Choice of a stabilizer for the reaction of KOH with hydrogen peroxide to produce potassium superoxide

Article abstract of DOI:10.1023/B:RJAC.0000018700.21484.32

A stabilizer for the reaction of KOH and H₂O₂ yielding potassium superoxide was proposed. The stabilizer does not affect the main consumer properties of the regenerative product based on KO₂.

Full text of DOI:10.1023/B:RJAC.0000018700.21484.32

Russian Journal of Applied Chemistry, Vol. 76, No. 11, 2003, pp. 1858 1859. Translated from Zhurnal Prikladnoi Khimii, Vol. 76, No. 11,
003, pp. 1909 1910.
Original Russian Text Copyright
2
2003 by Gladyshev, Dvoretskii, Zhdanov, Ul’yanova, Ferapontov.
BRIEF
COMMUNICATIONS
Choice of a Stabilizer for the Reaction of KOH with Hydrogen
Peroxide To Produce Potassium Superoxide
N. F. Gladyshev, S. I. Dvoretskii, D. V. Zhdanov,
M. A. Ul’yanova, and Yu. A. Ferapontov
Tambov Research Chemical Institute, Federal State Unitary Enterprise, Tambov, Russia
Received April 1, 2003
Abstract A stabilizer for the reaction of KOH and H O yielding potassium superoxide was proposed.
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The stabilizer does not affect the main consumer properties of the regenerative product based on KO2.
Potassium superoxide KO is the most widely used
substance for self-contained human respiratory ap-
Up to now, there are no strict scientific principles
for the choice of stabilizers for H O solutions pre-
2
2
2
paratus. The use of KO is based on its capability to
venting their decomposition [6]. Therefore, the sta-
bilizers are mainly chosen empirically depending on
the composition of a particular solution containing
H O or other peroxides. Since H O alkaline solu-
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chemisorb moist carbon dioxide, generating oxygen
required for breathing [1].
Development of a new process for KO production
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2 2
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tion is used further for obtaining potassium superox-
ide and the regenerative product thereof, the suitable
stabilizers should meet certain requirements concern-
ing their toxicity, thermal stability, chemical resist-
ance to atomic oxygen, etc. Organic compounds are
unsuitable as stabilizers for H O alkaline solutions
involved certain problems related to the process con-
ditions and qualitative composition of the final prod-
uct. One of these problems is considered in this paper.
EXPERIMENTAL
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According to the suggested process [1 4], potassi-
um superoxide is produced from potassium hydroxide
and hydrogen peroxide by their mixing in the molar
because of the possibility of their oxidation with po-
tassium superoxide, accompanied by burning and ex-
plosion. Among inorganic salts, magnesium sulfate
ratio H O : KOH = 1.75 : 1 with subsequent dispro-
and Na P O are the best stabilizers of H O alkaline
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4 2 7 2 2
portionation of the intermediate adduct K O 2H O
solutions. These compounds were used in this work to
obtain potassium superoxide and the regenerative
product thereof.
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2 2
in a spray-type reactor. The process can be described
by the following reaction equations:
A specified amount of a stabilizer was dissolved in
a 50% H O solution. The solution was placed in a
2
KOH + 3H O = K O 2H O + 2H O,
(1)
(2)
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2
2
2
2
2
2
2
K O 2H O = 2KO2 + 2H O.
2
2
2
2
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reactor cooled with tap water stream, and a 50% KOH
solution was added slowly with stirring. We found that
KOH reacts with H O under these conditions without
The reaction of hydrogen peroxide with potassium
hydroxide is strongly exothermic under normal condi-
tions and is accompanied by decomposition of the per-
oxide products and evolution of atomic oxygen. There-
fore, to carry out the process, it is necessary either to
cool the reaction area, which requires additional
power consumption, or to add a stabilizer. By the sta-
bility of various solutions of peroxide compounds is
meant the capability to preserve their available oxygen
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decomposition of peroxide products (simple acid base
interaction) at the molar ratios H O : MgSO
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2
4
7
00 : 1 and H O : Na P O
590 : 1. According to
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2
4 2 7
the chemical analysis [11], the available oxygen con-
tent in the resulting solution is close to that calculated
theoretically. It is known from the literature that each
stabilizer has its own critical concentration up to
which it is effective. A greater amount of the sta-
bilizer could even promote peroxide solution decom-
position [7]. Furthermore, the process being developed
(
decrease in the absolute content of available oxygen
should not exceed 0.5 wt %) for a long time.
The best stabilizers of concentrated alkaline solu-
tions of H O are Na P O , magnesium salts of min-
eral acids, and certain organic compounds [5 10].
for producing KO requires that the H O alkaline
solutions be stable for no less than one day. Therefore,
to choose the optimal concentration of a stabilizer for
2 2 2
2
2
4 2 7
1
070-4272/03/7611-1858$25.00 2003 MAIK Nauka/Interperiodica

CHOICE OF A STABILIZER FOR THE REACTION OF KOH
1859
alkaline solutions. It should be noted that superoxide
ions remain stable in aqueous solution under study for
a rrelatively long time. This is important, because all
superoxides are known to readily decompose on con-
tact with water to the corresponding alkali with oxy-
gen evolution.
,
h
CONCLUSIONS
(1) A study of the stability of potassium peroxide
c, g dm 3
peroxosolvate solutions by chemical analysis showed
that the solution stabilized with MgSO (in the molar
4
Time of stability of H O alkaline solution as a func-
2
2
ratio MgSO : H O = 1 : 750) remains stable for
4
2 2
tion of the stabilizer concentration c: (1) MgSO and
4
one day at temperatures of up to 25 C.
2) Diamagnetic peroxide ions O2 disproportio-
(
2) Na P O .
4 2 7
(
2
the H O alkaline solution, we studied how the time
of stability of the resulting solution depends on the
stabilizer content in the starting H O solution. The
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nate to give paramagnetic superoxide ions O directly
in solution.
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2
results are shown in the figure.
REFERENCES
These data show that the amount of MgSO per
4
unit volume of the starting H O solution, required
2
2
1
. Morachevskii, A.G., Beloglazov, I.N., and Kasymba-
for the stabilization of the reaction between H O and
2
2
ev, B.A. Kalii: svoistva, proizvodstvo, primenenie
KOH and for the further storage of the resulting solu-
tion, is less than that of sodium diphosphate, all other
things being equal. Therefore, MgSO is preferable as
the stabilizer. In addition, MgSO is more readily
available and cheaper than Na P O .
(
Potassium: Properties, Production, Applications),
Moscow: Ruda i Metally, 2002.
4
2. Ferapontov, Yu.A., Simanenkov, S.I., Gur’ev, A.A.,
et al., Vestn. Tambov. Gos. Tekh. Univ., 2001, vol. 7,
no. 3, pp. 422 426.
4
2 7
4
According to the experimental data [2], MgSO4
does not affect the qualitative composition of the final
product, i.e., when hydrogen peroxide stabilized with
3. Zhdanov, D.V., Ferapontov, Yu.A., and Gur’ev, A.A.,
Tr. Tambov. Gos. Tekh. Univ., 2001, issue 8, pp. 210
219.
MgSO is used, the product obtained by the above-
4. Ferapontov, Yu.A., Zhdanov, D.V., and Glady-
shev, N.F., Sbornik trudov XV mezhdunarodnoi nauch-
noi konferentsii Matematicheskie metody v tekhnike i
tekhnologiyakh (Proc. XV Int. Scientific Conf.
Mathematical Methods in Industry and Technology ),
Tambov, 2002, vol. 3, pp. 161 166.
4
described technique is the same as the product ob-
tained from H O without adding magnesium sulfate
2
2
(
all other factors being the same). This conclusion is
confirmed by chemical analysis.
It was found that, with magnesium sulfate used as
a stabilizer for the reaction of H O with KOH, granu-
5
. Schumb, W.C., Satterfield, Ch.N., and Went-
worth, R.L., Hydrogen Peroxide, New York: Rein-
hold, 1955.
2
2
lated KOH could be used instead of the 50% KOH
solution. In this case, peroxide products did not de-
compose either.
6
. Khimiya i tekhnologiya perekisi vodoroda (The Chem-
istry and Technology of Hydrogen Peroxide), Sery-
shev, G.A., Ed., Leningrad: Khimiya, 1984.
Our experiments showed that, with time, the result-
ing H O alkaline solution acquired a distinct yellow
2
2
7. Pozin, M.E. Perekis’ vodoroda i perekisnye soedine-
niya (Hydrogen Peroxide and Peroxide Compounds),
Moscow: Goskhimizdat, 1951.
color suggesting the presence of superoxide ion. That
is, colorless diamagnetic peroxide ions O2 dispropor-
2
tionate directly in the solution to give colored para-
8
9
. FRG Patent 594806.
. UK Patent 433470.
magnetic superoxide ions O . We found no indica-
2
tions on this phenomenon in the available literature.
Kazarnovskii [12] studied this process only for solid
compounds. To confirm the occurrence of this process
in solution, we started the magnetic susceptibility
measurements. The preliminary results confirm the
1
0. US Patent 405532.
11. Seyb, E., and Kleinberg, J., J. Am. Chem. Soc, 1951,
vol. 73, p. 2308.
12. Kazarnovskii, I.A., Dokl. Akad. Nauk SSSR, 1975,
presence of diamagnetic ions in the resulting H O2
vol. 221, no. 2, pp. 353 356.
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 76 No. 11 2003