Kinetics of destruction of diisopropyl methylphosphonate in corona discharge

Article abstract of DOI:10.1002/kin.10055

The kinetics of the destruction of diisopropyl methylphosphonate (DIMP) in corona discharge has been studied using a flow tubular coaxial wire dielectric barrier corona discharge reactor. The identification and quantitative determination of DIMP, its destruction intermediates, and phosphorus-containing destruction products were performed using molecular beam mass spectrometry and gas chromatography/mass spectrometry. Active discharge power was varied in the range 0.01-5 W. The destruction products such as isopropyl methylphosphonate, methylphosphonic acid, and orthophosphoric acid were found on the reactor walls. The dependence of the extent of the destruction, D(D = 1 - X/X₀, where X and X₀ are DIMP mole fractions at the outlet and the inlet of the reactor), on the specific energy deposition E_x(E_x = PF^-1 X₀^-1, where F is the carrier gas flow and P is the power dissipated in discharge reactor) was measured over the DIMP mole fraction range 60-500 ppm at the pressure of 1 bar and the temperature of 340 K. Over the range of the experimental conditions studied the destruction obeys the pseudo-first-order kinetic law: 1n(1 - D) = -KE_x. Plausible mechanisms of the destruction are discussed. It was concluded that ion mechanism is the major one responsible for the destruction process.

Full text of DOI:10.1002/kin.10055

Kinetics of Destruction
of Diisopropyl
Methylphosphonate
in Corona Discharge
OLEG P. KOROBEINICHEV,1 ANATOLY A. CHERNOV,1 VLADIMIR V. SOKOLOV,1
LEV N. KRASNOPEROV2
1Institute of Chemical Kinetics and Combustion, Siberian Branch Russian Academy of Sciences, Intitutskaya Street 3,
Novosibirsk, 630090, Russia
2Department of Chemical Engineering, Chemistry and Environmental Science, New Jersey Institute of Technology, Newark,
New Jersey 07102
Received 26 September 2000; accepted 14 January 2002
DOI 10.1002/kin.10055
ABSTRACT: The kinetics of the destruction of diisopropyl methylphosphonate (DIMP) in corona
discharge has been studied using a flow tubular coaxial wire dielectric barrier corona dis-
charge reactor. The identification and quantitative determination of DIMP, its destruction inter-
mediates, and phosphorus-containing destruction products were performed using molecular
beam mass spectrometry and gas chromatography/mass spectrometry. Active discharge power
was varied in the range 0.01–5 W. The destruction products such as isopropyl methylphospho-
nate, methylphosphonic acid, and orthophosphoric acid were found on the reactor walls. The
dependence of the extent of the destruction, D(D = 1 X /X0, where X and X0 are DIMP mole
fractions at the outlet and the inlet of the reactor), on the specific energy deposition Ex (Ex =
PF 1X0 1, where F is the carrier gas flow and P is the power dissipated in discharge reactor)
was measured over the DIMP mole fraction range 60–500 ppm at the pressure of 1 bar and the
temperature of 340 K. Over the range of the experimental conditions studied the destruction
obeys the “pseudo-first-order” kinetic law: ln(1 D) = KEx . Plausible mechanisms of the
destruction are discussed. It was concluded that ion mechanism is the major one responsible
C
for the destruction process. 2002 Wiley Periodicals, Inc. Int J Chem Kinet 34: 331–337, 2002
of pollutants (volatile organic compounds (VOCs),
NOx , SOx ) from stack emissions [1–21]. During the
last few years a significant progress was achieved in
the application of corona discharge plasma for the con-
version of VOCs [1–6], silicon-containing compounds
[7], NOx [2,3,8–11], and SOx [11–13], and in the
understanding of the kinetics of the destruction of these
pollutants. Initial research on the decontamination
of organophosphorus compounds (OPCs), simulants
of sarin in corona discharge, was performed in the
mid-80s [14–17]. Fraser, et al. [15–17] determined
INTRODUCTION
Recently, corona discharge emerged as a promising
novel technologyfor the treatment oflowconcentration
Correspondence to: Oleg P. Korobeinichev; e-mail: korobein@
ns.kinetics.nsc.ru.
Contract grant sponsor: USA Army Research Office.
Contract grant number: DAAG55-98-1-0512.
Contract grant sponsor: NATO.
Contract grant number: DISRM.LG 961353.
2002 Wiley Periodicals, Inc.
c

332
KOROBEINICHEV ET AL.
hydrocarbons as DMMP (dimethyl methyl phospho-
nate) destruction products. But phosphorus-containing
compounds (PCCs, except phosphine) have not been
detected as destruction products and therefore the
balance on phosphorus has not been determined. The
approach based on the determination of the kinetics of
pollutants destruction and the measurement of electri-
cal power consumed by discharge has been developed
in [2,3]. The obtained data have been presented using
coordinates Xout/Xin and Ex = P/(FXin)(Xout, Xin are
concentrations of pollutant at the outlet and the inlet
of the reactor, P is the consumed power, and F is the
flow). For many investigated compounds (VOCs—
methyl chloride, methane, chlorobenzene, toluene,
mehtyl ethyl ketone, 1-pentene, and cyclohexene—as
well as NO and NO2) the obtained data follow the
law Xout/Xin = exp( KP/(FXin)). It was concluded
[2,3] that ion mechanism is the major one responsible
for the destruction process. Some other researchers
[4,10,13] came to the same conclusion. In contrast,
other groups of researchers [18] consider that the
radical mechanism is the major one responsible for
the destruction of toluene and dichloromethane. We
have initiated a systematic study of the destruction
of simulants of sarin [19–21] in corona discharge.
However, the research on the destruction of actual
chemical warfare agents as well as their surrogates
is still very limited. In the current study, the kinetics
and the products of the destruction of a simulant of
sarin—diisopropyl methylphosphonate (DIMP)—in a
dielectric barrier corona discharge were studied over
a range of experimental conditions. The objectives of
this research were to apply the approach based on the
determination of kinetics of DIMP destruction and on
the measurement of power consumed by discharge to
destruction of DIMP in corona discharge, to determine
intermediate and final destruction products of DIMP
as a function of parameter Ex , to check out the balance
on phosphorus, to measure OPC destruction extent as
a function of parameter Ex , to determine whether the
law (1-D) = exp( KP/FX0) describes the destruction
of OPC in corona discharge, and to use the obtained
data for discussion of possible mechanism of the
destruction of OPC in corona discharge.
spectrometer was used. The reactor consisted of a
quartz tubing 115 cm long, 1.2 cm OD, 0.9 cm ID,
with a coaxial nichrome wire 0.5 mm in diameter
which served as one of the electrodes. The tube was
wrapped with nickel copper braid which was the sec-
ond, grounded, electrode. The active length of the re-
actor determined by the wrapped length was 105 cm.
The reactor tube was located inside a water jacket.
The reactor temperature was kept at 340 K by cir-
culating water from a bath circulator. Carrier gases
(N2, He) were supplied from cylinders (“SibTechGas,”
purity 99.7%). A mass-flow controller (MKS Instru-
ments) controlled the carrier gas flow. The OPC (DIMP
in this study) was introduced to the reactor by pass-
ing the carrier gas above the surface of the liquid
reactant in an evaporator. The mass flow of the re-
actant was established by measuring the mass loss
of the evaporator to the accuracy of 0.1 mg. Typical
mass loss at the gas carrier flow rate of 2.5 sccm was
20 mg/h. The mole fraction of DIMP was varied in
the range 60–500 ppm. Organophosphorus compounds
were obtained from Aldrich: diethylmethylphospho-
nate (DEMP), 97% (683-08-9); orthophosphoric acid
(OPA), 85% (7664-38-2); methylphosphonic acid
(MPA), 98% (13590-71-1). The DIMP, 98%, was pur-
chased from Alfa AESAR (Johnson Matthey). N,O-
bis(trimethylsilyl)trifluoroacetamide (BSTFA), 99.5%
(25561-30-2), was obtained from Supelco. Inc.
The output voltage from a 1 kW high voltage AC
power supply was controlled by a variac. The active
power measurements were based on the electrical mea-
surements [2,3,19]. The maximum amplitude of the
output voltage was 20 kV (frequency 50 Hz). The volt-
age and the current were recorded using a digital oscil-
loscope (LeCroy, Model 9310AL). The measurements
were performed by summing up five hundred 100 ms
(five periods) sweeps of the voltage and current. The
voltage and current obtained in this way were multi-
plied and averaged. The active power (P) dissipated in
the plasma reactor was determined by subtracting the
measured power without load from that measured with
load.
The samples were analyzed using a molecular beam
inlet system with a quadrupole mass spectrometer
MC7302 produced by the Experimental Plant of the
Russian Academy of Sciences. The detection system
allowed to determine the extent of DIMP destruction
at mole fractions as low as 1 ppm with the accuracy
of 10%. The mole fractions of DIMP and of the de-
struction products were determined via measuring peak
intensities of their parent ions and the calibration coef-
ficients. In addition, mole fractions of DIMP and other
PCCs at the inlet (X0) and the outlet (X) of the re-
actor were measured using gas chromatography/mass
EXPERIMENTAL
The setup represents a molecular beam mass spectrom-
etry(MBMS)basedexperimentalfacility[19]modified
for the kinetic studies on the destruction of DIMP in
a corona discharge flow reactor. A flow tubular dielec-
tric barrier corona discharge reactor coupled to an on-
line molecular beam inlet system of quadrupole mass

KINETICS OF DESTRUCTION OF DIISOPROPYL METHYLPHOSPHONATE IN CORONA DISCHARGE
333
spectrometry (GC/MS). In these measurements, the
gas was passed through a system of three liquid
nitrogen traps. A glass wool filter was placed in the
last trap to trap possible aerosols. To control the initial
mole fraction of DIMP it was measured twice, before
and after the experiment. To increase the accuracy of
measurements of the initial mole fraction of DIMP the
gas was passed through the trapping system for 1 h and
more. After that the traps were removed and rinsed with
acetone. The resulting solution was evaporated using a
rotor evaporator, producing a residue. The volume of
the residue (0.3–0.4 ml) was determined in additional
test experiments. The efficiency of the trapping and re-
covery of DIMP under the conditions of trapping and
the solution evaporation used was better than 95%. The
typical scatter of the experimental data was ca. 5–20%
for molecular beam inlet system of mass spectrometer
and 7–30% for GC/MS analysis, depending on their
mole fractions.
To detect and to quantify the low volatile PCCs by
GC/MS, the procedure of silylation was used [22,23].
This procedure consists of the substitution of the hy-
drogen atom in hydroxyl group of PCC by trimethylsi-
lyl radical [7,8]. Organophosphorus compounds sily-
lated in this way are volatile and can be detected
using GC/MS. The silylating solution used was a mix-
ture of acetonitrile and BSTFA (9:1 v/v). To account
for the effect of the column aging a reference sub-
stance was introduced in the silylating solution of
BSTFA and acetonitrile. Diethyl methylphosphonate
(DEMP: PO(CH3)(OC2H5)2) was used as a reference
compound. About 10 mg of DEMP was added to
10 ml of silylating solution. It gives a known con-
centration of DEMP as reference compound in each
sample. These portions of the silylating solution were
added to the evaporated samples, which were obtained
by rinsing the traps or the walls of the reactor. After
mixing and moderate heating to accelerate the reac-
tion these mixtures were analyzed by GC/MS. For
the determination of the absolute amounts of PCC
in the samples, calibration was used. A small known
amount of PCC was mixed with the silylating solu-
tion and analyzed by GC/MS. As a result of this pro-
cedure we obtained PCC calibrated peak areas which
corresponded to the known PCC concentrations. The
washings obtained from the reactor and the traps in
the experiments were evaporated, silylated, and ana-
lyzed using GC/MS. The calibrated PCC peak areas
obtained were used to determine the PCC concentra-
tions in the samples. For example, for DIMP, [Con-
centration DIMP] = [Area DIMP] [Calibrated Con-
centration DIMP]/([Calibrated Area DIMP] [Area
DEMP]/[Calibrated Area DEMP]). This formula al-
lowed to quantify PCC concentrations. The efficiency
of the OPC trapping depended on the gas flow rate. At
low gas flow rates (<20 sccs, the residence time of the
gas in the traps >10 s) the calibrated efficiency of DIMP
trapping was better than 95%. The analysis of the so-
lutions obtained by rinsing three traps in series showed
70% of PCC trapped in the first trap, 28% in the second
trap, and 1% in the third trap at the gas flow rate of
1.66 sccs. About 1% of the PCC was precipitated on the
glass wool filter. When calibrating DIMP initial mole
fraction, the data on the DIMP weight loss during the
experiments were used.
RESULTS AND DISCUSSION
Destruction Products: The Kinetics
of DIMP Destruction
The measurements of the extent of DIMP destruc-
tion were performed after establishing steady state of
DIMP concentration at the outlet of the reactor. It
was observed that the establishing of a steady state
of DIMP concentration requires a prolonged period of
time (about 10 min) when studying low volatile OPCs.
The results below were obtained by measuring the PCC
mole fractions at the inlet and the outlet of the reactor
after this time. The destruction products such as iso-
propyl methylphosphonate (IMP), methylphosphonic
acid, and orthophosphoric acid were found on the wall
of the reactor. No other phosphorus-containing destruc-
tion products (PCDPs) were detected. A small amount
(<10% of all PCDPs) of organophosphorus products
of DIMP destruction was found in the liquid nitrogen
traps. No aerosols were collected from the glass wool
when the gas flow was less than 2 sccs. The results of
the DIMP destruction in nitrogen carrier gas (99.7%
N2, 0.3% O2) are shown in Fig. 1. In this figure mole
Figure 1 Ex dependence of mole fraction of DIMP and
PCDP: 1–DIMP, 2–IMP, 3–MPA, 4–OPA, 5–phosphorus
element balance.

334
KOROBEINICHEV ET AL.
Table I DIMP Destruction Extent in Flux of Different
Gas Carriers at X0 = 250 ppm
fractions of DIMP and its destruction products at the
reactor outlet normalized on the inlet mole fraction of
DIMP are plotted against the specific deposited energy
1
Gas
Composition
V (J sccm
Ex . The latter was defined as energy per unit gas vol-
1
P (W)
ppm
)
Di (%)
Ki
1
ume per unit mole fraction of DIMP, Ex = PF 1 X0
,
Hea
N2
0.5
3.7
0.0008
0.0059
0.006
52
61
66
71
900 200
160 30
180 30
175 30
where P istheactivepowerdissipatedinthereactorand
F is the gas volumetric flow rate. The previous research
on VOCs and NOx destruction demonstrated that the
specific energy defined in this way is the parameter
characterizing the discharge efficiency of the corona
reactor. The mass balance on phosphorus was calcu-
lated by summing the mole fractions Xi of the species
containing phosphorus and comparing with the initial
DIMP mole fraction. Data on phosphorus element bal-
ance are in Fig. 1. The experimental data indicated no
dependence of the DIMP destruction products on the
nature of the carrier gas. The dependencies of the nor-
malized mole fraction X/X0 on the specific energy Ex
for different initial mole fractions of DIMP in the range
60–500 ppm are shown in Fig. 2. This dependency can
a
N2 (+0.3% O2) 3.8
Air 4.4
0.007
aEstimated amount of O2 10 ppm.
The power consumed by the reactor as a function of
the voltage applied for different carrier gases is listed
in Table I. The data are also plotted in Fig. 3. The
measurements of DIMP destruction in different carrier
gases were performed using mass spectrometric detec-
tion and the following set of experimental conditions:
F = 5 sccs, X0 = 250 ppm, U = 12 kV. It is apparent
from Table I that at these experimental conditions the
extent of the destruction was about 60% for all car-
rier gases studied. However, the power P dissipated in
the reactor (and, subsequently, Ex ) was approximately
five to six times lower in helium than that in nitrogen.
Therefore, the efficiency of DIMP destruction in he-
lium was approximately five to six times higher than
that in nitrogen and air.
be expressed by the following equation: ln(X/X0) =
KEx = KPF 1 X0
=
160Ex . The coefficient
1
K was determined experimentally with the accuracy
of 10%. The coefficient K has dimension as J 1 sccs
ppm. Similar dependence was observed previously in
the study of the destruction of VOCs in corona dis-
charge [2,3].
The Effect of the Carrier Gas on the
Efficiency of DIMP Destruction
Discussion
The experimental observations (kinetic laws, the effect
of the concentration, power and flow rate on the re-
moval efficiency) found for the destruction of DIMP in
corona discharge are very similar to those obtained ear-
lier for the destruction of some VOCs as well as NOx
in [2,3]. A successful mechanism of DIMP destruction
The corona onset voltage as well as the active power
dissipated in the reactor at the same applied voltage
strongly depend on the nature of the carrier gas. In the
current study, helium, dry air, and nitrogen (with ca.
0.3% oxygen impurity) were used as the carrier gases.
Figure 3 The discharge power against voltage for different
Figure 2 Ex dependence of X/X0.
gas carriers.

KINETICS OF DESTRUCTION OF DIISOPROPYL METHYLPHOSPHONATE IN CORONA DISCHARGE
335
(C3H7O)2(CH3)PO+ → (C3H7O)(CH3)(OH)PO
in corona discharge is to explain the following experi-
mental observations:
+
+ C3H6
1. The absolute energy efficiency of DIMP destruc-
tion.
In the case of the decay of excited molecules of
TBP radicals, C4H9 and (C4H9O)2OPO are formed.
The latter is a precursor of di-n-butilphosphate:
2. The same energy calculated per one DIMP
molecule is required to achieve a certain extent
of destruction at different initial concentrations.
3. The difference in DIMP destruction efficiency in
helium and nitrogen.
(C4H9O)2OPO + (C4H9O)3PO
→ (C4H9O)2(OH)PO+ + (C4H8O)(C4H9O)2PO
4. Primary products of DIMP destruction.
In Ref. [27] it was postulated that the initial ion
(C4H9O)3PO+ can be decomposed by the following
reaction:
Obtained data showed that primary intermediate of
DIMP destruction is IMP. This can be explained on the
basis of both ion and radical mechanisms. As it was
shown in [24] the formation of IMP takes place during
DIMP destruction in flame as a result of the following
reaction of displacement:
(C4H9O)3PO+ → (C4H9O)2P(OH)2+ + C4H7
At subsequent abstraction of H+ from (C4H9O)2-
+
P(OH)2 ion, di-n-butilphosphate is formed. Similar
(C3H7O)2(CH3)PO + OH → (C3H7O)(CH3)(OH)PO
+ C3H7O
processes with the formation of IMP can be expected
during the radiolysis of DIMP, too:
+
(C3H7O)2(CH3)PO+ → (C3H7O)(CH3)P(OH)2
Similar processes occur during the destruction
of other organophosphorus compounds, for example,
trimethyl phosphate (TMP) in flame [25]:
+ C3H5
(C3H7O)2(CH )P(OH)+ → (C3H7O)(CH3)(OH)PO
2
3
+ H+
(CH3O)3PO + OH → (CH3O)2(OH)PO + CH3O
On the other hand the formation of IMP can take
place as a result of fast reaction of DIMP ionization by
charge exchange and the following reaction of DIMP
ion destruction:
Haase et al. [29] also assumed the possibility of
dissociative addition of an electron to a molecule of
TBP. Breakage of the bond in molecule of DIMP was
observed at electron impact ionization in ion source of
mass spectrometer [30,31]. Negative and positive flame
ions from a premixed low-pressure ethylene/oxygen
flame doped with TMP were analyzed by mass spec-
trometer [32].
DIMP + O2 → DIMP+ + O2
+
DIMP+ → IMP + C3H6
+
However radical-based mechanism is incapable to
explain the above-mentioned experimental observa-
tions 1, 2, and 3. It was reported [33] that facts similar
to the above cited 1, 2, and 3 have been observed on
ethane destruction in corona discharge. The modeling
of ethane destruction based on the mechanism involv-
ing radicals and atoms [33] failed to explain the de-
struction efficiency (discrepancy up to a factor of 104)
and the product composition.
Plausible destruction mechanisms in corona dis-
charge were discussed in [2,3]. In [2], only one mecha-
nism was pointed out as potentially capable to explain
all the experimental observations. This mechanism is
based on the physical and chemical processes involv-
ing ions. Substantially higher energies are required for
ion production ( 9.6 eV molecule 1) as compared
to those required for the production of free radicals
Endothermic effect of the second reaction is high,
but is less than the exothermic one of the first reaction.
Possibly, both stages take place nearly simultaneously.
Another pathway may be suggested by analogy with
radiolysis of tributyl phosphate (TBP) [26–28] which
is similar to that of DIMP. The main process of the
TBP destruction is dealkylation [26]. It leads to the
formation of di- and mono-n-butylphosphate. The pro-
cess of breakage of C O bond with the formation of
di-n-butylphosphate was observed during the decay of
excitedmoleculesofTBPandinthereactionsinvolving
ions [27]. Similarly one can expect IMP to be formed
by the reactions during the radiolysis of DIMP:
(C3H7O)2(CH3)PO + e
→ 2e + (C3H7O)2(CH3)PO+

336
KOROBEINICHEV ET AL.
( 3–4 eV molecule 1). However the fast charge ex-
change reactions provide more effective pathway for
an impurity molecule destruction. This can explain
high efficiency and concentration independence down
to very low concentrations. Such a mechanism infers
high efficiency of the destruction for those molecules
which have ionization potential lower than that of oxy-
genmolecules(themainsourceofionizationinair). For
molecules with ionization potential higher than that of
oxygen (such as CH4, SO2) low destruction efficiency
as well as the decrease of the destruction efficiency
(calculated per one molecule of the contaminant) at
low concentrations is anticipated.
Processing of experimental data shows that G-value
(a number of destroyed molecules per 100 eV) for
DIMP is about 0.07. G-value for the ion production in
the reduced electric field of 130 Td (the reduced critical
field) is 0.17 ion per 100 eV, which is close to G-value
measured for DIMP. So ion mechanism enables one to
explain high DIMP destruction efficiency. Not all facts
can be explained now. The task of future investigation
is to develop a model which can explain quantitatively
the dependence of Xout/Xin on E = P/FXin.
CONCLUSIONS
Such correlation was indeed observed in the study
of the VOCs and SOx destruction [2]. The results
of this study are in line with such mechanism. The
ionization energies of OPC under investigation (Ei =
9.65 eV for DIMP) are lower than that of oxygen (Ei =
12.07 eV). The measured destruction efficiency as well
as the concentration dependence are similar to those
previously observed for VOCs with low ionization
energy.
The highest efficiency of OPC destruction was
achieved using helium as a gas carrier. The law
ln(X/X0) = KPF 1 X0 1 proposed for destruction of
VOCs was confirmed for OPC destruction.
BIBLIOGRAPHY
The higher efficiency of destruction in helium can
be rationalized as follows. Helium atom has a very high
ionization energy (Ei = 24.6 eV). Moreover, the first
excited state of this atom lies at relatively high en-
ergies (E1 20 eV). Therefore, the elastic collisions
of electrons with helium atoms prevail at lower en-
ergies. Electrons can gain substantially high energies
before they start to loose energy on excitation and ion-
ization in collisions with helium atoms. This is in line
with substantially lower corona breakdown voltage in
helium compared with nitrogen and air. In such a case,
an impurity with low ionization/excitation energy can
serve as the major sink of the energy gained by elec-
trons even at very low concentration. Because of the
much higher electron temperature a higher energy yield
of ionization and electronic excitations is expected.
This is consistent with higher destruction efficiency
in helium observed in this work. The mechanisms of
the destruction of a number of compounds in corona
discharge are currently discussed and developed. They
were based on the consideration of electron-beam pro-
cessing, ion-molecular reactions, and neutral reactions
chemistry [2,3,7,18,34–36]. The following mechanism
for the destruction of DIMP is suggested:
1. Nunez, C. M.; Ramsey, G. H.; Ponder, W. H. et al. Air
Waste 1993, 43, 242.
2. Krasnoperov, L. N.; Krishtopa, L. G.; Bozzelli, J. W.
J Adv Oxid Technol 1997, 2, 248.
3. Krasnoperov, L. N.; Krishtopa, L. G. In Fifth Interna-
tional Conference on Chemical Kinetics, Program and
Abstracts, Gaithersburg, MD, USA, July 16–20, 2001,
p. 207. Available at www.nist.gov/kinetics2001.
4. Green, D. S.; Herron, J. T.; Sieck, L. W. Paper presented
at the Second International Symposium on Environmen-
tal Applications of Advanced Oxidation Technologies,
Proceedings, San Francisco, Feb 28–March 2, 1996.
5. Evans, D.; Rosocha, L. A.; Anderson, J. K.; Coogan,
J. J.; Kushner, M. J. J Appl Phys 1993, 74, 5378.
6. Yamamoto, T.; Ramanathan, K.; Lawless, P. A.; Ensor,
D. C.; Newsome, J. R.; Plaks, N.; Ramsey, G.H. IEEE
Trans Indus Appl 1992, 28, 528.
7. Kushner, M. J. J Appl Phys 1993, 74, 6538.
8. Ohkubo, T.; Kanazawa, S.; Nomoto, Y.; Chang, J.-S.;
Adachi, T. IEEE Trans Indus Appl 1994, 30, 856.
9. Masuda, S. Pure Appl Chem 1988, 60, 727.
10. Chang, J.-S. J Aerosol Sci 1989, 20, 1087.
11. Chang, M. B.; Kusner, M. J.; Rood, M. J. Environ Sci
Technol 1992, 26, 777.
12. Sardja, I.; Dhali, S. K. App Phys Lett 1990, 56, 21.
13. Potapkin, B. V.;Rusanov, V. D.;Fridman, A. A. Doklady,
Phys Chem 1989, 308, 804.
14. Clothiaux, E. J.; Koropchak, J. A.; Moore, R. R. Plasma
Chem Plasma Process 1984, 4, 15.
15. Fraser, M. E. In Proceedings of the CRDC Joint Ser-
vice Technical Symposium on Plasma Air Purification
Technology, 1984, p. 8.
16. Fraser, M. E.; Fee, D. A.; Sheinson, R. S. Plasma Chem
Plasma Process 1985, 5, 163.
O2 + e → O2+ + 2e
O2+ + DIMP → O2 + DIMP+
O2+ + DIMP → O2 + IMP+ + C3H6
DIMP+ + e → IMP + C3H6
DIMP+ → IMP + C3H6
+

KINETICS OF DESTRUCTION OF DIISOPROPYL METHYLPHOSPHONATE IN CORONA DISCHARGE
337
17. Fraser, M. E.; Eaton, H. J.; Sheinson, R. S. Environ Sci
Technol 1985, 19, 946.
27. Wilkinson, R. W.; Williams, T. F. J Chem Soc 1961,
4098.
18. Fitzimons, C.; Ismail, F.; Whitehead, J. C.; Wilman, J. J.
In Book of Abstracts,16th International Symposium on
Gas Kinetics, Cambridge, July 2000, PC 20.
19. Korobeinichev, O. P.; Chernov, A. A.; Krasnoperov, L.
N. In Proceedings of the International CW Destruction
Symposium, Munster, Germany, March 22–25, 1998:
Starrock, D.; Krippendorf, A. (Eds.); p. 225.
28. Pikaev, A. K. Modern Radiation Chemistry; Nauka:
Moscow, 1986, p. 427 (in Russian).
29. Haase, K. D.; Shutle-Forhlinde, D.; Kourim, P.; Vacek,
K. Int J Radiat Phys Chem 1973, 5, 351.
30. Wils, E. R. J. J Anal Chem 1990, 338, 22.
31. Sass, S.; Fisher, T. L. Org Mass Spectrom 1979, 14,
257.
20. Korobeinichev, O. P.; Chernov, A. A.; Sokolov, V. V.;
Krasnoperov, L. N. In Program and Abstracts,
Fifth International Conference on Chemical Kinetics,
Gaithersburg, July 16–20, 2001, p. 197. Available at
www.nist.gov/kinetics2001.
21. Korobeinichev, O. P.; Chernov, A. A.; Sokolov, V. V.;
Krasnoperov, L. N. In Book of Abstracts, 16th Inter-
national Symposium on Gas Kinetics, Cambridge, UK,
July 23–27, 2000, PC 15.
32. Hebgen, P.; Homann, K. H. In Abstracts of Work-
In-Progress Posters, 27th International Symposium on
Combustion, Pittsburgh, PA, 1998, p. 497. The Com-
bustion Institute.
33. Chernov, A. A.; Krishtopa, L. G.; Korobeinichev, O. P.;
Krasnoperov, L. N. In Proceedings of the Third In-
ternational Symposium on Non-Thermal Technologies
for Pollution Control (ISNPT-3), Seogwipo KAL Hotel,
Cheju Island, Korea, 2001, p. 192.
22. Rapp, D. C.; Nogueira, M. F. M.; Fisher, E. M.; Gouldin,
F. C. Environ Eng Sci 1997, 14, 133.
23. Bauer, G.; Vogt, W. A. Anal Chem 1981, 53, 917.
24. Korobeinichev, O. P.; Chernov, A. A.; Bolshova, T. A.
Combust Flame 2000, 123, 412.
25. Korobeinichev, O. P.; Ilyin, S. B.; Bolshova, T. A.;
Shvartsberg, V. M.; Chernov, A. A. Combust Flame
2000, 121, 593.
34. Chernov, A. A.; Krishtopa, L. G.; Korobeinichev, O. P.;
Krasnoperov, L. N. In Program and Abstracts, Fifth In-
ternational Conference on Chemical Kinetics, Gaithers-
burg, July 16–20, 2001, p. 272.
35. Penetrane, B. M.; Bardsley, N. J.; Hsiao, Mark C. Jpn J
Appl Phys 1997, 36(7B, Part 1), 5007.
36. Penetrante, B. M.; Hsiao, M. C.; Bardsley, J. N.; Merritt,
B. T.; Vogtlin, G. E.; Wallman, P. H.; Kuthi, A.; Burkhart,
C. P.; Bayless, J. R. Phys Lett A 1995, 209, 69.
26. Burr, J. Radiat Res 1958, 8, 214.