If you know the OG, then a good estimate is to divide by ten, and you have alcohol by volume. For example, an pale ale with an original gravity of 54 will have about 5.4 % alcohol by volume. This assumes a normal 75% or so apparent conversion, with a finishing gravity about 12-14.
A good fractional distillation will give you the answer, but you need a distillation column that will give good separation of the alcohol from the water. Also, you will get all the alcohol but some of the water since alcohol and water form a 95% alcohol 5% water azeotrope, so you would have to add back 5% of the weight of collected alcohol/water mixture to get an accurate calculation.
I'd stick to the OG divided by ten, it's easier and now equipment and time is needed.