Room-temperature reactions of the chemical warfare agents VX, GD, and HD wi
th nanosize CaO (AP-CaO), and HD with commercial CaO have been studied usin
g solid-state MAS NMR. VX and GD hydrolyze to yield surface-bound complexes
of nontoxic ethyl methylphosphonate and pinacolyl methylphosphonate, respe
ctively. The kinetics are characterized by an initial fast reaction followe
d 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-Ca
O (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 wh
ich 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, wh
ich apparently reside as surface alkoxides. Such kinetic behavior was not e
vident for the common mustard simulant 2-chloroethyl ethyl sulfide (CEES) o
n partially hydrated AP-CaO, which exhibited only the typical fast/diffusio
n-limited reaction.