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Often, you can see which step of a reaction is slow by looking at its rate law. If there is a certain reactant in the rate law, you can tell that reactant is involved in the slow step of the reaction because it is the slow step that determines the rate. Whatever isn't involved in the rate is most likely part of the fast step.
I think it will usually tell you which one is the slow step and the fast step when calculating. Another way to find out is by looking at the rate law and if there is a particular reactant in that law that is the same in one of the reactants of the steps then you can find out which is the slow step. This is because the rate is determined by the slow step.
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