Gliding Arc Plasma Processing for Decomposition of

Chloroform

Antonius Indarto† , Jae-Wook Choi, Hwaung Lee, and Hyung Keun Song

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

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

Abstract- The decomposition of chloroform diluted in air was studied. The experiment

was carried out by using a gliding arc plasma. Different values of initial concentrations

of chloroform, total gas flow rates, and input power frequencies have been used to

investigate this effects on the conversion reaction products both qualitatively and

quantitatively. Experimental results indicate that the maximum conversion of

chloroform was 97% at a total gas flow rate of 180 L/h containing 1% chloroform.

Using air as carrier gas, decomposition of chloroform produces CCl4, CO2, CO, and Cl2

as the main products. Small amounts of HCl and COCl2 are also detected. Liquid

products were also produced.

Keywords: Plasma, gliding arc plasma, chloroform, decomposition

†
Corresponding author: E-mail:indarto_antonius@yahoo.com

1
1. Introduction

Chloroform (CHCl3) is classified as toxic and carcinogenic and it is an important task to

remove it from indoor or outdoor ambient atmosphere [1,2]. Chloroform is used as

solvent in production of various chemicals, and existed in some pesticide formulations.

Chloroform is suspected to have Global Warming Potential (GWP) and to contribute to

the destruction of the ozone layer in the stratosphere [3].

Two approaches are generally used to remove this pollutant from air, i.e. by thermal or

catalytic oxidation. Several procedures of thermal oxidation have been developed and

established [4,5]. This process requires high burning-temperature (between 760 - 980oC)

and relatively long residence time to complete the oxidation reaction [4]. To avoid these

problems, many researchers have proposed the use of catalysts. Although this could

reduce the duration of residence time, the removal efficiency was found to be lower

than by thermal oxidation. At low temperature, the catalyst’s lifetime is short [6] and

different catalysts when the target material consists different VOC species.

To overcome these problems, gliding arc discharge has a bright prospect, especially for

industrial scale application. Gliding arc discharge is the subject of renewed interest for

applications to various chemical reactions [7]. Therefore, the main recent improvement

for utilizing gliding arc discharge are more powerful electrical discharges under thermal

non-equilibrium conditions [8], short resident time, and concentration capacity.

Kinetic destruction of chloroform using photosensitized oxidation [9], thermal oxidation

[10], or photocatalysis [11,12] have been studied previously but, unfortunately, the

reaction pathway under gliding arc discharge condition was not studied in detail. In the

2
present work, the reaction mechanism of decomposition of chloroform diluted in

compressed air was studied by gliding arc discharge. The main products CO, CO2, Cl2,

and CCl4 were the object of analysis.

2. Experimental setup

Figure 1

A diagram of experimental setup is shown in Fig. 1. Chloroform and compressed air are

used as input gas. The setup is described in detail in the following section.

2.1. Plasma reactor and applied power system

The reactor was made from a quartz-glass tube of an inner diameter of 45 mm and a

length of 300 mm. Top and bottom of the reactor are equipped with teflon seals the

lower comprising two electrodes made of stainless steel, length of the electrodes being

100 mm. The distance of the electrodes in the narrowest section is 1.5 mm. The gas

mixture is fed between the electrodes with a capillary of 0.8 mm inner diameter. A

thermocouple, located 10 cm above the electrode, is provided to measure the outlet gas

temperature. A high frequency AC power supply (Auto electric, A1831, Korea) is

connected to the gliding arc electrode to generate the plasma. In this experiment, the

total power can not be adjusted; it is a function of the breakdown voltage and changes

into stable-equilibrium automatically when the arc is formed. The supplied power is

3
calculated for equilibrium condition when the plasma has been operated for 30 minutes.

Figure 2 shows the typical waveforms of voltage and discharge current used in these

experiments.

Figure 2

2.2. Input gas

Chloroform (CHCl3) (Junsei Chemical Co., Japan) purity of ~99.0%, is varied in its

concentration to 1, 3, 5, 8% volume of total gas flow. Air used as carrier gas and is

controlled by a Mass Flow Controller (Tylan, FC-280S) at flow rates of 180, 240, and

300 L/h. Air entering the reactor first passes through a scrubber and is mixed with

chloroform. Chloroform is introduced by passing a portion of air through a bubble flash

placed in a water bath. The concentration of chloroform is controlled both by the

temperature of the water bath and the gas flow rate through the flask. The input lines are

heated by means of heating tape to avoid the condensation. The composition of the

mixture is analyzed at the outlet reactor with the plasma operation on and off.

2.3. System of Measurements

The outlet gas composition is examined by an electrone-impact ionization quadrupole

mass spectrometer (Balzers, QMS 200) with software Quadstar 421, for the qualitative

and quantitative analysis of reactants and products. Two GC’s are been: chlorinated

4
methane compounds in the product gas mixture is qualitatively determined by GC-FID

(YoungLin, M600D, Korea, Column: 5 m x 2.5 cm i.d. Bentone), for CO and CO2 by

GC-TCD (YoungLin, M600D, Korea, Column: 5 m x 2.5 cm i.d. SK Carbon). Chlorine

gas (Cl2) is determined by bubbling the reacting gas through 0.05 M aqueous KI for a

given experiment time, followed by iodometric titration with 0.05 M Na2SO3 [13].

The evaluation of system as to its performance, selectivity and conversion, is

formulated as:
moles of (CO + CO2 ) produced
Selectivity of (CO + CO2 ) = × 100% (1)
moles of chloroform converted

2 × moles of Cl 2 produced
Selectivity of Cl 2 = × 100% (2)
3 × moles of chloroform converted

moles of chloroform converted

Conversion of chloroform(η ) = × 100% (3)
moles of initial chloroform

These parameters are used to study the effect of initial chloroform concentration, total

gas flow rate, and input power frequency.

The supplied power is shown as function of voltage and current determinated by

oscilloscope (Agilent, 54641A, USA) and calculated to power term by following

equation:

Supplied power = ∫ (V (t ) × I (t ) ) dt × frequency (Watt ) (4)

In this study the experimental data were taken 30 minutes after the initiation of the

gliding arc plasma referred to the stable temperature of the outlet bulk gas measured by

thermocouple.

5
3. Results and Discussion

With the gliding arc plasma, the destruction of chloroform (CHCl3) produces CO2, CO,

Cl2, and CCl4, as the main products. The yields of CO and Cl2 are higher than that of

CO2 and CCl4. The concentration of CO2 is 3-5 times lower than the concentration of

CO. CCl4 is formed at yields between 8 to 15% by mol basis. HCl and COCl2, are also

detected by mass spectrometer (QMS), but in low concentration. The destruction

performance was studied as functions of initial chloroform concentration, total gas flow

rate, and input frequency. The gaseous product analysis is focused on CO, CO2, and Cl2

compounds because these are the main products and can be measured precisely.

3.1. Effect of initial concentration.

Figure 3

Figure 3a shows the effect of various initial concentrations of chloroform on its

conversion at an input power frequency of 20 kHz. The maximum conversion reached

97% at the lowest concentration of chloroform, 1%, and a total gas flow rate of 180 L/h.

Conversion of chloroform gradually decreases when the initial concentration increases.

The decrement rate reaches 2.5% per 1% of increase of initial chloroform concentration

in the inlet stream. One factor that contributes to the decrease is the power supplied to

the reactor which decreases when the initial concentration of chloroform increases (Fig.

3b). Thus, less energy is supplied for initiation of gas molecules.

The supplied power is highly dependent on the breakdown process producing the arc by

6
breaking bonds or exciting molecules [8]. Chloroform has less strong chemical bonds

compared to components such as O2 and N2 that are mostly existing in the inlet stream.

It means that the required energy to initiate the first arc plasma is less also. Higher

concentrations of chloroform decrease the required breakdown energy which decreases

the supplied power automatically. Therefore, as mentioned above, the stabilized

equilibrium power is automatically adjusted by the system.

Different values of initial concentration of chloroform have significant effects on the

energy efficiency of the system. The energy consumed per converted chloroform is

rising from 18.6 to 114 Watt⋅h/L when the concentration of chloroform is decreasing

from 8 % to 1 %. At a higher initial concentration of chloroform the collisions are more

effective although the percentage of conversion is lower.

Small increments of gas temperature due to increasing initial chloroform concentration

are measured, reaching 250oC and rising 2-3oC per 1 % increment of initial chloroform.

It reflects the energy released from the exothermic plasma reaction and calculated

following formula 5 and 6.

[(
Q = m ⋅ C p ) un−reacted species + ∑ ( m ⋅ C p ) products ] × (Tg ,t − Tg ,0 ) (5)

∆H reaction = Q − W power supply (6)

When the plasma reaction occurs, a portion of chemical energy is converted to thermal

energy and rises the temperature. Compared to the supplied electrical energy,

exothermic plasma reaction constitutes 70-80% of the energy increasing the product gas

temperature (calculated using formula 5 and 6). Higher initial concentrations of

chloroform produce more heat. By calculating the converted chloroform, the ratio leads

7
to 97.03 (1%×180 L/h ×97.03%) and 274.44 (3%×180 L/h ×91.48%) for the chloroform

concentration at 1% and 3% and total gas flow rate 180 L/h. This means that the

molecule collision probability at higher concentration of chloroform, i.e. 3%, is

approximately 3 times higher than that at lower concentration, i.e. 1%.

The yields of gas products, (CO+CO2) and Cl2, is shown in Fig. 3c and d. No significant

differences in yields of (CO+CO2) are observed at different initial concentrations of

chloroform. The maximum yield of (CO+CO2) is around 50%. It shows that almost half

fraction of reaction produced CO or CO2. Conversion into CCl4 was detected not exceed

than 15% in all experimental conditions. The remaining carbon possibly transforms into

solid (shoot) or liquid products which are also produced during experiment. In the case

of Cl2, the yields increase slightly with increasing chloroform concentration.

Oxygen and nitrogen in the input stream should be considered as factors for determining

the product selectivity. Oxygen and nitrogen can be transformed into high-energy state

species or radicals by collision. Calculated from mass spectra data, the difference of

oxygen concentration before and after the plasma reaction approaches 10% and for

nitrogen 5%, independent of the initial chloroform concentration. The role of radical

species, such as oxygen and oxygen radical to maintain the decomposition process, has

been studied before [14, 15].

3.2. Effect of total gas flow rate

Figure 4

The effect of total gas flow rate, determining the residence time of chloroform in the

8
reactor, was examined. Figure 4a shows the chloroform conversion according to the

various total gas flow rates at initial chloroform concentrations of 1, 3, 5 % and power

supply frequency of 20 kHz. The conversion of chloroform decreases with the increase

of total flow rate. Raising the total gas flow rate reduces the residence time of

chloroform in the reactor and the chance and time of a molecule to collide with

electrons and other high-energy state species which have enough energy to destroy

carbon-hydrogen or carbon-chloride bonds. Lower conversion is also caused by

decreasing power as gas flow rate increased (Fig. 4b). This phenomenon has been

observed previously [16].

In terms of energy efficiency the effect of total gas flow rate is rather smaller. The

consumed energy per converted chloroform decreases from 149 to 122 Watt⋅h/L when

the flow rate increases from 180 to 300 L/h.

With increasing of total gas flow rate (Fig. 4b), the (CO+CO2) yield increases, Fig. 4c,

while the yield of Cl2 tends to decrease.

3.3. Effect of applied frequency

Figure 5

Decomposition of chloroform increases slightly from 92 % to 97 % when the frequency

of input power is increased from 15 to 20 kHz at 180 L/h (Fig. 5a). The same trend is

observed at 300 L/h with yields between 42% to 60%. Radu et al. mention that a change

9
in frequency will change the basic breakdown mechanism [17]. Higher frequency will

increase the extent of sudden-fluctuating pulsed current and voltage peak per cycle.

Furthermore, it will increase the total power supplied to the plasma (fig. 5b) which

provides more energy for the gas ionization process.

However, the ratio of power consumed versus converted chloroform is increased from

92 Watt⋅h/L at 15 kHz to 142 Watt⋅h/L at 20 kHz. It means that at lower frequency,

although the conversion of chloroform is lower, the energy efficiency is better that at

higher frequency.

Increasing frequency decreases the yields of (CO+CO2) (Fig. 5c). However, the yield of

Cl2 increases from 18% to 25% at 180 L/h and achieves maximum of 38% at a total gas

flow rate 300 L/h (Fig. 5d).

3.4. Mass Spectra

Figure 6

A mass spectrum of the chloroform decomposition mixture is shown in Fig. 6. The main

fragment of chloroform is m/z 82/84/86 ( ). CO2 has its molecular ion at m/z 44 (
+
CCl 2

) but overlaps with N2O ( ) which may form as gas product. CO is at 28 (

CO2+ N 2O +
) but overlaps minor N2 spectra 29 ( ). Some additional peaks are m/z 63/65, for

CO + N 2+

10
 + + +
COCl2 ( COCl ), m/z 70/72 for Cl2 ( Cl 2 ), m/z 117 for CCl4 ( CCl 3 ).

4. Conclusions

The performance of chloroform conversion in gliding arc plasma at atmospheric

pressure, in respect to initial concentration of chloroform, total gas flow rate, and input

power frequency, was studied. Gliding plasma generates enough active species to

fragment chloroform molecules. The maximum conversion of 97% is achieved for a

feed gas stream containing 1% of chloroform and a total air flow rate 180 L/h. Four

gaseous compounds, CO, CO2, CCl4 and Cl2, are the major products. Cl2 yields are

relatively high and reached maximum of 50%. Yields of CO and CO2 reaches up to 78%

mol at 15 kHz of frequency and total gas flow rate at 180 L/h. Conversion into CCl4 was

detected in case of chloroform decomposition, but not exceeds than 15%. COCl2 has an

important role as intermediate species to produce Cl2 and CO. Development is still

needed to remove some traces of unwanted compounds in the final product, such as:

COCl2 and CCl4 which are also classified as toxic gases.

Acknowledgements

This work was supported by the National Research Laboratory of the Korea Minister

11
Ministry of Science and Technology of Korea.

References

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Catal. 1998; 178: 214.
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Combust. Sci. 1999; 25: 211.
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Saunders College Publishing. 2000.
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12
 vent to
atmosphere

FID GC
Bentone

MFC- 1
TCD GC
SK Carbon

Compressed Quadrapole
air Scrubber
Mass
Spectrometer

MFC- 2
Plama
zone

Capilary Electrode
CHCl3 tube

waterbath
KI solution

Plasma
Reactor

Figure 1. Schematic diagram of experimental set up

13
 6000

4000

2000
Voltage (V)

-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

Time (s)

Figure 2. Voltage and current profile

14
 100
CHCl3 conversion

CHCl3 conversion (%) 80

60

40 180 L/h
240 L/h
300 L/h
20

300
Supplied Power
280

260
Power (Watt)

240

220

200
180 L/h
180 240 L/h
300 L/h
160

60 (CO + CO2)

50
Molar yields (%)

40

30

20 180 L/h
240 L/h
300 L/h
10

60 Cl2

50
Molar yields (%)

40

30

20 180 L/h
240 L/h
300 L/h
10

0 2 4 6 8 10
initial CHCl3 concentration (%)

Figure 3. Effect of initial chloroform concentration on (a) chloroform conversion,

(b) supplied power, (c) yields of (CO + CO2) , and (d) of Cl2.

15
 CHCl3 conversion
100

CHCl3 conversion (%)

80

60

1%
3%
40
5%

300 Supplied Power

Power (Watt)

250

200

1%
3%
150 5%

60
(CO + CO2)
50
Molar yields (%)

40

30

20 1%
3%
5%
10

60 Cl2

50
Molar yields (%)

40

30

20 1%
3%
10 5%

160 180 200 220 240 260 280 300 320

Total gas flow rate (L/h)

Figure 4. Effect of total gas flow rate on (a) chloroform conversion,

(b) supplied power, (c) yields of (CO + CO2), and (d) of Cl2.

16
 100 CHCl3 conversion

CHCl3 conversion (%) 80

60

40

180 L/h
20 300 L/h

300 Supplied Power

250
Power (Watt)

200

150

180 L/h
100 300 L/h

(CO + CO2)
80
Molar yields (%)

60

40

20 180 L/h
300 L/h

60 Cl2

50
Molar yields (%)

40

30

20
180 L/h
300 L/h
10

14 15 16 17 18 19 20 21

Frequency (kHz)

Figure 5. Effect of applied power frequency on (a) chloroform conversion,

(b) supplied power, (c) yields of (CO + CO2), and (d) of Cl2.

17
 1.2e-9

1.0e-9

8.0e-10
Intensity

6.0e-10

4.0e-10

2.0e-10 COCl2
CHCl3
Cl2 CCl4

0 20 40 60 80 100 120 140 160 180 200

AMU (m/z)

Figure 6. Mass spectrum of chloroform decomposition (taken at applied frequency 20

kHz, 1% of chloroform, total gas flow rate 240 L/h).

18