Interaction between gaseous ozone and crystalline potassium bromide

Article abstract of DOI:10.1134/S0036024416070189

The formation of nonvolatile products of the oxidation of a bromide ion during the interaction between gaseous ozone and powdered crystalline KBr is studied. It is found that potassium bromate KBrO₃ is the main product of the reaction. The influence of major experimental factors (the duration of ozonation, the concentration of ozone, the humidity of the initial gas, and the temperature) on the rate of formation of bromate is studied. The effective constants of the formation of bromate during the interaction between O₃ and Br^– in a heterogeneous gas–solid body system and in a homogeneous aqueous solution are compared.

Full text of DOI:10.1134/S0036024416070189

ISSN 0036-0244, Russian Journal of Physical Chemistry A, 2016, Vol. 90, No. 7, pp. 1312–1318. © Pleiades Publishing, Ltd., 2016.
Original Russian Text © A.V. Levanov, I.B. Maksimov, O.Ya. Isaikina, E.E. Antipenko, V.V. Lunin, 2016, published in Zhurnal Fizicheskoi Khimii, 2016, Vol. 90, No. 7, pp. 986–992.
CHEMICAL KINETICS
AND CATALYSIS
Interaction between Gaseous Ozone
and Crystalline Potassium Bromide
A. V. Levanova, I. B. Maksimova, O. Ya. Isaikinab, E. E. Antipenkoa, and V. V. Lunina,b
a Faculty of Chemistry, Moscow State University, Moscow, 119991 Russia
b Topchiev Institute of Petrochemical Synthesis, Russian Academy of Sciences, Moscow, 119991 Russia
e-mail: levanov@kge.msu.ru
Received July 14, 2015
Abstract—The formation of nonvolatile products of the oxidation of a bromide ion during the interaction
between gaseous ozone and powdered crystalline KBr is studied. It is found that potassium bromate KBrO3
is the main product of the reaction. The influence of major experimental factors (the duration of ozonation,
the concentration of ozone, the humidity of the initial gas, and the temperature) on the rate of formation of
bromate is studied. The effective constants of the formation of bromate during the interaction between O3 and
Br– in a heterogeneous gas–solid body system and in a homogeneous aqueous solution are compared.
Keywords: ozone, bromide, bromate, kinetics, topochemical reactions
DOI: 10.1134/S0036024416070189
INTRODUCTION
At the same time, very few works have been
devoted to the interaction between ozone and crystal-
line bromides. In [29], the interaction between ozone
and sodium chloride, bromide, and iodide was studied
in a fluid bed reactor. The concentration of ozone is
reduced slightly when it is passed through powdered
NaBr. In [26], the heterogeneous reaction between
ozone and sodium bromide was conducted by passing
an ozone-containing gas through a plate made of
porous glass, on which a sample of NaBr had been
placed. No interaction between the ozone and the dry
NaBr was detected. Molecular bromine has been
detected in gaseous reaction products after adding
water vapor to an initial gas mixture. Here, the con-
centration of water vapors was close to deliquescence
of sodium bromide. The heterogeneous decomposi-
tion of ozone over crystals of alkali metal bromides
and samples of sea salt was studied in [30]. The
decomposition of ozone over samples of pure alkali
metal bromides has never been detected. Ozone
decomposes quite rapidly over sea salt, and a certain
amount of Br2 molecular bromine evolves into the gas
Halogens are crucial to the atmospheric chemistry
[1, 2]. Bromine in various forms has a substantial
effect on the concentration of atmospheric ozone [3,
4]. Atomic bromine in particular initiates a sequence
of chemical reactions leading to a very strong reduc-
tion in the concentration of ozone in the arctic tropo-
sphere as the sun appears [5–10]. A humid or dry
aerosol of sea salt is a powerful source of halogens in
the marine atmospheric boundary layer.
Despite a great many studies, the mechanism
behind the evolution of active forms of halogens from
a marine aerosol has not been conclusively established
[1, 11, 12]. It is believed that the heterogeneous oxida-
tion of halogenides is an important route of their acti-
vation. The chemical reaction between ozone and bro-
mide ions in an aqueous solution [13–19] or on the
surface of a liquid aerosol [20–24] has been studied in
multiple works. The evolution of bromine from a
humid aerosol containing bromide ions into the gas
phase has been studied in some detail [21, 23–28]. It
appears that the rate of formation of Br2(gas) is much phase. All of the cited works contain only qualitative
data on the interaction between ozone and crystalline
alkali metal bromides, and only the gaseous products
of interaction have been determined. It has been
firmly established that under certain conditions,
Br2 molecular bromine can evolve into the gas phase
higher than the one predicted using a mechanism
developed on the basis of known chemical reactions in
an aqueous solution and in the gas phase. In order to
explain this phenomenon, a hypothesis regarding the
substantial increase in the reactivity of bromide ions
on the surface of the liquid aerosol (when compared to during interaction between ozone and bromides.
bromide ions in a volume) was proposed and con- Products that could have formed in the solid phase
firmed by calculations and a series of experimental (the main products of interaction) have yet to be
data [24].
studied.
1312

INTERACTION BETWEEN GASEOUS OZONE
1313
The aim of this work was to study the interaction to 320°C was 0.01%. The specimen of potassium bro-
between gaseous ozone and dry polycrystalline potas- mide was not specially purified or dried; when prepar-
sium bromide to determine the qualitative composi- ing an experiment, all operations with it were per-
tion of the products formed in the solid phase and the formed in an ordinary laboratory atmosphere at 20–
kinetics of their accumulation. No such studies have 25°C. Prior to treatment with ozone, the specimen of
ever been performed. The O3(gas) + KBr(cryst) sys- potassium bromide was kept in the reactor in a flow of
oxygen at the specified temperature and humidity for
tem was chosen because it simulates the natural pro-
cess of interaction between ozone and dry marine
aerosol. Dry sea salt is itself not suited for laboratory
studies because it is a complex multicomponent sys-
tem in which the content of bromide ions is not high.
20 min.
The specific surface area of crystalline potassium
bromide was estimated by measuring the dimensions
of its crystals with a microscope. As is well known,
potassium bromide forms crystals with a face-centered
cubic lattice of the NaCl type. Using a microscope, it
is easy to measure the length of diagonal d of the
EXPERIMENTAL
Powdered potassium bromide was treated with square face of a small crystal. This parameter varied
ozone in a glass thermostatted reactor. The working within the range of 525–675 μm for seven samples,
section of the reactor was a vertically positioned glass and the average value was 581 μm. Assuming that the
cylinder, in the lower part of which a disk made of crystals were regular cubes, the specific surface area
was calculated using the formula S/m = 3 × 23/2/(ρd),
where ρ = 2.75 g/cm3 is the density of crystalline KBr.
We found that S/m = 46–59 cm2/g, and the average
value was 53 cm2/g.
porous glass was sealed. During the experiments, pow-
dered potassium bromide was placed onto this disk,
and the gases entered the reactor through the disk as
well. The amount of potassium bromide in the reactor
was either 10 or 25 g. In order to ensure effective con-
tact between the surfaces of small crystals of potassium
bromide and the gases, the reactor was shaken verti-
cally during the experiments. The amplitude of move-
ments was ~10 cm, and the frequency of shaking
(7 s‒1) was specially selected.
Ozone was obtained by passing extra pure oxygen
through a barrier discharge in an ozone generator. The
concentration of ozone was measured using a Medo-
zon photometric ozone measuring device and verified
with an Agilent 8453 spectrophotometer. The maxi-
mum concentration of ozone was 3.5–4 vol %. The
flow rate of the initial oxygen was 21.75 L/h (STP) in
all experiments. The gas pipelines were made of
polytetrafluoroethylene or polyvinylchloride tubing
resistant to ozone.
In [31], the specific surface area of powdered crys-
talline KBr was determined via the Brunauer–
Emmett–Teller (BET) method and was 440 (by water)
and 600 cm2/g (by krypton) for the 125–200-μm frac-
tion. If we extrapolate this data to the sizes of our small
crystals of KBr under the assumption that the specific
surface area is inversely proportionate to the length of
the diagonal of the square face, we obtain values of
100 (water) and 137 cm2/g (Kr).
A qualitative analysis of our sample of powdered
potassium bromide after the treatment with ozone was
performed by means of IR spectroscopy. The sample
was pressed into a pellet that was placed into a cell
holder of an EQUINOX 55/S IR spectrometer
(Bruker), and the IR absorption spectrum was regis-
tered in the range of 360–4000 cm−1.
Quantitative determination of the bromate in our
ozonated powdered KBr was performed based on the
concentration of tribromide ions formed upon dis-
solving the sample in an acid, using an indirect spec-
trophotometric method. It is known that the following
reaction occurs during the acidification of an aqueous
solution containing bromate and bromide ions:
The humidity of the initial oxygen was estimated
from the increase in the weight of a trap placed into a
cooling bath with temperatures of −65 to −70°C,
through which the gas was passed at a constant rate
over a certain time. Since the increase in the weight
was due only to the condensation of water, we found
that the content of water vapor (the absolute humidity
of the oxygen) was 0.15 vol %.
BrO3− + 5Br− + 6H+ → 3Br3− + 3H2O,
as a result of which one bromate ion forms three
tribromide ions [32]. A tribromide ion has strong UV
absorbance (λmax is 266 nm and ε is 40900 M–1 cm–1)
[33].
For the quantitative determination of bromate, 5 g
of the sample of potassium bromide was dissolved in
50 mL of 2.5 M H2SO4, the solution was placed into an
To add known concentrations of water vapor into
the gas mixture, the gases were passed through a ther-
mostatted bubble flask filled with distilled water
upstream of the inlet to the reactor. The humidity of
the gases was determined by the temperature of the
bubble flask. In order to avoid the condensation of
water vapor in the gas pipelines, the temperature of the
bubble flask did not exceed room temperature in our
experiments.
Chemically pure grade potassium bromide (GOST optical cell with a path length of 1 cm, and the absorp-
(State Standard) 4160-74) with an assay of 99.97% was tion spectrum was registered relative to air. An Agilent
used in the experiments. The weight loss upon heating 8453 spectrophotometer was used. The concentration
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1314
LEVANOV et al.
793 сm−1
432 сm−1
1
2
3
0
1000
2000
3000
4000
Wave number, сm−1
Fig. 1. Infrared absorption spectra of (1) ozone-treated powdered crystalline KBr, (2) KBrO in a KBr pellet, and (3) pure KBr.
3
The initial gases contained 3.3 vol % O , 0.15 vol % H O, and the remainder was O ; the temperature was 60°C; and the duration
3
2
2
was 50 min.
of bromate was determined from the value of the O3(gas) and NaCl(cryst) [42], and potassium iodate
absorbance density at 266 nm (low concentrations of
bromate), 380 nm (medium concentrations), or
445 nm (high concentrations) using preliminarily
constructed calibration dependences. The detection
limit was ~1 × 10–6 M bromate in the solution, which
corresponded to ~0.25 μmol of bromate in 25 g of
potassium bromide. The relative error of the proce-
dure did not exceed 5%.
KIO3 is the product of the reaction between O3(gas)
and KI(cryst) [43–45].
The rest of this work is devoted to studying the
quantitative kinetics of the formation of bromate. The
number of moles of KBrO3 formed during the experi-
ment was directly proportional to the size of the sam-
ple of the initial potassium bromide. It is worth to note
that the amount of bromate is also proportional to the
duration of ozonation, allowing for the error (Fig. 2).
In other words, the rate of formation of bromate is
roughly constant during the experiment. Generally
speaking, the process of interaction of gaseous ozone
with solid potassium bromide is a topochemical reac-
tion. Specific kinetics, particularly the S-shaped
appearance of the integral kinetic curve, the presence
of an induction period, and the transiting of the reac-
tion rate through the maximum and its subsequent
substantial drop to zero or some time-independent
value are characteristic of such reactions [46]. Our
understanding is that under the conditions of our
experiments, the constancy of the rate of formation of
the product is determined by the emergence of a
RESULTS AND DISCUSSION
New strong absorption bands with maxima at 432
and 793 cm−1 emerged in the IR spectrum of ozone-
treated powdered KBr (Fig. 1, spectrum 1). A com-
parison to the experimental spectrum of potassium
bromate (diluted 50-fold by weight, in a KBr pellet)
(Fig. 1, spectrum 2) and to the literature data [34–41]
−
shows that these bands belong to a bromate ion
.
BrO3
There were no other new bands in the spectrum of the
sample of KBr. It was therefore found for the first time
in this work that potassium bromate KBrO3 was the
only nonvolatile product of the interaction between steady-state concentration of the nucleation centers of
solid KBr and gaseous ozone. It is interesting that sim- a new phase of KBrO3. Due to the shaking of the reac-
ilar salts formed during the interaction between ozone
and crystalline chlorides and iodides; sodium chlorate
NaClO3 is thus a product of the reaction between
tion substrate, the nucleation centers, once they form,
are constantly reproduced rather than blocked by a
layer of the product, as happens in the normal mode of
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INTERACTION BETWEEN GASEOUS OZONE
1315
−
−
n(BrO3)/(Δt × m(KBr)), μmol g−1 min−1
n(BrO3)/m(KBr), μmol/g
5
4
3
2
1
0.20
0.15
0.10
0.05
0
1
2
3
0
10
20
30
40
50
t, min
C(O3), vol %
Fig. 3. Typical dependences of the specific rate of forma-
tion of bromate on the content of ozone in the initial gas
mixture. The temperature is 60°C and the content of water
Fig. 2. Dependences of the amount of bromate formed in
treating powdered KBr with ozone on the duration of
treatment. The initial gases contained 3.3 vol % O ,
3
vapor is (⬤) 0.15 and ( ) 2.4 vol %.
▲
0.15 vol % H O, and the remainder was O ; the tempera-
2
2
ture was 60°C. The dashed lines show the margins of the
error interval of the linear regression at a confidence level
of 95%.
surface was not renewed but was blocked by a layer of
the product, a substantial drop in the rate of formation
of bromate would have been observed in our experi-
ments (duration, 20–60 min). However, this does not
actually occur.
performing topochemical reactions. The probable
mechanism of formation of the new phase of potas-
sium bromate can be described as follows: At the initial
stage, as in all topochemical reactions, nucleation
centers form. Crystallites of KBrO3 grow quite rapidly
over these nucleation centers. With the gain in the size
of the crystallites, they detach from the surface of the
crystals of the substrate because of the mutual colli-
sions during shaking. At the same time, a small
amount of the new phase stays at the place of detach-
ment. This residue is an already formed nucleation
center over which the crystallite grows once again, and
so on.
Since the amount of bromate is directly propor-
tional to the weight of KBr and the duration of treat-
ment, the kinetics of its formation can be character-
ized using the specific rate n(
BrO3
− )/(Δtm(KBr)),
μmol min−1 g−1, which is equal to the ratio of the num-
ber of moles of bromate n(
− ), μmol, to the dura-
BrO3
tion of ozonation Δt, min, and weight of initial potas-
sium bromide, m(KBr), g. The typical dependences of
the specific rate of formation of potassium bromate on
the concentration of ozone in the gas phase at the inlet
of the reactor are presented in Fig. 3. In all our exper-
iments, the specific rate was directly proportional to
the concentration of O3. It was therefore logical to
determine the effective rate constant of the formation
of bromate, which is equal to the ratio of the specific
rate, μmol min−1 g−1, to the concentration of ozone in
the gas phase C(O3), μmol/L:
These perceptions are confirmed by the character-
istic value of the rate of formation of bromate in our
experiments being 0.1 μmol g−1 min−1 = 6 × 1014 par-
ticles cm−2 min−1 (assuming that the reaction proceeds
over the surface of a crystal of potassium bromide,
while the value of the specific surface area s =
100 cm2/g). The number of superficial bromide ions
can be estimated using the formula nBr–
=
n(BrO3−)
C(O3)Δtm(KBr)
(ρKBrNA/MKBr
)
2/3, where ρKBr = 2.75 g/cm3 is the den-
k(
− ) =
BrO3
, L g−1 min−1.
sity of crystalline KBr [47], NA = 6.02 × 1023 mol−1 is
the Avogadro constant, and MKBr = 199.00 g/mol is
the molecular weight of KBr. It is 5.8 × 1014 parti-
Humidity and temperature are the key factors affect-
ing the formation of bromate. The rate constant of the
cles/cm2, i.e., nearly equal to the number of bromate formation of bromate k(
− ) grows substantially
BrO3
ions formed on the surface over 1 min. If the reactive with a rise in the humidity of the initial gases (Fig. 4).
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1316
k, L g−1 min−1
LEVANOV et al.
lnk [L g−1 min−1]
−8
0.0004
0.0003
0.0002
0.0001
−9
−10
−11
−12
ln k = 10.12 − 6387/T
0.0028
0.0030
0.0032
0.0034
0
1
2
3
C(H2O), vol %
1/T, K−1
Fig. 5. Dependences of the effective rate constant of for-
Fig. 4. Dependence of the effective rate constant of the for-
mation of bromate on temperature. The concentration of
mation of bromate on the content of water vapor in the ini-
water vapor in the initial gases is (⬤) 0.15 and ( ) 2 vol %.
tial gases. The initial gases contained 1.6 vol % O and the
▲
3
remainder was O and H O; the temperature was 60°C.
2
2
factors such as the temperature and amount of
Note that when dried oxygen (passed through a trap adsorbed water. At low temperatures, when the mobil-
cooled to −70°C) is used, the rate of formation of bro- ity of ions is relatively low, it would seem adsorbed
mate is almost the same as when the content of water water can partially block the reactive surface. At an
vapor is 0.15 vol % in the initial gas. This is probably elevated temperature, under the conditions of a sub-
due to the water absorbed from the atmosphere, with stantial increase in the mobility of ions, adsorbed
which the substrate comes into contact prior to the water, on the contrary, promotes higher freedom of
experiment, remaining on the surface of the potassium movement of bromide ions and thus facilitates their
bromide.
The dependence of the logarithm of the rate con-
stant of formation of bromate k(
− ) on the recipro-
cal temperature is shown in Fig. 5. The Arrhenius law
is obeyed in the temperature range of 24–70°C and at
the water vapor content of 0.15 vol % in the initial gas;
the expression for the temperature dependence of the
constant is written as
contact with ozone.
It is known that the formation of a bromate ion in
the reaction between bromide and an ozone molecule
in an aqueous solution occurs according to the mech-
anism [16]
BrO3
Br– + O3 → BrO– + O2,
BrO– + O3 → Br– + 2O2,
(1)
(2)
k(
BrO3
− ) = 2.48 × 105exp(−6390/T), L g−1 min−1.
−
BrO– + O →
+ O2,
(3)
BrO2
3
The deviations at high temperatures are most likely
due to the drop in the actual concentration of ozone
near the surface of the crystals as a result of the ther-
mal decomposition of ozone or the transition to the
diffusion mode.
BrO2−
+ O → … →
− + O2.
BrO3
3
The formation of hypobromite is the limiting stage.
The hypobromite ion interacts quite readily with the
second ozone molecule and can either transform back
into bromide or oxidize into bromite. The bromite ion
readily interacts with ozone to form bromate [48].
During the interaction between ozone and crystalline
potassium bromide, bromate probably also forms as a
result of the successive oxidation of the bromide ion
according to the scheme
At a 2 vol % content of moisture, the dependence
of ln k(
− ) on T−1 has a more complex character. At
BrO3
a temperature of 30°C, the constant is lower when
compared to the dry gas. At higher temperatures, the
constant becomes higher in the humid gas, compared
to the dry gas. Our understanding is that this character
of the dependence is due to an increase in the mobility
of superficial bromide ions under the action of two
Br– → BrO– → BrO2− → BrO3− .
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INTERACTION BETWEEN GASEOUS OZONE
1317
It was of interest to compare our kinetic data on the
k (
BrO3
− ), cm3 particle−1 s−1, and the ratios of con-
het
interaction between gaseous ozone and a bromide ion
in the composition of crystalline KBr with the kinetics
of the reaction between O3 and Br– in an aqueous
solution. We perform this comparison for 60°C
because most of the results of this work are related to
this particular temperature. In the solution, the effec-
tive constant of formation of bromate is determined by
stants k (
− )/k (
− ) at 60°C:
BrO3 BrO3
het
aq
Concentration of H2O
in the initial gas, vol %
0.15
2.4
3.1
−
k (
)
3.2 × 10–20 7.2 × 10–20 1.0 × 10–19
3− ) 0.04–0.06 0.10–0.14 0.13–0.20
het BrO3
k (
− )/k (
het BrO3 aq BrO
the formula k (
BrO3
− ) = k1/(1 + k2/k3), where k1, k2,
aq
The above data show that bromide ion reacts with
ozone faster in an aqueous solution than on the surface
of a crystal of KBr. The humidity (and thus the
amount of superficially adsorbed water) has a strong
influence on the reactivity of a superficial Br– bromide
ion toward ozone. With an increase in humidity, the
rate of interaction increases substantially; in our
experiments, the rate constant of the heterogeneous
reaction reached ~20% of the value of the constant in
our aqueous solution.
and k3 are the rate constants of stages (1)–(3).
At 60°C, the constant k1 adopts values of 1.5 ×
103 L mol−1 s−1 = 2.5 × 10−18 cm3 particle−1 s−1 [14],
1.0 × 103 L mol−1 s−1 = 1.7 × 10−18 cm3 particle−1 s−1
[16], and 1.3 × 103 L mol−1 s−1 = 2.2 × 10−18 cm3 par-
ticle−1 s−1 [17]. The value of the ratio k2/k3 is only
known at 25°C and is 3.3 [16]. We assume that k2/k3 ≈
3.3 at 60°C as well, and we find that the effective con-
stant of formation of bromate k (
BrO3
− ) = (5.0–7.5) ×
10−19 cm3 particle−1 s−1 at this temperature. By defini-
tion, parameter k (
− ) is equal to the fraction of
aq
CONCLUSIONS
It was found for the first time that potassium bro-
mate KBrO3 is the main product of the reaction
between gaseous ozone and powdered crystalline
BrO3
aq
those bromide ions in 1 cm3 of the solution that
undergo oxidation with ozone with the formation of potassium bromide. The influence of significant
experimental factors (the duration of ozonation, con-
centration of ozone, humidity of the initial gas, and
temperature) on the rate of formation of bromate was
studied. In our experiments, this rate did not depend
on time and grew along with the concentration of
ozone and temperature. In most experiments, the
effective rate constant of formation of bromate during
the heterogeneous reaction was one to two orders of
magnitude lower than that of the O3(sol) + Br–(sol)
process in an aqueous solution. At temperatures above
45°C, an increase in the humidity leads to a substantial
rise in the constant of formation of bromate.
bromate over a time of 1 s at a concentration of ozone
in the solution of 1 molecule/cm3.
The effective rate constant of the formation of bro-
mate during the interaction between O3(gas) and
KBr(cryst) is presented in Fig. 4, depending on the
humidity of the initial gas at 60°C. It is obvious that
the reaction proceeds over the surface of the crystal,
and we express the constant in units such as cm3 parti-
cle−1 s−1, allowing us to compare it to the similar
parameter in the solution using the ratio k (
BrO3
− ) =
het
(1000/60) × k(
− )/(snBr–). In this formula,
BrO3
− ) and k( − ) is the constant in such units
ACKNOWLEDGMENTS
This work was supported by the Russian Founda-
tion for Basic Research, project no. 10-05-01136-a.
k (
BrO3 BrO3
het
as cm3 particle−1 s−1 and L g−1 min−1, respectively; s,
cm2/g, is the specific surface area of the crystals of
KBr; nBr– = 5.8 × 1014 particles/cm2 is the number of
bromide ions on the surface of the crystal (see the esti-
mate above). Based on the data presented above, we
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2016