Viscosity measurements and structural properties in aqueous NiCl2 solutions

G. Maisano, P. Migliardo, F. Wanderlingh, and M. P. Fontana

Citation: The Journal of Chemical Physics 68, 5594 (1978); doi: 10.1063/1.435689
View online: http://dx.doi.org/10.1063/1.435689
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Viscosity measurements and structural properties in aqueous

NiCI 2 solutions
G. Maisano, P. Migliardo, and F. Wanderlingh
Istituto di Fisica dell'Universita' and Gruppo Nazionale Struttura della Materia del CNR, Messina, Italy

M. P. Fontana
Istituto di Fisica and Gruppo Nazionale Struttura della Materia del CRN, Universita' di Parma and
Libera Universita'di Trento, Italy
(Received 17 May 1977)

We measured viscosity as a function of concentration in an aqueous solution of NiCI 2 We also measured

compressibility and density in the same system. The data are discussed in the frame of existing
phenomenological theories. In all cases it appears that some structural changes take place at a given
concentration. We also propose a new phenomenological equation that describes the viscosity in terms of a
function of the concentration, that turns out to have a rather universal character being able to describe
also the behavior of other properties such as compressibility and density. The building up of some sort of
structure can easily be revealed by such a treatment, also in comparison with other experimental results.

I. INTRODUCTION
experiments 1 2

On the ground of neutron scattering

and Raman spectroscopy3.4 it has been suggested that
some electrolytic solutions of IT-I salts of transition
metals can exhibit some sort of order at high enough
concentrations.
Thermodynamic considerations, based on an experimental evaluation of the chemical potential 5, 6 also seem
to support this point of view. In particular it seems
that a rather drastic change in the structural properties
of the solution takes place at a given concentration x*,
that in the case of NiCl 2 turns out to be in the range
2X 10- 2 to 3x 10- 2 molar fraction. In particular: (0 The
depolarization ratio, in Raman scattering, experiments,
decreases rapidly as the concentration changes from
o to x* and then stays nearly constant 4; (ii) The long
wavelength limit of the correlation between fluctuations
of concentration in solutions of II-I salts of transition
metals shows, at x*, a departure from the regular behavior, exhibited, for example, by solutions of II-I
salts of alkaline-earth metals 5; (iii) The long wavelength
limit of the cross correlation between the fluctuation of
density and fluctuation of concentration goes to zero at
x*, being positive for concentrations lower than x* and
negati ve for concentrations higher than X*. 6 Such a
circumstance is due to the fact that at the concentration x* the partial molar volumes of both solute and
solvent become equal.
In the present paper we report measurements of viscosity in NiCl 2 solutions at concentrations ranging from
8x10- s molar fraction to the saturation, and at the
temperatures of 20, 30, 40, and 50C. Measurements
of density and compressibility are also performed. The
latter, among other things, allow us to discuss viscosity
data in terms of the Einstein modified theory (see Sec.
III).

The first aim of this work is to show whether these

kinds of electrolytic solutions show any anomalies reflecting possible structural changes in the transport properties.
5594

J. Chern. Phys. 68( 121. 15 Jun. 1978

In Sec. IT we briefly describe our experimental procedure and results. In Sec. III we discuss our experimental data in terms of some semi -empirical equatiom
In each case we show that, although the above-mentioned equation can fit the data, drastic variations take
place at concentrations between 2 x 10- 2 and 3 x 10- 2 mo1ar fraction.
In Sec. IV we propose an empirical equation, based
on the assumption that the relevant quantity is the fractional increase of the viscosity. We will show that this
kind of formalism not only adequately describes our experimental data of viscosity over the entire range of
concentrations, but also the data concerning denSity and
compressibility measurements.
In addition, we shall show that a drastic change takes
place in our system at a concentration X"" 3X 10- 2 molar
fraction. We discuss this result as a further indication
that in the electrolytiC solutions we are concerned with,
the structural properties play an important role and that
at concentrations higher than some critical ones, a
sudden change of structure seems to take place.
II. EXPERIMENTAL PROCEDURE AND RESULTS

As mentioned in Sec. I, we performed measurements

in a solution of NiCl 2 in water. We used an RS purity
grade salt, from which a saturated solution was prepared, filtered, and centrifugated in order to remove
any dust particles that could be troublesome in the viscosity measurement. The obtained saturated solution
was then chemically analyzed for the total Ni content.
We found a saturation concentration of 7. 58 x 10- 2 molar
fraction. This values agrees well with the literature
data of 7. 65x 10-2 7 From this mother solution we prepare our samples by means of successive dilutions. In
any case a given volume of saturated solution is diluted
until a fixed final volume is reached. In such a way we
can obtain directly any molar concentration, whatever
the mixing volume. The knowledge of the density then

00219606178/68125594$01.00

1978 American Institute of Physics

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5595

Maisano, Migliardo, Wanderlingh, and Fontana: Viscosity in aqueous NiCI 2 solutions

details on acoustic velocity and absorption measurements will be given elsewhere. 9

Our experimental results concerning the viscosity
measurements are shown in Fig. 1. Each curve refers
to a different temperature. As can be shown the viscosity shows a dramatic increase as a function of the
concentration. Such an increase turns out to be noticeably more pronounced than that usually found in electrolytic solutions of salts other than those with which we
are concerned.
<i
u

III. SEMIEMPIRICAL EQUATIONS

O~-L~2~O--~~

60
3

80

In this section we briefly 'discuss our experimental

data in the frame of some semiempirical equations. At
very low concentrations, in the range of validity of the
Debye-Hiickel theory, the contribution of the dissolved
salt to the viscosity of the solution can be calculated in
terms of deformation of ioniC atmosphere. 10 Such a
calculation leads to a viscosity dependence on the square
root of concentration. However at concentrations higher than 0.01 M the above-mentioned treatment ceases
to be valid. Jones and Dole ti showed that up to 0.1 N
the following equation can fit the data of many solutions

X x10 (mol. frac)

FIG. 1. Experimental results of viscosity measurements in
NiCl 2 solutions as a function of concentration.

allows the evaluation of the concentration expressed as

a molar fraction.
The main goal of the present work is concerned with
viscosity measurements. The viscosity measurements
were performed with a standard Ubbelhode viscometer,
that furnishes the kinematic viscosity. Experimental
data turn out to be reproducible with an indetermination
lower than one part per thousand.
However, in order both to calculate shear viscosity
from the kinematic one and to discuss our experimental
results in a more general frame we also need the knowledge of density and compressibility.
As far as the density is concerned, we use a modified precision scale that allows an accuracy of 10-6 In
some cases we also make a check, comparing the density of our samples with some data reported in literature. 8 A very close agreement with the literature data
is always found. Such a procedure can also be considered as a check concerning the concentration values.

where 1]0 is the viscosity of water, x the concentration,

and a and b are parameters characteriZing the electrolyte. The physical meaning of the parameter a (that
accounts for the intertonic interaction) is quite clear
and well understood in terms of the Debye-Hiickel theory.
The meaning of the parameter b seems less clear and
is probably to be related to some kind of ion-solvent
interaction.
In Fig. 2 we plot our data, at low concentrations,
versus the square root of concentration, as the lefthand side of the equation
(1]/170)-1

IX

a+brx.

(2)

The data falls on a straight line up to a concentration of

- - - - - ---- - - - - - - - - - - - - - - - - - - - - - ,
/

.'

//
/-'
/

The compressibility data are obtained from acoustic

velocity measurements. The latter were performed
with an echo-pulse method, using a standard MATEC
apparatus. We used an interferometer in which the distance between transducer and reflector could be continuously changed so that the data turns out to be accurate enough. In addition, we repeated the measurements at different frequencies (in the range between
10 MHz and 50 MHz. No dispersion is expected to hold
in such a range. Actually we found a frequency independent velocity, from which the compressibility data
can be computed with an adequate precision. Further

"..-,'
....:'".

Ie

1/210

vX x10 (mol. frac.J

FIG. 2. Jones and Dole fit of viscosity data at 20C. The

values of parameters are given in the text.

J. Chem. Phys., Vol. 68, No. 12,15 June 1978

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5596

Maisano, Migliardo, Wanderlingh, and Fontana: Viscosity in aqueous NiCI 2 solutions

shape of particles (k= 2.5 for spheres) and A an "interaction factor. "
As can be seen, in Eq. (3) the concentration does not
enter at all. Its role is rather indirect, and would determine both the size of rf> and the values of k and A as
characterizing the structure of the system.
In Fig. 3 we plotted the experimental quantity
(In(111 110) t1, (110 being the viscosity of water) as a function of 1/ cpo The latter quantity was experimentally
found from data of compressibility obtained through
acoustic velocity measurements. 9 Because cp turns out
to be an increasing function of concentration, in the
scale of abscissae the latter decreases from left to
right. For the sake of clarity, the data are plotted in
two different scales. The lower part of the figure refers to data at lower concentrations, while the upper
part refers to data at higher concentrations. In addition only the data taken at the temperatures of 20 and
50C are reported. Data taken at intermediate temperatures show the same behavior, falling between the two
extreme curves drafted in the figure.

1
4

h:/
0'/

//

{/

10

15

1/$

20

FIG. 3. Viscosity data as a function of the incompressible

volume fraction. Lower part: low concentration data. Upper
part: high concentration data.

about 5x 10-3 molar fraction. The values of the fit

parameters are a = O. 235 (molfract1/ 2 and b = 20.4
(molfract1. These values are in the expected range.
For the sake of clarity only the data taken at 20C are
reported. Data at different temperatures give similar
results.
The Jones and Dole equation cannot fit the data at
high concentrations. Up to now the dependence of viscosity on the concentration cannot be given in a single
equation, unless a trivial series expansion is used. In
our opinion this is due to the fact that concentrated solutions are so different from pure solvent that the concentration itself no longer behaves like a parameter
(like, e.g., the temperature). On the contrary, solutions of different concentrations are to be conSidered
as different physical systems. There is an equation,
based on a model originally proposed by Einstein, and
phenomenologically improved by Mooney12 and Padova 13
that, in a sense, follows this point of view. In such a
model the solution is considered as a mixing between a
continuous phase and a number of small rigid (incompressible) particles. Usually the latter are interpreted
as hydrated ions, although such an interpretation is not
required by the theory itself. In fact in the theory the
viscosity is not related to the concentration, but to the
fraction of incompressible volume, whatever its origin.
In the form proposed by Padova13 one writes
(3)

where 110 is the viscosity of the continuous phase (usually assumed to be pure water), rf> the fraction of incompressible volume, k a form factor depending on the

It can be seen that our data (at each temperature) falls

on two straight lines. In the frame of Eq. (3) the slope
of the straight line is given by F1, while the x axis
intercept gives the value of A. On the side of the lower
concentration (lower part of Fig. 3) the interaction factor AO turns out to be temperature independent while on
the side of higher concentrations (upper part of Fig. 3)
A changes with the temperature. There is a sharp separation between the two behaviors that corresponds to
a concentration of about 2. 5X 10- 2 molar fraction. It
seems therefore that at lower concentrations the interaction between incompressible particles (whatever they
are) is quite insensitive to the temperature. This is
just the behavior one would expect if A involves ionic
interaction. However at higher concentrations it seems
that a different structure takes place, that turns out to
be temperature dependent. In Sec. IV we shall show
that the dependence of 11 on rf> can be better clarified because of the common dependence of both quantities on
the structural properties of the system.
An alternative way for the treatment of experimental
results, consists in the fitting of the data as a function
of the temperature for any given concentration. Then
some physical information can be drawn by plotting the
obtained values of the parameters involved in the fit,
as a function of concentration.
As far as the temperature dependence of viscosity is
concerned, the more commonly used equation is the
following
(4)

Equation (4) is known as the Vogel-Tammann-Fulcher

equation (VTF) and can be seen as an improvement of
the Arrhenius equation. 14
Recently the viscosity of glass forming systems was
investigated from a new point of view. 15 The system is
treated like a lattice of bonds. A transport property

J. Chern. Phys., Vol. 68, No. 12,15 June 1978

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Maisano, Migliardo, Wanderlingh, and Fontana: Viscosity in aqueous NiCI 2 solutions

800

B,oK

,"
I

\
700

10, K
0

B,'

,'O" .. tJ..

"

, 'b..

'0..'0-',1

.25

150

\..,,

\,

',>-,

600
I
I

.20
500

Equation (7), however, allows us to interpret the function/1)(x) as a kind of self-energy contribution. It is to
be noted that, with/1)(x)< 1 always, the quantity
1/[1 - /1)(x)] turns out to be the sum of an infinite power
series of /1) (x). In addition, Eq. (7) could allow us to
separate the temperature dependence of viscosity into a
trivial part, due to the variation of 1]0 and an indirect
contribution that modifies the structural change introduced by the dissolved salt. One can think that viscosity
is due to the product of two factors

160

~.To
~,

'

140
'\

b.. ,

"-,

//

"'-,

1](x,T) =w(x,T)rp(T)

"-

130

.15

400
0

40

20

60

120
80

X)( 10 (moL frac,)

FIG. 4. Various parameters of semiempirical equations as a
function of the concentration (see text).

The first one would characterize the structure of the

system (that in an electrolytic solution turns out to be a
variable parameter dependent on the concentration x),
while the second one gives account for the variation of
the phySical properties with temperature in the given
structure. Such a dependence, obviously, is still present also in pure water. The viscosity of the latter,
then, will be written as
1]0

like viscosity, will depend on the fraction N of broken

bonds according to
1]=

5597

where l: is a constant of order of unity.

In Fig. 4 we plot the parameters B and To of Eq. (4)
and the parameter N of Eq. (5) as a function of the concentration, as obtained from our experimental data.
Although both the above-mentioned equations can be
used to fit our experimental data, this kind of fit cannot
provide a fruitful interpretation because of the lack of a
precise physical meaning of the parameter involved,
In any case the fit again reveals that some sort of drastic variation takes place in our system at a concentration between 2x 10-2 and 3x 10- 2 molar fraction.

IV. A NEW PHENOMENOLOGICAL EQUATION

In the previous section we showed that, whatever the
kind of fit, our experimental data revealed that a rather
drastic change took place in the system at a given concentration, In order to show such a behavior in a better
way, we look for a quantity, related to the viscosity,
that could be connected to the variations of the system
as the concentration increases. A hint for this kind of
problem can be found in the treatment of viscosity due
to Onsager and Fuoss. They show that the electrostatic
contribution to the viscosity (in the Debye-Hiickel approximation) is proportional to the viscosity itself, so
that the relevant quantity turns out to be the fractional
increase

Then Eq. (7) becomes identical to:

Wo
w(x,T) = l-/1)(x,T) .

(5)

eON,

=worp(T)

The temperature, in the/1)(x,T) plays a role only if the

structure of the systems turns out to be temperature
dependent, as happens, e.g., in a phase transition.
Obviously the quantity /1) (x) will be useful only if its
behavior turns out to be simpler or its meaning more
fundamental than 1](x) itself, otherwise there is no
point in substituting the function 1](x) with the function
/1)(x). Because we expect a rather trivial increase of
/1)(x) as the concentration increases, we report in Fig.
5 the quantity /1)(x)/x, i.e., the contribution per mole of
dissolved salt in a log-log plot. In such a figure, full
circles refer to 20C, open circles to 30 C, triangles
to 40C and squares to 50 C . Other symbols will be
discussed later. However, at concentrations higher
than 2 x 10- 2 molar fraction, the data at various temperatures are no longer distinguishable on this scale,
so full circles refer to the four nearly coincident values
at different temperatures.

SHEAR

vise.

020"C
o30C
640'C

osoGe

DENSITY x }
BULK MOD.+ 20'C
KINEM. VISC.'

~3

>

2.5

1--) _ 1](x) -1]Q

f,,,"'- 7) (x)

1.5

(6)

2.5

where

1]0

is the viscosity of water.

0.1

Trivially, in terms of such a function, the viscosity

of the solution will be given by
1](X) = 1]0/(1

/,,(x)] .

X x 103 ( mol.frac.)10

100

FIG. 5. Relative fractional increase of shear viscosity as a

function of concentration. Analogous quantities are also shown
referring to kinematic viscosity, denSity, and bulk modulus.

J. Chem. Phys., Vol. 68, No. 12, 15 June 1978

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5598

Maisano, Migliardo, Wanderlingh, and Fontana: Viscosity in aqueous NiCI 2 solutions

justify the results obtained in the treatment of data in

terms of the Einstein theory [see Eq. (3)]. It seemS
that the dependenc e of viscosity on tjJ actually takes
place because both 1) and depend in the same way on
the structural properties of the system. In particular
the independence of the "interaction parameter" A = Ao
on the temperature, at lower concentrations, turns out
to be quite obvious because in this region both 1] and 13
behave sensibly in the same way.

0.9

O.B

10
Xxl0 3

100

FIG. 6. Departures from a single power law of the relative

fractional increase of viscosity.

Although not evident on the scale of Fig. 5, the detailed behavior of the data point at different temperatures is quite interesting. In order to provide evidence
for such a behavior, we plot in Fig. 6 the ratio, h(x) ,
between the data point and the values falling onto the full
straight line of Fig. 5. Such a straight line fits the
data at very low concentrations and turns out to be
given by
f.(x) = 10. 8X- O 125
X

The behavior of the data points clearly shows the

changes in the properties of the system. The data fall
roughly on two straight lines, the change in the slope
taking place at a concentration of 3 x 10- 2 molar fraction.
Now, if Eq. (7), as it seems, is a useful tool to describe the change in the structure of the system, the
same circumstance is expected to hold also for properties of the system other than the viscosity. In the same
Fig. 5 we report the following quantities:

.!. JP.". ( ) _p(x) x

p(x)

P!l.

where p(x) is the density of solution and Po the denSity

of water

'!'f
( ) - K(x)
- Kg
x K X K(x)

where K is the bulk modulus, Ko being the value for

pure water; and

.!. f. (x) = vex) x

Vo

vex)

where v is the kinematic viscosity v == 1]/p, Vo being the

value for pure water.
All these quantities behave like f~(x). In addition, at
concentrations lower than 3 x 10- 2 molar fraction, the
slopes of the straight lines are practically coincident.
In our opinion such a circumstance strongly suggests
that a function of the kind of I (x) has a real phySical
meaning, related to the structural properties of the
system. The latter, in turn, drastically changes at a
concentration of 3 x 10-2 molar fraction, so that, correspondingly, the variation of the properties of the system changes discontinuously.
It is to be noted that

( ) = K(x) - Kg _ 130 - J3(x)

fK x
K(x)
130'
where 13= 11K is the compressibility, so that the functionlK turns out to be the same as the fraction of "in_
compressible volume" tjJ. The plots of Fig. 5 can then

(8)

We shall return later to this point. Let us now briefly

discuss the behavior shown in Fig. 6. The relevant
point is that in the range of concentration between
2x 10- 2 and 3X 10- 2 molar fraction, the difference between the curves at various temperatures becomes
vanishingly small, in the limit of experimental errors.
There is a point, close to 2. 5x 10- 2 molar fraction, in
which all curves pass through the same point, with a
value very close to unity. This means that at such a
concentration the viscosity becomes temperature independent-apart from the trivial, although relevant, dependence introduced by '110' It is interesting to note that
such a concentration seems to playa noticeable role in
the phYSics of this kind of solution, as mentioned in
Sec. 1.
In particular, as far as viscosity is concerned, although it increases drastically as the solution becomes
more concentrated, the quantity f~(x)/x that measures
the fractional increase of viscosity per mole of dissolved salt, turns out to be a decreasing function of concentration. This means that the effect of the dissolved
salts is not simple additive, so that a cooperative process seems to take place. At concentrations higher
than 3 x 10- 2 molar fraction the negative slope of the
quantity f~(x)1 x changes, becoming larger; this is just
the behavior that one would expect if some sort of ordered structure built up.
The plot of Fig. 6 also points to the same conclusion. At very low concentrations Eq. (8) fits the data
practically at all temperatures. The same happens at
higher concentrations, although with a different power
law. The function f~ (x) turns out to be noticeably dependent on the temperature only between 2. 5 x 10-3 and
2. 5x 10- 2 molar fraction. We recall that the larger, but
trivial, contribution of temperature to viscosity, enters
in Eq. (7) through the terms 1]0' The function f~(x) still
depends on temperature only through the modification
introduced by the latter in the structural properties of
the system. The intermediate range of concentrations
therefore seems a transition one, in which the system
evolves from a structure characterizing water (in which

J. Chem. Phys., Vol. 68, No. 12,15 June 1978

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Maisano, Migliardo, Wanderlingh, and Fontana: Viscosity in aqueous NiCI 2 solutions

dissolved salts act as a perturbation} to a different

structure built up by the salt itself.
In the range in which the two structures are competitive, a rather strong dependence on temperature is expected to hold, while when a Simple stable structure
dominates, the dependence would be less sensitive. Obviously the hypothetical structure introduced by the salt
vanishes as the concentration goes to zero: It is perhaps a curious coincidence that the quantity fn(x)/x diverges, as x goes to zero, with an exponent 0.125, that
is the critical index provided for the weak singularity
that characterizes the fluctuation of the thermodynamical potential conjugate to the variable that drives the
transition. However the existence of cooperative effect, as revealed by abrupt changes in the physical properties of the systems and the suggestion of a possible
interpretation as structural change of phase, has been
pointed out elsewhere. 16
V. CONCLUDING REMARKS
We have measured the viscosity of an electrolytic solution of NiCI 2 , from very low concentration to the saturation, and at different temperatures ranging from
20 to 50C. The density and the compressibility of the
solution have also been measured. At low concentrations we found agreement with the Jones and Dole equation, with values of parameter in the expected range.
At intermediate and high concentrations we tried to fit
our data with an equation due to Mooney and Padova, in
which the viscosity is correlated to the fraction of "incompressible volume" following Einstein's theoI;y. It
turns out that a single fit cannot represent our data over
the entire range of concentration. There are a critical
concentration that separates two distinct behaviors,
with different values of the parameter, and different
temperature dependence.
Also the treatment of the data in terms of other empirical equations shows evidence of the existence of a
transition region. In our opinion the failure of a simple
equation able to fit the data at all concentrations is due
to the fact that solutions at different concentrations are
to be conSidered as different systems, whose structure
can change almost continuously as the concentration increases. A small increase of concentration then acts
as a perturbation upon a given system, whose properties are continuously changing. In other words the relevant parameter turns out to be the fractional increase
of viscosity, with respect to the actual viSCOSity itself
rather than to that of pure water. In such a way, in
addition, one can separate the trivial temperature dependence introduced by processes like those implied
for example in the VFT equation, that are also at work
in pure water, from the dependence introduced by the
temperature as a structure-modifying agent. Following this kind of consideration, we propose an equation,
in which the role played by the concentration is contained in a function, l/xfn(x) that describes the fractional increase in the Viscosity per mole of dissolved
salt.
In our opinion such an equation can be very useful be-

5599

cause it allows the treatment of data over the entire

range of concentration, the function f~(x) turning out to
be a very simple one, describable in terms of a simple
power law of the concentration. In addition functions
of exactly the same behavior describe, in the same way,
other properties of the system as the bulk modulus,
the density, and the kinematic viscosity. It seems
therefore that the electrolytic solution can be characterized by a simple function of the concentration, that
plays a fundamental role in the description of the
structural properties.
As far as our data are concerned, the behavior of the
function clearly shows a rather discontinuous change in
the properties of the system at a concentration close to
2. 5 xl 0- 2 molar fraction. Such a concentration behaves,
in a sense, as a critical one that separates phases of
different structure. These results agree with the conclusions furnished by other physical experiments (neutron and Raman scattering, thermodynamical considerations) and support the possibility that some sort of
ordered structure can take place in the electrolytic solutions of salt of transition metals at high enough concentrations.
It is to be noticed that the kind of model that arises
from our treatment has some features in common with
the picture developed by Angell and co-workers. 17,18
In such a picture a dominant role is played, as in our
case, by the structural properties of the system.

The above-mentioned authors make the hypothesis

that the solution under suitable conditions can separate
into two distinct phases, one of which turns out to be
dispersed into the other. Such a phase separation actually could be the ultimate result of structural changes
in the system.
We are indebted to Prof. Angell for bringing this
point to our attention.

lR . A. Howe, W. S. Howells, and J. E. Enderby, J. Phys. C

7, Ll11 (1974).
2J. E. Enderby, R. A. Howe, and W. S. Howells, Chem.
Phys. Lett. 21, 109 (1973).
3M. P. Fontana, Solid State Commun. 18, 765 (1976),
4M. P. Fontana, G. Maisano, P. Migliardo, and F. Wanderlingh (to appear in Solid state Commun. 1977).
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