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Comoving entropy is the entropy density multiplied by the physical volume factor $a^3$ for a fixed comoving region in an expanding homogeneous universe. In adiabatic expansion it is conserved. Separate decoupled radiation sectors conserve their own comoving entropy, so disappearance of massive species can heat the still-equilibrated sector relative to a decoupled species.

For an adiabatically expanding homogeneous universe, the entropy density satisfiesso the entropy $s{a}^3$ in a comoving volume is constant.

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]

For a single-component equilibrium system with extensive internal energy $E(S,V,N)$, scaling its entropy, volume and particle number together gives $E(\lambda S,\lambda V,\lambda N)=\lambda E(S,V,N)$. The Euler theorem for homogeneous functions therefore gives $E=S{\partial }_{S}E+V{\partial }_{V}E+N{\partial }_{N}E$. The first law of thermodynamics identifies these derivatives as $T,-P,\mu$, respectively, proving $E=TS-PV+\mu N$. Dividing by volume yields the entropy density formula $s=(\rho +P-\mu n)/T$. This step fixes the entropy normalization rather than merely identifying its differential. Differentiating the Euler relation and subtracting $dE=TdS-PdV+\mu dN$ gives the Gibbs-Duhem equation $SdT-VdP+Nd\mu =0$. The argument requires extensivity; it is not an assumption about arbitrary nonadditive systems.

The baryon asymmetry is an excess of net baryon number over zero, conveniently measured by ${\eta }_B=(n_B-n_{\bar{B}})/n_{\gamma }$. Ordinary matter contains abundant baryons, whereas no comparable primordial antibaryon population is observed. Large nearby domains of matter and antimatter would produce radiation through particle-antiparticle annihilation at their boundaries. Antiparticles produced in energetic collisions are not evidence for a cosmological antimatter domain. The small nonzero baryon-to-photon ratio inferred from Big Bang nucleosynthesis is independently tested by baryon-density consistency between nucleosynthesis and the microwave background.

Starting with zero net baryon number, the Sakharov conditions require baryon-number violation, C and CP violation, and departure from thermal equilibrium. Conservation of baryon number would keep the initial value zero. C symmetry or CP symmetry would pair baryon production with equal antibaryon production; CP rate cancellation in baryogenesis explains why C violation alone does not suffice. In thermal equilibrium with zero imposed charge chemical potentials, CPT symmetry forbids the required net baryon number. An asymmetric rate in one reaction must not be mistaken for net production after all reverse reactions are included.

A simple example is heavy-boson decay baryogenesis. Take equally many heavy $X$ bosons and their antiparticles, with decay channelsThe symbols in parentheses are branching fractions. The two $X$ channels carry baryon numbers $2/3$ and $-1/3$, so both cannot conserve one assigned baryon number for $X$. Their mean baryon number is $r-1/3$, while the mean for $\bar{X}$ is $-\bar{r}+1/3$. Consequently,where $ϵ$ is the asymmetry per decaying particle. CP violation permits $r\ne \bar{r}$ without violating the equality of total decay widths required by CPT symmetry. Microscopically a direct CP asymmetry requires interference between decay amplitudes with both relative weak phases and absorptive phases; specifying complex couplings alone would not establish unequal partial decay widths.

For radiation domination, a sufficient decay condition is ${\Gamma }_X\lesssim H(T=M_X)=1.66\sqrt{g_{\ast }}{M}_X^2/m_P$. The heavy population can then survive as the equilibrium abundance drops, before decaying while inverse production is suppressed. Its actual abundance differs from its thermal equilibrium value. If subsequent baryon-number washout is negligible and cosmological entropy conservation holds, an initial total abundance $Y_X=(n_X+n_{\bar{X}})/s$ producesHere $s$ is the entropy density. Residual baryon-number washout multiplies this expression by an efficiency factor below one. The example realizes all three Sakharov conditions; it illustrates a mechanism, rather than identifying the actual cosmological source of the baryon asymmetry.

Work in natural units $k_B=\hslash =c=1$, initially neglecting helium and excited hydrogen states. The reaction $p+e^{-}\leftrightarrow H+\gamma$ is in chemical equilibrium when ${\mu }_p+{\mu }_e={\mu }_H$, since equilibrium photons have zero chemical potential. Substitution of the nonrelativistic Maxwell-Boltzmann distribution for the three densities givesFor ground-state hydrogen use $g_e=g_p=2$, $g_H=4$, and $m_H\simeq m_p$ in the translational prefactor. Writing its Hydrogen binding energy as $I$, this becomes $(m_{e}T/(2\pi ){)}^{3/2}{e}^{-I/T}$. Charge neutrality gives $n_p=n_e=X_e{n}_B$, while baryon conservation gives $n_H=(1-X_e)n_B$. Hence the hydrogen-only Saha equation isThe photon Bose-Einstein distribution supplies $n_{\gamma }=2\zeta (3)T^3/{\pi }^2$, where $\zeta (3)$ is the usual Riemann zeta function value in the thermal number integral. With baryon-to-photon ratio ${\eta }_{\gamma }=n_B/n_{\gamma }$, substitution yieldsThis reproduces the requested numerical coefficient, with the printed $\xi (3)$ interpreted as the thermal $\zeta (3)$ value. There is a normalization ambiguity in the PDF: it writes $\eta =n_B/s$ without defining $s$. To reproduce this coefficient, $s$ must mean photon number density. If $s$ has its usual entropy density meaning, the Saha baryon-abundance normalization instead givesThe two forms agree through ${\eta }_{\gamma }=[{\pi }^4{g}_{\ast s}/(45\zeta (3))]{\eta }_s$, with the entropy sector specified. A baryon-to-entropy ratio cannot simply be inserted into the photon-normalized expression.

As the universe cools, the Boltzmann factor favors neutral atoms and cosmological recombination sharply lowers $X_e$. For an order-one ionized fraction the photon-normalized equation gives the balanceup to an order-one ionization-fraction factor. The small baryon abundance means that there are very many photons per baryon: even a small high-energy photon tail can ionize most atoms. Thus the recombination temperature is far below the microscopic binding scale $I\simeq 13.6\mathrm{eV}$, typically a few tenths of an eV for the standard abundance, rather than of order $I$.

Photon decoupling is a related but distinct kinetic event. The Thomson scattering rate $n_e{\sigma }_T$ falls relative to $H$ as free electrons disappear, and photons begin free streaming. The precise last-scattering epoch depends on integrated optical depth, not only the local equality of rates. At still lower density the effective recombination rate per electron also drops below the expansion rate. Residual electron freeze-out leaves a small nonzero ionized fraction, larger than the vanishingly small equilibrium Saha prediction; radiative atomic bottlenecks mean the entire history cannot be obtained from equilibrium alone.

The temperature comparison in the last request needs an interpretation. If “reionisation temperature” means the microscopic thermal ionization scale, the large photon-to-baryon ratio explains why cosmological recombination requires $T\ll I$. If it means later cosmic reionization, there is no universal thermal threshold: stars or other sources supply ionizing photons and can reheat gas. The cosmological photon background is actually colder at that later epoch, because $T_{\gamma }\propto a^{-1}$. Its temperature therefore cannot literally be higher than the background temperature at recombination merely because hydrogen is reionized.

An adiabatic change of box size preserves the mode labels, whose momenta scale as $p\propto L^{-1}$. Since $V=L^3$, differentiation gives $dp/dV=-p/(3V)$. Occupation numbers are fixed under this slow mechanical change, so summing the changes in the individual particle energies givesComparison with $dE=-PdV$ at fixed entropy and particle number yieldsThe integration notation means summing over the original momentum-mode labels; it does not assume that the density in momentum space is unchanged after rescaling. In the ultrarelativistic limit $E(p)=cp$, so $p{E}^{\prime }(p)=E(p)$ and $P=E/(3V)=\rho c^2/3$.

Adiabatic radiation obeys $d(E{a}^3)=-Pd(a^3)$, giving energy density proportional to $a^{-4}$. Equilibrium photon energy density is proportional to $T^4$, so $T\propto a^{-1}$. Therefore the photon number in a comoving volume, $n_{\gamma }{a}^3\propto T^3{a}^3$, is constant. Its entropy is also constant: photon entropy density is $({ϵ}_{\gamma }+P)/T\propto T^3$. Photon number is not a microscopic conserved charge, but equilibrium processes maintaining the spectrum do not alter this comoving-number scaling in adiabatic expansion; entropy-producing processes would invalidate the assumptions.

For a relativistic species at zero chemical potential, $p=ϵ/3$ and $s=(ϵ+p)/T_i$, so its entropy density is proportional to $g_i{T}_i^3$. The Bose-Einstein distribution gives the bosonic normalization, while the fermionic thermal integral is $7/8$ of it. Species still in thermal equilibrium have $T_i=T$; freely streaming decoupled species can have another temperature and therefore contribute an extra factor $(T_i/T{)}^3$ when the total is expressed in units of $T^3$. This gives the two terms $N_{\ast }$ and $N_{SD}$ and their stated effective-degree-of-freedom weights.

After neutrino decoupling, the comoving entropy of the photon-electron-positron plasma is conserved separately from the neutrinos. Before electron-positron annihilation its effective entropy count is $2+(7/8)4=11/2$; afterwards it is $2$. Consequentlywhereas $a{T}_{\nu }$ stays equal to its pre-annihilation value. HenceThis is the instantaneous-decoupling, negligible residual-electron approximation used in the question. Heating of the still-coupled plasma, not cooling peculiar to neutrinos, creates the temperature difference.

The photon number density is obtained by integrating the Planck photon distribution. With $x=h\nu /(kT)$,The integral converges, since its integrand is of order $x$ near zero and decays exponentially at infinity. Hence $n=\alpha T^3$, with $\alpha$ independent of temperature.

For equilibrium radiation undergoing adiabatic expansion, the total entropy in a comoving volume is constant. Since the entropy density is $\beta T^3$, this means $\beta T^{3}V$ is constant. A comoving volume scales as the cube of the scale factor, soThis agrees with the cosmological redshift of each photon frequency. The conclusion uses entropy conservation during the expansion.

When the number-changing reaction is in chemical equilibrium, its chemical balance condition is $2{\mu }_{\varphi }=3{\mu }_{\varphi }$. Therefore zero chemical potential from number-changing reactions gives $\boxed{{\mu }_{\varphi }=0}$. Elastic scattering maintains kinetic equilibrium but imposes no independent condition on ${\mu }_{\varphi }$. The conclusion requires the number-changing rate to remain large compared with the Hubble parameter; merely listing an allowed reaction does not guarantee this after freeze-out.

Before thermal decoupling in cosmology, the sectors have a common temperature $T$. For relativistic species at that temperature their entropy densities aresoThese are the effective number of relativistic degrees of freedom for entropy. The paper's $g_{\ast }$ agrees with $g_{\ast s}$ for relativistic components at a common temperature. For one real scalar field, $g_{\ast s}^{\varphi }=1$. At temperatures where all Standard Model species are relativistic, both counts are constant, and so is $\xi$ before decoupling; thresholds can change this equilibrium ratio if they occur while the sectors remain coupled.

After decoupling, adiabatic isolation gives separately conserved visible and dark entropy: $s_{\mathrm{SM}}{a}^3$ and $s_{\varphi }{a}^3$ are individually constant. Thus $\boxed{\xi (T<T_d)=\xi (T_d)}$ even when either sector's entropy degrees of freedom change. Changes in particle content then alter their temperature ratio rather than the ratio of their comoving entropies. This assumes no late inter-sector transfer or entropy injection.

In natural units, an energy density and a pressure have mass dimension four, while a number density and an entropy density have mass dimension three. Since $m$ and $T$ each have mass dimension one,

For a relativistic species the supplied relation $P=ϵ/3$ makes its entropy density proportional to $T^3$. The fermion-to-boson thermal integral ratio gives the factor $7/8$ for each fermionic degree of freedom, so the electromagnetic plasma immediately before electron-positron annihilation in cosmology hasAfter annihilation only the two photon polarizations remain, so $g_{\ast s,\mathrm{after}}=2$.

The neutrinos have already undergone neutrino decoupling. They therefore receive none of the electron-positron entropy and cool as $T_{\nu }\propto a^{-1}$. In the still-coupled electromagnetic plasma, cosmological entropy conservation gives $g_{\ast s}{T}_{\gamma }^3{a}^3=\mathrm{constant}$. If $T_d$ and $a_d$ denote the common temperature and scale factor just before annihilation, then at a later scale factor $a$,Dividing gives the Cosmic neutrino background temperature ratio

The entropy density isFor the homogeneous cosmological plasma, adiabaticity gives the cosmological entropy conservation equationor equivalently $s{a}^3=\text{constant}$ in a comoving volume.

For a hydrogen-only gas with $g_e=g_p=2$, $g_H=4$ and $m_H\simeq m_p$, the Saha equation is $(1-X_e)/X_e^2=n_B[2\pi /(m_{e}T){]}^{3/2}{e}^{I/T}$. Defining ${\eta }_{\gamma }=n_B/n_{\gamma }$ and using $n_{\gamma }=2\zeta (3)T^3/{\pi }^2$ gives coefficient $2\zeta (3){\eta }_{\gamma }/{\pi }^2$ multiplying $(2\pi T/m_e{)}^{3/2}{e}^{I/T}$. If instead ${\eta }_s=n_B/s$, with entropy density $s=(2{\pi }^2/45)g_{\ast s}{T}^3$, that coefficient is $(2{\pi }^2/45)g_{\ast s}{\eta }_s$. The two expressions agree because $s/n_{\gamma }={\pi }^4{g}_{\ast s}/[45\zeta (3)]$. The reference entropy sector must be specified, especially after particles have decoupled.

After thermal decoupling in cosmology, two homogeneous sectors that evolve adiabatically without entropy injection satisfy $s_{\mathrm{SM}}{a}^3=\mathrm{constant}$ and $s_{\varphi }{a}^3=\mathrm{constant}$, hence their entropy density ratio $\xi$ is fixed. At a common relativistic temperature before decoupling, $\xi =g_{\ast s}^{\mathrm{SM}}/g_{\ast s}^{\varphi }$. Internal annihilations can change each sector's temperature and effective entropy degrees of freedom without changing its total comoving entropy.