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Received 14 September 2000; received in revised form 20 December 2000; accepted 26 December 2000
Abstract
Hydroxyl radicals are very powerful oxidizing agents. They are involved in hydroxylation reactions, in biological and
atmospheric phenomena. A recent application of these radicals is their use in decontamination of water polluted by toxic organic
substances like pesticides. Chemically, these radicals are produced by the use of a mixture of (H2O2 + Fe2 + ), the so called
Fentons reagent. In this work Fentons reagent is generated by electrochemistry in a catalytic way. The reaction of the hydroxyl
radicals with pentachlorophenol (PCP) was studied. These radicals generated in situ in aqueous solution react with PCP and thus
lead to its degradation. The evolution of the composition of the solution was followed by chromatographic analysis, COD analysis
and the measurement of the total organic carbon (TOC) of the studied aqueous solution. Tetrachloro-o-benzoquinone and
tetrachloro-p-benzoquinone (TCBQ) are the only aromatic intermediates identified. They result from the oxidation of the
corresponding tetrachlorohydroquinones (TCHQ). Just like PCP, the TCBQs are degraded and disappear in their turn. The
mineralization of the initial toxic substrate is confirmed on the one hand, by the regular decrease in quantity of the total organic
carbon of the solution (TOC analysis) and on the other hand, by the quantitative release of chloride ions according to the
electrical charge passed during electrolysis. The degradation of PCP appears relatively slow compared to that of the other organic
pollutants studied by the electro-Fenton process and also to the degradation of other less substituted chlorophenols. The kinetic
rate of the appearance of chloride ions is slower than that in the degradation of PCP. This phenomenon highlights the formation
of chlorated aliphatic intermediates. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Fentons reagent; Hydroxyl radicals; Pentachlorophenol; Ion chromatography; Total organic carbon; Chemical oxygen demand
1. Introduction
Pentachlorophenol (PCP) is a molecule which has a
broad spectrum of pesticidal efficacy.
Since its introduction around 1930, PCP has been
produced and used in large quantities. Its main uses
before being restricted were as a wood preservative but
0022-0728/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved.
PII: S 0 0 2 2 - 0 7 2 8 ( 0 1 ) 0 0 3 6 9 - 2
2. Experimental
2.1. Materials
Pentachlorophenol (PCP), tetrachlorohydroquinone
(TCHQ), tetrachlorobenzoquinone (TCBQ), chemicals
used as standards for chromatographic analyses and all
other products were commercially available (Across,
Aldrich, Prolabo, Sigma, Fluka). They were of the
highest purity and were used as received without further purification. Mohrs salt, (NH4)Fe(SO4)26H2O,
97
98
(1)
O2 + 2H+ + 2e H2O2
Fe
3+
+e
X Fe
2+
E=0.69 V (SHE)
E=0.77 V (SHE)
(2)
(3)
Fentons reaction (Eq. (1)) takes place then in homogeneous medium leading to the formation of hydroxyl
radicals.
The anodic reaction is the oxidation of water to
molecular oxygen (Eq. (4)) which is used for optimal
production of hydrogen peroxide (Eq. (2)) necessary for
Fentons reaction.
2H2O X O2 + 4H+ + 4e
(4)
99
Fig. 3. Chloride ions formation during potential controlled electrolysis for a 0.03 mM PCP solution (125 cm3) as a function of charge
passed.
(7)
100
4. Conclusion
We showed by this work that the electro-Fenton
process, which leads to the total degradation of PCP
with a quantitative release of chloride ions in solution,
can constitute an interesting alternative for the decontamination of wastewater polluted by PCP. The effective mineralization of a molecule such as PCP
consolidates the non selective character of this process.
This result constitutes a new proof of the generalization
of this process with respect to depollution of wastewater. The electrocatalytic in situ generation of Fentons
reagent constitutes, from the ecological and economic
point of view, a significant advantage compared to the
photo-Fenton or chemical Fenton processes.
The PCP concentration in solution after treatment by
the electro-Fenton process is lower than 0.5 ppm which
is the detection limit of our HPLC analysis apparatus.
This value is higher than the limit set by the Environ-
101
Acknowledgements
The authors thank Mr Olivier Bulteau (EDF, Division Recherche et Developpement) for running the
TOC analyses.
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