Fluid Phase Equilibria 295 (2010) 163–171

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Fluid Phase Equilibria

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Activity coefficients of KCl in PEG 4000 + water mixtures at 288.15,

298.15 and 308.15 K
Felipe Hernández-Luis a,∗ , Raquel Rodríguez-Raposo a , Héctor R. Galleguillos b , Jaime W. Morales b
a
Departamento de Química Física, Universidad de La Laguna, Tenerife, Spain
b
Departamento de Ingeniería Química, CICITEM, Universidad de Antofagasta, Chile

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

Article history: The electromotive force of the cell containing two ion-selective electrodes (ISE), K-ISE|KCl(m), PEG
Received 8 March 2010 4000(Y), H2 O(100 − Y)|Cl-ISE has been measured at temperatures of 288.15, 298.15, and 308.15 K as
Received in revised form 21 April 2010 a function of the weight percentage Y of PEG 4000 in a mixed solvent. Y was varied between 0 and
Accepted 23 April 2010
25 wt.% in five-unit steps and the molality of the electrolyte (m) was between ca. 0.05 mol kg−1 and
Available online 31 May 2010
almost saturation. The values of the standard electromotive force were calculated using routine methods
of extrapolation together with extended Debye-Hückel and Pitzer equations. The results obtained pro-
Keywords:
duced good internal consistency for all the temperatures studied. Once the standard electromotive force
KCl
PEG 4000
was determined, mean ionic activity coefficients for KCl, Gibbs energy of transfer from the water to PEG
Emf 4000 + water mixtures, interaction parameters (gEN , hEN , sEN , cp,EN ), salting constants, and the KCl primary
Ion-selective electrode (ISE) hydration number were estimated and comparatively discussed in terms of a model of structural and
Activity coefficient electrostatic interactions with those of the LiCl and NaCl previously obtained in similar mixtures.
© 2010 Elsevier B.V. All rights reserved.

1. Introduction imental methodology (measurement of the electromotive force,

Liquid–liquid extraction using aqueous two-phase systems
(ATPS) has been demonstrated to be a greatly efficient separa-
tion technique for both protein partitioning and with metallic
ions and small organic species [1–3]. Therefore, in recent
years there have been a growing number of studies provid-
ing experimental data on liquid–liquid equilibrium and on
physical–chemical and thermodynamics properties for this type of
system [4,5]. The majority of studies from the last 2 years report
liquid–liquid equilibrium data of ATPS formed with poly(ethylene
glycol) (PEG), also known as poly(ethylene oxide) (PEO), of
diverse molecular weight and different inorganic salts. Recall
that the PEGs are a linear branched uncharged polyethers of
structure HO–CH2 –(CH2 –O–CH2 –)n –CH2 –OH, molecular formula
C2n+2 H4n+6 On+2 , molar mass (44n + 62), and very soluble in water
and most organic solvents.
There have few studies in recent years on the properties of sys-
tems containing electrolytes in PEG + H2 O mixtures. Owing to the
lack of bibliographic information on mean ionic activity coefficients
of electrolytes in PEG + H2 O, in two previous works [4,5] we stud-
ied the LiCl + PEG 4000 + H2 O and NaCl + PEG 4000 + H2 O systems
at temperatures of 288.15, 298.15, and 308.15 K, using an exper-
∗ Corresponding author. Tel.: +34 922 318471; fax: +34 922 318514.
E-mail address: ffhelu@ull.es (F. Hernández-Luis).
emf of electrochemical cells without transport containing two ion-
selective electrodes) similar to previous works done by our group
[4–6]. In the present work, we studied the KCl + PEG 4000 + H2 O
system.
The information obtained in this research is discussed in com-
parison to the data previously reported for systems containing both
LiCl and NaCl. As well, the information obtained for these three sys-
tems will be very useful in modelling MCl partitioning in quaternary
systems such as MCl + MX + PEG 4000 + H2 O (M: Li, Na or K; X: NO3 ,
ClO4 or BF4 ), studies that we are currently carrying out.
2. Experimental
Potassium chloride (Merck pro analysis, 99%) was dried in vacuo
at 373 K for 2 days before use. It was stored over silica gel in desicca-
tors and used without further purification. Analytical grade (Fluka)
poly(ethylene glycol), with an average molar mass of 4000 and a
minimum purity of 99%, was also used without further purification.
For each set of experiments (corresponding to a wt.% of PEG
4000), working solutions were obtained by adding successive
known masses of solid KCl to a solution previously prepared of PEG
4000 and bidistilled water ( < 10−6 S cm−1 ). The uncertainties in
the electrolyte molality and wt.% of PEG were ±0.0001 and ±0.01,
respectively. The solutions were continually stirred with a mag-
netic stirrer and the temperature was controlled with a precision
of ±0.02 ◦ C.

0378-3812/$ – see front matter © 2010 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2010.04.012
164 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171

Table 1
Experimental electromotive force E and mean ionic activity coefficients  at different KCl molality and wt.% of PEG 4000 in PEG 4000 + water mixture at 288.15, 298.15, and
308.15 K.

m (mol kg−1 ) −E (mV)  m (mol kg−1 ) −E (mV)  m (mol kg−1 ) −E (mV) 

288.15 K

0 wt.% 5 wt.% 10 wt.%

0.0513 −75.98 0.807 0.0522 −72.42 0.809 0.0528 −67.20 0.784
0.1067 −43.30 0.763 0.1033 −41.57 0.775 0.1172 −31.35 0.742
0.1996 −15.82 0.721 0.2154 −9.15 0.728 0.2267 −2.33 0.701
0.3613 9.77 0.678 0.3930 16.77 0.683 0.3835 20.42 0.664
0.5302 26.22 0.649 0.6245 36.63 0.649 0.5521 35.90 0.636
0.7227 39.35 0.626 0.8724 50.50 0.619 0.7541 48.96 0.610
1.0741 56.31 0.598 1.2127 64.10 0.590 1.0238 61.76 0.586
1.7289 76.87 0.569 1.5761 74.73 0.566 1.4451 75.87 0.556
2.2984 89.30 0.554 2.2524 89.26 0.536 1.9974 89.00 0.528
3.0150 101.28 0.542 3.1200 102.45 0.508 2.7181 101.43 0.502
4.0309 114.41 0.532 3.3823 109.92 0.482
3.6153 112.14 0.472

15 wt.% 20 wt.% 25 wt.%

0.0578 −58.69 0.757 0.0593 −52.53 0.742 0.0521 −53.60 0.738
0.1377 −20.12 0.707 0.1252 −19.51 0.697 0.1439 −9.02 0.673
0.2566 6.90 0.665 0.2778 14.86 0.641 0.2369 12.35 0.637
0.3857 24.30 0.634 0.4725 37.32 0.600 0.3791 32.21 0.601
0.5982 42.84 0.601 0.7121 54.34 0.567 0.4779 41.85 0.582
0.8454 57.28 0.573 0.9488 66.17 0.544 0.6542 54.87 0.557
1.0980 67.95 0.551 1.3835 81.48 0.512 1.0160 72.94 0.522
1.8440 88.99 0.507 1.8252 92.53 0.488 1.3964 85.82 0.496
2.3708 98.97 0.485 2.4256 103.84 0.465 2.0841 101.81 0.463
2.8104 105.65 0.470 2.8878 110.75 0.450 2.5871 110.46 0.446
3.2402 111.04 0.456 3.0053 112.27 0.447 2.8026 113.49 0.438

298.15 K

0 wt.% 5 wt.% 10 wt.%

0.0497 −86.47 0.805 0.0501 −81.32 0.794 0.0511 −75.74 0.785
0.0580 −79.18 0.799 0.0660 −68.13 0.783 0.0791 −55.44 0.760
0.0844 −61.74 0.776 0.0850 −56.45 0.768 0.1591 −23.27 0.718
0.1132 −48.22 0.758 0.1218 −39.76 0.748 0.2253 −7.38 0.696
0.1564 −33.53 0.736 0.1451 −31.67 0.737 0.3015 5.98 0.679
0.1926 −23.99 0.723 0.1946 −18.79 0.711 0.4436 23.22 0.651
0.2641 −9.69 0.701 0.2412 −8.81 0.700 0.6344 39.26 0.627
0.3673 5.21 0.679 0.3255 4.91 0.682 0.8789 53.87 0.606
0.5259 21.20 0.652 0.5037 24.38 0.650 1.1257 64.96 0.590
0.7362 36.35 0.630 0.8479 47.86 0.617 1.6534 81.79 0.562
1.0292 51.47 0.610 1.2742 65.53 0.584 2.3619 98.25 0.547
1.3125 62.48 0.596 1.6926 83.16 0.625 3.0378 110.31 0.540
1.9596 80.82 0.575 2.4607 100.53 0.608 3.5566 117.82 0.536
2.6145 94.60 0.567 3.2438 114.42 0.609
3.3056 106.26 0.566
4.0710 116.86 0.568

15 wt.% 20 wt.% 25 wt.%

0.0546 −68.21 0.750 0.0494 −67.00 0.737 0.0495 −60.39 0.718
0.0795 −50.83 0.729 0.0896 −39.63 0.702 0.1369 −14.16 0.653
0.1437 −23.83 0.691 0.1377 −20.05 0.675 0.2375 10.39 0.614
0.2471 0.72 0.656 0.2321 3.26 0.638 0.3807 31.16 0.580
0.3443 15.69 0.635 0.3115 16.38 0.617 0.5986 51.01 0.548
0.5093 33.15 0.608 0.4184 30.81 0.613 0.7870 63.01 0.529
0.7201 48.42 0.583 0.5987 46.24 0.583 1.0138 74.14 0.513
1.3013 74.51 0.543 0.8486 60.22 0.544 1.4735 90.61 0.490
1.9418 92.51 0.521 1.1928 76.06 0.530 2.0148 104.48 0.473
2.0905 96.05 0.520 1.7270 92.34 0.507 2.5635 115.65 0.465
2.3088 100.88 0.518 2.3094 105.81 0.496 2.8298 120.32 0.462
2.5624 105.77 0.515 2.6187 111.83 0.493 2.9589 122.56 0.462
2.8958 111.82 0.514 2.9962 118.25 0.490
3.2775 117.62 0.510 3.2487 121.95 0.487
3.4367 119.80 0.508

308.15 K

0 wt.% 5 wt.% 10 wt.%

0.0496 −93.01 0.808 0.0505 −87.70 0.798 0.0493 −82.84 0.759
0.0968 −60.64 0.766 0.1043 −51.76 0.765 0.1386 −33.08 0.695
0.1633 −35.68 0.730 0.2072 −16.33 0.755 0.2266 −9.70 0.663
0.2402 −17.41 0.702 0.3020 1.55 0.728 0.3426 9.84 0.636
0.3514 0.64 0.677 0.4257 16.51 0.686 0.4670 24.40 0.615
0.4713 14.49 0.656 0.6464 37.47 0.673 0.5579 32.83 0.605
0.6497 29.60 0.635 0.8578 50.07 0.644 0.7599 47.35 0.585
 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171 165

Table 1 (Continued )

m (mol kg−1 ) −E (mV)  m (mol kg−1 ) −E (mV)  m (mol kg−1 ) −E (mV) 

0.9004 45.14 0.615 1.1360 63.55 0.629 0.9876 59.71 0.569

1.2778 61.93 0.597 1.4036 71.63 0.593 1.2673 71.72 0.558
1.9813 83.46 0.579 1.9277 87.03 0.579 1.5274 80.74 0.549
2.6684 98.64 0.574 2.5099 100.21 0.571 1.9527 92.88 0.541
3.2563 109.82 0.582 3.1369 111.79 0.570 2.6984 109.06 0.532
4.2926 125.12 0.590 3.8987 123.25 0.570 3.3364 120.25 0.533
4.5659 128.61 0.593 4.0842 125.93 0.572 4.1377 131.53 0.532

15 wt.% 20 wt.% 25 wt.%

0.0483 −77.78 0.729 0.0523 −68.08 0.690 0.0490 −64.21 0.670
0.0948 −45.42 0.688 0.0960 −39.23 0.651 0.1201 −21.82 0.611
0.1856 −13.75 0.641 0.2418 4.12 0.589 0.2160 5.52 0.571
0.2838 6.20 0.613 0.3697 23.74 0.559 0.3122 22.53 0.546
0.3730 19.02 0.595 0.5202 39.55 0.537 0.4225 36.56 0.527
0.4657 29.45 0.581 0.6577 50.61 0.524 0.5809 51.30 0.507
0.6025 41.53 0.565 0.7975 59.82 0.515 0.7282 61.81 0.494
0.7980 54.65 0.547 0.9624 68.72 0.505 0.9399 73.41 0.477
1.3273 78.63 0.519 1.2570 81.54 0.494 1.1696 83.86 0.468
1.8207 93.91 0.506 1.6126 93.50 0.483 1.6326 99.90 0.455
2.4682 109.33 0.500 2.1520 107.53 0.472 2.0899 112.24 0.449
2.8475 116.80 0.500 2.6924 119.01 0.470 2.5793 123.22 0.448
3.4848 127.22 0.498 3.3192 129.94 0.469 3.1404 133.51 0.448
3.8435 132.59 0.500

K-ISE (mod. 6.0504.110) and Cl-ISE (mod. 6.0502.120) were
obtained from Metrohm Company. Cells, apparatus, temperature
control system, as well as the measurement procedure employed
in the present study have been amply described in previous works
[4–6].
3. Results
Mean ionic activity coefficient values for KCl in PEG 4000 + water
mixtures were determined from the emf measurements of the fol-
lowing bi-ISE cells without transference:
K-ISE|KCl(m), PEG 4000(Y ), H2 O(100 − Y )|Cl-ISE
In these cells, m is the molality of KCl (mol KCl kg−1 mixed sol-
vent) in the working solution in the mixed solvent and Y the wt.%
of PEG 4000 in the mixture.
Applying the Nernst-Nikolsky equation, the following expres-
sion is obtained:
E = E 0∗ − 2k log m (2)
where E is the emf of the cell, k = (ln 10)RT/F, is the Nernst theoret-
ical slope and m and  are the molality and mean ionic coefficients
of KCl. E0* is the apparent electromotive force (molal scale) of the
cell and contains the potential of asymmetry of both selective elec-
trodes. In general, we have verified [4–6] that these asymmetric
potentials are small, independent of the solvent composition and
remain practically constant during the period of time that this type
of study lasts.
Table 1 shows E values for different temperatures and different
mixtures of PEG 4000 + water as a function of KCl molality. In total,
(1)
the potentials of 227 solutions were measured. Since the activity
coefficients of KCl in pure water are well known for each tempera-
ture [7], the values of E that appear in Table 1 for 0 wt.% of PEG 4000,
allow for carrying out a calibration of the electrode system using Eq.
(2). A very good linear relationship is obtained when E vs. −2 log m

Table 2
Values of molar fraction (XPEG4000 ), average molecular mass (M), density (), relative permittivity (εr ), Debye-Hückel (A, B) and Pitzer (A ) constants, and Bjerrum parameter
(q) as a function of the weight percentage of PEG 4000 in PEG 4000 + water mixtures at 288.15, 298.15, and 308.15 K.

wt.% 104 XPEG4000 M (g mol−1 )  (g cm−3 ) εr A (kg1/2 mol−1/2 ) B (kg1/2 mol−1/2 Å−1 ) A (kg1/2 mol−1/2 ) q (Å)

288.15 K
0 0.000 18.015 0.9991 82.06 0.5016 0.3269 0.3850 3.53
5 2.370 18.959 1.0077 76.10 0.5641 0.3409 0.4330 3.81
10 5.002 20.007 1.0169 71.80 0.6183 0.3526 0.4746 4.04
15 7.942 21.177 1.0260 66.10 0.7031 0.3691 0.5397 4.38
20 11.247 22.494 1.0352 62.90 0.7608 0.3801 0.5840 4.61
25 14.990 23.984 1.0443 60.00 0.8202 0.3909 0.6296 4.83

298.15 K
0 0.000 18.015 0.9970 78.38 0.5100 0.3285 0.3915 3.57
5 2.370 18.959 1.0053 72.40 0.5768 0.3432 0.4428 3.87
10 5.002 20.007 1.0140 67.10 0.6493 0.3580 0.4984 4.17
15 7.942 21.177 1.0227 60.80 0.7560 0.3777 0.5803 4.61
20 11.247 22.494 1.0315 56.10 0.8566 0.3949 0.6576 4.99
25 14.990 23.984 1.0402 52.60 0.9475 0.4096 0.7273 5.33

308.15 K
0 0.000 18.015 0.9940 74.86 0.5192 0.3301 0.3986 3.62
5 2.370 18.959 1.0020 68.40 0.5969 0.3467 0.4582 3.96
10 5.002 20.007 1.0103 60.30 0.7241 0.3708 0.5558 4.49
15 7.942 21.177 1.0186 52.70 0.8898 0.3983 0.6831 5.14
20 11.247 22.494 1.0269 45.60 1.1101 0.4299 0.8521 5.94
25 14.990 23.984 1.0353 41.50 1.2837 0.4525 0.9854 6.53
166 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171

is plotted at each temperature studied. The k values obtained, 1/2 −1

B = 50.2901 kg1/2 mol−1/2 Å (3b)
when applying a least-squares regression analysis to the previ- 1/2
(εr T )
ous plots, were 55.52 ± 0.36, 57.70 ± 0.27, and 60.57 ± 0.05 mV at
288.15, 298.15, and 308.15 K, respectively, with correlation coeffi-
cients greater than 0.9999 in all cases. The standard deviations were • Pitzer equation [7]
0.40, 0.48, and 0.23 mV at 288.15, 298.15, and 308.15 K, respec-
tively. The difference between the values of k and the corresponding ln  = f  + B m + C  m2 (4)
theoretic values are between 0.9% at 308.15 K and 2.9% at 288.15 K.
These values are more than tolerable levels for a system contain-
 √ 
m 2 √
ing two ion-selective electrodes, with one of these (that of ISE-K) f  = −A √ + ln(1 + b m) (4a)
1+b m b
being a liquid membrane electrode. In these calculations it has been
assumed that kK ∼ = kCl ∼
=k∼
= (kK + kCl )/2 [4–6].    
2ˇ1 √ ˛2 m √
Once the electrodes were calibrated and found to be function- B = 2ˇ0 + 1− 1+˛ m− exp(−˛ m) (4b)
ing correctly, the next very important step was the determination ˛2 m 2
of E0* for each wt.% PEG 4000 and temperature studied. The deter-
mination of E0* was carried out following a method similar to that 1/2
A = 1.4006 × 106 kg1/2 mol−1/2 (4c)
proposed by Hitchcock [8] and using the equations of extended (εr T )3/2
Debye-Hückel and Pitzer, to represent the dependency of log  on
molality. For 1:1 electrolytes, these equations may be written as: All symbols have their usual meaning. The values of the physical
properties and the values of the different constants are shown in
• Extended Debye-Hückel equation [9] Table 2. The density values were taken from the literature [10],
√ while the relative permittivity values were measured by us [4,5].
A m By combining Eqs. (2) and (3) or (2) and (4), the values of E0* ,
log  = − √ + cm + dm2 − log(1 + 0.002mM) + Ext (3)
1 + Ba m according to the different models used, can be optimized, as well
as the characteristic ionic interaction parameters of each model.
1/2
A = 1.8247 × 106 kg1/2 mol−1/2 (3a) These values are presented in Table 3, as well as the corresponding
(εr T )3/2 standard deviation of the fit.

Table 3
Summary of both standard emf for the cell K-ISE|KCl(m), PEG 4000 (Y), H2 O (100 − Y)|Cl-ISE and KCl ionic parameter values obtained for the extended Debye-Hückel and
Pitzer equations, in the different PEG 4000 + water mixtures at 288.15, 298.15, and 308.15 K.

wt.% E0* (mV) a (Å) c (kg mol−1 ) d (kg2 mol−2 )  (mV) E0* (mV) ˇ0 (kg mol−1 ) ˇ1 (kg mol−1 ) C (kg2 mol−2 )  (mV) E0*  (mV)

288.15 K
0 −77.64 3.94 0.0166 −0.00066 0.23 −77.63 0.0417 0.2035 −0.00015 0.38 −77.64 ± 0.01
−77.64 3.99 0.0144 0.21
5 −79.97 6.49 −0.0208 −0.00202 0.14 −80.35 −0.0022 0.6071 0.00854 0.19 −80.21 ± 0.12
−80.30 6.37 −0.0252 0.28
10 −85.74 6.11 −0.0052 −0.00616 0.26 −86.10 0.0182 0.6503 0.00002 0.27 −86.40 ± 0.49
−87.36 5.38 −0.0148 0.81
15 −91.38 6.20 −0.0053 −0.00868 0.19 −91.92 0.0215 0.7817 0.00149 0.23 −92.20 ± 0.57
−93.30 5.31 −0.0136 0.80
20 −97.16 6.29 −0.0089 −0.00958 0.15 −97.85 0.0191 0.8778 0.00548 0.20 −98.08 ± 0.60
−99.22 5.26 −0.0121 0.72
25 −102.66 6.31 −0.0092 −0.01080 0.16 −103.45 0.0199 0.9776 0.00836 0.24 −103.58 ± 0.57
−104.62 5.36 −0.0122 0.70

298.15 K
0 −74.83 4.02 0.0207 0.00015 0.26 −74.83 0.0481 0.2187 −0.00118 0.46 −74.83 ± 0.01
−74.83 4.00 0.0216 0.25
5 −80.36 4.55 0.0335 −0.00098 0.43 −80.39 0.0714 0.3767 −0.00506 0.42 −80.34 ± 0.03
−80.28 4.69 0.0282 0.41
10 −84.86 6.27 0.0026 −0.00523 0.18 −85.30 0.0266 0.7181 0.00068 0.19 −85.46 ± 0.39
−86.20 5.52 −0.0008 0.59
15 −91.07 6.20 0.0073 −0.00804 0.23 −91.71 0.0405 0.8572 0.00578 0.27 −91.92 ± 0.56
−92.97 5.15 0.0085 0.59
20 −97.76 6.81 0.0075 −0.01720 0.25 −98.84 0.0359 1.1069 0.01050 0.30 −99.01 ± 0.78
−100.43 5.25 0.0109 0.81
25 −105.63 6.81 −0.0002 0.01730 0.13 −107.09 0.0430 1.2067 0.01190 0.27 −106.89 ± 0.68
−107.95 5.59 0.0041 0.57

308.15 K
0 −76.21 3.98 0.0244 0.00050 0.18 −76.22 0.0533 0.2318 −0.00203 0.25 −76.21 ± 0.01
−76.21 3.90 0.0277 0.19
5 −80.59 6.68 −0.0005 0.00466 0.54 −80.97 0.0158 0.7015 0.00971 0.52 −81.26 ± 0.49
−82.21 5.38 0.0041 0.79
10 −89.20 5.60 0.0199 −0.00537 0.19 −89.63 0.0624 0.7117 −0.00230 0.24 −90.00 ± 0.60
−91.18 4.82 0.0187 0.69
15 −97.12 6.41 0.0119 −0.01180 0.11 −98.41 0.0714 1.0195 −0.00023 0.28 −98.23 ± 0.59
−99.16 5.47 0.0120 0.57
20 −104.64 7.76 0.0038 −0.03960 0.31 −107.95 0.0920 1.4237 −0.00055 0.32 −106.66 ± 1.02
−107.38 6.59 −0.0124 0.87
25 −112.38 9.06 −0.0032 0.10230 0.31 −117.84 0.0849 1.8121 0.01080 0.52 −115.58 ± 1.65
−116.53 7.61 −0.0640 1.41
 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171 167

Table 4
Average ion size parameter, a, for MCl in the MCl + PEG 4000 + H2 O systems (M: Li, Na or K) at 288.15, 298.15, and 308.15 K, and sum of ionic radii according to Marcus [11]
and Pauling [9].

a (Å) (r+ + r− )M (Å) (r+ + r− )P (Å)

288.15 K 298.15 K 308.15 K

LiCl 1.01 ± 0.36 1.80 ± 0.17 3.04 ± 0.24 2.51 ± 0.02 2.41
NaCl 4.24 ± 0.09 4.63 ± 0.10 5.83 ± 0.38 2.77 ± 0.02 2.76
KCl 5.58 ± 0.26 5.41 ± 0.28 6.11 ± 0.45 3.21 ± 0.02 3.14

Fig. 1. Values of (a − q) for LiCl (䊉) [4], NaCl () [5], and KCl () in PEG 4000 + water mixtures at 288.15, 298.15, and 308.15 K, as a function of wt.% of PEG 4000.

Fig. 2. Plot of Pitzer’s interaction parameters, ˇ0 (), ˇ1 (), C ( ), for KCl in PEG 4000 + water mixtures at 288.15, 298.15, and 308.15 K, as a function of the inverse of the
relative permittivity.

4. Discussion The values obtained for parameter a in the Debye-Hückel

As can be observed from Table 3, except for higher wt.% PEG
4000, the values of E0* obtained with both models are in good
agreement (standard errors inferiors to 1 mV).
Despite the wide range of concentrations studied, the extended
Debye-Hückel equation, with the inclusion of the additional param-
eter d, offers excellent standard deviations for the fits, comparable
to those obtained with the Pitzer model.
model (related to the size of the ions) remain approximately
constant at 288.15 and 298.15 K, while at 308.15 K the value
of this parameter presents greater variation. Table 4 shows the
average values of this parameter together with those obtained
for the LiCl [4] and NaCl [5], as well as the sum of the ionic
radii according to Marcus [11] and Pauling (crystallographic radii)
[9]. In general, the average values of a are always greater than
those of (r+ + r− ), which can be explained by the solvation of

Fig. 3. Plot of log  vs. m1/2 for KCl in PEG 4000 + water at 288.15, 298.15, and 308.15 K for different wt.% of PEG 4000: (䊉) 0%, () 5%, () 10%, () 15%, () 20%, ( ) 25%.
168 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171
Fig. 4. Plot of log  vs. m1/2 for LiCl (䊉) [4], NaCl () [5], and KCl () at 298.15 K in PEG 4000 + water mixtures with 0, 10, and 20 wt.% of PEG 4000.
ions. Values less than (r+ + r− ) can be related to possible ionic
association.
In effect, according to Bjerrum’s theory [12], ion-pairs formation
requires an inter-ionic distance that is less than a critical distance,
q, defined as:
e2
q = |z+ z− |
2εr kT
where all the symbols have their usual meaning. Table 2 shows the
values of the parameter q together with those of the other con-
stants. Fig. 1 clearly shows that both for the NaCl and KCl, (a − q)
is always positive and increases with the wt.% PEG 4000. On the
contrary, for the LiCl, (a − q) is negative and decreases with the co-
solvent percentage, which indicates that a slight increase in the
ionic association may be occurring.
The values of ˇ0 (which can be identified with interaction of
like and unlike charged ions), ˇ1 (which can be identified with the
interactions between unlike charged ions) and C (which repre-
sents triple-ionic interactions) obtained in the fit using the Pitzer
model are plotted in Fig. 2 against of the reciprocal value of the
relative permittivity of the PEG 4000 + water mixture, for the three
temperatures studied. It is interesting to note that these parameters
(at least ˇ0 and ˇ1 ) present a linear tendency with 1/εr , follow-
ing behaviour similar to other electrolytes 1:1 in different aqueous
mixtures of organic solvents [4–7,13]. In relation to the parameter
C it is not a simple matter to reach a conclusion concerning the
variation with 1/εr given its low value and the major uncertainty
in its determination.
The average values for E0* , which appear in the last column of
Table 3, were used to calculate the mean ionic coefficients  (Eq.
(2)) that are listed in Table 1 for different molalities of KCl and
wt.% of PEG 4000 at studied temperature. The standard deviations
of our activity coefficients compared to those reported in the lit-
erature [7] were calculated to be less than ±0.005, ±0.005, and
±0.003, in pure water at 288.15, 298.15, and 308.15 K, respectively,
showing good agreement between both sets of data, particu-
Fig. 5. Plot of the standard Gibbs energy of transference vs. wt.% of PEG 4000 for LiCl (䊉) [4], NaCl () [5], and KCl () at 288.15, 298.15, and 308.15 K.
larly if the wide range of concentrations studied is taken into
account.
Fig. 3 shows log  vs. m1/2 for the three temperatures and for
the 6 wt.% of PEG 4000 studied. Likewise, for comparison purposes,
Fig. 4 shows the log  vs. m1/2 variation at 298.15 K, for 3 wt.% of
co-solvent, for the three systems being compared. The behaviour is
(5) very similar at other temperatures. The following are noteworthy
points from Figs. 3 and 4.
(a) All the curves show a typical profile of the variation of log 
with molality, which, as is well known, is governed by two types
of short-range interactions including those of ion-ion and ion-
solvent.
(b) In all cases, for KC1, a monotone decrease is observed (at least
up to the studied molalities) of log  vs. m1/2 , while for LiCl and
NaCl the plot shows a minimum.
(c) For the three electrolytes being compared, regarding those
obtained in pure water, log  clearly decreases with the rise
of wt.% of co-solvent (decrease in dielectric constant of the PEG
4000 + water mixture).
The standard Gibbs energy of transfer, G◦ t , defined as the dif-
ference between the standard Gibbs energy per mole of electrolyte
in a pure solvent, usually water, and that in another pure or mixed
solvent, is a measure of the change in the total energy of the solute
when it is transferred from one solvent to another at infinite dilu-
tion and can be easily calculated from the values of E0* according
to the expression:
G◦ t = −zF(Es0 − Ew
0
) = −zF[(Es0∗ − Ew
0∗
) − (Es
asym asym
− Ew )] (6)
where E0 , E0* , and Easymstand for the standard potential, the appar-
asym asym
ent standard potential and the asymmetry potential (εK + εCl ),
respectively. Subscript ‘s’ refers to mixed solvent and w to water. All
the other symbols have their usual meaning. As mentioned previ-
ously, in our case, Easym is a constant value, small and independent
 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171 169

of the composition of the solvent, which allows us to affirm, that where gij , gijk , gijkl are pair, triple, and quadruple Gibbs energy inter-
asym asym
(Es − Ew ) is negligible compared to (Es0∗ − Ew 0∗ ), and thus Eq. action parameter, respectively. In dilute solution (mE → 0) Eq. (8) is
(6) may be used without any inconvenience. Note that any extra- reduced to
thermodynamic assumption has been explicitly made a priori.
G◦ t
m(W )
(W → W + N) = 2 gEN mN +3 gENN m2N + 4 gENNN m3 +· · ·
Fig. 5 shows a plot of the standard Gibbs energy of transfer,
G◦ t , for LiCl, NaCl, and KCl against wt.% of PEG 4000 in the PEG (9)
4000 + water system, at 288.15, 298.15, and 308.15 K. In all cases
it is verified that G◦ t > 0, which indicates that the transfer pro-
cess is not spontaneous. On the other hand, G◦ t becomes more This removes any complicating effects of ion-ion interactions.
positive with an increases in the wt.% of PEG 4000, indicating that In a first approximation, only considering the ion pair interac-
the thermodynamic stabilization of the alkali halide decreases in tions, the behaviour of the two systems investigated here can be
the mixed solvent, in the LiCl > NaCl > KCl order. In other words, the described by analyzing the gEN parameter (sign and magnitude), as
transfer of LiCl from the water to the mixed solvent is more disad- well as its dependence on temperature. The relationship between
vantageous than that of the NaCl and the latter more than that of gEN and temperature can be well represented by the empirical equa-
the KCl. This effect is less pronounced as temperature increases. tion [18]:
In accordance with Zhuo et al. [14–17], it is possible to evaluate
gEN = a + bT + cT 2 (10)
the Gibbs energy interaction parameters, based on the standard
transfer Gibbs energy expressed in mol per kilogram of pure water, with a, b, and c being mathematical fit parameters without physical
m(W )
G◦ t . It was first necessary to convert the standard transfer significance.
Gibbs energy expressed in mol per kilogram of the mixed solvent, Based on the fundamental thermodynamic relationships, the
m(M)
G◦ t (which until now we have termed for simplicity G◦ t ), in following equations can be derived
the standard transfer Gibbs energy expressed in mol per kilogram
m(W ) sEN = −(b + 2cT ) (11)
of pure water, G◦ t , in accordance with the expression:
2
hEN = a − cT (12)
G◦ t = G◦ t
m(W ) m(M)
− RT ln(1 + 0.001mN MN ) (7)
cp,EN = −2cT (13)
where mN and MN is the molality of the PEG 4000 (in mol kg−1
water) and its molecular mass, respectively. in order to calculate the entropic, enthalpic and isobaric capacity
m(W )
According to the McMillan-Mayer theory, G◦ t , can be pair interaction parameters, respectively, at different tempera-
expressed as [7]: tures. In all cases, the interaction parameters characterize the mean
behaviour of the interaction between the PEG 4000 and each of
G◦ t
m(W )
(W → W + N) the ions (anion and cation) in which the electrolyte dissociates. It
should be kept in mind that the latter parameters thus obtained
= 2 gEN mN + 6 2 gEEN mE mN + 3 gENN m2N + 12 3 gEEEN m2E mN
have a larger error than those obtained directly from calorimetric
+ 12 2 gEENN mE m2N + 4 gENNN m3N + · · · (8) measurements.

Fig. 6. Plot of gEN , TsEN , hEN , and cp,EN vs. temperature for the MCl-PEG 4000 interaction: LiCl (䊉), NaCl (), and KCl ().
170 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171
Table 5
Gibbs energy interaction parameters, gEN , and salting constant, ks , for MCl + PEG 4000 + H2 O system (M: Li, Na or K) at 288.15, 298.15, and 308.15 K.
2 gEN (kJ kg mol−2 )
288.15 K 298.15 K
LiCl 91.5 72.2
NaCl 17.3 26.1
KCl 3.7 19.7
As well, based on the following relation [19,20]:
2 2
ks = gEN = (a + bT + cT 2 )
RT RT
the salting constant, ks , can be estimated.
m(W )
Fig. 6 shows the variation of gEN (obtained by fitting G◦ t
data to Eq. (9)) with the temperature for the three studied systems
and those of TsEN , hEN , and cp ,EN (calculated from Eqs. (11)–(13) after
adjusting the gEN values obtained to Eq. (10)). The values of 293.15
and 303.15 K were calculated by interpolation. Notably, the values
of gEN , and consequently those of the other parameters, are unusu-
ally large. This is due, among other things, to the large molecular
mass of the PEG 4000, which results in mN being very low. It can be
seen that gEN > 0 and cp,EN > 0 at all temperatures, for the three ana-
lyzed systems, while sEN and hEN are positive (endothermic process)
for LiCl, except at 288.15 K, and negative (exothermic process) for
NaCl and KCl, except at 308.15 K. All of these parameters decrease
with decreasing temperature, with the exception of gEN for LiCl.
According to Zhuo et al. [18] and Jiang et al. [21], all this can be
interpreted on the basis of a model of structural and electrostatic
interaction. Structural interaction consists principally of solva-
tion/desolvation of solutes and reorganization of solvent. Thus,
following to Zhuo et al. [18] and Jiang et al. [21], the interaction
between PEG 4000 and MCl (M: Li, Na or K), should include R–M+ ,
R–Cl− , O–M+ and O–Cl− (R stands for hydrophobic-non-polar alkyl
groups and O stands for hydrophilic-polar OH or –O– groups). The
sign, extension and temperature dependence of the contribution of
each of the four types of pair interactions to the different thermo-
dynamics parameters, have been widely analyzed and justified by
the cited authors [18,21] for systems containing non-electrolytes
such as alcohols, amino acids or saccharides. Although the chem-
ical structure and the physiochemical properties of PEG 4000 are
very different from those of the previously cited compounds, some
basic qualitative data will be sketched out very briefly.
Generally, R–M+ and R–Cl− interactions are mainly structural
and contributes a positive value to gEN . O–M+ interaction is mainly
electrostatic-attractive (contributes a negative value to gEN ) and
O–Cl− is mainly electrostatic-repulsive (contributes a positive
value to gEN ). Since, the values of gEN are primarily determined
by the electrostatic interactions [18,21] and are always positive
in the present systems, it can be affirmed that the values of
gEN are predominantly controlled by the interaction O–Cl− . In
Fig. 6, the dependence of gES on cation size shows the sequence
Fig. 7. Variation of E0 with mass fraction of water in PEG 4000 + water mixtures at 288.15, 298.15, and 308.15 K.
ks (kg mol−1 )
308.15 K 2.88.15 K 298.15 K 308.15 K
3.1 38.2 29.4 1.2
28.8 7.2 10.5 11.2
20.9 1.6 7.9 8.1
LiCl > NaCl > KCl. Given that the anion is common to the three elec-
trolytes that we are comparing, the decrease in the gEN value could
(14) be due to an increase in the O–M+ interaction and/or a decrease in
the R–M+ and R–Cl− interaction with the passing of Li+ to K+ .
The structural interaction between MCl and PEG 4000 con-
sist principally of the desolvation of solutes that interact with
each other and the solvent reorganization in the nearness of
the hydrophobic groups of the non-electrolyte. Has been widely
accepted [21] that structural interaction should make positive
contributions to the enthalpy interaction parameters, while the
electrostatic interaction should make negative contributions. So,
the two interactions of electrolyte with polar and non-polar groups
of PEG 4000 have opposite effects on hEN . Fig. 6 suggest that the
electrostatic interaction of MCl with polar groups is the dominant
interaction and hEN becomes more negative (less positive) both
with the increment of the cation size (the anion is common to the
three electrolytes) and decrease of temperature. This negative con-
tribution would be partly counteracted by the positive contribution
from the R–M+ interaction that is mainly a structural interaction
[21]. Typically, the structural interactions are more dependent on
temperature that the electrostatic interactions.
The sEN and cp,EN values (sign and magnitude) are fundamen-
tally related to the formation or rupture of structures in solution,
and consequently related to the increase or decrease in order of the
same. Negative sEN values for the NaCl-PEG 4000 and KCl-PEG 4000
interactions indicate a decrease in disorder (an increase in order),
while the positive sEN value for the LiCl-PEG 4000 interactions indi-
cates an increase in disorder (a decrease in order). On the other
hand, the cp,EN values, which are a very sensitive probe for the study
of structural interactions, are positive in the three case, which indi-
cates an increase in the structure of the solution. A more exhaustive
discussion about all these parameters can be found in the works of
Zhuo et al. [18] and Jiang et al. [21]. In our case, it serves to keep
in mind that, in accordance with Marcus [22], Li+ is a “structure-
making ion”, while Cl− and K+ are “structure-breaking ions”. Na+ is
a “borderline ion” that can sometimes act as a “structure-making
ion” and other times as a “structure-breaking ion”. On the other
hand, in accordance with Bertoluzzo et al. [23], PEG 4000 is also a
“structure-making solute”.
As can be seen in Table 5, in general the values of both gEN and ks
decrease going from LiCl to KCl, this effect being less accentuated
with an increase in temperature. These positive values indicate that
the PEG 4000 is salted-out by the electrolytes present in the solution
 F. Hernández-Luis et al. / Fluid Phase Equilibria 295 (2010) 163–171 171

Table 6 sEN entropic interaction parameters

Primary hydration number, nhydr , for MCl in the MCl + PEG 4000 + H2 O systems (M:
w mass fraction of water in the mixture
Li, Na or K) at 288.15, 298.15, and 308.15 K, and sum of the more probable integer
values of the primary ionic hydration number (nhydr,+ + nhydr ,− ) [26]. wt.% weight percent
z ion charge
nhydr (nhydr,+ + nhydr,− )

288.15 K 298.15 K 308.15 K Greek letters

LiCl 8.3 7.8 7.7 7±2 ˛ constant of Pitzer equation
NaCl 5.3 5.3 5.8 6±2 ˇ0 , ˇ1 solute-specific interaction parameters of the Pitzer equa-
KCl 3.2 4.1 4.7 5±2 tion
 mean ionic activity coefficient
εr relative dielectric constant
[16,17]. Given that the anion is common to the three electrolytes,
 density
the intensity of this effect should be marked by the properties of
 standard deviation
the cation, such as its hydration capacity, for example.
Using the Feakins and French equation [24,25], it is possible to
make a rough estimate of the primary hydration number of the Subscripts
electrolyte, based on the dependency between the standard elec- E electrolyte
tromotive force of the cell and the logarithm of the mass fraction N non-electrolyte
of water in the mixture according to: s mixed solvent
t transfer
0 ∼ 0∗
E 0 = Es0 − Ew 0∗
= Es − Ew = nhydr k log w (15) w water
Fig. 7 shows the relationship between E0
vs. −k log w, where
excellent linear correlations can be observed for all the cases. The Acknowledgements
values found for nhydr were 3.2 (r = 0.990), 4.1 (r = 0.999), and 4.7
(r = 0.991) at the temperatures of 288.15, 298.15, and 308.15 K, The authors thank CONICYT-Chile for the support provided
respectively. Independently of temperature, the values of nhydr for through Fondecyt Project No. 1070909 and the ORI (International
the KCl in (PEG 4000 + water) are in good agreement with the value Relations Office) of the Universidad de La Laguna for its collabora-
5 ± 2 reported in the bibliography [26]. tion that made the stay of Héctor R. Galleguillos possible.
Table 6 shows the values of nhydr for the three electrolytes that
are being compared. It can clearly be observed that hydration fol- References
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