Abstract: | The volumes of activation in cm3 mol?1 for the aquation of Co(CN)5X3? were determined at 40°C and μ = 1 M (NaClO4) to be + 7.8 ± 0.5 for X = Cl?, + 7.6 ± 0.6 for X = Br?, + 14.0 ± 0.7 for X = I?, and + 16.8 ± 0.5 for X = N3? (0.1 M HClO4), respectively. The volumes of activation for the aquation of Co(CN)5Cl3? at μ = 0.1 M are + 10.0 ± 0.6 cm3 mol?1 and ± 9.1 ± 0.3 cm3 mol?1 at 40°C and 25°C, respectively. The corresponding values for the anation of Co(CN)5OH22? (at 40°C) and μ = 1 M by Br?, I?, and NCS? are +8.4 ± 1.0, +9.4 ± 1.6, and +8.2 ± 0.9 cm3 mol?1, respectively. These data are discussed in terms of a dissociative (D) mechanism. |