A high-pressure stopped-flow apparatus has been exploited which enables us to follow reactions with a half-life longer than 0.1 s under pressure up to 1600 kg cm-2. The rate for the formation of the peroxo complex of (nitrilotriacetato)dioxovanadate(V) (VO2(nta)2-) is expressed as d[VO(O2)(nta)2-]/dt = (k1 + k2[H+])[VO2(nta)2-] [H2O2], where k1 = 7.05 m-1 s-1, k2 = 1.46 X 104 m-2 s-1 at 25 °C and I = 1.05 m at atmospheric pressure and the volumes of activation for the k1 and k2 paths are -3.4 ± 0.5 and 1.5 ± 0.5 cm3 mol-1, respectively. An associative mechanism is most probably operative.
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Inorganic Chemistry