Fluid Phase Equilibria 243 (2006) 51–56

Liquid–liquid equilibria for the system (water + carboxylic

acid + chloroform): Thermodynamic modeling
Aynur Senol ∗
Istanbul University, Faculty of Engineering, Department of Chemical Engineering, 34320 Avcilar, Istanbul, Turkey
Received 27 October 2005; received in revised form 17 February 2006; accepted 18 February 2006
Available online 28 February 2006

Abstract
Liquid–liquid equilibrium (LLE) data of the solubility curves and tie-line end compositions are presented for mixtures of [water (1) + acetic
acid, or pyruvic acid, or valeric acid (2) + chloroform (3)] at T = 293.15 K and atmospheric pressure. Among the studied ternary systems, the largest
separation factors give valeric acid. A solvation energy relation (SERLAS) has been used to estimate the liquid–liquid equilibria of associated
systems containing a protic solvent. The tie-lines were also predicted through the UNIFAC-original model. The reliability of both models has been
analyzed against the LLE data with respect to the distribution ratio and separation factor. SERLAS matches LLE data relatively accurately, yielding
a mean error of 18.5% for all the systems considered.
© 2006 Elsevier B.V. All rights reserved.

Keywords: Liquid–liquid equilibria; Carboxylic acid; Chloroform; UNIFAC; SERLAS

1. Introduction chloroform as a polar and protic extracting agent was made. It

The efficient separation of carboxylic acids from aqueous
solutions is an important concept in the chemical fermentation
industry where many solvents have been tested to improve such
recovery [1–6]. Especially, extractive recovery of acetic acid
by selective solvent systems from aqueous solutions, such as
fermentation broth and wastewater including lower than 10%
(w/w) acid concentrations has received increasing interest [7,8].
Three major factors have been found to influence the equilibrium
characteristics of solvent extraction of a carboxylic acid from
aqueous solutions, i.e., the nature of acid, the concentration of
acid, and the type of organic solvent. Simultaneously, the impact
of additional controlling factors, such as the swing effect of a
mixed solvent and the third-phase formation, can also modify
the equilibrium. Process considerations dealing with the physi-
cal extraction of hydrophobic acids through hydrogen bonding
or dipole–dipole interaction are still challenging because such
systems show extremely nonideal behavior.
Regarding the technical and economic merits of low boiling
solvents during the regeneration by distillation, the selection of
∗ Fax: +90 212 4737180.
E-mail address: senol@istanbul.edu.tr.
has lower boiling temperatures than water and carboxylic acids.
Most chlorinated hydrocarbon solvents used to extract a car-
boxylic acid show a distribution coefficient less than one [1,9].
Nevertheless, such studies, besides other purposes, are indis-
pensable in calibration and verification of analytical models.
Liquid–liquid equilibrium (LLE) data for extraction of a car-
boxylic acid from water through chlorinated hydrocarbons are
scarce in the literature [9,10].
As continuation of the previous study [11–13], the present
work aims to produce new LLE data for the extraction of C2–C5
carboxylic acids from water using a proton-donating chlorinated
hydrocarbon compound (chloroform) of high vapor pressure
than water and acid. The LLE data have been determined for each
of the systems (water + acetic acid, or pyruvic (2-oxopropanoic)
acid, or valeric (pentanoic) acid + chloroform) at 293.15 K.
In this study, the properties and liquid + liquid equilibria of
associated ternary mixtures have been correlated through a sol-
vation energy relation (SERLAS) [11]. The model incorporates
the solvatochromic parameters [14,15] with the thermodynamic
factors derived from the UNIFAC-Dortmund model [16] in a
relation including expansion terms and two correction factors.
The tie-lines were also predicted using the UNIFAC-original
model [17,18], and compared with the distribution data evalu-
ated through SERLAS.

0378-3812/$ – see front matter © 2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2006.02.017
52 A. Senol / Fluid Phase Equilibria 243 (2006) 51–56

2. Experimental

Chloroform (99.5%, GC) and C2–C5 carboxylic acids of

analytical grade (≥99%, GC) were supplied by Fluka. All the
chemicals were used as received without further purification.
Mass fractions of impurities detectable by GC were found to be
<0.002. Deionized and redistilled water was used throughout all
experiments.
The binodal (solubility) curves were determined by the
cloud point method in an equilibrium glass cell with a water
jacket to maintain isothermal conditions [11–13]. The temper-
ature in the cell was kept constant by circulating water from
a water bath (Julago Labortechnik GMBH, Germany), which
is equipped with a temperature controller capable of maintain-
ing the temperature within ±0.1 K. The major central part of
the solubility curves was obtained by titrating heterogeneous
mixtures of (water + chloroform) with the acid until the turbid-
ity had disappeared. For the water-side and solvent-side lim- Fig. 1. Liquid–liquid equilibria (mole fraction) for the system (x1 water + x2
ited regions in which the curve and the sides of the triangle acetic acid + x3 chloroform) at 293.15 K: () solubility (binodal curve) data;
are close and exhibit similar slopes, binary mixtures of either () experimental tie-lines (solid line); (♦) UNIFAC-predicted end compositions
(dashed line).
(water + acid) or (solvent + acid) were titrated against the third
component until the transition from homogeneity to cloudiness
was observed. All mixtures were prepared by mass with a Met- and xi refer to the mole fractions of the ith component in
tler scale accurate to within ±10−4 g. Mutual solubility values of the aqueous and solvent phases, respectively. The experimental
the (water + chloroform) binary were measured using the method and calculated tie-lines through UNIFAC-original and solubility
based on the detection of the cloud point [11–13]. The transi- isotherms of the studied ternaries are plotted on equilateral tri-
tion point between the homogeneous and heterogeneous zones angular diagrams in Figs. 1–3. The shape of the binodal curves
was determined visually. The reliability of the method depends and the slopes of the tie-lines in Figs. 1–3 show that the dis-
on the precision of the Metrohm microburette with an accu- tribution of acid in the (water + chloroform) mixture is very
racy of ±0.01 cm3 , and is limited by the visual inspection of much dependent on the carbon number and the type of the trans-
the transition across the apparatus. Concentration determina- ferred solute. In the ternary systems, water is most soluble in
tions were made with an uncertainty of ±0.001 mass fraction. the system containing acetic acid. Figs. 1–3 show that the area
End-point determinations of the tie-lines were based upon the of the two-phase heterogeneous region for the studied mixtures
independent analysis of the conjugate phases that were regarded decreases in the order: acetic acid < pyruvic acid < valeric (pen-
as being in equilibrium. Mixtures of known masses of water, tanoic) acid. This implies that an increase in the carbon chain
solute (acid) and chloroform lying within the heterogeneous gap
were introduced into the extraction cell and were stirred vigor-
ously for at least 2 h, and then left for 5 h to settle down into
raffinate (aqueous) and extract (solvent) layers. The composi-
tions of liquid samples withdrawn from the conjugate phases
were analyzed using a Hewlett-Packard GC Analyzer, model
5890A, equipped with flame ionization (FI) detector. A cross-
linked methyl silicone capillary column, HP1-type (50 m long,
0.2 mm i.d., 0.5 ␮m film thickness) was utilized to separate the
organic components of samples at tailorized oven programs
suitable for each ternary. The detector temperature was kept
at 523.2 K, while the injection port temperature was held at
473.2 K. Injections were performed on the split 1/100 mode.
Nitrogen was used as a carrier at a rate of 6 cm3 /min.

3. Results and discussion

The compositions of mixtures on the binodal curve and the

mutual binary solubilities of water and chloroform at 293.15 K
are given in Figs. 1–3, in which xi denotes the mole fraction
of the ith component. Table 1 summarizes the experimental
tie-line compositions of the equilibrium phases, for which xi
Fig. 2. Liquid–liquid equilibria (mole fraction) for the system (x1 water + x2
pyruvic acid + x3 chloroform) at 293.15 K: () solubility (binodal curve) data;
() experimental tie-lines (solid line); (♦) UNIFAC-predicted end compositions
(dashed line).
 A. Senol / Fluid Phase Equilibria 243 (2006) 51–56 53

Table 2
Distribution coefficient (D), separation factor (S) and distribution ratio (DM ) for
the systems (water + carboxylic acid + chloroform), observed and modeled due
to the UNIFAC-original model
System D S DM

Observed Modeled Observed Modeled Observed Modeled

Acetic 1.12 1.18 38.0 66.1 508.7 531.6

acid
1.35 1.23 34.2 40.3 100.5 97.3
1.44 1.30 23.9 22.5 34.9 32.8
1.46 1.38 15.5 13.9 16.4 15.5
1.39 1.42 10.1 8.6 8.4 8.2
Pyruvic 0.61 0.93 10.6 92.4 296.9 398.3
acid
0.86 0.87 12.3 50.9 88.9 107.2
0.92 0.86 8.7 28.5 38.1 43.3
0.83 0.90 6.3 14.4 17.8 18.3
0.69 1.04 3.6 7.7 8.1 9.0
Fig. 3. Liquid–liquid equilibria (mole fraction) for the system (x1 water + x2 Valeric 46.0 95.7 662.3 1304.4 1937.3 6002.3
valeric acid + x3 chloroform) at 293.15 K: () solubility (binodal curve) data; acid
() experimental tie-lines (solid line); (♦) UNIFAC-predicted end compositions 56.8 102.7 384.4 818.8 496.6 1240.7
(dashed line). 66.8 92.5 339.2 502.7 213.5 388.6
72.5 75.9 287.6 308.3 120.6 164.9
75.5 63.9 270.5 208.4 85.3 95.6
length of the transferred solute results in an increase in the area
of the two-phase region, and also that water is most soluble in
the (chloroform + acetic acid) mixture and least soluble in the The slope of the tie-lines, i.e., the distribution coefficient
(chloroform + valeric acid) mixture. defined as the ratio of the mole fractions of the carboxylic
acid (2) in the chloroform-rich phase to the water-rich phase
(D = x2 /x2 ), shows that pyruvic acid is more soluble in the
Table 1 aqueous phase than the organic phase, as compared to valeric
Thermodynamic factors (Γ L ) and experimental tie-line compositions (mole acid yielding extremely large D > 1 (Table 2). As evident from
fraction) of the conjugate solutions, x1 , x2 and x1 , x2 for the system Fig. 1 and Table 2, acetic acid is slightly more soluble in the
(water + carboxylic acid + chloroform) at T = 293.15 K organic phase than the aqueous phase, yielding D about 1. From
Water-rich Chloroform-rich Γ La (GE )b the tested C2–C5 acids, the lowest D values show pyruvic acid in
(J mol−1 ) the (water + chloroform) mixture. The distribution of valeric acid
x1 x2 x1 x2
in chloroform is about 15–30 times larger as compared to acetic
Water (1) + acetic acid (2) + chloroform (3) and pyruvic acids (Figs. 1–3). The same remarks hold for the
0.9989c 0 0.0092c 0
0.9691 0.0296 0.0286 0.0332 0.9987 342.8
separation factor (S) and distribution ratio of these acids given
0.9277 0.0707 0.0367 0.0956 0.9959 405.3 in Table 2. This may be attributed to the solubilising effect of the
0.8792 0.1187 0.0531 0.1711 0.9920 489.5 methyl group for valeric acid having the longest R-chain struc-
0.8276 0.1692 0.0770 0.2476 0.9877 557.1 ture and a low ionizing strength (pKa,V = 4.842), categorizing the
0.7571 0.2381 0.1041 0.3305 0.9834 575.2 acid structure as a less hydrophilic and more capable of associa-
Water (1) + pyruvic acid (2) + chloroform (3) tion with the protic chlorinated hydrocarbon solvent. However,
0.9989c 0 0.0092c 0 the existence of only one methyl group on acetic acid makes the
0.9593 0.0388 0.0547 0.0235 0.9943 554.5
structure moderately hydrophobic, whereas the carbonyl group
0.9197 0.0776 0.0640 0.0667 0.9844 526.7
0.8807 0.1157 0.0925 0.1063 0.9751 580.8 (CO) on pyruvic acid is responsible for a highly hydrophilic acid
0.8071 0.1873 0.1051 0.1546 0.9649 510.7 structure. These concepts can be verified by the results from
0.6887 0.2997 0.1327 0.2062 0.9538 460.7 Figs. 1–3 and Tables 1 and 2, indicating the fact that the con-
Water (1) + valeric acid (2) + chloroform (3) trolling factor for the physical extraction is the hydrophobicity
0.9989c 0 0.0092c 0 of the acid. Referring to Figs. 1–5, the extraction degree of the
0.9966 0.0015 0.0692 0.0701 1.0023 606.8 solute in chloroform decreases in the order, pyruvic acid < acetic
0.9948 0.0032 0.1469 0.1828 1.0090 880.9 acid < valeric acid. It is also expected that the ionizing strength
0.9929 0.0050 0.1955 0.3327 1.0173 923.2
0.9913 0.0064 0.2499 0.4663 1.0251 1034.8
of acid (pKa,Py = 2.490; pKa,Ac = 4.756; pKa,V = 4.842 [25]) will
0.9900 0.0076 0.2762 0.5733 1.0293 1101.4 affect the extraction equilibria.
a
The effectiveness of extraction of carboxylic acids (2) by a
Thermodynamic factors of the solute (acid) in terms of Eq. (2).
b protic chlorinated hydrocarbon is indicated by its selectivity (or

energy function for organic phase due to UNIFAC-
Excess Gibbs free
separation factor, S) defined in the mole-fraction scale as the
Dortmund, GE = RT i xi ln γ i .
c Mutual solubility value. ratio of distribution coefficients of the solute (2) to water (1),
54 A. Senol / Fluid Phase Equilibria 243 (2006) 51–56

yielding a mean relative error ē (%) with regard to the acid mole
fraction (x2 ) variable of 21.7% considering all of the systems
studied.

4. Correlation of LLE data by SERLAS

In the previous study [11], the properties (Pr) of ternary liquid

Fig. 4. Variation of separation factor (S) with the initial acid mole fraction (xi )
for the ternary systems (water + carboxylic acid + chloroform), experimental and
theoretical through SERLAS, solid line Eq. (1).
S = D2 /D1 = (x2 /x2 )/(x1 /x1 ), and is presented in Fig. 4 and
Table 2. The prime refers to the water-rich phase, and the double
prime refers to the chloroform-rich phase. From the selectivity
and distribution ratio data, it can be concluded that the sepa-
ration of the C2–C5 carboxylic acids from water by extraction
with chloroform is feasible, yielding S > 1 (Figs. 4 and 5, and
Table 2). Chloroform is a less favorable solvating agent for pyru-
vic acid and acetic acid. It is also apparent from Figs. 4 and 5 that
chloroform is the most appropriate solvent for the separation of
a mixture of water and valeric acid.
The end compositions of the tie-lines for the studied ternaries
were predicted using the UNIFAC-original model along with the
LLE-UNIFAC group interaction parameters [17,18]. A program
of multivariate (Levenberg-Marquardt) convergence was used
to solve the implicit LLE equations [19,20]. Consequently, the
UNIFAC-original model proved to be moderately accurately,
systems, such as the separation factor (S = (x2 /x1 )/(x2 /x1 ))
and the modified distribution ratio (DM = {(x2 + x3 )/(1 −
x3 )}/{(x2 + x3 )/(1 − x3 )}), were estimated using a solvation
energy relation (SERLAS). x and x designate solvent-rich
and water-rich compositions of water (1), acid (2) and sol-
vent (3), respectively. The model includes a part accounting
for the properties at the composition limit of acid x2 = 0(Pr0 ),
and an expansion term with respect to the thermodynamic fac-
tor (Γ L ), the Hildebrand solubility parameter (δH ), and the
modified solvatochromic parameters π* , α* and β* . The cor-
responding Pr0 properties attributed to the mutual solubility
region (x2 = 0) are defined as, S0 = (x03  /x )/(x /x ) and
01 03 01
   
DM0 = (x03 /1 − x03 )/(x03 /1 − x03 ), where x03 and x01 denote
the mole fractions of mutual solubility of solvent and water,
respectively [11]:

Pr = F1 Pr0 + F2 · {CΓ,k (ΓL )k + CH,k (δ∗H )k + Cπ,k (π∗ )k
k
+ Cβ,k (β∗ )k + Cα,k (α∗ )k } (1)
Composition dependent correction factors (F) represent a
solvent-basis composition ratio (F1 = x3 /x3,max = (x3 −
x3 )/(x03
 − x )) and a water free correction factor (F =
03 2
 
x3 /(x2 + x3 ) − x3 /(x2 + x3 )), respectively. For a n-component
system, thermodynamic factor (Γ L ) in terms of the transferring
solute (acid) composition (x2 ) relative to the organic phase is
obtained by Eq. (2) due to Taylor and Kooijman [21]:

∂(ln γ2 ) 
ΓL = 1 + x2 · (2)
∂x2 Σ
where the symbol Σ (constrained condition) means that the dif-
ferentiation with respect to the acid composition (x2 ) is to be
carried out while keeping all other mole fractions xk (k = j, k = 1,
. . ., n − 1) constant except the nth. In this study, Γ L values were
predicted from UNIFAC-Dortmund model using the derivative
approaches for the activity coefficient (γ i ) of Mori et al. [22]. The

Table 3
Hildebrand solubility parameter (δH ), and solvatochromic parameters of
compounds

Compound πa,b βa,b αa,b δH c,d (MPa0.5 ) δa,b

Acetic acid 0.60 0.45 0.71 20.7 0.0

Pyruvic acid 0.62 0.45 0.60 23.6 0.0
Valeric acid 0.54 0.45 0.56 22.1 0.0
Chloroform 0.58 0.10 0.20 19.0 0.5
Water 1.09 0.47 1.17 47.9 0.0
a Ref. [14].
Fig. 5. Plot of distribution ratio (DM ) against initial acid mole fraction (xi ) b Ref. [15].
for the ternary systems (water + carboxylic acid + chloroform), experimental vs. c Ref. [24].
modeled through SERLAS, solid line Eq. (1). d Ref. [25].
 A. Senol / Fluid Phase Equilibria 243 (2006) 51–56 55

Table 4
Coefficients Ci of Eq. (1) and root-mean-square deviation (σ), and mean relative error (ē, %)a evaluated for different properties Pr of the ternary systems
(water + carboxylic acid + chloroform)
Ternary system CΓ CH Cπ Cβ Cα

Pr = ln(S); Pr0 = ln(S0 ); σ(S); ē(S)

Acetic acid (σ = 0.93; ē = 2.7%) 12.35 0.00006 −109.53 86.32 19.94
Pyruvic acid (σ = 1.66; ē = 17.0%) 112.85 −0.00005 −726.38 106.79 473.01
Valeric acid (σ = 158.33; ē = 39.4%) 134.56 0.00025 −1029.36 −535.97 907.35
Pr = ln(DM ); Pr0 = ln(DM0 ); σ(DM ); ē(DM )
Acetic acid (σ = 7.12; ē = 3.6%) −81.72 −0.00030 407.69 −410.09 −36.29
Pyruvic acid (σ = 17.08; ē = 10.2%) −61.65 0.00011 336.54 −299.98 −128.33
Valeric acid (σ = 72.95; ē = 38.0%) 103.77 0.00018 −774.43 −429.18 681.39

N
a ē, % = (100/N) i=1
|(Yi,obs − Yi,mod )/Yi,obs |.

variation of Γ L and excess Gibbs free energy function (GE ) with
composition attributed to the organic phase species are shown
in Table 1.
Modified solvatochromic parameters are evaluated as [11]:
δH,2 δH,m
δ∗H = ; π∗ = (π2 − 0.35δ2 )πm ; β∗ = β2 βm ;
1000
α∗ = α2 αm (3)
SERLAS was processed assuming the degree of expansion
k = 1. Index “2” designates the properties of the distributed
(extracted) solute component. The subscript “m” denotes the
parameters related to the mixture in terms of x composition in
the organic phase,
assuming the
additional parameter estimation

the associated systems capable of hydrogen-bond formation.
rule, i.e.,

δH,m = i x i δ H,i ; π m = i xi (π i − 0.35δi ); βm = i xi β i ;
αm = i xi αi , where δH is the Hildebrand solubility parameter.
π, δ, α and β are the solvatochromic parameters that measure
the abilities of components to dipole–dipole interaction and
hydrogen-bond formation [11]. The coefficients Ci of Eq. (1)
were obtained by application of multivariable regression pro-
cedures of linpack algorithm [23], using the parameters from
Table 3, and the thermodynamic factors according to Eq. (2)
applied to the UNIFAC-Dortmund model by Mori et al. The
resulting C coefficients corresponding to S and DM properties
as well as a comparison with the observed performance in terms
of the mean relative error (ē, %) and root-mean-square deviation
(σ) are presented in Table 4.
5. Model reliability analysis
Distribution data of C2–C5 acids obtained for the ternary
systems (water + carboxylic acid + chloroform) have been pro-
cessed to analyze the reliability of both SERLAS and UNIFAC-
original models. Figs. 4 and 5 and Tables 2 and 4 present a quan-
titative assessment of the predictions achieved for these models
in terms of S and DM variables. It is apparent from Figs. 4 and 5
that SERLAS matches the distribution data of a carboxylic
acid for (water + acid + chloroform) system reasonably over the
entire composition range,

yielding the overall mean relative
error (ē, % = (100/N) N i=1 |(Yi,obs − Yi,mod )/Yi,obs |) and root-
mean-square deviations (σ) of ē(S) = 19.7% and σ(S) = 53.64,
and ē(DM ) = 17.3% and σ(DM ) = 32.38 considering all the sys-
tems studied. The reliability of Eq. (1) proved to be slightly less
accurate for valeric acid in terms of S and DM , yielding ē(S) =
39.4% (σ(S) = 158.33) and ē(DM ) = 38.0% (σ(DM ) = 72.95).
Conversely, the UNIFAC-original model reproduces the distri-
bution behavior of carboxylic acids less accurately with mean
errors and deviations ē(S) = 130.9% (σ(S) = 136.67), ē(DM ) =
39.6% (σ(DM ) = 635.48) and ē(D) = 26.8% (σ(D) = 11.05),
considering all of the systems studied (Table 2).
Besides the accuracy of the model prediction, SERLAS also
conforms the trend of the extraction equilibrium, as evident from
Figs. 4 and 5. However, it is essential that this phenomenon
will have a significant impact on the implementation of a simu-
lation algorithm incorporating the prediction by SERLAS for
It is expected that Eq. (1) will predict the extraction behavior
of an organic acid attributed to all types of solvents with sol-
vatochromic parameters being evaluated through Marcus and
co-workers [14,15].
6. Conclusions
LLE data for the three ternary mixtures [water (1) + acetic
acid, or pyruvic acid, or valeric acid (2) + chloroform (3)] were
determined at 293.15 K. It is apparent from the distribution and
selectivity data that the separation of C2–C5 acids from water
by extraction with chloroform is feasible for valeric and acetic
acids (Table 2 and Figs. 1–5). The distribution of C2–C5 car-
boxylic acids in the (water + chloroform) two-phase system is
better for acetic and valeric acids than pyruvic acid. The differ-
ences among S and DM factors indicate the fact that the protic
solvent chloroform is an effective separation agent for a partic-
ular hydrophobic acid (Figs. 4 and 5).
SERLAS is presumably an improved method for pro-
cessing LLE data, which clarifies the simultaneous impact
of hydrogen bonding, solubility and thermodynamic factors
of components on the extraction equilibria of the ternaries
(water + acid + chloroform). Referring to Figs. 4 and 5, it can
be concluded that the SERLAS model, along with the evalu-
ated coefficients, matches the experimental data for acetic and
pyruvic acids quite well. The prediction through SERLAS for
valeric acid is presented by a scattered line that does not appear
to correlate the data well. This looks like a case where the regres-
56 A. Senol / Fluid Phase Equilibria 243 (2006) 51–56
sion program met the convergence criteria but convergence was
not actually achieved. The SERLAS model could be modified
with a view to improving its capability of representing the sys-
tem covered hydrophobic valeric acid by applying the degree
of expansion term greater than one. It is disputable whether
the accuracy of prediction may be improved using more than
five variables. From the tested two models, UNIFAC-original
predicts less accurately the extraction equilibria of the ternary
systems yielding a mean error and deviation of ē = 85.2% and
σ = 386.07, as compared to ē = 18.5% and σ = 43.01 for the
SERLAS model in terms of S and DM factors, respectively.
Acknowledgments
The author is grateful to the Research Fund of Istanbul Uni-
versity for the technical support of this study. Project number:
BYP-146/06012003.
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