Illustrated Physics
physics, drawn
Concept

Statistical mechanics — where it appears

The derivation of thermodynamic behaviour from the counting of a system's microscopic states. It supplies both the equilibrium properties and the size of the fluctuations about them, which is what makes it a stronger theory than thermodynamics alone.

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

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 Runs that break the second law, and how often. The work done in a process repeated many times, and the same for the process run in reverse with its work reflected, for a free-energy change of 4 kT and a dissipation of 3 kT. The average work exceeds the free-energy change, which is the second law, and individual runs do not have to: the shaded tail is the fraction of runs that do less work than the free energy — trajectories in which the entropy of the universe went down — and it is 11.03% here. The two curves cross exactly at the free-energy change, whatever the dissipation, which is what makes an irreversible measurement able to report an equilibrium quantity.

The second law, with a probability attached

Entropy increases, on average. For a small system pulled quickly, individual runs go the other way — and how often is not a matter of taste but an exact number, fixed by a relation with no adjustable constant in it and no requirement that anything be near equilibrium.

thermodynamics · Entropy 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.

thermodynamics · Equipartition 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.

thermodynamics · Equipartition

Named alongside it

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

Degrees of freedomEquipartitionFluctuationsMeasurementTemperatureThermal equilibriumArrow of timeBlackbodyThe Boltzmann factorBrownian motionDark matterDetailed balance

All concepts