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TITOVA et al.
The synthesized peroxosolvates were analyzed for the
by an appreciable endothermic effect. After 170°С the
weight loss comes to the end. The tetraethylammonium
solvate is also decomposed with an endothermic effect,
but, unlike the tetramethylammonium solvate, in two
stages. The first stage takes place at 125–175°С, then
from 175 up to 225°С the disintegration process of the
solvate stops, and the final disintegration occurs in the
range of 225–250°С.
hydrogen peroxide content by the permanganatometric
titration. Contents of hydrogen, carbon, and nitrogen were
determined on a VARIO MIKRO cube analyzer. Chlorine
contents were found by argentometry after determination
of the H2O2 content by the permanganatometric titration.
(CH3)4NCl·H2O2. Found (%): C 32.94, Cl 32.30, N 9.50;
H2O2 23.60, Htotal(without H2O2) 10.20. C4H14NClO2.
Calculated (%): C 33.45, Cl 32.43, N 9.76; H2O2 23.70.
Tetramethylammonium chloride peroxosolvate is
readily soluble in water, which is important in view of
its possible practical application. The saturated solution
of the solvate at 20°С contains 10.6% of H2O2, which
corresponds to 44.7% of (СН3)4NCl·Н2О2. The solution
is rather stable: for 25 days (Table 2) it loses one fourth
part of hydrogen peroxide.
Htotal(without H2O2) 9.76. (C2H5)4NCl H2O2. Found (%):
C 47.27, Cl 17.7, N 7.00; H2O2 16.95, Htotal(without
H2O2) 10.3. C8H22NClO2. Calculated (%): C 48.12,
Cl 17.70, N 7.00; H2O2 17.00, Htotal(without H2O2) 10.00.
The X-ray patterns were recorded by the powder tech-
nique on anADP-2-01 diffractometer (CuKα radiation, Ni
filter) using the program developed for “DRON” X-ray
diffractometers for automation of the processes of the ob-
taining, treatment, and analyzing of data. The IR spectra
of the synthesized solvates were recorded on a UR-20
spectrophotometer over the range of 400–4000 cm–1.
Samples were prepared in the form of suspensions in
liquid paraffin. Thermograms were recorded on a 1500D
derivatograph with a Pt-Pt/Rh thermoelectric couple,
Al2O3 standard at the heating rate of 5 deg min–1.
Solubility of tetraethylammonium chloride peroxo-
solvate in water is of the same order as that of tetraethyl-
ammonium. The saturated solution of (С2Н5)4NCl·H2O2
contains 16.44% of H2O2, which corresponds to 83.6%
of the solvate. In the initial stage of storage the solution
is more stable than the solution of the tetramethylammo-
nium peroxosolvate. The enhanced stability of the tetra-
ethylammonium peroxosolvate solution is also retained
in the late storage stages.
Obviously the synthesized peroxosolvates shall dis-
sociate in aqueous solutions in two stages. The first stage
will follow the equation
Table 1 contains the IR spectra of the synthesized
compounds and, for comparison, the IR spectrum of
potassium fluoride peroxosolvate, which in essence is
the spectrum of bound hydrogen peroxide. Coincidence
or proximity of bands of these spectra confirms the sol-
vation of tetraalkylammonium chlorides under study by
hydrogen peroxide.
(CH3)4NCl·H2O2 ↔ (CH3)4N+ + [Cl·H2O2]–,
and the second stage, the equation
[Cl·H2O2]– ↔ Cl– + H2O2.
Tetramethylammonium chloride peroxosolvate does
not lose weight and keeps H2O2 content close to initial
on continuous heating up to 125°С. Decomposition of
the solvate begins at about 130°С and is accompanied
The cation (CH3)4N+ will not undergo any transfor-
mations. The anion [Cl·H2O2]– will be able to exhibit
Table 1. Absorption bands (cm–1) of O–O and O–O–H groups in synthesized peroxosolvates and in KF·H2O2
(СН3)4NCl.H2O2
960 s, stretching O–O
735 s, torsion
(С2Н5)4NCl.H2O2
900 s, stretching O–O
730 s, torsion
KF.H2O2
885 s, stretching O–O
960 s, torsion
1410 s, bending O–O–H
1475 с, деформ. O–O–H
2790 s, stretching O–H
1410 s, bending O–O–H
1470 с, деформ. O–O–H
2790 s, stretching O–H
1485 s, bending O–O–H
1670 ср, деформ. O–O–H
2600–2800 s.br, stretching O–H
3000–3200 s, unsymmetric stretching
O–H
3000–3400 s, unsymmetric stretching O–H 3200 s, unsymmetric stretching O–H
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 84 No. 1 2011