Chemosphere 47 (2002) 915–924

www.elsevier.com/locate/chemosphere

Kinetic modeling of Fenton oxidation of phenol and

monochlorophenols
Namgoo Kang a, Dong Soo Lee a,*
, Jeyong Yoon b,*

a
Graduate School of Environmental Studies, Seoul National University, Kwanak Ku, Shilimdong san 56-1,
Seoul 151-742, South Korea
b
School of Chemical Engineering, College of Engineering, Seoul National University, Kwanak Ku,
Shilimdong san 56-1, Seoul 151-742, South Korea
Received 15 August 2001; received in revised form 3 January 2002; accepted 30 January 2002

Abstract

A kinetic model, consisting of 28 reactions, was proposed to understand the key mechanism of the Fenton oxidation
of phenol and o-, m-, and p-chlorophenols. Particular attention is paid to the interactions of the organic intermediates
with the Fe species. The proposed model reasonably predicts the decomposition kinetics and by-product formation for
the different phenols at widely varying levels of Fe2þ , H2 O2 , and the phenols. For the phenols and intermediates, change
in concentrations with time was predicted within 20–30% deviation from the measured data. The single model predicts
the overall kinetics of Fenton oxidation of all the tested phenols by adjusting the rate constant of hydroxyl radical for
each phenol. Sensitivity analysis indicates that the key reactions are those that directly govern the levels of OH radical
and Fe2þ . Both the model prediction and the experimental results show that the decomposition rate could be complicated
particularly by the availability of Fe2þ . Understanding the interactions of the organic intermediates with Fe2þ is thus of
critical importance to improve the decomposition performance. Ó 2002 Elsevier Science Ltd. All rights reserved.

Keywords: Fenton oxidation; Chlorophenols; Mechanism; Intermediates; Kinetic model

1. Introduction Ross, 1977; Rush and Bielski, 1985), the mechanisms of

Early works on Fenton oxidation were typically
limited in their scopes to the investigation of the influ-
ences of process parameters such as chemical oxygen
demand, the amount and the ratio of hydrogen perox-
ide and iron salt, and pH. In-depth understanding of
the mechanisms of the processes has remained relatively
limited until recently. However, as extensive knowledge
has become available on the aqueous hydroxyl radical
and related chemistry (Sehested et al., 1969; Walling and
Kato, 1971; Walling and Goosen, 1973; Farhataziz and
*
Corresponding authors. Tel.: +82-2-880-8522; fax: +82-2-
886-2361.
E-mail address: leeds@snu.ac.kr (D.S. Lee).
0045-6535/02/$ - see front matter Ó 2002 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 2 ) 0 0 0 6 7 - X
Fenton processes could be better understood. In some
works, reaction pathways were suggested by identifying
the intermediates and products (Sedlak and Andren,
1991; Scheck and Frimmel, 1995). Subsequently, ki-
netic models were proposed that integrated the avail-
able knowledge and the reaction pathways (Dong, 1993;
Potter and Roth, 1993; Stefan et al., 1996; Pignatello
and Chen, 1997; Laat et al., 1999). The reactions
adopted in the models may be divided into three major
groups. In the first group are the principal inorganic
reactions that represent the interactions among various
inorganic species including OH, HO2 , O 2þ
2 , H2 O2 , Fe ,
3þ
and Fe . The second group includes the interactions
among organic species (parent compounds and their
break-down intermediates and/or products) and the re-
active inorganic species except the Fe species. In the
916 N. Kang et al. / Chemosphere 47 (2002) 915–924
third group are the reactions among Fe and the organic
species that influence the Fe-redox cycle. The first group
is now considered relatively well established. In the
second group, identification of the unstable intermedi-
ates is critical but often incomplete. Among the inter-
actions in the third group, of particular concern is the
roles of the organic intermediates or final products in the
Fe-redox cycle. They might accelerate Fe(III) reduction
to Fe(II) (Tamagaki et al., 1989a,b) and/or potentially
deactivate iron by forming stable complexes (Martell
and Smith, 1977; Zuo and Hoigne, 1992; Kwon et al.,
1999). Given certain experimental conditions, initial
oxidation rates by Fenton’s reagent appear primarily
to depend on the rate between  OH and the parent
compounds. However, as a significant portion of ini-
tial Fe2þ is rapidly consumed, the subsequent decom-
position rate is likely to be affected by the third group
types of interactions among the intermediates and the
Fe species.
Phenol (Potter and Roth, 1993; Chen and Pignatello,
1997) and chlorophenols (Barbeni et al., 1987; Dong,
1993; Potter and Roth, 1993; Kwon et al., 1999; Yoon
et al., 2000) have been investigated for their Fenton
oxidation kinetics. The observed decomposition rates of
phenol and chlorophenols were not significantly differ-
ent under similar reaction conditions. Furthermore,
H2 O2 appeared to decompose at a similar rate during
the decompositions of the different phenols, suggesting
that the type of interactions between the intermediates
and the Fe species might also be similar for phenol and
chlorophenols. However, in Chen and Pignatello’s
(1997) work, the phenol decomposition profiles were
distinct in that significant initial lag periods were pre-
sent, which was possibly ascribed to removing impurities
in phenol used in their experiments. Although the true
cause of the lag periods was not confirmed, the observed
phenol decomposition and Fe(II) regeneration kinetics
were successfully predicted by a proposed model where
the interactions of all the three groups were integrated in
a quantitative manner. While providing valuable insight
into the roles of organic intermediates in the Fe-redox
process, the model might have limited applicability as it
was tested at fairly limited reaction conditions and, more
importantly, since no such initial lag period has been
reported in previous studies of phenols/H2 O2 /Fe2þ .
Therefore, the present work was undertaken to develop
and evaluate a kinetic model that provides in depth
understanding of the mechanisms and kinetics of the
Fenton oxidation of monochlorophenols as well as
phenol. With p-chlorophenol as a main model com-
pound, particular attention was paid to the roles of in-
termediates and to the evaluation of the model at widely
varying conditions to assure that the model represents
the key mechanism. Further evaluation of the model was
performed by using experimental data taken from other
studies for phenol (Eisenhauer, 1964), o-chlorophenol,
m-chlorophenol (Sims, 1981; Dong, 1993), and their
daughter products.
2. Materials and methods
To evaluate the kinetic model, the effects of p-chlo-
rophenol, hydrogen peroxide, and Fe2þ concentrations
and their input rate and pattern were experimentally
explored on the decomposition kinetics of p-chlorophe-
nol. The experiments were conducted in both batch and
semi-batch modes. The reactors were shielded with
aluminum foil to prevent light from penetrating to
the reaction solution. The details of the experimental
procedure of the batch mode are presented elsewhere
(Kwon et al., 1999). Briefly, as a reactor, a 4-l glass
vessel was used with four necks at the top to allow the
introduction of an impeller, a pH probe, a thermometer,
and Fenton’s reagent. A pH control system was con-
nected to the reactor to keep pH constant at a prede-
termined level.
Each test typically began with 3.0 or 3.5 l of p-
chlorophenol solution. The reaction started upon adding
Fenton’s reagent made up of H2 O2 and FeSO4 . Effluents
were collected at predetermined reaction time through
the stopcock drain at the reactor’s bottom. Potential
reactions by OH radical and hydrogen peroxide in the
collected effluents were quenched by using a solution of
6 N NaOH (Potter and Roth, 1993).
The experimental procedure of the semi-batch tests
was the same as that of the batch mode except that a
predetermined quantity of Fe2þ or hydrogen peroxide
was fed continuously at a constant rate for the duration
of a given reaction time.
The concentration of aqueous p-chlorophenol was
determined by using gas chromatograph/FID (Hewlett
Packard 5890 II) with a fused capillary column (HP-5,
30 m  0:32 mm, 0.25 lm film thickness). The oven
temperature was ramped at 8 °C/min from 80 to 290 °C
and a split ratio of 4:1 was used. Prior to the instru-
mental analysis, the aqueous sample was acidified by
HCl for extraction with an equal volume of diethyl
ether. The concentration of 1,4-benzenediols and ben-
zoquinone were determined by using high pressure liq-
uid chromatograph/fluorescence detector (Young-Lin
M930 System & Waters 474 scanning fluorescence de-
tector) with a C18 symmetry column (Waters Co.). The
emission wavelength of 290 nm and excitation wave-
length of 320 nm were used. The solvent used was a
mixture of acetonitrile and water at the ratio of 40/60.
The retention times for 1,4-benzenediol and benzoqui-
none were 4.0 and 5.4 min, respectively.
The Fe(II) and hydrogen peroxide concentrations
were determined by the o-phenanthroline colorimetric
method (Sandell, 1959) and the titanium sulfate spec-
trophotometric method (Eisenberg, 1943), respectively.
 N. Kang et al. / Chemosphere 47 (2002) 915–924 917

The concentration of Fe(III) was determined by sub-
tracting the Fe(II) concentration from the total Fe
concentration. The total Fe concentration was deter-
mined by measuring the Fe(II) concentration after
Fe(III) was reduced with 1 N hydroxyl amine.
3. Results and discussion
3.1. Model set-up
The proposed kinetic model consists of 28 reactions
as listed in Table 1. In this model, the potential reactions
involving organic peroxyl radical were assumed negli-
gible as the dissolved oxygen was observed to deplete in
a few seconds after the commencement of the dark
Fenton reactions (Yoon et al., 2001). The reactions R1
through R15 represent the principal inorganic reactions
which are considered common to the Fenton reaction
systems. The reactions specific to p-chlorophenol de-
composition are represented by R16 through R28. In
R16, the OH radical addition to the ortho or para po-
sition is favored over the meta position (Dong, 1993;
Potter and Roth, 1993). As para position is already
occupied by chlorine in p-chlorophenol, addition to the
ortho position dominates. The benzenediols in R17 in-
clude 4-chloro-1,2-benzenediol, 4-chloro-1,3-benzene-
diol, and 1,4-benzenediol as identified in the preceding

Table 1
The reactions used in the model of Fenton oxidation of p-chlorophenol
Reaction k (M1 s1 ) References
2þ 3þ  
(R1) Fe þ H2 O2 ! Fe þ OH þ OH 63 Metelitsa (1971)
(R2) Fe3þ þ H2 O2 ! Fe2þ þ Hþ þ HO2 0.01 Walling and Goosen (1973)
(R3)  OH þ H2 O2 ! HO2 þ H2 O 2:7  107 Christensen et al. (1982)
(R4) HO2 ! O 2 þH
þ
1:58  105 s1 Bielski et al. (1985)
(R5) O2 þ Hþ
! HO 
2 1:0  1010 Bielski et al. (1985)
(R6) OH þ Fe ! Fe3þ þ OH
 2þ
3:2  108 Stuglik and Zagorski (1981)
þ
(R7) HO2 þ Fe ðþH Þ ! Fe3þ þ H2 O2
 2þ
1:2  106 Jayson et al. (1969)
(R8) HO2 þ Fe3þ ! Fe2þ þ Hþ þ O2 3:1  105 Rush and Bielski (1985)
(R9) O 2þ þ
2 þ Fe ðþ2H Þ ! Fe
3þ
þ H2 O2 1:0  107 Rush and Bielski (1985)
 3þ 2þ
(R10) O2 þ Fe ! Fe þ O2 5  107 Rothschild and Allen (1958)
(R11)  OH þ  OH ! H2 O2 4:2  109 Sehested et al. (1969)
(R12) HO2 þ HO2 ! H2 O2 þ O2 8:3  105 Bielski et al. (1985)
(R13)  OH þ HO2 ! O2 þ H2 O 1  1010 Sehested et al. (1969)
(R14)  OH þ O 2 ! O2 þ OH

1  1010 Sehested et al. (1969)
(R15) HO2 þ O 2 ðþHþ
Þ ! H 2 O2 þ O2 9:7  107 Bielski et al. (1985)
(R16)  OH þ p-chlorophenol ! ðC1ÞDHCD 9:3  109 Stafford et al. (1994)
(R17) ðClÞDHCD þ Fe3þ ! Fe2þ þ ðC1Þbenzendiols 7000a Metelitsa (1971)
(R18)  OH þ ðClÞDHCD ! THB þ Cl 2  1010 Sanchez et al. (1996)
(R19) ðClÞbenzenediols þ Fe3þ $ Fe2þ þ ðC1Þsemiquinones k19f ¼ 1 Mentasti et al. (1973),
Tamagaki et al. (1989a,b)
k19r ¼ 24b Chen and Pignatello (1997)
(R20) THB þ Fe3þ ! Fe2þ þ ðHÞAA 10a Mentasti et al. (1973)
(R21)  OH þ ðClÞbenzenediols ! THCD 7  109 Stafford et al. (1994)
(R22) ðClÞsemiquinones þ Fe3þ $ Fe2þ þ ðC1Þbenzoquinones k22f ¼ 1000b Chen and Pignatello (1997)
k22r ¼ 10:8 Mentasti et al. (1973)
(R23) THCD þ Fe3þ ! Fe2þ þ THB 7000a Metelitsa (1971)
(R24) 
OH þ ðClÞbenzoquinones ! MA 1:2  109 Adams and Michael (1967)
(R25) 
OH þ THB ! ðHÞAA 4  1010a Oturan and Pinson (1995)
(R26) 
OH þ MA=ðHÞAA ! ðHÞAA 5  108 Scheck and Frimmel (1995)
(R27) MA =ðHÞAA þ Fe3þ ! Fe2þ þ MA=ðHÞAA 10c Kwon et al. (1999)
Walling and El-Taliawi (1973)
(R28) Fe3þ þ aðHÞAA ! FeðIIIÞ-organic complexes 1.0c Kwon et al. (1999)

(C1)DHCD : (chloro)dihydroxycyclohexadienyl radical; (C1)benzendiols: (chloro)benzenediols.
(C1)semiquinones : (chloro)semiquinones radical; THB: trihydroxybenzene.
THCD : trihydroxycyclohexadienyl radical; (Cl)benzoquinones: (chloro)benzoquinones.
MA/MA : cis, cis-muconic acid/radical; (H)AA/(H)AA : (hydroxylated) aliphatic acids/radicals.
a: fraction of (HAA) that takes part in the Fe scavenging.
a
Adopted from the analogous reactions.
b
A constant ratio of k19r –k22f (¼ 0:024) was used.
c
The reaction was suggested to occur but no rate constant was reported.
918 N. Kang et al. / Chemosphere 47 (2002) 915–924

work (Kwon et al., 1999) and others (Sedlak and An-

dren, 1991). Benzenediols were known to reduce Fe(III)
in acidic solution (R19 and R22) (Mentasti et al., 1973;
Chen and Pignatello, 1997; Kwon et al., 1999). For in-
stance, 1,4-benzenediol was suggested as a main Fe(III)
reducing intermediate in phenol decomposition (Chen
and Pignatello, 1997). A number of studies (Barbeni
et al., 1987; Dong, 1993; Chen and Pignatello, 1997;
Kwon et al., 1999) reported that Fe(II) is regenerated
by some intermediates of ring structure. The first
intermediate, chlorodihydroxycyclohexadienyl radical
((Cl)DHCD), may reduce Fe(III) to form the benzen-
diols (R17) (Barbeni et al., 1987; Potter and Roth, 1993;
Chen and Pignatello, 1997), which is analogous to the
Fe(III) reduction by monohydroxycyclohexadienyl rad-
ical (MHCD) (Metelitsa, 1971). Trihydroxybenzene
(THB) and trihydroxycyclohexadienyl radical (THCD)
may also reduce Fe(III) (R20 and R23) (Potter and
Roth, 1993), which are analogous to the Fe(III) reduc-
tion by (Cl)benzenediols and (Cl)DHCD, respectively.
However, these intermediates, produced at an early
stage, are subject to decomposition by  OH (R18, R21,
R24, and R25) as evidenced by the 1,4-benzenediol and
benzoquinone levels declining essentially to zero (Fig.
1a). If those were the only Fe(III) reducing intermedi-
ates, the Fe(II) regeneration would stop as the inter-
mediates decompose to form a number of ring-opened Fig. 1. Model prediction as compared to measured data for the
products. The ring-opened products found from the time changes of (a) p-chlorophenol, H2 O2 , Fe2þ and interme-
Fenton oxidation of p- and o-chlorophenols include diates (1,4-benzenediol and benzoquinone) at ½p-CP0 ¼ 2 mM,
valeric acid, propionic acid, propanoic acid, tartaric ½H2 O2 0 ¼ 6 mM, ½Fe2þ 0 ¼ 0:3 mM, and pH ¼ 3:0 (b) o-
acid, and glyoxylic acid (Dong, 1993; Kwon et al., 1999). chlorophenol and intermediates ((Cl)benzenediols and THB) at
½H2 O2  ¼ 0:674 mM/min, ½Fe2þ 0 ¼ 1 mM, and pH ¼ 3:0 (data
Also, muconic acid and oxalic acid were identified in
from Dong (1993)).
other studies of phenol oxidation (Scheck and Frimmel,
1995). However, Fig. 1 shows that the Fe(II) regenera-
tion continues even after H2 O2 depletes, indicating some available from existing literature. The values of the re-
of the ring opened products may contribute to the Fe(II) maining eight unknowns were assumed by adopting
regeneration. It has been observed that the presence of from analogous reactions (k17 , k23 , and k25 ) or by fitting
muconic and propionic acids promote the p-chlorophe- against a set of observed data (k19f and k19b , k22f , k27 and
nol decomposition by a factor of two to three (Kwon k28 ) with the considerations given below. An equilibrium
et al., 1999), which indirectly supports that these acids calculation indicates that Fe(II) species would predom-
or acid radicals may regenerate Fe(II) (Walling and El- inantly take the form of Fe2þ at pH ¼ 3 or below. Al-
Taliawi, 1973). Therefore, it is reasonable to propose the though Fe-complexes might form in the presence of
reactions R24 through R27. organic substances, it was assumed in this study that
It was also observed that some of these acids and the Fe2þ was a dominant form among potential Fe(II) spe-
unknown organic products scavenged iron and inhibited cies. The values of k17 and k23 were assumed identical
the p-chlorophenol decomposition rate (Kwon et al., and adopted from the analogous reaction of MHCD
1999). Oxalic acid and salicylic acid were such examples radical (Metelitsa, 1971). For k25 , the average rate con-
(Potter and Roth, 1993). Therefore, the reaction R28 stant value was taken from the analogous reactions of
was proposed to account for the iron scavenging effect. 2,3,4-trihydroxybenzoic acid and 3,4,5-trihydroxyben-
In R28, a denotes the portion of the produced organic zoic acid (Oturan and Pinson, 1995). Limited rate data
acids that takes part in the Fe scavenging. It is to be indicated that k19f could have a wide range of values. For
noted that each reaction from R16 to R28 except R25 4-chloro-1,2-benzenediol and 1,4-benzenediol, respec-
potentially represents a group of parallel reactions ra- tively, the values were approximately 400 M1 s1
ther than a single reaction. (Tamagaki et al., 1989a) and 27 M1 s1 (Tamagaki
For the reactions R1 through R16, and R18, R21, et al., 1989b). Comparatively, the rate constant for 1,2-
R22r, R24, and R26, all the rate constant values were benzenediol was reported as ‘‘too fast’’ (Tamagaki et al.,
 N. Kang et al. / Chemosphere 47 (2002) 915–924
1989a). In the present model, the value of k19f should be
on the order of 101 –102 M1 s1 to obtain a reasonable
model fit to the data. The value of k20 was assumed the
same as k19f . The ratio of k19r to k22f was fixed at 0.024
(Chen and Pignatello, 1997). The rate constant of R27
was considered similar to or larger than k20 . It was noted
that R28 influenced practically the tailing phase of p-
chlorophenol decomposition and the ultimate extent of
Fe(II) regeneration. As a in R28 was not separately
determined, the suggested k28 value contains a (i.e.,
r28 ¼ k28 ½Fe3þ  a½HAA ¼ k28 0
½Fe3þ ½HAA). Given these
considerations, the rate constants (k19f , k19b , k22f , k27 , and
k28 ) were adjusted such that the model prediction rea-
sonably agreed with a single batch data set concerning
the p-chlorophenol decomposition and Fe(II) regenera-
tion at the conditions of ½p-chlorophenol0 ¼ 2 mM,
½H2 O2 0 ¼ 6 mM, ½Fe2þ 0 ¼ 0:3 mM, and pH ¼ 3:0. A
more rigorous approach to minimize the prediction er-
rors was not attempted because each rate constant from
k19 through k28 except k25 should be interpreted as a sum
of the rate constants of parallel reactions for which the
reactants and/or products were only loosely defined.
Furthermore, although assumed constant, a number of
rate constants (k1 , k2 , k4 , k5 , k8 , and k18f , and potentially
k24 and k28 ) vary as a function of pH or redox potential.
Therefore, order of magnitude estimates for the un-
known rate constants were considered adequate.
The model was solved by using the Runge–Kutta
method of 4th order. The usual pseudo steady state as-
sumption was used concerning the concentrations of
OH, HO2 , and O 2 radicals.
It is fruitful to compare the important Fe(II) regen-
erating intermediates in the present model to those in the
phenol model (Chen and Pignatello, 1997) which origi-
nally emphasized the significance of Fe(III) reduction by
organic intermediates. Notably, R17 was indispensable
to the present model whereas it either showed negligi-
ble effects or rendered the model prediction unaccept-
able depending on the magnitude of its rate constant in
the phenol model. Contrarily, R29 is an important re-
action in the phenol model whereas its inclusion in the
present model completely fails to predict the observed
trends of p-chlorophenol, Fe(II), and H2 O2 changes with
time.
ðClÞDHCD þ ðClÞbenzoquinones
¼ ðClÞsemibenzoquinones ðR29Þ
There were other organic radical reactions which
were used in the phenol model but proved to be un-
necessary in the present model as the presence/absence
of an initial lag period would require different key re-
actions in the two models. Moreover, in contrast to the
present model, the potential Fe(III) reduction by some
ring-opened products was absent in the phenol model.
In the phenol oxidation, the Fe(II) regeneration profile
919
coincided with that of 1,4-benzoquinone and was
ascribed to Fe(III) reduction mainly by 1,2- and 1,4-
benzenediols. The concentration of 1,4-benzoquinone
leveled off once reached a maximum, indicating that OH
radical was not available to further decompose the in-
termediate. The OH radical was not available due to a
limited use of H2 O2 (substrate:H2 O2 ¼ 2 mM:4 mM). In
the present work, however, an increased use of H2 O2
(substrate:H2 O2 ¼ 2 mM:6 mM) resulted in the signifi-
cant decomposition of benzoquinone. Furthermore, the
total Fe level was an order of magnitude higher (0.3 mM
vs. 0.05 mM) in the present work, revealing that the
Fe(II) regeneration lasted over a longer period that
could not be accounted for solely by the early interme-
diates such as benzendiols. Therefore, the phenol model
may be valid only under H2 O2 limiting conditions. It
follows from the comparisons that new key reactions
may have to be added to the phenol model to account
for the decomposition of the early formed intermediates
and the Fe reduction and scavenging which may occur at
a later phase of the reaction.
3.2. Model evaluation
The proposed model was evaluated by testing against
a number of independent phenol and monochlorophenol
data sets obtained at widely different experimental con-
ditions used in the present and other works. Particularly,
the model prediction was evaluated concerning the ef-
fects of varying levels of Fe2þ , H2 O2 , and the phenols.
For predicting the decomposition kinetics of phenols
other than p-chlorophenol, only the value of k16 was
altered to 6:6  109 M1 s1 (Laat and Gallard, 1999),
1:2  1010 M1 s1 (Field et al., 1982), 7:2  109 M1 s1
(Getoff and Solar, 1986), for phenol, o-chlorophenol,
and m-chlorophenol, respectively.
In Fig. 1a, the model prediction is compared to the
observation of important species including p-chloro-
phenol, Fe(II), H2 O2 , 1,4-benzenediol, and benzoqui-
none. The time change in the Fe(II) level is slightly
under-predicted at the later phase while that in the H2 O2
level is perfectly predicted. The under-prediction for
Fe(II) might occur as the measured value denotes the
total Fe(II) while the predicted value is that for Fe2þ .
However, the complete recovery of Fe2þ shown in Fig.
1a is suspect because Fe scavenging was observed to
occur (Kwon et al., 1999) and the Fe2þ data were subject
to measurement interference by a strong color developed
during the reaction. Both the data and the model pre-
diction indicate that the substrate decomposition may be
limited during the Fe2þ sag occurrence after the rapid
initial Fe2þ depletion. Without the intermediates regen-
erating Fe2þ , the decomposition could completely stop.
Therefore, avoiding the Fe2þ limiting conditions may
require control of input timing and the quantity if Fe2þ
is to be directly added. Other means to keep Fe2þ
920 N. Kang et al. / Chemosphere 47 (2002) 915–924

available is to increase the rate of pathways that reduce

ferric ion to ferrous ion. This has been accomplished
electrochemically (Sudoh et al., 1986) and by UV radi-
ation (Sun and Pignatello, 1993; Safarzadeh-Amiri et al.,
1996; Stefan et al., 1996; Voelker and Sulzberger, 1996;
Kim and Vogelpohl, 1998).
For 1,4-benzenediol and benzoquinone, the predic-
tion is in agreement with the observation only quali-
tatively. However, the over-prediction is reasonable as
the
P model prediction represents
P the total quantities
ð ðClÞbenzenediols and ðClÞbenzoquinonesÞ.
The model was tested against for the o-chlorophenol
data from (Dong (1993)). As shown in Fig. 1b, the
model predicts concentrations higher by 20–30% than
the observed ones. Excellent agreement was obtained for
the change in THB concentration with time. However,
(Cl)benzendiols lasted longer than predicted. A primary
removal reaction for (Cl)benzenediols is represented by
R21. The rate constant used in the model, which is for
1,4-benzenediol, is likely to over-estimate the true re-
moval rate for (Cl)benzendiols as the chlorine substitu-
tion retards the decomposition.
For p-chlorophenol, the model closely predicts the
effect of the initial Fe2þ concentration varying two or-
ders of magnitude (from 0.01 to 1.0 mM) at two different
H2 O2 levels (3 and 6 mM). As partly shown in Fig. 2a,
the predicted values are within 10 % deviation from the
observed data. The effect of Fe2þ is also predicted mostly
within 20% deviation for the phenol decomposition as
Fig. 2. Effect of initial Fe2þ level on (a) p-chlorophenol at ini-
observed by Eisenhauer (1964).
tial H2 O2 levels of 3.0 mM and pH ¼ 3:0 and (b) phenol at
When Fe3þ was initially used, a lag time for the Fe3þ
½phenol0 ¼ 0:53 mM, ½H2 O2 0 ¼ 4:79 mM, and pH ¼ 3:0 (data
reduction preceded the decomposition of both p-chloro- from Eisenhauer (1964)).
phenol (present work) and o-chlorophenol (Dong,
1993). As shown in Fig. 3, the model over-predicts the
length of the lag time for both the phenols. The pre- with the observed data of o-chlorophenol (Dong, 1993)
dicted concentration change with time would have better and phenol (Potter and Roth, 1993) decomposition at
agreed with the observed data if the predicted lag period the conditions of continuous feed of H2 O2 (Fig. 5). The
had been shorter. The overestimation may in part be widely different ratios of the substrate to Fe2þ or H2 O2
ascribed to impurities in the phenols used in the experi- are to be noted. Again, the decomposition of the three
ments. It was observed in the present work that H2 O2 phenols can be explained by the single model, which
hardly decomposed in the sole presence of Fe3þ . How- supports anticipation that key reactions are shared by
ever, adding p-chlorophenol to the H2 O2 /Fe3þ mixture these phenols.
accelerated the H2 O2 decomposition, suggesting that the In Fig. 6a, the predicted decomposition profiles show
initial Fe3þ reduction was promoted by the impurities as good agreements with the observed data as the initial
p-chlorophenol itself does not reduce Fe3þ . concentration of p-chlorophenol changes at constant
Fig. 4a shows that the hydrogen peroxide effect is initial H2 O2 and Fe2þ conditions. Fig. 6b shows that the
successfully predicted for the batch decomposition of p- model under-predicts the effect of the initial concentra-
chlorophenol observed in the present and other works tion of the o-chlorophenol on its decomposition in the
(Sims, 1981). As H2 O2 is a costly oxidant, determination semi-batch operation (Dong, 1993). The disparity is
of optimal quantity to use is of concern. It was previ- mostly within 20% of the observed data.
ously observed that approximately two moles of H2 O2
are consumed per mole of p-chlorophenol decomposi- 3.3. Sensitivity analysis and its implication to the mech-
tion (Kwon et al., 1999) under H2 O2 limiting conditions. anism
Fig. 4b shows that the model is also capable of pre-
dicting the H2 O2 demand of p-chlorophenol. Further- Sensitivity analysis was performed by varying the
more, the model prediction is in excellent agreement magnitude of one rate constant of concern while keeping
 N. Kang et al. / Chemosphere 47 (2002) 915–924
Fig. 3. Predicted and observed initial lag periods due to
Fe3þ use for the decomposition of (a) p-chlorophenol at
½p-chlorophenol0 ¼ 2 mM, ½H2 O2 0 ¼ 6 mM, and pH ¼
3:0, and (b) o-chlorophenol at ½o-chlorophenol0 ¼ 1:0 mM,
½H2 O2 0 ¼ 0:67 mM/min, and pH ¼ 3:0 (data from Dong
(1993)).
all others constant to identify the reactions that could
play key roles in the p-chlorophenol decomposition. A
total of 10 reactions (R1, R16, R17, R18, R19f, R22f,
R23, R25, R27, and R28) are shown in Fig. 7 that were
identified as having relatively sensitive effects on the p-
chlorophenol decomposition rate.
The reaction R1 is apparently important as it pro-
duces OH radical, a key chemical species to the de-
composition of p-chlorophenol. It is to be noted that the
other reactions are either those competing directly with
p-chlorophenol for OH radicals (R16, R18, and R25) or
those affecting the Fe2þ level by reducing (R17, R19f,
R22f, R23, and R27) or scavenging Fe3þ (R28). Among
a number of the  OH competing reactions used in the
present model, R18 and R25 appear to exert a stronger
effect on the p-chlorophenol decomposition. In the two
reactions, the OH consuming species are formed prin-
cipally when p-chlorophenol is still present in significant
quantity and their rate constants were assumed higher
than the others. As indicated by their positive slopes, an
increase in the rate of the OH radical competing reac-
921
Fig. 4. (a) Effect of H2 O2 on p-chlorophenol decomposition at
½p-chlorophenol0 ¼ 2 mM, ½Fe2þ 0 ¼ 0:3 mM, and pH ¼ 3:0.
(The data indicated by open triangle (Sims, 1981) are obtained
at ½p-chlorophenol0 ¼ 0:78 mM, ½Fe2þ 0 ¼ 0:179 mM, and
pH ¼ 4:0:) (b) Model prediction and experimental observation
of H2 O2 consumption during the decomposition of p-chloro-
phenol at ½p-chlorophenol0 ¼ 2 mM, ½Fe2þ 0 ¼ 0:3 mM, pH ¼
3:0, and initial H2 O2 levels of 0.5, 1.0, 2, and 3 mM.
tions would decrease the p-chlorophenol decomposition
rate by reducing the OH radical available to p-chlor-
ophenol. The reactions R17, R19f, R22f, R23, and R27
exert their positive effects on the p-chlorophenol de-
composition rate by increasing the Fe2þ level that leads
to enhanced production of OH via R1. Although their
rate constants are small compared to those of other Fe
involving reactions such as R6, R7, R9 and R10, the
reactions appear more influential because the organic
reactant concentrations used in the present work are
high enough to overcome the lower rate constants. In
summary, the key reactions involve those species that
directly affect the levels of OH and/or Fe2þ . It is to be
noted that some of the organic intermediates play con-
trasting roles in the p-chlorophenol decomposition by
922 N. Kang et al. / Chemosphere 47 (2002) 915–924
Fig. 5. Model prediction for the decomposition of o-chloro-
phenol at ½Fe2þ 0 ¼ 1 mM and pH ¼ 3 (data from Dong (1993))
and phenol at ½Fe2þ 0 ¼ 0:4 mM and pH ¼ 3:5 (data from
Eisenhauer (1964)).
Fig. 6. Effects of initial levels of substrate on the decomposition
kinetics (a) p-chlorophenol at ½H2 O2 0 ¼ 6 mM, ½Fe2þ 0 ¼ 0:3
mM, and pH ¼ 3:0 and (b) o-chlorophenol at ½H2 O2 0 ¼ 0:67
mM/min, ½Fe2þ 0 ¼ 1:0 mM, and pH ¼ 3:0 (o-chlorophenol
data from Dong (1993)).
simultaneously consuming OH radicals and regenerating
Fe2þ . Furthermore, while some intermediates accelerate
Fig. 7. Selected reactions and their sensitivities for p-chloro-
phenol decomposition (k: varied rate constant value; k0 : rate
constant value listed in Table 1; [p-CP]k and [p-CP]k0 : p-chloro-
phenol concentration calculated by using k and k0 , respec-
tively).
the p-chlorophenol decomposition by the Fe2þ regener-
ation, others may decrease it by scavenging Fe. There-
fore, the significance of a quantitative and detailed
understanding of these interactions should again be
emphasized for a more complete description of the
mechanisms and kinetics of Fenton processes.
The inorganic reactions from R2 to R15 show little
or no effect on the model outcomes because the con-
centrations of the participating species and/or the rate
constants were significantly low as compared to those
of the reactions to which organic species participate.
However, these reactions were retained in the model as
those may become important depending on the reaction
conditions such as the type and concentration range of
organic substrates and the presence/absence of the or-
ganic intermediates’ effects on the Fe-redox cycle.
4. Conclusion
The prediction by the proposed model is generally
within 20–30% deviation from observed data for phenol
and monochlorophenols as varied by Fe, H2 O2 , and the
phenol concentration conditions. Taking into consider-
ation the fact that the model was initially adjusted to fit
only a single experimental data set of p-chlorophenol
and only order of magnitude estimates were used for the
unknown rate constants, the proposed model appeared
to adequately represent the key mechanism and kinetics
shared by the tested phenols.
The sensitivity analysis indicates that the reactions
directly governing the levels of OH radical and Fe2þ are
key to the overall decomposition kinetics. Both the
model prediction and the experimental results show that
 N. Kang et al. / Chemosphere 47 (2002) 915–924
the decomposition rate could be complicated particu-
larly by the availability of Fe2þ because Fe2þ is critical to
the formation of OH radical. It’s availability varies by a
set of Fe-redox reactions involving a number of organic
radicals and intermediates formed at an early stage of
the Fenton reaction. Besides, iron species might be
permanently scavenged by ring-opened products formed
at a later stage of the reaction. Therefore, in depth un-
derstanding of the interactions between the organic in-
termediates and Fe2þ is critically important to improve
the decomposition performance.
Acknowledgements
Financial support from Seoul National University
(Eng: 81500-50) and the Brain Korea 21 Program (the
Ministry of Education) is gratefully acknowledged.
References
Adams, G.E., Michael, B.D., 1967. Pulse radiolysis of ben-
zoquinone and hydroquinone, semiquinone formation by
water elimination from trihydroxy-cyclohexadienyl radicals.
Trans. Faraday Soc. 63, 1171–1180.
Barbeni, M., Minero, C., Pelizzetti, E., 1987. Chemical degra-
dation of chlorophenols with Fenton’s reagent. Chemo-
sphere 16, 2225–2237.
Bielski, B.H., Cabelli, D.E., Aruda, R.L., Ross, A.B., 1985.
Reactivity of HO2 /O2 radicals in aqueous solution. J. Phys.
Chem. Ref. Data 14, 1041–1077.
Chen, R., Pignatello, J., 1997. Role of quinone intermediates
as electron shuttles in Fenton and photoassisted Fenton
oxidation of aromatic compounds. Environ. Sci. Technol.
31, 2399–2406.
Christensen, H., Sehested, K., Corfitzen, H., 1982. Reactions
of hydroxyl radicals with hydrogen peroxide at ambient
and elevated temperatures. J. Phys. Chem. 86, 1588–
1590.
Dong, C., 1993. Destruction of hazardous organic contami-
nants by advanced oxidation processes. Ph.D. Dissertation,
University of Delaware, Newark, DL.
Eisenberg, G.M., 1943. Colorimetric determination of hydro-
gen peroxide. Ind. Eng. Chem. Anal. 15 (5), 327–328.
Eisenhauer, H.R., 1964. Oxidation of phenolic wastes. Water
Pollut. Control Fed. 36 (9), 1116–1128.
Farhataziz, T., Ross, A.B., 1977. In: Selected specific rates of
reactions of transitients in water and aqueous media III.
Hydroxyl radical and their radical ions. National Standard
Reference Data Service, p. 59.
Field, R.J., Raghavan, N.V., Brummer, J.G., 1982. A pulse-
radiolysis investigation of BrO2 with Fe(CN)4
6 , Mn(II), the
reactions of phenoxide ion, and phenol. J. Phys. Chem. 86
(13), 2443–2449.
Getoff, N., Solar, S., 1986. Radiolysis and pulse-radiolysis of
chlorinated phenols inaqueous-solutions. Radiat. Phys.
Chem. 28 (5/6), 443–450.
923
Jayson, G.G., Keene, J.P., Stirling, D.A., Swallow, A.J., 1969.
Pulse-radiolysis study of some unstable complexes of iron.
Trans. Faraday Soc. 65, 2453–2464.
Kim, S., Vogelpohl, A., 1998. Degradation of organic pollu-
tants by the photo-Fenton-process. Chem. Eng. Technol. 21
(2), 187–191.
Kwon, B.G., Lee, D.S., Kang, N., Yoon, J.Y., 1999. Charac-
teristics of p-chlorophenol oxidation by Fenton’s reagent.
Water Res. 33 (9), 210–218.
Laat, J.D., Gallard, H., 1999. Catalytic decomposition of
hydrogen peroxide by Fe(III) in homogeneous aqueous
solution: mechanism and kinetic modeling. Environ. Sci.
Technol. 33, 2726–2732.
Laat, J.D., Gallard, H., Ancelin, S.W., Legube, B., 1999.
Comparative study of the oxidation of atrazine and acetone
by H2 O2 /UV, Fe(III)/UV, Fe(III)/H2 O2 /UV. Chemosphere
39 (15), 2693–2706.
Martell, A.E., Smith, R.M., 1977. Critical Stability Constants,
Volume 3: Other Organic Ligands. Plenum press, New
York.
Mentasti, E., Pelizzetti, E., Saini, G., 1973. Reactions between
iron(III) and catechol (o-dihydroxybenzene). Part I. Equi-
libria and kinetics of complex formation in aqueous acid
solution, Part II. Equilibria and kinetics of the Redox
reaction in aqueous acid solution. J. Chem. Soc. Dalton
Trans. 3, 2605–2608.
Metelitsa, D.I., 1971. Mechanisms of hydroxylation of aro-
matic compounds. Russ. Chem. Rev. 40 (7), 563–580.
Oturan, M., Pinson, J., 1995. Hydroxylation by electrochem-
ically generated OH radicals––mononhydroxylation and
polyhydroxylation of benzoic acid––prodcuts and isomers
distribution. J. Phys. Chem. 99, 13948–13954.
Pignatello, J., Chen, R., 1997. Iron reactivity in Fenton and
photo-Fenton reaction as influenced by organic species
in solution. The Fourth International Conference on Ad-
vanced Oxidation Technologies for Water and Air Reme-
diation, Abstract, 5–6.
Potter, F.J., Roth, J.A., 1993. Oxidation of chlorinated phenols
using fenton reagent. Hazard Waste Hazard 10 (2), 151–170.
Rothschild, W.G., Allen, A.O., 1958. Studies in Radiolysis of
Ferrous Sulfate Solutions, III. Air-Free Solutions at Higher
pH. Radiat. Res. 8, 101–110.
Rush, J.D., Bielski, B.H., 1985. Pulse radiolytic studies of the
reactions of HO2 /O 2 with Fe(II)/Fe(III) ions. The reactivity
of HO2 /O 2 with ferric ions and its implication on the
occurrence of the Haber–Weiss reaction. J. Phys. Chem. 89,
5062–5066.
Safarzadeh-Amiri, A., Bolton, J.R., Cater, S.R., 1996. The use
of iron in advanced oxidation processes. J. Adv. Oxid.
Technol. 1, 18–26.
Sanchez, L., Peral, J., Domenech, X., 1996. Degradation of 2,4-
dichlorophenoxyacetic acid by in situ photogenerated Fen-
ton reagent. Electrochimica 41, 1981–1985.
Sandell, E.B., 1959. In Colorimetric Determination of Trace
Metals. Interscience, New York.
Scheck, C., Frimmel, F.H., 1995. Degradation of phenol and
salicylic acid by ultraviolet radiation/hydrogen peroxide/
oxygen. Water Res. 29, 2346–2352.
Sedlak, D.L., Andren, A.W., 1991. Oxidation of chloroben-
zene with Fenton’s reagent. Environ. Sci. Technol. 25, 777–
782.
924 N. Kang et al. / Chemosphere 47 (2002) 915–924
Sehested, K., Bjergbakke, E., Rasmussen, O.L., 1969. Reac-
tions of H2 O3 in the pulse-irradiated Fe(II)–O2 system. J.
Chem. Phys. 51, 3159–3166.
Sims, A.F.E., 1981. Phenol oxidation with hydrogen-peroxide.
Effluent and Water Treat. J. 21 (3), 109–112.
Stafford, U., Gray, K.A., Kamat, P.V., 1994. Radiolytic
and TiO2 -assited photocatalytic degradation of 4-chlor-
ophenol––a comparative study. J. Phys. Chem. 98 (25),
6343–6351.
Stefan, M.I., Hoy, A.R., Bolton, J.R., 1996. Kinetics and
mechanism of the degradation and mineralization of
acetone in dilute aqueous solution sensitized by the UV
photolysis of hydrogen peroxide. Environ. Sci. Technol. 30,
2382–2390.
Stuglik, Z., Zagorski, Z.P., 1981. Pulse-radiolysis of neutral
iron(II) solutions––oxidation of ferrous-ions by OH radi-
cals. Radiat. Phys. Chem. 17 (4), 229–233.
Sudoh, M., Kodera, T., Sakai, K., Zhang, J.Q., Koide, K., 1986.
Oxidative degradation of phenol effluent with electrogener-
ated Fenton’s reagent. J. Chem. Eng. Jpn. 19, 513–518.
Sun, Y., Pignatello, J., 1993. Photochemical reactions involved
in the total mineralization of 2,4-D by Fe3þ /H2 O2 /UV.
Environ. Sci. Technol. 27, 304–310.
Tamagaki, S., Suzuki, K., Tagaki, W., 1989a. Aromatic hy-
droxylation with an iron(III)–catechol–H2 O2 system. Mech-
anistic implication of the role of catechol. Bull. Chem. Soc.
Jpn. 62, 148–152.
Tamagaki, S., Sasaki, M., Tagaki, W., 1989b. Fe(III)-catalyzed
aromatic hydroxylation with H2 O2 in the presence of a
variety of electron-transfer agents. Bull. Chem. Soc. Jpn. 62,
153–158.
Voelker, B.M., Sulzberger, B., 1996. Effects of fulvic acid on
Fe(II) oxidation by hydrogen peroxide. Environ. Sci. Tech-
nol. 30, 1106–1114.
Walling, C., El-Taliawi, G.M., 1973. Fenton’ reagent. II. Reac-
tions of carbonyl compounds and a,b-unsaturated acids. J.
Am. Chem. Soc. 95 (3), 844–847.
Walling, C., Goosen, A., 1973. Mechanisms of the ferric ion
catalyzed decomposition of hydrogen peroxide. Effect of
organic substrates. J. Am. Chem. Soc. 95, 2987–2991.
Walling, C., Kato, S., 1971. The oxidation of alcohols by
Fenton’s reagent. The effect of copper ion. J. Am. Chem.
Soc. 93, 4275–4280.
Yoon, J., Lee, Y., Kim, S., 2001. Investigation of the reaction
pathway of OH radicals produced by Fenton oxidation in
the conditions of wastewater treatment. Water Sci. Technol.
44 (5), 15–21.
Yoon, J., Kim, S., Lee, D.S., Huh, J., 2000. Characteristics of p-
chlorophenol degradation by photo Fenton oxidation.
Water Sci. Technol. 42 (3/4), 219–224.
Zuo, Y., Hoigne, J., 1992. Formation of hydrogen peroxide and
depletion of oxalic acid in atmospheric water by photolysis
of iron(III)–oxalato complexes. Environ. Sci. Technol. 25,
1014–1022.