Illustrated Physics
physics, drawn
Concept

Chemical potential — where it appears

The free-energy cost of adding one more particle to a system, which fixes how particles distribute themselves between phases and reservoirs. For anything whose number is not conserved — photons in a cavity, for instance — it is exactly zero, and every unusual property of a photon gas follows from that.

Named by 8 essays across 2 fields — each of them below, with the objects they name alongside it.

The column a dissolved thing holds up. Two arms of one vessel, joined below by a membrane that passes water and not solute. On the right is 10 mol/m³ of dissolved particles at 25 °C; on the left, pure water. Water crosses into the solution until the extra weight of the right-hand column has raised its pressure by the osmotic pressure — 24.8 kPa, which is 2.53 m of water, drawn here to scale. Nothing is pulling. The solvent is at a lower chemical potential where it is mixed, so it moves that way, and it stops when mechanical pressure has made up the difference. A solute a thousand times more dilute than seawater lifts a column taller than a person.

The pressure that comes from counting

Dissolve a teaspoon of anything in a litre of water, put a membrane between it and pure water, and the solution will hold up a column of water two and a half metres tall. Nothing is pulling. The pressure does not depend on what was dissolved, only on how many particles it made — which is the ideal gas law, with the solute in place of the gas.

fluids · Osmosis 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 Three curves that can only meet at a point. Water's phase diagram within a kelvin of its triple point, with each boundary drawn at the slope Clausius and Clapeyron give it from measured latent heats and densities: 44.4 Pa/K for boiling, 50.3 for sublimation, and -135 bar per kelvin for melting — negative, and so steep that it is drawn vertical here, because ice is the less dense phase and pressure therefore melts it. Two things follow that no amount of measurement could adjust. The three slopes are not independent: the sublimation and vaporisation curves differ in slope by 5.92 Pa/K, which is exactly what the fusion latent heat predicts, because going solid → gas directly and solid → liquid → gas must cost the same enthalpy. And the sublimation curve is the steeper of the two, so the two cross rather than touch — which is why the triple point is a crossing and not a tangency, and why ice sublimes below it and melts above it.

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.

thermodynamics · Phase change The pressure a charged gel develops. The swelling pressure against the gel's fixed charge density, for several salt concentrations, on logarithmic axes. Each curve has two straight parts with different slopes, and both limits are checked against the solution rather than read off the plot. Where the fixed charge is small compared with the salt the pressure goes as the square of the charge divided by four times the salt: the bath's ions screen the fixed ones, and doubling the salt halves the pressure. Where the fixed charge dominates, every counterion it demands is an extra particle in the gel and the pressure goes as the charge itself. At 15 mM salt, a gel with 200 mM of fixed charge develops 427 kPa; At 50 mM salt, a gel with 200 mM of fixed charge develops 306 kPa; At 150 mM salt, a gel with 200 mM of fixed charge develops 150 kPa; At 500 mM salt, a gel with 200 mM of fixed charge develops 49 kPa. Cartilage carries a fixed charge of a couple of hundred millimolar from the sulphated sugars on its proteoglycans, sits in a bath of about 150 mM, and develops a swelling pressure of an atmosphere and a half — which is what holds a joint apart and carries the load across it.

The swelling a membrane cannot stop

Give the thing a membrane holds back an electric charge and the small ions that can cross are no longer free to distribute themselves. Two conditions — neutrality on each side, and equal chemical potential for the salt — fix where every ion goes, and they leave the charged side with more particles than the other. That excess is what holds a joint apart, and it is why a cell has to spend a third of its energy pumping.

fluids · Osmosis The pore size the air decides. The largest pore radius that holds condensed water in equilibrium with air at a given relative humidity, for water at 25 °C, on a logarithmic radius axis. A concave meniscus lowers the vapour pressure over it by exp(−2γVₘ/rRT), so a pore whose meniscus would be tighter than a radius set by the humidity is in equilibrium only when full. The upper curve is the emptying condition, through a hemispherical meniscus with two curvatures; the lower is the filling condition, through the cylindrical film that lines a pore before it closes, with one — so the same pore fills at a higher humidity than it empties at. At 50% humidity a pore empties below 1.51 nm and fills below 0.76 nm; at 90% humidity a pore empties below 9.96 nm and fills below 4.98 nm; at 99% humidity a pore empties below 104 nm and fills below 52 nm. The radii run from molecular at low humidity to a tenth of a micrometre at 99 per cent, and every one was checked by putting it back into the vapour-pressure relation.

The pore that fills from dry air

Water condenses when the air is saturated — on a flat surface. Over a curved one the vapour pressure is different, higher over a drop and lower over a meniscus, and in a pore a few nanometres across it is low enough that the pore fills with liquid from air at half humidity. The water it holds is under a tension of a hundred megapascals, and the pore empties at a lower humidity than it filled at, for a reason that needs no roughness at all.

fluids · Capillarity 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 Every reaction's free energy has its lowest point inside. An ideal reaction A ⇌ B at 298 K. Across: how far it has gone, from pure A towards pure B. Up: the Gibbs energy of the mixture per mole, relative to pure A. Left, for standard reaction Gibbs energies ΔG° of −4, 0, +4 kJ/mol: the dashed straight lines are what the energy would be if A and B did not mix, and the solid curves add the entropy of mixing them. For ΔG° = −4 kJ/mol the lowest point is at 83.4 per cent B; for ΔG° = 0 kJ/mol the lowest point is at 50.0 per cent B; for ΔG° = +4 kJ/mol the lowest point is at 16.6 per cent B. Right, magnified near pure A, a reaction with ΔG° = +10 kJ/mol, whose straight line climbs from the start and which looks as if it should not proceed at all: its curve first falls, to a minimum of −43 J/mol at 1.74 per cent B, because the mixing term falls infinitely steeply away from a pure end. Each minimum was found by search and sits where the ratio of B to A equals exp(−ΔG°/RT).

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.

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

The glow that carries a voltage

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

thermodynamics · Chemical potential

Named alongside it

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

EquilibriumBlackbodyEntropyEntropy of mixingFree energyOsmosisOsmotic pressureAdiabatic indexAvailable workBand gapBinomial distributionBiological physics

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