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1.
The reduction of Pu(IV) with butanal oxime in nitric acid solution in the presence of excess reductant follows the equation 4Pu4
+ + 2C3H7CHNOH + H2O = 4Pu3
+ + 2C3H7CHO + N2O + 4H+, and its rate is given by the equation -d[Pu(IV)]/dt = k[Pu(IV)]2[C3H7CHNOH]/{[Pu(III)][H+]}. The rate constant is k = 3.65±0.14 min-
1 at 20.2°C and the solution ionic strength = 2. The activation energy is E = 88.8±10.3 kJ mol-
1. The probable reaction mechanism is discussed. 相似文献
2.
3,3'-Bis(diaziridinyl), H2N2C2H2N2H2, is oxidized with Pu(IV) ions in excess of reductant to bis(diazirinyl), N2C2H2N2, and in excess of oxidant, to nitrogen and acetic acid. The reaction rate in the HNO3 solution at a constant ionic strength is described by the equation -d[Pu(IV)]/dt = k[Pu(IV)]2× [H2N2C2H2N2H2]1
.
7[H+]-
3, where k = 28400±1400 mol0
.
3 l-
0
.
3 min-
1 at 35°C. The activation energy of the reaction amounts to 126±11 kJ mol-
1. 相似文献
3.
Reduction of Pu(VI) to Pu(III) with acetaldoxime (CH3CHNOH) in an HNO3 solution involves three consecutive steps Pu(VI) → Pu(V) → Pu(IV) → Pu(III), and also reproportionation of Pu(IV). Complete kinetics equations of these steps were derived and the rate constants and activation energies of these steps were determined by computer treatment of the experimental kinetic data for all Pu valence forms. The mechanisms of these reaction steps based on the experimental results were discussed.__________Translated from Radiokhimiya, Vol. 47, No. 1, 2005, pp. 67–71.Original Russian Text Copyright © 2005 by V. Koltunov, Pastushchak, Mezhov, G. Koltunov. 相似文献
4.
The rate of Pu(IV) reduction with tert-butylhydrazine in an HNO3 solution is described by the equation-d[Pu(IV)]/dt = k[Pu(IV)]2[(CH3)3CN2H 4 + ]/[H+], where k = 69.4 ⊥ 3.0 l mol?1 min?1 at 50°C. The activation energy is E = 122 ⊥ 4 kJ mol?1. Probable reaction mechanisms are discussed. 相似文献
5.
Reduction of Pu(VI) to Pu(III) with hydroxyethylhydrazine (HOC2H4N2H3) in HNO3 solutions involves the following consecutive steps2: Pu(VI) + HOC2H4N2H4 Pu(V) + ...; Pu(V) + HOC2H4N2H4
+ Pu(IV) + ...; Pu(V) + Pu(III) 2Pu(IV); and Pu(IV) + HOC2H4N2H4
+ Pu(III) + .... The overall kinetic equations of these steps were suggested, and their rate constants and activation energies were determined. The mechanisms of the four reaction steps, consistent with the experimental kinetic data, are discussed. 相似文献
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