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 Trevor R.,Volkovich Vladimir A.,Carper W. Robert // STRUCTURAL CHEMISTRY. - 2010. - V. 21, l. 2, SI. - P. 291-297.

ISSN/EISSN:

1040-0400 / нет данных

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.

Author keywords:

Nitrate-peroxide adduct; Molten Salt Oxidation; Chemical warfare arsenicals; Density Functional Theory; Superoxide SODIUM-CARBONATE; GRAPHITE OXIDATION; URANATE; WASTES; MELTS

DOI:

10.1007/s11224-009-9530-0

Web of Science ID:

ISI:000275544900003

Соавторы в МНС:

—

Другие поля

Поле	Значение
Month	APR
Publisher	SPRINGER/PLENUM PUBLISHERS
Address	233 SPRING ST, NEW YORK, NY 10013 USA
Language	English
Keywords-Plus	SODIUM-CARBONATE; GRAPHITE OXIDATION; URANATE; WASTES; MELTS
Research-Areas	Chemistry; Crystallography
Web-of-Science-Categories	Chemistry, Multidisciplinary; Chemistry, Physical; Crystallography
Author-Email	t.r.griffiths@gmail.com
ResearcherID-Numbers	Volkovich, Vladimir/K-8339-2012
ORCID-Numbers	Volkovich, Vladimir/0000-0003-4438-1194
Funding-Acknowledgement	Leeds University, UK; Manchester University, UK
Funding-Text	V. A. V. thanks British Nuclear Fuel plc for a Post-Doctoral Research Fellowship at Leeds University, UK, and a Research Fellowship at Manchester University, UK. We also thank Professor W. R. (Bob) Carper, Wichita State University, Wichita, Kansas, USA, for the DFT calculations.
Number-of-Cited-References	17
Usage-Count-Last-180-days	1
Usage-Count-Since-2013	11
Journal-ISO	Struct. Chem.
Doc-Delivery-Number	568TD