Fluid Phase Equilibria 275 (2009) 116–126

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Fluid Phase Equilibria

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Activity coefficients of NaCl in aqueous mixtures with ␧-increasing co-solvent:

Formamide–water mixtures at 298.15 K夽
Felipe Hernández-Luis a,∗ , Héctor R. Galleguillos b , Luis Fernández-Mérida a , Oscar González-Díaz c
a
Departamento de Química Física, Universidad de La Laguna, Tenerife, Spain
b
Centro de Investigación Científica y Tecnológica para la Minería, Universidad de Antofagasta, Chile
c
Departamento de Química, Universidad de Las Palmas de Gran Canaria, Spain

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),
Received 17 July 2008
Received in revised form Na-ISE|NaCl(m), formamide(Y ), H2 O(100 − Y )|Cl-ISE
17 September 2008
Accepted 2 October 2008 has been measured at a temperature of 298.15 K as a function of the weight percentage Y of formamide
Available online 15 October 2008 in a mixed solvent. Y was varied between 0 and 100% in ten-unit steps and the molality of the elec-
trolyte (m) was between ca. 0.01 and saturation. The values of the standard electromotive force, E0 (molal
Keywords: scale), were determined using routine methods of extrapolation together with Debye-Hückel, Pitzer and
NaCl Scatchard equations. The results obtained produced good internal consistency, within the normal limits of
Formamide experimental error encountered in these types of measurement. Once E0 was determined, the mean ionic
Emf activity coefficients for NaCl, the Gibbs energy of transfer from the water to the formamide–water mixture,
Ion selective electrode (ISE) the standard solubility product and the primary NaCl hydration number were calculated. The variation
Activity coefficient of these magnitudes with the composition of this mixture with ␧-increasing co-solvent is discussed in
comparison with those previously obtained with ␧-decreasing methanol–water and ethanol–water sys-
tems in terms of the ion–solvent and ion–ion interactions and their changes with the properties of the
medium.
© 2008 Elsevier B.V. All rights reserved.

1. Introduction
Aquo-organic electrolyte solutions are important for a wide
number of applications, and therefore new data are always wel-
come. In previous works by our group, the behaviour of the
NaF has been studied both in organic-water mixtures with ␧-
decreasing co-solvent (i.e. methanol–water, ethanol–water) [1],
as in organic–water mixtures with (-increasing co-solvent (i.e.
formamide-water, ethylene carbonate–water) [2,3]. The activity
coefficients of the NaF were determined in these media based on
emf measured in galvanic cells containing electrodes selective for
F− and Na+ ions. A simple methodology was developed and applied
to obtain the maximum possible information about these systems.
Thus, for example, the activity coefficients were correlated as a
function of the properties of the solvent, as expressed by its dielec-
夽 Dedicated to Prof. Dr. Agustín Arévalo (Emeritus) and Prof. Dr. Andrés Vivo on
the occasion of their retirement, and to Dr. Miguel A. Esteso, at present in University
of Alcalá de Henares, after many years at the University of La Laguna.
∗ Corresponding author. Fax: +34 922 318514.
E-mail address: ffhelu@ull.es (F. Hernández-Luis).
tric constant. The Gibbs energy of transfer from the water to the
organic–water mixture, the standard solubility product and the pri-
mary hydration number of the electrolyte were also calculated and
their variation with the composition of the mixture comparatively
discussed.
The objective of the present research is to carry out a simi-
lar study for NaCl in formamide–water mixtures and to compare
the results with those obtained previously for NaF. In the litera-
ture there are numerous potentiometric studies of NaCl in mixtures
with ␧-decreasing co-solvent [4–19] but very few in mixtures with
␧-increasing co-solvent [19].
It is well known [20,21] that formamide is a highly ionized
polar liquid with a dipole moment and dielectric constant higher
than water, with which is completely miscible throughout the
complete composition range, and forms a hydrogen-bonded net-
work. In contrast to methanol–water or ethanol–water mixtures, in
formamide–water mixtures the dielectric constant, the density and
the viscosity uniformly increase with the co-solvent content. The
dielectric constant reaches a maximum value at 80–90% [2,3,22].
Moreover, formamide shows two other important character-
istics. The first, is its highly hygroscopic nature, which makes it
difficult to maintain in a pure state for a long period. This property

0378-3812/$ – see front matter © 2008 Elsevier B.V. All rights reserved.
doi:10.1016/j.fluid.2008.10.001
 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126
has been demonstrated by exposing a recently prepared aliquot to
open air and noting that a weight gain of 0.2% within 1 h, of 1%
within 5.5 h, and of 10% within 141 h takes place. Fortunately, it
has also been shown [20] that a water content change of 1–2% did
not appreciably affect conductivity or potentiometric experiments,
and is probably negligible when working with water–formamide
mixtures.
The second important feature of formamide is its notable capac-
ity for hydrolysis, especially in very acid or very basic media [20].
Kinetic experiments on the determination of electromotive forces
in cells containing hydrochloric acid in formamide–water media
have been carried out by Kozlowski and Wasiak [23]. These authors
determined the time required such that 2–3% of formamide hydrol-
ysis takes place in this system. This percentage was considered to
be the limit at which potentiometric measurements began to be
affected. For higher concentrations of HCl in the cell (pH ∼ = 1) this
time fluctuated from 1 h, when the formamide content was 5%, to
6 h when formamide content was 32%.
With regard to the used electrolyte, it is well known that NaCl,
unlike NaF, is much more soluble in water (6.146 mol kg−1 against
0.983 at 298.15 K) and has a smaller capacity for the association and
formation of ion pairs. This electrolyte is present in many natural
systems, from seawater to biological fluids such as urine.
The studies presented here were carried out using potentio-
metric techniques which have been greatly improved in recent
decades mainly due to the development and improvement of the
ion-selective electrodes (ISE) [1–6,10,12–14,16,18,19]. These elec-
trodes are not only valuable for analytical use, but also may be
employed in determining thermodynamic and transport proper-
ties. In the electrodes used in the present study are those which
have recently been developed, in which a glass membrane is used
for the Na+ and a solid-state membrane for the Cl− ion. These elec-
trodes have been shown to function accurately both in water and
in organic–water solutions.
The measurements were carried out at 298.15 K since very few
data of the dielectric constant of these mixed solvents at other
temperatures are available.
2. Experimental
NaCl, Merck pro analysi (99%), was vacuum-dried at 373 K for
72 h and then stored in a desiccators over silica gel. Formamide,
Sigma puris (99.5%), was used without prior treatment. Correction
for the very small water content of the original product was consid-
ered unnecessary. All solutions were prepared by direct weighing.
For each set of experiments (corresponding to a wt.% of formamide)
working solutions were obtained by successively adding weighed
amounts of solid NaCl to the corresponding solution prepared
from formamide and double-distilled water ( < 1 × 10−6 S cm−1 ).
Fig. 1. Calibration of the electrodic system. (a) E0* = −262.21 ± 0.17 mV; k = 59.40 ± 0.17 mV; r = 0.99996;  = 0.59 mV and (b) E0* = −262.17 ± 0.06 mV; k = 59.73 ± 0.05 mV;
r = 0.99999;  = 0.22 mV.
117
The solutions were continuously stirred by using a magnetic stir-
rer.
The last addition of NaCl in the different studied formamide-
water mixtures corresponded to saturated solutions, since some
salt crystals remained undissolved. The procedure to estimate the
saturation molality of the NaCl, in each of the mixtures, was as fol-
lows: (a) the solution (with excess of NaCl) was decanted for 10 h,
maintaining a constant temperature of 298.15 K; (b) approximately
1 g of sample was taken from the supernatant solution; (c) the sam-
ples were dried by solvent evaporation until a constant weight was
reached.
On the basis of this weight and that of the initial sample, the
saturation molality was then calculated. In order to obtain a good
estimation, the process was quadruplicated and the average value
subsequently calculated.
The electrodes, cells, apparatus, temperature control system, as
well as the measurement procedure employed in the present study
have been described previously [1–4,24–26].
3. Results
Mean ionic activity coefficient values for NaCl in formamide–
water mixtures were determined from the emf measurements of
the following galvanic cells without transference:
Na-ISE|NaCl(m), formamide(Y ), H2 O(100 − Y )|Cl-ISE (1)
In these cells, m is the molality of NaCl (moles NaCl/kg mixed-
solvent) in the working solution and Y the wt.% of formamide in the
mixture.
Applying the Nernst equation, the following expression 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 theoretical
slope and m and  are the molality and stoichiometric mean ionic
activity coefficient of NaCl. E0* is the apparent standard potential
(molal scale) of the cell and contains the potential of asymmetry of
both selective electrodes [1–3,27–29].
Table 1 shows E values for different mixtures of formamide-
water as a function of NaCl molality. As can be observed in this
table, two studies were carried out in pure water (0 wt.% of for-
mamide), one when the experiments began and another after 15
days, when all the studies were completed.
Since the activity coefficients of NaCl in pure water are well
known [30], the values of E that appear in Table 1 for 0 wt.% of
formamide allow a calibration of the electrode system to be carried
out, using Eq. (2). Fig. 1 shows a very good linear relationship in
both cases when E vs. −2 log m is plotted.
118 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126

Table 1
Experimental electromotive force E and mean ionic activity coefficients  at different NaCl molality and wt.% of formamide in formamide–water mixtures at 298.15 K.

m −E  m −E  m −E  m −E 

0 wt.% 10 wt.% 20 wt.% 30 wt.%

0.1439 148.07 0.764 0.2481 179.74 0.736 0.0584 112.91 0.832 0.0940 140.76 0.823
0.2283 169.95 0.735 0.2999 188.59 0.722 0.2464 182.72 0.760 0.1866 174.80 0.801
0.3001 181.87 0.705 0.4758 210.83 0.700 0.3002 192.27 0.751 0.2999 198.03 0.780
1.0082 239.67 0.641 0.7996 236.32 0.682 0.4199 208.82 0.739 0.3166 200.71 0.779
1.2154 250.15 0.651 1.2776 259.88 0.673 0.6948 233.93 0.726 0.4738 220.76 0.767
1.5120 261.92 0.657 2.4674 297.19 0.716 1.0179 253.61 0.724 0.5529 228.69 0.766
1.8234 272.30 0.666 2.5952 300.49 0.726 1.4686 273.71 0.740 0.8863 253.01 0.765
2.4032 288.17 0.686 2.9992 309.77 0.752 1.6963 281.82 0.750 1.5010 281.70 0.786
3.0598 303.27 0.722 3.2451 315.16 0.771 2.3128 300.30 0.786 2.3585 308.90 0.846
3.8481 318.91 0.777 3.6425 323.16 0.802 2.7194 310.56 0.815 2.5953 315.28 0.870
4.5920 331.67 0.833 4.0026 329.67 0.827 3.2096 321.71 0.857 3.0389 325.79 0.910
5.3276 342.86 0.891 3.7592 332.23 0.897 3.6271 336.93 0.946
4.2173 339.76 0.924 4.1155 344.70 0.969
4.7884 348.10 0.956 4.3256 347.45 0.972

40 wt.% 50 wt.% 60 wt.% 70 wt.%

0.1381 165.38 0.808 0.0355 105.93 0.880 0.0648 140.63 0.872 0.0358 119.25 0.899
0.1867 180.55 0.801 0.1350 172.13 0.831 0.1234 173.25 0.861 0.0596 145.18 0.891
0.3000 203.93 0.784 0.2177 195.70 0.813 0.2170 201.57 0.846 0.2999 226.81 0.857
0.3086 205.44 0.784 0.3001 211.69 0.804 0.3002 218.06 0.842 0.4395 245.98 0.847
0.4754 227.16 0.775 0.2786 208.03 0.806 0.3077 219.41 0.843 0.8302 280.20 0.869
0.5938 238.06 0.766 0.3912 225.01 0.797 0.4468 238.52 0.840 0.8689 283.02 0.877
0.7758 253.06 0.783 0.4903 236.57 0.795 0.5695 251.34 0.844 0.9375 287.29 0.883
1.1239 272.89 0.793 0.7388 257.87 0.797 0.9760 280.67 0.868 1.0360 293.19 0.895
1.4938 289.01 0.815 0.9663 272.44 0.807 1.3000 297.14 0.896 1.2728 305.10 0.917
2.1189 310.04 0.863 1.7053 305.25 0.863 1.6159 310.18 0.928 1.6499 319.65 0.938
2.6566 324.57 0.911 2.4072 326.31 0.918 2.0340 323.59 0.955
3.1927 335.64 0.939 2.7069 333.10 0.931 2.3031 330.39 0.962
4.0402 348.53 0.952 2.9081 337.01 0.935 2.9217 342.74 0.963
3.2620 343.06 0.937

80 wt.% 90 wt.% 100 wt.% 0 wt.%

0.0602 152.86 0.899 0.0446 149.25 0.906 0.0254 136.65 0.937 0.0609 105.55 0.796
0.1276 191.55 0.896 0.0955 188.35 0.901 0.0442 165.21 0.936 0.1754 156.20 0.736
0.2529 226.59 0.890 0.2065 227.82 0.894 0.0818 196.48 0.925 0.2121 165.55 0.728
0.3001 235.56 0.892 0.2535 238.52 0.895 0.1323 221.05 0.920 0.3000 182.03 0.709
0.3030 236.08 0.892 0.2998 247.18 0.894 0.2043 243.26 0.915 0.3228 185.45 0.704
0.4544 257.24 0.896 0.3894 260.59 0.893 0.3001 262.86 0.910 0.4385 200.10 0.687
0.5415 266.61 0.901 0.4930 273.14 0.899 0.3089 264.35 0.910 0.5779 213.46 0.675
0.6981 280.46 0.913 0.7484 296.03 0.922 0.7232 307.97 0.903 0.7290 224.76 0.666
0.8012 288.23 0.925 0.8254 301.27 0.925 0.8114 230.23 0.665
0.9642 298.88 0.944 0.9077 306.40 0.928 0.9682 238.99 0.660
1.3957 319.01 0.962 1.0612 314.49 0.929 1.4191 258.32 0.654
1.5227 323.43 0.961 1.2617 322.85 0.918 2.0188 277.74 0.670
1.6065 326.06 0.958 2.4660 289.35 0.686
2.8481 298.25 0.706
3.3892 309.52 0.737
3.5127 312.08 0.747

Units: m in mol kg−1 ; E in mV.

The value obtained for Nernst slope, k, when applying a
least-squares regression analysis to the previous plots, were
59.40 ± 0.17 mV and 59.73 ± 0.05, respectively, with correlation
coefficients greater than 0.9999 in both cases.
The different work ranges produce small differences between
the k values, as well as between the standard deviations obtained.
The average value of k (59.57 ± 0.11 mV) differs only by about
0.7% from the theoretical value and will be taken heretofore as
the value of k for the successive calculus achieved in this work.
This is above acceptable levels for a system containing two ion
selective electrodes. In this calculation it has been assumed that
kNa ∼= kCl ∼
=k∼= (kNa + kCl )/2.
In Fig. 1 it is also observed that the intercepts in both cases
are practically equal. This is very important since it indicates that
the potential of asymmetry of the electrodes has scarcely var-
ied in the 15 days that elapsed between both calibrations. This
allows us to work with the Na-ISE cell|NaCl (m), formamide (Y),
H2 O (100 − Y)|Cl-ISE directly, applying Eq. (2), and without using
a reference cell to correct the daily changes of the asymme-
try potential, as occurred in some previous works by our group
[4,24,25].
Once the electrodes have been calibrated and found to be
operating correctly, the most important and decisive goal in
this type of study is to determine the apparent standard poten-
tial in the cell, E0* , as accurately as possible for each mixture
studied, since this affects the accuracy of the activity coef-
ficients and the other thermodynamic functions subsequently
calculated.
The determination of E0* was carried out following a method
similar to that proposed by Hitchcock [31] and using the extended
equation of Debye–Hückel [32,33] and those of Pitzer [34,35] and
Scatchard [36,37], to represent the dependency of log ( on concen-
tration. For 1:1 electrolytes, these equations may be written as:
- Extended Debye–Hückel equation [32,33]
√
A m
log  = − √ + cm + dm2 − log(1 + 0.002mM) + Ext (3)
1 + Ba m
 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126 119

Table 2
Values of average molecular mass (M), relative permittivity (εr ), density (), Debye–Hückel (A, B), Pitzer (A ) and Scatchard (S) constants, and Bjerrum parameters (q) as a
function of the weight percentage of formamide in formamide–water mixtures at 298.15 K.

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

0 18.015 78.38 0.99705 0.5100 0.3285 0.3915 −1.1745 3.57

10 19.165 82.99 1.01116 0.4714 0.3215 0.3618 −1.0856 3.37
20 20.472 87.31 1.02506 0.4398 0.3156 0.3376 −1.0129 3.21
30 21.970 91.62 1.03879 0.4119 0.3101 0.3162 −0.9486 3.06
40 23.704 96.02 1.05233 0.3864 0.3049 0.2966 −0.8898 2.92
50 25.736 100.44 1.06568 0.3635 0.3000 0.2790 −0.8370 2.79
60 28.149 104.67 1.07886 0.3438 0.2957 0.2639 −0.7916 2.68
70 31.061 108.32 1.09185 0.3285 0.2924 0.2522 −0.7565 2.59
80 34.645 110.85 1.10466 0.3192 0.2907 0.2450 −0.7350 2.53
90 39.165 111.56 1.11728 0.3179 0.2915 0.2440 −0.7322 2.51
100 45.040 109.57 1.12972 0.3284 0.2957 0.2521 −0.7564 2.56

with a the ion size parameter, c and d the ion-interaction param-
eters, M the average molecular mass of mixed solvent and Ext the
contribution of the extended terms. A and B are the Debye–Hückel
constants given by:
A = 1.8247 × 106 1/2 /(εr T )3/2 kg1/2 mol−1/2
−1
B = 50.29011/2 /(εr T )1/2 kg1/2 mol−1/2 Å
where , εr and T stand for the density, relative permittivity (static
dielectric constant) of the solvent and the temperature, respec-
tively. An additional parameter, d, has been including in Eq. (3) to
cover the entire concentration range studied [32,33].
- Pitzer equation [34,35]
ln  = f  + B m + C  m2
where
 √  100 wt.% of formamide, where the value of a is greater than usual.
m 2 √
f  = −A √ + ln(1 + b m)
1+b m b
2ˇ1 √ √
B = 2ˇ0 + [1 − (1 + ˛ m − ˛2 m/2) exp(−˛ m)]
˛2 m
In these equations ˛ and b are assumed to be constant with
values of 2.0 and 1.2 kg1/2 mol−1/2 , respectively, both in water
and in formamide–water mixtures [34,35,38–40]; ˇ0 , ˇ1 and
C are solute-specific interaction parameters and A is the
Debye–Hückel constant for the osmotic coefficients defined by:
A = 1.4006 × 106 1/2 /(εr T )3/2 kg1/2 mol−1/2
all symbols having their usual meaning. For those
formamide–water mixtures where the solubility of the NaCl
did not reach 2.0 mol kg−1 , Eq. (4) with C = 0, was also tried as
suggested by Pitzer [34,35].
- Scatchard equation [36,37]
 
1 2Sm1/2 3 4 5 mixtures with ␧-decreasing co-solvent such as methanol [1],
ln = +2a(1) m+ a(2) m2 + a(3) m3 + a(4) m4
2 1 + am1/2 2 3 4
where S = −3A and a, a(1) , a(2) , a(3) and a(4) are the characteristic
interaction parameters of the model. Although this equation is no
longer widely applied, it has been applied here to further verify
and ratify the values of E0* obtained by the other two methods.
The values of dielectric constant and density for the formamide–
water mixtures were taken from the literature [22,41,42] and they
are shown in Table 2 for the different mixed solvents used, together
with those for M, A, B, A , S and q (Bjerrum parameter).
By combining Eqs. (2) and (3), (2) and (4) or (2) and (5) the val-
ues of E0* , according to the different models used, can be optimized,
as well as the characteristic interaction parameters of each model.
In Table 3, these values are presented as well as the corresponding
standard deviation of the fit. The values of the adjustable param-
eters of the Scatchard equation are not included, as they do not
provide any additional significant information.
4. Discussion
(3a)
As can be observed from Table 3, the values of E0* obtained with
(3b)
each one of the tried models are in very good agreement. The stan-
dard deviations of the fits are also comparable, although each of the
studied models has a different number of adjustable parameters.
Optimization using the Debye–Hückel extended equation with
the inclusion of the parameter d allows the fit to be made in the
entire range of concentration with a very good standard deviation.
Whether the extended terms are considered or not does not sig-
(4)
nificantly alter the results. Both the a and c parameters are within
the expected order of magnitude, with the exception perhaps of
(4a) Up to 50–60 wt.% of formamide, the values of a are of the order of
the sum of the crystallographic radii of Na+ and Cl− (3.76 Å) [43].
Above 60 wt.% of formamide, which approximately corresponds to
(4b) a molar fraction of 0.4, the a values increase considerably, which
may be explained as an increase in the presence of formamide in
the solvation layer, as will be discussed later.
With respect to ion association, according to Bjerrum’s theory
[44], the ion pair formation requires an interionic distance smaller
than the critical one, q, defined as:
q = |z+ z− | e2 /2εr kB T (6)
(4c)
where all the symbols have their usual meaning. The said values
are shown in the last column of Table 2. As in the correspond-
ing systems containing NaF, Fig. 2 clearly shows that for the
formamide–water mixture (a–q) is always positive and it increases
with the co-solvent percentage, indicating that ion pair formation
is not enhanced in these media. On the contrary, for organic–water
(5) ethanol [1], ethylene glycol [15], acetonitrile [15] or 1,4-dioxane
[15], in the same Fig. 2 it is seen that (a–q) is negative and decreases
with this co-solvent percentage, indicating that an increase in ion
association takes place. In Fig. 2 are also shown the corresponding
values for NaCl in urea–water, which were interpolated from the
isopiestic data obtained by Bower and Robinson [45]. In this case,
as occurred with NaF in ethylene carbonate–water [3], it remains
unclear whether ion association takes place, since the difference
(a–q) is small and practically constant in the range of percentages
of urea or ethylene carbonate under study. It should be pointed
out that neither urea nor ethylene carbonate is a liquid at the nor-
mal working temperature of 25 ◦ C (their melting points are 132.7
and 36.4 ◦ C, respectively) and many authors therefore consider that
mixtures of these with water should not really be called solvent
mixtures [22].
 120
Table 3
Summary of both standard emf for the cell Na-ISE|NaCl(m), formamide (Y), H2 O(100 − Y)|Cl-ISE and the NaCl ionic parameter values obtained for the Debye–Hückel (DH), Pitzer (P) and Scatchard (S) equations, in the different
formamide–water mixtures at 298.15 K.

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

0 −262.29 ± 0.19 4.06 ± 0.17 0.0504 ± 0.0041 0.0013 ± 0.0005 0.65 −262.31 ± 0.18 0.0765* 0.2664* 0.0019* 0.61 −262.21 ± 2.38 0.75 −262.27 ± 0.03
10 −268.85 ± 0.54 3.36 ± 0.35 0.0621 ± 0.0083 0.0013 ± 0.0011 0.19 −268.31 ± 0.48 0.0828 ± 0.0051 0.1609 ± 0.0433 0.0004 ± 0.0018 0.17 −266.00 ± 0.94 0.11 −268.05 ± 0.55
20 −269.85 ± 0.41 3.53 ± 0.32 0.0867 ± 0.0070 −0.0035 ± 0.0070 0.33 −269.57 ± 0.34 0.1087 ± 0.0044 0.1525 ± 0.0330 −0.0103 ± 0.0014 0.28 −268.70 ± 0.16 0.09 −269.37 ± 0.34
30 −274.04 ± 0.64 3.65 ± 0.57 0.0974 ± 0.0114 −0.0059 ± 0.0015 0.44 −273.78 ± 0.33 0.1185 ± 0.0077 0.1478 ± 0.0576 −0.0154 ± 0.0027 0.41 −272.60 ± 0.38 0.13 −273.47 ± 0.44
40 −279.64 ± 0.58 2.75 ± 0.53 0.1332 ± 0.0148 −0.0122 ± 0.0019 0.38 −279.34 ± 0.56 0.1470 ± 0.0087 0.0286 ± 0.0607 −0.0291 ± 0.0033 0.37 −277.55 ± 0.93 0.28 −278.82 ± 0.64
50 −285.67 ± 0.38 3.25 ± 0.50 0.1283 ± 0.0135 −0.0133 ± 0.0024 0.35 −285.54 ± 0.35 0.1462 ± 0.0095 0.0599 ± 0.0474 −0.0333 ± 0.0044 0.32 −284.62 ± 0.12 0.07 −285.28 ± 0.33
60 −289.72 ± 0.45 4.29 ± 0.72 0.1333 ± 0.0130 −0.0185 ± 0.0026 0.32 −289.70 ± 0.40 0.1554 ± 0.0111 0.1418 ± 0.0557 −0.0454 ± 0.0054 0.31 −288.31 ± 0.42 0.16 −289.24 ± 0.47

70 −297.11 ± 0.49 5.69 ± 1.65 0.1090 ± 0.0209 −0.0111 ± 0.0098 0.35 −297.21 ± 0.42 0.1287 ± 0.0353 0.2242 ± 0.1155 −0.0289 ± 0.0257 0.35 −297.08 ± 0.49 0.35 −297.08 ± 0.06
−296.92 ± 0.33 0.0895 ± 0.0058 0.0895 ± 0.0058 – 0.36

80 −303.78 ± 0.63 8.00 ± 2.09 0.1245 ± 0.0211 −0.0273 ± 0.0078 0.28 −304.17 ± 0.48 0.1400 ± 0.0322 0.3334 ± 0.1073 −0.0614 ± 0.0240 0.29 −303.75 ± 0.63 0.27 −303.74 ± 0.18
−303.26 ± 0.40 0.0581 ± 0.0051 0.5946 ± 0.0416 – 0.36

F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126

90 −315.34 ± 0.55 7.42 ± 2.07 0.1495 ± 0.0279 −0.0505 ± 0.0129 0.28 −315.61 ± 0.44 0.1638 ± 0.0428 0.3145 ± 0.0279 −0.1154 ± 0.0388 0.29 −315.32 ± 0.55 0.28 −315.25 ± 0.19
−314.72 ± 0.44 0.0381 ± 0.0095 0.7606 ± 0.0581 – 0.40

100 −329.36 ± 0.20 30.57 ± 2.93 0.0189 ± 0.0022 0.000 ± 0.0010 0.08 −330.38 ± 0.23 −0.3058 ± 0.0866 1.3671 ± 0.1791 0.3973 ± 0.1173 0.13 −329.25 ± 0.43 0.09 −330.01 ± 0.43
−331.05 ± 0.23 −0.0112 ± 0.0137 0.7644 ± 0.0538 – 0.24

0 −262.18 ± 0.06 4.06 ± 0.08 0.0504 ± 0.0020 0.0013 ± 0.0002 0.25 −262.18 ± 0.07 0.0765* 0.2664* 0.0019* 0.27 −262.07 ± 0.59 0.32 −262.14 ± 0.04
*
Fixed values.
of the inverse of the relative permittivity.
eters, c (䊉) and d (), for NaCl in formamide–water mixtures at 298.15 K, as a function
Fig. 3. Plot of Pitzer’s parameters, ˇ0 (), ˇ1 (), C ( ), and Debye–Hückel’s param-

relative permittivity for the different formamide–water mixtures.

Pitzer equation (ˇ0 , ˇ1 and C ) are plotted against the reciprocal of
the equation of Debye–Hückel (c, d), and those obtained with the

of these factors.
and ˇ1 parameters, which govern the coefficient, absorb the effect
coefficient is a complicated function of many interactions and ˇ0
ion sizes, and the distance of closest approach. The second virial
take into consideration the differences in the solvation of the ions,
the same for all electrolytes of the same valence type and does not
dynamic treatment of electrolyte solutions, the electrostatic term is
at all concentrations studied. As is well known in Pitzer’s thermo-
able values to be obtained for E0* with good standard deviations

E: ethanol, EG: ethylene glycol, U: urea).

the wt.% co-solvent. (AC: acetonitrile, F: formamide, M: methanol, DI: 1,4-dioxane,
Fig. 2. Values of (a–q) for NaCl in organic–water mixtures at 298.15 K as a function of
In Fig. 3, both the parameters of ionic interaction in the fit with

Optimization using the Pitzer equation also allowed reason-

 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126 121

Both the ion-interaction parameter of the Debye–Hückel equa-

tion, c, and the parameters of the Pitzer equation, ˇ0 (which can
be identified with interactions of like and unlike charged ions) and
ˇ1 (which can be identified with the interactions between unlike-
charged ions) change linearly with 1/εr , although the uncertainty
in the determination of this last parameter, plotted by error bars, is
much greater than for the others. Although in the Pitzer thermody-
namic treatment there is no explicit dependence of ˇ0 on relative
permittivity of the solvents, it was found [35,38] that the radial
distribution function at hard-core contact (g+− , g++ and g−− ) was
a function of the relative permittivity, which may be the cause of
the variation of ˇ0 . On the other hand [35,38], in the discussion
of hard-core effects on osmotic and activity coefficients in terms
of the Debye–Hückel theory, Pitzer has pointed out that ˇ1 would
be a function of 2 ( being the reciprocal of average radius of ion
atmosphere), that involves the reciprocal of relative permittivity.
Thus the linear dependence of ˇ1 on 1/εr observed in this study is
reasonable.
Although Fig. 3 presents the usual linear variation profile of ˇ0 Fig. 4. Plot of log  vs. m1/2 for NaCl in formamide–water at 298.15 K.

and ˇ1 with 1/εr , a break point is also observed around 50–60 wt.%
of formamide, where a change in slope takes place (also for parame-
ter c). This same break was observed by Gupta [38] for LiCl, NaCl and
KCl in methanol–water mixtures and accounted for on the basis of a
more fundamental change in ion–solvent and ion–ion interactions.
Nonetheless, it is clear that more high-precision measurements are
required before the variation of the parameters with the properties
of the medium can be fully understood.
In relation to the parameters d and C (which represents triple
ionic interactions) it is not a simple matter to reach conclusions con-
cerning their variation with 1/εr . It is also interesting to note that
the Debye–Hückel ion-interaction parameters c and d are numeri-
cally close to the Pitzer parameters ˇ0 and C , respectively.
The average values for E0* which appear in the last column of
Table 3 were calculated considering the three models studied. These
average values were used to calculate the mean ionic coefficients
 which are listed in Table 1 for each molality of NaCl and each
percentage weight of formamide. The standard deviations of our
activity coefficients compared to those reported in the literature
were calculated to be less than ±0.003 in pure water, showing good
agreement between both sets of data, particularly if the wide range
of concentrations studied is taken into account.
Fig. 4 shows log  vs. m1/2 for several of the percentages in weight
of formamide studied as well as for pure water. The broken line
corresponds to NaCl activity coefficients obtained by way of the
Debye–Hückel limiting law in pure water. Likewise, for comparison
purposes, in Fig. 5 is shown the log  vs. m1/2 variation for three wt.%
of co-solvent, both for the mixtures with ␧-increasing co-solvent,
formamide–water and urea–water, and for those with ␧-decreasing
co-solvent, methanol–water and ethanol–water. The following are
noteworthy points from Figs. 4 and 5:
All the curves show a typical profile of the variation of log  with
concentration which, as is well known, is governed by two types
of short-range interactions [32,33,46], including those of ion–ion
(“ion-pair”) and ion–solvent (“solvation”).
(a) Regarding those obtained in pure water, for each given con-
centration, log  clearly increases with the wt.% of co-solvent
(increase in dielectric constant) in mixtures with ␧-increasing
co-solvent and decrease with the wt.% of co-solvent (decrease in
dielectric constant) in mixtures with ␧-decreasing co-solvent.
Noting, as shown by various authors [32,33,46–48], that when
ion-pair association decreases, ionic solvation increases and
viceversa, it is concluded that in the system containing for-
mamide or urea as co-solvent the ion–solvent interactions
(solvation) are much more important than the ion–ion inter-
actions (association), in contrast with the methanol–water and
ethanol–water mixtures, in which association may be favoured
with respect to solvation.

Fig. 5. Plot of log  vs. m1/2 for NaCl in organic–water mixtures with 20, 40 and 60 wt.% of co-solvent at 298.15 K (F: formamide, M: methanol, E: ethanol and U: urea).
*
54.57 wt.% of urea.
122 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126

(b) Given that all measurements were carried approximately to sat-

uration molality, it is clearly observed that the solubility of NaCl
decreases in all the cases with the increase of the wt.% of co-
solvent, both for ␧-increasing or ␧-decreasing co-solvent. No
direct relationship appears to exist therefore between solubility
and ionic association.

◦
The standard Gibbs energy of transfer, Gt (“medium effect”)
[49–51], is probably one of the most useful parameters available
for understanding the different behaviours of a solute in both pure
and mixed solvent. It is defined as the difference between the stan-
dard Gibbs energy per mole of electrolyte in a pure solvent, usually
water, and that in another pure or mixed solvent. It is a measure
of the change in the total solvation energy of the solute when it is 0
Fig. 6. Test of the Born equation for the variation of Em against the inverse of the
transferred from one solvent to another at infinite dilution, so as to relative permittivity.
remove the complicating effects of solute–solute interactions, and
it can be easily calculated from the values of E0* according to the
expression [1–3,29]:
 mw  w 
◦
Gt = RT ln = −nF(Es0 − Ew
0
)
ms  s
asym asym
= −nF[(Es0∗ − Ew
0∗
) − (Es − Ew )] (7)

where E0 , E0* and Easym stand for the standard potential, the appar-
asym asym
ent standard potential and the asymmetry potential (εNa + εF ),
respectively. Subscript s refers to mixed solvent and w to water.
All the other symbols have their usual meaning. As mentioned
previously, in our case, Easym is a constant value with time and
independent of the composition of the solvent (the asymmetry
potential of an electrode depends on the characteristics of the mem-
brane and not on the medium in which it is immersed [52,53]),
asym asym
which allows us to affirm that (Es − Ew ) is negligible com-
pared to (Es0∗ − Ew0∗ ), and thus Eq. (7) may be used without any

problems.
◦
Prior to calculation of Gt , the Born condition for the func-
0*
tional dependency of E with 1/εr was tested. A linear variation
(cor = 0.998 and  < 1.0 mV) of the standard emf with the recipro-
cal of the dielectric constant is presented in Fig. 6, at least to the Fig. 7. Plot of the standard Gibbs energy of transfer vs. wt.% of co-solvent for
NaCl and NaF at 298.15 K. () NaCl–water–formamide, () NaCl–water–methanol,
40–50 wt.% of formamide, approximately. ( ) NaCl–water–ethanol, (䊉) NaF–water–formamide, () NaF–water–methanol, ()
Fig. 7 shows a plot of the standard Gibbs energy of trans- NaCl–water–ethanol.
◦
fer, Gt , for both NaF and NaCl, against wt.% co-solvent in the
formamide–water, methanol–water and ethanol–water mixtures.
◦ For the purpose of discussing the behaviour of each ion in these
The positive values of Gt suggest that the process of disso- ◦
mixtures, it would be worthwhile to split the value of Gt into its
lution is not favoured in any of the cases. Also the increasing
ionic components. That is:
order of energies for a given wt.% of co-solvent (formamide–water
◦ ◦ ◦
<methanol–water <ethanol–water) could indicate that both NaF Gt = Gt,Na+ + Gt,X− (8)
and NaCl are more solvated in the formamide–water mixtures than
in the alcohol–water mixtures and that, in turn, NaCl would always Since no thermodynamically precise method exists to carry
be more solvated than NaF. out the said ionic splitting, it is customary to resort to different

Fig. 8. Plot of the ionic standard Gibbs energy of transfer vs. wt.% of co-solvent for () Na+ , () Cl− and ( ) F− at 298.15 K.
 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126 123

assumptions that use a reference electrode in order to establish a

comparative scale [51]. One of the most widely used assumptions
is TATB, that utilizes tetraphenylarsonium tetraphenylborate as ref-
◦
erence electrode. Thus, utilizing the values of Gt,Na+ tabulated by
Kalidas et al. [51], ionic splitting of the standard Gibbs energy of
transfer was achieved as shown in Fig. 8 for the different systems
being compared.
As can be seen, with the exception of Na+ in formamide–water,
◦ ◦
Gt,i always increases with the co-solvent content. Gt,i is
◦
assumed to be composed of an electrostatic contribution, Gt,i (el),
◦
a non-electrostatic contribution, Gt,i (non − el), and/or a short-
◦
range contribution, Gt,i (sr) [54]. The sum of the first two
contributions for Na+ in formamide–water has been estimated
by Suzuki [54] and was between 0 and −2 kJ mol−1 and were
almost independent of the formamide content in the mixture. Thus,
the short range interaction cannot be neglected for Na+ because
◦
Gt,Na+ values become more negative than −2 kJ mol−1 , as the for-
mamide content increases, reaching −8.2 kJ mol−1 at 100 wt.% of 0
Fig. 9. Variation of ln Ksp,s of NaCl on the wt.% co-solvent at 298.15 K. ()
formamide. This suggests that Na+ is solvated preferentially by for- NaCl–water–formamide, () NaCl–water–methanol ( ) NaCl–water–ethanol (䊉)
mamide molecules which replace water molecules in the solvation NaF–water–formamide () NaF–water–methanol () NaCl–water–ethanol.

sphere of the cations when formamide is added to water.

For the case of the anions, Susuki [54] found that the short-
◦
range interaction also seems to be present because Gt,i values are
more positive than the sums of electrostatic and non-electrostatic
◦ ◦
contribution. In accord with this author, the increase in Gt,i is
not attributable to preferential solvation and can be explained by
the weakening of the hydrogen bond between the anions and water
owing to addition of formamide to water, which may be induced by
the formation of a hydrogen bond between water and formamide.
Although the studies of Susuki [54] are referred to Br− and I− , all the
above appears to indicate that for the ions compared in this work,
Cl− and F− , the behaviour would be analogous.
For the case of the alcohol–water mixtures, the behaviour of
the anions is similar to that which occurs in the formamide–water
mixtures but for the cation Na+ it is totally opposite, that is to say
◦
that a positive increase appears in Gt,Na+ , that corresponds to a
less favourable solvation of the ions compared to water.
A more detailed explanation of the behaviour of these systems
should take into account the properties of the solvent, the ion prop-
erties and the knowledge of the enthalpic and entropic changes
corresponding to the transfer between the two solvents [29,55].
According to Kalidas et al. [51], the standard Gibbs energy of
transfer to the whole salt, Gt , is related to the standard solubility
0
product, Ksp , of the electrolyte in the two solvents by:
◦ 0 0
Gt = RT ln(Ksp,w /Ksp,s ) (9)
0
where Ksp,w 0
and Ksp,s represent the standard solubility product of
NaCl in water (38.051 mol2 kg−2 [30]) and in organic–water mix-
0
ture, respectively. In Fig. 9 a significant decrease of ln Ksp,s with
co-solvent wt.% is clearly observed, both for NaF and for NaCl, in the
order ethanol–water > methanol–water > formamide–water mix-
tures. This agrees well with the order of the NaCl solubility shown
in the plots of Fig. 10, where in addition to the values obtained in
this work for the saturation molality of NaCl in formamide–water
mixtures, are presented those values obtained for the mixtures
methanol–water [56], ethanol–water [56], ethylene glycol–water
[57], glycerol–water [57] and pyridine–water [58].

Fig. 10. Influence of the co-solvent content on the variation of the saturation at 298.15 K. (a) ms vs. wt.% co-solvent; (b) ln(ms /m0s ) vs. molar fraction of co-solvent. ()
formamide, () glycerol, ( ) ethylene glycol, (䊉) pyridine, () methanol and () ethanol.
124 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126

water in the solvent mixture, w , according to:

◦
(Gt )c /F = Ec0 = Ecs
0 0
− Ecw = nhydr (RT/F) ln w (10)

where

Ec0 = Em
0
+ 2k log ds (11)

and

w = (ww /dw )/(ww /dw + wEC /dEC ) (12)

0
Em is the standard electromotive force in molal scale (up to
now we have denoted it E0 for simplicity), nhydr indicates the pri-
mary hydration number of the electrolyte (number of firmly bound
s ) = A(1/εr − 1/εr ). ()
Fig. 11. Test of the Izmailov et al. equation [60]: log(mss /mw s w

formamide (A = 100.2), () glycerol (A = −69.3), ( ) ethylene glycol (A = −73.8); (䊉)
pyridine (A = −77.9), () methanol (A = −89.0), () ethanol (A = −88.4).
Fig. 10a presents the absolute decrease in saturation molal-
ity as the co-solvent content of the mixture increases; Fig. 10b
shows the deviation, with respect to the ideal solubility behaviour
[59], of ln(mss /mw s ) versus the co-solvent molar fraction (ms and
s others), and has obtained quite reasonable results [1–3,24–26]. This
w
ms represent the saturation molality in water and in the mix-
ture). It can be observed that the said deviation is minimal in
(Es0∗ − Ew 0∗ ). Note that no extra-thermodynamic
moles of water per mol of electrolyte) and all the other symbols
have their usual meaning. Eq. (10) is only fulfilled in mixtures
rich in water and, in principle, is thermodynamically exact only if
E0 means standard electromotive force of reversible cell [62,63].
Nonetheless, our research group has applied the said equation
to cells containing selective electrodes (cells that are not exactly
reversible, due to the presence of the asymmetric potential, among
“stroke of luck” is possibly due to the fulfilment of the condition
asym asym
(Es − Ew )

the formamide–water mixture and maximal in pyridine–water, the
excess solubility function being positive for the pyridine–water and
ethanol–water mixtures and negative for the remainder. A wider
discussion on the sign of this excess function can be found in the
work of Lorimer [59].
In Fig. 11 a plot is given of log(mss /mw s w
s ) versus ((1/εr ) − (1/εr )),
an approximately linear behaviour being observed, similar to that
obtained by Izmailov et al. [60] for several electrolytes in dif-
ferent alcohol–water mixtures. Two aspects of this plot can be
pointed out: On one hand, the positive value of the slope for
the formamide–water mixture (a consequence of the ␧-increasing
behaviour of formamide) in contrast to what occurs with the other
mixtures. On the other hand, the similarity between the slopes of
the methanol and ethanol containing mixtures, possibly due to the
similar chemical nature of both co-solvents. Although ethylene-
glycol (ethane-1,2-diol) and glycerol (propane-1,2,3-triol) are also
alcohols, their slopes are quite different due to the presence of two
and three OH groups, respectively.
Finally, in order to complete the thermodynamic description
of NaCl dissolved in formamide-water, an interesting correlation
deduced by Feakins and French [61] will be utilised and which has
been widely used and discussed by Mussini et al. [7,15,62]. For a
1:1 electrolyte, the said correlation connects the primary medium
◦
effect on the molal scale (Gt )c with the volume fraction of the
supposition has been imposed a priori for this research to be car-
ried out. It is worthwhile to remember that earlier Bald [29] verified
that the effect of the asymmetric potentials upon the determina-
◦
tion of Gt did not prove to be significant and can be disregarded.
Likewise, Clune et al. [64] stress the excellent agreement found
◦
between the values of Gt obtained with amalgam electrodes and
◦
those obtained with selective electrodes. Moreover, Gt , it does not
necessarily have to be calculated by means of electromotive force
measurements, but rather it can be obtained by way of an isopiestic
method or by a solubility-measurement method [21].
Fig. 12 is a plot of Ec0 vs. (RT/F) ln w , showing a very good linear
relation (r = 0.999) up to 40 wt.%, approximately, with the value of
nhydr obtained for NaCl of 3.1. The same value is found in this case if
the improvement proposed by Faverio et al. [62] is used to take into
account the fact that the correlation is valid for water-rich zones
and consists in calculating (dEc0 /d ln w )w =1 .
In Table 4 are given the values of nhydr obtained for NaCl
in different aquo-organic mixtures, together with the more rel-
evant properties of the co-solvents compiled from the literature
[21,22,41,65]. The corresponding values for NaF are also shown for
comparison purposes.
Falciola et al. [63], who presented an interesting review of
Feakins’ theory, state that five contributions to the primary medium
effect should be considered each one described by the variation,

Table 4
Primary hydration number, nhydr , of NaF and NaCl, obtained by Feakins and French methods [61] for co-solvent+water mixtures at 298.15 K.

Co-solvent V (cm3 mol−1 ) εr

(D) ˛ (10−30 m3 ) DN (kcal mol−1 ) AN (kcal mol−1 ) nhydr (NaF) nhydr (NaCl)

Water 18.1 78.4 1.83 1.46 18.0 54.8 (8 ± 2)a (6 ± 2)a

Formamide 39.9 110 3.37 4.23 36.0 39.8 4.0c 3.1f
Ethylene Carbonate 66.6 89.8 4.87 6.69 16.4 – 2.9d –
Methanol 40.7 32.7 2.87 3.26 19.0 41.3 6.0e 7.4g
Ethanol 58.7 24.6 1.66 5.13 32.0 37.1 7.0e 7.2g
Ethylene Glycol 55.9 37.7 2.28 2.28 20.0 40.7b – 3.4g
Acetonitrile 52.9 37.5 3.44 4.41 14.1 18.9 – 4.4g
1,4-Dioxane 85.7 2.21 0.45 8.60 14.8 10.4 – 7.0g
a
Ref. [66].
b
Ref. [67].
c
Ref. [2].
d
Ref. [3].
e
Ref. [1].
f
This work.
g
Ref. [15].
 F. Hernández-Luis et al. / Fluid Phase Equilibria 275 (2009) 116–126 125

Ext contribution of the extended terms of Debye–Hückel

equation
e electron charge
F Faraday constant
◦
Gt standard Gibbs energy of transfer
I ionic strength
ISE ion selective electrode
0
Ksp standard solubility product constant
k Nernst’s theoretical slope [(ln 10)RT/F = 59.158 mV at
25 ◦ C]
kB Boltzman constant
M average molecular mass of mixed solvent
m molality
n number of electrons
nhydr primary hydration number
q Bjerrum interionic distance parameter
R gas constant
Fig. 12. Plot of Ec0 vs. a function of the water volume fraction for NaCl in T absolute temperature
formamide–water mixtures at 298.15 K. wt.% weight percent

with respect to water, of a specific physical property, namely: Greek letters

relative permittivity ε (accounting for ion–dielectric interaction), ˛ polarisability
dipole moment
(accounting for ion–dipole interactions), donor ˇ0 , ˇ1 solute-specific interaction parameters of Pitzer equation
or acceptor numbers DN and AN (accounting for solvent cation and  mean ionic activity coefficient
solvent anion acid–base interactions, respectively), and polarisabil- εr relative dielectric constant
ity ˛ (accounting for induced dipole-induced dipole interactions). w Volume fraction of water in the mixed solvent
Logically, in accord with Eq. (10), these same five contributions will
dipole moment
also appear to influence the values of the primary hydration num-  density
bers, nhydr , shown in Table 4. In a simplified manner and in accord  standard deviation
with Mussini et al. [7,62,63], it appears that an essential condition
for reliable determinations nhydr is that in the aquo-organic solvent, Subscripts
the organic component must have a dipole moment close to 0, to c molar scale
avoid competitive solvation. Indeed, for NaCl in formamide–water, m molal scale
a value of 3.1 is obtained for nhydr , which is lower than the value s mixed solvent
(6 ± 2) given by Bockris and Reddy [66], as the mean of diverse t transfer
methods of determination. This is due to the value of
= 3.37 D w water
for formamide (quite larger than that of water,
= 1.83 D) and that
prone to solvate preferentially the cations thus displacing water Acknowledgement
from the primary hydration sheath.
The same occurs with NaCl in ethylene glycol–water and The authors thank the ORI (Oficina de Relaciones Interna-
acetonitile–water and with NaF in formamide–water and ethylene cionales), La Laguna University which made possible the stay of
carbonate–water. Values closer to those of Bockris and Reddy [66] H.R.G.
are obtained when the co-solvent used is methanol, ethanol and,
above all, 1,4-dioxane that has a dipole moment of 0.45 D. References
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