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Temperature labels thermal equilibrium: two internally equilibrated bodies have the same temperature when contact permitting only heat exchange produces no net heat transfer. The zeroth law of thermodynamics makes the comparison transitive. If bodies A and B separately reach thermal equilibrium with the same thermometer without appreciably disturbing either body, they agree with each other. This is what lets a gas thermometer compare a metal block with water, despite their different internal energies and heat capacities. Insulation alone makes no such comparison: it can prevent heat transfer between bodies at different temperatures. ^[ref]

The zeroth law of thermodynamics establishes equality comparisons, but does not choose a numerical scale. Thermodynamic temperature supplies an absolute scale consistent with Carnot's theorem and entropy. For a simple compressible system at thermodynamic equilibrium with fixed particle number $N$ and composition,Here $U$ is internal energy, $S$ is entropy, and $V$ is volume; the second equality assumes the derivative can be inverted. Temperature is a thermodynamic conjugate variable to entropy and belongs to the intensive and extensive thermodynamic quantities as an intensive quantity. Its partial derivative tells us how much internal energy must change per unit change of entropy under the stated constraints. More general systems require their other mechanical and material variables to be held fixed too. ^[ref]

For an infinitesimal quantity $\delta Q>0$ of heat transferred from A to B, with no work or matter exchange, the equilibrium entropy changes giveFor ordinary positive temperatures, spontaneous heat transfer from $T_A>T_B$ increases total entropy; thermal equilibrium has $T_A=T_B$. This comparison uses changes in entropy, rather than the total internal energy contained in either body. A small hot object can have less internal energy than a large cool one. See entropy maximization under thermal contact for the equilibrium criterion and negative temperature for the special case of bounded energy spectra.

Express absolute thermodynamic temperature $T$ in kelvin, and a Celsius reading $t_C$ in degree Celsius:The offset is exact: $300\mathrm{K}$ corresponds to $26.85{}^{\circ }\mathrm{C}$, and $400\mathrm{K}$ to $126.85{}^{\circ }\mathrm{C}$. Their absolute temperature ratio is $4/3$; dividing their Celsius readings gives a different number. Thus gas thermometer pressure ratios and Carnot's theorem require thermodynamic temperature. The modern SI definition of the kelvin fixes the Boltzmann constant $k_B=1.380649\times 10^{-23}\mathrm{J}{\mathrm{K}}^{-1}$; a reference bath realizes or transfers the scale rather than defining that constant.^[ref]

Temperature is not universally the mean kinetic energy of a particle. In a classical, nonrelativistic ideal gas at thermal equilibrium, the equipartition theorem gives the mean translational kinetic energy relative to the gas's bulk motion:Here $m$ is particle mass, $\mathbf{v}$ its velocity, and $\mathbf{u}$ the mean flow velocity. In this regime, different particle masses at the same temperature have equal mean translational kinetic energies but different characteristic speeds. A moving gas can also carry bulk kinetic energy without being hotter in its rest frame. Internal molecular modes and quantum statistics require further care; the equipartition theorem has classical assumptions, whereas the equilibrium entropy definition applies more widely. ^[ref]

The gas-only condition $\Delta U=0$ requires negligible heat exchange with the apparatus. If the insulated isolated system instead includes the walls, sensors and water, the first law of thermodynamics fixes their combined energy. Once everything returns to a common final temperature, a constant apparatus heat capacity $C_a$ givesDefine $A=U_g(T_1,V_2)-U_g(T_1,V_1)$, the gas's internal energy increase for the same expansion evaluated at the initial temperature. For a small temperature change, linearizing at the final volume givesHere $C_{V,g}$ is the whole gas sample's heat capacity at constant volume at the reference state. Compared with an isolated gas sample's $-A/C_{V,g}$, the common final signal is reduced by $C_{V,g}/(C_{V,g}+C_a)$. This energy accounting explains why a massive bath can conceal a real-gas effect. Fitzpatrick gives the corresponding apparatus correction for the Van der Waals equation. ^[ref]

For a toy calculation, stipulate $A=5\mathrm{J}$, $C_{V,g}=10\mathrm{J}{\mathrm{K}}^{-1}$ and $C_a=990\mathrm{J}{\mathrm{K}}^{-1}$, all constant in this example. The predicted cooling magnitude changes from $0.5\mathrm{K}$ for the gas alone to $0.005\mathrm{K}$ for the combined apparatus. An illustrative effective detection threshold of $0.01\mathrm{K}$ would miss the latter. These are chosen numbers, not Joule's measurements. In this approximation a null observation only bounds $|A|\lesssim (C_{V,g}+C_a){ϵ}_T$, where ${ϵ}_T$ is the detectable temperature change after allowing for drift and other experimental uncertainties; a display's smallest digit is not automatically this threshold.

The historical limitation was recognized explicitly: Joule and Thomson later estimated that the common apparatus in Joule's experiment would cool by only about $0.003\mathrm{K}$, explaining why the earlier external thermal effect was undetectable. This was a later calculation about the apparatus, not a measured cooling trace. ^[ref]

Thermal conduction transfers heat through microscopic interactions without bulk transport of matter. To predict the heating load through a bar, combine Fourier's law with conservation of energy and the imposed end temperatures. In the isotropic model with positive thermal conductivity $k$, the conductive heat flux points from high to low temperature, opposite to the temperature gradient. A spoon warming along its handle and heat escaping through a wall are familiar examples.

Consider a bar of length $L=0.10\mathrm{m}$, constant cross-sectional area $A=0.010{\mathrm{m}}^2$ and constant thermal conductivity $k=2\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$. Maintain its ends at $T_h=40{}^{\circ }\mathrm{C}$ and $T_c=20{}^{\circ }\mathrm{C}$, with $x$ increasing toward the colder end. Assume a steady state, one-dimensional thermal conduction, no internal sources and no heat transfer through the sides. The temperature falls by $20\mathrm{K}$ over $0.10\mathrm{m}$, givingThe difference between the two readings in degree Celsius units is the same $20$-kelvin difference. The positive heat flux carries heat toward increasing $x$.

The general solution under these assumptions isA proof outline is enough to explain the straight line: conservation of energy in any small slice, with no accumulation, sources or side losses, gives $d\dot{Q}/dx=0$. Constant cross-sectional area gives $dq/dx=0$; constant thermal conductivity and Fourier's law then give $d^{2}T/d{x}^2=0$. Two integrations and the end boundary conditions determine the displayed affine function. This is why a visually simple temperature profile can encode a continuous flow of energy. ^[ref]

Doubling the length halves the rate, while doubling the cross-sectional area doubles it, at fixed end temperatures and thermal conductivity. This explains why a long narrow support can limit unwanted heat transfer, while a short broad path can help remove heat. Joining materials leads to thermal resistance in series. During initial warming, internal energy can accumulate and the temperature profile need not be a straight line; the time dependence is described by the heat equation and thermal diffusivity.

Now join two layers, each of length $L_1=L_2=0.10\mathrm{m}$, with constant cross-sectional area $A=0.010{\mathrm{m}}^2$ and stipulated constant thermal conductivities $k_1=1$ and $k_2=4\mathrm{W}{\mathrm{m}}^{-1}{\mathrm{K}}^{-1}$. Keep the outer ends at $40$ and $20{}^{\circ }\mathrm{C}$. Assume a steady state, one-dimensional thermal conduction, no internal sources or side losses, and perfect contact: the temperature is continuous at the interface, with no extra contact drop. For each layer, use the area-specific thermal resistance $r_i=L_i/k_i$ and $R_i=r_i/A$. The series calculation gives

The heat flux is continuous: otherwise energy would accumulate at the interface. Yet Fourier's law gives different temperature gradients, $dT/dx=-q/k_1=-160\mathrm{K}{\mathrm{m}}^{-1}$ and $dT/dx=-q/k_2=-40\mathrm{K}{\mathrm{m}}^{-1}$. Lower thermal conductivity requires a steeper temperature gradient to carry the same heat flux; equal lengths therefore give drops in the ratio $4:1$. A kink in the temperature profile records the change of material while perfect contact keeps the temperature itself continuous.

Thermal convection is fluid motion driven by temperature-dependent buoyancy. It transports heat by bulk motion in addition to thermal conduction.

Thermal diffusivity is $\kappa =k/(\rho c_p)$, the ratio of thermal conductivity to volumetric heat capacity. It sets the diffusion length $\sqrt{\kappa t}$ over time $t$.

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]

A thermodynamic system is in thermodynamic equilibrium when its macroscopic state has no spontaneous tendency to change through any exchange allowed by its constraints. For an isolated system, stable thermodynamic equilibrium maximizes entropy over the accessible states at fixed total energy and conserved material inventories. A wall can forbid an exchange, so always specify what can cross or move. Thermal, mechanical and chemical conditions answer different questions about that same constrained state. ^[ref]

For example, two compartments separated by a rigid, impermeable wall that transmits heat can reach thermal equilibrium while retaining different pressures and compositions. Allowing an unloaded piston to move adds a mechanical equilibrium condition. Allowing one chemical species to cross adds chemical potential equality for particle exchange; allowing a chemical reaction adds its chemical equilibrium condition. A fixed barrier can therefore support a constrained thermodynamic equilibrium that ceases to be an equilibrium when the barrier is removed.

Uniformity is not the definition of thermodynamic equilibrium. An isothermal atmosphere in hydrostatic equilibrium can have a common temperature while its pressure and mass density vary with height: the pressure gradient balances gravity. In an external field, the exchange condition must include the relevant potential energy; for charged matter this leads to the electrochemical potential. Relativistic gravitational corrections to thermal equilibrium are described separately by the Tolman temperature law.

A steady state only says that the macroscopic description is constant in time. A bar maintained between hot and cold thermal reservoirs has steady heat flux and produces entropy, so it is not in thermodynamic equilibrium. Even matching temperatures at one perfect-contact interface can coexist with heat transfer through the surrounding material; matching those two local values does not establish equilibrium of the whole apparatus. See thermal conduction for that spatial transport problem.

The useful simplification is that equilibrium conditions predict an endpoint without computing every collision or flow during relaxation. The first law of thermodynamics supplies the conserved quantities, and the Second law of thermodynamics supplies the direction of change. For a system held at fixed temperature and volume, the corresponding criterion is minimization of Helmholtz free energy; at fixed temperature and pressure, it is minimization of Gibbs free energy, with the material and exchange constraints still imposed.

A free energy is a thermodynamic potential that compares possible states under specified environmental constraints. For a closed system of fixed composition, treated as a simple compressible system with only pressure-volume work, stable thermodynamic equilibrium minimizes Helmholtz free energy at fixed temperature and volume, or Gibbs free energy at fixed temperature and pressure. The choice follows the experiment: a rigid sealed vessel and a sealed cylinder with a freely moving loaded piston impose different constraints. Both may exchange heat with a thermal reservoir. See W. C. Carter, MIT thermodynamics notes, sections 2-1.14 and 2-1.19.

The useful insight is that internal energy alone cannot rank these alternatives: exchanging heat also changes the surroundings' entropy. Subtracting $TS$ packages that accounting into a property of the chosen system. Adding $pV$ additionally accounts for displacing the surroundings at fixed pressure. A free energy is a state function; supplied heat describes a transfer during a process. Under the stated constraints, supplied heat is $Q=\Delta U$ at fixed volume or $Q=\Delta H$ at fixed pressure, whereas neither $\Delta F$ nor $\Delta G$ generally equals $Q$.

A lower free energy identifies a thermodynamic preference, without specifying a timescale. A barrier can trap a system in a local minimum, producing metastability although a lower global minimum exists. The enzyme example illustrates the corresponding distinction for chemical reactions: changing the route can change the reaction rate while preserving the endpoint Gibbs free energy difference and chemical equilibrium.

A thermodynamic process changes a thermodynamic system between states. A quasistatic process supplies equilibrium intermediate states and therefore a path on equilibrium coordinates. An irreversible thermodynamic process can have equilibrium endpoints while lacking a uniform intermediate temperature or pressure. Endpoint values still determine changes in a state function; computing heat and work requires the actual interaction history.

Thermodynamics studies energy transfers and the constraints on macroscopic changes. Its vocabulary connects internal energy, entropy, temperature, pressure and volume to heat and work. The first law of thermodynamics balances energy; the Second law of thermodynamics decides which changes can occur spontaneously and limits how much work a heat engine can deliver. These principles let us bound performance before choosing a material or a detailed machine design. Applications include power generation, propulsion and refrigerators. ^[ref]

Start by choosing a system boundary. A closed system can exchange energy but no matter; an isolated system exchanges neither. A state function, such as internal energy or entropy, depends on the equilibrium state. A process specifies how that state changes. Thus a body's temperature is a property it has, whereas heat records energy crossing its boundary during a process. A body contains internal energy, rather than a stored quantity of heat.

Two insulated bodies initially at different positive temperatures approach thermal equilibrium when brought into thermal contact. Their combined energy is conserved, but their combined entropy increases. They do not spontaneously separate again into a hotter body and a colder one. This familiar asymmetry makes thermodynamics interesting: conserving energy leaves many imaginable changes available, and entropy supplies a further constraint. The same distinction underlies both entropy maximization under thermal contact and the thermal efficiency limit in Carnot's theorem.