It's not arbitrary. Lithium batteries charging uses voltage termination, and the usual cutoff for 100% on lithium-cobalt batteries (so not LiFePO which is not yet widely used on phones) is 4.2 volts. It's the same for all batteries I've ever used or heard about. You can charge it to higher voltages, but basically nobody sane does that as it quickly becomes dangerous, and 4.2 is pretty much the standard voltage.