IONIC HYDRATION

MODEL
FOR UNI-UNIVALENT
ELECTROLYTES.
CALCULATION
OF THE MEAN
HYDRATION
NUMBER
FROM EXPERIMENTAL
SOLUTE
ACTIVITY
COEFFICIENT
AND WATER ACTIVITY
DATA
M.R.

GENNERODECHIALVO~II~

A.C.

CHIALVO

Programa de Electroquimica Aplicada e lngenieria Electroquimica (PRELINE), Facultad de Ingenieria

Quimica (U.N.L.), Santiago de1 Ester0 2829, 3000 Santa Fe, Argentina
(Received

16 July 1985; in revisedform 14 July 1986)

Abstract-A
new thermodynamic treatment is proposed to evaluate the mean hydration number and to
correlate the experimental mean molal activity coefficients. The model is interpreted in terms of consecutive
hydration equilibria. The results are comparable to those given in the literature.

NOMENCLATURE

A,,
i
_i
m

l?Z*
n1

n:
n2

Y
Y

PSRS
IDSRS

distance of closest approach

solvent activity (PSRS, scale concentration:
molar fraction)
mean hydration number
mean ionic hydration number
hydration degree of the cation
hydration degree of the anion
molality (referred to the total solvent)
molality (referred to the free solvent)
number of moles of free solvent
number of moles of total solvent
number of moles of solute (electrolyte as a
whole)
number of moles of the i-hydrated cation
number of moles of the j-hydrated anion
anion
cation
ionic specific constants
chemical potential of the solvent
chemical potential of the solute
chemical potential of the i-hydrated cation
chemical potential of the j-hydrated anion
standard state chemical potential of the solute
(IDSRS, scale concentration: molality)
activity coefficient (IDSRS, scale concentration: molar fraction)
activity coefficient (IDSRS, scale concentration: molality)
mean ionic activity coefficient (scale concentration: molality)
mean ionic activity coefficient (scale concentration: molar fraction)
Perfect Solution Reference State
Ideal Solution Reference State

INTRODUCTION
Different
ionic hydration
models[l-61
have been
proposed to quantitatively
explain discrepancies observed between the experimental activity coefficients of
aqueous electrolyte solutions and the theoretical ones
calculated using the Debye-Huckel
equation. More
recent
theoretical[7-91
and
experimental[ 10-121
331

studies have shown that water structure surrounding

an ion in solution cannot be described by simple
models such as those included in the previously
mentioned literature. In this respect, an important step
forward was made by Stokes and Robinson[13]
by
extending their primitive model and taking into account the occurrence of consecutive equilibrium steps
in the cation hydration process. Critical comments
were made since anion hydration was neglected in their
model and there is enough experimental evidence on
both ions being hydrated[1&12].
Besides, similar
models for the anion hydration
in gas phase had
already been developed[ 14, 151.
This paper describes a new approach
to ionic
hydration, taking into account the ion-solvent interaction of both species. On this basis, the mean hydration
number of uni-univalent electrolytes is evaluated.

FUNDAMENTALS
The behavior of water molecules around an ion in
solution may be described by the changes produced in
their spatial distribution. In the closest region around
simple ionic species, the solvent exhibits a more
ordered structure.
This order decreases with an increasing distance to the ion, the mobility of water
molecules consequently increasing. A dynamic equilibrium between both free and bound solvent molecules is
thus established. This description ignores the presence
of other species originated by ion-ion interactions such
as ion-pairing,
dissociation
equilibria,
etc.
Consequently,
this model based on a mechanism
of
consecutive
hydration equilibria is restricted to the
case of simple, uni-univalent, unassociated electroiytes
having low to moderate concentrations.
The fundamental hypotheses in the proposed model
are:
(a) The hydration process is developed through a
series of consecutive equilibria:
A- +jH20=[A(H10)j]-

0 <j

< S(m)

(1)

C+ + iHzO+[C(H,O)i]+

0 =5 i < S(m).

(2)

M. R. GENNERO DE CHIALVO AND A. C. CHIALVO

332

The assumed extreme value for the hydration of

each ion is S(m) = 55.51/2 m, which corresponds to the
maximum availability of solvent molecules for each
ion.
The total free energy of the solution may be written
as
S(m)

SW

G=

%PI

n(iMj)+

WA4

(3)

i=o

j-0

and also in the form

By considering

and the following

(6)

S(m)

S(m)

S(m)

j=O

Equations

n(i).

(8)

i=o

(3)-(8)

p2 = p( j = 0) + ~(i = 0).
the chemical potentials

(9) in the ideal dilute solution

reference
state
(IDSRS-scale
concentration: molality) and taking into
account that the molal concentration
of a hydrated
species is m* (j) = m(j)/(l
-0.018 m2 h), the following
can be obtained:

= O)m*(i

= p (j = 0) + p (i = 0)
= O)[y,

(j = 0, i = O)]}.
(10)

By reordering Equation (10) and taking limit values,

the equation of the solute chemical potential becomes:
&

= p (j = 0) + pO(i = 0) + RT In x( j = 0) x(i = 0)
(11)

(14)

= O)x(i = 0)

(15)

= x(j)

(12)

lim m*(i)
__
= x(i).
mJ-~ m2

(13)

Equations (12) and (13) give the ratio between the

species having a given hydration degree (j or i) and the
total of species having different hydration degrees, at
infinite dilution
for the anion and the cation,
respectively.
From Equations (lo)-(13), a basic relation between
the exnerimental and the mean ionic activity coefficient
corresponding
to the non-hydrated
ionic species is

condition:

m2mzh)
m: = (1 - 0.018

(16)

where the mean hydration number, which is the sum of

the mean ionic hydration numbers of the anion and the
cation, is defined as:
s(m)
s(m)
1 jm*(j)
C im*(i)
h=h,+h,=j=mr
By combining

+=Om$

Equations

= 0) =

(17)

(15) and (16)

m2

.(18)

A similar equation can be obtained for the cation.

(b) At infinite dilution, the relation between the
species having a hydration degree j and all hydrated
species has been defined as x(j). It is assumed that the
amount of the anhydrous species [x( j = 0)] as well as
that of highly hydrated species [x(j B hA)] are negligible. Hence, the functional dependence between x(j)
and the hydration degree is approached through a
simple distribution law given by:
x(j)

= (x(j

= O)+k,j)K,j

= K(j)x(j

= 0). (19)

By taking into account the boundary condition:

Xx(j) = 1, and considering x(j = 0) & 1, k, can be
eliminated, the x(j) expression becoming:
j2K;j

(20)

x(j) = _,

where
lim m*(j)
~
m2-10 m2

= m:x(j

boundary

jzom*(i)

(9)
in Equation

m*(j

/1; + RTln (mz y:,,)

with the following

(7)

in(i)

i=o

n(j)

The resolution of Equation (14) requires first to

evaluate the concentration
of non-hydrated
ions.
Using the hydration equilibrium constants of the
reaction (l), Equation (5) and developing the solvent
chemical potential in the perfect solution reference
state (PSRS-scale
concentration: molar fraction), it
follows:

SW

j=O

+ RTln {m*(j

y+ (j = 0, i = 0)

S(m)

n1 = n, + 1 in(j)+ C
C

m*(j = O)m*(i = 0)

m*(j)=r.(~~o)i_(j=O)

mass balances:

n2 =

r;,,

(5)

= di = 0) +jh

p(i) = p(i = O)+ip,

By developing

(1) and (2)

di)

From

obtained:

For the cation, a similar equation is obtained. The

hydration
constant can also be written as K(j)
= x(j)/x(j
= 0). Therefore, by combining Equations
(18) and (20), and assuming that m(j = 0) 4 I: m(j > l),
it follows that:

m*(j

= 0) =

Hi = 0)

(21)

Ionic hydration model for uni-univalent electrolytes

where activity coefficients

remain to be evaluated.
(c) Finally, it should be noted that, apart from the
coulombic
effect, there is a contribution
to deviation
from the ideal behavior due to the increase in the ionic

species size with an increasing hydration

degree.
Conway and Verrall[16]
analyzed this effect by splitting the activity coefficient into two contributions (y
= y,y.,), where ye is the activity coefficient calculated
using the Debye-Hucket
equation and y,, is the nonelectrostatic contribution in this case given by:

Y,(i 2 1) =

m*(j)
(-+55.5J
m2

m2

.m*(i)

55.51
I -_

r
x

m2

~m*(A

Table 1. Sodium chloride

>
m

0.1

2.521
2.518
2.515
2.512
2.509
2.506
2.503
2.499
2.496
2.493
2.486
2.419
2.471
2.464
2.456
2.435
2.412
2.387
2.360
2.330
2.296
2.258
2.218

m2

55.51
--_+++_.
1 m2 Jm2 jJ
1.

(22)

(23)

Taking into account Equation (23), and considering

that the electrostatic effect is the same for both species,
it follows
y(j)ly(j

the DebyeHuckel
expression. In the latter, the molar
concentration
was employed in ionic strength calculations, the distance of closest approach being taken as
adjustable parameter.
The following
electrolytes
were analyzed: NaCl,
NaBr, LiCl, LiBr. KC1 and KBr. Tables 1-6 show the
results obtained by computer calculations, the variation of the mean hydration number being given as a
function of electrolyte
composition.
Similarly, the
experimental activity coefficients are compared with
those correlated using Equation (26), such comparison

exp(j--1)

m*(j)

yne(j=O)=

333

= 0) = r.,(j).

(24)

Expressions similar to Equations (19b(24) are obtained for the cations.

The molality activity coefficient y* (j = 0, i = 0), on
the other hand, is calculated using the molar fraction
activity coefficient y + (j = 0, i = 0) which is obtained
from the Debye-Huckel
expression, using the following conversion equation[l]
y,~ ci = o i = o) = Y f (j = 0, i = O)(L -O.Olgm&)
,
[l-O.O18m,(h-v)]

0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0

Yexo
0.778
0.735
0.710
0.693
0.681
0.673
0.667
0.662
0.659
0.657
0.654
0.655
0.657
0.662
0.668
0.688
0.714
0.746
0.783
0.826
0.874
0.928
0.986

&al
0.775
0.730
0.105
0.689
0.678
0.67 1
0.666
0.662
0.660
0.659
0.659
0.662
0.665
0.671
0.677
0.696
0.722
0.755
0.190
0.830
0.873
0.924
0.976

(25)
By introducing Equations (21) and (25) in Equation
(14), the final expression relating experimental data
with the parameters of the proposed model is:

Table 2. Lithium chloride

m

The other expressions

needed for numerically
evaluating
Equation
(26) are obtained
replacing
Equation (21) in Equations (17) and (22).

RESULTS
The calculation of mean hydration numbers was
made using experimental data on ionic activity coefficients and water activity at 25C, the concentration
ranging from 0.1 to l.Om[17].
The correlation
was
carried out, at each concentration,
by applying
Equation (26)along with Equations (17), (21), (24) and

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0

h
4.941
4.907
4.872
4.836
4.798
4.174
4.745
4.702
4.670
4.628
4.554
4.488
4.410
4.317
4.260
4.063
3.770
3.611
3.435
3.304
3.203
3.105
3.024

ysxp
0.790
0.757
0.744
0.740
0.739
0.743
0.748
0.755
0.764
0.774
0.196
0.823
0.853
0.885
0.921
1.026
1.156
1.317
1.510
1.741
2.020
2.340
2.720

Yt
0.799
0.755
0.741
0.735
0.735
0.737
0.742
0.749
0.757
0.766
0.788
0.813
0.841
0.878
0.904
0.991
1.098
1.223
1.356
1.524
1.712
2.129
2.223

M. R. GENNERO DE CHIALVO

334
Table

3. Potassium

Table

Yex,

&II

0.1
0.2
0.3
0.4
0.5

2.078
2.078
2.077
2.077
2.076

0.770
0.718
0.688
0.666
0.649

0.762
0.711
0.681
0.661
0.646

Z:!:
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5

2.076
2.075
2.075
2.074
2.074
2.073
2.072
2.070
2.069
2.068
2.066
2.064
2.061
2.059
2.056

0.637
0.626
0.618
0.610
0.604
0.593
0.586
0.580
0.576
0.573
0.569
0.569
0.572
0.577
0.583

0.635
0.626
0.619
0.614
0.610
0.604
0.601
0.599
0.599
0.600
0.607
0.614
0.633
0.650
0.670

4. Sodium

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0

2.712
2.707
2.702
2.697
2.692
2.687
2.681
2.676
2.670
2.665
2.655
2.640
2.637
2.619
2.606
2.578
2.545
2.504
2.464

A. C.CHIALVO

chloride

Table

AND

Ysxp

0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0
5.5
6.0

5.123
5.092
5.061
5.030
4.997
4.964
4.929
4.893
4.855
4.817
4.736
4.623
4.526
4.423
4.325
4.110
3.915
3.705
3.535
3.470
3.245
3.140
3.070

bromide

Y&i

0.782
0.741
0.719
0.704
0.697
0.692
0.689
0.687
0.687
0.687
0.692
0.699
0.706
0.718
0.731
0.768
0.812
0.865
0.929

0.779
0.741
0.718
0.705
0.696
0.691
0.688
0.686
0.685
0.686
0.689
0.695
0.702
0.711
0.721
0.751
0.787
0.828
0.875

being made up to concentrations

appreciably
than the one. used in fitting calculations.

5. Lithium

greater

The specific constants calculated for each ion,

having an inverse dependence on the mean ionic
hydration number, are:

Table

6. Potassium

bromide
7-P

0.796
0.766
0.756
0.752
0.753
0.758
0.767
0.777
0.789
0.803
0.837
0.874
0.917
0.964
1.015
1.161
1.341
1.584
1.897
2.280
2.740
3.270
3.920

Y'cal

0.794
0.764
0.752
0.748
0.750
0.754
0.761
0.770
0.780
0.792
0.818
0.858
0.892
0.930
0.970
1.084
1.218
1.377
1.561
1.785
2.011
2.286
2.609

bromide

0.1
0.2
0.3
0.4
0.5

2.270
2.268
2.266
2.264
2.262

0.772
0.722
0.693
0.673
0.657

0.766
0.718
0.689
0.670
0.656

E
0.8
0.9
1.0
1.2
1.4
1.6
1.8
2.0
2.5
3.0
3.5
4.0
4.5
5.0

0.258
2.260
2.257
2.254
2.252
2.248
2.244
2.240
2.237
2.233
2.224
2.213
2.204
2.196
2.189
2.182

0.636
0.646
0.629
0.622
0.617
0.608
0.602
0.598
0.595
0.593
0.593
0.595
0.600
0.608
0.6 16
0.626

0.648
0.641
0.635
0.630
0.626
0.623
0.623
0.622
0.622
0.627
0.639
0.655
0.674
0.694
0.718
0.749

YeXp

YL

KLi: 2.15
K,,:
K,:

DISCUSSION

9.0
140.0

K,,:

80.0

K,,:

17.0

and the values for the a constant obtained for each

salt are:
a&,:

4.16

(I&~~,: 3.89
a&:

3.22

C&s,: 4.47
a&,,:

4.28

agB,: 3.40.

The expression herein dealt with takes into account

different contributions to the experimental activity
coefficient of simple, unassociated, uni-univalent electrolytes for concentrations ranging from 0.1 to 1.0 m.
The influence of ion-ion interaction appreciably decreases as concentration increases. The Debye-Huckel
approach including well-known mechano-statistical
deficiencies, was used to evaluate the coulombic contribution; its use seems adequate since, in the concentration range considered, the contribution of long-range
interactions is lower than the one related to the

Ionic hydration model for u&univalent

hydration process. The ionic hydration phenomenon,
on the other hand, originates a decrease of the free
water content in the solution, thus increasing actual
concentration
and appreciably affecting the activity
coefficient. Finally, deviations from ideality, produced
by species having different size, and stemming from
different ionic hydration degrees, are considered.
The hydration process occurs in successive equilibrium steps between the ions and the solvent, yet
following
an evolution clearly different from that
proposed by Stokes and RobinsonC13J. The variation
of the hydrated species ratio at infinite dilution, x(j or
i). as a function of the hydration
degree (j or i)
corresponds to a distribution of solvation states formally similar to the one experimentally
found by
Kebarle et al.[ 151 for the hydration of ions in the gas
phase, or to the distribution of coordination numbers
theoretically calculated by Chandrasekhar et ~I.[93 for
ions in solution.
The results obtained show an inverse dependence
between the mean ionic hydration number, II,-, and the
ionic radius for the cations. In the case of the anions, h,
increases when the ionic radius increases. These facts
could be explained
by considering
the differention-solvent
interactions
on the part of cations and
anions[ 133.
On the other hand, a direct relation between the
distance of closest approach and the hydration degree
of the electrolyte should be noticed. This fact could be
explained by considering a0 as the sum of the anhydrous ion radius and the average radius of the ionic
species with different hydration degrees, which form
the ionic cloud of the Debye-Huckel
model. For
obtained
for
the
series
example,
the
results
LiCl-NaCl-KC1
show that, despite the cation radius
of the
increasing, a decreases as a consequence
marked reduction of the average radius of the hydrated
species produced by the reduction of the hydration
degree.
Finally, it is concluded that the mean ionic hydration
number, representing a weighted average of the different states occurring in solution. greatly depends on

electrolytes

335

concentration. This can be clearly appreciated in the

case of LiCl, where it was found to have a value close to
5 at infinite dilution, while in a 6 m solution its value
became 3.02. Similar situations are given in the remaining systems analyzed in this work.
Another remarkable fact appeared when analyzing
the prediction capability of the equations developed in
this work: using the parameters correlated at concentrations up to 1 m, a good fitting of the experimental
data at molalities as high as 6 was observed.

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1870 ( 1948).
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