Science in China Series B: Chemistry 2006 Vol.49 No.

4 379384 379

DOI: 10.1007/s11426-006-0379-4

The mechanism and pathway of the ozonation of

4-chlorophenol in aqueous solution
PI Yunzheng & WANG Jianlong
Laboratory of Environmental Technology, Institute of Nuclear Energy Technology, Tsinghua University, Beijing 100084, China
Correspondence should be addressed to Wang Jianlong (email: wangjl@tsinghua.edu.cn)

Received June 22, 2005; accepted September 26, 2005

Abstract The removal efficiency of 4-chlorophenol by ozonation was studied, and the reaction
mechanism and characteristic of ozonation of 4-chlorophenol were investigated. Ozone and hydroxyl
radicals are two strong oxidants during the process of ozonation. The experimental results showed
that when there was no scavenger to inhibit OH radicals, an intermediate product, hydrogen peroxide
was formed during the ozonation of 4-chlorophenol. Hydrogen peroxide reacted with ozone at neutral
pH and produced hydroxyl radicals. Ozone at the dosage of 113 mg/L could remove 20 mg/L
4-chlorophenol and 39% TOC. With the complete inhibition of hydroxyl radicals, molecular ozone
could effectively destroy 4-chlorophenol to form 4-quinone, which was subsequently oxidized to formic
acid and oxalic acid. Two reaction pathways of the degradation of 4-chlorophenol by ozone and
O3/OH were proposed in this study. Ozonation is an effective method for reducing 4-chlorophenol,
and has potential to practical application.

Keywords: 4-chlorophenol, ozone, hydrogen peroxide, 4-quinone, hydroxyl radicals.

Chlorophenols (CPs) have been widely used in dif- substituted phenols[4].

ferent formulations as preservatives, herbicides, insec-
ticides, bactericides and solvents. Parts of chlorophe-
nols were released to the natural environment during
the usage. As a result, many water sources were con-
taminated with CPs[1,2]. Furthermore, they also can be
formed during the disinfection of phenol containing
water by chlorination. Several CPs are recognized as
the priority pollutants by the United States EPA (En-
vironmental Protection Agency)[3]. Chlorophenols are
poorly biodegradable due to their aromatic structure
and the existence of chlorine. Microorganisms are af-
fected by the toxicity of CPs. The conventional physi-
cal/chemical and biological treatment technologies
usually proved to be ineffective. 4-CP is especially
resistant to biodegradation among the one chlorine
Therefore, CPs removal techniques, such as cata-
lytic oxidation, were investigated in recent years. Ad-
vanced Oxidation Processes (AOPs), such as photo
catalytic oxidation[5,6], were used to remove CPs.
Ozonation is a promising choice for the degradation of
CPs. However, only limited studies of the ozonation of
CPs were performed[7]. Ozone may decompose in wa-
ter before reacting with substrates. This decomposition
leads to more reactive oxidants. Among these secon-
dary oxidants, hydroxyl radicals (OH) are extremely
powerful and non-specific oxidants that react with
many organic and some inorganic species. The objec-
tive of this research was to investigate the removal
efficiency and some intermediate products during the
degradation of 4-CP by ozone and O3/OH. Moreover,

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 380 Science in China Series B: Chemistry

the mechanism and the reaction pathway were also proximately 113 mg/L. The rate of disappearance of
proposed in order to make the most efficient use of the TOC is also shown in Fig. 1. Its removal efficiency at
oxidant O3 and OH in practice. 21 min was 39%, which was obviously lower than that
of 4-CP (100%). This indicated that the primary attack
1 Experimental of ozonation broke 4-CP to low molecular weight in-
termediate products, instead of the direct mineraliza-
0.1 g DPD (N, N-diethyl-p-phenylenediamine) was tion to carbon dioxide.
dissolved in 10 mL 0.05 mol/L H2SO4 to make DPD
solution. 10 mg POD (horseradish peroxidase) was
dissolved in 10 mL water to make POD solution ac-
cording to the literature[8]. Hydrogen peroxide was
measured by the DPD/POD method. In the method of
DPD/POD, DPD and POD are subsequently added to a
sample. H2O2 will oxidize POD to a higher valence
state, which in turn oxidizes DPD to a pink colored
radical cation-DPD+. The color can be measured by
adsorption at 551 nm[8]. H2O2 itself cannot oxidize
DPD.
Semi-batch tests (continuous for ozone gas supply,
fixed volume of water sample) were run with a labo- Fig. 1. The changes of the concentration of 4-chlorophenol and TOC
during ozonation.
ratory ozonation unit, consisting of an ozone generator,
reactor (2 L), and pump etc. The injected ozone gas
In this work, some intermediate products were de-
was about 24 mg/L. And the flow rate was 27 L/h[9].
tected to investigate the reaction pathway and mecha-
The dosage of ozone within one minute was 5.4 mg/L.
nism. The changes of pH and hydrogen peroxide are
TOC was detected by a TOC analyzer (Elementar
shown in Fig. 2. The value of pH dropped to 3.25 after
High TOC). The concentrations of chloride, oxalate
28 min ozonation. This suggested that there might be a
(oxalic acid), formate (formic acid) and succinate
strong formation of organic acid during the ozonation
(succinic acid) were determined by ion chromatogra-
of 4-CP. Their dissociation led to the decrease of the
phy (Dionex DX 100). UV absorbency measurements
pH. Hydrogen peroxide was identified as an interme-
were detected by a Shimadzu UV-3100 model UV-
diate by-product during the ozonation (see Fig. 2). Part
VIS-NIR recording Spectrophotometer. 4-CP was
of H2O2 dissociated to HO2 at neutral pH. HO2 has a
measured by HPLC (HP1100) using eluent A (60%
high reaction ability (kO3/HO2 = 2.8106 (mol/L)1
ethanol)/eluent B (40% pure water), and UV-detection
at 280 nm (Detection limit 80 g/L). s1)[10]. And it could tremendously promote ozone to

2 Results and discussion

2.1 Ozonation of 4-CP
4-CP solution was prepared in deionized water with
a concentration of 20 mg/L (0.155 mmol/L) and pH
was adjusted to 7.5 by NaOH solution. Ozonation was
conducted at room temperature. Ozonation could eas-
ily remove 4-CP, as indicated in Fig. 1. 4-CP de-
creased to 1.12 mg/L after 9 min reaction. And the
concentration of 4-CP was under the detection limit
after 21 min. The corresponding ozone dose was ap- Fig. 2. The changes of hydrogen peroxide and pH during ozonation.
 Mechanism & pathway of ozonation of 4-chlorophenol in aqueous solution
decompose to OH radical. OH radical is an ex-
tremely powerful oxidant that can oxidize almost all
organic and inorganic substances with the rate con-
stants of 1081010 (mol/L)1s1[11], and its standard
reduction potentials of 2.8 eV, compared to 2.07 eV of
ozone[12]. Consequently, there were two strong oxi-
dants, ozone molecule and OH radicals during ozona-
tion. The disappearance of 4-CP was a combination
effect of the reactions of the molecular ozone and OH
radicals.
The concentrations of chloride, formic acid and ox-
alic acid are depicted in Fig. 3. The detected formic
acid (pKa = 3.8) and oxalic acid (pKa1 = 1) proved the
above assumption. Their appearance contributed to the
decrease of the pH. The detected chloride indicated
that ozonation could split chlorine from 4-CP. How-
ever, the measured chloride after the ozonation was
still lower than the initial amount of 4-CP. This
showed that there were some residual chlorine-con-
taining intermediate compounds in the solution.
Fig. 3. The changes of the concentration of Cl-, formate, oxalate and
4-CP during ozonation. , 4-CP; *, Cl; , formate; +, oxalate.
2.2 Detection of OH
In order to directly demonstrate the effect of the
formed OH radicals initiated by the intermediate
product H2O2, a hydroxyl radical probe compound,
succinic acid (succinate), was developed in our re-
search to detect the formation of OH radicals. Under
the same experimental situations (such as injected
ozone concentration and ozonation time), ozonation
cannot degrade succinate. Only AOPs, such as O3/
H2O2 process, produced a lot of OH radicals, which
then destructed succinate. Therefore, the decrease of
381
succinate could express the formation of OH radicals.
A small amount of succinate was added in the 0.155
mmol/L 4-CP solution. And the batch ozonation ex-
periment was run again. As it is observed in Fig. 4,
succinate decreased obviously during ozonation treat-
ment. And the main removal of succinate occurred in
the initial stage. At the beginning of the first 3 min, the
detected formic acid and oxalic acid were about 0
mg/L, and pH was still kept in the neutral range. The
generated H2O2 could dissociate to HO2 (pKa =
11.6)[10], which subsequently reacted with ozone and
caused the formation of many OH radicals. They then
oxidized succinate. The concentrations of the pro-
duced intermediate organic acids, such as formic acid
and oxalic acid, increased with the increasing of the
time. And this organic acids resulted in the decrease of
pH to acid range (34). The transformation of OH
radicals from HO2 was scarce. Therefore, succinate
could not be further degraded.
Fig. 4. The changes of succinic acid during ozonation.
2.3 Ozonation of 4-CP with the presence of t-butanol
Natural waters contain different amounts of scav-
engers, such as carbonate and bicarbonate, which were
the main existing forms under neutral pH condition.
The scavengers can react with OH, and then inhibit
the reactions between OH and pollutants. In order to
clarify the reaction mechanism of only molecular
ozone with 4-CP, t-butanol was spiked in the 4-CP
solution. T-butanol was often used as a scavenger
(kOH/t-buta = 6108 (mol/L)1s1)[13]. Its scavenging
ability is 1.5 times higher than that of carbonate and
71 times higher than that of bicarbonate[13]. 26.6
 382
mmol/L t-butanol was spiked in the 4-CP solution. The
maximum constant of OH radicals with solutes is 1010
(mol/L)1s1[14]. The reaction constant of 4-CP with
OH radicals was supposed to be the maximum con-
stant due to the absence of the data in literature.
The reaction rate of t-butanol with OH =
kOH/t-buta[t-butanol][OH] = 26.6 kOH/t-buta[OH].
The reaction rate of 4-CP with OH = kOH/max
[4-CP][OH] = 0.155 kOH/max[OH].
The ratio of the above two equations = 26.6
kOH/t-buta/0.155 kOH/max = 10.3.
The employed t-butanol reacted with OH at least
10 times stronger than 4-CP with OH radicals.
Therefore, the indirect reaction between OH radicals
and 4-CP can be effectively inhibited, and the reaction
between ozone and 4-CP can be separated and inves-
tigated.
From the results in Fig. 5 it can be seen that with
the presence of t-butanol to inhibit OH radicals,
ozone molecule can itself remove 4-CP. A complete
degradation was reached after 9 min. The pH value
decreased to 3.2, which was similar to the above ex-
periment without t-butanol. Chloride, formate and ox-
alate were also detected (Fig. 6). The concentration of
the produced formate was 3 times higher than the
above experiment (see Fig. 3). Molecular ozone and
OH can both oxidize formate. The reaction constants
are kO3/form100 (mol/L)1s1[15]; kOH/form2.8109
(mol/L)1s1 respectively[16]. In the above experiment
without t-butanol, the generated formate was further
destructed by ozone and OH together. However, in
this experiment, t-butanol inactivated the OH reac-
tions. The appearing formate was oxidized only by
Fig. 5. The changes of succinic acid during ozonation with the pres-
ence of t-butanol.
Science in China Series B: Chemistry
Fig. 6. The changes of Cl, formate, oxalate and 4-CP during ozona-
tion with the presence of t-butanol.
ozone molecule. This might lead to a slow degradation
rate and therefore an accumulation of formate in the
solution.
In the experiment with the spiked t-butanol, the
colorless solution changed to be yellow at the begin-
ning of ozonation. After 6 min, the yellow solution
turned to be colorless again. Since OH radicals were
inhibited, the changes of the color demonstrated that a
new intermediate product emerged, and a new reaction
pathway between molecular ozone with 4-CP occurred.
When DPD was added to the yellow sample to detect
the concentration of H2O2, colorless DPD was oxi-
dized to the pink colored radical cation-DPD+. After
analysis, the yellow color compound was 4-quinone.
There are 4-quinone (golden color) and 2-quinone (red
color). Quinine has strong oxidation ability. It can oxi-
dize DPD to DPD+[17]. Singer et al. also reported that
intermediate product 4-quinone was formed when phe-
nol was ozonated[18].
H2O2 was also detected in this experiment. Its con-
centration and changes were similar to the results in
Fig. 2. The inactivation of OH radicals indicated that
the appearing H2O2 could be ascribed to the direct re-
action of ozone molecule with 4-CP. Ozone molecule
oxidized 4-CP to 4-quinone. And then ozone reacted
with the C=C bonds of 4-quinone to form H2O2. When
an intermediate product containing C=C bonds ap-
peared during ozonation, the reaction of ozone with
C=C bonds can lead to the generation of H2O2[19] (see
Fig. 7). Although H2O2 was produced in this experi-
ment, the existence of t-butanol inhibited OH radi-
 Mechanism & pathway of ozonation of 4-chlorophenol in aqueous solution 383

Fig. 7. The reaction model of ozone with olefins with C=C bonds.

cals, and OH radicals played a limited role in this
experiment.
2.4 The pathway of the ozonation of 4-CP
There are many organic compounds promoting
ozone decomposition to OH radicals. Different water
samples contain different kinds of promoters and
scavengers, and their concentrations change greatly.
Therefore, the appearing OH radicals in different wa-
ter samples play different roles during the ozonation
process. However, the above experiments showed that
both ozone molecule and OH radicals could destroy
4-CP. The direct reaction pathway of ozone with 4-CP
is reported in Fig. 8(a). Molecular ozone firstly oxi-
dized 4-CP to 4-quinone, which was subsequently de-
graded to formic acid, oxalic acid and other low mo-
lecular weight compounds.
When there are not enough scavengers in water to
inhibit OH radicals, the reaction pathway of O3/OH
with 4-CP is listed in Fig. 8 (b). The reaction of ozone
with 4-CP led to the emergence of a small amount of
hydrogen peroxide. The dissociated HO2 reacts with
ozone and generates OH radicals. Then the chain re-
action was initiated. The strong oxidant, OH radicals

Fig. 8. The mechanism and pathway of ozonation of 4-chlorophenol. (a) Ozone molecular oxidize 4-CP; (b) ozone and OH oxidize 4-CP.
 384
destroy the aromatic ring of 4-CP to olefins with C=C
bonds. The olefins reacted further with ozone to form
more hydrogen peroxide. The reaction pathway run as
the dotted line listed in Fig. 8(b).
3 Conclusions
(1) When the scavenger completely inactivated OH
radicals, molecular ozone alone could degrade 4-CP.
4-CP was firstly oxidized to 4-quinone, and then was
destructed further to formic acid and oxalic acid.
(2) When there were not enough scavengers in the
samples, there was another combination reaction
pathway. A small amount of H2O2 was produced dur-
ing the oxidation of 4-CP by ozone. The generated
H2O2 strongly promoted ozone decomposition to OH
radicals. OH radicals degraded 4-CP to low molecular
weight organic compounds, such as, formic acid and
oxalic acid.
(3) A hydroxyl radical probe compound, succinate,
was tested in this work to demonstrate the formation
and the concentration of the generated OH radicals
during the ozonation of 4-CP. The results indicated
that there was a strong formation of OH radicals at
neutral pH at the beginning of the ozonation.
Acknowledgements This work was supported by the Ex-
cellent Young Teacher Program of Ministry of Education of
China and the National Natural Science Foundation of
China (Grant No. 50325824).
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