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Title: Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)

Abstract

Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100 C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment tomore » regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.« less

Authors:
; ;
Publication Date:
Research Org.:
Lawrence Livermore National Lab. (LLNL), Livermore, CA (United States)
Sponsoring Org.:
USDOE, Washington, DC (United States)
OSTI Identifier:
212671
Report Number(s):
UCRL-JC-121999; CONF-9509340-1
ON: DE96008750
DOE Contract Number:  
W-7405-ENG-48
Resource Type:
Conference
Resource Relation:
Conference: Workshop on advances in alternative demilitarization technologies, Reston, VA (United States), 25-27 Sep 1995; Other Information: PBD: 11 Oct 1995
Country of Publication:
United States
Language:
English
Subject:
45 MILITARY TECHNOLOGY, WEAPONRY, AND NATIONAL DEFENSE; 40 CHEMISTRY; CHEMICAL WARFARE AGENTS; DECOMPOSITION; OXIDATION; OXIDIZERS; REGENERATION

Citation Formats

Cooper, J F, Krueger, R, and Farmer, J C. Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation). United States: N. p., 1995. Web.
Cooper, J F, Krueger, R, & Farmer, J C. Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation). United States.
Cooper, J F, Krueger, R, and Farmer, J C. 1995. "Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)". United States. https://www.osti.gov/servlets/purl/212671.
@article{osti_212671,
title = {Destruction of VX by aqueous-phase oxidation using peroxydisulfate (direct chemical oxidation)},
author = {Cooper, J F and Krueger, R and Farmer, J C},
abstractNote = {Chemical warfare agents may be completely destroyed (converted to H{sub 2}O, CO{sub 2}, salts) by oxidation at 90--100 C using acidified ammonium peroxydisulfate, with recycle of NH{sub 4}SO{sub 4} byproduct. The process requires no toxic or expended catalysts and produces no secondary wastes other than the precipitated inorganic content of the agents. To determine oxidative capability of peroxydisulfate at low reductant contents, we measured rate data for oxidation of 20 diverse compounds with diverse functional groups; 4 of these have bonds similar to those found in VX, HD, and GB. On an equivalence basis, integral first-order rate constants for 100 C oxidation are 0.012{plus_minus}0.005 min{sup {minus}1} for di-isopropyl-methyl-phosphonate, methyl phosphonic acid, triethylamine, and 2,2{prime}-thiodiethanol at low initial concentrations of 50 ppM(as carbon) and pH 1.5. To provide scale-up equations for a bulk chemical agent destruction process, we measured time-dependent oxidation of bulk model chemicals at high concentrations (0.5 N) and developed and tested a quantitative model. A practical process for bulk VX destruction would begin with chemical detoxification by existing techniques (eg, hydrolysis or mild oxidation using oxone), followed by mineralization of the largely detoxified products by peroxydisulfate. Secondary wastes would be avoided by use of commercial electrolysis equipment to regenerate the oxidant. Reagent requirements, mass balance and scaleup parameters are given for VX destruction, using peroxydisulfate alone, or supplemented with hydrogen peroxide. For the use of 2.5 N peroxydisulfate as the oxidant, a 1 m{sup 3} digester will process about 200 kg (as C) per day. The process may be extended to total destruction of HD and hydrolysis products of G agents.},
doi = {},
url = {https://www.osti.gov/biblio/212671}, journal = {},
number = ,
volume = ,
place = {United States},
year = {Wed Oct 11 00:00:00 EDT 1995},
month = {Wed Oct 11 00:00:00 EDT 1995}
}

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