Russian Journal of Applied Chemistry, Vol. 75, No. 12, 2002, pp. 190331906.

Translated from Zhurnal Prikladnoi Khimii, Vol. 75, No. 12, 2002,
pp. 194331946.
Original Russian Text Copyright C 2002 by Titova, Nikol’skaya, Buyanov, Suprun.

INORGANIC SYNTHESIS
ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ ÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍÍ
AND INDUSTRIAL INORGANIC CHEMISTRY

Methods for Concentration of Hydrogen Peroxide

To Obtain It in Anhydrous Form
K. V. Titova, V. P. Nikol’skaya, V. V. Buyanov, and I. P. Suprun

Institute for Problems of Chemical Physics, Russian Academy of Sciences, Chernogolovka, Moscow oblast, Russia
Gosudarstvennyi Naucho-Issledovatel’skii Institut Biologicheskogo Priborostroeniya State Scientific Center,
Moscow, Russia

Received February 11, 2002

-
Abstract Methods for concentrating hydrogen peroxide and obtaining this compound in anhydrous form,
based on removal or binding of water from the surface of solution in an open vessel or in a closed volume and
also on binding of water directly in a H2O2 solution, are described.

Methods for concentration of aqueous solutions of
hydrogen peroxide in order to raise its concentration
up to 90 399% H2O2 markedly differ from methods
for obtaining anhydrous H2O2, containing no other
impurities, suitable for measuring physical parameters
of hydrogen peroxide. In the first case, water is re-
moved from aqueous solutions of H2O2 by ordinary
distillation or rectification [1]. This is done at mod-
erate temperatures and pressures of about 20 mm Hg.
A large number of old investigations in this field had
been devoted to concentration of diluted H2O2 solu-
tions obtained from solid peroxides, mainly BaO2 [2].
These studies are of only historical interest.
Anhydrous, high-purity hydrogen peroxide to be
used in physical measurements or in single-crystal
growth is commonly obtained by multiple freezing
of the solid phase from concentrated (95399%) solu-
tion [3]. This method involves considerable loss of
hydrogen peroxide and low yield of the target prod-
uct. Anhydrous hydrogen peroxide can be obtained
by extraction from a concentrated solution with ether
dehydrated with CaCl2 or P2O5 [4]. It should be noted
that the problem of obtaining anhydrous H2O2 of high
purity remains topical until now. This is so since
numerous physical properties of hydrogen peroxide,
reported in the literature, have been determined by
extrapolation to the anhydrous state of the system
H2O 3H2O2 at high hydrogen peroxide concentrations.
All the above techniques for concentration of H2O2
solutions involve gross energy expenditure, loss of
substance, and explosion hazard. It is known that
1070-4272/02/7512-1903 $27.00 C 2002 MAIK
microimpurities of many solids, catalysts for decom-
position of hydrogen peroxide, favor fast or explosive
decomposition of this compound upon heating. Ex-
plosive mixtures with hydrogen peroxide are also
formed in a wide range of compositions by numerous
organic substances used as solvents.
The authors made an attempt to develop safe and
energy-saving methods for concentrating and obtain-
ing anhydrous hydrogen peroxide. The methods de-
veloped are based on a fundamentally new technique,
specifically, removal or binding of water from the
surface of solutions of hydrogen peroxide or directly
in its solution. The methods require no heating, de-
sign of rectification apparatus, or use of organic sol-
vents.
EXPERIMENTAL
It is known [2] that, on keeping hydrogen peroxide
solutions in open state, their concentration increases
since the pressure of water vapor exceeds by more than
an order of magnitude the vapor pressure of hydrogen
peroxide (17.5 against 1.36 mm Hg at 20oC). How-
ever, account should be taken of the fact that, si-
multaneously with an increase in the concentration
of hydrogen peroxide, its decomposition is possible
under the catalytic action of the surface of a vessel
used or because of the ingress of catalytic impurities
into the solution from the air. No quantitative char-
acteristics of the process of H2O2 concentration by
water evaporation have been reported in the literature.
[Nauka/Interperiodica]
1904 TITOVA et al.

Table 1. Process of concentration of H2O2 (30%) solutions by natural evaporation of water

ÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ Without airflow ³ Air flow velocity 0.5 m s31
cf H2O2,*
ÃÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄ
³ h = 10 mm ³ h = 21 mm ³ h = 37 mm ³ h = 8 mm ³ h = 17 mm
% ÃÄÄÄÄÄÄÄÂÄÄÄÄÄÄÅÄÄÄÄÄÄÄÂÄÄÄÄÄÄÅÄÄÄÄÄÄÄÂÄÄÄÄÄÄÅÄÄÄÄÄÄÄÂÄÄÄÄÄÄÅÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄ
t t t t
³ , days ³ A, % ³ , days ³ A, % ³ , days ³ A, % ³ , days ³ A, % ³ , days ³ A, % t
ÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÅÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄ
50 ³ 4.5 ³ 93.0 ³ 10.0 ³ 94.0 ³ 14.5 ³ 92.5 ³ 1.7 ³ 91.0 ³ 4.0 ³ 94.0
55 ³ 6.0 ³ 89.5 ³ 12.5 ³ 91.5 ³ 17.5 ³ 90.5 ³ 2.5 ³ 89.0 ³ 6.1 ³ 89.8
60 ³ 7.5 ³ 86.0 ³ 16.0 ³ 89.8 ³ 21.0 ³ 86.6 ³ 3.4 ³ 86.0 ³ 6.0 ³ 86.9
65 ³ 9.5 ³ 81.0 ³ 18.0 ³ 88.5 ³ 27.0 ³ 83.5 ³ 4.5 ³ 81.8 ³ 6.8 ³ 84.1
70 ³ 13.0 ³ 70.0 ³ 22.0 ³ 79.0 ³ 35.0 ³ 77.0 ³ 6.0 ³ 74.9 ³ 7.9 ³ 79.0
ÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÁÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄ
* c H O is the final concentration of H O ; the same for Table 2.
f 2 2 2 2

Previously, the concentration of hydrogen perox-
ide solutions by means of natural evaporation of water
at room temperature and humidity has been studied.
A relationship between the degree of concentration
and loss of H2O2, on the one hand, and height of
solution layer and air flow velocity over the solution,
on the other, has been established [5]. Experiments
have been carried out in a laboratory compartment
with forced ventilation, with 30% H2O2 solutions.
The solutions were placed in polymeric cuvettes and
kept at 20oC in the absence of airflow over solution
or at 0.5 m s31 flow velocity. The air humidity was
varied between 35 and 45%. Every 24 h the solutions
were stirred and, after the intervals of time t, indi-
cated in Table 1, were weighed and analyzed for the
content of hydrogen peroxide by permanganatometric
titration to within +0.1%.
It was found that keeping a 30% solution of H2O2
in an open state is accompanied by a considerable
increase in H2O2 concentration without pronounced
loss of H2O2 ( Table 1). The time necessary for obtain-
ing a sufficiently concentrated, e.g., 60% solution of
H2O2 strongly depends on the height of the solution
layer, being equal to 7.5, 16, and 21 days for h 10,
Table 2. Process of concentration of H2O2 solutions in
a closed vessel over H2SO4
ÄÄÄÄÄÂÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄ
³ ³ cf H2O2 (%) after indicated ³
VH O , ³ h, ³ time , days t ³ AH2O2,*
ml ³ mm ÃÄÄÄÄÄÂÄÄÄÄÄÂÄÄÄÄÄÂÄÄÄÄÄ´ %
2 2
³ ³ 1 ³ 3 ³ 5 ³ 7 ³
ÄÄÄÄÄÅÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄ
300 ³ 40 ³ 40.3 ³ 49.6 ³ 53.8 ³ 75.5 ³ 63.2
150 ³ 20 ³ 45.3 ³ 51.7 ³ 76.9 ³ 99.6 ³ 31.6
100 ³ 13 ³ 49.4 ³ 55.1 ³ 80.3 ³ 99.1 ³ 30.4
50 ³ 7 ³ 53.3 ³ 77.2 ³ 98.8 ³ 98.0 ³ 26.6
30 ³ 4 ³ 67.7 ³ 81.0 ³ 99.7 ³ 3
³ 21.1
ÄÄÄÄÄÁÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄÁÄÄÄÄÄ
* At the highest concentration.
RUSSIAN JOURNAL OF APPLIED CHEMISTRY
21, and 37 mm, respectively. The yield A (%) of hy-
drogen peroxide was calculated by the formula
A = (mf cf ) / (ms cs ) 0 100,
where ms, mf is the mass of the starting and final so-
lutions (g); cs, cf is the concentration of the starting
and final H2O2 solution (wt %), respectively.
The yield of H2O2 in the form of a 60% solution
is (%) 86 for h = 10 mm, 90 for h = 21 mm, and 87
for h = 37 mm. Attempts to obtain more concentrated
solutions by making the exposure longer failed be-
cause of a considerable increase in the rate of H2O2
evaporation. At a cuvette area of 73.5 cm2 the output
capacity of the process for obtaining a 60% solution
was (g day31) 1.9 for h = 10 mm, 3.2 for h = 21 mm,
and 3.4 for h = 37 mm. Thus, raising the height of
the solution layer leads, on the one hand, to an in-
crease in the time necessary for a prescribed temper-
ature to be reached and, on the other, to a rise in
output capacity, with the loss of hydrogen peroxide
varying only slightly. With an air flow over solution,
the process of H2O2 concentration is much faster:
a 60% solution can be obtained in 3.5 3 6.0 days at
a flow velocity of 0.5 m s31, depending on the layer
height. In this case, the yield of H2O2 is 86 3 87%.
The process of concentration of hydrogen peroxide
solutions in a closed vessel over a desiccant is much
faster than that in the case of natural evaporation of
water [6]. H2O2 solutions were kept in a desiccator
over sulfuric acid. The acid volume was 560 ml; acid
surface area, 75 cm2; concentration of the starting
H2O2 solution, 31.7%. The process of concentration
occurs at both reduced and atmospheric pressure.
Solutions of any concentration can be obtained, in-
cluding nearly anhydrous solutions ( Table 2). Both
under natural evaporation of water and with its ab-
sorption from the gas phase over solution in a closed
Vol. 75 No. 12 2002
 METHODS FOR CONCENTRATION OF HYDROGEN PEROXIDE 1905

volume, the time in which a prescribed concentra- Table 3. Final H2O2 concentration cf in relation to the
tion of hydrogen peroxide is reached depends on concentration cs of the starting H2O2 solution and to the
the thickness of the solution layer. A concentration molar ratio Mg(ClO4)2 : H2O
close to 50% H2O2 is reached in 3 days at h = 20 and ÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄ
40 mm and in 1 day at h = 13 mm. A concentration cs H2O2, %
³ Mg(ClO4)2 : H2O, ³ c H O , %
close to 99% H2O2 is reached in 7 days at h = 20 mm ³ mol : mol ³ f 2 2
and 5 days at h = 4 mm. The loss of H2O2 grows
ÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄ
29.9 ³ 1.05 : 6 ³ 80.8
with increasing time of exposure and concentration, 30.2 ³ 1.07 : 6 ³ 82.0
to become 70 379% at H2O2 solution concentration 30.2 ³ 1.25 : 6 ³ 94.4
of 98 3 99%. A single example of H2O2 concentration 31.4 ³ 1.40 : 6 ³ 93.3
by a similar method has been reported in the litera- 45.8 ³ 1.00 : 6 ³ 90.9
ture: an 88% solution was obtained in a vacuum de- 72.8 ³ 1.00 : 6 ³ 94.2
siccator over H2SO4 in 3 days, with hydrogen perox- 76.6 ³ 1.40 : 4 ³ 95.6
ide loss of 19% [7]. The method developed in the 76.7 ³ 1.70 : 4 ³ 97.5
present study is a convenient laboratory technique 78.5 ³ 1.20 : 2 ³ 100.0
for obtaining minor amounts of highly concentrated 87.2 ³ 1.20 : 2 ³ 100.0
solutions and anhydrous hydrogen peroxide. 95.9 ³ 1.00 : 2 ³ 100.0
96.0 ³ 1.10 : 2 ³ 100.0
To significant disadvantages of the method based ÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÄÁÄÄÄÄÄÄÄÄÄÄÄ
on removal of water from the gas phase over an H2O2
solution belong pronounced loss of hydrogen peroxide (1.231.4) : 6. Introduction of a greater amount of mag-
and preservation of all impurities present in the start- nesium perchlorate into a 30% solution of H2O2 is in-
ing solution in the preparations obtained. The method expedient since a thick inhomogeneous suspension is
in which water is bound directly in solution is devoid formed in this case, with the process of hydrogen
of these disadvantages [8]. This technique yields H2O2 peroxide evaporation decelerated dramatically. Rais-
solutions of any concentration and anhydrous hydro- ing the concentration of the starting solution to 46 3
gen peroxide of high purity. It employs anhydrous 73% H2O2 at a constant ratio of 1 : 6 between mag-
magnesium perchlorate, capable of binding water to nesium perchlorate and water contained in solution
give hydrates Mg(ClO4)2 . nH2O (n = 2, 4, 6), as dry- does not make higher the concentration of the final
ing agent. Anhydrous magnesium perchlorate was ob- solution. Apparently, the forming magnesium perchlo-
tained by dehydration of a dihydrate Mg(ClO4)2 . 2H2O rate hexahydrate is partly dehydrated in vacuum evap-
in a vacuum with temperature gradually raised from oration of hydrogen peroxide. Finding its way into
20 to 220oC. the trap, water liberated in the process makes the con-
centration of hydrogen peroxide lower.
The device for concentration comprised a vessel for
reagent mixing, connected to a trap and, further, to To obtain a 953 98% H2O2 solution, it is necessary
a pumping system. To a H2O2 solution cooled to 0oC to use a 70% starting solution and introduce magne-
was added, in a [dry] box, anhydrous magnesium sium perchlorate in an amount corresponding to the
perchlorate. In most cases, viscous solutions were ratio Mg(ClO4)2 : H2O = (1.4 31.7) : 4, which leads
obtained because of the high solubility of Mg(ClO4)2 to formation of a mixture of magnesium perchlorate
in water [9] and in hydrogen peroxide [6]; suspen- tetra- and dihydrate. Anhydrous hydrogen peroxide is
sions were obtained when large amount of magne- formed upon treatment with magnesium perchlorate
sium perchlorate was added to a 30% solution of of a H2O2 solution with initial concentration of 80%
H2O2. Hydrogen peroxide was separated from the and more at a molar ratio Mg(ClO4)2 : H2O = (1.0 3
mixture obtained by vacuum distillation at 20oC into 1.2) : 2, which exceeds somewhat the ratio required
a trap cooled to 3196oC. A single treatment of a 30% for Mg(ClO4)2 dihydrate to be formed. In all exper-
H2O2 solution with magnesium perchlorate taken in iments, the loss of H2O2 does not exceed 1%.
a ratio Mg(ClO4)2 : H2O close to 1 : 6 [which corre-
To determine the stability of H2O2 during stor-
sponds to formation of magnesium perchlorate hexa-
age of solutions obtained using various concentration
hydrate (Table 3)] can bind most part of water pres-
methods in unstabilized form and stabilized with var-
ent in solution, with 813 82% hydrogen peroxide ob-
ious stabilizing additives known for hydrogen per-
tained by keeping in a vacuum.
oxide, the solutions were placed in nonhermetically
Solutions with higher concentrations (93394% H2O2) closed glass vessels and stored under identical condi-
can be prepared with molar ratio Mg(ClO4)2 : H2O = tions (20 + 2oC). After the intervals of time indicated
RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 12 2002
1906 TITOVA et al.

Table 4. Stability of H2O2 solutions obtained by removal CONCLUSION

or binding of water
ÄÄÄÄÄÄÄÄÂÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÂÄÄÄÄÄÄÄÄÄÄÄÄÄ The methods developed for concentrating hydro-
³ ³ ³ Loss of H2O2 (%) gen peroxide and obtaining it in anhydrous form are
Concentra- ³ c , ³ ³ in indicated based on (i) evaporation of water from the solution
tion ³ H2O2 ³ Stabilization
technique
³ time, days surface in an open vessel with and without air flow,
method ³ % ³ ÃÄÄÄÄÂÄÄÄÄÂÄÄÄ
³ ³ ³ 10 ³ 19 ³ 50 (ii) keeping a solution in a closed vessel over de-
ÄÄÄÄÄÄÄÄÅÄÄÄÄÄÅÄÄÄÄÄÄÄÄÄÄÄÅÄÄÄÄÅÄÄÄÄÅÄÄÄ hydrating agent, and (iii) binding of water directly
With ³ 65.1 ³ 3 ³ 3.1 ³ 6.7 ³ 9.1 in the H2O2 solution with anhydrous magnesium
air flow ³ ³ ³ ³ ³ perchlorate and separation of hydrogen peroxide by
³ ³Na4P2O7, 0.1% ³ 2.6 ³ 4.1 ³ 6.5 vacuum evaporation at 20oC.
³ ³Sn(OH)4, 0.3% ³ 3.7 ³ 5.0 ³ 7.4
³ ³Vacuum ³ 0.7 ³ 2.6 ³ 2.7 REFERENCES
³ ³evaporation ³ ³ ³
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RUSSIAN JOURNAL OF APPLIED CHEMISTRY Vol. 75 No. 12 2002