RESUMEN
The mechanism for hydrocarbon ring growth in sooting environments is still the subject of considerable debate. The reaction of phenyl radical (C6H5) with propargyl radical (H2CCCH) provides an important prototype for radical-radical ring-growth pathways. We studied this reaction experimentally over the temperature range of 300-1000 K and pressure range of 4-10 Torr using time-resolved multiplexed photoionization mass spectrometry. We detect both the C9H8 and C9H7 + H product channels and report experimental isomer-resolved product branching fractions for the C9H8 product. We compare these experiments to theoretical kinetics predictions from a recently published study augmented by new calculations. These ab initio transition state theory-based master equation calculations employ high-quality potential energy surfaces, conventional transition state theory for the tight transition states, and direct CASPT2-based variable reaction coordinate transition state theory (VRC-TST) for the barrierless channels. At 300 K only the direct adducts from radical-radical addition are observed, with good agreement between experimental and theoretical branching fractions, supporting the VRC-TST calculations of the barrierless entrance channel. As the temperature is increased to 1000 K we observe two additional isomers, including indene, a two-ring polycyclic aromatic hydrocarbon, and a small amount of bimolecular products C9H7 + H. Our calculated branching fractions for the phenyl + propargyl reaction predict significantly less indene than observed experimentally. We present further calculations and experimental evidence that the most likely cause of this discrepancy is the contribution of H atom reactions, both H + indenyl (C9H7) recombination to indene and H-assisted isomerization that converts less stable C9H8 isomers into indene. Especially at low pressures typical of laboratory investigations, H-atom-assisted isomerization needs to be considered. Regardless, the experimental observation of indene demonstrates that the title reaction leads, either directly or indirectly, to the formation of the second ring in polycyclic aromatic hydrocarbons.
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The unimolecular isomerisation of the prompt propargyl + propargyl "head-to-head" adduct, 1,5-hexadiyne, to fulvene and benzene by the 3,4-dimethylenecyclobut-1-ene (DMCB) intermediate (all C6H6) was studied in the high-pressure limit by threshold photoelectron (TPE) spectroscopy. TPE spectra (TPES) were recorded with photoelectron photoion coincidence spectroscopy using synchrotron vacuum ultraviolet radiation. Reference TPES, obtained using pure compounds or judiciously extracted from the pyrolysis data, served as basis functions for pyrolysis quantification. From these spectra, we measured a revised fulvene ionisation energy of 8.401 ± 0.005 eV. Temperature-dependent pyrolysis spectra were decomposed using these basis functions. The basis function coefficients were converted to product yields relying on assumed integral threshold photoionisation cross sections obtained by three, partially mutually exclusive sets of assumptions. Thus, the product yields of DMCB, fulvene, and benzene have been established, as well as their uncertainty. The derived mole fractions are consistent with modeling based on the C6H6 potential and RRKM master equation model of Miller and Klippenstein [J. Phys. Chem. A, 2003, 107, 7783]. Although our results are fully consistent with the parallel isomerisation pathways to benzene and fulvene found by Miller and Klippenstein, we observe the onset of fulvene at a lower temperature than that of the onset of benzene, in agreement with the master equation model but in contrast to the previous experiments of Stein et al. [Proc. Combust. Inst., 1990, 23, 85]. This work promotes the use of photoion mass-selected threshold photoelectron spectroscopy as a rapid, sensitive, isomer-selective, and quantitative detection tool among the panoply of established analytical techniques.
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Gas-phase reactions of the o-methylphenyl (o-CH3C6H4) radical with the C3H4 isomers allene (H2C[double bond, length as m-dash]C[double bond, length as m-dash]CH2) and propyne (HC[triple bond, length as m-dash]C-CH3) are studied at 600 K and 4 Torr (533 Pa) using VUV synchrotron photoionisation mass spectrometry, quantum chemical calculations and RRKM modelling. Two major dissociation product ions arise following C3H4 addition: m/z 116 (CH3 loss) and 130 (H loss). These products correspond to small polycyclic aromatic hydrocarbons (PAHs). The m/z 116 signal for both reactions is conclusively assigned to indene (C9H8) and is the dominant product for the propyne reaction. Signal at m/z 130 for the propyne case is attributed to isomers of bicyclic methylindene (C10H10) + H, which contains a newly-formed methylated five-membered ring. The m/z 130 signal for allene, however, is dominated by the 1,2-dihydronaphthalene isomer arising from a newly created six-membered ring. Our results show that new ring formation from C3H4 addition to the methylphenyl radical requires an ortho-CH3 group - similar to o-methylphenyl radical oxidation. These reactions characteristically lead to bicyclic aromatic products, but the structure of the C3H4 co-reactant dictates the structure of the PAH product, with allene preferentially leading to the formation of two six-membered ring bicyclics and propyne resulting in the formation of six and five-membered bicyclic structures.
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We investigated the reaction of O(3P) with cyclopentene at 4 Torr and 298 K using time-resolved multiplexed photoionization mass spectrometry, where O(3P) radicals were generated by 351 nm photolysis of NO2 and reacted with excess cyclopentene in He under pseudo-first-order conditions. The resulting products were sampled, ionized, and detected by tunable synchrotron vacuum ultraviolet radiation and an orthogonal acceleration time-of-flight mass spectrometer. This technique enabled measurement of both mass spectra and photoionization spectra as functions of time following the initiation of the reaction. We observe propylketene (41%), acrolein + ethene (37%), 1-butene + CO (19%), and cyclopentene oxide (3%), of which the propylketene pathway was previously unidentified experimentally and theoretically. The automatically explored reactive potential energy landscape at the CCSD(T)-F12a/cc-pVTZ//ωB97X-D/6-311++G(d,p) level and the related master equation calculations predict that cyclopentene oxide is formed on the singlet potential energy surface, whereas propylketene is first formed on the triplet surface. These calculations provide evidence that significant intersystem crossing can happen in this reaction not only around the geometry of the initial triplet adduct but also around that of triplet propylketene. The formation of 1-butene + CO is initiated on the triplet surface, with bond cleavage and hydrogen transfer occurring during intersystem crossing to the singlet surface. At present, we are unable to explain the mechanistic origins of the acrolein + ethene channel, and we thus refrain from assigning singlet or triplet reactivity to this channel. Overall, at least 60% of the products result from triplet reactivity. We propose that the reactivity of cyclic alkenes with O(3P) is influenced by their greater effective degree of unsaturation compared with acyclic alkenes. This work also suggests that searches for minimum-energy crossing points that connect triplet surfaces to singlet surfaces should extend beyond the initial adducts.
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We have used 308 nm photolysis of acetaldehyde to measure a photoionization spectrum of the formyl (HCO) radical between 8 and 11.5 eV using an 11 meV FWHM photoionization energy resolution. We have confirmed that the formyl radical is the carrier of the spectrum by generating an identical spectrum of the HCO product in the Cl + H2CO reaction. The spectrum of HCO and its deuterated isotopologue (DCO) have several resolved autoionizing resonances above the Franck-Condon envelope, which we assign to autoionization after initial excitation into neutral 3sσ and 3p Rydberg states converging to the first triplet excited state of HCO+(ã 3A'). The quantum defects for these states are δ3sσ = 1.06 ± 0.02 and δ3p = 0.821 ± 0.019. We report absolute photoionization cross-section measurements of σHCOPI(9.907 eV) = 4.5 ± 0.9 Mb, σHCOPI(10.007 eV) = 4.8 ± 1.0 Mb, σHCOPI(10.107 eV) = 6.0 ± 1.2 Mb, σHCOPI(10.107 eV) = 5.7 ± 1.2 Mb, and σHCOPI(10.304 eV) = 10.6 ± 2.2 Mb relative to the photoionization cross section of the methyl radical. The absolute cross-section measurements are a factor of â¼1.5 larger than those determined in past studies, although the presence of strong autoionizing features supports a dependence on photoionization energy resolution. We propose that the semiempirical model of Xu and Pratt for estimation of free radical photoionization cross sections is more accurate when applied with a reference species containing the same atoms as the free radical rather than isoelectronic species with different atoms.
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Product detection studies of the gas-phase oxidation of o-methylphenyl radicals and m-methylphenyl radicals are reported at ambient temperature (ca. 298 K) and 4 Torr (533.3 Pa) using VUV synchrotron photoionisation mass spectrometry. It is shown that cyclopentadienone (c-C5H4[double bond, length as m-dash]O) + CH3CO and o-quinone methide (o-CH2[double bond, length as m-dash]C6H4[double bond, length as m-dash]O) + OH are unique product pathways to the o-methylphenyl + O2 reaction due to mechanisms requiring the CH3 group to be adjacent to the phenyl radical site. Common product pathways include methylphenoxy radical + O(3P) and isomers of methylcyclopentadienone (CH3C5H4[double bond, length as m-dash]O) + HCO. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-methylphenyl and m-methylphenyl radical oxidation. The o-quinone methide formation mechanism from o-methylphenyl + O2 is analogous to the formation of o-benzoquinone from o-hydroxyphenyl + O2 where, after O2 addition, the ortho-substituent in the phenylperoxyl intermediate undergoes a 1,5-H shift and eliminates OH. Other reaction products, including methylcyclopentadienone species and methylphenyoxy radicals, are rationalised by applying known phenyl oxidation mechanisms. Transition state bifurcations are present in both radical systems and have exclusive end products (with different molecular mass). Compared to previous o-hydroxyphenyl and charged-tagged methylphenyl radical oxidation studies, there are significantly more products owing to the activation in this radical system and the competitiveness of rate limiting pathways.
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Methyl vinyl ketone (MVK) and methacrolein (MACR) are important intermediate products in atmospheric degradation of volatile organic compounds, especially of isoprene. This work investigates the reactions of the smallest Criegee intermediate, CH2OO, with its co-products from isoprene ozonolysis, MVK and MACR, using multiplexed photoionization mass spectrometry (MPIMS), with either tunable synchrotron radiation from the Advanced Light Source or Lyman-α (10.2 eV) radiation for photoionization. CH2OO was produced via pulsed laser photolysis of CH2I2 in the presence of excess O2. Time-resolved measurements of reactant disappearance and of product formation were performed to monitor reaction progress; first order rate coefficients were obtained from exponential fits to the CH2OO decays. The bimolecular reaction rate coefficients at 300 K and 4 Torr are k(CH2OO + MVK) = (5.0 ± 0.4) × 10-13 cm3 s-1 and k(CH2OO + MACR) = (4.4 ± 1.0) × 10-13 cm3 s-1, where the stated ±2σ uncertainties are statistical uncertainties. Adduct formation is observed for both reactions and is attributed to the formation of a secondary ozonides (1,2,4-trioxolanes), supported by master equation calculations of the kinetics and the agreement between measured and calculated adiabatic ionization energies. Kinetics measurements were also performed for a possible bimolecular CH2OO + CO reaction and for the reaction of CH2OO with CF3CHCH2 at 300 K and 4 Torr. For CH2OO + CO, no reaction is observed and an upper limit is determined: k(CH2OO + CO) < 2 × 10-16 cm3 s-1. For CH2OO + CF3CHCH2, an upper limit of k(CH2OO + CF3CHCH2) < 2 × 10-14 cm3 s-1 is obtained.
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The absolute photoionization spectrum of the hydroxyl (OH) radical from 12.513 to 14.213 eV was measured by multiplexed photoionization mass spectrometry with time-resolved radical kinetics. Tunable vacuum ultraviolet (VUV) synchrotron radiation was generated at the Advanced Light Source. OH radicals were generated from the reaction of O(1D) + H2O in a flow reactor in He at 8 Torr. The initial O(1D) concentration, where the atom was formed by pulsed laser photolysis of ozone, was determined from the measured depletion of a known concentration of ozone. Concentrations of OH and O(3P) were obtained by fitting observed time traces with a kinetics model constructed with literature rate coefficients. The absolute cross section of OH was determined to be σ(13.436 eV) = 3.2 ± 1.0 Mb and σ(14.193 eV) = 4.7 ± 1.6 Mb relative to the known cross section for O(3P) at 14.193 eV. The absolute photoionization spectrum was obtained by recording a spectrum at a resolution of 8 meV (50 meV steps) and scaling to the single-energy cross sections. We computed the absolute VUV photoionization spectrum of OH and O(3P) using equation-of-motion coupled-cluster Dyson orbitals and a Coulomb photoelectron wave function and found good agreement with the observed absolute photoionization spectra.
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Product formation, in particular ketohydroperoxide formation and decomposition, were investigated in time-resolved, Cl-atom initiated neopentane oxidation experiments in the temperature range 550-675 K using a photoionization time-of-flight mass spectrometer. Ionization light was provided either by Advanced Light Source tunable synchrotron radiation or â¼10.2 eV fixed energy radiation from a H2-discharge lamp. Experiments were performed both at 1-2 atm pressure using a high-pressure reactor and also at â¼9 Torr pressure employing a low-pressure reactor for comparison. Because of the highly symmetric structure of neopentane, ketohydroperoxide signal can be attributed to a 3-hydroperoxy-2,2-dimethylpropanal isomer, i.e. from a γ-ketohydroperoxide (γ-KHP). The photoionization spectra of the γ-KHP measured at low- and high pressures and varying oxygen concentrations agree well with each other, further supporting they originate from the single isomer. Measurements performed in this work also suggest that the "Korcek" mechanism may play an important role in the decomposition of 3-hydroperoxy-2,2-dimethylpropanal, especially at lower temperatures. However, at higher temperatures where γ-KHP decomposition to hydroxyl radical and oxy-radical dominates, oxidation of the oxy-radical yields a new important channel leading to acetone, carbon monoxide, and OH radical. Starting from the initial neopentyl + O2 reaction, this channel releases altogether three OH radicals. A strongly temperature-dependent reaction product is observed at m/z = 100, likely attributable to 2,2-dimethylpropanedial.
RESUMEN
The Criegee intermediate acetone oxide, (CH3)2COO, is formed by laser photolysis of 2,2-diiodopropane in the presence of O2 and characterized by synchrotron photoionization mass spectrometry and by cavity ring-down ultraviolet absorption spectroscopy. The rate coefficient of the reaction of the Criegee intermediate with SO2 was measured using photoionization mass spectrometry and pseudo-first-order methods to be (7.3 ± 0.5) × 10-11 cm3 s-1 at 298 K and 4 Torr and (1.5 ± 0.5) × 10-10 cm3 s-1 at 298 K and 10 Torr (He buffer). These values are similar to directly measured rate coefficients of anti-CH3CHOO with SO2, and in good agreement with recent UV absorption measurements. The measurement of this reaction at 293 K and slightly higher pressures (between 10 and 100 Torr) in N2 from cavity ring-down decay of the ultraviolet absorption of (CH3)2COO yielded even larger rate coefficients, in the range (1.84 ± 0.12) × 10-10 to (2.29 ± 0.08) × 10-10 cm3 s-1. Photoionization mass spectrometry measurements with deuterated acetone oxide at 4 Torr show an inverse deuterium kinetic isotope effect, kH/kD = (0.53 ± 0.06), for reactions with SO2, which may be consistent with recent suggestions that the formation of an association complex affects the rate coefficient. The reaction of (CD3)2COO with NO2 has a rate coefficient at 298 K and 4 Torr of (2.1 ± 0.5) × 10-12 cm3 s-1 (measured with photoionization mass spectrometry), again similar to rate for the reaction of anti-CH3CHOO with NO2. Cavity ring-down measurements of the acetone oxide removal without added reagents display a combination of first- and second-order decay kinetics, which can be deconvolved to derive values for both the self-reaction of (CH3)2COO and its unimolecular thermal decay. The inferred unimolecular decay rate coefficient at 293 K, (305 ± 70) s-1, is similar to determinations from ozonolysis. The present measurements confirm the large rate coefficient for reaction of (CH3)2COO with SO2 and the small rate coefficient for its reaction with water. Product measurements of the reactions of (CH3)2COO with NO2 and with SO2 suggest that these reactions may facilitate isomerization to 2-hydroperoxypropene, possibly by subsequent reactions of association products.
RESUMEN
Gas-phase product detection studies of o-hydroxyphenyl radical and O2 are reported at 373, 500, and 600 K, at 4 Torr (533.3 Pa), using VUV time-resolved synchrotron photoionisation mass spectrometry. The dominant products are assigned as o-benzoquinone (C6H4O2, m/z 108) and cyclopentadienone (C5H4O, m/z 80). It is concluded that cyclopentadienone forms as a secondary product from prompt decomposition of o-benzoquinone (and dissociative ionization of o-benzoquinone may contribute to the m/z 80 signal at photon energies â³9.8 eV). Ion-trap reactions of the distonic o-hydroxyphenyl analogue, the 5-ammonium-2-hydroxyphenyl radical cation, with O2 are also reported and concur with the assignment of o-benzoquinone as the dominant product. The ion-trap study also provides support for a mechanism where cyclopentadienone is produced by decarbonylation of o-benzoquinone. Kinetic studies compare oxidation of the ammonium-tagged o-hydroxyphenyl and o-methylphenyl radical cations along with trimethylammonium-tagged analogues. Reaction efficiencies are found to be ca. 5% for both charge-tagged o-hydroxyphenyl and o-methylphenyl radicals irrespective of the charged substituent. G3X-K quantum chemical calculations are deployed to rationalise experimental results for o-hydroxyphenyl + O2 and its charge-tagged counterpart. The prevailing reaction mechanism, after O2 addition, involves a facile 1,5-H shift in the peroxyl radical and subsequent elimination of OH to yield o-benzoquinone that is reminiscent of the Waddington mechanism for ß-hydroxyperoxyl radicals. These results suggest o-hydroxyphenyl + O2 and decarbonylation of o-benzoquinone serve as plausible OH and CO sources in combustion.
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The reaction of small hydrocarbon radicals (i.e.ËCN, ËC2H) with trace alkenes and alkynes is believed to play an important role in molecular weight growth and ultimately the formation of Titan's characteristic haze. Current photochemical models of Titan's atmosphere largely assume hydrogen atom abstraction or unimolecular hydrogen elimination reactions dominate the mechanism, in contrast to recent experiments that reveal significant alkyl radical loss pathways during reaction of ethynyl radical (ËC2H) with alkenes and alkynes. In this study, the trend is explored for the case of a larger ethynyl radical analogue, the 1-propynyl radical (H3CC[triple bond, length as m-dash]CË), a likely product from the high-energy photolysis of propyne in Titan's atmosphere. Using synchrotron vacuum ultraviolet photoionization mass spectrometry, product branching ratios are measured for the reactions of 1-propynyl radical with a suite of small alkenes (ethylene and propene) and alkynes (acetylene and d4-propyne) at 4 Torr and 300 K. Reactions of 1-propynyl radical with acetylene and ethylene form single products, identified as penta-1,3-diyne and pent-1-en-3-yne, respectively. These products form by hydrogen atom loss from the radical-adduct intermediates. The reactions of 1-propynyl radical with d4-propyne and propene form products from both hydrogen atom and methyl loss, (-H = 27%, -CH3 = 73%) and (-H = 14%, -CH3 = 86%), respectively. Together, these results indicate that reactions of ethynyl radical analogues with alkenes and alkynes form significant quantities of products by alkyl loss channels, suggesting that current photochemical models of Titan over predict both hydrogen atom production as well as the efficiency of molecular weight growth in these reactions.
Asunto(s)
Alquenos/química , Alquinos/química , Atmósfera/química , Saturno , Radicales Libres/química , Estructura Molecular , Peso MolecularRESUMEN
The reaction of O((3)P) + propyne (C3H4) was investigated at 298 K and 4 Torr using time-resolved multiplexed photoionization mass spectrometry and a synchrotron-generated tunable vacuum ultraviolet light source. The time-resolved mass spectra of the observed products suggest five major channels under our conditions: C2H3 + HCO, CH3 + HCCO, H + CH3CCO, C2H4 + CO, and C2H2 + H2 + CO. The relative branching ratios for these channels were found to be 1.00, (0.35 ± 0.11), (0.18 ± 0.10), (0.73 ± 0.27), and (1.31 ± 0.62). In addition, we observed signals consistent with minor production of C3H3 + OH and H2 + CH2CCO, although we cannot conclusively assign them as direct product channels from O((3)P) + propyne. The direct abstraction mechanism plays only a minor role (≤1%), and we estimate that O((3)P) addition to the central carbon of propyne accounts for 10% of products, with addition to the terminal carbon accounting for the remaining 89%. The isotopologues observed in experiments using d1-propyne (CH3CCD) and analysis of product branching in light of previously computed stationary points on the singlet and triplet potential energy surfaces (PESs) relevant to O((3)P) + propyne suggest that, under our conditions, (84 ± 14)% of the observed product channels from O((3)P) + propyne result from intersystem crossing from the initial triplet PES to the lower-lying singlet PES.
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The absolute vacuum ultraviolet (VUV) photoionization spectra of the hydroperoxyl radical (HO2), hydrogen peroxide (H2O2), and formaldehyde (H2CO) have been measured from their first ionization thresholds to 12.008 eV. HO2, H2O2, and H2CO were generated from the oxidation of methanol initiated by pulsed-laser-photolysis of Cl2 in a low-pressure slow flow reactor. Reactants, intermediates, and products were detected by time-resolved multiplexed synchrotron photoionization mass spectrometry. Absolute concentrations were obtained from the time-dependent photoion signals by modeling the kinetics of the methanol oxidation chemistry. Photoionization cross sections were determined at several photon energies relative to the cross section of methanol, which was in turn determined relative to that of propene. These measurements were used to place relative photoionization spectra of HO2, H2O2, and H2CO on an absolute scale, resulting in absolute photoionization spectra.
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Low-temperature propane oxidation was studied at P = 4 Torr and T = 530, 600, and 670 K by time-resolved multiplexed photoionization mass spectrometry (MPIMS), which probes the reactants, intermediates, and products with isomeric selectivity using tunable synchrotron vacuum UV ionizing radiation. The oxidation is initiated by pulsed laser photolysis of oxalyl chloride, (COCl)2, at 248 nm, which rapidly generates a â¼1:1 mixture of 1-propyl (n-propyl) and 2-propyl (i-propyl) radicals via the fast Cl + propane reaction. At all three temperatures, the major stable product species is propene, formed in the propyl + O2 reactions by direct HO2 elimination from both n- and i-propyl peroxy radicals. The experimentally derived propene yields relative to the initial concentration of Cl atoms are (20 ± 4)% at 530 K, (55 ± 11)% at 600 K, and (86 ± 17)% at 670 K at a reaction time of 20 ms. The lower yield of propene at low temperature reflects substantial formation of propyl peroxy radicals, which do not completely decompose on the experimental time scale. In addition, C3H6O isomers methyloxirane, oxetane, acetone, and propanal are detected as minor products. Our measured yields of oxetane and methyloxirane, which are coproducts of OH radicals, suggest a revision of the OH formation pathways in models of low-temperature propane oxidation. The experimental results are modeled and interpreted using a multiscale informatics approach, presented in detail in a separate publication (Burke, M. P.; Goldsmith, C. F.; Klippenstein, S. J.; Welz, O.; Huang H.; Antonov I. O.; Savee J. D.; Osborn D. L.; Zádor, J.; Taatjes, C. A.; Sheps, L. Multiscale Informatics for Low-Temperature Propane Oxidation: Further Complexities in Studies of Complex Reactions. J. Phys. Chem A. 2015, DOI: 10.1021/acs.jpca.5b01003). The model predicts the time profiles and yields of the experimentally observed primary products well, and shows satisfactory agreement for products formed mostly via secondary radical-radical reactions.
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The present paper describes further development of the multiscale informatics approach to kinetic model formulation of Burke et al. (Burke, M. P.; Klippenstein, S. J.; Harding, L. B. Proc. Combust. Inst. 2013, 34, 547-555) that directly incorporates elementary kinetic theories as a means to provide reliable, physics-based extrapolation of kinetic models to unexplored conditions. Here, we extend and generalize the multiscale informatics strategy to treat systems of considerable complexity-involving multiwell reactions, potentially missing reactions, nonstatistical product branching ratios, and non-Boltzmann (i.e., nonthermal) reactant distributions. The methodology is demonstrated here for a subsystem of low-temperature propane oxidation, as a representative system for low-temperature fuel oxidation. A multiscale model is assembled and informed by a wide variety of targets that include ab initio calculations of molecular properties, rate constant measurements of isolated reactions, and complex systems measurements. Active model parameters are chosen to accommodate both "parametric" and "structural" uncertainties. Theoretical parameters (e.g., barrier heights) are included as active model parameters to account for parametric uncertainties in the theoretical treatment; experimental parameters (e.g., initial temperatures) are included to account for parametric uncertainties in the physical models of the experiments. RMG software is used to assess potential structural uncertainties due to missing reactions. Additionally, branching ratios among product channels are included as active model parameters to account for structural uncertainties related to difficulties in modeling sequences of multiple chemically activated steps. The approach is demonstrated here for interpreting time-resolved measurements of OH, HO2, n-propyl, i-propyl, propene, oxetane, and methyloxirane from photolysis-initiated low-temperature oxidation of propane at pressures from 4 to 60 Torr and temperatures from 300 to 700 K. In particular, the multiscale informed model provides a consistent quantitative explanation of both ab initio calculations and time-resolved species measurements. The present results show that interpretations of OH measurements are significantly more complicated than previously thought-in addition to barrier heights for key transition states considered previously, OH profiles also depend on additional theoretical parameters for R + O2 reactions, secondary reactions, QOOH + O2 reactions, and treatment of non-Boltzmann reaction sequences. Extraction of physically rigorous information from those measurements may require more sophisticated treatment of all of those model aspects, as well as additional experimental data under more conditions, to discriminate among possible interpretations and ensure model reliability.
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Product formation from R + O2 reactions relevant to low-temperature autoignition chemistry was studied for 2,5-dimethylhexane, a symmetrically branched octane isomer, at 550 and 650 K using Cl-atom initiated oxidation and multiplexed photoionization mass spectrometry (MPIMS). Interpretation of time- and photon-energy-resolved mass spectra led to three specific results important to characterizing the initial oxidation steps: (1) quantified isomer-resolved branching ratios for HO2 + alkene channels; (2) 2,2,5,5-tetramethyltetrahydrofuran is formed in substantial yield from addition of O2 to tertiary 2,5-dimethylhex-2-yl followed by isomerization of the resulting ROO adduct to tertiary hydroperoxyalkyl (QOOH) and exhibits a positive dependence on temperature over the range covered leading to a higher flux relative to aggregate cyclic ether yield. The higher relative flux is explained by a 1,5-hydrogen atom shift reaction that converts the initial primary alkyl radical (2,5-dimethylhex-1-yl) to the tertiary alkyl radical 2,5-dimethylhex-2-yl, providing an additional source of tertiary alkyl radicals. Quantum-chemical and master-equation calculations of the unimolecular decomposition of the primary alkyl radical reveal that isomerization to the tertiary alkyl radical is the most favorable pathway, and is favored over O2-addition at 650 K under the conditions herein. The isomerization pathway to tertiary alkyl radicals therefore contributes an additional mechanism to 2,2,5,5-tetramethyltetrahydrofuran formation; (3) carbonyl species (acetone, propanal, and methylpropanal) consistent with ß-scission of QOOH radicals were formed in significant yield, indicating unimolecular QOOH decomposition into carbonyl + alkene + OH.
Asunto(s)
Hexanos/química , Temperatura , Espectrometría de Masas , Estructura Molecular , Oxidación-Reducción , Procesos Fotoquímicos , Teoría CuánticaRESUMEN
Rate coefficients are directly determined for the reactions of the Criegee intermediates (CI) CH2 OO and CH3 CHOO with the two simplest carboxylic acids, formic acid (HCOOH) and acetic acid (CH3 COOH), employing two complementary techniques: multiplexed photoionization mass spectrometry and cavity-enhanced broadband ultraviolet absorption spectroscopy. The measured rate coefficients are in excess of 1×10(-10) â cm(3) s(-1) , several orders of magnitude larger than those suggested from many previous alkene ozonolysis experiments and assumed in atmospheric modeling studies. These results suggest that the reaction with carboxylic acids is a substantially more important loss process for CIs than is presently assumed. Implementing these rate coefficients in global atmospheric models shows that reactions between CI and organic acids make a substantial contribution to removal of these acids in terrestrial equatorial areas and in other regions where high CI concentrations occur such as high northern latitudes, and implies that sources of acids in these areas are larger than previously recognized.
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The reaction of the methylidyne radical (CH) with acetone ((CH(3))(2)C[double bond, length as m-dash]O) is studied at room temperature and at a pressure of 4 Torr (533.3 Pa) using a multiplexed photoionization mass spectrometer coupled to the tunable vacuum ultraviolet synchrotron radiation of the Advanced Light Source at Lawrence Berkeley National Laboratory. The CH radicals are generated by 248 nm multiphoton photolysis of bromoform and react with acetone in an excess of helium and nitrogen gas flow. The main observed reaction exit channel is elimination of a hydrogen atom to form C(4)H(6)O isomers. Analysis of photoionization spectra identifies dimethylketene and methacrolein as the only H-elimination products. The best fit to the data gives branching ratios of 0.68 ± 0.14 for methacrolein and 0.32 ± 0.07 for dimethylketene. A methylketene spectrum measured here is used to reanalyze the photoionization spectrum obtained at m/z = 56 for the CH + acetaldehyde reaction, (Goulay et al., J. Phys. Chem. A, 2012, 116, 6091) yielding new H-loss branching ratios of 0.61 ± 0.12 for acrolein and 0.39 ± 0.08 for methylketene. The contribution from methyleneoxirane to the reaction product distribution is revised to be negligible. Coupled with additional product detection for the CD + acetone reaction, these observations pave the way for development of general set of reaction mechanisms for the addition of CH to compounds containing an acetyl subgroup.
Asunto(s)
Acetona/química , Acroleína/análogos & derivados , Etilenos/química , Radicales Libres/química , Cetonas/química , Acroleína/química , Etilenos/síntesis química , Cetonas/síntesis química , Cinética , Fotólisis , Temperatura , Trihalometanos/químicaRESUMEN
Product formation in the laser-initiated low-temperature (575-700 K) oxidation of n-butane was investigated by using tunable synchrotron photoionization time-of-flight mass spectrometry at low pressure (â¼4 Torr). Oxidation was triggered either by 351 nm photolysis of Cl2 and subsequent fast Cl + n-butane reaction or by 248 nm photolysis of 1-iodobutane or 2-iodobutane. Iodobutane photolysis allowed isomer-specific preparation of either n-C4H9 or s-C4H9 radicals. Experiments probed the time-resolved formation of products and identified isomeric species by their photoionization spectra. For stable primary products of butyl + O2 reactions (e.g., butene or oxygen heterocycles) bimodal time behavior is observed; the initial prompt formation, primarily due to chemical activation, is followed by a slower component arising from the dissociation of thermalized butylperoxy or hydroperoxybutyl radicals. In addition, time-resolved formation of C4-ketohydroperoxides (C4H8O3, m/z = 104) was observed in the n-C4H9 + O2 and Cl-initiated oxidation experiments but not in the s-C4H9 + O2 measurements, suggesting isomeric selectivity in the combined process of the "second" oxygen addition to hydroperoxybutyl radicals and subsequent internal H-abstraction/dissociation leading to ketohydroperoxide + OH. To further constrain product isomer identification, Cl-initiated oxidation experiments were also performed with partially deuterated n-butanes (CD3CH2CH2CD3 and CH3CD2CD2CH3). From these experiments, the relative yields of butene product isomers (cis-2-butene, trans-2-butene, and 1-butene) from C4H8 + HO2 reaction channels and oxygenated product isomers (2,3-dimethyloxirane, 2-methyloxetane, tetrahydrofuran, ethyloxirane, butanal, and butanone) associated with OH formation were determined. The current measurements show substantially different isomeric selectivity for oxygenated products than do recent jet-stirred reactor studies but are in reasonable agreement with measurements from butane addition to reacting H2/O2 mixtures at 753 K.