Thermodynamics

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.

Entropy is a count, and the arrow of time is arithmetic

Nothing in mechanics prefers a direction. Entropy is not a force pushing things toward disorder — it is the observation that some outcomes have vastly more ways of happening than others.

The ceiling on every engine, set before it was designed

There is a maximum efficiency no heat engine can exceed, and it depends on nothing but two temperatures. Not the fuel, not the working substance, not the cleverness of the engineer.

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.

The equation that only runs forwards, and the walk underneath it

A drop of ink spreads and never gathers. The equation describing it is one of the few in physics that is not reversible — and underneath it is nothing but a coin being tossed.

The heat that changes no temperature, and where it actually goes

A kettle reaches a hundred degrees in a minute and takes five more to boil dry. The heat going in during those five minutes changes nothing a thermometer can see, and it is most of the energy in the whole process.

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.

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.

The jiggle that proved atoms

A pollen grain in still water never stops moving. For eighty years that was a curiosity with no explanation; then it became the measurement that settled whether matter is made of particles, by turning a microscope and a stopwatch into a count of how many molecules are in a mole.

The entropy that lives on a surface

Throw a cup of tea through a horizon and the entropy of the outside world falls. Either the second law is wrong or the horizon has an entropy of its own — and the only quantity available for it turns out to be its area, in units of a length made from gravity, quantum mechanics and the speed of light together.

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.

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.

What a system actually minimises

A ball falls to the bottom of a bowl and a gas fills a room, and neither of those is the rule. A system in contact with a large reservoir minimises U − TS, and the minus sign is the reservoir's own entropy written in the system's variables — which is why a rubber band pulls harder when it is heated.

A boiling point is a pressure, not a temperature

Nothing about water names one hundred degrees; the air does. Where a liquid turns to vapour in its bulk is fixed by what pushes on it, which makes the familiar figure a coordinate on a curve — 71 °C on Everest, 119.5 °C in a sealed pot — and one latent heat draws the whole curve.

The engine that pays back more than it takes

Carnot's argument puts a ceiling on how much work a flow of heat can be made to do. Run the same cycle backwards and the ceiling inverts into a floor that is greater than one — so a machine can deliver three or four joules of heat for every joule it consumes, and a perfectly efficient electric heater is the worst way to warm a room.

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.

The part of the curve no fluid follows

One equation for a real gas produces isotherms with a rising middle section, which says a substance would expand as the pressure on it grows. Nothing does that. What replaces it is a horizontal line whose height is fixed by making two areas equal, and the condition is not a convenience.

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.

Why heating a perfect spring changes nothing

A harmonic solid vibrates harder when heated and does not get any longer. Thermal expansion lives entirely in the term that the harmonic approximation throws away — and so does the fact that a solid conducts heat at a finite rate, which is the same discarded term doing a second job nobody would have connected to the first.

The point at which the two become one

Heat a sealed tube of carbon dioxide and the meniscus inside it does not boil away — it fades, the two densities converging until there is nothing to separate. Twenty millikelvin before that happens the fluid turns milky, and the exponent describing the last approach is a number van der Waals got wrong and could not have got right.

The bit that has to be paid for

One molecule in a box, a partition, and the knowledge of which side it went — enough, between them, to extract work from a single reservoir, which the second law forbids. The engine is real and the arithmetic is right. What closes the loophole is that the cycle does not finish until the knowledge has been thrown away, and throwing away one bit costs exactly what the expansion delivered.

The engine that has to finish

Carnot's ceiling is exact and it is reached only by an engine that takes for ever, because a reversible heat flow needs a vanishing temperature difference to drive it. Ask instead for the most power rather than the most work per joule of heat, and the answer is a different function of the same two temperatures — and three measured power stations sit on it rather than on the ceiling.

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.

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.

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.

The walk that comes home

A particle wandering at random on a line returns to where it started, with certainty. On a plane it returns, with certainty. In three dimensions the probability is 0.3405 — so two out of three molecules released in a room never pass through their starting point again, and the difference between the cases is not a matter of degree.

The entropy that is still there at zero

The third law says a perfect crystal has no entropy at absolute zero. Ice has 3.41 joules per kelvin per mole left over, and the number can be recovered from one line of counting — two hydrogens near each oxygen and two far, six legal arrangements out of sixteen, R ln(3/2). The law has an escape clause and the escape clause is measurable.

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.

The barrier a new phase has to climb

Water vapour three times supersaturated is thermodynamically desperate to condense and will sit there indefinitely if it is clean enough. The obstacle is that a droplet has to start small, and a small droplet is nearly all surface — so the first nanometre of every phase transition costs energy rather than releasing it, and what decides whether anything happens is the height of that cost divided by kT.

Hotter than any temperature there is

A system whose energy has a ceiling can be pushed past the point where adding energy adds entropy. Its temperature is then negative — and negative temperatures are not cold. They sit above every positive temperature on the only scale that decides which way heat flows, and a working laser is at one.

The gas that cools by being let go

Push a gas through a plug and its temperature changes, although no work is done on anything and no heat goes anywhere. Which way it changes depends on where it starts: inside a dome in the pressure–temperature plane it cools, outside it warms, and hydrogen at room temperature is outside — which is why liquid hydrogen needed liquid air first.

The gas that nobody counted

A box of gas holds however many molecules were put in it. A box of radiation holds however many photons the temperature says, because the walls make and destroy them until the free energy is least — and one dropped assumption changes every result. The pressure becomes a third of the energy density instead of two thirds, the entropy goes as the cube of the temperature, and the adiabatic index comes out at exactly four thirds.

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.

The transition with nothing to order

Every transition in this collection so far has an order parameter — a quantity that is zero on one side and not on the other. In two dimensions a continuous symmetry cannot break at any temperature above zero, so there is nothing for such a quantity to be, and by the usual reckoning there can be no transition. There is one anyway, and what changes at it is whether vortices are bound in pairs.

The summer that reaches the cellar in December

Drive the diffusion equation at its boundary instead of releasing something into it and the solution is a decaying, lagging oscillation with a single length in it. That length governs both the shrinking and the delay, which is why the depth at which the ground is coldest in August is fixed by the same number as the depth at which the seasons stop being felt at all.

Why the triple point is a point

Three phases of one substance coexist at one temperature and one pressure and nowhere else, and the reason is arithmetic rather than chemistry: count the numbers that describe the state, count the conditions equilibrium imposes, and subtract. The same subtraction says four phases of one substance are impossible, and it says so without knowing what the substance is.

The temperature a molecule does not have

Temperature fixes a system's average energy and nothing more. The actual energy wanders, by an amount tied to the heat capacity, and the relative size of the wandering falls as one over the square root of the number of degrees of freedom — so a mole has a temperature and a molecule does not.

The melting curve that leans the wrong way

The slope of any coexistence line is the latent heat divided by the temperature and the change in volume. Latent heat is always positive, so the sign of the slope is the sign of the volume change — and for water the volume change is negative, which is the whole of why ice floats and why the melting curve leans backwards.

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.

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.

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.

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.

The energy that refuses to be shared

Put all the energy of a chain of masses into its longest mode and add a few per cent of nonlinearity, and equipartition says it should spread out among all thirty-two modes and stay there. It does not. It leaks into three or four neighbours and then comes back — almost exactly — and goes on doing so, and the calculation that found this was expected to be a demonstration that it would not happen.

The height a planet is seen from

A body in sunlight settles where it radiates away what it absorbs, and that takes two numbers and one line of arithmetic. It gets the Moon right and Earth wrong by thirty-three kelvin. The correction is not that the atmosphere traps heat but that it moves the level space sees the planet from, and the rest is done by a lapse rate that is not a radiative quantity at all.

The entropy that depends on how fast it was cooled

Ice's residual entropy is a count, and it comes out the same whoever measures it. A glass's does not. A glass keeps whatever entropy it happened to have when its own relaxation time crossed the experiment's, so cooling ten times more slowly leaves less behind — and extrapolating the equilibrium liquid below that point takes its entropy under the crystal's at a finite temperature, which cannot happen and does not, for a reason that is still argued about.

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.

The temperature an engine really takes its heat at

Carnot's ceiling is set by two temperatures, and no engine that burns fuel takes its heat in at one temperature or gives it out at another. It takes heat over a range, from the moment combustion starts to the moment it ends. For any reversible cycle there is an exact replacement for Carnot's two numbers: the average temperature at which heat arrives and the average at which it leaves, each weighted by the entropy the heat carries. The gap between a real cycle and Carnot is a gap between those averages and the extremes.

The work left in two buckets of water

Carnot's ceiling assumes reservoirs so large that taking heat from one and giving it to the other changes neither temperature. Two buckets of water are not reservoirs. Run the best possible engine between a hot one and a cold one and both temperatures move, the efficiency available shrinks as they do, and the engine stops when they meet — at the geometric mean of the starting temperatures, not the ordinary one. The work it delivered is exactly the difference between those two meeting points, and it is far less than the starting temperatures promise.

The count that decides which entropy is right

There are two ways to count the states of an isolated system: the states at its energy, which is Boltzmann's entropy, and the states at or below it, which is Gibbs's. For large systems in ordinary conditions they agree to the last measurable digit. For a system whose energy has a ceiling, past the halfway point, one gives negative temperatures and the other forbids them. Definitions cannot settle which is right, but a temperature is for something — saying which way heat will flow — and putting two such systems in contact lets the count of states answer.

The gas that flows towards more of itself

Fick's law says a substance diffuses from where there is more of it to where there is less. In a mixture of three gases, nitrogen can do the opposite for hours — flowing into the bulb that already holds more nitrogen, and then stopping while a difference remains — and in a welded bar of steel, carbon crosses into the side that is already richer. Nothing is wrong with the second law. Diffusion flattens chemical potential, and with more than two components, or a second element changing it, that is not the same as flattening concentration.

The condition three modes never meet

Whether two modes of a chain can hand energy to a third is arithmetic on the dispersion relation, and for a chain of masses the answer is never: a sine is concave, so the sum of two frequencies always exceeds the frequency of their sum. The smallest shortfall anywhere on a chain of N masses is π³/4(N+1)³ — never zero, and never far from it — and a shortfall turns a transfer into a beat.

Half a kT in a piece of wire

Count the quadratic terms in a molecule's energy and equipartition gives a heat capacity. Count them on a transmission line instead and the same theorem gives a resistor's noise voltage — 4kTRΔf, with nothing in it about what the resistor is made of. A fifty-ohm input at room temperature says 0.91 nanovolts in every root hertz, and no design removes it.

Weighing what cannot be put on a scale

Summed over every coordinate of a bound system, equipartition stops being a statement about temperature and becomes a relation between two averages: twice the kinetic energy equals n times the potential energy for a potential going as the nth power. For gravity that fixes a bound system's total energy from how fast its parts move — so a Doppler shift and an angular size return a mass, and for the Coma cluster the mass they return is fifty times the mass that shines.

A fridge with no work going into it

Every engine here so far turns heat into work or work into a heat flow. A machine exchanging heat with three reservoirs and doing no work at all can still move heat from cold to hot, and the ceiling on how much is the product of two Carnot expressions — an engine's efficiency times a fridge's coefficient of performance. A gas flame makes ice, and the accounting is one inequality in three entropy flows.

An engine with one number in it

A thermoelectric couple has no moving part and no working fluid, and its efficiency is the Carnot value multiplied by a factor containing exactly one dimensionless group of material properties. Sixty years of effort have moved that group from about one to about two, and the reason it is hard is that its three ingredients are not independent: raising the conductivity ruins the coefficient it is squared against, and the only lever that is really free is the heat the lattice carries.

The reaction that cannot go all the way

Chemistry speaks of reactions that go to completion and reactions that do not happen, and at equilibrium there are neither. The reason is a logarithm. The free energy of a half-finished reaction contains the entropy of mixing, whose slope is infinite at both pure ends, so every reaction's lowest point lies strictly inside — and the slope of that free energy, the chemical potential, is to particles what temperature is to heat.

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.

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.

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.

The voltage that is a chemical potential

A battery, a nerve cell and a pH meter all turn a difference in chemical potential into a voltage, and the conversion is the same in each: fifty-nine millivolts for every factor of ten in concentration, at room temperature, whatever the ion. The voltage a battery holds as it discharges is the chemical potential of the atoms stored in its electrodes — and a battery whose voltage barely changes is one whose electrode is going through a phase transition.

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.

The electron that leaves because there is room

It takes 13.6 electronvolts to pull the electron off a hydrogen atom, the energy of a particle at a temperature of 158,000 kelvin. Hydrogen is half ionised at the surface of a star at 14,000 kelvin, in a thin nebula at 7,000, and in the early universe at under 4,000 — a fortieth of its binding energy. The electron leaves not because it has enough energy but because a free electron has so much more room to be in than a bound one, and at equilibrium room counts as much as energy. Saha's equation is that trade written down, and it turned out to be the key to what stars are made of.

The melting curve that has to arrive flat

The slope of every line on which two phases coexist is their difference in entropy divided by their difference in volume. The third law says that entropy differences vanish at absolute zero, so every such line — melting, boiling, a superconductor's critical field — must reach the bottom of the temperature scale lying flat. Helium-3 reaches it in the strangest way available: below a third of a kelvin its solid is more disordered than its liquid, the melting curve runs backwards, and squeezing the liquid into solid absorbs heat. That backwards curve was the refrigerator in which superfluid helium-3 was found, and it is now the definition of temperature below one kelvin.

The speed limit that does not care how big the molecules are

Two molecules in water cannot react faster than they can find each other, and how fast they find each other is set by diffusion. A bigger molecule is an easier target, so it seems a reaction between big molecules should be faster. It is not: a molecule twice as big is twice as easy to hit and wanders half as fast, and the two cancel exactly. Every reaction that happens at the first touch runs at the same rate, about seven billion per molar per second in water, whether the partners are ions or proteins — a speed limit written by the viscosity of water and the temperature, and nothing else.

The noise a high Q moves out of the way

Anything held by a spring at a temperature jiggles, and equipartition says exactly how much: the mean square of its displacement is kT divided by the spring's stiffness, whatever the spring is made of and however it is damped. That looks like a floor no measurement can go below. It is a floor on the total, and the total can be moved. An oscillator with little damping puts almost all of its thermal motion into a narrow peak at its own frequency and leaves every other frequency quiet — which is why the mirrors of gravitational-wave detectors hang from fibres of glass that ring for minutes.

The pressure that ionises

Squeeze a hot gas of hydrogen and Saha's equation says it recombines: a free electron has less room to be in, and room was what paid for its freedom. Squeeze it far enough and it comes apart again, completely, at any temperature — not because the room has grown but because the atom has nowhere left to be. Crowded to within a few atomic radii of each other, hydrogen atoms have no bound state, and their electrons, freed by pressure alone, form a metal. Deep inside Jupiter most of the planet's hydrogen is in that state.

The protons a star cannot afford

A free neutron decays in fifteen minutes into a proton, an electron and an antineutrino. Inside a neutron star it cannot, and the star is made of neutrons because of it. Beta decay is a reaction like any other, and at equilibrium the neutron's chemical potential must equal the proton's plus the electron's. In a crowded star an electron can only be added at the top of a sea tens of megaelectronvolts deep. So the matter settles where protons are rare: half a per cent of the nucleons at nuclear density, if nucleons were free, and never more than one in nine at any density.

The two laws absolute zero will not allow

The ideal-gas law and Curie's law are the first two equations of state most people meet. The third law of thermodynamics says both must be wrong at low temperature, and it says so without any model of what replaces them. A Maxwell relation turns every derivative of the entropy into something measurable with a ruler or a magnetometer: the thermal expansion, the slope of the magnetisation with temperature. If the entropy stops depending on pressure and field at absolute zero, those must vanish. The classical gas expands as 1/T and Curie's magnetisation climbs as 1/T, and both slopes grow without limit instead.

The diffusion that slows the longer it is watched

A random walker whose steps come at irregular times still diffuses normally, provided the waits have a finite average. Let the waits have no average — mostly short, occasionally enormous, as they are for a molecule that keeps getting stuck — and three things change at once. The spread grows more slowly than time. A diffusion coefficient measured by following one particle depends on how long it was followed. And following one particle for a long time no longer tells what many particles do: averages along a path and averages over a crowd give different laws. Tracking single molecules inside living cells runs straight into all three.

The melting line that turns round

Squeeze water and it freezes at a lower temperature — the backwards slope of its melting line, and the reason ice floats. Keep squeezing and the slope reverses. Past two thousand atmospheres ordinary ice gives way to a denser ice, then another, and from there on every ice melts at a higher temperature under more pressure, exactly as a normal substance's does. At twenty thousand atmospheres water freezes into an ice that is still solid at a hundred degrees Celsius; at two hundred thousand, one still solid at four hundred. The famous anomaly belongs to one ice out of five, and the same relation that explained it explains its end.

The boiling curve that turns back

Heat a surface under water and more heat flows from it the hotter it gets — up to a point. Past about twenty degrees above boiling the bubbles crowd together, merge, and begin to blanket the surface with vapour, and from then on a hotter surface passes less heat, not more, until by a few hundred degrees above boiling it is wrapped in an insulating film and passes fifty times less than it did at its best. Shigeo Nukiyama found the turn in 1934 by melting wires. It is why a water drop skates for a minute on a very hot pan but vanishes in two seconds on a merely hot one, and why every boiler, steam generator and water-cooled reactor is designed around a number called the critical heat flux.

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.

The ice that grows more slowly the thicker it gets

A lake under air ten degrees below freezing grows eleven centimetres of ice on the first day and only another eighteen in the following six. The ice forms at its underside, and every gram of it releases latent heat that must be carried up through the ice already there before more can form: the ice is its own insulation. The thickness therefore grows as the square root of time, and the rule, Stefan's, depends on temperature and time only through their product — the freezing degree-days that lake-ice forecasters count. A few centimetres of snow on top slows it more than any amount of cold speeds it up.

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.

The degree a spoonful of solute buys

Dissolve anything in water and the water freezes lower and boils higher. The two shifts come from one cause — the solute lowers the liquid water's chemical potential, so the liquid wins against ice and against vapour over a wider range — but they are not the same size. For every mole of particles per kilogram the freezing point falls 1.86 degrees and the boiling point rises only 0.51, three and a half times less, and the reason is in the entropies: ice and water are so alike that a small push moves their crossing a long way. The same arithmetic says salting pasta water does nothing a cook could notice, weighed molecules for a century of chemistry, and in 1887 showed that salts in water are made of ions.

The ice that grows by stealing from the droplets

Most clouds colder than freezing are not made of ice. They are made of droplets of liquid water, some tens of degrees below their freezing point, waiting for something to start them freezing. When a few ice crystals do appear among them, the crystals grow and the droplets shrink, without touching, because supercooled water has a higher chemical potential than ice and so a higher vapour pressure: air balanced with the droplets is ten per cent supersaturated, to an ice crystal, at minus ten degrees. A few crystals among a hundred thousand droplets each take everything, grow heavy enough to fall, and that is how most of the rain outside the tropics begins — as snow.

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.

The frost that lifts by drinking

Frozen ground rises in winter, sometimes by tens of centimetres, and the usual explanation — water expands by nine per cent when it freezes — is wrong: soil soaked in benzene, which shrinks as it freezes, heaves too. The lift comes from layers of clear ice that grow by pulling liquid water up through the soil from below. Ice and water touching each other need not be at the same pressure, and when the water is free to flow, ice a degree below its melting point can push with 1.12 megapascals while it drinks — twelve times less than freezing water in a sealed pipe, and enough to lift a house at a tenth of a degree.

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.

The entropy every liquid gains on boiling

Divide the heat it takes to boil a liquid by the temperature at which it boils, and for benzene, chloroform, acetone, hexane, ether and carbon tetrachloride the answer comes out within a few per cent of the same number — about ten and a half times the gas constant. Frederick Trouton noticed it in 1884. It is a statement about entropy, and once it is read that way the liquids it fails for become the interesting ones: water and the alcohols, whose hydrogen bonds hold the liquid in order; acetic acid, whose vapour is made of pairs; and helium, whose liquid is already as disordered as quantum mechanics allows.

The cluster that grows where the walkers arrive

Let particles wander in one at a time from far away, each sticking where it first touches a growing clump. The rule has nothing in it about shape, and the clump that results is a lacy, branched thing whose mass grows more slowly than its area, so it gets emptier the bigger it gets. The reason is that a random walker reaches the outermost tips long before it can find its way into a gap between branches. The same arithmetic — the probability that a walker arrives is a solution of Laplace's equation — shapes electrodeposits, lightning-like discharges in plastic, fingers of water pushed into oil, and colonies of bacteria short of food.

The heat capacity that goes up and comes down

Equipartition promises every way a system can move a fixed share of heat, and for a harmonic oscillator the promise is kept: once the temperature is high enough, it holds one k per oscillator and goes on holding it. A system with only two levels cannot keep it. It absorbs heat while its upper level is filling, then stops — the two levels equally full and nowhere higher to go — so its heat capacity rises to a peak and falls back to zero. The hump, named after Walter Schottky, is the signature of a degree of freedom with a ceiling, and the area under it counts how many states were there.

The metal that feels colder than the wood

A steel railing and a wooden bench in the same shade are at the same temperature, and the railing feels much colder. The usual explanation, that metal conducts heat better, is half the answer, and it gets water wrong. When two bodies touch, the surface between them jumps at once to a temperature that then stays fixed, a weighted average of the two in which each body's weight is the square root of its conductivity times its heat capacity per volume. Skin at 33 °C touching steel at 20 °C meets it at 21; touching wood, at 30. The nerves report the meeting temperature, not the object's.

The cold reservoir overhead

On a clear, still night a car roof can grow frost while the air around it is several degrees above freezing. Nothing in the air is cold enough to freeze water. The roof is radiating its heat upward to a sky whose radiation back is that of something twenty degrees colder than the air — part of it the cold upper atmosphere, part of it space itself, seen through a window in the infrared where the air is transparent. The clear sky is a cold reservoir available everywhere, and it can be used: to make frost, to cool buildings below the air temperature even in sunshine, and in principle to run an engine at night.

The supercooled water that only partly freezes

Water can be cooled well below 0 °C and stay liquid, and when a crystal finally starts, the whole bottle seems to turn to ice at once. It does not. Freezing releases heat, and with nowhere for that heat to go in the instant of freezing, it warms everything back to 0 °C — at which point freezing must stop. Water cooled to −15 °C freezes about a fifth at once; to −38 °C, the coldest liquid water gets, about half. The rest has to wait for the surroundings to take the heat away, and a hand warmer is the same arithmetic run above body temperature.

The insulation that makes a wire lose more heat

Wrap a hot water pipe in glass wool and it loses less heat. Wrap a thin electrical wire in PVC and it loses more — four times more, at the best thickness — and runs cooler for it. The insulation adds a resistance to heat flowing through it, but it also adds surface for the heat to leave from, and around a thin enough cylinder the surface wins. The crossover is a radius, k/h, set by the insulation and the air; below it, more insulation means more heat lost, and a small enough ball cannot be insulated by anything wrapped round it.

The thin foils that stop radiant heat

In a vacuum, heat can cross a gap only as radiation, and a single sheet of foil a few hundredths of a millimetre thick, hung in the gap and touching nothing, halves it. Two sheets cut it to a third, thirty to a thirty-first. The foil does not need to be thick or cold or clever; it needs only to be shiny, because a sheet that absorbs little also emits little, and each one becomes a radiator in its own right, floating at a temperature between its neighbours. The golden blankets on spacecraft and the silvering inside a vacuum flask are the same arithmetic of resistances in series.

The heap that sets itself alight

A haystack, a coal stockpile, a bin of oily rags or a silo of damp grain can catch fire with no spark at all. A slow reaction inside makes a little heat; the heap holds it in; the warmer middle reacts faster and makes more. Whether that ends in a warm heap or a burning one is decided by a single number built from the heap's size, the air's temperature and the reaction's speed — and past one value of it there is no steady temperature at all. The critical size shrinks steeply as the weather warms, and the heap gives almost no warning before it goes.

The ball that weighs how a gas stores heat

Drop a steel ball into a glass tube that fits it closely, on top of a flask of gas, and it does not fall to the bottom. It bounces, up and down, on the gas trapped beneath it, with a period of about a second. The gas is a spring, and its stiffness is the pressure multiplied by a number that counts how many ways the gas's molecules can hold energy. So a stopwatch on a bouncing ball measures something that otherwise needs a calorimeter: whether the molecules can rotate, whether they can vibrate, and how far a vibration has woken up at the temperature of the room.

The squeeze a petrol engine is not allowed

Every textbook gives a petrol engine's ideal efficiency as one minus the compression ratio raised to a small negative power, and every reader can see that the efficiency keeps climbing as the ratio rises. Real petrol engines stop near ten or eleven. Nothing in the thermodynamics stops them. The fuel does: the charge being compressed is already fuel and air, and the burning gas behind the flame squeezes the rest until it ignites on its own, in a hammer-blow that wrecks pistons. An octane number buys nothing but time against that, and a diesel escapes it by compressing air and adding the fuel only when it wants ignition.

The ring that forgets and then remembers

Put a few hundred balls on a ring, all white, and mark a handful of the gaps between them. Each tick, every ball moves one place round and changes colour if it crosses a mark. Nothing is random and everything can be run backwards. Yet the colours mix, half and half, exactly as Boltzmann's equation for a gas says they should, and the entropy rises to its maximum and stays there — until, after one full turn, every ball is white again. Mark Kac built the model in 1956 to show where the arrow of time in Boltzmann's equation comes from, and what it quietly assumes.

The rings a reaction lays down in a gel

Let one salt soak into a tube of jelly that holds another, and where they meet a solid should form, spreading smoothly behind the advancing front. It does not. It forms in sharp, separate bands, close together near the entrance and further and further apart, each one a fixed multiple of the distance of the last. Raphael Liesegang saw the rings in 1896 and they have been found since in rocks, in agate, in gallstones and in microchips. Nothing in the jelly is patterned to begin with. The pattern comes from a solid that will not start until the solution is overloaded, and that then empties the solution around it.

The salt that dissolves in the air's own water

Leave a dish of salt in a bathroom and it does not just clump; on a humid enough day it turns into a puddle, though no water was poured on it. Above 75 per cent humidity, common salt pulls water out of the air until it has dissolved itself. The number is not a property of salt's attraction for water in any vague sense. It is the vapour pressure of a saturated salt solution, read as a fraction of pure water's: wherever the air holds more water than that, the solution is the state with the lower chemical potential. Bring the humidity back down, and the puddle does not turn back into salt until the air is far drier — about 45 per cent.

The column that boils from the middle

Water at the bottom of a geyser's tube is hotter than water anywhere else in it, and it is not the water that boils first. The weight of the column raises the boiling point with depth faster than the heat from below raises the temperature, so the column reaches its boiling curve partway down, under a cooler surface layer. A little boiling there lifts the water above. Everything beneath is then at a lower pressure than the one it was heated under, so it is superheated and flashes, and the eruption feeds itself: past about fourteen centimetres of water thrown out, each slug of steam makes more room than it was given.

The note that fixed the kelvin

A sphere of argon, struck, rings at a pitch set by the speed of sound in it, and the speed of sound in argon contains only one quantity nobody could compute: the constant that converts a temperature into an energy. Argon's atoms can hold energy in exactly three ways, so its heat capacity is a count rather than a measurement, and its speed of sound is (5/3)kT/m with nothing left over. Ring the sphere at the temperature of melting ice, measure its size with radio waves in the same cavity, and Boltzmann's constant comes out to a part in a million. In 2019 that number stopped being measured and became the definition.

The engine that expands further than it compresses

A petrol engine's efficiency is usually quoted as a function of its compression ratio, and its compression ratio is held near ten because a higher one makes the fuel detonate. But the efficiency does not come from the compression. It comes from the expansion — from how far the burned gas is allowed to push the piston before it is thrown away — and an ordinary engine expands its gas exactly as far as it compressed it, simply because the same cylinder does both. Let the gas expand further than it was compressed and most of what a higher compression ratio would have given comes back with no knock at all. The price is paid in power, and it is why the most efficient petrol engines on the road are built this way.

The geyser that remembers one eruption

Old Faithful is famous for being predictable, and its predictability has an odd shape. Its eruptions come in two kinds, short and long, and the wait after each is short or long to match — about an hour after a short eruption, about an hour and a half after a long one. So the next eruption can be forecast from the last, to within about ten minutes, and from nothing else. The reason is a bookkeeping of water. An eruption throws out a volume of water that the geyser must take back from below before it can erupt again, and a long eruption throws out more. The geyser carries a memory of exactly one eruption: how much it has to refill.

The attraction that is the small ones' room

Put large particles into a crowd of small ones that cannot get inside them, and the large ones begin to stick together — though nothing in the mixture attracts anything. Each large particle keeps the small ones' centres out of a thin shell around it. When two large particles touch, their shells overlap, and the overlap is handed back to the small particles as room to move in. More room is more arrangements, more arrangements is more entropy, and the large particles are pushed together by the pressure of the small ones on their outer sides. Fumio Oosawa and Sho Asakura worked it out in 1954. The force is now used to purify DNA, sort colloids onto patterned surfaces and explain why the inside of a cell behaves as though its proteins were stickier than they are.

The mixture that stays mixed at absolute zero

The third law says a mixture's entropy must vanish at absolute zero, so every mixture must either separate completely or order into a compound as it is cooled. Liquid helium-3 dissolved in helium-4 does neither. Below 0.87 kelvin it splits into two liquids, but the one that is mostly helium-4 keeps 6.6 per cent helium-3 however cold it gets — and the third law permits it, because the dissolved atoms are a degenerate Fermi gas with a single ground state and no entropy of mixing to lose. Pushing helium-3 across that boundary absorbs heat the way evaporation does, from a 'vapour' that never thins out. That is the dilution refrigerator, the machine that holds every superconducting quantum computer at ten millikelvin.

The markers that move because atoms are unequal

In 1947 Ernest Kirkendall and Alice Smigelskas wound fine molybdenum wires around a bar of brass, plated it thickly with copper, and heated it for fifty-six days. The wires, which do not dissolve in either metal, ended closer together: the brass inside them had shrunk. Zinc had diffused out of the brass faster than copper diffused in, and the lattice planes of the brass had been taken away along with the zinc. If atoms in a metal moved by swapping places with each other, the two flows would have had to be equal. They were not, and the only way the books balance is if atoms move by jumping into vacancies — empty lattice sites — that flow the other way. The wires were the first direct evidence that diffusion in metals runs on holes.

The cylinder that must not be cooled

The first steam engines that did useful work, Thomas Newcomen's pumps of 1712, made a vacuum by spraying cold water into a cylinder full of steam. It worked, and on every stroke it cooled the cylinder, so that the next charge of steam condensed on the cold iron until the walls were hot again — several cylinders' worth of steam spent heating metal that the next spray would cool. James Watt saw in 1765 that the vessel was being asked to be hot and cold at once, and moved the cold to a separate condenser. The improvement was a factor of three or four in coal. A century later the reason had a name: heat passing from hot to cold across a large difference, doing nothing on the way, is work thrown away.

The pipe that carries heat as vapour

A copper rod six millimetres across and thirty centimetres long, asked to carry thirty watts from a laptop's processor to its fan, would need its hot end eight hundred degrees above its cold end. The flattened copper tube that actually does the job manages it with less than a degree. It is a heat pipe: sealed, emptied of air, and holding a few drops of water and their vapour. The water boils at the hot end, the vapour rushes to the cold end and condenses, and a wick of sintered copper powder drags the liquid back by capillarity. The heat goes as latent heat, and vapour needs almost no temperature difference to flow — which makes the pipe a thousand times better than copper, as long as its wick can keep up.

The age a cooling Earth gives

In 1862 William Thomson, later Lord Kelvin, took a thermometer reading from the bottom of a mine and a piece of mathematics from Fourier and computed the age of the Earth: about a hundred million years. Geologists, needing far longer, had no physics with which to reply. The arithmetic was right. The usual story blames radioactivity for overturning it, but half the heat is not radioactive, and the error lay in assuming the inside of the planet stays still.