Abstract
The empirical form of the rate law for the oxidation of HNO 2 by Np(VI) and Am(VI) in aqueous perchlorate media at 25° and I = 1.0 M is −d Am(VI)/d t = [Am(VI)][HNO 2] ( k 1 + k 2/[H +]). For Np(VI), k 1 = 2.01 ± 0.45 M −1 sec −1, k 2 =1.56 ± 0.07 sec −1, ΔH 1Psu∗ = 11.7 kcal/mol, ΔS 1 ∗ = = −17.9 e.u., ΔH 2 ∗ = 16.1 kcal/mol and ΔS 2 ∗ = −3.7 e.u. For Am(VI), k 1 (11.5 ± 0.3) × 10 3 M −1 sec −1, k 2 = 656 ± 32 sec −1, ΔH 1 ∗ = 9.2 kcal/mol, ΔS 1 ∗ = −9.0 ΔH 2 ∗ = 7.9 kcal/mol and ΔS 2 ∗ = -19.1 e.u. These results are compared with those obtained for Mn(III) and Co(III) as oxidants.
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