IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 39, NO.

4, APRIL 2011 1099

Plasma Degradation of Acid Orange 7 With

Contact Glow Discharge Electrolysis
Xinglong Jin, Hang Bai, Fan Wang, Xiucheng Wang, Xiaoyan Wang, and Hongxia Ren

Abstract—This paper focused on how different parameters af- TABLE I

fect plasma degradation of Acid Orange 7 (AO) with contact VARIABLES AND T HEIR VALUES C ORRESPONDING
TO T HEIR L EVELS IN THE E XPERIMENTS
glow discharge electrolysis (CGDE). These varied parameters
were temperature, applied voltage, discharge time, initial pH of
solution, initial dye concentration, and electrolyte concentration.
It could be concluded from orthogonal design that applied voltage
and discharge time had major effect on the degradation of AO. Un-
der the optimized condition, the reproducibility of the experiment
and the catalytic effect of ferric and ferrous ions were also studied.
The degradation rate of AO in CGDE was stable and over 95%
in reduplicative experiment. Ferric and ferrous ions had apparent
catalytic effect on the degradation of AO. In particular, they could
greatly reduce the degradation time. In addition, the ferrous ions
showed the better catalytic effect than the ferric ions.
Index Terms—Acid Orange 7 (AO), contact glow discharge
electrolysis (CGDE), plasma degradation. Although we have investigated the degradation of several
dyes with CGDE [10], [11], there still exists much doubt to
I. I NTRODUCTION further study. For example, we have studied the effects of
applied voltage initial concentration on the reaction rate in the

W ITH the development of printing and dyeing industry,

more and more dyeing wastewater is discharged into
the environment, which is threatening human health. In ad-
dition, dyes are changing to antiphotolysis, antioxidation and
antibiodegradation [1]. Therefore, much attention has been paid
to dye wastewater treatment.
In recent years, advanced oxidation processes (AOPs), which
are based on the production of hydroxyl radicals, have been
effectively applied for dye removal [2]. Contact glow discharge
electrolysis (CGDE) is an unconventional process in AOPs,
where the glow discharge takes place in close proximity to the
water surface, and plasma is sustained between the anode and
electrolytic surfaces. Using a thin platinum anode in contact
with an electrolyte solution, normal electrolysis spontaneously
develops to CGDE if the applied voltage is sufficiently high
[3], [4]. During CGDE, many active species such as ·OH, H·,
O·, H2 O2 are produced with yields much higher than those in
conventional electrolysis [5], [6]. Furthermore, these species,
particularly hydroxyl radicals (·OH), are particularly reactive
to organic pollutants in water. Many organic pollutants could
be mineralized with CGDE [7]–[9].
Manuscript received October 7, 2010; revised December 9, 2010; accepted
January 12, 2011. Date of publication March 2, 2011; date of current version
April 13, 2011. This work was supported by the National Nature Science
Foundation of China under Contract 20807030.
X. Jin, H. Bai, F. Wang, X. Wang, and X. Wang are with the School of Envi-
ronmental Science and Safety Engineering, Tianjin University of Technology,
Tianjin 300384, China (e-mail: xljin7911@126.com).
H. Ren is with the College of Chemistry, Nankai University, Tianjin 300071,
China (e-mail: csxh3605@nankai.edu.cn).
Color versions of one or more of the figures in this paper are available online
at http://ieeexplore.ieee.org.
Digital Object Identifier 10.1109/TPS.2011.2109402
CGDE of acridine orange. However, it is still not clear which
condition is the major factor that influences the degradation of
the dye in CGDE. In this paper, we choose Acid Orange 7 (AO)
as the target substrate to examine how varied parameters affect
the plasma degradation.
II. E XPERIMENTAL
The apparatus was similar to our previous paper [12]. The
anode was a platinum wire (0.3 mm) held in the brass support
sealed into a glass tube. The cathode was a stainless steel stick
placed in another glass tube, which was covered at the bottom
by a sinter glass disk of medium porosity. AO was dissolved in
different mediums from which dissolved oxygen was removed.
The platinum wire was immersed into the solution to a depth
of approximately 1.0 mm. In addition, the reaction cell was
placed in a temperature-controlled water bath. In the course of
the reaction, the solution was gently stirred with a magnet bar.
A Cary 50 ultraviolet–visible (UV-vis) spectrometer (Varian,
America) was used to determine the concentration of AO and
its absorption spectra in the process of CGDE.
The degradation rate was calculated based on the following
equation:
Degradation rate = (C0 − Ct )/C0
where C0 stands for the initial concentration of AO; Ct denotes
the concentration of AO in the degraded solution at a different
time.
In order to optimize the treatment process, the effects of
the varied parameters on AO degradation was investigated by
means of an orthogonal design known as a the mathematical

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1100 IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 39, NO. 4, APRIL 2011

TABLE II
E XPERIMENTAL R ESULTS OF THE S TANDARD L25 (56 ) ORTHOGONAL A RRAY

method. The investigated variables and their levels were given

in Table I. The variables chosen for this investigation were
discharge time, initial pH of the solution, initial AO concen-
tration, concentration of sodium sulfate, applied voltage, and
temperature. The experimental design was conducted to change
the settings of the various process parameters.

III. R ESULTS AND D ISCUSSION

A. Optimized Condition
The experimental results, based on standard L25 (56 ) or-
thogonal array, were shown in Table II. The order of
influence, from strong to weak, of the six variables on the degra-
dation rate was E > A > F > B > C > D (54.02 > 52.60 >
29.14 > 21.51 > 20.05 > 13.21), which demonstrated that the
discharge time and applied voltage played important roles Fig. 1. Reproducibility of experiment at optimized condition.
among the aforementioned six variables in the degrada-
tion of AO. ditions that we adopted were not the extreme conditions. Some
According to the aforementioned results, the optimum con- condition parameters were adopted for cost and convenience.
ditions that we chose were as follows: 1) 515-V applied For example, higher applied voltage and higher concentration
voltage; 2) 90-min discharge time; 3) 303-K temperature; electrolyte were beneficial for efficient dye removal. However,
4) initial pH = 3.0; 5) 25.0 mg/L initial AO concentration; and increasing the applied voltage and conductivity also provided
6) 2.0 g/L Na2 SO4 . It was worth noticing that the optimum con- excess energy to melt the anode. Therefore, in this experiment,
JIN et al.: PLASMA DEGRADATION OF ACID ORANGE 7 1101

Fig. 2. UV-vis spectra of AO during CGDE.

we chose 515 V and 2.0 g/L Na2 SO4 as the optimum parame-
ters. For temperature and discharge time, lower temperature and
increasing discharge time benefit for higher removal efficiency.
However, considering the cost, 303 K and 90 min were the
best choice. For the initial pH value, it was just a temporary
value because the pH rapidly decreased when glow discharge
started due to the formation of organic acids. Therefore, the
initial pH value of the solution was chosen as 3.0. The lower
concentration of AO could be efficiently degraded. However,
the concentration of the dye wastewater was usually higher. The
degradation rate was over 95.0% when the initial concentration
of AO was 25.0 mg/L when other optimized variables were
employed. Therefore, 25.0 mg/L was chosen for the initial
concentration of AO.
The reproducibility of the experiment under optimum condi-
tions was also investigated. The results were shown in Fig. 1.
Obviously, the degradation rates of four reduplicate experi- Fig. 3. pH and conductivity changes of the solution during CGDE.
ments were over 95.0%. It could be concluded that the re-
producibility of the experiment under the optimum conditions C. Catalytic effect of Iron Ions
was well. It has been demonstrated that H2 O2 formed during anodic
discharge region [5], [6]. Therefore, the addition of iron salts
B. Absorption Spectra could enhance the dye removal through the Fenton’s reaction
[13]. In this experiment, the effect of ferrous ions was studied,
Under the optimum condition, we investigated the UV ab- and the results were shown in Fig. 4. The degradation of
sorption spectra of the AO samples that were demonstrated in AO was most efficient, and the degradation rate was more
Fig. 2. Before the degradation reaction, the initial absorption than 95.2% after 5 min when the concentration of Fe2+ was
curve had absorption between 350–550 nm and its maximum 10.0 mg/L. This was because the additional hydroxyl radicals
absorption at 485 nm. At 310 nm, there was a weak peak. were produced through the following reaction:
The absorbance at these two wavelengths decreased with the
discharge time. After 120 min, it became much weaker. It can H2 O2 + Fe2+ → Fe3+ + ·OH + OH− .
be inferred that the chromophore had been damaged in CGDE.
Meanwhile, the curve had very strong absorption at 200– Fe2+ could capture H2 O2 and produce powerful oxidizing
240 nm. It is clearly shown in Fig. 2 that the absorbance at agents ·OH. The concentration of the hydroxyl radical was
225 nm increased with the discharge time. It could be concluded enough to oxidize a reactant in a short time. However, when
that the cleavage of the conjugate system of AO led to the for- the concentration of Fe2+ was over 10.0 mg/L, the difference
mation of some carboxylic acids. In other words, AO underwent in degradation rates was not obvious. That is perhaps because
oxidative degradation in CGDE. of the following reaction:
The changes of pH and conductivity during the CGDE treat- ·OH + Fe2+ → Fe3+ + OH− .
ment were shown in Fig. 3. It can be observed in Fig. 3 that
the pH of the solution rapidly dropped, and the conductivity Excess Fe2+ consumed the hydroxyl radical instead. There-
accordingly increased. It also indicated that some of the organic fore, the amount of Fe2+ could not be excessively added.
acids were produced, which was consistent with that shown in The UV-vis spectra (see Fig. 5) also showed the efficient
UV-vis spectra. degradation. The absorbance at 485 nm abruptly decreased to
1102
Fig. 4. Effect of ferrous ion on the degradation rate of AO.
Fig. 5. UV-vis spectra of the AO solution in the presence of the Fe2+ .
Fig. 6. Effect of Fe3+ on degradation rate.
a stable value in 10 min. However, it was worthy to notice
that absorption at 305 nm, 230 nm dropped first and then
increased to a stable value, which was different from that
without Fe2+ . Perhaps it was because the cleavage of AO led
to small molecule substance.
The ferric ion also showed apparent catalytic effect on the
degradation rate of AO (see Fig. 6). When the concentration of
Fe3+ was 20.0 mg/L, the degradation rate was more than 96.0%
after the 5-min CGDE treatment. The following reaction may
explain the aforementioned phenomenon:
Fe3+ + H2 O2 → Fe2+ + HO2 · +H+ .
IEEE TRANSACTIONS ON PLASMA SCIENCE, VOL. 39, NO. 4, APRIL 2011
However, when the concentration of Fe3+ was 40.0 mg/L, the
effect was similar to that of 20.0 mg/L. Therefore, 20.0 mg/L
was the best addition.
IV. C ONCLUSION
In this paper, the impact of several electrolyte parameters
(pH, temperature, applied voltage, discharge time, initial AO
concentration, and electrolyte concentration) on plasma degra-
dation of AO with CGDE has been experimentally investigated.
It could be concluded that the applied voltage and the discharge
time had a major effect on the degradation of AO. According
JIN et al.: PLASMA DEGRADATION OF ACID ORANGE 7
to orthogonal design, the optimum conditions that we chose
were as follows: 1) 515-V applied voltage; 2) 90-min discharge
time; 3) 303-K temperature; 4) initial pH = 3.0; 5) 25.0 mg/L
initial AO concentration; and 6) 2.0 g/L Na2 SO4 . Under these
optimized conditions, the degradation rates in reduplicate ex-
periments were over 95.0%. In addition, ferrous and ferric ions
were added under optimum conditions. It could be concluded
that ferrous ion had better catalytic effect than ferric ion on the
degradation of AO, which demonstrated that ferrous ion was
applicable for CGDE water treatment in practice.
ACKNOWLEDGMENT
The authors would like to thank the National Innovation
Experiment Program for University Students of China in 2009.
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Author photographs and biographies not available at the time of publication.