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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=hν?
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?
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?
The result appears when you choose, say you have one in mind, or skip.
600.0 THz: each quantum carries 2.481 eV
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
Quantity
Value
Radiation energy E
9.056 nJ
Frequency ν
600.0 THz
Volume ratio V/V₀
0.5
Number of independent quanta, neff
2.2778 × 1010
Energy of each, hν
3.9756 × 10−19 J
Energy of each, hν
2.4814 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, 3kBT
0.77556 eV
Mean kinetic energy of a gas molecule, (3/2)kBT
0.38778 eV
Ratio of the two
2
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.
Boltzmann's principle ties entropy to probability: S − S0 = (R/N) ln W, where R/N, the gas constant divided by the number of molecules in a mole, is 1.381 × 10−23 J/K. Take n independent points moving about a box of volume v0. The chance that one of them is, at a given moment, in a part v of the box is v/v0. Because they move independently, the chance that all n are there together is the product, (v/v0)n. With 10 points and half the box, that is (1/2)10 = 1/1024. The entropy difference is then (R/N) ln[(v/v0)n] = (R/N) n ln(v/v0) = 1.381 × 10−23 × 10 × ln 0.5 = −9.57 × 10−23 J/K. Now the radiation. Section 4 gives S − S0 = (E/βν) ln(v/v0). Pull R/N out in front, E/βν = (R/N) × (N/R)(E/βν), and use the rule that a number times a logarithm is the logarithm of a power: S − S0 = (R/N) ln[(v/v0)(N/R)(E/βν)]. Set this beside the gas. The two have the same form if n = (N/R)(E/βν). Divide the energy by that count to find the energy of one part: E/n = Rβν/N. With today's constants Rβ/N is Planck's h, 6.626 × 10−34 J s, so each part carries hν = 6.626 × 10−34 × 6.00 × 1014 = 3.976 × 10−19 J, or 2.48 eV. The defaults hold E = 9.056 × 10−9 J, so n = 9.056 × 10−9/(3.976 × 10−19) = 2.28 × 1010. The radiation's coefficient E/βν is n times R/N, 2.28 × 1010 × 1.381 × 10−23 = 3.145 × 10−13 J/K, and halving the volume changes the entropy by 3.145 × 10−13 × ln 0.5 = −2.18 × 10−13 J/K. The probability that all that light is in one half at once is 1/2 raised to the power 2.28 × 1010, too small to write out. Last, the mean quantum. Over a whole Wien spectrum at temperature T, the energy per unit frequency is αν3e−βν/T, and the number of quanta per unit frequency is that divided by Rβν/N; the ratio of the two integrals is 3(R/N)T. At 3000 K that is 3 × 1.381 × 10−23 × 3000 = 1.243 × 10−19 J, or 0.776 eV, twice a gas molecule's (3/2)(R/N)T = 0.388 eV. A 600 THz quantum, at 2.48 eV, is 3.20 times the mean.
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). */exportfunctioneffectiveIndependentCount(E:number,nu:CyclicFrequency|number,setOrB?:ConstantSet|number,):Readonly<{status:"value";quantityId:"effectiveIndependentCount";unit:"";count:number;quantumEnergy:number;quantumEnergyEv:number;linearRepresentable:true;}>{letelementEnergy:number;if(typeofsetOrB==="number"){elementEnergy=setOrB*nu;}elseif(setOrB&&"entries"insetOrB){const{h}=quantumConstantsSI(setOrB,constantReaders);elementEnergy=h*nu;}else{// Modern SIconsth=6.62607015e-34;elementEnergy=h*nu;}constcount=E/elementEnergy;constquantumEnergyEv=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).
*/exportfunctionmeanQuantumEnergyWien(T:number,set:ConstantSet,options:{epsilonW?:number}={},):MeanQuantumEnergyWienResult{const{kB,h}=quantumConstantsSI(set,constantReaders);constmeanWienJoules=3*kB*T;constmeanWienEv=meanWienJoules/JOULES_PER_EV;constresonatorJoules=kB*T;constresonatorEv=resonatorJoules/JOULES_PER_EV;constmoleculeKineticEv=(1.5*resonatorJoules)/JOULES_PER_EV;constratioToMoleculeKinetic=meanWienEv/moleculeKineticEv;// Exactly 2// Ratio h * nu / (3 * k_B * T) at 600 THzconstnu600THz=6.0e14;constquantumEnergy600THz=h*nu600THz;constratioAt600THz=quantumEnergy600THz/meanWienJoules;constepsilonW=options.epsilonW??0.01;constwienBoundaryX=Math.log(1/epsilonW);// Shares below boundary x0constenergyShareBelowBoundary=gamma4(wienBoundaryX)/6;constcountShareBelowBoundary=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 E and frequency ν in the Wien regime, changing the enclosing volume from V0 to V changes the entropy by:
In §5, Einstein evaluated Boltzmann's principle S−S0=NRlnW for a system of n independent particles in a container, finding that the statistical probability of finding all n particles in a subvolume V is W=(V/V0)n, leading to:
To make the two equations directly comparable, Einstein rewrites the radiation entropy formula with Boltzmann's constant factor R/N outside the logarithm:
Comparing this with the gas probability law reveals that the statistical probability that all the monochromatic radiation energy E is found in subvolume V is:
Using the 1905 experimental values for the gas constant R=8,31⋅107 erg/K, Wien's constant β=4,866⋅10−11 K⋅s, and Avogadro's number N=6,17⋅1023, the product is:
NRβ=6,5537⋅10−27 erg⋅s
Einstein does not print this product. It is the constant Planck called h, 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 T by integrating over the full Wien spectrum:
This is exactly twice the average translational kinetic energy of a monoatomic gas molecule, ⟨Ekin⟩=23kBT.
The three logical roles
Derivation (Mathematical Identity): The radiation entropy volume law and the ideal gas entropy volume law agree identically for all volume ratios V/V0 if and only if n=NE/(Rβν)=E/(hν).
Heuristic Inference (Thermodynamic Analogy): In the Wien regime of low radiation density, monochromatic radiation behaves thermodynamically as though it consisted of neff mutually independent energy quanta hν.
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 hν (demonstrated in §7 for Stokes' rule, §8 for photoelectricity, and §9 for gas ionization).
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.