Chemosphere 45 (2001) 85±90

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Kinetic model for phenolic compound oxidation by
Fenton's reagent
Jesus Beltran De Heredia
a

a,*

, Joaquin Torregrosa a, Joaquin R. Dominguez a,
Jose A. Peres b

Departamento de Ingenieria Quimica y Energetica, Universidad de Extremadura, Badajoz 06071, Spain
Departamento de Quimica, Universidade de Tr
as-os-Montes e Alto Douro, Vila Real 5001, Portugal

b

Received 14 June 2000; received in revised form 25 January 2001; accepted 13 February 2001

Abstract
A kinetic model is developed for the oxidation of phenolic compounds by Fenton's reagent. In the ®rst stage a
rigorous kinetic model is applied to calculate the di€erent kinetic rate constants for the oxidation process of p-hydroxybenzoic acid.
In a second phase a competitive method is applied to calculate these kinetic constants for another 10 phenolic
compounds present in agroindustrial and pulp paper wastewaters. These 10 phenolic compounds were: b-resorcylic
acid, 3-(4-hydroxyphenyl)-propionic acid, ferulic acid, protocatechuic acid, ca€eic acid, p-coumaric acid, vanillic acid,
syringic acid, veratric acid and 3,4,5-trimethoxybenzoic acid. Ó 2001 Elsevier Science Ltd. All rights reserved.
Keywords: Fenton's reagent; Kinetics; Phenolic compounds; p-hydroxybenzoic acid; AOPs

1. Introduction
Olive oil extraction and table olive production give
rise to highly contaminant wastewaters. This is a major
environmental problem in Mediterranean countries in
general, and particularly in certain areas of Spain and
Portugal where there are many small plants.
Most of their pollutant properties have been attributed to the phenolic compounds, because of their toxicity (Hamdi, 1992) and inhibitory character (Gonzalez
et al., 1990) to the anaerobic digestion. Likewise, distillation of di€erent wine fractions and pulp paper processing produce wastewaters containing important
amounts of these phenolic compounds.

*

Corresponding author. Tel.: +34-24-289-385; fax: +34-24271-304.
E-mail address: jbelther@unex.es (J. Beltran De Heredia).

As a result of this situation and the more stringent
regulations concerning e‚uents released into rivers and
streams, new technologies have been developed to reduce these refractory contaminants.
For example, Fenton's reagent is a system based on
the generation of very reactive oxidising free radicals,
especially hydroxyl radicals, which have a stronger oxidation potential than ozone, 2.8 V for  OH and 2.07 V
for ozone (Prengle and Mauk, 1978). The Fenton's oxidation process has also been employed successfully to
treat di€erent industrial wastewaters (Lin and Peng,
1995; Lin and Lo, 1997).
In this work a kinetic model is developed for the
oxidation of phenolic compounds by Fenton's reagent.
In the ®rst phase a rigorous kinetic model is developed
and applied to calculate the kinetic rate constant for the
reaction between hydroxyl radicals and p-hydroxybenzoic acid. In a second phase a competitive method is
applied to calculate this kinetic constant for another 10
phenolic compounds, which are very common in a great

0045-6535/01/$ - see front matter Ó 2001 Elsevier Science Ltd. All rights reserved.
PII: S 0 0 4 5 - 6 5 3 5 ( 0 1 ) 0 0 0 5 6 - X

At regular times of reaction. ferulic acid.4. 5. p-hydroxybenzoic acid. protocatechuic acid. 3-(4-hydroxyphenyl)-propionic acid and ferulic acid. ®nally for the group 3. Oxidation of p-hydroxybenzoic acid by Fenton's reagent Analytical grade phenolic acids were obtained from Sigma. Materials and methods 3. using a Waters chromatograph with a 996 photodiode array detector and a Nova-Pak C18 Column.0.2 6. Beltran De Heredia et al.4 and 10.46 12.1. 3.3 and 23.6 min. 3. 1.9 min.1 min.5-trimethoxybenzoic acid. respectively. 5. The ®rst stage was the kinetic study of the degradation of p-hydroxybenzoic acid by Fenton's reagent.3 and 13. wine-distilleries. the kinetic rate constants of the radical reaction between the hydroxyl radical and each one of the phenolic compounds was determined. sampling and measuring the temperature) for the development of the experiments.5:2. Retention times were: for the group 1 of compounds. Finally. b-resorcylic acid. These 10 phenolic compounds were: b-resorcylic acid. 3.38 3. 3-(4-hydroxyphenyl)-propionic acid. syringic acid. syringic acid. pulp paper processing.4. etc. ca€eic acid. vanillic acid. After having carried out this kinetic study and evaluated their kinetic rate constant. 5. Phenolic compounds. p-hydroxybenzoic acid. pcoumaric acid.5 in volume) at a ¯ow rate of 1 ml/ min. protocatechuic acid.8. samples were withdrawn to determine the phenolic acids remaining. veratric acid and 3. 14. Results and discussion variety of industrial wastewaters (olive oil processing industries. 6.4 11. respectively. a similar study was performed to test the degradation of three mixtures of phenolic compounds using a competitive method.4. / Chemosphere 45 (2001) 85±90 The reactor consisted of a 1000 ml glass cylinder provided with the necessary elements (inlets for stirring. veratric acid and 3.43 5. 3 3 4 3 3 3 ‰BŠ0 (mol/l) 1:45  10 7:24  10 3:62  10 1:45  10 7:24  10 3:62  10 3 4 4 3 4 4 …d‰BŠ=dt†0  106 (mol/l s) 6. ca€eic acid and p-coumaric acid. 2. Fig.86 J. respectively. Hydrogen peroxide (33% w/v) and ferrous sulfate heptahydrate were obtained from Merck. Initially. 1). Detection was at 280 nm with a mobile phase composed of a methanol:water:acetic acid mixture (15:82. This reactor was kept at the desired temperature within 0. p-hydroxybenzoic acid.8.05 . These samples were analysed by HPLC. the reactor was loaded with 500 ml in all cases. vanillic acid. 7. 2.3.5-trimethoxybenzoic acid (see Fig. Oxidation experiments of p-hydroxybenzoic acid by Fenton's reagent were carried out by varying the initial Table 1 Degradation experiments of p-hydroxybenzoic acid by Fenton's reagenta Experiment R (mol/mol) ‰H2 O2 Š0 (mol/l) F-1 F-2 F-3 F-4 F-5 F-6 2 2 2 4 4 4 2:90  10 1:45  10 7:24  10 5:80  10 2:90  10 1:45  10 a 2‡ ‰Fe Š0 ˆ 1:45  10 4 mol/l.0. 3.8. and the initial concentration of each phenolic compound was 100 ppm. table olive industries.5°C. for the group 2.).

with a constant value of ‰Fe2‡ Š0 ˆ 1:45  10 4 mol/l. reactions (6) and (7) indicate the possible ways of reaction of Fe3‡ with H2 O2 and new generation of Fe2‡ . was reported by Dorfman and Adams (1973). k1 k3 k1 k3 ‰Fe2‡ Š0 …12† where R is the initial concentration ratio ‰H2 O2 Š0 =‰BŠ0 . therefore its degradation reaction rate can be written as: …5† HO2 87 …6† k1 ‰H2 O2 Š‰Fe2‡ Š : k3 ‰BŠ ‡ k4 ‰H2 O2 Š ‡ k5 ‰Fe2‡ Š d‰BŠ ˆ k2 ‰BŠ‰H2 O2 Š ‡ k3 ‰BŠ‰OH Š: dt …9† …10† Substituting expression (9) in (10).J. Fig. (12). (4) and (5) imply the OH radical. Finally. As it is observed. Reactions (1). Table 1 details the experimental conditions of these experiments. 1975) which react with the organic compound (reaction (3)). On the other hand. Therefore. Buxton et al. It shows a continuous decrease of the phenolic acid concentration by e€ect of the generated radicals. and k5 for the oxidation of Fe2‡ .. it can be considered that k2 ˆ 0. Beltran De Heredia et al. As previous experiments carried out for the oxidation of this phenolic compound with hydrogen peroxide alone revealed that no degradation was obtained. In addition. as well as the rate constant k1 . by generation or consumption. ‰BŠ0 ‰H2 O2 Š0 d‰BŠ dt k2 ‰BŠ‰H2 O2 Š  ˆ 0 k5 k3 ‡ k4 R ‡ ‰BŠ0 . being k5 ˆ 3  108 l/(mol s). The oxidation mechanism of an organic compound by Fenton's reagent is very complex. Experiments F-1. the organic compound is destroyed by reactions (2) and (3). 1988). Evolution of the p-hydroxybenzoic acid concentration in oxidation by Fenton's reagent using a relationship ‰H2 O2 Š0 =‰BŠ0 ˆ 2 mol/mol. 2. (11) is rewritten in the form:  Fig. the concentration of these radicals can be expressed in the form: …3† ‰OH Š ˆ …4† On the other hand. (3). F-2 and F-3. k4 value was provided by Walling (1975). Eq. a plot of the ®rst term versus . there is an increase in the degradation rate ()d[B]/dt) of the phenolic compound when the ‰H2 O2 Š0 is increased. while reactions (4) and (5) show the scavenger e€ect of hydroxyl radicals due to the Fe2‡ ion and the hydrogen peroxide (Walling and Kato. According to this Eq. 1971. we obtain: d‰BŠ ˆ k2 ‰BŠ‰H2 O2 Š ‡ k3 ‰BŠ dt k1 ‰H2 O2 Š‰Fe2‡ Š  : k3 ‰BŠ ‡ k4 ‰H2 O2 Š ‡ k5 ‰Fe2‡ Š …7† …11† This equation includes ®ve rate constants. 2 shows the evolution of the phenolic concentration versus time for the experiments carried out to a value of R ˆ 2. reaction (2) shows the direct action of hydrogen peroxide towards the phenolic compound. / Chemosphere 45 (2001) 85±90 concentrations of hydrogen peroxide and the phenolic compound. their net reaction rate of generation can be expressed as follows: d‰OH Š ˆ k1 ‰H2 O2 Š‰Fe2‡ Š k3 ‰OH Š‰BŠ dt  ‰OH Š k5 ‰OH Š‰Fe2‡ Š: k4 ‰H2 O2 Š …8† …2† Assuming the steady state condition for hydroxyl radicals (d‰OH Š=dt ˆ 0). and thought to occur in the following stages: k1 H2 O2 ‡ Fe2‡ ! Fe3‡ ‡ OH ‡ OH k2 B ‡ H2 O2 ! Box k3 B ‡ OH ! Box k4 H2 O2 ‡ OH ! HO2 ‡ H2 O k5 OH ‡ Fe2‡ ! Fe3‡ ‡ OH Fe 3‡ k6 ‡ H2 O2 ! Fe k7 2‡ ‡ ‡H ‡ …1† Fe3‡ ‡ HO2 ! O2 ‡ Fe2‡ ‡ H‡ Reaction (1) shows the generation of hydroxyl radicals (Walling. As an example. and with hydroperoxyl radicals. and keeping the ratio between both concentrations (R ˆ ‰H2 O2 Š0 =‰BŠ0 ) constant between the values 2 and 4. In order to evaluate the rate constant of the reaction between p-hydroxybenzoic acid and hydroxyl radicals k3 . being k4 ˆ 3  107 l/(mol s).

The slope of this plot can be expressed as follows: Slope ˆ k3 ‡ k4 R : k1 k3 ‰Fe2‡ Š0 …13† In this expression all the parameters are known except the kinetic rate constants k1 and k3 . / Chemosphere 45 (2001) 85±90 ‰BŠ0 must provide a straight line for every series of experiments with the same R value. syringic acid. As can be seen. respectively.8. The initial concentration of catalyst ‰Fe2‡ Š0 was constant in all the experiments. All the parameters required for the ®rst member calculation. Evolution of the concentration of each phenolic compound along the oxidation experiment of the group 1. This method has been previously used by several authors for the degradation of some organic compounds by oxidants like ozone. This determination could be performed under certain speci®c conditions. k1 and k3 . Lastly. The value obtained for k3 was 2:19  109 l/(mol s) at 30°C (the rate constant for the reaction between p-hydroxybenzoic acid and hydroxyl radicals) and the value for k1 . UV radiation or hydroxyl radicals. .88 J. 13. 3. included the values of …d‰BŠ=dt†0 are shown in Table 1. Due to the existence of ana- Fig. veratric acid. the group 3 was composed of: vanillic acid. if the value of this slope is determined for the experiments carried out with R ˆ 2 and R ˆ 4. 4 shows the disappearance curves of the phenolic compounds of the group 1. whose rate constant is known.. In all the experiments a progressive decrease of the di€erent compounds is appreciated with reaction time. Fig. Similar plots were observed in the groups 2 and 3.4. 3. According to the previous mechanism. The group 2 was composed of: protocatechuic acid. 1988. 3.01 l/(mol s). 4.5-trimethoxybenzoic acid and p-hydroxybenzoic acid. This process of oxidation by  OH radicals could be carried out in a system containing a mixture of compounds B and a reference compound R. Oxidation of the phenolic compounds mixtures by Fenton's reagent In this second stage. p-coumaric acid and the reference compound. by means of a competitive kinetic model. The radical reaction constant between the hydroxyl radical and p-hydroxybenzoic acid is into the usual range 108 ±1010 l/(mol s) of these reaction rate constants (Buxton et al. Determination of k3 constant in oxidation experiments of p-hydroxybenzoic acid by Fenton's reagent. lytical interferences among them. Haag and Yao.2. The purpose of this series of experiments was to determine the mentioned rate constant k3 for the reaction between the hydroxyl radicals and each individual phenolic compound. Beltran De Heredia et al. Therefore. ca€eic acid. 3-(4-hydroxyphenyl)-propionic acid. ferulic acid and as reference compound p-hydroxybenzoic acid. the simultaneous decomposition of a mixture of phenolic compounds by Fenton's reagent was carried out at 30°C. for each slope. they were divided in three compound groups. the equation of the reaction between each organic B and the  OH radical can be expressed by the reaction (3): k3 B ‡ OH !Box …3† Assuming a ®rst-order reaction with respect to the radical concentration and the phenolic acid concentration. the values 559. Fig. Carrying out one least-squares regression analysis is obtained.3 and 544. one will have a two equations system with two constants. for R ˆ 4 and R ˆ 2. the reaction rate can be expressed as: Fig. 1992). 3 shows this plot for the experiments carried out for both R values. The group 1 was composed of: b-resorcylic acid. the points lie satisfactorily around straight lines.

kB can be determined for each phenolic compound.567 0. the slopes kB =kR for each compound are deduced.36 0. d‰BŠ ˆ kB ‰BŠ‰OH Š. the rate constants kB for the remaining acids are determined. ln ‰BŠ kR ‰RŠ …17† where kR is now the already deduced rate constant for the reference compound (p-hydroxybenzoic acid) and kB is the rate constant for each one of the remaining phenolic compounds.97 0 0.84 2.80 2.25 0. 5 shows this plot as an example for the group 3 of phenolic compounds.17 0.99 1. The values are exposed in Table 3.32 0.5 3 4 5 10 15 0 0.57 1. As kR is already known (kR ˆ 2:19  109 l/(mol s)). and using the previously known kR . dt …14† where kB is the rate constant of reaction (3) for every compound B.73 2.66 1.754 0.98 0 0.58 0. Beltran De Heredia et al.59 0.16 2.011 3. As can be seen.33 0.76 1.58 0.80 0. Similary to the Eq.23 0.66 2 2.47 0.33 1.155 0.30 1.13 0.00 1.22 Table 3 kB =kR and kB values for each phenolic compound Phenolic compound kB =kR kB  10 9 (l/(mol s)) 3-(4-hydroxyphenyl)-Propionic acid Ferulic acid b-Resorcylic acid Protocatechuic acid Ca€eic acid p-Coumaric acid 3. .991 0. the reference compound presents the following rate equation: d‰RŠ ˆ kR ‰OH Š‰RŠ: dt …15† By dividing both Eqs.172 2.02 1.4.53 3.19 0.06 1.46 1.89 3.08 0. 5.J.47 1.791 1.18 0. Table 2 shows the calculated values of ln…‰BŠ0 =‰BŠ† and ln…‰RŠ0 =‰RŠ† for the group 1.81 1.83 2.21 0.53 1. / Chemosphere 45 (2001) 85±90 89 Table 2 Values of ln…‰BŠ0 =‰BŠ† and ln…‰RŠ0 =‰RŠ† in the oxidation of phenolic mixture 1 by Fenton's reagent ln…‰BŠ0 =‰BŠ† Time (min) ln…‰RŠ0 /[R]) p-Hydroxybenzoic acid b-Resorcylic acid Ferulic acid 3-(4-hydroxyphenyl)-Propionic acid 0 0.75 1 1.34 0.59 1. (14) and (15) it is obtained: d‰BŠ kB ‰BŠ ˆ d‰RŠ kR ‰RŠ and integrating between t ˆ 0 and t ˆ t: …16† ‰BŠ0 kB ‰RŠ0 ˆ .08 0.52 1. Fig.672 0. After regression analysis. Plot of ln…‰BŠ0 =‰BŠ† versus ln…‰RŠ0 =‰RŠ† for the group 3 of phenolic compounds.63 0.88 1.26 0.74 1.19 0.12 0.71 0 0.90 1.17 0. A plot of ln…‰BŠ0 =‰BŠ† versus ln…‰RŠ0 =‰RŠ† yields a straight line.18 1.08 0. (14).307 0.47 0.67 1.821 1.23 1.47 1.12 0.21 ln Fig.26 0.50 0.5-Trimethoxybenzoic acid Vanillic acid Syringic acid Veratric acid 1.45 2. As an example. whose slope is the ratio of rate constants kB =kR .84 2.24 1. the excellent alignment of the points around straight lines con®rms the goodness of the described method.

. The oxidation of alcohols by Fenton's reagent: the e€ect of copper ion. 26. under Project AMB 97-0339 and by the Junta de Extremadura. Biotechnol. Soc.8 7 1. Water Res. Beltran De Heredia et al. C. M.. Radiat.6 ± Haag and Yao (1992). Int. C. Lin. all the rate constants are in an order of 109 l/(mol s) except methoxychlor whose rate constant is 2  1010 l/(mol s). 125±131. Treatment of textile wastewater by Fenton's reagent.. Walling..E. Sci. S. Joaquõn R. 4.90 J. Conclusions A kinetic model is applied for the oxidation of phenolic compounds by Fenton's reagent. Quevedo. L. 1971. J. 89±101. J. Health A 30. Reactivity of the hydroxyl radical in aqueous solutions. 1973. Peng.9 ± 2. Yao. 1992. 1988. K. 773±785.3. C.. Asmus.. D. 1992). 93. Rate constants for the reaction of halogenated organic radicals. Chem..1 4 ± 2. Ref. Chem.W. Schoeneich. G. 1988. Domõnguez Vargas wishes to thank Ministerio de Educaci on y Cultura for the ®nancial support to his Ph.0 5 4 ± ± ± 5...D. 1978. Chem. Ser.2 7 2. / Chemosphere 45 (2001) 85±90 Table 4 Hydroxyl radical rate constants in aqueous solution Compound Pentachlorophenol Diethyl phthalate 1.6 ± 5. A. AIChE Symp. the application of a competitive method allows to calculate this rate constant for an other 10 phenolic compounds. Technol. (1988). W.5 ± ± 20 2. Walling. 1992. ..C. 155±163. S. Studies on antibacterial activity of waste waters from olive oil mills: inhibitory activity of phenolic and fatty acids. 1005±1013. Adams. Lal.. Lin.. Environ. Phys.. hydrogen atoms and hydroxyl radicals …OH =O  † in aqueous solutions. NSRDS-NBS-46.. G. H. Buxton et al. Gonzalez.C. Greenstock. Haag. 1997. 1975.. Prengle. M. S. The application of this model for p-hydroxybenzoic acid leads to the determination of the radical production rate constant (k1 ˆ 13:01 l/(mol s)) and to the rate constant for the reaction between hydroxyl radicals and p-hydroxybenzoic acid (k3 ˆ 2:19  109 l/(mol s)).B.8-Tetrachlorodibenzodioxin Methoxychlor Hexachlorocyclopentadiene Alachlor Atrazine Simazine Carbofuran Lindane Dinoseb a b kHO  10 9 (l/(mol s))a kHO  10 9 (l/(mol s))b 4 4 4 5. Biol.4-Trichlorobenzene m-Dichlorobenzene 2. Helman. J. Lo. Dorfman..6-Pentachlorodiphenyl 2. C. Fenton's reagent revisited.. Grant. Appl.5.P. New technology ozone/UV chemical oxidation wastewater process for metal complexes. After this determination. Mauk. C. Ross. 31. 1995. Washington. Kato. 1990. Moreno. 228±242.. Acknowledgements This research has been supported by the ``Comision Interministerial de Ciencia y Tecnologia'' (CICYT) of Spain. Rate constants for reaction of hydroxyl radicals with several drinking water contaminants.. 54.7. Data 17.9 5. References Buxton. E.3. Toxicity and biodegradability of olive mill wastewaters in batch anaerobic digestion. organic species and desinfection. M. 2050±2056.. Amer. Hamdi.6 2. (1988) or Lal et al. under Project IPR 98A014. Fenton process for treatment of desizing wastewater..2. 74. 37.. As can be seen in Table 4.F. C. Res.H. Environ. 8. J.M.R.C. 423±432.. 4275±4281.3'. These values are concordant with the deduced values for other similar compounds (Haag and Yao. J.H.E. A. Acc..L.D. Sci. Moenig. Critical review of rate constants for reactions of hydrated electrons. Chemosphere 20. 513±886. W. Biochem.. Ramos.. C.D. J.V.