Environ. Sci. Technol. 1998, 32, 2106-2112
Products of the Gas-Phase Reactions of a Series of Methyl-Substituted Ethenes with the OH Radical
SCHEME 1
ERNESTO C. TUAZON, SARA M. ASCHMANN, JANET AREY,† AND R O G E R A T K I N S O N * ,† Air Pollution Research Center, University of California, Riverside, California 92521
reactions of the OH radical with alkenes have been studied previously (4, 5, 8). While the kinetics of these OH radical reactions are now reasonably well understood for a large number of alkenes (4, 5, 8), for acyclic alkenes product studies have only been carried out for a few simple compounds at room temperature and atmospheric pressure of air (5, 9-20). The gas-phase reactions of the OH radical with alkenes proceed mainly by initial addition of the OH radical to the >CdC< bond(s) to form β-hydroxyalkyl radicals (5), which in the troposphere rapidly add O2 to form the corresponding β-hydroxyalkyl peroxy radicals (5). In the presence of NO, β-hydroxyalkyl peroxy radicals react to form either the β-hydroxynitrate or the β-hydroxyalkoxy radical plus NO2 (5). For example, for the β-hydroxybutyl peroxy radical formed after internal OH radical addition to 1-butene:
Alkenes are a significant component of ambient air in urban areas, and in the atmosphere they react with OH radicals, NO3 radicals, and O3, with the OH radical reaction often dominating as the tropospheric removal process. Products of the gas-phase reactions of the OH radical with 2-methylpropene, cis-2-butene, 2-methyl-2-butene, and 2,3dimethyl-2-butene in the presence of NO have been investigated at room temperature and 740 Torr total pressure of air by gas chromatography with flame ionization detection, in situ Fourier transform infrared absorption spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry (API-MS). For all four alkenes, hydroxynitrate formation from the β-hydroxyalkyl peroxy radical plus NO reaction accounted for ∼10% of the overall products observed, with decomposition of the intermediate β-hydroxyalkoxy radical dominating over the alternative reaction with O2 (isomerization via a six-member transition state is not possible for any of the intermediate β-hydroxyalkoxy radicals formed in these reactions) and leading to the formation of the carbonyls expected from >Cd C< bond cleavage in ∼90% yield each. These data are consistent with estimates of the rates of the various reactions of β-hydroxyalkoxy radicals under atmospheric conditions. API-MS analyses of the OH radical-initiated reactions of propene, 2-methylpropene, cis- and trans-2-butene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene in the absence of NO indicated the formation of the hydroxyhydroperoxides, dihydroxyalkanes, and hydroxycarbonyls expected from the reactions of intermediate β-hydroxyalkyl peroxy radicals with HO2 and organic peroxy radicals, in addition to the carbonyl compounds formed from decomposition of the β-hydroxyalkoxy radicals also formed from the peroxy plus peroxy radical reactions.
Introduction Alkenes are a significant component of ambient air in urban areas (1-3), and in the atmosphere they react with OH radicals, NO3 radicals, and O3 (4, 5) with the daytime OH radical reaction often dominating as the tropospheric removal process (6, 7). The kinetics and products of the gas-phase * To whom correspondence should be addressed. Also Department of Chemistry, University of California, Riverside, CA 92521. † Also at the Environmental Toxicology Graduate Program and Department of Environmental Sciences, University of California, Riverside, California 92521. 2106
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ENVIRONMENTAL SCIENCE & TECHNOLOGY / VOL. 32, NO. 14, 1998
(1a) (1b) At low NO concentrations or in the absence of NO, the β-hydroxyalkyl peroxy radicals are expected to react with HO2 radicals and organic peroxy radicals (including the selfreaction) (5).
(2a) (2b) (3a) (3b) The β-hydroxyalkoxy radicals formed from the reactions of the β-hydroxyalkyl peroxy radicals with NO (reaction 1b) and with RO˙ 2 radicals (reaction 3b) then react with O2, decompose, or isomerize via a six-member transition state (5, 18, 20, 21). These alkoxy radical reactions are illustrated in Scheme 1 for the CH3CH2CH(OH)CH2O˙ radical formed after internal OH radical addition to 1-butene (note that the CH3CH2CH(O˙ )CH2OH radical formed after terminal OH radical addition to 1-butene cannot undergo isomerization via a six-member transition state). The R-hydroxyalkyl radicals formed in the decomposition pathway react rapidly with O2 to form the corresponding carbonyl compound (4, 5), as shown for the CH3CH2C˙ HOH radical formed in Scheme 1.
CH3CH2C˙ HOH + O2 f CH3CH2CHO + HO2
(4)
The alkoxy radical O˙ CH2CH2CH(OH)CH2OH formed after the isomerization reaction in Scheme 1 is predicted to undergo a further isomerization, eventually leading to the dihydroxycarbonyl product HOCH2CH2CH(OH)CHO (5, 20, 21). Previous studies have shown that, at room temperature and atmospheric pressure of air containing NO, the HOCH2S0013-936X(98)00153-9 CCC: $15.00
1998 American Chemical Society Published on Web 05/30/1998
CH2O˙ radical formed from OH radical addition to ethene reacts with O2 and decomposes (10), while the β-hydroxyalkoxy radicals formed from propene, 1-butene, and trans2-butene predominantly decompose (9, 11). However, the carbonyl products observed and quantified from the OH radical reactions with isoprene (13, 14, 17) and 1-butene through 1-octene (15, 18) suggest that decomposition of the intermediate β-hydroxyalkoxy radicals is not the sole process and that other reaction pathways, including isomerization (20, 21), must be occurring. Indeed, Kwok et al. (20), employing atmospheric pressure ionization mass spectrometry to study the products of the OH radical-initiated reactions of 1-butene through 1-octene, observed the formation of Cn-dihydroxycarbonyls from the Cn-1-alkene reactions and hence obtained direct evidence for isomerization of the β-hydroxyalkoxy radicals involved. Atkinson (21) has used the literature product data for the alkanes and alkenes to propose methods to calculate the reaction rates of alkoxy and β-hydroxyalkoxy radicals under tropospheric conditions, and these estimation methods predict that decomposition of the β-hydroxyalkoxy radicals will dominate over their reaction with O2 at around room temperature and atmospheric pressure of air (21). In this work, we have used gas chromatography with flame ionization detection (GC-FID), in situ Fourier transform infrared (FT-IR) absorption spectroscopy, and in situ atmospheric pressure ionization tandem mass spectrometry (APIMS) to investigate the products formed from the reactions of the OH radical with the methyl-substituted ethenes propene, 2-methylpropene, cis- and trans-2-butene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene at 297 ( 2 K and 740 Torr total pressure of air.
Experimental Section Experiments were carried out in a 5800 L evacuable, Tefloncoated chamber containing an in situ multiple reflection optical system interfaced to a Nicolet 7199 Fourier transform infrared (FT-IR) absorption spectrometer and with irradiation provided by a 24 kW xenon arc filtered through a 0.25 in. thick Pyrex pane (to remove wavelengths 300 nm (13, 18, 22):
RCH2ONO + hν f RCH2O˙ + NO
(5)
RCH2O˙ + O2 f RCHO + HO2
(6)
HO2 + NO f OH + NO2
(7)
where R ) H or CH3. NO was added to the reactant mixtures to suppress the formation of O3 and hence of NO3 radicals (22). Experiments were carried out in the 7900 L Teflon chamber for GC-FID measurements of the formation yields of carbonyls other than HCHO (18, 23) and in the 5800 L evacuable, Teflon-coated chamber for FT-IR absorption spectroscopic determination of the HCHO (and other carbonyl) formation yields (18, 23). Because HCHO is the primary photolytic product of methyl nitrite (see above), the photolysis of ethyl nitrite in air was used as the OH radical source for the determination of HCHO formation yields in
the 5800 L evacuable chamber (13,18). In the 6500 and 7900 L Teflon chambers with analyses by GC-FID and API-MS, OH radicals were generated by the photolysis of CH3ONO in air. Additional experiments were carried out in the 6500 L Teflon chamber with API-MS analyses in which OH radicals were generated in the absence of NO from the reaction of O3 with the alkene being studied (24). Teflon Chamber with Analysis by GC-FID. For the experiments carried out in the 7900 L Teflon chamber, the initial reactant concentrations (in molecules per cubic centimeter units) were CH3ONO, (1.85-2.25) × 1014; NO, (1.95-2.30) × 1014; and alkene, (2.28-2.50) × 1013. Irradiations were carried out at 20% of the maximum light intensity for 1-6 min. The concentrations of the alkenes and the carbonyl (apart from HCHO) products were measured during the experiments by GC-FID as described previously (23). Evacuable Chamber with Analysis by FT-IR Absorption Spectroscopy. The initial concentrations of the alkenes, methyl or ethyl nitrite, and NO in the experiments with FTIR absorption spectroscopic analyses in the 5800 L evacuable chamber were (2.4-4.8) × 1014 molecule cm-3, 2.4 × 1014 molecule cm-3, and (1.8-2.4) × 1014 molecule cm-3, respectively. Intermittent irradiations of 0.5-1.0 min duration were carried out with analysis by FT-IR spectroscopy during the dark periods, with 64 coadded interferograms (scans)/ spectrum (1.8 min measurement time) recorded with a full width at half-maximum (fwhm) resolution of 0.7 cm-1 and a path length of 62.9 m (23). FT-IR absorptions of the alkenes were obtained by measuring known partial pressures of the gaseous compound into a 5.25 L Pyrex bulb with an MKS Baratron 0-100 Torr sensor and flushing the contents of the bulb into the 5800 L chamber with FT-IR detection of the authentic compound. IR reference spectra of the products measured were available from previous IR calibrations in this laboratory (23). Teflon Chamber with Analysis by API-MS. In the experiments with API-MS analyses, the chamber contents were sampled through a 25 mm diameter × 75 cm length Pyrex tube at ∼20 L min-1 directly into the API mass spectrometer source. The operation of the API-MS in the MS (scanning) and MS/MS [with collision activated dissociation (CAD)] modes has been described elsewhere (19, 20, 25). Use of the MS/MS mode with CAD allows the “daughter ion” or “parent ion” spectrum of a given ion peak observed in the MS scanning mode to be obtained (19, 20, 25). The positive ion mode was used in these API-MS and API-MS/MS analyses, with protonated water hydrates [H3O+(H2O)n] generated by the corona discharge in the chamber diluent gas being responsible for the protonation of analytes.
H3O+(H2O)n + M f MH+(H2O)m + (n - m + 1)H2O (8) Ions are drawn by an electric potential from the ion source through the sampling orifice into the mass-analyzing first quadrupole or third quadrupole. For these experiments, the API-MS instrument was operated under conditions that favored the formation of dimer ions in the ion source region (25). Neutral molecules and particles are prevented from entering the orifice by a flow of high-purity nitrogen (“curtain” gas), and as a result of the declustering action of the curtain gas on the hydrated ions, the ions that are mass analyzed are mainly protonated molecular ions ([M + H]+) and their protonated homo- and heterodimers (25). For the reactions of 2-methylpropene, cis-2-butene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene carried out in the presence of NO, OH radicals were generated by the photolysis of methyl nitrite. The initial concentrations of CH3ONO, NO, and alkene were ∼4.8 × 1013 molecule cm-3 each, and irradiations were carried out for 1-2 min at 20% of the maximum light intensity. For reactions carried out in VOL. 32, NO. 14, 1998 / ENVIRONMENTAL SCIENCE & TECHNOLOGY
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TABLE 1. Products and Their Formation Yields Observed from the Reactions of the OH Radical with Alkenes in the Presence of NO at 296 ( 2 K and 740 Torr Total Pressure of Air formation yield
alkene 2-methylpropene
product
acetone formaldehyde hydroxynitrate cis-2-butene acetaldehyde hydroxynitrate 2-methyl-2-butene acetaldehyde acetone
2,3-dimethyl-2butene
FIGURE 1. Plots of the amounts of acetone formed, corrected for reaction with the OH radical, against the amounts of 2-methylpropene and 2,3-dimethyl-2-butene reacted with the OH radical in the presence of NO, with analyses by GC-FID. the absence of NO, OH radicals were generated by the dark reaction of O3 with the alkene (24), with the initial concentration of the alkene being ∼4.8 × 1013 molecule cm-3 and with two additions of 50 cm3 volume of O3 in O2 diluent (each addition corresponding to an initial concentration of O3 in the chamber of ∼6 × 1012 molecule cm-3) being made to the chamber during an experiment. The alkenes studied in the experiments in the absence of NO also included propene and trans-2-butene. Chemicals. The chemicals used (acetaldehyde, acetone, cis-2-butene, trans-2-butene, 2,3-dimethyl-2-butene, 2-methyl-2-butene, 2-methylpropene, propene, and NO) were all of g99.0% stated purity. Methyl nitrite was prepared as described by Taylor et al. (26), and ethyl nitrite was distilled from a commercial 15% (by weight) solution of C2H5ONO in ethanol (Aldrich Chemical Co.), and both nitrites were stored at 77 K under vacuum. O3 in O2 diluent was prepared as needed using a Welsbach T-408 ozone generator.
GC-FIDa
FT-IRb
0.78 ( 0.06
0.90 ( 0.07 0.92 ( 0.08 ∼0.09c 1.58 ( 0.12 ∼0.06c 0.84 ( 0.10 0.81 ( 0.08
1.85 ( 0.25 0.98 ( 0.10 0.92 ( 0.09d 0.88 ( 0.07d 0.90 ( 0.08e
hydroxynitrate acetone 1.70 ( 0.17 hydroxynitrate
∼0.13c 1.60 ( 0.15 ∼0.07c
a Indicated errors are two least-squares standard deviations combined with estimated overall uncertainties in the GC-FID response factors for the alkene and carbonyl products of (5% each. b Indicated errors are two least-squares standard deviations combined with the errors arising from FT-IR measurement uncertainties due to errors in calibrations and in the subtractive method of spectral analysis of (4% each for the products and alkenes, except for 2-methyl-2-butene which has an estimated (6% uncertainty. c The hydroxynitrate yields have estimated uncertainties of (35% (see text). d Independent sets of experiments, each with separately measured GC-FID calibration factors. e For combined data sets.
Results Reactions in the Presence of NO. Teflon Chamber with GC-FID Analyses. GC-FID analyses showed the formation of acetone from the OH radical-initiated reactions of 2-methylpropene, 2-methyl-2-butene, and 2,3-dimethyl-2-butene and of acetaldehyde from the reactions of cis-2-butene and 2-methyl-2-butene. Because the carbonyl products react with the OH radical (4, 8), secondary reactions of the products with the OH radical were taken into account as described previously (27), using the recommended OH radical reaction rate constants for the alkenes and carbonyl products (4, 5, 8). Corrections to the measured carbonyl compound concentrations to take into account secondary reactions were