Series

Kinetic theory — the series

9 essays on one idea, from the one that introduces it to the one that assumes the rest.
  1. Molecular speeds at 4 temperatures. The distribution of molecular speeds in a gas, with each curve enclosing the same area. Raising the temperature moves the peak right and lowers it: the same molecules, spread over a wider range of speeds.

    The speeds in a still room

    The air in a quiet room is not still. Every molecule in it is moving at hundreds of metres per second, and temperature is a single number summarising an entire distribution.

    part 1 · thermodynamics
  2. Pressure, counted as momentum arriving at a wall. Molecules with speeds drawn from the Maxwell–Boltzmann distribution and directions drawn uniformly in the plane of the figure. Those moving toward the wall will bounce off it, reversing the component perpendicular to it and delivering twice that momentum each — and pressure is nothing but the rate at which that momentum arrives. Because the directions here lie in a plane rather than in space, the perpendicular component carries half the energy rather than the third it carries in a real gas.

    Pressure is a rate of arrival, and the gas law falls out of counting

    Nothing in a gas is pushing on the walls. Molecules arrive, bounce, and leave, and pressure is the momentum they deliver per second — from which the ideal gas law follows with no thermodynamics in it at all.

    part 2 · thermodynamics
  3. The isothermal atmosphere against the real one. Pressure as a fraction of its sea-level value, against altitude. The curves are the isothermal barometric formula at 220, 288, 400 kelvin, whose scale heights are 6.4, 8.4, 11.7 kilometres. The points are the measured standard atmosphere. At 20 kilometres the 288 kelvin model is 71 per cent out, because the air up there is not at 288 kelvin.

    Why the air thins with height, and why that is the same law as the speeds

    The pressure of the atmosphere falls exponentially with altitude, and the distribution of molecular speeds falls exponentially with energy. These are not two results that happen to look alike. They are one statement read on two axes.

    part 3 · thermodynamics
  4. A path through a crowd. A point crossing a field of 90 scatterers, rebounding off each. The mean length of 4000 such segments is 0.2983 box widths, against the textbook form 1/2nr = 0.3086 — a departure of -3.3 per cent, from a measurement that knows nothing of the formula. It does not agree exactly and should not: the closed form is derived for a vanishingly dilute field and these discs cover 9.2 per cent of the plane. Two finite-density effects pull opposite ways — crowding shortens the path, and discs shadowing one another lengthen it — so which side of the formula a given field lands on is not something the formula can tell.

    How far a molecule gets

    A molecule of air travels about sixty-eight nanometres between collisions — some two hundred times its own size, and a ten-millionth of the width of a room. That ratio is the reason a gas can be treated as a continuous substance at all, and the reason it sometimes cannot.

    part 4 · thermodynamics
  5. The same law, across twenty-eight decades. The mean free path 1/nσ against cross-section, for a target density of 6.83·10³⁰ targets per cubic metre — solid lead. It is a straight line of slope minus one, because there is only one thing in the law. At 10⁻²⁸ m² the path is 1.46 mm; at 10⁻⁴⁷ m² the path is 1.55 light-years. Nothing about the physics changes between those ends. Only the area does.

    How far a neutrino gets

    A mean free path is one over the number density times the cross-section, and nothing else. Change only the cross-section — by twenty-eight powers of ten — and the same arithmetic that gives a molecule seventy nanometres in air gives a neutrino a light-year of solid lead.

    part 5 · astrophysics
  6. The viscosity of a gas, over 8 decades of pressure. The viscosity of 3 gases at 300 K against pressure, on a logarithmic pressure axis and a linear viscosity one. The lines are flat, and that is the whole figure. Viscosity is the rate at which momentum is carried across a shear, which is the density of carriers times the distance each one carries it: ⅓ρv̄λ. Doubling the pressure doubles the density and halves the free path, and the two cancel exactly, so the same gas at a hundredth of an atmosphere is exactly as viscous as at one — which is not what anybody expects of a thinner gas and is what is measured. nitrogen comes out at 17.9 μPa·s against a measured 17.9, helium comes out at 19.3 μPa·s against a measured 19.9, argon comes out at 21.7 μPa·s against a measured 22.7. The flatness ends when the free path reaches the apparatus rather than the next layer of gas: at a vessel 10 mm across that is around 0.68 Pa for nitrogen, 1.94 Pa for helium, 0.69 Pa for argon, below which there is no gas-to-gas hand-off left to make.

    The viscosity that does not care how much gas there is

    Pump most of the air out of a vessel and the air that is left is exactly as viscous as it was. Maxwell derived that in 1860, did not believe it, and spent six years building an apparatus to measure it — which is a better description of how a prediction becomes knowledge than any amount of agreement would have been.

    part 6 · thermodynamics
  7. The gas that leaves is not the gas inside. The distribution of molecular speeds inside a container at 300 K and in the beam that escapes through a small hole in it, each normalised to its own peak. They are not the same distribution. A molecule's chance of reaching the hole in a given time is proportional to how fast it is going, so the beam carries one more factor of speed than the gas does — v³ rather than v² times the Boltzmann factor — and the beam is therefore faster and hotter than what it came from. The mean speed inside is 476 m/s and in the beam 561 m/s, a ratio of 1.1781 against the exact 3π/8; and the mean kinetic energy is 1.500 kT inside against 2.000 kT in the beam, which are exactly 3/2 and 2. That difference is not a subtlety. A molecular beam made by effusion has a temperature, in the sense of a mean energy, a third higher than its source; a gas slowly leaking from a container leaves the remainder cooler than it would be if a fair sample had gone; and every calculation of a rate through an aperture that uses the bulk distribution is wrong by this factor.

    The gas that leaves is not the gas inside

    Put a small hole in a container of gas and what comes out is faster and hotter than what stays behind — its mean kinetic energy is 2kT against the 3/2 kT of the gas it came from. Nothing has heated it. A fast molecule simply reaches the hole more often than a slow one, so the sample that escapes is biased by exactly one factor of speed, and every consequence of effusion is that factor.

    part 7 · thermodynamics
  8. Nine hundred steps and hardly anywhere. On the left, a walk of 900 steps of unit length in uniformly random directions, which is what a photon does inside a star: it goes a mean free path, scatters, and starts again in a direction that has forgotten the last one. After 900 steps it is 7.5 lengths from where it began, against 900 if it had gone straight. On the right, the root-mean-square distance over 240 independent walks against the number of steps, both logarithmic: a straight line of slope 0.4920 against an exact one half. The square root is the whole of the result and it is brutal. Escaping a body of radius R takes not R/λ steps but (R/λ)² of them, so a mean free path a thousand times smaller costs a million times as long. That is the difference between a photon leaving the Sun's core and a neutrino doing it: one takes a hundred thousand years and the other takes two and a third seconds, through the same material, and the only thing that differs is λ. What the picture cannot show is the sense in which the escaping energy is not the photon that started: it is absorbed and re-emitted countless times, at falling temperature, so what leaves is a gamma ray's worth of energy arriving as a great many visible photons.

    The light that takes a hundred thousand years to leave

    A neutrino made in the Sun's core is at the surface in two and a third seconds. A photon made beside it takes something like a hundred thousand years, through the same material, over the same seven hundred thousand kilometres — and the whole of the difference is one length, entering the answer squared.

    part 8 · astrophysics
  9. The pair potential, and the two things it does to a gas. The Lennard-Jones potential between two molecules, in units of its own depth and range, with the Mayer function it produces at 1, 3, 8 times the well depth in temperature. The virial coefficient is minus the integral of that function over volume, so the two parts of the potential contribute with opposite signs: the steep repulsive core makes the function minus one there, giving a positive contribution — molecules take up room — and the attractive well makes it positive, giving a negative one. At low temperature the attraction dominates and a gas is easier to compress than an ideal one; at high temperature the core dominates and it is harder. Between them is one temperature at which they cancel.

    The first correction to the gas law

    An ideal gas has no forces between its molecules. The first correction to what it does is computable from those forces alone — one integral over the pair potential — and its sign flips at a temperature where a real gas obeys the ideal law without being ideal at all.

    part 9 · thermodynamics

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