Illustrated Physics
physics, drawn
Concept

Chemical equilibrium — where it appears

The state in which a reaction and its reverse run at equal rates, so the amounts of every species stop changing. It is reached when the chemical potentials of reactants and products balance, and it fixes the ratio of their concentrations at a given temperature.

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

Also named here as equilibrium constant — the same set of essays touches all of them, so they are one junction rather than several.

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 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.

thermodynamics · Chemical potential

Named alongside it

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

Chemical potentialEquilibrium constantBand gapBinomial distributionThe Boltzmann factorDetailed balanceDopingEntropy of mixingFree energyLe chateliers principleLight emitting diodePartial pressure

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