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A steady state does not by itself give every fluctuating observable an entropy production symmetry. If the dimensionless total entropy production ${\Sigma }_t$ has the same-law finite relation and a large deviation principle with rate function $I$ for ${\Sigma }_t/t$, then, on its common domain,The first expression denotes leading exponential scaling; the second follows by taking the scaled logarithm of the probability ratio. A finite-state, autonomous Markov process with time-even states, positive bidirectional rates and a positive stationary distribution supplies a standard setting for a finite total-entropy production relation. The stochastic system entropy is then bounded, so its endpoint contribution does not change the long-time rate function of bath entropy production. ^[ref]

Unbounded state spaces can have endpoint fluctuations on the scale relevant to a large deviation principle. Dropping system entropy, changing the measured observable to heat, or changing the reverse preparation therefore requires a fresh argument. The exact finite integral fluctuation theorem, a same-law finite relation, and an asymptotic rate function symmetry are distinct claims.

Two internally equilibrated systems are in thermal equilibrium if bringing them into contact that permits only heat exchange causes no net heat transfer. In ordinary nonrelativistic thermodynamics without appreciable gravitational temperature shifts, their thermodynamic temperatures are equal. Merely preventing heat transfer with insulation does not establish thermal equilibrium: two insulated bodies can have different temperatures. ^[ref]

A thermometer illustrates the definition. Its own temperature settles to the object's temperature after thermal contact, provided its effect on the object is negligible. The existing zeroth law of thermodynamics makes this comparison transitive: two objects separately in thermal equilibrium with the same thermometer are in thermal equilibrium with each other. This lets one calibrated scale compare different materials.

Equal temperatures do not imply equal internal energies or equal heat capacities. Nor does thermal equilibrium by itself imply mechanical equilibrium or chemical equilibrium; these require additional allowed exchanges. There is also a distinction between no net exchange in thermal equilibrium and a constant temperature maintained by equal incoming and outgoing heat. The latter can be a steady state with ongoing entropy production. Microscopic exchanges can continue at thermal equilibrium, but their opposing contributions balance on average.

Historically, OpenStax credits the name “zeroth law” to Ralph Fowler in the 1930s: the already numbered laws needed a logically earlier statement about thermal equilibrium. ^[ref]

The chosen steady-state model isHere $U$ is the terminal voltage drop along positive electric current through the module. Its Seebeck effect term opposes the cooling supply. The cold Peltier effect term removes heat; Joule heating and returning heat conduction reduce the available cooling. At zero electric current, $Q_c=Q_h=-K\Delta T$: the passive leak warms c and removes heat from h, consistent with the stated signs. Subtracting the two face equations cancels heat conduction and gives the electrical power, an independent conservation of energy check.

The factor one half is an ideal-model result, not a universal rule for every contact. To see its origin, let $x$ run from cold to hot along a uniform equivalent leg of length $L$, cross-sectional area $A$, electrical resistivity $\rho$ and thermal conductivity $\kappa$. With constant coefficients, insulated sides and no Thomson effect, steady conservation of energy givesThe Fourier's law heat current in the positive $x$ direction is $-\kappa A{T}^{\prime }$. At $x=0$ it equals $-K\Delta T-I^{2}R/2$, and at $x=L$ it equals $-K\Delta T+I^{2}R/2$, using $K=\kappa A/L$ and $R=\rho L/A$. Adding the local transported heat current $\alpha TI$ gives the two face equations. Summing equivalent legs preserves this accounting. Nonuniform material properties, side losses or asymmetric contact dissipation require a revised model.

For an original toy module, stipulate $\alpha =0.040V/K$, $R=2.0\Omega$, $K=0.40W/K$, $T_c=280\mathrm{K}$ and $T_h=300\mathrm{K}$. At $I=3.0\mathrm{A}$,The coefficient of performance is defined here only for refrigeration with $Q_c>0$ and $P_{\mathrm{in}}>0$. The hot-side assembly must remove $37.0\mathrm{W}$, not just the extracted $16.6\mathrm{W}$. These are stipulated calculations, not measurements or a commercial module specification.

At the same fixed face temperatures but $I=-3.0\mathrm{A}$, the same boundary definitions give $Q_c=-50.6\mathrm{W}$, $Q_h=-35.0\mathrm{W}$, $U=-5.2\mathrm{V}$ and $P_{\mathrm{in}}=15.6\mathrm{W}$. The formerly cold face is now heated; the formerly hot reservoir supplies $35.0\mathrm{W}$. Still $Q_h-Q_c=15.6\mathrm{W}$. Reversal changes the linear terms, while $I^{2}R$ and the leak at fixed temperatures remain unchanged. Holding the old labels fixed makes this check meaningful.

The corresponding steady entropy production of the module is the outgoing reservoir entropy minus the incoming reservoir entropy:The Peltier effect terms cancel because they carry the same entropy $\alpha I$ at each end. This cancellation explains the reversible coupling; it does not make finite-resistance operation reversible. In the toy example the two positive contributions are approximately $0.06214$ and $0.001905W/K$, giving ${\dot{S}}_{\mathrm{gen}}=0.06405W/K$ for either current direction. In cooling operation, combining this inequality with the energy balance gives the Carnot refrigerator limit $\mathrm{COP}\le T_c/(T_h-T_c)$, equal to $14$ for these reservoir temperatures. A coefficient of performance above one would describe transported heat per electrical work, not the creation of energy.

Take a closed system consisting of one mole of a classical monatomic gas, idealized as an ideal gas with constant heat capacity at constant volume $C_V=3nR/2$. Stipulate amount of substance $n=1\mathrm{mol}$ and molar gas constant $R=8.314\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}{\mathrm{K}}^{-1}$ for this calculation. Set initial temperature $T_0=300\mathrm{K}$ and volume $V_0=0.010{\mathrm{m}}^3$, and define $E_0=nR{T}_0=2.4942\mathrm{kJ}$ and $p_0=E_0/V_0=249.42\mathrm{kPa}$. The specified equilibrium endpoints areThus $B$ has volume $0.030{\mathrm{m}}^3$, temperature $600\mathrm{K}$ and pressure $166.28\mathrm{kPa}$. The fixed material inventory and ideal gas law make these complete endpoint specifications for this model. All numbers below are calculated values, rather than measurements of a particular gas.

Use a frictionless piston, ignore bulk mechanical energy changes, and allow only pressure-volume work. Each step is the limit of a reversible thermodynamic process: adjust loads by infinitesimal pressure differences, and supply heat through infinitesimal temperature differences. Heating with changing temperature requires a succession of matching thermal reservoirs; contact with a single hotter heat bath would give an irreversible finite difference. On a fixed-volume leg the piston is locked. These assumptions justify using the actual equilibrium path's pressure inAn endpoint chord is not the path; substituting a guessed straight line would compute a different thermodynamic process.^[ref]

The upper route heats at fixed volume from $A$ to $C=(V_0,2T_0,2p_0)$, then undergoes isothermal expansion at $2T_0$ to $B$. The lower route undergoes isothermal expansion at $T_0$ from $A$ to $D=(3V_0,T_0,p_0/3)$, then heats at fixed volume to $B$. The tuples use the same $(V,T,p)$ ordering as the endpoints. Vertical legs do zero expansion work, and the two curved legs have different pressures at every shared intermediate volume.

The internal energy of an ideal gas gives the same endpoint difference for both routes:On either fixed-volume heating leg, $W_{\mathrm{by}}=0$ and $Q=3E_0/2$. On each isothermal expansion, $\Delta U=0$, so the first law of thermodynamics gives $Q=W_{\mathrm{by}}$. The ideal gas law and the integral of $1/V$ then giveHere $\ln$ is the natural logarithm. Rounded to $0.001\mathrm{kJ}$, the upper route has $(Q,W_{\mathrm{by}},\Delta U)=(9.222,5.480,3.741)\mathrm{kJ}$ and the lower route has $(6.481,2.740,3.741)\mathrm{kJ}$. Subtracting separately rounded entries can differ by $0.001\mathrm{kJ}$; the unrounded balances are exact in the stipulated model.

The shaded area between the curves explains the entire difference:Following the upper route forward and the lower route backward makes a thermodynamic cycle with this positive net work and matching net heat. Its internal energy change is zero. The two open routes themselves are reversible, so their different work outputs should not be mistaken for a loss caused by entropy production: they receive different heat transfers at different temperatures.

Two other state functions provide independent endpoint checks. With enthalpy $H=5nRT/2$ in this model,To obtain the entropy change along either route, integrate $C_{V}dT/T$ on its heating leg, giving $C_V\ln 2$, and $nRdV/V$ on its isothermal expansion, giving $nR\ln 3$. Reordering the legs changes their heat totals but leaves the sum of their entropy changes unchanged. In particular, neither route's total $Q$ divided by its final temperature equals $\Delta S$, and neither total $Q$ equals $\Delta H$: both routes include an isothermal expansion, rather than a single fixed-pressure heating step.