Effusion 2026-10-14
Effusion is molecular passage through a small opening whose dimensions, including its thickness, are much smaller than the intermolecular mean free path. For an equilibrium ideal gas, the one-way particle rate through a thin hole of area is . This weights molecules by their wall-normal velocity, rather than just counting all molecules in the reservoir. [ref]
Thermal transpiration 2026-10-14
Thermal transpiration is gas transport driven by an imposed temperature difference in a rarefied connection. Gas can move from cold to hot even when the two end pressures start equal. If the reservoirs are closed, redistribution builds a counteracting pressure difference until the net transfer stops. This final stationary state is not global thermal equilibrium: the two temperatures remain different. It explains why a heated pressure sensor can read a different pressure from the vessel to which it is connected. The correction depends on gas, connection geometry and molecular interaction with its surfaces. [ref]
The simple molecular limit is beautiful: equal opposing particle rates need not mean equal pressures. Consider effusion through a thin hole connecting two locally equilibrated reservoirs of the same gas, at . Equating their one-way rates gives
At equal pressure, the hotter reservoir has lower number density; its faster molecules do not fully compensate for that reduction in outgoing particle rate. With and , the ideal zero-transfer ratio is . The hydrodynamic, zero-flow limit instead has equal pressures when other forces are absent. These are limiting models, not an interpolation formula for a glass capillary. [ref] In a real tube, incomplete exchange of molecular energy with the wall can alter the limiting ratio; a Knudsen number does not specify that exchange. [ref]