Chemosphere 47 (2002) 915924 www.elsevier.

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Kinetic modeling of Fenton oxidation of phenol and monochlorophenols

Namgoo Kang a, Dong Soo Lee
a

a,*

, Jeyong Yoon

b,*

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 dierent phenols at widely varying levels of Fe2 , H2 O2 , and the phenols. For the phenols and intermediates, change in concentrations with time was predicted within 2030% 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 Fe2 . Both the model prediction and the experimental results show that the decomposition rate could be complicated particularly by the availability of Fe2 . Understanding the interactions of the organic intermediates with Fe2 is thus of critical importance to improve the decomposition performance. 2002 Elsevier Science Ltd. All rights reserved.
Keywords: Fenton oxidation; Chlorophenols; Mechanism; Intermediates; Kinetic model

1. Introduction Early works on Fenton oxidation were typically limited in their scopes to the investigation of the inuences of process parameters such as chemical oxygen demand, the amount and the ratio of hydrogen peroxide 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: +82-2886-2361. E-mail address: leeds@snu.ac.kr (D.S. Lee).

Ross, 1977; Rush and Bielski, 1985), the mechanisms of 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, kinetic models were proposed that integrated the available 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 rst group are the principal inorganic reactions that represent the interactions among various inorganic species including OH, HO2 , O , H2 O2 , Fe2 , 2 and Fe3 . The second group includes the interactions among organic species (parent compounds and their break-down intermediates and/or products) and the reactive inorganic species except the Fe species. In the

0045-6535/02/$ - see front matter 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

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third group are the reactions among Fe and the organic species that inuence the Fe-redox cycle. The rst group is now considered relatively well established. In the second group, identication of the unstable intermediates is critical but often incomplete. Among the interactions in the third group, of particular concern is the roles of the organic intermediates or nal 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 Fentons reagent appear primarily to depend on the rate between OH and the parent compounds. However, as a signicant portion of initial Fe2 is rapidly consumed, the subsequent decomposition rate is likely to be aected 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 signicantly dierent under similar reaction conditions. Furthermore, H2 O2 appeared to decompose at a similar rate during the decompositions of the dierent 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 Pignatellos (1997) work, the phenol decomposition proles were distinct in that signicant initial lag periods were present, which was possibly ascribed to removing impurities in phenol used in their experiments. Although the true cause of the lag periods was not conrmed, 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 /Fe2 . 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 compound, particular attention was paid to the roles of intermediates 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 eects of p-chlorophenol, hydrogen peroxide, and Fe2 concentrations and their input rate and pattern were experimentally explored on the decomposition kinetics of p-chlorophenol. 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). Briey, 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 Fentons reagent. A pH control system was connected to the reactor to keep pH constant at a predetermined level. Each test typically began with 3.0 or 3.5 l of pchlorophenol solution. The reaction started upon adding Fentons reagent made up of H2 O2 and FeSO4 . Euents were collected at predetermined reaction time through the stopcock drain at the reactors bottom. Potential reactions by OH radical and hydrogen peroxide in the collected euents 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 Fe2 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 lm 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 instrumental analysis, the aqueous sample was acidied by HCl for extraction with an equal volume of diethyl ether. The concentration of 1,4-benzenediols and benzoquinone were determined by using high pressure liquid chromatograph/uorescence detector (Young-Lin M930 System & Waters 474 scanning uorescence detector) with a C18 symmetry column (Waters Co.). The emission wavelength of 290 nm and excitation wavelength 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 benzoquinone 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 spectrophotometric method (Eisenberg, 1943), respectively.

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The concentration of Fe(III) was determined by subtracting the Fe(II) concentration from the total Fe concentration. The total Fe concentration was determined 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 specic to p-chlorophenol decomposition are represented by R16 through R28. In R16, the OH radical addition to the ortho or para position 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 include 4-chloro-1,2-benzenediol, 4-chloro-1,3-benzenediol, and 1,4-benzenediol as identied in the preceding

Table 1 The reactions used in the model of Fenton oxidation of p-chlorophenol Reaction (R1) Fe H2 O2 ! Fe OH OH (R2) Fe3 H2 O2 ! Fe2 H HO2 (R3) OH H2 O2 ! HO2 H2 O (R4) HO2 ! O H 2 (R5) O H ! HO2 2 (R6) OH Fe2 ! Fe3 OH (R7) HO2 Fe2 H ! Fe3 H2 O2 (R8) HO2 Fe3 ! Fe2 H O2 (R9) O Fe2 2H ! Fe3 H2 O2 2 (R10) O Fe3 ! Fe2 O2 2 (R11) OH OH ! H2 O2 (R12) HO2 HO2 ! H2 O2 O2 (R13) OH HO2 ! O2 H2 O (R14) OH O ! O2 OH 2 (R15) HO2 O H ! H2 O2 O2 2 (R16) OH p-chlorophenol ! C1DHCD (R17) ClDHCD Fe3 ! Fe2 C1benzendiols (R18) OH ClDHCD ! THB Cl (R19) Clbenzenediols Fe3 $ Fe2 C1semiquinones
2 3

k (M1 s1 ) 63 0.01 2:7 107 1:58 105 s1 1:0 1010 3:2 108 1:2 106 3:1 105 1:0 107 5 107 4:2 109 8:3 105 1 1010 1 1010 9:7 107 9:3 109 7000a 2 1010 k19f 1 k19r 24b 10a 7 109 k22f 1000b k22r 10:8 7000a 1:2 109 4 1010a $5 108 10c 1.0c

References Metelitsa (1971) Walling and Goosen (1973) Christensen et al. (1982) Bielski et al. (1985) Bielski et al. (1985) Stuglik and Zagorski (1981) Jayson et al. (1969) Rush and Bielski (1985) Rush and Bielski (1985) Rothschild and Allen (1958) Sehested et al. (1969) Bielski et al. (1985) Sehested et al. (1969) Sehested et al. (1969) Bielski et al. (1985) Staord et al. (1994) Metelitsa (1971) Sanchez et al. (1996) Mentasti et al. (1973), Tamagaki et al. (1989a,b) Chen and Pignatello (1997) Mentasti et al. (1973) Staord et al. (1994) Chen and Pignatello (1997) Mentasti et al. (1973) Metelitsa (1971) Adams and Michael (1967) Oturan and Pinson (1995) Scheck and Frimmel (1995) Kwon et al. (1999) Walling and El-Taliawi (1973) Kwon et al. (1999)

(R20) THB Fe3 ! Fe2 HAA (R21) OH Clbenzenediols ! THCD (R22) Clsemiquinones Fe3 $ Fe2 C1benzoquinones (R23) (R24) (R25) (R26) (R27) THCD Fe3 ! Fe2 THB OH Clbenzoquinones ! MA OH THB ! HAA OH MA=HAA ! HAA MA =HAA Fe3 ! Fe2 MA=HAA

(R28) Fe3 aHAA ! FeIII-organic complexes

(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 ( 0:024) was used. c The reaction was suggested to occur but no rate constant was reported.

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work (Kwon et al., 1999) and others (Sedlak and Andren, 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 instance, 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 rst intermediate, chlorodihydroxycyclohexadienyl radical ((Cl)DHCD), may reduce Fe(III) to form the benzendiols (R17) (Barbeni et al., 1987; Potter and Roth, 1993; Chen and Pignatello, 1997), which is analogous to the Fe(III) reduction by monohydroxycyclohexadienyl radical (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) reduction 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 intermediates, the Fe(II) regeneration would stop as the intermediates decompose to form a number of ring-opened products. The ring-opened products found from the Fenton oxidation of p- and o-chlorophenols include valeric acid, propionic acid, propanoic acid, tartaric acid, and glyoxylic acid (Dong, 1993; Kwon et al., 1999). Also, muconic acid and oxalic acid were identied in other studies of phenol oxidation (Scheck and Frimmel, 1995). However, Fig. 1 shows that the Fe(II) regeneration continues even after H2 O2 depletes, indicating some of the ring opened products may contribute to the Fe(II) regeneration. It has been observed that the presence of muconic and propionic acids promote the p-chlorophenol decomposition by a factor of two to three (Kwon et al., 1999), which indirectly supports that these acids or acid radicals may regenerate Fe(II) (Walling and ElTaliawi, 1973). Therefore, it is reasonable to propose the reactions R24 through R27. It was also observed that some of these acids and the unknown organic products scavenged iron and inhibited the p-chlorophenol decomposition rate (Kwon et al., 1999). Oxalic acid and salicylic acid were such examples (Potter and Roth, 1993). Therefore, the reaction R28 was proposed to account for the iron scavenging eect. In R28, a denotes the portion of the produced organic acids that takes part in the Fe scavenging. It is to be noted that each reaction from R16 to R28 except R25 potentially represents a group of parallel reactions rather than a single reaction. For the reactions R1 through R16, and R18, R21, R22r, R24, and R26, all the rate constant values were

Fig. 1. Model prediction as compared to measured data for the time changes of (a) p-chlorophenol, H2 O2 , Fe2 and intermediates (1,4-benzenediol and benzoquinone) at p-CP0 2 mM, H2 O2 0 6 mM, Fe2 0 0:3 mM, and pH 3:0 (b) ochlorophenol and intermediates ((Cl)benzenediols and THB) at H2 O2 0:674 mM/min, Fe2 0 1 mM, and pH 3:0 (data from Dong (1993)).

available from existing literature. The values of the remaining eight unknowns were assumed by adopting from analogous reactions (k17 , k23 , and k25 ) or by tting against a set of observed data (k19f and k19b , k22f , k27 and k28 ) with the considerations given below. An equilibrium calculation indicates that Fe(II) species would predominantly take the form of Fe2 at pH 3 or below. Although Fe-complexes might form in the presence of organic substances, it was assumed in this study that Fe2 was a dominant form among potential Fe(II) species. The values of k17 and k23 were assumed identical and adopted from the analogous reaction of MHCD radical (Metelitsa, 1971). For k25 , the average rate constant value was taken from the analogous reactions of 2,3,4-trihydroxybenzoic acid and 3,4,5-trihydroxybenzoic acid (Oturan and Pinson, 1995). Limited rate data indicated that k19f could have a wide range of values. For 4-chloro-1,2-benzenediol and 1,4-benzenediol, respectively, the values were approximately 400 M1 s1 (Tamagaki et al., 1989a) and 27 M1 s1 (Tamagaki et al., 1989b). Comparatively, the rate constant for 1,2benzenediol was reported as too fast (Tamagaki et al.,

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1989a). In the present model, the value of k19f should be on the order of 101 102 M1 s1 to obtain a reasonable model t to the data. The value of k20 was assumed the same as k19f . The ratio of k19r to k22f was xed 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 inuenced practically the tailing phase of pchlorophenol 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., 0 r28 k28 Fe3 aHAA k28 Fe3 HAA). Given these considerations, the rate constants (k19f , k19b , k22f , k27 , and k28 ) were adjusted such that the model prediction reasonably agreed with a single batch data set concerning the p-chlorophenol decomposition and Fe(II) regeneration at the conditions of p-chlorophenol0 2 mM, H2 O2 0 6 mM, Fe2 0 0:3 mM, and pH 3:0. A more rigorous approach to minimize the prediction errors 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 dened. 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 unknown rate constants were considered adequate. The model was solved by using the RungeKutta method of 4th order. The usual pseudo steady state assumption was used concerning the concentrations of OH, HO2 , and O radicals. 2 It is fruitful to compare the important Fe(II) regenerating intermediates in the present model to those in the phenol model (Chen and Pignatello, 1997) which originally emphasized the signicance of Fe(III) reduction by organic intermediates. Notably, R17 was indispensable to the present model whereas it either showed negligible eects or rendered the model prediction unacceptable depending on the magnitude of its rate constant in the phenol model. Contrarily, R29 is an important reaction 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. ClDHCD Clbenzoquinones Clsemibenzoquinones R29

coincided with that of 1,4-benzoquinone and was ascribed to Fe(III) reduction mainly by 1,2- and 1,4benzenediols. The concentration of 1,4-benzoquinone leveled o once reached a maximum, indicating that OH radical was not available to further decompose the intermediate. The OH radical was not available due to a limited use of H2 O2 (substrate:H2 O2 2 mM:4 mM). In the present work, however, an increased use of H2 O2 (substrate:H2 O2 2 mM:6 mM) resulted in the signicant 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 intermediates 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 dierent experimental conditions used in the present and other works. Particularly, the model prediction was evaluated concerning the effects of varying levels of Fe2 , 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 (Geto 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-chlorophenol, Fe(II), H2 O2 , 1,4-benzenediol, and benzoquinone. 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 Fe2 . However, the complete recovery of Fe2 shown in Fig. 1a is suspect because Fe scavenging was observed to occur (Kwon et al., 1999) and the Fe2 data were subject to measurement interference by a strong color developed during the reaction. Both the data and the model prediction indicate that the substrate decomposition may be limited during the Fe2 sag occurrence after the rapid initial Fe2 depletion. Without the intermediates regenerating Fe2 , the decomposition could completely stop. Therefore, avoiding the Fe2 limiting conditions may require control of input timing and the quantity if Fe2 is to be directly added. Other means to keep Fe2

There were other organic radical reactions which were used in the phenol model but proved to be unnecessary in the present model as the presence/absence of an initial lag period would require dierent key reactions 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 prole

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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 radiation (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 prediction is in agreement with the observation only qualitatively. However, the over-prediction is reasonable as the model prediction represents the total quantities P P Clbenzenediols and Clbenzoquinones. The model was tested against for the o-chlorophenol data from (Dong (1993)). As shown in Fig. 1b, the model predicts concentrations higher by 2030% 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 removal rate for (Cl)benzendiols as the chlorine substitution retards the decomposition. For p-chlorophenol, the model closely predicts the eect of the initial Fe2 concentration varying two orders of magnitude (from 0.01 to 1.0 mM) at two dierent 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 eect of Fe2 is also predicted mostly within 20% deviation for the phenol decomposition as observed by Eisenhauer (1964). When Fe3 was initially used, a lag time for the Fe3 reduction preceded the decomposition of both p-chlorophenol (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 predicted concentration change with time would have better agreed with the observed data if the predicted lag period had been shorter. The overestimation may in part be ascribed to impurities in the phenols used in the experiments. It was observed in the present work that H2 O2 hardly decomposed in the sole presence of Fe3 . However, adding p-chlorophenol to the H2 O2 /Fe3 mixture accelerated the H2 O2 decomposition, suggesting that the initial Fe3 reduction was promoted by the impurities as p-chlorophenol itself does not reduce Fe3 . Fig. 4a shows that the hydrogen peroxide eect is successfully predicted for the batch decomposition of pchlorophenol observed in the present and other works (Sims, 1981). As H2 O2 is a costly oxidant, determination of optimal quantity to use is of concern. It was previously observed that approximately two moles of H2 O2 are consumed per mole of p-chlorophenol decomposition (Kwon et al., 1999) under H2 O2 limiting conditions. Fig. 4b shows that the model is also capable of predicting the H2 O2 demand of p-chlorophenol. Furthermore, the model prediction is in excellent agreement

Fig. 2. Eect of initial Fe2 level on (a) p-chlorophenol at initial H2 O2 levels of 3.0 mM and pH 3:0 and (b) phenol at phenol0 0:53 mM, H2 O2 0 4:79 mM, and pH 3:0 (data from Eisenhauer (1964)).

with the observed data of o-chlorophenol (Dong, 1993) and phenol (Potter and Roth, 1993) decomposition at the conditions of continuous feed of H2 O2 (Fig. 5). The widely dierent ratios of the substrate to Fe2 or H2 O2 are to be noted. Again, the decomposition of the three phenols can be explained by the single model, which supports anticipation that key reactions are shared by these phenols. In Fig. 6a, the predicted decomposition proles show good agreements with the observed data as the initial concentration of p-chlorophenol changes at constant initial H2 O2 and Fe2 conditions. Fig. 6b shows that the model under-predicts the eect of the initial concentration of the o-chlorophenol on its decomposition in the semi-batch operation (Dong, 1993). The disparity is mostly within 20% of the observed data. 3.3. Sensitivity analysis and its implication to the mechanism Sensitivity analysis was performed by varying the magnitude of one rate constant of concern while keeping

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Fig. 3. Predicted and observed initial lag periods due to Fe3 use for the decomposition of (a) p-chlorophenol at p-chlorophenol0 2 mM, H2 O2 0 6 mM, and pH 3:0, and (b) o-chlorophenol at o-chlorophenol0 1:0 mM, H2 O2 0 0:67 mM/min, and pH 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 identied as having relatively sensitive eects on the pchlorophenol decomposition rate. The reaction R1 is apparently important as it produces OH radical, a key chemical species to the decomposition 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 aecting the Fe2 level by reducing (R17, R19f, R22f, R23, and R27) or scavenging Fe3 (R28). Among a number of the OH competing reactions used in the present model, R18 and R25 appear to exert a stronger eect on the p-chlorophenol decomposition. In the two reactions, the OH consuming species are formed principally when p-chlorophenol is still present in signicant 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-

Fig. 4. (a) Eect of H2 O2 on p-chlorophenol decomposition at p-chlorophenol0 2 mM, Fe2 0 0:3 mM, and pH 3:0. (The data indicated by open triangle (Sims, 1981) are obtained at p-chlorophenol0 0:78 mM, Fe2 0 0:179 mM, and pH 4:0:) (b) Model prediction and experimental observation of H2 O2 consumption during the decomposition of p-chlorophenol at p-chlorophenol0 2 mM, Fe2 0 0:3 mM, pH 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-chlorophenol. The reactions R17, R19f, R22f, R23, and R27 exert their positive eects on the p-chlorophenol decomposition rate by increasing the Fe2 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 inuential 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 aect the levels of OH and/or Fe2 . It is to be noted that some of the organic intermediates play contrasting roles in the p-chlorophenol decomposition by

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Fig. 5. Model prediction for the decomposition of o-chlorophenol at Fe2 0 1 mM and pH 3 (data from Dong (1993)) and phenol at Fe2 0 0:4 mM and pH 3:5 (data from Eisenhauer (1964)).

Fig. 7. Selected reactions and their sensitivities for p-chlorophenol decomposition (k: varied rate constant value; k0 : rate constant value listed in Table 1; [p-CP]k and [p-CP]k0 : p-chlorophenol concentration calculated by using k and k0 , respectively).

the p-chlorophenol decomposition by the Fe2 regeneration, others may decrease it by scavenging Fe. Therefore, the signicance 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 eect on the model outcomes because the concentrations of the participating species and/or the rate constants were signicantly 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 organic intermediates eects on the Fe-redox cycle.

4. Conclusion The prediction by the proposed model is generally within 2030% deviation from observed data for phenol and monochlorophenols as varied by Fe, H2 O2 , and the phenol concentration conditions. Taking into consideration the fact that the model was initially adjusted to t 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 Fe2 are key to the overall decomposition kinetics. Both the model prediction and the experimental results show that

Fig. 6. Eects of initial levels of substrate on the decomposition kinetics (a) p-chlorophenol at H2 O2 0 6 mM, Fe2 0 0:3 mM, and pH 3:0 and (b) o-chlorophenol at H2 O2 0 0:67 mM/min, Fe2 0 1:0 mM, and pH 3:0 (o-chlorophenol data from Dong (1993)).

simultaneously consuming OH radicals and regenerating Fe2 . Furthermore, while some intermediates accelerate

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the decomposition rate could be complicated particularly by the availability of Fe2 because Fe2 is critical to the formation of OH radical. Its 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 understanding of the interactions between the organic intermediates and Fe2 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 benzoquinone and hydroquinone, semiquinone formation by water elimination from trihydroxy-cyclohexadienyl radicals. Trans. Faraday Soc. 63, 11711180. Barbeni, M., Minero, C., Pelizzetti, E., 1987. Chemical degradation of chlorophenols with Fentons reagent. Chemosphere 16, 22252237. 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, 10411077. 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, 23992406. Christensen, H., Sehested, K., Cortzen, 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 contaminants by advanced oxidation processes. Ph.D. Dissertation, University of Delaware, Newark, DL. Eisenberg, G.M., 1943. Colorimetric determination of hydrogen peroxide. Ind. Eng. Chem. Anal. 15 (5), 327328. Eisenhauer, H.R., 1964. Oxidation of phenolic wastes. Water Pollut. Control Fed. 36 (9), 11161128. Farhataziz, T., Ross, A.B., 1977. In: Selected specic 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 pulseradiolysis investigation of BrO2 with Fe(CN)4 , Mn(II), the 6 reactions of phenoxide ion, and phenol. J. Phys. Chem. 86 (13), 24432449. Geto, N., Solar, S., 1986. Radiolysis and pulse-radiolysis of chlorinated phenols inaqueous-solutions. Radiat. Phys. Chem. 28 (5/6), 443450.

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, 24532464. Kim, S., Vogelpohl, A., 1998. Degradation of organic pollutants by the photo-Fenton-process. Chem. Eng. Technol. 21 (2), 187191. Kwon, B.G., Lee, D.S., Kang, N., Yoon, J.Y., 1999. Characteristics of p-chlorophenol oxidation by Fentons reagent. Water Res. 33 (9), 210218. 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, 27262732. 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), 26932706. 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. Equilibria 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, 26052608. Metelitsa, D.I., 1971. Mechanisms of hydroxylation of aromatic compounds. Russ. Chem. Rev. 40 (7), 563580. Oturan, M., Pinson, J., 1995. Hydroxylation by electrochemically generated OH radicalsmononhydroxylation and polyhydroxylation of benzoic acidprodcuts and isomers distribution. J. Phys. Chem. 99, 1394813954. Pignatello, J., Chen, R., 1997. Iron reactivity in Fenton and photo-Fenton reaction as inuenced by organic species in solution. The Fourth International Conference on Advanced Oxidation Technologies for Water and Air Remediation, Abstract, 56. Potter, F.J., Roth, J.A., 1993. Oxidation of chlorinated phenols using fenton reagent. Hazard Waste Hazard 10 (2), 151170. Rothschild, W.G., Allen, A.O., 1958. Studies in Radiolysis of Ferrous Sulfate Solutions, III. Air-Free Solutions at Higher pH. Radiat. Res. 8, 101110. Rush, J.D., Bielski, B.H., 1985. Pulse radiolytic studies of the reactions of HO2 /O with Fe(II)/Fe(III) ions. The reactivity 2 of HO2 /O with ferric ions and its implication on the 2 occurrence of the HaberWeiss reaction. J. Phys. Chem. 89, 50625066. Safarzadeh-Amiri, A., Bolton, J.R., Cater, S.R., 1996. The use of iron in advanced oxidation processes. J. Adv. Oxid. Technol. 1, 1826. Sanchez, L., Peral, J., Domenech, X., 1996. Degradation of 2,4dichlorophenoxyacetic acid by in situ photogenerated Fenton reagent. Electrochimica 41, 19811985. 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, 23462352. Sedlak, D.L., Andren, A.W., 1991. Oxidation of chlorobenzene with Fentons reagent. Environ. Sci. Technol. 25, 777 782.

924

N. Kang et al. / Chemosphere 47 (2002) 915924 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, 153158. Voelker, B.M., Sulzberger, B., 1996. Eects of fulvic acid on Fe(II) oxidation by hydrogen peroxide. Environ. Sci. Technol. 30, 11061114. Walling, C., El-Taliawi, G.M., 1973. Fenton reagent. II. Reactions of carbonyl compounds and a,b-unsaturated acids. J. Am. Chem. Soc. 95 (3), 844847. Walling, C., Goosen, A., 1973. Mechanisms of the ferric ion catalyzed decomposition of hydrogen peroxide. Eect of organic substrates. J. Am. Chem. Soc. 95, 29872991. Walling, C., Kato, S., 1971. The oxidation of alcohols by Fentons reagent. The eect of copper ion. J. Am. Chem. Soc. 93, 42754280. 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), 1521. Yoon, J., Kim, S., Lee, D.S., Huh, J., 2000. Characteristics of pchlorophenol degradation by photo Fenton oxidation. Water Sci. Technol. 42 (3/4), 219224. 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, 10141022.

Sehested, K., Bjergbakke, E., Rasmussen, O.L., 1969. Reactions of H2 O3 in the pulse-irradiated Fe(II)O2 system. J. Chem. Phys. 51, 31593166. Sims, A.F.E., 1981. Phenol oxidation with hydrogen-peroxide. Euent and Water Treat. J. 21 (3), 109112. Staord, U., Gray, K.A., Kamat, P.V., 1994. Radiolytic and TiO2 -assited photocatalytic degradation of 4-chlorophenola comparative study. J. Phys. Chem. 98 (25), 63436351. 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, 23822390. Stuglik, Z., Zagorski, Z.P., 1981. Pulse-radiolysis of neutral iron(II) solutionsoxidation of ferrous-ions by OH radicals. Radiat. Phys. Chem. 17 (4), 229233. Sudoh, M., Kodera, T., Sakai, K., Zhang, J.Q., Koide, K., 1986. Oxidative degradation of phenol euent with electrogenerated Fentons reagent. J. Chem. Eng. Jpn. 19, 513518. Sun, Y., Pignatello, J., 1993. Photochemical reactions involved in the total mineralization of 2,4-D by Fe3 /H2 O2 /UV. Environ. Sci. Technol. 27, 304310. Tamagaki, S., Suzuki, K., Tagaki, W., 1989a. Aromatic hydroxylation with an iron(III)catecholH2 O2 system. Mechanistic implication of the role of catechol. Bull. Chem. Soc. Jpn. 62, 148152.