Reactions of VX, GD, and HD with Nanosize CaO: Autocatalytic Dehydrohalogenation of HD

Abstract

Room-temperature reactions of the chemical warfare agents VX, GD, and HD with nanosize CaO (AP-CaO), and HD with commercial CaO have been studied using solid-state MAS NMR. VX and GD hydrolyze to yield surface-bound complexes of nontoxic ethyl methylphosphonate and pinacolyl methylphosphonate, respectively. The kinetics are characterized by an initial fast reaction followed by a slower, diffusion-limited reaction. Similar behavior is observed for HD on either dried or hydrated AP-CaO and CaO. On partially hydrated AP-CaO (but not CaO), a rather fast steady-state elimination of HCl occurs after an induction period. This behavior is attributed to acid-catalyzed surface reconstruction (to regenerate fresh surface) and the formation of CaCl2, which is known to be more reactive than CaO. The product distribution for HD is about 80% divinyl sulfide and 20% thiodiglycol and/or sulfonium ions, which apparently reside as surface alkoxides. Such kinetic behavior was not evident for the common mustard simulant 2-chloroethyl ethyl sulfide (CEES) on partially hydrated AP-CaO, which exhibited only the typical fast/diffusion-limited reaction.

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Document Details

Document Type
Technical Report
Publication Date
Jan 01, 2000
Accession Number
ADA388589

Entities

People

  • Erik Lucas
  • George W. Wagner
  • Kenneth J. Klabunde
  • Olga B. Koper
  • Shawn Decker

Organizations

  • Kansas State University

Tags

Communities of Interest

  • Air Platforms
  • Human Systems

DTIC Thesaurus Topics

  • Abstracts
  • Body Weight
  • Chemical Warfare
  • Chemical Warfare Agents
  • Chemistry
  • Diffusion
  • Elimination
  • Elimination Reactions
  • Hydrolysis
  • Materials
  • Nerve Agents
  • Oxides
  • Particle Size
  • Particles
  • Physical Chemistry
  • Steady State
  • Vapor Pressure

Readers

  • Analytical Chemistry
  • Materials Science and Engineering.