ARTICLE IN PRESS

Water Research 38 (2004) 27822790

Improvement of oxidative decomposition of aqueous phenol

by microwave irradiation in UV/H2O2 process and
kinetic study
Do-Hung Han*, Sang-Yeob Cha, Hae-Young Yang
School of Chemical Engineering and Technology, Yeungnam University, 214-1 Gyongsan, Gyongbuk 712-749, South Korea
Received 22 August 2003; received in revised form 1 March 2004; accepted 23 March 2004

Abstract
2.5 GHz of microwave irradiation can cause a considerable improvement of oxidative decomposition of aqueous
phenol in a UV/H2O2 system. The experimental results showed that the microwave irradiation can raise both the phenol
conversion and the TOC removal efciency up to or above 50%. Also, the microwave irradiation could considerably
enhance the oxidative degradation of phenol in the UV/H2O2 system even under a suppression of thermal effect.
Addition of hydrogen peroxide by more than a stoichiometric amount was critical to mineralize aqueous phenol to
create a short reaction time. Also, microwave irradiation can accelerate the degradation rate of intermediates,
hydroquinone and catechol, produced in the course of phenol oxidative decomposition.
From the kinetic study, the disappearance rate of phenol can be expressed as dX =dt kPH M0 a  X 1  X ; where
a  H2 O2 0 =M0 kOH OH =kPH M0 ; shows a good correlation with the experimental data. The kinetic analysis
showed that an indirect reaction of phenol with OH radical might be dominant in the absence of microwave irradiation,
meanwhile a direct reaction of phenol with hydrogen peroxide might be dominant in the presence of microwave
irradiation except for low concentrations of hydrogen peroxide.
r 2004 Elsevier Ltd. All rights reserved.
Keywords: Phenol; Decomposition; UV/hydrogen peroxide; Microwave irradiation; TOC; Kinetics

1. Introduction
Advanced oxidation processes (AOPs) are related to
the formation of OH radicals, which will accelerate an
oxidative degradation of numerous organic compounds
dissolved in wastewater. It has been found that AOPs
include several processes such as ultraviolet/ozone (UV/
O3), ultraviolet/hydrogen peroxide (UV/H2O2), and
ozone/hydrogen peroxide (O3/H2O2). Various researches
have discovered that ozone is a powerful oxidant for
*Corresponding author. Tel.: +82-53-810-2518; fax: +8253-810-4631.
E-mail address: dhhan@yumail.ac.kr (D.-H. Han).

removing phenol from wastewater. It also showed that

aqueous phenol and its derivatives can effectively be
removed by ozone, hydrogen peroxide, UV, and their
combination, carrying out studies on the dynamics and
the kinetics of phenol oxidation [18]. OH radicals
generated by these AOPs are capable of accelerating the
oxidative degradations of nearly all organic species,
whereas ozone can be effective for cleavage of chemical
species with unsaturated structures such as multiple
bonds and aromatic bonds [9]. The ultraviolet/ozone
system is a highly reactive process, but because of its
high cost for ozone generation and its clouding and
penetration limitation for ultraviolet rays in solutions, it
has been somewhat restricted in the commercial

0043-1354/$ - see front matter r 2004 Elsevier Ltd. All rights reserved.
doi:10.1016/j.watres.2004.03.025

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D.-H. Han et al. / Water Research 38 (2004) 27822790

applications with a large capacity of wastewater. The

UV/H2O2 process might be more economical than UV/
O3 one since hydrogen peroxide is much cheaper than
ozone. But, under UV irradiation, the molar extinction
coefcient of hydrogen peroxide at 254 nm is only
19.6 M1 s1 [10], when compared with 3300 M1 s1 of
ozone. Therefore, in order to generate as many OH
radicals as possible, a large amount of hydrogen
peroxide must be added into a reacting system [9].
Berglind et al. [11] studied the hydrogen peroxide
process combined with ultraviolet irradiation for the
oxidative degradation of humic substances, methylisoborneol, 3,4-benzopyrene (sic), chloroform, and bromodichloromethane.
Several studies have proved that microwaves can lead
to the improvement on several types of oxidation
processes. Cha et al. [12, 13] showed that microwave
irradiation can accelerate the degradation of phenol in a
UV reacting system, even under a suppression of the
thermal effect. Horikoshi et al. [14] illustrated that
simultaneous UV and microwave radiation in the
presence of TiO2 was superior in the degradation of
the Rhodamine-B dye than the TiO2 photocatalytic
degradation alone with UV radiation; they also examined the formation of OH radicals during TiO2
photocatalyzed oxidations under microwave irradiation
by using ESR analysis [15]. Kataoka et al. [16] employed
microwave irradiation in the heterogeneous photocatalytic oxidation of ethylene on the TiO2/ZrO2 catalyst
with the injection of water. Microwave was able to
disinfect typical pathogenic or facultative pathogenic
microorganisms contained in drinking water, combined
with a UV lamp [17].
Most of the research with regard to microwave
irradiation has utilized the thermal effects of galvanic
heating. One of them was to completely degrade the
phenol adsorbed on the activated carbon using microwave energy [18]. In the other studies, microwaves were
used for metal fractionation in a sewage sludge sample
collected from an urban wastewater processing plant
and from a domestic olive oil factory [19, 20]. Also,
galvanic heating by microwave irradiation can make
organic compounds completely degraded with some
amounts of hydrogen peroxide at a high temperature,
eventually analyzing a minute quantity of metal ions
dissolved precisely in wastewater [21, 22]. Only a
galvanic heating by microwave irradiation is likely
difcult to apply in a large scale of wastewater treatment
since it is unrealistic to raise the temperature of a large
volume of wastewater so high as it need to become
degradable.
This study will examine a microwave effect on the
oxidative degradation of aqueous phenol in the UV/
H2O2 system under the suppression of heat effect and
also theoretically perform a kinetic on the degradation
of phenol.

2783

2. Experimental
2.1. Equipment
An experimental apparatus is depicted in Fig. 1. One
low-pressure mercury lamp of 8 W (G10T8, Toki Ltd.,
Co.) was located at the center of the pyrex tube (45 mm
inner diameter and 300 mm length), irradiating a 300 ml
volume of aqueous phenol. Such UV-lamp location is
capable of absorbing almost all of the ultraviolet-rays
irradiated into the reacting uid. 2.45 GHz of microwaves generated with 1-kW of power was concentrically
focused into a pyrex reactor zone through a wave-guide
with 3 tuners. Changing the electrical powers of the
microwave generator controlled the absorbed energy of
the irradiated microwave in solution. To prohibit the
reacting uid temperature from overheating as a result
of microwave irradiation, the reacting uid in the
reactor was cooled through a cooler with 0.6 l/min of
recycling rate.
Thermocouple in a thin stainless-steel tube was
inserted into the reactor to measure the reacting uid
temperature and was grounded to earth to prevent a
possible electrical discharge from the accumulation of
microwave on the tube. The thermal effect on a
decomposition of phenol was examined without microwave irradiation at several solution temperatures, which
were controlled by using the heating tape rolled around
the reactor and the PID temperature controller. The
stainless steel net grounded to the earth shielded some of
microwaves which leaked from the reactor.
2.2. Materials and analysis
All chemical reagents were of chemical grade.
Hydrogen peroxide concentration was 30%, which had
been stored in a dark place in the refrigerator to prohibit
a possible degradation by light.
Phenol and intermediates were analyzed by HPLC
(LC10A, Simazdzu Co.) and two kinds of columns were
used for analyzing aromatic compounds and organic
compounds, i.e. CLC-ODS(M) column (Shimadzu Co.)
for phenol, hydroquinone, catechol, etc. and POLYSEPGFC-P column (Phenomenex Co.) for maleic acid,
glyoxalic acid, formic acid, etc. A TOC analyzer
(TOC5000-A, Shimadzu Co.) analyzed total organic
carbon (TOC) during the course of phenol decomposition.

3. Results and discussion

3.1. Estimation of microwave power and control of
reacting fluid temperature
Microwave irradiation could abruptly raise the water
temperature under an adiabatic condition. Input current

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D.-H. Han et al. / Water Research 38 (2004) 27822790

2784

Fig. 1. Experimental apparatus for oxidative decomposition of phenol using UV/microwave irradiation system.

of 35 amp was found to linearly raise the water

temperature with different rates. Slopes obtained from
the straight lines can estimate the microwave power
absorbed into the water by a means of the following
equation [23]:
P cm

DT
;
t

conrmed that the measurement of uid temperature by

means of thermocouple was precise even during
microwave irradiation. And also, any hot-spot
phenomena were not found during microwave irradiation, which could arise from a discharge of accumulated
microwave.

Where P is the absorbed power of microwave (W), m

is a mass of water (g), c is the heat capacity of water
(4.184 J/g
C), DT is the temperature rise (
C), and t is
an irradiation time (s). The water irradiated with 3, 4,
and 5 amp of input currents presented 0.258, 0.283, and
0.367
C/s of temperature rises (DT=t) and 323.8, 355.2,
and 460.7 of absorbed powers, respectively. 0.6 l/min of
recycling rate of the irradiated water through the cooler
could control steadily the water temperature by 5072
C
with 5 amp-input current of microwave. By checking the
temperature of reacting uid by thermocouple immediately when stopping to irradiate microwave, it could be

3.2. Effect of microwave on oxidative decomposition of

phenol
Fig. 2 indicates that a microwave irradiation in the
UV/H2O2 system could accelerate the decomposition
rate of phenol at a constant reaction temperature: 90%
decomposition of phenol was reached in about 9 min
without irradiation of microwave but it occurred in
5 min with microwave irradiation. From pseudo rstorder expression for the data of Fig. 2, rate constant
with the presence of microwave irradiation was found to
be 60% higher than that with the absence of the
microwave irradiation.

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D.-H. Han et al. / Water Research 38 (2004) 27822790

0.4

microwave irradiation was likely to give a large effect on

the TOC removal than the disappearance of phenol. It
means that microwave combined with UV/H2O2 can
effectively decompose several kinds of intermediates
produced in the course of phenol decomposition,
eventually mineralizing the intermediates into CO2 and
H2O. Fig. 3 also shows that, even though TOC removal
efciency increased with the reaction temperature without microwave irradiation in the UV/H2O2 process,
TOC removal efciency under the microwave irradiation
at 50
C was much higher than at 70
C under no
microwave irradiation. It has been found that microwave irradiation induces a rotation and a migration
violently for the motion of polar molecules, resulting in
a fast increase of the solution temperature due to
friction. Also, the violent motion of polar substances can
lead the molecules to a higher-excited state through an
increase of collision numbers between reactants, thereby, resulting in accelerating the rate of phenol decomposition in the UV/H2O2 oxidative process even under a
suppression of thermal effect.

0.2

3.3. Effect of H2O2 concentration on phenol

decomposition

Fig. 3 illustrates that the microwave irradiation could

also give a signicant effect on decreases of the total
organic compound. Wherein, at the initial concentrations of 200 ppm phenol and 1200 ppm hydrogen
peroxide, the removal efciency at 50
C reached nearly
95% with microwave irradiation, for a 30 min reaction.
Whereas, it reached only 40% without microwave
irradiation. When comparing Fig. 3 with Fig. 2, the

1.0

0.8

[phenol]/[phenol]o

2785

UV+MW
UV+Heating

0.6

0.0
0

10

15
20
Time, min

25

30

Fig. 2. Effect of microwave on phenol decomposition under

UV/H2O2 system (initial concentrations of phenol and H2O2 :
200 and 600 ppm; reaction temp. : 50oC).

Phenol decomposition rate was strongly dependent on

initial concentration of hydrogen peroxide as shown in
Fig. 4. TOC removal efciency for 600 ppm hydrogen
peroxide was leveled off by 60% near 70 min, but
1200 ppm of hydrogen peroxide could greatly accelerate
the TOC removal rate, leading TOC removal efciency
to 100% within 40 min.

1.0

1.0

H2O2 conc.
600ppm
1050 ppm
1200 ppm
1800 ppm
2400 ppm

0.8

[TOC]/[TOC]o

[TOC] / [TOC]o

0.8

0.6

0.4
UV + heating(50C)
UV + heating(60C)
UV + heating(70C)
UV + MW(50C)

0.2

0.6

0.4

0.2

0.0

0.0
0

10

20

30

40

Time [min]
Fig. 3. Comparison of thermal effect at several temperatures
with microwave effect for TOC changes in phenol decomposition under UV/H2O2 system (initial concentration of phenol
and H2O2 : 200 and 1200 ppm, respectively).

20

40

60

80

100

120

Time [min]
Fig. 4. Effect of [H2O2] on TOC decomposition from phenol
oxidative degradation under UV/H2O2 system combined with
microwave irradiation (initial phenol concentration: 200 ppm ;
reaction temp. : 50
C).

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D.-H. Han et al. / Water Research 38 (2004) 27822790

3.4. Intermediates formed from oxidative decomposition

of phenol
UV/H2O2 system combined with a microwave irradiation (1200 ppm H2O2, 200 ppm phenol) formed a large
amount of aromatic compounds, such as hydroquinone
and catechol, in the early reaction steps, which almost
disappeared within 20 min (Fig. 5a). Whereas, the
complete removal of TOC required a reaction time of
more than 30 min since a simultaneous formation and
decomposition of low molecular organic acids should be
involved during the period.
In the UV/H2O2 system without microwave irradiation (1200 ppm H2O2, 200 ppm phenol), the TOC
removal efciency was a very low value of 40% at
30 minutes, even though the aromatic compounds
almost disappeared after 30 min (Fig. 5c). The UV/
H2O2 system combined with microwave irradiation with
600 ppm H2O2 and 200 ppm phenol (Fig. 5b) presented
nearly the same trend as in Fig. 5c.
From Fig. 5, hydroquinone intermediate was produced much more than catechol and the maximum
concentration existed later than catechol. According to
another study [6], it was known that a parallel pathway
in a course of phenol oxidation formed catechol and
hydroquinone. But, from this experimental result, it
looks as if phenol rst oxidized into catechol which was
then followed by the formation of hydroquinone as a
series reaction [24]. It is possible that the OH group of
ortho-position in catechol is transferred into paraposition in hydroquinone.
A chromatograph of HPLC for the oxidative decomposition of phenol under the UV/H2O2 system combined
with microwave irradiation (200 ppm phenol and
600 ppm H2O2) could conrm the formation of several
organic acids such as maleic acid, glyoxalic acid, and
formic acid at a 40 min reaction. The decomposition rate
of these organic acids, which were produced at nearly

[TOC] / [TOC]o
phenol
hydroquinone
catechol

200

1.0

100

0.5

0
200

0.0
1.0

(b)

100

0.5

0
200

0.0
1.0

Y Axis 2

(a)

[TOC] / [TOC]o

Decrease of TOC with H2O2 is related to mineralizing

phenol into CO2 and H2O: C6H6O + 14H2O2 - 6CO2
+ 17H2O. Wherein, a theoretical requirement of
H2O2 for the complete mineralization of phenol can
be calculated by H2 O2  14 34:02=94:11 C6 H6 O:
Therefore, 200 ppm of phenol requires 1012 ppm of
H2O2 theoretically for the complete removal of TOC. As
shown in Fig. 4, 1050 ppm of H2O2 could perfectly
remove TOC value within a nite time. This gure
also illustrates that the TOC removal rate no more
increased above 1800 ppm of H2O2 even though it
increased considerably with H2O2 concentrations between 1050 and 1800 ppm. From Figs. 3 and 4, a perfect
decomposition of phenol within nite time could be
accomplished at least by the addition of H2O2, more
than a stoichiometric amount, regardless of microwave
irradiation.

Concentration [ppm]

2786

(c)

100

0.5

0.0
0

10

15

20

25

30

35

Time [min]
Fig. 5. Intermediates produced in a course of phenol decomposition under UV/H2O2 process combined with microwave
irradiation (a,b) and without microwave irradiation (c) (initial
concentration of phenol: 200 ppm ; initial concentrations of
H2O2 : 1200 ppm (a,c), 600ppm (b) ; reaction temp.: 50
C ).

the nal reaction steps, seemed to play a signicant role

in the removal efciency of TOC, since the TOC had
high value even after the aromatic compounds disappeared completely as already shown in Fig. 5. Therefore,
microwave irradiation is likely to be considerably
effective in the decomposition of low molecular organic
acids.

4. Kinetic study
4.1. Formation of OH radicals in UV/H2O2 system
It is known that one of the direct methods for the
generation of OH radicals is accomplished by a cleavage
of hydrogen peroxide. Photolysis of hydrogen peroxide
directly yields hydroxyl radicals with a quantum yield of
two OH radicals per quantum of absorbed radiation, as
shown in reaction 1 of Table 1. Wherein, the molar
extinction coefcient of hydrogen peroxide at 254 nm is
only 19.6 M1 s1, which is very low for a primary
absorber in a photochemical process, compared to

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D.-H. Han et al. / Water Research 38 (2004) 27822790

2787

Table 1
Elementary reactions and rate constant values related to formation of OH radicals from radiolysis of H2O2 by UV irradiation

hn

H2 O2 ! 2OH
H2 O2 2HO2  H
OH H2 O2 -H2 O HO2
HO2 2O2  H
2OH -H2 O2
2HO2 -H2 O2 O2
H2 O HO2 O2  -H2 O2 O2 OH

Rate constant
1 1

k1 19:6 M s
pK2 11:8
k3 2:7  107 M1 s1
pK4 4:8
k5 4:0  109
k6 8:3  105
k7 9:7  107

ozone with 3300 M1 s1. In a UV/H2O2 system, the

formation of OH radicals through photolysis of hydrogen peroxide can be related to several elementary
reactions as listed in Table 1.
Decomposition rate of phenol can be expressed as two
pathways including a direct reaction with hydrogen
peroxide and an indirect reaction with OH radical:
dM
kPH H2 O2 M kOH OH M;

dt

where [M], [H2O2] and OH  are molar concentrations

of phenol, H2O2, OH radical, respectively, t is time in
minutes, and k is rate constant in [M1 min1]. Net rate
of formation of OH radicals can be derived by reactions
1, 3 and 5 in Table 1, where the reaction between
phenol and hydroxyl radical (kOH OH M) was neglected compared with other radical reactions, because
phenol disappearance required several periods of 10 min
as shown in Figs. 2 and 5 (in the later part of this paper,
each rate in Eq. (3) will be compared with kOH OH M
in Fig. 9).
dOH 
2k1 H2 O2   k3 OH H2 O2   2k5 OH 2 : 3
dt
With the steady-state approximation for Eq. (3), the
positive root of a quadratic equation for the steady state
of OH  was selected
q
k3 H2 O2  k32 H2 O2 2 16k1 k5 H2 O2 
OH 
: 4
4k5

Step

Reference

1
2
3
4
5
6
7

[10]
[25]
[26]
[27]
[28]
[29]
[29]

1e-5

[OH], mol/liter

Elementary reaction

1e-6

1e-7
1

10

100

1000

[H2O2], ppm
Fig. 6. [OH.] values calculated by Eq. (4) for several hydrogen
peroxide concentrations.

of H2O2, the concentrations of phenol and hydrogen

peroxide can be related to the phenol conversion (X) as
follows:
For Phenol; M M0 1  X

For hydrogen peroxide; H2 O2  M0 a  X

OH radical concentrations, [OH.], were plotted in

Fig. 6 after calculating them with several values of
[H2 O2 ] ranging from 1 to 3000 ppm from the Eq. (4). In
the gure, [OH.] was almost invariant at around
1:4  106 mol/l in the ranges from 200 to 3000 ppm of
hydrogen peroxide. The [OH.] values decrease slightly
with the decrease of [H2 O2 ] at below 200 ppm of [H2O2],
reaching 3:3323  107 mol/l at 1 ppm of [H2O2]. Therefore, it could be approximated that [OH.] is nearly
constant in the moderate ranges of [H2O2], putting

where a H2 O2 0 =M0 : Inserting Eqs. (5), (6) and (7)

into Eq. (2) can be expressed as follows:

0
kOH OH :
kOH

ln

Assuming that 1 mol of phenol disappearance, which

is transferred into quinone and catechol, requires 1 mol

dX
kPH M0 a  X 1  X ;
dt

0
=kPH M0 a b and
where a  a kOH
0
=kPH M0 :
b  kOH

With the integration of Eq. (8) the following equation is

obtained:
aX
kobs t;
a1  X

where kobs  kPH M0 a  1:

10
11

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D.-H. Han et al. / Water Research 38 (2004) 27822790

To test the rate form obtained above, four experimental

data ([M]0=2.1277  103 mol/l (200 ppm), [H2O2]0=
17.6471  103 mol/l (600 ppm), 35.2942  103 mol/l
(1200 ppm) without or with microwave) were used as
shown in Table 2. First, to simplify the test procedure, it
was assumed that an indirect reaction with OH radical
in phenol disappearance was neglected, i.e. aDa
H2 O2 0 =M0 : From slopes of the straight lines with a
good linear correlation, the observed rate constants,
kobs ; were 0.2792 (kobs;1 ) and 0.3131 (kobs;2 ) for 600 and
1200 ppm of [H2O2]0 for exp. 1 and exp. 2, respectively.
From Eq. (11), the ratio of kobs;2 to kobs;1 (kobs;2 =kobs;1 )
should be equal to a2  1=a1  1 2:1371: But, since
the ratio of the observed rate constant obtained from
experimental data is 1.1214, it might be unreasonable to
neglect an indirect reaction with OH radical for the
phenol disappearance in Eq. (2). So, this work suggests a
procedure to determine the correct value of b and
eventually to estimate the rate constants kPH and kOH.
Wherein, the intersection of two curves, kobs;2 =kobs;1 (or
kobs;4 =kobs;3 ) versus b and a2  1=a1  1 (or a4  1=
a3  1) versus b, could determine a correct value of b
using two couples of experimental data (exps. 1 and 2;
exps. 3 and 4). Its procedure with a graphical method is
shown in Fig. 7, where each line was intersected together
at b= 60.8351 in the absence of microwave irradiation
and at b=0.4358 in the presence of microwave irradiation. The resultant values for kobs, kPH and kOH are
listed in Table 2. The compatibilities for kPH and kOH
values are excellent at each two couples of experimental
data, respectively. Plot of ln[a(1X)/(aX)] versus t
using b values determined in Fig. 7 showed a good
linearity for the experimental data from 1 to 4.
From the values calculated in Table 2, in the course of
phenol degradation, the roles on an indirect reaction
with OH radical and a direct reaction with hydrogen
peroxide could be summarized as shown in Fig. 8. On a
basis of phenol conversion (X) in range from X=0 to 1,
the indirect reaction is dominant in the absence of
microwave irradiation, meanwhile in the presence of
microwave irradiation the direct reaction is dominant

(Fig. 8a). In a view of TOC degradation, each role of

the indirect reaction and the direct one was same
as in Fig. 8a except for near the end of reaction,
wherein the indirect reaction with microwave irradiation
might compete with the direct reaction near the
end of reaction (Fig. 8b). These results can be related
to hydrogen peroxide concentration existing during
reaction as shown in Fig. 8c, wherein, under microwave
irradiation, the direct reactions become much smaller
than the indirect reaction at low concentrations of
hydrogen peroxide under the microwave irradiation. In
Fig. 8(b), given values of the removal efciency based
on TOC, 1  TOC=TOC0 ; can be related to [H2O2]
with the equation: H2 O2  H2 O2 0  14M0 1
TOC=TOC0 :
As shown in Fig. 9, reaction between the hydroxyl
radical and the phenol (kOH OH M) is very slow

2.4
kobs,2 /kobs,1 , kobs,4 / kobs,3 , (15.588+)/(7.294+)

2788

= 0.4358

2.0
(15.588+)/(7.294+)
kobs,2 / kobs,1
kobs,4 / kobs,3

1.6

= 60.8351

1.2

0.8

20

40

60

80

Fig. 7. Graphical determination of b value with experimental

data 14.

Table 2
b, kobs, kPH and kOH values calculated by means of graphical method in Fig. 7 with experimental data 14
Parameters

Experimental
Without microwave

[M]0 (ppm)
[H2O2]0 (ppm)
b
kobs (min1)
kPH (M1 min1)
kOH (M1 min1)

With microwave

Data 1 (Fig. 2)

Data 2 (Fig. 5c)

Data 3 (Fig. 5b)

Data 4 (Fig. 5a)

200
600

200
1200

200
600

200
1200

0.3131
1.9256
1.7803  105

0.2807
17.0674
1.1303  104

60.8351
0.2792
1.9261
1.7808  105

0.4358
0.5818
17.0648
1.1302  104

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D.-H. Han et al. / Water Research 38 (2004) 27822790
1e+1

exp(1) : without MW
exp(2) : without MW
exp(3) : with MW
exp(4) : with MW

1e+0
1e-1

101

Rates [M/sec]

kPH[H2O2] / kOH[OH]

102

100
10-1
10-2
0.2

(a)

0.4

0.6

0.8

1e-3

2k1[H2O2]
.

k3[OH ][H2O2]

1e-4

2k5[OH.]2
.

kOH[OH ][M]

1.0

X = 1-[M]/[M]o

1e-6

102

kPH[H2O2] / kOH[OH]

1e-2

1e-5
0.0

1e-7
0.0

101

0.2

0.4

0.6

0.8

1.0

Conversion (X)
Fig. 9. Comparison of kOH OH Mwith rates in Eq. (3) by
using exp. data 2.

100
10-1
10-2
0.0

0.2

0.4

0.6

0.8

1.0

1-[TOC]/[TOC]o

(b)
102

kPH[H2O2] / kOH[OH]

2789

101
100
10-1
10-2
10-3
10-4
0

(c)

200

400

600

800

1000

1200

hydrogen peroxide, above a stoichiometric amount, was

critical to mineralize aqueous phenol to create a short
reaction time.
The kinetic analysis showed that an indirect reaction
of phenol with OH radical might be dominant in the
absence of microwave irradiation, meanwhile a direct
reaction of phenol with hydrogen peroxide might be
dominant in the presence of microwave irradiation
except for low concentrations of hydrogen peroxide.
Rate expression for the oxidative degradation of
aqueous phenol was different in the other studies, not
showing an explicit form with rst or second order.
Derived rate form could become well correlative with
experimental data.

[H2O2], ppm

Fig. 8. (ac) Comparison of direct reaction kPH H2 O2 M

with indirect reaction kOH OHM:

compared to rates in Eq. (3), it was reasonable that the

kOH OH M was omitted in Eq. (3).

5. Conclusion
Microwave irradiation could considerably enhance
the oxidative degradation of phenol in the UV/H2O2
system even under a suppression of thermal effect.
Microwave irradiation was particularly effective on
TOC removal as well as on the oxidation of phenol.
Also, the microwave might be powerful enough to
degrade several organic compounds such as glyoxalic
acid, formic acid, etc., eventually leading to mineralization of the compounds into H2O and CO2. Addition of

References
[1] Niegowskii SJ. Destruction of phenols by oxidation with
ozone. Ind Eng Chem 1953;45:6324.
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