One- and two-equivalent paths in the reaction of vanadium(II) with mercury(II). A recalculation of kinetic parameters

Abstract

Kinetic parameters for the one- and two-electron paths in the reaction of vanadium(II) with mercury(II) have been recalculated. The one-electron path (a=k_a) is independent of [H⁺]; at 25°k_a= 1·04 ± 0·11 l mol^–1 s^–1, ΔH_a^‡= 15·8 ± 0·8 kcal mol^–1, and ΔS_a^‡=–5·6 ± 2·7 e.u. There is now no detectable contribution from an [H⁺]-independent path for the two-electron reaction (b=k_b[H⁺]^–1), and at 25°k_b= 8·69 ± 0·02 s^–1, ΔH_b^‡= 14·8 ± 0·2 kcal mol^–1, and ΔS_b^‡=–4·6 ± 0·8 e.u.