FTIR and mass-spectrometric measurements of the rate constant for the C6H5+H2 reaction

Article abstract of DOI:10.1021/jp972162w

The rate constant for the C₆H₅+H₂→C₆H₆+H reaction has been measured by pyrolysis/Fourier transform infrared spectrometry (P/FTIRS) in the temperature range of 548-607 K and by pulsed-laser photolysis/mass spectrometry (PLP/MS) in the temperature range of 701-1017 K. By P/FTIRS, the reaction was studied by measuring time-resolved concentration profiles of the reactant (C₆H₅NO) and the product (C₆H₆) using highly diluted mixtures of C₆H₅NO in H₂ (with or without Ar dilution). In PLP/MS experiments, the C₆H₅ radical was generated by the photolysis of C₆H₅COCH₃ at 193 nm in the presence of several Torr of H₂. The C₆H₅+H₂ rate constant was determined by the absolute yields of C₆H₆ and C₆H₅CH₃ products. The results of these two spectrometric measurements agree closely with our theoretically predicted expression, k = 5.72×10⁴ T^2.43 exp (-3159/T) cm³/(mol·s) and with that of a shock-tube study by Troe and co-workers (ref 20) in the temperature range of 1050-1450 K. Preliminary kinetic data on the CH₃+C₆H₅ association reaction are also presented.

Full text of DOI:10.1021/jp972162w

J. Phys. Chem. A 1997, 101, 8839-8843
8839
FTIR and Mass-Spectrometric Measurements of the Rate Constant for the C6H5 + H2
Reaction
J. Park, I. V. Dyakov, and M. C. Lin*
Department of Chemistry, Emory UniVersity, Atlanta, Georgia 30322
X
ReceiVed: July 3, 1997; In Final Form: September 9, 1997
The rate constant for the C
6
H
5
2 6 6
+ H f C H + H reaction has been measured by pyrolysis/Fourier transform
infrared spectrometry (P/FTIRS) in the temperature range of 548-607 K and by pulsed-laser photolysis/
mass spectrometry (PLP/MS) in the temperature range of 701-1017 K. By P/FTIRS, the reaction was studied
by measuring time-resolved concentration profiles of the reactant (C
highly diluted mixtures of C NO in H (with or without Ar dilution). In PLP/MS experiments, the C
radical was generated by the photolysis of C COCH at 193 nm in the presence of several Torr of H . The
+ H rate constant was determined by the absolute yields of C and C CH products. The results
of these two spectrometric measurements agree closely with our theoretically predicted expression, k ) 5.72
6 5 6 6
H NO) and the product (C H ) using
6
H
5
2
6 5
H
H
6 5
3
2
C
6
H
5
2
6
H
6
6
H
5
3
4
2.43
3
×
10 T exp (-3159/T) cm /(mol‚s) and with that of a shock-tube study by Troe and co-workers (ref 20)
in the temperature range of 1050-1450 K. Preliminary kinetic data on the CH
are also presented.
3
6 5
+ C H association reaction
I. Introduction
Phenyl radical has been considered as one of the most
important reactive species in hydrocarbon combustion chemistry,
especially in the formation of polycyclic aromatic hydrocarbons
(
PAH’s) which are pivotal to soot formation in its incipient
1-5
stages.
For the kinetic studies of phenyl radical reactions,
we have carried out experiments using the cavity ringdown
(
5
CRD) technique, covering a typical temperature range of 298-
23 K.6
-15
Temperature broadening of the rovibronic transition
of C6H5 in the visible region limits its kinetic measurements
by CRD to about 523 K, above which its S/N ratio deteriorates
rapidly with temperature. This temperature limit (T E 523 K)
precludes the studying of slower reactions such as C6H5 + H2
and CH4. In order to circumvent the shortcoming, in this work
we employed two complementary methods for the kinetic study
of the C6H5 + H2 reaction using pyrolysis/Fourier transform
infrared spectrometry (P/FTIRS) and pulsed-laser photolysis/
mass spectrometry (PLP/MS). The methods effectively extend
the kinetically useful temperature range to ∼1000 K. The latter
method has been successfully applied to obtain the rate constant
for the recombination reaction of C6H5 radicals,16 and the total
rate constants and product branching ratios for the reactions of
NH2 with NOx.1
Figure 1. Typical FTIR spectra of pyrolyzed and unpyrolyzed samples.
II. Experimental Section
As alluded to above, two methods complementary to the CRD
technique have been developed for the slow abstraction reaction
of C6H5 with H2. The experimental procedures of the P/FTIRS
16-18,25,26
and PLP/MS methods have been given previously,
a brief description of each is presented below.
and
7,18
The mechanism of the C6H5 + H2 reaction has been
1
. P/FTIRS. With this method, C6H5NO was used as the
investigated theoretically using a modified Gaussian 2 method
phenyl source. Highly diluted mixtures of C6H5NO in H2 (with
or without further dilution with Ar) were pyrolyzed in the 548-
607 K temperature range at atmospheric pressure. Pyrolyzed
or unpyrolyzed reference samples were expanded into the
absorption cell inside the analysis chamber for determination
of the concentrations of the C H product and the unreacted
1
9
(
G2M). The reaction was predicted to occur exclusively by
direct abstraction with a barrier of 8.8 kcal/mol. The transition
state (TS) was found to have a linear C-H-H structure with
C2V symmetry. The rate constant calculated according to the
predicted geometries and molecular parameters (frequencies and
moments of inertia) of the TS and the reactants using the
transition-state theory (TST) with tunneling corrections was
found to be in good accord with the recent shock tube results
of Troe and co-workers.20 Comparison of the theory with the
6
6
C H NO reactant. The pressures of the samples after expansion
6
5
are approximately 270 Torr. To minimize the effect of pressure-
broadening, the pressure of calibration mixtures containing
varying amounts of C6H6 and C6H5NO was maintained at 270
21-24
-1
present and other available data in the literature
discussed.
will be
( 10 Torr. Absorption peaks at 673.1 and 1130.0 cm were
employed for the determination of C6H6 and C6H5NO, respec-
tively.
Figure 1 presents typical FTIR spectra for pyrolyzed and
unpyrolyzed samples. This set of spectra illustrates that the
*
Corresponding author. E-mail: chemmcl@emory.edu.
Abstract published in AdVance ACS Abstracts, November 1, 1997.
X
S1089-5639(97)02162-2 CCC: $14.00 © 1997 American Chemical Society

8840 J. Phys. Chem. A, Vol. 101, No. 47, 1997
Park et al.
trace amount of C6H6. Addition of H2 to the system noticeably
reduced the yields of C12H10 and C6H5CH3, with a concomitant
increase in the yield of C6H6. Table 2 summarizes the
experimental conditions employed and the yields of C6H6 and
C6H5CH3 measured in the PLP/MS experiment. Kinetic model-
ing of the absolute concentrations of these products, determined
by careful calibrations using standard mixtures sampled at the
same total pressure employed in each run, gave the rate constants
for the formation of C6H6 and C6H5CH3 by the following
respective reaction:
C H + H f C H + H
6
5
2
6
6
C H + CH f C H CH
3
6
5
3
6
5
CH4 is present in these experiments in a much lower concentra-
tion than C6H6 and was presumed to be formed by the CH3 +
H2 f CH4 + H reaction. The comparison of the measured
and predicted yields will be discussed in the following section.
6 5 6 6
Figure 2. Time-resolved C H NO decay (solid points) and C H
formation (open circles) profiles in P/FTIR experiments at T ) 598 K.
Lines are the modeled results. Reaction conditions are given in Table
1
.
III. Results and Discussion
a
TABLE 1: Experimental Conditions and Modeled Rate
Constants in P/FTIR Experiment for the Reaction of C
at Temperatures Studied
1
. Kinetics of the C6H5 + H2 Reaction. The rate constant
6
5
H +
H
2
of the C6H5 + H2 reaction can be obtained by kinetic modeling
in a straightforward manner. The mechanisms employed for
the modeling are presented in Tables 3 and 4 for the pyrolysis
of C6H5NO-H2 mixtures and the photolysis of C6H5COCH3-
H2 mixtures, respectively.
3
(cm /mol‚sec)b
T (K) [C NO] [Ar]
6
H
5
0
0
[H
2
]
0
k
4
-
8
8
8
8
8
8
8
8
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-5
-6
-6
-6
8
5
5
5
5
5
5
5
6
48 1.70 × 10
0.00 × 10
1.17 × 10
1.04 × 10
1.02 × 10
1.00 × 10
1.10 × 10
1.09 × 10
1.07 × 10
2.22 × 10
1.02 × 10
1.13 × 10
1.11 × 10
1.09 × 10
9.64 × 10
9.49 × 10
9.35 × 10
7.45 × 10
-
-
-
-
-
-
-
9
58 1.43 × 10
63 1.58 × 10
73 1.55 × 10
83 1.53 × 10
89 1.35 × 10
98 1.33 × 10
07 1.31 × 10
(1.18 ( 0.66) × 10
9
1.14 × 10
9
9
9
9
9
(1.20 ( 0.18) × 10
(1.44 ( 0.15) × 10
(1.35 ( 0.14) × 10
(1.48 ( 0.20) × 10
(1.99 ( 0.13) × 10
In the thermally initiated C6H5NO and H2 reaction, the
formation of C6H6 was influenced by the following primary
processes:
C H NO ) C H + NO
(1, -1)
(2)
6
5
6
5
a
3
b
The concentration units are in mol/cm . For each temperature
except 548 and 563 K), typically 3-5 runs were carried out. The
(
C H + C H f C H
6 5 6 5 12 10
uncertainty represents 1σ.
C H + C H NO f C H NO
(3)
major absorption peaks of the reactant and product are clearly
separated. The C6H6 peak at 673.1 cm overlaps with a small
peak of C6H5NO; the overlap can be readily corrected. Figure
6
5
6
5
12 10
C H + H f C H + H
(4)
6
5
2
6
6
2
shows a typical set of the concentration vs time plots for the
All but reaction 4 have been determined recently by us.16,26 The
results of our sensitivity analysis (see Figure 3) bear this out.
In order to account for the loss of C6H5, several secondary and
tertiary reactions were included in the modeling, employing
formation of C6H6 and the decay of C6H6NO. The correspond-
ing curves represent kinetically modeled values. The values
of the rate constant for C6H5 + H2 obtained by modeling are
summarized in Table 1. The mechanism employed for modeling
will be discussed later.
“
reasonably” assumed values of radical-radical reaction rate
constants (see Table 3). The values of rate constant for the
C6H5 + H2 reaction are presented in Table 1 and Figure 5 (vide
infra).
2. PLP/MS. By the mass-spectrometric method, the pulsed
photolysis of C6H5COCH3 at 193 nm was employed as the C6H5
radical source. C6H5COCH3, carried by an excess amount of
He was premixed in corrugated stainless steel tubing with H2
In the photoinitiated reaction of C6H5COCH3 in the presence
of excess amounts of H2, the production of C6H6 was found to
be influenced by the following primary processes:
2
7,28
before being introduced in the Saalfeld-type quartz reactor
which can be heated to 1200 K. The reactants and the products
of the photoinitiated reaction were supersonically sampled and
ionized by electron-impact ionization. The mole fraction of
C6H5COCH3 was typically <0.5% and that of H2 >75%, with
C H + C H f C H
12 10
(2)
(4)
(5)
(6)
6
5
6
5
C H + H f C H + H
6
5
2
6
6
[H2]/[C6H5COCH3 ] > 150. The conversion of C6H5COCH3
by the unfocused ArF laser beam ranged from 15% to 40%.
The mechanism for the fragmentation of C6H5COCH3 at 193
nm has been studied by using NO or HBr as the C6H5 radical
scavengers.29 The kinetic modeling of measured yields of C6H5-
NO or C6H6 and CH4 under fully inhibited conditions revealed
that ∼80% of the fragmentation reaction gave rise to C6H5. This
result is consistent with the measured yield of C6H5CH3 without
NO or HBr. The introduction of an excess amount of NO, for
example, eliminated the formation of toluene.29
C H + CH f C H CH
3
6
5
3
6
5
CH + CH f C H
6
3
3
2
The result of sensitivity analysis carried out at 887 K (see Figure
4) clearly bears this out. Again, in order to minimize the loss
of C6H5 in our simulation, several secondary and tertiary
reactions were included in the model as shown in Table 4. A
sensitivity analysis of this system shown in Figure 4 reveals
that the yield of C6H6 is most strongly and positively affected
by reaction 4 and negatively influenced by its competitive
reactions 2 and 5.
In the absence of H2, the major molecular products from the
C6H5COCH3 photolysis were C6H5CH3, C2H6 and C12H10
(which was not quantitatively determined in this study), with a

Rate Constant for the C6H5 + H2 Reaction
J. Phys. Chem. A, Vol. 101, No. 47, 1997 8841
a
b
TABLE 2: Experimental Conditions and Product Yields in the PLP/MS Experiment at the Temperatures Studied
[C
6 6
H
]
t
[C
expt
6 5 3 t
H CH ]
temp (K)
P (Torr)
[C
H
6 5
COCH
3
]
0
[C
6
H
5
]
0
[He]
0
[H
2
]
0
expt
model
model
7
7
8
8
8
8
9
9
01
51
11
33
87
88
04
75
3.57
3.66
3.74
3.70
3.00
3.78
3.00
3.00
3.62
3.00
3.66
3.59
1.19
3.41
1.30
1.37
1.27
1.18
1.24
1.56
1.38
1.23
0.97
0.98
0.30
0.90
0.30
0.28
0.59
0.24
126
121
115
110
122
104
119
111
88
682
654
623
596
419
575
411
381
486
365
0.35
0.41
0.42
0.47
0.20
0.46
0.21
0.23
0.40
0.20
0.35
0.41
0.42
0.47
0.20
0.46
0.21
0.22
0.40
0.19
0.38
0.29
0.23
0.20
0.04
0.20
0.04
0.03
0.10
0.02
0.38
0.31
0.23
0.19
0.05
0.20
0.04
0.03
0.09
0.02
1
1
007
017
106
a
All concentrations are in units of 10-10 mol/cm3. b Product yields were measured at t ) 15 ms in their plateau regions. Typically 3-5 runs were
carried out for each temperature. To avoid congestion, the kinetically modeled values of k from the C yields are summarized in Figure 4 and
4
6 6
H
those of k
5
from the C
H
7 8
yields are given in the text.
a
TABLE 3: Reactions and Rate Constants Used in the Modeling of the C
6
H
5
2
+ H Reaction in the P/FTIR Experiment
reactions
A
n
E
a
ref
key reactions
1. C
2. C
3. C
4. C
6
6
6
6
H
5
H
5
H
5
H
5
NO ) C
6
H
5
+ NO
1.42E+17b
1.39E+13
4.90E+12
5.72E+04
0.00
0.00
0.00
2.43
55060
111
68
6276
26
16
16
19
+ C
+ C
6
H
H
5
) C12
NO f C12
+ H
H
10
6
5
H10NO
+ H
2
f C
6
H
6
minor reactions
7
8
9
1
1
1
1
1
. C12
H
10NO f C
10NO + C
NO + H f C
6
H
5
NO + C
6
H
5
5.00E+14
1.00E+12
4.00E+13
1.00E+12
5.00E+12
7.80E+13
1.00E+13
5.40E+15
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
45000
0
4310
0
4500
0
c
c
c
c
c
31
c
. C12H
6
H
5
f C12
H
10N + C
6
H
5
O
. C
6
H
5
6
H
6
+ NO
+ HNO
NO f C12
+ H f C
0. C
1. C
2. C
6
6
6
H
H
H
5
NO + H f C
H
6 5
5
+ C
6
H
5
H10 + NO
5
6
H
6
3. C12
H
10N + NO f C12
H10NNO
0
596
4. H + NO + M ) HNO + M
31
a
n
3
is in the units of cal/mol. b Read as 1.42 × 10 . Assumed.
17 c
Rate constants are defined by k ) AT exp(-E
a
/RT) and in units cm , mol, and s; E
a
a
TABLE 4: Reactions and Rate Constants Used in the Modeling of the C
6
H
5
2
+ H Reaction in the PLP/MS Experiment
reactions
A
n
E
a
ref
key reactions
2
4
5
6
. C
. C
. C
6
6
6
H
H
H
5
5
5
+ C
+ H
+ CH
6
H
5
) C12
H
10
1.39E+13b
5.72E+04
1.38E+14
1.50E+15
0.00
2.43
-0.30
-0.64
111
6276
0
16
19
30
30
2
) C
) C
) C
6
H
6
+ H
3
6
H
5
CH
3
. CH
3
+ CH
3
H
2 6
0
minor reactions
1
1
1
1
1
2
2
2
2
2
2
2
2
2
5. C
6. CH
6
H
3
5
+ H ) C
+ H ) CH
COCH
f C
COCH
6
H
4
6
7.80E+13
2.89E+02
3.39E+11
7.94E+11
5.01E+10
3.39E+09
1.00E+11
5.00E+12
5.00E+12
1.00E+12
4.00E+14
1.00E+08
4.04E+15
8.74E+42
0.00
3.12
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
0.00
-0.80
-8.62
0
8710
5890
11100
7400
5890
4000
0
30
32
33
33
33
33
c
c
c
c
c
2
+ H
f C
+ CH
f CH
7. C
8. C
6
H
H
5
+ C
6
H
4
5
3
6
H
3
6
6 5 2
+ C H COCH
6
5
+ CH
6
H
6
9. CH
3
+ C
6
H
5
3
4
+ C
6
H
5
COCH
CO
2
0. C
1. C
2. C
3. C
4. C
5. C
6
6
6
6
6
6
H
H
H
H
H
H
5
+ C
+ C
COCH
COCH
COCH
COCH
6
H
H
5
COCH
COCH
3
f C12H
10 + CH
10COCH
3
5
6
5
3
f C12
H
COC
3
5
2
+ CH
3
) C
6
H
5
H
2 5
5
2
2
2
+ C
+ C
6
H
H
5
f C12H
10COCH
2
0
0
5
6
5
COCH
+ CH
2
f (C
H
6 5
COCH
2
)
2
5
f C
6
H
5
2
CO
29400
0
6. C12
7. CH
8. CH
H
3
10COCH
3
f C12
H
3
10 + CH
3
CO
c
32
32
+ CH
3
CO ) CH
COCH
3
0
3
CO + M ) CH
3
+ CO + M
22420
a
n
3
is in the units of cal/mol. b Read as 1.39 × 10 . Assumed.
13 c
Rate constants are defined by k ) AT exp(-E
a
/RT) and in units cm , mol, and s; E
a
The kinetically modeled values of k4 based on the absolute
yields of C6H6 are summarized in Figure 5 for comparison with
those obtained by FTIR spectrometry and by Troe and co-
workers using UV absorption spectrometry carried out in a shock
tube at temperatures between 1050 and 1450 K.20 The three
independent, more direct measurements agree closely with our
theoretically predicted values covering the entire temperature
range investigated, 548-1450 K.19 In the figure, we also
compare these three sets of experimental data and the theoreti-
cally predicted curve with the existing, mostly kinetically
modeled results obtained by shock-heating of C6H6 at high
2
1-23
temperatures.
Among them, the data of laser schlieren
2
3
measurements by Kiefer and co-workers agree most closely
with the theory.
Also included in the figure are the data obtained by Fielding
2
1
and Pritchard with a relative rate method using the C6H5
recombination reaactin as the reference standard. The relative
rate data, after being converted to absolute values with our C6H5
17
recombination rate constant appear to be much lower than our
FTIR and theoretically predicted results.

8842 J. Phys. Chem. A, Vol. 101, No. 47, 1997
Park et al.
Figure 5. Arrhenius plot of the rate constant for the C
reaction. O, this work by P/FTIRS; 0, this work by PLP/MS; 4, ref
0; 1, theoretical results of Mebel et al., ref 19; 2, ref 22; 3, ref 23; 3,
6
H
5
+ H
2
2
ref 21 using the rate constant for the recombination of C
6 5
H reported
by Park and Lin (ref 17).
agree reasonably well with the expression recommended by
1
3
0.3
3
30
Tsang and Kiefer, k5 ) 2.5 × 10 (300/T) cm /(mol‚s).
A
more detailed discussion on k5 determined by this and other
related experiments will be presented elsewhere.
Figure 3. Sensitivity analysis at T ) 589 K for C
6
H
6
and C
6
H
5
NO in
29
a P/FTIRS experiment.
IV. Concluding Remarks
In this investigation, two complementary experimental tech-
niques (pyrolysis/FTIR and PLP/MS) have been developed for
the kinetic study of C6H5 radical reactions. These techniques
have effectively extended the range of temperature from the
upper limit of the cavity ringdown method (523 K) to 1000 K.
The values of a rate constant covering the wide temperature
range of 300-1000 K can be utilized for a reliable extrapolation
to the combustion regime (1500-2500 K), particularly with the
aid of the TST or the RRKM theory using transition-state
parameters obtained by high-level ab initio MO calculations as
has been demonstrated in the present C6H5 + H2 case.
For the C6H5 + H2 reaction, the results determined with the
two techniques covering the temperature range 548-1017 K
agree closely with the theoretically predicted rate constant, k
4
2.43
3
19
)
5.72 × 10 T exp(-3159/T) cm /(mol‚s), by Mebel et al.
and with the results of a shock tube study by Troe and co-
2
0
workers in the temperature range of 1050-1450 K using UV
absorption spectroscopy. The above expression is recommended
for combustion modeling.
Acknowledgment. The authors gratefully acknowledge the
support of this work by the Division of Chemical Sciences,
Office of Energy Sciences, DOE, under contract no. DE-FGO5-
9
1ER14192.
6 6 6 5 3
Figure 4. Sensitivity analysis at T ) 887 K for C H and C H CH in
References and Notes
a PLP/MS experiment.
(
1) Glassman, I. Combustion, 2nd ed.; Academic Press: New York,
986.
2) Bittner, J. D.; Howard, J. B. 18th Symposium (International) on
1
2. Kinetics of the CH3 + C6H5 Association Reaction. The
(
absolute yield of toluene measured in the present experiment
can be directly utilized for estimation of the rate constant for
the association reaction:
Combustion, [Proceedings]; The Combustion Institute: Pittsburgh, 1983;
p 1105.
(
3) Brezinsky, K.; Litzinger, T. A.; Glassman, I. Int. J. Chem. Kinet.
984, 16, 1053.
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1
(
C H + CH f C H CH
(5)
6
5
3
6
5
3
(
The values of k5 obtained by kinetic modeling lie in the range
(
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13
3
of (1.8 ( 0.2) × 10 cm /(mol‚s) at 701-1017 K. These values
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Rate Constant for the C6H5 + H2 Reaction
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(
(
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(
(
(
(
(
(
(
(
(
(
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(
1
(
(
(
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