Rate-determining step

In chemical kinetics, the overall rate of a reaction is often approximately determined by the slowest step, known as the rate determining step (RDS) or rate-limiting step. For a given reaction mechanism, the prediction of the corresponding rate equation (for comparison with the experimental rate law) is often simplified by using this approximation of the rate determining step.

In principle, the time evolution of the reactant and product concentrations can be determined from the set of simultaneous rate equations for the individual steps of the mechanism, one for each step. However the analytical solution of these differential equations is not always easy, and in some cases numerical integration may even be required. The hypothesis of a single rate-determining step can greatly simplify the mathematics. In the simplest case the initial step is the slowest, and the overall rate is just the rate of the first step.

Also, the rate equations for mechanisms with a single rate-determining step are usually in a simple mathematical form whose relation to the mechanism and choice of rate-determining step is clear. The correct rate-determining step can be identified by predicting the rate law for each possible choice and comparing the different predictions with the experimental law, as for the example of NO₂ and CO below.

The concept of the rate-determining step is very important to the optimization and understanding of many chemical processes such as catalysis and combustion.

Given a reaction coordinate (energy diagram), the rate determining step can be determined by taking the largest energy difference between any starting material or intermediate on the diagram and any transition state that comes after it. That transition state will then be the rate-determining step of a given reaction. The transition state with highest absolute energy may not necessarily correspond to the rate determining step.

As an example, consider the gas-phase reaction NO
2 + CO → NO + CO₂. If this reaction occurred in a single step, its reaction rate (r) would be proportional to the rate of collisions between NO
2 and CO molecules r = k[NO
2][CO], where k is the reaction rate constant and square brackets indicate a molar concentration.

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