I think there's a saturated solution of sodium acetate inside. The metal clickie causes the solution to crystallize, which happens to happen exothermically.
They are a supersaturated Sodium acetate solution.
Liquids give off energy when they freeze and take energy in when they melt.
When you heat these and melt them they can stay stable as a saturated liquid until you create a small site for them to start freezing around - they then give off energy when they freeze. The 'clicker' is all that's required to localy concentrate it enough to form a single crystal seed to start the freezing
http://www.amazon.co.uk/Magic-Gel-Reusable-Hand-Warmer/dp/B0...
I've seen them in person and they're remarkable if you've never encountered them before.