Heat capacities and volumes of NaCl, MgCl,, CaCl,, and NiClz up to 6 molal in water

GERALDPERRON,ALAINROUX',A N D JACQUESE. DESNOYERS~

Drpcirttnrtzt of Chrmistrv, Uni~rrsitPdr Sl~erbrookr,Shrrbrooke IQnP.). Canada J I K 2RI
Received April 2. 1981

GERALDPERROY, ALAINROUX.and JACQUES E. D~SNOYERS. Can. J. Chem. 59. 3049 (1981).

It has been claimed by Enderby and co-workers that changes in long-range order occur in NiCI, aqueous solutions at high
concentrations. To investigate the possibility of a transition. the partial molar heat capacities and volumes of NiCl,, CaCI,, MgCI,.
and NaCl were measured a n d ~ o m p a r e din water at 25°C up to 6 mol kg-'. In the case of NaCI, data were also measured at 5 and 45°C.
A slight change in slope of C,,, is observed for NiCI, around 4mol kg-' which may suggest a third or higher order transition.
However, the change is too small to support unambiguously any particular model for the high concentration region.
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22

GERALDPERRON, ALAINROUXet JACQUES E. DESNOYERS. Can. J . Chem. 59.3049 (1981)

Enderby et ses collaborateurs ont pretendu qu'il se produit des changements tres importants dans des solutions aqueuses tres
concentres de NiCI,. Afin d'etudier la possibilite d'une transition, on a mesure les capacites calorifiques molaires partielles et les
volumes molaires partiels du NiCI,. du CaCI,. du MgCI, et du NaCl et on les a compares dans I'eau a 25°C jusqu'a 6 mol. k g ' . Dans
le cas du NaCI, on a egalement mesure les donnees a 5°C e t a 4j°C. On a observe un leger changement dans la pente de Cp,,pour le
NiCI, a environ 4 mol kg-' ce qui suggere une transition d'ordre trois ou une transition d'ordre plus elevee. Cependant le changement
est trop faible pour servir de preuve formelle a tout modele particulier dans la region de forte concentration.
[Traduit par le journal]

Introduction reference for this purpose. If the hydration of Niii

Enderby and co-workers (1, 2 ) reported in 1974 is responsible for any anomalous behavior, then
For personal use only.

data on the neutron scattering of aqueous solutions
of NiCl, and concluded that, at high concentration,
the Ni ions were arranged in a quasi-lattice and that
the solutions possessed a substantial degree of
long-range order. This unexpected conclusion has
prompted numerous investigations, namely, Raman
scattering (3, 4). thermodynamic measurements
( 5 ) , viscosity (6), diffusion (7), and X-ray scattering
(8). However, the interpretation of many of these
data is subject to criticism and other explanations
can be offered to explain the anomalous neutron
scattering (9).
Of all the thermodynamic properties, heat capac-
ity is probably the most sensitive to transitions in
the condensed state. On a suggestion from Profes-
sor H. L. Friedman, we therefore decided to make
a careful investigation of this property up to the
region where the transitions are said to Our
flow microcalorimeter measures heat capacities
per unit and densities of comparable
precision are required to calculate apparent and
partial molar heat capacities. The densities were
therefore measured with a flow densimeter on the
same solutions.
It will be necessary to compare the data On NiC1,
with other systems where such transitions are not
expected to occur. &(I', seems to be a good
'Present address: Laboratoire de thermodynarnique et cine-
tique chimique. U.E.R. Sciences, Universite de Clermont 11,
B.P. 45, 63170 Aubiere, France.
,Author to whom correspondence should be addressed.
0008-40421811213049-06$01.W/O
01981 National Research Council of CanadalConseil national de recherches du Canada
similar trends would be expected for MgCl2. Data
0" these two electrolytes are available in the
literature. For example, data in our own laboratory
were reported on these two salts at low concentra-
tion (10). However, it is important to compare the
properties of all these electrolytes under very
conditions.
Volumes and heat capacities of NaCl have been
measured as a function of temperature UP to
3 mo1 kg-' (1 I). Many authors interested in the data
of this salt have asked US to extend our measure-
ments to higher concentration. We therefore mea-
sured these properties UP to 6 mol kg-' at 5325, and
45°C. A comparison with the 1:2 electrolytes might
Prove to be
Experimental
The techniques for measuring heat capacities and densities by
flow microcalorimetry (12, 13) and flow densimetry (14) have
been well described. and the method of calculating apparent
molar heat capacities (4,) and volumes (4,) are given therein.
The origin and purification procedure of the chemicals are the
following. NaCl (Fisher Certified) was used as such after drying
under vacuum at 150°C. NiCI, (Ultra-pur Alfa Product). MgCI,
(Analar, BDH Chemicals), and CaCI, (Fisher Certified) were
recrystallized in water at a pH of 5. NiC1, was analyzed by
precipitation with EDTA and also by conductometric titration
with AgNO, with a concentrated and with two dilute samples.
MgCl, and CaCI, were analyzed gravimetrically and conduc-
tometrically with AgN03. In all cases the analyses agreed within
0.05%. All solutions were prepared by weight dilution of the
same stock solution. The uncertainty in the concentration plus
the 0.5% uncertainty in the relative change in heat capacity per
unit volume limits the precision in 4, to f0.8J K-' mol-I. At
low concentration this uncertainty may increase.
 3050 CAK J . CHELI. V O L 59. 1981

TABLEI . Apparent molar volumes and heat capacities of some electrolytes in watct
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22

NaCl T=25Oc
For personal use only.

NaCl ~ = 4 5 " ~

Results are the theoretical slopes of the limiting Debye-

The measured densities and heat capacities per
unit volume and the derived 4 , and 4, are given in
Table 1.
The volumes and heat capacities of MgCl,,
CaC1,. and NaCl have been well investigated at low
concentration and need not be discussed here. On
the other hand. only one set of reliable data seems
to exist for NiCl, (15). This electrolyte was there-
fore studied to fairly low concentration. The values
of 4 , - A,mu2 and 4, - ACmli2,where A , and A,
Hiickel theory. are plotted against m and compared
with the data of Hepler et nl. ( 1 5 ~in ) Fig. 1.
Two sets of measurements. corresponding to
two different stock solutions of NiCl,, agree well
inside the expected uncertainty. Our data are also
in reasonably good agreement with those of Hepler
et ul.. especially at their higher concentrations. An
extrapolation of the straight lines at low concentra-
tion to infinite dilution will give the standard partial
molal values at 25°C.
 PERRON ET A L . 305 1

-
VO
-
+
, = 6.20 0.05 cm' mol These plots are shown in Fig. 2 for 4, and in Fig. 3
for 4,. These functions will be discussed separately.
C,,O = -306 f 1J KF1mol-I The scatter of data points for 4, of NaCl is about
The data of all the electrolytes up to 6 mol k g 1 0.01 cm3 molF1at 5 and 45°C and somewhat higher
were fitted with eq. [I]: at 25°C. At 5" and 25°C the present data agree with
our earlier ones within 0.02 cm3 molF'. At 45°C the
difference is more of the order of 0. 10cm3 mol-I.
Recently, Rogers and Pitzer (15b) have analyzed
the literature data of volumetric properties of NaCl
where Y stands for V or C,. In eq. [l] 4,O should be over a large range of temperature and pressure.
equal to YZO,the standard value. and A, should be They proposed parametric equations to represent
the Debye-Hiickel limiting slope. However, 4, 4 , as a function of concentration up to about
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22

varies significantly at low concentration and much saturation. These predicted 4, are systematically
less at high concentration. As a result, if and A, lower than ours, the mean deviation being 0.046 cm'
are fixed before the least-squares analysis, many m o l l . Our weights were not corrected for vacuum.
parameters are required to fit the data. A better This can cause an error of about 0.06% in m and of
extended form of the Debye-Hiickel theory would about 0.02 cm3molF1in 4,. Assuming the predicted
probably give a better fit. However. since in the
4, data are the correct ones then the probable
present case we are not interested in the high source of error in our data would be in the
dilution region, it was found simpler to treat 4," calibration of the densimeter. Dry nitrogen and
and A, as adjustable parameters like the other distilled water were used for this purpose (14).
coefficients since this allowed a very good repre- Probably aqueous NaCl solutions should be used as
sentation of all our high concentration data with a a standard instead. For the present purpose a
For personal use only.

minimum of parameters. Parameters such as A , recalculation of our data is not warranted since a
then include any specific interactions such as a maximum error of 0.05 cm3 molF1 in 4, causes a
small degree of association. negligible error in 4,.
The coefficients of eq. [ l ] are given in Table 2. Our volume data for MgCI, and CaCI, are in very
Again we stress that no physical significance should good agreement with most literature valueu (16- 19).
be given to the parameters +,O and A,. The data of Wirth and Bangert for MgC1, (19. 20)
The uncertainty in the data and a co~nparison (not shown) show a scatter of 0.20cm3 mol-I but
with the literature are best illustrated through overlap our data. The data of Vasilev et ul. (2 1 ) for
deviation plots A(+,"" - $ ~ , ( ~ l ~where ), 4,ca1cis MgCI, diverge by as much as 1.4cm3 mol-' and
obtained from eq. [I] and the parameters in Table 2. cannot be considered reliable. Their data for CaCl,
are better but still show much scatter.
It was shown in Fig. 1 that our low concentration
data for 4, of NiC1, were in good agreement with
those of Hepler er al. (15). At high concentration
(see Fig. 2) a systematic difference of 0.10cm3
molF1 is observed with the data of Stokes et ul.
(22). The agreement would be worse if corrections
such as those discussed for NaCl were made on our
data. It is therefore more probable that the obser-
rnol kg"
ved difference could be accounted for by the
uncertainty in the analyses of the NiCl, stock
solutions in both laboratories. The data of Kara-
pet'yants et al. (23) are quite different from ours
and those of Stokes r t nl.
The heat capacities are shown in Fig. 3. The
present data for NaCl are in excellent agreement
rnol k g ' with our earlier data (11) at all temperatures and
also with the recent data of Tanner and Lamb (24)
FIG.1. '4pparent molal volumes and heat capacities of NiCI,
at low concentrations at 25°C; 3:present data. low concentra- at 25 and 45°C. A difference of about 2 J M-I m o l l
tion stock solution; @: present data. high concentration stock is observed at 5°C. For CaCI, the agreement with
solution; +: ref. 150. the literature (21,25) is acceptable. With MgCI, the
 3052 C A Y . J CHEM VOL. 59. 1981

TABLE2. Parameters of eq. [I] for the volumes and heat capacities of various electrolytes in water at 2joC

Solute TC 4, A1 B, CI D1 0"

NaCl 5 13.4228 2.91796 -0.088435 0.121670 -0.043552 0.007

25 17.2928 0.074893 1.658656 -0.58 1732 0.061657 0.004
45 18.5501 -0.3 10934 1.91820 -0.730121 0.0959 13 0.007
MgCIZ 25 15.0030 4.38801 0.7922 11 0.107646 -0.127300 0.02
CaClz 2.5 18.3549 4.03473 2.42792 - 1.26686 0.230971 0.03
NiCI, 25 6.8372 6.2164 - 1.05872 1.36201 -0.42965 1 0.04

Solute T"C +to Ac Bc Cc Dc 0

NaCl 5 -204.667 132.187 - 12.069 -0.92839 0.049905 0.3

25 -85.46 25.072 30.116 - 10.6986 1.16001 0.3
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22

45 -50.768 4.4499 31.577 - 10.8616 1.38434 0.4

MgClz 25 252.545 50.8894 36.2508 -9.63046 1 .0
CaCl, 25 -278.326 133.147 -67.3016 47.7742 -9.44019 1.0
NiCI, 25 -295.270 114.882 -33.0619 38.4626 - 10.5031 0.5
For personal use only.

FIG.2. Apparent molal volumes of various electrolytes in water. Deviation plots from eq. [I]: 8 : present data; +: ref. 11;
Vasilev e t c11. (21); *: I.C.T. (18); x : Phang and Stokes (16); A: Chen e t d l . (17); 0 :Stokes et
0: ill. (22); H: Dunn (20).

agreement is less satisfactory since the data of Discussion

Fedyainov et a l . (25) and of Rutskov (26) diverge
by as much as 6 5 K-' molp'. Since the densities
from the same laboratory (21) showed large differ-
ences, such disagreement is not unexpected. We
could not find any reliable data for NiCl, at high
concentration for comparison. Our scatter of points
is of the order of 0.5 J M-I mol-'.
Transitions in aqueous solutions have been well
investigated by heat capacity measurements, espe-
cially in the case of the micellization process (27). If
the partial molar heat capacities of the initial and
final states are different and if there is a correspond-
ing enthalpy change. then the transition can be
considered of first order and C,,, will go through a
 PERROU ET 4 L .
-0
-E
k
-
7
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22
- 5.
For personal use only.
1 I I I
0 2.0
rnol
FIG.3. Apparent molal heat capacities of various electrolytes in water. Deviation plots from eq. [I]: C : present data: A: Tanner
and Lamb (24); +: Perron et (11. ( 1 1): 3: Fedyainov et a/.(25): x : Vasilev e r a / . (21): " : Ruskov (26); 0:
hump or maximum before dropping rapidly to its
final value as the concentration crosses the transi-
tion zone. If there is no corresponding enthalpy
change, C,,, will still change rapidly in the transi-
tion concentration but no hump (relaxational con-
tribution) will be observed. This would be a second
order transition. A break in a C,,, curve would
therefore indicate a transition-of a higher order.
The partial molar volumes V2 and heat capacities
G,, of the solutes were calculated in twoways:
from eq. [I] knowing that d(&m)ldm = Y, and
from a plot of A($,rn)lA~?z against the mean molality.
The first technique is the simplest but may lead to
erroneous results at the concentration limits since
the least-squares analysis may not be reliable at
these edges unless many data points were available.
For example, the C,,, of rare earth chlorides of
Spedding et a l . (28), obtained by this technique,
give very pronounced curvature at high concentra-
tions which may not be real. Ip our case both
approaches to the calculation of Y2 gave the same
results except at very high concentrations where
the graphical procedure was better. The values of
V, and &a,, are shown in Figs. 4 and 5.
The trends in V, of NiCl,, MgCl,, and CaCl, are
quite similar at intermediate concentrations as seen
N a C l 25'C
NiCI,
I I 1 I
4.0 6.0
kg-'
Ruskov (26).
from Fig. 4. At concentrations above 3 mol k g ' the
data for WiCl, and MgC1, level off more rapidly
than those for CaC1,. However, no break in these
I/, curves can be seen. NaCl shows less curvature
than the-1 :2 electrolytes.
The C,,, data are shown in Fig. 5 . The trends
with NgCI. MgCI,, and CaCI, are all quite s~nooth
while C,,, of WiC1, levels off at about 4mol kg-'.
The derivative of this curve, dC,,2/di7z suggests
that there might be a change in slope with NiCI, at
about that concentration. However, this may also
be true of CaCI, near 6 mol k g t .
The present data therefore exclude the possibil-
ity of a sharp transition in aqueous NiC1, near 4 mol
kg-I but not a transition of a high order. It would be
of course possible to find methods of plotting our
data so as to show a definite break with our heat
capacities (6). but unless the function has a sound
scientific justification such plots are meaningless.
The heat capacity is very sensitive to local average
structure but the effect of long-range ordering is
small. The structures proposed by Enderby rt ul.
(1, 2) are long range and the transitions could be
gradual. Under such circumstances heat capaci-
ties, or any other thermodynamic properties, would
not be expected to change significantly. There are
 3054 C A N . J . C H E M . VOL. 5 9 . 1981

aqueous NiCl,, they do not offer strong evidence

for such changes.
Ackno\vledgemenls
We are grateful to the Natural Sciences and
Engineering Research Council of Canada for finan-
cial support and to NATO for a fellowship to one of
us (A.R.). We would also like to thank Daniel Hetu
for his help with some of these measurements.
Can. J. Chem. Downloaded from cdnsciencepub.com by 202.5.148.177 on 10/24/22

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