Extensive quantity

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.

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.