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Gibbs-Duhem relation : ウィキペディア英語版
Gibbs–Duhem equation
In thermodynamics, the Gibbs–Duhem equation describes the relationship between changes in chemical potential for components in a thermodynamical system:〔''A to Z of Thermodynamics'' Pierre Perrot ISBN 0-19-856556-9〕
: \sum_^I N_i\,\mathrm\mu_i = - S\,\mathrmT + V\,\mathrmp \,
where N_i\, is the number of moles of component i\,, \mathrm\mu_i\, the infinitesimal increase in chemical potential for this component, S\, the entropy, T\, the absolute temperature, V\, volume and p\, the pressure. It shows that in thermodynamics intensive properties are not independent but related, making it a mathematical statement of the state postulate. When pressure and temperature are variable, only I-1\, of I\, components have independent values for chemical potential and Gibbs' phase rule follows. The law is named after Josiah Willard Gibbs and Pierre Duhem.
The Gibbs−Duhem equation cannot be used for small thermodynamic systems due to the influence of surface effects and other microscopic phenomena.
==Derivation==

Deriving the Gibbs–Duhem equation from the fundamental thermodynamic equation is straightforward.〔''Fundamentals of Engineering Thermodynamics, 3rd Edition'' Michael J. Moran and Howard N. Shapiro, p. 538 ISBN 0-471-07681-3〕 The total differential of the Gibbs free energy G\, in terms of its natural variables is
:\mathrmG
=\left. \frac\right | _\,\mathrmp
+\left. \frac\right | _\,\mathrmT
+\sum_^I \left. \frac\right | _N_i \,.
Since the Gibbs free energy is the Legendre transformation of the internal energy, the derivatives can be replaced by its definitions transforming the above equation into:
:\mathrmG
=V \,\mathrmp-S \,\mathrmT
+\sum_^I \mu_i \, \mathrmN_i \,
As shown in the Gibbs free energy article, the chemical potential is simply another name for the partial molar (or just partial, depending on the units of N) Gibbs free energy, thus the gibbs free energy of a system can be calculated by collecting moles together carefully at a specified T, P and at a constant molar ratio composition (so that the chemical potential doesn't change as the moles are added together), i.e.
: G = \sum_^I \mu_i N_i \,.
The total differential of this expression is〔
: \mathrmG = \sum_^I \mu_i \, \mathrmN_i + \sum_^I N_i \,\mathrm\mu_i \,
By subtracting the two expressions for the total differential of the Gibbs free energy gives the Gibbs–Duhem relation:〔
: \sum_^I N_i\,\mathrm\mu_i = - S\,\mathrmT + V\,\mathrmp \,

抄文引用元・出典: フリー百科事典『 ウィキペディア(Wikipedia)
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