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Lecture 2: Thermodynamics and Equilibrium: D RTDLNF

Thermodynamics and equilibrium concepts are introduced. Fugacity is related to chemical potential and describes a species' escaping tendency. At equilibrium, the fugacities of each component are equal between phases. Fugacity can be calculated using the fugacity coefficient and activity is related to concentration through the activity coefficient. The phase equilibrium ratio, or K-value, is the ratio of a component's mole fractions between phases at equilibrium. Raoult's law results when activity and fugacity coefficients are set to ideal values. Separation factor indicates the ease of separating two components based on their individual K-values.

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67 views

Lecture 2: Thermodynamics and Equilibrium: D RTDLNF

Thermodynamics and equilibrium concepts are introduced. Fugacity is related to chemical potential and describes a species' escaping tendency. At equilibrium, the fugacities of each component are equal between phases. Fugacity can be calculated using the fugacity coefficient and activity is related to concentration through the activity coefficient. The phase equilibrium ratio, or K-value, is the ratio of a component's mole fractions between phases at equilibrium. Raoult's law results when activity and fugacity coefficients are set to ideal values. Separation factor indicates the ease of separating two components based on their individual K-values.

Uploaded by

Rinaldi Saputra
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© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Fall 2008

ChE 545: Mass Transfer Operations I

Lecture 2: Thermodynamics and Equilibrium


Chemical potential ( ) is related to fugacity f (escaping tendency of a species) by
the relation:
d = RT d ln f
The equality of chemical potentials at equilibrium translates into the equality of
fugacities for any component.

Fugacity for a component can be calculated using the equation

where
is the fugacity coefficient, which can be calculated using equations
listed in Table 2.6.
Activity (ai) for a component is defined as the ratio of the actual fugacity fugacity
in some standard state.

The standard state is usually selected to be the pure species at the same pressure
and temperature. The equality of fugacities translates into the equality of activities
for the component at equilibrium.
Activity is related to the concentration (mole fraction) of the component through
the activity coefficient .
ai =

xi

The activity coefficient is 1 for an ideal solution.


The phase equilibrium ratio (also known as K-value, K-factor, distribution
coefficient or partition coefficient) for a component is the ratio of mole fractions
of that component in two different phases at equilibrium.
Ki = yi/xi

Vapor-liquid equilibrium K-factor expressed in terms of fugacity and activity


coefficients is

Setting the activity and fugacity coefficients equal to 1 (ideal liquid solution, ideal
gas mixture) and using the above definition of standard state results in Raoults
law:

where the numerator represents the saturation pressure (or vapor pressure) at that
temperature.
For species at their supercritical temperature, saturation pressure is undefined, and
instead Henrys constant (Hi) is used as the standard state fugacity.

The separation factor (also known as relative volatility or relative selectivity) of


component i with respect to component j is the ratio of the K-factors for the two
components.
ij

= Ki/Kj

The separation factor indicates the ease (or difficulty) of separation between the
two components.

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