Why does chocolate only melt smoothly in a pot inside hot water, but not in a pot that is directly heated?
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In addition to modulating temperature to avoid burning and uneven heating, melting chocolate over hot water such as with a double boiler is how you can create tempered chocolate. Tempered chocolate has been heated gently and cooled slowly such that the fat molecules in the cocoa butter arranges itself in a crystalline structure. This is how you create that ultra smooth, snappy chocolate texture you see in fresh high-quality chocolate bars, candies, truffles, and cake decorations. Melting chocolate more aggressively will destroy the structure, creating a bendy, chewy, dull-looking thing once cooled, and must be re-tempered via seeding (adding additional tempered chocolate and trying again) or letting it cool while stirring constantly.
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