A study of the kinetics of the reduction of neptunium(VI) by acetohydroxamic acid in perchloric acid

The kinetics of reduction of NpO22+ to NpO2+ by acetohydroxamic acid in 1 mol·L−1perchloric acid media at 10 and 22°C were studied. The reaction rate was monitored using stopped-flow and standard infrared spectroscopy. Under conditions such that acetohydroxamic acid was in excess relative to Np, the...

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Bibliographic Details
Published in:IOP conference series. Materials Science and Engineering 2010-03, Vol.9 (1), p.012073-012073
Main Authors: Matteson, Brent S, Precek, Martin, Paulenova, Alena
Format: Article
Language:English
Subjects:
Acids
Conferences
Infrared spectroscopy
Kinetics
Mathematical analysis
Neptunium
Oxidation
Perchloric acid
Reaction kinetics
Reduction
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Summary:The kinetics of reduction of NpO22+ to NpO2+ by acetohydroxamic acid in 1 mol·L−1perchloric acid media at 10 and 22°C were studied. The reaction rate was monitored using stopped-flow and standard infrared spectroscopy. Under conditions such that acetohydroxamic acid was in excess relative to Np, the reduction rate of NpO22+ is described by the following: where k 2.57x103 mol−1·L·sec−1 at 10°C. However, when neptunium is in a significant molar excess relative to acetohydroxamic acid, the reduction mechanism is dictated by two distinct reactions. An initial and incomplete reduction occurs as the result of the oxidation of AHA, while a slower and partial reduction of NpO22+ is likely caused by the oxidation products of AHA. The reaction rate of this first-order mechanism was calculated as 3.7x10−4 sec−1 at 10°C and 0.001 sec−1 at 22°C.
ISSN:1757-899X
1757-8981
1757-899X
DOI:10.1088/1757-899X/9/1/012073