Hot air rises, but the atmosphere cools the higher up you go. The reason for this apparent contradiction is that pressure decreases the higher you go, which allows the air to expand. And when gases expand, they cool down.
The hottest places on Earth are the result of warm, moist air rising, rain falling on high mountains, and then the resulting dry air falling on the other side. Moist air heats and cools by a smaller amount as it rises and falls than dry air does, so what happens in those settings is you get something like:
30 C moist air -> rises up and becomes 10 C moist air (loses 20 C as it rises) -> rain falls -> now is 10 C *dry* air -> descends the other side of the hill -> heats up by more than it cooled down before and hits the valley as 40 C dry air (gains 30 C as it descends).
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