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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 ...
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 ...
The discontinuity in , and other properties, e.g. internal energy, , and entropy,, of the substance, is called a first order phase transition. [12] [13] In order to specify the unique experimentally observed pressure, (), at which it occurs another thermodynamic condition is required, for from Fig.1 it could clearly occur for any pressure in the range .
Gibbs’ collection of papers provided the first unified body of thermodynamic theorems from the principles developed by others, such as Clausius and Sadi Carnot. During the early 20th century, two major publications successfully applied the principles developed by Gibbs to chemical processes and thus established the foundation of the science ...
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.
Josiah Willard Gibbs Born (1839-02-11) February 11, 1839 New Haven, Connecticut, U.S. Died April 28, 1903 (1903-04-28) (aged 64) New Haven, Connecticut, U.S. Nationality American Alma mater Yale College (BA, PhD) Known for List Statistical mechanics Chemical thermodynamics Chemical potential Cross product Dyadics Exergy Principle of maximum work Phase rule Phase space Physical optics Physics ...