Title Page

Thermodynamic Modeling of Solute Solubility in Supercritical

Carbon Dioxide Based on Equation of State:
Abstract:
In this paper, for thermodynamic modeling of the solubility of various solid components in
supercritical carbon dioxide the Peng-Robinson equation of state is used. Moreover, the
effects of three mixing rules (van der Waals, Panagio-topoulos and Reid, and modified Kwak
and Mansoori mixing rule) results were studied on the accuracy of calculation. Good
correlations between calculated and experimental data were obtained in a wide temperature
and pres-sure range. A comparison between the used models showed that modified Kwak and
Mansoori mixing rules gave better correlations in comparison with the other mixing rules.

Keywords: solid solubility; supercritical carbon dioxide; equation of state; mixing rules

Introduction:
In recent years, there has been increasing interest in the use of clean technologies that reduce
pollution or waste, as well as energy or material use compared traditional technologies.
Supercritical fluid technology is one of the most important clean technologies that can be
used in many important industries, such as in extraction and purification processes, chemical
and biochemical reactions, particle production recently in material and polymer processing.
To develop or improve these processes for producing better products, it is necessary to know
the phase behavior of the solute component in supercritical or pressurized fluid. Experimental
methods were used to determine the solubility of solids in supercritical fluids (SCF). Since
these methods are very costly and time consuming, models are often used to provide
correlations. Several models have been developed in order to correlate and predict solubility
data at various pressures and temperatures. Some of these models are empirical, while others
have fundamental basis.
Generally, for prediction of solid solubilities in supercritical fluids, an equation of state
(EOS) approach, a density-based approach or a solubility parameter approach is used.
Density-based models and solubility parameter-based models are used because of their
relative ease of application in comparison to models based on equations of state. But
equations of state-based models have been used because of their proper abilities to predict the
phase properties. Equation of state-based models are applied in many industries including oil
and gas industries, separation and purification industries and some supercritical assisted
industries. first two-parameter cubic equation of state was developed by Van der Waals. In
this equation, the effect of intermolecular forces and size of molecules are considered in two
terms of repulsive and attractive terms. Redlich and Kwong, Soave and Peng and Robinson
modified the repulsive and attractive terms of van der Waals EOS and proposed new
equations of state in which parameters were defined as functions of reduced temperature and
acentric factor. These models were proposed for pure substances; however, for mixtures,
mixing rules must be used.
Cubic equations of state are valuable engineer-ing tools for process design of any complex
system. These equations are remarkably successful in modeling of phase equilibrium with
supercritical components. The Peng-Robinson equation of state (PR-EOS) is a well-known
cubic EOS that gives a good qualitative picture of all types of SCF phase behavior and
reasonably it gives good quantitative fits for a wide variety of systems.
For example, many researchers used the PR-EOS for modeling of vapor liquid equilibrium or
solid vapor equilibrium which contains supercritical carbon dioxide. More-over, PR-EOS has
also been attempted to model the solubility of polar solutes in supercritical CO2 in the
presence of a polar co-solvent with some degree of success. Mixing rules has applications in
wide range and used for modeling of phase equilibrium in the mixtures. Conventional mixing
rules such as van der Waals mixing rules or Panagioto-poulos and Reid mixing rules were
used in many literatures for modeling of phase equilibrium of various systems in solid, liquid
or gas phase. Kwak and Mansoori proposed new mixing rules based on statistical mechanical
arguments. By making relevance between the parameters of EOS and the parameters (energy
and volume) of potential function in which the constants used for the mixing rules are
temperature independent they both presented new mixing rules. Valderrama and Alvarez
have considered the application of the original Kwak and Mansoori mixing rules and a
simplification of the combining rules for bijand dij. They presented new simplified mixing
rules based on original Kwak and Mansoori mixing rules and they modeled the solubility of
some solid components in supercritical carbon dioxide. In the present report, we study
temperature independent mixing rules for PR-EOS, MKM mixing rules and Reid mixing
rules, and Panagiotopoulos to predict the solubility of various solutes in supercritical carbon
dioxide. The solutes studied here have a very different molecular structure and have been
used in many important industries, e.g., textile, polymer, food and cosmetic industries.

Thermodynamic model:
When equilibrium between a fluid mixture (solute i+ solvent j) and a solid (i) is reached, the
general condition of equilibrium is as follows (it is assumed that the solid phase is pure and
does not contain solvent)

where is the fugacity of solute i in the fluid mixture, is the fugacity of pure solute i at
the same temperature and pressure in the solid phase. Since the solid phase is pure, the
fugacity of solute i is given by:

The solubility of solute i can be expressed as:

By supposing that the molar volume of the solid is independent of pressure and the fugacity
coefficient of pure solid is unity, a simplified equation can be obtained:
In above eq is the fugacity coefficient of solute component i in the fluid phase, in this
paper was calculated by using of PR EOS plus three different mixing rules: Reid mixing
rules and MKM mixing rules, Panagiotopoulos and van der Waals one fluid mixing rules.
The PR-EOS combined with VDW mixing rules gives flowing Eq. for fugacity coefficient:

In these equations ai and bi are the attraction and repulsion parameters for the pure
substances, but aij and bij are the unlike interaction parameters. For PR EOS these parameters
can be calculated by the following equations:

--------(a)

The Panagiotopoulos and Reid mixing rules are as follow

 -------------(b)

Detailed method for calculation of the fugacity coefficient by PR-EOS and Panagiotopoulos
and Reid mixing rules was presented in our last work. The fugacity coefficient for a
component (i) in a mixture can be obtained by following equation:

where n is the total number (moles) of molecules, ni is the number of molecule (i) in the
mixture and V is the total volume of mixture. For calculation of the fugacity coefficient by
this equation, energy parameter for the mixture (a) and the volume parameter for the mixture
(b) must be calculated by Eqs. a and b.

Valderrama and Alvarez modified the Kwak and Mansoori mixing rules and a new equation
for fugacity coefficient was derived:
And

Results and Discussion:

The solubility of various solid components, with different molecular weights, like climbazole,
cinnamic acid and spiroindolinonaphthoxazine photochromic dye have been successfully
predicted by using a thermodynamic model which consisted of the PR-EOS with various
mixing rules.
The experimental data of the solubility of solid components in supercritical CO2 used in this
paper have been given from various literatures. The critical constants, acentric factors, molar
volume of solids and constants for Antoine equation of these components are listed in Table 1
(for Irgacure 2959 photoinitiator and spiroindolinonaphthoxazine photochromic dye, the
estimated vapor pressure at required temperatures were reported).

Table 2 shows a comparison of the results of PR-EOS with three various mixing rules: van
der Waals one fluid, Panagiotopoulos and Reid, and MKM mixing rules. Comparison
between the used models is based on Average Absolute Relative Deviation (AARD) between
calculations and experimental solubility data (Eq. below)
In this paper, solubility of nine different solid components in supercritical CO2 was predicted
by using of PR-EOS with three various mixing rules. Moreover, calculation results are
compared with the experimental data which were reported in various literatures. Good
estimating results are achieved by using of this calculating method. For example, clim-basole
is one of the solids which were studied in this paper. The results of calculations for this
component are plotted in Figure 1. As can be seen in this figure, the best calculation results in
comparison with experimental data are the results of calculations obtained using PR-EOS
with MKM mixing rules.

Experimental solubility of triclocarbon in supercritical CO2 at various temperatures of 313.2,

323.2, 333.2 K, and the results of calculations by the proposed model are shown in Figure 2.
These figures show the experimental and calculation solubility data from 10 to 35 MPa.
These figures show that by increasing pressure, deviation between experimental data and
calculation results of the model by two mix-ing rules of Panagiotopoulos & Reid and van der
Waals mixing rules increased. But MKM mixing rules show good results at all ranges of
pressure.

For Irgacure 2959 photoinitiator a comparison between experimental data and the results of
calculations by the proposed models with three mixing rules of Van der Waals one fluid
mixing rules, Panagioto-poulos and Reid mixing rules, and MKM mixing rules are shown in
Figure 3. This figure shows that at pressures higher than 20 MPa, deviation between
experimental data and calculation results by two mixing rules of Van der Waals one fluid
mixing rules and Panagiotopoulos and Reid mixing rules becomes very large. The MKM
mixing rule showed good calculation results in all pressure ranges.

Based on the results reported in Figures 1-3 it can be concluded that the performance of
MKM mixing rules in comparison with other applied models is the best. The reported values
of AARD show that for the MKM mixing rules, the deviation between calculated results and
experimental data is very small.

PR-EOS with Kwak-Mansoori mixing rules is an equation of state with three temperature
independent parameters. In this equation, the thermodynamic variables were separated from
constants of PR-EOS. MKM mixing rules are based on original Kwak-Man-soori mixing
rules but they have been simplified by [19]. As can be shown in Figures 1-3, by using MKM
mixing rules, the accuracy of calculated results increased in comparison with other mixing
rules such as Panagiotopoulos and Reid mixing rules.

The calculated results of other researchers (by different models) are reviewed in Table 3. The
used thermodynamic models, number of adjustable para meters (that were used in the
proposed model), number of used experimental data for estimation of adjustable parameters
and the AARD between experimental and calculated values are reported in this table.

Comparison between the reported AARD in Table 2 and those in Table 3 can be useful for
comprehension of accuracy of different models.
It can be shown from Tables 2 and 3 that for climbazole and triclocarbon, the values of
AARD by MKM mixing rules are about half in comparison with those for other proposed
models.

For Irgacure 2959 photoinitiator and spiroindoli-nonaphthoxazine photochromic dye, AARD

of PR and SRK models in combination with temperature dependent mixing rules with six
adjustable parameters are about 0.1 and 0.13. These values with MKM mixing rules are also
about 0.1 and 0.13 but by use of three adjustable parameters.

For other components, the values in Tables 2 and 3 show that the PR-EOS in combination
with MKM mixing rules gives better results in comparison with other models.

Conclusion:
This paper studies the performance of different thermodynamic models for calculation of
solid solubility in supercritical fluids. The results showed that the type of mixing rules and
the number of adjustable parameters used in the mixing rules have major effects on the
accuracy of model.

Based on the comparison between experimental data and calculation results for nine studied
components it can be concluded that in comparison with the van der Waals mixing rules and
Panagiotopoulos and Reid mixing rules the MKM mixing rules with three adjustable
parameters show better results for modeling of solid solubility in SCF .

Table 1. Properties of the solids which were studied in this paper

Table 2. Average absolute relative deviations between the experimental data and calculation
results of CO2-solid systems by using the PR EOS with three temperature independent
mixing rules
Figure 1: Solubility of Climbasole in supercritical CO2 at various temperatures (A: 313.2, B:
323.2 and C: 333.2 K). (- - -): Calculation results by PR-EOS and van der Waals one fluid
mixing rules, (⋅⋅⋅): calculation results by PR-EOS and Panagiotopoulos and Reid mixing
rules, (─): calculation results by PR-EOS and MKM mixing rules and (●): experimental data
Figure 2: Solubility of Triclocarbon in supercritical CO2 at various temperatures (A: 313.2,
B: 323.2 and C: 333.2 K). (- - -): Calculation results by PR-EOS and van der Waals one fluid
mixing rules, (⋅⋅⋅): calculation results by PR-EOS and Panagiotopoulos and Reid mixing
rules, (─): calculation results by PR-EOS and MKM mixing rules and (●): experimental data
Figure 3: Solubility of Irgacure 2959 photoinitiator in supercritical CO2 at various
temperatures (A: 308.2, B: 318.2 and C: 328.2 K). (- - -): calculation results by PR-EOS and
van der Waals one fluid mixing rules, (⋅⋅⋅): calculation results by PR-EOS and
Panagiotopoulos and Reid mixing rules, (─): calculation results by PR-EOS and MKM
mixing rules and (●): experimental data
Table 3: Comparison between different thermodynamic models
Nomenclature

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