Illustrated Physics
physics, drawn
Concept

Latent heat — where it appears

The energy a substance absorbs to change phase at fixed temperature, which no thermometer registers and which sets the slope of the boundary curve. It goes into breaking the bonds rather than into raising the kinetic energy, and it falls to zero at a critical point where the two phases have become one.

Named by 7 essays across one field — each of them below, with the objects they name alongside it.

Heating 1 kg of water from -20°C to 130°C. Temperature against heat added for 1 kilogram of water taken from -20 to 130 degrees Celsius. The two flat stretches are the melting and the boiling, where 334 and 2260 kilojoules go in and the temperature does not move. Melting costs as much as warming the water by 80 degrees; boiling costs as much as warming it by 541, which is 73 per cent of the whole journey.

The heat that changes no temperature, and where it actually goes

A kettle reaches a hundred degrees in a minute and takes five more to boil dry. The heat going in during those five minutes changes nothing a thermometer can see, and it is most of the energy in the whole process.

thermodynamics · Phase change Ways to arrange 12 coins. The number of distinct arrangements giving each number of heads, for 12 coins. Every individual arrangement is equally likely; the middle wins because there are more ways to reach it.

What a system actually minimises

A ball falls to the bottom of a bowl and a gas fills a room, and neither of those is the rule. A system in contact with a large reservoir minimises U − TS, and the minus sign is the reservoir's own entropy written in the system's variables — which is why a rubber band pulls harder when it is heated.

thermodynamics · Entropy The phase boundary of water, from one equation. Pressure against temperature for water on a logarithmic pressure axis spanning 6.6 decades. The vaporisation curve is integrated from Clausius–Clapeyron between the triple point at 273.16 kelvin and 611.7 Pa and the critical point at 647.096 kelvin, with a single latent heat of 43.32 kilojoules per mole — the value the two published points on the curve imply. The measured latent heats are 45.05 at the triple point and 40.65 at the reference point, and the fitted value sits between them, because a constant latent heat is an average over the interval. The sublimation curve below the triple point is not measured but predicted, from the two latent heats adding where all three boundaries meet: 51.1 kilojoules per mole, which reaches 103.2 Pa at 253.1 kelvin against a measured 253.15. The melting curve is drawn at the slope Clapeyron gives it, -13.5 megapascals per kelvin, which is a volume ratio and nothing else: water's solid is 917 against 1000 kilograms per cubic metre for its liquid, so melting shrinks it and the line leans backwards. Across the whole 6.6 decades of this axis that line moves 5.2 kelvin, and one atmosphere shifts the melting point by 0.0075 kelvin. At 1 atmosphere the boundary is crossed at 373.1 kelvin, where water boils. The one place the curve fails is its top end: a constant latent heat reaches 37.4 MPa at the critical temperature where the measured critical pressure is 22.1 MPa, 70 per cent high, because the latent heat falls to zero at the critical point and this curve does not know that.

A boiling point is a pressure, not a temperature

Nothing about water names one hundred degrees; the air does. Where a liquid turns to vapour in its bulk is fixed by what pushes on it, which makes the familiar figure a coordinate on a curve — 71 °C on Everest, 119.5 °C in a sealed pot — and one latent heat draws the whole curve.

thermodynamics · Phase change 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 part of the curve no fluid follows. Van der Waals' isotherms in reduced units, at 5 temperatures either side of the critical one, so that nothing about any particular substance appears. Above the critical temperature the pressure falls monotonically as the volume grows, which is what a fluid does. Below it the curve develops a loop with a rising section in the middle, and that section says the pressure increases as the substance expands — a material with negative compressibility, which cannot exist, because any fluctuation would run away. What happens instead is drawn as the horizontal line: the substance separates into two phases at one pressure, and the volume moves along the line as the proportions change. Its height, 0.6470 of the critical pressure, is fixed by requiring the two areas the line cuts off to be equal, which is the condition that the two phases have the same Gibbs energy. It meets the curve at volumes 0.603 and 2.349, a ratio of 3.9, and those are the densities of the liquid and its vapour. The two turning points of the loop, at 0.72 and 1.53, bound the part that is not merely unobserved but impossible; between them and the construction the substance can be made to sit, superheated or supercooled, until something nucleates.

The part of the curve no fluid follows

One equation for a real gas produces isotherms with a rising middle section, which says a substance would expand as the pressure on it grows. Nothing does that. What replaces it is a horizontal line whose height is fixed by making two areas equal, and the condition is not a convenience.

thermodynamics · Phase change Three curves that can only meet at a point. Water's phase diagram within a kelvin of its triple point, with each boundary drawn at the slope Clausius and Clapeyron give it from measured latent heats and densities: 44.4 Pa/K for boiling, 50.3 for sublimation, and -135 bar per kelvin for melting — negative, and so steep that it is drawn vertical here, because ice is the less dense phase and pressure therefore melts it. Two things follow that no amount of measurement could adjust. The three slopes are not independent: the sublimation and vaporisation curves differ in slope by 5.92 Pa/K, which is exactly what the fusion latent heat predicts, because going solid → gas directly and solid → liquid → gas must cost the same enthalpy. And the sublimation curve is the steeper of the two, so the two cross rather than touch — which is why the triple point is a crossing and not a tangency, and why ice sublimes below it and melts above it.

Why the triple point is a point

Three phases of one substance coexist at one temperature and one pressure and nowhere else, and the reason is arithmetic rather than chemistry: count the numbers that describe the state, count the conditions equilibrium imposes, and subtract. The same subtraction says four phases of one substance are impossible, and it says so without knowing what the substance is.

thermodynamics · Phase change Melting curves, and the one that leans the wrong way. Melting temperature against pressure for water, benzene, naphthalene, each measured from its own melting point at one atmosphere, with pressure in bars. The slope of every coexistence line is the latent heat divided by the temperature and the change in volume, and the latent heat of melting is positive for everything — so the sign of the slope is the sign of the volume change, and nothing else. Almost everything expands on melting and its line leans forwards. Water's solid is less dense than its liquid, so its line leans backwards at 135 bars a kelvin: pressing on ice at just below zero melts it, and it takes 135 atmospheres to gain a single degree. The anomaly is not in the thermodynamics; it is in the fact that ice floats.

The melting curve that leans the wrong way

The slope of any coexistence line is the latent heat divided by the temperature and the change in volume. Latent heat is always positive, so the sign of the slope is the sign of the volume change — and for water the volume change is negative, which is the whole of why ice floats and why the melting curve leans backwards.

thermodynamics · Phase change

Named alongside it

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

Phase transitionEntropyEquilibriumTemperatureFree energyThe Boltzmann factorDensityEquation of stateMetastabilityMicrostatesNucleationPressure

All concepts