Illustrated Physics
physics, drawn
Concept

Entropy production — where it appears

The rate at which an irreversible process creates entropy, written as a sum over flows of each flux times the force driving it. The second law requires only that the sum be positive, which leaves room for one flow to run against its own force.

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

Two experiments, two computations, one coefficient. The Seebeck coefficient of a resonant conductor against where its resonance sits relative to the chemical potential, together with the Peltier coefficient divided by the temperature. The first is obtained by applying a temperature difference and finding the voltage that stops the current; the second by applying a voltage at uniform temperature and taking the ratio of the heat flow to the current. Different driving, different measurement, different integral — and the two curves agree to 3.8e-7 of the sweep's own scale across the whole of where they pass through zero and change sign. That equality is Kelvin's relation Π = ST, guessed in 1854 from an argument its author knew was not sound and proved by Onsager in 1931 from microscopic reversibility. It is not a property of this conductor; it holds for every one.

The second experiment that cannot disagree

Heat one end of a wire and a voltage appears across it. Pass a current through the same wire at uniform temperature and it carries heat. Those are two different experiments with two different apparatus, and the coefficient in front is the same number in both — not approximately, and not for some materials. The reason is that the equations of motion underneath look the same run backwards.

thermodynamics · Diffusion Nitrogen that runs the wrong way. The nitrogen mole fraction in each of two bulbs joined by a capillary, as in Duncan and Toor's experiment: one bulb starts with 0.50086 nitrogen and the rest carbon dioxide, the other with 0.49879 nitrogen and the rest hydrogen, at 35 °C. Solid curves: the capillary solved at each instant from the Maxwell–Stefan equations with the three pairs' diffusivities, 83.8, 68.0 and 16.8 mm²/s. Dashed: Fick's law for nitrogen alone, which can only let the two start values relax together. At the start the nitrogen gradient is 0.00207, yet nitrogen flows at 309 times the rate that gradient would drive. From 0.1 to 6.5 hours it flows from the bulb with less nitrogen into the bulb with more, opening a difference of 0.1468 at 6.5 hours; at 6.6 hours its flux passes through zero with a difference of 0.1468 still in place. Each gas is conserved to a part in 10⁹. The carbon dioxide moving out of the first bulb drags nitrogen with it, because the nitrogen–carbon dioxide pair has by far the smallest diffusivity and so the strongest friction.

The gas that flows towards more of itself

Fick's law says a substance diffuses from where there is more of it to where there is less. In a mixture of three gases, nitrogen can do the opposite for hours — flowing into the bulb that already holds more nitrogen, and then stopping while a difference remains — and in a welded bar of steel, carbon crosses into the side that is already richer. Nothing is wrong with the second law. Diffusion flattens chemical potential, and with more than two components, or a second element changing it, that is not the same as flattening concentration.

thermodynamics · Diffusion The price of precision never falls below two. For a clock ticking forwards and backwards with a free-energy drop a per step, the product of its squared relative uncertainty and the entropy it has produced, in units of k: exactly a·coth(a/2), whatever the time elapsed. It approaches the bound of 2 only as the driving vanishes and grows as a once the driving is strong; the three clocks compared elsewhere sit at 2.04 (0.5 kT), 2.63 (2.0 kT), 8.01 (8.0 kT). No steady-state process of any design lies below the line at 2 — the thermodynamic uncertainty relation.

The precision a clock pays for in heat

Anything that counts — a molecular motor stepping along a filament, a chemical oscillator keeping time in a bacterium, a clock ticking on a wall — has to be driven, because a count that is not driven runs backwards as often as forwards. The heat it gives off buys it regularity, and there is an exact floor under the price: the squared relative uncertainty of the count, times the entropy produced, is never less than two in units of Boltzmann's constant.

thermodynamics · Entropy Newcomen's dilemma. Two consequences of how cold a Newcomen engine's injection spray leaves its cylinder, against that temperature: the pressure difference the atmosphere then pushes the piston down with, one atmosphere less the vapour pressure of the water left in the cylinder; and the steam the next stroke wastes reheating the cylinder's iron skin, as a fraction of the most it wastes at 30 °C (8.2 cylinder-fulls). A cylinder cooled to 40 °C gives a push of 0.93 atmospheres and wastes 7.0 cylinder-fulls of steam a stroke; one left at 70 °C wastes half as much but pushes with only 0.69. Every choice was bad, because the one vessel had to be both hot, to receive the steam, and cold, to make the vacuum. Newcomen's engineers ran it in between.

The cylinder that must not be cooled

The first steam engines that did useful work, Thomas Newcomen's pumps of 1712, made a vacuum by spraying cold water into a cylinder full of steam. It worked, and on every stroke it cooled the cylinder, so that the next charge of steam condensed on the cold iron until the walls were hot again — several cylinders' worth of steam spent heating metal that the next spray would cool. James Watt saw in 1765 that the vessel was being asked to be hot and cold at once, and moved the cold to a separate condenser. The improvement was a factor of three or four in coal. A century later the reason had a name: heat passing from hot to cold across a large difference, doing nothing on the way, is work thrown away.

thermodynamics · Heat engines

Named alongside it

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

IrreversibilityCross effectDetailed balanceOnsager relationsThe second lawTransport coefficientDiffusionEquilibriumFluctuationsHeat engineKelvin relationLatent heat

All concepts