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CCL4 DECOMPOSITION BY GLIDING ARC PLASMA:
ROLE OF C2 COMPOUNDS ON PRODUCTS
DISTRIBUTION
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 Chem. Eng. Comm., 194:1111–1125, 2007
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ISSN: 0098-6445 print/1563-5201 online
DOI: 10.1080/00986440701293363
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CCl4 Decomposition by Gliding Arc Plasma:

Role of C2 Compounds on Products Distribution

ANTONIUS INDARTO1, DAE RYOOK YANG2,

JAE-WOOK CHOI1, HWAUNG LEE1,
AND HYUNG KEUN SONG1
1
Plasma-Catalyst Chemical Process, Korea Institute of Science and
Technology, Seoul, Korea
2
Department of Chemical and Biological Engineering, Korea University,
Seoul, Korea

The goal of this work is to investigate the role of existing C2 compounds in the
plasma reactions of carbon tetrachloride (CCl4) decomposition. The experiment
of CCl4 decomposition was carried out by gliding arc plasma. The decomposition
products were dominated by CO, CO2, and Cl2. The conversion of CCl4 into Cl2
and (CO þ CO2) reaches
50% and
40%, respectively. Other chlorinated com-
pounds were suspected to be produced, such as COCl, COCl2, and C2 compounds. In
order to prove the existence of those compounds, for example, chlorinated C2 com-
pounds, a kinetic simulation was performed and cross-checked with the experimental
results to clarify the reactions mechanism.

Keywords CCl4 decomposition; Gliding arc; Plasma; Reaction mechanism

Introduction
Emissions from various industries of chlorinated volatile organic compounds
(CVOCs), such as carbon tetrachloride (CCl4), create environmental problems
(Butler, 2000; WMO, 2002). Chemical degradation of CVOCs in our atmosphere will
produce another toxic chloride compound, HCl, which is classified as the main
component of acid rain (Sanhueza, 2001). Some studies report that CCl4 will pro-
duce very active chlorine radicals by solar radiation reactions. These species will
react and destroy ozone molecules in the stratosphere (Butler, 2000; U.S. EPA,
2002). Moreover, the most severe problem of the emission of CCl4 is due to its toxic
and carcinogenic damage to human health (IARC, 1987). Thus there are reasons to
find effective methods to reduce the emission of CVOCs.
The most widely adopted technique for the treatment of CVOCs is thermal com-
bustion or incineration (Cheremisinoff, 2000). The decomposition process is done by
direct thermal reaction with oxidant, e.g., air and oxygen. Although this method is
simple, it requires high burning temperature (between 800 and 1,100C) to achieve
the optimum decomposition rate. Taylor and Dellinger reported that incomplete

Address correspondence to Antonius Indarto, Plasma-Catalyst Chemical Process, Korea

Institute of Science and Technology, P.O. Box 131, Cheongryang, Seoul 130–650, Korea.
E-mail: indarto_antonius@yahoo.com

1111
 1112 A. Indarto et al.

combustion conditions could produce a large amount of complex chlorinated

products (Taylor and Dellinger, 1988).
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To overcome these problems, many studies were carried out on the application
of new technologies. Plasma-assisted technology is one of the promising ways to
decompose CVOCs. Low thermal plasma processes, such as RF plasma (Lee et al.,
1996), surface discharge reactor (Oda et al., 2002), dielectric barrier discharge reactor
(Tonkyn et al., 1996), pulsed discharge reactor (Yamamoto et al., 1992), and capil-
lary-tube type discharge reactor (Kohno et al., 1998), have been investigated and
developed. In this study, gliding arc plasma was used to decompose carbon tetra-
chloride. Previously, we successfully conducted experiments with gliding arc plasma
to treat CH2Cl2 (Indarto et al., 2006a, b), CHCl3 (Indarto et al., 2005b, 2006b), CO2
(Indarto et al., 2006c), and methane (Indarto et al., 2005b, 2006d). Compared with
the above plasma methods, there is a greater chance that gliding arc plasma can be
applied in the chemical industry (Fridman et al., 1999; Fanmoe et al., 2003). This
method allows the higher flame temperature and energy that are necessary to destroy
the chemical bond of toxic compounds in contrast to other plasmas, such as corona
and DBD. In addition, gliding arc is applicable for high input flow rate conditions.
Kinetic reaction models of CCl4 decomposition using electron beam in dry air
(Penetrante et al., 1995; Koch et al., 1995; Nichipor et al., 2000) and liquid (Mak
et al., 1997) have been investigated. The models suggested that the main products
were dominated by chlorinated C1 compounds, such as COCl2, CO, CO2, ClNO3,
ClO3, and Cl2. Fragmentation of CCl4 occurred by two reaction mechanisms
(Penetrante et al., 1995). In the oxygen-rich condition, the atomic oxygen species,
such as ground state of atomic oxygen O(3P) and excited atomic oxygen O(1D), have
enough energy to destroy the bonds of CCl4.
Oð3 PÞ þ CCl4 ¼ ClO þ CCl3 ð1Þ
Oð1 DÞ þ CCl4 ¼ CCl3 þ ClO2 ð2Þ
The second mechanism occurred via reaction with secondary electron. Secondary
electrons will dissociate CCl4 into CCl3 and negative chlorine ion (Cl ):
e þ CCl4 ¼ CCl3 þ Cl  ð3Þ
Radical ClO and CCl3 were suspected to be the most important intermediate species
to determine the final products of CCl4 decomposition. The concentration of O and
Cl could also be influenced by the radical reactions, both initiation and termination
reactions.
Nichipor’s (2000) investigation showed that CO, Cl2, and CO2 were formed by
dissociation process between electron and COCl2:
e þ COCl2 ¼ CO þ Cl2 k ¼ 107 cm3 =mol ð4Þ
Then, CO was oxidized by ClO and produced CO2:
CO þ ClO ¼ CO2 þ Cl ð5Þ
However, there has been less research on the importance of chlorinated C2 in the
decomposition reaction of CCl4. In this study, we investigate the role of chlorinated
C2 compounds on the reactions mechanism and product selectivity, especially CO,
CO2, and Cl2. Two different schemes of reaction mechanism are proposed and
compared with experimental results. Some reaction mechanisms, obtained from
 CCl4 Decomposition by Gliding Arc 1113

microwave plasma and the combustion process, were used to approach the real
system of gliding arc plasma. The simulation results were compared to the experi-
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mental ones to satisfy the kinetic models.

Experimental Setup
The schematic diagram of experimental setup is shown in Figure 1. Carbon
tetrachloride and dry atmospheric air were used as the source gases. Each part of
the system is described in detail in the following section.
The reactor was made from a quartz tube with an inner diameter of 45 mm and
length of 300 mm. The upper and bottom part of the reactor were supplied with
polytetrafluoroethylene (PTFE) seals, the lower one holding two electrodes. The
electrode, made of stainless steel, has a triangular form with a height of 100 mm.
The shortest gap between two electrodes was only 1.5 mm. The gas was injected
between these electrodes through a capillary of inner diameter of 0.8 mm. A thermo-
couple, located 10 cm above the electrode, was installed to measure the outlet gas
temperature.
A high-frequency alternating current (AC) power supply (Auto Electric A1831,
Korea) was connected to the electrodes of gliding arc to generate plasmas. Figure 2
shows the typical wave form of voltage and current obtained in this experiment.
Liquid carbon tetrachloride (CCl4) was purchased from Kanto Chemical Co.,
with purity of more than 99.5%. The concentrations of CCl4 in the input gas were
varied by 1, 3, 5, and 8 vol% of total flow rate. Dry atmospheric pressure air was
used as the carrier gas and controlled by a mass flow controller (Tylan FC-280S,
USA). The flow rates of air were 180, 240, and 300 L=h. CCl4 was introduced to
the reactor by passing a portion of dry air through a bubbling tube of liquid
CCl4, which was immersed in a water bath. Concentration of CCl4 was adjusted
by controlling both the temperature of the water bath and injected gas flow rate

Figure 1. Schematic diagram of experimental setup.

 1114 A. Indarto et al.
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Figure 2. Voltage and current profile.

to the bubbling tube. The feed line stream was covered by a heating band to avoid
the condensation of CCl4.
Mass spectroscopy and two gas chromatographers (GCs) were used for the
qualitative and quantitative analysis of the reactants and products. The concentra-
tions of CCl4 in the gas mixture before and after the reaction were determined by
a GC flame ionized detector (YoungLin M600D, column: Bentone, Korea), and
the concentrations of CO and CO2 were measured by a GC thermal conductivity
detector (YoungLin M600D, column: SK Carbon, Korea). Species analysis of the
decomposition products was done by quadruple mass spectroscopy (Balzers QMS
200, USA) with Quadstar 421 software. Chlorine gas (Cl2) was determined by bub-
bling the output gas through 0.05 M of aqueous KI during measured-experiment
time, followed by iodometric titration 0.05 M of Na2SO3 (Skoog et al., 2000).
Selectivity of products and conversion of CCl4 were defined as:
moles of Cl2 formed
Selectivity of Cl2 ¼  100% ð6Þ
2  moles of CCl4 converted
moles of CO formed
Selectivity of CO ¼  100% ð7Þ
moles of CCl4 converted
 CCl4 Decomposition by Gliding Arc 1115

moles of CO2 formed

Selectivity of CO2 ¼  100% ð8Þ
moles of CCl4 converted
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moles of CCl4 consumed

Conversion of CCl4 ¼  100% ð9Þ
moles of CCl4 introduced
moles of Cl2 formed
Cl2 =ðCO þ CO2 Þratio ¼ ð10Þ
moles of CO formed þ moles of CO2 formed
The consumed power for the process was calculated as the products of voltage and
current wave form captured by an oscilloscope (Agilent 54641A, USA). In this
experiment, we limited the power from 286 to 304 watts. Sample data were obtained
after 30 min operation, referring to the stable temperature condition of the output
line measured by the thermocouple.

Kinetics Study and Model

To investigate the reaction mechanism, a chemical kinetic reaction model of CCl4
decomposition was constructed. The gas-phase reaction model consists of the 21
elementary reactions that are proposed by literatures as the most significant pathway
of reactions (Lou and Chang, 1997; Chang and Senkan, 1989; NASA, 1994;
Penetrante et al., 1995, Koch et al., 1995, Nichipor et al., 2000). The rate constant
of each reaction is expressed in a modified Arrhenius form:


Ej
kj ¼ Aj T bj exp  ð11Þ
RT
The simulation was focused on the reactions of Cl2, CO, CO2, and chlorinated C1
production. Other products, such as chlorinated C2, were considered only as inter-
mediate species because the concentrations of those components in the product line
were small. Table I is a list of elementary chemical reactions of CCl4 decomposition.
The model was coded in the MATLAB program (MathWorks, USA) and
numerically solved using the shooting method (Walas, 1991; Chapra and Canale,
1990). The algorithm of the program is shown in Figure 3(a). MATLAB modules
of ode23s and fmins were utilized to solve simultaneously the 15 sets (15 species)
of differential equations (shown in Equations (12) and (13)) and minimize the
absolute error.
dxi X m  
¼ fj kj ; xi ðtÞ; . . . ; xn ðtÞ ð12Þ
dt j¼1

xi ðt0 Þ ¼ xinput
i ; xi ðtÞ ¼ xproduct
i ð13Þ
The concentration of Cl2 in the products was used as the basis (boundary condition)
to calculate the Cl2 to (CO þ CO2) ratio and converted CCl4. To verify the validity of
the model, the simulation and experimental results were compared for each point.
The absolute error was calculated as:
n    
product product
De ¼ abs xsimCl2  xCl2 þ abs xsim
ðCOþCO2 Þ  xðCOþCO2 Þ
 o2
product
þabs xsim
CCl4  xCCl4 ð14Þ
 1116 A. Indarto et al.

Table I. Chemical kinetics for decomposition of CCl4

Reactiona log A n E DHr(298 K) Ref.
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1. CCl2 þ Cl2 ¼ CCl3 þ Cl 12.70 0 3.0 7.8b

2. CCl2 þ O2 ¼ ClO þ COCl 13.00 0 1.0 37.1b
3. CCl3 þ O ¼ COCl2 þ Cl ðÞ 14.00 0 0 102.8b
4. CCl3 þ O2 ¼ COCl2 þ ClOðÞ 13.00 0 28.0 47.7b
5. CCl3 þ Cl2 ¼ CCl4 þ Cl 12.40 0 6.0 11.4b
6. CCl3 þ CCl3 ¼ C2 Cl6 36.15 7.48 6.7 67.5b
7. CCl3 þ CCl3 ¼ C2 Cl4 þ Cl2 26.35 4.43 9.0 40.7b
8. CCl4 ¼ CCl3 þ Cl ðÞ 35.87 6.52 75.4 70.8b
9. CCl4 þ O ¼ CCl3 þ ClOðÞ 10.40 0 2.3 5.0b
10. CO þ ClO ¼ CO2 þ Cl 11.78 0 7.4 62.2b
ðÞ
11. COCl þ Cl ¼ CO þ Cl2 13.10 0.5 0.5 52.4b
12. COCl þ M ¼ CO þ Cl þ M ðÞ 14.30 0 6.5 7.1b
13. COCl þ O ¼ CO þ ClO 14.00 0 0 58.7b
ðÞ
14. COCl2 þ Cl ¼ COCl þ Cl2 13.50 0.5 20 18.5b
15. C2 Cl4 þ O ¼ COCl2 þ CCl2 13.00 0 5.0 54.3b
16. C2 Cl4 þ Cl ¼ C2 Cl5 35.42 7.71 5.3 17.8c
17. C2 Cl5 þ Cl ¼ CCl3 þ CCl3 27.23 4.01 12.1 1.0
18. C2 þ Cl5 Cl ¼ C2 Cl4 þ Cl2 27.10 4.73 8.9 41.7c
19. C2 Cl6 ¼ Cl2 þ C2 Cl4 35.21 6.53 63.2 26.8c
20. C2 Cl6 ¼ Cl þ C2 Cl5 36.13 6.48 74.4 68.5c
21. C2 Cl6 þ Cl ¼ Cl2 þ C2 cl5 13.80 0 18.3 9.0c
a
k ¼ AT n expðE=RTÞ, in cm, kcal, s, and mole units.
b
Lou and Chang, 1997.
c
Chang and Senkan, 1989.

Most significant reactions in this experiment.

The model stiffness was checked by varying input guesses. Figure 3(b) shows that the
model produces an almost similar absolute error although the input guess is varied
from 3.9 to 6.5.

Results and Discussion

CCl4 Conversion
Figure 5(a) shows the effect of initial concentration of CCl4 on the conversion at a
frequency of 20 kHz. Conversion decreases gradually when the initial concentration
of CCl4 is increased. The maximum conversion reaches 80% at the concentration of
1 vol% and flow rate of 180 L=h. Increasing concentration of CCl4 will decrease the
ratio of high-energy energetic species (e.g., electron and radical atoms=molecules) to
CCl4. This is because at the same flow rate and supplied energy, the amount of high-
energy energetic species, both quality and quantity, can be assumed to be same. This
condition will decrease the relative probability of a single CCl4 molecule colliding
with energetic species that are able to destroy the CCl molecule bonds. However,
although the collision probabilities are lower, the effectiveness of absolute collision
at higher initial concentration of CCl4 is higher that that at lower concentration of
 CCl4 Decomposition by Gliding Arc 1117
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Figure 3. (a) The algorithm of simulation; (b) error sensitivity of model as a function of input
guess variation.

CCl4. For example, at 1% and 3 % CCl4 concentration, it can be calculated as 1 (%

of input concentration)  80 (% of conversion) and 3  73, respectively. This will
lead to the ratio of 80:219, which shows that the process at 3% CCl4 concentration
produces 219=80 times more effectively than that at 1% of CCl4 concentration.
Analysis of QMS spectrum (Figure 8) shows that the main gaseous products are
CO, CO2, and Cl2. In addition to those products, other chlorinated compounds are
also detected but the concentrations are small.
 1118 A. Indarto et al.
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Figure 4. Model scenario of CCl4 decomposition; (a) first scenario, (b) second scenario.

CO þ CO2 Selectivity
Increasing initial concentration of CCl4 will affect lowering the selectivity of
CO þ CO2. As shown in Figure 5(b), the selectivity of CO þ CO2 decreases around
2% when the concentration of CCl4 is increased from 1% to 8%. Our kinetic simula-
tion calculates that higher initial concentration of CCl4 produces higher concen-
tration of single chlorine species (Cl) in the reactor. The reactions will follow
(Chang and Senkan, 1989):
CCl4 ¼ CCl3 þ Cl ð15Þ
CCl3 þ O ¼ COCl2 þ Cl ð16Þ
Cl atom will compete with carbon atom (C) to react with oxygen (O). Higher con-
centration of Cl makes the probability of C and O reaction to produce CO smaller.
Kinetic reaction studies of CO, CO2, and Cl2 formation in thermal oxidation
show similar reaction mechanisms to those proposed by the literature (Chang and
Senkan, 1989; Lou and Chang, 1997). The major pathways responsible for the
formation of CO2 are:
COCl þ Cl ¼ CO þ Cl2 ð17Þ
COCl þ M ¼ CO þ Cl þ M ð18Þ
CO2 is mainly generated from the reaction of CO and ClO:
CO þ ClO ¼ CO2 þ Cl ð19Þ
 CCl4 Decomposition by Gliding Arc 1119
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Figure 5. Effects of initial CCl4 concentration on (a) CCl4 conversion, (b) (CO þ CO2) selec-
tivity, and (c) Cl2 selectivity.

and ClO is formed via:

CCl4 þ O ¼ CCl3 þ ClO ð20Þ
CCl3 þ O2 ¼ COCl2 þ ClO ð21Þ

Koch et al. (1995) reported a similar radical mechanism, as mentioned above, using
an electron beam process for CCl4 decomposition in the presence of O2.
However, Equation (19) is not counted as the main mechanism for Cl
production because the concentration of CO2, measured in the output stream, was
relatively low. The concentration of CO2 was five to ten times lower than CO in
all of the experimental ranges.
An interesting phenomenon was found in the case of nitrogen. The
concentration of nitrogen in the air was around 80%. Analysis of the QMS spectrum
shows no significant different of the concentration before and after plasma reaction.
It means that although it has a lower excitation level, N2 acted as an inert gas in the
gliding arc plasma. Products analysis by QMS also shows that there were no signifi-
cant N-containing compounds detected, except a small concentration of N2O. In
gliding arc plasma, oxygen tends to have an influence more than nitrogen. Our
previous research on oxygen showed that atomic oxygen, both ground-state and
excited form, could be more active than nitrogen (Indarto et al., 2005a; 2006c).
 1120 A. Indarto et al.

The importance of ground-state atomic oxygen O(3P) and metastable atomic

oxygen O(1D) in the reaction kinetics has been rigorously investigated (Davidson
et al., 1978). Both O(3P) and O(1D) can be produced from dissociation reactions
Downloaded By: [Indarto, Antonius] At: 18:28 2 May 2007

(Penetrante et al., 1995):

e þ O2 ¼ e þ Oð3 PÞ þ Oð3 PÞ ð22Þ
e þ O2 ¼ e þ Oð3 PÞ þ Oð1 DÞ ð23Þ
In this experiment, the initial concentration of oxygen was around
20%, as we
used atmospheric air as the dilution gas for CCl4. QMS spectrum analysis shows that
in the output stream, the peak intensity of O2 in the product stream was slightly
lower than that in the feed stream. Moreover, the magnitude of decreasing peak
intensity of oxygen was not changed significantly when the initial concentration of
CCl4 was varied. Based on this result, it can be assumed that the concentrations
of oxygen atoms are similar for each process at the same power and flow rate. On
the other hand, increasing concentration of CCl4 in the feed stream will increase
the concentration of intermediate Cl atoms. It will effect a smaller probability of
C and O reaction as the probability of Cl and O reaction is increasing. This analogy
can be the reason why the selectivity of (CO þ CO2) decreases when the initial
concentration of CCl4 is increased.

Cl2 Selectivity
Different from previous phenomena of CO and CO2 production, the selectivity of
Cl2 increases when the initial concentration of CCl4 is also increased (Figure 5(c)).
The existence of Cl atom will affect the termination reactions of intermediate chlor-
ine molecules that produce Cl2. The major pathways of Cl2 formation can be:
COCl2 þ Cl ¼ COCl þ Cl2 ð24Þ
COCl þ Cl ¼ CO þ Cl2 ð25Þ
The existence of COCl2 and COCl were detected by our QMS (Figure 8) and it gives
a greater possibility for the above reaction to occur. In the higher initial concentra-
tions of CCl4, the concentration of Cl will increase and produce more Cl2, following
Equations (24) and (25).

Simulation of Cl2, CO, and CO2

In the above reaction mechanisms, only chlorinated C1 compounds are counted
as the intermediate species in the production of CO, CO2, and Cl2. In order to
investigate the role of chlorinated C2 compounds in the decomposition reaction of
CCl4, especially for CO, CO2, and Cl2 production, we constructed two types of reac-
tion mechanisms based on the elementary reactions listed in Table I. The first scen-
ario considers Equations (17)–(19) and (24)–(25) as the main reaction pathways to
produce CO, CO2, and Cl2 and neglects the production of those compounds from
the chlorinated C2 compounds, such as C2H4, C2H5, and C2H6 (Figure 4(a)). This
reaction pathway is chosen to examine the dependence of Cl2, CO, and CO2 pro-
duction from the proposed Equations (17)–(19) and (24)–(25). The second scenario
will consider the existence of higher carbon-chloride and calculate its effects on the
decomposition reactions (Figure 4(b)).
 CCl4 Decomposition by Gliding Arc 1121

Figure 6 shows the party comparison plot of those two models. The horizontal
axis shows the experimental results, and the vertical axis shows the simulation
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calculation. The second model shows that the results of simulation are closer to
the experimental results than those of the first model. The first scenario of the model
gives 8–50% error value, much higher than the second model, which produces error
values of only 2–10%. Based on these two models, neglecting the existence of chlori-
nated C2 compounds in the reactions mechanism of CO, CO2, and Cl2 production
will produce lower selectivity of chlorine gas (Cl2) and higher selectivity of CO
and CO2 than the experimental results.
Direct conversion of chlorinated C2 compounds to Cl2 could be counted as a
significant pathway of Cl2 production. Lou and Chang (1997) also identified the
production of Cl2 from chlorinated C2 compounds, e.g., C2Cl5:

C2 Cl5 þ Cl ¼ CCl3 þ CCl3 ð26Þ

On the other hand, the existence of chlorinated C2 compounds will reduce the
selectivity of CO and CO2. Instead of oxidation reactions, couple reactions of
CCl3 can produce chlorinated C2 compounds:

CCl3 þ CCl3 ¼ C2 Cl6 ð27Þ

CCl3 þ CCl3 ¼ C2 Cl4 þ Cl2 ð28Þ

Although the results of the first model are not matched exactly with experimental
results, it can still be concluded that Equations (17)–(19) have an important role in

Figure 6. Parity plot of products selectivity comparison between experimental and simulation
results.
 1122 A. Indarto et al.
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Figure 7. Main routes of CO, CO2, and Cl2 production from CCl4 decomposition.

the production of CO and CO2 and Equations (24)–(25) likewise in Cl2 production.
Calculation of the first model shows that Equations (17)–(19) and (24)–(25) can
enhance more than 50% of the production of CO, CO2, and Cl2. The existence of
COCl2, which is obtained using our QMS, shown in Figure 8(b), can be good evi-
dence for this case. COCl2 is one of the most important intermediate species in
Cl2 production (Equation (24)). Figure 7 shows the main routes of Cl2, CO, and
CO2 formation from CCl4 decomposition by gliding arc plasma.

QMS Spectra
QMS spectra of CCl4 decomposition diluted in atmospheric arc by gliding arc
plasma are shown in Figure 8. Figure 8(a) shows the compounds spectra of 1 vol%
of CCl4 diluted in 180 L=h of atmospheric air. The main spectra of CCl4 are m=z
83=85 ðCCl2þ Þ and m=z 117 ðCCl3þ Þ. CO2 has its molecular ion at m=z 44 ðCOþ 2 Þ.
CO molecular ion spectrum is colliding with minor N2 at m=z 29 ðCOþ =N2þ Þ. The
main N2 is at m=z 28 ðN2þ Þ. However, due to the small concentration of CO in the
atmospheric air, CO compound can be neglected in this spectrum line.
The spectra of the products of CCl4 decomposition are shown in Figure 8(b).
The peak intensity of m=z 83=85 is decreased as well as the intensity of m=z 117,
and a new spectrum of Cl2 appeared at m=z 71 ðCl2þ Þ. Intensity of CO2 increases
but the difference between before and after plasma condition is small. High
magnification of spectrum intensity occurred at m=z 29 of N2 and CO. Because
N2 is classified as a stable compound and there is no available source of nitrogen
(N) in this system to produce N2, it must be that the increment intensity of m=z
29 is caused by production of CO. At high initial concentration of CCl4, the
spectrogram of products produces a new spectrum at m=z 63 ðCClOþ Þ. Based on
the QMS library, it can be suspected to be COCl or COCl2. There is good evidence
 CCl4 Decomposition by Gliding Arc 1123
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Figure 8. QMS spectra of CCl4 decomposition; (a) input stream, (b) products stream. Note:
obtained at 1 vol% of CCl4 and total gas flow rate of 180 L=h.

that COCl and COCl2, which have a significant role, especially in the production of
CO, CO2, and Cl2, existed in the reaction mechanisms. Another intermediate species
that possibly exists is CCl2 at m=z 84 (CCl þ ).

Conclusion
The decomposition of CCl4 in gliding arc plasma as well as the kinetic study was
investigated. The maximum conversion of CCl4 was 80% at 1 vol% of CCl4 and
total flow rate of 180 L=h. CO, CO2, and Cl2 were identified as the main products
of the decomposition process. CCl3, COCl2, and COCl were the important
intermediate species in CO, CO2, and Cl2 production. The existence of chlorinated
C2 compounds has to be also counted as the source of Cl2 production in the final
products. However, formation of chlorinated C2 compounds can reduce the selec-
tivity of CO and CO2 due to coupling reactions of intermediate species, e.g., CCl3.
 1124 A. Indarto et al.

Acknowledgments
This study was supported by the National Research Laboratory Program of the
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Korea Ministry of Science and Technology.

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