Determination of the rate constant of the reaction of CCl2 with HCl

Article abstract of DOI:10.1002/kin.20856

The rate constant of the reaction between CCl₂ radicals and HCl was experimentally determined. The CCl₂ radicals were obtained by infrared multiphoton dissociation of CDCl₃. The time dependence of the CCl₂ radic

Full text of DOI:10.1002/kin.20856

Determination of the Rate
Constant of the Reaction of
CCl with HCl
2
1
1
1
1
´
´
NICOLAS D. GOMEZ, VIOLETA D’ACCURSO, FRANCISCO A. MANZANO, JORGE CODNIA,
1
,2
´
M. LAURA AZCARATE
1DEILAP (CITEDEF), J. B. de La Salle 4397 (B1603ALO), Buenos Aires, Argentina
2Carrera del Investigador, Consejo Nacional de Investigaciones Cient ´ı ficas y T e´ cnicas (CONICET), Buenos Aires, Argentina
Received 21 January 2014; revised 24 March 2014; accepted 31 March 2014
DOI 10.1002/kin.20856
Published online 22 April 2014 in Wiley Online Library (wileyonlinelibrary.com).
ABSTRACT: The rate constant of the reaction between CCl2 radicals and HCl was experimentally
determined. The CCl2 radicals were obtained by infrared multiphoton dissociation of CDCl3. The
time dependence of the CCl2 radicals’ concentration in the presence of HCl was determined by
laser-induced fluorescence. The experimental conditions allowed us to associate the decrease
in the concentration of radicals to the self-recombination reaction to form C2Cl4 and to the
reaction with HCl to form CHCl3. The rate constant for the self-recombination reaction was
determined to be in the high-pressure regime. The value obtained at 300 K was (5.7 ± 0.1) ×
−
13
3
−1 −1
10
cm molecule s , whereas the value of the rate constant measured for the reaction
−14
3
−1 −1
with HCl was (2.7 ± 0.1) × 10
cm molecule s
. ꢀC 2014 Wiley Periodicals, Inc. Int J Chem
Kinet 46: 382–388, 2014
INTRODUCTION
conditions, making the technique ideal for detailed
kinetic studies. Mono- and dihalocarbenes were par-
ticularly well studied regarding the determination of
kinetic rate constants. The determination of the steps
that follow CHCl3 pyrolysis has been the subject of
numerous investigations [1–15]. Flow and shock tube
techniques have been employed using diverse detection
methods to resolve the kinetics [2–4,16–20]. Herman
et al. [5], in a molecular beam study of the multiphoton
dissociation of chloroform (CDCl3), showed that the
three-center DCl elimination is the dominant dissocia-
tion pathway:
The determination of the dissociation steps in pyroly-
sis and infrared multiphoton dissociation (IRMPD) of
molecules is not always straightforward due to subse-
quent homogeneous and heterogeneous chemistry. A
study of the kinetic mechanisms of the fragments is
important for a complete understanding of the process.
IRMPD opened an additional way of preparing this
type of fragments. Many free radicals and metastable
species can be generated via multiphoton dissociation.
Appreciable concentrations of these species are pro-
duced under low-pressure and short-time irradiation
CDCl3 + nhν → CCl2 + DCl
Correspondence to: M. Laura Azc a´ rate; e-mail: lazcarate
@citedef.gob.ar.
Contract grant sponsor: CONICET, Argentina.
Contract grant number: PIP 1220100100425.
Later, we determined that this was the only dissoci-
ation pathway occurring under IRMPD [21].
ꢀ
C
2014 Wiley Periodicals, Inc.

RATE CONSTANT OF THE REACTION OF CCl2 WITH HCl
383
Additionally, we have demonstrated that one of the
dominant removal mechanism of CCl2 is recombina-
tion [22]:
ied the reactions of CH2 with HCl and HBr. The rate
constants were measured in a direct manner by elec-
tron beam and laser magnetic resonance techniques.
The measurements were done at temperatures in the
296–670 K range. The temperature dependence ob-
k1
CCl2 + CCl2 + M−→ C2Cl4 + M
−12
tained for the rate constant with HCl was 2.82 × 10
−
1
3
–1 –1
exp(−0.87 kcal mol /RT) cm molecule s . Ku-
maran et al. [29] studied the thermal decomposition of
CF2HCl. The temperature dependence obtained for the
rate constant of the reaction of CF2 with HCl, in the
The time dependence of the CCl2 radicals’ con-
centration in the presence of Ar was determined by
laser-induced fluorescence (LIF). The rate constant for
this reaction was measured in both the falloff and the
high-pressure regimes at room temperature.
−12
range 1100–1700 K, was 4.62 × 10 exp(−7.2 kcal
−1 −1
mol /RT) cm molecule s . Melnikovich et al. [30]
−1
3
LIF is a highly sensitive technique for the detection
of molecules, concentration measurements of molec-
ular species, spectroscopy, and the study of energy
transfer processes. Simple carbenes such as methylene
studied by gas chromatography the kinetics of the reac-
tion of CF2 with C5H6 and HCl. The rate constant ex-
pression determined for the reaction between CF2 and
HCl in the 433–523 K temperature range was 1.1 ×
−12
−1
3
−1 −1
(CH2) and halomethylenes (HCX or CX2, X = F, Cl,
10
exp(–12 kcal mol /RT) cm molecule s .
Br) are important intermediates in many chemical re-
actions, particularly in organic chemistry, atmospheric
chemistry, and materials chemistry. Tie et al. [23] stud-
ied the excitation spectra of CCl2 and CFCl radicals by
LIF. The CCl2 radicals were obtained by photodisso-
ciation of CCl4, whereas CFCl radicals were obtained
by photodissociation of CCl3F with an ArF laser. The
radicals were electronically excited with a dye laser
pumped by a N2 laser. In a later work, they studied
the reaction kinetics with different gases [24]. LIF is
also employed for the study of ultrafast energy transfer
processes. Zarate et al. [25] studied the reaction kinet-
ics of the CHF radical with various alkenes, obtaining
Kushina et al. [31] studied the thermal transformation
of dichlorofluoromethane by gas chromatography. In
the temperature range 823–943 K, they obtained the
−
12
−1
rate expression 1.05 × 10 exp(−8.8 kcal mol /RT)
3
−1 −1
cm molecule
s for the reaction between CFCl and
HCl.
1
The spectroscopy of the electronic transition A B1
1
← X A1 of the dichlorocarbene radical, CCl2, has been
extensively studied to derive its physical and chemical
properties [32,33,36–38]. The values of the harmonic
and anharmonic constants are well defined [35]. In this
work, the CCl2 radicals were produced by IRMPD of
CDCl3 and the reaction rate constant of the reaction be-
tween CCl2 (X(0,0,0)) and HCl was measured by LIF.
The LIF technique allowed us to simplify the analysis
of the reaction mechanism paths so as to determine
the rate constant in a direct manner. The CCl2 radi-
−
12
3
−1
rate constants of the order of 10
s
cm molecule
−1
. The radicals were obtained by IRMPD of CH2F2
with a TEA CO2 laser. They studied the vibrational,
rotational, and translational energies of the CHF rad-
ical by LIF and reported bimolecular rate constants
for the removal of CHF by the reactions with several
1
1
cals were excited in the A B1(0,5,0) ← X A1(0,0,0)
transition. The probe pulse was delayed with respect
to the dissociation pulse, and the time-dependent rad-
ical concentration was evaluated from the intensity of
the fluorescence emitted by the excited species as they
returned to the electronic ground state.
−
12
3
−1
alkenes to be in the order of 10
s
cm molecule
−1
. Liu et al. [26] employed the LIF technique for
the determination of the rate constants of the reaction
at room temperature of the CCl2 radical with C2H4,
NO, N2O, and different halomethanes. The radicals
obtained from the photodissociation of CCl4 with a
frequency quintupled Nd:YAG laser were excited by
a dye laser pumped by a Nd:YAG laser. Merelas and
co-workers [27] studied the rate of reaction of CCl2
radicals in the electronic ground state with different
alkenes. The radicals were obtained by IRMPD of
C2F2Cl2 with a TEA CO2 laser and were electroni-
cally excited with a dye laser pumped by a Nd:YAG
laser. The rate constants of the reactions with differ-
EXPERIMENTAL
The time dependence of the CCl2 radicals concentra-
tion generated in the IRMPD of CDCl3 was deter-
mined by LIF. The experimental arrangement is shown
in Fig. 1.
The IRMPD of CDCl3 was performed with a home-
made multimode, pulsed TEA CO2 laser with a repe-
tition rate of 1 Hz, 80 ns full width at half maximum
(FWHM) pulse length, tuned to the 10P(48) emission
line. The frequency of this line is resonant with that of
the ν4 vibrational mode of CDCl3. The laser radiation
−
12
ent alkenes were found to be in the order of 10
cm molecule
3
−1 −1
s . There is limited information re-
garding the reaction rate constants of the reactions of
dihalocarbenes with HCl. Goldbach et al. [28] stud-
International Journal of Chemical Kinetics DOI 10.1002/kin.20856

384
G O´ MEZ ET AL.
Figure 1 Experimental setup scheme. Abbreviations: EM, energy meter; L1, L2, quartz lenses; L3, ZnSe lens; BS, beam
splitters; TEK, digital oscilloscope with incorporated personal computer (PC); PMT, photomultiplier; F, filter; i, iris; PD,
photodiode; M, mirror.
was focused into the center of the reaction cell with a
.4 cm focal length ZnSe lens determining a beam’s
spot diameter at the focus and a Rayleigh range of 0.74
of the Nd:YAG laser. The Nd:YAG laser trigger was
delayed with respect to that of the TEA CO2 laser. The
Nd:YAG and TEA CO2 lasers’ energies at the entrance
to the cell, 8 mJ and 1.5 J, respectively, were controlled
from the beams’ reflections on different beam splitters
and registered by two GenTec meters. In all the exper-
iments, the TEA CO2 laser fluence at the focus was
9
±
0.05 and 3.6 ± 0.4 mm, respectively.
The radicals were electronically excited with the
second harmonic of a Nd:YAG laser pulsed at a rep-
etition rate of 10 Hz and with a 5 ns FWHM pulse
length. The lasers’ beams entered into the reaction cell
collinearly, and the fluorescence signal was detected
at 90° as shown in Fig. 1. A photomultiplier tube,
RCA 1P28, was used for the detection of the fluores-
cence signal, and a long-pass interference filter and an
iris were disposed at the entrance of the photomulti-
plier tube. To increase the solid angle of detection, part
of the fluorescence emitted by the CCl2 radicals was
directed to the photomultiplier tube by a two lenses
system (10 and 24 cm focal distances, respectively).
The iris’s diameter was fixed, so that the detection vol-
ume was a region of constant IR fluence and uniform
beam profile. On the one hand, the TEA CO2 laser flu-
ence at the focus ensures that every CDCl3 molecule
within this region is dissociated. On the other hand, the
experimental detection geometry ensures that the LIF
signals obtained are not the result of spatial integration
or average over the beam profile [21].
−2
500 J cm and the Nd:YAG fluence at the observation
−2
volume was 250 mJ cm . The fluorescence signals for
the different delay times as well as the pulse-to-pulse
TEA CO2 and Nd:YAG lasers’ output energies were
acquired with an oscilloscope, Tektronix DPO 7054.
The delay times were varied in a geometric pro-
gression between 1 μs and 10 ms so as to characterize
mechanisms with different timescales with the same
resolution. In addition, to eliminate history effects, the
delay times of each experiment were chosen at ran-
dom. A specific program was developed for the con-
trol of the whole experiment by a PC. The samples
of CDCl3 (Merck Qu ´ı mica Argentina; 99.98%) and
HCl (Air Liquide Argentina; N50) were prepared in a
−7
high vacuum system (10 Torr), consisting of a tur-
bomolecular pump (Leybold, Turbovac) pumped by a
rotary vane pump (Leybold, Trivac) and introduced in
a cylindrical Pyrex glass cell 3 cm in diameter and 10
cm long. The partial pressures of reactants and products
were controlled by FTIR spectrometry. In all the ex-
periments, the CDCl3 pressure was fixed at 1 Torr and
the HCl pressure was varied in the 0–40 Torr range. To
consider that the CCl2 concentration produced in each
pulse was constant, the global dissociation was kept
less than 10%.
The synchronization between the Nd:YAG and TEA
CO2 lasers’ pulses was externally controlled with a
Stanford Research Systems delay unit, DG 535. One
channel of the delay unit was used to trigger the TEA
CO2 laser. The output of this channel was connected to
the entrance of a frequency divider to obtain a repeti-
tion rate of 1 Hz. Another channel was used as a trigger
International Journal of Chemical Kinetics DOI 10.1002/kin.20856

RATE CONSTANT OF THE REACTION OF CCl2 WITH HCl
385
Figure 3 Normalized LIF signal dependence on the delay
time between the dissociation laser and the probe beam.
Figure 2 Dependence of the LIF signal detected (SD) on
the delay time between the dissociation and the probe beams.
where kT is the rate constant of the termolecular re-
action and kHCl the rate constant of the reaction with
HCl. Therefore, the time dependence of the CCl2 con-
centration will be given by
RESULTS
Figure 2 illustrates two typical LIF signal intensity
decays as the delay time between the dissociation and
the probe lasers increases. The open circles represent
the experimental data for a mixture of 1 Torr of CDCl3
and 30 Torr of Ar. The filled circles correspond to the
experimental data obtained in mixtures of 1 Torr of
CDCl3 with 30 Torr of HCl. Owing to the large time
range, the delay time is shown in a logarithmic scale.
This decay is caused by the removal of the CCl2 radical
in the electronic ground state. It can be seen that the
rate of reaction in mixtures with HCl is faster than in
mixtures with Ar.
k [CCl2]0
[CCl2](t)=
0
exp (kt) (k + 2kT [CCl2] )−2kT [CCl2]0
(5)
where k = k
HCl
[HCl] defines the pseudo–first-order
decay coefficient associated with the reaction between
CCl radicals and HCl. [CCl ] represents the initial
2
2 0
concentration of radicals. In [22], we have demon-
strated that with the TEA CO laser fluence at the
2
Thus the generation and subsequent reaction of the
dichlorocarbene radicals in our experimental condi-
tions can be described by Eqs. (1)–(3),
focus of this work, every CDCl molecule within the
observation volume is dissociated; so that in all the ex-
3
periments, the initial concentration of CCl radicals is
2
1
Torr. Considering that the LIF signal is proportional
CDCl3 + nhν −→ CCl2+DCl
(1)
(2)
(3)
to the radicals’ concentration, the detected signal (SD)
will be given by
kT
CCl2 + CCl2 + M−→ C2Cl4 + M
SD = qi [CCl ](t) + S0
(6)
2
kHCl
CCl2 + HCl−→ CHCl3
where S0 is the background signal in the absence of
CCl2 radicals, qi is a constant that accounts for experi-
mental factors such as the photomultiplier responsivity,
the proportion of the fluorescence signal emitted in the
observation solid angle, the ratio of the number of rad-
icals in the observation volume to the total number of
radicals excited by the dye laser and the lenses, filter,
and iris transmission. The CCl2 LIF peak amplitude
dependence on the delay time between the dissocia-
tion and probe lasers is plotted on a semilog graph in
Fig. 3.
The FTIR spectra showed that the major products
obtained following photolysis were C2Cl4 and CHCl3
and that there is no evidence of other halogenated hy-
drocarbons different from CDCl3, consistent with the
mechanism determined by (1)–(3).
The rate of CCl2 radicals’ removal after the photol-
ysis of CDCl3 can be expressed by
d [CCl2]
2
=
−2kT [CCl2] − kHCl [HCl] [CCl2]
dt
In mixtures of CDCl3 with Ar, the experimental data
are well described by a hyperbolic decay showing that
(4)
International Journal of Chemical Kinetics DOI 10.1002/kin.20856

386
G O´ MEZ ET AL.
in 760 Torr Ar in the 800–1073 K temperature range.
Gas chromatographic analysis was used to determine
the reactant and products concentrations as a function
of temperature at different reaction times. In 2003, Zhu
and Bozzelli [14] analyzed previous literature results
of the thermal conversion of CHCl3 to CCl4 in the pres-
ence of Cl2 in the 846–908 K temperature range using a
detailed mechanism. The following mechanisms were
proposed for the insertion reaction CCl2 + CHCl3:
CCl2 + CHCl3 → C2HCl5
CCl2 + CHCl3 → C2Cl4 + HCl
CCl2+CHCl3 → CHCl2 CCl2 + Cl
CCl2 + CHCl3 → CHCl2 + CCl3
(9)
(10)
(11)
(12)
Figure 4 HCl pressure dependence of the rate coefficients
of reactions (2) and (3).
the radicals’ disappearance follows a second-order ki-
netic decay due to the self-recombination reaction (2).
At high HCl pressures, the decays were found to be
described by a single exponential. In intermediate HCl
pressure conditions, the fittings of the curves must be
performed considering the occurrence of both mecha-
nisms, (2) and (3). In Fig. 3, it is shown that the rate of
the reaction with HCl increases with pressure of HCl.
The dependence on HCl pressure of the
pseudo–first-order decay coefficients and the self-
recombination rate coefficients derived from the fit-
tings of the experimental data with Eq. (6) are plotted
in Fig. 4. As mentioned above, the rate of the reaction
with HCl increases with pressure of HCl. The slope of
the linear fit to the filled circles is the rate constant of
the reaction between CCl2 radicals and HCl.
The rate constants’ temperature dependence of
mechanisms (9)–(12) was studied by the authors ob-
−21
−27
3
taining values of 2.6 × 10
[9] and 3.1 × 10
cm
−1 −1
molecule
s
[14] for reaction (9) at 300 K. For re-
−29
action (10) the values obtained were 5.9 × 10
and
−29
3
−1 −1
1
.7 × 10 cm molecule
s , respectively. The rate
−29
constants derived for reaction (11) were 1.7 × 10
−17
3
−1 −1
and 2.4 × 10
cm molecule
s , respectively. Fi-
nally, Zhu and Bozzelli obtained for the rate constant of
−17
3
−1
reaction (12) a value of 3.1 × 10
cm molecule
−1
s
at 300 K. Thus, the values obtained for the dif-
ferent reaction rate constants of the insertion reaction
CCl2 + CHCl3 are negligible compared to the values
of kT and kHCl determined in this work, supporting the
hypothesis that the insertion reaction can be neglected.
In the IRMPD of molecules, the radiation interacts
resonantly with one of the species present in the sample
whereas the other compounds act as a thermal bath
For all HCl pressures, the self-recombination re-
action takes place in the high-pressure limit regime.
The value of the self-recombination rate constant was
obtained from the mean value of the rate constants ob-
tained for HCl pressures between 5 and 40 Torr and
resulted in
[
39,40]. The absorbed energy initially circumscribed to
the excited mode, rapidly spreads to other modes and
finally induces the unimolecular IRMPD with a high
decomposition rate [41]. The result is a distribution
of energized fragments which then undergo different
energy transfer mechanisms [5,25,34].
kT = (5.7 ± 0.1) × 10− cm molecule
13
3
−1 −1
s
(7)
in excellent agreement with that obtained in a previous
work [22]. The rate constant obtained for the reaction
between CCl2 radicals in their ground state and HCl
was
Herman et al. [5] determined a threshold energy
−1
of 63 kcal mol for the IRMPD of CDCl through
3
the DCl elimination channel. The excess energy accu-
mulated above this threshold depends strongly on the
kHCl = (2.7 ± 0.1) × 10− cm molecule
14
3
−1 −1
s
(8)
dissociation rate of the CDCl molecules (ࣈ10 ns)
3
−2
[
41]. For an irradiation fluence of 35 J cm , the
authors determined a mean translational energy of
−
1
Won and Bozzelli [9] studied the pyrolysis of
CHCl3 in a reaction system consisting of 1% CHCl3
2.8 kcal mol for the fragments, which is equivalent
−1
to the energy of an IR quanta (ࣈ1000 cm ), showing
International Journal of Chemical Kinetics DOI 10.1002/kin.20856

RATE CONSTANT OF THE REACTION OF CCl2 WITH HCl
387
that, in those conditions, the CDCl3 molecules are not
highly excited above the dissociation threshold. Given
the value of the rate constant kHCl obtained in this work,
the reaction process can be estimated to occur in about
The value obtained for the rate constant of the reac-
tion of CCl2 with HCl was
kHCl = (2.7 ± 0.1) × 10− cm molecule
14
3
−1 −1
s
10,000 collisions so that we can consider that the CCl2
radicals would be completely thermalized before the
reaction takes place. We can therefore affirm that in the
present work the rate constants have been determined
at 300 K.
We have presented the first determination of the
rate constant for the reaction between CCl2 radicals
and HCl at 300 K, and we are actively engaged in
performing theoretical and experimental studies for the
determination of the mechanistic route.
There is a limited knowledge of the rate constants
of the reactions between dihalocarbenes and HCl. Ku-
maran et al. [29] determined the rate constant value
of the reaction between CF2 radicals and HCl in the
−
13
1
100–1700 K temperature range to be between 10
−12
3
−1 −1
s . In a previous work,
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International Journal of Chemical Kinetics DOI 10.1002/kin.20856