Illustrated Physics
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Equipartition — the series

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

    part 1 · thermodynamics
  2. 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.

    part 2 · thermodynamics
  3. 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.

    part 3 · thermodynamics
  4. The energy that goes and comes back. A chain of 32 masses with springs a few per cent nonlinear, started with all its energy in its longest mode, with the energy of the first five modes followed against time in units of that mode's own period. The first mode gives up most of what it has — down to 9 per cent by 104 periods — and the energy appears in the second, third and fourth. Then it comes back: at 154 periods the first mode holds 98 per cent of the total again. Equipartition would put an equal share in every one of the thirty-two modes and leave it there. What happens instead is that a handful of modes trade with each other and return almost exactly to where they began, and go on doing so. The total energy is checked against its starting value throughout and holds to 9.2e-5, so nothing here is the integrator losing track of what it was given.

    The energy that refuses to be shared

    Put all the energy of a chain of masses into its longest mode and add a few per cent of nonlinearity, and equipartition says it should spread out among all thirty-two modes and stay there. It does not. It leaks into three or four neighbours and then comes back — almost exactly — and goes on doing so, and the calculation that found this was expected to be a demonstration that it would not happen.

    part 4 · thermodynamics
  5. The condition three modes never quite satisfy. By how much three modes of a thirty-two mass chain fail to be in resonance — the sum of two mode frequencies minus the frequency of their sum, on a logarithmic scale, against the second of the two modes for four choices of the first. The leading nonlinear term couples modes in threes and the exchange accumulates only where this quantity is zero. It never is: the chain's dispersion is a sine, a sine is concave, and the sum of two of its values always exceeds the value at their sum. The smallest mismatch anywhere on the chain is at the two lowest modes and equals 2.156e-4 — which the scan finds and which is the cube of pi over four times the cube of one more than the mode count, checked here on chains from eight masses to two hundred and fifty-six. That closed form is the whole of why this is a finite-chain problem: the mismatch falls as the cube of the length, so a long enough chain is arbitrarily close to resonant and the continuum limit is exactly resonant, which is where the solitary waves come from.

    The condition three modes never meet

    Whether two modes of a chain can hand energy to a third is arithmetic on the dispersion relation, and for a chain of masses the answer is never: a sine is concave, so the sum of two frequencies always exceeds the frequency of their sum. The smallest shortfall anywhere on a chain of N masses is π³/4(N+1)³ — never zero, and never far from it — and a shortfall turns a transfer into a beat.

    part 5 · thermodynamics
  6. The modes of a wire, counted. Nyquist's argument of 1928, with its count performed. Two resistors joined by a lossless line are in equilibrium, and the line is a one-dimensional cavity whose standing waves are spaced c/2L apart in frequency. Each mode has an electric and a magnetic energy, both quadratic, so equipartition gives it kT — the same half a kT per quadratic term that a heat capacity counts. The upper points are how many modes fall in a band of a hundred and thirty-seven megahertz, for five line lengths, from 17 on a thirteen-metre line to 8,558 on one of six kilometres. The lower points are the power each end therefore receives, as a fraction of kTΔf, and they converge on one: a longer line has proportionally more modes and takes proportionally longer to deliver them, so the length cancels. The longest line lands within 0.005 per cent and the shortest is 4.5 per cent low, because thirteen metres holds only seventeen whole modes in the band and the remainder is a real granularity rather than an error. What is left in the limit is kTΔf — a noise power with no resistance in it at all, and none of the line's properties either.

    Half a kT in a piece of wire

    Count the quadratic terms in a molecule's energy and equipartition gives a heat capacity. Count them on a transmission line instead and the same theorem gives a resistor's noise voltage — 4kTRΔf, with nothing in it about what the resistor is made of. A fifty-ohm input at room temperature says 0.91 nanovolts in every root hertz, and no design removes it.

    part 6 · thermodynamics
  7. Twice the kinetic energy, and what it equals. Twice the time-averaged kinetic energy of a bound orbit, divided by its time-averaged potential energy, against the power with which that potential depends on separation. Each point is a measurement: an eccentric orbit integrated for more than a hundred radial periods, with the two averages accumulated along it, and the radius checked to vary by at least a fifth so that the orbit is not trivially circular. The line is the exponent itself, and the points miss it by at most 6.6e-4. Two cases carry everything. At n = 2, a harmonic well, the two energies are equal — which is the ordinary equipartition statement, half a kT to the kinetic term and half a kT to the potential one. At n = −1, which is gravity and the Coulomb force, twice the kinetic energy equals minus the potential energy, so the total energy of a bound system is minus its kinetic energy. Nothing about temperature entered, and nothing about equilibrium: the relation holds for one orbit averaged over time as well as for a crowd averaged over members.

    Weighing what cannot be put on a scale

    Summed over every coordinate of a bound system, equipartition stops being a statement about temperature and becomes a relation between two averages: twice the kinetic energy equals n times the potential energy for a potential going as the nth power. For gravity that fixes a bound system's total energy from how fast its parts move — so a Doppler shift and an angular size return a mass, and for the Coma cluster the mass they return is fifty times the mass that shines.

    part 7 · thermodynamics
  8. The same thermal motion, spread three ways. How the thermal jiggling of a spring-mounted mass is distributed over frequency, for quality factors 3, 30, 300, with frequency in units of the resonance and the spectrum in units that make the area under each curve its mean-square displacement. All three curves enclose exactly the same area, kT/k — 1.000, 1.000, 1.000 of it in the units drawn — because equipartition fixes the energy in the spring and not how fast it changes. What the damping chooses is where that motion goes: a high Q concentrates it in a peak 100 times taller than the low-Q one, and leaves the rest of the spectrum 100 times quieter at 10 times the resonance frequency.

    The noise a high Q moves out of the way

    Anything held by a spring at a temperature jiggles, and equipartition says exactly how much: the mean square of its displacement is kT divided by the spring's stiffness, whatever the spring is made of and however it is damped. That looks like a floor no measurement can go below. It is a floor on the total, and the total can be moved. An oscillator with little damping puts almost all of its thermal motion into a narrow peak at its own frequency and leaves every other frequency quiet — which is why the mirrors of gravitational-wave detectors hang from fibres of glass that ring for minutes.

    part 8 · thermodynamics
  9. A heat capacity that goes up and comes down. The heat capacity per system, in units of Boltzmann's constant, against temperature in units of the level spacing over k: for a system with two levels (red), Schottky's hump x²eˣ/(1 + eˣ)², x = Δ/kT, and for a harmonic oscillator with the same spacing (blue), which climbs to one k and stays there. Both are frozen out when kT is well below the gap. The oscillator then fills its unending stack of levels and reaches equipartition's value. The two-level system peaks at 0.439k when kT = 0.417Δ, and then, with both levels nearly equally occupied and nothing higher to go to, it stops absorbing heat: its capacity falls back towards zero as 1/T².

    The heat capacity that goes up and comes down

    Equipartition promises every way a system can move a fixed share of heat, and for a harmonic oscillator the promise is kept: once the temperature is high enough, it holds one k per oscillator and goes on holding it. A system with only two levels cannot keep it. It absorbs heat while its upper level is filling, then stops — the two levels equally full and nowhere higher to go — so its heat capacity rises to a peak and falls back to zero. The hump, named after Walter Schottky, is the signature of a degree of freedom with a ceiling, and the area under it counts how many states were there.

    part 9 · thermodynamics
  10. The period of a ball bouncing on a gas. The period of a 16 mm steel ball (16.8 g) oscillating in a vertical tube that fits it on top of a flask, against the flask's volume on a logarithmic axis, for helium, air and carbon dioxide at room temperature, if every compression is adiabatic: T = 2π√(mV/γPA²). On a 10 litre flask the ball swings with a period of 0.983 s on helium, 1.072 s on air and 1.117 s on carbon dioxide. The gas is the spring, and its stiffness is γ times the pressure: the gas whose molecules have fewest ways to store energy is the stiffest, because less of the work done in compressing it goes into motions that do not push on the walls.

    The ball that weighs how a gas stores heat

    Drop a steel ball into a glass tube that fits it closely, on top of a flask of gas, and it does not fall to the bottom. It bounces, up and down, on the gas trapped beneath it, with a period of about a second. The gas is a spring, and its stiffness is the pressure multiplied by a number that counts how many ways the gas's molecules can hold energy. So a stopwatch on a bouncing ball measures something that otherwise needs a calorimeter: whether the molecules can rotate, whether they can vibrate, and how far a vibration has woken up at the temperature of the room.

    part 10 · thermodynamics
  11. How a sphere of gas rings. The acoustic pressure against distance from the centre of a spherical cavity, for its three lowest radial modes, in which the gas breathes in and out in spherical shells: sin(zr/a)/(zr/a), with z = 4.4934, 7.7253, 10.9041 the roots of tan z = z that make the gas's motion vanish at the wall. Filled with argon at the triple point of water, 273.16 K, a sphere 62 mm in radius rings in these modes at 3551, 6104, 8616 Hz. Radial modes are the ones precision work uses: they have no motion along the wall, so the wall's roughness and the gas's viscosity there barely touch them, and their frequencies are set by the volume rather than the shape — a slightly imperfect sphere shifts them only at second order.

    The note that fixed the kelvin

    A sphere of argon, struck, rings at a pitch set by the speed of sound in it, and the speed of sound in argon contains only one quantity nobody could compute: the constant that converts a temperature into an energy. Argon's atoms can hold energy in exactly three ways, so its heat capacity is a count rather than a measurement, and its speed of sound is (5/3)kT/m with nothing left over. Ring the sphere at the temperature of melting ice, measure its size with radio waves in the same cavity, and Boltzmann's constant comes out to a part in a million. In 2019 that number stopped being measured and became the definition.

    part 11 · thermodynamics

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