Russian Journal of General Chemistry, Vol. 73, No. 2, 2003, pp. 161!164.

Translated from Zhurnal Obshchei Khimii, Vol. 73, No. 2, 2003,

pp. 177!181.
Original Russian Text Copyright + 2003 by Khripun, Kiselev.

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Reason for Different Solubility of Alkali Metal Chlorides

in Cadmium Nitrate Solution
M. K. Khripun and A. A. Kiselev

St. Petersburg State University, St. Petersburg, Russia

Received November 27, 2001

-
Abstract An idea that concentrated solutions of salts forming several crystal hydrates can be considered
as systems of mixed solvents was developed within the framework of a phenomenological model of solution
structure for the systems Cd(NO3)23MCl3H2O (M = Li, Na, K, Cs). It was supposed that LiCl and CsCl pre-
ferentially interact with a solvent like Cd(NO3)2 nanohydrate, whereas NaCl and KCl, with a solvent like
Cd(NO3)2 tetrahydrate.

In our formation studies on cadmium chloride
complexes [1, 2] we noted that lithium, sodium, and
cesium chlorides have different solubility at cadmium
nitrate concentrations of 0.9 and 4.1 M. The aim of
the present work was to accurately measure maximal
solubilities of salts MCl (M = Li, Na, K, Cs) in
cadmium nitrate solutions with various concentrations
up to saturating. The complexity of such multicom-
ponent systems results from the great diversity and
changeability of their microcomposition at varied salt
concentrations. It is known [3] that different crystal
hydrates [Cd(NO3)2 . 9H2O, Cd(NO3)2 . 4H2O, and
Cd(NO3)2 . 2.5H2O] crystallize from posteutectic
cadmium nitrate solutions as the temperature de-
creases. According to our model concepts [1], as the
concentration of cadmium nitrate increases, different
cybotactic groups sequentially dominate in the solu-
tion. In preeutectic solutions, water is a solvent,
whereas a concentrated solution, where various cybo-
tactic groups are formed, can be considered as a
system of mixed solvents. In such systems, a com-
bination of similar cybotactic groups plays the role of
a separate solvent component, and these components
are in dynamic equilibrium. Thus, the solubility of
chlorides in various-concentration cadmium nitrate
solutions and the formation of cadmium chloride
complexes will depend on their preferential interaction
with one on another solvent (certain cybotactic group).
We measured the solubility of MCl by an unusual
method, since we set ourselves a different task,
namely, to determine the greatest possible quantity of
chloride, which can be dissolved in a cadmium nitrate
solution of a certain concentration. Therefore, we
added anhydrous MCl salts into Cd(NO3)2 solutions
in portions with continuous stirring until first crystals
appeared. Then the solution was filtered, and the
1070-3632/03/7302-0161 $25.00 C2002 MAIK
composition of the liquid phase was determined. To
this end, excess MCl was added into the same solu-
tion, and the solid phase was analyzed. The experi-
mental data are shown in the figure.
Let us first compare solubility trends for cesium
and lithium chlorides (Fig. 1a, curve 1 and Fig. 1b,
curve 5). These salts are rather different in nature. The
Li+ cation is a positively hydrated ion, and LiCl forms
several crystal hydrates; the Cs+ ion, vice versa, is a
negatively hydrated ion, and CsCl crystallizes on
saturation in the anhydrous state. At preeutectic
concentrations of cadmium nitrate, the solubility of
cesium chloride is low but it increases with increasing
Cd(NO3)2 concentration (Fig. 1a, curve 1). A classical
complex formation occurs in the solution to give
various cadmium chloride complexes which are cha-
racterized by a very low solubility and crystallize
from the solution without water [4].
Cd2+(H2O)6 + nCl!aq 76 CdCl(n
n
! 2) + nH O.
2
As a result of the complex formation water is
liberated, which is the reason for increased solubility
of cesium chloride. In this case, CsNO3 passes into
the solid phase which crystallizes from these solutions.
At a cadmium nitrate concentration of ~4.5 mol/kg
H2O, a bend is observed in the cesium chloride so-
lubility curve, and then the solubility increases again.
This bend corresponds to an eutectic in the solubility
polytherm which we measured earlier [2] for the
Cd(NO3)2 : CsCl = 2.5 : 1 solution.
Analysis of the solid phase showed that the complex
CsCdCl3 crystallizes from the solution at Cd(NO3)2
concentrations higher than 4.5 mol/kg H2O. In our
opinion, after the eutectic, structurally enforced effects
are superimposed on the classical acido complex
[Nauka/Interperiodica]
162 KHRIPUN, KISELEV

concentration of Cd(NO3)2 is increased over

6 (a) ~3.5 mol/kg H2O, the solubility of lithium chloride
5 changes insignificantly but continues to decrease.
2
4
As for low concentrations of cadmium
3 1 nitrate, it is better to speak not about lithium chloride
2 solubility but about cadmium nitrate solubility in the
1 LiCl crystal hydrate structure. As shown in [2], at
0 high concentrations of lithium chloride and low
(b) concentrations of cadmium nitrate (0.9 mol/kg H2O),
complex formation occurs by the mechanism of struc-
7 turally enforced conjugation of crystal hydrate struc-
6 tures of lithium chloride and cadmium chloride com-
5 3
4 plexes through common water molecules (one or more,
3 depending on LiCl concentration). According to the
2 4 solid-phase analysis, lithium nitrate crystallizes from
1 the solution at these concentrations. At cadmium
0 nitrate concentration above ~3.5 mol/kg, complex
25 CdCl2 . nH2O was found in the bottom phase. Note
(c) that the sharp bend in the curve of LiCl solubility
20 takes place in the region of the eutectic in the solu-
15 bility polytherm of Cd(NO3)2 : LiCl = 1.7 : 1 solution
[2].
10
5 We have measured lithium chloride solubility in
5 various-concentration solutions of cadmium perchlo-
6 rate (Fig. 1c, curve 6). The lithium chloride solubility
0
1 2 3 4 5 6 7 sharply decreases up to a cadmium perchlorate con-
m[Cd2+], mol/kg H2O centration of ~3 mol/kg H2O [a concentration close to
the eutectic in the solubility polytherm of Cd(ClO4)23
Solubility of MCl. (a): (1) CsCl and (2) KCl in H2O, 3.4 mol/kg H2O]. Here, like in the system with
Cd(NO3)2 solutions; (b): LiCl in (3) Cd(NO3)2 and cadmium nitrate, cadmium chloride complexes are
(4) Cd(ClO4)2 solutions; and (c): NaCl in (5) Cd(NO3)2 formed by the mechanism of structurally enforced
and (6) Cd(ClO4)2 solutions. conjugation. However, in system 5, too, lithium
nitrate ionic melt appears in the solution as a result of
formation. At posteutectic concentrations of cadmium complex formation [2]. In system 6, LiClO4 is gene-
nitrate, dissociation of cesium chloride added to the rated, which itself forms a stable LiClO4 . 3H2O
solution is suppressed because of the absence of suf- crystal hydrate structure [3] structurally incompatible
ficient amount of free water, and cesium chloride with lithium chloride crystal hydrate cybotactic
exists in the solution in the associated state. In parti- groups (not forming joint compounds they cannot
cular, CdCl2 . nH2O complexes are formed in the realize a common bond system in the solution). This
Cd(NO3)23CsCl3H2O system. Within the framework all results in a sharp decrease in lithium chloride
of our model, at posteutectic concentrations, struc- solubility in system 6. At posteutectic concentrations
turally enforced displacement of water from CdCl2 . of cadmium perchlorate, Cd(ClO4)2 . 6H2O cybotactic
nH2O crystal hydrate cybotactic groups by Cs3Cl groups dominate in the solution. It was shown earlier
associates occurs. As a result, CsCdCl3 complexes are [1] that complex formation with these groups is
formed, water is liberated, and the solubility of hindered. Here cadmium chloride complexes are
cesium chloride increases. formed by interaction of free Cd2a+q ions, which are
present in the solution in a small amount, with chloride
CdCl2 . nH2O + Cs3Cl 76 CsCdCl3 + nH2O. ions supplied by lithium chloride. This explains such
a low solubility of lithium chloride in a concentrated
In contrast to cesium chloride, the solubility of solution of cadmium perchlorate. Like with the
lithium chloride decreases with increasing cadmium cesium chloride system, water is liberated during
nitrate concentration (Fig. 1c, curve 5). The sharpest complex formation in the solutions under considera-
decrease is observed near the eutectic composition of tion. However, this does not result in increased LiCl
the Cd(NO3)2 solution (2.6 mol/kg H2O). When the solubility, since water is redistributed between the
RUSSIAN JOURNAL OF GENERAL CHEMISTRY Vol. 73 No. 2 2003