Abstract
The aquation rate constant of the ion [Co(NH3)5Br]2+ is (3·9 ± 0·08)× 10–6 s–1 at 25·0 °C 1·00M ionic strength, and 0·0100M-HClO4. The anation rate constant for the same conditions is (1·32 ± 0·06)× 10–6 l mol–1 s–1 over the range 0·1000M⩽[Br–]⩽ 0·750M and shows no saturation effect with increasing bromide-ion concentration. The mechanistic implication of this result is discussed. By independent measurements the concentration quotient for formation of the inner-sphere bromo-complex has been found to be 0·283 ± 0·030 l mol–1 for the same conditions. Attempts to determine ion-pairing constants of Br– with [Co(NH3)5H2O]3+ and [Co(NH3)5Br]2+ failed.
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