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The entropy density of a photon gas is its entropy per physical volume, $s=S/V$. For homogeneous equilibrium vacuum radiation with two states of electromagnetic polarization and zero photon chemical potential,The first equality is the entropy density at zero chemical potential, obtained from the thermodynamic Euler relation $U=TS-pV+{\mu }_{\gamma }{N}_{\gamma }$ with internal energy $U=uV$. The second uses the photon gas equation of state, $u=a_R{T}^4$ and $p=u/3$. If an independently constrained photon number gives a nonzero chemical potential, the general entropy density is $(u+p-{\mu }_{\gamma }{n}_{\gamma })/T$ and $u=a_R{T}^4$ need not hold. This distinction explains why the absence of a conserved number matters for entropy as well as for the spectral shape. ^[ref]

A short first law of thermodynamics check, for neighboring equilibrium states with ${\mu }_{\gamma }=0$, isThe thermodynamic Euler relation fixes the additive normalization. Equivalently, this radiation entropy tends to zero with temperature at fixed volume; no contribution from the containing walls is included. Interpreting $TdS$ as transferred heat and $pdV$ as boundary work requires a reversible thermodynamic process. For a reversible thermodynamic process that is also an adiabatic process, there is no entropy production or entropy exchange, soAn irreversible adiabatic process can produce entropy even without heat exchange, so the word adiabatic alone is insufficient to infer $T^{3}V=\text{constant}$.

For an analytic example, expand an initially equilibrated photon gas reversibly from $V_0$ to $8V_0$, keeping only the same two photon states of electromagnetic polarization. Its temperature halves, its energy density becomes $u_0/16$, its entropy density of a photon gas becomes $s_0/8$, and its total entropy stays $S_0$. The internal energy halves rather than remaining fixed: the missing half leaves as work against radiation pressure,This is a stipulated reversible radiation model, not a report of a piston experiment. Maintaining a real cavity along this path requires controlling wall heat exchange and including the wall heat capacity in any actual apparatus balance.

For a computed scale at stipulated $T=2.725\mathrm{K}$, $s\simeq 2.04122\times 10^{-14}\mathrm{J}{\mathrm{K}}^{-1}{\mathrm{m}}^{-3}$. Combining this with the photon number density givesThis is the total equilibrium radiation entropy divided by its mean photon number, not a separately assigned entropy carried by each labeled particle. During the ideal expansion, $n_{\gamma }\propto T^3$ and $T^{3}V$ is fixed, so the mean number $N_{\gamma }=n_{\gamma }V$ also stays constant. This follows from the path; it was not imposed as the independent number constraint used to establish chemical potential.

The beautiful connection is that expansion lowers each typical photon energy and dilutes the radiation in just the proportions needed to retain its equilibrium spectral shape and total entropy. For the cosmic microwave background, homogeneous expansion of the universe has physical volume proportional to the cube of the scale factor; fixed-species cosmological entropy conservation therefore gives $T\propto a^{-1}$. This describes preservation of an already established Planck photon distribution and connects the FIRAS spectral observation in photon gas to an entropy prediction; FIRAS did not perform a direct entropy measurement. When other equilibrated species disappear and transfer energy into radiation, use the effective number of relativistic entropy degrees of freedom, $g_{\ast s}$: the conserved quantity for the combined sector is $g_{\ast s}{T}^{3}V$, under the corresponding equilibrium and no-entropy production assumptions. A changing species population, separate decoupled sectors or entropy production requires an appropriate entropy balance rather than the pure photon gas formula. ^[ref]

Write the photon energy density as $ϵ=a_R{T}^4$, where $a_R=4\sigma /c$ by the Stefan–Boltzmann law. The photon gas has pressure $P=ϵ/3$ and zero photon chemical potential. The first law of thermodynamics therefore givesDividing by $T$ and integrating gives the entropy density of a photon gas:The integration constant is fixed to zero at zero temperature, consistently with the third law of thermodynamics.

The inequality $\Gamma \gg H$ says interactions act much faster than the expansion time, maintaining local thermal equilibrium. For adiabatic reversible expansion with no additional source of entropy, cosmological entropy conservation fixes the entropy in a comoving volume. Since that volume scales as $a^3$, and the relativistic degrees of freedom are fixed here, $T^3{a}^3$ is constant. ThusDuring radiation domination, the Friedmann equation gives $H^2\propto \rho \propto T^4$, and hence $\boxed{H\propto T^2}$. Fast interactions alone would not exclude an additional entropy-producing process; changing relativistic species likewise changes the simple temperature scaling.

A photon gas is a collection of photons described statistically as radiation. Here the equilibrium model is homogeneous, isotropic electromagnetic radiation in vacuum at temperature $T>0$: each photon has energy $E=c|\mathbf{p}|=h\nu$, with momentum $\mathbf{p}$ and frequency $\nu$, and there are two independent transverse states of electromagnetic polarization. An absorbing cavity with walls at a common temperature provides a way to establish this thermal equilibrium. The bulk formulas assume cavity dimensions much larger than the typical wavelength $hc/(k_{B}T)$, so the electromagnetic mode density in a box can replace individual cavity modes by a continuum. ^[ref]

The crucial constraint is whether photon emission and photon absorption, or other number-changing processes, can equilibrate the photon population. When they can, photon number is not an independently conserved quantity and the equilibrium photon chemical potential is ${\mu }_{\gamma }=0$. For each polarization and frequency, the mean occupation number then follows the Bose-Einstein distribution:If number-changing processes are ineffective but number-conserving interactions redistribute energy, a constrained Bose-Einstein distribution can instead have $f=[\exp ((h\nu -{\mu }_{\gamma })/(k_{B}T))-1{]}^{-1}$ with chemical potential ${\mu }_{\gamma }\le 0$ fixed by the number constraint. Thus thermal equilibrium with respect to energy exchange alone does not establish ${\mu }_{\gamma }=0$. The zero value can also persist in an already prepared Planck photon distribution during suitable subsequent evolution; continual photon emission is not required to preserve it. ^[ref]

Combining $f$ with the two-polarization density of states, $g_{\nu }/V=8\pi {\nu }^2/c^3$, gives the Planck photon distribution and the spectral photon energy density:Here $B_{\nu }$ is the spectral radiance in Planck's law; $u_{\nu }$ is stored energy density per unit frequency, not outgoing power per area. Their different units are connected by the full-sphere solid angle and the speed of light $c$. The Boltzmann constant is $k_B$, and $h$ is the Planck constant. ^[ref]

The equilibrium equation of state is particularly simple:The radiation constant $a_R$ is the same constant called $a_{\mathrm{rad}}$ in black-body radiation; $\sigma$ is the Stefan-Boltzmann constant. An outline of the energy density calculation substitutes $x=h\nu /(k_{B}T)$ and uses ${\int }_0^{\infty }{x}^3/(e^x-1)dx={\pi }^4/15$. The radiation pressure follows because the angular average of the squared directional component of photon momentum is $1/3$ for isotropy; the thermodynamic derivation of blackbody radiation pressure supplies an independent route. These formulas describe the radiation contribution, not the cavity walls. The isotropic massless relation $p=u/3$ survives a different isotropic spectrum, whereas the coefficient in $u=a_R{T}^4$ requires the zero-chemical potential Planck photon distribution.

For a computed example with stipulated $T=2.725\mathrm{K}$, the photon energy density is $u\simeq 4.17174\times 10^{-14}\mathrm{J}{\mathrm{m}}^{-3}$ and the radiation pressure is $p\simeq 1.39058\times 10^{-14}\mathrm{Pa}$. The photon number density in the International System of Units isHere $\zeta$ is the Riemann zeta function. The mean photon energy differs from the energy at the peak of a spectral curve: counting photons and weighting them by energy emphasize different frequencies. The calculations use the exact International System of Units values of the Planck constant, Boltzmann constant and speed of light. ^[ref]

A motivating observation is the cosmic microwave background spectrum measured by the Far Infrared Absolute Spectrophotometer (FIRAS) aboard COBE. Its apparatus used a polarizing Michelson interferometer, with one input viewing a roughly seven-degree sky patch and the other an internal blackbody. Scanning mirrors changed the optical path length difference; heat-sensitive detectors recorded the varying power, and Fourier transform spectroscopy recovered the spectral difference. Operation outside the terrestrial atmosphere removed atmospheric emission and absorption, while shielding and cooling the optics in a helium cryostat suppressed the instrument's own radiation. ^[ref]

Absolute calibration came from moving an external blackbody into the sky aperture, filling the same beam used for the sky. This was an iron-loaded epoxy absorber shaped as a re-entrant cone. Repeated reflections made it a close approximation to a blackbody, while thermometers supplied its temperature. Mather and colleagues explicitly evaluated reflections, temperature gradients, radiation leaking through the material and leakage around its edge. These are limits on how faithfully the calibrator realizes thermal equilibrium radiation, rather than details that can be eliminated merely by calling it black. ^[ref]

During sky observations the internal blackbody temperature was adjusted to nearly null the spectral difference, reducing gain and drift errors. Fixsen and colleagues' 1996 analysis used calibrated spectra over wavenumbers $2$ to $21\mathrm{c}{\mathrm{m}}^{-1}$, about $60$ to $630\mathrm{GHz}$. They separated the sky's spatially uniform component, its dipole and Galactic emission, and varied sky cuts and foreground templates as controls. The resulting cosmic microwave background spectrum agreed with a single Planck function, with reported RMS deviations below 50 parts per million of its peak brightness. This is a residual statistic over the analyzed spectrum, not a pointwise relative error bound at every frequency. ^[ref]

The observation motivates using a photon gas as a physical model rather than merely a formal counting exercise. Its interpretation has a clear boundary: agreement with Planck's law constrains departures from an equilibrium spectral shape within the calibrated band and foreground assumptions; it does not directly measure radiation pressure or entropy density of a photon gas. Nor does it establish that today's cosmic microwave background is continually re-equilibrating with matter. A previously thermal spectrum can retain its Planck function shape as expansion of the universe lowers every photon frequency in the same proportion. The usefulness of the model is that one measured spectral temperature, together with its equilibrium assumptions, predicts energy density, radiation pressure, photon number density and entropy density of a photon gas consistently.