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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 .
When both temperature and pressure are held constant, and the number of particles is expressed in moles, the chemical potential is the partial molar Gibbs free energy. [ 1 ] [ 2 ] At chemical equilibrium or in phase equilibrium , the total sum of the product of chemical potentials and stoichiometric coefficients is zero, as the free energy is ...
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.
Boltzmann's distribution is an exponential distribution. Boltzmann factor (vertical axis) as a function of temperature T for several energy differences ε i − ε j.. In statistical mechanics and mathematics, a Boltzmann distribution (also called Gibbs distribution [1]) is a probability distribution or probability measure that gives the probability that a system will be in a certain ...
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 ...