Chemosphere 52 (2003) 10691077

www.elsevier.com/locate/chemosphere

Mechanism and kinetic model for the decolorization

of the azo dye Reactive Black 5 by hydrogen peroxide
and UV radiation
A. Mohey El-Dein

*,1,

J.A. Libra, U. Wiesmann

Institut f
ur Verfahrenstechnik, Technische Universitat Berlin, Strae des 17. Juni 135, 10623 Berlin, Germany
Received 14 March 2002; received in revised form 13 February 2003; accepted 13 February 2003

Abstract
A kinetic model for the decolorization of C.I. Reactive Black 5 by the combination of hydrogen peroxide and UV
radiation was developed based on experimental results and known chemical and photochemical reactions. The observed
kinetic reaction coecient was determined and correlated as a function of hydrogen peroxide concentration and UV
intensity. The validity of the rate expression was tested experimentally in a parameterization study. The decolorization
rate follows pseudo-rst order kinetics with respect to dye concentration. The rate increases linearly with UV intensity
and nonlinearly with increasing hydrogen peroxide concentration, going from a linear relationship at low H2 O2 concentrations to a maximum as hydrogen peroxide concentration continues to increase. The decolorization rate expression derived from the proposed reaction mechanism was reconciled with that used for correlating the experimental
data.
2003 Elsevier Science Ltd. All rights reserved.
Keywords: Reactive azo dye; Advanced oxidation process; H2 O2 ; UV intensity; Kinetic model

1. Introduction
Azo dyes represent the largest class of textile dyes in
industrial use. Current environmental concern with
these dyes revolves around the carcinogenic potential of
these dyes and their intermediates. In many developing
countries textile wastewater contaminated with these
dyes is directly discharged without treatment to rivers,
lakes or the ocean. Ecient and economical methods for
color removal and total dissolved organic carbon (DOC)

Corresponding author. Tel.: +44(0)115-9513053; fax:

+44(0)115-9514115.
E-mail addresses: abdallah.moheyeldein@nottingham.ac.
uk, deinoeec@mailbox.tu-berlin.de (A. Mohey El-Dein).
1
Present address: The School of Chemical, Environmental
and Mining Engineering, The University of Nottingham,
University Park, Nottingham, NG7 2RD, UK.

reduction in textile wastewater before its discharge is

needed. Common treatment processes, e.g. adsorption
and occulation, are not ecient methods because they
result in solid wastes, thus creating other environmental
problems requiring further treatment.
Advanced oxidation processes (AOPs) provide a
promising treatment option for textile wastewater. The
UV-driven AOPs use UV light with an oxidizer such as
H2 O2 and/or ozone to generate hydroxyl radicals (OH )
that attack organic compounds nonselectively with a
high reaction rate. Studies of the decolorization of textile
dyes using H2 O2 /UV have shown it to decolorize dilute
aqueous solutions (20 mg l
1 ) of azo dyes (Shu et al.,
1994; Galindo and Kalt, 1998).
The photolysis of H2 O2 by UV radiation generates
two hydroxyl radicals (Baxendale and Wilson, 1957).
Experimental studies of the oxidation of organic compounds have demonstrated that the OH concentration
is the important parameter to quantify kinetics of the

0045-6535/03/$ - see front matter 2003 Elsevier Science Ltd. All rights reserved.
doi:10.1016/S0045-6535(03)00226-1

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A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

Nomenclature
Cd
Cd0
Cd-OH
CH2 O2
COH
Cs
Cs0
I
Imax
I0
k
k0
ki
ki1

concentration of RB5, mg l
1

initial concentration of RB5 at t 0, mg l
1
concentration of metabolites, mg l
1
concentration of H2 O2 , mM
concentration of hydroxyl radical, mM
DOC concentration of RB5, mg l
1 DOC
initial DOC concentration at t 0, mg l
1
DOC
applied UV radiation intensity, einst l
1
min
1
maximum UV radiation intensity, einst l
1
min
1
dimensionless UV radiation intensity (I0
I=Imax ),
rate coecient (k kd k1 =k4 ), min
1
rate coecient (k k7 =k4 ),
rate coecient for radiation intensities (Eq.
(17)), l einst
1
rate coecient of H2 O2 inhibition in the
presence of UV radiation, l min einst
1

AOPs. Many models have been postulated over the

years to describe the kinetics of these reactions using
the steady-state approximation, in which the concentration of hydroxyl radicals does not change with the
reaction time (Gottschalk et al., 2000). Progress has
been made with nonsteady state modeling of the OH
concentration in drinking water (Crittenden et al., 1999).
However, for wastewater with its many contaminants
and reactions, most proposed models rely on the steady-

ki2
k1 k8
kobs
QIC
QR
t
TIC
DOC
VE
VT
VUV
u
eH2 O2
eRB5
k

rate coecient of H2 O2 inhibition in the

absence of UV radiation,
rate coecient for single reaction mechanism step, M
1 S
1
observed rate coecient (kobs kd COH ),
min
1
pH integral quality controller
recycle ow rate, l h
1
time, min
temperature integral controller
dissolved organic carbon, mg l
1
volume of external stirred vessel, l
total volume of reactor, l
volume of photoreactor, l
quantum yield, mol photon
1
molar absorption coecient of H2 O2 ,
M
1 cm
1
molar absorption coecient of RB5,
M
1 cm
1
wavelength, nm

state approximation to eliminate the nonmeasurable

radicals concentration, correlating it as a function of
hydrogen peroxide concentration (CH2 O2 ).
An overview of the various types of kinetic models
that have been developed to describe the oxidation of
organic compounds or decolorization of certain azo dyes
is given in Table 1. The rst type of kinetic model is a
rate expression derived from an empirically determined
correlation. For example, the power law model was

Table 1
Review of some kinetic rate expressions for oxidation of organic compounds with H2 O2 /UV
Type

Organic compound

UV source

Oxidation rate

Source

Benzene, toluene, phenol,

and dimethylphthalate

Low-pressure-Hg lamp

Sundstrom et al. (1989)

Isoprene

Low-pressure-Hg lamp

Reactive Black 5

Medium-pressure-Hg
lamp

dCs
kUV Csm kh CHn 2 O2 Cso


dt
dCs
kUV Csm I n kh cos CHp 2 O2 I q


dt
dCd
ka ICH2 O2

Cd
dt
kb CH2 O2

Protocatechuic acid

Low-pressure-Hg lamp

dCs 2ufH2 O2 kh I

Cs
VT kb CH2 O2
dt

Benitez et al. (1996)

Azo-acid dyes

Medium-pressure-Hg
lamp

dCd 2ufH2 O2 kh I

Cd
kb Cd0
dt

Colonna et al. (1999)

fH2 O2
m, n, o, p, q reaction order.
ka and kb constants used for the empirical correlation.
kh reaction coecient with H2 O2 /UV, min
1 .
kUV reaction rate coecient with UV alone, min
1 .

eH2 O2 CH2 O2
eH2 O2 CH2 O2 ed Cd

Elkanzi and Kheng (2000)

Mohey El-Dein et al. (2001)

A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

found to correlate experimental data for the oxidation of

several aromatic compounds such as benzene, toluene
and chlorophenols (Sundstrom et al., 1989). Yue and
Legrini (1992) tested it for correlating the reduction of
the total organic carbon (TOC) during oxidation of
phenols with H2 O2 /UV, and concluded that this model
gives a good prediction of oxidation data but the value
of the power of organic substrate concentration varies
with varying initial concentration of H2 O2 . Another
drawback is that this model ignores the eect of the UV
intensity on the oxidation rate. Elkanzi and Kheng
(2000) extended the use of the power law model by
adding the eect of UV intensity to the power law expression. They found a good t between their model and
experimental data from the oxidation of isoprene. Mohey El-Dein et al. (2001) used an empirical correlation to
correlate decolorization experimental data successfully,
which describes the eect of both CH2 O2 and UV intensity on the decolorization rate.
A second type of kinetic model based on known reaction mechanisms has been proposed (Benitez et al.,
1996; Colonna et al., 1999). These models used photochemical literature values for photolyzing H2 O2 as well
as applying the steady-state approximation. Colonna
et al. (1999) developed their model from a postulated
mechanism for the decolorization of azo dyes. The
proposed mechanism does not include the scavenging of
OH by H2 O2 , although they reported that the decolorization rate increased with increasing H2 O2 concentration to a maximum value and then declined with further
increases in H2 O2 .
Most of these kinetic models were developed for low
concentrations of the organic target compounds and a
low-pressure-Hg lamp was used as UV source. Therefore, they are based on the relevant photochemical data
for the photolysis of H2 O2 , i.e. the molar absorption
coecient of H2 O2 eH2 O2 and quantum yield u at 254
nm. However, since eH2 O2 and u both increase with de-

1071

creasing wavelength in the UV region (Loriane and

Glaze, 1999), these literature values cannot be used with
medium-pressure lamps that also emit below 254 nm.
The aim of this work is to develop a kinetic model for
the decolorization of C.I. Reactive Black 5 (RB5) using
H2 O2 /UV with a medium Hg UV lamp. An empirical
correlation was suggested to describe the experimental
relationship between observed rate coecient (kobs ) and
H2 O2 concentration. A decolorization reaction mechanism based on known chemical and photochemical reactions is suggested and reconciled with the empirical
correlation. This expression is directly a function of two
eective measurable parameters H2 O2 concentration
and UV intensity. The validity of the rate expression was
tested experimentally in a parameterization study.

2. Experimental set-up
Experiments were carried out in a batch reactor
system (Fig. 1), which consists of two parts, an external
stirred vessel (VE 2:1 l) with a variable speed stirrer
and a cylindrical photoreactor (VUV 0:95 l). The total
volume of the reactor system (VT ) was 3.8 l, including the
tubing. A coaxial medium-pressure-Hg lamp (TQ 150,
150 W input energy, with higher emission 18% between
200 and 280 nm, Heraeus Noblelight Company, Kleinostheim, Germany) was inserted in a quartz tube with a
UV transmission level of 92%. The quartz tube enclosing
the lamp was immersed in a cooling jacket to dissipate
the radiant heat produced and to protect the lamp from
overheating. The applied UV intensity I was varied in
some experiments. It was measured using the hydrogen
peroxide actinometry method according to Nicole et al.
(1990) and reported in dimensionless as a fraction of the
maximum radiation intensity (Imax ) i.e. I0 I=Imax . Imax
was measured at 4.5  10
3 einst l
1 min
1 . Initial
experiments with the circulation ow rate QR varied

Fig. 1. Reactor set-up.

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A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

between 50 and 580 l h
1 showed that the decolorization

rate is not aected by mass transfer. A high ow rate
was chosen for all experiments (QR 580 l h
1 ) to insure
a well-mixed system. The temperature was kept constant
at 25  0.5 C using a thermostat, and pH was regulated
at the desired value by dosing 0.5 M NaOH using a
membrane pump. At the start of each experiment, the
lamp was warmed up for 30 min before adding H2 O2 to
achieve a constant UV radiation intensity and to eliminate variations in temperature. One experiment of each
series was repeated several times to conrm reproducibility of the results.

3. Reagent and analytical methods

The diazo reactive dye RB5 was obtained from DyStar, Germany as a commercial product, a powder
containing 52% (wt.) dye, and used without purication. Fig. 2 shows the chemical structure of the RB5
molecule. RB5 was hydrolyzed in an aqueous solution of
0.1 M NaOH at the boiling point for 20 min before use
(Karcher et al., 1999) to produce the main form of the
dye found after the dyeing process. Samples were taken
periodically during the runs, ltered (0.2 lm, cellulose
acetate; Sartorius, G
ottingen, Germany) and diluted if
necessary. The dye concentration (Cd ) was measured
with a spectrophotometer (UV-1202, Shimadzu, Kyoto,
Japan) at the wavelength k 583 nm. DOC was measured using a DIMA-TOC100 (Dimatec, Essen, Germany). 30% analytical grade hydrogen peroxide (Merck,
Germany) was used. Residual H2 O2 concentration was
determined using the photometric method based on
cobalt(II) reagent, hexametaphosphate and saturated
solution of sodium bicarbonate, and absorption was
measured at 260 nm (Masschelein et al., 1977).

4. Results and discussion

The decolorization kinetics of the diazo dye RB5 in
aqueous solution with UV/H2 O2 was investigated with
the goal of determining a rate expression. The rate of
decolorization was measured in a parameterization
study, considering the dye concentration, the initial dye
concentration (Cd0 ), the H2 O2 concentration, and the
UV intensity:

Fig. 2. Structure of C.I. Reactive Black 5 in hydrolyzed form.

Fig. 3. First order representation of the decolorization of RB5

versus time, CH2 O2 140 mM; I0 I=Imax 1; Imax 4:5  10
3
einst l
1 min
1 ; pH 7; T 25 C.

dCd
f Cd ; Cd0 ; CH2 O2 ; I0
dt

Initial results demonstrated that neither H2 O2 nor

UV alone was able to appreciably decolorize RB5. The
combination of H2 O2 /UV is necessary for the production of OH radicals to initiate the decolorization reaction of RB5. Fig. 3 shows that the decrease in the dye
concentration over time as a function of the initial dye
concentration for constant initial CH2 O2 140 mM and
I0 . The straight lines in the semi-log plot indicate that the
decolorization rate is pseudo-rst order with respect to
Cd . The dierence in the resultant kobs shows that the
reaction conditions were not comparable in the four
runs due to the change in Cd0 . kobs decreased as Cd0 increased, although the initial H2 O2 concentration was the
same. This can be explained by considering that both
the aromatic dye and H2 O2 absorb UV radiation in the
range emitted from the lamp (200280 nm). However,
the molar absorption coecient eRB5 at 254 nm is approximately 11 times greater than that of hydrogen
peroxide, 224 versus 19 M
1 cm
1 . The increased absorption of UV radiation by the higher dye concentrations, decreased the absorption by H2 O2 and thus
decreased the production of OH radicals.
The use of the molar ratio of the two concentrations
RCH2 O2 0 =Cd0 was inadequate to correlate the changes
due to the change in the initial dye concentration. In Fig.
3, R decreased from 2295 to 194 mM H2 O2 /mM RB5 for
the increase in Cd0 from 87 to 1040 mg l
1 RB5. However, the addition of more H2 O2 to achieve the same
ratio R at Cd0 2100 mg l
1 showed that the higher
H2 O2 concentration could not compensate for the UV
absorption by the dye (not shown). Therefore, a constant initial concentration of RB5 was used in all the
following experiments in order to determine the eect of
the other parameters on the decolorization rate. Closer
inspection of Fig. 3 reveals that the decolorization rate

A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

1073

follows pseudo-rst order kinetics with respect to dye

concentration up to a conversion of 90% in all experiments. After 90% of the color removal, the data points
deviate from linearity. This deviation may be caused by
competition between the dye metabolites and RB5 for
OH .
Summarizing the above results, the decolorization
rate equation can be written as follows:

dCd
kobs Cd
dt

with
kobs kd COH

The decolorization rate of RB5 increased with increasing H2 O2 concentration, as CH2 O2 varied from 0 up
to 615 mM (R 01760 mM H2 O2 /mM RB5) (Fig. 4a).
The relative dye concentration Cd =Cd0 decreased more
rapidly over radiation time as the H2 O2 concentration
was increased, up to CH2 O2 140 mM. Further increases
in CH2 O2 resulted in only slight acceleration in the decolorization rate. Although the increase in CH2 O2 increases the formation of OH , the decolorization rate
becomes increasingly independent of CH2 O2 . The increased photolysis of H2 O2 at higher concentrations may
be counterbalanced by OH scavenging by H2 O2 as seen
in the reaction scheme (Table 2).
The amount of UV radiation absorbed by H2 O2
plays an important role in the formation of plentiful
OH in the solution. The well-known disadvantage of the
H2 O2 /UV process is the poor absorption of H2 O2 in the
UV region. A medium-pressure lamp which emits maximum UV radiation between 200 and 280 nm rather than
only at 254 nm can exploit the higher eH2 O2 at the lower
wavelengths, e.g. eH2 O2 decreases from 99 M
1 cm
1 at
222 nm to 19 M
1 cm
1 at 254 nm (Loriane and Glaze,

Fig. 4. Relative concentration Cd =Cd0 of RB5 versus time as

a function of: (a) H2 O2 concentration CH2 O2 , I0 I=Imax 1;
Imax 4:5  10
3 einst l
1 min
1 . (b) UV intensity I0 , CH2 O2
140 mM; Cd0 500 mg l
1 ( 0.35 mM) pH 7; T 25 C.

1999). The decolorization of RB5 for several UV intensities I0 at constant CH2 O2 (CH2 O2 140 mM) is presented in Fig. 4b. The decolorization rate increases with
increasing UV intensity, as the amount of UV radiation
absorbed by H2 O2 is increased. The photolysis of H2 O2
is enhanced (Reaction 1, Table 2) producing abundant
OH in the dye solution which can be used for decolorization.

Table 2
Reaction scheme of the proposed mechanism for decolorization of RB5 with H2 O2 /UV
Reaction steps

Source

Initiation
k1 hv
1. H2 O2
! 2OH

Baxendale and Wilson (1957)

Hydroxyl radical propagation and termination

k2 2:7107 M
1 S
1

2. H2 O2 + OH ! HO2 + H2 O
3.
4.
5.
6.

k3 3:0 M
1 S
1

H2 O2 + HO2 ! OH + O2 + H2 O
k4 2:7107 M
1 S
1

H2 O2 + OH ! O

2 + H + H2 O

1
1

k5 0:13 M S



H2 O2 + O2 ! OH + OH + O2
pka 14
OH
+ H ! H2 O
 k7 ?

7. Dye + OH
! dye-OH
k8 ?

8. Dye-OH + OH
! dye-(OH)2

Overall reaction
hv
5H2 O2 + dye ! dye-(OH)2 + 4H2 O + 2O2

Buxton et al. (1988)

Koppenol et al. (1978)
Buxton et al. (1988)
Weinstein and Bielski (1979)

1074

A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

dCOH
k1 CH2 O2
k2 CH2 O2 COH k3 CHO2 CH2 O2
dt

k4 CH2 O2 COH k5 CH2 O2 CO


k7 Cd COH
2

k8 Cd-OH COH

dCHO2
k2 CH2 O2 COH
k3 CHO2 CH2 O2
dt

For steady-state approximation, it follows that:

dCOH
0
dt
Fig. 5. Changes in H2 O2 concentration and DOC concentration during the decolorization of RB5, I0 I=Imax 1; Imax
4:5  10
3 einst l
1 min
1 ; Cd0 500 mg l
1 ( 0.35 mM);
CH2 O2 140 mM; Cs0 124 mg l
1 DOC; pH 7; T 25 C.

Measurements of H2 O2 concentration showed that it

was only slightly consumed throughout the decolorization process, as shown in Fig. 5 (upper curve). The
catalytic eect of hydrogen peroxide can be explained by
the chain reaction mechanism proposed by Baxendale
and Wilson (1957). This catalytic behavior of H2 O2 has
been observed by other authors (Benitez et al., 1996;
Elkanzi and Kheng, 2000). After 90% decolorization the
depletion in H2 O2 concentration accelerated rapidly as
shown in Fig. 5, which shows the variation in DOC
concentration (middle curve) as decolorization proceeds.
It was found that 90% decolorization of RB5 corresponded to a 30% removal in DOC. After 90% of the
color was removed, the rate of DOC removal increased
signicantly, accompanied by a rapid decrease in the
H2 O2 concentration. This coupled disappearance of
DOC and H2 O2 is due to the hydrogen abstraction
mechanism, which dominates during the further oxidation of the metabolites by OH , causing the production
of CO2 . The increased consumption of OH results in
increasing the decomposition of H2 O2 .

and
dCHO2
0
dt

From Eqs. (4)(7) the concentration of COH can be

calculated
COH

k1 k5 CO

CH2 O2
2
k7 Cd k8 Cd-OH k4 CH2 O2

from the rst step of decolorization, we can write

Cd Cd0
Cd-OH

and considering the following assumptions:

k7 k8

10

and
k5 CO

1
2

11

the concentration of OH can be written as follows:

COH

k1 CH2 O2
k7 Cdo k4 CH2 O2

12

Eq. (12) is substituted into Eq. (3) and the following is

introduced, and the observed reaction coecient can be
written as follows:

5. Derivation of kinetic model for decolorization by H2 O2

and UV radiation

kobs

The kinetic model for decolorization of RB5 was

derived using the reaction mechanism in Table 2. In this
model two main steps are proposed to be responsible for
decolorization: the formation of OH by the photolysis of
hydrogen peroxide as well as the reaction between H2 O2
and OH . Reverse osmosis water was used in all experiments. Therefore, there are few scavengers in the dye
water mixture. The reaction of OH with RB5 results in
the formation of intermediates, OH reacts further with
those intermediates to complete decolorization.
The formation rates of OH and HO2 in a batch reactor can be expressed as follows using the mechanisms
in Table 2:

where
k

kCH2 O2
k 0 Cd0 CH2 O2

kd k1
k4

and

k0

13

k7
k4

The presence of the initial concentration of RB5 in

Eq. (13) indicates that the decolorization reaction is a
pseudo-rst order reaction, because kobs aected with
varying initial concentration of RB5, otherwise kobs did
not vary with varying Cd0 as described previously. The
initial concentration of RB5 Cd0 was held constant in all
experiments at 500 mg l
1 ( 0.35 mM).
Eq. (13) can be tested using experimental data by
transforming it into an equation of a straight line:

A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

CH2 O2 CH2 O2 k 0
Cd0

kobs
k
k

14

Fig. 6 shows a plot of CH2 O2 =kobs versus CH2 O2 . These

experimental data were collected for dierent UV intensities of I0 I=Imax 0:21.0. Using a linear regression method, the coecients k and k 0 for all I0 , could be
determined. They are characterized by linear dependence on I0 as presented in Fig. 7 and described by

1075

k ki I0

15

where ki represents that kobs follows pseudo-rst order

kinetics with respect to UV intensity.
And
k 0 ki1 I0 ki2

16

Fig. 6. Test of Eq. (13) in order to determine k and k 0 .

where ki1 represents the scavenger eect of H2 O2 to OH

radicals, and ki2 is the inhibition eect of H2 O2 in the
absence of UV radiation.
Substitution of Eqs. (15) and (16) in Eq. (13) can be
used to describe the inuence of both CH2 O2 and I0 . The
values of k, k 0 , and ki , ki1 after adjusting them for any
applied UV intensity I are given in Table 3, if the I0 is
used both ki and ki1 will be dimensionless.
Fig. 8 shows the comparison between model predication and observed calculated data of the relation between kobs and CH2 O2 for dierent UV intensities. It
appears that the model closely predicts the experimental
data for all UV intensities and for low and high CH2 O2
fairly well. Thus, at low CH2 O2 the decolorization rate
increases linearly with CH2 O2 suggesting a rst order kinetic with respect to CH2 O2 . As CH2 O2 is increased above
140 mM, the decolorization rate become independent of
CH2 O2 , suggesting a zero order kinetic with respect to

Fig. 7. Relation between k, k 0 and UV intensity I0 and determination of ki , ki1 and ki2 .

Fig. 8. Comparison between experimental and model prediction of observed reaction rate coecient kobs versus hydrogen
peroxide concentration CH2 O2 at dierent UV intensities.

Table 3
Values of k and k 0 determined by linear regression for dierent UV intensities
I0 I=Imax (Imax 4:5  10
3
einst l
1 min
1 )

k min
1

k0

0.2
0.4
0.6
0.8
1.0

0.01
0.016
0.023
0.033
0.042

77
85
103
103
111

ki l einst
1

ki1 l min einst
1

ki2

0.0404

43

68

1076

A. Mohey El-Dein et al. / Chemosphere 52 (2003) 10691077

CH2 O2 . This observation holds true at all UV intensities

studied and the model could be used successfully to
describe both inuences.
Returning to the detailed mechanism of Table 2, to
Eq. (13) and to the denitions of k and k 0 (Eqs. (15) and
(16)) three extreme conditions can be identied:

At high concentrations of the dyes, more UV is absorbed by the dyes, reducing OH production rates at
equivalent H2 O2 concentrations and a higher amount of
DOC is present to react with OH , retarding the scavenging behavior of H2 O2 .

1. For CH2 O2  k 0 , kobs is not inuenced by CH2 O2 . This

may be possible at high CH2 O2 . Eq. (13) gives

6. Summary

kobs ki I0

17

although H2 O2 is needed for oxidation. There is a

mechanistic explanation that at higher CH2 O2 , CH2 O2
does not inuence the decolorization rate because
H2 O2 reacts with OH to form HO2 (Reaction 2,
Table 2), where the oxidation power of HO2 is much
lower than that of OH . A signicant amount of OH
available for decolorization may be consumed by
Reaction 2.
2. For CH2 O2 k 0 , kobs is inuenced by CH2 O2 to a great
degree. Eq. (13) becomes
kobs

ki I0 CH2 O2
ki1 Io ki2 Cd0

18

For ki1  ki2 , no inuence of I0 can be expected, although I0 is necessary for oxidation. The simplest
explanation for this case is that at low CH2 O2 , CH2 O2 is
not high enough to absorb the amount of UV radiation required for production of a signicant number
of OH for the decolorization.
3. For CH2 O2 k 0 and
ki1 I0 ki2

ki CH2 O2
I0
ki2
Cd0

dCd
ki ICH2 O2

Cd
dt
ki1 I ki2 Cd0 CH2 O2

21

For higher CH2 O2 and at low applied intensities I, the

reaction is only controlled by I

dCd
ki ICd
dt

22

For lower CH2 O2 and higher I, the reaction rate depends

on CH2 O2 only

dCd
ki CH2 O2

Cd
dt
ki1 Cd0

23

The model is able to predict the decolorization rate as

a function of Cd , CH2 O2 and I in very good agreement
with experimental results.

19

both CH2 O2 and I0 are parameters with a high inuence on the decolorization rate:
kobs

A kinetic model for the decolorization of the diazo

dye RB5 by H2 O2 /UV was developed, which is based on
experimental results as well as on a reaction kinetic
mechanism of the photolysis of H2 O2 . This mechanism
depends on known chemical reactions. For a batch reactor and any applied UV intensity the decolorization
rate of RB5 can be described by:

20

This could be possible if OH produced by the photolysis of H2 O2 would be used for decolorization of
RB5 and there is no side reaction of H2 O2 with OH .

Acknowledgements
The study presented here is part of a research project
funded by the Egyptian Ministry of Higher Education,
and the Berlin Education Program Nachwuchsf
orderungsgesetz (Naf
og).

References
Comparison of the results presented in Fig. 8 with
other studies on the decolorization of various dyes at
low concentration (2038 mg l
1 ) showed some deviations. The other studies reported a similar increase in
the decolorization rate with increasing CH2 O2 up to a
threshold value, however, they then found a decline with
further increases in H2 O2 concentration (Shu et al.,
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