Illustrated Physics
physics, drawn
Concept

Critical point — where it appears

The end of a coexistence line, where two phases become identical and the distinction between them stops existing. Approaching it, the order parameter, the compressibility and the correlation length all follow power laws whose exponents are shared by systems with nothing else in common.

Named by 4 essays across 2 fields — each of them below, with the objects they name alongside it.

The part of the curve no fluid follows. Van der Waals' isotherms in reduced units, at 5 temperatures either side of the critical one, so that nothing about any particular substance appears. Above the critical temperature the pressure falls monotonically as the volume grows, which is what a fluid does. Below it the curve develops a loop with a rising section in the middle, and that section says the pressure increases as the substance expands — a material with negative compressibility, which cannot exist, because any fluctuation would run away. What happens instead is drawn as the horizontal line: the substance separates into two phases at one pressure, and the volume moves along the line as the proportions change. Its height, 0.6470 of the critical pressure, is fixed by requiring the two areas the line cuts off to be equal, which is the condition that the two phases have the same Gibbs energy. It meets the curve at volumes 0.603 and 2.349, a ratio of 3.9, and those are the densities of the liquid and its vapour. The two turning points of the loop, at 0.72 and 1.53, bound the part that is not merely unobserved but impossible; between them and the construction the substance can be made to sit, superheated or supercooled, until something nucleates.

The part of the curve no fluid follows

One equation for a real gas produces isotherms with a rising middle section, which says a substance would expand as the pressure on it grows. Nothing does that. What replaces it is a horizontal line whose height is fixed by making two areas equal, and the condition is not a convenience.

thermodynamics · Phase change 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 The pair potential, and the two things it does to a gas. The Lennard-Jones potential between two molecules, in units of its own depth and range, with the Mayer function it produces at 1, 3, 8 times the well depth in temperature. The virial coefficient is minus the integral of that function over volume, so the two parts of the potential contribute with opposite signs: the steep repulsive core makes the function minus one there, giving a positive contribution — molecules take up room — and the attractive well makes it positive, giving a negative one. At low temperature the attraction dominates and a gas is easier to compress than an ideal one; at high temperature the core dominates and it is harder. Between them is one temperature at which they cancel.

The first correction to the gas law

An ideal gas has no forces between its molecules. The first correction to what it does is computable from those forces alone — one integral over the pair potential — and its sign flips at a temperature where a real gas obeys the ideal law without being ideal at all.

thermodynamics · Kinetic theory

Named alongside it

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

CompressibilityEquation of stateFluctuationsScatteringVan der waalsAbsorptionThe Boltzmann factorCoherenceCorrelation lengthCritical exponentGibbs energyThe ideal gas law

All concepts