Kinetic and mechanistic study of the atmospheric oxidation by OH radicals of allyl acetate

Article abstract of DOI:10.1021/es0200138

A potential source of acetates, including allyl acetate, is combustion of esterified rape oil used as substitution fuel. This new formulation of diesel fuel significantly reduces the emission of particulate matter. To better evaluate the environmental impact of acetates, OH-induced oxidation kinetic and mechanism of allyl acetate were studied at room temperature and 1 atm using three environmental chambers (an indoor Teflon-film bag, an indoor Pyrex photoreactor, and the outdoor smog chamber EUPHORE. The main oxidation products were acetoxyacetaldehyde and formaldehyde. A mechanism was developed to describe the OH-induced oxidation of the acetate in the presence of NO_x. Reaction with OH radicals was the main tropospheric fate of allyl acetate. When it reacted with OH radicals, it could contribute to the formation of photooxidants close to the emission sources. Acetoxyacetaldehyde yield was slightly smaller in the experiment at low NO_x since some peroxides could be produced from peroxy radical + HO₂ reaction and compete with the acetoxyacetaldehyde production.

Full text of DOI:10.1021/es0200138

Environ. Sci. Technol. 2002, 36, 4081-4086
allyl acetate (4-6), but no mechanistic data have been
published yet. The present study is focused on the oxidation
of allyl acetate.
Kinetic and Mechanistic Study of
the Atmospheric Oxidation by OH
Radicals of Allyl Acetate
2. Experimental Section
Experiments were performed using three environmental
chambers: an indoor Teflon-film bag (LISA, Cre´teil), an
indoor Pyrex photoreactor (LISA, Cre´teil), and the outdoor
Smog chamber EUPHORE (Valencia). These three photo-
reactors are briefly presented here.
B . P I C Q U E T - V A R R A U L T , * J . - F . D O U S S I N ,
R . D U R A N D - J O L I B O I S , O . P I R A L I , A N D
P . C A R L I E R
Laboratoire Interuniversitaire des Syste`mes Atmosphe´riques,
UMR-CNRS 7583, Universite´s de Paris 7 et Paris 12,
61 Avenue du Ge´ne´ral de Gaulle, 94010 Cre´teil Cedex, France
2.1. Indoor Teflon-Film Bag. All kinetic experiments were
performed using a Teflon-film bag of approximately 250 L
surrounded by three sets of fluorescent tubes (10 tubes Philips
TUV15, 18 Philips TL05, and 18 Philips TL03). The emissions
of these “black lamps” are respectively centered on 254, 360,
and 420 nm. Hydroxyl radicals were generated by photolyzing
hydrogen peroxide. Concentrations of selected reactants were
in the ppm range in purified air (Section Chemicals and gases)
and were recorded by gas chromatography using a Carlo
Erba gas chromatograph GC 6000 Vega Series 2 equipped
with a Megabore DB 225 column (30 m × 0.53 mm, film
thickness: 1 µm) and a flame ionization detector.
2.2. Indoor Evacuable Photoreactor. Mechanistic study
was mainly carried out in an evacuable environmental
chamber comprising a Pyrex reactor of 977 L surrounded by
two sets of 40 fluorescent tubes (Philips TL05 and TL03). The
emissions of these black lamps are respectively centered on
360 and 420 nm. Moreover,16 arc lamps (Osram, 400 W)
provide an irradiation with a broad spectral range from 360
to 600 nm. The reactor contains a multiple reflection optical
system interfaced to a FTIR spectrometer (BOMEM DA8-
ME). Details of this environmental chamber are given by
Doussin et al. (7). Hydroxyl radicals were generated by
photolyzing methyl nitrite or nitrous acid. The initial
concentrations of the reactants (acetate, methyl nitrite, and
NO) were in the ppm range in a synthetic mixture of 80% N2
and 20% O2 (NO was added to limit formation of nitrate
radicals and ozone). All experiments were conducted at 298
(5 K with continuous irradiation during 1 or 2 h. Compounds
were monitored by acquiring infrared spectra every 4 min
(corresponding to 100 co-added interferograms) with a
resolution of 0.7 cm-1 and a path length of 96 or 186 m.
C . F I T T S C H E N
Laboratoire de Cine´tique et Chimie de la Combustion,
UMR-CNRS 8522, Universite´ des Sciences et Technologies de
Lille, Bat. C11, 59655 Villeneuve d’Ascq Cedex, France
Acetates are emitted into the atmosphere by several
anthropic and natural sources. To better evaluate the
environmental impact of these compounds, OH-induced
oxidation kinetic and mechanism of allyl acetate (CH C(O)OCH -
3
2
CHdCH ) have been investigated at room temperature
2
and atmospheric pressure using three environmental
chambers: an indoor Teflon-film bag (LISA, Cre´teil), an
indoor Pyrex photoreactor (LISA, Cre´teil), and the outdoor
Smog chamber EUPHORE (Valencia). Rate constant of
the reaction of allyl acetate with OH radicals was determined
by relative rate technique in the indoor Teflon-film bag.
It is (30.6 ( 3.1) × 10-12 cm3 molecule-1 s-1. Mechanistic
experiments were performed in the indoor photoreactor
and in the outdoor Smog chamber EUPHORE. The main
oxidation products observed by FTIR in both chambers were
acetoxyacetaldehyde and formaldehyde. From these
data, a mechanism was developed to describe the OH-
induced oxidation of this acetate in the presence of NOx.
Finally, atmospheric impact of allyl acetate emissions
was evaluated using kinetic and mechanistic results.
2.3. Outdoor Sm og Cham ber EUPHORE. Additional
mechanistic experiments were carried out in the outdoor
simulation chamber EUPHORE in Valencia (Spain). The
chamber is made of a half-spherical 204 m3 Teflon-film bag
submitted to sunlight irradiation. The reactor contains a
multiple reflection optical system interfaced to a FTIR
spectrometer (Nicolet Magna 550). Details of this chamber
are given by Becker et al. (8). Hydroxyl radicals were generated
by photolyzing nitrous acid which was formed in the chamber
by reaction of NOx with water adsorbed on the walls of the
reactor. Typical initial concentrations were 1 ppm acetate
and ∼100 ppb NO in purified air. All experiments were
conducted at 303 ( 3 K with continuous solar irradiation
during approximately 3 h. Compounds were monitored by
acquiring infrared spectra every 5 min (corresponding to
250 co-added interferograms) with a resolution of 1 cm-1
and a path length of 553.5 m.
1. Introduction
Acetates have been widely released for decades into the
atmosphere during their use in industrial activities. Moreover,
they are also emitted from natural sources (vegetation and
biomass combustion) (1). An additional potential source of
these compounds, including allyl acetate (CH3C(O)OCH2-
CHdCH2), is combustion of esterified rape oil used as
substitution fuel (2). This new formulation of diesel fuel
significantly reduces the emission of particulate matter (2,
3), but aldehydes and esters emissions are increased (2). When
released into the atmosphere, these oxygenated compounds
can undergo photochemical transformations which can lead
to the production of ozone and other photooxidants. To
evaluate the potential impact on health and environment of
a massive use of this substitution fuel, a precise knowledge
of the atmospheric oxidation of acetates by OH radicals is
needed as this process is their main daytime fate. Few
previous kinetic studies have already been carried out for
A slight excess of pressure in the chamber is necessary to
stabilize the Teflon bag against the wind. Therefore, to
counteract the loss due to slight leaks, small amounts of
dried air are periodically introduced in the chamber and
cause small dilution of the mixtures. The dilution rate τ was
determined by introducing an inert dilution tracer (SF6) and
* Corresponding author phone: (33) 1 45 17 15 90; fax: (33) 1 45
17 15 64; e-mail: picquet@lisa.univ-paris12.fr.
9
10.1021/es0200138 CCC: $22.00
Published on Web 09/04/2002
2002 Am erican Chem ical Society
VOL. 36, NO. 19, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 4 0 8 1

by following its concentration during the experiments by
FTIR.
TABLE 1. Integrated Band Intensities of the Main Infrared
Absorption Bands of Allyl Acetate and Its Oxidation Products
2.4. Relative Rate Technique. Relative rate technique was
used to determine the rate constant of the OH-induced
oxidation of allyl acetate. Since this method has already been
described numerous times (9), we only present briefly its
principle here. If the reaction with OH is the only fate of the
studied compound (X) and of the reference compound (R)
and if no secondary reaction occurs
main
absorption
compound
allyl acetate
band/cm-1
IBI/cm molecule-1
ref
1325-1155 (5.64 ( 0.18) × 10-17 this work
acetoxyacetaldehyde 1300-1170 (3.2 ( 0.6) × 10-17
this work
form aldehyde
form ic acetic
anhydride
3000-2630 (3.03 ( 0.13) × 10-17 this work
1095-1005 (5.99 ( 0.13) × 10-17 this work
X + OH f products kX
R + OH f products kR
acetic acid
1840-1712 (4.36 ( 0.24) × 10-17 this work
it can be shown that
[X]0
[X]t
k
[R]0
[R]t
ln
)
X ln
kR
where [X]0 and [R]0 and [X]t and [R]t are, respectively, the
concentrations of the selected compound and the reference
compound at times 0 and t. A plot of ln([X]0/ [X]t) vs ln([R]0/
[R]t) yields a straight line with a slope ofkX/ kR and an intercept
of zero. The uncertainty on this value was determined using
the software developed by Brauers and Finlayson-Pitts (10).
This method performs linear regressions of the plots of ln-
([X]0/ [X]t) vs ln([R]0/ [R]t) by taking into account errors in both
[R] and [X].
The kinetic experiments were performed at 298 ( 4 K and
at atmospheric pressure using H2O2 as OH precursor and
n-octane as reference compound (kn-octane + OH ) 8.71 × 10-12
cm3 molecule-1 s-1 (11)). To verify that none of the reference
nor the studied compounds were photolyzed at our experi-
mental conditions, these compounds were irradiated ap-
proximately 2 h (twice the duration of a kinetic experiment).
No significant loss was observed.
2.5. Determ ination of the Form ation Yields of Oxidation
Products. For experiments carried out in the indoor pho-
toreactor at LISA, formation yields of oxidation products were
determined by calculating the initial slopes of the curves
[products] vs -∆[allyl acetate]. In EUPHORE, since the
mixtures are subject to dilution during the experiments,
formation yields were calculated as follows: assuming the
reaction
FIGURE 1. Plot of the kinetic data for the reaction of OH radicals
with allyl acetate vs n-octane.
TABLE 2. OH Reaction Rate Constant of Allyl
AcetatesComparison with Previous Data
k × 1012 cm3
reactant
molecule-1 s-1
technique
ref
allyl acetate 30.6 ( 3.1
RR (n-octane) this work
24.57 ( 0.24 RR (n-octane) Ferrari et al. (4)
A + OH f B Rk
27.1 ( 3.0
28.9 ( 4.5
LP-LIF
Le Calve´ et al. (6)
RR (propene) Le Calve´ (5)
where R is the formation yield of B and k is the global rate
constant of the oxidation of A by OH.
For both sets of experiments, indicated errors of yields
take into account the estimated uncertainties in reactant
and products IR absorption bands calibrations (see Table 1)
and the uncertainties in the calculation of yields. Errors due
to the calculation of yields are two standard deviations on
the calculation of Rat EUPHORE and two standard deviations
of the initial slope of the curve [product] vs -∆[acetate] in
the indoor photoreactor. Errors due to the quantification of
compounds in infrared spectra have been disregarded
because they are not significant compared to the previous
ones.
d[A]
) -τ[A] - k[A][OH] w
dt
d[A]
dt
R
) -Rτ[A] - Rk[A][OH]
and
d[B]
dt
) -τ[B] + Rk[A][OH]
2.6. Chem icals and Gases. Methyl nitrite used as OH
precursor was prepared by slowly adding a dilute solution
of H2SO4 to a mixture of NaNO2 and methanol (12). Nitrous
acid was synthesized by slowly adding a dilute solution of
NaNO2 to diluted H2SO4 (13). Methyl nitrate, formic acetic
anhydride, and acetoxyacetaldehyde which were supposed
to be oxidation products of allyl acetate were also synthesized
(14). Other organic reagents were obtained from commercial
sources: allyl acetate was from Aldrich (99%) and acetic acid
was from Prolabo (g 99%). Synthetic air used to fill the indoor
From these equations, we can deduce that
d[B]
+ τ[B]
dt
R ) -
d[A]
+ τ[A]
dt
τ is calculated for each experiment using the dilution tracer.
It is commonly between 5 × 10-6 and 7 × 10-6 s-1
.
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FIGURE 2. Residual infrared spectrum obtained after the photolysis of HONO/allyl acetate mixture: (a) residual spectrum obtained by
subtraction of remaining reactants, compared with reference spectra of acetoxyacetaldehyde (b), formic acetic anhydride (c), and formaldehyde
(d).
FIGURE 4. Experimental plots of the formation of oxidation products
FIGURE 3. Experimental plots of the formation of oxidation products
vs loss of allyl acetate, obtained at EUPHORE.
vs loss of allyl acetate, obtained at LISA.
(∼5 min). From the amounts of allyl acetate and n-octane
evacuable photoreactor (LISA) was generated using O2
measured during the experiments, ln([allyl acetate]0/ [allyl
(quality N45, g 99.99%, Air Liquide) and N2 (from liquid
acetate]t) vs ln([n-octane]0/ [n-octane]t) was plotted (see
nitrogen evaporation, g 99.995%, Linde). The air used in the
Figure 1).
Teflon-film bag was purified through cartridges filled with
The rate constant was found equal to (30.6 ( 3.1) × 10-12
silicagel, soda lime, vegetal charcoal and molecular sieve.
cm3 molecule-1 s-1 and was compared to previous data in
The experiments in EUPHORE reactor were also performed
Table 2. From these data, we can see that the value of the
in dried and purified air (8).
rate constant obtained in this study is in good agreement
with those of Le Calve´ et al. (5, 6) obtained by absolute and
relative rate determinations and that the value of Ferrari et
Results and Discussion
3.1. Relative Rate Study. To determine the rate constant of
the reaction of allyl acetate with OH radicals, n-octane, allyl
acetate, and H2O2 were introduced into the dark chamber.
Organic reactants concentrations were between 1 and 2 ppm.
Several samples of gases were taken to accurately determine
the initial amount of each organic reactant. Then the bag
was irradiated continuously for approximately 1 h and
samplings were performed at short and steady time intervals
al. (4) is slightly lower than ours. Ferrari et al. used a rate
constant for the reaction of OH radicals with n-octane (their
reference compound) equal to 8.42 × 10-12 cm3 molecule-1
s-1 whereas this study used 8.71 × 10-12 cm3 molecule-1 s-1
(11) for the same reference compound. By using this last
value for the determination of Ferrari et al., kallyl acetate + OH
was found equal to 25.4 × 10-12 cm3 molecule-1 s-1 and still
be slightly different from ours. However, it can be seen that
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VOL. 36, NO. 19, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 4 0 8 3

SCHEME 1. Oxidation Scheme of Allyl Acetate Obtained from the Generally Accepted Process of VOC Oxidation and from
Formation Yields of the Detected Products (Framed)
the uncertainties range given by these authors is very small
(∼1%) and may not take into account the errors in both [R]
and [X]. Therefore, they may be underestimated. and we
cannot really state that the difference between these values
is significant.
3.2. Mechanistic Study. The mechanism of OH-induced
oxidation of allyl acetate was investigated in the indoor
environmental chamber by photolyzing CH3ONO/ allyl ac-
etate/ NOx and HONO/ allyl acetate/ NOx mixtures in the
evacuable photoreactor. Acetate and NOx concentrations
were close to 1 ppm. An additional experiment was carried
out in the photoreactor EUPHORE by photolyzing allyl
acetate/ NOx mixture (1.2 ppm/ 100 ppb) in order to compare
the results obtained under different experimental conditions
(irradiation, NOx level, surface/ volume ratio, ...). In both kinds
of experiments, reactants and products were analyzed by
FTIR spectrometry. Figure 2 shows an example of a residual
spectrum acquired after ∼5000 s of irradiation, obtained by
subtraction of remaining reactants (allyl acetate, HONO, NO)
and inorganic compounds. Remaining products which are
attributed to oxidation of allyl acetate are acetoxyacetalde-
hyde, formic acetic anhydride, and formaldehyde. Small
amounts of acetic acid have also been detected but its
absorption bands are not visible on the scale of the figure.
Examples of the plots [products] vs -∆[allyl acetate] for
an experiment carried out in the indoor reactor using HONO
as OH source and for the experiment performed at EUPHORE
are respectively shown in Figures 3 and 4. On these figures,
it can be seen that acetoxyacetaldehyde and formaldehyde
whose plots have initial slope different from zero are primary
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SCHEME 2
products whereas acetic acid and formic acetic anhydride
are secondary products. Acetoxyacetaldehyde and formal-
dehyde which are the main oxidation products, can be formed
by an addition of OH radicals on the double bond followed
by a decomposition of the two alkoxy radicals formed:
CH3C(O)OCH2CH(OH)CH2O• and/ or CH3C(O)OCH2CH(O•)-
CH2OH (see Scheme 1A, channels 2 and 3).
For the experiment performed at LISA, the decrease of
the slopes indicates that formaldehyde and to a lesser extent,
acetoxyacetaldehyde are subject to secondary loss pro-
cesses: formaldehyde can react with OH and HO2 radicals
and can be photolyzed. Here, this last process is of minor
importance since its photolysis constant in the indoor reactor
was measured to be ∼2.5 × 10-5 s-1 leading to a photolysis
lifetime of formaldehyde of about 11 h. Acetoxyacetaldehyde
may be photolyzed and may react with OH radicals (see
Scheme 2). These two processes can lead to the formation
of the CH3C(O)OCH2O• radical which reacts with O2 to form
formic acetic anhydride or undergoes an R-ester rearrange-
ment to form acetic acid (15).
TABLE 3. Oxidation Products of Allyl Acetate and Their
Formation Yields
indoor photoreactor
acetate/
3
acetate/
HONO/NOx
EUPHORE
acetate/NOx
product
CH ONO/NOx
acetoxyacetaldehyde
form aldehyde
form ic acetic
anhydride
0.97 ( 0.25
0.90 ( 0.15
<0.02
1.00 ( 0.25
0.97 ( 0.15
<0.02
0.90 ( 0.24
0.37 ( 0.08
<0.02
acetic acid
<0.02
<0.02
<0.02
aldehyde obtained in the three experiments are in good
agreement within the experimental uncertainties whereas
those of formaldehyde are significantly different: the form-
aldehyde yield obtained in EUPHORE is much lower than
those obtained in the indoor photoreactor. This experimental
result may be related with the NOx level which was much
lower in the EUPHORE chamber than in the indoor pho-
toreactor (100 ppb and 1 ppm). Under high NO condition,
•
At EUPHORE, no significant loss of acetoxyacetaldehyde
and formaldehyde was observed but the plots are not very
precise because of the dilution process in the chamber.
Moreover, OH and HO2 concentrations are smaller in the
outdoor reactor than at LISA ([OH] ∼ 107 molecule/ cm3 at
LISA and [OH] ∼ 106 molecule/ cm3 at EUPHORE) leading to
a slighter secondary chemistry.
the exothermic reactions of CH3C(O)OCH2CH(OH)CH2O2
•
and CH3C(O)OCH2CH(O2 )CH2OH radicals with NO may lead
to excited alkoxy radicals: CH3C(O)OCH2CH(OH)CH2O•* and
CH3C(O)OCH2CH(O•*)CH2OH. The fraction of excited alkoxy
radicals would then be larger in the indoor photoreactor (at
, high NOx .) than at EUPHORE (at , low NOx .), and
these radicals would be more prone to decompose than those
produced at lower NO level, in the less exothermic peroxy
self-reaction. Therefore, a possible explanation of this
observation is that excited CH3C(O)OCH2CH(OH)CH2O•*
radicals would mainly decompose to form acetoxyacetal-
dehyde and formaldehyde, whereas nonexcited radicals
would preferably react with O2. The reaction with O2 leads
to the formation of CH3C(O)OCH2CH(OH)CHO which might
rapidly form acetoxyacetaldehyde and HC•O (by decomposi-
tion, reaction with OH or photolysis ?). In conclusion, the
decomposition of CH3C(O)OCH2CH(OH)CH2O• radicals would
lead to acetoxyacetaldehyde + HCHO, whereas its reaction
with O2 would lead to acetoxyacetaldehyde only (see Scheme
1). This reaction scheme offers an explanation why the
formaldehyde yield was lower in EUPHORE. It also explains
that acetoxyacetaldehyde yield is slightly smaller in the
experiment at , low NOx . since some peroxides may be
produced from peroxy radical + HO2 reaction and compete
with the acetoxyacetaldehyde production. Similar chemical
activation effects have already been reported in the literature
for other alkoxy radicals when experiments were performed
with and without NOx (15, 19, 20). Christensen et al. (15)
who have studied the atmospheric oxidation of methyl acetate
have shown that the decomposition branching ratio of CH3C-
(O)OCH2O• radicals was higher in the presence of NOx than
in absence of NOx.
Since photolysis and OH-induced oxidation of acetoxy-
acetaldehyde have not been studied and since HO2 con-
centrations cannot be precisely determined, the quantifi-
cation of secondary processes involving acetoxyacetalde-
hyde and HCHO was not possible. Hence the curves
[products] vs -∆[allyl acetate] were not corrected for
secondary reactions. As a result, formation yields were
determined using only the initial slopes of the curves. This
method allows also for disregarding the reactions of allyl
acetate with NO3 and O3 which have been found negligible
during the first half-hour of the experiments. Hence, by
comparing k(allyl acetate + OH) × [OH], k(allyl acetate + NO3) × [NO3],
and k(allyl acetate + O3) × [O3], it was shown that during the first
half-hour of the experiment, the chemistry induced by O3
and the chemistry induced by NO3 count for less than 5%
compared to the reaction with OH. The rate constants used
were k(allyl acetate + O3) ) 2.4 × 10-18 cm3 molecule-1 s-1 (6) and
5 × 10-14 cm3 molecule-1 s-1 (estimation by Wayne et al. (16)
and Sabljic et al. (17)). Since N2O5 was not detected during
the experiments, the upper limit of NO3 concentration was
determined using the infrared detection limit of N2O5 and
the equilibrium constant of the reaction NO2 + NO3 S N2O5,
2.89 × 10-11 cm3 molecule-1 s-1 (18).
Final products yields are shown in Table 3. From these
results, we observe that formation yields of acetoxyacet-
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VOL. 36, NO. 19, 2002 / ENVIRONMENTAL SCIENCE & TECHNOLOGY 4 0 8 5

Finally, according to FTIR detection limit of acetic acid
and formic acetic anhydride, we can deduce that any primary
formation of these two products would have a molar yield
< 0.02. This observation confirms that OH radicals add to
the double bond rather than abstracting a hydrogen atom.
Unfortunately, since the addition on both carbons of the
double bond leads to the same products, we cannot
distinguish these two pathways.
mans and her collaborators for their help in the synthesis of
acetoxyacetaldehyde.
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Acknowledgments
We thank the French ministry of environment for supporting
this research as part of PRIMEQUAL and PNCA programs.
We acknowledge Klaus Wirtz and EUPHORE team for their
cooperation. We also gratefully thank Prof. Franc¸oise Hey-
Received for review January 23, 2002. Revised manuscript
received July 9, 2002. Accepted July 10, 2002.
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