The structures of the active intermediates in Catalyst-Enhanced Molten Salt Oxidation and a new method for the complete destruction of chemical warfare arsenicals / Griffiths T.R., Volkovich V.A., Carper W.R. // Structural Chemistry. - 2010. - V. 21, l. 2. - P. 291-297.

ISSN:

10400400

Type:

Article

Abstract:

Catalyst-Enhanced Molten Salt Oxidation (CEMSO) is our improvement of the earlier process, Molten Salt Oxidation (MSO), originally employed for the destruction of hazardous materials by high temperature oxidation in a carbonate melt. MSO was abandoned because it was slow and only partially oxidized cotton, paper, and plastics. It was very efficient for many other chemicals and had oxidized the nerve gas sarin with >99.9999% efficiency. We came to realize that the concentration of the oxidizing species, superoxide and peroxide ions, produced from the oxygen entering the carbonate melt, could be increased and maintained by the addition of nitrate ions as catalyst. The structure and interatomic distances for the various possible adducts between nitrate and nitrite with oxygen and peroxide have been calculated for the first time by Density Functional Theory (DFT). Their calculated enthalpies, as a function of temperature, revealed which adducts can be formed in the carbonate melt. The Japanese still have large stocks of the chemical warfare arsenicals Clark I and Clark II awaiting a destruction procedure that ensures removal of all volatile As(III) compounds. We have established that As(V) salts are stable at high temperature and here discuss how CEMSO can efficiently achieve this for the Clark arsenicals. © Springer Science+Business Media, LLC 2009.

Author keywords:

Chemical warfare arsenicals; Density Functional Theory; Molten Salt Oxidation; Nitrate-peroxide adduct; Superoxide

Index keywords:

Gossypium hirsutum

DOI:

10.1007/s11224-009-9530-0

Смотреть в Scopus:

https://www.scopus.com/inward/record.uri?eid=2-s2.0-77952289990&doi=10.1007%2fs11224-009-9530-0&partnerID=40&md5=bcae39029862ae6d30669061ad2e3d9f

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Другие поля

Поле	Значение
Link	https://www.scopus.com/inward/record.uri?eid=2-s2.0-77952289990&doi=10.1007%2fs11224-009-9530-0&partnerID=40&md5=bcae39029862ae6d30669061ad2e3d9f
Affiliations	Redston Trevor Consulting Ltd, 58 High Ash Avenue, Leeds LS17 8RF, United Kingdom; Department of Rare Metals, Ural State Technical University - UPI, Ekaterinburg 620002, Russian Federation; Department of Chemistry, Wichita State University, Wichita, KS 67260, United States
Author Keywords	Chemical warfare arsenicals; Density Functional Theory; Molten Salt Oxidation; Nitrate-peroxide adduct; Superoxide
References	Navratil, J.D., Stewart, A.E., (1996) Nukleonika, 41, p. 57; Stelman, D., Gay, R.L., (1993) Fundamental Chemical and Process Differences between Molten Salt Oxidation and Incineration, , California, USA: Report for Rockwell International; Dunks, G.B., Stelman, D., Yosim, S., (1980) J Carbon, 18, p. 363; Dunks, G.B., Stelman, D., (1983) Inorg Chem, 22, p. 2168; Dunks, G.B., (1984) Inorg Chem, 23, p. 828; Lefrancoiss, P.A., Barclay, K.M., (1971), U. S. Patent No. 3,567,412; Birk, J.R., Huber, D.A., (1973), U. S. Patent No. 3,708,270; Birk, J.R., (1973), U. S. Patent No. 3,710,737; Stelman, D., Darnell, A.J., Christie, J.R., Yosim, S.J., (1976) Molten Salts, p. 299. , Princeton, NJ, USA: The Electrochemical Society; Dunks, G.B., Stelman, D., (1982) Inorg Chem, 21, p. 108; Bell, J.T., Hass, P.A., Rudolph, J.C., (1995) Sep Sci Tech, 30, p. 1755; Ismagilov, Z.R., Kerzhentsev, M.A., Adamson, M., (1996) Scientific Advances in Alternative Demilitarization Technologies, p. 29. , F. W. Holm (Ed.), Holland: Kluwer; Cooley, C.R., (1998) Status review of molten salt oxidation for mixed low-level waste, , EM-50, Memorandum. Dep. Energy, U. S. Government, 17 December, 1998; Carnall, W.T., Neufeldt, S.J., Walkers, A., (1965) Inorg Chem, 4, p. 1808; Volkovich, V.A., Griffiths, T.R., Fray, D.J., Thied, R.C., (2000) J Nucl Mater, 282, p. 152; Volkovich, V.A., Griffiths, T.R., Thied, R.C., (2003) J Nucl Mater, 323, p. 49; Thilo, E., (1962) Advances in Inorganic Chemistry and Radiochemistry, 4, p. 1. , H. J. Emeleus and A. G. Sharpe (Eds.), New York: Academic Press
Correspondence Address	Griffiths, T. R.; Redston Trevor Consulting Ltd, 58 High Ash Avenue, Leeds LS17 8RF, United Kingdom; email: t.r.griffiths@gmail.com
CODEN	STCHE
Language of Original Document	English
Abbreviated Source Title	Struct Chem
Source	Scopus