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474 Chapter 3: Estimation of the Gibbs Energy and Fugacity of a Component in a Mixture
Traditionally, in the petroleum and natural gas industries, where mostly low- and
moderate-molecular-weight hydrocarbons (with only small concentrations of aromatic
and inorganic compounds) are involved, equation-of-state.meth0d.s with the van der
WaaIs one-fluid mixing r u l ~ are
j generally used for the prediction of both liquid- and
vapor-phase properties. In the chemicals industry, on the other hand, where oxygen,
nitrogen, sulfur, or halogen-containing organic compounds and inorganic (electrolyte)
compounds are involved, activity coefficient or Gibbs energy models are used for the
prediction of liquid-phase properties, with equation-of-state models used for the vapor
phase if the pressure is abo\-e ambient. However, in recent years the equation-of-state
methods of Sec. 9.9 have also been used to model both the vapor and liquid phases of
such mixtures.
The critical point of a mixture. to be discussed in the next chapter, is similar to
the critical point of a pure component in that it is the temperature and pressure at
which the wpbr and liquid phases of a mixture of given composition become identical.
Although \ye have not yet discussed phase equilibrium in multicomponent mixtures
(see Chapters 10 to 12), we can guess that if'we are to predict the point at which two
phases become identical (the critical point) with some accuracy, the models we use
for the'vapor and liquid phases must give identical results for all properties at this
point. This will occur only .if we use the same equation-of-state model to describe
both the vapor and liquid phases. but clearly cannot, in general, be expected to occur
if we use different models. such as an activity coefficient model for the liquid phase
and an equation of state for the vapor phase. This ability to predict critical phenomena
is an important advantage of using the same equation-of-state model for both phases.
Another advantage of the equation-of-state description is that the concept of standard
states, and especially hypothetical or extrapolated standard states, never arises. -.Finally, since a number of different activity coefficient (or excess Gibbs energy)
models have been discuskd. it is useful to consider their range of application. The
most important observation is that none of the completely predictive methods, such
as regular solution theory. UNIFAC, or ASOG, can be regarded as highly accurate.
Therefore, these methods shouId be used only when no experimental data are available
for the system of interest. Of the predictive methods, UNIFAC is the best developed
and regular solution theory is the least accurate. .
As we'have considered a number of activity coefficient models in this section, it
is useful to discuss which might be best for different types of mixtures. To start this
discussion, it is useful to classify seven different types of chemicals that one might
encounter.
Nonpolar compo~~nds:
Chemical species without significant dipole moments, such as
n ~ s hydrocarbons,
t
and some very symmetri.~compounds such as tetrachloromethane
and hexafluorobenzene.
Weaklypolar compounds: Aldehydes, ethers, and ketones
Very polar compounds: Alcohols, arnines
Water
Carboxylic acids
Polymers
Electrolyte systems
'
As a general rule, a mixture containing components from more than one of the
classes above exhibits greater nonidedity than a mixture containing only components
from the same class. For example, a mixture containing an aldehyde and a ketone
Weakly polar weakly polar compounds: All of the models (Margules, van Laar, Wilson.
UNIQUAC, and NRTLj can be used, although it appears that the UNIQUAC model is better for
mixtures that are more nonideal.
Weakly polar +strongly polar compounds: All of the models (Margules, van Laar, Wilson.
UNIQUAC, and NRTL) can be used, although it appears that the UNIQUAC model is better for
mixtures that are more nonideal.
Strongly polar strongly polar compounds: The UNIQUAC model appears to best correlate
data, though all models give reasonable results.
.
,
Water nonpolar compounds: These mixtures generally have limited mutual solubility and
are discussed in Sec. 1 1.2.
Water weakly polar compounds: These mixtures generally have limited mutual solubility
and are discussed in Sec. 1 1.2.
Water strongly polar compounds: The UNIQUAC model appears to best correlate data for
aqueous mixturss.
Solutions containing carboxylic acids: The Wilson model appears to best correlate data for
mixtures containing carboxyli? adlhs if the components are mutually soluble. (The Wilson
model does not predict liquid-liquid phase splitting, as discussed in Sec. 11.2). Otherwise, the
UNIQUAC, van Laar, or NRTL model should be used.
Solutions containing polymers: Use the Flory-Huggins model.
Solutions containing ionizable safts, strong acids, o r bases: Use the extended Debye-Hiickel
model.
~Multicomponentmixtures: Choose the model that, based on the suggestions above, best describes the dominant components in the mixture.
476 Chapter 9: Estimation of the Gibbs Energy and Fugacity of a Component in a Mixture
1. Low pressures, no components that associate (such as carboxylic acids or HF): Assume the mixture is an ideal gas mixture.
(T, P, y ) = yi P
2. Low pressure for a mixture that contains a n associating component: Use the virial
equation of state, retaining only the second virial coefficient, and search for experimental
pure component and cross virial coefficient data for all components in the mixture.
3. Slightly elevated pressures: Use choice 1 or 2 above. Alternatively, use 4 below if [here
are no associating components, or 5 if associating components are present.
4. Elevated pressures for a vapor mixture that contains hydrocarbons, nitrogen, osygen,
carbon dioxide, and/or other inorganic gases (but not HF): Use an equation of state,
such as the Peng-Robinson or Soave-Redlich-Kwong equation with van der Waals m e fluid mixing rules (see Sec. 9.4).
5. Elevated pressures for a vapor mixture that contains one or more polar and/or associating compounds: Use an equation of state, such as the Peng-Robinson or SoaveRedlich-Kwong equation with the excess Gibbs energy-based mixing rules (see Sec. 9.9)
and the appropriate activity coefficient model (see Table 9.1 1-1).
fY
Liquid Mir~rrtres
Liquid mixtures at low pressure are generally described using the activity coefficient models as
described in Table 9.1 1- 1, and the behavior of a liquid mixture is generally not much affecred by
pressure, unless the pressure is very high. However, as we will see in Sec. 10.3, for phase equilibrium calculations at high presslires, especially as the critical point of a mixture is approached,
there are important advantages to using the same thermodynamic model for both phases. In such
cases the same equation-of-state model should be used for the vapor and liquid phases.
1. Liquid mixture a t el:vated pressure that contains only hydrocarbons, nitro,Oen. osygen, carbon dioxide, and/or other inorganic gases (but not HF) :Use equation of state,
such as Peng-Robinson or Soave-Redlich-Kwong with van der Waals one-fluid mixing
rules (see Sec. 9.4).
2. Liquid mixture at elevated pressure that contains that contains one o r more polar
and/or associating compounds. Use equation of state, such as Peng-Robinson or SoaveRedlich-Kwong with the excess Gibbs energy-based mixing rules (see See. 9.9) and the
appropriate activity coefficient model (see Table 9.1 1- 1).
.
Appendix A9.2