Illustrated Physics
physics, drawn
Concept

Entropy — where it appears

The logarithm of the number of microscopic arrangements consistent with a system's macroscopic state. Taking the logarithm is what makes it add for independent systems, since independent counts multiply, and it is why entropy is extensive while the count itself is not.

Named by 39 essays across 5 fields — each of them below, with the objects they name alongside it.

Ways to arrange 10 coins. The number of distinct arrangements giving each number of heads, for 10 coins. Every individual arrangement is equally likely; the middle wins because there are more ways to reach it.

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.

thermodynamics · Entropy Heating 1 kg of water from -20°C to 130°C. Temperature against heat added for 1 kilogram of water taken from -20 to 130 degrees Celsius. The two flat stretches are the melting and the boiling, where 334 and 2260 kilojoules go in and the temperature does not move. Melting costs as much as warming the water by 80 degrees; boiling costs as much as warming it by 541, which is 73 per cent of the whole journey.

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.

thermodynamics · Phase change One mass, two entropies. The entropy of a solar mass as ordinary gas, generously counted at ten Boltzmann constants per proton, against the entropy of a solar-mass horizon. The first is 1.19·10⁵⁸ k and the second 1.05·10⁷⁷ k — a factor of 8.83·10¹⁸. This is why a horizon had to be given an entropy: without one, dropping anything at all through it destroys entropy and the second law fails.

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.

thermodynamics · Entropy 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 Ways to arrange 12 coins. The number of distinct arrangements giving each number of heads, for 12 coins. Every individual arrangement is equally likely; the middle wins because there are more ways to reach it.

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.

thermodynamics · Entropy The phase boundary of water, from one equation. Pressure against temperature for water on a logarithmic pressure axis spanning 6.6 decades. The vaporisation curve is integrated from Clausius–Clapeyron between the triple point at 273.16 kelvin and 611.7 Pa and the critical point at 647.096 kelvin, with a single latent heat of 43.32 kilojoules per mole — the value the two published points on the curve imply. The measured latent heats are 45.05 at the triple point and 40.65 at the reference point, and the fitted value sits between them, because a constant latent heat is an average over the interval. The sublimation curve below the triple point is not measured but predicted, from the two latent heats adding where all three boundaries meet: 51.1 kilojoules per mole, which reaches 103.2 Pa at 253.1 kelvin against a measured 253.15. The melting curve is drawn at the slope Clapeyron gives it, -13.5 megapascals per kelvin, which is a volume ratio and nothing else: water's solid is 917 against 1000 kilograms per cubic metre for its liquid, so melting shrinks it and the line leans backwards. Across the whole 6.6 decades of this axis that line moves 5.2 kelvin, and one atmosphere shifts the melting point by 0.0075 kelvin. At 1 atmosphere the boundary is crossed at 373.1 kelvin, where water boils. The one place the curve fails is its top end: a constant latent heat reaches 37.4 MPa at the critical temperature where the measured critical pressure is 22.1 MPa, 70 per cent high, because the latent heat falls to zero at the critical point and this curve does not know that.

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.

thermodynamics · Phase change The ceiling, inverted. How many joules of heat a perfect machine can move per joule of work, against the outside temperature, with the inside held at 21 °C. The upper curve is heating — T_h/(T_h − T_c), which is what the Carnot argument becomes when the cycle is run backwards — and the lower one is cooling the outside, T_c/(T_h − T_c). They differ by exactly one everywhere, to 1.8e-15 across the whole range as drawn, because the work put in is delivered as heat along with whatever was moved. The dashed line at one is a resistive heater, which is 100% efficient and is the worst option on the figure. At 7 °C and −7 °C the ideal coefficients are 21.0 and 10.5; a real machine reaching 25% of the ideal gets 5.3 and 2.6, which is still several times what burning the same energy would give.

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.

thermodynamics · Heat engines 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 The work one molecule and one bit are worth. The pressure of a gas of one molecule against its volume, at 300 K, in units of the volume it starts in. The shaded area is the work the molecule does pushing a partition out isothermally, and it is measured here by integrating the drawn curve rather than written down: expanding by 1.5× yields 0.4055 kT against ln 1.5 = 0.4055; expanding by 2× yields 0.6931 kT against ln 2 = 0.6931; expanding by 4× yields 1.3863 kT against ln 4 = 1.3863; expanding by 8× yields 2.0794 kT against ln 8 = 2.0794, agreeing to 2.0e-10. The doubling is the one that matters, because a partition inserted in the middle leaves the molecule on one side or the other, and knowing which is what lets the load be attached to the right face. That single expansion delivers kT·ln2 = 2.87 zeptojoules at 300 K. It looks like work extracted from one temperature, and it is — until the engine is asked to run again, which requires forgetting which side the molecule was on.

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.

thermodynamics · Entropy The ceiling, the estimate, and three power stations. Two efficiencies against the ratio of the cold reservoir's temperature to the hot one. The upper curve is Carnot's 1 − Tc/Th, which is a ceiling on the work per unit of heat and is reached only by an engine that runs infinitely slowly, because a reversible heat flow needs a vanishing temperature difference to drive it and therefore infinite time. The lower curve is 1 − √(Tc/Th), the efficiency of an engine with finite thermal contact run for the most power rather than the most work. Three measured plants are marked: West Thurrock, coal runs at 36 per cent against a ceiling of 64 and a finite-time estimate of 40; CANDU, nuclear runs at 30 per cent against a ceiling of 48 and a finite-time estimate of 28; Larderello, geothermal runs at 16 per cent against a ceiling of 33 and a finite-time estimate of 18. Every one of them is closer to the lower curve — within 4.4 points at worst, against 16.5 at best from the ceiling. The second law is not what limits a working power station. What limits it is that somebody wants the electricity this year.

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.

thermodynamics · Heat engines 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 Entropy that is still there at absolute zero, counted and measured. Four substances whose entropy does not go to zero when they are cooled as far as anybody can cool them, with the entropy counted from the arrangements they froze into beside the entropy measured by integrating their heat capacities. Ice is the famous one: every oxygen has four hydrogen bonds and the rule is that two hydrogens sit near it and two far, which leaves six of the sixteen placements legal, and Pauling's count of the whole crystal collapses to R ln(3/2) = 3.371 J per mole per kelvin against a measured 3.41 — an agreement to one per cent from an argument on one line. Carbon monoxide and nitrous oxide are the easy cases, molecules that can lie either way round in the lattice and have too little to gain by choosing. The worst of the four is off by 25 per cent, which is the honest state of this subject: the counts are crude, they ignore the correlations between neighbouring choices, and they still land within sight of a calorimeter. What the figure is really about is that the third law has an escape clause and the escape clause is measurable. A perfect crystal has one arrangement and zero entropy; a crystal that ran out of time while it had many has the logarithm of however many it stopped at, permanently.

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.

thermodynamics · Third law The height a 1 mK difference lifts helium. The head of liquid that a temperature difference of 1 millikelvin can support across a superleak — a plug fine enough that the normal fluid cannot pass and the superfluid can — against the temperature it is done at. Only the normal component carries entropy, so warming one side makes the superfluid flow toward the warm side until the pressure difference balances, and equilibrium is at ΔP = ρSΔT. The height that supports is SΔT/g, in which the density cancels exactly; computed both ways here the two agree to machine precision. The numbers are the striking part: 2.0 mm at 1.2 K, 4.6 mm at 1.4 K, 9.2 mm at 1.6 K, 19.4 mm at 1.8 K, 46.9 mm at 2 K, from a temperature step a thousand times smaller than anything a hand could feel. Aim a light at the warm side and the liquid does not merely rise but jets out of the tube, which is the fountain effect Allen and Jones found in 1938 and the most direct demonstration that helium II is two fluids rather than one. The entropies used are measured values; everything else on this chart is computed from them.

The fountain a lamp can drive

Below two degrees above absolute zero, liquid helium behaves as though it were two fluids occupying the same space — one carrying all the entropy and all the viscosity, the other carrying neither. It is not a metaphor and not a mixture. Shine a light on one side of a fine plug and the liquid jets out of the tube, because a temperature difference of a thousandth of a degree is a pressure of a hundred pascals.

fluids · Superfluidity The temperature that runs off the top of the scale. On the left, the entropy of a collection of two-level systems against how many of them are in the upper level. It rises, reaches 0.69314 per spin — which is ln 2, and is where half of them are up — and then falls, because a system with every spin up is as orderly as one with every spin down. On the right, the slope of that curve, which is one over the temperature. Below the maximum it is positive and ordinary: adding energy adds entropy, and the temperature is what everybody expects. At the maximum it is zero, which means the temperature is infinite. Past it the slope is negative — adding energy now removes entropy — and the temperature is negative. Such a system is not cold. It is hotter than any positive temperature whatever: put it in contact with anything at all and energy flows out of it, because that raises the total entropy. The quantity that orders systems by which way heat flows is not the temperature but its reciprocal, which runs smoothly from large and positive through zero to negative, and it is the temperature that has the discontinuity. None of this is possible unless the energy has a ceiling, which is why it happens in a spin system and not in anything that can move: a gas has no upper bound on its kinetic energy, so its entropy never turns over and its temperature is never negative.

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.

thermodynamics · Third law Energy, pressure and entropy of a gas nobody counted. The energy density, pressure and entropy density of blackbody radiation against temperature, on logarithmic axes, together with the pressure a monatomic gas of the same energy density would have. Every curve is a power of the temperature — the fourth for energy and pressure, the third for entropy — because the only length in the problem is the thermal wavelength and the only energy is kT. The pressure is exactly a third of the energy density, where an ordinary gas's is two thirds, a factor of 2: a photon carries momentum E/c and a slow molecule carries √(2mE), and that difference is the whole of it. Some values: at room temperature the radiation pressure is 1.86e-6 pascals, which is a ten thousand millionth of an atmosphere; at 1e+7 kelvin it is 2.52e+12, which is where radiation rather than matter holds a star up.

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.

thermodynamics · Blackbody The speed of a wave that carries no pressure. Second-sound speed against temperature, computed from the two-fluid equations with the normal component treated as a phonon gas — which it is below about six-tenths of a kelvin. The upper line is ordinary sound at 238 m/s, which moves the two components together. The lower curve is the other mode, and at low temperature it sits at 137.4 m/s, which is 238/√3 to three figures: a result with no adjustable constant in it, and the reason to believe the two-fluid model rather than merely to use it. What oscillates in this wave is not the density — the two components move in opposite directions and their sum stays put — but the fraction that is normal, which is a temperature. So a temperature disturbance in helium II propagates, with a speed, a reflection and a resonance, where in every ordinary liquid it diffuses and has none of those. Above a kelvin the rotons take over from the phonons and the measured curve falls to about 20 m/s; the model here is the low-temperature one and it is drawn only where it holds.

The heat that arrives as a wave

Two fluids with two velocities give two wave equations, not one. In the first the components move together and the density oscillates, which is ordinary sound. In the second they move oppositely, the density stays put, and what oscillates is the temperature — so a heat pulse in liquid helium has a speed, a front and a reflection.

fluids · Superfluidity The two holes a grain can fall through, and their exact sizes. Three equal spheres in contact, and four, drawn with the largest sphere that passes between them. The numbers are geometry and nothing else. Three mutually touching spheres put their centres on an equilateral triangle of side 2R, whose circumradius is 2R/√3, so the gap admits a sphere of radius 0.154701R — about a seventh. Four in a square admit 0.414214R, nearly half. A real packing contains both arrangements and everything between, so a grain smaller than the first threshold gets through everywhere, one larger than the second gets through nowhere, and one in between percolates slowly through the loosest routes. That is the whole size-dependence of segregation by percolation, and it is why the effect is reliable below about a seventh and erratic between a seventh and a half.

The big one comes to the top

Shake a jar of mixed grains and it sorts itself, which is the opposite of what shaking a mixture of gases does. There is no thermodynamic paradox in it because there is no temperature to speak of — and the mechanism is a piece of geometry with an exact number in it: a sphere fits through the gap between three touching spheres only below a radius ratio of 0.1547.

fluids · Granular matter 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 Colder the bigger it is. The Hawking temperature against mass, on logarithmic axes, with the microwave background drawn across it. The slope is minus one exactly, so a heavier hole is colder — a negative heat capacity, which is the fact everything else here follows from. The two lines cross at 4.50e+22 kg, about a hundredth of the Moon's mass. Anything heavier than that is colder than the sky it sits in and absorbs more than it emits, so it grows rather than evaporates. A stellar-mass hole is at 6.2e-8 kelvin and will not begin to lose mass until the background has cooled below that, which takes something like 10¹² years. Evaporation is not something happening now to any hole anybody has observed.

The hole that outlives everything and then does not

A black hole radiates at a temperature that rises as it shrinks, so losing energy makes it lose faster. The whole history follows from that one sign: a life proportional to the cube of the mass, nearly nothing happening for almost all of it, and an end that arrives in a second.

astrophysics · Horizons The quantity that went down, and the one that went up. The books for GW150914: two black holes of 36 and 29 solar masses merging into one of 62, with a final spin of 0.67. 3.0 solar masses left as gravitational waves, so the mass fell by 4.6 per cent. The total horizon area rose, from 107417 to 168330 in units of the Sun's gravitational radius squared — an increase of 57 per cent. The two progenitors are taken as non-spinning, which is the assumption that makes the test hardest to pass: a spinning hole of the same mass has a smaller horizon, so any spin they actually had would only widen the gap. Mass is the quantity that behaves the way energy usually does and it is not the one with a direction. Area is, and it is the reason the area has been read as an entropy ever since.

The area that is not allowed to shrink

Two black holes merge and the result weighs less than the sum, because three solar masses left as gravitational waves. The horizon area went up by more than half. Mass is the quantity that behaves like energy and it is not the one with a direction; area is, and the theorem saying so has been tested against a real merger.

astrophysics · Horizons The entropy a substance keeps depends on how fast it was cooled. The entropy of a supercooled liquid in excess of its crystal's, against temperature, for a substance melting at 305 K with an entropy of fusion of 43 joules per kelvin per mole and a liquid heat capacity exceeding the crystal's by 62. The equilibrium curve — the one the liquid follows while it can still relax — falls steadily and would reach the crystal's entropy at 152.4 kelvin. It never gets there, because the liquid falls out of equilibrium first, at a temperature that depends on how long it is given: 0.01 s/K freezes at 196.1 K with 15.61 left, 1 s/K freezes at 188.1 K with 13.03 left, 100 s/K freezes at 182.1 K with 11.03 left. Ice's residual entropy is a count and does not move; a glass's is whatever it happened to have when it stopped being able to change, and that is a property of the experiment.

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.

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 The rectangle every cycle is equal to. An ideal Otto cycle for air on a temperature–entropy diagram: compression ratio 9, intake at 300 K, 1400 kJ/kg added at constant volume. Compression takes the charge to 722 K, combustion to 2672 K, expansion back to 1110 K, and the exhaust cools at constant volume. The shaded loop is the work; the region under the lower curve is the heat rejected. Heat enters over a range of temperatures, and its entropy-weighted mean — heat divided by the entropy it brings — is 1491 K; the heat leaves at a mean of 619 K. The dashed rectangle between those two temperatures has exactly the loop's area, and 1 − 619/1491 = 58.5%, which is the Otto efficiency, checked to rounding. A Carnot engine between the coldest and hottest points of the same cycle would reach 88.8%.

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.

thermodynamics · Heat engines Two bodies an engine draws together. Two equal bodies of 4.186 kJ/K — a kilogram of water each — one at 90.0 °C and one at 10.0 °C, against the heat drawn from the hot one. The solid curves are the best possible engine running between them, a reversible one, which leaves the product of the two temperatures unchanged and brings both to the geometric mean, 320.7 K (47.5 °C). It draws 177.8 kJ from the hot body and delivers 20.8 kJ of work, C(√T₁ − √T₂)², checked against the heat balance. The dashed lines are the same bodies simply touching: they meet at the arithmetic mean, 323.1 K, having exchanged 167.4 kJ and delivered nothing. The 2.5 K between the two endpoints is the work, left behind as heat.

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.

thermodynamics · Heat engines Two entropies that agree until half filling. The entropy per unit of 100 two-level units against the fraction excited, by Boltzmann's definition, the logarithm of the number of arrangements at that energy, and by Gibbs's, the logarithm of the number at or below it. Below half filling they nearly coincide: at a quarter excited they are 0.538 and 0.542 per unit, and both approach the dashed large-system curve. Boltzmann's entropy then turns over and falls back to zero when every unit is excited; at three-quarters it is 0.538. Gibbs's cannot fall, because a running total cannot, and it levels off at ln 2 = 0.693, reaching 0.693 at three-quarters. The slope of each is one over its temperature.

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.

thermodynamics · Third law Most of a chain's counterions never leave it. The fraction of a charged rod's counterions lying within a distance r of it, against r in rod radii on a logarithmic axis, for a charge parameter ξ = 4.2 — the Bjerrum length of water, 0.7135 nm, over a charge spacing of 0.17 nm, which is DNA's. Each curve is the Poisson–Boltzmann solution for the rod at the centre of a cell of radius 10², 10⁴, 10⁶ rod radii, with its counterions checked to neutralise it exactly. Diluting the solution widens the cell by four decades at a time, and a counterion free to go anywhere in the cell ought to spread with it; instead each curve keeps a plateau near the rod whose height does not change. At the inflection of every curve the enclosed fraction is 0.762, which is Manning's 1 − 1/ξ, and the plateau sits there: 76 per cent of the counterions stay bound to the chain however dilute the solution, and only 24 per cent spread through it.

The counterions that never leave the chain

Dilute a solution of DNA a million times and its counterions ought to scatter through the whole volume. Three quarters of them do not. A line of charges closer together than the Bjerrum length — 0.71 nm in water — holds on to its counterions however much room they are given, until the chain's charge is cut back to one per Bjerrum length, and every osmotic pressure, swelling gel and packed virus built from such chains is set by that length rather than by the chemistry.

fluids · Osmosis 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 A fridge with no work going into it, and its ceiling. How much heat a three-reservoir machine can lift out of a cold space per unit of heat supplied to drive it, against the temperature of the driving heat, for 3 cold temperatures and an ambient of 300 kelvin. No work enters or leaves: the machine takes heat in at the top, takes heat in at the bottom, and rejects the sum at ambient. That it can do anything at all is the surprise — the second law allows heat to be moved up a gradient provided a larger flow is moved down one, and the accounting is a single inequality in the three entropy flows. The ceiling is the product of two familiar expressions, and at 450 kelvin driving a 253-kelvin space it is 1.79. The marks are what real machines achieve, which is a fifth to a third of it — absorption refrigeration is not efficient and is chosen when the heat is free and the silence and the absence of moving parts are worth something.

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.

thermodynamics · Heat engines What a boost leaves alone, and what it does not. How each quantity of a box of blackbody radiation changes when the observer moves at 0.8 of the speed of light, a Lorentz factor of 1.667, on a logarithmic axis with one at the centre. The top four do not change at all, and the reason is the same in each case: they are counts, or logarithms of counts, or invariants built from four-vectors. A number of photons is a number, and every observer arrives at the same number. The rest change, by powers of the Lorentz factor that follow from the first four. And the entry that matters is the last two together: the energy density rises as the square of the factor while the entropy density rises as the factor itself, so the ratio between them that would define a temperature does not stay fixed — which is why the boosted radiation cannot be a blackbody at any temperature at all.

The count that no observer can disagree about

A moving body, it turns out, has no temperature. What it does have is an entropy, and every observer agrees about it — because entropy is the logarithm of a count of arrangements, and a count is a number. That one invariant, with energy and momentum being parts of one object, is enough to compute everything a temperature could not: what happens to the energy density, the entropy density, and the relation between them that having a temperature consists of.

relativity · Relativistic thermodynamics Equilibrium is where the entropy peaks, and there the temperatures differ. Two cavities of radiation, one high in a gravitational field and one low, free to exchange energy, with the clock at the bottom running at 0.8 of the rate of the one at the top. What is conserved is the energy either would deliver to a distant observer, so energy held at the bottom counts for 0.8 of its local value. Across: the share of that conserved energy held at the top. Above: the total entropy of the two gases. Below: the temperature a thermometer in the top cavity reads, as a fraction of one in the bottom cavity. The entropy peaks at a share of 0.339, found by search, and there the top cavity is at 0.800 of the bottom's temperature — the clock-rate ratio exactly. Where the two local temperatures are equal, at a share of 0.556, the entropy is 1.82 per cent below its peak and energy still flows downward, into the deeper cavity.

The column that is hotter at the bottom

Two bodies in equilibrium have the same temperature — that is what equilibrium was supposed to mean. In a gravitational field it is false. A column left alone until nothing in it changes is warmer at the bottom by exactly the factor by which clocks there run slow, a part in ten million billion per metre on the Earth and more than a per cent across the outer kilometre of a neutron star, and near a black hole's horizon the equilibrium temperature grows without limit.

relativity · Relativistic thermodynamics Hydrogen comes apart far below its binding temperature. The fraction of hydrogen that is ionised in equilibrium, against temperature on a logarithmic axis, for densities of hydrogen nuclei of 10²³, 10¹⁸, 10¹², 10⁶ per cubic metre, from Saha's equation. Hydrogen's binding energy, 13.6 eV, corresponds to 157,803 K. It is half ionised at 13,980 K at 10²³ per cubic metre, 7,235 K at 10¹⁸ per cubic metre, 4,519 K at 10¹² per cubic metre, 3,270 K at 10⁶ per cubic metre — at a temperature where kT is between an eleventh and a fiftieth of the energy needed to free the electron. The thinner the gas, the cooler the temperature at which it comes apart, because a free electron in a thin gas has vastly more room to be in than a bound one.

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.

thermodynamics · Chemical potential The melting curve that turns back, then lies flat. The pressure at which liquid and solid helium-3 coexist, against temperature from 0.9 millikelvin to 1 kelvin on a logarithmic axis, from the international provisional low-temperature scale PLTS-2000, which is defined by this curve. Above 315.2 mK the curve behaves like any other: a higher temperature needs a higher pressure to freeze the liquid. Below it the curve turns back — at its minimum, 2.93113 MPa, it takes a higher pressure to freeze colder helium — and it rises to 3.4391 MPa at 1 mK, where it lies almost flat, as the third law requires of every coexistence line. The kinks that mark the liquid becoming superfluid and the solid's spins ordering sit on that flat end, at 2.444, 1.896 and 0.902 mK.

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.

thermodynamics · Third law How a solute moves both ends of the liquid range. The molar chemical potential of water against temperature near its freezing point (left) and its boiling point (right): liquid (blue), ice (green), vapour (red), each a line whose slope is minus its entropy, drawn relative to the liquid at the transition. A solute at mole fraction 0.05 — about 2.9 mol/kg — lowers the liquid's line by RTx (dashed) and leaves the ice and the vapour unchanged. The crossings move: the freezing point down by RTx divided by the entropy of melting, 5.16 K, the boiling point up by RTx divided by the entropy of boiling, 1.42 K. The same vertical shift moves the freezing crossing 3.6 times as far, because ice's line is nearly parallel to the liquid's — melting changes the entropy by 22.0 J/mol K — while the vapour's line crosses steeply, with 109 J/mol K between them. Lowering the liquid makes it the winner over a wider range of temperature at both ends: the solution is liquid from below 0 °C to above 100 °C.

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.

thermodynamics · Chemical potential Four operations on one half, four states of the pair. The sender holds one half of an entangled pair prepared in the state |Φ+⟩ = (|00⟩ + |11⟩)/√2, the receiver the other. To send two bits she applies one of four operations to her half alone — do nothing, flip it (X), shift its phase (Z), or both — and sends it. The table gives, computed from the state vectors, the probability that the receiver's joint measurement of both halves in the Bell basis returns each of the four Bell states: one on the diagonal, zero everywhere else. Four perfectly distinguishable outcomes from one transmitted qubit is two bits. Sent without the pair, a qubit can carry at most one.

The qubit that carries two bits

A single quantum two-state system, sent from one person to another, can carry at most one bit of message — a theorem, not an engineering limit. If the two already share half each of an entangled pair, the sender can do one of four things to her half alone, send just that half, and the receiver can tell which of the four she did. Two bits arrive on one qubit. Nothing is free: the shared pair had to be delivered, and counted honestly the rate is still a bit per qubit. What entanglement buys is the freedom to send half the message before the message exists, and it also buys privacy, since the qubit in transit carries nothing at all on its own.

quantum · Entanglement Latent heat of boiling against boiling point. The heat needed to boil one mole of a liquid at its normal boiling point, against that boiling point, both on logarithmic axes, for twenty-one substances from helium to sodium. The line is ΔH = 87.2 J/(mol K) × Tb, the mean entropy of boiling of the ordinary liquids boiling between 250 and 700 K, which scatter about it by 3.3 per cent; the ordinary liquids as a whole (blue), from neon at 27 K to sodium at 1,156 K, by 10.0 per cent, the coldest lying low. Water, ammonia and the alcohols (red) need more heat than the line predicts, acetic acid (green) less; the quantum liquids helium and hydrogen (violet) fall far below.

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.

thermodynamics · Phase change A heat capacity that goes up and comes down. The heat capacity per system, in units of Boltzmann's constant, against temperature in units of the level spacing over k: for a system with two levels (red), Schottky's hump x²eˣ/(1 + eˣ)², x = Δ/kT, and for a harmonic oscillator with the same spacing (blue), which climbs to one k and stays there. Both are frozen out when kT is well below the gap. The oscillator then fills its unending stack of levels and reaches equipartition's value. The two-level system peaks at 0.439k when kT = 0.417Δ, and then, with both levels nearly equally occupied and nothing higher to go to, it stops absorbing heat: its capacity falls back towards zero as 1/T².

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.

thermodynamics · Equipartition A ring of balls that forgets, and then remembers. Kac's ring: 400 balls on 400 sites round a circle, all white at the start, with 52 of the edges between sites marked; each tick every ball moves one site and changes colour if it crosses a marked edge. The solid line is the excess of white over black, as a fraction of all the balls, against ticks; the dashed line is Boltzmann's prediction (1 − 2μ)^t with μ = 0.1, the fraction of edges marked. For the first few dozen ticks the ring follows Boltzmann's decay exactly as an irreversible process would: the colours mix and the excess falls to zero, then wanders by a few hundredths. At tick 400 every ball has gone once round, through all 52 markers — an even number of colour changes — and the ring is all white again. A rule with no randomness in it, run forward, looked irreversible for 400 ticks and then undid itself.

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.

thermodynamics · Entropy An attraction found by counting. How often two large discs are found at each gap between their surfaces, relative to how often they are found far apart, in a direct simulation of two discs among 270 small particles that pass through each other freely and do not enter the discs (dots), and the prediction from counting the small particles' available area (line); small particles a quarter of the large radius. Nothing in the simulation attracts anything: every move that does not put a small particle inside a large one is accepted. Yet the discs are found touching 2.7 times as often as apart (2.6 predicted), because touching returns the overlap of their exclusion zones to the small particles, and the probability of a separation is proportional to the number of arrangements the small particles have at it. Beyond a gap of twice the small radius the zones no longer overlap and the effect vanishes. Written as a potential, −kT times the logarithm of that ratio, it is an attraction about 1.0 kT deep.

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.

thermodynamics · Entropy

Named alongside it

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

IrreversibilityThe second lawTemperatureEquilibriumMicrostatesReversibilityHeat capacityPhase transitionThe Boltzmann factorLatent heatChemical potentialEfficiency

All concepts