Flour changes character when heated and this is generally a desirable factor – bread, cakes sauces, roux etc. Ultimately, most powders will also burn if heated beyond a certain point. This will certainly lead to off flavors. There is nothing inherent in anything in powder form that prevents them from change due to high temperature.
powders are not meant to be exposed to heat. the high surface area and dryness makes them burn quickly. powders are meant to mixed well into the whole dish and not cooked directly or separately. for a different angle – powdered substances are usually highly flammable for the same reason.
So let’s give an example: a fundamental technique in french cuisine is making a roux out of flour and butter, to be used as a base to a sauce. When making a roux, you heat butter while mixing flour in. Cook too long or forget to stir frequently, and this mixture quickly burns, changing the aroma and tast drastically – creating the different, but still tasty browned butter, or if left too long, an unpalatable and burned roux. The powdered flour simply burns very quickly in that semi-naked form, and the change in taste and function shift distracally.
For the brownies, the cocoa powder is included in a very wet mixture of butter, egg, and sugar. If the cocoa powder is being “cooked,” it must mean that it is either not mixed into the batter, or the batter is so dried out that it cooks the powder.
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