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What does flouring the pan do?
Some recipes call for dusting the pan with flour.
What exactly does it do for the cake?
It keeps the cake from sticking to the pan. This is what happens:
You put oil or melted butter or rub a stick of butter in the pan, and then dust the pan with flour. The fat will melt and the flour and fat mixture will allow the cake to slip out relatively easily. It's the best way to do it. And if you're doing a chocolate cake, you should switch out cocoa powder for the flour, so the cake doesn't have the white flour around the edges.
Gene Autry (Dust Pan Blues).