Concept

Correlation length — where it appears

The distance over which fluctuations at one point in a material still influence those at another. Beyond it the disturbances are independent, so it sets the size of the units a solution, magnet or fluid behaves as though it were made of.

Named by 3 essays across 2 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
Chains counted, and then blobs. The osmotic pressure of a polymer solution in a good solvent against concentration, on logarithmic axes, for chains of 1,000, 10,000, 100,000 segments. Dilute, each chain is one particle and the pressure is van 't Hoff's, proportional to the number of chains: a line of slope one, lower for longer chains by the ratio of their lengths. Past the overlap concentration of each, marked, the coils interpenetrate and the curves bend up onto a single line of slope 2.31 that does not depend on chain length at all. The overlap concentration falls as the chains lengthen, by a factor of 5.8 for each tenfold increase in length, which is why the longest chains leave the counting of molecules first.

The pressure that stops counting molecules

Van 't Hoff's law counts dissolved particles, and for a dilute polymer each chain is one particle, however many thousand segments it has. That is how osmometers weigh polymers. Concentrate the solution until the coils overlap and the count changes. The pressure stops depending on how long the chains are and grows as the 2.3 power of the concentration, the same for chains a thousand segments long and a hundred thousand. The unit being counted is no longer a molecule. It is a stretch of chain as long as the mesh of its neighbours allows, and it has no chemical identity at all.

fluids · Osmosis
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

Named alongside it

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

Critical exponentCritical pointMean-field theorySurface tensionUniversalityCompressibilityFluctuationsInterfaceOrder parameterOsmotic pressureOverlap concentrationPhase change

All concepts