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To add to what the person above said, it also usually is the step with that has a buildup quantity of its starting reactant. The reactant is present in large amounts, so we know that the rate of the slow reaction is dependent on the reaction itself, not due to a lack of reactants.
Adding on, when looking at which step's rate law matches the experimentally found rate law, if something doesn't look exactly the same, there is a probability that there's a transition step. In that case, look for the step that matches the rate law the most (has the same number of components maybe) and try substitution.
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