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Entropy is an extensive quantity and a state function of an equilibrium system, measured in $\mathrm{J}{\mathrm{K}}^{-1}$. Differences between equilibrium states are calculated along a reversible thermodynamic process:Here heat entering the system is positive and $T$ is its absolute thermodynamic temperature. The reversible path used for calculation need not be the path actually taken. Dividing the actual heat by a single temperature generally fails for an irreversible process.

For example, put two rigid bodies, each with constant heat capacity $C=100\mathrm{J}{\mathrm{K}}^{-1}$, at $600\mathrm{K}$ and $300\mathrm{K}$ in an otherwise isolated system. Assume each body has a uniform internal temperature, no phase transition occurs, and no work is extracted. Their final thermal equilibrium is at $450\mathrm{K}$, because the internal energy lost by one equals that gained by the other. Using entropy from heat capacity,so $\Delta S_{\mathrm{tot}}=C\log (9/8)=11.78\mathrm{J}{\mathrm{K}}^{-1}$. One body's entropy decreases while the total increases. ^[ref]

In statistical mechanics, Boltzmann's entropy formula counts equally likely microstates compatible with a macrostate; Gibbs entropy handles a specified probability distribution over microstates. If the number of equally likely microstates doubles, entropy increases by $k_B\log 2$. The logarithm makes multiplicative counts additive for independent systems. These are precise statements about states and probabilities, not a universal measure of visible messiness. Calling entropy merely "disorder" obscures the thermal calculation above and hides which microstates are being counted. ^[ref]

The usefulness of entropy is that measurable heat capacities determine its changes, and the Second law of thermodynamics turns those changes into constraints on processes. It also connects macroscopic measurements to microscopic descriptions without requiring us to track every particle.

Let $f$ be a differentiable function on an open domain stable under positive rescaling, with $f(\lambda x)={\lambda }^{k}f(x)$ for $\lambda >0$. The chain rule differentiates this homogeneous function identity at $\lambda =1$ to giveIf $f$ is twice differentiable, differentiating once more gives ${\sum }_i{x}_i{\partial }_i{\partial }_{j}f=(k-1){\partial }_{j}f$. In degree one its Hessian matrix therefore annihilates the radial vector $x$. This is the identity used in the no-scale identity from degree-one homogeneity. For an extensive quantity, the degree-one formula also supplies the thermodynamic identity behind the Gibbs-Duhem equation.

Two related properties of an extensive quantity must be distinguished. Additivity says that a quantity $X$ for independent subsystems A and B obeysThe subsystems may be in different states. Extensivity expressed through a homogeneous function says that the equilibrium fundamental relation obeyswith composition held fixed. This is degree-one homogeneity along a replication ray; it does not say that internal energy is a linear function of arbitrary independent changes of entropy, volume and amount of substance.

Additivity gives integer replication by repeated addition. Subdividing a uniform bulk sample into $b$ equivalent parts gives rational scaling $a/b$; continuity then extends it to positive real factors. This argument requires negligible boundary contributions and a consistently prepared state. Conversely, a degree-one homogeneous function need not be additive between different rays: $f(x,y)=\sqrt{x^2+y^2}$ has $f(\lambda x,\lambda y)=\lambda f(x,y)$, but $f(1,0)+f(0,1)=2\ne \sqrt{2}=f(1,1)$. Thus a scaling identity alone cannot justify summing arbitrary states.

For finite samples, the surface correction to thermodynamic free energy can matter. Under geometric enlargement with volume multiplied by $\lambda$, surface area grows as ${\lambda }^{2/3}$, so a surface energy term is not a bulk extensive quantity. Replicating separated droplets retains every original surface, whereas merging them changes the total surface area. Likewise, appreciable mutual gravitational potential energy makes interacting subsystems fail the independent-copy premise. The thermodynamic limit explains when bulk scaling becomes accurate; it does not remove these qualifications for every small or strongly interacting system.

The Euler theorem for homogeneous functions applied to an extensive quantity, together with $dE=TdS-pdV+\mu dN$ give

The Gibbs-Duhem equation constrains changes of the intensive quantities describing one uniform thermodynamic phase. For a mixture with $k$ independently specified component amounts, its molar form isHere $S$ is entropy, $V$ is volume, $T$ is temperature, $p$ is pressure, $n_i$ is the amount of substance of component $i$, and ${\mu }_i$ is its molar chemical potential. This assumes a simple compressible system whose bulk internal energy is an extensive quantity; additional work coordinates require additional terms.^[ref]

The proof exposes the source of the constraint. For internal energy $E(S,V,n_1,\dots ,n_k)$, replication of the whole thermodynamic phase by a factor $\lambda$ gives $E(\lambda S,\lambda V,\lambda n_1,\dots ,\lambda n_k)=\lambda E(S,V,n_1,\dots ,n_k)$. The Euler theorem for homogeneous functions and the fundamental differential of internal energy therefore giveTaking the differential of the first equation produces all the terms in the second, plus $SdT-Vdp+{\sum }_i{n}_{i}d{\mu }_i$. Subtraction proves the Gibbs-Duhem equation. Thus the constraint comes from two descriptions of the same state function, rather than an assumed microscopic interaction model.

At fixed temperature and pressure, divide by $n={\sum }_i{n}_i>0$ and introduce the mole fractions $x_i=n_i/n$:The chemical potentials cannot be varied independently. In a two-component mixture, put $x_A=x$ and $x_B=1-x$. Within a smooth single-thermodynamic phase region with $0<x<1$,One chemical potential fixes the other's change, but determining its absolute value still requires a reference value. This does not say ${\mu }_A={\mu }_B$: equality at phase coexistence concerns the same chemical species in different thermodynamic phases. Nor does the constraint say $dG=0$ whenever temperature and pressure are fixed; changing composition still contributes ${\sum }_i{\mu }_{i}d{n}_i$ to the Gibbs free energy.

An extensive quantity measures how much of a thermodynamic system there is; an intensive quantity describes its state independently of that amount. The clean comparison is replication: take independent identical systems at the same thermodynamic equilibrium, with the same substance, composition and thermodynamic phase. Combining their accounting boundaries multiplies internal energy $U$, entropy $S$, volume $V$, mass $m$ and amount of substance $n$, while leaving temperature $T$, pressure $p$ and chemical potential $\mu$ unchanged.^[ref]

For $\lambda$ copies the ledger isAn integer $\lambda$ counts actual copies; a positive real $\lambda$ describes the corresponding bulk scaling law. Copies can remain separated: replication need not involve removing a partition, changing a container or performing any work. Distinguish $n$, the amount of substance measured in moles, from $N=n{N}_A$, the dimensionless count of specified entities, where $N_A$ is the Avogadro constant in ${\mathrm{mol}}^{-1}$. For example, $2\mathrm{mol}$ contains $1.204428152\times 10^{24}$ specified entities; tripling it gives $6\mathrm{mol}$ and $3.613284456\times 10^{24}$ entities. This uses the exact Avogadro constant $N_A=6.02214076\times 10^{23}{\mathrm{mol}}^{-1}$, which does not triple. In the differential $dU=TdS-pdV+\mu dn$, $\mu$ is a molar chemical potential in $\mathrm{J}\mathrm{mo}{\mathrm{l}}^{-1}$; the coefficient of $dN$ instead has units of energy per entity.

As a direct check, the ideal gas law $pV=nRT$ givesFor a monatomic ideal gas with only translational degrees of freedom active, internal energy of an ideal gas gives $U=3nRT/2$, so $U^{\prime }=\lambda U$ at unchanged temperature. Here $R$ is the molar gas constant. The scaling distinction lets a small sample supply an equation of state for a much larger amount: material state and inventory become separate questions.

Replication does not mean multiplying every linear dimension by $\lambda$: a geometrically similar container then has ${\lambda }^3$ times the volume. Nor does it mean combining samples at different states. Equal temperature establishes thermal equilibrium but does not imply equal pressure, composition or mass density. Density of a composite system makes this distinction concrete.

An intensive quantity is unchanged under replication at the same thermodynamic equilibrium. Temperature, pressure, chemical potential and the mass density of a uniform substance are examples. Independence from sample size does not mean independence from state: a material's mass density can change with temperature or pressure.

The relation to extensive quantities is particularly elegant for a differentiable bulk fundamental relation. Put $\mathbf{x}=(S,V,n)$ and writeTaking a partial derivative with respect to $x_i$ and cancelling $\lambda$ givesThe equilibrium differential $dU=TdS-pdV+\mu dn$ identifies these derivatives with temperature, minus pressure and molar chemical potential. They are degree-zero homogeneous functions. The same degree-one assumption yields the Euler relation in thermodynamics, but a surface energy contribution requires extra care.

An intensive quantity generally has no meaningful sum across samples: two equal temperatures do not add to a doubled temperature. Neither is the final temperature after thermal contact generally an unweighted average; heat capacities and the first law of thermodynamics determine the balance. Ratios of additive inventories lead to the useful weighted rules in normalizing extensive quantities.

Dividing two extensive quantities with the same replication factor produces an intensive quantity:Division by volume gives a density, such as mass density $\rho =m/V$ or energy density $U/V$. Division by mass gives a specific quantity, such as specific internal energy $u=U/m$ or specific volume $v=V/m$. Division by amount of substance gives a molar quantity, such as molar volume $V_m=V/n$. Their units are respectively $\mathrm{kg}{\mathrm{m}}^{-3}$, $\mathrm{J}{\mathrm{m}}^{-3}$, $\mathrm{J}\mathrm{k}{\mathrm{g}}^{-1}$, ${\mathrm{m}}^3\mathrm{k}{\mathrm{g}}^{-1}$ and ${\mathrm{m}}^3\mathrm{mo}{\mathrm{l}}^{-1}$. The denominator must be stated: “per particle”, “per mole” and “per unit mass” are different normalizations.

For a hypothetical uniform parcel with mass $2\mathrm{kg}$, volume $0.002{\mathrm{m}}^3$ and internal energy $40\mathrm{kJ}$ relative to a specified reference, $u=20\mathrm{kJ}\mathrm{k}{\mathrm{g}}^{-1}$ and $\rho =1000\mathrm{kg}{\mathrm{m}}^{-3}$. Three independent copies have $6\mathrm{kg}$, $0.006{\mathrm{m}}^3$ and $120\mathrm{kJ}$; both ratios remain unchanged. This permits comparison of materials without confusing the amount tested with the state tested.

If $X$ and $Y$ are additive but the parcels have different $r_i=X_i/Y_i$, their composite ratio is a weighted arithmetic mean:The denominator supplies the weights: specific internal energy uses mass weights, while mass density uses volume weights. This identity is accounting for the specified subsystems; predicting a new state after mixing also needs the relevant equation of state.

Let $V$ be the physical volume of a region with fixed comoving coordinates, so $V\propto a^3$, and write $U=\rho V$. The first law of thermodynamics is $dU=TdS-PdV+\mu dN$. Use extensive quantities: under replication, $U(\lambda S,\lambda V,\lambda N)=\lambda U(S,V,N)$. The Euler theorem for homogeneous functions givesSetting $\mu =0$ yieldsThis is the entropy form of the Gibbs-Duhem equation; it fixes the normalization by extensivity, rather than adding an arbitrary volume-independent entropy constant.

For equilibrium expansion of the same region, the first law and the cosmological perfect-fluid continuity equation implyTherefore $\boxed{\dot{S}=0}$, establishing cosmological entropy conservation for adiabatic equilibrium evolution. Here “comoving volume” means a patch moving with the cosmological fluid; its physical volume $V$ changes. The corresponding coordinate volume is constant. The local TeX's $\dot{V}/P$ in the continuity-equation hint is a transcription error: the PDF correctly has $\dot{V}/V$.

The thermodynamic limit describes a sequence of larger systems, not a single enormous specimen: particle number $N$ and volume $V$ tend to infinity with number density $n=N/V$ fixed. Hold the chosen intensive and extensive thermodynamic quantities such as temperature $T$ and an applied magnetic field fixed along that sequence. In the canonical ensemble the controls are $T,N,V$; in the grand canonical ensemble one instead fixes $T$ and chemical potential, and the limiting number density is a result, possibly with a jump at phase coexistence. These are different specifications of a limiting experiment.

The useful limit is usually an intensive and extensive thermodynamic quantities normalization of the Helmholtz free energy, not a finite limit of the total extensive quantity itself:Here $Z_{N,V}$ is the canonical partition function, $k_B$ is the Boltzmann constant, $f$ is free-energy density, and $a$ is Helmholtz free energy per particle. Thus $F_{N,V}=Vf+o(V)$ when the limit exists; finite systems need not be exactly extensive quantities because of the surface correction to thermodynamic free energy.

Specify the interactions and the growing containers too. For a conventional fluid, use a fixed stable pair potential with a tempered pair potential tail, and containers whose boundary layer of any fixed thickness occupies a vanishing fraction of the volume; uniformly enlarged cubes work, a tube of fixed cross-section does not give the same bulk limit. For a finite-range Ising model, keep the lattice spacing and bond coupling fixed while enlarging all intended spatial directions. Ordinary bounded wall interactions or periodic boundary conditions can then give the same bulk free-energy density, although boundary conditions can select different spontaneous symmetry breaking states. This is a set of hypotheses, not a theorem that every interaction has a boundary-independent limit.^[ref]

The Curie–Weiss model below deliberately uses a different limiting prescription: its all-to-all coupling is divided by $N$. Without that factor its interaction energy would grow as $N^2$, rather than as an extensive quantity. The model has no spatial wall or correlation length to compare with a container; it is an exactly summable illustration of finite-size rounding, not a quantitative model of the fluid experiment below.