Concept

Fluctuations — where it appears

The departures of a quantity from its average, arising from the finite number of things being averaged over. Their mean square is fixed by a susceptibility — for a fluid's density it is ρkTκ_T, which is exactly one for an ideal gas and 0.062 for water — and it is the fluctuations rather than the molecules that scatter light.

Named by 5 essays across 3 fields — each of them below, with the objects they name alongside it.

Two straight lines that are not the same line. Half the difference between the liquid and vapour densities, in units of the critical density, against the distance from the critical temperature — both logarithmic, over 5 decades. The van der Waals curve is solved for the coexisting pair at each temperature and its slope in the last decade is 0.500, which is the mean-field ½. Real fluids give 0.326. The two differ by 11 per cent at t = 0.1 and by a factor of 7.9 at the bottom of the axis, which is why an equation with the wrong exponent in it looked right for eighty years.

The point at which the two become one

Heat a sealed tube of carbon dioxide and the meniscus inside it does not boil away — it fades, the two densities converging until there is nothing to separate. Twenty millikelvin before that happens the fluid turns milky, and the exponent describing the last approach is a number van der Waals got wrong and could not have got right.

thermodynamics · Phase change
N when the phases are random, N² when they are not. Scattered intensity against the number of scatterers, both logarithmic, for two ways of adding the same amplitudes. The lower curve averages 400 draws of N unit amplitudes with independent random phases and grows as N^1.000; the upper one adds them in phase and grows as N². At 3000 scatterers the two differ by a factor of 2921. Nothing about the scatterers is different between the two — same number, same strength, same wavelength. Only the arrangement is, and it is worth three decades here.

Why a litre of water is not blue for the reason the sky is

The same molecules that make the sky blue also make the refractive index of air, and the two numbers agree because the sideways sum has random phases and the forward one does not. Condense those molecules into a liquid and the sideways sum collapses by a factor of sixteen — and what is left is thirty-four times smaller than the absorption that actually colours the water.

optics · Scattering
A magnetisation curve, and the same curve magnified. On the left, the position of a domain wall against the applied field, over the whole of a crystal. It looks like a curve. On the right, a window 2.0% of its width, taken 42% of the way across, at the magnification a sensitive measurement reaches: the wall does not move at all while the field rises, then jumps, then stops again. The largest jump in the window covers 0.67 units of wall position in no field change at all. There is nothing smooth underneath this — the smooth curve on the left is a staircase with 1400 steps in it, drawn small.

The curve that is really a staircase

A magnetisation curve is drawn as a smooth line and is nothing of the sort. Measured finely enough it is a sequence of jumps of every size, audible as a crackle in a coil, with no typical jump and no smooth motion underneath.

electromagnetism · Magnetisation
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 5, 12, 20 times kT are factors of 10^-2.2, 10^-5.2, 10^-8.7. At 295 K, kT is 25.4 meV, so a barrier of 0.4 eV is 15.7 kT and a factor of 1.5e-7. 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 temperature a molecule does not have

Temperature fixes a system's average energy and nothing more. The actual energy wanders, by an amount tied to the heat capacity, and the relative size of the wandering falls as one over the square root of the number of degrees of freedom — so a mole has a temperature and a molecule does not.

thermodynamics · Equipartition
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

Named alongside it

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

CompressibilityCritical pointIrreversibilityScatteringStatistical mechanicsUniversalityAbsorptionArrow of timeAvalancheThe Boltzmann factorBrownian motionCoherence

All concepts