The molecules are excited when something is heated and allows for a greater volume of those molecules to escape into the air and spread out. As for the biology side, Why does eating anything warm seem more fresh/less stale? This boils down to heat presenting a greater sensation of smell along with taste. You cannot smell a cold cookie as well as a freshly baked steaming one, could you? This probably comes from our hunter gatherer ancestors. After they hunted food, they were able to tell how fresh a carcass was by the temperature and smell of the insides.
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