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At fixed temperature and pressure, a closed reacting system is in thermochemical equilibrium when its Gibbs free energy is minimal subject to elemental-abundance constraints. For every independent reaction,with a positive second variation in every allowed direction.

An atmosphere can be driven into disequilibrium chemistry in an exoplanet atmosphere by vertical mixing faster than chemical conversion, which causes chemical quenching; ultraviolet atmospheric photochemistry; and atmospheric escape. Lightning, energetic particles, horizontal transport, condensation, and rainout provide further mechanisms.

At fixed temperature and pressure, thermochemical equilibrium minimizes the Gibbs free energy subject to elemental conservation. For every independent reaction with stoichiometric coefficients ${\nu }_i$,Equivalently, forward and reverse rates satisfy detailed balance. For ideal gases,

For $A+B\rightleftharpoons C+D$, the forward and reverse rates areAt thermochemical equilibrium, $r_f=r_r$ by detailed balance, whileafter the appropriate standard-concentration factors are included. The standard reaction Gibbs free energy isConsequentlyFor other stoichiometries, the same argument uses the corresponding activity product and its standard-state factors.