Mass transfer

01.09.2005

Thermodynamic properties

General (1)
•  In mass transfer calculations thermodynamic properties and phase equilibrium knowledge are needed. In practical design one uses simulation packages which includes databases and programmed calculation sequences. However it is important that the user in principle understand how these values are calculated and knows that one must be careful using the data in design.
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1

Mass transfer

01.09.2005

General (2)
•  The relationship between pressure, volume and temperature for fluids can be expressed in equations of state.The simplest is perhaps the ideal gas law, which well can be used in moderate conditions both fore pure gases and mixtures of ideal components. •  Deviations can be taken into account using a compressibility factor Z. We get from the ideal gas law:
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Real gases (1)
pVm=ZRT where p= Vm = Z= R= T= V= n= pressure molar volume (=V/n) compressibility factor gas constant absolute temperature volume moles of material

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2

Mass transfer

01.09.2005

Real gases (2)

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3

Mass transfer

01.09.2005

Real gases (3)
•  Because the compressibility factor depends on the temperature, pressure and composition of the gas mixture, it need to be described as a function. Known equations describing the non ideal behaviour of gases are: virial equation of state, van der Waals equation of state and methods used in the thermodynamic packages in simulation programs such as Soave-Redlich-Kwong (SRK) and most used Peng-Robinsonin (PR) cubic equations.
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4

Mass transfer

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5

Mass transfer

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Real gases (4)
Peng-Robinsonin (PR) EOS:

Z=
where

V aV − V − b RT (V 2 + 2bV − b 2 )
V = molar volume a, b =constants calculated from gas properties

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Real gases(5)
•  Because the equation can be rearranged in cubic form, there will be three roots at the most. The smallest root is the molar volume for the liquid phase and the largest for the gas phase . The third root is not used in predicting properties. For subcooled liquids and superheated gases only one root should be found. For mixtures the following mixing rules are used for the constants a and b.
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Mass transfer

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Real gases (6)
NC
NC NC

b = ∑ xi bi
i

a = ∑∑ xi xj ai aj (1− kij )
i j

•  where

NC = xi, xj =


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number of components molar fractions of the components i and j

Liquid phase (1)
•  For non ideal liquid phase properties activity coefficient models are used.Common methods are: Wilson, NRTL, UNIFAC and UNIQUAC. •  Some of these are also suitable for liquid-liquid phase calculations.

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Mass transfer

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Wilson

NRTL

8

Mass transfer

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UNIQUAC

9

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