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In thermodynamics, the phase rule is a general principle governing multi-component, multi-phase systems in thermodynamic equilibrium.For a system without chemical reactions, it relates the number of freely varying intensive properties (F) to the number of components (C), the number of phases (P), and number of ways of performing work on the system (N): [1] [2] [3]: 123–125
When pressure and temperature are variable, only of components have independent values for chemical potential and Gibbs' phase rule follows. The Gibbs−Duhem equation cannot be used for small thermodynamic systems due to the influence of surface effects and other microscopic phenomena. [2] The equation is named after Josiah Willard Gibbs and ...
This equal area rule can also be derived by making use of the Helmholtz free energy. [24] In any event the Maxwell construction derives from the Gibbs condition of material equilibrium. However, even though g f = g g {\displaystyle g_{f}=g_{g}} is more fundamental it is more abstract than the equal area rule, which is understood geometrically.
The definition of the Gibbs function is = + where H is the enthalpy defined by: = +. Taking differentials of each definition to find dH and dG, then using the fundamental thermodynamic relation (always true for reversible or irreversible processes): = where S is the entropy, V is volume, (minus sign due to reversibility, in which dU = 0: work other than pressure-volume may be done and is equal ...
Yet also other variables may be used in that form. It is directly related to Gibbs phase rule, that is, the number of independent variables depends on the number of substances and phases in the system. An equation used to model this relationship is called an equation of state.
Experimentally, phase lines are relatively easy to map due to the interdependence of temperature and pressure that develops when multiple phases form. Gibbs' phase rule suggests that different phases are completely determined by these variables. Consider a test apparatus consisting of a closed and well-insulated cylinder equipped with a piston.
Calculating the number of components in a system is necessary when applying Gibbs' phase rule in determination of the number of degrees of freedom of a system. The number of components is equal to the number of distinct chemical species (constituents), minus the number of chemical reactions between them, minus the number of any constraints ...
This definition is clearly parallel to the definition of an ordinary critical point as the point at which two-phase coexistence terminates. A point of three-phase coexistence is termed a triple point for a one-component system, since, from Gibbs' phase rule, this condition is only achieved for a single point in the phase diagram (F = 2-3+1 =0 ...