Kinetic and product study of the gas-phase reaction of sabinaketone with OH radical

Article abstract of DOI:10.1002/kin.20252

Sabinaketone is one major photooxidation product of sabinene, an important biogenie volatile organic compound. This article provides the first product study and the second rate constant determination of its reaction with OH radicals. Experiments were investigated under controlled conditions for pressure and temperature in the LISA indoor simulation chamber using FTIR spectrometry. Kinetic study was carried out at 295 ± 2 K and atmospheric pressure using the relative rate technique with isoprene as the reference compound. The rate constant was found to be k_{sabinaketone + OH} = (7.1 ± 1.0) × 10^-12 molecule^-1 cm³ s^-1. Acetone and formaldehyde were detected as products of the reaction with the respective yields of R_acetone= 0-9 ± 0.2 and R_HCHO = 1.2 ± 0.3.

Full text of DOI:10.1002/kin.20252

Kinetic and Product Study
of the Gas-Phase Reaction
of Sabinaketone with OH
Radical
1
2
2
NATHALIE CARRASCO, BENEDICTE PICQUET-VARRAULT, JEAN-FRAN C¸ OIS DOUSSIN
1
Laboratoire de Chimie Physique, CNRS UMR 8000, Universit e´ Paris-Sud, Orsay, F-91405, France
Laboratoire Interuniversitaire des Syst e` mes Atmosph e´ riques, Universit e´ Paris 12, 61 av. du Gal de Gaulle,
2
94010 Cr e´ teil Cedex, France
Received 24 May 2006; revised 26 October 2006, 21 December 2006; accepted 21 December 2006
DOI 10.1002/kin.20252
Published online in Wiley InterScience (www.interscience.wiley.com).
ABSTRACT: Sabinaketone is one major photooxidation product of sabinene, an important bio-
genic volatile organic compound. This article provides the first product study and the second
rate constant determination of its reaction with OH radicals. Experiments were investigated
under controlled conditions for pressure and temperature in the LISA indoor simulation cham-
ber using FTIR spectrometry. Kinetic study was carried out at 295 ± 2 K and atmospheric
pressure using the relative rate technique with isoprene as the reference compound. The rate
−
12
−1
3
−1
constant was found to be k
= (7.1 ± 1.0) × 10
molecule cm
s . Ace-
sabinaketone + OH
tone and formaldehyde were detected as products of the reaction with the respective yields of
Racetone= 0.9 ± 0.2 and RHCHO = 1.2 ± 0.3. ꢀC 2007 Wiley Periodicals, Inc. Int J Chem Kinet 39:
415–421, 2007
INTRODUCTION
and Tringali [3] pinpointed the importance of the re-
actions of terpenes with OH radical as a source of par-
ticles in the atmosphere. Among the large number of
monoterpenes observed as plant emissions, sabinene
has been reported to be abundantly emitted by sev-
eral common tree species [4–7]. Mechanistic studies
[8–11] identified sabinaketone as a major product from
the reaction of sabinene with both OH radicals and
ozone. The respective structures of sabinene and sabi-
naketone are given in Fig. 1. The only work previously
published about sabinaketone reactivity is a kinetic
study [12] concerning the reactions of sabinaketone
Large quantities of nonmethane biogenic volatile or-
ganic compounds (BVOCs) are emitted into the at-
mosphere from vegetation. Thus, the worldwide emis-
sion rate of nonmethane BVOCs is estimated to be
−
1
1
150 TgC year [1] and of the estimated 84 TgC
−1
year emitted in the United States, 20% are monoter-
pene compounds (C10H16) [2]. Moreover, Librando
Correspondence to: Fran c¸ ois Doussin; e-mail: doussin@lisa.
univ-paris12.fr.
Contract grant sponsor: INERIS (Institut National de
l’Environnement et des RISques).
with OH and with NO radicals. Our work provides
3
a second determination of the rate constant of the re-
action of sabinaketone with OH and the first product
study for this reaction.
Contract grant sponsor: PNCA.
ꢀ
c 2007 Wiley Periodicals, Inc.

4
16
CARRASCO, PICQUET-VARRAULT, AND DOUSSIN
O
radiation and were monitored by acquiring infrared
spectra about every 5 min (corresponding to 100 coad-
ded interferograms) with a resolution of 0.5 cm and
a path length of 156 m.
−1
Quantification of sabinaketone, isoprene, acetone,
and formaldehyde by FTIR spectroscopy was enabled
by previous calibrations of these species in the range
of a few hundred ppb to ppm. Infrared spectra of reac-
tants and products were calibrated by flushing known
amounts of the vapor of these compounds (determined
by measuring the pressure into a calibrated 0.55-L
Pyrex bulb) into the chamber. The integrated bands
intensities (IBI) of the main infrared absorptions are
given in Table II.
Figure 1 Structures of sabinene (left) and sabinaketone
right).
(
EXPERIMENTAL
Smog Chambers
The LISA chamber is a 977-L cylindrical Pyrex
evacuable reactor, equipped with a multiple-reflection
optical system coupled to a Bomem DA8-ME FTIR
spectrometer. This experimental device has been de-
scribed elsewhere [13], and only a brief overview will
be given there. The path length in the chamber was
adjusted to 156 m. Between each experiment, the sim-
ulation chamber was conditioned by lowering pressure
Relative Rate Technique
The relative rate technique [14] was used to determine
the rate constant of the OH-induced oxidation of sabi-
naketone. If the reaction with OH is only the fate of
the studied compound (X) and of the reference com-
pound (R) and if no secondary reaction occurs, it can
be shown that
−3
down to 10 mbar. The chamber was then filled with
synthetic air (80% N2, 20% O2) at atmospheric pres-
sure, and the temperature was kept at 295 ± 2 K during
all the experiments. The reactor is surrounded by 80
visible lamps: 40 lamps centered on 420 nm, Philips
TL03 40 W and 40 lamps centered on 360 nm, Philips
TL05 40 W.
[
X]0
kX [R]0
ln
ln
=
kR [R]t
[
X]t
where [X]0 and [R]0, and [X]t and [R]t are, respec-
tively, the concentrations of the selected compound
and the reference compound at times 0 and t. A
plot of ln([X]0,/[X]t ) versus ln([R]0,/[R]t ) yields a
straight line with a slope of kX/kR and an intercept of
zero.
Methodology
Once the chamber had been filled with synthetic air,
sabinaketone was introduced in the simulation cham-
ber. For the kinetic study, isoprene was additionally
introduced as reference compound. The rate coeffi-
cient of the reaction of sabinaketone with OH radicals
was determined using the relative rate method (see
later). Isoprene was chosen as the reference compound
in spite of a relative high-rate constant with OH radi-
cals because of its characteristic and unambiguous IR
Chemicals
Isoprene (Acros Organics, Halluin, France; purity
>99%) was used without further purification. HONO
was synthesized by slowly adding a diluted NaNO2
solution to diluted sulfuric acid [15].
−1
absorption band at 830–950 cm
.
Sabinaketone was previously synthesized by
ozonolysis in liquid phase [16]. Ozone was generated
by flowing high-purity oxygen through a silent dis-
charge ozonizer (Kaufmann Umwelttechnik, GmBH,
No significant wall or photolysis effect was ob-
served after 30 min of irradiation with the TL03 lamps.
HONO was added directly after its synthesis. The
hydroxyl radical reactions were initiated using the pho-
tolysis of HONO with the TL03 lamps.
The initial concentrations of all reactants (sabinake-
tone, isoprene, and HONO) were in the range of a few
hundred parts per billion (ppb) to parts per million
◦
Wehr, Germany). A cold (−78 C) and magnetically
stirred solution of sabinene (Interchim, Montlu c¸ on,
France; purity > 99%) (10 mL) in dichloromethane
(50 mL) was ozonolyzed (around 2 h) until a blue color
persisted [17]. The excess ozone was flushed from the
solution with nitrogen for 20 min. To reduce the previ-
ously formed ozonides into sabinaketone and formic
(ppm) (see Table I).
Chemical Analysis
◦
acid, water (5 mL) was carefully added at −78 C.
Chemical analysis was made by FTIR spectroscopy.
All experiments were conducted with continuous ir-
Then the solution was warmed up to room tempera-
ture and was stirred for three additional hours. The
International Journal of Chemical Kinetics DOI 10.1002/kin

KINETIC AND PRODUCT STUDY OF THE GAS-PHASE REACTION OF SABINAKETONE
417
Table I Experimental Conditions of the Kinetic and the Mechanistic Sabinaketone + OH Experiments
Initial Mixing Ratios (ppmv)
T (K)
P
Relative rate experiments
[Sabinaketone]0 = 0.3
295 ± 1
Atmospheric pressure
Atmospheric pressure
[
Isoprene]0 = 0.6
[
HONO]0 = 9.0
Sabinaketone]0 = 1.0
Isoprene]0 = 1.0
HONO]0 = 6.0
[Sabinaketone]0 = 0.3
HONO]0 = 3.4
Sabinaketone]0 = 0.2
HONO]0 = 6.8
[
294 ± 1
[
[
Mechanistic experiments
295 ± 2
295 ± 2
[
[
[
organic phase was treated by a diluted soda solution
until pH neutral. Then solvent was removed by reduced
pressure. The remaining liquid phase was analyzed by
GC-MS. Its composition included more than 95% of
sabinaketone.
sink for sabinaketone and isoprene was their reaction
with OH radicals.
Sabinaketone + OH → products k1
Isoprene + OH → products k2
[
Sabinaketone]
k1
[Isoprene]0
[Isoprene]t
0
Uncertainties
Ln
=
Sabinaketone]t
× Ln
(1)
[
k2
All the linear regression described in this article (in-
cluding FTIR calibrations) were made by taking in
account uncertainties on both the coordinates, x and y,
for each measurement. This method avoids systematic
bias on the slope of the plot [18]. Errors correspond to
twice the standard deviations.
According to Eq. (1), ratio k1/k2 is given by the slope
of the plot Ln([sabinaketone]o/[sabinaketone]t ) ver-
sus Ln([isoprene]o/[isoprene]t ), where [sabinaketone]o
and [isoprene]o are the initial concentrations and
[sabinaketone]t and [isoprene]t are varying concen-
trations during the reaction (see Fig. 2). Knowing k2 =
−
10
3
−1 −1
s (most recent
(
1.01 ± 0.10) ×10 cm molecule
RESULTS AND DISCUSSION
Kinetics
determination, [18]) and the ratio k1/k2, k1 value was
deduced. Relative error on k1 was obtained by adding
relative errors on k2 and on ratio k1/k2. The ratio k1/k2
−2
Relative rate experiments were performed using iso-
prene as the reference compound. Experimental con-
ditions are reported in Table I. Temperature and pres-
sure were adjusted to 295 ± 2 K and atmospheric
pressure.
It was checked that both sabinaketone and isoprene
were stable in the chamber over the timescale of a
typical experiment in different conditions. The only
was found equal to (7.02 ± 0.28) × 10 , giving a
−12 3
rate constant equal to k1 = (7.1 ± 1.0) × 10
cm
−1
−1
s .
molecule
Considering the error bars on the values, our de-
termination is in agreement with the publication of
Alvarado et al. [12], who carried out a relative rate
determination with cyclohexane as the reference com-
pound. In their study, sabinaketone was generated
Table II Integrated Band Intensities (IBI) of the Main IR Absorption Bands of Sabinaketone, Isoprene, Acetone, and
Formaldehyde
Main Absorption Band (cm 1)
−
IBI (cm molecule
−1
)
Reference
Compound
−
−
−
17
17
17
17
Sabinaketone
Isoprene
Acetone
1700–1800
830–950
1260–1150
3000–2630
(3.71 ± 0.39) × 10
(1.03 ± 0.02) × 10
(1.02 ± 0.02) × 10
This work
This work
[29]
−
Formaldehyde
(1.33 ± 0.06) ×10
[29]
e
All values are given in log .
International Journal of Chemical Kinetics DOI 10.1002/kin

4
18
CARRASCO, PICQUET-VARRAULT, AND DOUSSIN
constants have to be considered (on carbons C2, C3,
C5, C6, C7, C8, and C9 in Fig. 5, i.e., all carbon sites
except the carbonyl group and the quaternary carbon
holding the tertio-butyl group).
In the SAR model of Neeb, one obtains
kNeeb = kR-CH -C(O) + kR2-CH-C(O) + 2kR2-CH
2
2
+
kR3-CH + 2kR-CH3
kNeeb = (4.08 + 11.9 + 2 × 1.42 + 1.81 + 2 × 0.21)
−
12
3
−1 −1
×
10
cm molecule
s
−
12
3
−1 −1
kNeeb = 21.0 × 10
cm molecule
s
Figure 2 Kinetic study of the sabinaketone + OH reaction
by relative rate technique using isoprene as the reference
compound (result from both kinetic experiments detailed in
Table I).
whereas in the model of Kwok and Atkinson, one ob-
tains
kKwok = kR-CH -C(O) + kR2-CH-C(O) × F3 + kR2-CH2
2
in situ from the gas-phase reaction of ozone with
sabinene and the rate constant for OH + sabinaketone
was determined relative to that for OH + cyclohex-
+
kR2-CH × F3 + kR3-CH + 2kR-CH
2
3
with F3 the attenuation factor for a three-member ring,
−12
ane. They found the value k1 = (5.1 ± 1.4) × 10
3
−1 −1
cm molecule
s . Such an order of magnitude for
kKwok = (0.86 + 2.20 × 0.020 + 1.41 + 1.41 × 0.020
the rate constant of the reaction sabinaketone + OH is
consistent with the well-studied reaction of the sim-
ilar compound cyclohexanone with OH radicals (k
−12
3
−1 −1
+
3.61 + 2 × 0.17) × 10
cm molecule
s
−12
3
−1 −1
−12
3
−1 −1
[19]). The
kKwok = 6.3 × 10
cm molecule s
=
(6.4 ± 0.5) × 10
cm molecule
s
slight difference between both experimental studies is
not easy to explain. However, in the study of Alvarado
et al., sabinaketone was generated in situ from the gas-
phase reaction of sabinene with ozone. This method
is not without possible artifacts coming from the pres-
ence of a number of coproducts during the reaction
with OH radicals. In particular, it has been shown that
ozonolysis of sabinene produces considerable amount
of particles containing sabinaketone [20]. In the case
of Alvarado et al., the equilibrium of sabinaketone in
both gaseous and particulate phases during the rela-
tive rate study could possibly explain the slight dif-
ference observed with our study, these artifacts being
avoided in our case because of the previous synthesis of
sabinaketone.
The major differences between the SAR
parametrization of Neeb and the parametrization of
Kwok and Atkinson are, on the one hand, the specific
treatment of the H abstraction on a C-atoms adjacent
to a carbonyl group in the work of Neeb, and on the
other hand the treatment of the ring strains in the work
of Kwok and Atkinson.
Despite this refinement in the SAR parametrization
for H abstraction on a C-atom adjacent to a carbonyl
−
12
group, the model of Neeb gives a value of 21.0 × 10
3
−1 −1
cm molecule
s for the rate constant of the reac-
tion sabinaketone with OH which overestimates by a
factor of 2–3 the experimental determinations. Neeb
suggests that the tertiary hydrogen adjacent to the car-
bonyl group could be deactivated by the three-member
ring. And thus, if one considers his contributions of
each structural group and additionally the deactivat-
ing factor calculated by Kwok and Atkinson for three-
These two experimental determinations are also to
be compared with the structure–activity relationship
(SAR) models developed by Neeb [22] and Kwok
and Atkinson [23] for the reactions of volatile organic
compounds with OH radicals. The same empirical ap-
proach was used in both SAR models, giving rise to a
parametrization of the molecular structure of the main
classes of chemical compounds. The total reactivity of
a molecule is calculated by addition of the different
contributions of each structural group in the molecule.
In the case of sabinaketone, seven H-abstraction rate
ꢁ
−12
member ring strains, a value of k
cm molecule
= 8.0 × 10
Neeb
3
−1 −1
s is found, which is, such as the
SAR of Kwok and Atkinson, in agreement with our
experimental determination. This seems to confirm
the refinement in the SAR description performed by
Neeb, but also the importance of the three-member ring
deactivation.
International Journal of Chemical Kinetics DOI 10.1002/kin

KINETIC AND PRODUCT STUDY OF THE GAS-PHASE REACTION OF SABINAKETONE
419
Figure 3 Concentration versus time plot of an experiment between sabinaketone and OH radicals in the presence of NOx
second mechanistic experiment in Table I).
(
Product Study
Experiments were performed to study the mechanism
of the reaction between sabinaketone and OH radi-
cals in the presence of NOx (for more details see
Table I). The only source of NO in the LISA chamber
is from the photolysis of HONO. The complexity of
the spectra, due to the presence of water (cointroduced
with HONO) and a number of unidentified products,
allowed us to identify only two major sabinaketone
oxidation products: acetone and formaldehyde. A con-
centration versus time plot of a typical experiment is
given in Fig. 3. In this figure, acetone shows only a
primary production, whereas formaldehyde presents
first a primary production, followed by an additional
secondary production. Thus, one (at least) unidentified
product of the reaction between sabinaketone and OH
is also sensitive to OH radicals and leads to an addi-
tional secondary production of formaldehyde. Forma-
tion yields were determined by calculating the initial
slopes of the plots [product] versus –ꢀ[sabinaketone]
Figure 4 Production of acetone and formaldehyde during a
reaction between OH and sabinaketone (second mechanistic
experiment in Table I). Lines correspond to linear regres-
sions for acetone and formaldehyde productions. [Color fig-
ure can be viewed in the online issue, which is available at
www.interscience.wiley.com.]
(see Fig. 4). The results are reported in Table III and
show a large uncertainty on the production yields, in
particular on the production yield of acetone. This un-
certainty is probably the result of several parameters,
such as the weak IR absorption bands of acetone and
sabinaketone.
acetone and formaldehyde measured in this study do
not allow the branching ratio assignment among ev-
ery possible alkoxy radical pathways. However, as de-
scribed in the kinetic part, the OH radical can abstract
seven different hydrogens on the sabinaketone, lead-
We calculated average yields for both products of
Racetone = 0.95 ± 0.24 and Rformaldehyde = 1.19 ± 0.26.
These results imply that sabinaketone is massively con-
verted into formaldehyde and acetone through its reac-
tion with OH radicals.
ing, after reaction with O and NO, to seven different
alkoxy radicals. In order to illustrate the numerous pos-
2
sible pathways leading to acetone and formaldehyde,
we have then shown in Fig. 6 the evolution scheme
of one probably favored alkoxy radical, AR1: the one
coming from the H-abstraction in the carbon C6, adja-
cent to a carbonyl group [21], and not deactivated by
Numerous pathways can possibly lead to acetone
and formaldehyde, and the total production yields of
International Journal of Chemical Kinetics DOI 10.1002/kin

4
20
CARRASCO, PICQUET-VARRAULT, AND DOUSSIN
Table III Production Yields of Acetone and Formaldehyde Produced by the Reaction of Sabinaketone with OH
Radicals
Experiment
Acetone
Formaldehyde
Carbon Balance
Experiment 1
Experiment 2
Average
1.04 ± 0.24
0.79 ± 0.20
0.95 ± 0.22
1.17 ± 0.24
1.22 ± 0.28
1.19 ± 0.26
0.48 ± 0.11
0.40 ± 0.10
0.45 ± 0.10
the three-member ring [22] (see Fig. 5). It has been
shown that hindered compounds could undergo rapid
decompositions, and that competition with the reaction
with oxygen was almost negligible [24]. Decomposi-
tion pathways of AR1 are then more probable than H-
abstraction in the presence of O2 because sabinaketone
is sterically ramified. This scheme also shows that nu-
merous coproducts of acetone and formaldehyde could
be considered, which could help to explain the incom-
plete carbon balance of 0.45 ± 0.10 (see Table III).
However, in this work, the complexity of the resid-
ual infrared spectra did not allow us to identify other
specific compounds. Further complementary analysis
would then be useful to understand more completely
the decomposition scheme of sabinaketone with OH
radicals.
CONCLUSION AND ATMOSPHERIC
IMPLICATIONS
O
In conclusion, a kinetic and product study of sabi-
naketone diurnal reactivity was presented in this paper.
C1
C6
C5
C2
C3
−12
3
A value of kOH + sabinaketone = (7.1 ± 1.0) × 10
cm
−1
s was determined, corresponding to a
−1
C4
C7
molecule
6
lifetime of τOH = 20 h at OH concentration of 2 × 10
C8
C9
−3
molecule cm [25]. Sabinaketone has then a lifetime
Figure 5 Index of the different carbons of the sabinaketone.
long enough to be transported into the air masses at
Figure 6 Evolution of alkoxy radical 1 (AR1), produced by the reaction between sabinaketone and OH radicals.
International Journal of Chemical Kinetics DOI 10.1002/kin

KINETIC AND PRODUCT STUDY OF THE GAS-PHASE REACTION OF SABINAKETONE
421
regional scale during daytime. Moreover, the reaction
of sabinaketone with OH radical leads to considerable
production of formaldehyde and acetone, which have
strong atmospheric impact [26]. Thus it has been shown
that the photolysis of acetone in the upper troposphere
is the dominant source of HOx radicals (OH + HO2
radicals) when [H2O] < 100 ppmv [27]. Sabinake-
tone is one major photooxidation product of sabinene.
Reissel et al. [28] and Carrasco et al. [11] have shown
that acetone was also produced by the decomposition
of sabinene. A considerable quantity of acetone may
also be produced in the regions with abundant sabinene
emissions through additional primary and secondary
chemistry of this biogenic volatile organic compound.
In spite of the quantification of the two major prod-
ucts acetone and formaldehyde, the carbon balance
for the reaction of sabinaketone with OH radicals is
still incomplete (carbon balance = 0.45 ± 0.10). Fur-
ther complementary analysis would be useful to under-
stand more completely the decomposition scheme of
sabinaketone with OH radicals.
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International Journal of Chemical Kinetics DOI 10.1002/kin