J. Chem.

Thermodynamics 142 (2020) 105986

Contents lists available at ScienceDirect

J. Chem. Thermodynamics
journal homepage: www.elsevier.com/locate/jct

Water activity, density, sound velocity, refractive index and viscosity of

the {(NH4)6Mo7O24 + poly(ethylene glycol) + H2O} system in the
temperature range from 313.15 to 333.15 K: Experiment and modelling
Grecia Villca a,b, Francisca J. Justel a, Yecid P. Jimenez a,⇑
a
Departamento de Ingeniería Química y Procesos de Minerales, Facultad de Ingeniería, Universidad de Antofagasta, Av. Angamos 601, Antofagasta, Chile
b
Carrera de Ingeniería Química, Facultad Nacional de Ingeniería, Universidad Técnica de Oruro, Av. Cnel. Alejandro Dehene, Ciudadela Universitaria, Oruro, Bolivia

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

Article history: Experimental data of water activity, density, sound velocity, refractive index and viscosity of unsaturated
Received 27 July 2019 solutions of {ammonium heptamolybdate + poly(ethylene glycol) + water} at (313.15, 323.15 and
Received in revised form 1 October 2019 333.15) K were obtained. The concentration range of the solutions was from 0 to 0.4 mass fraction of
Accepted 20 October 2019
poly(ethylene glycol) with an average molar mass of 4000 g
mol1 and from 0 to 0.17 mass fraction of
Available online 24 October 2019
(NH4)6Mo7O24. Additionally, water activities and physical properties of the constituent binary systems,
{(NH4)6Mo7O24 + H2O and PEG 4000 + H2O}, were measured and modeled at the same temperatures of
Keywords:
the ternary system. The modified Pitzer model for the representation of water activity was applied and
Water activity
Physical properties
the physical properties were correlated by the Othmer’s rule. Good agreement between the experimental
Ammonium heptamolybdate and correlated data was obtained.
Poly(ethylene glycol) Ó 2019 Elsevier Ltd.
Pitzer

1. Introduction
Aqueous two-phase systems (ATPSs) have numerous uses in
biotechnology [1,2], chemical partitioning [3–5], and extractive
crystallization of inorganic salts [6]. These systems are recognized
as an economical and efficient separation process.
A knowledge of the thermodynamic and physical properties of
(polymer + salt + water) solutions is very important in chemical
engineering and in other areas involved in separation processes,
wastewater treatment, fluid transport, etc. Water activity data
are of great utility in studying the salting effects in these types of
system [7,8], and also allow the obtaining of other important ther-
modynamic properties such as activity and osmotic coefficients,
and vapour pressures. All these properties are useful for the extrac-
tion equipment design through the phase equilibrium calculations
and for the development of theoretical models that allow the pre-
diction of the partitioning behaviour of the ATPS. Sadeghi [9,10]
and Sadeghi et al. [11–13] have reported experimental data of
water activity of diverse ternary systems containing (polymer
+ salt + water), incorporating in some of these studies the correla-
tion of experimental data with the Wilson model and the extended
form of Chen’s non-random two liquid (NRTL) model. Cortes et al.
⇑ Corresponding author.
E-mail address: yecid.jimenez@uantof.cl (Y.P. Jimenez).
[14,15], Salabat et al. [16], Jiménez [17], Jahani et al. [18,19], and
Zafarani-Moattar et al. [20,21] have reported similar studies of
ternary systems.
Properties, such as density and viscosity, are also indispensable
for pipe sizing, mass balance calculations, and equipment design
(crystallizers, settlers, etc.). There are some reported data on the
physical and chemical properties of aqueous polymer-salt solu-
tions. Claros et al. [22] reported experimental data of the density,
refractive index, viscosity, electrical conductivity, and pH of the
{copper sulfate + poly(ethylene glycol) 4000 + water} system in
the temperature range from 288.15 K to 308.15 K. Othmer’s rule
was used to correlate the experimental data. Mei et al. [23]
reported experimental data of the density and viscosity of aqueous
solutions of {PEG + (NH4)2SO4 or K3PO4} at 293.15 K using several
values of molar mass of PEG (1000, 2000, 4000, 6000, and
20000 g
mol1). Muruchi et al. [24] measured experimental den-
sity, sound velocity, refractive index, viscosity and electrical con-
ductivity data of the {ferrous sulfate + poly(ethylene glycol) 4000
+ water} system at T = (288.15, 298.15 and 308.15) K. Similar
works are reported by Silva et al. [25], Zafarani-Moattar et al.
[26], Zafarani-Moattar and Mehrdad [27], Barani et al. [28].
In the present work, the water activity and the physical proper-
ties of unsaturated solutions of the ternary {(NH4)6Mo7O24 + PEG
4000 + H2O} system and the constituent binary systems at three
different temperatures from (313.15 to 333.15) K were measured.
The interval concentrations of (NH4)6Mo7O24 were between 0

https://doi.org/10.1016/j.jct.2019.105986
0021-9614/Ó 2019 Elsevier Ltd.
2 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986

and 0.17 mass fraction, and for PEG 4000, the interval concentra- 0.002 K). Each measurement was conducted in triplicate and uti-
tions were between 0 and 0.4 mass fraction. The values of water lized 0.5 mL of solution.
activity were correlated by the modified Pitzer model [29,30] and The kinematic viscosities were measured with calibrated micro-
the density, sound velocity, refractive index and viscosity data Ostwalt viscometers. A Schott-Gerate automatic measuring unit
were correlated by the Othmer’s rule [22,31]. It is important to (model AVS 310) equipped with a thermostat (Schott-Gerate,
mention, there has been no report on the water activity and phys- model CT 52) in which the temperature was regulated to within
ical properties of the {(NH4)6Mo7O24 + PEG 4000 + H2O} system. ±0.05 K was used for the measurements. The viscometer was cali-
brated using deionized water as reference measuring standard,
using two millilitres of water for each measurement. It was per-
2. Experimental formed by means of flow-through measurement of the water in
the viscometer to be inspected in a temperature bath,
2.1. Materials The absolute viscosity is obtained by multiplying the kinematic
viscosity by the corresponding density. The measurements were
Synthesis grade samples of PEG with an average molar mass of conducted in triplicate, and 2 mL were used for each experiment.
4000 (3500–4500) g
mol1 (CAS No. 25322–68-3) was procured All the solutions were prepared by mass in a Mettler Toledo
from Sigma-Aldrich. Ammonium heptamolybdate tetrahydrate analytical balance (model AX204) with a precision of ±0.1 mg.
(CAS No. 12054–85-2) with mass fractioon purity > 0.993 and The experimental error in concentration was less than 0.01%. The -
sodium chloride (CAS No. 7647-14-5) with mass fraction pur- water content in the ammonium heptamolybdate was accounted
ity > 0.995 were procured from Merck. All reagents were used for upon solution preparation.
without further purification. Deionised water was used in all
experiments (Milli-Q, Millipore, j = 0.054 mS
cm1). Table 1 shows
3. Thermodynamic framework
the chemical specifications.
The general expression of the excess Gibbs energy of the sys-
2.2. Apparatus and procedures tem, GE, for the modified Pitzer model, can be written as [30]:

 N
X
GE Na j X 1 N X
N
The water activities for the ternary system and the constituent ¼ ni Zi 2 e2 sðjaÞ þ kij ri rj ni nj
RT 3D i¼1 nw i–w j–w
binary systems were determined using a KNAUER K-7000 vapour

 N X
pressure osmometer with temperature control of ±0.001 K at T = 1 X N X N

(313.15, 323.15 and 333.15) K. The equipment was calibrated þ l ri rj rk ni nj nk ð1Þ

using aqueous NaCl solutions of known osmolality with water as
reference, for which the osmotic coefficient data were taken from
literature [32]. The details of the calibration of the osmometer
for aqueous solutions have been described previously [17]. The
combined uncertainty of the water activity of the calibration solu-
tions was ±3
104. During the measurements, the concentration of
PEG was fixed at 0.05, 0.10, 0.15, 0.20, and 0.22 mass fraction,
whereas the salt concentration was fixed at (0.02, 0.05, 0.07,
0.10, 0.12, 0.15, 0.17 and 0.20) mass fraction.
Approximately a total of 40 g of a solution of known composi-
tion was prepared by mass to determine the properties in the
unsaturated zone of density, sound velocity, refractive index and
kinematic viscosity. The densities and sound velocities of the solu-
tions were measured using a density and sound velocity meter
(Anton Paar DSA 5000 M, measuring range from (0 to 3) g
cm3,
resolution 1  106 g
cm3) with a precision of ±0.001 K. The
working frequency of the speed of sound meter is of 3 MHz. 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, where density and sound velocity
were measured simultaneously. The measurements were con-
ducted in triplicate and the reported data represent the average.
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  105nD units,
temperature probe accuracy 0.03 K, temperature probe stability
Table 1
Chemical reagents used in the experiments.
nw i–w j–w k–w ijk
2
where the first term on the right-hand side is the long-range elec-
trostatic contribution taken from the expression of Fowler and
Guggenheim [33], and the second and third terms are the short-
range virial contributions. In Eq. (1), all summations run through
all species except water; nw is the number of kilograms of water,
and ni, ri are the numbers of moles and segments of species i,
respectively, Na represents the Avogadro constant, N equals the
number of species, both ionic and non-ionic, s is a function of the
reduced Debye length (ja)
" #
ðjaÞ2
sðjaÞ ¼ 3ðjaÞ3 ln ð1 þ jaÞ  ja þ ð2Þ
2
where kij and lijk are symmetric matrices and, in effect, second and
third virial coefficients which represent, respectively, the short-
range forces between ions, segments of polymers or ions and seg-
ments. The assumptions similar to those in the original Pitzer model
[34] are still used to specify the virial coefficients, but the virial-
type coefficients between segments are independent of ionic
strength, and the virial-type coefficients between ions have differ-
ent values from those in the Pitzer model, and should be re-
correlated. Based on the above assumptions and by appropriate dif-
ferentiation of Eq. (1) with respect to ni, the activity coefficients of
the components in the system can be obtained. However, since the
derivation of the general case for any numbers of polymers and salts
is tedious, the simplest system formed by a polymer (1), a salt (2)
and water (3) is considered and presented here. From Eq. (1), the
activity coefficients, c, of non-electrolyte components may be writ-
ten as:

Chemical name Source Purity Purification lnc ¼ lncLR

 þ lnc
SR
ð3Þ
(mass fraction) method
where the superscripts, LR and SR, stand for long-range and short-
PEG 4000 Sigma-Aldrich – None range contributions, respectively. For the salt,
(NH4)6Mo7O24
4H2O Merck >0.993* None


NaCl Merck >0.995* None 1 1
lnc ¼ ðtc lncLR
c þ ta lnca Þ þ
LR
ðtc lncSR
c þ ta lnca Þ
SR
ð4Þ
*Purity of the chemical reagents are provided by the suppliers. t t
 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986 3



where the subscripts, c and a, denote cations and anions, respec- M3 nw 0
lncSR ¼ B11 r21 m21 þ B12 þ IB12 r1 m1 m2
tively, and mj (j = c or a) is the number of cations or anions in a salt, 3
1000 ns


m = mc + va. Based on the above framework, lncLR may be expressed as: nw 0
þ 2vc va B22 þ IB m2 þ 2C111 r31 m31 þ 2C112 r21 m21 m2
2
ns 22
jZc Za jAI1=2 
lncLR
 ¼ ð5Þ 3
1 þ bI1=2 þ 2C122 r1 m1 m22 þ 2ðvc va Þ2 C/222 m32 ð17Þ
For the non-ionic components,
 where:
2AVi d  
1 1
 
lnc
1 1
LR
¼ 1 þ bI  1 þ bI2
2  2 ln 1 þ bI2 ð6Þ ni
i 3 mi ¼ ði ¼ 1:2Þ ð18Þ
b nw
where
B11 ¼ k11 ð19Þ
X
N
0 2
I ¼ 0; 5 m j Zj ð7Þ
C111 ¼ l111 ð20Þ
j–w

vc va
nj B22 ¼ kca þ kcc þ kaa ð21Þ
m0 j ¼ ð8Þ 2va 2vc
ns
3
ns ¼ nw þ
M i ni
ð9Þ C/222 ¼ 1
ðlcca vc þ lcaa va Þ ð22Þ
1000 ðva vc Þ2
and Vi is the molar volume in m3
mol1 of pure non-ionic species i, d
c 3 /
is the mixed-solvent density, and A and b are Debye-Hückel con- C222 ¼ C ð23Þ
2 222
stants; based on a value of 4 Å for a, they are calculated as:

1; 327757  105 d
0;5 B12 ¼ 2ðk1c vc þ k1a va Þ ð24Þ
A¼ 1;5
ð10Þ
ðDTÞ
C112 ¼ 3ðl1cc v2c þ l1aa v2a Þ ð25Þ
0;5
6; 359696d
b¼ ð11Þ C122 ¼ 3ðl1cc v2c þ 2l1ca vc va þ l1aa v2a Þ ð26Þ
ðDTÞ0;5
0 0
and B12 and B22 are the derivatives of BI2 and B22 with respect to
D and d are the properties of the mixed solvent; they are empir-
I, respectively. Using the same treatment as in the original Pitzer
ically calculated as follows:
X model, for uni-bivalent salts, the overall second virial coefficients
0
D¼ /i Di ð12Þ can be further expressed as:

2bij h    i
ð1Þ
X
1  1 þ a1;ij I2 exp a1;ij I2
0 ð0Þ 1 1
d¼ /i di ð13Þ Bij ¼ bij þ ð27Þ
a1;ij
2

0
where /i is the salt-free volume fraction of non-ionic species i in the The derivative of Eq. (27) is:
liquid phase, and is defined as:
ð1Þ
  
2bij 1 2
a a a
1 1
0
/i ¼ P
ni Vi
ð14Þ B0 ij ¼ 1 þ 1 þ ð I Þ2 þ I exp  ð I Þ 2 ð28Þ
j–ion nj Vi
a21;ij I2 2

The physical properties to calculate the Debye–Hückel con- where b(0), b(1) and a have similar meanings as in Pitzer’s virial
stants A and b, for PEG 4000 and water were taken from Kell [35] model. The correlation of the ternary VLE data shows that it is not
and Wu et al. [30], and are listed in Table 2. sensitive to the a parameter, and any value of a selected near the
The short-range contributions, lncSRi , may be written as:
one given by Pitzer [34] is acceptable. Therefore, we set
a1,12 = a1,22 = 2.0.
M1
lncSR
1 ¼ 2B11 r1 m1 þ B12 r1 m2 
2
1000
nw  0  4. Results and discussion
0
 I B12 r1 m1 m2 þ 2vc va B22 m22 þ 3C111 r31 m21
ns
4.1. Water activity
þ 2C112 r21 m1 m2 þ C122 r1 m22 ð15Þ

h Water activities of the {(NH4)6Mo7O24 + PEG 4000 + H2O} sys-
1  0 
lncSR
0 tem at T = (313.15, 323.15 and 333.15) K were determined from
 ¼ B12 r1 m1 þ 4vc va B22 m2 þ I B12 r1 m1 þ 2vc va B22 m2
v osmolality data and then vapour pressures were calculated. More-
3 c
i
þ C112 r21 m21 þ 2C122 r1 m1 m2 þ 2ðvc va Þ2 C222 m22 ð16Þ over, water activities of the constituent binary systems were mea-
sured at the same temperature range.

Table 2
Densities (q), Dielectric constant (Di), and Molar Volume (Vi) of PEG 4000 [30] and H2O [35] pure substances at different temperatures.

T/K q/kg
m3 Di Vi  106/m3
mol1

PEG 4000 H2O PEG 4000 H2O PEG 4000 H2O
313.15 1088.74 992.22 2.206 73.151 3444.36 18.16
323.15 1081.72 988.04 2.206 69.910 3466.69 18.23
333.15 1076.04 983.20 2.206 66.815 3485.01 18.32
4 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986

The water activity of the aqueous multicomponent solutions is
related to the total osmolality by [36,37]:
P determined at T = (313.15, 323.15 and 333.15) K for the (NH4)6-
osmolality ti mi
lnaw ¼  ¼ / ð29Þ
55:51 55:51
where mi is the number of ions produced on dissociation of ith com-
ponent, mi is the molality and / is the osmotic coefficient. 55.51 is
the number of moles in 1 kg of water.
From the experimental data of activity, the vapour pressure can
be calculated by:


p ðBw  V w Þðp  p0 Þ
lnaw ¼ ln 0
þ ð30Þ
p RT
where Bw is the second virial coefficient of water vapour, p° is the
vapour pressure of pure water, Vw is the molar volume of liquid
water, T is the temperature and R is the universal gas constant.
The values used for the second virial coefficients of water
vapour were  0.930  103, 0.812  103 and 0.715  103
m3
mol1 at T = (313.15, 323.15 and 333.15) K, respectively [38].
The molar volumes of liquid water calculated from density data
and reported in Table 2 were used. The vapour pressures of the
pure water at T = (313.15, 323.15 and 333.15) K used were
(7.381, 12.344 and 19.932) kPa, respectively [38].
4.1.1 . Binary (NH4)6Mo7O24 + H2O and PEG 4000 + H2O systems
Table 3 shows the water activity and the vapour pressure values
Mo7O24 + H2O system.
As can be seen, the high solubility of the ammonium hepta-
molybdate is reflected in the water activities, i.e. the water activity
decreases as salt concentration increases.
In Table 3, it is also possible to appreciate that the temperature
has no relevant effect on water activity. However, at high concen-
tration it is evident that with increasing temperature, the water
activity decreases, similar behaviour was reported by Jimenez
et al. [39] for the binary system (Na2MoO4 + H2O) system. On the
other hand, a significant effect of the temperature on the vapour
pressure is observed in Table 3, where vapour pressure increases
with increasing temperature.
Fig. 1 shows a comparison between the water activities of the
aqueous binary systems formed by (NH4)6Mo7O24 [this work]
and Na2MoO4 [39] at 313.15 K, in order to analyse the effect of
cations on the water activities of these systems. For the same con-
centration range, the water activities of the {(NH4)6Mo7O24 + H2O}
system are lower than the (Na2MoO4 + H2O) system, this would be
related to the fact that the ammonium salt is formed by seven
molybdate molecules unlike the sodium salt that is formed by
one. These bindings between water and molybdate molecules

Table 3
Water activity (aw) and vapour pressures (p) for the (NH4)6Mo7O24 + H2O system at different (NH4)6Mo7O24 mass fractions (wca) at T = (313.15, 323.15 and 333.15) K and pressure
P = 101.3 kPa.a

wca T = 313.15 K T = 323.15 K T = 333.15 K

awb p/kPac awb p/kPac awb p/kPac
0.0200 0.9977 7.373 0.9975 12.331 0.9980 19.910
0.0500 0.9961 7.357 0.9969 12.305 0.9966 19.867
0.0700 0.9950 7.348 0.9953 12.289 0.9956 19.841
0.1000 0.9936 7.335 0.9939 12.267 0.9941 19.807
0.1200 0.9927 7.327 0.9929 12.254 0.9930 19.788
0.1500 0.9916 7.317 0.9914 12.237 0.9913 19.762
0.1700 0.9908 7.311 0.9904 12.225 0.9901 19.747
a
The standard uncertainties u are u(wi) = 0.0001, u(T) = 0.01 K and u(P) = 1 kPa. The combined standard uncertainties uc, are uc(aw) = 3
104.
b
Measured values.
c
Calculated values.

Fig. 1. Water activities (aw) of the (d) (NH4)6Mo7O24 + H2O system and (s) Na2MoO4 + H2O system [39] at 313.15 K; the black lines are guides for the eye.
 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986 5

Table 4
Water activity (aw) and vapour pressures (p) for the (NH4)6Mo7O24 + PEG 4000 + H2O system for different mass fractions of (NH4)6Mo7O24 (wca) and PEG 4000 (wp), at T = (313.15,
323.15 and 333.15) K and pressure P = 101.3 kPa.a

wca wp T = 313.15 K T = 323.15 K T = 333.15 K

awb p/kPa c
awb p/kPac awb p/kPac
0.0200 0.0500 0.9984 7.369 0.9976 12.323 0.9967 19.892
0.0500 0.0500 0.9961 7.352 0.9955 12.293 0.9948 19.841
0.0700 0.0500 0.9947 7.341 0.9942 12.275 0.9936 19.811
0.1000 0.0500 0.9927 7.326 0.9923 12.250 0.9919 19.772
0.1200 0.0500 0.9914 7.318 0.9911 12.236 0.9909 19.749
0.1500 0.0500 0.9896 7.306 0.9894 12.215 0.9894 19.719
0.1700 0.0500 0.9885 7.298 0.9882 12.202 0.9885 19.700
0.2000 0.0500 0.9870 7.287 0.9866 12.181 0.9873 19.674
0.0200 0.1000 0.9972 7.362 0.9970 12.310 0.9958 19.868
0.0500 0.1000 0.9948 7.342 0.9944 12.277 0.9940 19.811
0.0700 0.1000 0.9933 7.330 0.9929 12.257 0.9927 19.780
0.1000 0.1000 0.9910 7.313 0.9908 12.230 0.9907 19.740
0.1200 0.1000 0.9895 7.302 0.9896 12.214 0.9893 19.719
0.1500 0.1000 0.9873 7.288 0.9879 12.192 0.9871 19.692
0.0200 0.1500 0.9957 7.350 0.9959 12.292 0.9948 19.838
0.0500 0.1500 0.9926 7.328 0.9931 12.257 0.9925 19.780
0.0700 0.1500 0.9908 7.313 0.9914 12.236 0.9910 19.752
0.0200 0.2000 0.9932 7.333 0.9940 12.268 0.9935 19.800
0.0500 0.2000 0.9899 7.308 0.9906 12.231 0.9908 19.750
0.0200 0.2200 0.9925 7.325 0.9931 12.256 0.9928 19.783
0.0500 0.2200 0.9888 7.298 0.9895 12.219 0.9902 19.740
a
The standard uncertainties u are: u(wi) = 0.0001, u(T) = 0.01 K and u(P) = 1 kPa. The combined standard uncertainties uc are uc(aw) = 3
104.
b
Measured values.
c
Calculated values.

could result in the reduction of the free water content in the
solution.
The water activity of the (PEG 4000 + H2O) system were
reported in a previous work [15]. However, the water activities
for this system at T = (313.15, 323.15 and 333.15) K were measured
again to validate in some way the measurements of the present
Fig. 2. Water activities (aw) of the (NH4)6Mo7O24 + PEG 4000 + H2O system at
313.15 K for different mass fraction of PEG and different mas fractions of (NH4)6-
Mo7O24 (wca) for different temperatures: (d) 0.05; (j) 0.1; (▲) 0.15; (r) 0.2; (*)
0.22; (—) Pitzer model.
work, this comparison is presented in the Table and Fig. 1S of the
Supplementary Material and as can be seen, the deviation obtained
are of the order of the experimental uncertainty.
4.1.2. Ternary (NH4)6Mo7O24 + PEG 4000 + H2O system
Table 4 shows the water activity and the vapour pressure values
determined at T = (313.15, 323.15 and 333.15) K for the ternary
{(NH4)6Mo7O24 + PEG 4000 + H2O} system.
Fig. 2 shows the water activities obtained at 313.15 K for differ-
ent PEG and salt mass fractions.
Fig. 2 shows that in the PEG–salt–water system, salt has a sig-
nificant effect on the water activities and therefore on the vapour
pressures.
Fig. 2 and Table 5 allow inferring that at the same mass fraction,
vapour pressure depression for the salt solution is higher than
those for the polymer solution. This is because the molar mass of
the polymer is higher than the molar mass of the salt and conse-
quently, the number of moles of polymer in the polymer solution
is less than the number of moles of ions in the salt solution with
same concentration [12,40]. Table 5 shows that the vapour pres-
sure depression for the ternary {(NH4)6Mo7O24 + PEG 4000 + H2O}
system is higher than the sum of the vapour pressure depressions
of their constituent binary solutions {(NH4)6Mo7O24 + H2O} and
(PEG 4000 + H2O) at different temperatures [12,14]. It addition,
Table 5 shows that as the temperature and solutions concentra-

Table 5
Vapour pressure depression (p°p) for several (NH4)6Mo7O24 + PEG 4000 + H2O solutions and for the constituent binary solutions at different temperatures and mass fraction of
(NH4)6Mo7O24 (wca) and PEG (wp).

wca wp T/K (p°-p)/kPa

(NH4)6Mo7O24 + PEG 4000 + H2O (NH4)6Mo7O24 + H2O* PEG 4000 + H2O*
0.05 0.05 313.15 0.029 0.029 0.000
0.10 0.10 313.15 0.067 0.047 0.006
0.05 0.05 323.15 0.055 0.038 0.013
0.10 0.10 323.15 0.114 0.075 0.017
0.05 0.05 333.15 0.103 0.068 0.033
0.10 0.10 333.15 0.185 0.118 0.026

*For the constituent binary systems (NH4)6Mo7O24 + H2O and PEG 4000 + H2O, only the concentration values wca and wp must be considered in the calculations, respectively.
6 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986
Fig. 3. Vapour pressures depressions (p°  p) of the (NH4)6MO7O24 + PEG 4000
+ H2O system at 0.05 mass fraction of PEG and different mas fractions of (NH4)6-
Mo7O24 (wca) for different temperatures: (d) 313.15 K; (h) 323.15 K; (▲) 333.15 K;
the black lines are guides for the eye.
tions increase, for binary and ternary systems, vapour pressure
depression is higher. In order to better visualize this behaviour,
Fig. 3 shows the effect of the temperature on the vapour pressures
depressions of the {(NH4)6Mo7O24 + PEG 4000 + H2O} system at a
PEG mass fraction of 0.05. It should be noted that a similar beha-
viour is observed at the other PEG mass fractions.
Fig. 4. Temperature effect on the water activities (aw) of the binary and ternary solutions at different temperatures: a) (NH4)6Mo7O24 + H2O system, b) PEG 4000 + H2O
system, and c) (NH4)6Mo7O24 + PEG 4000 + H2O system at 0.05 mass fraction of PEG and different mas fractions of (NH4)6Mo7O24 (wca). (d) 313.15 K; (h) 323.15 K; (▲)
333.15 K; (—) Pitzer model.
In aqueous solutions, each segment of PEG is hydrated strongly
with several water molecules, since PEG is highly soluble in water.
Such binding between water and PEG molecules would result in a
reduction of the free water content and would induce an increase
in the effective concentration of the salt. Likewise, an increase in
the effective concentration of the polymer would be expected by
the hydration of the ions present in the aqueous solution.
Table 4 shows that the temperature has a small effect on the
water activities for the {(NH4)6Mo7O24 + PEG 4000 + H2O} system,
where at 333.15 K, the activities are slightly lower than at
313.15 K. These results agree with those of Guendouzi and Dinane
[41], who reported the water activities, osmotic and activity coef-
ficients of aqueous electrolyte solutions of KCl (aq), Na2SO4 (aq),
and NaNO3 (aq) at different concentrations over a wide tempera-
ture range, and concluded that the water activities are highly
affected by the solute concentration; but slightly influenced by
the temperature. Nevertheless, the temperature effect on the ther-
modynamic properties for aqueous polymer solutions is greater
than for the aqueous electrolyte solutions. This last is because as
temperature increases the hydrogen bond interactions of PEG are
weakened. For that reason, with increasing temperature, water is
driven from the PEG-rich solutions to the vapour phase. At high
PEG concentrations the temperature effect will be appreciated
more clearly. The temperature effect on the water activities of
the binary and ternary solutions is better exemplified in Fig. 4.
Also, the non-ideality of studied aqueous solutions was anal-
ysed and for this purpose water activities of ideal solutions for
 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986 7

water molecules to the polymer. Also, the authors suggest that at

low PEG concentrations, the smaller negative slopes are related
with the hydrophobic hydration of PEG, which is a relevant factor
in the behaviour of the dilute solutions.
Similar behaviour between the calculated ideal water activities
for the ternary {(NH4)6Mo7O24 + PEG 4000 + H2O} system and for
the binary systems was observed. Since, at high PEG concentra-
tions, the calculated ideal water activities are higher than the
experimental values and the ideal water activities are lower than
the experimental data at low PEG concentrations.

4.2. Physical properties

Experimental values of density, sound velocity, refractive index

Fig. 5. Water activity (aw) of the (NH4)6Mo7O24 + H2O system as a function of the
molality at 313.15 K: (d) experimental values, (—) correlated values by the Pitzer
model, (  ) calculated for ideal solution.
the {(NH4)6Mo7O24 + H2O} system have been calculated from the
w ¼ expðM w mmca Þ. Fig. 5 shows the dependence of the
equation aid
water activity of the binary system as a function of the molality
of solute. This figure shows that for the aqueous salt solutions,
the non-ideality for the water is higher. In a previous work, it
was reported that for the aqueous PEG solution, the non-ideality
for the water is also higher because the interaction between the
water and PEG at high mass fractions of PEG must be of a very
stable nature [14]. Sadeghi and Shahebrahimi [42] attributed the
larger negative slopes of the water activity against concentration
at high PEG concentrations to the greater hydrogen bonding of
and viscosity of unsaturated solutions of {(NH4)6Mo7O24 + PEG
4000 + H2O} and its constituent binary systems at (313.15,
323.15 and 333.15) K were measured. The ammonium hepta-
molybdate and poly(ethylene glycol) concentrations chosen to
determine the physical properties were selected below the satura-
tion concentration of ammonium heptamolybdate. These experi-
mental data are presented in Tables 6, 7 and 8.
As shown in Tables 7 and 8, the concentration of PEG directly
and linearly correlates with the density, sound velocity and refrac-
tive index at constant temperature and salt concentration; the vis-
cosity also directly correlates with the PEG concentration, but this
relationship is not linear. At constant temperature and PEG con-
centration, all properties directly correlated with the salt concen-
tration (Tables 6 and 8).
For the viscosity, the PEG concentration has more influence
than the salt concentration over the magnitude of the property

Table 6
Experimental refractive index (nD), density (q), sound velocity (s) and viscosity (m) data in aqueous solutions of (NH4)6Mo7O24 for different mass fractions of (NH4)6Mo7O24 (wca)
at T = (313.15, 323.15 and 333.15) K and pressure P = 101.3 kPa.a

wca T = 313.15 K T = 323.15 K T = 333.15 K

nD q/g
cm 3
s/m
s 1
v/mm
s 2 1
nD q/g
cm 3
s/m
s 1
v/mm
s 2 1
nD q/g
cm3 s/m
s1 v/mm2
s1
0.0200 1.3339 1.00591 1528.03 0.710 1.3324 1.00177 1541.43 0.595 1.3302 0.99639 1550.47 0.514
0.0500 1.3392 1.02777 1525.63 0.667 1.3381 1.02331 1539.07 0.567 1.3364 1.01782 1547.45 0.487
0.0700 1.3428 1.04284 1524.30 0.679 1.3413 1.03816 1537.35 0.568 1.3405 1.03303 1545.50 0.489
0.1000 1.3482 1.06583 1521.56 0.671 1.3467 1.06111 1534.57 0.570 1.3467 1.05582 1543.03 0.490
0.1200 1.3524 1.08176 1519.90 0.685 1.3506 1.07702 1533.17 0.579 1.3508 1.07158 1540.85 0.494
0.1500 1.3582 1.10667 1517.76 0.677 1.3574 1.10195 1530.49 0.580 1.3570 1.09655 1538.14 0.498
0.1700 1.3623 1.12389 1516.44 0.689 1.3619 1.11910 1529.11 0.583 1.3611 1.11345 1536.70 0.503
a
The standard uncertainties, u, are u(P) = 1 kPa, u(T) = 0.01 K (for the refractive index, density and sound velocity), u(T) = 0.05 K (for the viscosity), u(wi) = 0.0001, u(nD)
= 4
104, u(q) = 1.6
104 g
cm3, u (s) = 0.9 m
s1, u(m) = 2
102 mm2
s1.

Table 7
Experimental refractive index (nD), density (q), sound velocity (s) and viscosity (m) data in aqueous solutions of PEG 4000 for different mass fractions of PEG (wp) at T = (313.15,
323.15 and 333.15) K and pressure P = 101.3 kPaa.

wp T = 313.15 K T = 323.15 K T = 333.15 K

nD q/g
cm3 s/m
s1 v/mm2
s1 nD q/g
cm3 s/m
s1 v/mm2
s1 nD q/g
cm3 s/m
s1 v/mm2
s1
0.0500 1.3374 0.99994 1550.51 1.2075 1.3360 0.99548 1560.96 0.9968 1.3346 0.99052 1566.24 0.8448
0.0700 1.3401 1.00322 1559.47 1.5470 1.3388 0.99869 1568.30 1.2748 1.3373 0.99351 1572.31 1.0580
0.1000 1.3439 1.00789 1572.70 2.1205 1.3431 1.00318 1579.15 1.7174 1.3413 0.99783 1581.08 1.4291
0.1500 1.3507 1.01593 1594.80 3.4220 1.3493 1.01104 1597.84 2.7339 1.3481 1.00545 1596.39 2.2444
0.1700 1.3536 1.01912 1604.10 4.0892 1.3519 1.01384 1605.12 3.2537 1.3508 1.00810 1602.15 2.6619
0.2000 1.3580 1.02419 1617.58 5.3026 1.3562 1.01867 1615.97 4.2372 1.3548 1.01282 1610.81 3.4181
0.2200 1.3608 1.02748 1626.50 6.2490 1.3596 1.02182 1622.96 4.9645 1.3575 1.01589 1616.26 4.0229
0.2500 1.3649 1.03251 1640.42 8.0431 1.3628 1.02678 1634.25 5.8571 1.3616 1.02066 1624.69 5.1539
0.2700 1.3677 1.03589 1648.97 9.4320 1.3657 1.03001 1641.25 7.5201 1.3643 1.02356 1630.20 6.1266
0.3000 1.3722 1.04075 1662.89 11.9905 1.3704 1.03486 1651.72 9.3197 1.3683 1.02808 1637.96 7.5113
0.3500 1.3801 1.04986 1684.06 17.7270 1.3774 1.04318 1668.55 13.6127 1.3751 1.03639 1650.21 11.0647
0.4000 1.3874 1.05818 1701.33 25.6398 1.3846 1.05115 1681.12 19.3015 1.3818 1.04375 1660.16 15.1623
a
The standard uncertainties, u, are u(P) = 1 kPa, u(T) = 0.01 K (for the refractive index, density and sound velocity), u(T) = 0.05 K (for the viscosity), u(wi) = 0.0001, u(nD)
= 3
104, u(q) = 1.3
104g
cm3, u (s) = 0.9 m
s1, u(m) = 3
102mm2
s1.
8 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986

Table 8
Experimental refractive index (nD), density (q), sound velocity (s) and viscosity (m) data in aqueous solutions of (NH4)6Mo7O24 and PEG 4000 for different mass fraction of
(NH4)6Mo7O24 (wca) and PEG (wp) at T = (313.15, 323.15 and 333.15) K and pressure P = 101.3 kPa.a

wca wp T = 313.15 K T = 323.15 K T = 333.15 K

nD q/g
cm3 s/m
s1 v/mm2
s1 nD q/g
cm3 s/m
s1 v/mm2
s1 nD q/g
cm3 s/m
s1 v/mm2
s1
0.0200 0.0500 1.3418 1.01585 1550.93 1.237 1.3396 1.01032 1560.20 1.038 1.3383 1.00491 1565.33 0.891
0.0200 0.1000 1.3480 1.02423 1572.95 2.083 1.3464 1.01821 1578.13 1.727 1.3454 1.01298 1580.55 1.451
0.0200 0.1500 1.3557 1.03483 1596.88 3.458 1.3528 1.02624 1596.44 2.772 1.3518 1.02079 1594.92 2.327
0.0200 0.2000 1.3641 1.04374 1623.66 5.886 1.3610 1.03451 1615.34 4.345 1.3595 1.02940 1610.92 3.693
0.0200 0.2200 1.3677 1.04819 1634.48 7.263 1.3631 1.03785 1622.83 5.015 1.3631 1.03241 1616.61 4.311
0.0200 0.2500 1.3721 1.05303 1648.20 9.581 1.3678 1.04248 1633.34 6.527 1.3657 1.03710 1624.74 5.483
0.0500 0.0500 1.3474 1.04197 1548.22 1.262 1.3456 1.03250 1557.22 1.053 1.3442 1.02968 1562.42 0.909
0.0500 0.1000 1.3544 1.04826 1570.99 2.155 1.3530 1.04196 1576.20 1.771 1.3531 1.03712 1577.73 1.503
0.0500 0.1500 1.3629 1.06036 1597.39 3.800 1.3595 1.05005 1594.74 2.865 1.3600 1.04521 1593.37 2.410
0.0500 0.2000 1.3683 1.06489 1616.90 5.613 1.3674 1.05847 1613.68 4.510 1.3655 1.05295 1606.49 3.585
0.0500 0.2200 1.3706 1.06722 1624.56 6.465 1.3710 1.06283 1621.65 5.456 1.3685 1.05757 1614.70 4.529
0.0700 0.0500 1.3512 1.05689 1546.17 1.257 1.3500 1.05010 1555.61 1.067 1.3493 1.04510 1560.51 0.905
0.0700 0.1000 1.3591 1.06668 1571.20 2.264 1.3580 1.05845 1574.85 1.798 1.3580 1.05365 1576.13 1.521
0.0700 0.1500 1.3654 1.07354 1593.54 3.633 1.3647 1.06720 1594.29 2.987 1.3635 1.06244 1592.20 2.493
0.1000 0.0500 1.3583 1.07684 1544.54 1.335 1.3570 1.07555 1553.18 1.089 1.3564 1.07156 1557.70 0.930
0.1000 0.1000 1.3645 1.08506 1567.68 2.206 1.3650 1.08430 1572.73 1.847 1.3649 1.08029 1574.43 1.578
0.1200 0.0500 1.3621 1.04091 1543.12 1.332 1.3619 1.09283 1551.91 1.094 1.3598 1.08864 1556.00 0.940
0.1200 0.1000 1.3698 1.11001 1567.72 2.385 1.3679 1.10130 1571.35 1.872 1.3675 1.09734 1572.49 1.586
a
The standard uncertainties, u, are u(P) = 1 kPa, u(T) = 0.01 K (for the refractive index, density and sound velocity), u(T) = 0.05 K (for the viscosity), u(wi) = 0.0001, u(nD)
= 6
104, u(q) = 1.4
104 g
cm3, u (s) = 0.9 m
s1, u(m) = 2
102 mm2
s1.

and is different than the rest of properties because the salt or PEG
concentration effect is similar over the density, sound velocity and
refractive index.
Table 8 shows that at constant PEG and (NH4)6Mo7O24 concen-
trations, the density and viscosity inversely correlate with the tem-
perature. However, the sound velocity directly correlated with the
temperature because the added energy due to a temperature
increase perturbs molecules to cause vibrations that are transmit-
ted via collisions between particles [24]. Fig. 6 shows the effect of
the temperature on the refractive index, density, sound velocity,

Fig. 6. (a) Refractive index (nD), (b) Density (q), (c) Sound velocity (s), (d) Viscosity (v) for the (NH4)6Mo7O24 + PEG 4000 + H2O system at 0.02 mas fraction of (NH4)6Mo7O24
(wca) and different mas fractions of PEG (wp): 313.15 K (d), 323.15 K (h) and 333.15 K (▲); (—) calculated values by Othmer equation.
 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986 9

and viscosity, where an interesting behaviour is observed in the Y

ln yR ¼ ln ¼ A þ BlnyW ð32Þ
case of sound velocity: at constant salt concentration, the effect yW
of the temperature diminishes as the PEG concentration increases
and at a certain concentration of PEG, the isotherms are joined to where yR is the relative property and represents the ratio between
reverse their behaviour, i.e. sound velocity decreases as tempera- the value of the physical property of the mixture (density, sound
ture increases. velocity, refractive index or viscosity), y, and the physical property
The refractive index also negatively correlates with the temper- of the water, yW , at the same temperature. A and B are parameters
ature. The property describes the ability of the material to refract that depend on the mass fractions of ammonium heptamolybdate
the light that moves from one medium to other; the magnitude (wca) and PEG (wp), as shown in Eqs. (33) and (34).
of the refractive index directly correlates with the degree of refrac-
A ¼ A1 wca þ A2 wp ð33Þ
tion. The refractive index of a solution is higher when its molecules
are more ‘‘tightly packed” [24]. Therefore, the density directly cor-
relates with the refractive index at constant salt concentrations, as B ¼ B1 wca þ B2 wp ð34Þ
shown in Table 8.
A1 ; A2 ; B1 and B2 are the parameters of Othmer’s equation.
4.3. Modeling of vapour-liquid equilibrium The refractive index, density, sound velocity and kinematic vis-
cosity values of water used to fit the experimental data at different
The experimental data of water activity were correlated by the temperatures are presented in Table 10.
extended modified Pitzer model [30], minimizing the following All the physical properties were correlated over the entire tem-
objective function: perature range; Tables 11, 12 and 13 show the obtained parame-
ters at different temperatures.
NP 
X 2
OF ¼ aexp
w;k  aw;k
cal
ð31Þ
k¼1 Table 10
Refractive index (nDw), density (qw), sound velocity (sw) and viscosity (vw) of water
where aexp
w;k and acal
w;k are the experimental and calculated values of the (w) at T = (313.15, 323.15 and 333.15) K [35,43,44].
water activity, respectively. NP is the number of experimental data
T/K nDw qw/g
cm3 sw/m
s1 vw/mm2
s1
points. Pitzer interaction parameters were estimated using the
least-squares method and in the correlation procedure, the water 313.15 1.33095 0.99222 1526.00 6.56
101
323.15 1.32937 0.98804 1542.87 5.48
101
activity data of the binary and ternary systems were fitted in
333.15 1.32757 0.98320 1551.30 4.68
101
simultaneously.
The calculated interaction parameters with the corresponding
deviations are shown in Table 9. According to the obtained average
Table 11
absolute deviations, the modified Pitzer model correlates satisfac-
Parameters of Other’s equation for the refractive index (nD), density (q), sound
torily the experimental data. velocity (s) and viscosity (v) of the (NH4)6Mo7O24 + H2O system in the temperature
The AADs obtained by the correlation of the experimental water range from 313.15 to 333.15 K.
activities of the binary and ternary systems at three different tem-
Physical A1 A2 B1 B2 AAD
peratures (0.0008, 0.0014 and 0.0034 for 313.15, 323.15, and Properties
333.15 K, respectively) show a good agreement between experi-
nD 1.64148 0.19879 5.28026 0.69393 0.00031
mental and correlated data. As an example of the quality of the cor- q/g
cm3 0.72697 0.16708 0.21416 1.00651 0.00052
relation, in Figs. 2 and 4 are shown the correlated data by the s/m
s1 10.64385 10.65144 1.45659 1.39840 0.38219
modified Pitzer model. v/mm2
s1 0.07515 8.51683 0.54871 2.22019 0.00514

4.4. Correlation of physical properties

The experimental density, sound velocity, refractive index and Table 12

viscosity values were correlated using Othmer’s rule. The general Parameters of Othmer’s equation for the refractive index (nD), density (q), sound
velocity (s) and viscosity (v) of the PEG 4000 + H2O system in the temperature range
expression for this correlation independent of temperature is:
from 313.15 to 333.15 K.

Table 9 Physical A1 A2 B1 B2 AAD

Interaction parameters of the modified Pitzer model for the water activities of the Properties
(NH4)6Mo7O24 + PEG 4000 + H2O, (NH4)6Mo7O24 + H2O, and PEG 4000 + H2O systems
nD 0.12975 0.00713 0.92168 0.38067 0.00015
at T = (313.15, 323.15 and 333.15) K.
q/g
cm3 0.73314 0.16852 1.00209 1.15118 0.00010
1
Parameters T = 313.15 K T = 323.15 K T = 333.15 K s/m
s 135.02114 45.55526 18.39895 6.17556 1.08369
b
v/mm2
s1 0.63804 9.84943 0.80715 1.29380 0.34773
b111 23.686 17.164 13.043
ð0Þ 958.953 1138.336 1605.124
b12
ð1Þ
b12 5886.714 1140.391 5604.385
ð0Þ
b22 a 2810.639 2679.643 2923.965
Table 13
ð1Þ
b22 a 72121.582 73639.213 68465.904 Parameters of Other’s equation for the refractive index (nD), density (q), sound
C 111 b 16.583 8.781 3.276 velocity (s) and viscosity (v) of the (NH4)6Mo7O24 + PEG 4000 + H2O system in the
C 112 950.894 2261.815 7684.590 temperature range from 313.15 to 333.15 K.
C 122 3.492 0.335 2.151
ð/Þ 165.740 13.297 104.541 Physical A1 A2 B1 B2 AAD
C 222 a
Properties
AAD* 0.0008 0.0015 0.0029
nD 2.90951 0.63296 9.67582 2.58541 0.00035
Superscripts a and b indicate the Pitzer parameters of the (NH4)6Mo7O24 + H2O and q/g
cm3 0.54197 0.23789 15.51575 5.70219 0.00156
PEG 4000Pn+ H 2O systems, respectively. s/m
s 1
8.01817 53.29706 1.09833 7.22827 0.46634
jaexp acal j
*AAD ¼ i iN i ; where N equals is the number of data points used in the v/mm2
s1 0.33894 11.70981 4.08312 2.74948 0.06753
correlation.
10 G. Villca et al. / J. Chem. Thermodynamics 142 (2020) 105986
The standard deviations obtained show a good agreement
between experimental and correlated values. As an example,
Fig. 6 shows this good agreement between both values.
5. Conclusions
Water activities and vapour pressures of the ternary (NH4)6-
Mo7O24 + PEG 4000 + H2O system at (313.15, 323.15 and 333.15)
K were studied. As part of the study, vapour pressure depressions
and thermodynamic properties of the constituent binary systems
{(NH4)6Mo7O24 + H2O} and (PEG 4000 + H2O) were analysed.
To correlate the equilibrium results, a modification of the Pitzer
model was applied; as a result, a good agreement between corre-
lated and experimental data for the ternary and binary systems
was obtained.
The temperature effect on the thermodynamic properties is
higher for aqueous polymer solutions than for the aqueous elec-
trolyte solutions. In addition, the vapour pressure depression of
the ternary system is higher than the sum of the vapour pressure
depressions of their constituent binary solutions.
The refractive index, density, sound velocity and kinematic vis-
cosity were measured at different temperatures. The magnitudes
of all physical properties positively correlate with the PEG concen-
tration, and they all positively correlated with the salt concentra-
tion. The temperature inversely correlated with the magnitudes
of all physical properties, except for the sound velocity. All the
physical properties were correlated using Othmer’s equation and
in all cases, a good agreement between experimental and calcu-
lated values was obtained.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgments
The authors thank CONICYT-Chile for financing this research
through Fondecyt Project N° 11130012. Authors are also grateful
of the Project ING2030 CORFO Code 16ENI2-71940.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.jct.2019.105986.
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JCT 2019-610