Gas-Phase Reaction of Methyl n-Propyl Ether with OH, NO3, and Cl: Kinetics and Mechanism

Article abstract of DOI:10.1021/acs.jpca.7b06877

Rate constants at room temperature (293 ± 2 K) and atmospheric pressure for the reaction of methyl n-propyl ether (MnPE), CH₃OCH₂CH₂CH₃, with OH and NO₃ radicals and the Cl atom have been determined in a 100 L FEP-Teflon reaction chamber in conjunction with gas chromatography-flame ionization detector (GC-FID) as the detection technique. The obtained rate constants k (in units of cm³ molecule^-1 s^-1) are (9.91 ± 2.30) × 10^-12, (1.67 ± 0.32) × 10^-15, and (2.52 ± 0.14) × 10^-10 for reactions with OH, NO₃, and Cl, respectively. The products of these reactions were investigated by gas chromatography-mass spectrometry (GC-MS), and formation mechanisms are proposed for the observed reaction products. Atmospheric lifetimes of the studied ether, calculated from rate constants of the different reactions, reveal that the dominant loss process for MnPE is its reaction with OH, while in coastal areas and in the marine boundary layer, MnPE loss by Cl reaction is also important.

Full text of DOI:10.1021/acs.jpca.7b06877

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Article
Gas Phase Reaction of Methyl n-Propyl Ether
3
with OH, NO and Cl: Kinetics and Mechanism
Jianqiang Zhu, Shuyan Wang, Narcisse T Tsona, Xiaotong Jiang, Yifeng Wang, Maofa Ge, and Lin Du
J. Phys. Chem. A, Just Accepted Manuscript • DOI: 10.1021/acs.jpca.7b06877 • Publication Date (Web): 24 Aug 2017
Downloaded from http://pubs.acs.org on August 25, 2017
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The Journal of Physical Chemistry A is published by the American Chemical Society.
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Gas Phase Reaction of Methyl n-Propyl Ether with OH, NO3
and Cl: Kinetics and Mechanism
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Jianqiang Zhu,†,‡ Shuyan Wang,† Narcisse T. Tsona,† Xiaotong Jiang,† Yifeng Wang,§
Maofa Ge,ǁ Lin Du*,‡,†
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† Environment Research Institute, Shandong University, Ji’nan 250100, China
‡ Shenzhen Research Institute, Shandong University, Shenzhen 518057, China
§ Key Lab of Colloid and Interface Science of the Education Ministry, Department of
Chemistry and Chemical Engineering, Shandong University, Ji’nan 250100, China
ǁ
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
Email: lindu@sdu.edu.cn
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ABSTRACT
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Rate constants at room temperature (293 ± 2) K and atmospheric pressure for the
reaction of methyl nꢀpropyl ether (MnPE), CH3OCH2CH2CH3, with OH and NO3
radicals, and Cl atom have been determined in a 100 L FEPꢀTeflon reaction chamber
in conjunction with gas chromatographyꢀflame ionization detector (GCꢀFID) as the
detection technique. The obtained rate constants k (in units of cm3 moleculeꢀ1 sꢀ1) are
(9.91 ± 2.30) × 10ꢀ12, (1.67 ± 0.32) × 10ꢀ15, and (2.52 ± 0.14) × 10ꢀ10 for reactions with
OH, NO3, and Cl, respectively. The products of these reactions were investigated by
gas chromatographyꢀmass spectrometry (GCꢀMS), and formation mechanisms are
proposed for the observed reaction products. Atmospheric lifetimes of the studied
ether, calculated from rate constants of the different reactions, reveal that the
dominant loss process for MnPE is its reaction with OH, while in coastal areas and in
the marine boundary layer, the MnPE loss by Cl reaction is also important.
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INTRODUCTION
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Oxygenated volatile organic compounds (OVOCs) belong to the large family of
organic compounds present in the global atmosphere.1 Atmospheric sources of
OVOCs include direct emissions from a variety of anthropogenic and natural sources,
and gas phase oxidation of organic compounds in the atmosphere.2ꢀ3 OVOCs may
contribute to organic carbon in aerosols and participate in other atmospheric processes,
which determine the oxidizing capacity of the atmosphere.1,4ꢀ5 In addition to their
photochemical impact, many of these compounds are harmful to human health,
especially in urban environments. Upon release into the troposphere, OVOCs can
undergo either photolysis or photochemical oxidation by OH radical during daytime
and by NO3 radical during nighttime and Cl atom in the coastal regions.6 Reactions
with OH, NO3 or Cl are all important processes in the chemistry of natural and
polluted atmosphere.7ꢀ8 However, their removal processes are well understood only
for a few compounds. Although the chemistry of oxygenated organic compounds has
been extensively explored over the past 50 years, much is yet to be discovered.3
Ethers form a class of OVOCs that have a wide range of practical applications,
including fuel additives, alternative fuels and intermediates in chemical industries.9ꢀ13
The use and emissions of these compounds have led to increased interest into
determining kinetics and mechanisms of their atmospheric degradation.14 The possible
atmospheric significance of ethers is, thus, considered in terms of their reactions with
oxidants,15 while reactions with O3 are negligible.16 The kinetics of the symmetric
short nꢀchain ethers, dimethyl ether (DME, CH3OCH3) and diethyl ether (DEE,
CH3CH2OCH2CH3), have been the subject of numerous studies in the past. Rate
constants of dimethyl ether oxidation by OH over the temperature range 299ꢀ427 K
were measured using flash photolysisꢀresonance fluorescence (FPꢀRF) technique.17
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The kinetics was described by an Arrhenius expression, k(CH3OCH3) = 1.29×10ꢀ11
e
ꢀ(770±300)/RT cm3 moleculeꢀ1 sꢀ1, with a rate constant at room temperature of (3.50 ± 0.35)
× 10ꢀ12 cm3 moleculeꢀ1 sꢀ1. Using the FPꢀRF technique, reactions of dimethyl ether
with Cl were studied and a rate constant of (1.76 ± 0.15) × 10ꢀ10 cm3 moleculeꢀ1 sꢀ1
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was obtained over the temperature range 200ꢀ500 K.18 An upper limit value of 4 ×
10ꢀ16 cm3 moleculeꢀ1 sꢀ1 for the rate constant of the reaction of NO3 with CH3OCH3
was determined at 298 ± 2 K using flash photolysis technique.19 The relative rate
method was used to measure the rate constants for the reaction of diethyl ether with
OH, NO3 and Cl, and values of (5.6 ± 1.1) × 10ꢀ12, (2.80 ± 0.23) × 10ꢀ15, and (35.6 ±
2.8) × 10ꢀ10 cm3 moleculeꢀ1 sꢀ1 were reported, respectively.20ꢀ22
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In contrast, only few studies on the kinetics and mechanism of reactions for
asymmetric short nꢀchain ether have been reported. The kinetics and mechanism of
methyl ethyl ether (MEE, CH3OCH2CH3) were examined using FTꢀIR/relativeꢀrate
method, and rate constants of (7.53 ± 2.86) × 10ꢀ12 and (2.35 ± 0.43) × 10ꢀ10 cm3
moleculeꢀ1 sꢀ1 were obtained at 297 ± 2 K for reactions with OH and Cl,
respectively.23 The rate constants for gas phase reactions between MEE with OH/Cl
were determined using a relative rate technique and average values of kMEE+OH
=
(6.60ꢀ2.62+3.88) × 10ꢀ12 and kMEE+Cl = (34.9 ± 6.7) × 10ꢀ11 cm3 moleculeꢀ1 sꢀ1 were
reported over the temperature range 274ꢀ345 K.24 The measured rate constant of (7.81
± 0.36) × 10ꢀ16 cm3 moleculeꢀ1 sꢀ1 for MEE reaction with NO3 was measured by means
of a relative rate method at 298 K.25 To our knowledge, there is only one theoretical
study on the kinetics of the oxidation reaction of methyl nꢀpropyl ether (MnPE,
CH3OCH2CH2CH3) in the literature,26 while no experimental study is available.
However, MnPE was reported to be used as anesthetic and as organic solvent in some
composite additives for gasoline systems,27 and may be highly present in the
atmosphere. High exposure to MnPE may lead to loss of appetite, headache, and
dizziness followed by sleepiness and loss of consciousness.
We perform an experimental study on MnPE reactions with OH, NO3 and Cl, at (293
± 2) K and atmospheric pressure, using the relative method with GCꢀFID and GCꢀMS
as detection techniques. Reactions kinetics are determined and formation mechanisms
of products are proposed. This study is essential to determine the lifetime and
persistence of MnPE in the atmosphere, which can help to evaluate its impact on
health and the environment.
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EXPERIMENTAL AND METHODS
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2.1. Kinetics Experiments
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The experiments were performed in a 100 L FEPꢀTeflon reaction chamber (Figure 1)
under room temperature (293 ± 2) K and atmospheric pressure. A Teflon made inlet
and a similar outlet were used for the introduction of reactants and gas sampling, and
Teflon tubes were used to connect the chamber and analytical instruments. The
chamber was surrounded by a set of three UV fluorescent lamps (Philips TUV 36 W)
with maximum intensity at 254 nm. Purified air was produced by a zeroꢀair gas
generator (Thermo Scientific, MODEL 111ꢀD3R) and was used as bath gas. A drying
tube was added after the zeroꢀair gas generator to make sure the purified air had a low
level relative humidity (<5%). The total volume of the gas in the chamber was
measured with mass flow accumulator (Beijing Sevenstar, D80ꢀ8C/ZM). Liquid
reactants were introduced into the chamber using graduated micro syringes and were
evaporated into a stream of purified air as the chamber was filled. Prior to each
experiment, the chamber was flushed with dried and purified air for at least three
times.
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Each reaction was measured with at least two reference standards. The reaction
process was controlled by the exposure time in OH/Cl experiments and the adding
mass of N2O5 in NO3 experiments. Concentrations of MnPE and the reference
compound were measured using a gas chromatograph equipped with a flame
ionization detector (Agilent Technologies, GCꢀFID 7890B). The initial reactant
concentrations are given in Table 1. The reaction gas in the chamber was extracted
intermittently using a glass syringe and then introduced via a 0.5 mL Teflon loop
mounted in a sixꢀway valve onto a DBꢀ624 capillary column (Agilent Technologies,
30 m length × 1.8 ꢁm film thickness × 0.32 mm i.d.). To make sure that the peaks for
each reference would not overlap with the reactant, different reference standards used
different column temperatures. The chromatographic conditions used for the analysis
were as follows: injector 523 K; split less injection; column flow 5 mL minꢀ1; FID
heater 573 K.
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2.2. Product Experiments
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The product experiments followed similar procedure to that described above, except
for the absence of reference compounds. Initial reactant concentrations are given in
Table 1. In order to detect the products, two methods were used: thermal desorption
and selfꢀmade cold trap.28 Thermal desorption measured products by preconcentrating
them on Tenax TA adsorption tubes (Markes International, 3.5ꢀinch length and
0.25ꢀinch O.D.). An air sampler (Beijing Municipal Institute of Labour Protection,
QCꢀ1S) was withdrawn from the chamber at a flow rate of 1.5 L minꢀ1 through Tenax
TA adsorption tubes. The contents of the tubes were thermally desorbed at 473 K for 1
min in the stream of helium with a thermally desorption (Huashenpuxin,
ATDSꢀ3400A). The sample was rapidly heated to 523 K to inject the sample onto the
HPꢀ5ms capillary column (Agilent Technologies, 30 m length × 0.50 ꢁm film
thickness × 0.25 mm i.d.). The column was kept at 303 K for 14 min and then heated
to 373 K at a heating rate of 5 K minꢀ1 and finally to 523 K at 10 K minꢀ1. The column
was connected to a mass spectrometer (Agilent Technologies, 5977D MSD) operated
in the total ion mode. Several samples were drawn through two Tenax TA adsorption
tubes in series, which were both analyzed in the same way to check for breakthrough
of the compounds in the adsorption tube.
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A selfꢀmade cold trap using liquid nitrogen (77 K) was employed as the
complementary method to concentrate the products. Gas samples were withdrawn
through the cold trap until the chamber was evacuated. The trapped material was
dissolved in 10 mL methanol and l ꢁL solution were injected into the GCꢀMS. Mass
spectrometry detection was performed in electron impact (EI) mode with a detector
temperature of 473 K. The conditions used for the analysis were as follows: injector
523 K; ion source 503 K; quadrupole 423 K; temperature program from 303 K to 403
K at a rate of 5 K minꢀ1 and finally to 523 K at 10 K minꢀ1.
2.3. Methods
Rate constants for the gas phase reactions of MnPE with OH, NO3 radicals and Cl
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atom were determined using the relative rate method, at (293 ± 2) K and atmospheric
pressure. In the presence of oxidants (Ox), the substrate and the reference compounds
decay through the following reactions:
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ꢀꢁ + ꢂꢃꢄꢅ → ꢆꢇꢈꢉꢊꢋꢌꢍ
(R1)
(R2)
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ꢀꢁ + ꢎꢏꢐꢏꢇꢏꢃꢋꢏ → ꢆꢇꢈꢉꢊꢋꢌꢍ
These decays are governed by the following rate equations:
ꢑ
ꢒ⁄ ꢒ
ꢑ
ꢒ ꢑ
ꢉ ꢂꢃꢄꢅ ꢉꢌ = ꢓꢔꢕꢖꢗ ꢂꢃꢄꢅ ꢀꢁ
(1)
(2)
ꢑ
ꢒ⁄ ꢒ ꢑ
ꢑ
ꢒ
ꢉ ꢎꢏꢐ ꢉꢌ = ꢓꢘꢙꢚ ꢎꢏꢐ ꢀꢁ
where kMnPE and kRef are rate constants of reactions (R1) and (R2), respectively.
Assuming the reactant and the reference compound are only decayed by reactions (R1)
and (R2), integration and rearrangement of equations (1) and (2) lead to the
expression:
ꢜꢑ
ꢛꢃ ꢂꢃꢄꢅ
ꢒ ⁄ꢑ
ꢂꢃꢄꢅ
ꢒ ꢟ
⁄
ꢜꢑ
ꢒ ⁄ꢑ
ꢒ ꢟ
ꢎꢏꢐ
ꢞ
= ꢓꢔꢕꢖꢗ ꢓꢘꢙꢚ ꢛꢃ ꢎꢏꢐ
(3)
ꢝ
ꢞ
ꢝ
where, [MnPE]0, [Ref]0, [MnPE]t and [Ref]t are the concentrations of MnPE and
reference compound at times t = 0 and t, respectively. Therefore, a plot of
ln([MnPE]0/[MnPE]t) versus ln([Ref]0/[Ref]t) should be a straight line passing
through the origin point with a slope of kMnPE/kRef, and kMnPE can then be obtained by
multiplying the slope with the known value of kRef.
OH radicals were generated effectively by 254 nm photolysis of H2O2.29 Cl atoms
were produced in site by 254 nm photolysis of SOCl2 and CCl3C(O)Cl. NO3 radicals
were generated from the thermal decomposition of dinitrogen pentoxide (N2O5).30
N2O5 was prepared by reaction of fuming nitric acid with phosphorus oxide, and was
intermittently introduced into the reaction chamber by a glass syringe.
The uncertainty on a rate constant measured with the relative rate method is
determined with 2σ statistical error (∆(expt)) from the regression analysis, consisting
of random and systematic error, and the uncertainty of the reference rate constant
(∆k(ref)), according to the equation:6,31
ꢡ
ꢜ
ꢟ
ꢑ
ꢒꢡ
∆ꢓ target = ꢠꢑ∆ꢓꢜꢇꢏꢐꢟꢒ + ∆ꢜꢏꢢꢆꢌꢟ
(4)
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One of the advantages of the relative rate measurements is that uncertainties in
absolute concentrations of either reactant do not lead to an error in the measured rate
constant values.32 The concentrations of the reactant and the reference compound
were measured by using the same GCꢀFID system. The calibration curves for the
VOC concentration versus their signals were linear. The precision of the measured
signal contributes to the precision of the measured rate constants.32 The error in the
values of ∆(expt) are twice the standard deviation (2σ) in the leastꢀsquares fit of the
measured losses to equation (3). In addition to the precision, the accuracy of the
measured rate constant depends also on the accuracy of the rate constants for the
reference reactions. The experiments were performed under the temperature of (293 ±
2) K, therefore, the reference rate constants were chosen at a similar temperature. We
combined the precision of our measured values with the quoted uncertainties in the
rate coefficient for the reference reaction to estimate the overall accuracy of the
measured rate constants using equation (4).
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2.4. Chemicals
The chemicals were obtained commercially and were used without further purification:
methyl nꢀpropyl ether (C4H10O, >95.0%, TCI), thionyl chloride (SOCl2, 99%,
Adamas), trichloroacetyl chloride (CCl3C(O)Cl, 99%, Adamas), cyclohexane (C6H12,
≥99.9%, Aladdin), furan (C4H4O, ≥99.0%, Aladdin), hydrogen peroxide solution
(H2O2, 30wt% in H2O, Aladdin), nitric acid fuming (HNO3, ≥98.0%, Sinopharm),
phosphorus oxide (P2O5, ≥98.0%, Tianjing Damao), tetrahydrofuran (C4H8O, 99%,
TCI), acetaldehyde (CH3CHO, 99.5%, Acros) and methanol (CH3OH, ≥99.9%,
Aladdin). Propene (1%, N2 as bath gas), He (≥99.999%), N2 (≥99.999%), H2
(≥99.999%) and synthetic compressed air were supplied by Jinan Deyang Special Gas
Company, Shandong.
RESULTS AND DISCUSSION
3.1. Kinetics Studies
Several control experiments concerning wall loss, photolysis and dark reactions were
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performed before the kinetics measurements to verify the assumption that reactants
were solely removed by reactions with OH, NO3 and Cl. Mixtures of MnPE and
reference compounds were introduced into the chamber for the wall loss test in the
absence of the radical precursors. Stable concentrations of the investigated
compounds were monitored by GCꢀFID through at least ten measurements over the
course of 5 h, and the integrated peak areas decreased by less than 3% of their initial
values. Then, the mixtures were subjected to photolysis for twice the duration of each
kinetics experiment without the radical precursors. Moreover, dark reactions were
carried out between the radical precursors and mixtures of MnPE and reference
compounds for the duration of each kinetics experiment. Based on the above
described experiments, it was found that the loss caused by wall loss, photolysis and
dark reactions was negligible compared to the loss occurred on the conversion of
MnPE and reference compounds in the same time span of the radical reaction
experiments.
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3.1.1. Rate Constant of MnPE with OH
Cyclohexane, propene and furan were used as reference compounds because the rate
constants of their reactions with OH were of same order of magnitude as the expected
rate constant for the studied substrate. The rate constants for the reactions of OH with
the reference compounds used were (in units of cm3 moleculeꢀ1 sꢀ1): (6.97 ± 1.39) ×
10ꢀ12 for cyclohexane,33 (2.51 ± 0.25) × 10ꢀ11 for propene,34 and (4.01 ± 0.30) × 10ꢀ11
for furan.35 Figure 2 shows examples of the kinetics data obtained from the
experiments plotted according to equation (3) for MnPE, using cyclohexane, propene
and furan as reference compounds. As expected for relative rate plots, straight lines
with intercept at zero were obtained, indicating that the heterogeneous or secondary
reactions were insignificant. For each reference compound, five experiments were
carried out under different initial concentration ratios.
The obtained rate constants for MnPE reaction with OH are summarized in Table 2.
The rate constants using different reference compounds are in reasonable agreement.
The final rate constant for the reaction of OH with MnPE were concluded by
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averaging the rate constants obtained with each reference compound. The obtained
rate constant for MnPE react with OH is (9.91 ± 2.30) × 10ꢀ12 cm3 moleculeꢀ1 sꢀ1. An
equation was given to evaluate the overall rate constants k for ethers containing only
primary and secondary CꢀH bonds,17
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ꢓ = ꢣꢤꢥꢦꢧꢓꢤꢥꢦꢧ + ꢣꢨꢙꢩꢓꢨꢙꢩ
(5)
where Nprim, Nsec are the numbers of primary and secondary CꢀH bonds, respectively,
and kprim, ksec are the rate constants for the reaction of the OH per primary or
secondary CꢀH bond, respectively. Values of primary and secondary CꢀH bond are
kprim = 6.0 × 10ꢀ13 and ksec = 1.7 × 10ꢀ12 cm3 moleculeꢀ1 sꢀ1 at 305 ± 2 K, respectively.17
The calculated rate constant, kMnPE + OH = 10.4 × 10ꢀ12 cm3 moleculeꢀ1 sꢀ1 agrees well
,
with the experimental value.
A comparison of rate constants determined in this study with the literature data is
shown in Table 3. There are a few reports about the rate constants for the reactions of
OH with dimethyl ether (DME), methyl ethyl ether (MEE), diethyl ether (DEE) and
methyl nꢀbutyl ether (MnBE) by using absolute or relative rate methods at room
temperature. For the studies of DME + OH, the largest rate constant of (3.50 ± 0.35) ×
10ꢀ12 cm3 moleculeꢀ1 sꢀ1 was determined by using absolute method and the smallest
rate constant of (2.32 ± 0.23) × 10ꢀ12 cm3 moleculeꢀ1 sꢀ1 was determined by using
relative method.17,36 Discrepancy exists in the values obtained by using different
methods. The accuracy of the results obtained in absolute rate methods might be
limited by the concentration measurement.37 In fact, a potential source of discrepancy
could be an underestimation of the DME concentration in the experiment which
would result in an overestimation of the rate coefficient. For the gasꢀphase
atmospheric chemistry of MnPE with OH radicals, there was only one theoretical
investigation carried out at 298.15 K using a variational transition state theory.26 The
obtained rate constant was 12.3 × 10ꢀ12 cm3 moleculeꢀ1 sꢀ1, which is somewhat larger
than our determination, but well within the stated uncertainly of ± 25%.31
Rate constants for OH reactions with DME, MEE, MnPE and MnBE are in the order:
23,36
kDME + OH < kMEE + OH < kMnPE + OH < kMnBE + OH
.
Moreover, going from MEE to
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MnBE there is approximately a factor of 1.5 increase when adding a methyl group.
The data are reasonably selfꢀconsistent and the results confirm the expected trend of
the rate constants increasing as the molecules become larger and contain weaker CꢀH
bonds.38 Otherwise, reactions may occur mainly at the CH2 groups, which explains
the trend of increasing reactivity with increasing alkyl chain lengths.23
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Rate constants of DEE, MnPE and methyl iꢀpropyl ether (MiPE) reactions with OH
26,29
are in the order: kMiPE + OH < kMnPE + OH < kDEE + OH
.
From the comparison, we can
see that the symmetric ether, DEE, has largest rate constant and the asymmetric ether,
MiPE, has smallest rate constant, which probably means that branched chains will
decrease the reaction rate constant. The rate constant for OH reaction with ethyl
tꢀbutyl ether is nearly half of the rate constant of OH reaction with diethyl ether at
room temperature.39
Comparison of the rate constant for MnPE reaction with OH, (9.91 ± 2.30) × 10ꢀ12
cm3 moleculeꢀ1 sꢀ1, with the rate constant for butane reaction with OH, (2.71 ± 0.32) ×
10ꢀ12 cm3 moleculeꢀ1 sꢀ1,40 shows that the ꢀOCH3 group activates the CꢀH bond
towards OH abstraction more than the ꢀCH3 group. The CꢀH bonds in ethers are
significantly weaker than in corresponding alkanes. Owning to lower CꢀH bond
dissociation energies for a carbon bound to an ether oxygen, as expected, reactivity
toward OH is greatly enhanced.41 An analogous increase in the rate constant of OH
reaction with methyl vinyl ether due to ꢀCH3 substitution by ꢀOCH3 have been
observed.17 Such observations suggest that the ꢀCH2ꢀ groups in these molecules
display essentially similar reactivity, which are approximately a factor of 3 greater
than those observed in alkanes and not strongly dependent on their positions relative
to the oxygen atom. The oxygen atom has an activating effect which is operative over
long distances in aliphatic ether systems.42
3.1.2. Rate Constant of MnPE with NO3
The plots of rate constants of MnPE reaction with NO3 using propene, tetrahydrofuran
and acetaldehyde as reference compounds are shown in Figure 3, and numerical
values of these rate constants have been determined to be (in units of cm3 moleculeꢀ1
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sꢀ1): (9.45 ± 0.47) × 10ꢀ15 for propene, (5.10 ± 0.20) × 10ꢀ15 for tetrahydrofuran and
(2.60 ± 0.30) × 10ꢀ15 for acetaldehyde.43ꢀ45 For each reference compound, the
measurement was repeated three times under different initial concentration ratios of
MnPE and reference compounds. The obtained rate constants for MnPE with NO3 are
summarized in Table 2. The rate constant obtained after averaging the values from
different experiments was found to be kMnPE + NO3 = (1.67 ± 0.32) × 10ꢀ15 cm3
moleculeꢀ1 sꢀ1.
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In the literature, the rate constant for DME react with NO3 was studied using a flash
photolysis technique.19 The obtained value (3 × 10ꢀ15 cm3 moleculeꢀ1 sꢀ1) is
significantly larger than those values in other previous studies.21,25 The room
temperature rate constant for the reaction of DEE with NO3 has been reported with
relative method. Comparing the rate constant with available data for NO3 reaction
with DME and MEE,21,25 we found that rate constants are in the order: kDME + NO3
<
kMEE + NO3 < kMnPE + NO3. The rate constant for NO3 reaction with MEE is over two
times for NO3 reaction with DME. The rate constant of MnPE reaction with NO3 is
also over two times for NO3 reaction with MEE. The rate constant for NO3 reaction
with MnPE is significantly larger than the rate constant of NO3 reaction with butane
(2.71 ± 0.32) × 10ꢀ12.40 The abstraction in ethers primary CꢀH and secondary CꢀH has
low activation energy compared to the abstraction in alkanes. This lowering of the
activation energy may be explained by the decrease in the CꢀH bond dissociation
energy going from an ordinary carbon to a carbon bonded to an ether ꢀOꢀ group.21
3.1.3. Rate Constant of MnPE with Cl
SOCl2 and CCl3C(O)Cl were used as the chlorine source, and Cl atoms were
generated by in situ photolysis of SOCl2 or CCl3C(O)Cl, while cyclohexane and
propene were used as reference compounds. The rate constants of the reactions of Cl
with the references have been reported to be (in units of cm3 moleculeꢀ1 sꢀ1): (36.1 ±
1.5) × 10ꢀ11 for cyclohexane,22 (32.2 ± 1.3) × 10ꢀ11 for propene.46 For each reference
compound, the measurement was repeated five times under different initial
concentration ratios of MnPE and reference compounds. The loss of MnPE is plotted
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against the loss of the reference compounds in Figure 4.
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The obtained rate constants of MnPE reaction with Cl are summarized in Table 2.
Average rate constants when using SOCl2 or CCl3C(O)Cl are (2.51 ± 0.14) × 10ꢀ10 and
(2.53 ± 0.14) × 10ꢀ10 cm3 moleculeꢀ1 sꢀ1, respectively. The difference in rate constants
from the two precursors is very tiny. While averaging the values from different
experiments, the rate constant was kMnPE + Cl = (2.52 ± 0.14) × 10ꢀ10 cm3 moleculeꢀ1 sꢀ1.
There are some previous reports of the kinetics between DME and Cl atom.18,22,29,47ꢀ49
In addition, the kinetics of MEE with Cl has been carried out at (297 ± 2) K in the gas
phase using FTꢀIR/relativeꢀrate methods.23 The difference between rate constants of
Cl reaction with DME, MEE and MnPE are small. These rate constants are close to
collision controlled and it is possible that in this regime, substitution on the carbon
chain induces very little changes in reaction rate constants.50 Similar reason can
explain why the rate constant for Cl reaction with MnPE differs very weakly from that
of Cl reaction with butane, (2.11 ± 0.18) × 10ꢀ10 cm3 moleculeꢀ1 sꢀ1.51
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Comparison of the reactivity of the three oxidants towards MnPE shows that the rate
constant for the reaction with Cl is larger than those of reactions with OH (by two
orders of magnitude) and NO3 (by five orders of magnitude). It is important to
mention that rate constants for Cl reactions are close to the gas kinetics limited value
from gas collision theory, which means that the reaction probability is high regardless
of collision site and that chemical structure plays a limited role in determining the
reaction rate constant.6,50 Overall, the presence of oxygen atom in the ether linkage
has been shown to exhibit an activating effect, which is operative up to the distance of
5 carbon atoms away from the linkage. This suggests reasons that ethers are more
reactive than corresponding alkanes for OH, NO3, and Cl attacks.24
3.2. Reaction Mechanism
Seven main products were identified for the reaction of MnPE with OH radical as
shown in Scheme 1: CH3OCH2CH2CHO (14), CH3OCH2C(O)CH3 (15),
CH3OOCCH2CH3 (16), CH3CH2CH2OCHO (18), CH3CHO (21), CH3OCH3CHO (24)
and CH3OCHO (26). From the proposed mechanism shown in Scheme 1, it is seen
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that Hꢀatom is abstracted by the OH radical from the two primary and two secondary
CꢀH bonds in the molecule. The observed products, upon which the proposed
reactions are based, are highlighted in boxes in Scheme 1. Some analogous products,
such as CH3C(O)OCH3, CH3CH2OCHO, CH3OCHO and CH3CHO, were detected in
the CH3CH2OCH3 reaction with Cl experiment using FTꢀIR.23
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Path 1 shows the reaction occurring after Hꢀatom abstraction by OH radical from the
primary CꢀH bond on the propyl side of MnPE. The initial carbonꢀcentred radical is
formed by Hꢀatom abstraction, followed by O2 addition to form the peroxy radical (6).
The peroxy radical (6) undergoes selfꢀreaction and cross reaction with other peroxy
radicals to mainly produce the alkoxy radical (10). The intermediate alkoxy radical
(10) further reacts with O2 to yield the corresponding 3ꢀmethoxypropanal (14). In
addition, the alkoxy radical has been shown to undergo direct hydrogen atom
elimination which would yield the same end products.47 An additional decomposition
pathway leads to the formation of formaldehyde (19) and the alkoxy radical (20).
Path 2 shows the proposed reactions following Hꢀatom abstraction from the CH2
group which is far away from the methoxy group. The intermediate alkoxy radical (11)
decomposes mainly via the rupture of CꢀC bond to form methoxyacetaldehyde (24)
and methyl radical (27). The alkoxy radical (11) reacts with oxygen, leading to
1ꢀmethoxyacetone (15). Alternatively, the alkoxy radical (11) may decompose via
breakage of the CꢀC bond, yielding acetaldehyde (21) and alkoxy radical (22). Besides,
the 1,5ꢀhydrogen shift (Hꢀshift) is possible for the H abstraction at βꢀCH2 group. As a
further possibly important reaction, alkoxy radical (11) is expected to undergo
isomerization via 1,5ꢀH shift by abstracting an H atom from the primary CꢀH in the
methyl group of the ether. The resulting organic radical (29) leads most likely to the
formation of alkoxy radical (30) and formaldehyde (19) via breakage of the CꢀC bond.
Similar to the alkoxy radical [CH3CH2OCH2(O▪)] derived from formate,23 alkoxy
radical (11) is proposed to undergo reaction with oxygen leading to the organic
formate (31).
Path 3 shows the proposed reactions following Hꢀatom abstraction from the CH2
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group which is close to the methoxy group. The alkoxy radical (12) decomposes
through rupture of CꢀC bond to form the products, methyl formate (26) and ethyl
group (25). By analogy with forming 1ꢀmethoxyacetone (15), the alkoxy radical (12)
reacts with oxygen to generate methyl propanoate (16). The alternative decomposition
reaction would lead to propyl aldehyde (17) and methoxy radical (28).
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In path 4, the OH attack occurs on the methyl group of the methoxy side chain. The
resulting alkoxy radical (13) may react with oxygen to form propyl formate (18), or
decompose to form formaldehyde (19) and alkoxy radical (23). By analogy with
alkoxy radicals (10) derived from methyl ether [CH3OCH2(O▪)], the alkoxy radical
(13) is proposed to mainly undergo reaction with oxygen or CꢀH bond fission, leading
to alkoxy radical (23) and formaldehyde (19).
Overall the proposed mechanisms reasonably give observed products. Furthermore,
the proposed reaction mechanisms for the formation of the major products are based
entirely on the established gas phase reactions. Carbonyl compounds such as
aldehydes, ketones, and esters are first generation products from MnPE reactions. The
branching ratios for the different paths contributing to the overall reaction of MnPE
with OH were investigated with variational transition state theory.26 The overall rate
constants percentage for paths 1, 2, 3 and 4 were reported to contribute for 0.73%,
10.65%, 57.98% and 30.64% to the MnPE + OH reaction at 298.15 K, respectively.26
From branching ratios, we can see that the presence of the O atom in the vicinity of
the H abstraction site increases its reactivity toward OH radicals. This influence was
found to be even larger than that of the nature of the carbon site (primary, secondary,
tertiary).26
Methyl propanoate (16) and propyl formate (18) were detected for the reaction of
MnPE with Cl, and product (16) was also identified in the MnPE + NO3 reaction. The
three types of CꢀH groups in the MnPE molecule would lead to the formation of three
structurally different types of oxy radicals: type I [CH2(O▪)OCH2CH2CH3 or
CH3OCH(O▪)CH2CH3] has an alkoxy substituent in the αꢀposition relative to the
radical center; type II [CH3OCH2CH(O▪)CH3], derived from the propyl side, has an
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alkoxy substituent in the βꢀposition relative to the radical center; whereas type III
[CH3OCH2CH2CH2(O▪)] has an alkoxy substituent in the γꢀposition relative to the
radical center. In general, the OHꢀinitiated oxidation of ethers is believed to generate
mainly oxy radicals of type I.52 Analogous to the CH3OCH2CH3 and
CH3CH2OCH2CH3, CꢀH bonds at the α sites are weaker than the CꢀH bonds at the β
sites.25 For the same reason, we believe that by attacking MnPE on CꢀH at the
αꢀposition, reactions with Cl or NO3 are the dominant initial processes. These
reactions lead to the formation of the major product in the process, methyl propanoate
(16). Scheme S1 in the supporting information shows a general mechanism proposed
for the reaction of MnPE with the three atmospheric oxidants: OH, NO3 radicals and
Cl atoms.
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3.3. Atmospheric Implications
Ethers are released into the atmosphere from biogenic and anthropogenic sources and
are degraded in the troposphere almost exclusively via their reactions with OH, NO3
radicals and Cl atoms. Accurate kinetic data and mechanistic information, at
atmospheric temperatures, for the reactivity of OH, NO3, and Cl toward VOCs are
needed in order to determine the lifetimes of these compounds in the troposphere and
assess their impact on urban air pollution. In particular, tropospheric lifetimes with
respect to reactions with oxidants are key parameters in calculating the ozone
formation potential of VOCs.53
Atmospheric lifetimes (τ) of the studied MnPE based on its reactions with
atmospheric oxidants, are calculated using equation (6) below,
ꢫ
ꢪꢁ = ꢬ
(6)
ꢑꢁꢒ
ꢭ
where [X] is the concentration of the oxidant and kx is the reaction rate constant. The
calculated atmospheric lifetimes are presented in Table 4. Oxidants concentrations
considered in this study were as follow: 12 h average day time global concentration of
OH of 1 × 106 molecules cmꢀ3 (global weightedꢀaverage concentration), 24 h average
of Cl atom concentration of 5 × 103 molecules cmꢀ3 or the concentration in the marine
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boundary layer of 1 × 105 molecules cmꢀ3 and 12 h average night time concentration
of NO3 of 5 × 108 molecules cmꢀ3.54ꢀ58
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These results indicate that in the atmosphere, the degradation of MnPE is mainly due
to reaction with OH, since the calculated lifetime is 28 h. The lifetime of MnPE due to
reaction with NO3 is ten times higher than that due to reaction with OH. The reaction
with NO3 during night time may be negligible for MnPE at ambient conditions. The
MnPE lifetime due to reaction with Cl was estimated to be 220 h. However, it should
be noted that in the coastal areas and in the marine boundary layer, the concentration
of Cl atoms can be as high as 1 × 105 atoms cmꢀ3,55 making the Hꢀatom abstraction by
Cl atom an additional and possibly significant degradation pathway of MnPE. In the
marine boundary layer, this process could compete with the reaction with OH.
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CONCLUSION
In the light of our results, the kinetic and mechanistic data for reactions of methyl
nꢀpropyl ether (MnPE) with OH, NO3 and Cl are presented. Using the relative rate
method, the rate constants for MnPE reaction with OH, NO3 and Cl were determined
to be (9.91 ± 2.30) × 10ꢀ12, (1.67 ± 0.32) × 10ꢀ15 and (2.52 ± 0.14) × 10ꢀ10 cm3
moleculeꢀ1 sꢀ1, respectively. The obtained data show that MnPE reaction with Cl is
faster than those with OH and NO3. Reactions with the three oxidants mainly lead to
the formation of some esters and aldehydes, which are pollutants involved in
photochemical smog and likely to affect health. Formation mechanisms are proposed
for the observed reaction products. Atmospheric lifetimes of MnPE were calculated
with respect to reactions with OH/NO3/Cl using corresponding rate constants at room
temperature. The obtained lifetimes indicate that reaction with OH is the major
degradation process for MnPE in the atmosphere, while reaction with Cl becomes a
significant removal process only in the marine boundary layer.
ASSOCIATED CONTENT
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Supporting Information
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General mechanism proposed for the reaction of MnPE with the three atmospheric
oxidants: OH, NO3 and Cl.
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ACKNOWLEDGMENTS
This work was supported by the National Natural Science Foundation of China
(91644214) and Shenzhen Science and Technology Research and Development Funds,
China (JCYJ20150402105524052).
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1175ꢀ1186.
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3057ꢀ3063.
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Oxidation of heterocycles in the atmosphere: kinetic study of their reactions with NO3
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Berkowitz, C., Unexpectedly high concentrations of molecular chlorine in coastal air.
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2649ꢀ2654.
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Table 1. Reactant concentrations, for the kinetic experiments and the product evaluation for the
reactions of OH, NO3 and Cl with MnPE at 293 ± 2 K and atmospheric pressure
Reactants
Concentration
ppm
1015 molecules cmꢀ3
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Kinetics experiments
MnPE
57.8ꢀ115.6
377.6
1.4ꢀ2.8
9.3
H2O2
N2O5
283.0ꢀ424.5
256.9
7.0ꢀ10.4
6.3
SOCl2
CCl3C(O)Cl
Cyclohexane
Propylene
Furan
142.8
3.5
58.1ꢀ116.2
62.5ꢀ147.6
80.9ꢀ161.8
76.4ꢀ152.8
97.2ꢀ194.5
1.4ꢀ2.9
1.5ꢀ3.6
2.0ꢀ4.0
1.9ꢀ3.8
2.4ꢀ4.8
Tetrahydrofuran
Acetaldehyde
Products experiments
MnPE
H2O2
57.8
1.4
377.6
8.3
N2O5
283.0ꢀ424.5
256.9
7.0ꢀ10.4
6.3
SOCl2
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Table 2. Summary of rate constants for the reaction of MnPE with OH, NO3, and Cl at 293 ± 2 K and
atmospheric pressure of air
Oxidant Reference
kMnPE
kMnPE (average)
cm3 moleculeꢀ1 sꢀ1
(9.91 ± 2.30) × 10ꢀ12
cm3 moleculeꢀ1 sꢀ1
(10.03 ± 1.39) × 10ꢀ12
(9.82 ± 2.50) × 10ꢀ12
(9.88 ± 3.00) × 10ꢀ12
(2.51 ± 0.15) × 10ꢀ10
(2.51 ± 0.13) × 10ꢀ10
(2.55 ± 0.15) × 10ꢀ10
(2.50 ± 0.13) × 10ꢀ10
(2.08 ± 0.47) × 10ꢀ15
(1.33 ± 0.20) × 10ꢀ15
(1.61 ± 0.30) × 10ꢀ15
OH
Cl
Cyclohexane
Propene
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Furan
Cyclohexane a
Propene a
(2.52 ± 0.14) × 10ꢀ10
(1.67 ± 0.32) × 10ꢀ15
Cyclohexane b
Propene b
NO3
Propene
Tetrahydrofuran
Acetaldehyde
a SOCl2 as Cl atoms precursor.
b CCl3C(O)Cl as Cl atoms precursor.
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Table 3. Rate constant for the reaction of OH, NO3 radicals and Cl atom with selected short chain ethers
Compound
kOH a × 10ꢀ12
3.50 ± 0.35 17
2.95 ± 0.12 41
2.49 ± 0.22 42
2.32 ± 0.23 36
2.35 ± 0.24 29
3.19 ± 0.70 29
2.82 ± 0.21 53
2.95 ± 0.21 59
2.86 60
T, K
Method b
FPꢀRF
LPꢀLIF
FPꢀRF
RR
kCl a × 10ꢀ10
T, K
Method b kNO3 a×10ꢀ15
T, K
298 ± 2 FP
Method b
CH3OCH3
298.9
295
1.80 ± 0.09 18
2.05 ± 0.08 22
300
FPꢀRF
RR
3 19
0.26 ± 0.11 21
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Dimethyl ether (DME)
295 ± 2
295
RR
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296
295
1.51 ± 0.08 29
1.90 ± 0.10 47
1.30 ± 0.20 48
1.58 ± 0.14 49
298 ± 2
298
RR
0.11 ± 0.01 25
298
RR
298 ± 2
298 ± 2
298
PR
RR
PRR
298 ± 2
299.8
LPꢀRF
RR
PLPꢀLIF
LPꢀLIF
RR
295
298
2.67 ± 0.7 61
2.58 ± 0.75 62
298
PLPꢀLIF
PLPꢀLIF
RR
298
+3.72 24
CH3OCH2CH3
6.87ꢀ2.40
301
3.18 ± 0.34 24
2.35 ± 0.43 23
3.56 ± 0.28 22
303
RR
RR
RR
0.78 ± 0.036 25 298
RR
RR
Methyl ethyl ether (MEE)
CH3CH2OCH2CH3
Diethyl ether (DEE)
7.53 ± 2.86 23
9.4 ± 1.9 20
13.4 ± 0.6 41
13.6 ± 0.9 42
12.0 ± 1.1 38
10.0 ± 0.18 39
11.3 ± 0.10 29
12.8 ± 0.6 29
12.4 ± 1.15 63
13.6 ± 1.1 53
9.91 ± 2.30 c
12.3 26
297 ± 2
305 ± 2
295
FTꢀIR/RR
RR
297 ± 2
295 ± 2
2.80 ± 0.23 21
295
LPꢀLIF
FPꢀRF
RR
296
2.54 ± 0.17 29
2.58 ± 0.44 15
2.50 ± 0.30 48
298 ± 2
300 ± 3
298 ± 2
RR
3.1 ± 1.0 64
2.80 ± 0.10 25
298 ± 2 RR
298 RR
294 ± 2
294
RR
RR
LPꢀRF
298 ± 2
298 ± 2
298
PR
PRR
RR
298
PLPꢀLIF
RR
CH3OCH2CH2CH3
295 ± 2
298.15
2.52 ± 0.14 c
295 ± 2
RR
1.67 ± 0.32 c
295 ± 2 RR
Methyl nꢀpropyl ether (MnPE)
Theory
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CH3OCH(CH3)2
7.09 26
298.15
Theory
Methyl iꢀpropyl ether (MiPE)
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CH3OCH2CH2CH2CH3
16.4 ± 0.6 65
12.9 ± 0.3 36
15.0 ± 1.2 63
298
295
298
FPꢀRF
RR
Methyl nꢀbutyl ether (MnBE)
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RR
a Rate constant in units (cm3 moleculeꢀ1 sꢀ1).
b FPꢀRF, flashꢀphotolysisꢀresonance fluorescence; LPꢀLIF, laser photolysisꢀlaser induced fluorescence; PR, Pulseꢀradiolysis; PRR, photolytic relative rate; PLPꢀLIF,
pulseꢀlaser photolysisꢀlaser induced fluorescence; LPꢀRF, laser photolysisꢀresonance fluorescence.
c This work.
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Table 4. Atmospheric lifetimes for the reaction of MnPE with OH, NO3 radicals and Cl atom
Compound
τOHa (h)
τClb (h)
τClc (h)
τNO3d (h)
332.67
MnPE
28.03
220.46
11.02
a 12 h average day time global concentration of OH of 1 × 106 molecules cmꢀ3.
b 24 h average of Cl atom concentration of 5 × 103 molecules cmꢀ3.
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c Cl atom concentration in the marine boundary layer of 1 × 105 molecules cmꢀ3.
d 12 h average night time concentration of NO3 of 5 × 108 molecules cmꢀ3.
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Figure 1. Schematic diagram of the 100 L chamber used to study the reaction of OH, NO3 and Cl
with MnPE along with the analytical methods used to detect reactants and products.
Figure 2. Relative rate plots for OH reactions with MnPE, using cyclohexane (■), propene (●) and
furan (▲) as reference compounds.
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Figure 3. Relative rate plots for NO3 reactions with MnPE, using propene (■), tetrahydrofuran (●)
and acetaldehyde (▲) as reference compounds.
Figure 4. Relative rate plots for Cl reactions with MnPE, using cyclohexane (triangle) and propene
(circle) as reference compounds. Solid symbols represent CCl3C(O)Cl as the Cl source and empty
symbols represent SOCl2 as the Cl source.
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