Carbonate Ligand and Hydrogen Exchange Studies of Some Carbonatoamine Cobalt(III) Complex Ions: A General Mechanism for the Ligand Carbonate Exchange Reaction in Aqueous Solution

The Indirect Assessment of a Catalytic Path

“…it is seen that as fa increases, the shape of the rate curve, NiL-2 vs. i, changes until a limiting "wall" is reached at fa ~0.08 1. mole-1 sec.-1. Thus, if the catalytic paths (2) and (3) are operating it is possible, using this indirect approach, either to evaluate fa or at least to establish its lower limit.…”

“…A variation of concentrations shows that this indirect method is most sensitive to fa when conditions are arranged so that the velocities of the competing paths (1) and ( 2) are nearly identical: when the rate of either of the paths (1) or (2) becomes dominant over the other the catalytic path (3) exerts a relatively smaller effect on the rate of the NiL-2 disappearance. Under these latter conditions the concentration of the product of the catalyzed reaction is best measured directly.…”