Journal of Molecular Liquids 286 (2019) 110922

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Journal of Molecular Liquids

journal homepage: www.elsevier.com/locate/molliq

Measurement and modelling of water activity, density and viscosity of

the KClO4 + poly(ethylene glycol) + H2O system at various
temperatures
Yecid P. Jimenez a,⁎, Héctor R. Galleguillos a, Jaime W. Morales b, Felipe Hernández-Luis c
a
Departamento de Ingeniería Química y Procesos de Minerales, Facultad de Ingeniería, Universidad de Antofagasta, Av. Angamos 601, Antofagasta, Chile
b
Escuela de Ingeniería Química, Pontificia Universidad Católica de Valparaíso, Av. Brasil 2950, 2362803 Valparaíso, Chile
c
Departamento de Química Física, Universidad de La Laguna, Avenida Astrofísico Francisco Sánchez s/n, 38108 Tenerife, Spain

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

Article history: The water activities of unsaturated solutions of potassium perchlorate + poly(ethylene glycol) + water at
Received 19 March 2019 298.15, 308.15 and 318.15 K and densities and viscosities at 288.15, 298.15 and 308.15 K were measured exper-
Received in revised form 2 May 2019 imentally. The concentration range of the solutions was from 0.2 to 0.8 mass % of poly(ethylene glycol) with an
Accepted 4 May 2019
average molecular weight of 4000 and from 0.25 to 1.25 mass % of KClO4. The water activity data show that in the
Available online 9 May 2019
PEG–salt–water system, KClO4 has a significant effect on the water activities and the vapour pressures; a slight
Keywords:
increase in water activities with increasing temperature was also observed. Density and viscosity decrease as
Thermodynamic and transport properties temperature increases and both properties increase as KClO4 and PEG-4000 concentrations increase. The electro-
Electrolyte solutions lyte and polymer non-random two liquid models, extended for the representation of water activity, excess molar
Polymer volume and dynamic viscosity, were applied. Good agreement between the experimental and correlated data
NRTL model was obtained, since for the ternary system, the average absolute deviations calculated at all temperatures studied
for the water activity, density and viscosity were 0.0067, 0.72 and 2.91%, respectively.
© 2019 Elsevier B.V. All rights reserved.

1. Introduction
In recent years, numerous studies have been carried out on aqueous
two-phase systems (ATPSs), these systems that are usually formed by
poly(ethylene glycol) (PEG) and a salt have numerous uses in biotech-
nology [1,2], chemical partitioning [3–5], and extractive crystallisation
of inorganic salts [6].
Likewise, the thermodynamic and transport properties of aqueous
polymer–salt solutions are very important in chemical engineering
and in other areas involved in separation processes, fluid transport,
wastewater treatment, 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 thermodynamic properties
such as osmotic coefficients and vapour pressures. Sadeghi [9,10] and
Sadeghi et al. [11–13] have reported experimental data of water activity
of diverse ternary systems containing salt + polymer + water, incorpo-
rating in some of these studies the correlation of experimental data with
the Wilson model and the extended form of Chen's non-random two
liquid (NRTL) model. Salabat et al. [14], Jahani et al. [15,16], and
Zafarani-Moattar et al. [17,18] have reported similar studies of ternary
systems.
⁎ Corresponding author.
E-mail address: yecid.jimenez@uantof.cl (Y.P. Jimenez).
On the other hand, densities and viscosities of aqueous solutions are
useful in pipe sizing, pump calculations, material balance calculations,
design of crystallisers and evaporators, etc. In addition, they are useful
in determining the nature of solute–solvent and solute–solute interac-
tions. While density and viscosity data of aqueous PEG + salt systems
are available, there are few models with a thermodynamic basis to cor-
relate or predict them. There are some reports of thermodynamic and
transport properties, such as the works of Mei et al. [19], Zafarani-
Moattar et al. [20], Mehta et al. [21], and others that besides these, pres-
ent empirical or semiempirical equations to correlate them, such as the
works of Zafarani-Moattar and Mehrdad [22], Graber et al. [23], Telis-
Romero et al. [24], Gonçalves et al. [25], Taboada et al. [26], Zafarani-
Moattar and Hamzehzadeh [27], Murugesan and Perumalsamy [28],
Regupathi et al. [29], Sadeghi and Jamehbozorg [30], Sadeghi et al.
[31], Kalaivani et al. [32], and Barani et al. [33].
In previous works, the liquid–liquid equilibrium of the sodium ni-
trate + PEG 4000 + water system at 288.15 and 308.15 K and the par-
tition of perchlorate ion in this system were reported [3,34]. This
multicomponent system and its constituent systems are of great inter-
est, since ion perchlorate is present as an impurity in the mineral nitrate
deposits in northern Chile, affecting the quality of the produced nitrate
salts that are subsequently used as fertilizers. Thus, the possibility of
partition of the perchlorate ion in the sodium nitrate + PEG 4000
+ water system or the nitrate ion in the sodium perchlorate + PEG

https://doi.org/10.1016/j.molliq.2019.110922
0167-7322/© 2019 Elsevier B.V. All rights reserved.
2 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922

4000 + water system could make it in an alternative process for the at-
tenuation of this impurity [3,35]. As a continuation of the study of these
systems, this work presents experimental data of the water activity of
unsaturated solutions of the potassium perchlorate + PEG 4000
+ H2O system at 298.15, 308.15 and 318.15 K, and density and viscosity
at 288.15, 298.15 and 308.15 K.
The values of water activity, density and viscosity determined ex-
perimentally were correlated by the extended NRTL model [36–39];
however, to correlate the experimental data of the ternary system,
the corresponding binary systems reported in the literature were
first correlated [22,23,40–45]. As far as we know, the measured
properties of the present system have not been reported in the
literature.
2. Experimental section
2.1. Materials
Synthesis grade samples of poly(ethylene glycol) with an average
molecular weight of 4000 (3500–4500) and analytical reagent-grade
mass fraction purity 0.99 potassium perchlorate were procured from
Sigma-Aldrich and Merck, respectively. Potassium perchlorate was
dried at 120 °C for 48 h before use and stored over silica gel in desicca-
tors. These reagents were used without further purification. Deionised
water was used in all experiments (Milli-Q, Millipore, κ = 0.054
mS·cm−1).
2.2. Apparatus and procedures
The solutions were prepared by mass, using an analytical balance
with a precision of ±0.07 mg (Mettler Toledo Co., Model AX-204).
The experimental error in concentration was less than 0.01%.
Each solution was agitated using a Mini Vortexer (VWR Scientific
Products Co.).
The water activities for the ternary system and the constituent bi-
nary systems were determined using a KNAUER K-7000 vapour pres-
sure osmometer with temperature control of ±0.001 K at T =
298.15, 308.15 and 318.15 K. The equipment was calibrated using
aqueous NaCl solutions of known osmolality with water as reference,
for which the osmotic coefficient data were taken from literature
[46]. The details of the calibration of the osmometer for aqueous so-
lutions have been described previously [47]. The combined uncer-
tainty of the water activity of the calibration solutions was ±3
× 10 −4 . During the measurements, the concentration of PEG was
fixed at 0.002, 0.004, 0.006 and 0.008 mass fraction, whereas the
salt concentration was fixed at 0.0025, 0.0050, 0.0075, 0.0100 and
0.0125 mass fraction. The combined uncertainty in activity water
measurements was ±4 × 10−4.
The densities of the solutions were measured with a Mettler Toledo
DE50 vibrating tube densimeter, always obtaining an uncertainty of less
than ±5 × 10−5 g·cm−3. The densimeter was calibrated at atmospheric
pressure using air and distilled deionised water as reference substances
prior to the initiation of each run of measurements at a given tempera-
ture. The densimeter had self-contained Peltier system for temperature
control with an uncertainty of ±0.01 K. The time to reach a stable tem-
perature was 300 s.
The kinematic viscosities were measured with calibrated micro-
Ostwald viscometer. 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 measurements. The absolute viscosity was obtained by
multiplying the kinematic viscosity by the corresponding density. The
uncertainty in viscosity measurements was ±5 × 10−3 mPa·s. Both
density and viscosity were measured in triplicate; the averages of
these are presented here.

3. Thermodynamic framework

As mentioned above, to correlate the water activity, density and viscosity of the ternary system by the NRTL model is necessary to know the in-
teraction parameters of the constituent binary systems. Thus, in the following sections the equations for the binary and ternary systems are
developed.

3.1. Correlation of water activity

The molar excess Gibbs energy, gex⁎, considering the unsymmetric reference state is calculated as a sum of three contributions:

g ex
¼ g ex
;Comb þ g ex
;LR þ g ex
;SR ; ð1Þ

where gex⁎,Comb is the combinatorial contribution, gex⁎,LR the long-range interaction contribution and gex⁎,SR the short-range interaction contribution.
The expression for the activity coefficient (γI) of the component I (polymer, ions, water), is also considered as the sum of three contributions:

ln γI ¼ ln γComb
I þ lnγ LR SR
I þ ln γ I : ð2Þ

The Flory–Huggins expression [48], the Pitzer–Debye–Hückel (PDH) equation [49] and the extended NRTL model [39] are used to calculate gex⁎,
Comb
, gex⁎,LR and gex⁎,SR, respectively.
The Flory–Huggins equation [48] for gex⁎,Comb can be written as:
  X
g ex
;Comb X ϕ
¼ xI ln I − xI ln γ∞FH
I ; ð3Þ
RT I
xI I

where

r I xI
ϕI ¼ ð4Þ
∑Jr JxJ

In these relations, the species I and J can be water and polymer molecules or ions. A value of r = 1 is used for ions and water. For the polymer the
value of r is the ratio of the molar volume of polymer to that of water. γ∞FH
I is the infinite-dilution activity coefficient.
 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922 3

The PDH equation normalised to mole fractions of unity for solvent and zero for electrolytes has been used to calculate the gex⁎,LR. The expression
has the following form [49]:
!sffiffiffiffiffiffiffi
g ex
;PDH X 1 4Aφ Ix  pffiffiffiffi
LR
¼− xI ln 1 þ ρ Ix ; ð5Þ
RT I
M1 ρ

where
   3=2
1 2πNA 1=2 e2
Aφ ¼ ð6Þ
3 Vs εT KT

In the above relations, Aφ is the Debye–Hückel constant for the osmotic coefficient and ρ is the closest distance parameter (set to 14.9). The NA, K
X
and e are Avogadro's number, Boltzmann's constant and electronic charge, respectively. Ix, is the ionic strength on a mole fraction basis, I x ¼ 0:5
i
xi Z 2i . Vs and εT are the molar volume and dielectric constant of the solvent, respectively.
The extended NRTL model for gex⁎,SR can be written as [38,39]:

ex
;NRTL
g SR 2X c Gca;w τca:w þ rX s Gsw τsw 2X c Gca;s τca:s þ X w Gws τ ws
¼ xw þ rxp
RT 2X c Gca;w þ rX s Gsw þ X w 2X c Gca;s þ rX s þ X w Gws
rX s Gs;ca τs:ca þ X w Gw;ca τ w;ca rX s Gs;ca τs:ca þ X w Gw;ca τw;ca ð7Þ
þ Z c xc þ Z a xa
X a þ rX s Gs;ca þ X w Gw;ca X c þ rX s Gs;ca þ X w Gw;ca
−Z c xc lnγ ∞c −Z a xa ln γ ∞a −xp ln γ∞p

In the above equations the subscripts w, s, p, ca, c and a refer to water, segment of polymer, polymer, salt, cation and anion, respectively. XI is the
effective local mole fraction based on number of moles of segments, ions and solvent; it is expressed by:

X I ¼ ϕI K I ðK I ¼ Z I for ions and unity for polymer and waterÞ ð8Þ

G and τ are energy parameters and are given by:

Gmm0 ¼ expð−α mm0 τ mm0 Þ; ð9Þ

ðg mm0 −g m0 m0 Þ amm0
τmm0 ¼ ¼ ; τmc ¼ τma ¼ τm;ca τ cm ¼ τam ¼ τca;m ð10Þ
RT RT

where, gmm’ and gm’m’ are energy of interaction between m-m’ and m’-m’ species, respectively. These are inherently symmetric (gmm’ = gm’m). The
species m and m’ can be solvent molecules, salt or segments. α is the non-randomness factor and R is the gas constant.
From appropriate differentiation of Eqs. (3), (5) and (7), the following expressions are obtained:
  X ϕ J 
ϕI
ln γComb
I ¼ ln þ 1−r I ; ð11Þ
xI J
rJ

For a neutral molecule

2Aϕ I3=2
x
ln γPDH
i ¼ ð12Þ
1 þ ρI1=2
x

and
 
X p Gsw τsw þ 2X c Gca;w τca;w Xw
ln γ NRTL
w ¼ 1− þ
X w þ X p Gsw þ 2X c Gca;w
 X w þ X p Gsw þ 2X c Gca;w 
X p Gws X w Gws τ ws þ 2X c Gca;s τ ca:s
τ ws − þ ð13Þ
X w Gws þ X p þ 2X c Gca;s  X w Gws þ X p þ 2X c Gca;s 
2X c Gw;ca X w Gw;ca τ w;ca þ X p Gs;ca τs;ca
τw;ca − ;
X w Gw;ca þ X p Gs;ca þ X c X w Gw;ca þ X p Gs;ca þ X c

3.2. Correlation of density of binary aqueous solutions

For the KClO4 + H2O system, the relation between the density and the excess volume of a solution is established by the following equation [50]:

1000ð1 þ mM 2 Þ
d¼ ð14Þ
ð1=M1 ÞV 01 þ mV 02 þ V ex

where d is the density of solution (in g·cm−3) and V01, V02 and Vex are the molar volume of pure solvent, partial molar volume of salt at infinite dilution
and the excess volume of the solution (the first two in cm3·mol−1 and the last in cm3·kg−1), respectively. The V01 values are 18.0162, 18.0522 and
18.108 cm3·mol−1 at 288.15, 298.15 and 308.15 K, respectively. M1, M2 and m are the molar mass of the solvent, molar mass of the salt (both in
4 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922

kg·mol−1), and molality of the solution (in mol·kg−1), respectively. The partial molar volume at infinite dilution for each salt can also be regarded as
an adjustable parameter, so that its numerical value can be obtained by fitting of density data to the models. In the present work V02 is considered as an
adjustable parameter.
Also, the molar excess Gibbs energy and subsequently the excess volume are written as the sum of a long-range and a short-range term:

g ex
¼ g ex
;LR þ g ex
;SR ; ð15Þ

V ex ¼ V ex;LR þ V ex;SR ; ð16Þ

where LR and SR refer to long-range and short-range contributions, respectively. The value of Vex is calculated by Chen's NRTL model [37] derived by
Humffray [51]. In this sense, from appropriate differentiation of Eq. (5), the following expression for the long-range contribution of the excess volume
is obtained:
sffiffiffiffiffiffiffi
1 Ix  pffiffiffiffi
V ex;PDH ¼ Av ln 1 þ ρ I x ð17Þ
LR
M1 ρ

where
 
∂Aφ
Av ¼ −4RT ð18Þ
∂p T;n

Av is Debye–Hückel constant for volume. For the short-range contribution of the excess volume, the following expression reported by Humffray is
used [51]:
 
 

V ex;NRTL Xw ατca;w X w   X w Gw;ca αX c τ w;ca

SR
¼ 2X c Gca;w 1− − 1−ατca;w τvca;w þ 2X c 1− −1 τ vw;ca ð19Þ
RT θ1 θ1 θ2 θ2

θ1 ¼ X w þ 2X c Gca;w ¼ X w þ 2X a Gca;w ð20Þ

θ2 ¼ X a þ X w Gw;ca ¼ X c þ X w Gw;ca ð21Þ

where the subscripts w, c, a and ca stand for water, cation, anion and salt, respectively. The other terms are defined by Eqs. (8), (9) and (10). τvij represents
pressure derivatives of τij, (∂τij/∂p)T,x and for the interaction parameters τvw, ca and τvca, w, a temperature-dependent function is assumed, as follows:

avij
τvij ¼ ; ð22Þ
RT

and the temperature-dependent function used for partial molar volume of salt at infinite dilution is:

V 02 ¼ a þ bT ð23Þ

In the case of the PEG 4000 + H2O system, Eq. (14) was also used to established the relation between the density and the excess volume. In this
case, d is the density of solution (in g·cm−3), M1, M2 and m are the molar mass of the solvent, molar mass of the polymer (both in kg·mol−1) and
molality of the solution (in mol·kg−1), respectively. V01, V02 and Vex are the molar volume of pure solvent, molar volume of polymer at infinite dilution
and the excess volume of the solution (the units are those mentioned above), respectively. The molar volume of PEG has been calculated from the
infinite dilution apparent molar volume of polymer calculated from density data of aqueous solutions of PEG 4000 [22,23]. Finally, the value of Vex
is calculated by the NRTL polymer model [36] derived by Sadeghi et al. [52], but expressed in the unsymmetric convention, as follows:
" #
V ex;NRTL rX s Gsw τvsw ðð1 þ ln Gsw ÞðX w þ rX s Gsw Þ−rX s Gsw lnGsw Þ
¼ xw
RT
" ðX w þ rX s Gsw Þ2 #
X w Gws τws ðð1 þ ln Gws ÞðrX s þ X w Gws Þ−X w Gws ln Gws Þ
v ð24Þ
þ rxp
 v ðrX s þ X w Gws Þ2
v
−rxp τ ws þ Gsw τ sw ð1 þ ln Gsw Þ

where the subscripts w and s stand for water and segment of polymer, respectively. The terms Xi, Gji and τji are defined by Eqs. (8), (9) and (10).
A value of r = 1 is used for water. For the polymer the value of r is the ratio of the molar volume of polymer to that of water.

3.3. Correlation of density of ternary aqueous solutions

Eq. (14) is generalised as follows [50]:

1000ð1 þ mM 2 þ mM 3 Þ
d¼ ; ð25Þ
ð1=M1 ÞV 01 þ mV 02 þ mV 03 þ V ex

where the subscripts 1, 2 and 3 stand for solvent, salt and polymer, respectively. The notation has the usual meaning. For Eq. (25), the molar masses
and molar volumes are in kg·mol−1 and cm3·mol−1, respectively. Here, the poly(ethylene glycol) is considered as solute.
 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922 5

From appropriate differentiation of Eqs. (3) and (7), the following expressions for excess volume are obtained:
2    3
rX s Gsw τ vsw ð1 þ ln Gsw Þ þ 2X c Gca;w τvca;w 1 þ ln Gca;w rX s Gsw þ 2X c Gca;w þ X w −
6      7
6 rX G τ þ 2X G τ rX s Gsw −ατvsw þ 2X c Gca;w −ατ vca;w 7
ex;NRTL
V SR 6 s sw sw c ca;w ca;w 7
6
¼ xw 6  2 7
RT 7
6 rX s Gsw þ 2X c Gca;w þ X w 7
4 5

2     3
2X c Gca;s τ vca;s 1 þ ln Gca;s þ X w Gws τvws ð1 þ ln Gws Þ rX s þ 2X c Gca;s þ X w Gws −
6     7
6 2X G τ þ X G τ  2X G v
 v
 7
6 c ca;s ca;s w ws ws c ca;s −ατ ca;s þ X w Gws −ατ ws 7
rxp 6
6  2 7
7
6 rX s þ 2X c Gca;s þ X w Gws 7
4 5

2      3
rX s Gs;ca τ vs;ca 1 þ ln Gs;ca þ X w Gw;ca τ vw;ca 1 þ ln Gw;ca rX s Gs;ca þ X a þ X w Gw;ca −
6        7 ð26Þ
6 rX G τ þ X G τ rX s Gs;ca −ατvs;ca þ X w Gw;ca −ατvw;ca 7
6 s s;ca s;ca w w;ca w;ca 7
þ Z c xc 6
6  2 7
7
6 rX s Gs;ca þ X a þ X w Gw;ca 7
4 5

2      3
rX s Gs;ca τvs;ca 1 þ ln Gs;ca þ X w Gw;ca τvw;ca 1 þ ln Gw;ca rX s Gs;ca þ X c þ X w Gw;ca −
6       7
6 rX G τ þ X G τ rX s Gs;ca −ατvs;ca þ X w Gw;ca −ατ vw;ca 7
6 s s;ca s;ca w w;ca w;ca 7
þ Z a xa 6
6   2
7
7
6 rX s Gs;ca þ X c þ X w Gw;ca 7
4 5

    
−rxp τ vws þ Gsw τ vsw ð1 þ ln Gsw Þ −Z c xc τ vw;ca þ Gca;w τvca;w 1 þ ln Gca;w
  
−Z a xa τvw;ca þ Gca;w τvca;w 1 þ ln Gca;w

All the terms have the meaning mentioned above. As can be seen, the Flory–Huggins equation does not appear in the relation for the excess molar
volume; this is because the combinatorial term is independent of pressure or temperature. From Eq. (26), for the correlation of excess volume (or
density), the model requires four new binary interaction parameters τs,ca, τca,s, τvs, ca, and τvca, s for the segment–salt and salt–segment interaction
pairs, because the other interaction pairs are determined from binary systems. In this work, the first two were determined from the water activity
data and the last two from fitting the model to the density data.
Finally, the expression for the excess volume of the ternary system can be expressed as Eq. (16), i.e. considering Eqs. (17) and (26).

3.4. Correlation of viscosity of binary aqueous solutions

For the KClO4 + H2O system, the relation between viscosity and the molar excess Gibbs energy of activation for flow is established by the follow-
ing equation [53]:
!  ex

X
Nsolu
g
η−ηw ¼ Aηw ci exp ð27Þ
N¼i
RT

where η and ηw are solution viscosity and solvent viscosity (both Pa·s), respectively. ci is the molar concentration of the solute species i, gex⁎ and Nsolu
are the molar excess Gibbs energy of activation for flow and the total number of solute species, respectively. A (in L·mol−1) is taken as an empirical
adjustable parameter. Molar excess Gibbs energy of an aqueous electrolyte solution is assumed to be the sum of the contributions of a long-range
electrostatic interaction term, gex⁎,LR, and a short-range interaction term, gex⁎,SR, as Eq. (15).
The gex⁎ value is calculated by Chen's NRTL model extended by Sadeghi [37,54].
In the case of the PEG 4000 + H2O system, the relation used to correlated the viscosity data is the same as Eq. (27), with the difference that the
molar excess Gibbs energy in this case is the sum of the combinatorial contribution gex⁎,comb (Eq. (3)), and a short-range interaction term, gex⁎,SR [36];
this last can be expressed in unsymmetric convention as:

g ex
;NRTL rX s Gsw τ sw X w Gws τ ws

SR
¼ xw þ rxp −xp ln γ ∞p ð28Þ
RT rX s Gsw þ X w rX s þ X w Gws

3.5. Correlation of viscosity of ternary aqueous solutions

Eq. (27) is generalised, considering that the excess Gibbs energy is the sum of the three contributions above mentioned in Eq. (1). It is important to
say that for the ternary system the polymer is assumed to be another solute. Thus, Eqs. (3), (5) and (7) are used to calculate the combinatorial, g-
ex⁎Comb
, long-range interaction, gex⁎,LR and short-range interaction, gex⁎SR, contributions, respectively.
Also, the parameter A is assumed to be equal to A2 + A3 + A4, where A2 and A3 are adjustable parameters obtained from correlation of the viscosity
values of the binary aqueous solutions. On the other hand, the model requires two new binary interaction parameters τs,ca, τca,s for the segment–salt
and salt–segment interaction pairs, since the other interaction pairs are determined from binary systems. These parameters were obtained from
fitting the model to the viscosity data.
6 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922

Table 1 1.0000
Water activity (aw) and vapour pressures (p) for the KClO4 (ca) + PEG 4000 (p) + H2O 0.9995
(w) system at T = 298.15, 308.15 and 318.15 Ka. 0.9990
T = 298.15 K T = 308.15 K T = 318.15 K 0.9985
wca wp p/kPa aw p/kPa aw p/kPa aw 0.9980
0.0125 0.0020 3.1540 0.9962 5.6017 0.9964 9.5492 0.9966 0.9975
0.0125 0.0040 3.1537 0.9961 5.6012 0.9963 9.5472 0.9964 0.9970
0.0125 0.0060 3.1530 0.9959 5.6002 0.9961 9.5456 0.9962 0.9965
0.0125 0.0080 3.1521 0.9956 5.5988 0.9959 9.5440 0.9960
0.0100 0.0020 3.1571 0.9972 5.6062 0.9972 9.5559 0.9973 0.9960
0.0100 0.0040 3.1564 0.9970 5.6055 0.9971 9.5550 0.9972 0.9955
0.0100 0.0060 3.1559 0.9968 5.6044 0.9969 9.5537 0.9971
0.9950
0.0100 0.0080 3.1547 0.9964 5.6034 0.9967 9.5522 0.9969
0 0.002 0.004 0.006 0.008 0.01
0.0075 0.0020 3.1593 0.9979 5.6108 0.9980 9.5630 0.9980
0.0075 0.0040 3.1590 0.9978 5.6104 0.9979 9.5619 0.9979
0.0075 0.0060 3.1585 0.9976 5.6091 0.9977 9.5612 0.9978
0.0075 0.0080 3.1578 0.9974 5.6083 0.9976 9.5598 0.9977 Fig. 1. Water activities of the KClO4 (ca) + PEG 4000 (p) + H2O (w) system at 308.15 K for
0.0050 0.0020 3.1616 0.9986 5.6150 0.9987 9.5699 0.9987 different mass fraction of salt: (◆) wca = 0.0125; (■) wca = 0.0100; (▲) wca = 0.0075;
0.0050 0.0040 3.1611 0.9985 5.6142 0.9986 9.5686 0.9986 (×) wca = 0.0050; (✳) wca = 0.0025; (—) extended NRTL model.
0.0050 0.0060 3.1608 0.9984 5.6136 0.9985 9.5672 0.9985
0.0050 0.0080 3.1600 0.9981 5.6124 0.9983 9.5662 0.9984
0.0025 0.0020 3.1637 0.9993 5.6185 0.9994 9.5760 0.9994
0.0025 0.0040 3.1635 0.9992 5.6181 0.9993 9.5751 0.9993
0.0025 0.0060 3.1630 0.9991 5.6174 0.9992 9.5744 0.9992
0.0025 0.0080 5.6164 0.9990 9.5728 0.9990 Figs. 1 and 2 show that in the PEG–salt–water system, KClO4 has a
a
The standard uncertainties u are u(wi) = 0.0001, u(T) = 0.01 K and u(P) = 1 kPa. The
significant effect on the water activities and therefore on the vapour
combined standard uncertainties uc are uc(aw) = 4 × 10−4, uc(pi) = 0.0005 kPa. pressures.
On the other hand, the experimental values of density and viscosity
of the KClO4 + PEG 4000 + water ternary system at three temperatures
(288.15, 298.15 and 308.15 K) were measured. The potassium perchlo-
4. Results and discussion rate and poly(ethylene glycol) concentrations chosen to determine the
density and the kinematic viscosity were selected below the saturation
4.1. Experimental results concentration of potassium perchlorate. These experimental data are
presented in Table 2.
Water activities of the KClO4 + PEG 4000 + H2O system at T = This table shows that for any mixture composition, both density
298.15, 308.15 and 318.15 K were measured through osmolality and and viscosity decrease with an increase in temperature. The
then vapour pressures were calculated. dependence of these two properties on mass concentration at a
The water activity of the aqueous multicomponent solution is re- given temperature can be observed when the concentration of
lated to the total osmolality by [55,56]: KClO4 or PEG-4000 remains fixed. For a constant KClO4 concentra-
tion, the density and viscosity increase as PEG-4000 concentration
P increases, but for a constant PEG concentration is not possible
osmolality υi mi
ln aw ¼ − ¼− φ ð29Þ discern a defined tendency for the viscosity; this is due to the low
55:51 55:51
salt concentration in the system and the effect of this on the proper-
ties. With respect to the density, this increases as KClO4 concentra-
where νi is the number of ions produced on dissociation of the ith com- tion increases. This behaviour is observed at each of the three
ponent, mi is the molality and φ is the osmotic coefficient. The number temperatures studied in this work.
55.51 is the number of moles of water in 1 kg of water. Figs. 3 and 4 show the effect of the temperature on density and vis-
From the experimental data of activity, the vapour pressure can be cosity properties at different concentrations of KClO4 and PEG-4000.
calculated by:

   
p ðBw −V w Þ p−p0
ln aw ¼ ln þ ; ð30Þ
p0 RT 1.0000
0.9995

where Bw is the second virial coefficient of water vapour, p° is the va- 0.9990
pour pressure of pure water, Vw is the molar volume of liquid water, T 0.9985
is the temperature and R the universal gas constant. 0.9980
The values used for the second virial coefficients of water vapour
0.9975
were −1.157 × 10−3, −9.980 × 10−4 and − 8.680 × 10−4 m3·mol−1
at T = 298.15, 308.15 and 318.15 K, respectively [57]. Water density 0.9970
data at different temperatures were used to calculate the molar volumes 0.9965
of liquid water [58]. The vapour pressures used of pure water at T = 0.9960
298.15, 308.15 and 318.15 K were 3.166, 5.622 and 9.582 kPa, respec-
0.9955
tively [59]. 0 0.002 0.004 0.006 0.008 0.01 0.012 0.014
Table 1 shows the water activity and vapour pressure values deter-
mined at T = 298.15, 308.15 and 318.15 K for the ternary KClO4
+ PEG 4000 + H2O system. Fig. 2. Water activities of the KClO4 (ca) + PEG 4000 (p) + H2O (w) system at 308.15 K for
Figs. 1 and 2 show the water activities obtained at 308.15 K for differ- different mass fraction of PEG: (◆) wp = 0.0020; (■) wp = 0.0040; (▲) wp = 0.0060; (×)
ent salt and PEG mass fractions, respectively. wp = 0.0080; (—) extended NRTL model.
 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922 7

Table 2 a) 1.00900
Values for the density, ρ, viscosity, η, in aqueous solutions of KClO4 and PEG 4000 for dif-
ferent mass percent of potassium perchlorate (wca) and PEG (wp) at T = 288.15, 298.15 1.00800
and 308.15 Ka.
1.00700
ρ/g·cm−3 η/mPa·s ρ/g·cm−3 η/mPa·s ρ/g·cm−3 η/mPa·s

wca wp 288.15 K 298.15 K 308.15 K 1.00600

ρ/g·cm-3
1.25 0.20 1.00738 1.17 1.00504 0.91 1.00188 0.73
1.00500
1.25 0.40 1.00768 1.21 1.00538 0.94 1.00220 0.76
1.25 0.60 1.00797 1.25 1.00568 0.97 1.00250 0.79
1.00400
1.25 0.80 1.00831 1.29 1.00626 1.00 1.00280 0.82
1.00 0.20 1.00576 1.16 1.00342 0.93 1.00025 0.75 1.00300
1.00 0.40 1.00607 1.20 1.00375 0.95 1.00061 0.77
1.00 0.60 1.00638 1.25 1.00413 0.97 1.00095 0.79 1.00200
1.00 0.80 1.00675 1.30 1.00444 1.00 1.00132 0.81
0.75 0.20 1.00412 1.18 1.00192 0.94 0.99881 0.75 1.00100
0.75 0.40 1.00444 1.22 1.00227 0.96 0.99916 0.77
0.00 0.20 0.40 0.60 0.80 1.00
0.75 0.60 1.00484 1.26 1.00270 0.99 0.99948 0.78
0.75 0.80 1.00518 1.30 1.00299 1.01 0.99979 0.80 PEG(w/w%)
0.50 0.20 1.00264 1.19 1.00049 0.94 0.99734 0.76
0.50 0.40 1.00293 1.24 1.00079 0.97 0.99768 0.78
0.50 0.60 1.00321 1.27 1.00112 1.00 0.99805 0.80
0.50 0.80 1.00356 1.31 1.00148 1.02 0.99831 0.81 b) 1.00800
0.25 0.20 1.00106 1.18 0.99898 0.94 0.99551 0.76
0.25 0.40 1.00130 1.21 0.99919 0.96 0.99576 0.77 1.00600
0.25 0.60 1.00166 1.26 0.99956 0.99 0.99608 0.78
0.25 0.80 1.00200 1.30 0.99985 1.01 0.99647 0.80 1.00400
a
The standard uncertainties u are u(wi) = 0.01%, u(T) = 0.01 K for density, u(T) = 1.00200
0.02 K for viscosity, u(ρ) = 5 × 10−5 g·cm−3, u(η) = 5 × 10−3 mPa·s.
ρ/g·cm-3 1.00000

0.99800

4.2. Correlation of water activity 0.99600

0.99400
The experimental data on water activity were correlated by the ex- 0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40
tended NRTL model [39], by minimising the following objective func- KClO4 (w/w%)
tion:
Fig. 3. Density of the KClO4 + PEG 4000 + H2O ternary system at different temperatures:
NP 
X 2
(○) 288.15 K; (□) 298.15 K; (×) 308.15 K; and (—) calculated. a) For 1.25 mass % of KClO4
OF ¼ aexp
w;k
−acal
w;k ð31Þ
and b) for 0.2 mass % of PEG.
k¼1

where aexp cal

w, k and aw, k are the experimental and calculated values of the
water activity, respectively. NP is the number of experimental data
points. correlated by the NRTL model [61], where the temperature dependence
The calculated interaction parameters with the corresponding devi- of the NRTL binary interaction energy parameters is defined by:
ations are shown in Table 3.
The solid lines in Figs. 1 and 2 show the good agreement between aji
τji ¼ ð33Þ
the experimental and correlated data. RT

4.3. Correlation of density data of binary systems
The density values of the KClO4 + H2O binary system in the concen-
tration range of the ternary system are calculated by the Novotny model
(Eq. (32)) [40] and complemented by the data reported by the National
Research Council (U.S.) [45]:
ρ ¼ ρw þ Ac þ Bct þ Cct 2 þ Dc3=2 þ Ec3=2 t þ Fc3=2 t 2
The values obtained for the parameters aca,w and aw,ca were
26,208.4488 and 13,502.7255, respectively (overall AAD = 0.10%). For
this system the non-randomness factor, α, is fixed at a value of 0.2, be-
cause in the range of 0.2 to 0.3 it has no significant impact on the behav-
iour of the model. Also, the value of Debye–Hückel constant, Av is
obtained from Krumgalz et al. [62].
The parameters were evaluated using the following objective func-
ð32Þ tion (OF):

where ρw is density of water, A through F are adjustable constants, c is  2

the solute concentration in mol·l−1, t is the temperature in °C, and ρ
is the density of solution in kg·m−3. The A, B, C, D, E and F values
taken into account were 86.2, −0.997, 0.01848, −60.1, −0.9215 and
−0.004509, respectively [40]. Then, these density values are correlated
by the NRTL model derived by Humffray [51]. From this correlation are
obtained the pressure derivatives of NRTL model parameters. It is im-
portant to mention that the NRTL binary interaction energy parameters
at different temperatures are not available in the literature, but Bromley
[60] reported the B-value for potassium perchlorate at 298.15 K. With
the B-value, the mean ionic activity coefficient data for different salt
concentrations at 298.15 K were reproduced. These data were
X
n ρexp −ρcalc
OF ¼ ð34Þ
1¼1
ρexp
The fitting parameters of the pressure derivatives of NRTL model pa-
rameters at different temperatures and the infinite dilution apparent
molar volume of electrolyte are presented in Table 4.
The density data for the PEG 4000 + H2O system were taken from
Graber et al. [23] and Zafarani-Moattar and Mehrdad [22]. The same
methodology and values of the previous work were applied [50]. The in-
teraction parameters as,v w and avw, s are also presented in Table 4.
8 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922

a) Table 4
NRTL parameters for the binary and ternary systems.
1.40
T/K aca, aw, V02/cm3·mol−1 AAD
1.20 v –1b v
/J·mol–1b [%]a
w /J·mol ca
a b
102
1.00
288.15–308.15 1.2527 −81.9546 −9.1373 0.2758 0.44
0.80
η/mPa·s

as, aw,
v –1b v –1b
w /J·mol s /J·mol
0.60 288.15–308.15 −0.0862 −0.0027 7.00
as, aca, as, aca,
0.40 ca/J·mol
–1c
s/J·mol
–1c v
ca /J·mol
–1c v
s /J·mol
–1c

288.15–308.15 −114,000 4000.9511 −82.7006 −79.7720 0.72

0.20 a
Average absolute deviation (AAD) = (1/Np)∑[(ρexp–ρcal)/ρexp] × 100%.
b
0.00 NRTL parameters for the binary systems.
c
NRTL parameters for the ternary system.
0.00 0.20 0.40 0.60 0.80 1.00
PEG(w/w%)
4.5. Correlation of viscosity data of binary systems

b) In the present work, viscosity values of the KClO4 + H2O binary sys-
1.40 tem were calculated using the Jones–Dole equation. The parameters A
and B of the Jones–Dole equation for the potassium and perchlorate
1.20 ions at different temperatures were taken from the literature: the pa-
rameter A was calculated with data reported by Horvath [63] and the
values of B with data reported by Jenkins and Marcus [64]. The temper-
1.00
ature range was from 293.15 to 313.15 K. Once again, the corresponding
data at 288.15 K could not be found; for this reason, the interaction pa-
0.80 rameters determined at the other temperatures were fitted using
η/mPa·s

Eq. (35) as recommended by Chen and Evans [37]:

0.60
   
1 1 298:15−T T
τ ¼aþb − þc þ ln ð35Þ
0.40 T 298:15 T 298:15

0.20 The coefficients obtained were:

for τca,w a = 2.67E−8, b = 7.99E−6, c = 6.86E−9
0.00
for τw,ca a = 8.35E−9, b = 2.44E−6, c = −3.17E−8
0.00 0.20 0.40 0.60 0.80 1.00 1.20 1.40 Therefore, the values of τca,w and τw,ca at 288.15 K were extrapolated
KClO4(w/w%)
using the above coefficients. The interaction parameters are presented
in the Table 5. With respect to the empirical parameter, A, this has the
following temperature dependence:
Fig. 4. Viscosity of the KClO4 + PEG 4000 + H2O ternary system at different temperatures:
(○) 288.15 K; (□) 298.15 K; (×) 308.15 K; and (—) calculated. a) For 1.00 mass % of KClO4
and b) for 0.4 mass % of PEG. A2 ¼ A0 þ A1 ðT−298:15Þ ð36Þ

where A0 and A1 are adjustable parameters with values −0.0269 and

0.0014, respectively. The A2 value at 288.15 K was extrapolated with
4.4. Correlation of density data of ternary system the adjustable parameter values mentioned above. The model parame-
ters were estimated by minimising the following objective function:
The four new binary interaction parameters τs,ca, τca,s, τvs, ca, and τvca, s
 2
for the segment–salt and salt–segment interaction pairs are determined X
n ηexp −ηcalc
by fitting the ternary system density data with Eqs. (25) and (26), using OF ¼ ð37Þ
ηexp
the binary parameters determined previously; its temperature depen- 1¼1

dence is expressed by Eq. (22). The non-random parameter α was also

fixed at 0.2.
The function objective is that mentioned above and the parameters
are presented in Table 4.
To show the reliability of the model, the comparison between the ex-
perimental and correlated values is shown in Fig. 3. As the figure shows,
there is good agreement between the experimental and calculated data.
In the case of the PEG 4000 + H2O system, the viscosity data re-
ported by Silva et al. [44] were correlated by Eq. (27) and the method-
ology previously applied was used. The interaction parameters are
shown in Table 5. The adjustable parameter, A3, has the same tempera-
ture dependence as mentioned above, and the values of A0 and A1 are
also those obtained in the previous work; i.e., 98.7306 and −0.1271,

Table 3
Interaction parameters of the extended NRTL model of the water activity for the KClO4 (ca) + PEG 4000 (p) + H2O (w) system at T = 298.15, 308.15 and 318.15 K.

Extended NRTL model

aca,p/J·mol−1 ap,ca/J·mol−1 aca,w/J·mol−1 aw,ca/J·mol−1 ap,w/J·mol−1 aw,p/J·mol−1 AAD%a

4000.9 −114,000 −12,359.9 243,584.9 −3342.2 −6023.7 0.0067

n
a ∑i jaexp −acal j
AAD% ¼ i
N
i
100%; where N is the data number used to the correlation.
 Y.P. Jimenez et al. / Journal of Molecular Liquids 286 (2019) 110922
Table 5
Viscosity NRTL parameters for the binary and ternary systems.
T/K aca, w/J·mol–1b aw, ca/J·mol–1b
288.15 6.67E–5 2.04E–5
298.15
308.15
Overall
asw/J·mol–1b aws/J·mol–1b
288.15 −13,311.3013 16,772.4405
298.15
308.15
Overall
as, ca/J·mol–1c aca, s/J·mol–1c
288.15 −7.75E–6 −5.34E–5
298.15
308.15
Overall
a
Absolute average deviation (AAD) = (1/Np)∑[(ηexp–ηcal)/ηexp] × 100%.
b
NRTL parameters for the binary systems.
c
NRTL parameters for the ternary system.
respectively [50]. Also, the value of A3 at 288.15 K was interpolated. The
interaction parameters were evaluated by Eq. (37).
From Table 5, the binary parameters aca,w and as,w obtained have
positive and negative values, respectively. Also, the `aw,ca and aw,s have
positive values. According to Eq. (10), the electrolyte–solvent and
segment–solvent parameters, aca,w and as,w, are the differences between
the interaction energies between the ion–solvent molecule pair and the
solvent–solvent pair and between the segment–solvent molecule pair
and the solvent–solvent pair, respectively. Moreover, the solvent–
electrolyte and solvent–segment parameters, aw,ca and aw,s, are the dif-
ferences between the interaction energies between the solvent–ion
pair and the cation–anion pair and between the solvent–segment pair
and the segment–segment pair, respectively. The positive value of aca,
w indicates that for the activated state the interaction between two sol-
vent molecules is stronger than those between the solvent and the ionic
species, and the negative value of as,w indicates that the interaction be-
tween the segment and the solvent is stronger than those between two
solvent molecules. With respect to the positive values of the parameters
aw,ca and aw,s, these indicate that the interactions between the cation
and the anion and between two segments are stronger than those be-
tween the solvent molecule and the ionic species and between the sol-
vent molecule and the segment, respectively.
4.6. Correlation of viscosity data of ternary system
Likewise, when the methodology and equations above are applied to
this system, it is important to mention some aspects, such as that the pa-
rameter A is assumed to be equal to A2 + A3 + A4, where A2 and A3 are
adjustable parameters obtained from correlation of the viscosity values
of the binary aqueous solutions, and the temperature dependence of pa-
rameter A4 is defined by Eq. (36). The values of A0 and A1 obtained were
−98.4234 and 0.1313, respectively. α is fixed at 0.8 for the ternary sys-
tem, since better results were obtained with this value. The objective
function is the one mentioned above. The parameters are presented in
Table 5.
A comparison between the experimental and correlated values is
shown in Fig. 4. This shows good agreement between the experimental
and calculated results. As can be seen, the interaction parameters τi,j of
the binary salt and ternary systems have an insignificant numeric
value, so the correlation was tested when neglecting these parameters,
and the results were as good as when considering all parameters.
The negative values of the parameters as,ca and aca,s presented in
Table 5 indicate that the interactions between the segment and the
ionic species and between the ionic species and the segment are stron-
ger than those between cation and anion and between two segments,
respectively.
9
5. Conclusions
AAD [%]a Water activity at 298.15, 308.15 and 318.15 K, density and viscosity
–
data at 288.15, 298.15 and 308.15 K for the KClO4 + PEG 4000 + H2O
0.07 ternary system were reported. These experimental data were success-
0.02 fully correlated with the NRTL model, beginning from the binary sys-
0.04 tems and then using these interaction parameters to correlate the
ternary system data. The parameters of the PEG 4000 + H2O system re-
–
8.46 ported in previous work were used in the correlation; thus, fewer pa-
7.66 rameters were adjusted. According to a sensitivity analysis, the
6.92 interaction parameters of this binary system are more relevant than
the other interaction parameters. Moreover, some approximations
3.37
2.90
were made because experimental data were not found; fortunately,
2.47 these did not have a great effect on the final result and the results ob-
2.91 tained are appropriate for engineering calculations.
Acknowledgements
The authors thank CONICYT-Chile for the support provided through
Fondecyt Project No. 1070909 and CICITEM and the Universidad de An-
tofagasta for the publication scholarship. Y.J.B also thanks CONICYT-
Chile for the doctoral scholarship.
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