Concept

Efficiency — where it appears

The fraction of the heat drawn from a hot source that an engine delivers as work, whose ceiling depends on two temperatures and nothing else. That ceiling is one minus the ratio of the cold to the hot absolute temperature, and no working substance or mechanism beats it.

Named by 10 essays across 4 fields — each of them below, with the objects they name alongside it.

A Carnot cycle on pressure–volume axes. Two isothermal steps joined by two adiabatic ones, forming a closed loop. The gas expands 9.6-fold in reaching the cold reservoir at 0.50 of the hot one, and the area enclosed is the net work done over one cycle.

The ceiling on every engine, set before it was designed

There is a maximum efficiency no heat engine can exceed, and it depends on nothing but two temperatures. Not the fuel, not the working substance, not the cleverness of the engineer.

thermodynamics · Heat engines
The term that abolishes the inner orbits. The effective potential of the Schwarzschild geometry per unit mass, in units of c², at 4 angular momenta, against radius in Schwarzschild radii. Newton's version has a minimum — a stable circular orbit — at L̃²/GM for every angular momentum there is, however small, and it is the dashed curve at the same L̃, here with its minima at 10.13, 7.61, 6.00, 5.12 rs. General relativity adds one term, −GM L̃²/c²r³, and that minimum stops existing below a definite angular momentum. At L̃ = 4.50 GM/c the barrier and the well are still separate, at 1.83 and 8.29 rs. The two merge at L̃ = √12 GM/c, at 3 rs = 6GM/c² — the innermost stable circular orbit, where the curve drawn here has neither a maximum nor a minimum but a single inflection. Below that momentum — the curve at L̃ = 3.20 GM/c — there is no stationary point anywhere outside the horizon, so no circular orbit exists at all, at any angular momentum whatever. None of that is a property of matter; it is a statement about the geometry, and it fixes the energy of the innermost orbit at √(8/9) = 0.94281 of mc², so 5.719% of the rest mass has been radiated by anything that reached it. Every well drawn here was located on the emitted curve by golden section and checked against the closed form.

The orbit that cannot be made smaller

Newtonian gravity allows a stable circular path at every radius, however tight, and there is no innermost one. General relativity adds a single term to the expression that says so, and below 6GM/c² no stable circular path exists at any angular momentum whatever. Anything arriving there has radiated 5.72% of its rest mass, which is eight times what hydrogen fusion converts.

astrophysics · Orbit stability
The ceiling, inverted. How many joules of heat a perfect machine can move per joule of work, against the outside temperature, with the inside held at 21 °C. The upper curve is heating — T_h/(T_h − T_c), which is what the Carnot argument becomes when the cycle is run backwards — and the lower one is cooling the outside, T_c/(T_h − T_c). They differ by exactly one everywhere, to 1.8e-15 across the whole range as drawn, because the work put in is delivered as heat along with whatever was moved. The dashed line at one is a resistive heater, which is 100% efficient and is the worst option on the figure. At 7 °C and −7 °C the ideal coefficients are 21.0 and 10.5; a real machine reaching 25% of the ideal gets 5.3 and 2.6, which is still several times what burning the same energy would give.

The engine that pays back more than it takes

Carnot's argument puts a ceiling on how much work a flow of heat can be made to do. Run the same cycle backwards and the ceiling inverts into a floor that is greater than one — so a machine can deliver three or four joules of heat for every joule it consumes, and a perfectly efficient electric heater is the worst way to warm a room.

thermodynamics · Heat engines
The ceiling, the estimate, and three power stations. Two efficiencies against the ratio of the cold reservoir's temperature to the hot one. The upper curve is Carnot's 1 − Tc/Th, which is a ceiling on the work per unit of heat and is reached only by an engine that runs infinitely slowly, because a reversible heat flow needs a vanishing temperature difference to drive it and therefore infinite time. The lower curve is 1 − √(Tc/Th), the efficiency of an engine with finite thermal contact run for the most power rather than the most work. Three measured plants are marked: West Thurrock, coal runs at 36 per cent against a ceiling of 64 and a finite-time estimate of 40; CANDU, nuclear runs at 30 per cent against a ceiling of 48 and a finite-time estimate of 28; Larderello, geothermal runs at 16 per cent against a ceiling of 33 and a finite-time estimate of 18. Every one of them is closer to the lower curve — within 4.4 points at worst, against 16.5 at best from the ceiling. The second law is not what limits a working power station. What limits it is that somebody wants the electricity this year.

The engine that has to finish

Carnot's ceiling is exact and it is reached only by an engine that takes for ever, because a reversible heat flow needs a vanishing temperature difference to drive it. Ask instead for the most power rather than the most work per joule of heat, and the answer is a different function of the same two temperatures — and three measured power stations sit on it rather than on the ceiling.

thermodynamics · Heat engines
Thrust against the air it is supposed to be pushing on. The thrust of one F-1 engine against ambient pressure, in atmospheres. It is 6.78 meganewtons at sea level and 7.77 in vacuum — 14.6 per cent more with the air taken away. The line falls at exactly 9.787 newtons per pascal, which is the nozzle's exit area, because the term is (p_e − p_a)·A_e: the ambient pressure pushes on the exit plane from outside and there is nothing to push back on it. The account in which the exhaust shoves against the atmosphere makes the opposite prediction — thrust falling with the pressure and vanishing in vacuum — and it is not a small disagreement about a coefficient. It has the sign wrong. A rocket works better in vacuum than in air, and every engine ever fired has said so.

The push that needs nothing to push against

A rocket engine produces more thrust in vacuum than at sea level — fifteen per cent more, for the engine drawn here, and the extra is exactly the ambient pressure times the nozzle's exit area. The account in which the exhaust shoves against the atmosphere does not merely overstate a coefficient. It has the sign wrong, and every engine ever fired has said so.

mechanics · Momentum
Each stage takes 25.0 per cent of what is left. Entropy against temperature for a spin-½ paramagnet at 0.25 T and 1 T, with the cooling cycle drawn between them: a vertical drop is isothermal magnetisation, a horizontal move is adiabatic demagnetisation. Starting from 1 K the treads are at 1.000 K, 0.250 K, 0.062 K, 0.016 K, 3.91 mK. Each is 0.2500 of the one before — a ratio read back off the drawn treads rather than written into them, and equal to the field ratio 0.25/1 because this refrigerant's entropy depends on the field and the temperature only through their quotient. The steps therefore shrink in proportion to what is left, and no finite number of them arrives.

The staircase that never reaches the floor

Absolute zero is unreachable, and the reason is not that the apparatus is not good enough. Every stage of cooling removes a fixed fraction of what is left rather than a fixed amount, so the steps shrink in proportion to the distance remaining — and the fixed fraction cannot be made one, because the entropy curves at two field strengths are required to meet where the axis is.

thermodynamics · Third law
The least energy that fresh water can cost. The work needed to take fresh water out of a feed of 1150 mol/m³ of dissolved particles — seawater — against how much of the feed is taken, in kilowatt-hours per cubic metre of product. The lower curve is the reversible minimum, in which the pressure is raised continuously as the remaining feed gets saltier; the upper one is a single stage held throughout at the pressure the final, saltiest concentrate needs. At vanishing recovery both tend to the feed's own osmotic pressure, 28.5 bar or 0.79 kWh/m³, which is the floor for the first drop and is checked here against the limit of the formula. Taking more of the feed costs more per unit taken, because what is left behind is saltier: at 10% recovery 0.83 kWh/m³ reversibly and 0.88 in one stage, 30% recovery 0.94 kWh/m³ reversibly and 1.13 in one stage, 50% recovery 1.10 kWh/m³ reversibly and 1.58 in one stage, 60% recovery 1.21 kWh/m³ reversibly and 1.98 in one stage, 75% recovery 1.46 kWh/m³ reversibly and 3.17 in one stage. The horizontal line is what a good seawater plant actually uses, 3 kWh/m³, so the second-law efficiency of the industry is about 37 per cent. None of this is about membranes. It is the free energy of mixing salt into water, read backwards, and no technology of any kind can go below the lower curve.

What it costs to take the salt out

Salt dissolves in water because mixing is overwhelmingly the more probable arrangement, and separating the two again means paying back what the mixing gave away. The bill can be computed before any apparatus is chosen — 0.79 kilowatt-hours for the first cubic metre from seawater — and it rises with every further cubic metre taken, because what is left behind is saltier than what was started with.

fluids · Osmosis
One temperature, four pawls, and nothing gained. The net rate of a ratchet whose gas and whose pawl are at the same temperature, against the load, for notches 2, 5, 10, 20 times the thermal energy deep. Every curve passes through zero at zero load and is negative everywhere else. The device is not merely unable to lift a weight; under any load at all it turns the wrong way and lets the weight down, converting its potential energy into heat in the gas. Making the notch deeper slows everything down — an exponential in the depth — and does not change the sign anywhere. That is the second law arriving as a mechanism rather than as a prohibition. Nothing was assumed about entropy; the pawl was simply allowed to be as warm as everything else, and its own fluctuations undo exactly the rectification it was there to provide. Any rectifier small enough for thermal noise to matter has this problem, and the rectifier being clever does not help, because the same noise reaches the cleverness.

The engine a fluctuation cannot run

A ratchet lets a shaft turn one way and not the other. Put a paddle in a gas on the same shaft and molecular collisions appear to become a lifted weight — an engine running on one reservoir. It does not work, and following exactly why turns the second law from a prohibition into a mechanism: the pawl is as warm as the gas, and it lifts whenever it is asked to.

thermodynamics · Heat engines
The rectangle every cycle is equal to. An ideal Otto cycle for air on a temperature–entropy diagram: compression ratio 9, intake at 300 K, 1400 kJ/kg added at constant volume. Compression takes the charge to 722 K, combustion to 2672 K, expansion back to 1110 K, and the exhaust cools at constant volume. The shaded loop is the work; the region under the lower curve is the heat rejected. Heat enters over a range of temperatures, and its entropy-weighted mean — heat divided by the entropy it brings — is 1491 K; the heat leaves at a mean of 619 K. The dashed rectangle between those two temperatures has exactly the loop's area, and 1 − 619/1491 = 58.5%, which is the Otto efficiency, checked to rounding. A Carnot engine between the coldest and hottest points of the same cycle would reach 88.8%.

The temperature an engine really takes its heat at

Carnot's ceiling is set by two temperatures, and no engine that burns fuel takes its heat in at one temperature or gives it out at another. It takes heat over a range, from the moment combustion starts to the moment it ends. For any reversible cycle there is an exact replacement for Carnot's two numbers: the average temperature at which heat arrives and the average at which it leaves, each weighted by the entropy the heat carries. The gap between a real cycle and Carnot is a gap between those averages and the extremes.

thermodynamics · Heat engines
Two bodies an engine draws together. Two equal bodies of 4.186 kJ/K — a kilogram of water each — one at 90.0 °C and one at 10.0 °C, against the heat drawn from the hot one. The solid curves are the best possible engine running between them, a reversible one, which leaves the product of the two temperatures unchanged and brings both to the geometric mean, 320.7 K (47.5 °C). It draws 177.8 kJ from the hot body and delivers 20.8 kJ of work, C(√T₁ − √T₂)², checked against the heat balance. The dashed lines are the same bodies simply touching: they meet at the arithmetic mean, 323.1 K, having exchanged 167.4 kJ and delivered nothing. The 2.5 K between the two endpoints is the work, left behind as heat.

The work left in two buckets of water

Carnot's ceiling assumes reservoirs so large that taking heat from one and giving it to the other changes neither temperature. Two buckets of water are not reservoirs. Run the best possible engine between a hot one and a cold one and both temperatures move, the efficiency available shrinks as they do, and the engine stops when they meet — at the geometric mean of the starting temperatures, not the ordinary one. The work it delivered is exactly the difference between those two meeting points, and it is far less than the starting temperatures promise.

thermodynamics · Heat engines

Named alongside it

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

The Carnot cycleReversibilityEntropyThe second lawHeat capacityHeat engineIrreversibilityTemperatureFree energyThe p–V diagramThermal equilibriumAdiabatic process

All concepts