Photoionization Mass Spectrometer Research Articles

Experimental study on synchrotron radiation photoionization of secondary organic aerosol derived from styrene ozonolysis

AbstractSecondary organic aerosol (SOA) produced by ozonolysis of styrene and other alkene compounds is a major part of fine particles in urban atmospheres. The atmospheric ozonolysis process of styrene is simulated in a smog chamber, and the formed SOA particles are detected on‐line by a synchronous radiation vacuum ultraviolet photoionization mass spectrometer (VUV‐PIMS) in this study. Through molecular ion peaks in the photonionization mass spectra of SOA and the corresponding photoionization efficiency curve, combined with off‐line measurement verification of ultraviolet visible and infrared absorption spectra, it is determined that formaldehyde, formic acid, benzene, phenol, benzaldehyde, and benzoic acid are the main constituents of styrene SOA. These provide new information for studying the atmospheric ozonolysis oxidation mechanism of styrene. VUV‐PIMS can get over complicated sample preparation procedures, secondary pollution, and other shortcomings of the off‐line method and is a useful instrument to measure constituents and unveil the formation process of SOA particles.

A comparative study of oxidation of pure ammonia and ammonia/dimethyl ether mixtures in a jet-stirred reactor using SVUV-PIMS

Oxidation of pure ammonia or ammonia/dimethyl ether (NH3/DME) mixtures in O2/Ar in a jet-stirred reactor (JSR) at atmospheric pressure was experimentally studied using a synchrotron vacuum ultraviolet photoionization mass spectrometer (SVUV-PIMS) and a gas chromatograph (GC) to analyse the reaction intermediates and product species. Particular attention was given to the effect of DME addition on NH3 → NH2, a critical step that initiates NH3 oxidation and subsequent formation of nitrogen oxides. The initial mole fraction of NH3 was set to 0.01, and for the NH3/DME mixture, the NH3/DME molar ratio was set to 1. The experiments were performed at two equivalence ratios of ϕ = 1.0 and 0.2 in the temperature range of 500 – 1100 K. A kinetic model for NH3/DME oxidation was developed and kinetic analysis was performed. It was found that the addition of DME significantly promotes the NH3 to NH2 pathway and the mechanisms of this promotion effect are different at low and high temperatures. At a low temperature (∼ 600 K), NH3 → NH2 is mainly promoted by OH radicals produced from the DME low-temperature chain-branching reactions, while at a high temperature (∼ 1000 K), mainly by OH radicals produced from the reactions consuming HO2 and H radicals, which were formed from DME high temperature oxidation. At T > 800 K with ϕ = 0.2, the addition of DME promotes the formation of nitrogen oxides, however, at a low temperature of 600 K, the addition of DME only promotes the formation of N2O and NO2 but not NO. A reaction pathway analysis indicates that the oxidation of NO into NO2 at low temperature is promoted by HO2 and CH3OCH2O2, the intermediate products from the low temperature oxidation of DME.

A wide range experimental study and further development of a kinetic model describing propane oxidation

This work presents an experimental and kinetic modeling study of propane oxidation. Ignition delay times of propane were measured in a high-pressure shock tube and in rapid compression machines in the temperature range 689 – 1700 K at equivalence ratios of 0.5, 1.0 and 2.0 in ‘air’, for a wide range of pressures from 20 to 90 bar. CO and H2O mole fraction profiles for propane oxidation were measured in a shock tube behind reflected shock waves in the temperature range 1370–1840 K at equivalence ratios of 0.5, 1.0 and 2.0 and at a pressure of approximately 1.3 atm. Moreover, propane oxidation was studied using a jet-stirred reactor coupled to a synchrotron vacuum ultraviolet photoionization mass spectrometer at low temperatures in the range 565 – 690 K and at a pressure of 1 atm. This wide range of experimental datasets for propane oxidation was used to reoptimize and update our previous kinetic mechanisms, AramcoMech3.0 and NUIGMech1.1. In the current mechanism, NUIGMech1.3, the thermochemical parameters of all species relevant to low-temperature propane oxidation chemistry, including propyl-peroxyl, hydroperoxyl-propyl, hydroperoxyl-propyl-peroxyl, and carbonyl-hydroperoxide radicals, are updated based on newly calculated values at the CCSD(T)-F12/TZ-F12//B2PLYPD3/TZ///B2PLYP-D3/TZ level of theory. The improvements made in the thermochemical values and in the kinetic parameters for the low-temperature propane oxidation reactions in NUIGMech1.3 result in better model agreement with the new IDTs and speciation data, including carbon monoxide, formaldehyde, propene, acetaldehyde and various minor products such as ethylene, acetic acid, acrolein as well as various hydroperoxide and cyclic ether species.

An experimental and modeling study of tetramethyl ethylene pyrolysis with polycyclic aromatic hydrocarbon formation

Iso-olefins, in the C5–C8 range can potentially be blended with renewable gasoline fuels to increase their research octane number (RON) and octane sensitivity (S). RON and S increase with the degree of branching in iso-olefins and this is a desirable fuel anti-knock quality in modern spark-ignited direct-injection engines. However, these iso-olefins tend to form larger concentrations of aromatic species leading to the formation of polycyclic aromatic hydrocarbons (PAHs). Thus, it is important to understand the pyrolysis chemistry of these iso-olefins. In this study, a new detailed chemical kinetic mechanism is developed to describe the pyrolysis of tetramethyl ethylene (TME), a symmetric iso-olefin. The mechanism, which includes the formation of PAHs, is validated against species versus temperature (700–1160 K) measurements in a jet-stirred reactor at atmospheric pressure and in a single-pulse shock tube at a pressure of 5 bar in the temperature range 1150–1600 K. Synchrotron vacuum ultraviolet photoionization mass spectrometer (SVUV-PIMS) and gas chromatography (GC) systems were used to quantify the species in the jet-stirred reactor and in the single-pulse shock tube, respectively. The mechanism derives its base and PAH chemistry from the LLNL PAH sub-mechanism. The predictions are accurate for most of the species measured in both facilities. However, there is scope for mechanism improvement by understanding the consumption pathways for some of the intermediate species such as isoprene. The formation of 1, 2, and 3-ring aromatic species such as benzene, toluene, naphthalene and phenanthrene measured experimentally is analyzed using the chemical kinetic mechanism. It is found that the PAH formation chemistry for TME under pyrolysis conditions is driven by both propargyl addition reactions and the HACA mechanism.

Quantification of n-heptane low temperature oxidation products by proton-transfer-reaction mass spectrometry

While studies on the low temperature oxidation of organic compounds have been in depth, fast and accurate quantitative analysis of oxidation products, especially for those without standard samples, remains challenging and requires analytical developments. This work studied n-heptane low temperature oxidation in a jet-stirred reactor (JSR) using proton-transfer-reaction mass spectrometry (PTR-MS). The oxidation products were also analyzed by a synchrotron vacuum ultraviolet radiation photoionization mass spectrometer (SVUV-PIMS) for comparison. The results showed that PTR-MS was able to measure most oxygenated intermediates compared to SVUV-PIMS. Furthermore, the method for the quantification of low temperature oxidation products was studied. By employing a series of calibration gases, the sensitivities of PTR-MS were confirmed to be linearly related to proton-transfer reaction rates, which were calculated using the trajectory parameterization theory. Mole fraction profiles of oxidation products measured by PTR-MS were compared to SVUV-PIMS and literature gas chromatography data, and in most cases, the results showed good consistency. Special attention is needed for some molecules, such as carboxylic acids, formaldehyde, and peroxides. The effect of the humidity of the reaction environment and the fragment on the quantification need to be considered. Overall, PTR-MS is a promising instrument for the quantitative analysis of combustion products and has the potential to measure the total mole fraction of complex isomers (could not distinguish isomers) and to predict the mole fraction of products without a standard sample.

Study on the reaction mechanism of nitrogenous compounds in zeolite-catalyzed pyrolysis of blue-green algae

The ex-situ catalytic fast pyrolysis (CFP) of blue-green algae (BGA) and its nitrogenous model compounds over HZSM-5 was conducted in a microfluidized bed reactor (MFBR) combined with a U-shape fixed bed reactor (U-FBR). A single photoionization mass spectrometer (SPI-MS) was used for on-line studying the dynamics of volatiles formation with the biomass-to-catalyst ratio (BCR). In the CFP of BGA, six different groups of products were differentiated by statistical analysis of SPI mass spectra, which were obtained with the cumulative BCRs. The relative concentration of each group has its own evolution with catalyst deactivation, indicating the different formation pathways of six groups. In combination with results from the CFP of six model compounds, the reaction pathways of nitrogenous compounds in the CFP of BGA over HZSM-5 were proposed. The benzyl nitrile could be fully converted to hydrocarbons while this is hard to achieve N-cyclic compounds (particularly the pyridines). Besides, most of nitrogenous compounds could be interconvertible in the CFP process. Transmethylation is the favorite way for catalytic conversion. In addition, the CFP of BGA and its N-cyclic compounds would lead to the fast coking of HZSM-5, especially the hard coke.

Online analysis of chemical composition and size distribution of fresh cigarette smoke emitted from a heated tobacco product

Online analysis of chemical composition of cigarette smoke of a heated tobacco product (HTP) was performed by using a home-made vacuum ultraviolet (VUV) lamp-based photoionization time-of-flight (TOF) mass spectrometer. A capillary inlet and an aerodynamic lens were utilized to sample the gas- and particulate-phase of the HTP smoke, without dilution and pretreatment, which can be switched from each other within minutes. A thermal desorption unit was installed to vaporize the particulate-phase into gas and its vaporization temperature was determined, based on an equilibrium between the evaporation efficiency and the thermal decomposition of organic compounds. Then these species were softly ionized by VUV photons and their ions were measured by a reflectron TOF mass analyzer. Meanwhile, the puff-by-puff resolved size distributions of the HTP smoke were probed with a commercial scanning mobility particle sizers (SMPS). The mean diameters of particles firstly increase with the puff number, mainly located in the range of 200 – 300 nm, and then approached a steady state. This method was validated to measure the physical-chemical characteristics of the HTP cigarette smoke.•A capillary inlet and an aerodynamic lens were utilized to sample the gas- and particulate-phase of the HTP smoke.•Chemical composition of the HTP smoke was measured by using a compact VUV photoionization mass spectrometer.•The particle size distribution of the HTP smoke without dilution was measured online.

Exploring the reaction chemistry of biomass upgrading over HZSM-5 catalyst through model compounds

The catalytic fast pyrolysis of 17 biomass-derived model compounds over HZSM-5 was conducted in double microfixed-bed reactors (DFBRs) at 500 °C. Our single photoionization mass spectrometer (SPI-MS) allows the real-time monitoring the dynamics of volatiles formation as a function of catalyst deactivation, which provides interesting information on reaction chemistry of biomass catalytic upgrading. The roles of some important intermediates (e.g., benzofurans, benzaldehydes, benzenediols etc.) and their conversion in biomass upgrading are comprehensively discussed. The network of reaction pathways for the conversion of chosen model compounds is also proposed based on the release trend of different products. Strikingly, the favorite formation pathways of large aromatic hydrocarbons in catalytic upgrading are considered to be different between carbohydrate- and lignin-derived model compounds. The level of HZSM-5 deactivation is closely associated with their ability to remove the number of oxygen atoms in feeding model compounds. Besides, the impact fact on the catalyst deactivation in the upgrading of lignin model compounds is discussed. Overall, the performance of commercial HZSM-5 in biomass upgrading is unsatisfactory and has limited relevance to the type of model compounds except for oxygen-free intermediates.

Product Detection of the CH(X2Π) Radical Reaction with Cyclopentadiene: A Novel Route to Benzene

The reaction of the methylidyne radical (CH(X2Π)) with cyclopentadiene (c-C5H6) is studied in the gas phase at 4 Torr and 373 K using a multiplexed photoionization mass spectrometer. Under multiple collision conditions, the dominant product channel observed is the formation of C6H6 + H. Fitting the photoionization spectrum using reference spectra allows for isomeric resolution of C6H6 isomers, where benzene is the largest contributor with a relative branching fraction of 90 (±5)%. Several other C6H6 isomers are found to have smaller contributions, including fulvene with a branching fraction of 8 (±5)%. Master Equation calculations for four different entrance channels on the C6H7 potential energy surface are performed to explore the competition between CH cycloaddition to a C═C bond vs CH insertion into C-H bonds of cyclopentadiene. Previous studies on CH addition to unsaturated hydrocarbons show little evidence for the C-H insertion pathway. The present computed branching fractions support benzene as the sole cyclic product from CH cycloaddition, whereas fulvene is the dominant product from two of the three pathways for CH insertion into the C-H bonds of cyclopentadiene. The combination of experiment with Master Equation calculations implies that insertion must account for ∼10 (±5)% of the overall CH + cyclopentadiene mechanism.

Comparing the pyrolysis kinetics of dimethoxymethane and 1,2-dimethoxyethane: An experimental and kinetic modeling study

This work investigates the reaction kinetics of the thermal decomposition of dimethoxymethane (DMM) and 1,2-dimethoxyethane (1,2-DME), which are both representative molecules of the promising clean polyether fuels. Pyrolysis experiments are carried out with helium diluted mixtures containing individual fuels in a flow tube at two different pressures of 760 Torr and 30 Torr. By varying the temperature distributions along the flow tube, the resulting species composition is sampled downstream the reactor and analyzed by a photoionization mass spectrometer. A kinetic model, including sub-mechanisms for the thermal decomposition of both fuels, is proposed, which can well characterize important measurements, such as the fuel decomposition reactivity and the speciation of crucial products. Under identical conditions, 1,2-DME exhibits a higher decomposition reactivity than DMM, because of the characteristic C–C bond fission as well as the easier hydrogen abstraction reactions by methyl radical. Some fuel-specific intermediates are observed, including methyl formate in DMM pyrolysis, methyl vinyl ether and methoxy acetaldehyde in 1,2-DME pyrolysis. These species mainly come from fuel radical dissociations following the hydrogen abstractions from the central (–CH2O–) and (–CH2CH2O–) moieties in DMM and 1,2-DME, respectively. The formation of some other intermediates are closely related to the consumption of these fuel-specific species. Particularly, the decomposition of methyl formate produces high concentrations of methanol in DMM pyrolysis. In 1,2-DME pyrolysis, the consumption of methyl vinyl ether and methoxy acetaldehyde brings about the formation of C2 oxygenated intermediates such as acetaldehyde, ethenol and ketene. Higher concentrations of unsaturated C2 (ethylene and acetylene) and larger hydrocarbon intermediates present in 1,2-DME pyrolysis, due to the existence of C–C bond in the fuel molecule.

First direct kinetic measurement of i-C4H5 (CH2CHCCH2) + O2 reaction: Toward quantitative understanding of aromatic ring formation chemistry

The kinetics of the i-C4H5 (buta-1,3-dien-2-yl) radical reaction with molecular oxygen has been measured over a wide temperature range (275–852 K) at low pressures (0.8–3 Torr) in direct, time-resolved experiments. The measurements were performed using a laminar flow reactor coupled to photoionization mass spectrometer (PIMS), and laser photolysis of either chloroprene (2-chlorobuta-1,3-diene) or isoprene was used to produce the resonantly stabilized i-C4H5 radical. Under the experimental conditions, the measured bimolecular rate coefficient of i-C4H5 + O2 reaction is independent of bath gas density and exhibits weak, negative temperature dependency, and can be described by the expression k3 = (1.45 ± 0.05) × 10−12 × (T/298 K)−(0.13±0.05) cm3 s−1. The measured bimolecular rate coefficient is surprisingly fast for a resonantly stabilized radical. Under combustion conditions, the reactions of i-C4H5 radical with ethylene and acetylene are believed to play an important role in forming the first aromatic ring. However, the current measurements show that i-C4H5 + O2 reaction is significantly faster under combustion conditions than previous estimations suggest and, consequently, inhibits the soot forming propensity of i-C4H5 radicals. The bimolecular rate coefficient estimates used for the i-C4H5 + O2 reaction in recent combustion simulations show significant variation and are up to two orders of magnitude slower than the current, measured value. All estimates, in contrast to our measurements, predict a positive temperature dependency. The observed products for the i-C4H5 + O2 reaction were formaldehyde and ketene. This is in agreement with the one theoretical study available for i-C4H5 + O2 reaction, which predicts the main bimolecular product channels to be H2CO + C2H3 + CO and H2CCO + CH2CHO.

Looking at the bigger picture: Identifying the photoproducts of pyruvic acid at 193 nm.

Photodissociation of pyruvic acid (PA) was studied in the gas-phase at 193 nm using two complementary techniques. The time-sliced velocity map imaging arrangement was used to determine kinetic energy release distributions of fragments and estimate dissociation timescales. The multiplexed photoionization mass spectrometer setup was used to identify and quantify photoproducts, including isomers and free radicals, by their mass-to-charge ratios, photoionization spectra, and kinetic time profiles. Using these two techniques, it is possible to observe the major dissociation products of PA photodissociation: CO2, CO, H, OH, HCO, CH2CO, CH3CO, and CH3. Acetaldehyde and vinyl alcohol are minor primary photoproducts at 193 nm, but products that are known to arise from their unimolecular dissociation, such as HCO, H2CO, and CH4, are identified and quantified. A multivariate analysis that takes into account the yields of the observed products and assumes a set of feasible primary dissociation reactions provides a reasonable description of the photoinitiated chemistry of PA despite the necessary simplifications caused by the complexity of the dissociation. These experiments offer the first comprehensive description of the dissociation pathways of PA initiated on the S3 excited state. Most of the observed products and yields are rationalized on the basis of three reaction mechanisms: (i) decarboxylation terminating in CO2 + other primary products (∼50%); (ii) Norrish type I dissociation typical of carbonyls (∼30%); and (iii) O-H and C-H bond fission reactions generating the H atom (∼10%). The analysis shows that most of the dissociation reactions create more than two products. This observation is not surprising considering the high excitation energy (∼51 800 cm-1) and fairly low energy required for dissociation of PA. We find that two-body fragmentation processes yielding CO2 are minor, and the expected, unstable primary co-fragment, methylhydroxycarbene, is not observed because it probably undergoes fast secondary dissociation and/or isomerization. Norrish type I dissociation pathways generate OH and only small yields of CH3CO and HOCO, which have low dissociation energies and further decompose via three-body fragmentation processes. Experiments with d1-PA (CH3COCOOD) support the interpretations. The dissociation on S3 is fast, as indicated by the products' recoil angular anisotropy, but the roles of internal conversion and intersystem crossing to lower states are yet to be determined.

Isomer-sensitive characterization of low temperature oxidation reaction products by coupling a jet-stirred reactor to an electron/ion coincidence spectrometer: case of n-pentane.

Through the use of tunable vacuum ultraviolet light generated by the DESIRS VUV synchrotron beamline, a jet-stirred reactor was coupled for the first time to an advanced photoionization mass spectrometer based upon a double imaging PhotoElectron PhotoIon COincidence (i2PEPICO) scheme. This new coupling was used to investigate the low-temperature oxidation of n-pentane, a prototype molecule for gasoline or diesel fuels. Experiments were performed under quasi-atmospheric pressure (1.1 bar) with a residence time of 3 s for two equivalence ratios (1/3 and 0.5) with a fuel initial mole fraction of 0.01. The measured time-of-flight mass spectra are in good agreement with those previously obtained with other photoionization mass spectrometers and, like those previous ones, display several m/z peaks for which the related species assignation is ambiguous. This paper shows how the analysis of the coincident mass-tagged Threshold PhotoElectron Spectra (TPES) together with first principle computations, consisting of the determination of the adiabatic ionization energies and the spectra of some products, may assist products' identification. The results mostly confirm those previously obtained by photoionization mass spectrometry and gas chromatography, but also allow a more accurate estimation of the 1-pentene/2-pentene mole fraction ratio. Our data also indicate a higher formation of acetone and methyl ethyl ketone than what is predicted by current models, as well as the presence of products that were not previously taken into account, such as methoxyacetylene, methyl vinyl ketone or furanone. The formation of three, four and five membered ring cyclic ethers is confirmed along with linear ketones: 2- and 3-pentanone. A significant general trend in indicating higher amounts of ketones than are indicated by gas chromatography is noted. Finally, TPES of alkenylhydroperoxides are also provided for the first time and constrains on the isomers identification are provided.

Development and Optimization of an External-Membrane Introduction Photoionization Mass Spectrometer for the Fast Analysis of (Polycyclic)Aromatic Compounds in Environmental and Process Waters.

The development of sensitive analytical techniques for the real-time detection of aromatic hydrocarbons (AHs) and polycyclic aromatic hydrocarbons (PAHs) is of high importance, because of their impact on human health and the environment. A promising approach, regarding to direct determination of (P)AHs in aqueous samples, is resonance-enhanced multiphoton ionization (REMPI) coupled to external-membrane introduction mass spectrometry (eMIMS). In eMIMS, analytes are extracted from the water phase into the gas phase, which is supplied to the MS by using an external semipermeable membrane setup. As a result, no laborious enrichment techniques are needed. With REMPI, ions are formed by the subsequent absorption of two photons via an excited molecular state. The unique ionization scheme of REMPI provides selective and sensitive detection of (P)AHs. When combining the capabilities of REMPI and MIMS, direct measurements of sub-μg/L concentrations of small (polycyclic)aromatic compounds are feasible. In this study, we present an external sheet membrane probe (ESMP) for the determination of selected (polycyclic)aromatic species in water samples by using REMPI time-of-flight mass spectrometry (REMPI-TOFMS). This inlet design shows promising results with respect to the direct analysis of (P)AHs in aquatic environments. With this early stage system, concentrations down to tens of ng/L for selected small (polycyclic)aromatic compounds are accessible within minutes without any sample preparation.

Effect of Methyl Group Substitution on the Kinetics of Vinyl Radical + O2 Reaction.

The kinetics of (CH3)2CCH + O2 (1) and (CH3)2CCCH3 + O2 (2) reactions have been measured as a function of temperature (223-600 K) at low pressures (0.4-2 Torr) using a tubular laminar flow reactor coupled to a photoionization mass spectrometer (PIMS). These reactions are important for accurate modeling of unsaturated hydrocarbon combustion. Photolysis of a brominated precursor by a pulsed excimer laser radiation at 248 nm wavelength along the flow reactor axis was used for the production of radicals. The measured bimolecular rate coefficient of reaction 1 shows a negative temperature dependence over the temperature range 223-384 K and becomes temperature independent at higher temperatures. The bimolecular rate coefficient of reaction 2 exhibits a negative temperature dependence throughout the experimental temperature range. The bimolecular rate coefficients of reactions 1 and 2 are expected to be at the high-pressure limit under the current experimental conditions, and the following values are obtained at 298 K: k1(298 K) = (4.5 ± 0.5) × 10-12 cm3 s-1 and k2(298 K) = (8.9 ± 1.0) × 10-12 cm3 s-1. The observed products for reactions 1 and 2 were CH3COCH3 and CH3 + CH3COCH3, respectively. Substituting both β-hydrogens in the vinyl radical (CH2CH) with methyl groups decreases the rate coefficient of the CH2CH + O2 reaction by about 50%. However, the rate coefficient of the triply substituted (CH3)2CCCH3 radical reaction with O2 is almost identical to the CH2CH + O2 rate coefficient under the covered temperature range.

Description of Steam Cracker Fouling and Coking Residues by Thermal Analysis-Photoionization Mass Spectrometry

Two organic fouling samples obtained from downstream the cracking oven (DS) and from upstream the hot zone (US) of a steam cracker facility were characterized. For this purpose, a simultaneous thermal analyzer coupled to a photoionization mass spectrometer (STA-PI-MS) and a thermal desorption/pyrolysis gas chromatograph (TD/Py-GC-EI-MS) were used. Mass loss and differential scanning calorimetry information revealed the degradation of the materials beginning at 130 °C with two distinct maxima for US and one for DS (230–330 °C) as well as broad signals (330–500 °C) for both. Structural motives of different polymeric-like structures were assigned based on PI-MS of the effluent and separately conducted TD/Py-GC-EI-MS. The advantage of soft photoionization over hard ionization techniques such as electron ionization is the considerable reduction of fragmentation, yielding higher abundancies of molecular ions. Thus, even though complex samples are studied, evolving constituents can often be easily tracked in a time-resolved manner (1 Hz). While single photon ionization (SPI, 118 nm = 10.5 eV) ionizes most organic molecules, resonance-enhanced multiphoton ionization (REMPI, 2 × 266 nm = 9.4 eV) selectively addresses aromatic species. Differentiation of polymeric-like structures was achieved by exploiting this selectivity (SPI vs REMPI) and comparison of molecular patterns with GC-EI-MS data, which supports the identification of compounds by providing fragmentation patterns and chemical information based on retention time. US shows high inorganic content (∼50%) and more diversity in its organic part, as indicated by four types of patterns: polyethylene-like, Diels–Alder-like, polythioether/polysulfide-like, and polystyrene-like motives. In contrast, DS exhibits almost only signals of Diels–Alder-like and polystyrene-like structures and contains a less inorganic material (∼23%). Additionally, first attempts to quantify the Diels–Alder content by STA-SPI-MS were successfully conducted.

Gas-Phase Reaction Network of Li/MgO-Catalyzed Oxidative Coupling of Methane and Oxidative Dehydrogenation of Ethane

A gas-phase reaction network involving reactive intermediates such as alkyl and alkyl peroxide radicals and alkyl hydroperoxides have long remained a mystery in oxidative coupling of methane (OCM) and oxidative dehydrogenation of ethane (ODHE) reactions. Herein we report direct observations of gas-phase reactive intermediates including CH2, CH3•, C2H5•, CH3OO•, C2H5OO•, CH3OOH, and C2H5OOH during OCM and ODHE reactions over Li/MgO catalysts with an online synchrotron VUV photoionization mass spectrometer connected to a catalytic reactor with adjustable distances between the catalyst bed and the sampling nozzle of the mass spectrometer. Secondary reactions of these reactive intermediates in the gas phase are elucidated, and the reaction network of OCM and ODHE reactions is established. These results greatly deepen the mechanistic understanding of OCM and ODHE reactions necessary for developing efficient catalysts and designing proper reactors.

Kinetics of the Methyl-Vinyl Radical + O2 Reactions Associated with Propene Oxidation.

The bimolecular rate coefficients of reactions CH3CCH2 + O2 (1) and cis/trans-CH3CHCH + O2 (2a/3a) have been measured using a tubular laminar flow reactor coupled with a photoionization mass spectrometer (PIMS). These reactions are relevant in the combustion of propene. Pulsed excimer laser photolysis of a ketone or a bromide precursor molecule at 193 or 248 nm wavelength was used to produce radicals of interest homogeneously along the reactor. Time-resolved experiments were performed under pseudo-first-order conditions at low pressure (0.3–1.5 Torr) over the temperature range 220–660 K. The measured bimolecular rate coefficients were found to be independent of bath gas concentration. The bimolecular rate coefficients possess negative temperature dependence at low temperatures (T < 420 K) and appear to be independent of temperature at high temperatures (T > 420 K). Observed products of the reaction CH3CCH2 + O2 were CH3 and H2CO, while for the reaction cis/trans-CH3CHCH + O2, observed products were CH3CHO and HCO. Current results indicate that the reaction mechanism of both reactions is analogous to that of C2H3 + O2. Methyl substitution of the vinyl radical changes its reactivity toward O2 upward by ca. 50% if it involves the α-position and downward by ca. 30% if the methyl group takes either of the β-positions, respectively.

Investigation into reactions of methyl methacrylate and ethyl acrylate with chlorine atom

Reactions between chlorine and unsaturated esters in gas phase are examined in a slow-flow reaction tube inside the laboratory-built photoionization mass spectrometer at the energy range of 8–11 eV. 248 nm laser radiation is used to initiate the reaction. Products are distinguished, C5H8O2Cl for addition, and C5H7O2, C5H7O2Cl and C5H9O2Cl for abstraction. The direct or indirect products are detected, indicating secondary reactions. And experimental ionization potentials are procured for direct adducts of methyl methacrylate to be 8.30 eV and for that of ethyl acrylate to be 9.95 eV which are well consistent with theoretical ionization potentials of likely isomers. Theoretical reaction channels are also accounted for, optimized under M06-2X/6-31 + G(d,p) level and ionization potentials of products are calculated under M06-2X/6-31 + G(d,p) level also. Differences between experimental and theoretical details are discussed.

Investigation of Oxidation Reaction Products of 2-Phenylethanol Using Synchrotron Photoionization.

A photolytically Cl-initiated oxidation reaction of 2-phenylethanol (2PE) was carried out at the Advanced Light Source (ALS) in the Lawrence Berkeley National Laboratory. Using the multiplex photoionization mass spectrometer, coupled with the tunable vacuum ultraviolet radiation of the ALS, data were collected at low pressure (4-6 Torr) and temperature (298-550 K) regimes. Data analysis was performed via characterization of the reaction species photoionization spectra and kinetic traces. Products and reaction pathways are also computed using the CBS-QB3 composite method. The present results suggest primary products m/ z = 30 (formaldehyde), 106 (benzaldehyde), and 120 (phenylacetaldehyde) at 298 K, and m/ z = 120 (phenylacetaldehyde) at 550 K. Branching fractions at room temperature are 27 ± 6.5% for formaldehyde, 24 ± 4.5% for benzaldehyde, and 25 ± 5.8% for phenylacetaldehyde and 60 ± 14% for phenylacetaldehyde at 550 K.