Fluid Phase Equilibria 412 (2016) 29e38

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Fluid Phase Equilibria

j o u r n a l h o m e p a g e : w w w . e l s e v i e r . c o m / l o c a t e / fl u i d

Aqueous two-phase system of poly(ethylene glycol) 4000 and ferrous

sulfate at different temperatures

ctor R. Galleguillos a, b, Yecid P. Jimenez a, *
Lucy Muruchi a, He
a
Department of Chemical and Mineral Process Engineering, Universidad de Antofagasta, Av. Angamos 601, Antofagasta, Chile
b
n Científico y Tecnolo
Centro de Investigacio
gico para la Minería, CICITEM, Av. Jos

e Miguel Carrera 1701, 4
Piso, Antofagasta, Chile

a r t i c l e i n f o a b s t r a c t

Article history: Liquideliquid equilibrium (LLE) data for a FeSO4 þ polyethylene glycol 4000 (PEG 4000) þ H2O system
Received 22 September 2015 were experimentally determined at T ¼ (288.15, 298.15 and 308.15) K. The effects of temperature on the
Received in revised form solubility curves and tie-lines were studied to show in this case that an increasing the temperature
2 December 2015
expanded the two-phase region. The UNIQUAC model was used to correlate the experimental tie-line
Accepted 8 December 2015
Available online 18 December 2015
data, which yielded a good representation of the equilibrium.
Additionally, experimental density, sound velocity, refractive index, viscosity and electrical conduc-
tivity data were also determined at T ¼ (288.15, 298.15 and 308.15) K over a wide composition range in
Keywords:
Aqueous two-phase system
the monophasic zone. Othmer’s rule was used to correlate the experimental density, sound velocity,
Liquideliquid equilibrium refractive index and viscosity data. The electrical conductivity data were transformed to molar con-
Polyethylene glycol ductivity data and correlated with the percentage of poly(ethylene glycol). The experimental and
Ferrous sulfate correlated values were similar.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction
Systems containing two aqueous liquid phases at certain con-
centrations are very useful to extract and recover many types of
molecules and ions. These systems are usually formed by
combining polymer/polymer, polymer/salt or salt/salt dissolved in
water [1]. Aqueous two-phase systems (ATPSs) have been widely
studied [2e5] and are recognized as an economical and efficient
downstream processing method that offers several advantages,
such as low cost, environmentally friendliness, low viscosity and
short phase splitting times [6,7], in contrast with conventional
solvent extraction stages.
One of the most common polymers used to form ATPSs is
poly(ethylene glycol) (PEG), which is a hydrophilic polymer. This
polymer is mixed with a kosmotropic (water structuring) salt to
form an ATPS. This type of ATPS can be applied to separate,
concentrate or fractionate biological solutes and particles, such as
cells and proteins [8e10]. ATPSs can also be applied to selectively
separate metal ion species [3,7,11].
Pathak et al. [12] reported the phase diagram of the studied
* Corresponding author.
E-mail address: yecid.jimenez@uantof.cl (Y.P. Jimenez).
FeSO4 þ PEG 4000 þ H2O system at T ¼ (290.15, 303.15 and 313.15)
K, but did not note the physical properties at equilibrium or in the
monophasic zone, nor is analyzed the pH effect, nor did they model
the equilibrium data.
Furthermore, the physical and chemical properties of aqueous
solutions, including poly(ethylene glycol) and sulfate salt solutions,
have rarely been reported. Gonza
les-Tello et al. [13] studied the
effect of MgSO4 on the viscosity of PEG (8000 and 1000) þ H2O at
(277 and 298) K. Mei et al. [14] reported the density and viscosity
experimental data of aqueous solutions of PEG þ (NH4)2SO4 at
298.15 K for several molecular weights of PEG (1000, 2000, 4000,
6000 and 20000 g/mol). The density, electrical conductivity, vis-
cosity and refractive index of the aqueous system formed by lithium
sulfate þ PEG 4000 were measured by Silva et al. [15] over a tem-
perature range of (278.15e318.15) K. Zafarani-Moattar et al. [16]
measured the densities of aqueous solutions for several
PEG þ salt systems at (298.15, 308.15 and 318.15) K. These experi-
ments used salts of sodium sulfate, sodium carbonate, ammonium
sulfate and a mixture of dipotassium hydrogen phosphate and
potassium dihydrogen phosphate, and the experimental results
were correlated with a semi-empirical equation. Similar work was
also reported by Zafarani-Moattar and Mehrdad [17].
In the future, the liquideliquid equilibrium (LLE) data reported
herein could allow metal ion separation processes to be planned.

http://dx.doi.org/10.1016/j.fluid.2015.12.014
0378-3812/© 2015 Elsevier B.V. All rights reserved.
30 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38
Furthermore, the phase diagram of this system has not yet been
reported at T ¼ (288.15, 298.15 and 308.15) K. The refractive index,
density, sound velocity and kinematic viscosity of each phase at
equilibrium and T ¼ (288.15, 298.15 and 308.15) K were also
measured. Complementing the work, density, sound velocity,
refractive index, kinematic viscosity and electrical conductivity of
the monophasic zone were measured at the three temperatures
mentioned above.
The LLE phase diagrams of polymer-salt ATPSs are usually
modeled based on local composition concepts and their modifica-
tions [5,18,19]. In the present work, the extended UNIQUAC [20]
model was applied to correlate the experimental LLE data of the
aqueous FeSO4 þ PEG 4000 þ H2O system at T ¼ (288.15, 298.15 and
308.15) K. The PitzereDebyeeHückel equation [21] was used to
account for the long-range electrostatic interactions of the ions.
2. Experimental
2.1. Chemicals
Synthesis-grade polyethylene glycol with an average molar
mass of 4000 (3500e4500) g mol1 and analytical grade reagent
ferrous sulfate heptahydrate with a purity >0.99 mass fraction were
procured from SigmaeAldrich and Riedel-de Hae €n, respectively.
The water content in the PEG 4000 was determined to be 0.0031
mass fraction by the Karl Fisher method and was neglected in the
calculus of total solution mass. Sulfuric acid, with a purity of
0.95e0.97 mass fraction (density: 1.84 g cm3), was procured from
Merck. All chemicals were used without further purification. Milli-
Q quality deionized water was used in all experiments
(k ¼ 0.054 mS cm1).
2.2. Apparatus and procedure
The pH values of the aqueous solutions of FeSO4 must be acidic,
preferably less than 3, to prevent ferrous ions from being oxidized
to ferric ions and precipitating [22]. At pH values below 3, these
solutions are stable for several days. Thus, we utilized acidified
water to ensure that the ferrous ions remained stable.
The deionized water was acidified in a jacketed vessel by adding
sulfuric acid at a constant temperature until the solution reached a
pH value of 1.06. The pH values were measured using an Accumet
pH meter 50 with a measurement range from 2 to 20 between
(268.15 and 378.15) K and a relative accuracy of ± 0.002. To main-
tain a constant temperature, a thermostatically controlled Julabo
bath F25-ME Refrigerated/Heating Circulator was used with
working temperature range 245.15e473.15 K and an uncertainty of
± 0.01 K. The solutions were agitated using a VWR® Professional
magnetic stirrer with operating conditions from 278.15 to 313.15 K
and a speed range from 60 to 1600 rpm. The acidified water needed
to be prepared at each temperature under study because the pH
value is a function of the temperature (more sulfuric acid was
necessary at higher temperatures).
The turbidimetric method was used to determine the solubility
curve; this procedure consisted of adding a small amount of FeSO4
or PEG (approximately 0.01 g) to the respective acidified aqueous
solution of FeSO4 or PEG with known mass composition. The so-
lutions were prepared by mass in a Mettler Toledo analytical bal-
ance (model AX204) with a precision of ± 0.1 mg. These solutions
were then agitated for two minutes using a Vortex Mixer Classic
Model F202A0173 (Velp Scientific). Subsequently, the solutions
were placed in a thermostatic bath (F25-ME Julabo) at constant
temperature (± 0.1 K) for several minutes; this procedure was
repeated until a change in the turbidity appeared, which indicated
the formation of a second liquid phase. The procedure was similar
for the three tested temperatures.
Once the solubility curve was determined, the properties in the
monophasic zones of density, sound velocity, refraction index and
kinematic viscosity were determined. Approximately 40 g of a so-
lution of known composition was prepared by mass. The densities
and sound velocities of the solutions were measured using a den-
sity and sound velocity meter (Anton Paar DSA 5000M, measuring
range from 0 to 3 g cm3, resolution 1$106 g cm3) with a precision
of ± 0.001 K. The obtained uncertainties were ±1  105 g cm3 and
±0.03 m s1 for the density and sound velocity, respectively. The
density and sound velocity meter was calibrated using air and
deionized water as reference substances. Two milliliters of solution
was used for each measurement, and measurements were con-
ducted in triplicate. The reported data represent the average.
Density and sound velocity were measured simultaneously.
The refractive indices were measured using a refractometer
(Anton Paar Abbemat 550, measuring range from 1.30 to 1.72 nD
units, resolution 1$106 nD units, accuracy ±2$105 nD units, tem-
perature probe accuracy 0.03 K, temperature probe stability
0.002 K). Each measurement was conducted in triplicate and uti-
lized 0.5 ml of solution; the average of these measurements is re-
ported. The uncertainty of these measurements was ±1$104.
The kinematic viscosities were measured with calibrated micro-
Ostwalt viscometers. A Schott-Gerate automatic measuring unit
(model AVS 310) equipped with a thermostat (Schott-Gerate, model
CT 52) in which the temperature was regulated to within ± 0.05 K
was used for the measurements. We obtained the absolute viscosity
by multiplying the kinematic viscosity by the corresponding den-
sity. The uncertainty of the kinematic viscosity measurements was
±5$103 mm2$s2. The measurements were conducted in triplicate,
and 2 ml were used for each experiment.
The electrical conductivities were measured in a conductivity
meter (Orion Orion, model 19700-27, accuracy <0.5% and repro-
ducibility ±0.07%). Forty milliliters of solution were incubated in a
jacketed vessel maintained at the working temperature by a ther-
mostatically controlled bath. The solutions were continuously
stirred with a magnetic stirrer. The above-described thermostati-
cally controlled bath and magnetic stirrer were used. The average of
three measurements is reported. The uncertainty of these mea-
surements was ± 0.01 mS cm1.
The tie-lines were determined for mixtures of known overall
composition (typically 80 g), which were agitated for 48 h in a
rotatory bath, whose temperature was controlled within ± 0.1 K.
The obtained biphasic solutions were allowed to settle for 24 h at
constant temperature, and extending the time periods of agitation
and sedimentation did not affect the results.
Once equilibrium was reached, the top and bottom phases were
withdrawn using syringes and needles to determine the ion
Fe2 þ concentration of each phase and measure the physical prop-
erties (density, sound velocity, refractive index and kinematic vis-
cosity) in the same way as explained above.
The concentration of FeSO4 was determined by analyzing the
iron content using atomic absorption spectroscopy (AAS). The AAS
measurements were performed using a Varian Atomic Absorption
Spectrophotometer, model 220; using acetylene gas burner, at
wavelengths of 248.3 nm and a lamp current of 5 mA. The PEG
concentration was determined using the Merchuk equation
(equation 15), which related the concentrations of ferrous sulfate
and PEG, and the water content is given by the difference between
the iron and PEG concentrations.
 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38 31

3. Thermodynamic framework
3.1. Modeling
The excess Gibbs energy, GE, for the extend UNIQUAC model is
the sum of two contributions [20]:
GE ¼ GE;LR þ GE;UQ
where GE,LR and GE,UQ are the long-range interaction contribution
and the value from the UNIQUAC equation, respectively.
Thus, the expression for the activity coefficient of component I
(polymer, ions, water) also consists of the sum of two
contributions:
[23]. The value of r ¼ 14.9, which has been frequently used for
electrolyte solutions [24], was applied in this work.
3.1.2. The UNIQUAC equation
The extended UNIQUAC model [20,25] was used to calculate the
GE,UQ term. The activity coefficient equations for aqueous poly-
meresalt system have been presented by Barrueto et al. [26].
(1) Here, the ferrous sulfate was assumed to have completely
dissociated into ions in the aqueous phase. For PEG, the volume and
surface parameters were 145.70 and 121.50, respectively [19]. The
volume and surface parameters for Fe2 þ were 0.073 and 0.175,
respectively, and 2.02 and 1.602 for SO24 , respectively. These pa-
rameters were estimated from the ionic radiuses, 7.6$109 cm for
Fe2 þ and 2.3$108 cm for SO2 4 [27].

UQ
ln gI ¼ ln gLR
I þ ln gI : (2) 4. Results and discussion
The PitzereDebyeeHückel equation (PDH) [21] and the UNI-
4.1. Monophasic zone
QUAC equation [20] were used to calculate the GE,LR and GE,UQ
terms, respectively.
4.1.1. Effect of salt or PEG concentration
As shown in Table 1, the concentration of PEG directly and lin-
3.1.1. Long-range interaction contributions early correlates with the density, sound velocity and refractive in-
The PitzereDebyeeHückel (PDH) equation normalized to the dex at constant temperature and salt concentration; the viscosity
pure liquid electrolyte reference state was used to calculate the also directly correlates with the PEG concentration, but this rela-
GE,LR term. Appropriate differentiation yields the following tionship is not linear. The electric conductivity inversely correlates
expression for the activity coefficient of species i: with the PEG concentration because the large PEG molecules
" ! # intertwined to form a network that caught the ions [28]; this
1=2 1=2 3=2
2Zi2 1 þ rIx Zi2 Ix  2Ix phenomenon decreased the ionic movements in the system.
ln gPDH
i ¼ Ax ln    þ (3)
r 1 þ rZi 21=2 1=2
1 þ rIx At constant temperature and PEG concentration, all properties
directly correlated with the salt concentration, including to the
where electrical conductivity, due to the inverse of the above-mentioned
effect.
0z 11=2 For the viscosity and the electrical conductivity, the PEG con-
 3=2
1 @ 2 лNA A e2 centration has more influence than the salt concentration over the
Ax ¼ (4)
3 Vs 4лεεT KT magnitude of the property and is different than the rest of prop-
erties because the salt or PEG concentration effect is similar over
and for a neutral molecule: the density, sound velocity and refractive index.

2Ax Ix
3=2 4.2. The temperature effect
ln gPDH
i ¼ 1=2
(5)
1þ rIx Table 1 shows that at constant PEG and FeSO4 concentrations,
In the above relations, Zi is the charge number of ion i. r is the the density, viscosity and electrical conductivity inversely correlate
closest distance parameter. NA, K, ε and e are Avogadro’s number, with the temperature. However, the sound velocity directly corre-
Boltzmann’s constant, the permittivity of the vacuum and the lated with the temperature because the added energy due to a
electronic charge, respectively. Ix is the ionic strength on a mole temperature increase perturbs molecules to cause vibrations that
P
fraction basis, Ix ¼ 0; 5 xi Zi2 . Vs and εT are the molar volume and are transmitted via collisions between particles. Thus, the sound
dielectric constant of the mixed solvent (here, the polymer was velocity increases [29]. Fig. 1 shows the effect of the temperature on
assumed to be the pseudo-solvent), respectively. These values are the sound velocity. An interesting behavior is observed: at constant
calculated from the following: salt concentration, the effect of the temperature diminishes as the
PEG concentration increases and the isotherms tend to join. Thus, a
VS ¼ x2 V2 þ x3 V3 (6) change in temperature likely does not affect the sound velocity but
only at a specific composition. Similar effect was found for the
X
εT ¼ 4j εTj (7) electrical conductivity.
j The refractive index also negatively correlates with the tem-
perature. The property describes the ability of the material to
and refract the light that moves from one medium to other; the
magnitude of the refractive index directly correlates with the de-
nj Vj gree of refraction. The refractive index of a solution is higher when
4j ¼ (8)
n2 V2 þ n3 V3 its molecules are more “tightly packed” [30]. Therefore, the density
directly correlates with the refractive index at constant salt con-
where V2 and V3 are the molar volume of the polymer and water, centrations, as shown in Table 1.
respectively. εTj is the dielectric constant of component j, and 4j is
the salt-free volume fraction for polymer and water. The dielectric 4.2.1. Correlations
constant of PEG, εT,2 ¼ 2.2, and those of water, εT,3 ¼ (82.22, 78.30, The experimental density, sound velocity, refractive index and
74.82), were used at T ¼ (288.15, 298.15 and 308.15 K), respectively viscosity values were correlated using Othmer’s rule. The general
32 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38

Table 1 1700
Experimental density (r), refractive index (nD), electrical conductivity (k), viscosity
(n) and sound velocity (s) data in aqueous solutions of FeSO4 and PEG 4000 for 1650
different mass fraction of FeSO4 (w1) and PEG (w2) at T ¼ (288.15, 298.15 and 308.15)
K.a 1600

s [m s-1]
w1 w2 r/(g cm3) nD k/(mS cm1) n/(mm2 s2) s/(m s1)
1550
T ¼ 288.15 K
0.0199 0.2498 1.070723 1.37470 11.3 20.561 1654.99 1500
0.0201 0.2000 1.061473 1.36716 15.6 12.797 1617.75
0.0199 0.1500 1.052161 1.35972 20.7 7.710 1580.40 1450
0.0200 0.1000 1.043448 1.35248 26.7 4.540 1543.92 0 0.05 0.1 0.15 0.2 0.25 0.3
0.0200 0.0500 1.034778 1.34539 33.5 2.494 1508.84 w2
0.0200 0.0000 1.026247 1.33841 41.2 1.315 1475.20
0.0400 0.1999 1.083315 1.37095 15.5 14.364 1633.98 Fig. 1. Sound velocity for 0.02 w1 at 288.15 (-), 298.15 (C) and 308.15 (A) K.
0.0400 0.1500 1.073800 1.36392 20.9 8.590 1597.92
0.0400 0.1000 1.064540 1.35650 27.4 4.979 1560.56
0.0401 0.0501 1.055961 1.34937 34.3 2.375 1524.47
0.0400 0.0000 1.047440 1.34227 43.2 1.416 1489.70 expression for this correlation independent of temperature is
0.0609 0.1015 1.085219 1.36057 28.6 5.531 1577.75
0.0600 0.0499 1.078503 1.35351 36.7 3.045 1541.82 Y
0.0600 0.0000 1.068470 1.34606 45.6 1.561 1504.61 ln yR ¼ ln ¼ A þ BlnyW (9)
yW
0.0800 0.0499 1.099897 1.35741 38.3 3.369 1558.69
0.0801 0.0000 1.090943 1.35009 48.4 1.712 1521.34
0.0000 0.3000 1.058766 1.37804 11.4 28.518 1675.58 where yR is the relative property and represents the ratio between
0.0000 0.2500 1.049342 1.37035 14.9 18.202 1638.55 the value of the physical property of the mixture (density, sound
0.0000 0.2000 1.040432 1.36303 19.0 11.443 1602.43 velocity, refractive index or viscosity), y, and the physical property
0.0000 0.1500 1.031329 1.35564 24.0 6.998 1565.02 of the water, yW, at the same temperature. A and B are parameters
0.0000 0.1000 1.022688 1.34850 29.5 4.156 1529.67
that depend on the mass fractions of ferrous sulfate (w1) and PEG
0.0000 0.0500 1.014260 1.34155 35.8 2.327 1495.79
T ¼ 298.15 K (w2), as shown in equations 10 and 11.
0.0200 0.2501 1.064972 1.37298 8.9 14.123 1658.36
0.0200 0.1999 1.055690 1.36526 12.1 8.845 1626.40 A ¼ A1 w1 þ A2 w2 (10)
0.0200 0.1500 1.046997 1.35806 16.0 5.538 1595.77
0.0199 0.1000 1.038283 1.35086 20.6 3.324 1564.76
0.0200 0.0500 1.029510 1.34390 25.8 1.876 1534.62 B ¼ B1 w1 þ B2 w2 (11)
0.0199 0.0000 1.021405 1.33713 31.6 1.018 1506.28
0.0400 0.1500 1.068044 1.36215 18.2 6.151 1611.63 A1 ; A2 ; B1 and B2 are the parameters of Othmer's equation.
0.0400 0.1000 1.059594 1.35500 23.7 3.628 1580.26
0.0400 0.0500 1.051022 1.34786 29.7 2.061 1549.50
The refractive index and dynamic viscosity values of water used
0.0401 0.0000 1.042665 1.34094 36.6 1.121 1519.72 to fit the experimental data at different temperatures were calcu-
0.0600 0.0000 1.064299 1.34484 41.9 1.221 1534.16 lated using the following [31]:
0.0599 0.0500 1.072305 1.35177 33.7 2.245 1564.40
0.0600 0.1000 1.081768 1.35920 26.7 3.995 1595.96
   
0.0800 0.0500 1.095786 1.35607 37.4 2.512 1580.80 nD ¼ 1; 18 þ 1; 7535*103 ðT=KÞ  7; 193*105 ðT=KÞ3=2
0.0801 0.0000 1.086707 1.34882 46.3 1.356 1549.21
0.1000 0.0500 1.119148 1.36040 40.2 2.845 1598.15
(12)
0.1000 0.0000 1.108263 1.35264 50.2 1.491 1564.57
0.0000 0.3000 1.051888 1.37574 8.5 18.997 1671.89  
0.0000 0.2500 1.043290 1.36849 10.9 12.779 1642.71 hw =mPa$s ¼ 1; 05256$103 e2011=ðT=KÞ (13)
0.0000 0.1500 1.025657 1.35379 17.2 4.933 1580.41
0.0000 0.0500 1.009159 1.34003 25.4 1.724 1522.15 The experimental and correlated density and refractive index
T ¼ 308.15K values were similar, with standard deviations of 0.0019 and 0.0018,
0.0199 0.2500 1.058667 1.37086 8.6 10.756 1655.15
respectively. Table 2 shows the obtained parameters.
0.0199 0.1999 1.050117 1.36341 11.6 6.983 1629.70
0.0199 0.1500 1.041550 1.35637 15.3 4.244 1603.85 The viscosity and sound velocity were correlated at each tem-
0.0200 0.1000 1.033280 1.34923 19.5 2.577 1578.37 perature because better results were obtained; Table 3 shows the
0.0201 0.0500 1.025235 1.34240 24.3 1.505 1553.36 obtained parameters at different temperatures.
0.0199 0.0000 1.017137 1.33560 29.5 0.839 1528.92
The experimental electrical conductivity data could not be
0.0401 0.2000 1.072131 1.35761 12.1 3.100 1606.86
0.0400 0.1500 1.063301 1.36068 17.7 4.800 1619.31

satisfactorily fitted to a single 
equation. The values were expressed
2
0.0400 0.1000 1.054709 1.35340 23.6 2.841 1592.60 as normal conductivity DN cm eq
S and correlated with the PEG
0.0400 0.0500 1.046586 1.34653 29.9 1.646 1567.39 concentration and temperature for each constant salt concen-
0.0400 0.0000 1.037980 1.33944 36.5 0.881 1541.49 tration.The values obtained for normal conductivity were fitted
0.0599 0.1000 1.071794 1.36782 27.8 7.680 1643.97
using the following:
0.0600 0.0500 1.067489 1.35036 35.3 1.780 1580.16
0.0600 0.0000 1.059136 1.34326 43.2 0.963 1554.40
0.0800 0.0500 1.090129 1.35446 40.2 1.989 1595.15 a þ bw2 þ cw22 þ dT
0.0800 0.0000 1.081270 1.34722 49.4 1.072 1568.07 DN ¼ (14)
1 þ ew2 þ fT þ gT 2
0.0000 0.3000 1.046148 1.37368 7.9 14.631 1665.83
0.0000 0.2500 1.037198 1.36627 8.5 9.607 1641.35
0.0000 0.2000 1.028838 1.35922 10.7 6.121 1616.35 where a, b, c, d, e, f and g are adjustment parameters, which are
0.0000 0.1000 1.012897 1.34536 15.3 2.389 1566.71 reported in Table 4.
0.0000 0.0500 1.004499 1.33877 19.3 1.398 1541.69 The standard deviations given in Table 4 indicate that the
a
The standard uncertainties, u, are u(T) ¼ 0.01 K for the density, sound velocity calculated and experimental values were similar.
and refractive index, u(T) ¼ 0.05 K for the viscosity, u(T) ¼ 0.05 K for the electrical
conductivity, u(r) ¼ 1$105 g cm3, u (s) ¼ 0.03 m s1, u(nD) ¼ 1$104, u(n) ¼ 4.2 Solubility curve
0.005 mm2 s2 and u(k) ¼ 0.01 mS cm1.
4.2.1 Solubility curve data
 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38 33

Table 2 Table 5
Parameters of Othmer’s equation for the density and refractive index. Solubility curve data for the FeSO4 (1) þ PEG 4000 (2) þ H2O (3) system at 288.15,
298.15 and 308.15 K.a
Othmer parameters Density Refractive index
T ¼ 288.15 K T ¼ 298.15 K T ¼ 308.15 K
A1 1.0995 0.0603
A2 0.1976 1.0752 w1 w2 w1 w2 w1 w2
B1 9.6013 0.7513
0.1206 0.0654 0.0788 0.1290 0.1156 0.0424
B2 4.8468 4.1164
0.0688 0.1710 0.1027 0.0777 0.0553 0.1838
S.D. 0.0019 0.0018
0.0292 0.3169 0.1179 0.0529 0.0300 0.2745
0.0395 0.2711 0.0198 0.3468 0.1136 0.0424
0.0455 0.2451 0.0600 0.1780 0.1000 0.0679
Table 3 0.0519 0.2196 0.0535 0.1995 0.0212 0.3355
Othmer parameters for the viscosity and sound velocity at T ¼ (288.15, 298.15 and 0.0700 0.1655 0.0491 0.2135 0.0736 0.1258
308.15) K. 0.1019 0.0960 0.0466 0.2212 0.0215 0.3349
0.1088 0.0855 0.0416 0.2444 0.0253 0.3095
Othmer parameters Viscosity Sound velocity 0.0946 0.1104 0.0383 0.2564 0.1240 0.0278
0.0858 0.1290 0.0347 0.2690 0.0789 0.1152
T ¼ 288.15 K
0.0766 0.1488 0.0326 0.2768 0.0618 0.1586
A1 8.5998 0.8560
0.0689 0.1701 0.0298 0.2910 0.0448 0.2161
A2 10.6414 0.8553
0.0631 0.1878 0.0276 0.3021 0.0415 0.2311
B1 1.9308 0.0494
0.1184 0.0684 0.0255 0.3132 0.0386 0.2415
B2 2.1810 0.0548
0.1220 0.0616 0.1200 0.0480 0.0347 0.2575
S.D 0.6807 1.0963
0.1369 0.0371 0.1035 0.0778 0.0315 0.2693
T ¼ 298.15 K
0.1327 0.0431 0.0901 0.1030 0.0485 0.2023
A1 7.4830 0.1255
0.1346 0.0402 0.0846 0.1115 0.0571 0.1725
A2 10.2530 0.8544
0.1448 0.0275 0.0804 0.1242 0.0666 0.1427
B1 2.2665 0.0831
0.1552 0.0161 0.0718 0.1436 0.0698 0.1334
B2 0.8689 0.0643
0.1768 0.0072 0.0667 0.1569 0.0747 0.1202
S.D 0.4460 1.0040
0.1643 0.0094 0.0616 0.1696 0.0822 0.1055
T ¼ 388.15 K
0.1701 0.0082 0.0544 0.1950 0.0870 0.0946
A1 8.5042 0.8560
0.0450 0.2266 0.0914 0.0849
A2 9.5795 0.8533
0.0421 0.2394 0.0930 0.0837
B1 0.5629 0.0545
0.0853 0.1135 0.0926 0.0818
B2 1.8087 0.0741
0.1181 0.0532 0.1022 0.0644
S.D 0.3191 2.2458
0.0961 0.0904 0.1067 0.0572
0.1104 0.0631 0.1064 0.0528
0.1245 0.0413 0.1153 0.0394
Table 4 0.1250 0.0394 0.1198 0.0321
Parameters for the normal conductivity equation, equation 14. 0.1334 0.0306 0.1306 0.0201
0.1452 0.0137 0.1384 0.0174
Parameters Salt mass fraction 0.1477 0.0129 0.1455 0.0138
0.1502 0.0113
w1 ¼ 0.02 w1 ¼ 0.04 w1 ¼ 0.06 w1 ¼ 0.08
0.0287 0.2836
a 0.14551 2.08334 0.14359 0.14866 0.0241 0.3103
b 8.30430 0.91128 3.81012 2.94855 0.0216 0.3269
c 11.77920 4.89845 3.15127 3.18014 0.0260 0.2984
d 0.00615 0.00416 0.00281 0.00196 0.0326 0.2648
e 0.01374 0.03816 0.00532 0.00521 0.0442 0.2170
f 0.00655 0.00677 0.00675 0.00685 0.0626 0.1558
g 0.00001 0.00001 0.00001 0.00001 a
The standard uncertainties, u, are u(wi) ¼ 0.003 and u(T) ¼ 0.1 K.
S.D. 0.67896 0.40265 0.07226 0.20733

0.4
The equilibrium compositions of the aqueous two-phase system
0.35
of ferrous sulfate-poly(ethylene glycol) determined at 288.15,
298.15 and 308.15 K are shown in Table 5. 0.3
The effect of the temperature on the solubility curve curves is
0.25
illustrated in Fig. 2. Increasing the temperature expanded the two-
phase area. The temperature effect in the extremes diminishes, and
w2

0.2
the solubility curves tend to join.
0.15

4.2.2. Correlation of the solubility curve 0.1

The experimental data at all temperatures were correlated using 0.05

the Merchuk equation [32] via the regression least-squares
method. 0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14 0.16 0.18 0.2
  w1
w2 ¼ t*exp rw0:5 3
1  uw1 (15)
Fig. 2. Solubility curves of the FeSO4 þ PEG 4000 þ H2O system at (-) 288.15, (:)
298.15 and (C) 308.15 K; d calculated values from Merchuk equation.
where w2 is the concentration of the polymer and w1 is the con-
centration of salt. t, r and u are correlation parameters. This equa-
tion has been successfully used to correlate solubility curves for results, the Merchuk equation satisfactorily represents the experi-
ATPSs of polymers and ionic liquids. The obtained parameters and mental data.
the standard deviations are reported in Table 6. According to these
34 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38
4.2.3. Gibbs free energy, enthalpy and entropy of phase separation
The cloud-point (CP) temperatures as a function of the PEG and
ferrous sulfate mass fractions show that the ferrous sulfate con-
centration negatively correlates with the PEG concentration
required to reach the CP. At constant salt concentration, the PEG
concentration required to reach the CP inversely correlates with the
temperature. Similarly, the salt concentration required to reach the
CP inversely correlates with the PEG concentration, and the salt
concentration required to reach the CP inversely correlates with the
temperature for a constant PEG concentration.
The free energy of phase separation or clouding (DGc) can be
calculated using the following equation:
DGc ¼ RT ln x2ð1Þ
where x2ð1Þ is the mole fraction concentration of PEG or ferrous
sulfate at the CP. Tables 7 and 8 present the values of DGc. The DGc
values at different temperatures were processed according to the
following equation to obtain DHc from the slope of the linear (least-
squares) plot of (DGc/T) versus (1/T):
dðDGc =TÞ
¼ DHc
dð1=TÞ
The entropy changes were calculated using
GibbseHelmholtz equation:
DHc  DGc
DSc ¼
T
The calculated DHc and DSc values as functions of the salt and
polymer concentration are also reported in Tables 7 and 8,
respectively.
The positive values of the calculated entropy suggest loose,
disorderly and desolvated PEG segment assemblies in solution; the
positive entropy values are primarily due to the desolvated PEG
segments. According to the DHc values, the aqueous two-phase
formation process is endothermic, and this process must be
driven by entropy increase [18]. Furthermore, the obtained values
of DHc and DSc positively correlate with the salt or PEG mass
fraction.
4.3. Tie-lines
4.3.1. Tie-line data
The tie-line data are given in Table 9. Additionally, the physical
properties of both phases, i.e., the density, refractive index, vis-
cosity and sound velocity, are also reported in Table 9.
4.4. Slope and length of tie-lines, temperature effect
The effect of the temperature on the phase equilibrium was
analyzed by applying the slope of the tie-line (STL) and the tie-line
length (TLL) concepts. The values of the slopes of the tie-lines and
the tie-line lengths as a function of temperature are reported in
Table 10.
The STL values were calculated using the following equation:
Table 6
Parameters of the Merchuk equation.
T/K t r u S.D.
288.15 0.79142 5.31337 411.05934 0.0028
298.15 0.74297 5.35265 520.65945 0.0022
308.15 0.77150 5.75924 629.77444 0.0025
wT2  wB2 Dw2
STL ¼ ¼ (19)
wT1  wB1 Dw1
The tie-lines lengths were determined using the following:
 1=2
TLL ¼ Dw22 þ Dw21 (20)
where w1 and w2 are the ferrous sulfate and PEG concentration,
respectively. The superscripts “T” and “B” refer to the top and bot-
tom phases, respectively.
Table 10 and Fig. 3 show that the magnitude of the tie-line slope
(16) positively correlates with the temperature, which resulted in an
increase in the PEG concentration in the top phase and a decrease in
the salt concentration in the bottom phase. These relationships
arise because increasing the temperature increases the hydropho-
bicity of the PEG. Consequently, water is driven from the PEG-rich
phase to the salt-rich phase, which increases the weight of the
bottom phase at the expense of the top phase. The tie-line lengths
are related with this behavior because an increase in the temper-
ature increases the biphasic area. Therefore, for a sample of known
(17) global composition, the tie-line length also directly correlates with
the temperature [26].
the Table 10 also reports the STL average at each temperature, which
must be constant at constant temperature. Moreover, the STL ap-
proaches infinity as the temperature increases.
(18) Moreover, the pH effect is analyzed comparing the STLs ob-
tained in this study with the data reported by Pathak et al. [12]. The
average STLs reported at T ¼ (293.15, 303.15 and 313.15) K are
0.8453, 0.8983 and 1.0198, respectively [12]. As can be seen, these
values are lower than the determined values in the present work;
this behavior can be attributed to the pH effect. The attraction be-
tween PEG and water will decrease with an decrease in pH and
therefore by decreasing pH of the aqueous two-phase system,
water is driven from the PEG-rich phase to the salt-rich phase,
hence the PEG concentration of the PEG-rich phase increases, while
the salt concentration of the salt-rich phase decreases.
4.4.1. Physical properties of the tie-lines
The physical properties of both phases were analyzed at
T ¼ (298.15 and 308.15) K because the observed behavior is similar
to the other temperatures. Table 9 shows that at constant tem-
perature and different system global compositions, the salt con-
centration in the bottom phase always exceeds that in the top
phase. Thus, the density of the bottom phase also exceeds the
density of the other phase. Fig. 4 shows this behavior at 298.15 K.
Fig. 5 shows that the refractive index of the top phase exceeds
that of the bottom phase because the molecules are more tightly
packed, as mentioned above.
The viscosity values of the top phase always exceed that of the
other phase because the PEG concentration is higher in the top
phase. Similar behavior was observed for the sound velocity.
When considering systems of variable composition, the water
concentration of the bottom generally inversely correlates with the
magnitudes of the density, refractive index, dynamic viscosity and
sound velocity. Except for the density, these properties directly
correlate with the water concentration of the top phase. This
behavior is presented in Fig. 4.
For a constant global composition, the temperature inversely
correlates with the density, refractive index and viscosity of both
phases, similar to the behavior observed in the monophasic region.
However, the sound velocity directly correlates with the
temperature.
 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38 35

Table 7
Gibbs free energy, enthalpy and entropy of phase separation at different temperatures and ferrous sulfate mass fraction, w1.

w1 DHc/(kJ mol1) DSc/(kJ mol1 K1) DGc/(kJ mol1)

T ¼ 288.15 K T ¼ 298.15 K T ¼ 308.15 K

0.15 35.1980 0.1962 21.3502 23.2289 25.2770

0.12 21.7220 0.1419 19.1794 20.5472 22.0195
0.1 15.5910 0.1166 18.0252 19.1595 20.3593
0.08 11.2360 0.0981 17.0387 18.0073 19.0015
0.06 8.2896 0.0848 16.1510 17.0095 17.8472
0.04 6.4140 0.0753 15.2595 16.0521 16.7628

Table 8
Gibbs free energy, enthalpy and entropy of phase separation at different temperatures and PEG mass fraction, w2.

w2 DHc/(kJ mol1) DSc/(kJ mol1 K1) DGc/(kJ mol1)

T ¼ 288.15 K T ¼ 298.15 K T ¼ 308.15 K

0.30 8.0674 0.0711 12.3787 13.1838 13.7956

0.25 7.6653 0.0675 11.7700 12.4986 13.1177
0.20 7.2830 0.0642 11.1954 11.8618 12.4774
0.15 6.9549 0.0611 10.6601 11.2806 11.8825
0.10 6.6897 0.0585 10.1523 10.7399 11.3212
0.08 6.5921 0.0574 9.9464 10.5226 11.0943
0.06 6.4922 0.0563 9.7280 10.2925 10.8538
0.04 6.3875 0.0551 9.4790 10.0305 10.5803

Table 9
Experimental phase equilibrium compositions for the FeSO4 (1) þ PEG 4000 (2) þ H2O (3) system, density (r), refractive index (nD), viscosity (n) and sound velocity (s) at
different temperatures.a

Total system Top phase Bottom phase

100 w1 100 w2 100 w1 100 w2 r/(g cm3) nD n/(mm2 s2) s/(m s1) 100 w1 100 w2 r/(g cm3) nD n/(mm2 s2) s/(m s1)

T ¼ 308.15 K
8.9394 12.0624 4.4032 21.8343 1.08061 1.3683 7.424 1649.33 11.9550 3.5908 1.14635 1.3613 1.564 1619.70
9.3972 14.9072 2.7153 29.4923 1.07569 1.3764 13.574 1675.10 15.3857 0.8130 1.18465 1.3660 1.490 1641.10
9.7963 15.6984 2.2698 32.1601 1.07514 1.3809 15.718 1688.24 15.9389 0.6043 1.19380 1.3677 1.521 1648.15
11.0051 16.5057 1.8487 35.1182 1.07436 1.3846 21.035 1697.69 17.9394 0.1774 1.22592 1.3715 1.677 1671.48
12.4943 17.2993 1.4097 38.8694 1.07405 1.3910 28.143 1716.49 20.3570 0.0283 1.25095 1.3772 1.925 1692.80
T ¼ 298.15 K
9.0037 12.1014 5.1309 20.5998 1.09032 1.3717 9.481 1648.91 13.1025 3.3181 1.16124 1.3643 2.043 1614.46
9.3086 13.0311 4.4593 22.9102 1.08662 1.3719 10.145 1650.00 14.0687 2.3409 1.16777 1.3648 1.967 1617.32
9.4003 14.8975 3.3539 27.3345 1.08390 1.3784 16.319 1676.81 16.3272 0.8861 1.19372 1.3682 2.025 1633.42
9.5980 15.7016 2.5584 31.2867 1.08326 1.3799 18.327 1683.71 16.6281 0.7646 1.20181 1.3694 2.017 1639.63
11.0181 16.4985 2.2504 33.0876 1.08265 1.3853 26.106 1704.45 18.6353 0.2536 1.23015 1.3739 2.286 1663.48
T ¼ 288.15 K
8.7879 13.5089 6.0214 19.6421 1.10564 1.3743 12.350 1641.35 14.1040 3.3957 1.17794 1.3679 3.497 1604.32
8.9793 14.2326 5.5951 20.9558 1.10033 1.3755 14.824 1649.27 15.6245 2.0199 1.19065 1.3690 - 1610.97
9.3514 15.3941 4.5149 24.6411 1.09593 1.3789 19.883 1669.86 17.1247 1.1142 1.20713 1.3713 3.363 1623.28
9.6515 16.3984 3.9354 26.8999 1.09445 1.3806 23.042 1679.28 17.5276 0.9355 1.21539 1.3724 3.438 1628.71
9.8830 17.334 3.8532 27.2411 1.09393 1.3815 24.169 1683.34 17.9980 0.7562 1.22046 1.3732 3.554 1634.24
a
The standard uncertainties, u, are u(T) ¼ 0.1 K, u(T) ¼ 0.01 K for the density, sound velocity and refractive index, u(T) ¼ 0.05 K for the viscosity, u(r) ¼ 8$105 g cm3, u (s) ¼
0.02 m s1, u(nD) ¼ 2$104 and u(n) ¼ 0.008 mm2 s2.

Table 10 plait point, a critical point at which both liquid phases are identical.
STL and TLL values of the FeSO4 þ PEG 4000 þ H2O system at different temperatures. In this work, the location of the plait point was estimated by
Tie-line T ¼ 288.15 K T ¼ 298.15 K T ¼ 308.15 K extrapolation from the auxiliary curve, which satisfactorily fitted
with the following linear equation [33]:
STL TLL STL TLL STL TLL

1 2.0100 0.1815 2.1679 0.1903 2.4158 0.1974

2 1.8880 0.2143 2.1405 0.2270 2.2635 0.3135
3 1.8657 0.2669 2.0387 0.2946 2.3085 0.3439
4 1.9103 0.2931 2.1693 0.3361 2.1715 0.3847
5 1.8724 0.3002 2.0039 0.3670 2.0499 0.4322
Average 1.9093 2.1041 2.2418 w1 ¼ i þ j *w2 (21)
S.D 0.0526 0.0692 0.1241
where i and j are parameters that were calculated by lineal
regression. The values of these parameters and the determination
4.4.2. Plait point coefficients are reported in Table 11.
The liquid and liquid portions of the solubility curve meet at the For example, the locus of the estimated plait point for the
studied system is presented in Fig. 6 at T ¼ 288.15 K.
36 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38

0.4 Table 11
Plait point of the FeSO4 þ PEG 4000 þ H2O system at 288.15, 298.15 and 308.15 K.
0.35
T/K i j R2 Plait point
0.3
100 w1 100 w2 100 w3

0.25 288.15 0.1059 2.0920 0.9392 0.0988 0.1003 0.8009

298.15 0.1003 2.3536 0.9425 0.0880 0.1066 0.8055
w2

0.2 308.15 0.0174 2.0370 0.9788 0.0722 0.1295 0.7983

0.15

0.1 0.4

0.05 0.35

0 0.3
0 0.05 0.1 0.15 0.2
w1 0.25

Fig. 3. Tie-lines of the FeSO4 þ PEG 4000 þ H2O system at (C) 288.15, (:) 298.15 and

w2
0.2
(-) 308.15 K.
0.15

0.1
1.2400
0.05
1.2200
0
1.2000 0 0.05 0.1 0.15 0.2
1.1800 w1
ρ[g cm-3]

1.1600 Fig. 6. Plait point of the FeSO4 þ PEG 4000 þ H2O system at (C) 298.15 K.

1.1400

X X  2

1.1200 2 
1.1000 Fob ¼ wtop
t;l;exp
 wtop
t;l;cal
 wbot
t;l;exp  wbot
t;l;cal
t¼1 l¼1
1.0800
(22)
1.0600
0.00 0.05 0.10 0.15 0.20 where wt;l is the mass fraction of the component “t” of the lth tie-
w1 line, and the subscripts “calc” and “exp” refer to the calculated
and experimental values, respectively. The superscripts “top” and
Fig. 4. Density of the (C) top and (:) bottom phases of the tie-lines at 298.15 K as “bot” refer to the top and bottom phases, respectively. To correlate
function of the ferrous sulfate concentration, w1. the experimental data, the following equilibrium condition was
also used:

1.3950
ðXt gt Þtop ¼ ðXt gt Þbot (23)
1.3900
The interaction parameters and the standard deviations are re-
1.3850 ported in Table 12.
1.3800 According to the obtained standard deviation, the extended
UNIQUAC model satisfactorily correlates the experimental data.
nD

1.3750

1.3700
5. Conclusions
1.3650
The LLE of the ATPS formed by FeSO4 þ PEG 4000 þ H2O at
1.3600
T ¼ (288.15, 298.15 and 308.15) K and at pH values lower than 3 was
1.3550 studied. The density, refractive index, kinematic viscosity, electrical
0.0000 0.0500 0.1000 0.1500 0.2000 0.2500
conductivity and sound velocity in the monophasic region were
w2
measured at different temperatures. Except for the electrical con-
Fig. 5. Refractive indices of the (:) top and (C) bottom phases of the tie-lines at ductivity, the magnitudes of all physical properties positively
308.15 K. correlate with the PEG concentration, and they all positively
correlated with the salt concentration. The temperature inversely
correlated with the magnitudes of all physical properties, except for
4.5. Modeling of LLE the sound velocity.
The density and refractive index data were correlated using
The parameters of the UNIQUAC model were calculated by Othmer’s equation, yielding standard deviations of 0.0019 and
minimizing the following objective function: 0.0018, respectively. The viscosity and sound velocity data were
correlated at each temperature because this methodology
improved the results. To correlate the electrical conductivity data,
these data needed to be expressed as normal conductivity and
 L. Muruchi et al. / Fluid Phase Equilibria 412 (2016) 29e38 37

Table 12
Interaction parameters of the UNIQUAC model for the FeSO4 (1) þ PEG (2) þ H2O (3) system at 288.15, 298.15 and 308.15 K.

A23 A32 A12 A21 A13 A31 104 SDa

2879.1731 3012.7994 3618.7601 6.0655 6357.3442 3545.2603 1.17

a ðwtop wtop Þ2 ðwbot wbot Þ2
SD ¼ t;l;exp t;l;cal
np *nd
t;l;exp t;l;cal
, where np and nd are number of model parameters and number of worked compositions, respectively.

correlated with the PEG concentration and temperature at constant STL slope of the tie-line
salt concentrations. In all cases, a good agreement between Fob objective function
experimental and calculated values was obtained. The solubility np number of model parameters
curves and tie-lines of the studied system were determined at nd number of worked compositions
different temperatures, which indicated that the STL and biphasic
area increase as the temperature increase. Thus, the capacity of Greek symbols
ferrous sulfate to induce the phase separation directly correlates gi activity coefficient of species i
with the temperature because the free electrolyte content in the r closest distance parameter
bulk solution directly correlates with the temperature. Moreover, DGc free energy of phase separation
the phase separation is driven by entropy. The plait points at each DHc enthalpy of phase separation
temperature were satisfactorily determined from the tie-line data. DSc entropy of phase separation
Additionally, the density, refractive index, viscosity and sound ε permitivity of vacuum
velocity of both phases were measured for the tie-lines. These εT dielectric constant of the mixed solvent
measurements indicate that the water content inversely correlates εTj dielectric constant of component j
with the magnitudes of these parameters for the bottom phase, k electrical conductivity
whereas this relationship is direct in the top phase, except for the 4j the salt-free volume fraction for polymer and water
density. In both phases, the temperature directly correlates with all m absolute viscosity
parameters, except for the sound velocity, which exhibited inverse
behavior. Superscripts
Finally, the extended UNIQUAC model was used to correlate the T top
equilibrium results. The model fit the data well, with a standard B bottom
deviation of 1.17$104. LR long-range
PDH PitzereDebyeeHückel
Acknowledgments SR short-range

The authors thank CONICYT-Chile for financing this research References

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