Zero-order reactions

In some reactions, the rate is apparently independent of the reactant concentration. The rates of these zero-order reactions do not vary with increasing nor decreasing reactants concentrations. This means that the rate of the reaction is equal to the rate constant, k, of that reaction. This property differs from both first-order reactions and second-order reactions.

Origin of Zero Order Kinetics

Zero-order kinetics is always an artifact of the conditions under which the reaction is carried out. For this reason, reactions that follow zero-order kinetics are often referred to as pseudo-zero-order reactions. Clearly, a zero-order process cannot continue after a reactant has been exhausted. Just before this point is reached, the reaction will revert to another rate law instead of falling directly to zero as depicted at the upper left.

There are two general conditions that can give rise to zero-order rates:

  1. Only a small fraction of the reactant molecules are in a location or state in which they are able to react, and this fraction is continually replenished from the larger pool.
  2. When two or more reactants are involved, the concentrations of some are much greater than those of others

This situation commonly occurs when a reaction is catalyzed by attachment to a solid surface (heterogeneous catalysis) or to an enzyme.