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Say you're given two known variables and one unknown, for example you need to find the number of atoms and you have the Molarity and volume, you would use n=M/v. So that would be an example of where you can't use MiVi=MfVf
That equation basically comes from the fact that in a dilution the amount of moles does not change. It's just a rewritten form of C(molarity)= moles/vol. There could be other questions asking to reorganize the formula to find a different unknown. But for most dilution problems the formula you gave is the go to.
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