Light quanta · Section 6

The radiation entropy law matches the gas entropy law. The exponent identifies the light quantum.

Why does equating the volume dependence of Wien radiation entropy to Boltzmann's independent-particle entropy law suggest that monochromatic radiation behaves as independent energy quanta of magnitude Rβν/N=hνR\beta\nu / N = h\nu?

The move in §6

Matching the entropy laws to find the light quantum

Static worked example

Model note
  • Radiation energy (radiationEnergy), Frequency (frequency), Volume ratio (volumeRatio) and Independent point count (independentPointCount): Host calculation, by the site's own reference code. Computed in lq06.acceptedInputs.
  • Effective independent count (effectiveIndependentCount), Quantum energy (quantumEnergy), Energy of one quantum, hν (quantumEnergyEv), Mean quantum energy over a Wien spectrum (meanQuantumEnergyWien), Mean quantum energy over a Wien spectrum (meanQuantumEnergyWienEv), Mean kinetic energy of a gas molecule (moleculeMeanKineticEnergyEv), Ratio of the mean quantum energy to a molecule's mean kinetic energy (meanEnergyRatio) and hν at 600 THz over the mean quantum energy (ratioAt600THz): Host calculation, by the site's own reference code. Computed in radiation.quanta.
  • Radiation entropy (radiationEntropy) and Entropy-volume coefficient (entropyVolumeCoefficient): Host calculation, by the site's own reference code. Computed in radiation.entropy.
  • Gas: entropy change (gasEntropy) and Gas: coefficient of ln(V/V₀) (gasEntropyVolumeCoefficient): Host calculation, by the site's own reference code. Computed in radiation.configurations.
  • Whether the radiation and gas coefficients agree (correspondenceVerdict): Host calculation, by the site's own reference code. Computed in lq06.correspondence.
  • Computed from the settings last applied (settings revision 1, result 1).
  • Not modeled: Radiation outside the Wien regime; Mechanism of emission and absorption (reserved for §§7–9); Cavity wall dynamics and boundary interactions; Wave interference patterns inside the volume.

Predict before the numbers

The radiation's entropy is S − S₀ = (R/N) ln[(V/V₀)NE/(Rβν)], and a gas of n molecules has S − S₀ = (R/N) n ln(V/V₀). Which expression plays the part of n?

Three relations the model could have

Predict before the numbers

Over a Wien spectrum, how does the mean energy of a light quantum compare with a gas molecule's mean kinetic energy at the same temperature?

Three relations the model could have

The result appears when you choose, say you have one in mind, or skip.

Which expression plays the part of n, the number of things?

600.0 THz: each quantum carries 2.481 eV

Try
Experiment settings volume ratio, the comparison gas, temperature

Side-by-side entropy volume laws (§6, the move)

V/V₀ = 0.50

Wien monochromatic radiation (§4)

E = 9.056 nJ, ν = 600.0 THz

S − S₀ = (E/βν) · ln(V/V₀)

Written with Boltzmann’s constant, k = R/N:

= (R/N) · [ ? ] · ln(V/V₀)

Ideal gas / solute molecules (§5)

n = 10 independent particles

S − S₀ = (R/N) · ln W

Independent positions, W = (V/V₀)n:

= (R/N) · [ n ] · ln(V/V₀)

Which expression goes in the bracket? Choose one in the controls. Coefficients of ln(V/V₀) now: radiation 3.145 × 10−13 J/K, gas 1.381 × 10−22 J/K.

Wien spectrum mean quantum energy against a gas molecule’s kinetic energy (§6)

T = 3000 K

Integrating over a full Wien spectrum, the average energy of a light quantum is exactly twice the average translational kinetic energy of a gas molecule (at 600 THz, monochromatic h·ν is 3.20× this mean quantum energy):

Mean energy of a light quantum in a Wien spectrum, ⟨ε⟩ = 3kBT

0.7756 eV

Mean translational kinetic energy of a gas molecule, ⟨Ekin⟩ = (3/2)kBT

0.3878 eV

Ratio of the two: 2.0 : 1

The three logical roles of the match

1. Derivation (algebra)

The Wien radiation entropy and the Boltzmann gas entropy have the same form exactly when n = NE/(Rβν) = E/(hν).

2. Heuristic inference

Monochromatic radiation of low density, in the Wien regime, behaves thermodynamically as though it consisted of independent energy quanta of size hν.

3. Further hypothesis

Are the production of light (Stokes's rule, §7) and its transformation (the photoelectric effect, §8; ionization, §9) also exchanges in amounts of hν?

Values at these settings

QuantityValue
Radiation energy E9.056 nJ
Frequency ν600.0 THz
Volume ratio V/V₀0.5
Number of independent quanta, neff2.2778 × 1010
Energy of each, hν3.9756 × 10−19 J
Energy of each, hν2.4814 eV
Radiation: coefficient of ln(V/V₀)3.1448 × 10−13 J/K
Gas: coefficient of ln(V/V₀)1.3806 × 10−22 J/K
Radiation: entropy change−2.1798 × 10−13 J/K
Gas: entropy change−9.5699 × 10−23 J/K
Mean quantum energy over a Wien spectrum, 3kBT0.77556 eV
Mean kinetic energy of a gas molecule, (3/2)kBT0.38778 eV
Ratio of the two2

When faint light of one colour is squeezed into half the room, its entropy falls by the same rule as a gas of independent particles does. Matching the two rules says how many particles the light would have to contain, and so how much energy each one carries, an amount set by the colour of the light.

Section 4 found that radiation of energy E in a narrow band at frequency ν, where Wien's law holds, changes its entropy with volume as S − S0 = (E/βν) ln(v/v0). Section 5 used Boltzmann's principle, S − S0 = (R/N) ln W: for n independent moving points the probability that all of them are in a part v of the volume v0 is W = (v/v0)n, so S − S0 = (R/N) n ln(v/v0). Section 6 writes the radiation result in the same form, S − S0 = (R/N) ln[(v/v0)(N/R)(E/βν)], and reads off the probability that all the radiation energy is in v. The exponent plays the part of n: the energy behaves as if it consisted of n = NE/(Rβν) independent quanta, each of size Rβν/N, which is hν. At the defaults, 9.06 × 10−9 J at 600 THz, that is 2.28 × 1010 quanta of 2.48 eV. Halving the volume lowers the radiation's entropy by 2.18 × 10−13 J/K, as it would for a gas of that many points; the instrument's gas of 10 points loses 9.57 × 10−23 J/K. Einstein then compared the mean quantum of a whole Wien spectrum, 3(R/N)T, with a molecule's mean kinetic energy, (3/2)(R/N)T: at 3000 K, 0.776 eV against 0.388 eV, a factor of 2.

Modern qualifications

Einstein wrote lg for the natural logarithm and v for the volume, and he never wrote h: the quantum is Rβν/N, built from the values of R, N and β that Planck had used. With R = 8.31 × 107 erg per mole and kelvin, N = 6.17 × 1023 and β = 4.866 × 10−11 s K, Rβ/N comes to 6.55 × 10−27 erg s, about 1.1 percent below the modern h; the paper does not print the product. He stated the conclusion with its limits: monochromatic radiation of low density, within the range of Wien's formula, behaves thermodynamically as if it consisted of mutually independent quanta. Planck had introduced energy elements hν in 1900 for the resonators of his cavity, not for the radiation itself. The comparison of 3(R/N)T with (3/2)(R/N)T is Einstein's own, at the end of Section 6.

Show the code

The site’s own reference code for this law, in TypeScript. It computes the numbers above when the page runs it, and it is what the page uses wherever a FrankenSim result is not available.

effectiveIndependentCount · src/physics/reference/radiation/quanta.ts · this site’s source, as built · sha256:0d9da7e740ad17c4d05a650a48b86979a75de01a34c7f433d6861cf9b5abd0af

This function computes the listed outputs when it runs.

In words

The count paragraph 6 reads off the entropy comparison. Given an energy and a frequency it divides by the element energy and returns the count, that element energy in joules, and the same in electronvolts. The element energy arrives three ways: as a number, which is Einstein's printed R beta nu over N; from a declared constant set; or, with nothing passed, from the modern SI Planck constant.

Implementation

/** Effective independent particle count E / (h*nu) or E / (B*nu). */
export function effectiveIndependentCount(
  E: number,
  nu: CyclicFrequency | number,
  setOrB?: ConstantSet | number,
): Readonly<{
  status: "value";
  quantityId: "effectiveIndependentCount";
  unit: "";
  count: number;
  quantumEnergy: number;
  quantumEnergyEv: number;
  linearRepresentable: true;
}> {
  let elementEnergy: number;
  if (typeof setOrB === "number") {
    elementEnergy = setOrB * nu;
  } else if (setOrB && "entries" in setOrB) {
    const { h } = quantumConstantsSI(setOrB, constantReaders);
    elementEnergy = h * nu;
  } else {
    // Modern SI
    const h = 6.62607015e-34;
    elementEnergy = h * nu;
  }

  const count = E / elementEnergy;
  const quantumEnergyEv = elementEnergy / JOULES_PER_EV;

  return {
    status: "value",
    quantityId: "effectiveIndependentCount",
    unit: "",
    count,
    quantumEnergy: elementEnergy,
    quantumEnergyEv,
    linearRepresentable: true,
  };
}

The site’s own reference code for this law, in TypeScript. It computes the numbers above when the page runs it, and it is what the page uses wherever a FrankenSim result is not available.

meanQuantumEnergyWien · src/physics/reference/radiation/quanta.ts · this site’s source, as built · sha256:d3e624115b5f972b23acb0c8ef5d2170fb74a8749f1f5f5f1c4ca5e3fa23c92f

This function computes the listed outputs when it runs.

In words

It returns 3 k_B T in joules and electronvolts, beside the resonator energy k_B T and a molecule's 1.5 k_B T, and the ratio of the first to the last, which comes out at exactly 2. At 300 K that is 0.0776 electronvolts against 0.0388. It also returns the ratio of a 600 terahertz quantum's energy to this average, about 32, which says how far an optical quantum sits above the thermal average at room temperature.

Implementation

/**
 * Mean quantum energy over a full Wien spectrum: <epsilon> = 3 * k_B * T (paper 1 §6).
 * Distinct from meanResonatorEnergy (k_B * T) and quantumEnergy (h * nu).
 */
export function meanQuantumEnergyWien(
  T: number,
  set: ConstantSet,
  options: { epsilonW?: number } = {},
): MeanQuantumEnergyWienResult {
  const { kB, h } = quantumConstantsSI(set, constantReaders);

  const meanWienJoules = 3 * kB * T;
  const meanWienEv = meanWienJoules / JOULES_PER_EV;

  const resonatorJoules = kB * T;
  const resonatorEv = resonatorJoules / JOULES_PER_EV;

  const moleculeKineticEv = (1.5 * resonatorJoules) / JOULES_PER_EV;
  const ratioToMoleculeKinetic = meanWienEv / moleculeKineticEv; // Exactly 2

  // Ratio h * nu / (3 * k_B * T) at 600 THz
  const nu600THz = 6.0e14;
  const quantumEnergy600THz = h * nu600THz;
  const ratioAt600THz = quantumEnergy600THz / meanWienJoules;

  const epsilonW = options.epsilonW ?? 0.01;
  const wienBoundaryX = Math.log(1 / epsilonW);

  // Shares below boundary x0
  const energyShareBelowBoundary = gamma4(wienBoundaryX) / 6;
  const countShareBelowBoundary = gamma3(wienBoundaryX) / 2;

  return {
    status: "value",
    meanQuantumEnergyWien: meanWienJoules,
    meanQuantumEnergyWienEv: meanWienEv,
    meanResonatorEnergy: resonatorJoules,
    meanResonatorEnergyEv: resonatorEv,
    moleculeKineticEnergyEv: moleculeKineticEv,
    ratioToMoleculeKinetic,
    ratioAt600THz,
    integrationRange: "all-positive-frequencies",
    wienAdmittedBoundaryX: wienBoundaryX,
    energyShareBelowBoundary,
    countShareBelowBoundary,
    modelStatus: "stipulated-model-extrapolated-beyond-admitted-regime",
  };
}

What this model leaves out

  • Radiation outside the Wien regime
  • Mechanism of emission and absorption (reserved for §§7–9)
  • Cavity wall dynamics and boundary interactions
  • Wave interference patterns inside the volume
The rule this laboratory evaluates

From src/physics/reference/radiation/quanta.ts, the audited TypeScript reference evaluator.

// Paper 1, §6: matching the entropy coefficients
// Radiation entropy:     S - S_0 = (E / (beta * nu)) * ln(V / V_0)
// Boltzmann gas entropy: S - S_0 = (R / N) * n * ln(V / V_0)
//
// Equating the exponents in W = (V / V_0)^n:
// n_eff = (N / R) * (E / (beta * nu)) = E / (h * nu)
// Energy per quantum: epsilon = E / n_eff = (R * beta * nu) / N = h * nu
//
// Mean quantum energy over a Wien spectrum:
// <epsilon> = 3 * (R / N) * T = 3 * k_B * T, twice a molecule's 1.5 * k_B * T

The physical argument

The entropy volume laws placed side by side

In §4, Einstein showed that for monochromatic radiation of energy EE and frequency ν\nu in the Wien regime, changing the enclosing volume from V0V_0 to VV changes the entropy by:

S−S0=Eβνln⁡VV0S - S_0 = \frac{E}{\beta\nu}\ln\frac{V}{V_0}
Explain this equation

In §5, Einstein evaluated Boltzmann's principle S−S0=RNln⁡WS - S_0 = \frac{R}{N}\ln W for a system of nn independent particles in a container, finding that the statistical probability of finding all nn particles in a subvolume VV is W=(V/V0)nW = (V/V_0)^n, leading to:

S−S0=RN nln⁡VV0=kB nln⁡VV0S - S_0 = \frac{R}{N}\,n\ln\frac{V}{V_0} = k_B\,n\ln\frac{V}{V_0}
Explain this equation

The move: equating the functional forms

To make the two equations directly comparable, Einstein rewrites the radiation entropy formula with Boltzmann's constant factor R/NR/N outside the logarithm:

S−S0=RNln⁡[(VV0)NREβν]S - S_0 = \frac{R}{N}\ln\left[\left(\frac{V}{V_0}\right)^{\frac{N}{R}\frac{E}{\beta\nu}}\right]
Explain this equation

Comparing this with the gas probability law reveals that the statistical probability that all the monochromatic radiation energy EE is found in subvolume VV is:

W=(VV0)NREβνW = \left(\frac{V}{V_0}\right)^{\frac{N}{R}\frac{E}{\beta\nu}}
Explain this equation

The exponent neff=NERβν=Ehνn_{\text{eff}} = \frac{N E}{R\beta\nu} = \frac{E}{h\nu} plays precisely the role of the particle count nn.

Energy per element and historical constants

If a total energy EE is composed of neffn_{\text{eff}} independent quanta, each quantum carries an energy:

ϵ=Eneff=RβνN=hν\epsilon = \frac{E}{n_{\text{eff}}} = \frac{R\beta\nu}{N} = h\nu
Explain this equation

Using the 1905 experimental values for the gas constant R=8,31⋅107 erg/KR = 8{,}31\cdot 10^7\text{ erg/K}, Wien's constant β=4,866⋅10−11 K⋅s\beta = 4{,}866\cdot 10^{-11}\text{ K}\cdot\text{s}, and Avogadro's number N=6,17⋅1023N = 6{,}17\cdot 10^{23}, the product is:

RβN=6,5537⋅10−27 erg⋅s\frac{R\beta}{N} = 6{,}5537\cdot 10^{-27}\text{ erg}\cdot\text{s}

Einstein does not print this product. It is the constant Planck called hh, computed from the values Einstein takes from Planck, and it lies about 1.1% below the modern value, 6.626 × 10⁻²⁷ erg·s. So the energy of the packets found from the entropy of radiation alone is Planck's quantum of action, to that precision.

Mean quantum energy over a Wien spectrum

Einstein further calculated the average energy of light quanta in thermal radiation at temperature TT by integrating over the full Wien spectrum:

⟨ϵ⟩=∫0∞αν3e−βν/Tdν∫0∞NRβναν3e−βν/Tdν=3RNT=3kBT\begin{aligned}\langle \epsilon \rangle &= \frac{\int_0^\infty \alpha\nu^3 e^{-\beta\nu/T} d\nu}{\int_0^\infty \frac{N}{R\beta\nu}\alpha\nu^3 e^{-\beta\nu/T} d\nu} \\ &= 3\frac{R}{N}T \\ &= 3 k_B T\end{aligned}
Explain this equation

This is exactly twice the average translational kinetic energy of a monoatomic gas molecule, ⟨Ekin⟩=32kBT\langle E_{\text{kin}} \rangle = \frac{3}{2} k_B T.

The three logical roles

  1. Derivation (Mathematical Identity): The radiation entropy volume law and the ideal gas entropy volume law agree identically for all volume ratios V/V0V/V_0 if and only if n=NE/(Rβν)=E/(hν)n = N E / (R\beta\nu) = E / (h\nu).
  2. Heuristic Inference (Thermodynamic Analogy): In the Wien regime of low radiation density, monochromatic radiation behaves thermodynamically as though it consisted of neffn_{\text{eff}} mutually independent energy quanta hνh\nu.
  3. Further Physical Hypothesis (Emission and Absorption): This analogy suggests investigating whether the processes of emission and absorption of light also proceed by discrete quanta of size hνh\nu (demonstrated in §7 for Stokes' rule, §8 for photoelectricity, and §9 for gas ionization).

Before you draw a conclusion

A common wrong turn this instrument speaks to

  • The light-quantum paper is a paper about the photoelectric effect.

    The paper's argument is about the entropy of dilute radiation. The photoelectric effect is one of three applications that follow it, beside Stokes's rule for fluorescence and the ionization of gases.

    Read the full entry, with its sources

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