CCl4 Decomposition by Gliding Arc Plasma: Role of C2 compounds

on products distribution
Shortened title: CCl4 Decomposition by Gliding Arc

(manuscript id: 130-06)

Antonius Indarto1,2,†, Dae Ryook Yang3, Jae-Wook Choi2, Hwaung Lee2, and

Hyung Keun Song2

1
School of Environmental, Resources, and Development, Asian Institute of Technology,

P.O. Box 4, Klong Luang, Pathumthani 12120, Thailand

2
Clean Technology Research Center, Korea Institute of Science & Technology

P.O. Box 131, Cheongryang, Seoul 130-650, Korea

3
Department of Chemical and Biological Engineering,

Korea University, Seoul 136-701, Korea

†
Correspondence address: e-mail: indarto_antonius@yahoo.com, tel:+82-10-2296-3748

1
Abstract- 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+CO2)

reaches ~50% and ~40%, respectively. Other chlorinated compounds 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 compounds, a kinetic simulation was

performed and crossed check with the experimental results to clarify the reactions

mechanism.

Keywords: Plasma; Gliding Arc; CCl4 decomposition; Reaction mechanism.

2
INTRODUCTION

Emissions of chlorinated volatile organic compounds (CVOCs) from various industries,

such as carbon tetrachloride (CCl4), create environmental problems (Butler, 2000;

WMO-UNEP, 2002). Chemical degradation of CVOCs in our atmosphere will produce

another toxic chloride compound, e.g. HCl, which is classified as the main component

of acid rain (Sanhueza, 2001). Some studies report that CCl4 will produce very-active

chlorine radicals by solar radiation reactions. These species will react and destruct

ozone molecules in the stratosphere (Butler, 2000; US-EPA, 2002). Moreover, the most

severe problem of the emission of CCl4 is due to toxic and carcinogenic to the human

health (IARC, 1987). Those can be the reasons to find effective methods in reducing the

emission of CVOCs.

The most widely adopted technique for the treatment of CVOCs is thermal combustion

or incineration (Cheremisinoff, 2002). 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 1,100℃) to achieve the optimum

decomposition rate. Taylor and Delinger’s paper reported that incomplete combustion

condition could produce a large amount of complex chlorinated products (Taylor and

Dellinger, 1988).

To overcome these problems, many studies were carried out on the application of new

technologies. Plasma-assisted technology is one of the promising technologies 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

3
(Tonkyn et al., 1996), pulsed discharge reactor (Yamamoto et al., 1992), and capillary-

tube type discharge reactor (Kohno et al., 1998) have been investigated and developed.

In this study, gliding arc plasma was used to decompose carbon tetrachloride.

Previously, we successfully conducted experiments with gliding arc plasma to treat

CH2Cl2 (Indarto et al., 2006a; 2006b), CHCl3 (Indarto et al., 2005b; 2006b), CO2

(Indarto et al., 2006c), and methane (Indarto et al., 2005b; 2006d). Compared with the

above plasmas 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 than other plasmas, such as corona, DBD, etc. 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 was 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 destruct

the bonds of CCl4.

O( 3P ) + CCl 4 = ClO + CCl 3 (1)

O(1D) + CCl 4 = CCl 3 + ClO2 (2)

The second mechanism was occurred via reaction with secondary electron. Secondary

4
electrons will dissociate CCl4 into CCl3 and negative chlorine ion (Cl‾),

e + CCl 4 = CCl 3 + Cl − (3)

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 be also 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 + COCl 2 = CO + Cl 2 k = 10-7 cm3/mol (4)

then, CO was oxidized by ClO and produce CO2:

CO + ClO = CO2 + Cl (5)

However, less paper discussed about 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 products selectivity, especially CO, CO2,

and Cl2. Two different schemes of reaction mechanism are proposed and compared with

experimental results. Some reaction mechanisms, obtained from microwave plasma and

combustion process, were used to approach the real system of gliding arc plasma. The

simulation results were compared to the experimental ones to satisfy the kinetic models.

EXPERIMENTAL SETUP

5
 Figure 1

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 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 the 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 thermocouple,

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 waveform of voltage and current obtained in this experiment.

Figure 2

Liquid carbon tetrachloride (CCl4) was purchased from Kanto Chemical Co., Inc. The

purity was more than 99.5%. The concentrations of CCl4 in the input gas were varied by

1, 3, 5, 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, U.S.). The flow rates of

air were 180, 240, and 300 L/hr. CCl4 was introduced to the reactor by passing a portion

6
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 temperature of water bath and

injected gas flow rate 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 concentrations of CCl4 in

the gas mixture before and after the reaction was determined by GC flame ionized

detector (YoungLin M600D, Column: Bentone, Korea) and the concentrations of CO

and CO2 were measured by GC thermal conductivity detector (YoungLin M600D,

Column: SK Carbon, Korea). Species analysis of the decomposition products was done

by a quadruple mass spectroscopy (Balzers QMS 200, U.S.) with Quadstar 421

software. Chlorine gas (Cl2) was determined by bubbling the output gas through 0.05 M

of aqueous KI during measured-experiment time and 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 Cl 2 formed
Selectivity of Cl 2 = × 100% (6)
2 × moles of CCl 4 converted

moles of CO formed
Selectivity of CO = × 100%
moles of CCl 4 converted (7)

moles of CO2 formed

Selectivity of CO2 = × 100% (8)
moles of CCl 4 converted

moles of CCl 4 consumed

Conversion of CCl 4 = × 100% (9)
moles of CCl 4 introduced

7
 moles of Cl 2 formed
Cl 2 / (CO + CO2 ) ratio = (10)
moles of CO formed + moles of CO2 formed

The consumed power for the process was calculated as the products of voltage and

current waveform captured by oscilloscope (Agilent 54641A, U.S.). In this experiment,

we limit the power from 286 to 304 Watt. Sample data were obtained after 30 minutes

operation referring to the stable temperature condition of output line measured by

thermocouple.

KINETIC STUDY AND MODEL

Figure 3

Table 1

To investigate the reactions 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 reactions is

expressed in a modified Arrhenius form,

βj  Ej 
k j = A jT exp − 
(11)
 RT 

8
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

intermediate species because the concentrations of those components in the product line

were small. Table 1 shows list of elementary chemical reactions of CCl4 decomposition.

The model was coded in MATLAB program and numerically solved using shooting

method (Walas, 1991; Chapra and Canale, 1990). The algorithm of the program is

shown in Figure 3a. MATLAB modules of ode23s and fmins were utilized to solve

simultaneously the 15 sets (15 species) of differential equation (shown in formula 12

and 13) and minimize the absolute error (MathWorks, 1992).

= ∑ f j ( k j , xi (t ),..., x n (t ) )
dxi m

dt j =1
(12)

xi (t 0 ) = xiinput ; xi (t ) = xiproduct (13)

The concentration of Cl2 in the products was used as the basis of calculation (boundary

condition) to calculate the Cl2 to (CO+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:

{ (
∆ ε = abs xClsim2 − xClproduct
2
)
+ abs x (sim ( ) (
CO + CO2 ) − x ( CO + CO2 ) + abs x CCl 4 − xCCl 4
product sim product
)} 2
(14)

The model stiffness was checked by varying input guess. Figure 3b shows that the

model produces an almost similar absolute error although the input guess is varied from

3.9 to 6.5.

9
RESULTS AND DISCUSSION

CCl4 conversion

Figure 4

Figure 4a shows the effect of initial concentration of CCl4 on the conversion at

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/hr. Increasing concentration of CCl 4 will decrease the ratio

of high-energy energetic species (e.g. electron and radical atoms/molecules) to CCl4. It

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 single CCl4 molecule to collide with energetic

species which able to destruct the C-Cl 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. For example, at

1% and 3 % of CCl4 concentration, it can be calculated as 1 (% of input concentration) x

80 (% of conversion) and 3 x 73, respectively. This will lead to the ratio of 80:219

which shows that the process at 3% of CCl4 concentration produces 219/80 times more

effective than that at 1% of CCl4 concentration.

Analysis of QMS spectrum (Figure 8) shows that the main gaseous products are CO,

CO2, and Cl2. Instead of those products, other chlorinated compounds are also detected

10
but the concentrations are small.

CO+CO2 selectivity

Increasing initial concentration of CCl4 will affect on lowering selectivity of CO+CO2.

As shown in Figure 4b, the selectivity of CO+CO 2 decreases around 2 % when the

concentration of CCl4 is increased from 1% to 8%. Our kinetic simulation calculates

that higher initial concentration of CCl4 produces higher concentration of single chlorine

species (Cl) in the reactor. The reactions will follow (Chang 1989):

CCl 4 = CCl 3 + Cl (15)

CCl 3 + O = COCl 2 + Cl (16)

Cl atom will compete with carbon atom(C) to react with oxygen (O). Higher

concentration of Cl makes the probability of C and O reaction to produce CO becomes

smaller.

Kinetic reaction studies of CO, CO2, and Cl2 formation in thermal oxidation show the

similar reaction mechanisms as proposed by literatures (Chang and Senkan, 1989; Lou

and Chang, 1997). The major pathways responsible for the formation of CO2 are:

COCl + Cl = CO + Cl 2 (17)

COCl + M = CO + Cl + M (18)

11
CO2 is mainly generated from the reaction of CO and ClO:

CO + ClO = CO2 + Cl (19)

and ClO is formed via:

CCl 4 + O = CCl 3 + ClO (20)

CCl 3 + O2 = COCl 2 + ClO (21)

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, formula 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 5-10 times lower than CO in all of experimental ranges.

An interesting phenomenon was found in case of nitrogen. The concentration of

nitrogen in the air was around 80%. Analysis of QMS spectrum shows that no

significant different of the concentration before and after plasma reaction. It means that

although having lower excitation level, N2 was acted as an inert gas in the gliding arc

plasma. Products analysis by QMS also shows that there were no significant N-

contained compounds detected, except small concentration of N2O. In gliding arc

plasma, it tent that oxygen gave an influence more than nitrogen. Our previous

researches on oxygen showed that atomic oxygen, both ground-state and metastable

form, could be more active than ozone (Indarto et al., 2005a; 2006c). The production of

ozone was relatively small because in gliding arc plasma, the fragmentation reactions

12
were preferred than recombination reactions.

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

O(1D) in the reaction kinetic has been rigorously investigated (Davidson et al., 1978).

Both O(3P) and O(1D) can be produced from dissociation reactions (Penetrante et al.,

1995):
e + O2 = e + O ( 3 P ) + O ( 3 P ) (22)

e +O 2 = e + O( 3P ) + O(1D) (23)

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 product stream was slightly lower than that in

the feed stream. Moreover, the magnitude of decreasing peak intensity of oxygen was

not change 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 on smaller probability of C and O reaction as the probability of

Cl and O reaction is getting higher. This analogy can be the reason why the selectivity

of (CO+CO2) decreases when the initial concentration of CCl4 is increased.

Cl2 selectivity

13
Different from previous phenomena of CO and CO2 production, the selectivity of Cl2

increases when the initial concentration of CCl4 is also increased (Figure 4c). The

existence of Cl atom will affect on the termination reactions of intermediates chlorine

molecules that produce Cl2. The major pathways of Cl2 formation can be:
COCl 2 + Cl = COCl + Cl 2 (24)

COCl + Cl = CO + Cl 2 (25)

The existence of COCl2 and COCl were detected by our QMS (Figure 8) and it gives

higher possibility of above reaction to be occurred. In the higher initial concentrations

of CCl4, the concentration of Cl will increase and produce more Cl2 follows formula 24

and 25.

Simulation of Cl2, CO, and CO2

Figure 6

Figure 7

In above reaction mechanisms, it shows that only chlorinated C1 compounds is counted

as the intermediate species in the production CO, CO2, and Cl2. In order to investigate

the role of chlorinated C2 compounds in the decomposition reaction of CCl4, especially

14
for CO, CO2, and Cl2 production, we constructed two types of reactions mechanism

based on the elementary reactions listed in table 1. The first scenario considers the

formula (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 4a). This reaction pathway is chosen

to examine the dependence of Cl2, CO, and CO2 production from the proposed formulas,

(17) - (19) and (24) – (25). The second scenario will consider the existence of higher

carbon-chloride and calculate their effects on the decomposition reactions (Figure 4b).

Figure 6 shows the party comparison plot of those two models. The horizontal axis

shows the experimental result while the vertical axis shows the simulation calculation.

The second model shows that the results of simulation are closer to the experiment

results compared to the first model. The first scenario of the model gives 8-50% of error

value and it is much higher than the second model which only produces error values of

2-10%. Based on these two models, neglecting the existence of chlorinated 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 Cl 2

from chlorinated C2 compounds, e.g. C2Cl5.

C 2 Cl 5 + Cl = CCl 3 + CCl 3 (26)

On the other hand, the existence of chlorinated C2 compounds will reduce the selectivity

15
of CO and CO2. Instead of oxidation reactions, couple reactions of CCl3 can produce

chlorinated C2 compounds
CCl 3 + CCl 3 = C 2 Cl 6 (27)

CCl 3 + CCl 3 = C 2 Cl 4 + Cl 2 (28)

Although the results of first model are not match exactly with experimental results, still,

it can conclude that formula (17) – (19) have an important role on the production of CO,

and CO2 and formula (24) – (25) on Cl2 production. Calculation of the first model shows

that formula (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 8b, can be a good evidence for this case. COCl 2 is one of the most important

intermediate species in Cl2 production (formula 24). Figure 7 shows the main routes of

Cl2, CO, and CO2 formation from CCl4 decomposition by gliding arc plasma.

QMS spectra

Figure 8

QMS spectra of CCl4 decomposition diluted in atmospheric arc by gliding arc plasma

are shown in Figure 8. Figure 8a shows the compounds spectrum of 1 vol% of CCl 4

diluted in 180 L/hr of atmospheric air. The main spectrums of CCl4 are m/z 83/85 (

CCl 2+ ) and m/z 117 ( CCl 3+ ). CO2 has its molecular ion at m/z 44 ( CO2+ ). CO molecular

16
 + +
ion spectrum is colliding with minor N2 at m/z 29 ( CO / N 2 ). The main N2 is at m/z 28
+
( N 2 ). However, due to small concentration of CO in the atmospheric air, CO

compound can be neglected in this spectrum line.

The spectrum of the products of CCl4 decomposition is shown in Figure 8b. The peak

intensity of m/z 83/85 is decreased as well as intensity of m/z 117 and a new spectrum
+
of Cl2 is appeared at m/z 71 ( Cl 2 ). Intensity of CO2 increases but the difference

between before and after plasma condition is slightly small. High magnification of

spectrum intensity is occurred at m/z 29 of N2 and CO. Because N2 is classified as a

stable compound and no available source of nitrogen (N) in this system to produce N2, it

can be sure that the increment intensity of m/z 29 is caused by production of CO. At

high initial concentration of CCl4, spectrogram of products produces a new spectrum at

+
m/z 63 ( CClO ). Based on QMS library, it can be suspected to be COCl or COCl 2.

Good evidence that COCl and COCl2 which have a significant role especially to 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+).

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

17
flow rate of 180 L/hr. CO, CO2, and Cl2 were identified as the main products of the

decomposition process. CCl3, COCl2, and COCl were the important intermediate species

on CO, CO2 and Cl2 production. The existence of chlorinated C2 compounds has to be

counted also as the source of Cl2 production in the final products. However, formation

of chlorinated C2 compounds can reduce the selectivity of CO and CO 2 due to coupling

reactions of intermediate species, e.g. CCl3.

ACKNOWLEDGEMENTS

This study was supported by the National Research Laboratory Program of the Korea

Minister of Science and Technology.

18
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ferroelectric pellet reactor and a pulsed corona reactor.” IEEE Trans. Ind. Applicat., 28(3),
528-534.

21
 v e n t to
a tm o s p h e r e

F ID G C
B e n to n e

MFC- 1
TC D G C
S K C a rb o n

C o m p re s s e d Q u a d ra p o le
a ir M ass
S p e c t ro m e te r

MFC- 2

C C l4
w a t e rb a th
K I s o l u t io n

P la s m a
R e a c to r

Figure 1. Schematic diagram of experimental set up

22
 6000

4000

2000
Voltage (V)
0

-2000

-4000

-6000
0.4

0.2
Current (A)

0.0

-0.2

-0.4

-0.6
-2e-5 -1e-5 0 1e-5 2e-5

Cycle of time (s)

Figure 2. Voltage and current profile

23
 Start

Guess:
Cl2 selectivity

Set constant:
reaction formula

new guess
Calculate:
CCl4 conversion,
(CO+CO2) selectivity

solve the ODEs

Absolute Error:
(Cl2)exp.- (Cl2)sim.
(CO+CO2)exp.- (CO+CO2)sim.
(CCl4)exp.- (CCl4)sim.

unsatisfactory
Result:
(CCl4)sim.
(CO+CO2)sim.

End

1.8

3.9
1.6
4.55
1.4
4.55
1.2 5.85
6.5
1
rε

0.8

0.6

0.4

0.2

0
0 5 10 15 20 25 30 35 40

Number of iteration steps

Figure 3. (a) The algorithm of simulation;

24
(b) Error sensitivity of model as function of input guesses variation

25
 r5
CCl4 r 8,r9 CCl3
r1
r3
r9 r4
r13

r14
ClO COCl2 r5
Cl2
r10 r14 r11

CO2 r 10 CO r11 ,r12 ,r13 COCl

(a)

r1 r7
r17
r5
C C l4 r 8,r9 C C l3 r6 C 2C l6 r 20 ,r 21 C 2 C l5
r3 r19 r19
r9 r4 r21 r18 r16
r13 r1
r18
r14
C lO C O C l2 r5
C l2 C 2 C l4
r2
r10 r14 r11 r15

CO 2 r10 CO r11,r12,r 13 CO Cl r2
r2
C C l2
(b)

Figure 4. The model scenario of CCl4 decomposition;

(a) first scenario (b) second scenario

26
 100

90

80

70
Conversion (%)

60

50

40

30

20 180 L/min
240 L/min
10
300 L/min

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(a)

100

90 180 N/min (exp.)

240 L/min (exp.)
80
300 L/min (exp.)
(CO+CO2) selectivity (%)

70 simulation

60

50

40

30

20

10

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(b)

27
 100

90

80

70
Cl2 selectivity (%)

60

50

40

30
180 L/min (exp.)
20 240 L/min (exp.)
300 L/min (exp.)
10
simulation

0
0 1 2 3 4 5 6 7 8 9

CCl4 concentration (%)

(c)

Figure 5. Effects of initial CCl4 concentration on (a) CCl4 conversion,

(b) (CO + CO2) selectivity and (c) Cl2 selectivity

28
 100

Simulation Cl2, CO,CO2 selectivity (%)

80

60

40

180 Nl/hr1
180 Nl/hr2
20 240 Nl/hr1
240 Nl/hr2
300 Nl/hr1
300 Nl/hr2

0
0 20 40 60 80 100
Experimental Cl2, CO, CO2 selectivity (%)

Note: 1first model scenario, 2second model scenario

Figure 6. Parity plot of products selectivity comparison between experimental and

simulation results.

29
 C C l4 e
C C l3

O O

C C l3 Cl C O C l2

O 2
Cl
C lO
Cl CO Cl
CO CO
CO 2 C l2

Figure 7. Main routes of CO, CO2 and Cl2 production from CCl4 decomposition

30
 1.4e-9 (a) before

1.2e-9

1.0e-9
CO and N2
Intensity

8.0e-10

6.0e-10

4.0e-10

Cl2
CCl4
2.0e-10 CO2
CCl4

0.0
1.4e-9 (b) after

1.2e-9
CO and N2 COCl, COCl2
1.0e-9
Intensity

8.0e-10
0 20 40 60 80 100 120

6.0e-10

4.0e-10

CO2
2.0e-10
Cl2 CCl4

0.0
0 20 40 60 80 100 120 140 160 180 200

AMU (m/z)

Note: - obtained at 1 vol% of CCl4 and total gas flow rate of 180 L/h

Figure 8. QMS spectra of CCl4 decomposition; (a) input stream (b) products stream

31
Table 1. Chemical kinetic for decomposition of CCl4

reaction1 log A n E ∆Hr(298 K) Ref.

1. CCl 2 + Cl 2 = CCl 3 + Cl 12.70 0 3.0 -7.8 [2]

2. CCl 2 + O2 = ClO + COCl 13.00 0 1.0 -37.1 [2]

3. CCl 3 + O = COCl 2 + Cl (*) 14.00 0 0 -102.8 [2]

4. CCl 3 + O2 = COCl 2 + ClO (*) 13.00 0 28.0 -47.7 [2]

5. CCl 3 + Cl 2 = CCl 4 + Cl 12.40 0 6.0 -11.4 [2]

6. CCl 3 + CCl 3 = C 2 Cl 6 36.15 -7.48 6.7 -67.5 [2]

7. CCl 3 + CCl 3 = C 2 Cl 4 + Cl 2 26.35 -4.43 9.0 -40.7 [2]

8. CCl 4 = CCl 3 + Cl (*) 35.87 -6.52 75.4 70.8 [2]

9. CCl 4 + O = CCl 3 + ClO (*) 10.40 0 2.3 5.0 [2]

10. CO + ClO = CO2 + Cl 11.78 0 7.4 -62.2 [2]

32
 11. COCl + Cl = CO + Cl 2 (*) 13.10 0.5 0.5 -52.4 [2]

12. COCl + M = CO + Cl + M (*)

14.30 0 6.5 7.1 [2]

13. COCl + O = CO + ClO 14.00 0 0 -58.7 [2]

14. COCl 2 + Cl = COCl + Cl 2 (*) 13.50 0.5 20 18.5 [2]

15. C 2 Cl 4 + O = COCl 2 + CCl 2 13.00 0 5.0 -54.3 [3]

16. C 2 Cl 4 + Cl = C 2 Cl 5 35.42 -7.71 5.3 -17.8 [3]

17. C 2 Cl 5 + Cl = CCl 3 + CCl 3 27.23 -4.01 12.1 -1.0 [3]

18. C 2 Cl 5 + Cl = C 2 Cl 4 + Cl 2 27.10 -4.73 8.9 -41.7 [3]

19. C 2 Cl 6 = Cl 2 + C 2 Cl 4 35.21 -6.53 63.2 26.8 [3]

20. C 2 Cl 6 = Cl + C 2 Cl 5 36.13 -6.48 74.4 68.5 [3]

21. C 2 Cl 6 + Cl = Cl 2 + C 2 Cl 5 13.80 0 18.3 9.0 [3]

Note: 1 k = AT exp(− E / RT ) , in cm, kcal, s, and mole units; 2See reference: Lou and Chang,
n

1997; 3See reference: Chang and Senkan, 1989; (*) most significant reactions in this experiment.

33