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 8 essays across 4 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
Helium's excitations, and the line that decides how fast it can flow. The energy of an elementary excitation in superfluid helium-4 against its momentum, as a smooth fit through published neutron-scattering values: a phonon branch rising at the speed of sound, 238 m/s, a maximum near 13.9 K, and the roton minimum of 8.62 K at 1.92 Å⁻¹. A straight line from the origin has a slope that is a velocity. The steepest line that just touches the spectrum is Landau's critical velocity, 57 m/s, and it touches at 1.98 Å⁻¹, just past the roton minimum. A body moving slower than that cannot make any excitation at all and so cannot lose energy to the liquid; the dashed line is the speed of sound, far above it.

The speed below which nothing can be made

An object moving through an ordinary liquid always feels drag, because it can always pass some of its energy to the liquid. In a superfluid there may be nothing it can pass it to. Landau's argument turns the question into geometry: an excitation of momentum p and energy ε can be made only by a body moving faster than ε/p, so a liquid flows without friction below the smallest value of that ratio. For helium the smallest value is not the speed of sound but 57 m/s, set by the dip in its spectrum called the roton — and an ideal gas, with no dip and no sound, has no such speed at all.

quantum · Superfluidity
Water's surface tension, all the way to the critical point. The surface tension of water against its liquid vapour, from the international standard correlation, against temperature from 0 °C to the critical point at 373.946 °C. 20 °C: 72.7 mN/m; 100 °C: 58.9 mN/m; 200 °C: 37.7 mN/m; 300 °C: 14.4 mN/m; 370 °C: 0.4 mN/m. It falls almost in a straight line for most of the range and then bends down to reach zero exactly at the critical point, where liquid and vapour stop being two things. The bend is a power law, the gap to the critical temperature raised to 1.256.

The tension that vanishes where the phases meet

Surface tension is usually treated as a property of a liquid, like its density. It is a property of a boundary between two things, and it can only exist while there are two things. Heat water in a sealed tube and its surface tension falls steadily, then faster, and reaches exactly zero at 374 °C, where liquid and vapour stop being different. On the way the surface stops being a surface: the step in density spreads from a molecule's width to thousands, and the rate at which the tension dies turns out to be a number the whole family of critical points shares and the simplest theory gets wrong.

fluids · Surface tension
A hopper that runs in bursts. Grains discharged against time, on a logarithmic scale, from a silo of 1 mm glass beads through outlets 3.5, 4.0, 4.4 grain diameters wide; each time the outlet jams it is cleared after 2 s (a tap on the silo) and the flow restarts. Avalanche sizes are drawn at random from an exponential distribution with each outlet's mean. At 3.5 diameters the mean avalanche is 53 grains and the outlet jammed 57 times in two minutes, passing 2,537 grains; at 4.0 diameters the mean avalanche is 1,000 grains and the outlet jammed 37 times in two minutes, passing 33,568 grains; at 4.4 diameters the mean avalanche is 45,821 grains and the outlet jammed 3 times in two minutes, passing 116,983 grains. While it flows, each outlet runs at its full Beverloo rate; a narrower outlet does not flow more slowly, it stops more often, and the flat stretches are the waits.

The outlet that jams by chance

A hopper whose outlet is a few grains wide does not flow slowly. It flows at the full rate and then stops dead, when a handful of grains wedge into an arch across the opening, and it flows again only when something knocks the arch down. The number of grains that pass between one jam and the next is random and exponentially distributed, as if every grain leaving had the same small chance of being the last. Its average rises so steeply with the opening's size that it looks like a threshold, and whether there is one is still argued: two laws agree wherever an outlet can be watched, and they part only after millions of grains.

fluids · Granular matter
The pipe that out-conducts any solid. The temperature difference needed to carry 30 W along a rod 300 mm long and 6 mm across, on a logarithmic scale: for solid aluminium 1343 K, for copper 796 K, for diamond, the best conductor of heat at room temperature, 159 K; and for a water heat pipe of the same size 0.8 K, almost all of it across the thin wet wicks where the heat goes in and comes out. Solid metal could not do it at all: the hot end of the copper rod would have to be hundreds of degrees above the cold. The heat pipe carries the heat as latent heat in moving vapour, and the vapour needs almost no temperature difference to flow. As an effective conductivity that is 1000 times copper's — which is why every laptop and many satellites move their heat in pipes rather than through metal.

The pipe that carries heat as vapour

A copper rod six millimetres across and thirty centimetres long, asked to carry thirty watts from a laptop's processor to its fan, would need its hot end eight hundred degrees above its cold end. The flattened copper tube that actually does the job manages it with less than a degree. It is a heat pipe: sealed, emptied of air, and holding a few drops of water and their vapour. The water boils at the hot end, the vapour rushes to the cold end and condenses, and a wick of sintered copper powder drags the liquid back by capillarity. The heat goes as latent heat, and vapour needs almost no temperature difference to flow — which makes the pipe a thousand times better than copper, as long as its wick can keep up.

thermodynamics · Phase change

Named alongside it

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

CompressibilityVan der waalsCorrelation lengthCritical exponentEquation of stateFluctuationsLatent heatScatteringSurface tensionUniversalityAbsorptionThe Boltzmann factor

All concepts