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Kinetics of Np(4) oxidation reaction by persulphate in nitric acid solution in the presence of ferric ions as catalyst

Journal Article:

Abstract

The kinetics of the reaction Np(IV) + Fe(III) = Np(V) + Fe(II)was investigated by a spectrophotometric method according to observation of the consumption of Np(IV) at 720 nm in a solution of HNO/sub 3/ + NaNO/sub 3/ in the concentration range; (F(III))equal (5.12-102.4).10/sup -3/ M, (H+) equal 0.14-1 M, (NO/sub 3//sup -/) = 0.5-2 M at an ionic strength of the solution ..mu.. = 0.2-2 and temperatures of 25-46/sup 0/C. To exclude the reverse reaction, (3-6).10/sup -2/ M (NH/sub 4/)/sub 2/S/sub 2/O/sub 8/, which rapidly oxidizes Fe(II), was added to the solution. The possible oxidation of Np(V) to Np(VI) was prevented by the addition of small quantities of N/sub 2/H/sub 4/. It was shown that the reaction rate is described by the equation -d(Np(IV))/dt=k(Np(IV))(Fe(III))/(H/sup +/)/sup 3/. where k = 0.490 +- 0.026 M/sup 2/.min/sup -1/ at 25/sup 0/ and ..mu.. = 1. The No/sub 3//sup -/ ions inhibit the reaction in the interval (NO/sub 3//sup -/) = 0-1 M and do not influence it at (NO/sub 3//sup -/) > 1 M. On the basis of an investigation of the dependence of k on the temperature, the energy (E = 32.5 kcal/mole), free energy (..delta..F* = 20.3 kcal/mole), and entropy (..delta..S*  More>>
Publication Date:
Jan 01, 1976
Product Type:
Journal Article
Reference Number:
AIX-08-346243; EDB-78-028044
Resource Relation:
Journal Name: Radiokhimiya; (USSR); Journal Volume: 18:2
Subject:
38 RADIATION CHEMISTRY, RADIOCHEMISTRY, AND NUCLEAR CHEMISTRY; IRON; OXIDATION; CATALYSTS; CHEMICAL REACTION KINETICS; EQUATIONS; NEPTUNIUM NITRATES; NITRIC ACID; PERSULFATES; QUANTITY RATIO; TEMPERATURE DEPENDENCE; ACTINIDE COMPOUNDS; CHEMICAL REACTIONS; ELEMENTS; HYDROGEN COMPOUNDS; INORGANIC ACIDS; KINETICS; METALS; NEPTUNIUM COMPOUNDS; NITRATES; NITROGEN COMPOUNDS; OXYGEN COMPOUNDS; REACTION KINETICS; SULFUR COMPOUNDS; TRANSITION ELEMENTS; TRANSURANIUM COMPOUNDS; 400702* - Radiochemistry & Nuclear Chemistry- Properties of Radioactive Materials
OSTI ID:
5403961
Country of Origin:
USSR
Language:
Russian
Other Identifying Numbers:
Journal ID: CODEN: RADKA
Submitting Site:
INIS
Size:
Pages: 270-275
Announcement Date:

Journal Article:

Citation Formats

Koltunov, V S, and Marchenko, V I. Kinetics of Np(4) oxidation reaction by persulphate in nitric acid solution in the presence of ferric ions as catalyst. USSR: N. p., 1976. Web.
Koltunov, V S, & Marchenko, V I. Kinetics of Np(4) oxidation reaction by persulphate in nitric acid solution in the presence of ferric ions as catalyst. USSR.
Koltunov, V S, and Marchenko, V I. 1976. "Kinetics of Np(4) oxidation reaction by persulphate in nitric acid solution in the presence of ferric ions as catalyst." USSR.
@misc{etde_5403961,
title = {Kinetics of Np(4) oxidation reaction by persulphate in nitric acid solution in the presence of ferric ions as catalyst}
author = {Koltunov, V S, and Marchenko, V I}
abstractNote = {The kinetics of the reaction Np(IV) + Fe(III) = Np(V) + Fe(II)was investigated by a spectrophotometric method according to observation of the consumption of Np(IV) at 720 nm in a solution of HNO/sub 3/ + NaNO/sub 3/ in the concentration range; (F(III))equal (5.12-102.4).10/sup -3/ M, (H+) equal 0.14-1 M, (NO/sub 3//sup -/) = 0.5-2 M at an ionic strength of the solution ..mu.. = 0.2-2 and temperatures of 25-46/sup 0/C. To exclude the reverse reaction, (3-6).10/sup -2/ M (NH/sub 4/)/sub 2/S/sub 2/O/sub 8/, which rapidly oxidizes Fe(II), was added to the solution. The possible oxidation of Np(V) to Np(VI) was prevented by the addition of small quantities of N/sub 2/H/sub 4/. It was shown that the reaction rate is described by the equation -d(Np(IV))/dt=k(Np(IV))(Fe(III))/(H/sup +/)/sup 3/. where k = 0.490 +- 0.026 M/sup 2/.min/sup -1/ at 25/sup 0/ and ..mu.. = 1. The No/sub 3//sup -/ ions inhibit the reaction in the interval (NO/sub 3//sup -/) = 0-1 M and do not influence it at (NO/sub 3//sup -/) > 1 M. On the basis of an investigation of the dependence of k on the temperature, the energy (E = 32.5 kcal/mole), free energy (..delta..F* = 20.3 kcal/mole), and entropy (..delta..S* = 39 entropy units) of activation of the reaction were calculated. The reaction mechanism is discussed.}
journal = {Radiokhimiya; (USSR)}
volume = {18:2}
journal type = {AC}
place = {USSR}
year = {1976}
month = {Jan}
}