Illustrated Physics
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Chemical potential — the series

12 essays on one idea, from the one that introduces it to the one that assumes the rest.
  1. 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.

    part 1 · thermodynamics
  2. 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.

    part 2 · thermodynamics
  3. How full a surface is, against the pressure of the gas above it. The fraction of adsorption sites occupied on a surface that binds a molecule with 0.35 eV, against the gas pressure on a logarithmic axis, at 250, 300, 350 K. Each curve is θ = p/(p + p½) — Langmuir's isotherm — and each is the same S-shape moved along the axis: on a logarithmic pressure scale the coverage is a function of ln p alone, shifted by the binding energy over kT. The half-full pressure is 5.58 Pa at 250 K, 132 Pa at 300 K, 1341 Pa at 350 K. Warming the surface does not change the shape; it slides the curve to higher pressure by a factor that is a Boltzmann factor, e^(ε/kT), which is how a binding energy is read off a family of isotherms.

    The site that fills like an electron level

    A patch of catalyst holding a gas molecule, a haem in a muscle cell holding oxygen, an energy level in a metal holding an electron: each is a place that can hold one particle or none, in contact with a reservoir it trades particles with. Each fills according to the same function of one variable — how far the reservoir's chemical potential lies above the energy of the site. Langmuir's isotherm and the Fermi function are not analogous. They are the same law, and haemoglobin works because its sites break it.

    part 3 · thermodynamics
  4. Electrons and holes in silicon against the donors added. The concentrations of free electrons and holes in silicon at 300 K against the concentration of donor atoms added, on logarithmic axes, solved from charge neutrality and the product law n·p = nᵢ². Below the intrinsic concentration of 10¹⁰ per cubic centimetre the donors change almost nothing. Above it the electrons follow the donors one for one and the holes fall in exact proportion: a hundred times more donors, a hundred times fewer holes. At 10¹⁶ donors the electrons outnumber the holes by 10¹² to one. The dashed line is √(n·p), which does not move at all across ten decades of doping — checked to a part in a billion.

    The product doping cannot move

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

    part 4 · thermodynamics
  5. Fifty-nine millivolts for every factor of ten. The voltage that holds a singly charged ion at one concentration on one side of a boundary and another concentration on the other, in equilibrium, against the ratio of the concentrations on a logarithmic axis: (kT/e) ln(c₁/c₂), from requiring the electrochemical potential to be the same on both sides. At 0 °C, 54.20 mV per decade; at 25 °C, 59.16 mV per decade; at 37 °C, 61.54 mV per decade; at 100 °C, 74.04 mV per decade. The voltage depends on the ratio and the temperature and on nothing about the ion, the solvent or the boundary: it is the entropy of dilution, expressed per unit charge.

    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.

    part 5 · thermodynamics
  6. 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.

    part 6 · thermodynamics
  7. Hydrogen ionised by heat at one end and by crowding at the other. The ionised fraction of hydrogen against the density of nuclei, at 5,000 K, 10,000 K, 20,000 K, from Saha's equation with the binding energy lowered by the neighbouring charges (solid) and without the lowering (dashed). Thin gas is ionised by the room a free electron gains; compression takes the room away and the gas recombines, as the dashed curves continue to do for ever. The solid curves turn round: at 5,000 K the gas is least ionised, 2.5·10⁻⁴ per cent, near 10²⁶ per cubic metre; at 10,000 K the gas is least ionised, 0.41 per cent, near 10²⁷ per cubic metre; at 20,000 K the gas is least ionised, 12 per cent, near 10²⁸ per cubic metre, and by 6·10²⁸ per cubic metre — 0.10 g/cm³ — every curve is fully ionised, because the ground state no longer exists. That density does not depend on the temperature at all.

    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.

    part 7 · thermodynamics
  8. The proton fraction a cold star settles at. The fraction of nucleons that are protons in cold matter in beta equilibrium, where the neutron's chemical potential equals the proton's plus the electron's, against density on logarithmic axes, for free neutrons, protons and electrons with no nuclear forces. Below 1.22·10⁷ g/cm³ the electrons cannot pay the 1.29 MeV difference between a neutron and a proton and the matter is all protons. Above it the fraction collapses, to 0.014 per cent at its lowest near 7.9·10¹¹ g/cm³, and at nuclear density, 2.66·10¹⁴ g/cm³, it is 0.49 per cent. At higher densities it climbs slowly towards one ninth, 11 per cent, which it never reaches. The dashed part lies where real matter is made of nuclei rather than free nucleons.

    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.

    part 8 · thermodynamics
  9. 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.

    part 9 · thermodynamics
  10. How supersaturated a cloud is, to an ice crystal. The supersaturation over ice of air that is just saturated over liquid water, eᵥᵥ/eᵢ − 1, in per cent, against temperature; dashed, the same computed from the chemical potentials, exp(LΔT/RT·Tₘ) − 1, with L the latent heat of melting per mole, ΔT the supercooling and Tₘ the melting point. A supercooled cloud is in balance with its droplets, so to any ice crystal inside it the air is 5.1 per cent supersaturated at −5 °C, 10.5 at −10, 22.0 at −20 and 41.2 at −35. Over the droplets themselves it is exactly saturated, so they neither grow nor shrink by vapour. The excess is the chemical-potential difference between supercooled water and ice, 217 J per mole at −10 °C, expressed as a pressure ratio.

    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.

    part 10 · thermodynamics
  11. Why silt heaves and sand and clay do not. The relative rate at which water is drawn to a growing ice lens, against grain diameter on a logarithmic scale, for three loads on the soil above it, in a capillary model: the rate is the soil's permeability, which grows as the grain diameter squared, times the suction the lens can sustain less the load. The suction is capped both by the supercooling at the lens, here 2 K, and by the Gibbs–Thomson pressure at which ice would break into the pores. Coarse soil has open pores that ice simply invades, so the suction never exceeds the load: under 10 kPa, half a metre of soil, nothing heaves above 58 μm. Fine clay can sustain the full suction but passes water too slowly to feed it. Between lies a fastest grain size, 29 μm under 10 kPa, 10 μm under 30 kPa and 2.9 μm under 100 kPa: silt, the soil engineers have long called frost-susceptible. Real heave pressures exceed this model's, and the fit is to the shape, not the scale.

    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.

    part 11 · thermodynamics
  12. Salt that takes in water from the air at three-quarters humidity. The water held by a crystal of common salt, in grams per gram of salt, against the relative humidity of the air around it at 25 °C, with the humidity rising (solid) and falling (dashed). Rising, the crystal stays dry until 75.2 per cent and then dissolves at once into a drop holding 2.79 g of water per gram — the saturated solution — which goes on drinking as the air gets damper: 4.24 g at 85 per cent, 11.5 g at 95. Falling, the drop does not crystallise at 75 per cent. It sheds water along the same curve, becomes supersaturated, and stays liquid down to about 45 per cent before a crystal finally nucleates and it dries out at once.

    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.

    part 12 · thermodynamics

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