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I think the problem will usually tell you which is slower on the side in parentheses or something. If not it will give you the experimental rate law and you can tell from which reactants are included in the rate law which step is the slow step
The slow step is usually given to you where there are different steps in a reaction mechanism. If not, the rate constant, k maybe given to you for you to identity the slow step. bottom line is, there is probably always going to be a way for you to determine the slow step of a reaction.
The rate determining step is the slowest step in the reaction mechanism. You can determine which of the elementary steps is the slow step by comparing their activation energies. The step with the largest activation energy is the rate determining/slow step because it requires the largest input of energy to overcome this energy barrier. If activation energies are not given, the slow step will be stated in the problem.
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