Abstract
The kinetics of the reactions of [lr(NH3)5Cl]2+ and [lr(NH3)5Br]2+ with hydroxide ions are reported. Data were obtained in the temperature range 76–97 °C under conditions which allow extrapolation to zero ionic strength. The variation of the rate constants (units of l mol–1 s–1) at zero ionic strength are reproduced by the equations: for [lr(NH3)5Cl]2+, k°2= 2·262 × 1017 exp –(33,657 ± 700)/RT; and for [lr(NH3)5Br]2+, k°2= 1·258 × 1018 exp –(35,153 ± 800)/RT. A good linear correlation exists between the entropies of activation of the reactions of a variety of acidopenta-ammine complexes and the entropies of hydration of the replaced ligands.
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