Illustrated Physics
physics, drawn
Concept

Reaction rate — where it appears

How fast two species that must meet actually do so, which for a diffusion-limited process is set by the geometry of the search rather than by the chemistry. In three dimensions it is 4πDa and depends on the target's size; in two there is no steady rate at all, which is why a reaction confined to a membrane behaves quite differently from the same one in solution.

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

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 10, 20, 30 times kT are factors of 10^-4.3, 10^-8.7, 10^-13.0. At 300 K, kT is 25.9 meV, so a barrier of 0.35 eV is 13.5 kT and a factor of 1.3e-6. 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 exponential that decides everything

Maximising the number of ways a reservoir can arrange what is left after taking E out of it gives one factor, e to the minus E over kT. Its exponent is a ratio, which is why a barrier of a third of an electronvolt — nothing at all by chemical standards — is the difference between instantly and never.

thermodynamics · Entropy The fraction of walks that have come home, against how long they have walked. The proportion of 1,600 lattice random walks that have returned to their starting point at least once, against the number of steps taken, on a logarithmic horizontal axis, in one, two and three dimensions. In one dimension almost every walk is home almost at once and the fraction climbs toward one. In two it climbs more slowly — the return is still certain, but only logarithmically, so a two-dimensional walk that has not come back after a thousand steps is unremarkable. In three the curve flattens: it reaches 0.3481 and stops, against the exact value 0.3405, drawn as a line. That number is Watson's integral, and it is the probability that a three-dimensional walk ever comes home at all. The difference between the cases is not one of degree. In one and two dimensions the expected number of returns is infinite and a diffusing particle visits every site eventually; in three it is finite, and a molecule released in a room will, with probability two-thirds, never pass through its starting point again. The same statement runs the other way round: a reaction that needs two diffusing partners to meet is a very different problem on a membrane from what it is in a cell.

The walk that comes home

A particle wandering at random on a line returns to where it started, with certainty. On a plane it returns, with certainty. In three dimensions the probability is 0.3405 — so two out of three molecules released in a room never pass through their starting point again, and the difference between the cases is not a matter of degree.

thermodynamics · Diffusion The same rate for every size of molecule. The diffusion-limited rate constant for two equal spherical molecules meeting in water at 25 °C, against their radius from 0.1 to 100 nm: 8kT/3η = 7.43·10⁹ per molar per second, flat. The dashed line is what a larger target would give if its partner kept the mobility of a 0.3 nm molecule — 7.4·10¹¹ at 30 nm — the intuition that a bigger molecule is easier to hit. Stokes and Einstein's law takes it away again: a molecule twice as big is twice as easy to hit and diffuses half as fast, and the two cancel exactly. Every reaction whose partners react at the first touch runs at close to this one number, whether the partners are ions, small organic molecules or proteins.

The speed limit that does not care how big the molecules are

Two molecules in water cannot react faster than they can find each other, and how fast they find each other is set by diffusion. A bigger molecule is an easier target, so it seems a reaction between big molecules should be faster. It is not: a molecule twice as big is twice as easy to hit and wanders half as fast, and the two cancel exactly. Every reaction that happens at the first touch runs at the same rate, about seven billion per molar per second in water, whether the partners are ions or proteins — a speed limit written by the viscosity of water and the temperature, and nothing else.

thermodynamics · Diffusion

Named alongside it

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

Brownian motionDiffusionRandom walkActivation energyArrhenius lawBarrierThe Boltzmann factorCapacitanceDimensionalityEntropyFirst passageMean square displacement

All concepts