Abstract
The kinetics of oxidation of uranium (IV) by iron (III) in aqueous solutions of perchloric acid have been investigated at four temperatures between 3.1 °C. and 24.8 °C. The reaction was followed by measurement of the amount of ferrous ion formed. For the conditions (H+) = 0.1–1.0 M, ionic strength = 1.02, (FeIII) = 10−4–10−5 M, and (UIV) = 10−4–10−5 M, the observed rate law is d(Fe2+)/dt = −2d(UIV)/dt[Formula: see text]K1 and K2 are the first hydrolysis constants for Fe3+ and U4+, respectively, and K′ and K″ are pseudo rate constants. At 24.8 °C., K′ = 2.98 sec.−1, and K″ = 10.6 mole liter−1 sec−1. The corresponding temperature coefficients are ΔH′ = 22.5 kcal./mole and ΔH″ = 24.2 kcal./mole. The kinetics of the process are consistent with a mechanism which involves, as a rate-controlling step, electron transfer between hydrolyzed ions.
Publisher
Canadian Science Publishing
Subject
Organic Chemistry,General Chemistry,Catalysis
Cited by
45 articles.
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