Illustrated Physics
physics, drawn
Series

Phase change — the series

16 essays on one idea, from the one that introduces it to the one that assumes the rest.
  1. 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.

    part 1 · thermodynamics
  2. 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.

    part 2 · thermodynamics
  3. 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.

    part 3 · thermodynamics
  4. Two straight lines that are not the same line. Half the difference between the liquid and vapour densities, in units of the critical density, against the distance from the critical temperature — both logarithmic, over 5 decades. The van der Waals curve is solved for the coexisting pair at each temperature and its slope in the last decade is 0.500, which is the mean-field ½. Real fluids give 0.326. The two differ by 11 per cent at t = 0.1 and by a factor of 7.9 at the bottom of the axis, which is why an equation with the wrong exponent in it looked right for eighty years.

    The point at which the two become one

    Heat a sealed tube of carbon dioxide and the meniscus inside it does not boil away — it fades, the two densities converging until there is nothing to separate. Twenty millikelvin before that happens the fluid turns milky, and the exponent describing the last approach is a number van der Waals got wrong and could not have got right.

    part 4 · thermodynamics
  5. The barrier a new phase has to climb. The free energy of a droplet against its radius, at four supersaturations. Two terms compete: the volume term is a gain and goes as r³, the surface term is a cost and goes as r². At small radius the surface wins, so a droplet that forms by chance is more expensive than the vapour it came from and evaporates again; past a critical radius the volume wins and the droplet grows without limit. The maximum between them is the barrier. At S = 1.5 the critical radius is 2.66 nm and the barrier 533.8 kT, S = 2 the critical radius is 1.56 nm and the barrier 182.6 kT, S = 3 the critical radius is 0.98 nm and the barrier 72.7 kT, S = 5 the critical radius is 0.67 nm and the barrier 33.9 kT. The critical radius contains a few hundred molecules at low supersaturation and a handful at high, which is the first sign that a theory built on a surface tension and a bulk free energy is being applied outside its comfort. Both the critical radius and the barrier are located here by searching the drawn curve and checked against the closed forms 2γ/|Δg| and 16πγ³/3Δg², which agree to a part in a thousand.

    The barrier a new phase has to climb

    Water vapour three times supersaturated is thermodynamically desperate to condense and will sit there indefinitely if it is clean enough. The obstacle is that a droplet has to start small, and a small droplet is nearly all surface — so the first nanometre of every phase transition costs energy rather than releasing it, and what decides whether anything happens is the height of that cost divided by kT.

    part 5 · thermodynamics
  6. 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.

    part 6 · thermodynamics
  7. A stiffness that does not go to zero — it falls off a cliff. The renormalised stiffness of a two-dimensional superfluid against temperature, obtained by integrating the flow of the bare stiffness and the vortex fugacity, with the bare stiffness drawn for comparison. Below the transition the vortices are bound in pairs, screen one another and leave a finite stiffness; above it they unbind and there is none. What is remarkable is the value at which it disappears: 0.6430, against 2/π = 0.6366. That number does not depend on the material, on the bare fugacity, on the core energy, or on anything else — every two-dimensional superfluid loses its stiffness at exactly two over π times its own transition temperature, and measurements on helium films of widely different thicknesses fall on that line. A transition at which a quantity jumps to zero from a value nobody can adjust is unlike anything the usual classification of transitions describes.

    The transition with nothing to order

    Every transition in this collection so far has an order parameter — a quantity that is zero on one side and not on the other. In two dimensions a continuous symmetry cannot break at any temperature above zero, so there is nothing for such a quantity to be, and by the usual reckoning there can be no transition. There is one anyway, and what changes at it is whether vortices are bound in pairs.

    part 7 · thermodynamics
  8. 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.

    part 8 · thermodynamics
  9. 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.

    part 9 · thermodynamics
  10. The melting line of water, through five ices. The pressure at which water freezes, in megapascals on a logarithmic axis, against temperature, along each of the five solid phases that meet the liquid, from the international standard equations. Along ordinary ice, Ih, the melting pressure rises as the temperature falls, from 611 Pa at 273.16 K to 209 MPa at 251.165 K — the backwards slope of the familiar melting line. There the liquid meets ice III, and from then on every ice melts at a higher pressure as the temperature rises: ice V, ice VI, and ice VII, which reaches 20.6 GPa at 715 K. The dots are the four triple points where two ices and the liquid coexist. The lowest temperature at which liquid water can exist in equilibrium, 251.165 K, is at the first of them.

    The melting line that turns round

    Squeeze water and it freezes at a lower temperature — the backwards slope of its melting line, and the reason ice floats. Keep squeezing and the slope reverses. Past two thousand atmospheres ordinary ice gives way to a denser ice, then another, and from there on every ice melts at a higher temperature under more pressure, exactly as a normal substance's does. At twenty thousand atmospheres water freezes into an ice that is still solid at a hundred degrees Celsius; at two hundred thousand, one still solid at four hundred. The famous anomaly belongs to one ice out of five, and the same relation that explained it explains its end.

    part 10 · thermodynamics
  11. The boiling curve, which turns back. Heat flux from a horizontal surface into water boiling at one atmosphere, on a logarithmic axis, against how far the surface is above the boiling point, also logarithmic, from standard correlations. At a few degrees heat leaves by convection; from about 5 K bubbles nucleate and the flux climbs as the cube of the superheat, to the critical heat flux of 1.11 MW/m² at 20 K. Beyond it the flux FALLS as the surface gets hotter — the transition regime, drawn dashed as the interpolation it is — down to 19 kW/m² at 67 K, the Leidenfrost point, where a continuous film of vapour insulates the surface. Past that, film boiling and radiation let the flux rise again, slowly: 310 kW/m² at 1000 K above boiling. Between the crisis and the Leidenfrost point, a surface 3 times hotter passes 58 times less heat.

    The boiling curve that turns back

    Heat a surface under water and more heat flows from it the hotter it gets — up to a point. Past about twenty degrees above boiling the bubbles crowd together, merge, and begin to blanket the surface with vapour, and from then on a hotter surface passes less heat, not more, until by a few hundred degrees above boiling it is wrapped in an insulating film and passes fifty times less than it did at its best. Shigeo Nukiyama found the turn in 1934 by melting wires. It is why a water drop skates for a minute on a very hot pan but vanishes in two seconds on a merely hot one, and why every boiler, steam generator and water-cooled reactor is designed around a number called the critical heat flux.

    part 11 · thermodynamics
  12. Latent heat of boiling against boiling point. The heat needed to boil one mole of a liquid at its normal boiling point, against that boiling point, both on logarithmic axes, for twenty-one substances from helium to sodium. The line is ΔH = 87.2 J/(mol K) × Tb, the mean entropy of boiling of the ordinary liquids boiling between 250 and 700 K, which scatter about it by 3.3 per cent; the ordinary liquids as a whole (blue), from neon at 27 K to sodium at 1,156 K, by 10.0 per cent, the coldest lying low. Water, ammonia and the alcohols (red) need more heat than the line predicts, acetic acid (green) less; the quantum liquids helium and hydrogen (violet) fall far below.

    The entropy every liquid gains on boiling

    Divide the heat it takes to boil a liquid by the temperature at which it boils, and for benzene, chloroform, acetone, hexane, ether and carbon tetrachloride the answer comes out within a few per cent of the same number — about ten and a half times the gas constant. Frederick Trouton noticed it in 1884. It is a statement about entropy, and once it is read that way the liquids it fails for become the interesting ones: water and the alcohols, whose hydrogen bonds hold the liquid in order; acetic acid, whose vapour is made of pairs; and helium, whose liquid is already as disordered as quantum mechanics allows.

    part 12 · thermodynamics
  13. How much of supercooled water freezes in an instant. The fraction of a body of supercooled water that freezes at once when it is nucleated, against how far below 0 °C it had been cooled: the ice that forms releases latent heat until the whole of it is back at 0 °C, and freezing stops there until heat is taken away. Solid: with water's measured heat capacity, which rises steeply below about −20 °C; dashed: with the heat capacity it has at 0 °C. At −15 °C, 19.1 per cent freezes at once; at −20 °C, 25.7 per cent; at −38 °C, the coldest liquid water reaches before it freezes by itself, 51 per cent. The rest stays liquid at 0 °C. Water would have to be cooled about 80 degrees for all of it to freeze at once, and no liquid water survives that long.

    The supercooled water that only partly freezes

    Water can be cooled well below 0 °C and stay liquid, and when a crystal finally starts, the whole bottle seems to turn to ice at once. It does not. Freezing releases heat, and with nowhere for that heat to go in the instant of freezing, it warms everything back to 0 °C — at which point freezing must stop. Water cooled to −15 °C freezes about a fifth at once; to −38 °C, the coldest liquid water gets, about half. The rest has to wait for the surroundings to take the heat away, and a hand warmer is the same arithmetic run above body temperature.

    part 13 · thermodynamics
  14. The boiling point in a column of water, and the depth heating reaches it first. The temperature at which water boils against depth in a geyser's conduit 2240 m above sea level, where the air's pressure is 77.6 kPa (solid): 92.7 °C at the surface, 103.6 °C at 4 m, 115.5 °C at 10 m and 131.8 °C at 22 m — rising steeply near the top and more gently below, because each extra metre adds the same pressure to water whose boiling point responds less as it gets hotter. Dashed: the water as it heats from beneath, cooled to 80 °C at the top by the pool and below that warming by only 0.8 °C per metre, mixed by convection; 6 °C and 3 °C short of the curve at 4 m, and then touching it. It touches at 4 m, not at the bottom: there the water is still 13.7 °C below boiling.

    The column that boils from the middle

    Water at the bottom of a geyser's tube is hotter than water anywhere else in it, and it is not the water that boils first. The weight of the column raises the boiling point with depth faster than the heat from below raises the temperature, so the column reaches its boiling curve partway down, under a cooler surface layer. A little boiling there lifts the water above. Everything beneath is then at a lower pressure than the one it was heated under, so it is superheated and flashes, and the eruption feeds itself: past about fourteen centimetres of water thrown out, each slug of steam makes more room than it was given.

    part 14 · thermodynamics
  15. The wait after an eruption, against the eruption. For 400 simulated eruptions of the model geyser: the interval to the next eruption against the duration of the eruption just finished (dots), and the straight line through them, interval = 33.8 min + 10.5 × duration, with a correlation of 0.94. The eruptions fall in two clusters, short ones of about 2.2 minutes followed by waits near an hour and long ones of about 5.0 minutes followed by waits near an hour and a half, and the line runs through both. Its slope is the ratio of the discharge rate to the refill rate, 10.7: each minute of eruption throws out water that takes 10.7 minutes to replace. Plotted against the eruption that follows instead, the same intervals show a correlation of 0.05 — nothing. The interval is set by the past and tells nothing about the future.

    The geyser that remembers one eruption

    Old Faithful is famous for being predictable, and its predictability has an odd shape. Its eruptions come in two kinds, short and long, and the wait after each is short or long to match — about an hour after a short eruption, about an hour and a half after a long one. So the next eruption can be forecast from the last, to within about ten minutes, and from nothing else. The reason is a bookkeeping of water. An eruption throws out a volume of water that the geyser must take back from below before it can erupt again, and a long eruption throws out more. The geyser carries a memory of exactly one eruption: how much it has to refill.

    part 15 · thermodynamics
  16. The pipe that out-conducts any solid. The temperature difference needed to carry 30 W along a rod 300 mm long and 6 mm across, on a logarithmic scale: for solid aluminium 1343 K, for copper 796 K, for diamond, the best conductor of heat at room temperature, 159 K; and for a water heat pipe of the same size 0.8 K, almost all of it across the thin wet wicks where the heat goes in and comes out. Solid metal could not do it at all: the hot end of the copper rod would have to be hundreds of degrees above the cold. The heat pipe carries the heat as latent heat in moving vapour, and the vapour needs almost no temperature difference to flow. As an effective conductivity that is 1000 times copper's — which is why every laptop and many satellites move their heat in pipes rather than through metal.

    The pipe that carries heat as vapour

    A copper rod six millimetres across and thirty centimetres long, asked to carry thirty watts from a laptop's processor to its fan, would need its hot end eight hundred degrees above its cold end. The flattened copper tube that actually does the job manages it with less than a degree. It is a heat pipe: sealed, emptied of air, and holding a few drops of water and their vapour. The water boils at the hot end, the vapour rushes to the cold end and condenses, and a wick of sintered copper powder drags the liquid back by capillarity. The heat goes as latent heat, and vapour needs almost no temperature difference to flow — which makes the pipe a thousand times better than copper, as long as its wick can keep up.

    part 16 · thermodynamics

All series