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If you are given a reaction mechanism and an overall rate law, sometimes it is possible to intuitively determine the slow step. This is because the overall reaction rate is determined by the rate of the slow step (which is why it is also called the rate-limiting step). For example, the reaction NO2 + CO --> NO + CO2 follows rate = k[NO2]^2. If the elementary steps are 2NO2 --> NO + NO3 and NO3 + CO --> NO2 + CO2, the former is the slow step because it is the one that has the collision of two NO2 molecules as you would expect given the exponent of 2 on [NO2] in the overall rate law.
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