Concept

Equation of state — where it appears

The relation between a substance's pressure, density and temperature, which is what turns a set of conservation laws into a prediction. It decides everything from whether a gas cools when throttled to how heavy a neutron star can be, and above nuclear density it is not known.

Named by 14 essays across 4 fields — each of them below, with the objects they name alongside it.

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
Throttling a gas, and the curve that says which way it goes. Curves of constant enthalpy for a van der Waals gas, in temperature and pressure both measured against the critical values. A gas pushed slowly through a plug or a valve keeps its enthalpy, so it moves along one of these curves — from right to left, since the pressure falls. Where a curve slopes upward to the right the gas cools as it expands; where it slopes downward it warms. An ideal gas would give horizontal lines and no change at all, because its enthalpy depends on the temperature alone; every curve here is bent, and the bending is the attraction between molecules and the room they take up, fighting. The dashed line through the tops of the curves is the inversion curve, and the maxima were found on the drawn points rather than put there — they lie on the closed form to 0.65 per cent. Which side of it a gas starts on decides the sign of the effect, and that is the whole of why air can be liquefied by throttling at room temperature and hydrogen cannot: hydrogen has to be pre-cooled below its own inversion temperature first, which is why Dewar needed liquid air before he could get liquid hydrogen, and why Onnes needed liquid hydrogen before he could get helium.

The gas that cools by being let go

Push a gas through a plug and its temperature changes, although no work is done on anything and no heat goes anywhere. Which way it changes depends on where it starts: inside a dome in the pressure–temperature plane it cools, outside it warms, and hydrogen at room temperature is outside — which is why liquid hydrogen needed liquid air first.

thermodynamics · Phase change
The far end that has not been told yet. A rod 3 metres long, pushed at one end at time zero. On the left, position across and time upwards, for the two fastest disturbance speeds drawn here, with the light cone beside them: nothing may lean further to the right than that line, which crosses the rod in 10.0 nanoseconds. A rigid rod would be the vertical dashed line — the far end moving at the same instant as the near one — and it is not a limit that a hard material approaches. It is a signal at infinite speed. On the right, how long the far end actually waits, against how fast the disturbance travels, both logarithmic, with every material on it: 8.8 ms at 3.4e+2 m/s, 600.0 μs at 5.0e+3 m/s, 250.0 μs at 1.2e+4 m/s, 100.0 ns at 3.0e+7 m/s, 20.0 ns at 1.5e+8 m/s. The line has slope −1 and the light cone is a hard floor beneath it. Ordinary materials sit four to five decades above that floor, which is why rigidity is such a good approximation and why it is still not a limit: steel's delay is not small compared with light's, it is 6e+4 times larger. Everything usually derived from rigid bodies survives, because the delay is beneath notice in ordinary circumstances. What does not survive is the use of rigidity in an argument about simultaneity, which is where it does real damage: a rod pushed at one end is compressed for as long as the wave takes to cross it, and there is a frame in which its far end is still at rest while its near end is moving.

Nothing is allowed to be rigid

A rigid body would move its far end at the instant its near end was pushed, which is a signal at infinite speed. Relativity forbids it — not approximately, and not as a limit that a hard enough material approaches. What follows is a ceiling on how stiff matter may be, and that ceiling caps the mass of every neutron star.

relativity · Relativistic dynamics
Energy, pressure and entropy of a gas nobody counted. The energy density, pressure and entropy density of blackbody radiation against temperature, on logarithmic axes, together with the pressure a monatomic gas of the same energy density would have. Every curve is a power of the temperature — the fourth for energy and pressure, the third for entropy — because the only length in the problem is the thermal wavelength and the only energy is kT. The pressure is exactly a third of the energy density, where an ordinary gas's is two thirds, a factor of 2: a photon carries momentum E/c and a slow molecule carries √(2mE), and that difference is the whole of it. Some values: at room temperature the radiation pressure is 1.86e-6 pascals, which is a ten thousand millionth of an atmosphere; at 1e+7 kelvin it is 2.52e+12, which is where radiation rather than matter holds a star up.

The gas that nobody counted

A box of gas holds however many molecules were put in it. A box of radiation holds however many photons the temperature says, because the walls make and destroy them until the free energy is least — and one dropped assumption changes every result. The pressure becomes a third of the energy density instead of two thirds, the entropy goes as the cube of the temperature, and the adiabatic index comes out at exactly four thirds.

thermodynamics · Blackbody
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
The pair potential, and the two things it does to a gas. The Lennard-Jones potential between two molecules, in units of its own depth and range, with the Mayer function it produces at 1, 3, 8 times the well depth in temperature. The virial coefficient is minus the integral of that function over volume, so the two parts of the potential contribute with opposite signs: the steep repulsive core makes the function minus one there, giving a positive contribution — molecules take up room — and the attractive well makes it positive, giving a negative one. At low temperature the attraction dominates and a gas is easier to compress than an ideal one; at high temperature the core dominates and it is harder. Between them is one temperature at which they cancel.

The first correction to the gas law

An ideal gas has no forces between its molecules. The first correction to what it does is computable from those forces alone — one integral over the pair potential — and its sign flips at a temperature where a real gas obeys the ideal law without being ideal at all.

thermodynamics · Kinetic theory
A gas of grains that lose 51 per cent of their energy per collision, cooling into clumps. 2000 discs in a square box with periodic walls, covering 25 per cent of its area, started with random velocities and left alone. Each collision keeps a fraction e = 0.7 of the relative velocity along the line of centres. The panels are the same gas at three temperatures, where temperature means the mean kinetic energy of a grain: 0.85 T₀, 0.019 T₀, 0.00049 T₀. It starts uniform — the grain counts in a 10 × 10 grid have a variance 0.3 times their mean, more even than scattered points because discs cannot overlap — and ends in dense bands and clumps with empty space between, the variance 17 times the mean. Nothing attracts anything. The clumps form because a dense patch collides more often, cools faster, loses pressure and is squeezed denser by the hotter gas around it.

The gas that cools itself into clumps

Shake a box of grains hard enough and they fly about like the molecules of a gas. Stop shaking and the gas cools, because every collision destroys a little of the motion — and it does not cool evenly. A denser patch collides more often, cools faster, loses pressure, and is squeezed denser by the hotter gas around it. With nothing attracting anything to anything, the gas gathers itself into clumps and bands, and in the limit three grains can collide infinitely many times in a finite time.

fluids · Granular matter
Water gets denser the deeper it is. The density of seawater at 0 °C and a salinity of 35 against depth, from the surface to the 10.99 km of the Challenger Deep, with the pressure integrated down the column from the equation of state rather than assumed. At the surface it is 1028.1 kg/m³. At the ocean's mean depth of 3.68 km it is 1045.3, 1.67 per cent more; at the bottom of the deepest trench it is 1076.5, 4.71 per cent more. An incompressible ocean would be the vertical line. The curve is almost straight; what curvature it has, too little to see here, is the water stiffening as it is squeezed: its secant bulk modulus rises by 3.24 pascals for every pascal of pressure.

The sea that stands lower because water gives

Water is the textbook incompressible fluid, and at the bottom of the ocean it is 4.7 per cent denser than at the top. That squeezing lowers the whole sea by about thirty metres, adds the weight of 266 metres of water to the pressure in the deepest trench, and speeds sound up so steadily with depth that it digs a channel in which a low note can cross an ocean.

fluids · Hydrostatics
The stiffness that falls below four-thirds. The first adiabatic exponent Γ₁ — how steeply pressure rises when a gas is squeezed without heat escaping — of hot oxygen with its radiation and its equilibrium electron–positron pairs, against temperature, at densities of 10³, 10⁴, 10⁵, 10⁶ g/cm³. At 10³ g/cm³ its least value is 1.222, near 1.2 billion kelvin; at 10⁴ g/cm³ its least value is 1.235, near 1.3 billion kelvin; at 10⁵ g/cm³ its least value is 1.285, near 1.8 billion kelvin; at 10⁶ g/cm³ its least value is 1.339, near 3.1 billion kelvin. A star can hold itself up only if its core's Γ₁ averages above 4/3, the value for a gas of light alone; a core that dips below it has no stable size, and the pair production that pulls it below is strongest where the gas is hot and thin — the cores of the most massive stars.

The heat that turns into matter

Thermodynamics counts particles and relativity lets them be made. Heat a gas to a billion kelvin and its light carries enough energy to create electrons and positrons, which the gas then holds in equilibrium like any other ingredient. The heat spent making them raises neither the temperature nor the pressure, so the gas grows soft — softer, in the cores of the most massive stars, than a star can survive. Those stars collapse, ignite their oxygen all at once and blow themselves entirely apart; and the same pairs, vanishing a few seconds after the Big Bang, left the universe's light hotter than its neutrinos by a factor that is the cube root of eleven over four.

relativity · Relativistic thermodynamics
The heaviest star free neutrons can hold up. Mass against radius for cold stars of free neutrons, each point a different central density, held up by the pressure of the neutrons' exclusion alone: in general relativity and, with the same gas, in Newton's gravity. Relativity's curve reaches a highest mass of 0.71 solar masses at a radius of 9.5 km and turns back; Newton's keeps rising towards 5.8 solar masses as the stars shrink. The measured masses of neutron stars reach about 2.08 (dashed), three times what free neutrons allow, so the matter inside has to be stiffer than a gas of free neutrons: the repulsion between nucleons at short range is holding them up.

The pressure that weighs down what it holds up

In Newton's gravity a star is held up by pressure, and stiffer matter can hold up more: a star of free neutrons could reach almost six solar masses. In general relativity the pressure itself has weight. Every layer squeezed harder to hold up the layers above adds to the pull it is resisting, and past a point pressing harder makes things worse. The same gas of neutrons then tops out at 0.71 solar masses. Neutron stars twice as heavy exist, which says what their insides must be like — and no matter of any kind can hold a static body smaller than nine-eighths of its Schwarzschild radius.

astrophysics · Self-gravity
A beam of light pulls hardest on what comes towards it. The sideways pull of a long, thin beam of light on a body moving parallel to it at velocity βc, as a multiple of the pull the same body would feel from a static mass with the same energy per unit length, against β: 2(1 − β)²/(1 + β²). A body at rest beside the beam is pulled twice as hard as by a static mass — the beam's pressure along its length counts. A body moving with the beam is pulled less, and a ray of light running alongside it is not pulled at all (β = 1). A ray running against it is pulled 4 times as hard as a static mass of the same energy would pull it. Tolman, Ehrenfest and Podolsky found this in 1931. Two parallel laser beams do not attract each other; two opposed ones do.

The light that pulls twice as hard as its mass

Energy has mass, E/c², and a box of light weighs that much more than an empty one. But the gravity something produces is not set by its energy alone. Pressure counts too, three times over, and light's pressure is a third of its energy — so a beam of light pulls on things beside it twice as hard as its mass would suggest. The box weighs only E/c² because its walls, straining to hold the light in, pull with a negative amount that exactly cancels the difference. Two parallel beams of light do not attract each other at all; two opposed ones attract four times as hard. And a substance whose pressure is negative enough does not pull at all — it pushes.

relativity · Mass-energy
The stiffness a two-solar-mass star demands. The heaviest neutron star the model matter can support, in solar masses, against the constant square of the sound speed assumed above 300 MeV/fm³, as a fraction of c². At the conformal value, one-third (dashed), it is 1.92 solar masses; the heaviest star the model can make rises to 2.97 at the causal limit. To hold up the 2.08 solar masses of J0740+6620 (shaded) the square of the sound speed must exceed 0.394 of c² somewhere above that density — above the conformal one-third, by this model's reckoning. The conclusion depends on the model's low-density part, which the next figure varies.

The sound speed a neutron star needs

Heat any gas without limit and the speed of sound in it climbs towards a ceiling: not the speed of light, but light's speed divided by the square root of three, the sound speed of a gas of massless particles. For decades it was a natural guess that no matter could beat that ceiling, since the densest matter ought to behave like a gas of free quarks. Neutron stars say otherwise. A star of twice the Sun's mass, packed into a ball twenty-five kilometres across, can only be held up if its core is stiffer than the ceiling allows — unless nuclear physics fails at densities where it is believed to hold. Somewhere inside the heaviest neutron stars, sound almost certainly travels faster than it can in any free gas.

relativity · Relativistic thermodynamics
Why the mixture of two equal waters is heavier than either. A temperature–salinity diagram for seawater near the surface, with lines of equal density (curves) 0.3 kg/m³ apart. Two waters lie on the same line: one at 4 °C and 33.93 g/kg, the other at 16 °C and 36.53 g/kg, both 1026.00 kg/m³. Mixing them in any proportion moves along the straight line between them, because temperature and salt add linearly; the lines of equal density curve, because cold water's density responds less to temperature than warm water's. The straight line lies on the dense side of the curve. An even mixture, at 10 °C and 35.23 g/kg, is 0.182 kg/m³ denser than either parent, and sinks between them.

The mixture heavier than either water

Two bodies of seawater can have exactly the same density — one cold and fresh, one warm and salty — and sit side by side without either wanting to sink. Mix them, and the mixture is denser than both, and sinks. Nothing has been added and nothing removed; the extra weight comes from the fact that water's density is a curved function of temperature while mixing averages temperature in a straight line. The same curvature, at its most extreme, is why a lake overturns twice a year and freezes from the top, and why the open ocean, too salty to have a density maximum above freezing, does neither.

fluids · Stratification
The rise a watt-year buys at each depth. The rise in sea level, in millimetres, from one watt-year per square metre of heat (3.16 × 10⁷ joules) stored in a thin layer at each depth, for two water columns: a subtropical one, 24 °C at the surface cooling to 1.5 °C in the deep, and a polar one, 1.5 °C at the surface and 0.5 °C below. In the warm column the yield is 2.36 mm at the surface, falls to 1.02 mm near 2.0 km where the water is cold but the pressure still modest, and recovers to 1.49 mm at 6 km as pressure takes over. In the polar column the same heat buys 0.63 mm at the surface and 1.13 mm at 4 km. A joule stored in cold, deep water raises the sea about twice as much as one stored in the cold water above it.

The rise a joule of heat buys

Warm a column of seawater and it stands taller without weighing any more, so the sea rises while the pressure on the sea floor stays exactly the same. How much it rises depends on where the heat goes. Seawater's expansion coefficient grows with temperature and with pressure, so a joule stored in warm tropical water lifts the sea more than six times as far as the same joule in Arctic surface water. Cold water in the deep, squeezed by four kilometres above it, expands about twice as much per joule as the same cold water at the surface. That is why the budget of sea-level rise turns on thousandths of a degree in the least-measured part of the ocean.

fluids · Hydrostatics

Named alongside it

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

CompressibilityDensityNeutron starPressureSpeed of soundVan der waalsAdiabatic indexCausalityChemical potentialCritical pointEquilibriumGeneral relativity

All concepts