The book Predictably Irrational has a great section about this. Basically we have a "market" way of thinking and a "social/gift" way of thinking about goods. When something is free we think of it in the latter way, when it's not, we use the market mindset. And the transition can be jarring - say you're selling cookies. If you lower the price, people buy more cookies. Lower it a lot to, say $.01 per cookie and people will buy all of them. Then lower it all the way to free and people will suddenly take fewer again. Why? Because when you buy all the cookies at $.01 you're a shrewd merchant, but when you take all the free cookies, you're the asshole who took all the free cookies, so there's none left for everyone else. It's two different mindsets, leading to a discontinuity in the supply and demand graph.