Illustrated Physics
physics, drawn
Concept

Electrostatics — where it appears

The part of electromagnetism in which charges are at rest and the field is the gradient of a potential set by Poisson's equation. In a solution of ions it decides how charges crowd around a surface or a chain, and how much of that charge the surrounding ions screen.

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

The pressure a charged gel develops. The swelling pressure against the gel's fixed charge density, for several salt concentrations, on logarithmic axes. Each curve has two straight parts with different slopes, and both limits are checked against the solution rather than read off the plot. Where the fixed charge is small compared with the salt the pressure goes as the square of the charge divided by four times the salt: the bath's ions screen the fixed ones, and doubling the salt halves the pressure. Where the fixed charge dominates, every counterion it demands is an extra particle in the gel and the pressure goes as the charge itself. At 15 mM salt, a gel with 200 mM of fixed charge develops 427 kPa; At 50 mM salt, a gel with 200 mM of fixed charge develops 306 kPa; At 150 mM salt, a gel with 200 mM of fixed charge develops 150 kPa; At 500 mM salt, a gel with 200 mM of fixed charge develops 49 kPa. Cartilage carries a fixed charge of a couple of hundred millimolar from the sulphated sugars on its proteoglycans, sits in a bath of about 150 mM, and develops a swelling pressure of an atmosphere and a half — which is what holds a joint apart and carries the load across it.

The swelling a membrane cannot stop

Give the thing a membrane holds back an electric charge and the small ions that can cross are no longer free to distribute themselves. Two conditions — neutrality on each side, and equal chemical potential for the salt — fix where every ion goes, and they leave the charged side with more particles than the other. That excess is what holds a joint apart, and it is why a cell has to spend a third of its energy pumping.

fluids · Osmosis Most of a chain's counterions never leave it. The fraction of a charged rod's counterions lying within a distance r of it, against r in rod radii on a logarithmic axis, for a charge parameter ξ = 4.2 — the Bjerrum length of water, 0.7135 nm, over a charge spacing of 0.17 nm, which is DNA's. Each curve is the Poisson–Boltzmann solution for the rod at the centre of a cell of radius 10², 10⁴, 10⁶ rod radii, with its counterions checked to neutralise it exactly. Diluting the solution widens the cell by four decades at a time, and a counterion free to go anywhere in the cell ought to spread with it; instead each curve keeps a plateau near the rod whose height does not change. At the inflection of every curve the enclosed fraction is 0.762, which is Manning's 1 − 1/ξ, and the plateau sits there: 76 per cent of the counterions stay bound to the chain however dilute the solution, and only 24 per cent spread through it.

The counterions that never leave the chain

Dilute a solution of DNA a million times and its counterions ought to scatter through the whole volume. Three quarters of them do not. A line of charges closer together than the Bjerrum length — 0.71 nm in water — holds on to its counterions however much room they are given, until the chain's charge is cut back to one per Bjerrum length, and every osmotic pressure, swelling gel and packed virus built from such chains is set by that length rather than by the chemistry.

fluids · Osmosis Mean field always pushes; correlations pull. The pressure between two planes of equal charge with only their own counterions between them, against their separation, in units of the Gouy–Chapman length μ for the separation and 2πℓ_Bσ²kT for the pressure. The upper curve is the Poisson–Boltzmann result, solved from k·tan(kd/2) = 1: it is the density of counterions at the midplane and is positive at every separation, falling from the ideal-gas 2/d at contact to π²/d² far apart — 1.71 at 1μ, 0.290 at 4μ. The lower curve is the strong-coupling limit, 2/d − 1, which the same ions reach when their valence and the surface charge are high. It crosses zero at d = 2μ and is negative beyond, tending to −1: the two like-charged planes attract, and the separation 2μ is where they come to rest.

The like charges that pull together

Two surfaces carrying the same charge, with nothing between them but the ions that neutralise them, ought to repel, and the standard mean-field theory proves that they always do. With calcium or spermine as the counterions they attract, and come to rest a fraction of a nanometre apart. The mean field misses it because it averages the ions into a smooth cloud, and multivalent ions are too strongly repelled by each other to form one. Each keeps a patch of surface to itself, and the pressure between the plates becomes a single ion's business.

fluids · Osmosis

Named alongside it

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

Osmotic pressureBjerrum lengthCounterion condensationOsmosisPoisson boltzmann equationScreeningBiological physicsChemical potentialContact value theoremCorrelationCoupling parameterElectroneutrality

All concepts