Activity Coefficient Models Describe EVL Binay Systems Ionic Liquids
Activity Coefficient Models Describe EVL Binay Systems Ionic Liquids
Activity Coefficient Models Describe EVL Binay Systems Ionic Liquids
c Pleiades Publishing, Ltd., 2010.
Abstract—Isothermal vapor–liquid equilibrium data of binary mixtures containing ionic liquids are
correlated using three activity coefficient models: UNIQUAC, Wilson, and NRTL. Twenty binary
systems taken from the literature were selected for this study. A genetic algorithm is used to
determine the interaction parameters for the three models. The results given by the three models
have been compared with experimental data, and show that the UNIQUAC model is the best method
to correlate and predict the vapor–liquid equilibrium of this type of systems.
DOI: 10.1134/S1810232810030070
1. INTRODUCTION
In recent years, room temperature ionic liquids (RTILs) or just ionic liquids (ILs) have come into
focus because of their potential as alternatives for several engineering applications [1]. The ionic liquids
are typically composed of a large organic cation and an inorganic polyatomic anion. There is virtually no
limit in the number of possible ionic liquids since there is a large number of cations and anions that can
be combined [2]. At ambient room temperature, they exist as liquids and have a wide variety of unique
properties (for instance, a negligible vapor pressure, favorable salvation behavior, low viscosity, and high
reactivity and selectivity) [3].
The increasing utilization of ILs in chemical and industrial processes requires reliable and systematic
thermophysical properties such as activity coefficients, heats of mixing, densities, solubilities, vapor–
liquid equilibria (VLE), and liquid–liquid equilibria (LLE). In addition, the transport properties are also
needed (viscosity, electric conductivity, mutual diffusion coefficients, etc.) [4]. For better understanding
of their thermodynamic behavior and for development of thermodynamic models, reliable experimental
phase equilibrium data are required [5]. Nevertheless, the number of published VLE data sets is still very
limited. But, in particular, reliable VLE data would allow one to check whether gE -models can be used
for the description of the real behavior of binary systems with ionic liquids and whether binary gE -model
parameters can be applied for the prediction of the VLE behavior of higher systems containing ionic
liquids [6].
In this work, isothermal vapor–liquid equilibrium data of binary mixtures containing ionic liquids
were correlated using three activity coefficient models. Twenty binary systems taken from the literature
were selected for this study. A genetic algorithm was used to determine the interaction parameters for
the three models. The results for the three models were compared, and the best model is recommended
to describe the VLE for mixtures with ILs.
*
E-mail: jlazzus@dfuls.cl
170
ACTIVITY COEFFICIENT MODELS 171
As known, the phase equilibrium problem to be solved consists in calculating some variables of the
set T − P − x − y (temperature, pressure, liquid–phase concentration and vapor-phase concentration,
respectively), when some of them are known. For a vapor–liquid mixture in thermodynamic equilibrium,
the temperature and the pressure are the same in both phases, and the remaining variables are defined
by the material balance and the “fundamental equation of phase equilibrium.” The application of this
fundamental equation requires the use of thermodynamic models that normally include binary interaction
parameters [7].
Classical thermodynamic models commonly used in the literature to treat these mixtures at a low
pressure required a great amount of binary parameters to be determined from experimental data [8].
These binary parameters must be determined using experimental data for binary systems. Theoretically,
once these binary parameters are known, one could predict the behavior of multicomponent mixtures
using standard thermodynamic relations and thermodynamics models [7].
The fundamental equation of vapor–liquid equilibrium can be expressed as the equality of fugacities
of each component in the mixture in both phases [8]:
The fugacity of a component in the vapor phase is usually expressed through the fugacity coefficient ϕ̄Vi :
The fugacity of a component in the liquid phase is expressed through either the fugacity coefficient ϕ̄L
i
or the activity coefficient γi :
f¯iL = xi ϕ̄L
i P, (3)
In these equations, yi is the mole fraction of component in the vapor phase, xi is the mole fraction of
component in the liquid phase, and P is the pressure. The fugacity is related to the temperature, the
pressure, the volume, and the concentration though a standard thermodynamic relation [9].
If the fugacity coefficient is used in both phases, the method of solution of the phase equilibrium
problem is known as an equation of state method. Then, equation of state (EoS) and a set of mixing
rules are needed, to express the fugacity coefficient as a function of the temperature, pressure and
concentration [7]. Modern equations of state methods include an excess Gibbs free energy model (gE ) in
the mixing rules of the equation of state, giving origin to the so-called equation of state + gE model [10].
This means that an activity coefficient model (γ) is used to describe the complex liquid phase, and the
fugacity coefficient (ϕ) is calculated using a simple equation of state. If the fugacity coefficient is used for
the vapor phase and the activity coefficient is used for the liquid phase, the equilibrium problem is known
as a gamma–phi method. This method has given acceptable results for some systems [7, 8].
Most models available in literature for the activity coefficient are of the correlating type (Van Laar,
Margules, Redlich-Kister, NRTL, UNIQUAC and Wilson), meaning that experimental data are needed
to calculate certain empirical parameters; although some predictive models are also available (UNIFAC,
ASOG). These predictive models have been used in several applications, and recently including mixtures
with some ILs [5, 6, 11]. But to the best of authors’ knowledge, there is no systematic studies on binary
mixtures, such as the one presented here, which have included several compounds and ILs.
In this study, three activity coefficient models most commonly used (UNIQUAC, Wilson, and
NRTL), are analyzed for binary systems containing ILs. For all the models, the interaction parameters
(Aij for Wilson, Bij and αij for NRTL, and Uij for UNIQUAC) are calculated using VLE data.
Thus, the experimental vapor–liquid phase data can be correlated with the Peng–Robinson (PR) EoS,
and the Wong and Sandler (WS) mixing rule [7].
The PR EoS can be expressed as follows:
RT a
P = + , (6)
V − b V (V + b) + b(V − b)
R2 Tc2
a = 0.457235 α(Tr ), (7)
Pc
RTc
b = 0.077796 , (8)
Pc
2
α(Tr ) = 1 + κ(1 − Tr ) , (9)
The WS mixing rules used in this EoS can be summarized as follows [7]:
N
N a
xi xj b −
i j RT ij
bm = , (12)
xi ai
N AE
∞ (x)
1− −
i bi RT ΩRT
√
a 1 ai aj
b− = (bi + bj ) − (1 − kij ), (13)
RT ij 2 RT
N
xi ai AE (x)
am = bm + ∞ . (14)
bi Ω
i
In these equations am and bm are the EoS constants, kij is the adjustable parameter with Ω = 0.34657,
and AE ∞ (x), the excess Helmholtz free energy at the limit of infinite pressure is calculated using an
activity coefficient model and assuming that AE∞ ≈ A0 ≈ g0 [10].
E E
⎛ ⎞
E
gR
=− qi xi ln ⎝ θj τji ⎠. (17)
RT
i j
⎡ ⎛ ⎞ ⎤
θi τij
ln γiR = qi ⎣1 − ln ⎝ θj τji ⎠ −
⎦. (19)
θk τkj
j j
k
The volume (ϕi ) and surface (θi ) fractions are detailed as:
ri xi
ϕi =
, (20)
rj xj
j
qi xi
θi =
. (21)
rj xj
j
The required ri and qi parameters for UNIQUAC are calculated according to Bondi [13], and the
equation below must be satisfied with the coordination number (z) equal to 10:
z
li = (ri − qi ) − (ri − 1). (22)
2
The adjustable parameter τji is detailed as:
Aij − (Uij − Uji )
τji = exp (23)
RT
with
bij (Uij − Uji )
aij + = Aij + , aij = Aij , (24)
T RT
(Uij − Uji )
bij = − , (25)
R
where Uij and Uji represent the interaction energy difference between i − j and j − j pair molecules and
between j − i and i − i pair molecules, respectively, R is the universal constant of gases, and T is the
temperature.
Based on this equation, we obtained the expression for the liquid phase activity coefficients as [7]:
⎛ ⎞
N
N
xk Aki
ln γi = − ln ⎝ xj Aij ⎠ + 1 − . (27)
N
j=1 k xj Akj
j=1
In this expression,
Vj (λij − λii )
Aij = exp − , (28)
Vi RT
where Vi is the liquid molar volume of the component i, λij − λii is the empirical energy term, and xi
is the mole fraction of the component i. The parameters: Aij and Aji , represent the interaction energy
difference between i − j and j − j pair molecules and between j − i and i − i pair molecules, respectively.
In the non-random-two-liquid model (NRTL), the Gibbs free energy for a binary mixture is given
as [7]:
⎛ N ⎞
⎜ Gji τji xj ⎟
gE N
⎜ j ⎟
= xi ⎜ln N ⎟; (29)
RT ⎝
⎠
i Gki xk
k
and the expression of activity coefficient for this model has the following form [15]:
⎡ ⎤
N
τji Gji xi xj Gji ⎢ τki Gkj xk ⎥
j
N
j ⎢ k ⎥
ln γi = N + ⎢τij − N ⎥ (30)
N ⎣
⎦
Gki xk j Gkj xk Gkj xk
k k k
with
τji = Bji /T, (31)
where Bij and Bji represent the interaction energy difference between i − j and j − j pair molecules
and between j − i and i − i pair molecules, respectively; R is the universal constant of gases, and T
is the temperature. The terms Bij , Bij , and αij are the adjustable parameters usually calculated from
experimental VLE data.
Table 1. Nomenclature and structure of the ionic liquids involved in this study
Table 2 shows the thermodynamic properties for the ILs [17,18] and for the other compounds [19]
used. In the table, M is the molecular weight, Tc is the critical temperature, Pc is the critical pressure,
Vc is the critical volume, and ω is the acentric factor. The required Van der Waals parameters (ri and qi )
for the UNIQUAC model were estimated according to Bondi [13].
Twenty isothermal (P − x) VLE systems containing ILs were considered in this study. Phase
equilibrium data of these mixtures are necessary for further development of some physico-chemical
processes involving ILs. These systems are of interest for the conception of industrial operations as
environmental, chemical industries, among others. The experimental VLE data taken from the literature
for the ionic liquid systems [5, 6, 11] are described in Table 3. As seen in this table, the temperature and
pressure ranges are narrow and go from 353 to 373 K and from 1 to 227 kPa, respectively.
genotype of the new individual. Crossover occurs with a random probability. The mutation operator
simulates natural mutation of DNA. This simply involves flipping bits in the string in a stochastic
manner. Mutation should be fairly infrequent and should be applied following crossover [20].
The most significant differences between GA and more traditional search and optimization methods,
are: (i) GAs search a population of points in parallel, not a single point: (ii) GAs do not require derivative
information or other auxiliary knowledge; only the objective function and the corresponding fitness levels
influence the directions of search; (iii) GAs use probabilistic transition rules, not deterministic ones; and
(iv) GA work on an encoding environment of the parameter set rather than the parameter set itself [22].
The interaction parameters: Aij for Wilson, Bij and αij for NRTL, and Uij for UNIQUAC, were
determined using a GA optimization programmed in MATLAB version 6.5.0 [23]. The procedure was
based on the minimization of the overall objective function (OF):
ND
100 Pcalc − Pexp
,
OF = |%ΔP | = (34)
ND Pexp i
i=1
where ND is the number of data point, P is the system pressure, and the subscripts exp and calc refer to
the experimental and calculated values.
An exhaustive trial-and-error procedure was applied for tuning the GA parameters. Table 4 shows
the selected parameters for the GA optimization. Figure 1 shows a flow diagram of the GA optimization
used for the vapor–liquid equilibrium modelling.
Fig. 1. Flow diagram of the GA used for the vapor–liquid equilibrium modelling.
GA Parameters Value
Number of generations (Gen) 50
Number of individuals (Ni ) 25
Length of chromosome (L) 20
Length of individuals (Li ) 80
Crossover probability (Cros) 0.8
Mutation probability (Mut) 0.1
Crossover operator Multipoint
Mutation operator Binary
Objective function Eq. (34)
Fig. 2. Average deviations obtained for the interaction parameters: Uij for UNIQUAC (), Aij for Wilson (Δ), and
Bij for NRTL (), determined using GA optimization.
with the GA optimization show that the VLE of binary systems containing ILs can be correlated with
low deviations between experimental and calculated values. These results indicate that the UNIQUAC
model is reliable enough to estimate VLE for the twenty binary systems containing ILs used in this work
(see Table 3), with |%ΔP | deviations a bit higher than 5%. Although one model gives better results for
some particular cases, it is not possible to generalize the results and select one of the models used as the
best one for this type of complex mixtures containing ILs. If better results are desired, further studies are
needed with data restricted to narrow ranges of temperature, pressure, and concentration.
Figure 3 shows an example of the accuracy of the three models to describe VLE of binary systems
containing ILs. The figure shows experimental and correlated VLE of acetone (1), 2-propanol (1),
tetrahydrofuran (1), and water (1) in [emim] [Tf2N] (2). As is observed in the figure, the best method to
Table 5. Parameters (Uij , Aij , Bij , and αij ) for the models UNIQUAC, Wilson and NRTL calculated with GA
optimization from experimental VLE data
Acetone (1) 207.54 −257.92 3.6 −641.29 1911.42 5.4 601.29 −768.79 0.205 5.3
2-Propanol (1) 179.31 102.37 4.9 227.04 2460.10 6.6 911.51 −203.39 0.398 5.6
Tetrahydrofuran (1) 403.34 −216.26 4.4 −177.76 1649.33 5.3 −48.60 36.60 0.368 4.7
Water (1) −135.95 887.57 3.9 1661.02 2409.81 5.1 1436.82 −185.16 0.273 5.9
Acetone (1) 288.98 −314.52 2.9 −409.59 −208.34 4.5 422.33 −621.61 0.397 5.5
2-Propanol (1) 280.44 −293.90 3.8 −27.85 2403.20 4.2 1314.90 −617.66 0.204 4.6
Water (1) −142.93 1004.70 6.3 1609.80 2494.52 6.6 1508.50 −233.77 0.251 5.1
Octane (1) 95.43 353.02 5.2 1658.50 2343.80 7.4 1561.71 438.42 0.204 5.9
Nonane (1) 924.53 −75.32 4.1 1905.31 2498.71 6.9 674.48 788.17 0.218 5.2
Toluene (1) 927.19 −417.51 5.6 −74.49 2488.43 6.8 1567.82 −557.60 0.211 5.1
Acetone (1) 1548.33 −504.98 6.9 304.00 2494.34 6.7 2145.32 −684.02 0.202 5.8
Ethanol (1) −104.54 −508.85 5.2 −960.02 2485.00 6.7 316.38 −986.76 0.395 4.5
Tetrahydrofuran (1) 538.41 −45.77 5.8 971.42 2495.41 6.1 1568.01 −267.10 0.204 5.6
Water (1) −621.56 −799.31 6.8 −740.11 −999.27 5.9 −311.95 −998.89 0.396 5.4
Hexane (1) 235.60 187.34 5.7 932.61 2490.72 7.2 2247.00 10.19 0.201 6.4
Water (1) 56.49 815.46 6.8 1772.33 2383.91 7.5 −196.01 769.39 0.293 6.1
Hexane (1) 325.89 68.99 4.9 694.65 2498.62 7.1 2075.03 91.64 0.239 6.6
1-Butanol (1) 1201.01 −672.67 4.9 428.14 −947.57 6.9 −636.55 676.05 0.374 5.8
Ethanol (1) −673.68 863.52 5.8 −896.82 2481.83 6.7 713.24 −846.97 0.358 6.6
1-Propanol (1) −579.99 616.78 5.5 −382.80 −975.75 6.9 −870.88 −379.23 0.393 6.2
estimate VLE of the systems used is the UNIQUAC model. This figure ratifies the discussion presented
above.
8. CONCLUSIONS
In this work, three activity coefficient models (UNIQUAC, Wilson, and NRTL) were used to describe
the isothermal vapor–liquid equilibrium of twenty binary mixtures containing ionic liquids. Based on the
results and discussion presented in this study, the following main conclusions were obtained:
(i) the UNIQUAC model is appropriate to modeling VLE for binary systems that contain the ionic
liquids presented above;
(ii) although one model gives better results for some particular cases, it is not possible to generalize
the results and select one of the models used as the best one for this type of complex mixtures
containing ILs.
Fig. 3. Experimental vapor–liquid equilibrium of the systems [emim] [Tf2N] with: acetone (—), 2-propanol (– –),
tetrahydrofuran (- - -), water (· – ·), and correlated values of: () UNIQUAC, (Δ) Wilson, and () NRTL.
ACKNOWLEDGMENTS
The first author thanks the Direction of Research of the University of La Serena and the Department
of Physics of the University of La Serena for the special support that made possible the preparation of
this paper.
NOTATIONS
Symbols
Aij —Wilson parameter
Bij —NRTL parameter
M —molecular weight
ND —number of points in a data set
P —pressure
Pc —critical pressure
qi —Van der Waals area parameter
R—universal gas constant
ri —Van der Waals volume parameter
T —system temperature
Tc —critical temperature
Vc —critical volume
xi —mole fraction in the liquid phase
yi —mole fraction in the vapor phase
Abbreviations
GA—genetic algorithm
LLE—liquid-liquid equilibrium
OF—objective function
VLE—vapor-liquid equilibrium
Greek letters
α—NRTL parameter
ϕ—fugacity coefficient
γ—activity coefficient
ω—acentric factor
Super/subscripts
calc—calculated
exp—experimental
i, j—component
L—liquid
V —vapor
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