The phase boundary of water, from one equation
At its defaults it draws 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.
phase-boundary is one function in lib/figures/thermal.js —
cycles, distributions and the statistics underneath them. Everything below came out
of it during this build, at parameters taken from the essays rather than invented for this
page. A figure here is the figure a reader meets in an essay, and if the generator changes,
this page changes with it.
At its defaults
Drawn even though every essay passes options, because a default nothing exercises is a trap for the next essay to call this with none — which has happened here twice.
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.
The phase boundary of water, from one equation
The options are the ones A boiling point is a pressure, not a temperature passes. A branch drawn at its own defaults instead would be a picture no essay asked for and no assertion has been run against.
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.
Heating 1 kg of water from -20°C to 130°C
The options are the ones A boiling point is a pressure, not a temperature passes. A branch drawn at its own defaults instead would be a picture no essay asked for and no assertion has been run against.
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 phase diagram of water, integrated rather than traced
The options are the ones A boiling point is a pressure, not a temperature passes. A branch drawn at its own defaults instead would be a picture no essay asked for and no assertion has been run against.
Pressure against temperature for water on a logarithmic pressure axis. The vaporisation and sublimation curves are integrated from Clausius–Clapeyron with the latent heat held constant, and the fusion curve leans backwards with the slope Clapeyron gives, -13.5 megapascals per kelvin, because water expands when it freezes. Holding the latent heat constant puts the boiling point at one atmosphere at 382.3 kelvin against a measured 373.15, which is 2.5 per cent high.
Vapour pressure for 3 substances, on the axes that straighten it
The options are the ones A boiling point is a pressure, not a temperature passes. A branch drawn at its own defaults instead would be a picture no essay asked for and no assertion has been run against.
The logarithm of vapour pressure against a thousand over the temperature, for water, carbon dioxide, nitrogen. On these axes Clausius–Clapeyron with a constant latent heat is exactly a straight line of slope −L/R, so the slope is not a summary of the curve — it is the latent heat, in different units. Each line here is drawn from its substance's triple point to its critical point, and the slope of the drawn polyline is then fitted by least squares and turned back into a latent heat: water went in at 40.65 kJ/mol and comes back at 40.65, 1 part per million out over 41 vertices; carbon dioxide went in at 15.33 kJ/mol and comes back at 15.33, 10 parts per million out over 41 vertices; nitrogen went in at 5.58 kJ/mol and comes back at 5.58, 4 parts per million out over 41 vertices. Each line covers only its own substance's liquid range — water from 273 to 647 kelvin, carbon dioxide from 217 to 304 kelvin, nitrogen from 63 to 126 kelvin — and the steeper the line, the more heat it costs to leave. Where each line ends, the constant-latent-heat model is visibly done — water's reaches 26.0 MPa at its critical temperature against a measured 22.1 MPa; carbon dioxide's reaches 6.00 MPa at its critical temperature against a measured 7.38 MPa; nitrogen's reaches 2.90 MPa at its critical temperature against a measured 3.40 MPa.
The phase boundary of carbon dioxide, from one equation
The options are the ones A boiling point is a pressure, not a temperature passes. A branch drawn at its own defaults instead would be a picture no essay asked for and no assertion has been run against.
Pressure against temperature for carbon dioxide on a logarithmic pressure axis spanning 3.2 decades. The vaporisation curve is integrated from Clausius–Clapeyron between the triple point at 216.592 kelvin and 518 kPa and the critical point at 304.128 kelvin, with a single latent heat of 16.58 kilojoules per mole — the value the two published points on the curve imply. The measured latent heat at the triple point is 15.33, and the fitted value sits 8.2 per cent above it, which is the ideal-gas assumption showing: the vapour at these pressures is denser than an ideal gas, and an apparent latent heat fitted with the ideal law absorbs the difference. The sublimation curve below the triple point is not measured but predicted, from the two latent heats adding where all three boundaries meet: 24.3 kilojoules per mole, which reaches 101 kPa at 193.3 kelvin against a measured 194.686. The melting curve is drawn at the slope Clapeyron gives it, 4.5 megapascals per kelvin, which is a volume ratio and nothing else: carbon dioxide's solid is 1562 against 1178 kilograms per cubic metre for its liquid, so melting expands it and the line leans forwards. Across the whole 3.2 decades of this axis that line moves 5.0 kelvin. At 1 atmosphere the boundary is crossed at 193.3 kelvin, where carbon dioxide sublimes without ever being a liquid. The one place the curve fails is its top end: a constant latent heat reaches 7.33 MPa at the critical temperature where the measured critical pressure is 7.38 MPa, 0.6 per cent low, because the latent heat falls to zero at the critical point and this curve does not know that.
What checks it
physicscheck asserts something about phase-boundary that
could fail — it draws it and measures the result against a value reached some other
way.
Across the library: 100 interrogated, 2 exercised only, 1 untouched, of 103. Read out of the gate's source by the gate's own two patterns — and the gate's last claim fails the build if that read disagrees with what it was handed while running.
Where it is called
Changing this generator changes every figure on this list. That is what makes the list worth publishing rather than keeping in a check script.
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.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe degree a spoonful of solute buys
Dissolve anything in water and the water freezes lower and boils higher. The two shifts come from one cause — the solute lowers the liquid water's chemical potential, so the liquid wins against ice and against vapour over a wider range — but they are not the same size. For every mole of particles per kilogram the freezing point falls 1.86 degrees and the boiling point rises only 0.51, three and a half times less, and the reason is in the entropies: ice and water are so alike that a small push moves their crossing a long way. The same arithmetic says salting pasta water does nothing a cook could notice, weighed molecules for a century of chemistry, and in 1887 showed that salts in water are made of ions.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe frost that lifts by drinking
Frozen ground rises in winter, sometimes by tens of centimetres, and the usual explanation — water expands by nine per cent when it freezes — is wrong: soil soaked in benzene, which shrinks as it freezes, heaves too. The lift comes from layers of clear ice that grow by pulling liquid water up through the soil from below. Ice and water touching each other need not be at the same pressure, and when the water is free to flow, ice a degree below its melting point can push with 1.12 megapascals while it drinks — twelve times less than freezing water in a sealed pipe, and enough to lift a house at a tenth of a degree.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe ice that grows by stealing from the droplets
Most clouds colder than freezing are not made of ice. They are made of droplets of liquid water, some tens of degrees below their freezing point, waiting for something to start them freezing. When a few ice crystals do appear among them, the crystals grow and the droplets shrink, without touching, because supercooled water has a higher chemical potential than ice and so a higher vapour pressure: air balanced with the droplets is ten per cent supersaturated, to an ice crystal, at minus ten degrees. A few crystals among a hundred thousand droplets each take everything, grow heavy enough to fall, and that is how most of the rain outside the tropics begins — as snow.
ThermodynamicsThe melting curve that has to arrive flat
The slope of every line on which two phases coexist is their difference in entropy divided by their difference in volume. The third law says that entropy differences vanish at absolute zero, so every such line — melting, boiling, a superconductor's critical field — must reach the bottom of the temperature scale lying flat. Helium-3 reaches it in the strangest way available: below a third of a kelvin its solid is more disordered than its liquid, the melting curve runs backwards, and squeezing the liquid into solid absorbs heat. That backwards curve was the refrigerator in which superfluid helium-3 was found, and it is now the definition of temperature below one kelvin.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe 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.
ThermodynamicsThe salt that dissolves in the air's own water
Leave a dish of salt in a bathroom and it does not just clump; on a humid enough day it turns into a puddle, though no water was poured on it. Above 75 per cent humidity, common salt pulls water out of the air until it has dissolved itself. The number is not a property of salt's attraction for water in any vague sense. It is the vapour pressure of a saturated salt solution, read as a fraction of pure water's: wherever the air holds more water than that, the solution is the state with the lower chemical potential. Bring the humidity back down, and the puddle does not turn back into salt until the air is far drier — about 45 per cent.
ThermodynamicsThe 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.
ThermodynamicsWhy 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.