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When I use brownie mix products such as the standard Betty Crocker or Duncan Hines - the ones where you just mix up the ingredients, and then put it in the tray and bake it - I notice that the top just magically becomes flaky and delicious.

What causes that? The top is composed of the same mix as the bottom and sides; I realize it's exposed to the air, but how does that make the difference?

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I don't know for sure, but I suspect it's because in addition to air, the top is exposed to more direct heat. The sides and bottom have the pan conducting heat to them. –  Yamikuronue Apr 10 '12 at 16:09
    
Related: cooking.stackexchange.com/questions/2652/… –  KatieK Apr 10 '12 at 16:26
    
No @KatieK, that doesn't pertain, I don't think. I never have to do any of those things and it just happens naturally. –  Aerovistae Apr 10 '12 at 16:28
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If I could offer a possibility..... When you bake a loaf of bread, the surface, exposed part of the loaf has a different crust than the interior (even when baked in a pan). This is due to the carmelization of the sugars on the surface. I suspect that this is the case here as well.

I get the same effect baking a mix or a scratch recipe. I've always assumed it is due to the carmelization of the surface sugars coupled with a bit of dehydration due to direct heat exposure....

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Agreed. Commercial mixes usually contain sugar and corn syrup, which would contract on the heated surface during caramelization while the bread part expands. The difference in expansion of the two materials would explain a cracked, flaky top. –  Bizorke Apr 12 '12 at 0:41
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