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FUGACIO
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In chemical thermodynamics, the Fugacity of a real gas is an effective partial pressure which replaces the mechanical partial pressure in an accurate computation of the chemical equilibrium constant. It is equal to the pressure of an ideal gas which has the same molar Gibbs free energy as the real gas.Fugacities are determined experimentally or estimated from various models such as a Van der Waals gas that are closer to reality than an ideal gas. The ideal gas pressure and fugacity are related through the dimensionless fugacity coefficient φ.* * * * φ * = * * * f * P * * * * * * {\displaystyle \varphi ={\frac {f}{P}}\,} * The contribution of nonideality to the molar Gibbs energy of a real gas is equal to RT ln φ. For an ideal gas, fugacity and pressure are equal so φ = 1. * The fugacity is closely related to the thermodynamic activity. For a gas, the activity is simply the fugacity divided by a reference pressure to give a dimensionless quantity. This reference pressure is called the standard state and normally chosen as 1 atmosphere or 1 bar. * Accurate calculations of chemical equilibrium for real gases should use the fugacity rather than the pressure. The thermodynamic condition for chemical equilibrium is that the total chemical potential of reactants is equal to that of products. If the chemical potential of each gas is expressed as a function of fugacity, the equilibrium condition may be transformed into the familiar reaction quotient form (or law of mass action) except that the pressures are replaced by fugacities. * For a condensed phase (liquid or solid) in equilibrium with its vapor phase, the chemical potential is equal to that of the vapor, and therefore the fugacity is equal to the fugacity of the vapor. This fugacity is approximately equal to the vapor pressure when the vapor pressure is not too high. |
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