It *can* get more complicated, but not always. However, in general, it’s pretty simple. One of the components boils and the other does not.
In reality both components produce vapor, one just produces *more* vapor. Your distillate will favor the one with a higher vapor pressure, but you get both.
By doing multiple distillations you can improve your results, to a point. Some substances do actually ‘seek out’ a particular mixture when you distill them. Water and alcohol, for instance, and this makes alcohol distillation above 96% impossible.
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