The phase rule counts independent intensive controls compatible with coexistence of distinct bulk thermodynamic phases made from independent components:Here counts thermodynamic phases, not pressure, and does not count phase fractions. For the nonreacting one-component case, and : a single thermodynamic phase occupies a region with , two-thermodynamic phase coexistence a curve with , and a triple point an isolated point with . Fixing pressure externally removes one adjustable control wherever that constraint is independent.[ref]
Gibbs Phase Rule (MIT 10.213 course material). Gibbs Phase Rule, displayed nonreacting rule and pure-substance table
For an elementary count without chemical reactions, take chemical species. Each thermodynamic phase has independent composition fractions, since they sum to one. Shared temperature and pressure add two controls, giving . Equality of each species' chemical potential between one reference thermodynamic phase and the other thermodynamic phases supplies constraints. Subtraction gives . This argument assumes the constraints are independent and treats interfaces as negligible; chemical reactions, external fields or critical mergers require appropriate qualifications.
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The Phase Rule, formulated by the American scientist Josiah Willard Gibbs, is a principle in thermodynamics that provides a relationship between the number of components, phases, and degrees of freedom in a system at equilibrium.