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There are some number of factors involved here:

Firstly, it is true that warm air rises, but as it gradually rises, it becomes thinner and expands, which possesses a cooling effect. On the high mountain ranges, the surrounding atmospheric air is very thin: so that there is also not much surrounding air to hold the heat in when the sun does warm the mountain, and much of the warming effect escapes.

Secondly, mountain tops are further from the thermal heat at the earth's centre.

Thirdly, is the angle of incidence over which the sun's rays meet the earth's surface itself. An overhead sun, for instance, meets a flat earth surface very directly - an almost perpendicular 'attack', you might say. A 1 metre stretch of sun affects about 1 metre of earth's surface from directly above. However, if the sun meets the mountain side at [say] an angle of depression of 60 degrees, then the same amount of sun will cover 2 metres of ground; so its overall warming effect will be greatly lessened.

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