Gas-Phase Oxidation of Allyl Acetate by O3, OH, Cl, and NO3: Reaction Kinetics and Mechanism

Article abstract of DOI:10.1021/acs.jpca.7b10599

Allyl acetate (AA) is widely used as monomer and intermediate in industrial chemicals synthesis. To evaluate the atmospheric outcome of AA, kinetics and mechanism of its gas-phase reaction with main atmospheric oxidants (O₃, OH, Cl, and NO₃) have been investigated in a Teflon reactor at 298 ± 3 K. Both absolute and relative rate methods were used to determine the rate constants for AA reactions with the four atmospheric oxidants. The obtained rate constants (in units of cm³ molecule^-1 s^-1) are (1.8 ± 0.3) × 10^-18, (3.1 ± 0.7) × 10^-11, (2.5 ± 0.5) × 10^-10, and (1.1 ± 0.4) × 10^-14, for reactions with O₃, OH, Cl, and NO_3, respectively. While results for reactions with O₃, OH and Cl are in good agreement with previous studies, the kinetics for the reaction with NO₃ is reported for the first time in this study. On the basis of determined rate constants, the tropospheric lifetimes of AA are ρ_O3 = 9 days, ρ_OH = 5 h, ρ_Cl = 5 days, ρ_NO3 = 2 days. On the basis of the products study, reaction mechanisms for these oxidations have been proposed and the reaction products were detected using thermal desorption-gas chromatography-mass spectrometry (TD-GC-MS) and Fourier transform infrared spectroscopy (FTIR). Results show that the main products formed in these reactions are carbonyl compounds. In particular, 2-oxoethyl acetate was detected in all four AA oxidation reactions. Compared to previous studies, several new products were determined for reactions with OH and Cl. These results form a set of comprehensive kinetic data for AA reactions with main atmospheric oxidants and provide a better understanding of the degradation and atmospheric outcome of unsaturated acetate esters in the troposphere, during both daytime and nighttime.

Full text of DOI:10.1021/acs.jpca.7b10599

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Article
3
Gas-Phase Oxidation of Allyl Acetate by O, OH,
3
Cl and NO: Reaction Kinetics and Mechanism
Shuyan Wang, Lin Du, Jianqiang Zhu, Narcisse Tchinda
Tsona, Shijie Liu, Yifeng Wang, Maofa Ge, and Wenxing Wang
J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b10599 • Publication Date (Web): 01 Feb 2018
Downloaded from http://pubs.acs.org on February 1, 2018
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Gas-phase Oxidation of Allyl Acetate by O3, OH, Cl and NO3:
Reaction Kinetics and Mechanism
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Shuyan Wang,† Lin Du,*,† Jianqiang Zhu,† Narcisse T. Tsona,† Shijie Liu,† Yifeng
Wang,‡ Maofa Ge,§ and Wenxing Wang†
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† Environment Research Institute, Shandong University, Jinan 250100, China
‡
Key Lab of Colloid and Interface Science of the Education Ministry, Department of
Chemistry and Chemical Engineering, Shandong University, Jinan 250100, China
§
Beijing National Laboratory for Molecular Sciences (BNLMS), State Key Laboratory
for Structural Chemistry of Unstable and Stable Species, Institute of Chemistry, Chinese
Academy of Sciences, Beijing 100190, China
Correspondence to: Lin Du (lindu@sdu.edu.cn)
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ABSTRACT
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Allyl acetate (AA) is widely used as monomer and intermediate in industrial chemicals
synthesis. To evaluate the atmospheric outcome of AA, kinetics and mechanism of its
gasꢀphase reaction with main atmospheric oxidants (O3, OH, Cl and NO3) have been
investigated in a Teflon reactor at 298±3 K. Both absolute and relative rate methods were
used to determine the rate constants for AA reactions with the four atmospheric oxidants.
The obtained rate constants (in units of cm3 moleculeꢀ1 sꢀ1) are (1.8±0.3)×10ꢀ18,
(3.1±0.7)×10ꢀ11, (2.5±0.5)×10ꢀ10, and (1.1±0.4)×10ꢀ14, for reactions with O3, OH, Cl and
NO3, respectively. While results for reactions with O3, OH and Cl are in good agreement
with previous studies, the kinetics for the reaction with NO3 is reported for the first time
in this study. Based on determined rate constants, the tropospheric lifetimes of AA are:
τO3 = 9 days, τOH = 5 h, τCl = 5 days, τNO3 = 2 days. Based on the products study, reaction
mechanisms for these oxidations have been proposed and the reaction products were
detected using thermal desorptionꢀgas chromatographyꢀmass spectrometry (TDꢀGCꢀMS)
and Fourier transform infrared spectroscopy (FTIR). Results show that the main products
formed in these reactions are carbonyl compounds. In particular, 2ꢀoxoethyl acetate was
detected in all four AA oxidation reactions. Compared to previous studies, several new
products were determined for reactions with OH and Cl. These results form a set of
comprehensive kinetic data for AA reactions with main atmospheric oxidants, and
provide a better understanding of the degradation and atmospheric outcome of
unsaturated acetate esters in the troposphere, both at daytime and nighttime.
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1. INTRODUCTION
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Volatile organic compounds (VOCs) are ubiquitous in the environment and are directly
emitted into the atmosphere from a variety of natural and anthropogenic sources.1 Natural
sources include biogenic emissions, while anthropogenic sources include emissions from
vehicular exhaust, fuel evaporation, industrial processes, household products and solvent
usage.2ꢀ4 As a subset of VOCs, oxygenated volatile organic compounds (OVOCs) are
formed as oxidation products of all hydrocarbons present in the atmosphere and play a
significant role in atmospheric chemical processes.2 OVOCs may undergo complex
chemical reactions with the main atmospheric oxidants, O3, Cl atoms, OH, and NO3
radicals, leading to the formation of low volatile products, which contribute to the
formation of secondary organic aerosols (SOA).5 SOA are a major component of
atmospheric fine particles (PM2.5), which pose serious health risks and influence Earth’s
climate.6, 7 In addition, OVOCs are key precursors of O3. Both high concentration of
PM2.5 and O3 in the atmosphere can be used to characterize the photochemical smog,
which is one of the top environmental concerns.1 Moreover, OVOCs are generally more
reactive than parent alkanes and play an active role in the sequence of chemical
reactions.2 Therefore, the atmospheric chemistry of OVOCs is of relevance in processes
related to air quality and climate change.8
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Among OVOCs, acetate esters (CH3C(O)OR, R can be an alkenyl group) are used on a
large scale in industry, and many of them identified as highꢀproductive volume (HPV)
chemicals.9 Acetate esters are potential replacements for traditional solvents and diesel
fuels or fuel components, and are emitted into the atmosphere during their production,
processing, storage and disposal.10 A number of kinetic data have been published
concerning the gasꢀphase reactions of short chain esters such as methyl acetate, ethyl
acetate, and isopropenyl acetate with OH, Cl, and O3.11ꢀ13 The rate constants of reactions
of the isopropyl acetate, nꢀpropyl acetate, isopropenyl acetate, nꢀpropenyl acetate, nꢀbutyl
acetate, and ethyl butyrate with OH were determined by relative rate experimental
method in purified air under atmospheric conditions, at 750 Torr and 295±2 K.13
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Tropospheric lifetimes of these esters ranged from 5 hours for isopropenyl acetate to 5
days for nꢀpropyl acetate. Atmospheric oxidations of these esters by OH may also
generate O3. The rate coefficients have been measured for the reaction of Cl with a series
of alkyl esters at 298±2 K and atmospheric pressure in a large volume photoreactor using
the relative kinetic technique, which suggested that the values of the substituent factor
F(RC(O)Oꢀ) used in structure activity relationship (SAR) may depend on the nature of
the alkyl group R on the acyl side of the ester functionality.14 Rate coefficients for the
reactions of O3 with nꢀbutyl methacrylate, ethyl crotonate and vinyl propionate have been
determined at 298±1 K and atmospheric pressure.15 The following room temperature rate
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coefficients (in units of cm3 moleculeꢀ1 sꢀ1) were obtained: kCH2=C(CH3)C(O)OC4H9+O3
(1.0±0.3)×10ꢀ17, kCH3CH=CHC(O)OCH2CH3+O3 = (8.0±1.8)×10ꢀ18 and kCH3CH2C(O)OCH=CH2+O3
=
=
(5.3±1.3)×10ꢀ18. Furthermore, the reactivity trend of esters toward O3 was comparable to
that of reactions with other tropospheric oxidations such as OH and Cl. It was found from
the same unsaturated esters that reactions with O3 were more sensitive to the presence of
substituent groups than reactions with Cl and OH. For reactions of O3 with nꢀbutyl
methacrylate and ethyl crotonate, it could be observed that the replacement of a ꢀCH3
group of the double bond by a ꢀH atom produces a decrease of the rate coefficient in
connection with low susceptibility of π electrons of the double bond towards O3
electrophilic attack. Kinetics of the gasꢀphase reactions of O3 with unsaturated esters
(methyl methacrylate, vinyl acetate and methyl crotonate) have been investigated by
comparing their rates of decay with those of three corresponding reference compounds at
atmospheric pressure and ambient temperature (285ꢀ295 K).12 Atmospheric halfꢀlives
with respect to removal by O3, calculated from the measured rate constants, suggested
that removals by O3 and OH were of comparable magnitude.12
Allyl acetate (CH3C(O)OCH2CH=CH2, AA) has been detected as one of the products in
the combustion of esterified rape oil.10 As a monomer, coꢀmonomer or intermediate, AA
can be used in the synthesis of several chemicals, such as in the preparation of
copolymers with acrylonitrile, ethylene, methyl cyanoacrylate as well as in the
production of fire resistant rigid polyurethane foams.16ꢀ18 The healthy problems of
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irritation for human eyes, nose, skin and respiratory system could also be caused by the
release of AA. Once emitted to the atmosphere, AA would be subject to degradation by
photolysis and reaction with main atmospheric oxidants. It is therefore important to
assess the chemical outcome of AA through photooxidation, by exploring the kinetics
and mechanism of its atmospheric degradation by these oxidants.
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Previous studies on AA reactions with some atmospheric oxidants have been reported.
The rate constant of the reaction of AA with OH was measured by laser photolysisꢀlaser
induced fluorescence technique over the temperature range 243ꢀ372 K.10 The kinetic data
of this reaction were used to derive an Arrhenius expression (in units of cm3 moleculeꢀ1 sꢀ
1), k = (2.33±0.27)×10ꢀ12 exp[(732±34)/T], and the observed rate constant was
(2.71±0.30)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1 at 298 K.10 Using the relative rate method with
propene and nꢀoctane as reference compounds, the rate constants for AA + OH reaction
were determined to be (2.89±0.45)×10ꢀ11 and (2.46±0.24)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1,
respectively.19 The main oxidation products were 2ꢀoxoethyl acetate and formaldehyde
for the reaction of AA with the OH radical.19 By investigating the reaction mechanism, it
is seen that reactions proceed mainly by the addition of the oxidant to the C=C bond,
whereas, the initiation caused by Hꢀatom abstraction is negligible.20, 21 Additionally, the
yields of main products, 2ꢀoxoethyl acetate and formaldehyde, decreased in the absence
of NOx, which indicated that under such experimental conditions, 1,2ꢀhydroxyalkoxy
radicals formed after addition of OH to the double bond.18 The AA reaction with O3 was
investigated both theoretically and experimentally and rate constants of (2.40±0.70)×10ꢀ18
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and 2.43×10ꢀ18 were obtained, respectively.10,
The experimental reaction was
performed with the absolute rate method, and methyl vinyl ketone was used as the
reference compound.
While only one study has been reported on the kinetics and mechanism of the
atmospheric oxidation of AA by Cl,11 to our knowledge, the reaction of AA with NO3 has
not yet been investigated. Although the NO3ꢀinitiated degradation is not the prime loss
process for AA in the atmosphere, kinetic data and mechanism for the NO3 reaction with
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AA is needed to have a better understanding about the role of AA in the atmosphere
where its reaction with NO3 could potentially lead to nightꢀtime source of OH. On the
other hands, significant levels of NO3 have been detected over a wide range of
atmospheric conditions, indicating a potential role for NO3 in the oxidation chemistry
over large regions of the atmosphere. Moreover, NO3 reactions with VOCs are important,
or in some cases, even dominant in the atmosphere, therefore impacting the budgets of
these species and their degradation products. These reactions together with the ozonolysis
of VOCs are also responsible for the nighttime products and cycling of OH and peroxy
(HO2 + RO2) radicals. Reactions of NO3 with biogenic hydrocarbons are also known to
be responsible for the production of organic nitrates and SOA.23
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The present work determines the kinetics for reactions of AA with four atmospheric
oxidants (OH, NO3, Cl and O3) using relative rate and absolute rate methods. The
reaction with NO3 is investigated for the first time. Atmospheric lifetimes of AA based
on its reactions with the four oxidants were determined, and the reactions products were
characterized using thermal desorptionꢀgas chromatographyꢀmass spectrometry (TDꢀGCꢀ
MS) and Fourier transform infrared spectroscopy (FTIR) for the purpose of proposing
degradation mechanisms for AA in the atmosphere.
2. EXPERIMENTAL SECTION
2.1. Kinetics Study
All experiments were performed in a 100 L Teflon reactor in a chamber at room
temperature (298±3 K) and atmospheric pressure. This reactor was made of 0.05 mm
thick FEP Teflon film. An inlet and an outlet made of Teflon were used for the
introduction of reactants and sampling. Three UV lamps (F40T6BL, center wavelength
254 nm) mounted in parallel were used for radical precursors photolysis. The light
intensity and hence the radical production rate could be regulated by adjusting the
number of lamps and the time of irradiation. The reactor was flushed with purified air
from a zero air supply (111ꢀD3N, Thermo Scientific) three times before reactants were
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added into the reactor. The purified air flowed into the reactor through a mass flow
controller (D08ꢀ8C/ZM, Beijing Sevenstar Electron Corporation) which could record the
volume of purified air in the reactor. The background O3 concentration in zero air was
below 1.5 ppb, and the NOx concentration was below 1 ppb. Homogeneous mixing of the
reactants in the reactor was needed before starting the experiment. The concentrations of
reactants in the reactor were measured during the experiments by gas chromatography
with flame ionization detector (GCꢀFID) (7890B, Agilent Technologies). In all
experiments, a capillary column (30 m × 0.32 mm id × 1.8 ꢁm film thickness, DB 624,
Agilent Technologies) was used to separate the compounds. The chromatographic
conditions used for the analysis were as follows: injector 250°C, detector 300°C, column
temperature 110°C.
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The relative rate technique was used to determine rate constants for reactions of OH, Cl
and NO3 with AA. A number of factors were considered in the choice of reference
compounds: (i) the rate constants should be convinced, preferably the data from the
IUPAC recommendation, (ii) the rate constants of reference compounds are different
from one another, (iii) the wall loss and photolysis of the reference compounds should be
very low to minimize errors during the kinetics experiments. Cyclohexane, isoprene and
propene were used as reference compounds for the reaction with OH, propene and
cyclohexane were used for the Cl kinetic experiments, whereas, propene or acetaldehyde
were used for the NO3 kinetic experiments. Ratios of initial concentration of AA and
reference compounds were set as 1:1, 1:2, 2:1, 2:3 and 3:2 in order to eliminate the
influence of secondary reactions in the reaction process.24 The initial reactant
concentrations are listed in Table 1. The techniques and the reference compounds used in
the reactions of AA are listed in Table 2.
In order to verify the influence of precursor to the Cl atoms, the photolysis of thionyl
chloride (SOCl2) and trichloroacetyl chloride (CCl3COCl) were used to generate Cl
atoms. OH radicals were produced by the photolysis of hydrogen peroxide (H2O2). NO3
radicals were generated by the thermal decomposition of N2O5 in the dark:25, 26
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SOCl2 + hν(λ = 254nm) → SOCl⋅+Cl⋅
CCl3COCl + hν(λ = 254nm) → CCl3CO⋅+Cl⋅
H2O2 + hν(λ = 254nm) → 2OH⋅
(1)
(2)
(3)
(4)
N2O5 + M → NO3 ⋅+NO2 + M
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In the experiments performed with GCꢀFID, the reactant mixtures were photolyzed for 6ꢀ
25 s for SOCl2, 4ꢀ10 min for CCl3COCl and 5ꢀ15 min for H2O2 and a gas chromatogram
of the reactor contents was recorded. This photolysisꢀsampling procedure was repeated
until 74ꢀ92% depletion of AA and 65ꢀ92% depletion of the reference compounds were
achieved. Typically, 8ꢀ17 photolysisꢀsampling steps were carried out during each
experiment. During GCꢀFID experiments successive additions of N2O5 were performed.
Sampling was carried out approximately 6 min after the addition of N2O5 and at
subsequent intervals of 13 min. This procedure led to 33ꢀ55% depletion of AA and 26ꢀ48%
depletion of the reference compound. Overall, 7ꢀ9 additions were typically made to the
reactor during an experiment.
N2O5 was prepared via addition of 80ꢀ120 g phosphorus pentoxide powder to 30 mL
fuming nitric acid. Phosphorus pentoxide powder, whose number of moles was kept
seven times higher than that of nitric acid, was slowly added into fuming nitric acid
which was kept in a threeꢀneck flask at 233 K and mixed thoroughly with a stirrer. The
flask was then heated and kept at 313 K for 40 min. After that the volatile compounds
including N2O5 and NO2 in the threeꢀneck flask were collected by a cold trap. The
mixture in the cold trap was yellow powder. At last, the cold trap was continuously
extracted out by a pump at 263 K until the mixture became white powder. This indicated
that, NO2 had been extracted out, and the white powder was pure N2O5, exclusively.
N2O5 was kept in cold trap, held in liquid nitrogen in case of breakdown.
The produced Cl atoms, OH and NO3 radicals initiate the decay of AA and the reference
compounds through the following reactions:
X + AA kAA →products
(5)
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X + R kRef →products
(6)
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where X represents the oxidant (Cl, OH or NO3), kAA and kRef are the rate constants of
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reactions (5) and (6), respectively.
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The decay of AA and reference compounds is governed by the following rate equations:
d[AA]
= −kAA[AA][X]
(7)
dt
d[R]
= −kRef [R][X]
(8)
dt
Integration and rearrangement of equation (7) and equation (8) lead to the expression:
[AA]0 kAA [R]0
ln
=
ln
(9)
[AA]t kRef [R]t
where [AA]0 and [AA]t are the concentrations of AA at time t = 0 and time = t. [R]0 and
[R]t are the concentrations of the reference compound at time t = 0 and time = t. The plot
of ln([AA]0/[AA]t) versus ln([R]0/[R]t) yields a straight line passing through the origin
and whose slope gives the ratio of rate constants, kAA/kRef. Rate constants of reactions of
the reference compound with Cl, OH and NO3 are known and hence, rate constant kAA
can be readily calculated.
The relative rate technique relies on the assumption that both AA and the reference
compound are removed solely by reactions with the oxidants (Cl, OH and NO3).27 To
verify this assumption, mixtures of AA and reference compounds with H2O2 or SOCl2 or
CCl3COCl were prepared and allowed to stand in the dark. The reaction between AA and
reference compounds with the precursor was found to be negligible over the period of the
experiments. Possible photolysis loss of AA and the reference compounds was tested by
irradiating mixtures of AA and reference compounds with the UV lamps in the absence
of the radical precursors. Reactions with precursors (H2O2 or SOCl2 or CCl3COCl) and
photolysis were found to be negligible for AA and the reference compounds.
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The rate constant for the reaction of AA with O3 was determined using the absolute rate
method. The decay of O3 was measured in the presence of excess concentrations of AA.
The concentrations of O3 were governed by the following processes:
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O3＋wall → loss of O3
O3＋organic → products
(10)
(11)
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With the initial concentration of [AA]0 being in large excess over the initial O3
concentration ([AA]0/[O3]0 ＞50), the AA concentration essentially remains constant
throughout the reaction,28 and reaction (11) can be treated as a pseudoꢀfirstꢀorder reaction.
The following equation could be obtained:
−dln[O3 ]
= k1 + k2[AA]0
(12)
dt
where k1 and k2 are the rate constants of wall loss of O3 (equation 10) and O3 reaction
with AA (equation 11).
The total error, σAA, for the rate constants quoted in relative rate measurement is
combination of the 2σ statistical error (
2σk
) from the regression analysis σ (slope)
kRef
AA
and the error in measuring the rate constant for the reaction of AA with the reference
compound (σk ), according to equation (13):
Ref
2
σk
σk
kRef
2
]
AA
Ref
σAA = kAA
[
]2 +[
(13)
kAA kRef
kRef
Since relative measurements do not depend on the absolute concentrations of the
reactants, calibration errors can be ignored.29 The concentrations of AA and reference
compounds were measured using the same device, the GCꢀFID. The calibration curves
for reactants concentration versus their signals were linear, and the precision of the
measured signal contributes to the precision of the measured rate constants.30 The quoted
errors in the rate constant ratios (kAA/kRef) are twice the standard deviation (
2σk
) in
kRef
AA
the linear leastꢀsquares fit of the measured losses. In addition to the precision due to this
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ratio, the estimated uncertainty in the rate constant for reactions of OH, Cl and NO3 with
the reference compounds were included.
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O3 was produced using oxygen from an oxygen cylinder by high voltage discharge,
which was saved at a 50 L Teflon bag temporarily. For each reaction investigated, one
run was conducted in the presence of cyclohexane to scavenge OH radicals, which could
be produced during ozonolysis. The accurate concentration of O3 was measured by ozone
analyzer (Model 49i, Thermo Electron Corporation) with a flow rate of 0.7 L/min. To
insure that O3 concentration was not affected by the background air prior to experiments,
we measured its concentration in zero air in the reactor (below 1.5 ppb). There is no
obvious change after injection of 13.5×1014 molecules cmꢀ3 AA (the highest concentration
used in the kinetics experiments) into the reactor, suggesting no or negligible effect of
AA on O3 concentration. This further indicates that the current technique used to
determine the rate constant for the reaction of O3 with AA is reliable. During the
experiments, O3 concentrations were recorded every 1 min, until the final O3
concentration in the reactor decreased to be lower than 30% of the initial concentration.
The measurement lasted for 40ꢀ50 min. The initial AA concentrations in the reactor were
in the range of (2.7ꢀ13.5)×1014 molecules cmꢀ3, while the initial O3 concentrations were in
the range of (2.8ꢀ6.7)×1012 molecules cmꢀ3.
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2.2. Products Study
Product experiments were carried out at room temperature and atmospheric pressure in a
100 L Teflon reactor with three 254 nm UV lamps except NO3ꢀinitiated and O3ꢀinitiated
oxidation experiment. Products were detected using the TD (ATDSꢀ3400A,
Huashenpuxin) coupled with GCꢀMS (7890ꢀ5977B, Agilent Technologies) and a Bruker
Vertex 70 FTIR. In the product experiments the initial concentration of AA in the reactor
was 44 ppm (1 ppm = 2.46×1013 molecules cmꢀ3). The quantitative analysis was
performed using SOCl2 as the Cl source. The total photolysis time was 5ꢀ10 min for
SOCl2 and 2ꢀ3 h for H2O2, with about 80ꢀ90% conversion of AA. The NO3ꢀinitiated and
O3ꢀinitiated oxidation experiment lasted for 2ꢀ3 h to achieve 80ꢀ90% conversion of AA
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without the UV lamps. The qualitative determinations of products for the AA reactions
with OH, Cl and NO3 were carried out using TDꢀGCꢀMS. The samples were collected
into a Tenax TA (Markes International, 3.5ꢀinch length and 0.25ꢀinch O.D.) by a sampler
and the sampling lasted for 30 min. After that, the adsorption tube was put into the TD
instrument to desorb the sample into the capillary column by applying the following
temperature program: from 30°C (3 min) to 100°C (0 min) at a rate of 5°C minꢀ1, then to
230°C (10 min) at a rate of 10°C minꢀ1. The qualitative determination of products for AA
reactions with O3 and Cl was carried out using FTIR spectrometer equipped with a KBr
beam splitter and a DLaTGS detector. The IR spectral range was 370ꢀ7500 cmꢀ1 with a
resolution of 1 cmꢀ1.
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2.3. Chemicals
The chemicals used in the experiments were obtained commercially except N2O5. The
chemicals were used as received and their purities were as followed: AA (Aladdin, 99%),
cyclohexane (Aladdin, 99.9%), isoprene (Alfa Aesar, 99%), acetaldehyde (Aladdin,
99.5%), SOCl2 (Damasꢀbeta, 99+%), CCl3COCl (Damasꢀbeta, 99%). The following gases
were supplied by Jinan De Yang Special Gas Co., Ltd.: propene (1%, N2 as bath gas), N2
(> 99.999%), O2 (> 99.999%). Acetaldehyde and H2O2 were supplied by Beijing Fine
Chemicals Co., Ltd. with the purity of 98% and 30% respectively. Commercially
available phosphorus pentoxide (P2O5, ≥98.0%, Tianjin Damao) and fuming nitric acid
(HNO3, ≥98.0%, Sinopharm) were used to synthesize N2O5.
3. RESULTS AND DISCUSSION
3.1. Kinetics Studies
3.1.1. O3-initiated Reaction
The gas phase reaction of O3 with esters produces OH, which can further react with the
reactants and induce errors to the rate constants of the reaction.10 In this study, the
concentration of AA was almost constant during the reaction since a large excess of the
AA was used. As a result, the effect of AA loss by reaction with OH can be negligible.
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Nevertheless, to be more accurate, a certain amount of cyclohexane was added as OH
scavenger. In order to reduce the interference from the wall effect, the reactor operated
for at least 24 h in the presence of O3 prior to each set of experiments. Attenuation
experiment of O3 was performed to study the wall effect, which lasted 9 h, and the O3
decay rate constant of 3.9×10ꢀ6 sꢀ1 was obtained. This value is consistent with previously
reported value (6.09×10ꢀ6 sꢀ1), and is about 2 orders of magnitude lower than the pseudoꢀ
firstꢀorder rate constant of AA reaction.31 Thus, the background O3 decay accounts for
only a small part of all the loss of O3 in the reactor during experiments. Obviously, the O3
loss caused by background decay in this study was negligible.
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The rate constants were determined under pseudoꢀfirstꢀorder conditions. Decay of the O3
concentration was obtained as a function of time at 298±3 K. The logarithms of the ratios
of the O3 concentration in the presence of AA were plotted for different reaction times.
For reaction (11), straight lines were obtained for all pseudoꢀfirstꢀorder plots for five AA
concentrations. An example of the typical loss of O3 versus reaction time at different
concentrations of AA at 298±3 K is shown in Figure S1 in the Supplementary
Information. The slope of such plots yields the pseudoꢀfirstꢀorder rate constant, ꢀ
dln[O3]/dt. The value of ꢀdln[O3]/dt versus [AA]0 data were subjected to linear leastꢀ
squares analyses to obtain the rate constant of AA reaction with O3, kAA+O3. The plot of ꢀ
dln[O3]/dt versus the initial concentration of AA was linear with intercept close to zero
(see Figure 1). This indicates that if secondary reactions take place in the experiment,
their effect is negligible. Rate constants for the reaction of AA with O3 from this work
and from other references are listed in Table 2 for comparison. The errors are two
standard deviations from the leastꢀsquares analysis of the kinetic data plot. In some
previous studies, errors for rate constants determination included 2σ from the leastꢀ
squares analysis of the kinetic data plot and an estimated systematic error of 5ꢀ10%.32, 33
Considering these, the error for the rate constant of O3 reaction with AA includes 2σ from
the leastꢀsquares analysis and 10% systematic error.
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We determined a rate constant of (1.8±0.3)×10ꢀ18 cm3 moleculeꢀ1 sꢀ1 for the reaction of O3
with AA, in agreement with other reports listed in Table 2. Using the relative rate method,
a value of (2.40±0.70)×10ꢀ18 cm3 moleculeꢀ1 sꢀ1 was derived at 298±4 K,10 while quantum
chemical calculations were used to determine a rate constant of 2.43×10ꢀ18 cm3 moleculeꢀ1
sꢀ1 at 298 K.22 The slight discrepancy between our results and available literature values
might be due to the use of different experimental techniques10 and the error associated
with theoretical calculations.10, 22 Rate coefficients for O3 reactions with other unsaturated
esters have also been reported: (3.0±0.4)×10ꢀ18, (0.95±0.06)×10ꢀ18, and (1.28±0.06)×10ꢀ18
cm3 moleculeꢀ1 sꢀ1 for O3 reactions with CH3C(O)OCH=CH2, CH2=CHC(O)OCH3, and
CH2=CHC(O)OCH2CH3, respectively.34, 35 These values are of similar magnitude as the
(1.8±0.3)×10ꢀ18 cm3 moleculeꢀ1 sꢀ1 value reported in this study for the O3 reaction with
CH3C(O)OCH2CH=CH2, indicating a similar mode of reactivity in O3 reactions with
unsaturated esters. Moreover, unsaturated acetates are slightly less reactive towards O3
than corresponding alkenes (kCH3CH2CH=CH2+O3 = 9.64×10ꢀ18 cm3 moleculeꢀ1 sꢀ1 and
kCH3CH2CH2CH=CH2+O3 = (9.6±1.6) ×10ꢀ18 cm3 moleculeꢀ1 sꢀ1),36 and the electron withdrawing
effect of the C(O)OR substituent in unsaturated alkenes and reactions of corresponding
alkenes being electrophilic additions of O3 at the C=C bond can generally explain the
difference of reactivity.37
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3.1.2. OH Radical-initiated Reaction
Reported rate constants of the reaction of OH with reference compounds are as follows
(in units of cm3 moleculeꢀ1 sꢀ1): (6.97±1.39)
× ×
10ꢀ12 for cyclohexane, (1.00±0.06) 10ꢀ10 for
isoprene, 2.63
×
10ꢀ11 for propene.36, 38, 39 Several samplings, performed at short and steady
time intervals (~1 min), were executed to accurately determine the initial amount of AA
and reference compounds. The Teflon reactor was irradiated using UV lamps. From the
amounts of AA and reference compounds measured during experiments, ln([AA]0/[AA]t)
versus ln([R]0/[R]t) was plotted as shown in Figure 2.
The kAA/kRef ratio was obtained from leastꢀsquares regression analysis of the plots of
kinetic data for all the experiments performed on OH reaction with AA (see Table 2).
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Since the rate constants for AA reaction with OH obtained using three reference
compounds are in good agreement with each other, the final reaction rate constant was
quoted as the average of all rate constants determined using the different reference
compounds. This resulted in a rate constant value of (3.1±0.7)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1 for
the AA reaction with OH. This value is in very good agreement with available data
reported in the literature.10, 19 Using the pulsed laser photolysisꢀlaser fluorescence
technique over the temperature range 243ꢀ372 K, the kinetic data of OH reaction with
AA were used to derive an Arrhenius expression for the rate constant: (2.33±0.27)×10ꢀ12
exp[(734±34)/T] cm3 moleculeꢀ1 sꢀ1. At 298 K the rate constant obtained was
(2.71±0.30)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1.10 The rate constant of AA reaction with OH,
determined in purified air 750 Torr and 295±2 K using a relative rate method and
different reference compounds (nꢀheptane, nꢀoctane, and nꢀnonane with respective rate
constants for reactions with OH of 7.12×10ꢀ12, 8.42×10ꢀ12 and 9.70×10ꢀ12 cm3 moleculeꢀ1
sꢀ1), was found to be (2.46±0.24)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1.13 Slight discrepancies between
our results and literature results are likely due to differences in experimental conditions.
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The reaction of R1C(O)OR2 with OH seems to occur at OR2 entity and R1CO. For
compounds with same R1 as AA, the reactivity increases if the length of R2 chain
increases, as observed when comparing the rate constant for the reaction of vinyl acetate
with OH ( (2.3±0.3)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1) with that of AA reaction with OH.34 Also,
the rate constant for reaction with OH is higher than when R2 is an alkenyl than when it
is the corresponding alkyl, as indicated by the rate constant of OH reaction with nꢀpropyl
acetate ((1.97±0.24)×10ꢀ12 cm3 moleculeꢀ1 sꢀ1), compared to the rate constant for AA +
OH reaction.13 For compounds with same R2 as AA, the reactivity increases slightly if
the length of R1 chain increases: the rate constant of allyl butyrate is (2.89±0.31)×10ꢀ11
cm3 moleculeꢀ1 sꢀ1.40 For an isomeric group, the branched chain is more reactive than
linear chain, as illustrated by rate constant value for the OH reaction with isopropenyl
acetate, (6.25±1.24)×10ꢀ11 cm3 moleculeꢀ1 sꢀ1, more than twice higher than that of the AA
+ OH reaction.13 Furthermore, it was observed that rate constants of OH reactions with
AA and the corresponding alkene are very similar (kCH3CH2CH2CH=CH2
= 2.91×10ꢀ11
＋
OH
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cm3 moleculeꢀ1 sꢀ1).41 This indicates that the OH radicalꢀinitiated oxidation of AA
proceeds mainly by OH addition to the C=C bond, forming hydroxyalkyl radicals which
can react with O2 to form corresponding hydroxyalkyl peroxy radicals. These
observations are consistent with previous studies.42 There are two distinct pathways for
the methylacrolein reaction with OH: abstraction of the hydrogen atom, or addition of the
OH on the C=C double bond.43 The reactivity of the unsaturated esters is significantly
higher than those of the corresponding saturated esters. This can be explained by the
mechanistic difference of OH attack.13 At room temperature, Hꢀatom abstraction is the
minor channel with 5ꢀ10 % reaction probability.42
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3.1.3. Cl Atom-initiated Reaction
The kinetic data obtained from experiments, plotted according to equation (9) for the
reaction of Cl with AA, were measured relative to two reference compounds (see Figure
3). Good linear relationships with practically zero intercept were obtained in all
experiments, suggesting that secondary reactions could be neglected.
In order to calculate the rate constants for the reaction of Cl with AA, the following
values for rate constants of Cl reaction with the reference compounds at 298 K were used:
10ꢀ10 cm3 moleculeꢀ1 sꢀ1 for cyclohexane, and (2.3±0.3) 10ꢀ10 cm3 moleculeꢀ1
(3.50±0.25)× ×
sꢀ1 for propene.44, 45 Results obtained from linear leastꢀsquare analysis of the data are
shown in Table 2. The values for rate constants obtained using two different Cl
precursors and two reference compounds were in very good agreement within the
experimental uncertainties: kCl＋AA = (2.45±0.40)×10ꢀ10 cm3 moleculeꢀ1 sꢀ1 (using SOCl2 as
Cl precursor), kCl
= (2.60±0.40)×10ꢀ10 cm3 moleculeꢀ1 sꢀ1 (using CCl3COCl as Cl
＋
AA
precursor). The final rate constant for AA reaction with Cl was taken as the average of
the individual determinations with error limits, and is determined to be (2.5±0.5)×10ꢀ10
cm3 moleculeꢀ1 sꢀ1. This value differs from the rate constant in a previous study by a factor
of ~2, which found a rate constant of (1.30±0.45)×10ꢀ10 cm3 moleculeꢀ1 sꢀ1, determined at
298±3 K and a total pressure of 760 Torr using isobutene (kisobutene Cl = (3.40±0.28)×10ꢀ
＋
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10 cm3 moleculeꢀ1 sꢀ1) and 1,3ꢀbutadiene (k1,3ꢀbutadiene Cl = (4.2±0.4)×10ꢀ11 cm3 moleculeꢀ1 sꢀ
＋
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8
1) as reference compounds in a quartzꢀglass reaction chamber.11 The discrepancy might
originate from the choice of the reference compounds.
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On the other hand, the rate constant for the reaction of vinyl acetate with Cl,
(2.68±0.91)×10ꢀ10 cm3 moleculeꢀ1 sꢀ1, is slightly higher than that of AA + Cl reaction. This
observation can be attributed to the activation of the double bond toward Cl addition by
the conjugation effect of the lone pair electrons on the O atom of the vinyl acetate with
the olefin π electron system.11 However, in the AA structure, the ꢀCH2ꢀ entity separates
the O atom from the olefin π system, which makes the conjugation effect impossible.11
The rate constant for the AA + Cl reaction is 3 times higher than that of the Cl reaction
with nꢀpropyl acetate (kCH3C(O)OCH2CH2CH3+Cl = 7.76×10ꢀ11 cm3 moleculeꢀ1 sꢀ1), which
suggests that the double bond is highly reactive toward Cl addition and that addition is
seemingly the major reaction pathway.46 The reactivity of the ꢀOCH2ꢀ group in ꢀ
OCH2CH=CH2 and the rate of allylic Hꢀatom abstraction from AA have been studied in
the Clꢀinitiated oxidation of AA, vinyl acetate and butyl acrylate. Results show that Cl
addition to the C=C bond in AA dominates the reaction mechanism with a contribution
between 70 and 85%.11
3.1.4. NO3 Radical-initiated Reaction
The relative rate method was used to determine the rate constant for the AA reaction with
NO3. AA, the reference compound and N2O5 were introduced into the Teflon reactor
without UV lamps. The rate constants for the reaction of NO3 with reference compounds
were as follows: (6.1±1.3)× ×
10ꢀ15 cm3 moleculeꢀ1 sꢀ1 for propene, and (2.62±0.29) 10ꢀ15 cm3
moleculeꢀ1 sꢀ1 for acetaldehyde.25, 47 Typical plots of the kinetic data were obtained from
investigations on the reaction of NO3 with AA at 298±3 K and atmospheric pressure (see
Figure 4). The data give straight lines with zero intercepts (indicating that secondary
reactions are not important), having slopes of kAA/kRef. The weighted average kAA values
and the rate constant ratio kAA/kRef obtained by the GCꢀFID technique are given in Table
2. The rate constants for the AA reaction with NO3 obtained using propene and
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acetaldehyde as reference compounds are in good agreement with one another. Hence,
the final rate constant for this reaction, quoted as the average of the values obtained using
the two reference compounds, was determined to be kAA
= (1.1±0.4)×10ꢀ14 cm3
＋
NO3
moleculeꢀ1 sꢀ1.
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To our knowledge, the rate constant of the AA + NO3 reaction has not been determined
previously and no comparison with previous work is possible. However, comparison of
NO3 reactions with other unsaturated esters can be made. Using both absolute and
relative rate methods at atmospheric pressure and 293±3 K, the rate constant for the NO3
reaction with vinyl acetate was determined to be (7.1±1.9)×10ꢀ15 and (7.5±1.7)×10ꢀ15 cm3
moleculeꢀ1 sꢀ1, respectively, leading to an average value of (7.3±1.8)×10ꢀ15 cm3 moleculeꢀ1
sꢀ1.34 This is lower than the rate constant of AA reaction with NO3 reported in the present
study. Another study also reported rate constants, using the absolute rate method, of NO3
reaction with some aliphatic esters: (5±2)×10ꢀ17, (0.7±0.2)×10ꢀ17, and (1.3±0.3)×10ꢀ17 cm3
moleculeꢀ1 sꢀ1 for propyl acetate, methyl acetate, and ethyl acetate, respectively.48 It
follows from these data that the rate constant of NO3 reaction with AA is higher than the
rate constants of NO3 reactions with other aliphatic esters mentioned above, including
vinyl acetate. Furthermore, the rate constant of the vinyl acetate reaction with NO3 being
about two orders of magnitude higher than rate constants of NO3 reaction with the three
other aliphatic esters is a strong indication that the process of NO3 attacking the C=C
bond is the main reaction pathway. This conclusion can also be observed when
comparing rate constants of NO3 reactions with AA and propyl acetate
(CH3C(O)OCH2CH2CH3), and rate constants of NO3 reactions with vinyl acetate
(CH3C(O)OCH=CH2) and ethyl acetate (CH3C(O)OCH2CH3).48 Reactions of NO3 with
unsaturated esters proceed predominantly by addition to the carbon double bond. The
reactivity of NO3 toward esters could be made by applying the group reactivity factors
for alkanes, which show that the reactivity of acetate esters decreases with decreasing
number of carbon atoms,49 so that, in a 24 h period, the nighttime reaction with NO3 can
become an important factor in the budget. A common way of assessing the importance of
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NO3 versus OH, O3 and Cl reactions is to use averaged radical concentrations, daytime
and nighttime periods, and calculate the AA lifetime for the AA + radical reactions.
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As mentioned above, the rate constants of AA reaction with O3, Cl, OH and NO3 are
summarized in Table 2. The rate constant of AA reaction with Cl is 8 times higher than
the reaction with OH, 4 orders of magnitude higher than that for the reaction with NO3,
and 8 orders of magnitude higher than that for the reaction with O3. It is necessary to
mention that the rate constant for the reaction with Cl is close to the gas kinetic limited
value from gas collision theory, which means that the reaction probability in this case is
high regardless of the collision site and that the compound chemical structure plays a
limited role in determining the reaction rate constant.50
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3.2. Atmospheric Implications
Once emitted into the atmosphere, a volatile organic compound can be removed by
different atmospheric processes including photolysis, homogeneous and heterogeneous
reactions and wet and dry deposition. The residence times of AA in the atmosphere with
respect to reactions with O3, OH, NO3 and Cl can be estimated using the rate constants
obtained in this work. The tropospheric lifetime of AA is defined as the reciprocal of the
sum of loss rates of each removal process, and it is estimated by applying the following
equation:
1
τX
=
(14)
kX[X]
where X is the typical atmospheric concentration of O3, OH, NO3 or Cl, kx is the rate
constant of the reaction of AA with the oxidant X.
Typical atmospheric concentrations of the four oxidants are as follows: a 24 h average O3
concentration of [O3] = 7×1011 molecules cmꢀ3,51 a 12 h daylight average OH
concentration of [OH] = 2×106 molecules cmꢀ3,52 a 12 h nightꢀtime average NO3
concentration of [NO3] = 5×108 molecules cmꢀ3,53 and an average of Cl atom
concentration in the marine boundary layer, coastal areas, and some urban regions of [Cl]
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= 1×104 atoms cmꢀ3.54ꢀ56 As Table 3 shows, the reaction with OH is the main tropospheric
loss process of AA during the daytime. Based on this process, the lifetime of AA is 5 h,
while in areas with high O3 concentrations (as high as 5×1012 molecules cmꢀ3), the
reaction with O3 could equally become important. In coastal areas and in the marine
boundary layer, with peak concentrations of Cl atoms as high as 1×105 atoms cmꢀ3, the Cl
degradation of AA could compete with the OH degradation process.57 The lifetime of AA
based on the reaction with NO3 is two days. This reaction is an important degradation
process for AA at nighttime. The calculated short lifetimes of AA indicate that it may be
degraded close to the emission source areas, causing a local impact potentially leading to
its photoꢀoxidation in the atmosphere, which is responsible for the formation of
photochemical smog.
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3.3. Mechanism Study
To facilitate the discussion of the results, reaction schemes are shown in Schemes 1, S1,
S2, and S3 for AA reactions with OH, O3, Cl and NO3, respectively. The products of the
reactions of AA with O3 and Cl were detected using FTIR, whereas, the products of the
reactions of AA with Cl, OH and NO3 were detected using TDꢀGCꢀMS. The identified
products are marked in the oxidation schemes. Besides, compared to the loss that
occurred on photoꢀinduced degradation, the dark reactions, photolysis of AA in the
absence of oxidant precursors, and wall losses were negligible.58
2ꢀOxoethyl acetate (CH3CO(O)CH2CHO) and formaldehyde have been detected as main
products in the four reactions investigated. Their IR spectra were readily available from
previous study for comparison.18 Scheme S1 shows a proposed mechanism for the
ozonolysis of AA, based on the general knowledge on alkene ozonolysis reactions.59 The
reaction of AA with O3 will initially lead to the formation of the primary ozonide (POZ),
which can further decompose through two pathways, each forming a carbonyl compound
and a Criegee biradical. It has been shown that the Criegee biradical, [ꢂCH2OOꢂ]* can
form in the ozonolysis of VOCs of the type RꢀCH=CH2.34 The Criegee biradical formed
from the first pathway, [ꢂCH2OOꢂ]*, is believed to undergo a variety of reactions which
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can lead to the formation of formic acid, formic anhydride (HC(O)OC(O)H) and
hydroperoxymethyl formate (HOOCH2OCHO) under dry conditions.60, 61 However, there
was no evidence of the formation of these species from our spectra. The Criegee biradical
formed from the second pathway, [CH3C(O)OCH2C(ꢂ)H2O2ꢂ]*, could rearrange to 2ꢀ
oxoethyl acetate, although no plausible mechanism can be provided.
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Due to the electron deficiency of OH relative to the C=C bond of AA, the reaction with
OH proceeds essentially through addition of OH to the C=C bond, accounting for over 95%
of the reaction while the Hꢀatom abstraction is expected to account for about 5%.36, 62 The
addition of OH is mainly to the terminal carbon atom in the double bond,18, 36 forming
1,2ꢀhydroxyalkyl (1) and 2,1ꢀhydroxyalkyl (2) radicals.18 Analogous to alkyl radicals,
these hydroxyalkyl radicals are expected to react rapidly with O2 to yield the 1,2ꢀ
hydroxyalkyl peroxy (3) and 2,1ꢀhydroxyalkyl peroxy (4) radicals, respectively.63
Radicals (3) and (4) can then react with themselves to form 1,2ꢀhydroxyalkoxy (5) and
2,1ꢀhydroxyalkoxy (6) radicals, respectively. These hydroxyalkoxy radicals can in
principle react via three routes: reaction with O2, decomposition, and isomerization.63
Obviously, isomerization can only occur in the alkyl chain side with more than two
carbon atoms and, hence, does not appear to be of importance for products (5) and (6).64
The two hydroxyalkoxy radicals (5 and 6) may react further through four pathways: i)
decomposition to acetoxyacetic acid (CH3C(O)OCH2COOH) and formaldehyde (route
A1); ii) decomposition to form CH3C(O)OCH2· and glycolaldehyde (HC(O)CH2OH),
after which CH3C(O)OCH2· would undergo further reaction to form acetoxy
formaldehyde (CH3C(O)OCHO), acetic acid and CO (route B2); iii) decomposition to
formaldehyde and 2ꢀoxoethyl acetate (CH3C(O)OCH2CHO) (route B1); iv) reaction with
O2 to form CH3C(O)OCH2CH2OHCHO and CH3C(O)OCH2COCH2OH (routes A2 and
B3). CH3C(O)OCH2COOH and CH3C(O)OCHO have not been detected in previous
studies. It was also shown that both reaction with O2 and decomposition occur, with the
reaction with O2 occurring with 22±5% probability at 760 torr total pressure of air and
298 K.65, Peroxy radicals were shown to undergo selfꢀperoxy reactions in the absence of
NOx, which resulted in the formation of 1,2ꢀ and 2,1ꢀhydroxyalkoxy to a large extent.
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However, the molecular channels possibly contribute to the formation of multifunctional
products including hydroxy, carbonyl and ester functionalities.66 On the other hand, in the
presence of NOx, the peroxy radicals react with NO to mainly form 1,2ꢀhydroxyalkoxy
radicals.19, 34
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2ꢀOxoethyl acetate, acetoxyacetic acid, acetoxy formaldehyde and acetic acid were
detected by TDꢀGCꢀMS (see Scheme 1 and Figure S2). CH3C(O)OCH2CH(·)OH (7)
reacts with O2 to form acetoxyacetic acid. The acetoxy formaldehyde can be formed by
CH3COOCH2· (8) reaction with O2, and CH3COOCH2· (8) forms the acetic acid by
rearrangement. The NIST library does not include 2ꢀoxoethyl acetate. However, on the
basis that weakest bonds in a molecule break first, especially for long lived excited
intermediates where there is time for the energy to be randomized, combined with the
exploration of the mass spectrum fragments, the compounds can be conjectured.67
Aldehyde, ketone and ester which contain the carbonyl group could easily form by
breaking the CꢀO and the =CHꢀCH2ꢀ bonds as can be observed by analyzing the mass
spectrum. Hence, the main mass peaks at m/z 43 and 73 were tentatively assigned to
+
CH3CO+ and CH3COOCH2 , the characteristic fragment ions, which possibly result from
the 2ꢀoxoethyl acetate fragmentation.
The mechanism of OHꢀinduced oxidation of AA has been studied previously using FTIR
spectrometer,19 and 2ꢀOxoethyl acetate and formaldehyde were primary oxidation
products whereas acetic acid and acetoxy formaldehyde were secondary products. The
level of NOx affects the yields of 2ꢀoxoethyl acetate and formaldehyde, which are
smaller in experiments performed at low NOx. The different mechanisms observed with
and without NOx can be explained by the differences in exothermicities of the reaction
producing the alkoxy radicals.18
For the reaction of Cl with AA, the products CH3C(O)OCH2CHClCH2Cl (1), HCl (4),
CH3C(O)OCH2CHO (5), HC(O)CH2Cl (6) and CH3C(O)OCH2CH2OC(O)CH3 (7) (see
Scheme S2 and Figure S2) were detected by TDꢀGCꢀMS and the products CO and HCl
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were
detected
by
FTIR.
CH3C(O)OCH2CHClCH2Cl,
HCl,
and
CH3C(O)OCH2CH2OC(O)CH3 have not been detected in earlier studies.68 The
tropospheric chemical degradation of AA by Cl was also studied using FTIR in previous
studies.68 The results showed that the molar yields of 2ꢀoxoethyl acetate
(CH3C(O)OCH2CHO), acetoxy formaldehyde (CH3C(O)OCHO), acetic acid and
formaldehyde were <5% and the yield of CH3C(O)OCH2C(O)CH2Cl was ≥95%, as
estimated based on experimental observations.
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The mechanism of Cl reaction with AA is similar to the mechanism of OH reaction with
AA (see Scheme S2). The fate of alkoxy radical (2) formed in the Cl + AA reaction is
essentially its reaction with O2 to form acetic acid 3ꢀchloroꢀ2ꢀoxoꢀpropyl ester (3). The
formation of products (4), (5) and (6) suggests that the alkoxy radical (2), which
undergoes the CꢀC bond scission, is the main degradation pathway.
CH3C(O)OCH2CH2OC(O)CH3 (7) is likely
a
dimerization product of the
CH3C(O)OCH2(ꢂ) radical formed upon decomposition of the alkoxy radical (2).
CH3C(O)OCH2(ꢂ) also reacts with O2 to form CH3C(O)OCHO (8). Moreover,
CH3C(O)OCH2CHClCH2Cl (1) was formed and detected in our experiment, and may
probably be from Cl electrophilic addition to the C=C bond of AA, followed by reaction
of the CH3C(O)OCH2CH(ꢂ)CH2Cl radical with SOCl2.69 Based on observed products, the
main reaction pathways are routes A and C. The addition of Cl will be predominantly at
the terminal carbon of the C=C bond. A similar trend has also been observed in previous
studies.68, 70 Mass spectral analysis indicates the existence of similar fragments (CH3CO+
+
and CH3COOCH2 , indicative of the presence of 2ꢀoxoethyl acetate) to those observed in
the AA reaction with OH, as well as the fragment at m/z 102, which is the molecular ion
peak of 2ꢀoxoethyl acetate.
The main oxidation products of NO3 reaction with AA are 2ꢀoxoethyl acetate
(CH3C(O)OCH2CHO), nitrates and peroxynitrates (Scheme S3). The reaction of NO3
with unsaturated carbonyls proceeds by NO3 addition to the C=C bond.8 For the reaction
with AA, direct products are the nitroxyl radicals (1) and (2), which further undergo O2
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addition to form the peroxyl radicals (3) and (4). The formation of 2ꢀoxoethyl acetate
detected in this study suggests that the main sinks for (3) and (4) are reactions with RO2
species to form the corresponding oxyl radicals (5) and (6), which can then undergo CꢀC
bond scission to form product (7). Intermediates (5) and (6) may also form the dinitrate
(8) by addition of NO2 to the oxyl group, or the carbonyl nitrates (15) and (16) by
reaction with O2. Peroxy nitrates (13) and (14) may be formed by reversible addition of
NO2 to the peroxyl groups (3) and (4), which may undergo selfꢀreactions to form alcohols
(products (9) and (11)) and carbonyl compounds (products (10) and (12)). The
mechanism of NO3 reaction with AA proposed from these observations is similar to that
of the AA reaction with OH. Due the high electron density on the C=C bond, the
electrophilic NO3 addition on the C=C bond was considered to be more favorable than
the Hꢀabstraction which can hence be neglected.71 This was followed by an addition of
O2, and led to the formation of the alkylperoxy radical (channel A1 and B1). This
alkylperoxy radical can react with NO2 to form a peroxynitrate (channel A2 and B2), or
undergo selfꢀreaction to form a carbonyl, an alcohol (channel A3 and B3) or an alkoxy
radical (channel A4 and B4). The alkoxy radical can either undergo decomposition
leading to the formation of formaldehyde and 2ꢀoxoethyl acetate (channel A5 and B5),
Hꢀabstraction by O2 forming carbonyl (channel A6 and B6), or reaction with NO2
forming dinitrate (channel A7 and B7). The importance of the different reaction channels
of peroxynitrate in the real atmosphere is currently not clearly established, partly due to
the poorly known kinetics of peroxynitrate reactions. In addition, most of the laboratory
studies have been performed with only one VOC and thus a limited number of different
peroxynitrate species is available. Moreover, the NO3 addition at either position in the
C=C bond cannot be distinguished since each organic nitrate was not quantified
individually. For the same reason, it was not possible to determine branching ratios of
different channels.
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4. CONCLUSION
Kinetics and mechanism of allyl acetate (AA) reactions with main oxidants in the
atmosphere have been determined in a 100 L Teflon reactor at 298±3 K and atmospheric
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pressure. The obtained kinetic data in combination with other available kinetic data
suggest that the addition of oxidants to the C=C bond would be the dominant pathway,
while the Hꢀatom abstraction would be negligible. From the calculated tropospheric
lifetimes, the reaction of AA with OH is the main loss process of AA at the daytime,
while the reaction with NO3 would govern the degradation chemistry during the night. In
areas with high O3 concentrations (as high as 5×1012 molecules cmꢀ3), and in coastal areas
and in the marine boundary layer (where peak concentrations of Cl atoms are as high as
1×105 atoms cmꢀ3) the loss process of AA due to reactions with O3 and Cl could be
competitive processes to the reaction with OH.
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The main products of AA reactions with the four oxidants, detected by TDꢀGCꢀMS or
FTIR, are 2ꢀoxoethyl acetate, formaldehyde, and acetic acid. Formaldehyde is known to
cause serious health effects when it is present in the air at 0.1 ppm and above. Acetic acid
and acetoxyacetic acid, detected as products of the AA oxidation by OH, could be
removed by wet or dry deposition. These acids are common component of rain, clouds
and fogs, and are found in the condensed phase from remote to highly polluted urban
areas. Additionally, 2ꢀoxoethyl acetate, formed in the four studied reactions, can be
photolyzed and may also be reactive toward OH. From this study, it can be suspected that
these reactions lead to the formation of acetoxy formaldehyde, acetoxyacetic acid and
acetic acid, which are highly soluble and may be rapidly incorporated into cloud droplets.
However, these observations need to be confirmed with specific experiments on the
oxidation processes. Therefore, kinetic and mechanistic experiments on the chemistry of
2ꢀoxoethyl acetate are needed to evaluate the environmental impact of allyl acetate.
ASSOCIATED CONTENT
Supporting Information
The pseudoꢀfirstꢀorder loss rate of O3 at different AA concentrations; proposed reaction
mechanism of the O3ꢀ, Clꢀ and NO3ꢀinitiated oxidation of AA; the detected products of
the four reactions.
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Notes
The authors declare no competing financial interest.
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ACKNOWLEDGMENTS
This work was supported by National Natural Science Foundation of China (91644214),
Shandong Natural Science Fund for Distinguished Young Scholars (JQ201705), and
China Postdoctoral Science Foundation (2017M612276).
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