Illustrated Physics
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Series

Chemical potential — the series

2 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

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