressed water is performed at temperatures from 200 to 300 °C, pressures of 20 and 30 MPa, and residence times from 30 to 80 s to evaluate the effects of pressure and temperature on reaction kinetics. DMMP hydrolysis is observed to follow pseudo-first-order reaction behavior, producing methylphosphonic acid and methanol as the only detectable reaction products. This is significant for the practical implementation of a continuous hydrothermal reactor for chemical warfare agent neutralization, as the process only yields stable, less-toxic compounds. Pressure has no discernible effect on the hydrolysis rate in compressed liquid water. Pseudo-first-order Arrhenius parameters are determined, with an activation energy of 90.17 ± 5.68 kJ/mol and a pre-exponential factor of 107.51±0.58 s–1.

Topics & Concepts

Dimethyl methylphosphonateHydrolysisChemistryArrhenius equationMethanolActivation energyReaction rate constantKineticsChemical kineticsOrder of reactionOrganic chemistryQuantum mechanicsPhysicsInsect and Pesticide ResearchPesticide and Herbicide Environmental StudiesSubcritical and Supercritical Water Processes
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