Water Research 38 (2004) 22852292

Kinetic decomposition of ozone and para-chlorobenzoic acid

(pCBA) during catalytic ozonation
Jong-Sup Park, Heechul Choi*, Jaewon Cho
Department of Environmental Science and Engineering, Kwangju Institute of Science and Technology (K-JIST), Oryong-dong, Buk-gu,
Kwangju 500 712, Republic of Korea
Received 30 June 2003; received in revised form 19 December 2003; accepted 12 January 2004
Abstract
The decomposition of ozone and para-chlorobezoic acid (pCBA) using ozone and ozone/goethite were investigated
under various conditions to dene the characteristics of ozonation and catalytic ozonation. A continuous analysis of the
kinetics of the reaction between ozone and pCBA was established, and the decay rate of ozone and pCBA with/without
goethite was determined. The decay rate of ozone in the presence of goethite was much higher than in the absence of
goethite and was strongly pH dependent due to the reactivities of ozone with the three surface species (FeOH
2
+
,
FeOH, FeO

) of goethite. The removal pattern of ionized pCBA at different pHs agreed well with the instantaneous
ozone demand. The removal rate of pCBA and instantaneous ozone demand with/without t-butanol at different pHs
were compared to elucidate the reaction mechanisms associated with the three reaction sites: (i) on the surface of the
catalyst, (ii) at the catalystsolution interface, and (iii) in the bulk solution.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Ozone decay; para-chlorobenzoic acid; Goethite; Instantaneous ozone demand; Reaction mechanism
1. Introduction
Catalytic oxidation is receiving increasing attention
with respect to the removal of compounds that are
refractory to traditional oxidation processes. Homo-
geneous catalytic oxidation using dissolved metals has
been applied to oxidize contaminants with hydrogen
peroxide and/or ozone. Fentons reagent, which uses
hydroxyl radicals generated by the reaction between the
ferrous ion and hydrogen peroxide, is the most common
[13]. It has also been reported that the catalytic effects
of other metal ions like Mn(II) and Ag(I) in combina-
tion with ozone improve the oxidation of organics [4,5].
A small amount of Mn(II) in the presence of ozone
enhances the decomposition of atrazine or of organic
matter, compared to ozonation alone, via the generation
of hydroxyl radicals by reaction between ozone and
manganese species.
Heterogeneous catalytic oxidation using hydrogen
peroxide and iron oxides has been investigated. n-butyl
chloride oxidation using a mixture of hydrogen peroxide
and goethite showed that it was independent of pH and
that heterogeneous oxidation is more effective than
other radical processes [6]. It is demonstrated that the
hydroxyl radical production rates in a silica sand-
goethite slurry system were greater at neutral pH than
at acidic pH and that the removal rate of nitrobenzene
was higher at pH 7 than at pH 4, 5, or 6 [7]. It is reported
that the efciency of treating benzoic acid using a
Fenton-like oxidation is higher at pH 3.2 than at either
pH 6.0 or 10.0 [8,9].
Oxalic acid is a representative compound that is
recalcitrant to simple ozonation and rather treated in the
presence of manganese dioxide, titanium dioxide and
ozone [10,11]. Manganese dioxide catalyzed the ozona-
tion of oxalic acid at a low pH, via a mechanism
involving a surface associated manganese-oxalic acid
ARTICLE IN PRESS
*Corresponding author. Tel.: 82-62-970-2434; fax: 82-62-970-
2434.
E-mail address: hcchoi@kjist.ac.kr (H. Choi).
0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.01.040
complex. Catalytic ozonation for the removal of COD
required less ozone and showed a substantially reduced
effect upon dissolved radical scavengers, such as
carbonate or bicarbonate [12]. In addition, catalytic
ozonation was found to be equally effective under both
highly acidic and highly alkaline conditions. It is
reported that heterogeneous catalytic ozonation using
supported titanium dioxide as a solid catalyst showed a
slightly greater ability to remove TOC and UV
absorbance than ozone alone [13].
Our previous work indicated that catalytic ozonation
increased both DOC removal and aqueous ozone
consumption, compared to ozonation alone [14]. Cata-
lytic ozonation was found to be more efcient than
ozonation for the removal of natural organic matter
(NOM). It was also recently reported that hydroxyl
radicals are generated via a reaction between ozone
and sandy soil [15]. The catalytic ozonation in the
presence of goethite enhanced the removal rate of
para-chlorobenzoic (pCBA) by a radical reaction that
occurs on the solids surface and at the solidliquid
interface.
However, the reaction characteristics and main
mechanisms of catalytic oxidation using ozone and
goethite at various pHs remain unknown, and very little
information is available on the detailed mechanism of
the reaction. The objective of this study was to
investigate the decomposition characteristics of pCBA
and of dissolved ozone in an ozone/goethite system at
various pHs, and nally to elucidate the pertinent
reaction mechanisms.
2. Experimental
2.1. Chemicals and catalyst
pCBA was chosen as a model organic acid and as a
probe compound for hydroxyl radical measurements
due to its high reactivity with OH radicals, but very low
reactivity with other oxidants (i.e., k
OH
d
;pCBA
=
5 10
9
M
1
s
1
, k
O
3
; pCBA
p0:5 M
1
s
1
; [16]). All
reagent-grade chemicals were purchased from Aldrich
(Milwauke, Wisconsin), and all solutions were prepared
with puried water using the Milli-Q system (Ultrapure
System, Barnsterd), unless otherwise specied.
Goethite (a-FeOOH; hereafter FeOOH) was pur-
chased from Aldrich (Milwaukee, Wisconsin, USA) and
was selected as a catalyst because it is a very abundant
metal oxide in nature and has a low solubility in water.
The composition of the FeOOH used was determined by
X-ray uorescence spectroscopy (XRF, Philips PW
2400, Philips), its surface area was measured using a
BET surface area analyzer (ASAP 2400, Micromeritics),
and its isoelectric point (IEP) was determined using a
zeta potential analyzer (ELS 8000, Otsuka). The
physico-chemical characteristics of the FeOOH selected
are given in Table 1.
2.2. Decomposition kinetics of ozone and pCBA
Fig. 1 shows the schematic diagram of the continuous
analysis system used for decomposition kinetic experi-
ments with ozone and the model compound. The
analysis system was set up using automatic control
devices, which were connected to a closed reactor of
volume 0.5 L. After the reaction solution with/without
goethite had been pumped into the reactor, the reaction
was started by instantly injecting ozone-saturated water
(40 mg O
3
/L) into the vessel using a vacuum pump
(Wheaton). Ozone concentration was monitored in real
time by using the indigo method [17] as the reaction
solution passed through an outlet port by peristaltic
pump (Gilson, minipuls 3) during the reaction. Absor-
bance of the reaction solution immediately mixed with
indigo solution was continuously measured at 600 nm
using a UV/VIS detector (Younglin, UV 730D) located
at an outlet port, and data were accumulated in
Autochro 2000, a chromatogram data acquisition
program. Another outlet port was used to measure the
concentration of pCBA. An aliquot of 0.1 N Na
2
S
2
O
3
was added to quench the aqueous ozone remaining in
the reaction solution. The reaction solution was sampled
at set times, and analyzed for pCBA using high-
performance liquid chromatography. A pressure con-
troller was attached to the reactor to prevent undue
reactor pressure build-up caused by the injection of the
ozone-saturated water. The pH of the reaction solution
was monitored during the reaction using a pH meter
coupled with a data acquisition and control system
(DaqBook 120, USA). The reactor was continuously
stirred by an inline-mixer to suspend the goethite
granules. The ozone-saturated solution was prepared
in an ozone bubbling bottle. Gaseous ozone was
generated from dried oxygen using an ozone generator
(PCI-WEDECO, GL-1). The Teon tubing connecting
the volume pump, reactor and peristaltic pump was used
as minimized and Viton tubing was used for the pumps
because of its stability to ozone and strong acid.
Fig. 2 shows a raw signal obtained from the
continuous analysis system. The initial absorbance of
the indigo solution was adjusted to bring the absorbance
ARTICLE IN PRESS
Table 1
Physico-chemical characteristics of the selected metal oxide
Particle size
(mm)
Composition
(%)
Surface
area
(m
2
g
1
)
pH
iep
0.30.6 Iron oxide (97.2) 147 7.8
Silica oxide (0.5)
J.-S. Park et al. / Water Research 38 (2004) 22852292 2286
of the mixed solution into the range 200800 mV. Before
the reaction was started, the background absorbance of
the distilled water and the indigo solution was mon-
itored. The absorbance of the indigo solution sharply
decreased as soon as the saturated ozone water was
injected into the reactor, and as the ozone concentration
was depleted, the absorbance recovered back to its
original status. After transforming this raw signal into
ozone concentration, the instantaneous demand for and
the decomposition rate of ozone for simple ozonation
and catalytic ozonation were estimated. The instanta-
neous ozone demand (IOD) can be used for the
development of prediction model of ozone decomposi-
tion in water treatment processes.
The pCBA concentration was measured by high-
performance liquid chromatography (HPLC, Waters)
using a reversed-phase C18 Nova Pak column. Elution
was carried out by pumping acetonitrile and water
(60:40 v/v) isocratically at a ow rate of 1.0 mLmin
1
.
Absorbance was measured at a wavelength of 234 nm
using a photodiode array detector.
3. Results and discussion
3.1. Decomposition kinetics of ozone
3.1.1. Effect of pH
The decomposition kinetics of ozone was performed
using the continuous analysis system with/without
goethite at various pHs. The goethite and initial ozone
concentrations were 2 g/L
1
and 2 mg L
1
, respectively.
The decomposition of ozone was found to follow rst
order kinetics with respect to ozone at various pHs with/
without goethite. Table 2 summarizes rst order rate
constants (k
obs
) obtained at the pHs applied. The 7
number indicates standard deviation and all experiments
were at least triplicated:

dO
3

dt
k
obs
O
3
: 1
The decomposition rate constants of ozone equated
with half-lives were estimated to be 152400 s. The rate
of ozone decomposition increased upon increasing the
pH of the reaction solution, and became much larger at
pHs >7 [18]. As indicated in Table 2, the rate of ozone
decomposition in the presence of the catalyst was
approximately twice that without catalyst, because some
of ozone reacted with the catalysts surface.
3.1.2. Effect of goethite concentration
The ozone decomposition experiments were per-
formed at various goethite concentrations (0.55 g L
1
)
to determine the role of goethite in the decomposition.
The initial ozone concentration used was 2 mg L
1
and
ARTICLE IN PRESS
Reactor
Ozone Generator
S
Stirrer
Pressure Controller
Pump
Indigo
Solution
Na
2
S
2
O
3
Sample
UV Detector
Computer
Oxygen
Volume Pump
Saturated Ozone
Water
Fig. 1. Schematic diagram of the continuous analysis system used to monitor the decomposition of ozone and pCBA.
0
100
200
300
400
500
600
700
800
0 2 4 6 8 10 12 14 16
water
Adding Na
2
S
2
O
3
Time (min)
S
i
g
n
a
l

(
m
V
)
Adding saturated ozone
Fig. 2. A raw signal obtained from the continuous analysis
system.
J.-S. Park et al. / Water Research 38 (2004) 22852292 2287
pH was xed at 3.1. Fig. 3 illustrates that the
decomposition of ozone on goethite with a xed surface
area followed rst order kinetics and the rate of ozone
decomposition obtained was directly proportional to the
goethite concentration. Based on a linear relationship
between the goethite concentration and the rst-order
decay rate, the decomposition rate of ozone on the
catalysts surface could be described by rst order
kinetics with respect to the ozone and goethite
concentrations. Because ozone decomposition occurs
in two phases (on the surface of goethite and in the bulk
solution), its decomposition rate may be expressed by a
kinetic equation involving the two phases:

dO
3

dt
k
1
O
3
k
2
FeOOHO
3
; 2
where k
1
is the rst-order rate coefcient for the reaction
in the bulk solution and k
2
the second order rate
coefcient for the surface reaction between the goethite
and the ozone. The k
1
value obtained from a linear
regression of the data in Fig. 3 was 0.0253 min
1
and
corresponding k
2
value was 0.0127 min
1
(g L
1
FeOOH)
1
at pH 3.1 (R
2
=0.98). From Fig. 3, it became
apparent that from 2 g L
1
of goethite, the decomposi-
tion by the rate of the surface reaction is higher than by
that of the bulk solution.
Fig. 4 shows the ozone decomposition rates (k
2
) due
to the catalytic surface reaction at various pHs. The
decomposition rate of ozone at the reaction changed as
the pH changed. This was attributed to the different
reactivity of ozone toward the three different types of
surface functional groups (FeOH
2
+
, FeOH, FeO

)
of goethite, which are pH-dependent [19]. The respective
densities of these functional groups are inuenced by the
solution pH.
The surface acidity equilibrium constants of FeOOH
can be written as
FeOH

2
2 FeOHH

pK
s
a1
6:4; 3
FeOH2 FeO

pK
s
a2
9:2: 4
And, the total concentration of goethite, denoted as
[TOTFe], can be dened as
TOT Fe FeOH

2
FeOH FeO

:
5
Then the kinetics of ozone decomposition at the goethite
surface from equation (2) can be expressed as
dO
3
=dt k
2
TOT FeO
3
; 6
k
2
TOT Fe k

FeOH

2
k
0
FeOH
k

FeO

; 7
where k
+
, k
0
and k

are the second order rate constants

of FeOH
2
+
, FeOH and FeO

, respectively. Be-
cause these three species of catalyst have differed
reactivities for ozone, Eq. (7) can be written as
k
2
k

k
0
a
0
k

; 8
ARTICLE IN PRESS
Table 2
Ozone decomposition rate (k
obs
) at various pHs
([O
3
]
0
=2 mg L
1
, [FeOOH]=2 g L
1
)
pH Ozone only
(min
1
)
Ozone/FeOOH (min
1
)
2.1 0.017170.00191 0.036970.000212
3.1 0.020470.000707 0.050770.00665
4.0 0.025270.00177 0.055570.00605
5.1 0.028070.00120 0.060370.00226
6.0 0.037570.00106 0.063870.00671
6.9 0.049370.00130 0.081970.00445
8.1 0.10670.00658 0.15470.0133
8.9 0.24270.000 0.46370.0881
FeOOH (g/L)
0 1 2 3 4 5 6
O
z
o
n
e

d
e
c
o
m
p
o
s
i
t
i
o
n

r
a
t
e

(
m
i
n
-
1
)
0.00
0.02
0.04
0.06
0.08
0.10
Fig. 3. First-order rate constants for ozone decomposition as a
function of FeOOH concentration at pH 3.1: [O
3
]
0
=2 mg L
1
.
pH
2 4 6 8 10
C
a
t
a
l
y
t
i
c

O
3

d
e
c
o
m
p
o
s
i
t
i
o
n

r
a
t
e

(
M
-
1
s
-
1
)
0.00
0.05
0.10
0.15
0.20
0.25
0.30
Experimental data
Model
Fig. 4. Comparison of model tting and experimental data for
ozone decomposition at different pHs: [O
3
]
0
=2 mg L
1
,
[FeOOH]=2 g L
1
.
J.-S. Park et al. / Water Research 38 (2004) 22852292 2288
where a

1 K
s
a1
=H

K
s
a1
K
s
a2
=H

1
; a
0

=K
s
a1
1 K
s
a2
=H

1
; a

2
=K
s
a1
K
s
a2

H

=K
s
a2
1
1
: The three rate constants, estimated
by multiple regression using STATISTICA software,
were k
+
=0.0216 M
1
s
1
, k
0
=0.0113 M
1
s
1
, and
k

=0.463 M
1
s
1
(R
2
=0.99). These values imply that
the negatively charged goethite surface has a strong
reactivity toward ozone. This phenomenon is likely due
to the electrophilic characteristics of ozone, which has a
high afnity for molecular sites with a strong electronic
density. A similar situation was found for the reaction
between hydrogen peroxide and a goethite surface [8,9].
Hydrogen peroxide also favors the negative goethite
surface by forming strong complexes with negative sites.
The second-order rate constant (k
+
) of ozone with
FeOH
2
+
was found to be approximately twice as great
as k
0
. This can be explained by the resonance structures
of ozone, which give ozone both an electrophilic and a
nucleophilic character. Therefore, ozone shows a higher
reactivity towards a charged surface than an uncharged
goethite surface. A comparison of the kinetic model and
the experimental data for ozone decomposition on a
goethite surface at various pHs is shown in Fig. 4.
3.2. Decomposition of pCBA
3.2.1. pH effect
During the ozonation and the catalytic ozonation, the
concentrations of ozone and pCBA were monitored; the
results are plotted in Figs. 5 and 6. The FeOOH
concentration was 5 g L
1
and the pH of the reaction
solution was set at 2 and 3 using a buffer solution. The
initial ozone dosage and pCBA concentration were
3 mg L
1
and 1.2 mg L
1
, respectively. t-butanol
(10 mM) was added to suppress the reaction between
the OH radical and pCBA in the bulk solution (the
majority of OH radicals are scavenged by t-butanol [18]).
The decomposition rates of ozone and pCBA at pHs
between 2 and 3 revealed a substantially different
pattern. Catalytic ozonation in the presence of t-butanol
at pH 2 did not change the efciency of pCBA or ozone
decomposition. However, at pH 3, the decompositions of
both pCBA and ozone were signicantly increased in the
absence of t-butanol. Because the decomposition rates of
ozone and pCBA at pH 2 were unaffected by the
addition of t-butanol, it can be inferred that the pCBA
degradation at the pH condition was due to reaction with
the OH radical on the surface of goethite. And there was
no subsequent catalytic reaction of ozone to generate
OH radicals in the bulk solution. Though the initial
ozone demand for pCBA at pH>5 was so high that a
continuous measurement of ozone and pCBA was
impossible, the trend of the decompositions of ozone
and pCBA was the same as that shown at pH 3. The
ozone decomposition rates during pCBA degradation
with and without t-butanol at pH 2 were 0.060 and
0.062 min
1
, which were much higher than without
pCBA (see the 2nd column of Table 2). However,
catalytic oxidation without t-butanol at pH 3 increased
the decomposition rate of ozone and pCBA and the IOD
also increased exponentially. On the other hand, the
decomposition rate of pCBA, the ozone decay rate and
the IOD in the presence of t-butanol revealed little
change, compared to those at pH 2. The fractionated
degradation of pCBA was evaluated for O
3
/FeOOH/t-
butanol (surface reaction), O
3
(bulk reaction), and O
3
/
FeOOH (catalytic reaction+bulk reaction) by calculat-
ing area of each case for 10 min reaction in Fig. 6. It was
found that 0.0495, 0.775 and 0.966 of the initial pCBA
mass represented O
3
/FeOOH/t-butanol (surface reac-
tion), O
3
(bulk reaction), and O
3
/FeOOH (catalytic
reaction+bulk reaction), respectively. It is interesting
to note that the amount of pCBA removed by the
catalytic ozonation (O
3
/FeOOH) was higher than those
removed by surface reaction plus that removed by
ozonation alone, i.e., 0.966>0.0495+0.775. This result
implies that another reaction site, that is, a catalyst
surfacebulk solution interface may exist for the catalytic
oxidation reaction. A plausible reaction mechanism
involves the enhanced pCBA decomposition at the
ARTICLE IN PRESS
0 2 4 6 8 10
p
C
B
A

(
C
t
/
C
0
)
0.82
0.84
0.86
0.88
0.90
0.92
0.94
0.96
0.98
1.00
1.02
O
3
O
3
/FeOOH
O
3
/FeOOH/t-Butanol
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time (min)
O
z
o
n
e

(
C
t
/
C
0
)
O
3
O
3
/ FeOOH/ TB
O
3
/ FeOOH
Time (min)
Fig. 5. Decomposition of ozone and pCBA during ozonation
and catalytic ozonation at pH 2: [O
3
]
0
=3 mg L
1
,
[FeOOH]=5 g L
1
.
J.-S. Park et al. / Water Research 38 (2004) 22852292 2289
catalystsolution interface (i.e., boundary layer) via
the hydroxyl radicals produced by the reaction between
ozone and the surface of the catalyst. Because the
catalyst surface can adsorb oxidants and modify oxida-
tion intensity, the solid surfacesolution interface can
catalyze oxidation reactions [19]. The fractions removed
at the boundary layer and in the bulk solution were
estimated to account for 0.142 (=total catalytic ozona-
tion-bulk reaction-surface reaction) and 0.775 of the
initial pCBA concentration at pH 3. This means that the
main pCBA removal and ozone decomposition take
place in the catalystsolution interface and in the bulk
solution at pHs above 3. The higher consumption rate of
ozone during catalytic oxidation is caused by the reaction
on the catalysts surface and in the catalystsolution
boundary layer. The sorption of pCBA on the surface of
the goethite is an aspect of pCBA removal that may not
be neglected. However, it is not a signicant factor for
pCBA degradation because the amount of pCBA
adsorbed is negligible (about 30 mg pCBA/kgFeOOH).
More ozone was required during the IOD phase as the
pH increased as mentioned earlier. The initial drop of
the pCBA concentration appeared to match the IOD,
which was also measured at pH 5 and 7 under the same
experimental conditions: the initial concentrations of
ozone and pCBA 3 and 1.2 mg/L, respectively. The
IODs of catalytic ozonation at pH 2 and 3 was higher
than that of ozonation alone. Furthermore, almost the
same amount of ozone during the IOD phase was
consumed at pH between 5 and 7. This result implies
that the IOD has a close relationship with the ionized
form of the COOH of pCBA, which has a pKa value
of pH 3.98. The relative concentration of ionized pCBA
and the IOD at different pHs are shown in Fig. 7.
It is of interest that the amount of ionized pCBA at
various pHs agrees well with the relative concentration
of IOD. Though the mechanism of this phenomenon is
not clear, it can be hypothesized that the ionized pCBA
catalyzes the decomposition of ozone and the subse-
quent reactions required for hydroxyl radical genera-
tion. The dominant oxidant at the IOD phase is not
ozone but the hydroxyl radical because the rate
constants of the ionized and non-ionized forms
of pCBA with ozone are identical (k
O
3
; pCBA
p
0:15 M
1
s
1
; [20]). However, it remains to be investi-
gated whether other compounds containing an ionicable
benzoic acid moiety have a high IOD.
3.2.2. Surface reaction at different pHs
A kinetic study of pCBA removal in the presence of t-
butanol at different pHs (2,3,5 and 7) was carried out to
further delineate the surface reaction mechanism of the
catalyst. Fig. 8 presents the pseudo rst-order plots of
pCBA versus time at various pHs. The decomposition
rate of pCBA was found to decrease as the pH increased
and became constant at pH >5. This result shows the
same trend as the sorption of pCBA on the goethite
surface [14], which was found to be strongly pH-
dependent, and which occurred at less than pH 4. This
further implies that pCBA decomposition at the surface
of FeOOH was affected by the sorption of pCBA on the
goethite surface and not by the ozone decomposition
rate at the goethite surface.
ARTICLE IN PRESS
Time (min)
0 2 4 6 8 10 12
p
C
B
A

(
C
t
/
C
0
)
0.0
0.2
0.4
0.6
0.8
1.0
O
3
O
3
/FeOOH
O
3
/t-butanol
O
3
/FeOOH/t-butanol
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
1.1
0.0 1.0 2.0 3.0 4.0 5.0 6.0 7.0 8.0 9.0 10.0
Time (min)
O
z
o
n
e

(
C
t
/
C
0
)
O
3
/ TB
O
3
/ FeOOH
O
3
only
O
3
/ FeOOH/ TB
Fig. 6. Decomposition of ozone and pCBA during the
ozonation and catalytic ozonation at pH 3: [O
3
]
0
=3 mg L
1
,
[FeOOH]=5 g L
1
.
0
0.2
0.4
0.6
0.8
1
1.2
0 2 4 6 8
pH
R
e
l
a
t
i
v
e

c
o
n
c
.

o
f

I
O
D

a
n
d
i
o
n
i
z
e
d

p
C
B
A

(
C
/
C
0
)
only
O
3
O
3
/ FeOOH
pCBA- COO-
Fig. 7. The relative concentration of ionized pCBA and the ID
at different pHs: pKa of pCBA=3.98, [O
3
]
0
=3 mg L
1
.
J.-S. Park et al. / Water Research 38 (2004) 22852292 2290
3.2.3. Effect of goethite concentration
The inuence of the amount of metal oxide on the
degradation of pCBA was also investigated since the
main reaction of pCBA was known to have something to
do with the goethite surface at pHo3. The initial ozone
dosage and the pCBA concentration were 3 and
1.2 mg L
1
, respectively. Fig. 9 shows the pseudo rst-
order plots of pCBA removal versus different goethite
concentrations (215 g L
1
). The removal rate of pCBA
at the various goethite concentrations was found to be
linearly related with the ozone decomposition rate,
because the increased amount of goethite provides more
active sites for pCBA absorption and thus generate more
OH radical due to reaction with ozone.
Based on these results, it can be concluded that pCBA
removal via catalytic ozonation occurs at three loca-
tions: (i) on the surface of catalyst, (ii) in the catalyst
solution interface, and (iii) in the bulk solution.
Because the decomposition rate of ozone on the
catalysts surface can be described by rst order kinetics
with respect to the ozone and goethite concentrations,
the rate-limiting step for ozone decomposition on the
surface of goethite can be described as
FeOHO
3
-OH 8
This reaction involves a series of chain reactions, which
are proposed in Table 3. The initial step involves the
formation of a surface complex between ozone and the
goethite surface. The formation rate of the surface ozone
complex with the three different surface goethite species
depends on pH, which determines the rate of the ozone
decomposition.
The main limiting step of pCBA decomposition on the
surface of the catalyst involves the sorption of pCBA on
the goethite surface, which results from the formation of
outer-sphere complexes that have very weak and
unstable interactions, because pCBA sorption is depen-
dent on the ionic strength of the medium [19]. Outer
sphere complexes can be formed as a result of H-bond
formation between the carboxylate and hydroxyl groups
of organic molecules and singly and triply coordinated
surface groups. Therefore, acidity plays a signicant role
in the sorption of an organic acid:
FeOH

2
R-COOH2 FeOH

2
--HOOC-R: 9
The sorbed pCBA on the surface of goethite reacts with
the OH radical generated by the ozone surface reaction:
FeOH

2
--HOOC-ROH-Products: 10
A plausible mechanism for the catalystsolution inter-
face reaction is that the hydroxyl radical generated by
the ozone surface reaction decomposes the pCBA in the
vicinity of the surface.
Another possible mechanism is that the COOH of
pCBA (pCBACOOH) exists in the ionized form, due to
hydroxyl ions derived from the surface of goethite.
Thus, the ionized pCBA becomes an organic radical via
the reaction with ozone. The free radicals so produced
catalyze ozone decomposition, and the OH radical
might be formed as a result of chain reactions such as
free radicals with ozone. Two gram per litre of goethite
increased the pH of distilled water from 3 to 8 by
producing hydroxyl ions, which serves as indirect
ARTICLE IN PRESS
Time (min)
0 2 4 6 8 10 12
L
n

(
[
p
C
B
A
]
/
[
p
C
B
A
]
0
)
-0.16
-0.14
-0.12
-0.10
-0.08
-0.06
-0.04
-0.02
0.00
0.02
pH 2
pH 3
pH 5
pH 7
k=0.0139 min
-1
k=0.0085 min
-1
k=0.0026 min
-1
k=0.0022 min
-1
Fig. 8. The pseudo rst-order plots of pCBA versus time with t-
butanol at various pHs: [O
3
]
0
=3 mg L
1
, [FeOOH]=2 g L
1
, [t-
butanol]
0
=10 mM, [pCBA]
0
=1.2 mg L
1
.
Ln([O
3
]/[O
3
]
0
)
0.00 0.02 0.04 0.06 0.08 0.10
L
n
(
[
p
C
B
A
]
/
[
p
C
B
A
]
0
)
0.005
0.010
0.015
0.020
0.025
0.030
0.035
2 g/L FeOOH
5 g/L FeOOH
10 g/L FeOOH
15 g/L FeOOH
Fig. 9. The pseudo rst-order plots of pCBA versus the pseudo
rst-order plots of ozone at different FeOOH concentrations:
[FeOOH]=215 g L
1
, [O
3
]
0
=3 mg L
1
, pH=2.5.
Table 3
Proposed mechanism for ozone decomposition on goethite
surface
FeOH/FeO

+O
3
2FeOH(O
3
)
s
/FeO(O
3
)
s

FeOH(O
3
)
s
/FeO(O
3
)
s

2FeO+HO
3
/O
3

FeO+H
2
O-FeOH+OH
HO
3
2H
+
+O
3

HO
3
-OH+O
2
O
3

+H
2
O-OH+O
2
+OH

J.-S. Park et al. / Water Research 38 (2004) 22852292 2291

evidence for this hypothetical mechanism:
FeOHR-COOH2 FeO

R-COO

H
2
O;
11
R-COO

O
3
-R; 12
R-O
3
--Products: 13
The reaction mechanism in the bulk solution on the basis
of IOD and initial pCBA decomposition at various pHs
involves the generation of OH radicals that result from the
free radical reaction between pCBA-COO

and ozone,
which is similar to the secondary mechanism proposed
above for the catalystsolution interface reaction.
4. Conclusions
The rate of ozone decomposition in the presence of
the goethite catalyst was higher than without catalyst
because of a reaction between the ozone and the active
surface of the catalyst. The decomposition rate of ozone
on the surface of the goethite is strongly pH-dependent
due to the different reactivities of the three surface
species (FeOH
2
+
, FeOH, FeO

) with ozone. The

decomposition of pCBA during catalytic ozonation,
based on our results, seems to occur at three sites: (i) on
the surface of the catalyst, (ii) in the catalystsolution
interface, and (iii) in the bulk solution, and this
decomposition involves radical reactions. pCBA decom-
position occurs only on the surface of the catalyst at
pHs below three and the hydroxyl radicals generated by
the reaction between the catalyst surface and the ozone
were found to be the dominant oxidizing species.
However, at pHs>3 the main reactions were found to
take place in the catalystsolution interface and bulk
solution. Moreover, catalytic ozonation enhanced cata-
lystsolution interface pCBA decomposition by the
involvement of hydroxyl radicals generated from the
reaction between ozone and the catalyst surface or by a
free radical chain reaction initiated by the ionized pCBA
in the vicinity of the ozone/goethite surface.
Acknowledgements
This research was supported by a grant (4-1-1) from
the Sustainable Water Resources Research Center
(SWRRC) of the twenty rst century frontier R&D
program through the Water Reuse Technology Center
(WRTC) at Kwnagju Institute of Science and Technol-
ogy (K-JIST).
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