Russian Journal of Applied Chemistry, 2011, Vol. 84, No. 1, pp. 25−35.
Pleiades Publishing, Ltd., 2011.
Original Russian Text © I.M. Gusev, M.Yu. Skripkin, 2011, published in Zhurnal Prikladnoi Khimii, 2011, Vol. 84, No. 1, pp. 25−34.
INORGANIC SYNTHESIS AND INDUSTRIAL
Formation of Complex and Double Salts in Systems
O [M = Cd(II), Cu(II), Co(II), Mg(II);
X = Cl, Br; R = Me, Et, Bu] at 25°С
I. M. Gusev and M. Yu. Skripkin
St. Petersburg State University, St. Petersburg, Russia
Received April 8, 2010
Abstract—Results of an experimental research of phase equilibrium in ternary systems MX
O [M =
Cd(II), Cu(II), Co(II), Mg(II); X = Cl, Br; R = Me, Et, Bu] at 25°С were reported. A comparative analysis of
compositions of solid compounds and regions of their crystallization, which are equilibrium with liquid phase,
was conducted. An effect of hydration, association of salts of quaternary ammonium and acido complexation of
ions of d-elements on the formation of the complex and double salts in the systems was presented.
Development of Chemical Materials urgently requires
ﬁ nding of new and improving of known techniques of
synthesis of functional materials. At the same time more
and more attention is attracted to development of a di-
rected sort synthesis of chemicals: synthesis from liquid
phase systems including that from aqueous solutions. This
way is form a number of energy-saving technologies and
therefore completely corresponds to modern scientiﬁ c and
technological trends. Thus, researches aiming to establish
relationship between a solution composition and compo-
sition, structure, and properties of the compounds, which
are crystallized from it, become more and more urgent.
Complex salts possessing quaternary ammonium ions
as an outer-sphere cation is promising for contemporary
Chemical Materials. Combination of a lyophilic cation
and complex anion often having high catalytic activity
in the composition of one compound make this com-
pound promising catalyst for a number of organic reac-
tions. An important feature of these compounds is also
their ferroelectric and ferroelastic properties therewith a
transition to a paraelectric state occurs at relatively high
(up to 290 K) temperatures [2–4].
A purpose of the study was to consider an effect of the
complexation of a metal ion (Cd
ion does not form halide complexes in aqueous solutions
) and hydrophobic interactions in solution (NBu
) on a number, composition, and solubility
of complex salts in the systems containing quaternary
ammonium salts MХ
O [M = Co(II), Cu(II),
Cd(II), Mg(II); X = Cl, Br; R – Me, Et, Bu).
Investigation of solubility was conducted by isother-
mal saturation. Solutions were prepared by the method
of supplementation. Saturated solutions MX
which were in equilibrium with the corresponding solid
phases were taken as initial systems. A third component
with a step of 0.2–1.0 mol kg
O has been added.
The systems were placed in an air thermostat and kept at
a temperature of 25.0 ± 0.1°C for 1 day under constant
stirring using a magnetic stirrer. Due to the high viscos-
ity of solutions in systems MBr
a concentration of tetraalkylammonium bromide more
than 15 mol kg
O the systems were thermostated
with stirring for at least 3 days.
When analyzing a sample a metal ion concentration
and bromide ion one were determined with trilonomet-
ric and mercury titration, respectively. Concentration of
bromide and quaternary ammonium was calculated by
difference. A relative error of an analysis did not exceed