Abstract
The kinetics of the reaction [Ir(NH3)5I]2++ OH–→[Ir(NH3)5OH]2++ I–1 have been studied over the range 76–97° under conditions which allow the calculation of second-order rate constants at zero ionic strength. The results are in agreement with the Bronsted–Bjerrum theory of the primary salt effect. The variation of the rate constant at zero ionic strength with temperature is reproduced by the equation k20(mole I.–1 sec.–1)= 18·54 exp –(36,320 ± 630)/RT. The activation energies of the reactions [M(NH3)5I]2++ OH–→[M(NH3)5OH]2+(M = CrIII, CoIII, RhIII, and IrIII) increase linearly with ligand-field strengths. This suggests that these reactions proceed by a common mechanism. The magnitude of the ligand-field contribution to the observed activation energies is evidence against a displacement mechanism.
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