Catalysis of the reaction of ozone with chloride ions by metal ions in an acidic medium

Article abstract of DOI:10.1007/s10975-005-0021-z

It was found that VO²⁺, Fe³⁺, Co²⁺, and Cu²⁺ ions catalyze the reaction of O₃ with Cl^- in an acidic medium. The dependence of the rate of Cl₂ liberation in the reaction of O₃ with Cl^- on the concentrations of H⁺, VO²⁺, Fe³⁺, Co²⁺, and Cu ²⁺ ions in the reaction solution was studied. A reaction scheme was proposed to explain the experimentally found catalytic effects of these ions. The constants that characterize the steps of the proposed scheme were determined.

Full text of DOI:10.1007/s10975-005-0021-z

Kinetics and Catalysis, Vol. 46, No. 1, 2005, pp. 138–143. Translated from Kinetika i Kataliz, Vol. 46, No. 1, 2005, pp. 147–152.
Original Russian Text Copyright © 2005 by Levanov, Kuskov, Koiaidarova, Zosimov, Antipenko, Lunin.
Catalysis of the Reaction of Ozone with Chloride Ions
by Metal Ions in an Acidic Medium
A. V. Levanov, I. V. Kuskov, K. B. Koiaidarova, A. V. Zosimov, E. E. Antipenko, and V. V. Lunin
Department of Chemistry, Moscow State University, Moscow, 119899 Russia
Received July 23, 2003; in final form, August 3, 2004
Abstract—It was found that VO2+, Fe3+, Co2+, and Cu2+ ions catalyze the reaction of O3 with Cl– in an acidic
medium. The dependence of the rate of Cl2 liberation in the reaction of O3 with Cl– on the concentrations of
H+, VO2+, Fe3+, Co2+, and Cu2+ ions in the reaction solution was studied. A reaction scheme was proposed to
explain the experimentally found catalytic effects of these ions. The constants that characterize the steps of the
proposed scheme were determined.
INTRODUCTION
([HCl] + [NaCl] = 1 mol/l) and various metal salts
whose concentration was no higher than 0.1 mol/l. To
prepare the solutions, we used the following: distilled
water; hydrochloric acid standard titrimetric substance
(1 mol/l); chemically pure sodium chloride; potash
alum and iron(II) sulfate heptahydrate of analytical
grade; chromic potassium alum, potassium dichromate,
iron(III) chloride hexahydrate, cobalt(II) sulfate hep-
tahydrate, nickel nitrate hexahydrate, copper sulfate
pentahydrate, zinc chloride, and tin(II) chloride dihy-
drate of reagent grade; and vanadyl sulfate trihydrate
and cerium nitrate hexahydrate, which were prepared
from available reagents and recrystallized.
The catalytic effects of various metal ions in the
reaction of ozone with the chloride ion are of interest
from the standpoint of atmospheric chemistry. Marine
aerosol, which contains various transition metal salts
along with main components, is the main source of
atmospheric chloride ions. A great amount of chlorine
leaves the aerosol; however, the mechanism of this pro-
cess has not been conclusively established [1]. On the
other hand, the concentration of molecular chlorine in
the marine boundary layer cannot be explained by cur-
rently known chemical reactions [2]. It is likely that
these phenomena are due to the rapid reaction of ozone
with the chloride ion, catalyzed by various metal ions
and hydrogen ions.
In our experiments, we determined the ratio of the
rate of Cl2 release from the reactor to the volume of the
The aim of this work was to study the catalytic
effects of various metal ions in the reaction of ozone
with the chloride ion in acidic solutions and to examine
the effect of catalyst concentration on the kinetics of
this reaction.
Determination of the conditions under which the
reaction of O3 with Cl– is accelerated will furnish
insights into general methods for increasing the reactiv-
ity of ozone toward inert substrates.
dnCl
1
2
--- -----------
test solution,
(henceforth, the rate of chlorine
V dt
release), as a function of the concentrations of various
metal ions and hydrogen ions in the reaction solution.
The rate of chlorine release was related to the apparent
rate constant of the O3 + Cl– reaction (kapp) by the equa-
dnCl
1
2
--- -----------
tion
= kapp[Cl–][O3]. The current concentration
V dt
of the chloride ion in the reaction solution was virtually
equal to the initial concentration (1 mol/l) because the
amount of chlorine released from the reactor during the
EXPERIMENTAL
The reaction between ozone and acidic solutions experiment time was negligibly small, compared to the
containing chloride ions was performed in a bubbling initial amount of chloride ions. We did not determine
reactor at room temperature (20°C). The experimental the concentration of ozone in the reaction solution
setup was described previously in [3]. The experimen- because almost all of the metal compounds used in our
tal procedure was analogous to that described else- experiments exhibited considerable absorption in the
where [3]. In all the experiments, the flow rate of ozo- region of the spectrum used for the determination of
nized oxygen was 21 l/h and the concentration of ozone dissolved ozone in accordance with a previously pro-
at the reactor inlet was equal to 10.0 g/m3. Before the posed procedure [3]. Taking into account that metal
experiment, ~170 ml of a test solution was placed in the ions were present in low concentrations in solution and
reactor; the true volume of the solution was determined are relatively inert with respect to ozone (except for
by preliminary density measurement and weighing. reducing metals), the concentration of dissolved ozone
The test solutions contained 0.01–0.8 M HCl and NaCl in solution can be estimated based on previous data [3].
0023-1584/05/4601-0138 © 2005 MAIK “Nauka /Interperiodica”

CATALYSIS OF THE REACTION OF OZONE WITH CHLORIDE IONS
139
(dnCl2/dt)/V, µmol l–1 min–1
According to these data, the concentration of ozone is
equal to 49 µmol/l in an aqueous solution containing
HCl and NaCl ([HCl] + [NaCl] = 1 mol/l) at 20°C and
a 10.0 g/m3 concentration of ozone in the initial gas
mixture. This estimate of the concentration of dissolved
oxygen is true only when there are no substances in the
solution that rapidly react with ozone.
40
30
20
10
RESULTS AND DISCUSSION
0
0.01
0.02
0.03
[VO2+], mol/l
In experiments on the effect of the nature of metal
ions on the rate of the reaction of O3 with Cl–, the test
solution contained 0.4 M HCl, 0.6 M NaCl, and a metal
salt. In the absence of metal salts, the rate of chlorine
release was equal to 17–18 µmol l–1 min–1. The pres-
ence of KAl(SO4)2, KCr(SO4)2, Ni(NO3)2, CuSO4,
ZnCl2, and Ce(NO3)3 in a concentration of 0.01 mol/l or
K2Cr2O7 in a concentration of 0.005 mol/l did not result
in a change in the rate of chlorine release. Upon the
addition of VOSO4, FeCl3, or CoSO4 in a concentration
of 0.01 mol/l to the test solution, the rate of chlorine
release increased to 22, 23, or 115–120 µmol l–1 min–1,
respectively. At a concentration of H+ in the reaction
solution higher than 0.4 mol/l, the addition of 0.01 M
CuSO4 also resulted in an increase in the rate of chlo-
rine release. In the presence of SnCl2 or FeSO4 in a con-
centration of 0.01 mol/l in the reaction solution, the oxi-
dation of Sn2+ ions to Sn4+ (or Fe2+ to Fe3+) with ozone
occurred initially; in this case, chlorine was not liber-
ated. After oxidation was complete, the reaction of
ozone with the chloride ion began and chlorine was
released. The presence of tin ions in the solution did not
increase the rate of chlorine release. In the presence of
iron ions, the rate of chlorine release increased to
20 µmol l–1 min–1. In the case of the addition of a salt to
a Fe2+ salt solution, the rate of chlorine release was
somewhat lower than that with the addition of Fe3+; this
was likely due to the fact that only a portion of Fe2+ was
converted into a catalytically active species. Thus,
VO2+, Fe3+, Co2+, and Cu2+ ions catalyze the reaction of
O3 with Cl– in an acidic medium, whereas Al3+, Cr3+,
Fig. 1. Dependence of the rate of chlorine release on the
2+
concentration of VO in the reaction solution. Solution
composition: 0.4 M HCl + 0.6 M NaCl + VOSO . Points
4
and lines correspond to experimental data and model calcu-
lations, respectively.
(dnCl2/dt)/V, µmol l–1 min–1
40
30
1
20
2
10
0
0.5
[H+], mol/l
Fig. 2. Dependence of the rate of chlorine release on the
+
concentration of H in the reaction solution. Solution com-
position: [HCl] + [NaCl] = 1 mol/l. (1) 0.01 M VOSO was
4
present in solution; (2) blank experiment (VOSO was
4
absent). Points and lines correspond to experimental data
and model calculations, respectively.
(dnCl2/dt)/V, µmol l–1 min–1
50
40
30
20
10
Cr2O27– , Ni2+, Zn2+, Sn4+, and Ce3+ ions do not have a
catalytic effect. Note that the catalytic effects of the
above ions can be affected under changes in the acidity
of the test solution.
0
0.02 0.04 0.06 0.08 0.1
[Fe3+], mol/l
Fig. 3. Dependence of the rate of chlorine release on the
3+
We studied the effect of the concentration of cata-
lysts (VO2+, Fe3+, Co2+, and Cu2+), as well as hydrogen
ions in the presence of each of the above ions, on the
rate of chlorine release in the reaction of O3 with Cl– in
an acidic medium. Figures 1–6 illustrate the experi-
mental results.
concentration of Fe in the reaction solution. Solution
composition: 0.4 M HCl + 0.6 M NaCl + FeCl . Points and
3
lines correspond to experimental data and model calcula-
tions, respectively.
formed; these are capable of oxidizing the chloride ion
(charge-transfer catalysis). Second, a catalytic complex
that decomposes with the liberation of chlorine (coor-
dination catalysis) can be formed.
The catalytic effect of metal ions in the reaction of
ozone with chloride ions in an acidic medium can be
explained as described below: First, in oxidation with
ozone, metal ions in a higher oxidation state can be
The interactions of VO2+, Fe3+, Co2+, and Cu2+ with
KINETICS AND CATALYSIS Vol. 46 No. 1 2005

140
LEVANOV et al.
(dnCl2/dt)/V, µmol l–1 min–1
50
The spectroscopic data indicated that VO+2 was
formed on passing ozonized oxygen through a 0.02 M
VOSO4 solution in 1 M H2SO4. The resulting solution
of pentavalent vanadium did not react with HCl (con-
centration to 4 mol/l).
40
30
20
10
1
2
3
Based on a study of the spectra, we can conclude
that trivalent cobalt compounds were formed on the
treatment of 0.001–0.1 M CoSO4 solutions in 0.1–6 M
H2SO4 with ozonized oxygen. On mixing the resulting
Co3+ solutions with HCl or NaCl solutions, a rapid
reaction occurred, during which Co2+ and molecular
chlorine were formed. After mixing, the reaction was
complete in a few seconds.
0
0.2 0.4
0.6 0.8
[H+], mol/l
Fig. 4. Dependence of the rate of chlorine release on the
+
concentration of H in the reaction solution. Solution com-
position: [HCl] + [NaCl] = 1 mol/l. (1) 0.01 M FeCl was
3
present in solution; (2) 0.01 M CuSO was present in solu-
4
tion; (3) blank experiment (FeCl or CuSO was absent).
3
4
The Fe3+ (0.005 å Fe2(SO4)3 in 4.8 M H2SO4) and
Cu2+ (0.01 å CuSO4 in 4.8 M H2SO4) ions did not
react with ozone. This is consistent with the published
data [4].
Points and lines correspond to experimental data and model
calculations, respectively.
(dnCl2/dt)/V, µmol l–1 min–1
Thus, only coordination catalysis can occur in the
case of VO2+, Fe3+, and Cu2+ ions. Generally speaking,
both charge-transfer and coordination catalysis can
occur in the case of the Co2+ ion.
150
120
90
60
To explain the experimental dependence of the rate
of chlorine release on the concentration of a catalyst
(VO2+, Fe3+, Co2+, Cu2+, or H+ ions), we performed a
simplified simulation of the kinetics of chlorine release.
30
0
0.01 0.02 0.03 0.04 0.05
[Co2+], mol/l
To perform model calculations, we used the fact
that steady-state conditions were established in the
course of our experiments; that is, the rate of chlorine
release and the composition of the reaction solution,
particularly the concentration of dissolved ozone, did
not depend on time. The steady-state conditions were
due to the facts that the system was open, ozone was
supplied at a constant rate, and the amount of chlorine
released from the reactor was negligibly small, com-
pared to the initial amount of chloride ions. Previously
[3], we substantiated the occurrence of steady-state
conditions in a similar case. We estimated the concen-
tration of ozone in solution (49 µmol/l under condi-
tions of our experiments) based on previously pub-
lished data [3].
Fig. 5. Dependence of the rate of chlorine release on the
2+
concentration of Co in the reaction solution. Solution
composition: 0.4 M HCl + 0.6 M NaCl + CoSO . Points and
4
lines correspond to experimental data and model calcula-
tions, respectively.
(dnCl2/dt)/V, µmol l–1 min–1
150
1
120
90
60
2
30
0
0.2 0.4 0.6 0.8
The following processes that lead to the release of
chlorine into a gas phase were taken into consideration:
First, the reaction of ozone with chloride ions catalyzed
by H+ ions (in the absence of transition metal ions). The
kinetics of this reaction was studied in detail previously
[3]. Second, coordination catalysis by metal ions.
Third, charge-transfer catalysis (only for Co2+ ions).
[H+], mol/l
Fig. 6. Dependence of the rate of chlorine release on the
+
concentration of H in the reaction solution. Solution com-
position: [HCl] + [NaCl] = 1 mol/l. (1) 0.01 M CoSO was
4
4
present in solution; (2) blank experiment (CoSO was
absent). Points and lines correspond to experimental data
and model calculations, respectively.
Thus, the entire set of chemical processes leading to
the release of Cl2 in the reaction of ozone with chloride
ions in an acidic medium in the presence of metal salts
that exhibit a catalytic effect can be represented as the
reaction scheme given below (the constants at 20°C are
given):
ozone and of VO2+ and Co3+ with the chloride ion were
studied experimentally. The progress of the reaction
was monitored by measuring the absorption spectra of
reaction solutions in the UV and visible regions.
KINETICS AND CATALYSIS Vol. 46 No. 1 2005

CATALYSIS OF THE REACTION OF OZONE WITH CHLORIDE IONS
141
Cl– + O3
H+ + O3 + Cl–
ClO– + O2,
HO3Cl,
k1 = 0.088 l mol–1 min–1;
K2 = 0.079 l2/mol2;
k3 = 9.9 min–1;
(I)
(II)
HO3Cl
HOCl + O2,
(III)
(IV)
ClO– + Cl– + 2H+
Cl2 + H2O or
Cl2 + H2O,
HOCl + Cl– + H+
rapidly established equilibria;
Mm+ + O3 + nH+ + xCl–
HnMO3Clx,
the equilibrium constant K5 is determined based
on experimental data;
(V)
Mm+ + O2 + Cl2
the rate constant k6 is determined based on
experimental data;
(VI)
HnMO3Clx
+ H2O + (n – 2)H+ + (x – 2)Cl–,
Co2+ + O3
Co3+ + O2,
w7 = k7[Co2+][O3], the rate constant k7 is determined based
on experimental data;
(VII)
Co3+ + Cl–
Co2+ + Cl2,
the specific rate is high.
(VIII)
Notation: Mm+ is a metal ion; HnMO3Clx is a cata-
lytic complex containing the metal ion, ozone, H+ ions,
and chloride ions, which can decompose with the for-
mation of chlorine and the regeneration of the Mm+
metal ion (for simplicity, the charge of the complex is
not shown).
According to [3], the reaction of O3 with Cl– in an
acidic medium in the absence of transition metal ions
occurs via steps (I)–(III). The kinetic characteristics of
these steps were taken from [3]. The formation of
molecular chlorine and its release into a gas phase
results from rapidly established equilibria (IV).
We believe that the charge-transfer catalysis by Co2+
ions occurs via the steps of Co3+ formation in reaction
(VII) between O3 and Co2+ and in reaction (VIII) of the
oxidation of chloride ions with trivalent cobalt to result
in the liberation of Cl2 in an acidic medium as a conse-
quence of equilibria (IV). According to published data
[5], the rate of the reaction of O3 with Co2+ is propor-
tional to the product of the concentrations of these sub-
stances. Our data indicate that the interaction of O3 with
Co2+ is much slower than the interaction of Co3+ with
the chloride ion. This suggests that step (VII) of the
interaction of O3 with Co2+ is a rate-limiting step in
charge-transfer catalysis and a steady-state approxima-
tion is applicable to Co3+. Therefore, the rate of chlo-
rine formation in reaction (VIII) between Co3+ and the
chloride ion is equal to the rate of reaction (VII)
between O3 and Co2+. Thus, the rate of chlorine release
due to charge-transfer catalysis is proportional to the
product of the concentrations of O3 and Co2+, and the
rate constant k7 of the reaction of O3 with Co2+ is a
kinetic characteristic of charge-transfer catalysis.
Coordination catalysis by metal ions occurs via
steps (V) and (VI) of the formation and decay of a cata-
lytic complex, respectively. We assumed that the cata-
lytic complex of only a certain composition is formed
and its decomposition occurs in a single step. A quasi-
equilibrium approximation was used for the step of com-
plex formation and was characterized by the equilibrium
constant K5 (the stability constant of the catalytic com-
plex). The step of complex degradation was character-
ized by the rate constant k6. We believe that the catalytic
complex necessarily contained a metal ion, and that
ozone, a chloride ion, and (possibly) a H+ ion partici-
pated in its formation and/or degradation. The degrada-
tion of the complex results in the regeneration of the
metal ion and in the formation of ClO–, HOCl, or Cl2; in
an acidic medium, this is equivalent to the formation of
molecular chlorine (Cl2) due to equilibria (IV).
The constants K5, k6, and k7 were unknown parame-
ters of the model; they were determined by comparing
data obtained by simulation and experimental results.
The desired values of the unknown parameters were
those at which the functional of the relative difference
between the experimental and calculated rates of chlo-
rine release reached a minimum.
All of the constants were calculated with the use of
the total concentration of a metal ion in solution. This
was reasonable, since estimates based on published
data [6] demonstrated that varying the concentrations
of H+ and metal ions (over the range used in our exper-
iments) at constant ionic strength and the concentration
of chloride ions had practically no effect on the concen-
tration ratio between various metal species in solution.
Note that it is impossible to obtain information on
the effect of chloride ions on the kinetics of the test
reaction based on our experimental data, since they
were obtained at the same concentration of chloride
ions in the reaction solution, which was equal to
1 mol/l. In particular, it is impossible to determine
whether the catalytic complex contains chloride ions or
if it reacts with them at the stage of degradation.
KINETICS AND CATALYSIS Vol. 46 No. 1 2005

142
LEVANOV et al.
As a result of our calculations, we obtained the following constants and data on the composition of complexes:
Ion
Complex composition
K5
k6, min–1
k7, l mol–1 min–1
VO2+
Fe3+
Co2+
Does not contain H+
Contains two H+ and one O3
Contains one H+ and one O3
<10–2
50
k6K5 = 6.5
1.7
0
0
400
3.23
85
Note: Ionic strength, 1 mol/l; concentration of chloride ions, 1 mol/l; temperature, 20°C. The values of the stability constant K are given
5
on a mol/l concentration scale; however, the units are not specified because the true composition of the complexes is unknown.
The values of the rates of chlorine release were
In the case of catalysis by Co2+ ions (reaction (II))
obtained with the use of the above constants in model (Fig. 6), the catalytic effect increased with the concen-
calculations. A comparison between these values tration of H+; however, it also appeared at low concen-
(lines) and experimental data (points) is illustrated in trations of H+ ions. Hence, it follows that catalysis by
Figs. 1–6.
cobalt ions occurs via two reaction paths; H+ ions par-
ticipate in one of these and do not participate in the
other.
Let us consider the characteristics of the catalytic
effects of VO2+, Fe3+, Co2+, and Cu2+ ions in the reac-
tion of ozone with chloride ions in acidic solutions.
The reaction path in which the H+ ions do not partic-
ipate occurs either through the formation of trivalent
cobalt (reaction (VII)) and the oxidation of the chloride
ion by the trivalent cobalt (reaction (VIII)), or through
the formation of a particular catalytic complex (that
does not contain H+) and the degradation of this com-
plex, which results in the release of Cl2. These versions
are indistinguishable, given the condition that the sta-
bility constant of the catalytic complex is small. Note
that, although the formation of trivalent cobalt and its
capability to oxidize the chloride ion were supported
experimentally despite the catalytic complex being a
hypothetic species, it is impossible to exclude this com-
plex based on our experimental data.
As can be seen in Fig. 2, the difference between the
rates of chlorine release in the presence and in the
absence of VO2+ is independent of the concentration of
H+ ions and proportional to the concentration of VO2+.
This can be explained based on the assumption that a
catalytic complex free from H+ ions is formed, whose
stability constant is low. This complex reacts with the
formation of Cl2 and the regeneration of the vanadyl
ion. The following versions are indistinguishable: the
complex contains VO2+, Cl–, and O3 and decomposes in
a first-order reaction; the complex contains VO2+ and
Cl– and reacts with O3; and the complex contains VO2+
and O3 and reacts with Cl–.
In the catalysis by trivalent iron ions (Fig. 4), the
catalytic effect of Fe3+ increases with the concentration
of hydrogen ions. At sufficiently low concentrations of
H+, the catalytic effect of Fe3+ does not manifest itself.
Thus, the H+ ions take part in the catalysis by Fe3+ ions.
The catalysis by trivalent iron ions can be explained
based on the assumption that a catalytic complex is
formed that contains Fe3+; ozone; two H+ ions; and
(possibly) chloride ions; this complex decomposes with
the formation of chlorine and the regeneration of the
iron ion. The calculated and experimental curves of the
rate of chlorine release (the rate as a function of [H+] or
[Fe3+] is represented by a somewhat concave or convex
curve, respectively) coincide only on the assumption
that the complex contains two H+ ions and one ozone
molecule and decomposes in a (pseudo-)first-order
reaction. Thus, in this case, simulation allowed us to
draw conclusions on the composition of the catalytic
complex. The dependence of the rate of chlorine release
on [H+] and [Fe3+] in this system can be explained by
considering the release of chlorine without the partici-
pation of metal ions (reactions (I)–(IV)) and the steps of
complex formation and degradation (reactions (V) and
(VI), respectively).
The effects of the concentrations of H+ and Co2+ on
the rate of chlorine release in catalysis by bivalent
cobalt ions can be explained on the assumption that
catalysis with the participation of H+ ions occurs
through the formation of a catalytic complex containing
Co2+, ozone, one H+ ion, and (possibly) chloride ions.
This complex decomposes with the formation of chlo-
rine and the regeneration of Co2+. Coincidence between
the shapes of calculated and experimental curves of the
rate of chlorine release, plotted as a function of [Co2+]
and [H+] (both of these curves are convex and tend
toward saturation), is seen only upon the assumption
that the complex contains exactly one H+ ion and one
ozone molecule and decomposes in a (pseudo-) first-
order reaction. In this case, simulation allows one to
draw conclusions on the composition of the catalytic
complex.
Thus, the concentration dependence of the rate of
chlorine release in the test system can be explained by
considering the processes of chlorine liberation without
the participation of metal ions (reactions (I)–(IV)); a
catalytic reaction path without the participation of H+
(it is most likely that this path occurs via steps (VII) and
The catalytic effect of Cu2+ ions is analogous to that (VIII)); and a catalytic reaction path with the participa-
of Fe3+; however, it comes into play at higher concen- tion of H+, which occurs via steps (V) and (VI) of com-
trations of H+ (Fig. 4).
plex formation and decomposition, respectively.
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CATALYSIS OF THE REACTION OF OZONE WITH CHLORIDE IONS
143
Yeatts and Taube [7] were the first to find the cata-
ACKNOWLEDGMENTS
lytic effect of Co2+ ions in the reaction of ozone with
chloride ions in an acidic medium. However,Yeatts and
Taube [7] did not study the dependence of the catalytic
effect on the concentration of H+ ([H+] was equal to
~0.1 mol/l), and the concentration of Co2+ was varied
over a narrow range. Therefore, in contrast to this work,
Yeatts and Taube [7] revealed only partially the effect
of Co2+ on the occurrence of the reaction of ozone with
the chloride ion. Our data (Fig. 6) suggest that, at
[H+] = 0.1 mol/l, the catalysis by Co2+ ions mainly
occurs without the participation of hydrogen ions. That
is, the increase in the rate of chlorine formation that was
found by Yeatts and Taube [7], (39.3[Co2+][O3] mol l–1
min–1 at 0°C), corresponds to catalysis by Co2+ ions via
a reaction path without the participation of H+. The
result given in this work (85[Co2+][O3] mol l–1 min–1 at
20°C) is consistent with the above value, as well as with
the rate constant of the reaction of Co2+ with O3
(37 l mol−1 min–1 at 0°C) determined by hill [8].
According to the available information, the catalytic
effects of VO2+, Fe3+, and Cu2+ ions in the O3 + Cl–
reaction in an acidic medium have not been not
reported previously.
Thus, in this work, we for the first time performed
systematic studies on the catalytic activity various
metal ions in the reaction of ozone with chloride ions in
an acidic medium and determined the kinetic character-
istics of catalytic reactions.
This work was supported by the Russian Founda-
tion for Basic Research (project no. 04-03-32915)
and the State Program for Supporting Leading Scien-
tific Schools in the Russian Federation (grant
no. 1275.2003.3).
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