Illustrated Physics
physics, drawn
Concept

Partition function — where it appears

The sum of Boltzmann factors over every state of a system, from whose logarithm every thermodynamic quantity can be extracted. Energy, entropy, pressure and heat capacity are all derivatives of it, so computing one function once answers every equilibrium question about the system.

Named by 6 essays across 2 fields — each of them below, with the objects they name alongside it.

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 A ratio in the exponent. The Boltzmann factor against the energy of a state measured in units of kT, with the logarithm up the axis so that the straight line is the whole content. Every kT of energy costs a factor of e, so 10, 20, 30 times kT are factors of 10^-4.3, 10^-8.7, 10^-13.0. At 300 K, kT is 25.9 meV, so a barrier of 0.35 eV is 13.5 kT and a factor of 1.3e-6. That is the sense in which a third of an electronvolt is not a small energy: it is small compared with a chemical bond and enormous compared with kT, and it is the second comparison that decides whether anything happens.

The exponential that decides everything

Maximising the number of ways a reservoir can arrange what is left after taking E out of it gives one factor, e to the minus E over kT. Its exponent is a ratio, which is why a barrier of a third of an electronvolt — nothing at all by chemical standards — is the difference between instantly and never.

thermodynamics · Entropy The field a classical partition function cannot see. The momentum plane of one classical charge, in units of the root-mean-square thermal momentum. With no field the Boltzmann weight is a set of circles about the origin; with a field the same circles sit about p = qA, displaced and otherwise unaltered, because the energy depends on p only through p − qA. Integrating over the whole plane therefore cannot notice the displacement, and the numbers beside the drawing are that integral evaluated at 6 displacements: the largest departure from the zero-field value is 3.3e-16, which is the precision of the arithmetic and not a physical effect. The classical free energy has no B in it, so the classical magnetisation is exactly zero at every field and every temperature — no paramagnetism, no diamagnetism, no ferromagnetism. Every magnetic material is therefore evidence of something classical mechanics does not contain.

The magnetism classical physics forbids

Write down the partition function of any collection of classical charges in a magnetic field, and the field cancels out. Not approximately, not to leading order — the integral is over all of momentum space and the field only shifts where the middle of it is. So classical statistical mechanics predicts no paramagnetism, no diamagnetism and no ferromagnetism, and a compass needle is a quantum instrument.

electromagnetism · Magnetisation Each stage takes 25.0 per cent of what is left. Entropy against temperature for a spin-½ paramagnet at 0.25 T and 1 T, with the cooling cycle drawn between them: a vertical drop is isothermal magnetisation, a horizontal move is adiabatic demagnetisation. Starting from 1 K the treads are at 1.000 K, 0.250 K, 0.062 K, 0.016 K, 3.91 mK. Each is 0.2500 of the one before — a ratio read back off the drawn treads rather than written into them, and equal to the field ratio 0.25/1 because this refrigerant's entropy depends on the field and the temperature only through their quotient. The steps therefore shrink in proportion to what is left, and no finite number of them arrives.

The staircase that never reaches the floor

Absolute zero is unreachable, and the reason is not that the apparatus is not good enough. Every stage of cooling removes a fixed fraction of what is left rather than a fixed amount, so the steps shrink in proportion to the distance remaining — and the fixed fraction cannot be made one, because the entropy curves at two field strengths are required to meet where the axis is.

thermodynamics · Third law 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 How full a surface is, against the pressure of the gas above it. The fraction of adsorption sites occupied on a surface that binds a molecule with 0.35 eV, against the gas pressure on a logarithmic axis, at 250, 300, 350 K. Each curve is θ = p/(p + p½) — Langmuir's isotherm — and each is the same S-shape moved along the axis: on a logarithmic pressure scale the coverage is a function of ln p alone, shifted by the binding energy over kT. The half-full pressure is 5.58 Pa at 250 K, 132 Pa at 300 K, 1341 Pa at 350 K. Warming the surface does not change the shape; it slides the curve to higher pressure by a factor that is a Boltzmann factor, e^(ε/kT), which is how a binding energy is read off a family of isotherms.

The site that fills like an electron level

A patch of catalyst holding a gas molecule, a haem in a muscle cell holding oxygen, an energy level in a metal holding an electron: each is a place that can hold one particle or none, in contact with a reservoir it trades particles with. Each fills according to the same function of one variable — how far the reservoir's chemical potential lies above the energy of the site. Langmuir's isotherm and the Fermi function are not analogous. They are the same law, and haemoglobin works because its sites break it.

thermodynamics · Chemical potential

Named alongside it

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

The Boltzmann factorEntropyEquilibriumHeat capacityKinetic theoryMagnetisationPressureQuantum statisticsActivation energyAdiabatic processAngular momentumArrhenius law

All concepts