4108 Ind. Eng. Chem. Res.

1997, 36, 4108-4113

Kinetics of Oxidation of Ammonia in Solutions Containing Ozone

with or without Hydrogen Peroxide
Chiang-Hai Kuo,* Fang Yuan, and Donald O. Hill
Department of Chemical Engineering, Mississippi State University, Mississippi State, Mississippi 39762

This research investigates the kinetics of traditional ozonation and peroxone oxidation of
ammonia in alkaline solutions. The ozonation reaction is governed by the direct oxidation of
ammonia with ozone molecules, and the overall kinetics is second order, with first order each in
ozone and ammonia. The reaction rate increases slightly with temperature, and at 25 °C, the
overall rate constant varies from 12.3 to 27.0 1/Ms as the pH increases from 8 to 10. In the
presence of hydrogen peroxide, the peroxone oxidation is controlled mainly by the formation of
hydroxyl radical and its subsequent radical reactions. The depletion rate of ozone is first order
with respect to both concentrations of ozone and hydrogen peroxide but is nearly independent
of the ammonia concentration. The overall rate constant increases from 5860 to 133 000 1/Ms
in the pH range of 8-10 at 25 °C, indicating that the rate increases with the hydroxyl ion
concentration of the exponent of 0.71. The destruction rate of ammonia depends on concentra-
tions of various species, and for wastewaters containing high concentrations of ammonia, the
peroxone oxidation process can be effective and economical to achieve a high efficiency for ozone
utilization.

Introduction Kinetic Model

Ammonia is used in the manufacture of fertilizers, As suggested by results of some recent studies (Stae-
refrigerants, and many household cleaning agents and helin and Hoigne, 1982; Tomiyasu et al., 1985), a kinetic
stabilizers. The wide applications result in ammonia model is formulated here by considering the formation
contamination in air, surface, and underground waters. of a hydroperoxide ion as the initial step in the decom-
Ammonia can be removed from water streams by position of ozone in an alkaline solution.
physical, biological, and chemical methods. Chemical
oxidation is effective in the treatment of waters with O3 + OH- f HO2- + O2 (1)
low concentrations of ammonia, but the well-known
oxidation by breakpoint chlorination (Lewis, 1980) may In the presence of hydrogen peroxide, a weak acid, its
result in the formation of toxic chlorinated compounds partial dissociation in water results in the production
in treated waters. Another chemical method, ozonation, of additional hydroperoxide ions (Taube and Bray,
is a promising method, and unreacted ozone reverts to 1940).
oxygen without toxic residue. An advanced oxidation
using ozone and hydrogen peroxide mixtures as the H2O2 S HO2- + H+ (2)
combined oxidants (known as peroxone oxidation) also
may be effective for ammonia removal from waste- The hydroperoxide ions react further with ozone mol-
waters. ecules to produce hydroxyl free radical.
A drastic reduction in ammonia concentration at pH
10.6 following lime clarification was observed by Huibers O3 + HO2- f OH• + O2- + O2 (3)
et al. (1969) in their study of wastewater treatment by
ozone. Singer and Zilli (1975) and Ikehata (1975) found Once the hydroxyl radical is formed, it may react with
that the decomposition rate of ammonia increases with many species in chain reactions (Langlais et al., 1991;
pH in alkaline solutions. In a study of the ozonation of Hong et al., 1996). The most important reactions
ammonia in solutions of pH ranging from 7 to 8, Hoigne (Staehelin and Hoigne, 1982; Christensen et al., 1982)
and Bader (1978) yielded a second-order rate constant are
of 20 1/Ms at 20 °C. Improvement in ammonia oxida-
tion by ozone in the presence of bromide ion was O3 + OH• f HO2• + O2 (4)
observed by Haag et al. (1984). No literature informa-
tion is available regarding the kinetics of peroxone H2O2 + OH• f HO2• + H2O (5)
oxidation of ammonia. Therefore, this study was un-
dertaken to provide kinetic data for the ozonation of HO2- + OH• f HO2• + OH- (6)
ammonia in the pH range of 8-10 at temperatures
ranging from 15 to 35 °C and to investigate the kinetics HO2• S O2- + H+ (7)
of ammonia oxidation in the presence of ozone and
hydrogen peroxide mixtures. A kinetic model was OH- + OH• f H2O + O- (8)
developed and rate equations derived to assess major
mechanisms governing the ozonation and peroxone O3 + O2- f O3- + O2 (9)
oxidation of ammonia in basic solutions.
O3- + H+ f OH• + O2 (10)
* Author to whom all correspondence should be addressed.
E-mail: KUO@ChE.MsState.Edu. O- + H2O f OH• + OH- (11)

S0888-5885(97)00208-X CCC: $14.00 © 1997 American Chemical Society


The following equilibrium relationship is assumed valid:
H2O S H+ + OH- (12)
In the presence of ammonia as a contaminant in the
solution, it can react with both the hydroxyl radical and
ozone molecules as follows:
NH3 + OH• f Qs (13)
NH3 + rO3 f Rs (14)
In the direct oxidation of ammonia in reaction 14, it is
assumed that r moles of ozone are required for complete
conversion of each mole of ammonia. Many other
scavengers, if present in the solution, also may partici-
pate in the chain reactions (Glaze et al., 1987; Glaze
and Kang, 1989); these additional reactions are ne-
glected in this work.
Expressions for depletion rates of ozone and ammonia
can be derived using the steady-state approximations
for OH•, O-, O2-, and O3-, and the equilibrium relation-
ships given in reactions 2, 7, and 12. The depletion
rate of ozone can be written as
-d[O3]/dt ) {k1 + a(1 + b)[H2O2]}[O3][OH-] +
rk14[NH3]n[O3] (15)
and the oxidation rate of ammonia is
-d[NH3]/dt ) (k13/k4)ab[H2O2][NH3][OH-] +
k14[NH3]n[O3] (16)
In the above equations, the constant a is defined as
a ) 2k3K2/K12 (17)
and b is a function of various concentrations and rate
and equilibrium constants.
b ) 1/[1 + {(k5/k4) + (k6/k4)(K2/K12)[OH-]}[H2O2]/
[O3] + (k13/k4)[NH3]/[O3]] (18)
Equations 15 and 16 are expressed in terms of the
concentrations of ammonia, oxidants, and hydroxyl ion.
On the right hand side of eqs 15 and 16, the second term
denotes the direct oxidation rate between ammonia and
ozone molecules, and a(1 + b)[H2O2][O3][OH-] repre-
sents the rate of indirect oxidation of ammonia by the
hydroxyl radical.
In the absence of hydrogen peroxide, eqs 15 and 16
can be simplified to
-d[O3]/dt ) {k1[OH-] + rk14[NH3]n}[O3] (19)
and
n decomposition, ozonation, and peroxone oxidation are
-d[NH3]/dt ) k14[NH3] [O3] (20)
Equations 19 and 20 are expressions for the depletion
rates of ozone and ammonia, respectively, by direct
oxidation in the traditional ozonation process. Without
hydrogen peroxide or any contaminants, eq 19 is re-
duced further to
-d[O3]/dt ) k1[OH-][O3] ) kd[O3] (21)
Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997 4109
which is well recognized in the literature as the self-
decomposition rate of ozone in alkaline solutions (Lang-
lais et al., 1991).
Experimental Details
Ozone was produced from an Ozoteq Laboratory
Ozonator (Model L-50) using extra dry, pure oxygen.
The ozone-oxygen mixture was introduced into deion-
ized distilled water to oxidize any contaminants, and
then the preozonized water was used to prepare aqueous
solutions of dissolved ozone and ammonia. The initial
concentration of dissolved ozone was determined by both
iodometric titration and a spectrophotometric method.
An aqueous solution of ammonia was prepared by
adding appropriate quantities of ammonium chloride
and sodium hydroxide in the preozonized water. Hy-
drogen peroxide was also added in the ammonia solution
to maintain a desired initial concentration of hydrogen
peroxide in a peroxone oxidation experiment.
By utilizing a stopped-flow spectrophotometer system
(High-Tech Model SF-51), two reactant solutions (one
contained dissolved ozone, and another contained am-
monia and sodium hydroxide with or without hydrogen
peroxide) were mixed rapidly (complete within 0.001 s),
and absorbance changes of the mixed solution (at the
wavelength of 260 nm) were determined and recorded
at various reaction times during a kinetic experiment.
With excessive ammonia (and hydrogen peroxide, if
present) in the solution, the measured absorbances
during a reaction can be converted to the concentrations
of ozone, the limiting reactant (Espenson, 1981).
The dissociation of solid NH4Cl in the solution result-
ing in an equilibrium among the ammonium ion (NH4+),
un-ionized or free ammonia (NH3), and hydroxyl ion
(OH-). The concentration of dissolved ammonia (NH4+
and NH3 combined) was determined by an Ammonia
Combination Electrode (manufactured by Corning Co.).
The fraction of free ammonia in the solution of a fixed
pH can be calculated from
[NH3]/{[NH4+] + [NH3]} ) 10pH-14/{Kb + 10pH-14}
(22)
Using the ionization (dissociation) constant, Kb ) 1.774
× 10-5 at 25 °C (Weast and Astle, 1978), for example,
the fractions of free ammonia (NH3) can be calculated
as 0.00552, 0.0526, 0.357, and 0.847 respectively at pH
7, 8, 9, and 10. The preliminary tests in this work
showed that ammonium and chlorine ions are not
reactive toward ozone or hydrogen peroxide or mixtures
of the two oxidants and that free ammonia is not
reactive toward hydrogen peroxide alone. Therefore,
only free ammonia can be oxidized by ozone or mixtures
of ozone and hydrogen peroxide.
Kinetics of Ozonation
The concentration profiles of ozone during self-
illustrated in Figure 1 for three experiments carried out
at 25 °C in solutions with pH 9 at a constant initial
ozone concentration. By self-decomposition (case 1)
alone, the ozone concentration declines slowly in the
solution, but the depletion rate is accelerated in the
presence of free ammonia with or without hydrogen
peroxide (cases 2 and 3). In this figure, the ozone
concentration is plotted against the reaction time on a
semilogarithmic scale, yielding a straight line for each
4110 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997

Table 1. Overall Rate Constants

ozonation, 1/Ms
peroxone oxidation
pH 15 °C 25 °C 35 °C at 25 °C, 1/Ms
8 5.7 12.3 30.7 5 860
9 7.4 16.7 34.6 21 100
10 9.9 27.0 43.0 133 000

Figure 1.

run. This illustrates that the overall kinetics is first

order with respect to the ozone concentration for each
of the three reactions. The apparent rate constant for
an individual run can be obtained from the slope of the
straight line or, alternatively, from regression analysis
of the concentration data. The apparent rate constants
are calculated from the regression analysis; the correla-
tion coefficients are 0.98 or larger for all values reported
in this work.
For the ozonation reaction with excessive amounts of
ammonia in an experiment, eq 19 can be integrated to
yield
[O3]/[O3]0 ) exp[-k′t] (23)
where the apparent rate constant, k′, is defined as
k′ ) kd + rk14[NH3]0n (24)
The decomposition rate constant, kd, is equal to k1[OH-],
as shown in eq 21. For a series of experiments carried
out in solutions of a constant pH (ranging from 8 to 10)
at 25 °C, the apparent rate constant can be plotted
against the initial concentration of ammonia on a
logarithmic scale to yield a straight line. This confirms
that the ozonation reaction is first order with respect
to the concentration of ammonia (n ) 1) and that the
overall reaction is second order, as reported by the
previous investigators (Singer and Zilli, 1975; Hoigne
and Bader, 1978).
As shown in eq 24, the decomposition rate constant,
kd, and the stoichiometric ratio, r, are needed to
calculate the ozonation rate constant, k14. The decom-
position rate constant at fixed temperature and pH can
be obtained from the literature data (Kuo et al., 1977)
or from data obtained in the decomposition experiments
carried out in this work, as demonstrated in Figure 1
(case 1). Several tests were conducted to determine the
stoichiometric ratio of the ozonation. The results showed
that 3.9-4.6 mol of ozone were consumed for conversion
of each mole of ammonia and that the reacted ammonia
was converted completely to nitrate, NO3- (determined
by the spectrophotometric method at the wavelength of
Figure 2.
220 nm). Therefore, the stoichiometric ratio, r, is about
4, as reported earlier by Singer and Zilli (1975).
Using r ) 4 and n ) 1, the ozonation rate constant,
k14, can be calculated from eq 24 for each experiment.
Also, eqs 19 and 20 can be rewritten as
-d[O3]/dt ) {kd + 4k14[NH3]}[O3] (25)
and
-d[NH3]/dt ) k14[O3][NH3] (26)
For a series of experiments conducted at identical
temperature and pH, the calculated values (k14) were
averaged to yield an average constant shown in Table
1. The average deviation of the individual rate con-
stants from the average value at any given pH and
temperature is 15%. The results in the table indicate
that the ozonation reaction is slow and that the reaction
rate increases slightly with pH and temperature. As
mentioned earlier, Hoigne and Bader (1978) gave the
rate constant of 20 1/Ms for the ozonation at 20 °C in
the pH range of 7-8. They also suggested that above
pH 9 the oxidation mechanism may be controlled by the
hydroxyl radical reaction of ammonia. The gradual
change in the ozonation rate with pH (k14 is proportional
to [OH-]0.12, as shown in Figure 2) at a given temper-
ature seems to suggest that in the pH range of 8-10
investigated the hydroxyl radical reaction plays an
insignificant role.
Kinetics of Peroxone Oxidation
The peroxone oxidation experiments were carried out
at 25 °C to study the reaction kinetics in aqueous

solutions of pH varying from 8 to 10. The peroxone
oxidation rate is enhanced in the presence of hydrogen
peroxide at fixed initial concentrations of ozone and
ammonia, and the depletion rate of ozone by the self-
decomposition is negligible. As illustrated in Figure 1
(case 3) and discussed earlier, the depletion rate of ozone
is first order with respect to the ozone concentration.
At fixed pH and temperature, the apparent rate con-
stant, k′, can be plotted against the initial concentration
of ammonia on a logarithmic scale for a series of
experiments carried out at identical concentrations of
hydrogen peroxide and ozone. The results reveal that
the apparent rate constant increases with an ammonia
concentration of the exponent of less than 0.2. This
suggests that the peroxone oxidation is controlled
mainly by the hydroxyl radical reaction of ammonia and
that the depletion rate of ozone is influenced very little
by the ammonia concentration. Under the above condi-
tions, eq 15 can be simplified to
-d[O3]/dt ) k′[O3] ) a(1 + b)[H2O2][OH-][O3] (27)
By plotting the apparent rate constant against the
initial concentration of hydrogen peroxide on a loga-
rithmic scale, a straight line can be drawn from the data
obtained at fixed concentrations of ammonia and hy-
droxyl ion. The slopes for the individual lines are nearly
unity at pH 8 and 9 and about 0.8 at pH 10. For the
purpose of correlating the kinetic data to obtain an
overall rate constant at a given pH, therefore, the
reaction can be regarded as first order in ozone and
hydrogen peroxide and independent of the ammonia
concentration.
On the basis of the above results, the depletion rate
of ozone given in eq 27 can be rewritten in terms of the
overall rate constant, k, as follows:
-d[O3]/dt ) k[H2O2][O3] (28)
where k is equal to k′/[H2O2]0 for an experiment with
excessive amounts of hydrogen peroxide. For the ex-
periments carried out at identical pH and temperature,
the individual rate constants are averaged to yield an
average rate constant, as shown in Table 1. As stated
earlier, the correlation coefficients are 0.98 or higher
in obtaining apparent rate constants by regression
analysis for the individual runs. The average deviations
of the overall rate constants of the individual runs from
the average values are 8.2, 10.6, and 19.4% respectively
at pH 8, 9, and 10. Due to limitations of the stopped-
flow apparatus, reliable data were not obtainable in
solutions of higher than pH 10.
For the peroxone oxidation, the theoretical rate
expression for ammonia can be obtained from eq 16 by
neglecting the rate of direct oxidation. The resultant
equation can be combined with eqs 18 and 28 to yield
-d[NH3]/dt ) -c d[O3]/dt ) ck[H2O2][O3] (29)
where c is the ratio of the ammonia depletion rate to
the ozone consumption rate in the peroxone oxidation.
The theoretical expression for c is
c ) k13[NH3]/{2k4[O3] + [k5 +
k6(K2/K12)[OH-]][H2O2] + k13[NH3]} (30)
The above equation suggests that the rate ratio, c, varies
Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997 4111
depending upon relative magnitudes of the various
concentrations, and equilibrium and rate constants.
The equilibrium and rate constants at ambient tem-
peratures (about 20 °C) have been reported as k4 ) 2.0
× 109 1/Ms (Buhler et al., 1984), k5 ) 2.7 × 10 7 1/Ms
(Christensen et al., 1982), k6 ) 7.5 × 109 1/Ms (Chris-
tensen et al., 1982), k13 ) 1.0 × 108 1/Ms (Farhataziz
and Ross, 1977), K2 ) 10-11.8 (Behar et al., 1970), and
K12 ) 10-14, well-known in the literature. In the kinetic
experiments for the peroxone oxidation of ammonia, the
initial concentration of ozone was controlled at 1.5 ×
10-4 M for most runs. The initial concentration of
hydrogen peroxide varied from 9.80 × 10-4 to 1.95 ×
10-2 M, and that of ammonia ranged from 6.80 × 10-3
to 4.34 × 10-2 M. At the lowest concentrations of
hydrogen peroxide and ammonia, the initial c value is
estimated to decrease from 0.52 to 0.48 as the pH
increases from 8 to 10 on the basis of the above data.
In the same pH range, the initial c value varies from
0.79 to 0.56 at the highest concentrations of hydrogen
peroxide and ammonia. Since the ozone concentration
decreases with time, the c value also increases during
a reaction. The actual rates of consumption of both
ozone and ammonia, however, decline rapidly with the
reaction time because of rapid decrease in the ozone
concentration.
Discussion
The kinetic results suggest that it is technically
feasible to remove ammonia by the oxidation processes
at room temperatures in alkaline solutions of pH
ranging from about 8 to 11. The reaction rate is
negligible in acidic solutions because of complete dis-
sociation of ammonia to ammonium ion which is not
reactive toward the oxidants. On the other hand, the
dissolved ammonia exists mainly as free ammonia at
about pH 11 or above, and there are little advantages
in carrying out the treatment in solutions of higher pH.
Although a free radical, NH2•, might be formed as an
intermediate in the hydroxyl radical reaction of am-
monia (Hoigne and Bader, 1978), only the final product,
NO3-, was detected in this work. In a recent study of
the peroxone oxidation of toluene in alkaline solutions,
the ozone consumption rate was found to be nearly
independent of the pollutant concentration (Kuo and
Chen, 1996), as reported in this work for the peroxone
oxidation of ammonia. The experimental and calculated
results indicate that, at comparable conditions, the
depletion rate of ozone is enhanced greatly by the
presence of hydrogen peroxide. As shown in the kinetic
model, ozone, hydrogen peroxide, hydroxyl ion, and
others are competing with ammonia in consuming the
hydroxyl radical formed in the solution. Thus, the
oxidation rate of ammonia depends on the relative rates
of the hydroxyl radical reactions of various species, as
indicated in eqs 29 and 30.
In applications of the peroxone oxidation process for
wastewater treatment, the concentrations of ozone and
hydrogen peroxide are often comparable though the
ammonia concentration varies. When both concentra-
tions of ammonia and hydrogen peroxide are very low
compared with the ozone concentration, b approaches
unity, and the rate ratio, c, or eq 30, is reduced to
c ) 0.5k13[NH3]/{k4[O3]} (31)
The above equation implies that the ratio of the perox-
one oxidation rate of ammonia to that of ozone is
4112 Ind. Eng. Chem. Res., Vol. 36, No. 10, 1997
proportional to the ratio of the rate of hydroxyl radical
reaction of ammonia to that of ozone. Since k13/k4 )
0.05 according to the literature information (Farhataziz
and Ross, 1977; Buhler et al., 1984), the oxidation rate
of ammonia may be very slow relative to the depletion
rate of ozone. This may result in little improvement in
the destruction rate of ammonia by applying the per-
oxone oxidation process. Though the consumption rate
of ozone is accelerated greatly in comparison with the
traditional ozonation process, it is consumed mainly as
a scavenger in reacting with the hydroxyl radical
formed.
The benefit of addition of hydrogen peroxide for
ammonia removal in the peroxone oxidation process
may be realized for decontamination of wastewaters
containing high concentrations of ammonia at pH 11 or
less. If the concentration ratio, [NH3]/[O3], is larger
than 40, the depletion rates of ozone and ammonia are
comparable, as suggested by eqs 29 and 30. As the
concentration ratio increases further, c approaches
unity, indicating that the destruction rate of ammonia
is nearly identical with the consumption rate of ozone.
Under this circumstance, the peroxone oxidation process
is effective and economical for the ammonia removal,
and a high efficiency of ozone utilization can be ex-
pected.
Effects of the hydroxyl ion concentration on the
ozonation and peroxone oxidation rates can be examined
by plotting the second-order rate constant (k14 or k)
against the pH value, as shown in Figure 2. According
to the kinetic model dictated by eq 19, the ozonation
rate constant, k14, is independent of the hydroxyl ion
concentration. Nonetheless, the average slope of 0.12
obtained in the semilogarithmic plot in the figure
indicates that k14 increases slightly with the hydroxyl
ion concentration. The slight dependence of the oxida-
tion rate on the pH seems common in the ozonation of
many organic and inorganic compounds (Langlais et al.,
1991).
The influence of pH on the depletion rates of ozone
and ammonia is much more pronounced in the peroxone
oxidation process. The figure shows that at 25 °C the
overall rate constant increases with the hydroxyl ion
concentration of the exponent of 0.71. A theoretical
relationship between the overall rate constant and the
hydroxyl ion concentration can be derived by comparing
eq 29 with eqs 27 and 28.
k ) a(1 + b)[OH-] (32)
In appearance, the above equation tends to suggest that
the rate constant increases in direct proportion to the
hydroxyl ion concentration (if a and b remain constants).
However, b is a weak function of various concentrations,
and reaction 6 in the kinetic model suggests that
hydroxyl ions are also generated in the hydroxyl radical
reaction of hydroperoxide ions. The production of
hydroxyl ions in this reaction step may result in
reduction of the consumption rate of the hydroxyl ions
provided initially in the solution. Therefore, the in-
crease in the overall rate constant with the hydroxyl
ion concentration is less than linear, as observed by the
experimental and calculated results.
Conclusions
A kinetic model has been proposed and rate equations
derived for depletion of ozone and ammonia in aqueous
solutions containing ozone or ozone-hydrogen peroxide
mixtures. The ozonation reaction is predominated by
the direct oxidation of ammonia with ozone molecules.
The slow depletion rate of ozone is first order with
respect to both concentrations of ammonia and ozone,
and the reaction rate increases slightly with pH and
temperature. The peroxone oxidation of ammonia is
controlled mainly by the formation of hydroxyl radical
and its subsequent radical reactions with ammonia and
other species. The depletion rate of ozone is first order
with respect to both concentrations of ozone and hydro-
gen peroxide but is nearly independent of the ammonia
concentration. As the pH increases from 8 to 10, the
overall rate constant increases from 5860 to 133 000
1/Ms at 25 °C, indicating that the reaction rate increases
in proportion to the hydroxyl ion concentration of the
exponent of 0.71. The depletion rates of ozone and
ammonia are comparable at high concentrations of
ammonia in the solution. Under this circumstance, the
peroxone oxidation process can be effective and eco-
nomical (with a high efficiency of ozone utilization) for
decontamination of wastewaters containing ammonia.
Nomenclature
a ) constant defined by eq 17
b ) function defined by eq 18
k ) overall rate constant, 1/Ms
k′ ) apparent rate constant, 1/s
kd ) rate constant for self-decomposition of ozone, 1/s
kr ) rate constant for reaction r, 1/Ms
Kb ) ionization constant
Kr ) equilibrium constant for equilibrium reaction r
n ) order with respect to ammonia concentration in
ozonation
r ) stoichiometric ratio of ozonation, mol of ozone/mol of
ammonia
t ) reaction time, s
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Accepted June 23, 1997X
IE9702082
X
Abstract published in Advance ACS Abstracts, August 15,
1997.