Illustrated Physics
physics, drawn
Concept

Quantum statistics — where it appears

The counting rules for identical particles, which come in exactly two kinds and decide whether a state may be shared or must not. Bosons may crowd into one state and do so at low temperature; fermions may not, and the refusal is what makes matter take up room.

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

The entropy of mixing, and the entropy of not mixing. The entropy gained when two ideal gases at the same temperature and pressure are allowed to mix, per particle and in units of Boltzmann's constant, against the proportion of the mixture that is the first gas. The curve has no property of either gas in it — not their masses, not their sizes, not how strongly they interact, since ideal gases do not — and it is largest at 0.500, where it reaches ln 2 = 0.6931. Below it is the same quantity for two samples of the SAME gas, which is zero at every proportion: removing the partition between two halves of a box of nitrogen changes nothing that can be measured, and putting it back recovers the original state. The two results are correct and they do not join up. Make the two gases more and more alike — two isotopes, then two nuclear spin states, then nothing at all — and the upper curve does not descend to meet the lower one; it stays exactly where it is until the two species become identical, and then jumps. What the figure is really about is that the jump is in the counting and not in the gas.

Mixing what is already mixed

Let two different gases into each other's halves of a box and the entropy rises by a fixed amount that contains nothing about either gas. Do it with the same gas on both sides and it rises by nothing. Make the gases more and more alike and the answer does not converge — it jumps.

thermodynamics · Entropy Two costs, and the width that balances them. The energy of a particle in a harmonic well against how tightly its wavefunction is squeezed, in units of ħω and of the width that minimises the total. Two terms compete. Squeezing the particle into a smaller region raises its kinetic energy, because the uncertainty relation makes a narrow position spread a wide momentum spread and momentum is squared in the energy; that term rises as the inverse square of the width and goes to infinity as the particle is localised. Letting it spread out raises its potential energy, since the well gets steeper away from the bottom; that term rises as the square of the width. The sum has a minimum at a width of 1.0000 in these units, where the total is 0.5000 ħω and the two terms are equal at a quarter each. That number is exactly the true ground-state energy of a quantum harmonic oscillator, obtained here with nothing but the uncertainty relation and a minimisation. What the figure shows and the formula does not is why there is a floor at all: it is not that the particle happens to keep moving, but that every way of stopping it costs more than it saves.

The motion that cannot be stopped

A particle in a well cannot sit at the bottom of it. Squeezing it into a smaller region costs kinetic energy faster than it saves potential energy, so there is a width that minimises the total — and the minimum is not zero. Helium never freezes because of it.

quantum · Uncertainty How much of copper's electron sea a temperature can reach. The probability that a state of a given energy is occupied, in copper, at 4 temperatures, with energy measured in units of the Fermi energy — 7.04 eV here. At absolute zero the curve is a step: every state below the ceiling is full and every state above it is empty. Raising the temperature rounds the step, and rounds it over a range of about kT, which is the whole point — at room temperature kT is 0.0259 eV against a ceiling of 7.04 eV, so the rounding is 1.6 per cent of the way down the sea and everything deeper is untouched. An electron in the deep is not held there by a force; it simply has nowhere to go, because every state it could be promoted to is occupied. at 0 K the step is spread over 0.00 per cent of E_F, at 300 K the step is spread over 1.61 per cent of E_F, at 3000 K the step is spread over 16.13 per cent of E_F, at 20000 K the step is spread over 107.52 per cent of E_F.

The pressure that is not a temperature

Copper's conduction electrons are at a temperature of eighty thousand kelvin, in a wire that is at room temperature. That is not a figure of speech, it is what the exclusion principle does to a mole of particles, and it explains the largest unexplained number in the theory of metals.

quantum · Exclusion 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 entropy each degree of freedom has not yet given up. The entropy carried by each kind of degree of freedom, drawn against the temperature at which it orders and hands that entropy over. Lattice vibrations freeze out around room temperature; electron spins in a paramagnetic salt order in the millikelvin range, which is what makes adiabatic demagnetisation work; and nuclear spins hold R ln(2I+1) — 11.5 joules per kelvin per mole for copper — down to some tens of nanokelvin, where their own dipolar interactions finally sort them out. A copper sample at a microkelvin therefore has a large entropy and violates nothing: its nuclear spin system has not reached its ground state, and the third law is a statement about ground states rather than about thermometers.

A law about spectra, not about heat

The third law is usually met as a statement about cooling. Its statistical form is a statement about a spectrum: the entropy of a system in its ground state is k ln g, and it vanishes only when the ground state is unique. Every apparent exception is a degeneracy or a system that never reached its ground state — and copper nuclei carry eleven joules per kelvin per mole down to a hundred nanokelvin without violating anything.

thermodynamics · Third law 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.

EntropyEquilibriumThird lawDegeneracyGround stateHeat capacityMagnetisationMicrostatesPartition functionZero-point energyAdiabatic processBinding energy

All concepts