Illustrated Physics
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Series

Kinetic theory — the series

13 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
  10. How well a diamond-like crystal conducts heat, from 1 K to 1000 K. The thermal conductivity of a model crystal with diamond's sound speed and Debye temperature, from kinetic theory applied to its phonons, against temperature on logarithmic axes: natural carbon in a sample 1 mm across, isotopically enriched carbon, and natural carbon in a sample 0.1 mm across; copper's room-temperature 400 W/m K is marked for comparison. The model is calibrated to natural diamond's 2,200 W/m K at room temperature. At low temperature the conductivity rises as the cube of the temperature, limited by the sample's walls; at high temperature it falls as umklapp collisions shorten the phonons' paths. Between, it peaks: 3.7·10⁴ W/m K at 100 K for the natural crystal; 7.8·10⁴ W/m K at 94 K for the enriched crystal; 1.2·10⁴ W/m K at 126 K for the thin natural crystal. The model gets the shape — the rise as the cube of the temperature, a peak near 100 K, the fall — but overestimates the heights, because it leaves out the phonon collisions that conserve momentum and every defect but isotopes; measured enriched diamond peaks near 4 × 10⁴ W/m K. An insulator with no free electrons still conducts heat five times better than copper at room temperature.

    The gas of sound that carries a diamond's heat

    Diamond has no free electrons and conducts heat five times better than copper. What carries the heat is a gas — not of molecules but of quantised sound waves, phonons — and the kinetic theory that gives the conductivity of air gives the conductivity of a crystal with the same formula: a third of heat capacity times speed times mean free path. The gas is strange in two ways. At low temperature its particles cross the whole crystal without meeting anything, so the conductivity depends on how big the sample is. And at room temperature one atom in a hundred being a neutron heavier is enough to scatter its fastest-oscillating members.

    part 10 · thermodynamics
  11. The highest note the air can carry, with height. The frequency at which a sound wave in the air loses its amplitude by a factor e in a single wavelength, in hertz on a logarithmic scale, against height, with the band of human hearing shaded. Because viscosity does not depend on pressure, the collision time grows as the pressure falls, and the ceiling falls with it. It is about 212 MHz at sea level, 0.17 MHz at 50 km and 3 kHz at 80 km. It passes the top of human hearing, 20 kHz, at about 68 km, and the bottom, 20 Hz, at about 110 km; at 100 km it is 92 Hz. Above about a hundred kilometres the air cannot carry anything a person could hear, at any loudness: the molecules are too far apart to pass a compression on before it has dispersed.

    The note too high for thin air

    Sound in a gas is a compression handed from molecule to molecule by collisions, and it can only be handed on if the molecules collide many times in each period of the wave. At sea level they collide seven thousand million times a second, and the limit is far above anything audible. But a gas's viscosity does not depend on its pressure, so as the air thins with height the time between collisions grows in proportion, and the highest note the air can carry falls with it: two hundred megahertz at the ground, three kilohertz at eighty kilometres, below twenty hertz above a hundred and ten. The upper atmosphere is not silent for want of loudness. It is silent because its molecules are too far apart to pass a sound along.

    part 11 · thermodynamics
  12. A vane pushed by gas, and only while the gas is thin. The net push on a 1 cm vane per kelvin between its faces, against pressure, from the free-molecule result Δp = p ΔT/2T at low pressure and an interpolation that falls away above the point where the mean free path reaches the vane's size, about 0.67 Pa. The peak is about 335 times the pressure of bright sunlight on the same face. A bulb at ordinary pressure does nothing and a very hard vacuum does nothing either; the toy needs the range between.

    The vane that turns the wrong way

    The glass toy with four vanes spinning in sunlight looks as if light is pushing it. It runs in the wrong direction for that. The black faces retreat, where light's own pressure would push back the silver ones. Light's pressure is about three hundred times too feeble, in any case. The rotor is driven by gas, and only at a pressure where the gas's mean free path is about the size of the vane.

    part 11 · thermodynamics
  13. The distance at which the air takes over. Evaporation of water at 20 °C into dry air, in kilograms per square metre per second, against the thickness of the layer the vapour must cross before it is carried away, both on logarithmic scales, with the kinetic and diffusive resistances added in series: 1/u + δ/D, where u = √(RT/2πM) is the speed at which the kinetic flux carries vapour off and D the diffusion coefficient. Dashed, the kinetic ceiling. At one atmosphere the two resistances are equal at δ = D/u = 0.17 μm, about two and a half mean free paths of the air; a layer much thinner than that leaves the surface at its ceiling, and a layer much thicker throttles it in proportion to its thickness. At a tenth of an atmosphere diffusion is ten times faster and the crossover moves out to 1.7 μm. Only in vacuum, or across gaps shorter than a mean free path, does the liquid itself set the rate.

    The puddle that could dry in a second

    A liquid in equilibrium with its vapour loses molecules exactly as fast as the vapour delivers them, and kinetic theory says how fast that is. For water at room temperature it is two and a half kilograms per square metre every second — a puddle two and a half millimetres deep gone in a second. Puddles take hours because almost every molecule that leaves is knocked back by the air within a fraction of a micrometre. The ceiling binds only where the vapour can escape in a single free flight: in vacuum, where water freezes itself, in the smallest droplets, and on the filament of a lamp.

    part 12 · thermodynamics

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