Kinetics of the reactions of hydroxyl radicals with diacetylene and vinylacetylene

Article abstract of DOI:10.1515/zpch-2014-0618

Highly unsaturated hydrocarbons like diacetylene (C₄H₂) or vinylacetylene (C₄H₄) are important intermediates in combustion that can have impact on soot formation. One of their major loss channels is reaction with hydroxyl radicals (OH). We studied the reactions C₄H₂ + OH → products (1) and C₄H₄ + OH → products (2) in a quasi-static reactor with helium as bath gas. The hydroxyl radicals were produced by laser flash-photolysis of nitric acid at a wavelength of 248 nm and detected by laser-induced fluorescence with excitation at 282 nm. The rate coefficients were obtained from the intensity-time profiles under pseudo-first order conditions with respect to OH. We found a virtually temperature-independent rate coefficient for reaction (1): k₁ = (1.0 ± 0.3) × 10^-11 cm³ s^-1 (T = 290-670 K, P = 2.7-30.5 bar) and a weakly negative temperature-dependent rate coefficient for reaction (2): k₂(T) = (6.4 ± 1.9) × 10^-12 exp (486 K/T) cm³ s^-1 (T = 295-740 K, P = 1.7-19.2 bar). For neither of the two reactions pressure dependence was observed. From comparisons with analogous reaction systems, we conclude that the dominating reaction pathway is OH addition, where in the case of C₄H₄ the double bond is preferred over the triple bond.

Full text of DOI:10.1515/zpch-2014-0618

Z. Phys. Chem. 2015; 229(4): 495–505
Jörg Sommerer and Matthias Olzmann*
Kinetics of the Reactions of Hydroxyl
Radicals with Diacetylene and
Vinylacetylene
Abstract: Highly unsaturated hydrocarbons like diacetylene (C4H2) or vinylacety-
lene (C4H4) are important intermediates in combustion that can have impact on
soot formation. One of their major loss channels is reaction with hydroxyl radicals
(OH). We studied the reactions C4H2+OH →products (1)and C4H4+OH →prod-
ucts (2) in a quasi-static reactor with helium as bath gas. The hydroxyl radicals
were produced by laser flash-photolysis of nitric acid at a wavelength of 248 nm
and detected by laser-induced fluorescence with excitation at 282 nm. The rate
coefficients were obtained from the intensity-time profiles under pseudo-first or-
der conditions with respect to OH. We found a virtually temperature-independent
3
−1
rate coefficient for reaction (1): ꢀ1 =(1.0 0.3) × 10−11 cm s (ꢁ =290–670 K,
ꢂ =2.7–30.5 bar) and a weakly negative temperature-dependent rate coefficient
−12
3
for reaction (2): ꢀ2(ꢁꢃ = (6.4 1.9ꢃ×10 exp(486 K/ꢁꢃ cm s−1 (ꢁ =295–740 K,
ꢂ =1.7–19.2 bar). For neither of the two reactions pressure dependence was ob-
served. From comparisons with analogous reaction systems, we conclude that the
dominating reaction pathway is OH addition, where in the case of C H the double
4
4
bond is preferred over the triple bond.
Keywords: Reaction Kinetics, Elementary Chemical Steps, Laser-Induced Fluores-
cence, Diacetylene, Vinylacetylene, Hydroxyl Radicals.
DOI 10.1515/zpch-2014-0618
Received September 18, 2014; accepted October 22, 2014
||
Dedicated to Professor Henning Bockhorn on the occasion of his 70th birthday
*Corresponding author: Matthias Olzmann, Institut für Physikalische Chemie,
Karlsruher Institut für Technologie (KIT), Kaiserstr. 12, 76131 Karlsruhe, Germany,
e-mail: matthias.olzmann@kit.edu
Jörg Sommerer: Institut für Physikalische Chemie, Karlsruher Institut für Technologie (KIT),
Kaiserstr. 12, 76131 Karlsruhe, Germany
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J. Sommerer and M. Olzmann
1 Introduction
Highly unsaturated hydrocarbons are important intermediates in fuel-rich
flames [1–3]. Compounds like diacetylene (HC≡C–C≡CH, C4H2) and vinyl-
acetylene (H C=CH–C≡CH, C4H4) occur in relatively high concentrations and are
2
discussed to contribute to the formation of polycyclic aromatic hydrocarbons and
soot [4–9]. C H and C H are mainly formed in reactions of unsaturated radicals
4
2
4
4
with acetylene [4, 5, 8, 10]; one of their major loss channels is reaction with OH:
C H + OH → products
(1)
(2)
4
2
C H + OH → products
4
4
Kinetic data of these oxidation reactions are scarce.
First estimations of the rate coefficient of reaction (1) were published in 1982.
Warnatz et al. [11] inferred a value of ꢀ1 =5.0 × 10−11 cm s−1 with little or no tem-
3
perature dependence from experimental investigations and numerical simula-
tions of acetylene flames. This result was later adopted as recommendation in
[12] for ꢁ =300–2000 K with an estimated uncertainty of a factor of two. Bittner
and Howard [13] recommended a value in the range 5 × 10−11 to 12 × 10−11 cm s
3
−1
from their study of benzene flames with typical temperatures between 1700 and
1900 K. At about the same time, Atkinson and Aschmann [14] measured a rate
coefficient ꢀ1 =(1.62 0.06) × 10−11 cm s (relative to the rate coefficient of the
3
−1
OH + ꢄ-butane reaction) at ꢁ =297 K and atmospheric pressure. Perry [15], in
a temperature-dependent study, obtained an Arrhenius expression of ꢀ1(ꢁꢃ =
1.11 × 10 exp[(1.7 1.3ꢃ kJ mol /(RTꢃ] cm s−1 from experiments conducted
−11
−1
3
in the temperature range 296–688 K at pressures near 70 and 140 mbar. A value
of ꢀ1 =(2.0 1.0) × 10−11 cm s−1 that is consistent with these results was obtained
by Bartels et al. [16] in a discharge-flow tube study (ꢁ =295 K, ꢂ ꢅ 15 mbar).
Rate coefficients obtained from an extrapolation of the Arrhenius expression from
Perry [15] weresuccessfully used by Hidaka and coworkers[17] to model theresults
of their shock-tube investigation on the pyrolysis and oxidation of diacetylene.
A detailed theoretical study on the kinetics and product branching of reaction
(1) was published only in 2007 by Senosiain et al. [18] These authors character-
ized the relevant features of the potential energy surface with high-level quantum
chemical methods and calculated rate coefficients for the different product chan-
nels, using a RRKM/master-equation formalism. The resulting overall rate coef-
ficients are essentially in agreement with the experimental values at lower tem-
peratures but lie distinctly below the values inferred from complex kinetic mod-
eling of shock tube and flame experiments at high temperatures. Very weak neg-
ative temperature dependence and almost no pressure dependence for pressures
3
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Kinetics of the C H + OH and C H + OH reactions
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4
2
4
4
above ca. 25 mbar are predicted for temperatures below 500 K. To verify the cal-
culated rate coefficients and the missing pressure dependence (which is probably
due to the high-pressure limit [18]) and to supplement the measurements at lower
pressures from [15], we studied reaction (1) in a similar temperature range but at
higher pressures between 2 and 30 bar. In this pressure range, ꢀ1 is safely close
to its high-pressure limiting value. We determined the rate coefficient by directly
monitoring the intensity of laser-induced fluorescence of OH under pseudo-first
order conditions.
The situation regarding the kinetics of reaction (2)is much less satisfactory. To
the best of our knowledge, there is only one estimate of the rate coefficient for the
direct hydrogen abstraction reactions [4] that may become relevant at high tem-
peratures. These values were adopted in the modeling calculations of [5] and [17].
No other kinetic data on reaction (2) are available. Therefore, we studied reaction
(2) in the same way as reaction (1).
2 Experimental
The experiments were performed in a quasi-static (slow-flow) reactor with helium
as the bath gas by using pulsed laser photolysis of HNO for production and laser-
3
induced fluorescence for detection of OH radicals. An excess of C H or C H was
4
2
4
4
applied to ensure pseudo-first order conditions with respect to [OH]. Since the
experimental setup was already described in detail elsewhere [19, 20], only the
essentials are repeated here.
The T-shaped reaction cell with three Suprasil windows is made from stain-
less steel and can be heated with resistance wires up to 1000 K. The reaction mix-
tures were prepared in gas cylinders and were slowly flowed through the cell so
as to avoid depletion of the radical precursor and accumulation of reaction prod-
ucts. The pressure was measured by a membrane pressure transducer suitable for
pressures of up to 600 bar. The temperature in the reaction zone was determined
with two thermocouples located at the inlet and outlet of the reactor. Maximum
temperature differences of 20 K occurred at the highest temperatures (> 700 K)
and vanished at temperatures near 300 K. Considering these differences and the
location of the small reaction volume in the center between the inlet and outlet,
we estimated a maximum temperature uncertainty of 5 K at the highest temper-
atures.
Two windows positioned perpendicular to the gas flow at the front and back
side of the reactor allow flash-photolysis of the radical precursor from one direc-
tion and resonant excitation of the radicals from the opposite direction. The fluo-
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498
| J. Sommerer and M. Olzmann
rescence of the excited radicals was observed through a third window perpendicu-
lar to the gas flow and the laser beams. The fluorescence light was passed through
a monochromator and collected in a photomultiplier tube. The electronic signal
was transferred to a personal computer and analyzed. The time delay between the
flash-photolysis and the detection pulse was controlled with a delay generator.
Hydroxyl radicals were obtained from photolysis of nitric acid with a KrF ex-
cimer laser at 248 nm (see [21] and [22]). The laser pulses for fluorescence excita-
tion at 282 nm were generated by a tunable dye laser that was pumped with a XeCl
excimer laser and operated with Coumarin 153 in methanol.
Nitric acid was always freshly synthesized to suppress the competing reaction
of OH radicals with NO from unwanted decomposition of stored liquid HNO .
2
3
The synthesis from H SO and NaNO is described in [22]. Diacetylene and vinyl-
2
4
3
acetylene were synthesized by dehydrohalogenation of 1,4-dichloro-2-butyne and
1,4-dichloro-2-butene, respectively, as described in [23]. Briefly, in a three-necked
flask a flow of helium was passed through an alkalinized solvent (potassium hy-
droxide, H O with 10% dimethyl sulfoxide in the case of C H , ethylene glycol
2
4
2
∘
with 10% 2-butoxyethanol in the case of C4H4) that is kept at 50 C, and the halo-
genated hydrocarbon was added dropwise. The product hydrocarbon formed is
carried out with the helium flow and purified/isolated by passing a series of three
∘
cooling traps (−20, −80, and −200 C, respectively), where the last one contains
the clean product. This trap is then unfrozen, and the gaseous hydrocarbon is
collected in a bulb. Because both C H and C H tend to decompose explosively,
4
2
4
4
suitable safety precautions need to be taken.
Reaction mixtures were prepared manometrically in 50 liter stainless steel
cylinders. The partial pressures of nitric acid, the hydrocarbon, and helium were
determined with membrane pressure transducers. The freshly prepared mixtures
were then allowed for at least 12 hours to mix, and the total pressure was again
checked before use. The reaction mixtures were stable over several days, and no
systematic change in the measured rate coefficients was observed.
3 Data analysis and results
The C H + OH reaction was investigated in the temperature range 290–670 K at
4
2
pressures between 2.7 and 30.5 bar; the C H + OH reaction was studied in the
4
2
temperature range 295–740 K at pressures between 1.7 and 19.2 bar. The con-
−3
centrations of the hydrocarbons were varied in the ranges (0.45–2.6)× 1016 cm
in the case of C H and (1.3–10.2) × 1015 cm−3 in the case of C H . The initial con-
4
2
4
4
centrations of HNO were also in the order of 1016 cm which resulted in initial
−3
3
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Kinetics of the C H + OH and C H + OH reactions
| 499
4
2
4
4
Figure 1: LIF intensity-time profile and least-squares fit for C4H4 + OH at ꢀ = 370 K, ꢁ = 7.9 bar,
15
−3
and [C4H4]0 = 7.4 × 10 cm
.
Figure 2: Plot of the pseudo-first order rate coefficient ꢂ
vs. [C4H2]0 for ꢀ = (490 8) K
pseudo(1)
−11
3
−1
and 3 bar < ꢁ < 19 bar. The linear fit through the origin gives a slope of ꢂ1 = 1.06 × 10 cm s
.
concentrations of OH in the order of 1012 cm−3 (see [21]). With such HNO concen-
3
trations, competing reactions contributed less than 5% to the observed pseudo-
first order rate coefficient.
For both reactions the measured fluorescence intensity-time profiles showed
monoexponential decays. A typical case is displayed in Figure 1. Pseudo-first or-
der decay constants ꢀ
(ꢆ =1, 2) were obtained from the slopes of the lin-
pseudo(ꢃ)
earized plots. We analyzed in total 150 experiments for C H + OH and 216 exper-
4
2
iments for C H + OH.
4
4
The second-order rate coefficients ꢀꢃ were obtained from least-squares fits of
the pseudo-first order plots ꢀpseudo(ꢃ) =ꢀꢃ[C H ] , where we have lumped together
4
2ꢃ 0
data for a given temperature ꢁ within ꢁ 8 K. Exemplary results are shown in
Figures 2 and 3, and Arrhenius plots of the resulting rate coefficients ꢀ1 and ꢀ2
are given in Figures 4 and 5, respectively. For the C H + OH reaction we found
4
2
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500
| J. Sommerer and M. Olzmann
Figure 3: Plot of the pseudo-first order rate coefficient ꢂ
vs. [C4H4]0 for ꢀ = (380 8) K
pseudo(2)
−11
3
−1
and 5 bar < ꢁ < 10 bar. The linear fit through the origin gives a slope of ꢂ2 = 2.69 × 10 cm s
.
Figure 4: Arrhenius plot of the rate coefficients ꢂ1; the data points are averages over single
experiments within ꢀ 8 K, the error bars represent one standard deviation.
Figure 5: Arrhenius plot of the rate coefficients ꢂ2; the data points are averages over single
experiments within ꢀ 8 K, the error bars represent one standard deviation.
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Kinetics of the C H + OH and C H + OH reactions
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501
4
2
4
4
a temperature-independent rate coefficient of −11
3
−1
ꢀ1 = (1.0 0.3ꢃ × 10 cm s
(3)
(4)
and for the C H + OH reaction we obtained from a least-squares fit:
4
4
−12
3
−1
ꢀ2(ꢁꢃ = (6.4 1.9ꢃ × 10 exp(486 K/ꢁꢃ cm s .
Due to the multitude of parameters, which influence the uncertainty of the ex-
periments, and which are difficult to quantify exactly, a maximum error of 30%for
the rate coefficients was estimated. For neither of the two reactions a significant
pressure dependence was observed.
4 Discussion
4.1 The C H + OH reaction
4
2
In Figure 6 our experimental value for ꢀ1 is compared with results from
other works. As already outlined in the introduction section, there are three
more experimental studies in the temperature range of our experiments. In
1989, Bartels et al. [16] published a value of ꢀ1 =(2.0 1.0) × 10−11 cm s
3
−1
(ꢁ =295 K, ꢂ ꢅ 15 mbar) that was determined relative to the rate co-
efficient of ꢄ-C H + OH, for which these authors adopted an average
4
10
3
−1
value of ꢀref =3.3 × 10−12 cm s . Another relative rate measurement
was carried out earlier by Atkinson and Aschmann [14], who obtained
3
−1
ꢀ1 =(1.62 0.06) × 10−11 cm s (ꢁ =297 K, ꢂ =967 mbar) with a reference
value of ꢀref =2.58 × 10−12 cm s for ꢄ-C H + OH. Furthermore, Perry [15]
3
−1
4
10
performed a flash photolysis/resonance fluorescence study and obtained
−11
−1
3
−1
ꢀ1(ꢁꢃ = 1.11 × 10 exp[(1.7
1.3ꢃ kJ mol /(RTꢃ] cm s (ꢁ =296–688 K,
ꢂ =67–133 mbar). A detailed theoretical study was published by Senosiain
et al. [18] in 2007. These authors predict a weak, negative temperature de-
pendence for ꢀ1 and a vanishing pressure dependence below ꢁ =500 K and
ꢂ > 1 bar.
Our experimental values of ꢀ1 are in good agreement with the results of these
earlier studies and confirm the missing pressure and temperature dependences.
On an absolute scale our values are a factor of 1.5 to 2 smaller than these results, if
one leaves aside the rather large estimated value from [12]. Moreover, if the more
recent recommendation ꢀref =2.36 × 10−12 cm s−1 (ꢁ =298 K) for ꢄ-C H + OH is
3
4
10
used [24], the values from [14] and [16] decrease to almost identical values of
ꢀ1(ꢁ ∼ 300 K) ∼ 1.45 × 10−11 cm s which is in still better agreement with our
3
−1
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| J. Sommerer and M. Olzmann
Figure 6: Arrhenius plot of rate coefficients ꢂ1; experimental values from [16] (full circle), [14]
(empty circle), and [15] (dotted line), estimation from [12] (dash-dotted line) and calculated
values from [18] (dashed lines, upper branch: high-pressure limit, lower branch: ꢁ = 1 bar),
experimental result from this work, Eq. (3) (solid line).
result. We further note that in the calculations of [18] the energy of the transi-
tion state for non-terminal OH addition to C H was lowered by 4.2 kJ mol−1 to fit
4
2
the cited experimental data at room temperature. A slight increase of this energy
would also lead to smaller rate coefficients probably closer to our results. These
calculations also show that OH addition, mainly to a terminal C atom, is the dom-
inant reaction pathway below 1000 K.
4.2 The C H + OH reaction
4
4
To the best of our knowledge, no information about the rate coefficient of the
C H + OH reaction is available in the literature apart from the estimation by Miller
4
4
and Melius [4] on the hydrogen abstraction pathways, which are important only
at high temperatures probably above 1000 K.
In contrast to C H + OH, we observed in our experiments on C H + OH at
4
2
4
4
temperatures below 740 K a distinct, negative temperature dependence of the
rate coefficient, a behavior which is typical for olefin + OH addition reactions (see
e. g., [25]). Therefore, in Figure 7, we compare our results with rate coefficients of
OH + C olefin reactions. The similarities and differences are obvious.
4
Both the absolute values and the temperature dependence of ꢀ2 is very close
to the corresponding quantities of the OH + 1-butene reaction, which is a clear
indication that OH addition to the double bond is the dominating reaction step
for C H + OH. We also point to the factor-of-two difference between the data for
4
4
OH + 1-butene and OH + 1,3-butadiene, which is an obvious manifestation of a sta-
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Kinetics of the C H + OH and C H + OH reactions
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4
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Figure 7: Arrhenius plots of rate coefficients for reactions of OH with unsaturated hydrocarbons;
upper three lines: OH + 1,3-butadiene from [26] (dotted line), [27] (dashed line), and [28] (solid
line); lower three lines: OH + 1-butene from [29] (dashed line) and [12] (dotted line) as well as
OH + vinylacetylene from this work (solid line).
tistical factor. That is, if OH would add to both the double and the triple bond in
C H with similar rates, a larger rate coefficient close to those of the OH + diolefin
4
4
reactions would result. Accordingly, our experimental finding is also in line with
the observation that OH additions to terminal double bonds are faster than OH
additions to the analogous triple bonds. Factors of 4–10 at room temperature can
be inferred from literature data [25]. Further evidence for predominant addition
to the double bond can be obtained from the temperature dependence. The high-
pressure limiting rate coefficient of OH addition to acetylene (the most extensively
studied alkyne) exhibits a clearly positive temperature dependence [30]. This is in
contrast to what we observed for C H + OH. Studies on larger 1-alkynes to further
4
4
support this conclusion are scarce and uncertain; they indicate an at best weak
temperature dependence [25]. In summary, the reactivity of C H towards OH at
temperatures below 700 K seems to resemble the reactivity of a mono-olefin.
4
4
At the highest temperatures of our experiments, near 700 K, the values of ꢀ2
come closer to the values of ꢀ1 (cf. Figures 4 and 5), and addition to the triple
bond might come into play. On the other hand, there are indications for a turn
up in the temperature dependence of ꢀ2 in this range as can be realized from Fig-
ure 5, and hydrogen abstraction may also increasingly contribute. Unfortunately,
we were not able to extend our measurements to higher temperatures to unequiv-
ocally confirm this effect. Further studies are necessary to clarify this point and to
elucidate more details of the underlying reaction mechanism.
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| J. Sommerer and M. Olzmann
5 Summary and conclusions
The kinetics of the reactions of OH radicals with the highly unsaturated hydro-
carbons diacetylene and vinylacetylene has been experimentally studied with
laser photolysis/laser-induced fluorescence at temperatures between 290 and
740 K and pressures between 1.7 and 30.5 bar. In the case of C H + OH no
4
2
temperature dependence of the rate coefficient was observed, and we obtained
3
−1
ꢀ1(ꢁꢃ=(1.0 0.3) × 10−11 cm s . For this reaction our study was the first per-
formed at pressures above 1 bar. In the case of C H + OH a negative temper-
4
4
ature dependence was found, which can be expressed in the form ꢀ2(ꢁꢃ =
−12
3
−1
(6.4 1.9ꢃ×10 exp(486 K/ꢁꢃ cm s . Both rate coefficients exhibit no pressure
dependence under our experimental conditions. For C H + OH the kinetic data
4
2
obtained are in good agreement with results from earlier theoretical calculations
and in line with results of experimental studies at lower pressures. For C H + OH
4
4
no kinetic studies have been reported in the literature so far. From comparisons
of our results with kinetic data of similar compounds, we conclude that the dom-
inating steps under the conditions of our experiments for both reactions are OH
additions. In the case of C H + OH, addition to the double bond is likely to pre-
4
4
dominate over addition to the triple bond.
Acknowledgement: Financial support by the Deutsche Forschungsgemeinschaft
(SFB 606 “Non-stationary Combustion: Transport Phenomena, Chemical Reac-
tions, Technical Systems”) is gratefully acknowledged. We thank Isabelle Weber
for help with the experiments.
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