In-situ study for the reaction pathway of aqueous phenol degradation

by pulsed-corona discharges
D. Hayashi§, W.F.L.M. Hoeben¶, E.M. van Veldhuizen,
W.R. Rutgers and G.M.W. Kroesen

Technische Universiteit Eindhoven, P O Box 5600 513, 5600MB Eindhoven, The Netherlands
§
Present address: Philips Forscungslaboratorien Aachen, Weisshausstrasse 2 Aachen, Germany
¶
Present address: Philips Lighting, Mathildelaan 1, P.O. box 80020, 5600 JM Eindhoven, The Netherlands

The degradation processes of aqueous phenol and its reaction products by a pulsed corona
discharge treatment under atmospheric air are experimentally studied by means of laser
fluorescence spectroscopy. During the pulsed corona treatments, phenol (C6H5OH) is converted
first to di-.hydrobenzenes (C6H4-(OH)2). Two unidentified molecules are observed as the final
products, of which the molecules appear also as the final degradation products of aqueous C6H4-
(OH)2, C6H4-O2 and C6H3-(OH)3. They are most likely the byproducts of benzene ring cleavages.

1. Introduction triggered by a spark-gap switch. The maximum of

The removal of hazardous organic pollutants
from wastewater is currently a growing issue in
environmental science and technology. Recently,
pulsed-corona discharges over/in water have been
intensively studied for the degradation of phenol (an
important precursor in chemical synthesis of
thermosetting resins, dyes and medicines) in aqueous
solutions.1-7
The pulsed-corona discharges give rise to the
formation of strong oxidative products such as OH
radicals, oxygen atoms and ozone. These molecules
dissolve into the water and degrade phenol via
oxidation processes. Hence, phenol degradation is
strongly non-equilibrium diffusion-chemical reaction
system over both the gas and liquid phases. We have
recently adopted laser-induced fluorescence (LIF)
spectroscopy for in-situ diagnostics of phenol
degradation in an aqueous solution exposed by
pulsed-corona discharges above an aqueous
solution.8,9 It enables the in-situ studies of the
reaction chemistry of phenol and the intermediate
reaction products during the degradation processes.
In this paper, we experimentally elucidate the
reaction pathway of the phenol degradation in
aqueous solutions treated by pulsed-corona
discharges in an atmospheric air by means of LIF
spectroscopy.
2. Experiments
The experimental setup has been detailed in
earlier articles.8,9 A point-to-plain, pulsed-corona
discharge was generated in an atmospheric air above
a 300 ml-solution with the repetition rate of 10 Hz. A
positive voltage of 25 kV was applied to an anode at
1 cm from the surface of the solution for
approximately several tens ns. The discharge is
the corona current is about 10 A. The ultraviolet
laser radiation for exciting phenol and
hydroxybenzenes are obtained by the fourth
harmonic generation of a Nd-YAG laser. The laser-
induced fluorescence normal to the laser beam is
observed by a spectrometer with a 150-grooves/mm
grating and an array of multi-channel photocathode
plates combined with an ICCD. We prepared the
solutions of phenol (C6H5-OH), three isomers of di-
hydroxybenzenes (C6H5-(OH)2), 1,4-benzoquinone
(C6H4-O2) and three isomers of tri-hydroxybenzenes
(C6H5-(OH)3). The concentration of the solutions
was fixed at 1.0 x 10-1 mol/cm3.
3. Results
The LIF emission was measured in a phenol
solution exposed by pulsed-corona discharges. Fig. 1
shows the temporal variations of the concentrations
of phenol and the intermediate reaction products,
C6H4-(OH)2, during the degradation. The spectra of
the resction products were identical to that of
resorcinol (1,3-di-hydroxybenzene). The phenol
degradation exhibited fast and slow decay structures.
The change in the decay time constants of phenol
concentration coincided with the concentration of di-
hydroxybenzenes reaching the peak. After the
initiation of the discharges, phenol is hydroxylated
by the substitution by OH and di-hydroxybenzenes
are formed. Due to the increase in the concentration
of di-hydroxybenzenes, OH radicals are consumed
not only by the hydroxylation of phenol but also
secondary hydroxylation of di-hydroxybenzenes.
Then, the decay rate in the phenol concentration
decreases. Thus, the decay time constant in the first
20 minutes corresponds to that of phenol degradation
alone by pulsed-corona discharges.
 The degradation processes of pure solutions of
the expected intermediate products C6H4-(OH)2, phenol
C6H3-(OH)3, and their relates are investigated by 180 min.
LIF. We tabulate in table 1 the intermediate, and 0.1 mol. Y
final products of the corona-discharge degradation of mol. X

LIF signal (Arb. Units)

phenol, and C6H5-(OH)3. As a final product of all
except phenol, we observe an unidentified molecule
X.
Fig.2 shows the spectrum from the phenol
solution at 180 minutes in the final phase of the
degradation. The broken line is the contour of the
spectrum. The spectrum is not identical to any and
other hydroxybenzenes and benzoquinone. It can be
attributed to the superposition of the spectra of 0.0
300 350 400 450 500
molecules X and Y, which are shown as lines. Wavelength (nm)
Hence, in the final phase, the degradation products of
phenol are credibly molecule X and Y, which are Fig. 2 the spectrum from the phenol solution at 180
both observed in the degraded solutions of minutes in the final phase of the degradation.
resorcinol, catechol, benzoquinone and tri-
hydroxybenzenes. They are most likely the
byproducts of benzene ring cleavages. References
0 50 100 [1] P. Sunka, V. Babicky, M. Clupek, P. Lukes, M.
0.1
phenol
0.1 Simek, J. Schmidt and M. Cernak, Plasma Sources
hydroxybenzenes Sci. Technol. 8 (1999) 258.
Concentration (m mol/l)

total
[2] A. K. Sharma, B. R. Locke, P. Arce and W. C.
Finney, Hazard. Waste Hazard. Mater. 10 (1993)
209.
[3] A. A: Joshi, B. R. Locke, P. Arce and W. C:
Finney, Hazard. Waste Hazard. Mater. 41 (1993)
0.01 0.01
3.
[4] J. S: Clements, M. Sato and R. H. Davis, IEEE
Trans. Ind. Appl. IA-23 (1987) 224.
[5] M. Sato, T. Ohgiyama and J. S. Clements, IEEE
0 50 100 Trans. Ind. Appl. 32 (1996) 106.
Fig. 1 the temporal Time (min.)
variations of the
concentrations of [6] W. F. L. M. Hoeben, E. M. van Veldhuizen, W. R.
phenol and the intermediate reaction products, C6H4- Rutgers, and G. M. W: Kroesen, J. Phys. D 32,
(OH)2, during the degradation. (1999) L133.
[7] W. F. L. M. Hoeben, E. M. van Veldhuizen, W. R.
Rutgers, C. A. M. G. Cramer and G. M. W.
Kroesen, Plasma Sources Sci. Technol. 9 (2000) 1.
[8] D. Hayashi, W. F. L. M. Hoeben, G. Dooms, E. M.
van Veldhuizen, W. R. Rutgers and G. M. W.
Kroesen, J. Phys. D 33 (2000) 1484.
[9] D. Hayashi, W. F. L. M. Hoeben, G. Dooms, E. M.
van Veldhuizen, W. R. Rutgers and G. M. W.
Kroesen, Appl. Opt. 40 (2001) 986.

molecules Inter. product Final products

Phenol Resorcinol, di-hydroxybenzenes Molecules X, Y
Catechol (1,2-C6H4-OH2) Molecule Y Molecule X
Resorcinol (1,3-C6H4-OH2) ® Molecule X
Hydroquinone (1,4-C6H4-OH2) ® ?
Benzoquinone (C6H4-O2) ® Molecule X
Pyrogallol (1,2,3-C6H3-OH3) ® Molecule X
Benzenetriol (1,2,4-C6H3-OH3) ® Molecule X
Phloroglucinol (1,3,5-C6H3-OH3) ® Molecule X

Table. 1 The intermediate and final products of the corona degradation of phenol, and intermediate products.