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Temporal Development of Ozone Generation in Electron-Induced Corona-Discharge Plasma

T. Vijayan and Jagadish G. Patil
AbstractOzone (O3 ) generation and its temporal development to steady state are investigated in a precise model using all high-rate reactions for various conditions of gas pressure (P ), electron density (ne ), and temperature (T ) of an evolving electron-induced O2 corona plasma. Densities of O and (O3 ) radicals are determined from their gross formation and destruction. Net (O3 ) density so attained in steady state at T = 300 K is over 1025 m3 for P bar and ne 1015 m3 . However, net O density for the same is lower 1020 m3 even though O density exceeded (O3 ) density in early times of formation. It is shown that (O3 ) density reduced with temperature heated by discharge in corona, while O density reduced with T up to 500 K and thereafter increased to 1021 m3 with still higher T . Both O and (O3 ) densities varied proportional to the electron density enhanced by avalanche in corona. (O3 ) varied proportional to pressure, and O exhibited swing to inverse proportionality with larger P . Index TermsOxygen discharge, particle balance, radical evolution, reaction rates, steady state, temporal buildup.

I. I NTRODUCTION

HE subject of evolution and destruction of ozone (O3 ) is currently a live topic for theoretical as well as experimental studies particularly on the development of highconcentration ozone generators [1][4]. In nature, ultraviolet (UV) rays in sunlight impinge oxygen molecules O2 and produce O radicals. O radicals, in turn, join with free O2 and form ozone. These reactions are however reversible. In view of this and also as processes in nature are very weak, they yield only small (O3 ) concentrations less than subparts per million, whereas the reactions attain enhanced levels when carried out in a laboratory in controlled conditions and yield large concentrations useful for numerous applications including many biochemical processes. This is particularly so by using electrons [5] as source in place of UV. In the aforementioned context, most of the two-body and three-body interactions involving electron, O2 , O, and O3 are well known, and their reaction rates are available in the literature [1][4]. Of the same, however, only a few reactions, viz., (e, O2 ), (O, O2 , [O2 ]), (O, O2 , [O]), (O, O2 , [O3 ]), (e, O3 ), (O, O3 ), (O2 , O3 ), (O3 , O3 ), and (O, O, [O2 ]), are large enough

Manuscript received April 6, 2011; revised July 4, 2011; accepted August 24, 2011. Date of publication October 13, 2011; date of current version November 9, 2011. This work was supported by the Department of Science and Technology, Government of India. The authors are with the Pillais Institute of Information Technology, Engineering, Media Studies and Research, Dr. K. M. Vasudevan Pillais Campus, New Panvel 410 206, India. Color versions of one or more of the gures in this paper are available online at http://ieeexplore.ieee.org. Digital Object Identier 10.1109/TPS.2011.2166980

to contribute signicantly to net particles that evolved from the reactions. Particles in square brackets in aforementioned three-body reactions denote the catalyst particles aiding the reactions. The effect of other reactions, which are not listed here, are either negligible or all put together make only a minute correction to the overall results. In earlier work [5], the evolution of ozone was investigated in a cold corona discharge formed inside the anodecathode (AK) annular gap of cylindrical diode of axial symmetry. The axial cathode of this innovative diode is formed of a large number of pointed nozzles which are located symmetrically on different radial planes on the same cylindrical cathode mast. The nozzles here, in addition to injecting oxygen into the AK gap, created high electric elds over their tips causing eld emissions and paved the way for the formation of corona plasma discharge. Electrons in this plasma multiplied through avalanches and formed O radicals by two-body interactions in background O2 . Alongside, formation of O3 occurred in threebody interactions. Destruction of O3 also happened side by side through two-body collisions. Thus, the background gas evolved transiently into a steady-state mixture of O2 , O, and O3 . In previous work [5], ozone concentrations were not estimated precisely as there was a confusing picture regarding the important reactions to be included in modeling where aforementioned works [1][4] and others [6][10] employed only a few of aforementioned high-rate reactions in their models. For example, [6][8] did not include the all-important two-body O3 destruction term (e, O3 ). Also, (O3 , O3 ) destruction term, which is high in the high-O3 -density regime, was omitted. The aforementioned two terms are also important for reinduction of O radicals into the system. In addition, [6] and [8] did not include the three-body, namely, (O, O2 , [O3 ]) and (O, O2 , [O]), reactions of O3 formation which are peaked with higher O and O3 present particularly toward the steady state. Similar deciencies are noted in [9] and [10] even though reaction (e, O3 ) was included in their models. In view of these, it was hard to answer the question at that stage. In the situations, we estimated ozone concentrations in [5] in more of a qualitative way than quantitative. We now take up the aforementioned issues and nd appropriate answers in this paper through application of all the important reactions combined together in a self-consistent correct model and computation scheme. Thus, this paper provides near complete simulation model of oxygen radical evolution by including all-important reaction terms of formation and destruction. In addition, the present model is extended to determine the radical species created by enhanced electron densities in avalanche conditions of corona and also at the higher temperatures in a discharge-heated

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corona. The computed results are compared with observations in experiments, and the model is validated. After introducing the topic in Section I, major reactions leading to formation of radicals in oxygen corona plasma are described in Section II along with their rate equations. A simulation model on these lines, for given boundary conditions, is also presented in Section II. Results of simulation studies are described and discussed in Section III. Conclusions are offered in Section IV. All SI units are used in present theoretical treatment unless stated otherwise. II. M ODELING OF O ZONE F ORMATION A. Major Ozone-Forming Reactions Ozone (O3 ) is formed mainly in the following three-body interactions and respective reaction rates [4] k3a , k3b , and k3c in m6 /s O + O2 + [O] O3 + O k3a = 2.15 10
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k4c = 7.3 1016 exp (11400/T ) O3 + O3 O + O2 + O3 k4d = 1.65 10

15

(8a) (9)

exp (11400/T ).

(9a)

Depletion of O also takes place through reaction (7) while reinduction of O into the system takes place also through (6)(9). Accuracy of the rate equations previously mentioned is well known and generally accepted [1][10]. However, many have not included all of them in their models. Our attempt in present work is to include all the aforementioned reactions together in a self-consistent simulation model to enable precise determination of particles evolved in reactions. This was not done earlier. B. Simulation Model The number density rates attained by the particles from reactions (10)(18) are grouped in the following heads: (a) O3 formation nr112 = n1 n1 n2 k3a nr122 = n1 n2 n2 k3b nr123 = n1 n2 n3 k3c (b) O formation nre2 = ne n2 k1e (c) OO reversion nr112a = n1 n1 n2 k2 (14) (13) (10) (11) (12)

(1) (1a) (2) (2a) (3) (3a)

exp (345/T )

O + O2 + [O2 ] O3 + O2 k3b = 6.9 1046 (300/T )1.25 O + O2 + [O3 ] 2O3 k3c = 4.6 1047 exp (1050/T )

where T is temperature which could be high in a dischargeheated corona and limit the ozone output. O radicals in (1)(3) are initially made available from eO2 collisions with reaction rate k1 e + O2 O + O + e k1 = 2 1015 (m3 /s). (4) (4a)

(d) O3 reversion nre3 = ne n3 k4a nr13 = n1 n3 k4b nr23 = n2 n3 k4c nr33 = n3 n3 k4d (15) (16) (17) (18)

Oxygen dissociation by electron impact here depended on electron density and energy distribution as described in previous work [5]. Dependence of latter on discharge current, gas pressure, device geometry, electric eld (E), etc., also has been examined with ne and E shown to be nonuniform. Destruction of O radicals also takes place alongside O and (O3 ) formations. This occurs through (1)(3) as well as through the following reaction: O + O + [O2 ] 2O2 k2 = 3.8 10
42

(5) (m /s).
6

where ne , n1 , n2 , and n3 are the electron, O, O2 , and O3 densities, respectively. The resulting net O3 formation and destruction rates are n3f = nr112 + nr122 + nr123 n3d = nre3 + nr13 + nr23 + nr33 which give rise to increase in O3 density in time step t as n3 = (n3f n3d )t and density n3 (t) at any instant (t) given as n3 (t) = n3 (to ) + n3 where to = (t t). (22) (21) (19) (20)

exp (170/T )/T

(5a)

On the other hand, (O3 ) reverts to O2 through the two-body reactions given hereinafter with rates in m3 /s e + O3 O2 + O + e k4a = 5 10 O + O3 2O2 k4b = 1.8 1017 exp (2300/T ) O2 + O3 2O2 + O
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(6) (6a) (7) (7a) (8)

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Similarly, O formation/destruction rates and increase in its density are n1f = nre2 + nre3 + nr23 + nr33 n1d = nr13 + nr112a + nr112 + nr122 + nr123 n1 = (n1f n1d )t n1 (t) = n1 (to ) + n1 . (23) (24) (25) (26)

Then, resulting n2 (t) is given from continuity and conservation as n2 (t) = n2 (t = 0) 3n3 /2 n1 /2 (27)

which equals the sum of O2 reversals at steady state from (14)(18) n2 (t) = n1 n1 n2 k2 +ne n3 k4a +n1 n3 k4b +n2 n3 k4c +n3 n3 k4d . (28) C. Initial Conditions and Computations We describe here an innitely large volume corona plasma of unbounded limits, uniform densities, and temperature. The initial densities at time t = 0 are n1 = 0 and n3 = 0, and the predened nite values are n2 , ne , and T quantities. Employing (10)(28) transiently and solving them iteratively, n1 and n3 are evaluated to steady state for the condition of 3n3 /2 + n1 /2 + n2 (t) = n2 (t = 0). (29)
Fig. 1. Ozone formation rates computed from major reactions (1)(3) and plotted against time in given oxygen corona plasma with pressure (P ), temperature (T ), and electron density (ne ).

Time step t = 1 ns is used in the calculations. Results so obtained of O2 corona plasma of various temperatures T , electron densities ne , and gas pressures P are presented hereinafter and discussed. III. R ESULTS AND D ISCUSSIONS The temporal development of O3 formation rates at temperature T = 300 K, oxygen pressure P = 2 bar, and electron density ne = 1015 m3 calculated from (10)(12) is plotted and compared in Fig. 1. As seen in Fig. 1, the reaction (O, O2 , [O2 ]) is maximum at all times. Reactions (O, O2 , [O]), although higher than reactions (O, O2 , [O3 ]) in initial times, are lower than latter in later times. O3 destruction rates [(15)(18)] plotted in Fig. 2 in similar conditions show that the reaction (e, O3 ) is maximum followed by (O, O3 ), (O2 , O3 ), and (O3 , O3 ) in that order. A higher net O3 formation rate deduced from Fig. 1 compared to the net O3 destruction rate derived from Fig. 2 allowed the O3 concentration in reaction space to accumulate and increase with time. Moreover, nally, the two net rates equaled with passage of time and established a steady state of constant O3 concentration as shown in Fig. 3. Results of O formation reactions show that the rate of (e, O2 ) is maximum followed by (e, O3 ), (O2 , O3 ), and (O3 , O3 ) in that order, while O destruction rate given by (O, O2 , [O2 ]) is maximum followed by (O, O2 , [O]) and (O, O2 , [O3 ]). Destruction by (O, O2 , [O3 ]) overtook that by (O, O2 , [O]) as higher O3 was made available with time. The net formation and destruction
Fig. 2. Ozone destruction rates computed from major reactions (6)(9) and plotted against time in the same conditions with those in Fig. 1.

rates here show similar trends as those in O3 case and attained steady states with typical lower values than O3 . Here, the net O formed in early times is higher than that of O3 as shown in Fig. 3 which helped the creation of more O3 in later times. This along with high life times of O3 caused accumulation of more O3 and a net exceeding the O net in later times. In the process, saturation of both the species took place at steady state as in Fig. 3. In the event, concentration attained by O3 is a few orders higher than O, and n1 tended to a plateau earlier around 107 s due to short O life. These are accompanied by fall of O2 density toward steady state as shown in Fig. 3. Particle densities computed for different O2 pressures (P ) are also plotted in the same gure which shows higher O3 densities of order pressure. O density at higher pressures although higher in early times exhibited swing to lower values in later times. The temporal variation of O and O3 densities at different temperatures (T ) resulting from (1a)(9a) is shown in Fig. 4 for P = 2 bar and other conditions same as those in Fig. 3.

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Fig. 3. Temporal buildup of particles O2 , O, and O3 densities formed inside the reaction space at the various pressures (P ) in given conditions culminating to steady state. Reaction rates given in Figs. 1 and 2 were used for getting the O3 plot (2). Rates similarly computed were used in plots (1) and (3) of O3 and all O plots. Observed value of O3 at P = 1 bar is included for comparison.

Fig. 5. O3 and O density variations at different electron densities (ne ), P = 2 bar, and other things same as those in corona plasma in Fig. 3.

heating in gas by the discharge current in the diode experiments as reasoned in [1]. Similar experimental results with heating are noted in diode in [11]. These comparisons amply validate the present simulation model. IV. C ONCLUSION This paper gives a near complete model of O3 evolution in electron-induced O2 discharge plasma by including all major reaction terms. Results from the model show that, although the early O3 density attained was lower than that of O, ozone density steadily rose to orders of magnitude higher than O toward steady state as more and more O radicals are made available with time for the O3 genesis. Steady-state O and O3 densities so formed are 1020 and 1025 m3 , respectively, for pressure P bar, electron density ne 1015 m3 , and temperature T = 300 K. Ozone density however decreased with higher T that existed in a discharge-heated corona. O density for the same conditions indicated reduction up to 500 K and then increased with higher T . An avalanche-enhanced ne in corona gave higher densities of both O and O3 while higher pressures gave higher O3 , but O densities swung from higher side at early times to lower side at the later times to steady state. Simulation results are compared with observed values. ACKNOWLEDGMENT The authors would like to thank Dr. K. M. V. Pillai and Dr. D. Pillai for the encouragements and Dr. A. K. Das for the discussions. R EFERENCES
[1] K. Yanallah, F. Pontiga, A. Fernandez-Rueda, A. Castellanos, and A. Belasri, Ozone generation by negative corona discharge: The effect of Joule heating, J. Phys. D, Appl. Phys., vol. 41, no. 19, p. 195 206, Oct. 2008. [2] J. Kitayama and M. Kuzumoto, Theoretical and experimental study on ozone generation characteristics of an oxygen-fed ozone generator in silent discharge, J. Phys. D, Appl. Phys., vol. 30, no. 17, pp. 24532461, Sep. 1997.

Fig. 4. O3 and O density variations at different temperatures (T ), P = 2 bar, and other conditions same as those in reaction space in Fig. 3.

The temperatures here are representative of those in a corona heated by the discharge current in typical range of 10100 A of plasma diode [5]. O3 densities shown in Fig. 4 are lower with higher temperatures due to the larger O3 dissociations with T . O density as seen in Fig. 4 also reduced with higher temperatures up to 500 K but showed increasing trend with further increase in T . This is due to the overall net effect of (10)(18) with T . Fig. 5 plots the temporal O and O3 density variations with electron density ne as a parameter for P = 2 bar and other things same as those in Fig. 3. Higher ne here is attained through electron multiplication by avalanche in corona [5]. Fig. 5 shows that both O and O3 densities increased proportional to ne . O3 concentrations observed in [1] in steady-state generation for 1-bar pressure are around 6 1023 m3 and are shown along with the present simulation in Fig. 3. Smaller observed density compared to the simulation results here is attributed to

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[3] B. Eliasson, M. Hirth, and U. Kogelschatz, O3 synthesis from O2 in dielectric barrier discharges, J. Phys. D, Appl. Phys., vol. 20, no. 11, pp. 14211437, Nov. 1987. [4] R. Peyrous, P. Pignolet, and B. Held, Kinetic simulation of gaseous species created by an electrical discharge in dry or humid oxygen, J. Phys. D, Appl. Phys., vol. 22, no. 11, pp. 16581667, Nov. 1989. [5] J. G. Patil and T. Vijayan, Characteristics of high-tension induced corona-discharge plasma in ozone generator diode, IEEE Trans. Plasma Sci., vol. 38, no. 9, pp. 24222427, Sep. 2010. [6] K. Yanallah, S. Hadj Ziane, A. Belasri, and Y. Meslem, Numerical modeling of ozone production in direct current corona discharge, J. Mol. Struct.THEOCHEM, vol. 777, no. 13, pp. 125129, Nov. 2006. [7] P. Pignolet, S. Hadj-Ziane, B. Held, R. Peyrous, J. M. Benas, and C. Coste, Ozone generation by point to plane corona discharge, J. Phys. D, Appl. Phys., vol. 23, no. 8, p. 1069, Aug. 1990. [8] C. Gutierrez-Tapia, E. Camps, and O. Olea-Cardoso, Pertubative method for ozone synthesis from oxygen in a single discharge, IEEE Trans. Plasma Sci., vol. 22, no. 5, pp. 979985, Oct. 1994. [9] K. Ohe, K. Kamiya, and T. Kimura, Improvement of ozone yielding rate in atmospheric pressure barrier discharges using a time-modulated power supply, IEEE Trans. Plasma Sci., vol. 27, no. 6, pp. 15821587, Dec. 1999. [10] J. F. Loiseau, F. Lacassie, C. Monge, R. Peyrous, B. Held, and C. Coste, Numerical simulation of ozone axial and radial distribution in a cylindrical oxygen-fed ozonizer, J. Phys. D, Appl. Phys., vol. 27, no. 1, pp. 63 73, Jan. 1994. [11] T. Vijayan and J. G. Patil, High concentration ozone generation in laboratory for various applications, Int. J. Sci. Technol. Educ. Res., vol. 1, no. 6, pp. 132142, Nov. 2010.

T. Vijayan received the Ph.D. degree in physics from the University of Mumbai, Mumbai, India, in 1983. He started his carrier as a Teacher in physics with the Government College Kasaragod, Kasaragod, India. He is currently a Professor in physics with the Pillais Institute of Information Technology, Engineering, Media Studies and Research, Dr. K. M. Vasudevan Pillais Campus, New Panvel, India. Prior to that, he was a Senior Scientist with Bhabha Atomic Research Centre, Mumbai, and was engaged in research on generation and transport of particle beams and plasmas and their applications and interactions with various targets.

Jagadish G. Patil received the M.Sc. degree in physics from the University of Mumbai, Mumbai, India, in 2002. He is currently a Senior Research Fellow in physics with the Pillais Institute of Information Technology, Engineering, Media Studies and Research, Dr. K. M. Vasudevan Pillais Campus, New Panvel, India. Prior to that, he was a Project Assistant with the Indian Institute of Geomagnetism, Mumbai, and was engaged in observatory data analysis.