Kinetics and Mechanism of the Thermal Decomposition of Hexaamminecobalt(III) and Aquopentaamminecobalt(III) Ions in Acidic Aqueous Solution

The initial step in the thermal decomposition of Co(NH3)63+ in acidic aqueous solution is the replacement of NH3 by H2O, which occurs by a hydrogen-ion independent path, first order in complex, with rate coefficient k1 = 7.9 × 10−5 s−1 (140.4°), ΔH* = 36.6 kcal mol−1 and ΔS* = 10.7 cal deg−1 mol−1 in 0.1 M HClO4. For Co(NH3)5OH23+, there is a similar initial aquation path with k1 = 12.6 × 10−5 s−1 (140.6°), ΔH* = 41.9 kcal mol−1 and ΔS* = 24 cal deg−1 mol−1 and also a path first order in complex but inverse first order in [H+] with k2′ = 6.2 × 10−1 M s−1 (140.6°), ΔH* = 43.5 kcal mol−1 and ΔS* = 26.7 cal deg−1 mol−1 in perchlorate media of ionic strength 1.0 M. The effects of electrolyte type and concentration on the rates of these reactions have been examined. Subsequent aquation steps are relatively rapid because of the predominance of inversely [H+]-dependent pathways and are followed by redox to Co(H2O)62+, NH4+, N2, N2O, and a minor amount of O2. A mechanism involving OH and NH2 radicals is proposed for the redox step.