Past exam of the physics B course of the University of Cambridge / 2017 / Paper 2 / Section C / C12

For a classical dilute ideal gas in thermal equilibrium, the probability of a single-particle velocity is proportional to the Boltzmann factor for kinetic energy, $e^{-m{v}^2/(2k_{B}T)}$. Velocities with speed between $v$ and $v+dv$ fill a spherical shell of velocity-space volume $4\pi v^{2}dv$. The normalized Maxwell speed distribution is thereforeThe factor $v^2$ counts states, rather than representing an extra Boltzmann energy factor.

Set $\alpha =m/(2k_{B}T)$ and use $I_j={\int }_0^{\infty }{v}^j{e}^{-\alpha v^2}dv$. Normalization cancels in ratios, so the given recurrence givesConsequentlyThe root mean square speed is larger than the mean speed, consistent with the positive variance of the speed distribution.

Choose a flat wall and let $\theta$ measure the angle from the direction towards it. Particles of speed $v$ in solid angle $d\Omega$ occupy fraction $f(v)dvd\Omega /(4\pi )$ of an isotropic gas. In time $dt$, those within normal distance $v\cos \theta dt$ reach the wall. Their number per area per time is therefore $nf(v)dvv\cos \theta d\Omega /(4\pi )$.

Only the incoming hemisphere contributes. Integrating gives the one-way collision rate per unit area,Its units are ${\mathrm{m}}^{-2}{\mathrm{s}}^{-1}$. This is not $n\overline{v}/2$: selecting the incoming half of the particles must also account for their mean normal velocity. For effusion through a thin hole whose diameter is much less than the mean free path, the same one-way rate applies because collisions within the opening can be neglected.

Wall arrivals are not an unbiased sample of the gas: faster atoms arrive more frequently. The normalized speed distribution among incident atoms isThe angular factor in the arrival rate cancels when calculating the mean kinetic energy. ThusUsing $I_5=2I_3/\alpha$ givesBy contrast, an atom chosen randomly from the bulk has mean kinetic energy $3k_{B}T/2$. The arrival weighting raises the normal-direction contribution to $k_{B}T$ while each tangential direction still contributes $k_{B}T/2$. This is also the mean energy carried by atoms effusing through a thin aperture from an equilibrated reservoir.

Denote the heated and cold vessels by subscripts $h,c$. For argon, the opposing effusive particle rates are equal in the steady state:Because $\overline{v}\propto \sqrt{T}$ and $p=n{k}_{B}T$,This is thermal transpiration in the free-molecular limit. It fixes a ratio; the initial conditions determine the absolute pressures.

For the stated two identical vessels, take their fixed volume to be $V$ and the combined system sealed. Initially it contains $2p_{0}V/(k_B{T}_0)$ atoms. HenceLet $q=\sqrt{T_1/T_0}$. Combining this inventory with $p_h=q{p}_c$ gives the closed-vessel thermal transpiration resultHeating makes the hot side less dense but at higher pressure. Both expressions reduce to $p_0$ when $T_1=T_0$. For a small imposed temperature rise $\Delta T$, the pressure difference starts as $p_0\Delta T/(2T_0)$.

If instead the cold vessel is interpreted as an externally maintained pressure reservoir with $p_c=p_0$, the answer becomes $\Delta p=p_0(q-1)$. That alternative requires the fixed-pressure reservoir assumption; it does not conserve the initial particle inventory of two sealed equal-volume vessels. Merely describing the vessels as large does not keep their pressures fixed through the redistribution. The pressures in the boxed answer assume the natural closed-vessel interpretation.

Let L be the vessel initially containing argon and R the vessel initially containing helium. Both have volume $V$ and fixed temperature $T_0$, and the aperture has area $A_h$. The incoming and outgoing rates of each species must be considered separately. For species $s$,Thus its density difference relaxes exponentially with time constantThe two-vessel effusive mixing solution for the four densities isUsing atomic masses of approximately $40$ and $4$ atomic mass units gives ${\tau }_{\mathrm{He}}/{\tau }_{\mathrm{Ar}}\simeq 1/\sqrt{10}\simeq 0.32$. Helium therefore transfers faster. Each species eventually reaches $n_0/2$ in each vessel, but its transient is different. In particular, the total density temporarily rises in the initially argon vessel and falls in the initially helium vessel, before both return to $n_0$.

For unequal maintained temperatures $T_L,T_R$, replace the rate equation byWith each species' total density sum still $n_0$, its final densities and relaxation time areEvery species has the same final density ratio $\sqrt{T_R/T_L}$ and partial-pressure ratio $\sqrt{T_L/T_R}$. Thus there is no permanent composition separation in this ideal steady state, although the rates remain mass dependent. A maintained hot side has lower density and higher pressure. Equal particle rates do not imply thermal equilibrium: atoms arriving from the hotter side carry more energy, so external heating and cooling are required to hold different temperatures. The model assumes thin-hole effusion, local equilibrium within each vessel and negligible aperture volume.