Illustrated Physics
physics, drawn
Concept

Detailed balance — where it appears

The condition that each microscopic process and its reverse occur at equal rates in equilibrium, which is stronger than the requirement that the net rates balance. It is what forces an emitter to be as good an absorber, and it underlies the symmetry of the coefficients relating flows to forces in linear response.

Named by 15 essays across 4 fields — each of them below, with the objects they name alongside it.

What a thermal camera reads off a shiny surface. The temperature a camera calibrated for a black body reports, against the emissivity of the surface it is pointed at, for surfaces truly at 323 K, 373 K, 473 K in a room at 293 K. Every curve begins at the true temperature when the emissivity is one and ends at the room's temperature when it is zero, because a surface that emits nothing reflects everything and the camera is then looking at the room. polished aluminium at 0.05 reads 312 K; stainless steel, oxidised at 0.8 reads 451 K; matt black paint at 0.95 reads 468 K; human skin at 0.98 reads 471 K for a surface truly at 473 K. That is not a fault in the instrument. It follows from Kirchhoff's law — a poor emitter is a poor absorber and therefore a good reflector — so the shortfall in a shiny surface's own glow is made up almost exactly by whatever is reflected in it, and no measurement of the light leaving a surface can separate the two without knowing the emissivity in advance.

The glow that says nothing about the surface

A thermal camera pointed at a saucepan of boiling water reads a hundred degrees. Pointed at a polished aluminium block at the same temperature it reads about twenty-five, and the instrument is working perfectly. What it is measuring is emissivity as much as temperature — and a surface's emissivity is forced to equal its absorptivity, at every wavelength and every angle, by an argument with no physics of matter in it at all.

thermodynamics · Blackbody Two experiments, two computations, one coefficient. The Seebeck coefficient of a resonant conductor against where its resonance sits relative to the chemical potential, together with the Peltier coefficient divided by the temperature. The first is obtained by applying a temperature difference and finding the voltage that stops the current; the second by applying a voltage at uniform temperature and taking the ratio of the heat flow to the current. Different driving, different measurement, different integral — and the two curves agree to 3.8e-7 of the sweep's own scale across the whole of where they pass through zero and change sign. That equality is Kelvin's relation Π = ST, guessed in 1854 from an argument its author knew was not sound and proved by Onsager in 1931 from microscopic reversibility. It is not a property of this conductor; it holds for every one.

The second experiment that cannot disagree

Heat one end of a wire and a voltage appears across it. Pass a current through the same wire at uniform temperature and it carries heat. Those are two different experiments with two different apparatus, and the coefficient in front is the same number in both — not approximately, and not for some materials. The reason is that the equations of motion underneath look the same run backwards.

thermodynamics · Diffusion Effusion rate against molecular mass. The rate at which a gas escapes through a small hole, against its molar mass, normalised to hydrogen. The rate is a quarter of the number density times the mean speed times the area, and the mean speed goes as the inverse square root of the mass — so the rate does too, which is Graham's law of 1848. Hydrogen escapes four times faster than oxygen and 13.3 times faster than uranium hexafluoride. The practical consequence is isotope separation, and its difficulty is on this chart. The two uranium hexafluorides differ by 3 out of 352 in mass, so a single stage enriches by a factor of only 1.00429 — four parts in a thousand. Reaching 90 per cent from natural uranium's 0.72 per cent therefore takes about 1665 ideal stages, and a real cascade needs more because each stage is imperfect. That number is why gaseous-diffusion plants were among the largest industrial structures ever built, and why centrifuges — which separate by mass directly rather than by the square root of it — replaced them.

The gradient that drives the other thing

A concentration gradient drives a flow of matter and a temperature gradient drives a flow of heat. Each also drives the other, by coefficients that are equal — a relation nobody could have guessed and which follows from the fact that the underlying motion runs the same forwards and backwards in time.

thermodynamics · Diffusion Runs that break the second law, and how often. The work done in a process repeated many times, and the same for the process run in reverse with its work reflected, for a free-energy change of 4 kT and a dissipation of 3 kT. The average work exceeds the free-energy change, which is the second law, and individual runs do not have to: the shaded tail is the fraction of runs that do less work than the free energy — trajectories in which the entropy of the universe went down — and it is 11.03% here. The two curves cross exactly at the free-energy change, whatever the dissipation, which is what makes an irreversible measurement able to report an equilibrium quantity.

The second law, with a probability attached

Entropy increases, on average. For a small system pulled quickly, individual runs go the other way — and how often is not a matter of taste but an exact number, fixed by a relation with no adjustable constant in it and no requirement that anything be near equilibrium.

thermodynamics · Entropy One temperature, four pawls, and nothing gained. The net rate of a ratchet whose gas and whose pawl are at the same temperature, against the load, for notches 2, 5, 10, 20 times the thermal energy deep. Every curve passes through zero at zero load and is negative everywhere else. The device is not merely unable to lift a weight; under any load at all it turns the wrong way and lets the weight down, converting its potential energy into heat in the gas. Making the notch deeper slows everything down — an exponential in the depth — and does not change the sign anywhere. That is the second law arriving as a mechanism rather than as a prohibition. Nothing was assumed about entropy; the pawl was simply allowed to be as warm as everything else, and its own fluctuations undo exactly the rectification it was there to provide. Any rectifier small enough for thermal noise to matter has this problem, and the rectifier being clever does not help, because the same noise reaches the cleverness.

The engine a fluctuation cannot run

A ratchet lets a shaft turn one way and not the other. Put a paddle in a gas on the same shaft and molecular collisions appear to become a lifted weight — an engine running on one reservoir. It does not work, and following exactly why turns the second law from a prohibition into a mechanism: the pawl is as warm as the gas, and it lifts whenever it is asked to.

thermodynamics · Heat engines A hemisphere outside is a cone of 16.6° inside. Rays leaving a flat face from a material of index 3.5 into air. Every direction in the hemisphere above the face is reached by a ray from inside a cone of half-angle 16.6°, arcsin(1/n), because refraction at the face fans the cone out; rays steeper than that are reflected back, drawn in the warning colour. The squeeze is exact in the way the invariant requires. The projected solid angle of the inside cone is π sin²θc, which is π/12.25, and multiplied by n² it equals π, the projected solid angle of the whole hemisphere outside — checked on the drawn geometry. So the light that does get out has not gained anything: the radiance inside is n² times higher and the directions available are n² times fewer, and the étendue passing the face is the same on both sides.

The cone light has to find to get out

Inside a dense material the whole hemisphere of directions outside a flat face shrinks to a narrow cone, and light made inside can leave only if it happens to be travelling within it. For gallium arsenide that is two per cent of the light. Turned round, the same cone keeps light in: a slab of silicon with a rough surface holds the light it admits for fifty-one passes. Both numbers are the n² the optical invariant carries, and neither one breaks it.

optics · Etendue Two temperatures for the same sunlight. Sunlight described two ways, against how much it has been concentrated. The flat line is the temperature its spectrum belongs to — 5,762 K, the Sun's surface, which concentration does not change because a mirror does not alter a photon's energy. The rising curve is the temperature a blackbody would need in order to radiate the flux actually arriving: 394 K unconcentrated, 2213 K under a parabolic dish, and 5771 K at the geometric limit, where the two meet — computed here and checked against the Sun's own temperature, because a perfect concentrator reproduces the source's radiance and cannot exceed it. The gap between the two curves is the dilution, and dilution is entropy: the same energy spread over a hundred thousand times more directions occupies a hundred thousand times more modes. That is what a converter has to carry, and it is why the ceiling on solar conversion is not the Carnot efficiency between 5,762 K and 300 K.

The work a diluted beam will not do

Sunlight at the top of the atmosphere has the spectrum of a body at 5,762 kelvin and the energy flux of one at 394. The mismatch is not an accident of units: the light has been spread over a hundred thousand times more modes than it left in, and that dilution is entropy. Run it through a heat engine unconcentrated and five per cent of it is available as work.

optics · Etendue The light of a diode at room temperature is as bright as a surface thousands of kelvin hot. How many photons occupy each mode of the light, on a logarithmic scale, against photon energy. The lowest curve is the thermal glow of a 1.42 eV semiconductor at 300 K with no voltage across it. The solid curve above it is the same device with 1.3 V across it, emitting only above its gap. The dashed curve is a blackbody at 2571 K, the temperature whose light has the same occupation as the diode's at 1.472 eV, just above the gap. They cross there and nowhere else: the diode's occupation falls a factor e every 25.9 meV, as its lattice's temperature requires, and the blackbody's every 222 meV. No single temperature describes the diode's light. At each photon energy it has a brightness temperature, and that temperature is 300 K multiplied by ε/(ε − qV).

The glow that carries a voltage

Thermal radiation has no chemical potential, because walls make and destroy photons freely. A light-emitting diode is a body that glows at room temperature with a voltage written into its light — Planck's law with the voltage as the photons' chemical potential — which is why its light can be as bright as a surface thousands of kelvin hot, why at low voltage it can put out more light than the power it draws and cool itself doing so, and why a reverse voltage makes a surface look colder than it is.

thermodynamics · Chemical potential Electrons and holes in silicon against the donors added. The concentrations of free electrons and holes in silicon at 300 K against the concentration of donor atoms added, on logarithmic axes, solved from charge neutrality and the product law n·p = nᵢ². Below the intrinsic concentration of 10¹⁰ per cubic centimetre the donors change almost nothing. Above it the electrons follow the donors one for one and the holes fall in exact proportion: a hundred times more donors, a hundred times fewer holes. At 10¹⁶ donors the electrons outnumber the holes by 10¹² to one. The dashed line is √(n·p), which does not move at all across ten decades of doping — checked to a part in a billion.

The product doping cannot move

Add one phosphorus atom for every five million silicon atoms and the crystal's free electrons multiply a millionfold — and its holes fall a millionfold, although nothing was done to them. Add a drop of acid to water and the hydroxide ions vanish in exactly the proportion the hydrogen ions grow. Both are one law: when a reaction makes two species together, equilibrium fixes the sum of their chemical potentials, and so the product of their concentrations. Every semiconductor device is built on the minority carriers that law leaves behind.

thermodynamics · Chemical potential The price of precision never falls below two. For a clock ticking forwards and backwards with a free-energy drop a per step, the product of its squared relative uncertainty and the entropy it has produced, in units of k: exactly a·coth(a/2), whatever the time elapsed. It approaches the bound of 2 only as the driving vanishes and grows as a once the driving is strong; the three clocks compared elsewhere sit at 2.04 (0.5 kT), 2.63 (2.0 kT), 8.01 (8.0 kT). No steady-state process of any design lies below the line at 2 — the thermodynamic uncertainty relation.

The precision a clock pays for in heat

Anything that counts — a molecular motor stepping along a filament, a chemical oscillator keeping time in a bacterium, a clock ticking on a wall — has to be driven, because a count that is not driven runs backwards as often as forwards. The heat it gives off buys it regularity, and there is an exact floor under the price: the squared relative uncertainty of the count, times the entropy produced, is never less than two in units of Boltzmann's constant.

thermodynamics · Entropy The crests of one wave, meeting an observer who never stops accelerating. A spacetime diagram, time up and distance across, both scaled by the acceleration: the worldline of an observer with constant proper acceleration (a hyperbola), its horizon (the dashed light line it approaches and never crosses), and the crests of a plane wave of a single frequency travelling in the same direction, as parallel lines at 45°. Within the drawing the observer meets crests at proper times −0.18, −0.05, 0.11, 0.29, 0.51, 0.80, 1.20, 1.90 in units of c/a: the gaps lengthen, each crest having to chase the observer further, and after the last of them, at 1.90, it meets no more — every later crest lies beyond its horizon. One wave of one frequency therefore arrives as a signal whose frequency falls as e^(−aτ/c) for ever. Nothing about the wave is random, and the observer's clock is perfectly regular.

The heat hidden in a Doppler shift

An observer who accelerates without stopping sees empty space as warm. The usual derivation takes quantum field theory and several pages. There is a shorter one, and it needs no quanta at all. Watch a single wave of a single frequency from a steadily accelerating rocket: it is redshifted, and because the rocket keeps speeding away, the redshift grows exponentially. Take the spectrum of that fading signal, and it is exactly a Planck spectrum, at a temperature set by the acceleration and nothing else — the same whatever frequency the wave started with. The thermal distribution was hidden in the geometry of the horizon all along.

relativity · Accelerated frames The race to equilibrium that the hotter start wins. How far each system is from equilibrium with the bath — the relative entropy of its distribution from the bath's, in nats, on a logarithmic axis — against time since it was placed in the bath at 0.30, also logarithmic, for a start at 0.50 (warm, dashed) and one at 0.901 (hot, solid). The hot system starts further away: 1.243 against 0.254. Both close in quickly as their left wells equilibrate internally. Then the warm system must wait for probability to leak between the wells, and stalls, while the hot one, whose wells already had the right shares, carries on falling. The hot curve overtakes the warm one at a time of about 6.9, and from then on the hotter start is always nearer equilibrium.

The hotter start that cools first

Put two identical systems, one warm and one hot, into the same cold bath, and common sense says the warm one reaches the bath's temperature first, since the hot one has further to go. The claim that hot water sometimes freezes before warm water — the Mpemba effect — has been argued over for sixty years and does not survive careful measurement. But a cleaner version of it is real and has been observed: in systems whose relaxation has a slow route and a fast one, a hotter start can miss the slow route entirely and overtake a cooler start, exponentially. Whether a system cools quickly depends not on how far it is from equilibrium but on how much of the slowest way back it needs.

thermodynamics · Entropy 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.

thermodynamics · Kinetic theory The two lines a vibration adds to scattered light. The light scattered by silicon's optical vibration at 520 cm⁻¹, against its shift from the 532 nm laser line in cm⁻¹ (negative, lost to the crystal; positive, gained from it), on a logarithmic intensity axis, at 100 K, 300 K and 600 K; the strong unshifted line and its wings are cut out at the centre. The Stokes line, where the light gives up a quantum of vibration, barely changes: 1.00, 1.09 and 1.40 in relative strength. The anti-Stokes line, where it takes one, needs a vibration already excited and grows from 7·10⁻⁴ of the Stokes line at 100 K to 0.103 at 300 K and 0.36 at 600 K. The light comes back bluer only as often as the crystal is warm enough to pay for it.

The light that comes back bluer when it is warm

Shine a green laser on a crystal and a tiny fraction of the light comes back with a different colour: a little redder, having given a quantum of energy to one of the crystal's vibrations, or a little bluer, having taken one. Losing energy is always possible. Gaining it needs a vibration already excited, so the bluer light is fainter, and fainter still the colder the crystal. The ratio of the two is a Boltzmann factor, fixed by quantum statistics and nothing else. It is a thermometer that needs no contact and no calibration — and in a long glass fibre, it is thousands of thermometers at once.

optics · Scattering The spectrum two rates would make. Balance absorption against spontaneous emission alone, with level populations in the Boltzmann ratio, and the radiation comes out as x³ times e to the minus x, Wien's law; add stimulated emission, and the same balance gives x³ over e to the x minus one, which is Planck's. The two agree on the right, where a photon is much more energetic than the thermal energy and stimulated emission is negligible, and disagree on the left, where only Planck's approaches the classical count of waves. At x = 1 Planck's is 1.58 times Wien's. Measurements around 1900 at long wavelengths had already found that Wien's law failed, so experiment required the third rate seventeen years before anyone saw it in a laser or a maser.

The third process equilibrium demands

In 1916, with general relativity just finished, Einstein asked how atoms and light could reach equilibrium at all. Absorption and emission, balanced against each other, gave the wrong spectrum. A third process was needed, in which light makes an excited atom emit a copy of itself. Nobody had seen it, and it took forty years to be put to use. It also fixes a ratio that goes as the cube of the frequency, which is why X-ray lasers are so hard.

quantum · Blackbody

Named alongside it

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

The second lawThe Boltzmann factorIrreversibilityBlackbodyThermal equilibriumBand gapChemical potentialDiffusionEntropyEntropy productionEtendueFluctuations

All concepts