My personal experience is that these people are unhappy (self reported and observation). But that's kind of a stereotype and I think there are probably plenty of workaholics whom are quite happy.
This is interesting; my model predicts the exact opposite.
My model is that mental work does not make you tired, it makes you frustrated. There is a difference, because "tired" is related to how difficult the work is, while "frustrated" is more context-dependent -- a simple but time-consuming meaningless task can be very frustrating, while solving a difficult but interesting problem, if you believe that you can do it, is not frustrating. Even expecting a work with unpleasant connotations can make you feel tired.
When I have a lot of free ...
So, it's well-known (or, at least, oft-thought) that you can't just work 16 hours a day; if you want to get stuff done, you need to rest from time to time. You have to take breaks.
Today, just now, I realized that I don't really know what the best way to rest is. If I want to rest, should I do something that's fun and interesting, like reading a fantasy novel? Should I do something that's boring, like building roads in Minecraft, so that work will seem comparatively interesting when I get back? (And besides, reading a fantasy novel is a bit of a challenge, at least for me, whereas building roads in Minecraft is trivial.) Physical activity probably helps, but how much? Do relaxing activities, like taking a warm shower, help more than just sitting there? How can I tell when it's time to take a break? How can I tell when it's time to get back to work?
(Suggestions for tags would be appreciated.)