They are usually calculated with specific Pokemon or uses in mind. For example you may give a certain Pokemon enough Defense EVs to survive a Crunch from Tyranitar, if that is the most likely Pokemon you will face (or most powerful of the likely Pokemon).
Or you may only give Jolteon half it's EVs in Speed because that's enough to outspeed Garchomp (just an example, I don't know if that's right).
Also HP EVs are often calculated to give you an exact stat that makes the best of Substitute (a quarter of your HP rounded up).
If you check the movesets on Smogon, they often have explanation for unusual EV spreads like these.