Inorganic Chemistry p. 1302 - 1305 (1967)
Update date:2022-08-12
Topics:
Cleveland
The kinetics of the reaction between Pu(III) and XeO3, according to the equation 6Pu(III) + XeO3 + 6H+ → 6Pu(IV) + Xe + 3H2O, have been studied in perchlorate media by following the rate of disappearance of Pu(III) spectrophotometrically at 600 mμ. The rate law for the reaction is: -d[Pu(III)]/dt = k[Pu(III)][XeO3]. The reaction rate is independent of acidity in the 0.5-2 M range. From the variation of the reaction rate with temperature, the following thermodynamic quantities of activation at 25° were calculated: ΔH? = 15.3 ± 2.1 kcal/mole; ΔF? = 20.2 ± 0.1 kcal/mole; ΔS? = -16.0 ± 6.9 eu. The mechanism of the reaction appears to involve either successive one-electron changes or a two-electron change to form a Pu(V) species other than PuO2+, which then reacts with Pu(III) to form Pu(IV).
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