It seems kinda useless to have the Pyromancer’s skill stack five times if the 5th threshold is only reached when you trigger the overheat explosion, I can’t imagine how this might be useful, but that might be me being thick.
The passive ability of Pyro and Unchained work the same way in that they give stacks per heat. In both cases you gain a stack per 8 heat. Max Heat is 40.
Unchained however has a Talent which increases Max Heat by 15% (Form of the Fire Wind) thus she can gain 5 stacks without exploding.
Might matter in the future if the Devs ever introduce other ways to increase your max heat (eg. Talent Reworks or new Item properties).