Reduction of pertechnetate by acetohydroxamic acid: Formation of [TcNO(AHA)2(H2O)]+ and implications for the UREX process.
Reductive nitrosylation and complexation of ammonium pertechnetate by acetohydroxamic acid has been achieved in aqueous nitric and perchloric acid solutions. The kinetics of the reaction depend on the relative concentrations of the reaction components and are accelerated at higher temperatures. The reaction does not occur unless conditions are acidic. Analysis of the x-ray absorption fine structure spectroscopic data is consistent with a pseudo-octahedral geometry with the linear Tc-N-O bond typical of technetium nitrosyl compounds, and electron spin resonance spectroscopy is consistent with a the d{sup 5} Tc(II) nitrosyl complex. The nitrosyl source is generally AHA, but may be augmented by products of reaction with nitric acid. The resulting low-valency trans-aquonitrosyl(diacetohydroxamic)-technetium(II) complex (1) is highly soluble in water, extremely hydrophilic, and is not extracted by tri-n-butylphosphate in a dodecane diluent. Its extraction properties are not pH-dependent; titration studies indicate a single species from pH 4.5 down to -0.6 (calculated). This molecule is resistant to oxidation by H{sub 2}O{sub 2}, even at high pH, and can undergo substitution to form other technetium nitrosyl complexes. The formation of 1 may strongly impact the fate of technetium in the nuclear fuel cycle.
- Research Organization:
- Ernest Orlando Lawrence Berkeley National Laboratory, Berkeley, CA (US)
- Sponsoring Organization:
- Chemical Sciences Division
- DOE Contract Number:
- AC02-05CH11231
- OSTI ID:
- 948346
- Report Number(s):
- LBNL-97E
- Journal Information:
- Inorganic Chemistry, Journal Name: Inorganic Chemistry; ISSN 0020-1669; ISSN INOCAJ
- Country of Publication:
- United States
- Language:
- English
Similar Records
APPLICATION OF FORMOHYDROXAMIC ACID IN NUCLEAR PROCESSING: SYNTHESIS AND COMPLEXATION WITH TECHNETIUM-99
Gamma Radiolysis of Biphasic Acetohydroxamic Acid (AHA) Solvent Systems
Related Subjects
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ABSORPTION
BY-PRODUCTS
DODECANE
ELECTRON SPIN RESONANCE
FINE STRUCTURE
GEOMETRY
KINETICS
NITRIC ACID
NUCLEAR FUELS
OXIDATION
PERCHLORIC ACID
PERTECHNETATES
SPECTROSCOPY
TECHNETIUM
TITRATION
WATER
technetium acetohydroxamic acid UREX