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The mole fraction of species $i$ is $x_i=N_i/{\sum }_j{N}_j$, where $N_i$ is its amount in moles. It is dimensionless and equals the volume mixing ratio for an ideal gas mixture.

Assume a single-phase ideal gas mixture in a closed parcel, with common temperature $T$, total pressure $P$, and molar species amounts $N_i$. Define $N={\sum }_i{N}_i$ and volume mixing ratios $x_i=N_i/N$, so ${\sum }_i{x}_i=1$. Ideal mixing makes partial pressure $P_i=x_{i}P$.

For a pure ideal species, $d{\mu }_i=-{\bar{S}}_{i}dT+{\bar{V}}_{i}d{P}_i$, with molar volume ${\bar{V}}_i=\mathcal{R}T/P_i$. At fixed temperature, integration from standard pressure $P^{\circ }$ givesThe same logarithmic composition term follows from the ideal mixing entropy $\Delta S_{\mathrm{mix}}=-\mathcal{R}{\sum }_i{N}_i\log x_i$. Extensivity gives $G={\sum }_i{N}_i{\mu }_i$. Hence the Gibbs free energy of an ideal-gas mixture isEquivalently, write each standard chemical term as ${\mu }_i^{\circ }=h_i^{\circ }-T{s}_i^{\circ }$, using molar enthalpy and entropy. For zero abundance the limit $x\log x\to 0$ defines the extensive expression continuously.

The fractions alone do not specify the extensive Gibbs free energy: the total amount $N$ or an equivalent elemental inventory must also be fixed. Moreover, in a chemically closed reacting system $N$ need not remain constant; for example, hydrogenation of carbon monoxide changes the total molecular count while conserving atoms. Minimization is therefore over species amounts subject to elemental constraints, rather than over fractions with an artificially fixed molecular count. Nonideal gases require activities or fugacities; condensates contribute separate phase terms.

Let the closed atmospheric parcel exchange heat and volume work with reservoirs at fixed temperature $T$ and pressure $P$, while reactions rearrange its conserved elemental inventory. For a reversible differential between equilibrium states, the first law of thermodynamics, with chemical work included, isThe Gibbs free energy $G=U+PV-TS$ therefore obeysThe first law of thermodynamics supplies this differential but does not alone choose the direction of a reaction. The Second law of thermodynamics does: for the parcel plus its reservoirs, at fixed $T,P$ and with no non-volume work,Thus spontaneous reactions decrease Gibbs free energy, and stable thermochemical equilibrium is its constrained minimum. For an allowed reaction of extent $d\xi$, let $d{N}_i={\nu }_{i}d\xi$, with positive stoichiometric vector entries for products and negative entries for reactants. At an interior minimum,The condition must hold for every independent allowed reaction, with fixed total atoms of each element and any relevant charge constraint. At a boundary with absent species, only feasible one-sided variations are permitted. These are the hypotheses of constrained Gibbs minimization for chemical equilibrium.

For an ideal gas mixture, ${\mu }_i={\mu }_i^{\circ }(T)+\mathcal{R}T\log (x_{i}P/P^{\circ })$, where $x_i$ is the volume mixing ratio and $\mathcal{R}$ the molar gas constant. ThereforeThis is a dimensionless activity-based equilibrium constant, not a bare product of dimensional pressures.