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Chemical Physics 330 (2006) 506514

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Gas-phase Boudouard disproportionation reaction between highly


vibrationally excited CO molecules
Katherine A. Essenhigh, Yurii G. Utkin, Chad Bernard, Igor V. Adamovich *, J. William Rich
Nonequilibrium Thermodynamics Laboratories, Department of Mechanical Engineering, The Ohio State University, Columbus, OH 43202, USA

Received 3 September 2006; accepted 21 September 2006


Available online 30 September 2006

Abstract

The gas-phase Boudouard disproportionation reaction between two highly vibrationally excited CO molecules in the ground elec-
tronic state has been studied in optically pumped CO. The gas temperature and the CO vibrational level populations in the reaction
region, as well as the CO2 concentration in the reaction products have been measured using FTIR emission and absorption spectroscopy.
The results demonstrate that CO2 formation in the optically pumped reactor is controlled by the high CO vibrational level populations,
rather than by CO partial pressure or by ow temperature. The disproportionation reaction rate constant has been determined from the
measured CO2 and CO concentrations using the perfectly stirred reactor (PSR) approximation. The reaction activation energy,
11.6 0.3 eV (close to the CO dissociation energy of 11.09 eV), was evaluated using the statistical transition state theory, by comparing
the dependence of the measured CO2 concentration and of the calculated reaction rate constant on helium partial pressure. The dispro-
portionation reaction rate constant measured at the present conditions is kf = (9 4) 1018 cm3/s. The reaction rate constants obtained
from the experimental measurements and from the transition state theory are in good agreement.
 2006 Elsevier B.V. All rights reserved.

Keywords: CO disproportionation reaction; Vibrational excitation; Optical pumping

1. Introduction nario involves a reaction between a gas-phase CO molecule


and an adsorbed CO molecule. In the surface reaction of
The CO disproportionation reaction (Boudouard Eq. (1), the activation barrier is considerably reduced from
reaction), the gas phase values, which appear to exceed at least
CO CO ! CO2 C; 1 140 kcal/mole, although signicant surface reaction still re-
quires rather high temperatures [113]. The theoretical
is one of key free carbon formation processes occurring study of this disproportionation on surfaces of transition
both in high-temperature gas ows and in non-equilibrium metal oxides by Cheng et al. [3] indicates that the second
electric discharges. This reaction has long been observed at scenario is the totally dominant channel. Going beyond
high temperatures on oxidized surfaces such as iron oxide near-thermal equilibrium reaction, the enhanced reactivity
in the process known as metal dusting [1], which leads to of highly vibrationally excited molecules on metal surfaces
corrosion of metal surfaces and has been of great concern is a well-known eect. There is evidence [4] that vibrational
in various industrial processes. The mechanism of this reac- excitation of CO leads to production of CO2 on surfaces
tion is still debated and includes two possible scenarios. In (primarily copper oxide) at signicantly lower tempera-
the rst scenario, a reaction takes place between two CO tures, below 200 C. At these temperatures, thermal equi-
molecules absorbed on the surface, while the second sce- librium reaction on the same surface shows no detectable
CO2 production [4]. This suggests that vibrational excita-
*
Corresponding author. tion may contribute into overcoming the activation energy
E-mail address: adamovich.1@osu.edu (I.V. Adamovich). of the CO disproportionation reaction.

0301-0104/$ - see front matter  2006 Elsevier B.V. All rights reserved.
doi:10.1016/j.chemphys.2006.09.033
K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514 507

In the gas phase, reaction of Eq. (1) has been observed also occur at low temperatures, in collisions of highly vib-
in a glow discharge [5,6] and in experiments on isotopic rationally excited CO molecules in the ground electronic
enrichment of 13C using ultraviolet photolysis of carbon state,
monoxide [79]. In both cases, it has been concluded that COv COw ! CO2 C; 4
the mechanism responsible for the CO2 production
involves metastable CO(a3Pr) molecules produced by prepared by optical pumping of carbon monoxide by reso-
either electron impact excitation of CO (in a glow dis- nance absorption of CO laser radiation,
charge) or by resonance absorption of the 206.22 nm iodine COv hv ! COv 1: 5
atom line generated by a ash lamp (in UV photolysis),
However, the rate coecient of reaction of Eq. (4) was esti-
COa3 Pr CO ! CO2 C: 2 mated to be low, <1015 cm3/s. During optical pumping,
The activation energy of reaction of Eq. (2) is believed to only the low states of CO, v 6 10, are populated by reso-
be close to the excitation energy of the a3Pr electronic nance absorption, while higher vibrational levels of CO,
state, approximately 6 eV (140 kcal/mole) [5,9], and is v > 10, which are not directly coupled to the laser radia-
about half of the CO dissociation energy of 11.09 eV. tion, are populated by the anharmonic vibrationvibration
The rate constant of this reaction was estimated to be (VV) exchange processes (Treanor pumping [15,16]),
kf(a3P) = 1.3 1012 cm3/s, based on the concentration COv COw ! COv  1 COw 1; w > v: 6
of CO(a3Pr) and the rate of CO2 production in a glow
In previous CO optical pumping experiments [1720],
discharge [5]. The eect of vibrationally excited CO
vibrational levels up to v  40 were detected, which corre-
molecules, which were also present in the discharge, on
sponds to a vibrational energy of up to 7.7 eV. Note that in
the rate of the disproportionation reaction was not studied.
electric discharges, where both electronically excited and
A similar rate constant, kf(a3P) = 1.9 1012 cm3/s, was
highly vibrationally excited CO molecules are created by
reported in the UV photolysis experiments [9].
electron impact, the reaction channel of Eq. (4) may be ob-
The gas-phase disproportionation reaction which does
scured by reaction of Eq. (2). On the other hand, in the
not involve electronically excited species may only occur
optically pumped CO, in the absence of an externally ap-
if the activation barrier is overcome at the expense of the
plied electric eld, direct excitation of electronic levels by
translational or the vibrational energy of the reactants.
electron impact is a minor factor compared to electric dis-
The former channel would require extremely high gas
charges. Although UV emission from electronically excited
temperatures available only in shock tube experiments,
CO has been observed in previous optical pumping exper-
which is the main reason why Boudouard disproportion-
iments, such as 4th positive bands CO(A1P ! X3R+)
ation reaction is not commonly observed in the gas phase.
[17,19,21,22] and 3rd positive bands CO(b3R+ ! a3Pr)
On the other hand, temperatures behind strong reected
[21], the measured population of the electronically excited
shocks are suciently high to induce chemical reactions
CO(A1P) state was low, 1010  1011 cm3 [19]. Population
in carbon monoxide [1013]. In particular, Mick et al.
of the metastable CO(a3Pr) state in the optically pumped
[13] have studied CO decomposition behind the reected
CO, although never measured in the experiment, is also
shock by monitoring the time-dependent concentrations
likely to be low because of a very eective collisional
of C and O atoms, assuming that CO dissociation
quenching mechanism
CO M ! C O M; 3
COa3 Pr CO ! COw COv; 7
(M = Ar or CO) is the dominant chemical reaction. We
note that the Arrhenius t to the reaction rate constant with a rate coecient of 1010 cm3/s [23]. This makes
measured in Ref. [13], assuming the activation energy equal optically pumped CO an ideal environment to study reac-
to the CO dissociation energy, 11.09 eV, yields a strong tion of Eq. (4).
inverse temperature dependence of the pre-exponential fac- The main objective of the present work is to study kinet-
tor, T3.1 This indicates that an alternative reaction chan- ics of reaction of Eq. (4) in optically pumped CO, to mea-
nel, with a considerably lower activation energy, may sure its rate coecient, and to determine whether CO
aect the measured reaction rate. Interestingly enough, disproportionation may eciently occur in a reaction
the Arrhenius t with the activation energy near 6.0 eV between two vibrationally excited CO molecules in the
gives more reasonable pre-exponential factor temperature ground electronic state.
dependence, near the collision-frequency dependence of
T0.5 [4]. This result suggests that the disproportionation 2. Experimental setup
reaction of Eq. (2), rather than CO dissociation reaction
of Eq. (3), may in fact be the dominant reaction channel A schematic of the experimental setup is shown in
during high-temperature CO decomposition behind shock Fig. 1. A carbon monoxide (CO) laser is used to vibration-
waves. ally excite CO, initially at room temperature, in the owing
It has been previously suggested [14] that in the gas reactor (see Fig. 1). The CO laser used in the present exper-
phase, the Boudouard disproportionation reaction may iments is a c.w. liquid nitrogen cooled, electric discharge
508 K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514

Fig. 1. Schematic of experimental setup.

excited gas laser capable of lasing on multiple lines in cally reacting region is collected by an o-axis parabolic
broadband mode. Typically, the gas mixture composition mirror and focused into an emission port of an IFS-66 Bru-
and discharge conditions in the laser are optimized to pro- ker Fourier transform infrared spectrometer. The rst
duce a substantial fraction of its output on the v = 1 ! 0 overtone CO emission spectra are used to infer the CO
and v = 2 ! 1 fundamental band transitions, which is nec- vibrational distribution function (VDF) and the transla-
essary for the laser beam absorption by carbon monoxide tional/rotational temperature of the ow in the reaction
in the reactor, initially at room temperature. The present zone. The response function of the FTIR detector and col-
use of CO laser pumped absorption to study energy trans- lection optics was measured using a calibrated blackbody
fer processes in molecular gases at conditions of extreme course (InfraRed Industries Inc, Model 201). First, the R
vibrational disequilibrium is a further development of a branch of the 1 ! 0 band of the CO fundamental spectrum
technique with a considerable literature [1422,24]. was used to infer the translationalrotational temperature
The continuous ow reactor is a six-arm glass cell with a in the reaction zone. Self-absorption may be a signicant
total volume of approximately 112 cm3. The reactor con- factor at relatively high CO partial pressures in the cell
tains the gas mixture of CO, Ar, and He owing at a very (312 Torr) and long optical path (10 cm). For this rea-
slow ow rate, 24 cm3/s. The pressure inside the reactor is son, emission from high rotational levels, J 0 = 3040, was
kept constant, P = 110 Torr. The ow rates of all the gases used to infer the rotational temperature. Then, the CO rst
are measured by rotameters upstream of the reactor. The overtone spectrum was used as an input in a computer code
focused laser beam enters and exits the reactor through [20] to infer the VDF. Basically, the code infers relative
1 in. diameter CaF2 windows, as shown in Fig. 1. The populations of CO vibrational levels using the least squares
arm used to let the CO laser beam into the reactor is t of a synthetic infrared spectrum to a high-resolution
purged by argon ow to prevent the laser beam absorption experimental spectrum, at a known temperature.
by CO and resultant carbon deposit on the window. A The mixture of chemical reaction products owing from
cylindrical glass tube with a 5 mm diameter hole at one the reactor passes through an absorption cell mounted in a
end blocks carbon monoxide in the reactor from entering sample compartment of the same FTIR. Infrared absorp-
the purged region (see Fig. 1). The transmitted laser beam tion spectra of CO2 present in the product mixture are mea-
power is measured by a power meter placed at the opposite sured by the FTIR using an internal infrared source
arm of reactor (see Fig. 1). (globar) and calibrated using CO2-Ar mixtures of known
Spontaneous infrared emission from carbon monoxide composition at the same pressure, P = 110 Torr. The cali-
vibrationally excited by the CO laser beam absorption is brated CO2 absorption spectra are used to measure abso-
collected at 90 through another CaF2 window, as shown lute concentrations of carbon dioxide produced in the
in Fig. 1. The CO fundamental, rst overtone, and second reactor. Since the FT spectrometer can only perform one
overtone emission from the vibrationally excited, chemi- measurement (emission or absorption) at a time, the emis-
K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514 509

sion and absorption measurements were performed in a


quick succession one after the other and then repeated. 9 Torr CO partial pressure
14
6.0x10 12 Torr CO partial pressure

CO2 number density, cm-3


For the absorption measurements, a low spectral resolu-
tion of 2 cm1 was used, whereas high-resolution emission
spectra (0.25 cm1) were used to infer the ow temperature
and the VDF. Each measurement consisted of 24 FTIR 14
4.0x10
scans to improve the signal to noise ratio.
Small amounts of CO2 and water vapor present inside
the absorption compartment of the FTIR presented a 14
challenge. A commercial purge system (Puregas, model 2.0x10
PCDA), was used to remove water and carbon dioxide
from the FTIR. Since it was found that some CO2 was still
present in the system, the spectrometer was additionally 0.0
purged with nitrogen. Although we were unable to com- 0 1 2 3 4
pletely remove CO2 leaking into the spectrometer from He partial pressure, Torr
the atmosphere, background absorption (with the absorp-
tion cell pumped down below 0.1 Torr) was measured Fig. 3. CO2 number density vs. He partial pressure in the reactor.
and then subtracted from each CO2 absorption spectrum.
Absolute CO2 concentrations in the reactor were deter- function of helium partial pressure in the reactor at two dif-
mined by comparing the integrated absorption of the asym- ferent CO partial pressures, 9 Torr and 12 Torr. From
metric stretch band of carbon dioxide produced in the Fig. 3, one can see that the carbon dioxide number density
reactor and that of the known amount of CO2. The calibra- signicantly decreases as the helium partial pressure
tion was performed using a mixture of 2.5% CO2 in Air. increases. At both CO partial pressures, adding approxi-
Controlled amount of this mixture was diluted in Ar and mately 4 Torr of He to the mixture results in the CO2 con-
own through the reactor. The amount of CO2 added to centration reduction in the reaction products by about an
the mixture during calibration was in the same range as order of magnitude, from 6 1014 cm3 to (2  4.0)
produced in the actual optical pumping experiments. 1013 cm3 s (see Fig. 3). On the other hand, CO2 number
density as a function of CO partial pressure remains nearly
3. Results and discussion constant (see Fig. 4), varying by only 1020% as the CO
partial pressure is increased by a factor of 4, from 3 Torr
Fig. 2 shows a typical CO2 asymmetric stretch band to 12 Torr.
(2349.15 cm1) absorption spectrum measured in the ow Fig. 5 shows the ow temperature in the laser-excited
of chemical reaction products generated in the optically reaction zone inferred from the CO fundamental spectra,
pumped COArHe mixture. The CO2 number density cal- as discussed in Section 2. From Fig. 5, it can be seen that
culated from the absorption spectra using the calibration the temperature signicantly increases with CO partial
procedure described in Section 2 is plotted in Fig. 3 as a pressure, from 750 K to 1000 K, mainly due to stronger
CO laser beam absorption, and weakly decreases with He

0.04
14
8.0x10

0.03
CO2 number density, cm-3
Absorbance (ln(I0 /I))

14
6.0x10

0.02
14
4.0x10

0.01
14
2.0x10

0.00
2250 2300 2350 2400 2450 0.0
Frequency, cm-1 0 2 4 6 8 10 12
CO partial pressure, Torr
Fig. 2. CO2 absorption band (asymmetric stretch band, resolution
2 cm1); CO partial pressure 9 Torr. Fig. 4. CO2 number density vs. CO partial pressure in the reactor.
510 K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514

1100 0
a 10 Amount of He added:
1000 0 Tor r

Relative population
-1 1 Tor r
10
900 1.6 Tor r
2.4 Tor r
Temperature, K

800 -2 3.6 Tor r


10
4.5 Tor r
700 5.5 Tor r
-3
10
600
3 Torr CO -4
500 10
6 Torr CO
400 9 Torr CO
-5
12 Torr CO 10
300 0 5 10 15 20 25 30 35 40
0 1 2 3 4 5 Vibrational level
He partial pressure, Torr
17
Fig. 5. Gas temperature in the plasma region vs. He partial pressure at b 10
dierent CO partial pressures in the reactor. 6 Torr CO
9 Torr CO

Number density, cm -3
16
10
12 Torr CO

15
partial pressure (by approximately 10% with the addition 10
of 4 Torr of He). Summarizing the results of Figs. 35,
one can see that adding helium to the COAr mixture sub- 10
14

stantially reduces the resultant CO2 concentration,


although the ow temperature remains nearly constant. 13
10
On the other hand, adding CO to the mixture does not
aect the CO2 concentration although in this case both
12
the ow temperature and the reactant (CO) concentration 10
0 5 10 15 20 25 30 35 40
increase. This behavior clearly demonstrates that CO2 for-
Vibrational level
mation in the optically pumped cell is controlled by a non-
thermal chemical reaction, with a non-Arrhenius rate coef- Fig. 6. (a) CO VDFs at PCO = 6 Torr, at dierent helium partial
cient dependence. pressures, (b) CO VDFs at dierent CO partial pressures, without helium.
Fig. 6 shows CO vibrational distribution functions
(VDFs) in optically pumped COArHe mixtures at dier-
ent He and CO partial pressures, inferred from the rst the CO2 concentration in the reactor is primarily controlled
overtone CO spectra, as discussed in Section 2. Note that by the high CO vibrational level populations, rather than
Fig. 6(a) plots relative (normalized) CO vibrational level by ow temperature or by CO partial pressure.
populations at dierent He partial pressures, while To infer the rate constant of the CO disproportionation
Fig. 6(b) plots absolute CO vibrational level populations reaction (reaction of Eq. (4)) from the results of measure-
at dierent CO partial pressures. It can be seen that vibra- ments presented in Figs. 36, we have used a perfectly stir-
tional levels as high as v = 37 are detected. From Fig. 6(a), red reactor (PSR) approximation [25]. This approximation
it is apparent that adding He to the COAr mixture aects assumes that the chemical composition of the mixture at
only high vibrational level populations (v > 15), while the any point in the reactor is the same. Indeed, since the ow
low level populations remain very nearly the same as with- rate of the mixture through the reactor is very small
out helium. The eect of high CO vibrational level depop- (24 cm3/s), the ow residence time in the reactor is several
ulation by helium (helium titration) is due to rapid seconds. The excitation of the vibrationally excited CO
vibrational relaxation of CO in collisions with He atoms, reactants, by absorption of the c.w. laser pump beam and
and has been previously observed in optical pumping subsequent Treanor up-pumping is extremely rapid, on a
experiments [1719]. On the other hand, Fig. 6(b) shows much shorter time scale than the residence time in the reac-
that although adding CO to the mixture does increase tor; we have very rapid and spatially uniform excitation of
absolute populations of low vibrational levels, up to the reactants. The residence time is sucient to complete
v = 1520, the high level populations (v > 25) remain mixing of the reaction products before the ow exits the
nearly unchanged. reactor, so that at steady state the CO2 produced within
Comparing the results of Fig. 6 with the measurements the reaction zone is distributed uniformly over the entire
of the CO2 concentration, which decreases with helium par- volume of the reactor.
tial pressure and does not change with CO partial pressure Using the PSR model, the rate constant of reaction of
(see Figs. 3 and 4) suggests a straightforward conclusion: Eq. (4), kf, can be determined from the following equation:
K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514 511

dCO2   V reactor To infer the reaction activation energy from the present
CO2   F k f  CO  CO  V RZ ; 8
dt experimental results, we have used the statistical transition
where [CO2] and [CO] are the number densities [cm3] of state theory [28,29], which assumes that two vibrationally
carbon dioxide and of carbon monoxide in the reactor, F excited CO molecules form a transition complex, with the
is the volumetric ow rate [cm3/s]; VRZ is the volume of total vibrational energy randomly distributed among all
the reaction zone (optically pumped plasma), and Vreactor available vibrational modes of the complex. Then the over-
is the total volume of the reactor. The volume of the reac- all rate constant of reaction of Eq. (4) can be expressed as
tion zone was determined from the visible emission from follows:
the vibrationally excited region, which is almost entirely vmax X
X vmax

due to the C2 Swan bands emission (A3Pg ! X 0 3Pu transi- kf k vw


f ; 11
v0 w0
tion). Electronically excited C2, with a radiative lifetime of
3.16 ls, is also formed in chemical reactions of the optically where k vw
f is the state-specic rate constant,
pumped CO. The short radiative lifetime precludes signi- r   2  2
vw T Ea xeCO
cant diusion of electronically excited C2 out of the reac- kf kg   S  Avw  fv  fw  1  
tion volume, so that the size of the visible emission 300 Ev Ew xeCO2
region is close to the volume of the vibrationally excited re- 12
gion. The emission region is a long slender cylinder approx-
imately 10 cm length. The plasma diameter was also In Eq. (12), kg = 3 1010 cm3 s1 is the gas kinetic rate
measured using a probe (a thin wire) inserted into the plas- at room temperature, T is the temperature in the reaction
ma. The probe was moved perpendicular to the plasma to zone (optically pumped plasma), S 6 1 is the steric factor,
nd the positions where it clips the visible emission region Avw is the step function, Avw = 1 if Ev + Ew P Ea and
from two opposite sides. The distance between these two Avw = 0 if Ev + Ew < Ea,Ev and Ew are the vibrational
positions turned out to be d = (1.74 0.1) mm. A very sim- energies of two CO molecules, CO(v) and CO(w), Ea is
ilar result, d = (1.67 0.08) mm, was obtained by photo- the reaction activation energy, fv and fw are normalized
graphing the plasma and the CaF2 window from a large CO vibrational level populations, xeCO = 2214.24 cm1
distance and then comparing the size of the emission region and xeCO2 = 2226.85 cm1 are the vibrational quanta of
with the diameter of the window. The emission volume re- CO and of CO2 asymmetric stretch mode, respectively.
mained approximately constant in all experiments reported Basically, the state-specic rate coecient given by Eq.
here, although diminishing in radiative intensity with the (12) is a product of the gas kinetic collision frequency,
addition of helium. These dimensions give a reaction vol- the steric factor (i.e. the probability of the transition state
ume VRZ = (0.23 0.03) cm3. complex formation in a collision), and the probability of
Note that the reverse reaction of Eq. (4) is not included the vibrational energy pooling into one of the CO vibra-
in the present analysis. Indeed, nascent C product of the tional modes (with the CO bond breaking energy Ea).
Boudouard reaction is rapidly removed by a subsequent The steric factor in Eq. (12) accounts for the orientation
reaction with the most abundant reactive species in the of the colliding partners and is the probability that the col-
mixture, carbon monoxide, lision geometry will favor the transition state complex for-
mation. The double summation in Eq. (11) is over all CO
C CO M ! C2 O M; 9 vibrational levels populated at the present experimental
producing C2O and other carbon suboxide products conditions (vmax = 37, see Fig. 6).
detected in previous CO optical pumping experiments Since both the vibrational level populations and the
[14,26,27]. Therefore, at steady state Eq. (8) gives: temperature in the reaction zone are measured in the pres-
ent experiments, Eqs. (10)(12) allow evaluating the reac-
CO2   F tion activation energy, Ea. Specically, since the rate
kf 10 coecient of the reaction is proportional to the CO2 con-
CO  CO  V RZ
centration (see Eq. (10)), one can compare the behavior
Thus, the reaction rate constant predicted by the PSR of the measured CO2 number density and of the rate con-
model is proportional to the CO2 concentration in the reac- stant predicted by Eqs. (11) and (12), both as functions
tor, and inversely proportional to the square of the CO of He partial pressure. For the comparison, we have used
concentration, which are both measured in the present the CO vibrational level populations, fv and fw, measured
experiments. Note that the rate constant given by Eq. at dierent He partial pressures (see Fig. 6(a)) in Eq.
(10) does not explicitly depend on the high CO vibrational (12), while the activation energy Ea in Eq. (12) was consid-
level populations, which control the CO2 production rate in ered a parameter.
the optically pumped plasma (see Figs. 3,4 and 6 and the The results of the comparison for three dierent CO par-
discussion above). Therefore, while Eq. (10) allows infer- tial pressures are shown in Fig. 7(ac). For each case, the
ence of the rate constant from the CO2 and CO concentra- results are plotted for two activation energies, Ea = 6 eV
tion measurements, it cannot help determining the (the activation energy for the reaction of Eq. (2)), and
activation energy of the reaction of Eq. (4). the one that provides the best t with the experimentally
512 K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514

-17 Table 1
a 8.0x10
14
CO 2 number density
3.0x10
Rate constants of reaction of Eq. (4) obtained from the experiment and
k f 810-4 (Ea = 6 eV) calculated from the transition state theory using the experimental VDFs
k f (Ea = 11.6 eV) CO partial pressure, Torr k exp 3
f , cm /s k calc 3
f , cm /s S
CO2 number density, cm-3

kf, cm3 sec -1


14
6.0x10 17
2.0x10
-17 6 1.3 10 2.5 1017 0.5
9 4.5 1018 7.1 1018 0.6
12 9.6 1018 1.4 1017 1.4
14
4.0x10

1.0x10
-17
agreement with the experiment. Such high value of the acti-
2.0x10
14
vation energy suggests that the gas-phase Boudouard reac-
tion of Eq. (4) can occur only in collisions of two highly
vibrationally excited CO molecules by pooling their vibra-
0.0 0.0 tional energies together. Note that the inferred activation
0 1 2 3 4 5 6 energy of Ea = 11.6 0.3 eV is close to the CO dissociation
He partial pressure, Torr energy, 11.09 eV, which also suggests that the reaction pro-
14
ceeds via breaking one of the CO bonds in the transition
b 7x10
CO2 number density -18
state complex.
8.0x10
14
6x10 kf 310- 4(Ea = 6 eV) Having determined the activation energy of the Boudou-
ard reaction from the CO2 concentration dependence on He
CO2 number density, cm-3

kf (Ea = 11.9 eV)


14
5x10 6.0x10
-18 partial pressure (see Fig. 7), we can now evaluate the value
kf, cm3 sec -1

of the steric factor, S, in Eq. (12) by comparing the rate con-


stants given by Eq. (10) (k exp
14
4x10
f , from direct measurements of
14 4.0x10
-18
the CO and CO2 concentrations) and by Eqs. (11) and
3x10
(12) (k calc
f , using the statistical theory at S = 1). The results
14
2x10 are summarized in Table 1. The uncertainty in the Ay is
-18
2.0x10 about factor of 2 and is mostly due to the uncertainty in
14
1x10 determining the reaction region volume, V RZ The uncer-
tainty in the k calc
f is primarily determined by the uncertainty
0 0.0
0 1 2 3 4 in the activation energy determined from the data ts in
He partial pressure, Torr Fig. 7, and is also about a factor of two. From Table 1,
one can see that the values of the rate constants are of the
c 14 CO 2 number density 1.5x10-17
order of kf  1017 cm3/s, which is well below the estimates
6x10
k f 610- 4(Ea = 6 eV)
indirectly inferred from previous data of 1015 cm/s [4]. It
can also be seen that the two rate coecients are in rather
CO2 number density, cm-3

14
5x10 k f (Ea = 11.4 eV)
close agreement, within the accuracy of the present experi-
kf, cm3 sec -1

4x10
14
1.0x10
-17
mental results. From the comparison of the experimental
and the calculated rate constants, it can be concluded that
14
3x10 the steric factor for the rate constant of reaction of Eq. (4)
14 -18
is of the order of one, S  1. Qualitatively, this suggests that
2x10 5.0x10 nearly every collision between two CO molecules results in
14 formation of a transition state complex, regardless of the
1x10
collision geometry, and that at Ev + Ew  Ea the reaction
0 0.0 occurs an a near gas kinetic rate.
0 1 2 3 4 Fig. 8 shows relative contributions of state-specic reac-
He partial pressure, Torr tion channels into the overall reaction rate coecient,
k vw
f =k f , as functions of vibrational quantum numbers, cal-
Fig. 7. CO2 concentration and reaction rate constant, kf, vs. helium
partial pressure for two dierent activation energies; (a) 6 Torr CO, (b) culated from Eq. (12) using experimental VDFs at a CO
9 Torr CO, (c) 12 Torr CO in Ar, at 110 Torr total pressure. partial pressure of 12 Torr. In Fig. 8, vibrational quantum
numbers w and v are dened as follows:
COv COv w ! CO2 C: 13
measured CO2 concentrations. From Fig. 7, it can be seen
that the activation energy of Ea) = 6 eV predicts a much Each curve in Fig. 8 corresponds to a dierent value of
slower CO2 concentration reduction as a function of w = 0, 2, 4, . . . , 18 (indicated in the plot), with v being var-
helium partial pressure, compared with the experiment. ied from v = 0 to v = 37. From Fig. 8, it can be seen that
However, in all three cases, the activation energy near although vibrational levels as low as v = 16 can participate
Ea = 11 eV (11.6 eV at Pco = 6 Torr, 11.9 eV at Pco = in the reaction of Eq. (4), the main contribution comes
9 Torr, and 11.4 eV at Pco = 12 Torr) provides very good from the levels from v = 22 to v = 32. One can also see that
K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514 513

0.016 ond, there is the rapid quenching mechanism of Eq. (7),


which becomes dominant at high CO partial pressures.
Also, the estimated minimum CO(a3Pr) concentration
0.012 would have to exceed the measured electron density in opti-
cally pumped COAr plasmas, ne  1010 cm3, by about
two orders of magnitude [22,30]. Finally, the inferred reac-
kf / kf

tion activation energy, about 11 eV, considerably exceeds


vw

0.008
the activation energy of the reaction of Eq. (2). All this
indicates that the gas-phase Boudouard reaction in high-
12
14
10
8
pressure optically pumped plasmas occurs by collisions of
0.004 two highly vibrationally excited CO molecules in the
16 6
18 4 ground electron state (reaction of Eq. (4)). On the other
2
0
hand, in low-pressure CO glow discharges the alternative
0.000 channel with participation of CO(a3Pr) molecules pro-
10 15 20 25 30 35 duced by electron impact is likely to be the dominant chan-
v nel, because of low absolute populations of highly
vibrationally excited CO molecules at low pressures.
Fig. 8. Relative contributions of dierent reaction channels into the
overall reaction rate coecient k vw
f =k f as functions of v and w at a
12 Torr CO partial pressure (values of w are indicated in the plot). 4. Summary

above the activation energy threshold, the state-specic The gas-phase Boudouard disproportionation reaction
rate coecients plotted in Fig. 8 rst increase because of between two highly vibrationally excited CO molecules in
the energy factor in Eq. (12), 1  [(Ea/(Ev + Ew))]2, and the ground electronic state has been studied in optically
then gradually fall o because of the reduction of the vibra- pumped CO. The gas temperature and the CO vibrational
tional level populations, fv and fw, at higher vibrational lev- level populations in the reaction region, as well as the CO2
els. According to the statistical reaction rate model, the concentration in the reaction products have been measured
near resonant collisions (at small values of w) provide using FTIR emission and absorption spectroscopy. The
greater contribution to the overall reaction rate compared results demonstrate that CO2 formation in the optically
to collisions with a large vibrational energy dierence pumped reactor is controlled by a non-thermal chemical
between the collision partners (see Fig. 8). reaction, with a non-Arrhenius rate coecient dependence.
As discussed in Section 1, there is no evidence of pres- The CO2 concentration in the reactor is primarily con-
ence of electronically excited CO(a3Pr) molecules in the trolled by the high CO vibrational level populations, rather
optically pumped plasma at the present conditions. than by ow temperature or by CO partial pressure. The
However, this electronic level might be excited by the same disproportionation reaction rate constant has been deter-
vibration-to-electronic (VE) energy transfer mechanism, mined from the measured CO2 and CO concentrations
mediated by low-energy electrons, which results in using the perfectly stirred reactor (PSR) approximation.
production of CO(A1P) molecules at similar experimental The reaction activation energy, 11.6 0.3 eV (close to the
conditions [17,19,20]. Associative ionization in optically CO dissociation energy of 11.09 eV), was evaluated using
pumped COArHe mixtures occurs in collisions of highly the statistical transition state theory, by comparing the
vibrationally excited CO molecules [18,30]. Using Eq. (10), dependence of the measured CO2 concentration and of
the lower bound CO(a3Pr) number density necessary to the calculated reaction rate constant on helium partial
produce the amount of CO2 detected in the present exper- pressure. This suggests that the gas-phase Boudouard reac-
iments can be estimated as follows: tion occurs in collisions of two highly vibrationally excited
CO2   F CO molecules by pooling their vibrational energies
COa3 P ; 14 together. Finally, the reaction rate constants obtained from
kf a3 P
 CO  V RZ
the experimental measurements and from the transition
where kf(a3P)  1012 cm3/s is the rate constant of reac- state theory are in good agreement. This suggests that
tion of Eq. (2) [5,9], and other notations are the same as nearly every collision between two CO molecules results
in Eq. (10). From Eq. (14), the minimum number density in formation of a transition state complex (steric factor
of CO(a3Pr) molecules in the optically pumped mixture of 1), and that the reaction occurs an a near gas kinetic
should be 5 1011 cm3. Although such CO(a3Pr) EQ rate if the combined vibrational energy of the reactants
concentrations are somewhat high, they are attainable in exceeds the activation energy. The disproportionation reac-
low-pressure CO glow discharges where CO(a3Pr) mole- tion rate constant measured at the present conditions is
cules are produced by electron impact excitation. However, kf = (9 4) 1018 cm3/s. To the best of our knowledge,
they are unlikely to be achieved in the optically pumped this is the rst direct measurement of the rate constant of
plasma, for two reasons. First, there is no direct electron the gas phase Boudouard reaction in vibrationally excited,
impact excitation in the absence of electric eld, and sec- ground electronic state CO.
514 K.A. Essenhigh et al. / Chemical Physics 330 (2006) 506514

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