Water Air Soil Pollut (2017) 228: 284

DOI 10.1007/s11270-017-3465-7

Degradation of 4-Chlorophenol by Means of Fenton Oxidation

Processes: Mechanism and Kinetics
Shilong He & Yi Chen & Haibo Wang & Wan Yang &
Yingxin Gao & Yun Zhao

Received: 29 December 2016 / Accepted: 29 June 2017 / Published online: 18 July 2017
# Springer International Publishing AG 2017

Abstract Stopped-flow technology and HPLC anal- (HO2·) would take the main part in this process. In
ysis were used to study the degradation mechanism our study, there would exist two catalytic systems in
and reaction kinetics of 4-chlorophenol (4-CP) in Fenton process, and one was Fe2+and Fe3+, the other
Fenton oxidation process. The results indicated that was hydroquinone and benzoquinone. Moreover, the
benzoquinone and hydroquinone were simultaneous- rate constants of hydroquinone, benzoquinone, and
ly produced in process of Fenton oxidizing 4-CP by 4-chlorocatechol were 2.78 × 10 6 L s −1 mol −1 ,
stopped-flow technology analysis. The data obtained 9.38 × 108 L s−1 mol−1, and 6.47 × 106 L s−1 mol−1,
by HPLC showed that hydroquinone was generated respectively.
in great quantities following the decrease of benzo-
quinone. It could be inferred by batch experiments Keywords Fenton reagents . 4-Chlorophenol . Stopped-
that benzoquinone would be transformed into hydro- flow . Intermediates . Degradation mechanism . Kinetics
quinone in Fenton process and hydroperoxyl radical

1 Introduction
Electronic supplementary material The online version of this
article (doi:10.1007/s11270-017-3465-7) contains supplementary Because of the broad-spectrum antimicrobial properties,
material, which is available to authorized users.
chlorophenols (CPs) have been widely used as pesti-
S. He (*) : Y. Chen : H. Wang : W. Yang cides, herbicides, and preservatives. During the manu-
School of Environment and Spatial Informatics, China University facture, storage, transportation, and application, un-
of Mining & Technology, Xuzhou 221116, China avoidable emissions cause CPs into waters and soils,
e-mail: [email protected]
which will pose serious damage to ecological safe and
Y. Gao human health, and have been listed as the priority pol-
State Key Laboratory of Environmental Aquatic Chemistry, lutants in the USA and China (Glaze et al. 1979). Due to
Research Center for Eco-Environmental Sciences, Chinese the existent of benzene ring and chlorinated atoms basis,
Academy of Sciences, Beijing 100085, China
4-chlorophenol (4-CP) is especially difficult to be de-
Y. Gao (*) graded by conventional biological process. Therefore,
University of the Chinese Academy of Sciences, Beijing 100019, alternative methods, such as supercritical wet oxidation
China (Lee et al. 2002), electrochemical oxidation (Rodgers
e-mail: [email protected]
et al. 1999), and Fenton oxidation (Pera-Titus et al.
Y. Zhao 2004), have been introduced to eliminate the CPs. Es-
Xuzhou Capital Water Co., LTD, Xuzhou 221116, China pecially, Fenton oxidation technology have received
284 Page 2 of 9 Water Air Soil Pollut (2017) 228: 284

increasing attention for the destruction of bio-refractory from the abovementioned techniques are often af-
organic substrates because of its owns high efficiency, fected by mixing speed and detection sensitivity
low operating cost, and simple operating. because the Fenton reaction is a rapid response
Some studies indicated that (Zhang et al. 2007a; process. In addition, the data obtained by these
Wang et al. 2001; Du et al. 2007a) Fenton can methods are the amount of reactants or productions
efficiently destroy 4-CP and generally considered at a certain point that lack of continuity. For some
that intermediate (benzoquinone and 4- lively intermediates in the Fenton process, they
chlorocatechol) would directly further be oxidized would more quickly produce and disappear and are
by hydroxyl radical into carbon dioxide and H2O, as more difficult to be captured by the above methods.
expressed in Eqs. (1) and (2). However, Chen F. Some studies indicated that stopped-flow technology
et al. (Chen et al. 2002) reported that intermediates could continuously and fast detect the changes of
(phenoxyl radicals) would be generated by the reac- the test substance concentration in solution and was
tion of benzoquinone and HO2· and hydroquinone considered to be an efficient method for explaining
and benzoquinone were continuously generated the most possible reaction ways and investigating
from phenoxyl radicals in the Fenton process (as the intermediates in rapid reaction (Khorassania
shown in Eqs. (3) and (4)), which accelerated the et al. 2015; Jantschko et al. 2005; Huang et al.
Fenton reaction until they were finally oxidized into 2003).
CO2 and H2O. In this article, Fenton’s oxidation was used to treat 4-
CP wastewater. The intermediates of 4-CP degradation
Cl Cl
were identified, and their characteristics were analyzed
+ ·OH
by using HPLC and the stopped-flow spectrometer,
OH
respectively. Based on the intermediate analysis, the
OH OH mechanism of 4-CP degradation and reaction kinetics
were studied.

Cl OH O
2 Materials and Methods
electron transfer
+ ·OH
2.1 Materials
OH OH O
H2O2 (w/w, 30%), FeSO4·7H2O, H2SO4, and NaOH of
analytical grade were purchased from the Sigma Chem-
ical Company (USA). C6H5OCl, C6H6O2, C6H4O2,
(CH3)3COH, and C6H5ClO2 of guaranteed grade were
purchased from the Alfa Aesar; Sigma-Aldrich; Acros
Organic, New Jersey, USA; Sinopharm Chemical Re-
agent Company, and Japan MSDS, respectively.

2.2 Fenton Oxidation

Fenton oxidation was carried out in a lucifugal glass

reactor, equipped with a magnetic stirrer (600 rpm/min).
The reaction medium consisted of 100 mg/L 4-CP and
the desired concentration of Fe2+ (0.3 mmol/L) in pure
Moreover, high-performance liquid chromatogra- water. The initial pH value was adjusted to 3.0 with
phy (HPLC), gas chromatography-mass spectrome- H2SO4 and NaOH. The initial 30% (w/w) H2O2 concen-
ter (GC-MS), and ultraviolet spectrophotometry are tration (3 mmol/L) was stoichiometric amount required
more frequently used in researching the degradation for directly mineralizing 4-CP into CO2 and H2O. Sam-
mechanism 4-chlorophenol, but results obtained ples were withdrawn from the reaction medium and
Water Air Soil Pollut (2017) 228: 284 Page 3 of 9 284

properly amounts of tertiary butanol (0.1 mol/L) were 3 Results and Discussion
added to quench the residual H2O2.
All of the experiments were performed in triplicate. 3.1 Mechanisms of 4-CP Degraded by Fenton’s
Reagents
2.3 Measuring Methods
3.1.1 Changes of Intermediates During Fenton Process
2.3.1 HPLC Analysis
Some previous studies indicated that 4-chlorocatechol,
4-CP and its intermediates in aqueous samples were benzoquinone, and hydroquinone are the main interme-
monitored by HPLC (Waters 2690, Milford, USA), diate products during the 4-CP degradation process by
equipped with a Gemini C-18 column (Agilent Fenton oxidation (Lukes and Locke 2005; Zhang et al.
ZORBA-SB-C18, USA, Ф4.6 mm × 250 mm) which 2007b; Bian et al. 2013). Therefore, in our study, the
was maintained at 30 °C. The mobile phase com- changes of the abovementioned three intermediates
posed of formic acid (1.0‰, solvent A) and metha- were analyzed by stopped-flow technology, and the
nol (solvent B) was pumped by gradient elution at results were shown in Fig. 1. After the Fenton reaction
1 mL/min for 20 min. Automatic injection sample started, the concentrations of 4-chlorocatechol, benzo-
volume was 20 μL. quinone, and hydroquinone gradually increased. Within
5 s, the absorbance of 201.5 nm (4-chlorocatechol)
2.3.2 Stopped-Flow Analysis increased from 0.11 to 0.15 AU in Fig. 1a. At the same
time, benzoquinone and hydroquinone were simulta-
The sequential stopped-flow apparatus (model neously generated. Benzoquinone (245.9 nm) increased
Pistar180) and the associated computer system were from 0.008 to 0.0238 AU. However, the increasing
from the Photo Physics (UK). Before starting the mea- degree of absorbance for hydroquinone (289.7 nm)
surements, all tubes were purged several times with a was lower than that for benzoquinone, which rose from
nitrogen blow to remove trapped air from the system. 0.008 to 0.016 AU in Fig. 1b.
One syringe contained 4-CP and Fe (II); the other sy- In order to further investigate the variation trend of
ringe contained various concentrations of H2O2. The pH intermediates, batch experiments were conducted under
was controlled at 3.0 ± 0.05 and the constant tempera- the conditions of H2O2 = 3 mmol/L, Fe2+ = 0.3 mmol/L,
ture was kept at 25 °C. and 4-CP = 100 mg/L, and the concentrations of benzo-
Stopped-flow (multi-mixing) analysis was also used quinone and hydroquinone at different time interval
to determine the change and rate of the reaction of 4-CP were measured by HPLC as shown in Fig. 2, benzoqui-
with an excess of H2O2. 4-CP and Fe (II) (75 μL) were none and hydroquinone emerged together. Within the
premixed in the aging loop with 75 μL H2O2 under the short time after the Fenton starting, a mass of benzoqui-
pneumatic drive. The detection wavelength for 4-CP, none was produced, and at the around 3 min, its con-
benzoquinone, and hydroquinone were 225.9, 245.9, centration reached to the peak value of 1.670 mg/L.
and 289.7 nm at the PDA and UV detectors (see Subsequently, the concentration of benzoquinone
Supplementary materials), respectively. dropped rapidly and reached the minimum value of
In order to improve the smoothness of curve, collec- 0.102 mg/L after 15 min. In the case of hydroquinone,
tion points in stopped-flow were set up as shown in its concentration was very low at the initial reaction
Table 1 within the scan time specified. stage, but with the decreasing of benzoquinone con-
The kinetic traces were fitted and analyzed by Pro- centration, its concentration gradually increased, and
Data Viewer. its peak value came to 3.580 mg/L at about 10 min,
corresponding to the minimal value of benzoquinone
concentration. Then, hydroquinone concentration
Table 1 Number of data points collected by stopped-flow kept stability. The changing characteristics of ben-
zoquinone and hydroquinone were similar to Y.
Time (s) 0.01 0.05 0.5 1.0 5.0 10
Zhang’s report (Zhang et al. 2007a), who studied
Collection point 400 2000 10,000 10,000 10,000 10,000 the change trend of 1,4-benzoquinone and hydroqui-
none in the degradation of 4-CP using a novel gas-
284 Page 4 of 9 Water Air Soil Pollut (2017) 228: 284

Fig. 1 Changes of a 4-
chlorocatechol and b 0.15 a
benzoquinone and hydroquinone
during Fenton process
0.14
4-chlorocatechol

Absorbance (AU)
0.13

0.12

0.11

0.10

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s)
0.026
0.024 b
0.022 Benzoquinone
0.020
Absorbance (AU)

0.018
0.016 Hydroquinone
0.014
0.012
0.010
0.008
0.006
0.004
0.002
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s)

liquid hybrid discharge reactor. However, the above benzoquinone and hydroquinone were simultaneous-
phenomenon was difficult to be clearly explain by ly generated and their variation exhibited opposite
using the hydroxyl radical mechanism. In addition, trend. We inferred that that benzoquinone might be
although some researchers (Du et al. 2005; Ma et al. transformed into hydroquinone by using some radi-
2005) have reported that Fe3+ can oxidize hydroqui- cals which also exist in Fenton reaction process,
none to generate benzoquinone and Fe3+ is reduced such as HO2· or O2−·. Therefore, in the following
to Fe2+, which can accelerate the Fenton reaction, it study, we designed some experiments to verify this
was also difficult to illustrate that why assumption.
Water Air Soil Pollut (2017) 228: 284 Page 5 of 9 284

Under the conditions of 3.0 of pH, 10 mmol/L of

benzoquinone, 0.1 mmol/L of Fe2+, and 1 mmol/L of
H2O2, the change of benzoquinone was investigated in
Fenton reaction, and the results were shown in Fig. 3c, d.
In Fenton reaction process, the absorbance of benzoqui-
none rapidly decreasing from 0.241 to 0.197 AU, and the
absorbance of hydroquinone quickly increased from
0.027 to 0.034 AU. The changes of benzoquinone and
hydroquinone concentrations were also analyzed by
HPLC in the whole process, and the results were pre-
sented in Fig. 4. Initially, the concentration of benzoqui-
none dropped rapidly, and it nearly disappeared at
1.5 min. On the contrary, hydroquinone rapidly increased
Fig. 2 Changes of the benzoquinone and hydroquinone during and reached the maximum value of 4.050 mg/L at 3 min
Fenton process by HPLC
and then kept relative stability. The results were same as
that of stopped-flow analysis, which demonstrated that
benzoquinone would react with living radical to yield
3.1.2 Stability of Benzoquinone During Fenton Process hydroquinone during Fenton reaction. In addition, after
3 min, the concentration of hydroquinone decreased and
Under the conditions of 3.0 of pH, 10 mmol/L of ben- then almost unchanged in a low level. The phenomena
zoquinone and 0.1 mmol/L of Fe2+ or 1 mmol/L of were similar to the results of Du et al. (Du et al. 2007a, b)
H2O2, the reaction possibility of benzoquinone with who used Fenton to degrade the p-chlorophenol, and we
Fe2+ or H2O2 was investigated, and the results were inferred that the reaction between hydroquinone and
shown in Fig. 3a, b. It can be seen that the absorbance ferric came to a dynamical equilibrium, so maybe it is
values for benzoquinone were keeping invariable within the reason why no decrease of hydroquinone concentra-
5 s whatever individual addition of Fe2+ or H2O2, which tion occurs after some reaction time.
indicated that benzoquinone may not react with individ- Hydroperoxyl radical (HO2·) as a kind of living
ual Fe2+ or H2O2. radicals produced in the Fenton system is usually

Fig. 3 a Changes of 0.232 0.252

benzoquinone during reaction of 0.231 a 0.251 b

benzoquinone and Fe2+, b 0.230 0.250
Absorbance (AU)
Absorbance (AU)

0.229
changes of benzoquinone during 0.249
Benzoquinone
0.228
reaction of benzoquinone and 0.227
0.248
Benzoquinone
H2O2, c changes of 0.226
0.247

benzoquinone, and d changes of 0.246

0.225
hydroquinone during Fenton 0.245
0.224
0.244
process 0.223
0.222 0.243

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s) Time (s)
0.034
0.250

0.245
c 0.033
d
0.032 Hydroquinone
0.240 0.031
Absorbance (AU)
Absorbance (AU)

0.235 0.030
0.230 0.029
Benzoquinone
0.225 0.028

0.220 0.027
0.026
0.215
0.025
0.210
0.024
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s) Time (s)
284 Page 6 of 9 Water Air Soil Pollut (2017) 228: 284

3.1.3 Mechanisms of 4-CP Degraded by Fenton’s

Reagents

According to the intermediate oxidation process, the

main pathway of 4-CP in Fenton regents was sug-
gested in Fig. 5. It is known that hydroxylated
products can result from electrophilic attack on the
aromatic ring of 4-CP by hydroxyl radicals (·OH)
(Zhang et al. 2007a). Because of stronger oxidation
(redox potential was 2.80 V), ·OH produced from
Fenton reaction would attack the ortho-benzene ring
and meta-benzene ring to form 4-chlororesorcinol,
Fig. 4 Changes of benzoquinone and hydroquinone during the 4-chlorocatechol, and phenoxyl radicals. Among
degradation of benzoquinone by HPLC them, 4-chlorocatechol and 4-chlororesorcinol
would continue to react with ·OH to generate organ-
ic acids until mineralize into CO 2 and H 2 O.
Phenoxyl radicals had the properties of oxidation
abundant (Eqs. (5)–(6)) (Chen et al. 1997). The and reduction which reacted with ·OH and Fe3+ to
charge of oxygen in HO2· is O−, which means that
HO2· has both oxidation and reduction abilities
like hydrogen peroxide. Therefore, benzoquinone
as oxidizer maybe easily react with HO 2 ·
(reductant) to form hydroquinone, as reported by
Chen et al., Ma et al., and Du et al. (Chen et al.
2002; Ma et al. 2005; Du et al. 2005). Moreover,
it is possible that hydroxyl radical oxidizes benzo-
quinone, but the productions were reported to be
aliphatic acids not to be hydroquinone (Buxton
et al. 1988). Therefore, in our study, we inferred
that benzoquinone might be transformed into hy-
droquinone by reacting with HO2·.

Fe3þ þH2 O2 →Fe2þ þHO2  þ Hþ k ¼ 0:01‐0:02 M‐1 S‐1 ð5Þ

⋅OH þ H2 O2 →HO2  þ H2 O k ¼ 2:7  107 M‐1 S‐1 ð6Þ

Although it have been reported (Bian et al. 2013) that

hydroquinone can also be transformed into benzoqui-
none, the concentration of benzoquinone was difficult to
be detected after 3 min, which indicated that the reaction
rate of benzoquinone transformed was very faster than
that of hydroquinone. It put on higher demand for the
intermediate analysis when using HPLC, GC-MS, and
ultraviolet spectrophotometry, or else, it was difficult to
clearly illustrate the degradation process by the above Fig. 5 Proposed pathway for 4-CP decomposition by Fenton’s
three measuring methods. reagent
Water Air Soil Pollut (2017) 228: 284 Page 7 of 9 284
0.026
Fig. 6 Linear fitting of
generation of a hydroquinone, b
0.040
a 20.0 mg/L 0.024 b
0.035 0.022
benzoquinone, and c 4- 0.020

Absorbance (AU)
0.030

Absorbance (AU)
chlorocatechol 0.018
0.025 10.0 mg/L 20.0 mg/L
0.016
0.020
0.014 10.0 mg/L
5.0 mg/L 5.0 mg/L
0.015 0.012
2.5 mg/L
0.010 0.010
2.5 mg/L 0.008
0.005
0.006
0.000
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0 0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s) Time (s)

0.40

0.35
c 20.0 mg/L

0.30

Absorbance (AU)
0.25
10.0 mg/L
0.20

0.15 5.0 mg/L

2.5 mg/L
0.10

0.05

0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 4.5 5.0
Time (s)

form benzoquinone and hydroquinone at the same In our study, the first order reaction dynamic model
time. It formed a new catalytic reduction system in was used and shown in Eq. (7):
Fenton reaction which perfected the mechanism of  . 
Ln C C 0 ¼ −kt; ð7Þ
Fenton degradation of 4-CP.
where C0 and C are the initial and a given time (t)
3.2 Kinetics of Degradation of 4-CP by Fenton organic concentration, respectively, t is reaction time,
and k is apparent rate constant.
In order to set up the dynamic model and calculate According to Lambert-Beer law, the absorbance (A)
the kinetic coefficients, a series of assumptions were of solutions was proportional to their concentration (C),
put forward and presented as follows: (1) solutions so the Eq. (7) can be turned into Eq. (8).
(4-CP, Fe 2 + , and H 2 O 2 ) in the reactor were  . 
completely mixed, (2) ·OH as the main active inter- Ln A A0 ¼ −kt ð8Þ
mediate was so lively that would quick react with
organic matter, and (3) H2O2, HO2·, and O2−· could Linear analysis was made to get the slope which stood
not effectively degrade organic matter. for the apparent rate constant (k). Then, the k was used to

Table 2 The apparent rate constant of hydroquinone during Fenton process

4-CP concentration (mg/L) First order linear equation The apparent rate constant (k, s−1) The correlation R

2.5 y = −0.021*exp(−x/10.2614) + 0.0270 0.0975 0.994

5 y = −0.023*exp(−x/10.0241) + 0.0303 0.0998 0.985
10 y = −0.023*exp(−x/9.9045) + 0.0371 0.1010 0.988
20 y = −0.023*exp(−x/9.6610) + 0.0500 0.1040 0.997
284 Page 8 of 9 Water Air Soil Pollut (2017) 228: 284

Table 3 The apparent rate constant of benzoquinone during Fenton process

4-CP concentration (mg/L) First order linear equation The apparent rate constant (k, s−1) The correlation R

2.5 y = −0.0443*exp(−x/11.5792) + 0.0505 0.086 0.998

5.0 y = −0.0471*exp(−x/12.1449) + 0.0535 0.082 0.997
10 y = −0.0510*exp(−x/13.0900) + 0.0570 0.076 0.997
20 y = −0.0573*exp(−x/14.0260) + 0.0648 0.071 0.998

make a line with all kinds of concentration of 4-CP to 4-CP, which showed negative correlation (Fig. 6b and
obtain the formation rate constants of intermediates. Table 3). And benzoquinone formation rate constant was
9.38 × 108 L s−1 mol−1, which was lower than that
(1) The formation rate constant of hydroquinone reported by Buxton et al. (Buxton et al. 1988) who
thought that hydroquinone was first to generate and then
Under the conditions of pH = 3, Fe2+ = 0.1 mmol/L, oxidized into benzoquinone, and the rate constant was
and H2O2 = 1 mmol/L and different initial dosing of 4-CP (1.00 ± 0.22) × 109 L s−1 mol−1. Jia Hai Ma et al. (Ma
(2.5, 5.0, 10.0, 20.0 mg/L), respectively, the formation et al. 2005) considered that hydroquinone would react
rate constants of different intermediates in 4-CP degrada- with Fe3+ to form phenoxy radical whose rate constant
tion were studied. Figure 6a and Table 2 presented the was 4.4 × 102 L s−1 mol−1, and then benzoquinone was
linear fitting results by measuring the 289.7 nm absor- yielded by the reaction of phenoxy radical and Fe3+ whose
bance changes with time under different initial 4-CP rate constant was 4.4 × 104 L s−1 mol−1. Nevertheless, the
concentration. From the fitting results, it can be seen that rate constant of the benzoquinone which was measured by
the formation of hydroquinone rate constant was increas- us was different from the literature, perhaps because of
ing with the increase of the concentration of 4-CP, which different ratio and amount of Fenton reagent (H2O2/Fe2+).
showed positive correlation with the initial concentration
of 4-CP. Using the initial concentration of 4-CP and (3) The formation rate constant of 4-chlorocatechol
apparent rate constant, the formation rate constant of
hydroquinone was calculated as 2.78 × 106 L s−1 mol−1.
The values were lower than those of Buxton et al. Similar to the study process of benzoquinone and hy-
(Buxton et al. 1988) report (7.98 ± 0.77) × 108 L s−1 mol−1, droquinone, the rate constant of 4chlorocatechol was ana-
perhaps because of different ratio and amount of Fenton lyzed to 6.47 × 106 L s−1 mol−1 in the degradation of 4-CP
reagent (H2O2/Fe2+), which might play a significance role by using the fitting results shown in Fig. 6c and Table 4,
to the production of hydrogen radicals even in the forma- which was the first time to be reported in present studies.
tion of intermediate rate.

(2) The formation rate constant of benzoquinone 4 Conclusions

(1) By stopped-flow technology analyzing, benzoqui-

It can be seen that the benzoquinone formation rate none and hydroquinone were produced at the same
constant decreased with increasing initial concentration of time in the process of Fenton oxidizing 4-CP. The

Table 4 The apparent rate constant of 4-chlorocatechol during Fenton process

4-CP concentration (mg/L) First order linear equation The apparent rate constant (k, s−1) The correlation R

2.5 y = −0.1325*exp(−x/9.0953) + 0.4482 0.099 0.999

5 y = −0.1062*exp(−x/8.4564) + 0.2848 0.118 0.999
10 y = −0.0893*exp(−x/8.3078) + 0.1994 0.120 0.999
20 y = −0.0443*exp(−x/7.8792) + 0.0505 0.127 0.998
Water Air Soil Pollut (2017) 228: 284 Page 9 of 9 284

data obtained by HPLC showed that hydroquinone Du, Y. X., Zhou, M. H., & Lei, L. C. (2007b). Kinetic model of 4-
CP degradation by Fenton/O2 system. Water Research, 41,
generated in great quantities following the decrease
1121–1133.
of benzoquinone. It could be inferred that benzo- Glaze, W., Kang, J., & Chapin, D. (1979). Priority pollutants: a
quinone would react with some intermediates to be prospective view. Environmental Science & Technology, 13,
transformed into hydroquinone. 416–424.
Huang, C., Cheng, J., Wen, X., & Dai, S. (2003). Study on
(2) Benzoquinone may not react with Fe2+ or H2O2
fast reaction kinetics of ozonation by stopped-flow
when they were individually added, and maybe spectrophotometer. Chinese Journal of Scientific
react with peroxide hydroxyl radical (HO2·) to Instrument, 24(4), 59–61.
produce hydroquinone. Therefore, in the system Jantschko, W., Furtmülle r, P. G., Zederbauer, M.,
Neugschwandtner, K., Jakopitsch, C., & Obinger, C.
of Fenton, two catalytic systems would be formed,
(2005). Reaction of ferrous lactoperoxidase with hydro-
which were Fe 2 + /Fe 3 + and hydroquinone/ gen peroxide and dioxygen: an anaerobic stopped-flow
benzoquinone. study. Archives of Biochemistry and Biophysics, 434(1),
(3) The rate constant of hydroquinone, benzoquinone 51–59.
and 4-chlorocatechol were 2.78 × 106 L s−1 mol−1, Khorassania, S. M. H., Ebrahimia, A., Maghsoodlou, M. T.,
Shahraki, M., Price, D., & Paknahad, A. (2015). A novel
9.38 × 108 L s−1 mol−1, and 6.47 × 106 L s−1 mol−1, high performance stopped-flow apparatus equipped with a
respectively. special constructed mixing chamber containing a plunger
under inert condition with a very short dead-time to investi-
gate very rapid reactions. Arabian Journal of Chemistry, 10,
Acknowledgments This study was supported by the Fundamen- 873–884.
tal Research Funds for the Central Universities (2015XKMS053). Lee, B. N., Lou, J. C., & Yen, P. C. (2002). Catalytic wet oxidation
of 2, 4-dichlorophenolic solutions: activity of the manganese-
cerium composite catalyst and biodegradability of the efflu-
ent stream. Water Environment Research, 74(1), 28–32.
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