There is a chance of occurance of reaction even when the concentration of reactant on the catalyst surface is zero.
The rate of reaction is independent on concentration of reactant in case of zeroth order reactions. Then there is a possibility of reaction.
In some mechanisms the catalyst is required only till the intermediate cpmpound is formed. If the intermediate concentration in free space is non zero the possibility of reaction occurance can be observed even when the reactant concentration on catalyst surface is zero.
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