Concept

Kinetic theory — where it appears

The account of a gas as a large number of moving particles, from which pressure, temperature and transport are derived by averaging. It gives pressure as a rate of arrival of momentum, temperature as a mean kinetic energy, and viscosity as a transport of momentum across an imaginary surface.

Named by 10 essays across 3 fields — each of them below, with the objects they name alongside it.

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.

thermodynamics · Kinetic theory
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.

thermodynamics · Kinetic theory
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.

astrophysics · Kinetic theory
The staircase equipartition cannot climb. The heat capacity of hydrogen at constant volume, in units of R, against temperature on a logarithmic axis. The three translational directions contribute 3/2 at every temperature. The two rotations switch on near 85.4 K — the temperature at which kT matches the first rotational step — taking the total to 5/2, computed here by summing the rigid rotor's partition function over two hundred levels rather than by assuming the plateau. The vibration switches on near 6332 K, taking it to 7/2. At 50 K the value is 2.469; at 300 K the value is 2.502; at 5000 K the value is 3.376. Classical equipartition predicts 7/2 at every temperature, including at four kelvin, and the size of the steps is set by ħ — which is how a heat capacity measures a quantum constant.

Half a kT for every way of moving

A heat capacity ought to be a count. Every quadratic term in a system's energy carries half a kT of it, so warming a gas is a matter of enumerating the ways its molecules can move — and the fact that the count comes out wrong for hydrogen is how a thermometer measured Planck's constant.

thermodynamics · Equipartition
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.

thermodynamics · Kinetic theory
The line that slopes the wrong way. Mean temperature against total energy, for a self-gravitating sphere at nine radii. The points fall on a straight line of negative slope: taking energy away makes the body hotter. The heat capacity read off the drawing is -4.10e+34 J/K against the -4.10e+34 J/K the theorem gives, and the sign is the whole content. The dashed line is an ordinary gas in a rigid box, whose temperature rises when energy is added, as everything one can put a thermometer in does.

The ball of gas that heats up as it cools

Take energy away from a self-gravitating cloud and its temperature rises. Its heat capacity is negative, which nothing else stable does, and the consequence is that a star radiating into cold space is not cooling down — it is running up, and its whole life is a slow fall it cannot stop.

astrophysics · Self-gravity
What a coordinate is worth, by the shape of its energy. The mean energy stored in one coordinate, in units of kT, against the power with which that coordinate enters the energy. The curve is 1/n and the points are the same average obtained by integrating the Boltzmann weight numerically, agreeing to 3.3e-7 per cent at worst. an energy going as |x|^1 holds 1.0000 kT; an energy going as |x|^1.5 holds 0.6667 kT; an energy going as |x|^2 holds 0.5000 kT; an energy going as |x|^3 holds 0.3333 kT; an energy going as |x|^4 holds 0.2500 kT; an energy going as |x|^6 holds 0.1667 kT. The familiar half a kT is the case n = 2 and nothing more general than that: a coordinate whose energy is linear in it — the momentum of an ultrarelativistic particle, or a field with no restoring force but a constant tension — carries a whole kT, and one confined by a very steep wall carries almost nothing. Equipartition is a theorem about quadratic terms, and calling it a theorem about degrees of freedom is the substitution that makes it fail.

The share that is not half a kT

Equipartition is quoted as half a kT for every degree of freedom, and it is nothing of the kind. It is half a kT for every *quadratic* term. A coordinate whose energy is linear in it carries a whole kT, and a gas hot enough that its particles' energy is pc rather than p²/2m therefore holds twice what the counting says — which drops its ratio of specific heats to four thirds and puts a star on the edge of being able to hold itself up.

thermodynamics · Equipartition
One word, two mechanisms, opposite signs. Viscosity on a logarithmic axis against temperature over the range 280 to 360 kelvin, where gases and liquids can both be measured. The gases rise and the liquids fall, and the two families are separated by three decades of magnitude as well as by sign. The logarithmic slopes at the middle of the range are 0.76 for air, 0.69 for helium, -6.13 for water, -5.41 for ethanol, -23.00 for glycerol, so the steepest liquid responds 30 times more strongly than the gas and in the other direction. Nothing about the word viscosity requires this: what is being measured in both cases is the ratio of a shear stress to a shear rate, and that definition says nothing about what carries the momentum. In a gas it is molecules in free flight, so heating speeds up the carriers; in a liquid the molecules are permanently in contact and what has to happen is one of them getting past its neighbours, so heating removes an obstacle rather than adding a carrier. The obvious question this raises is what a dense gas near its critical point does, where neither picture holds, and the honest answer is that neither formula on this chart applies there at all.

The thickness that goes both ways

Heat a liquid and it thins; heat a gas and it thickens. The two are not a strong effect and a weak one but opposite signs, differing by a factor of thirty in size as well — and the word viscosity names one measurement made on two mechanisms that have almost nothing in common.

fluids · Viscosity
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.

thermodynamics · Kinetic theory
14 decades of fluid, and a floor none of them reaches. The ratio of viscosity to entropy density for 8 substances, in units of the proposed lower bound, on a logarithmic axis. The quantity is a viscosity divided by how much entropy a cubic metre of the substance holds, and it has the dimensions of Planck's constant over Boltzmann's — so a bound on it is a statement with no material properties in it at all. The span here is a factor of 1.6e+14, from pitch at 20 °C at the top to the quark–gluon plasma at the bottom, which sits a factor of 1.6 above the floor. The values marked as computed are worked out from a viscosity and a tabulated entropy; the rest are quoted from the compilations, because a minimum along an isobar is an inference from many measurements rather than a single one.

Whether a fluid can be made arbitrarily thin

Viscosity has no units anybody would call fundamental, and nothing obviously stops it being as small as you like. Divide it by the entropy in a cubic metre and the units become Planck's constant over Boltzmann's — and a conjecture from 2005 says that ratio has a floor. Across fourteen decades of ordinary fluid nothing has been measured below it, the closest thing to it is the hottest matter ever made, and a kinetic-theory argument reaches the same number from the opposite direction.

fluids · Viscosity

Named alongside it

The objects these essays reach for when they reach for this one.

Mean free pathEquipartitionViscosityHeat capacityThe Boltzmann factorContinuumCross-sectionDegrees of freedomIntermolecular forcesMaxwell–Boltzmann distributionNumber densityPartition function

All concepts