This came up in a discussion of the adiabatic lapse rate in the atmosphere. It's just basic physics (or thermodynamics, if you will), but to my chagrin, I found that I'm not sure of the answer. The question: given a column of gas inside a cylinder with perfectly insulating walls, standing in a gravitational field, what is the equilibrium distribution of temperature as a function of height within the cylinder?
There are two plausible answers: (1) uniform temperature independent of height within the column; and (2) cooler with increasing height, consistent with the adiabatic lapse rate for the gas in the column. There are reasonable sounding arguments supporting either answer, but they can't both be correct.
I believe the first answer is correct, because the second would lead to a violation of the second law of thermodynamics. The reason is that the adiabatic lapse rate depends on the average molecular weight of the gas in question. So you could have two cylinders side by side, holding different gases. If their bottom temperatures were equal, their equilibrium temperatures at the top would differ. One could then run a heat engine off of the temperature difference. The ensemble would be a perpetual motion machine of the second type.
That sounds pretty convincing, but so do the arguments for the first answer. If the pressure in the cylinder were reduced to a point where the mean free path of the gas molecules between collisions were long compared to the height of the cylinder, then the kinetic energy of the molecules bouncing around in the cylinder (off of its perfectly insulating / perfectly elastic walls) would certainly be a function of height within the cylinder. For every molecule, the sum of its kinetic plus potential energy must remain constant (between exchange in collisions between molecules). Otherwise, it would be a violation of the first law -- conservation of energy. So any molecule must lose kinetic energy as it rises within the cylinder, and gain kinetic energy as it falls. But temperature depends only on kinetic energy, not gravitational potential energy. So the temperature must be lower at the top of the cylinder than at the bottom.
It's not clear how the answer could transition from this "cooler at top" distribution in the case of zero or rare collisions between molecules to a uniform distribution when collisions are more frequent. I must be missing something.
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