Vacuum Ultraviolet Photoionization Research Articles

Gas-Phase Preparation of the 14π Hückel Polycyclic Aromatic Anthracene and Phenanthrene Isomers (C14H10) via the Propargyl Addition-BenzAnnulation (PABA) Mechanism.

Polycyclic aromatic hydrocarbons (PAHs) imply the missing link between resonantly stabilized free radicals and carbonaceous nanoparticles, commonly referred to as soot particles in combustion systems and interstellar grains in deep space. Whereas gas phase formation pathways to the simplest PAH - naphthalene (C10H8) - are beginning to emerge, reaction pathways leading to the synthesis of the 14π Hückel aromatic PAHs anthracene and phenanthrene (C14H10) are still incomplete. Here, by utilizing a chemical microreactor in conjunction with vacuum ultraviolet (VUV) photoionization (PI) of the products followed by detection of the ions in a reflectron time-of-flight mass spectrometer (ReTOF-MS), the reaction between the 1'- and 2'-methylnaphthyl radicals (C11H9⋅) with the propargyl radical (C3H3⋅) accesses anthracene (C14H10) and phenanthrene (C14H10) via the Propargyl Addition-BenzAnnulation (PABA) mechanism in conjunction with a hydrogen assisted isomerization. The preferential formation of the thermodynamically less stable anthracene isomer compared to phenanthrene suggests a kinetic, rather than a thermodynamics control of the reaction.

Experimental and kinetic modeling study of iso-propylamine oxidation with SVUV-time of flight mass spectrometry

Atmospheric oxidation experiments of iso-propylamine (IPA) were conducted in a jet-stirred reactor over the temperature range from 550 to 870 K at fuel-equivalence ratios of 0.5 and 2.0. A combination of synchrotron vacuum ultraviolet (SVUV) photoionization and time-of-flight mass spectrometry (TOFMS) was utilized to identify and quantify oxidation products and intermediates. Compared to the previous n-propylamine (NPA) low-temperature oxidation [Proc. Combust. Inst., 39 (2023) 295–303.], some intermediates and products were newly observed among the 34 detected species, including nitrosyl hydride, methylamine, acetonitrile, nitrous oxide, ethyl isocyanide, propanenitrile, 2-propanimine, n-methylformamide and 2-methylallylamine. A kinetic model consisting of 815 species and 4402 reactions was developed based on the iso-propanol model [Prog. Energy Combust. Sci. 67 (2018) 31–68.] and an ethylamine model [Prog. Energy Combust. Sci. 44 (2014) 40–102.]. The onset temperature of IPA and O2 consumption is 750 K under both lean and rich conditions. Rate-of-production (ROP) and sensitivity analyses were performed at 800 K to illustrate the reacting paths from parent fuel to major intermediates and products, and identify the most sensitive reactions. H2O2(+M) = 2OH(+M) is the most sensitive reaction with a promoting effect on IPA consumption while 2HO2 = H2O2+O2 is the most inhibiting one. Important N-containing pollutants like NH3, NOx, HCN, CH3NH2 and so on were analyzed with respect to their reaction routes. (CH3)2CNH is abundant due to the H-abstraction reactions between tC3H6NH2 radical with O2. This work was made for gaining a more comprehensive insight into the oxidation of IPA and make a foundation for further exploring amine chemistry.

A comparative pyrolysis study of tetraethoxysilane and tetraethoxymethane: Insight into congener substitution effects on pyrolysis chemistry of siloxane flame synthesis precursors

The pyrolysis of siloxane precursors, such as tetraethoxysilane (TEOS), is commonly employed in the flame synthesis and chemical vapor deposition of silica nanoparticles. In this work, the flow reactor pyrolysis of TEOS is studied using gas chromatography (GC) and synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS), and the congener substitution effects from the central C atom to the central Si atom are investigated through comparison with its hydrocarbon counterpart tetraethoxymethane (TEOM). Pyrolysis models of TEOS and TEOM are constructed and validated against the measured results. Modeling analysis, including rate of production analysis and sensitivity analysis, provides insights into chemistry in fuel consumption and product formation. In contrast, the observations of silicon-containing products in SVUV-PIMS experiments provide evidence for crucial decomposition pathways of TEOS. It is observed that TEOS exhibits significantly higher stability than TEOM under pyrolysis conditions. The most abundant products in the pyrolysis of TEOS and TEOM are ethylene and ethanol, and TEOS produces more hydrocarbon products than TEOM. The lower pyrolysis reactivity of TEOS is attributed to the slower unimolecular decomposition reaction which dominates the decomposition of TEOS than TEOM. This can be explained by the hindrance of the extremely strong Si-O bond resulting from the significantly different electronegativity between Si and O. The higher initial decomposition temperature of TEOS enhances the contribution of other decomposition channels, such as C-C bond dissociation and H-abstraction reactions, in TEOS consumption. This leads to the abundant formation of hydrocarbon productions such as methane, ethane, and acetaldehyde. As the main pyrolysis product, the ethanol produced by TEOM pyrolysis is four times that of TEOS due to the congener substitution effects. The ethanol formation pathway in TEOS pyrolysis is different from that in TEOM pyrolysis, which is mainly formed via a newly proposed multi-step mechanism, resulting in a lower yield in TEOS pyrolysis.

Pressure-Driven Switching of Photoelectron Impact Ionization-Chemical Ionization/Penning Ionization in Vacuum Ultraviolet Photoionization Mass Spectrometry.

Vacuum ultraviolet photoionization (VUV-PI) is a soft ionization technique that operates under pressures ranging from vacuum to ambient pressure. VUV-PI has played an essential role in direct sampling mass spectrometry. In this study, new ionization processes initiated by photoelectrons have been studied through the inclusion of a radio frequency (RF) electric field at different pressures. After deducting the contribution of single photoionization (SPI), the signal intensity of 1 ppmv toluene (C7H8+) in Ar was approximately 5-fold higher than that in N2. Mixed gases with different ionization energies (IEs) and excitation energies (EEs) were further investigated to reveal that metastable species were involved in the enhancement process. Reactant ions were produced by photoelectron impact ionization (PEI), which further triggered ion-molecule reactions, i.e., chemical ionization (CI). Metastable species were produced by photoelectron impact excitation (PEE), which further triggered Penning ionization (PenI). Analytes with IEs above 10.6 eV, such as CO2 (IE = 13.78 eV) and CHCl3 (IE = 11.37 eV), could be sensitively ionized by PenI with a sensitivity comparable to SPI. Except for the contribution of SPI, the dominant ionization process was switched from PEI-CI to PenI when the pressure was elevated from 50 to 500 Pa, as the electron energy gradually decreased and was only able to produce metastable states based on the kinetic energy balance equation of electrons. The conversion processes and conditions from PEI-CI to PenI will provide novel insights to develop new selective and sensitive VUV-PI sources and understand the ionization mechanism in other discharge ionization sources.

Interstellar formation of glyceric acid [HOCH2CH(OH)COOH]-The simplest sugar acid.

Glyceric acid [HOCH2CH(OH)COOH]-the simplest sugar acid-represents a key molecule in biochemical processes vital for metabolism in living organisms such as glycolysis. Although critically linked to the origins of life and identified in carbonaceous meteorites with abundances comparable to amino acids, the underlying mechanisms of its formation have remained elusive. Here, we report the very first abiotic synthesis of racemic glyceric acid via the barrierless radical-radical reaction of the hydroxycarbonyl radical (HOĊO) with 1,2-dihydroxyethyl (HOĊHCH2OH) radical in low-temperature carbon dioxide (CO2) and ethylene glycol (HOCH2CH2OH) ices. Using isomer-selective vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry, glyceric acid was identified in the gas phase based on the adiabatic ionization energies and isotopic substitution studies. This work reveals the key reaction pathways for glyceric acid synthesis through nonequilibrium reactions from ubiquitous precursor molecules, advancing our fundamental knowledge of the formation pathways of key biorelevant organics-sugar acids-in deep space.

Efficient Oxidative Decomposition of Jet-Fuel exo-Tetrahydrodicyclopentadiene (JP-10) by Aluminum Nanoparticles in a Catalytic Microreactor: An Online Vacuum Ultraviolet Photoionization Study.

The oxidation of gas-phase exo-tetrahydrodicyclopentadiene (JP-10, C10H16) over aluminum nanoparticles (AlNP) has been explored between a temperature range of 300 and 1250 K with a novel chemical microreactor. The results are compared with those obtained from chemical microreactor studies of helium-seeded JP-10 and of helium-oxygen-seeded JP-10 without AlNP to gauge the effects of molecular oxygen and AlNP, respectively. Vacuum ultraviolet (VUV) photoionization mass spectrometry reveals that oxidative decomposition of JP-10 in the presence of AlNP is lowered by 350 and 200 K with and without AlNP, respectively, in comparison with pyrolysis of the fuel. Overall, 63 nascent gas-phase products are identified through photoionization efficiency (PIE) curves; these can be categorized as oxygenated molecules and their radicals as well as closed-shell hydrocarbons along with hydrocarbon radicals. Quantitative branching ratios of the products reveal diminishing yields of oxidized species and enhanced branching ratios of hydrocarbon species with the increase in temperature. While in the low-temperature regime (300-1000 K), AlNP solely acts as an efficient heat transfer medium, in the higher-temperature regime (1000-1250 K), chemical reactivity is triggered, facilitating the primary decomposition of the parent JP-10 molecule. This enhanced reactivity of AlNP could plausibly be linked to the exposed reactive surface of the aluminum (Al) core generated upon the rupture of the alumina shell material above the melting point of the metal (Al).

Exploration on the combustion chemistry of p-xylene: A comprehensive study over wide conditions and comparison among C8H10 isomers

Pyrolysis and oxidation of p-xylene over wide conditions were studied in this work in order to provide a comprehensive insight into the combustion chemistry of p-xylene. Concerning this goal, the pyrolysis of p-xylene was investigated in a flow reactor at pressures from 0.04 to 1 atm over the temperature range of 1000–1600 K. Key radicals, isomers and PAH products including three xylyl isomers, benzyl, xylylene isomers, styrene, benzene, fulvene, indene, naphthalene and phenanthrene, were identified and quantified using synchrotron vacuum ultraviolet photoionization mass spectrometry. The oxidation of p-xylene was studied in a jet-stirred reactor at 10 atm, 800–1300 K and equivalence ratios of 0.5–2.0 with a residence time of 0.5 s. Oxidation products were quantified by using gas chromatography combined with mass spectrometry and Fourier transform infrared spectrometry. A kinetic model for p-xylene combustion over wide conditions was developed based on our previously proposed p-xylene oxidation model and validated against the new experimental measurements in this work and literature reported experimental data, including flow reactor oxidation, laminar premixed flame, ignition delay time and laminar burning velocity. In the flow reactor pyrolysis, p-xylene mainly undergoes unimolecular decomposition to yield p-xylyl, which mainly suffers the H-loss reaction to form p-xylylene and isomerization reaction to form o-xylyl. The resonantly stabilized fulvenallenyl and benzyl radicals play an important role in the formation of bicyclic and tricyclic PAHs including indene, naphthalene, and phenanthrene. In the JSR oxidation, p-xylene is predominantly consumed via H-abstraction by oxygenated radicals such as OH, O, and HO2 forming p-xylyl, which can be oxidized by HO2 and eventually converted to p-methylbenzaldehyde. As the most abundantly produced oxygenated aromatics, further consumption of p-methylbenzaldehyde results in the formation of other observed oxygenated aromatics such as cresol, benzofuran, and benzaldehyde. The combustion chemistry of three C8H10 isomers, i.e., p-xylene, o-xylene, and ethylbenzene, were also compared in terms of pyrolysis and oxidation fuel reactivity, and PAHs formation and growth, showing remarkable fuel isomeric effects.

Absolute Photoionization Cross Section and Dissociative Ionization Pathways of Alpha-Pinene.

The absolute photoionization cross section of the monoterpenoid, alpha-pinene (AP), is presented together with the relative photoionization cross sections of its dissociative fragments for the first time. Experiments are performed via multiplexed vacuum ultraviolet (VUV) synchrotron photoionization (PI) mass spectrometry in the 8.0-11.0 eV energy range. Experimental work is conducted at the Advanced Light Source of the Lawrence Berkeley National Laboratory. Dissociative fragments were identified at m/z 121, 94, 93, 92, and 80. The photoionization cross section for the parent mass at 11.0 eV was determined to be 17±4 Mb with a total ionization cross section of 92±23 Mb at the same photon energy. Experimental appearance energies of dissociative ionization fragments and potential dissociative ionization pathways calculated at the G4 level of theory are presented as well.

Elucidating the low temperature chemistry of o-xylene enhanced by the reaction pool of dimethyl ether

The branched aromatic hydrocarbon with short side chains, such as o-xylene, has weak low temperature oxidation reactivity, while it could proceed low temperature chain recycling reactions by blending a fuel component with higher oxidation reactivity. However, the study of low temperature oxidation kinetics of o-xylene is very scarce. Therefore, this work investigated the low temperature oxidation process of o-xylene in an atmospheric jet stirred reactor by adding a biofuel with higher low temperature oxidation reactivity, i.e. dimethyl ether (DME). A series of characteristic low temperature intermediates, such as phenyl hydroperoxides and ketohydroperoxide from the oxidation of o-xylene, were detected by using the synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS). The chemical structures of representative low temperature intermediates were determined by comparing the ionization thresholds from measured photoionization efficiency curves with calculated ionization energies. A kinetic model for o-xylene and DME mixture was developed and verified by literature and present experimental data. Rate of production (ROP) and sensitivity analyses were performed, which indicate that the low temperature oxidation chemistry of o-xylene, such as the negative temperature coefficient behavior, is enhanced by the reaction pool of DME. According to the classical low temperature oxidation mechanism of n-alkanes, the low temperature reactions of o-xylene were proposed. In particular, phenyl hydroperoxides and ketohydroperoxides were revealed to be key indicators for the occurrence of first and second O2 addition reactions during the oxidation of o-xylene, respectively. In addition, the sensitivity analysis uncovers the interaction kinetics between the reaction pools of o-xylene and DME, as well as their effects on fuel consumption and products formation. In summary, present evidence elucidates the low temperature chemistry of a representative branched aromatic, which could contribute to the development of future engines and control of combustion pollutants.

Bottom-Up Formation of Antiaromatic Cyclobutadiene (c-C4H4) in Interstellar Ice Analogs.

Antiaromatic cyclobutadiene (c-C4H4) is the simplest prototype of [n]annulenes and a key reactive intermediate with significant ring strain, serving as the model compound for antiaromatic systems in organic chemistry. Here, we report the first bottom-up formation of cyclobutadiene in low-temperature acetylene (C2H2) ices exposed to energetic electrons. Cyclobutadiene was isolated and detected in the gas phase upon sublimation utilizing vacuum ultraviolet photoionization reflectron time-of-flight mass spectrometry along with ultraviolet photolysis studies. These findings advance our fundamental understanding of the exotic chemistry and preparation of highly strained antiaromatic cycles through non-equilibrium chemistry in interstellar environments, thus affording a possible route for the formation of highly strained molecules such as the hitherto elusive tetrahedrane (C4H4). Because acetylene is a major product of the photolysis and radiolysis of methane (CH4) ice, an abundant component of interstellar ices, our results suggest that cyclobutadiene can likely be formed in methane-rich ices of cold molecular clouds.

A dopant-assisted iodide-adduct chemical ionization time-of-flight mass spectrometer based on VUV lamp photoionization for atmospheric low-molecular-weight organic acids analysis

Formic and acetic acids are the most abundant gaseous organic acids and play the key role in the atmospheric chemistry. In iodine-adduct chemical ionization mass spectrometry (CIMS), the low utilization efficiency of methyl iodide and humidity interference are two major issues of the vacuum ultraviolet (VUV) lamp initiated CIMS for on-line gaseous formic and acetic acids analysis. In this work, we present a new CIMS based on VUV lamp, and the ion-molecular reactor is separated into photoionization and chemical ionization zones by a reducer electrode. Acetone was added to the photoionization zone, and the VUV photoionization acetone provided low-energy electrons for methyl iodide to generate I−, and the addition of acetone reduced the amount of methyl iodide by 2/3. In the chemical ionization zone, a headspace vial containing ultrapure water was added for humidity calibration, and the vial changes the sensitivity as a function of humidity from ambiguity to well linear correlation (R2 > 0.95). With humidity calibration, the CIMS can quantitatively measure formic and acetic acids in the humidity range of 0%-88% RH. In this mode, limits of detection of 10 and 50 pptv are obtained for formic and acetic acids, respectively. And the relative standard deviation (RSD) of quantitation stability for 6 days were less than 10.5%. This CIMS was successfully used to determine the formic and acetic acids in the underground parking and ambient environment of the Shandong University campus (Qingdao, China). In addition, we developed a simple model based formic acid concentration to assess vehicular emissions.

Low-temperature oxidation of n-butanol in a jet-stirred reactor: Detailed species measurements and modeling studies

n-Butanol is a new generation of liquid biofuel. A detailed understanding of the low-temperature combustion chemistry of n-butanol is instructive for its practical application in advanced low-temperature engines. The high-temperature combustion chemistry of n-butanol has been extensively studied, but its low-temperature combustion chemistry remains underexplored, especially the detailed species distribution. In this work, ozone addition was used to enhance the low-temperature oxidation reaction activity to achieve the oxidation of n-butanol in a jet-stirred reactor (JSR) at atmospheric pressure and in the temperature range of 400–800 K. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) was used for detailed measurements of species distribution. The identification of some intermediate species contributed to elucidating and verifying the low-temperature oxidation reaction pathways of n-butanol, such as butanal, C4 hydroxyalkyl hydroperoxides, C4 hydroxyl cyclic ether, and C4 keto-hydroperoxide. Furthermore, the formation of several elusive intermediates was also identified (e.g., C2H4O2, C3H6O2, C4H6On (n = 1∼3), and C4H8O2), highlighting the necessity of further kinetic studies on the low-temperature oxidation of n-butanol. Based on detailed experimental measurements, the n-butanol model was further developed to improve the model predictions by updating the rate constants for the H-atom abstraction reactions of n-butanol by the ȮH radical, adding the detailed butanal sub-mechanism, etc. Especially, the premature formation of CO2 in the present experiment was satisfactorily explained and predicted by the addition of a generally accepted reaction class (i.e., RȮ2 + RȮ2 = RȮ + RȮ + O2 of butanal). Overall, this updated model satisfactorily predicts both the ignition delay time reported in the literature and the species distribution obtained in this work.

Visualization of the Active Sites of Zinc-Chromium Oxides and the CO/H2 Activation Mechanism in Direct Syngas Conversion.

Despite wide studies demonstrating the versatility of the metal oxide-zeolite (OXZEO) catalyst concept to tackle the selectivity challenge in syngas chemistry, the active sites of metal oxides and the mechanism of CO/H2 activation remain to be elucidated. Herein, we demonstrate experimentally the role of Cr in zinc-chromium oxides and unveil visually, for the first time, the active sites for CO activation employing scanning transmission electron microscopy-electron energy loss spectroscopy using the volumetric density of surface carbon species as a descriptor. The ZnCr2O4 spinel surface with atomic ZnOx overlayer is the most active site for C-O bond dissociation, particularly at the narrow ZnCr2O4(110) facets constrained between the (311) and (111) facets, followed by the Cr-doped wurtzite ZnO surface. In comparison, the surfaces of ZnCr2O4 with aggregated ZnOx overlayers, pure ZnO, and the stoichiometric ZnCr2O4 exhibit a significantly lower activity. In situ synchrotron-based vacuum ultraviolet photoionization mass spectrometric study on different temperature programmed surface reactions with isotopes of C18O, 13CO, and D2 validates direct CO dissociation over ZnCrn oxides in CO, forming CH2 and further to hydrocarbons if H2 is present and CH2CO intermediates in syngas. The activity of CO dissociation and hydrogenation over ZnCrn oxides correlates well with the syngas-to-light-olefins activity of ZnCrn-SAPO-18 composite catalysts as a function of the Cr/Zn ratio.

External standard calibration method for high-repetition-rate shock tube kinetic studies with synchrotron-based time-of-flight mass spectrometry.

The signal levels observed from mass spectrometers coupled by molecular beam sampling to shock tubes are impacted by dynamic pressures in the spectrometer due to rapid pressure changes in the shock tube. Accounting for the impact of the pressure changes is essential if absolute concentrations of species are to be measured. Obtaining such a correction for spectrometers operated with vacuum ultra violet photoionization has been challenging. We present here a new external calibration method which uses VUV-photoionization of CO2 to develop time-dependent corrections to species concentration/time profiles from which kinetic data can be extracted. The experiments were performed with the ICARE-HRRST (high repetition rate shock tube) at the DESIRS beamline of synchrotron SOLEIL. The calibration experiments were performed at temperatures and pressures behind reflected shock waves of 1376 ± 12 K and 6.6 ± 0.1 bar, respectively. Pyrolytic experiments with two aromatic species, toluene (T5 = 1362 ± 22 K, P5 = 6.6 ± 0.2 bar) and ethylbenzene (T5 = 1327 ± 18 K, P5 = 6.7 ± 0.2 bar), are analyzed to test the method. Time dependent concentrations for molecular and radical species were corrected with the new method. The resulting signals were compared with chemical kinetic simulations using a recent mechanism for pyrolytic formation of polycyclic aromatic hydrocarbons. Excellent agreement was obtained between the experimental data and simulations, without adjustment of the model, demonstrating the validity of the external calibration method.

Online quantification of nicotine in e-cigarette aerosols by vacuum ultraviolet photoionization mass spectrometry.

The growing popularity of e-cigarettes and the associated risks of nicotine addiction present a new challenge to global public health security. Measuring the nicotine levels in e-cigarette aerosols is essential to assess the safety of e-cigarettes. In this study, a rapid in situ method was developed for online quantification of nicotine in e-cigarette aerosols by using a homemade vacuum ultraviolet photoionization aerosol mass spectrometer (VUV-AMS). E-cigarette liquids with different nicotine concentrations were prepared to generate aerosols containing different levels of nicotine, which were employed as the calibration sources for nicotine quantification by VUV-AMS. The results showed that the mass concentration of nicotine in e-cigarette aerosols has a good linear relationship with its signal intensity in the mass spectrum, and the limits of detection and quantitation of nicotine by VUV-AMS were found to be 2.0 and 6.2 μg per puff respectively. Then the online method was utilized to measure five commercial e-cigarettes, and their nicotine yields were determined to be between 31 and 188 μg per puff with the nicotine fluxes from 7.7 to 70 μg s-1, agreeing with the results of the gas chromatography with a flame ionization detector (GC-FID). This study demonstrated the feasibility and advantages of VUV-AMS for quick quantification of nicotine in e-cigarette aerosols within seconds.

Revealing the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene sensitized by dimethyl ether

Low to moderate temperature oxidation has been a vital topic in the combustion chemistry due to its critical role in controlling the combustion characteristics such as autoignition and pollutant emissions. Low temperature oxidation kinetics of alkanes and oxygenated biofuels have been widely explored, while that of branched aromatics is poorly understood. This work aims to investigate the low to moderate temperature oxidation kinetics of 1,2,4-trimethylbenzene (TMB, C9H12), which is a multi-branched alkylbenzene with weak low temperature oxidation reactivity. To enhance the low temperature oxidation reactivity of TMB, dimethyl ether (DME) was added to efficiently provide chain initiators. The oxidation experiment of TMB/DME mixture was performed with an atmospheric jet stirred reactor coupled with synchrotron vacuum ultraviolet radiation photoionization mass spectrometry. The negative temperature coefficient (NTC) behavior, as well as featured aromatic intermediates, especially phenyl hydroperoxides and unexpected highly oxygenated molecules (HOMs), were observed in the experiment. The detection of these fingerprint aromatic intermediates provide crucial evidence for revealing the low to moderate oxidation kinetics of TMB. In addition, a kinetic model was developed to provide in-depth kinetic analysis. The results demonstrate that the active chain initiators produced from DME oxidation trigger the low temperature chain-branching reactions of TMB. The chain recycling process is further sustained due to the regeneration of active intermediates such as phenyl hydroperoxides and •OH radicals. Aromatic intermediates with chemical compositions of C9H12Ox and C9H10Ox were measured and identified to be key indicators for the low temperature chemistry of TMB. In particular, the aromatic HOMs (C9H12O6 and C9H10O5) are fingerprint intermediates produced from the third O2 addition and subsequent reactions of TMB. Besides, the sensitivity analysis indicates that the interaction kinetics between TMB and DME by sharing the highly sensitive reactions of hydroperoxides and •OH radicals. The present work extends the conceptual reaction schemes proposed in alkanes towards branched aromatics, especially sequential O2 addition reactions that contributing to the formation of phenyl hydroperoxides and HOMs.

Experimental and theoretical study of cyclopropanated fuel exo,exo-Tetracyclo[3.3.1.02,4.06,8]nonane pyrolysis in a jet-stirred reactor

Exo,exo-Tetracyclo[3.3.1.02,4.06,8]nonane (exo-TCN), a kind of cyclopropanated fuel with high tension three-membered ring, which has the characteristics of high density, high net heat of combustion and good low-temperature performance, is a potential high-energy-density liquid fuel. To deeply understand its combustion behavior, and lay a foundation for practical application, detailed experimental and theoretical study is necessary. The pyrolysis of exo-TCN was investigated in a jet-stirred reactor at a temperature range of 500–1010 K under atmospheric pressure with a residence time of 2 s. 54 products and intermediates ranging from m/z = 2–204 were identified and quantified by synchrotron vacuum ultraviolet photoionization mass spectrometry and online gas chromatography, the major products were hydrogen, ethylene, benzene, methane, propene, toluene and styrene. The potential energy surfaces of exo-TCN unimolecular decomposition reactions were calculated by quantum chemistry at CBS-QB3 level. It is found that the pyrolysis of exo-TCN experiences three stages. In the first stage, exo-TCN isomerizes into Tricyclo[3.3.1.02,4]non-6-ene (TCN-6) by ring expansion of the three-membered ring. In the second stage, TCN-6 generates two main isomers through ring expansion reactions, and decomposes into pyrolysis products. The third stage is the secondary reaction of the intermediate products. Finally, combined with the experimental results and theoretical calculation, the possible reaction mechanism of exo-TCN pyrolysis was proposed, and the related reaction rate constants were calculated.

Experimental and modeling study of the N, N-dimethylformamide pyrolysis at atmospheric pressure

As a polar solvent, N, N-Dimethylformamide (DMF) is a potential source of volatile organic compounds during industrial processing. The potential energy surface and pressure-dependent rate coefficients of DMF primary and secondary thermal decomposition were theoretically investigated by automatic ab initio calculations. A singlet aminohydroxycarbene route generating CO is found to be the most energetically favored channel among the unimolecular initiation reactions with a tight transition state. A kinetic model was proposed for DMF pyrolysis prediction and validated against the speciation data newly obtained from synchrotron vacuum ultraviolet photoionization mass spectrometry in a flow reactor within 773 K–1048 K and literature data in a jet stirred reactor within 450 K–900 K at atmospheric pressure. Satisfactory agreements were obtained for the major intermediates and products, but the model failed to capture the formation of some oxygenated compounds, possibly due to the missing reaction pathway for bimolecular addition. During pyrolysis, DMF is mainly consumed by the hydrogen abstraction reaction as the relatively high CN bond energy hinders the barrierless homolytic cleavage. Unlike aldehydes where the carbonyl site is favored, H-abstraction from DMF methyl sites is prevalent, although the acylamino group readily undergoes decarbonylation and β-scission forming oxygenated and nitrogenous parts. Consequently, CO and HCN are the major pyrolysis products. Besides, by incorporating essential high temperature kinetics, extended validation was conducted against the available intermediate temperature autoignition delay times (1000–1350 K, 2 bar) and laminar burning velocity data, and the reason for the discrepancy between the model prediction and experiments was inferred according to the sensitivity analyses.

Co-pyrolysis of Hami coal and mixed plastic: An interaction between primary volatiles study via in-situ Py-TOF-MS

Online detection of pyrolysis volatiles is essential for exploring the mechanism of coal and plastics co-pyrolysis. In-situ pyrolysis time-of-flight mass spectrometry (Py-TOF-MS) equipped with double ionization sources, vacuum ultraviolet photoionization (VUVPI) and electron ionization (EI), was used to analyze the release of primary volatiles during the pyrolysis and co-pyrolysis of Hami coal (HM) with mixed plastic (PP/LDPE and PP/LDPE/PS, with ratios of 3:2 and 12:8:1, respectively). Meanwhile, the interaction mechanism was discussed at the molecular level. According to the thermogravimetric (TG) results and the total ion currents (TIC) of primary volatiles with temperature, the inclusion of plastic shortens the overall reaction time. In-situ Py-TOF-MS results indicate that the volatiles produced from HM pyrolysis at lower temperatures induce the decomposition of PP and promote further dehydrogenation of long-chain C–C. Besides, the addition of PP visibly facilitates the transportation of hydrogen, which reacts with phenoxy from HM pyrolysis to produce diphenol. The further addition of LDPE after PP enhances the inhibitory effect of molten plastic on HM pyrolysis, resulting in a decrease in the content of diphenol, such as benzenediol (from 1.34% to 0.71%), methyl-benzenediol (from 1.12% to 0.68%) and dimethyl benzenediol/ethyl benzenediol (from 0.68% to 0.50%). The co-pyrolysis of HM with PP/LDPE/PS generates more aromatic products compared to that of theoretical value, such as styrene (from 0.29% to 3.16%), 1-ethenyl-3-methyl benzene (from 0.07% to 0.31%) and 1-butene-2,4-diphenyl (from 0.19% to 0.65%). This indicates that co-pyrolysis strengthens the breakage of Car-Cβ bond in the PS backbone. The addition of PS to the mixture plastic also promotes intramolecular and intermolecular hydrogen transfer in the system. For the evolution of inorganic gases, the addition of mixed plastics promotes the decomposition of aliphatic and aromatic carboxylic acids in coal at lower temperatures, resulting in a decrease in CO2.

Experimental and Modeling Investigation on the Pyrolysis of n-C10H22 Initiated by C2H5NO2

ABSTRACT To investigate the mechanism of the nitro-alkanes initiation effect on the pyrolysis of hydrocarbons, pyrolysis experiments were conducted on n-C10H22, C2H5NO2, and a binary mixture of both compounds using synchronous vacuum ultraviolet photoionization mass spectrometry. These experiments were performed within a heated flow tube under varying pressure conditions of 30 and 760 Torr. Identifying and measuring pyrolysis species, comprising stable species and radicals, provides insights into the mechanism underlying the pyrolysis and the interaction of n-C10H22 and C2H5NO2. The findings demonstrate that C2H5NO2 can reduce the initial decomposition temperature of n-C10H22, and the acceleration effect on pyrolysis becomes more pronounced with an increase in experimental pressure. The addition of C2H5NO2 also affects the distribution of alkanes, alkenes, dienes, and alkynes. A detailed elementary reaction-dynamics model comprising 223 species and 1730 reactions was established and used to simulate the distribution of C2H5NO2, n-C10H22, major species, and significant intermediates observed in the experiments. The results prove that the developed model exhibits good accuracy in predicting experimental results and enables a detailed analysis of the initiation mechanism of C2H5NO2 on n-C10H22. The impact of C2H5NO2 on the conversion rate and selectivity of pyrolysis products of n-C10H22 is highlighted and elucidated.