Illustrated Physics
physics, drawn
Concept

Heat capacity — where it appears

The energy a substance takes to warm by one degree, which counts the ways its molecules can hold energy at the temperature in question. Modes whose quantum of energy exceeds kT are frozen out and contribute nothing, which is why the value rises in steps as a substance is heated.

Named by 12 essays across 4 fields — each of them below, with the objects they name alongside it.

The staircase equipartition cannot climb. The heat capacity of hydrogen at constant volume, in units of R, against temperature on a logarithmic axis. The three translational directions contribute 3/2 at every temperature. The two rotations switch on near 85.4 K — the temperature at which kT matches the first rotational step — taking the total to 5/2, computed here by summing the rigid rotor's partition function over two hundred levels rather than by assuming the plateau. The vibration switches on near 6332 K, taking it to 7/2. At 50 K the value is 2.469; at 300 K the value is 2.502; at 5000 K the value is 3.376. Classical equipartition predicts 7/2 at every temperature, including at four kelvin, and the size of the steps is set by ħ — which is how a heat capacity measures a quantum constant.

Half a kT for every way of moving

A heat capacity ought to be a count. Every quadratic term in a system's energy carries half a kT of it, so warming a gas is a matter of enumerating the ways its molecules can move — and the fact that the count comes out wrong for hydrogen is how a thermometer measured Planck's constant.

thermodynamics · Equipartition Newton's answer, Laplace's, and the measurement. The speed of sound in 4 gases at 273.15 K. The short bar is Newton's √(RT/M), which assumes the compressions stay at one temperature; the long one is the same multiplied by √γ, which is what they come to if no heat crosses between a compression and the rarefaction beside it; the upright mark is the measured value. Newton's is 15.5% low for air, 22.5% low for helium, 22.5% low for argon, 12.0% low for carbon dioxide, and the corrected one is right to 0.05% for every gas here. Turning it round: γ read off each pair of bars is 1.400 for air, 1.665 for helium, 1.666 for argon, 1.290 for carbon dioxide, which is 1 + 2/f with f = 5.0, 3.0, 3.0, 6.9 ways of holding energy — three for the monatomic gases, five for the diatomic ones, and nearly seven for carbon dioxide, whose bending modes have begun to take a share at this temperature and its stretch has not. A speed measured with a stopwatch counts the ways a molecule can move.

The correction that took a century

Newton derived the speed of sound in 1687 and got 290 metres a second against a measured 340. The arithmetic was right; the assumption was not. Heat cannot cross a wavelength in a period, so the compressions are adiabatic — and the factor that repairs the answer turns out to be a count of the ways a molecule can move.

waves · Wave motion 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 How much of copper's electron sea a temperature can reach. The probability that a state of a given energy is occupied, in copper, at 4 temperatures, with energy measured in units of the Fermi energy — 7.04 eV here. At absolute zero the curve is a step: every state below the ceiling is full and every state above it is empty. Raising the temperature rounds the step, and rounds it over a range of about kT, which is the whole point — at room temperature kT is 0.0259 eV against a ceiling of 7.04 eV, so the rounding is 1.6 per cent of the way down the sea and everything deeper is untouched. An electron in the deep is not held there by a force; it simply has nowhere to go, because every state it could be promoted to is occupied. at 0 K the step is spread over 0.00 per cent of E_F, at 300 K the step is spread over 1.61 per cent of E_F, at 3000 K the step is spread over 16.13 per cent of E_F, at 20000 K the step is spread over 107.52 per cent of E_F.

The pressure that is not a temperature

Copper's conduction electrons are at a temperature of eighty thousand kelvin, in a wire that is at room temperature. That is not a figure of speech, it is what the exclusion principle does to a mole of particles, and it explains the largest unexplained number in the theory of metals.

quantum · Exclusion The line that slopes the wrong way. Mean temperature against total energy, for a self-gravitating sphere at nine radii. The points fall on a straight line of negative slope: taking energy away makes the body hotter. The heat capacity read off the drawing is -4.10e+34 J/K against the -4.10e+34 J/K the theorem gives, and the sign is the whole content. The dashed line is an ordinary gas in a rigid box, whose temperature rises when energy is added, as everything one can put a thermometer in does.

The ball of gas that heats up as it cools

Take energy away from a self-gravitating cloud and its temperature rises. Its heat capacity is negative, which nothing else stable does, and the consequence is that a star radiating into cold space is not cooling down — it is running up, and its whole life is a slow fall it cannot stop.

astrophysics · Self-gravity What a coordinate is worth, by the shape of its energy. The mean energy stored in one coordinate, in units of kT, against the power with which that coordinate enters the energy. The curve is 1/n and the points are the same average obtained by integrating the Boltzmann weight numerically, agreeing to 3.3e-7 per cent at worst. an energy going as |x|^1 holds 1.0000 kT; an energy going as |x|^1.5 holds 0.6667 kT; an energy going as |x|^2 holds 0.5000 kT; an energy going as |x|^3 holds 0.3333 kT; an energy going as |x|^4 holds 0.2500 kT; an energy going as |x|^6 holds 0.1667 kT. The familiar half a kT is the case n = 2 and nothing more general than that: a coordinate whose energy is linear in it — the momentum of an ultrarelativistic particle, or a field with no restoring force but a constant tension — carries a whole kT, and one confined by a very steep wall carries almost nothing. Equipartition is a theorem about quadratic terms, and calling it a theorem about degrees of freedom is the substitution that makes it fail.

The share that is not half a kT

Equipartition is quoted as half a kT for every degree of freedom, and it is nothing of the kind. It is half a kT for every *quadratic* term. A coordinate whose energy is linear in it carries a whole kT, and a gas hot enough that its particles' energy is pc rather than p²/2m therefore holds twice what the counting says — which drops its ratio of specific heats to four thirds and puts a star on the edge of being able to hold itself up.

thermodynamics · Equipartition 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 Entropy that is still there at absolute zero, counted and measured. Four substances whose entropy does not go to zero when they are cooled as far as anybody can cool them, with the entropy counted from the arrangements they froze into beside the entropy measured by integrating their heat capacities. Ice is the famous one: every oxygen has four hydrogen bonds and the rule is that two hydrogens sit near it and two far, which leaves six of the sixteen placements legal, and Pauling's count of the whole crystal collapses to R ln(3/2) = 3.371 J per mole per kelvin against a measured 3.41 — an agreement to one per cent from an argument on one line. Carbon monoxide and nitrous oxide are the easy cases, molecules that can lie either way round in the lattice and have too little to gain by choosing. The worst of the four is off by 25 per cent, which is the honest state of this subject: the counts are crude, they ignore the correlations between neighbouring choices, and they still land within sight of a calorimeter. What the figure is really about is that the third law has an escape clause and the escape clause is measurable. A perfect crystal has one arrangement and zero entropy; a crystal that ran out of time while it had many has the logarithm of however many it stopped at, permanently.

The entropy that is still there at zero

The third law says a perfect crystal has no entropy at absolute zero. Ice has 3.41 joules per kelvin per mole left over, and the number can be recovered from one line of counting — two hydrogens near each oxygen and two far, six legal arrangements out of sixteen, R ln(3/2). The law has an escape clause and the escape clause is measurable.

thermodynamics · Third law A ratio in the exponent. The Boltzmann factor against the energy of a state measured in units of kT, with the logarithm up the axis so that the straight line is the whole content. Every kT of energy costs a factor of e, so 5, 12, 20 times kT are factors of 10^-2.2, 10^-5.2, 10^-8.7. At 295 K, kT is 25.4 meV, so a barrier of 0.4 eV is 15.7 kT and a factor of 1.5e-7. That is the sense in which a third of an electronvolt is not a small energy: it is small compared with a chemical bond and enormous compared with kT, and it is the second comparison that decides whether anything happens.

The temperature a molecule does not have

Temperature fixes a system's average energy and nothing more. The actual energy wanders, by an amount tied to the heat capacity, and the relative size of the wandering falls as one over the square root of the number of degrees of freedom — so a mole has a temperature and a molecule does not.

thermodynamics · Equipartition Colder the bigger it is. The Hawking temperature against mass, on logarithmic axes, with the microwave background drawn across it. The slope is minus one exactly, so a heavier hole is colder — a negative heat capacity, which is the fact everything else here follows from. The two lines cross at 4.50e+22 kg, about a hundredth of the Moon's mass. Anything heavier than that is colder than the sky it sits in and absorbs more than it emits, so it grows rather than evaporates. A stellar-mass hole is at 6.2e-8 kelvin and will not begin to lose mass until the background has cooled below that, which takes something like 10¹² years. Evaporation is not something happening now to any hole anybody has observed.

The hole that outlives everything and then does not

A black hole radiates at a temperature that rises as it shrinks, so losing energy makes it lose faster. The whole history follows from that one sign: a life proportional to the cube of the mass, nearly nothing happening for almost all of it, and an end that arrives in a second.

astrophysics · Horizons The entropy a substance keeps depends on how fast it was cooled. The entropy of a supercooled liquid in excess of its crystal's, against temperature, for a substance melting at 305 K with an entropy of fusion of 43 joules per kelvin per mole and a liquid heat capacity exceeding the crystal's by 62. The equilibrium curve — the one the liquid follows while it can still relax — falls steadily and would reach the crystal's entropy at 152.4 kelvin. It never gets there, because the liquid falls out of equilibrium first, at a temperature that depends on how long it is given: 0.01 s/K freezes at 196.1 K with 15.61 left, 1 s/K freezes at 188.1 K with 13.03 left, 100 s/K freezes at 182.1 K with 11.03 left. Ice's residual entropy is a count and does not move; a glass's is whatever it happened to have when it stopped being able to change, and that is a property of the experiment.

The entropy that depends on how fast it was cooled

Ice's residual entropy is a count, and it comes out the same whoever measures it. A glass's does not. A glass keeps whatever entropy it happened to have when its own relaxation time crossed the experiment's, so cooling ten times more slowly leaves less behind — and extrapolating the equilibrium liquid below that point takes its entropy under the crystal's at a finite temperature, which cannot happen and does not, for a reason that is still argued about.

thermodynamics · Third law 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.

EntropyEquipartitionTemperatureDegrees of freedomEfficiencyEquilibriumIrreversibilityKinetic theoryReversibilityThird lawAdiabatic processThe Boltzmann factor

All concepts