Waste Management 21 (2001) 41±47

www.elsevier.nl/locate/wasman

Photochemical oxidation of p-chlorophenol by UV/H2O2 and

photo-Fenton process. A comparative study
Montaser Y. Ghaly, Georg HaÈrtel *, Roland Mayer, Roland Haseneder
Department of Environmental Processes Engineering, Freiberg University of Mining and Technology, Leipziger Strasse 28,
Freiberg, D-09596 Germany

Accepted 22 June 2000

Abstract
In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV/H2O2 and the photo-Fenton
reaction (UV+classical Fenton reaction) were investigated in lab-scale experiments for the degradation of p-chlorophenol. The
study showed that the photo-Fenton process, (a mixture of hydrogen peroxide and ferrous or ferric ion), was the most e€ective
treatment process under acidic conditions and produced a higher rate of degradation of p-chlorophenol at a very short radiation
time. It accelerated the oxidation rate by 5±9 times the rate for the UV/H2O2 process. The reaction was found to follow the ®rst
order, the reaction was in¯uenced by the pH, the input concentration of H2O2 and the amount of the iron catalyst and the type of
iron salt. The experimental results showed that the optimum conditions were obtained at a pH value of 3, with 0.03 mol/l H2O2, and
1 mmol/l Fe(II) for the UV/H2O2/Fe(II) system and 0.01mol/l H2O2 and, 0.4 mmol/l Fe(III) for the UV/H2O2/Fe(III) system. The
reactions were accompanied by the generation of Clÿ which reached its maximum value at a short reaction time when using the
photo-Fenton process. Finally a rough comparison of the speci®c energy consumption shows that photo-Fenton process reduced
the energy consumption by at least 73 to 83% compared with the UV/H2O2 process. # 2000 Elsevier Science Ltd. All rights
reserved.
Keywords: Photochemical advanced oxidation processes; Photo-Fenton reaction; p-Chlorophenol; UV/H2O2

1. Introduction remediation technologies and are gaining increasing

Advanced oxidation processes (AOPs) have been suc-
cessful in degrading most of the organic compounds
present in polluted water. The reason for the use of
AOPs is due to the inability of biological processes to
treat highly contaminated and toxic water. In AOP, the
hydroxyl radicals (OH ) are generated in solution and
these are responsible for the oxidation and mineraliza-
tion of the organic pollutants to water and carbon diox-
ide. In recent years, various advanced oxidation processes,
which produce hydroxyl radicals i.e. O3/UV, O3/H2O2,
UV/H2O2 and Fenton reagent [H2O2/Fe(II)] etc., have
been applied in wastewater treatment [1±5]. The photo-
chemical advanced oxidation processes including pho-
tolysis and photocatalysis, are attractive environmental
* Corresponding author. Tel.: +49-3731-392376; fax: +49-3731-
3923652.
E-mail addresses: haertel@tua.tu- freiberg.de (G. HaÈrtel), hasenede
@tua.tu- freiberg.de (R. Haseneder).
0956-053X/00/$ - see front matter # 2000 Elsevier Science Ltd. All rights reserved.
PII: S0956-053X(00)00070-2
importance for degradation of most of the organic pol-
lutants [6].
The photolytic induced oxidation with ozone or
hydrogen peroxide will result in expensive high energy
requirements if the organic or inorganic pollutants of
wastewater strongly absorb UV-radiation. The utiliza-
tion of the metal salt Fe(II) as Fenton's reagent pro-
duces inorganic sludge that may cause a waste disposal
problem [7].
A combination of H2O2 and UV radiation with Fe(II)
or Fe(III), the so-called photo-Fenton process, is a pro-
mising process based on this concept, where iron salts
serve as photocatalysts and H2O2 as oxidizing agent. It
represents an ecient and cheap method for wastewater
treatment [8±10] and produces more hydroxyl radicals in
comparison with the systems Fe(II)/H2O2 or UV/H2O2,
thus promoting the rate of degradation of various organic
pollutants. In this paper, two di€erent photochemical
processes employing UV light (UV/H2O2 and photo-
Fenton process) for the oxidation of p-chlorophenol in
42 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47
an aqueous solution were compared. The e€ect of the
pH value, hydrogen peroxide and iron compounds on
the photo-elimination of p-chlorophenol solution was
evaluated.
p-Chlorophenol is used as an intermediate in the
manufacture of higher chlorophenols and phenolic
resins and for extracting sulfur and nitrogen compounds
from coal. It is also used in organic synthesis (dyes).
Knowing di€erent problematic sites, this compound
was chosen for experiments.
2. Experimental
2.1. Reagents
p-Chlorophenol (4-chlorophenol, C6H5ClO) in the
purest form, is available from Merck Chemical Com-
pany Darmstadt. Ferrous (FeSO4.7H2O) and ferric
[Fe2(SO4)3.7H2O] sulphate heptahydrate used as sources
of Fe(II) and Fe(III), were all analytical grade and pur-
chased from Merck. Hydrogen peroxide solution (30% w/
w) in stable form was provided by Roth Company Karls-
ruhe. Catalase was obtained from bovine liver (Fluka
Biochemika). All reagents employed were not subjected to
any further treatment. Water used throughout was
ultrapure deionized water.
2.2. Experimental set-up
All experiments were performed in a batch reactor.
The schematic diagram of the experimental set-up used
in the study is shown in Fig. 1. The reactor was cylind-
rical with 0.85 l volume and was made from quartz glass
which was available for the transfer of the radiation.
Irradiation was achieved by using UV lamp (high pres-
sure mercury lamp TQ 718 of 700 W, radiation ¯ux used
for only degradation of 221 W/h of 200±600 nm, from
Fig. 1. Schematic diagram of photocatalytic oxidation system experi-
mental set-up.
Heraeus Noblelight Company in Germany) which was
immersed in the glass tube. The UV lamp was equipped
with a cooling water jacket system which was placed in
the reactor vessel. The reaction chamber was ®lled with
the reaction mixture, which was placed between the reac-
tor walls and UV lamp system. Mixing was accomplished
by means of a closed circulating loop by the use of a
pump. The ¯ow system was assembled with polytetra-
¯uorethylene (PTFE) or glass tubings and connectors.
2.3. Photodegradation procedures
For each experiment, synthetic aqueous solution of
100 mg/l p-chlorophenol (to simulate a high loaded p-
chlorophenol containing industrial wastewater) was
prepared in ultrapure deionized water as solvent. The
laboratory unit was ®lled with 0.85 l of the p-chlor-
ophenol solution. For runs using UV/H2O2 system,
hydrogen peroxide at di€erent amounts was injected in
the reactor before the beginning of each run. For runs,
using the photo-Fenton process, the pH value of the
solution was set at the desired value by the addition of a
H2SO4 solution before startup, then a given weight of
iron salt was added. The iron salt was mixed very well
with the p-chlorophenol before the addition of a given
volume of hydrogen peroxide. The time at which the
ultraviolet lamp was turned on was considered time zero
or the beginning of the experiment which was taking
place simultaneously with the addition of hydrogen
peroxide. The solution was circulated at a ¯ow rate of
200 l/h and irradiated for 45 min.
2.4. Analytical methods
Samples were taken at appropriate time intervals
from the reaction vessel and pipetted into (3 ml) glass
vials. The vials were ®lled so as to leave no headspace
and sealed with te¯on-lined silicon septa and screw
caps. The samples were immediately analyzed to avoid
further reaction. One drop of enzyme catalase was also
added to each sample to decompose any residual
hydrogen peroxide and prevent hydrogen peroxide from
reacting with organic substrates during the analysis.
Hydrogen peroxide was measured by the standard
iodometric titration method [11]. Concentration chan-
ges of p-chlorophenol were determined by a gas chro-
matgraph (Perkin-Elmer SIGMA 3) with a glass column
3.6 m0.53 mm2.65 mm ®lm thickness and FID
detector. The conditions were as follows: the injector
and detector temperatures were 200 and 240 C, respec-
tively, the initial and ®nal oven temperatures were 110
and 240 C, respectively, the ramp temperature was
15 C/min, and a retention time of 6.3 min was used for
p-chlorophenol. In addition, samples were also analyzed
to determine chloride by means of titration with silver
nitrate [12].
 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47
3. Results and discussion
3.1. UV/H2O2 process
In this process hydroxyl radicals are formed according
to Eq. (1) [13].
H2 O2 ‡ h ! 2OH: …
The combination of UV and a little amount of H2O2
enhances strongly the eciency of the degradation of p-
chlorophenol. Homogeneous photolysis methods, com-
pared with photocatalysis, do not demand a separation
procedure of solid catalyst after treatment. For e€ective
treatment, photolysis requires short wavelength of strong
energy UV light and other chemical oxidants such as
hydrogen peroxide and ozone.
3.2. The e€ect of the amount of H2O2
Although hydrogen peroxide did not oxidize p-chlor-
ophenol at all, as observed in this work, when it com-
bined with UV irradiation, the rate of p-chlorophenol
degradation increased signi®cantly compared to that of
direct photolysis. Fig. 2 illustrates the percent degrada-
tion of p-chlorophenol as a function of the irradiation
time at di€erent doses of H2O2 input. The photolysis of
p-chlorophenol in the absence of H2O2 gave rather
moderate results and resulted in a slow degradation of
p-chlorophenol. By addition of H2O2, the degradation
rate of p-chlorophenol ®rst increased when hydrogen
peroxide concentration increased however, the e€ect of
peroxide is negative for hydrogen peroxide concentra-
tions higher than 0.02 mol/l for which the p-chloro-
phenol degradation rate was even lower than that
obtained from direct photolysis. As can be seen from
Fig. 2, the percent degradation of p-chlorophenol at 20
min was 70 in a direct photolysis experiment and was 60
at the same time when the photolysis was carried out in
Fig. 2. Degradation of p-chlorophenol with UV/H2O2 system. The e€ect of initial hydrogen peroxide concentration.
43
the presence of an initial hydrogen peroxide concentra-
tion of 0.05 mol/l. In this process, hydroxyl radicals
generated from the direct photolysis of hydrogen per-
oxide were the main responsible species of p-chlor-
ophenol elimination. However hydrogen peroxide also
reacts with these radicals and hence acts as an inhibiting
agent of p-chlorophenol degradation [14]. As can be
1† deduced from Fig. 2, when the concentration of hydro-
gen peroxide was higher than 0.02 mol/l, its hydroxyl
radical scavenging e€ect became important and the p-
chlorophenol degradation rate decreased.
3.3. Photo-Fenton process
The formation of the hydroxyl radicals by using the
photo-Fenton process under application of Fe(II)
occurs according to the following Eq. (2) [15].
Fe2‡ ‡ H2 O2 ! Fe3‡ ‡ OHÿ ‡ OH …2†
Reaction (2), already known as the Fenton reaction,
possesses a high oxidation potential, but its revival in
the application to wastewater treatment began only
recently [16]. UV irradiation leads not only to the for-
mation of additional hydroxyl radicals but also to a
recycling of the ferrous catalyst by reduction of Fe(III).
By this the concentration of Fe(II) increases and there-
for the gross reaction is accelerated [19]. The reaction
time needed for the photo-Fenton reaction is extremely
low and depends on the operating pH value and the
concentrations of H2O2 and iron added. Within 5 min
nearly a complete destruction of p-chlorophenol could
be observed using photo-Fenton processes.
3.4. The e€ect of the pH value
The pH value a€ects the oxidation of organic sub-
stances both directly and indirectly. The photo-Fenton
reaction is strongly a€ected by the pH-dependence. The
44 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47

pH value in¯uences the generation of OH radicals and
thus the oxidation eciency. Fig. 3 shows the e€ect of
the pH value during the use of the photo-Fenton pro-
cess. A maximum degradation of 99.85% was obtained
with the system UV/H2O2/Fe(III) at a pH=3 and
degradation of 96.5%. with the system UV/H2O2/Fe(II)
at the same pH value. For pH values above 4 the
degradation strongly decreases because at higher pH
values iron precipitates as hydroxide and that reduces
the transmission of the radiation [15].
system or 0.01 mol/l for UV/H2O2/Fe(III) system did
not improve the respective maximum degradation. This
may be due to auto-decomposition of H2O2 to oxygen
and water and the recombination of OH radicals. Since
OH radicals react with H2O2, H2O2 itself contributes to
the OH scavenging capacity [14]. Therefore, H2O2
should be added at an optimal concentration to achieve
the best degradation.
3.6. The e€ect of the amount of iron salt

3.5. The in¯uence of initial hydrogen peroxide
concentration
Fig. 4 shows the e€ect of the initial hydrogen peroxide
on the degradation of p-chlorophenol with the use of
photo-Fenton processes. As expected, the degradation
of p-chlorophenol was increased by increasing the con-
centration of H2O2 added. This can be explained by the
e€ect of the additionally produced OH radicals. Addi-
tion of H2O2 exceeding 0.03 mol/l for UV/H2O2/Fe(II)
Iron in its ferrous and ferric form acts as photo-
catalyst and requires a working pH below 4. To obtain
the optimal Fe(II) or Fe(III) amounts, the investigation
was carried out with various amounts of the iron salt.
Fig. 5 shows the percent degradation of p-chlorophenol
as a function of the added Fe(II) and Fe(III). The ®gure
shows that the addition of either Fe2+ or Fe3+
enhanced the eciency of UV/H2O2 for p-chlorophenol
degradation. The degradation rate of p-chlorophenol
distinctly increased with increasing amounts of iron salt.

Fig. 3. p-Chlorophenol degradation as a function of the pH value by using photo-Fenton processes: [Fe(II)]0=1 mmol/l, [Fe(III)]0=0.4 mmol/l,
(H2O2)0=0.02 mol/l.

Fig. 4. Degradation of p-chlorophenol with the photo-Fenton process. The e€ect of initial hydrogen peroxide concentration.
 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47 45

Fig. 5. p-Chlorophenol degradation as a function of iron catalyst addition: (H2O2)0=0.02 mol/l, pH=3.

Addition of the iron salt above 1 mmol/l Fe(II) or 0.4 Table 1

mmol/l Fe(III) did not a€ect the degradation, even Values of reaction rate constants of the degradation of p-chlorophenol
when the concentration of the iron was doubled. A by di€erent types of oxidation processes
higher addition of iron salt resulted in brown turbidity Type of oxidation process k0 (minÿ1)
that hindered the absorption of the UV light required
UV 0.06
for photolysis and caused the recombination of OH UV/H2O2 0.15
radicals. In this case, Fe2+ reacted with OH radicals as UV/H2O2/Fe(II) 0.74
a scavenger [17]. UV/H2O2/Fe(III) 1.32
It is desirable that the ratio of H2O2 to Fe(II) should
be as small as possible, so that the recombination can be
avoided and the sludge production from iron complex is
also reduced. loss of p-chlorophenol was observed as a function of
irradiation time and data were ®tted to a ®rst-order rate
model
4. Comparison between UV/H2O2 system and photo-
Fenton process Ct
ln ˆ ÿk0 t …3†
C0
4.1. Degradation rate
where C0 and Ct are the concentration of p-chlor-
The photodegradation of p-chlorophenol was investi- ophenol at irradiation times 0 and t, k0 is a ®rst-order
gated in both systems UV/H2O2 and photo-Fenton rate constant (in minÿ1) and t is the irradiation time
process [UV /H2O2/Fe(II) and UV/H2O2/Fe(III)]. The (in min). The rate constants were determined using a

Fig. 6. First-order plot for degradation of p-chlorophenol by UV/H2O2 and photo-Fenton processes.
46 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47

®rst-order rate model [Eq. (3)]. The results are listed in
Table 1. The experimental data in Fig. 6 show that
photo-Fenton processes had a signi®cant accelerating
e€ect on the rate of oxidation of p-chlorophenol. The
data in Table 1 show that adding Fe(II) or Fe(III) to the
UV/H2O2 system enhanced the rate of p-chlorophenol
oxidation by a maximum factor 5 and 9 for Fe(II) and
Fe(III), respectively, over the UV/H2O2 system,
depending on both H2O2 and Fe doses. This phenom-
ena of enhanced eciency is also known from other
investigations with Fe(II) and Fe(III) [20].

4.2. Dechlorination of p-chlorophenol

In AOPs, the produced hydroxyl radical will attack

Fig. 7. Radicalic degradation of p-chlorophenol [6].
the aromatic ring of p-chlorophenol and the reaction is
shown in Fig. 7. As shown in Fig. 7, the radical
mechanism can be distinguished by the direct dechlor-
ination of p-chlorophenol [6,18]. Fig. 8 shows the
concentrations of the free chloride produced during the

Fig. 8. Resulting free chloride during the oxidation of p-chlorophenol by UV, UV/H2O2 and photo-Fenton processes.

Fig. 9. Comparison of the speci®c energy consumption: total UV-power 221 W,% degradation of p-chlorophenol is 99.95%, reaction times are 30.8
and 5 min for UV/H2O2, UV/H2O2/Fe(II) and UV/H2O2/Fe(III), respectively.
 M.Y. Ghaly et al. / Waste Management 21 (2001) 41±47
oxidation of p-chlorophenol at di€erent photochemical
oxidation processes. As shown in Fig. 8, the Clÿ gener-
ated had their maximum values in the case of the photo-
Fenton processes.
4.3. Comparison of the speci®c energy consumption
Fig. 9 provides a comparison of the energy required
to remove 1 kg of p-chlorophenol by di€erent photo-
chemical oxidation processes. The photo-Fenton pro-
cess is more economical than the UV/H2O2 process with
an energy reduction of 73% for the UV/H2O2/Fe(II)
system and 83% for the UV/H2O2/Fe(III) system,
respectively, over UV/H2O2 process. It may be noted
that the consumed speci®c energy was calculated only
from the transformed UV radiation which represented
only a part of the total electrical energy. The output UV
energy amount to 221 W.
5. Conclusion
The results from this study showed that the degrada-
tion rate of p-chlorophenol was strongly accelerated by
the photochemical oxidation processes. The photo-Fen-
ton process, the combination of homogeneous systems
of UV/H2O2/Fe compounds, produced the highest pho-
tochemical elimination rate for p-chlorophenol. The
oxidation rate was in¯uenced by many factors, such as
the pH value, the amount of hydrogen peroxide and
iron salt and the type of iron added. The optimum con-
ditions obtained for the best degradation were a pH=3,
a Fe(II) concentration of about 1 mmol/l and a H2O2
concentration of 0.3 mol/l for UV/H2O2/Fe(II) system
and a Fe(III) concentration of about 0.4 mmol/l, and a
H2O2 concentration of about 0.01 mmol/l for UV/
H2O2/Fe(III) system.
The advantages of the photo-Fenton process as an
oxidative pre-treatment step over other photochemical
oxidation processes are economics, eciency especially
if aromatic compounds are to be destroyed, easy hand-
ling of the method because no speci®c technical equip-
ment is necessary, low investment, less energy demand
and harmless process products. The acidic pH (<4) and
the secondary treatment to remove the added iron are
two major problems currently under examination.
Combination of an AOP with biological treatment is a
promising alternative because one can take advantage
of both methods and develop as result a potent waste-
water puri®cation method. Considering the photo-Fen-
47
ton method as a preliminary step prior to a biological
wastewater treatment, one has to adjust pH twice, ®rst
to an acidic pH below 4 to perform the photo-Fenton
method and then back to a neutral pH.
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