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Title: Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY

Abstract

The room-temperature reactions of the chemical warfare agents VX (O-ethyl S-2-(diisopropylamino)-ethyl methylphosphonothioate), HD (2,2{prime}-dichloroethyl sulfide, or mustard), and their common simulants, O,S-diethyl phenylphosphonothioate (DEPPT) and 2-chloroethyl phenyl sulfide (CEPS), with NaY and silver-exchanged (AgY) zeolites have been studied using solid-state magic angle spinning NMR. VX hydrolyzes via exclusive cleavage of the P{single{underscore}bond}S bond on both NaY and AgY to yield ethyl methylphosphonate (EMPA). The reaction is significantly faster on AgY than on NaY, suggesting catalysis by silver. On AgY, an intermediate silver salt of EMPA is apparently formed which is slowly converted to ethyl 2-(diisopropylamino)ethyl methylphosphonate (QB, the desulfurized analogue of VX) in about a 78% yield. DEPPT similarly hydrolyzes via P{single{underscore}bond}S cleavage on AgY to yield an apparent silver salt of ethyl phenylphosphonate, which does not undergo further reaction to the desulfurized analogue. No reaction is observed for DEPPT on NaY. HD on AgY forms both vinyl sulfide and the cyclic ether 1,4-thioxane. HD reacts faster on NaY to exclusively form the CH-TG sulfonium ion (HOCH{sub 2}CH{sub 2}SCH{sub 2}CH{sub 2}S{sup +}[CH{sub 2}CH{sub 2}OH]{sub 2}). CEPS also reacts faster on NaY, forming 2-hydroxyethyl phenyl sulfide. On AgY, CEPS does not give the vinyl product, but does yield the ether productmore » PhSCH{sub 2}CH{sub 2}OCH{sub 2}CH{sub 2}SPh. A mechanism is proposed for the silver-catalyzed hydrolysis of VX, the desulfurization of the cleaved thiol, and the formation of QB.« less

Authors:
;
Publication Date:
Research Org.:
Geo-Centers, Inc., Aberdeen Proving Ground, MD (US)
OSTI Identifier:
20004008
Resource Type:
Journal Article
Journal Name:
Langmuir
Additional Journal Information:
Journal Volume: 15; Journal Issue: 23; Other Information: PBD: 9 Nov 1999; Journal ID: ISSN 0743-7463
Country of Publication:
United States
Language:
English
Subject:
32 ENERGY CONSERVATION, CONSUMPTION, AND UTILIZATION; 45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE; CHEMICAL WARFARE AGENTS; ZEOLITES; SILVER COMPOUNDS; DESULFURIZATION; DECOMPOSITION; WASTE PROCESSING

Citation Formats

Wagner, G W, and Bartram, P W. Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY. United States: N. p., 1999. Web. doi:10.1021/la990716b.
Wagner, G W, & Bartram, P W. Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY. United States. https://doi.org/10.1021/la990716b
Wagner, G W, and Bartram, P W. 1999. "Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY". United States. https://doi.org/10.1021/la990716b.
@article{osti_20004008,
title = {Reactions of VX, HD, and their simulants with NaY and AgY zeolites. Desulfurization of VX on AgY},
author = {Wagner, G W and Bartram, P W},
abstractNote = {The room-temperature reactions of the chemical warfare agents VX (O-ethyl S-2-(diisopropylamino)-ethyl methylphosphonothioate), HD (2,2{prime}-dichloroethyl sulfide, or mustard), and their common simulants, O,S-diethyl phenylphosphonothioate (DEPPT) and 2-chloroethyl phenyl sulfide (CEPS), with NaY and silver-exchanged (AgY) zeolites have been studied using solid-state magic angle spinning NMR. VX hydrolyzes via exclusive cleavage of the P{single{underscore}bond}S bond on both NaY and AgY to yield ethyl methylphosphonate (EMPA). The reaction is significantly faster on AgY than on NaY, suggesting catalysis by silver. On AgY, an intermediate silver salt of EMPA is apparently formed which is slowly converted to ethyl 2-(diisopropylamino)ethyl methylphosphonate (QB, the desulfurized analogue of VX) in about a 78% yield. DEPPT similarly hydrolyzes via P{single{underscore}bond}S cleavage on AgY to yield an apparent silver salt of ethyl phenylphosphonate, which does not undergo further reaction to the desulfurized analogue. No reaction is observed for DEPPT on NaY. HD on AgY forms both vinyl sulfide and the cyclic ether 1,4-thioxane. HD reacts faster on NaY to exclusively form the CH-TG sulfonium ion (HOCH{sub 2}CH{sub 2}SCH{sub 2}CH{sub 2}S{sup +}[CH{sub 2}CH{sub 2}OH]{sub 2}). CEPS also reacts faster on NaY, forming 2-hydroxyethyl phenyl sulfide. On AgY, CEPS does not give the vinyl product, but does yield the ether product PhSCH{sub 2}CH{sub 2}OCH{sub 2}CH{sub 2}SPh. A mechanism is proposed for the silver-catalyzed hydrolysis of VX, the desulfurization of the cleaved thiol, and the formation of QB.},
doi = {10.1021/la990716b},
url = {https://www.osti.gov/biblio/20004008}, journal = {Langmuir},
issn = {0743-7463},
number = 23,
volume = 15,
place = {United States},
year = {Tue Nov 09 00:00:00 EST 1999},
month = {Tue Nov 09 00:00:00 EST 1999}
}