Photoionization Mass Spectrometry Research Articles

Research on the impact of nitromethane on the combustion mechanism of ammonia/methanol blends

Ammonia/methanol co-combustion is considered an effective liquid-liquid blending strategy to enhance the combustion performance of ammonia. However, both methanol and ammonia have high latent heats of vaporization, which necessitate significant heat absorption during the vaporization process. This often results in excessively low ambient temperatures before the ignition of the mixture, negatively affecting low-temperature ignition and combustion. To improve the combustion characteristics of ammonia/methanol blends, this study proposes the addition of nitromethane, forming a ternary blend of ammonia/methanol/nitromethane to enhance fuel performance. To evaluate the impact of nitromethane on the combustion mechanism of ammonia/methanol blends, this study utilizes synchronous vacuum ultraviolet photoionization mass spectrometry to analyze the oxidation reactions of the ammonia/methanol/nitromethane blends. Based on the Brequigny model, cross-reactions involving C-N bonds and reactions related to nitromethane were incorporated for model modification, resulting in the newly modified model, termed A-M. Pathway and sensitivity analyses, as well as ignition delay time simulations, were conducted to further understand the combustion process. The results indicate that the addition of nitromethane to the ammonia/methanol blend lowers the initial reaction temperature from 860 K to 740 K and increases nitrogen oxide (NOx) concentrations at 1050 K. At 800 K, nitromethane reduces the conversion of NH2 to NH3, thereby enhancing ammonia consumption and altering the NOx consumption pathway. Furthermore, at 1020 K, 98.6 % of H2NO reacts with H to form NH2, which is a crucial species in ammonia regeneration. Additionally, at 1020 K, 90.8 % of nitromethane decomposes through the reaction CH3NO2(+M) = CH3 + NO2(+M), contributing to increased NOx emissions. Moreover, the incorporation of nitromethane significantly reduces the ignition delay time of ammonia/methanol blends, demonstrating its potential to improve the overall combustion performance of these mixtures.

Free-radical triggered formation of dioxins from 2-chlorophenol pyrolysis investigated by synchrotron radiation photoionization mass spectrometry

Polychlorinated dibenzo-p-dioxins/dibenzofurans (PCDD/Fs) and polychlorinated naphthalenes (PCNs) are a category of highly toxic and environmentally persistent pollutants released particularly via thermal processes of chlorine-containing materials. However, the detailed reaction mechanism, especially the evolution of related radicals remains elusive for decades. Herein we have for the first time characterized the radicals and intermediates during pyrolysis of 2-chlorophenol resulting in PCDD/Fs and PCNs, using a flow tube reactor coupled with in-situ synchrotron radiation photoionization mass spectrometry (SR-PIMS). Transient species including 2-chlorophenoxy (C6H4ClO•), phenoxy (C6H5O•), chloro-cyclopentadienyl (•C5H4Cl), chloro-cyclopentadiene (C5H5Cl), fulvenone ketene (C6H4O) and o-benzyne (o-C6H4), were identified via m/z and photoionization efficiency profile. Potential energy surfaces of the early-stage mechanism and the associated rate constants and branching ratios were elucidated. Successively, the formation mechanisms of PCDD/Fs and PCNs from these transient intermediates at high temperatures were proposed which have experimentally validated and refined the previous mechanism. The results suggested that the combination of 2-chlorophenoxy radicals with another 2-chlorophenoxy, phenoxy, phenyl, or o-benzyne leads to the formation of PCDD/Fs, while PCNs are generated from the self-coupling of chloro-cyclopentadienyl.

Unraveling Chain Branching in Cool Flames.

In cool flames, autoxidation of organic compounds forms alkyl hydroperoxides and ketohydroperoxides, and this controls the critical rate of chain branching, but there have been large uncertainties in the decomposition rate constants. We synthesized a series of hydroperoxides and measured their decomposition rate constants in pyrolysis experiments by spray-vaporization jet-stirred-reactor synchrotron vacuum ultraviolet photoionization mass spectrometry. Structural variation of the hydroperoxides, including alkyl, cycloalkyl, aromatic, and heterocyclic functionalities, has only a slight effect on their decomposition rate constants. Calculated rate constants are in good agreement with the experiment. The rate constant of ketohydroperoxide decomposition was obtained by theoretical calculation of 3-hydroperoxy butanal and tested by the pyrolysis of synthesized 3-hydroperoxy-3-phenylpropionate. The rate constant of ketohydroperoxide decomposition is close to that of alkyl hydroperoxides. The new chain-branching rate constants improves the cool-flame kinetic model, which is essential for removing discrepancies in model predictions and for the design of high-efficiency and low-emission engines.

Insight into evolution characteristics of pyrolysis products of HLH and HL coal with Py-VUVPI-MS and DFT

To achieve a comprehensive understanding of the influence of chemical structure on the evolution characteristics of coal pyrolysis products, pyrolysis reaction of two kinds of low rank coal (Huolinhe and Huangling coal) were investigated with pyrolysis-vacuum ultraviolet photoionization mass spectrometry (Py-VUVPI-MS). The soft ionized mass spectral detection can provide evolved information of original pyrolysis product. The chemical structure of coal samples was characterized by solid-state 13C NMR, indicating HLH coal with more branched chain and longer aliphatic chain structure. The bond dissociation enthalpies (BDE) of β-Cal-Cal and β-Cal-O within model compounds were obtained with density functional theory. The difference of peak temperature with maximum evolution was collected to investigate the effect of the chemical environment on evolution behavior of pyrolysis products. The results reveal that branched and long aliphatic side-chains can reduces BDE of β-Cal-Cal and β-Cal-O, resulting in the lower peak temperature of pyrolysis products derived from HLH coal. Substituent groups (such as alkyl and hydroxyl groups) attached on the aromatic rings can reduce peak temperatures. Moreover, the effects of the different substituted position on the aromatic ring of the methyl group presented on differences of the BDE. An increase in aromatic ring size correlates with a certain degree of reduction in BDE for β-Cal-Cal; consequently, peak temperature of pyrolysis products with larger aromatic rings is lower. The pyrolysis behavior of coal were discussed based on the experimental observations and theoretical calculation, which are beneficial to understand the reaction route and mechanism of coal pyrolysis.

O2-Dependence of reactions of 1,2-dimethoxyethanyl and 1,2-dimethoxyethanylperoxy isomers

Reaction mechanisms of R˙ and ROO˙ radicals derived from low-temperature oxidation of 1,2-dimethoxyethane (CH3O(CH2)2OCH3) were investigated using speciation from multiplexed photoionization mass spectrometry (MPIMS) measurements via Cl-initiated oxidation, in conjunction with electronic structure calculations. The experiments were conducted at 5 bar, from 450 K – 650 K, and O2 concentrations from 1 · 1014 cm–3 – 6 · 1018 cm–3 to probe the effects on competing reaction channels of 1,2-dimethoxyethanyl (R˙) and 1,2-dimethoxyethanylperoxy (ROO˙) isomers. Several species were detected with photoionization spectral fitting – ethene, formaldehyde, methyl vinyl ether, and 2-methoxyacetaldehyde – and, as determined by electronic structure calculations, may form via unimolecular decomposition of 1,2-dimethoxyethanyl or 1,2-dimethoxyethanylperoxy. O2-dependent yield ratios show that the formation pathways for all species undergo a competition between O2-addition and unimolecular decomposition. Adiabatic ionization energies were also calculated and utilized along with exact mass determinations to infer contributions for other species derived exclusively from first- and second-O2-addition, including 1,2-dimethoxyethene, cyclic ethers, and dicarbonyls.In addition to species formed from conventional low-temperature oxidation pathways, an important conclusion is derived from the detection of species produced from an O2-addition step involving ĊH2CH2OCH3 (R˙′), which forms via prompt dissociation of the primary 1,2-dimethoxyethanyl radical (ĊH2O(CH2)2OCH3). Species derived from R˙′ + O2 – 1,3-dioxolane and methyl acetate – were detected at [O2] = 1.2 · 1017 cm–3 and formed on timescales parallel to the main R˙ + O2 reactions. In addition, ion signal at m/z 106 was detected and increased with O2 concentration from which connections are drawn to ketohydroperoxides produced by Q˙′OOH + O2. Detection of such species indicate that β-scission of 1,2-dimethoxyethanyl is sufficiently facile such that timescales of R˙′ + O2 compete with conventional R˙ + O2 pathways.

Theoretical and experimental study on the pyrolysis of N-methylpyrrolidone

As a widely used organic solvent, N-methylpyrrolidone (NMP) may suffer thermal decomposition during large-scale industrial usage. The complex potential energy surface and corresponding pressure-dependent rate coefficients of NMP and NMP radicals were obtained at a high level of theory. The intermediates and products of NMP pyrolysis within 900–1200 K were identified and measured by synchrotron vacuum ultraviolet photoionization mass spectrometry. Theoretical calculations show that the Keto-enol tautomerization and direct ring-opening channel yielding C2H4, CO, and CH3NCH2 exhibit the highest rate coefficient among NMP unimolecular reactions at low and high temperatures, respectively. However, the fuel decomposition process cannot be exclusively dominated by single low-barrier channel. The ring-opening reaction forming imino aldehyde radical and following decarbonylation reactions are favored channels during the NMP radical decomposition, while the formation of the dihydropyrrolidone via H or CH3 loss competes with them at higher temperatures. Various smaller heterocycle radicals can be produced and act as intermediates for the multi-step isomerization of the ring-opening products with a relatively low energy barrier, changing the position of the functional group and radical site. A variety of nitrogenous and oxygenated species were observed in the experiment, such as ketene, methyl isocyanate, pyrrole, benzene, and different kinds of imines. Among them, C2H4, HCN, and CO are the major products for NMP decomposition. Potential reaction pathways from NMP to the major experimentally observed products were inferred based on the calculated results and existing knowledge on the pyrolysis of nitrogenous and oxygenated compounds. These results shed light on the complex C/H/O/N reaction system. The calculated rate coefficients and extensive mole fractions data could provide good support for the modeling of a detailed reaction mechanism in the future.

Experimental and modeling investigation of the oxidation of n-hexylbenzene: Insight into the formation of low-temperature intermediates

As vital components in transportation fuels, an in-depth understanding of the oxidation mechanism of n-alkylbenzenes is pivotal for minimizing pollutant emissions during combustion processes. However, previous research was mostly focused on high-temperature oxidation, while investigations on low-temperature oxidation of long-chain n-alkylbenzenes remains scarce. In this work, n-hexylbenzene (C12H18) was selected to conduct low-temperature oxidation experiments in a jet-stirred reactor. A series of crucial intermediates and products were detected and then quantified by the synchrotron vacuum ultraviolet radiation photoionization mass spectrometry (SVUV-PIMS). In particular, characteristic aromatic oxygenated intermediates with compositions of C12H18Oy, C12H16Oy, C12H14Oy and C12H12Oy (0 ≤ y ≤ 3) were measured, which reveal the occurrence of first O2 addition, second O2 addition, and sequential oxidation reactions. To disclose the crucial reactions that control the fuel decomposition and formation of oxygenated intermediates, a detailed kinetic model of n-hexylbenzene was developed. This model was further utilized to explore the oxidation behaviors of C6 to C12n-alkylbenzenes. It was revealed that n-hexylbenzene exhibits the strongest low-temperature oxidation reactivity, while C6C10n-alkylbenzenes display little reactivity under present conditions. In conclusion, the reasonable performance of this model in predicting the oxidation behaviors of n-alkylbenzenes indicates its potential application in elucidating the low-temperature oxidation chemistry of heavier n-alkylbenzenes.

Probing the Reaction of Propargyl Radical with Molecular Oxygen by Synchrotron VUV Photoionization Mass Spectrometry.

Self-reaction of propargyl (C3H3) radical is the main pathway to benzene, the formation of which is the rate-controlling step toward the formation of polycyclic aromatic hydrocarbons (PAHs) and soot. Oxidation of C3H3 is a promising strategy to inhibit the formation of hazardous PAHs and soot. In the present study, we studied the C3H3 + O2 reaction from 650 to 1100 K in a laminar flow reactor and identified the intermediates and products by synchrotron VUV photoionization mass spectrometry. 2-Propynal, ethenone, formaldehyde, CO, CO2, C2H2, C2H4, and C3O2 were identified. Among them, 2-propynal, ethenone, and formaldehyde provided direct evidence for the branching reaction of C3H3 + O2 → HCCCHO + OH, C3H3 + O2 → H2CCO + CHO, and C3H3 + O2 → H2CO + CHCO, respectively. Potential energy surface calculation and mechanistic analysis of the C3O2 formations implied that C3H3 + O2 → CCCHO + H2O and C3H3 + O2 → HCCCO + H2O could occur, despite lacking direct observations of CCCHO and HCCCO radicals. The formation of ethenone and CO suggested the occurrence of the two CO elimination channels. We incorporated these validated reactions and the corresponding rate coefficients in the kinetic model of NUIGMech1.3, and the simulation showed obvious improvements toward the measured mole fractions of C3H3 and H2CCO, suggesting that the new C3H3 + O2 reaction channels were crucial in the overall combustion modeling of the important intermediate propyne (C3H4).

An experimental study of surrogates of diesel from indirect coal liquefaction and the development of an improved kinetic mechanism

The increasing energy shortage and environmental pollution make the use of clean and efficient alternative fuels an effective way to solve the emission problem. Diesel from indirect coal liquefied (DICL) is a clean and efficient alternative fuel for diesel engines. The composition and chemical kinetics mechanism of DICL research contributes to a better understanding of combustion and pollutant formation process. The components of DICL were analysed by gas chromatography-mass spectrometry (GC-MS). The proportion of normal alkanes contained in DICL is particularly high, 93.82%, which proves that its reactivity is particularly good. The mixture of n-dodecane and iso-octane was selected as the surrogates of DICL. The oxidation process of DICL surrogates was examined by a jet-stirred reactor (JSR) over the temperature range of 500–890 K. A detailed kinetic mechanism of surrogates encompassing 1356 species and 6008 reactions was constructed. The critical reactions associated with the reactivity of surrogates were adjusted by the sensitivity analysis method to increase the accuracy of mechanism prediction. The predicted value of the improved mechanism is in good agreement with the experimental value. The improved mechanism can reasonably predict the oxidation process and the ignition characteristics of DICL and the improved mechanism can provide a good reference value for the subsequent analysis of combustion and emission problems of DICL. Abbreviations: C/H, C/H ratio; CN, cetane number; DDCL, direct coal liquefy diesel; DICL, Diesel from indirect coal liquefied; GC-MS, gas chromatography-mass spectrometry; HMN, 2,2,4,4,6,8,8-heptamethylnonane; HXN, n-hexadecane; IDT, ignition delay time; JSR, jet-stirred reactor; LHV, low heating value; LLNL, Lawrence Livermore National Laboratory; NSRL, National Synchrotron Radiation Laboratory; NTC, negative temperature coefficient; PICS, photoionization cross section; PRF, gasoline substitute; PSR, perfectly stirred reactor; SVUV-PIMS, Synchrotron VUV photoionization mass spectrometry; TOF-MS, time-of-flight mass spectrometer

Enhancing extinguishing efficiency for lithium-ion battery fire: Investigating the extinguishing mechanism and surface/interfacial activity of F-500 microcapsule extinguishing agent

Due to the high flammability and combustion enthalpy, electrolyte solvents such as dimethyl carbonate (DMC) are regarded as the main fuel in combustion reactions for lithium-ion batteries (LIBs). Herein, to understand the combustion reaction kinetics of LIB fires and explore the efficient extinguishing agent, the chemical oxidation kinetics of DMC at 740–1160 K are studied through a jet-stirred reactor system coupled to the synchrotron vacuum ultraviolet photoionization mass spectrometry and GC. The major consumption path of DMC is the H-abstraction reaction of OH∙ and H∙ radicals. CH3∙ radicals produce to CH4, C2H4 and other common alkane gases in LIB fires through H-abstraction reactions and compound reaction. On this basis, the extinguishing mechanism of F-500 extinguishing agent for LIB fires is studied. The hydrophilic (-[CH2-CH2-O]5) and oleophilic ([C16H33]-) groups give F-500 molecules the amphiphilic characteristics of adsorbing on the solution surface and associating inside the solution to form micelles. Based on the results of dynamic light scattering and cryo-electron microscopy, the size and number of micelles continue to increase and the structure of micelles gradually changes from spherical to rod-shaped, which enhance the solubilization effect. F-500 can strengthen the extinguishing effectiveness of water mist by capturing and encapsulating the DMC inside the water to form “DMC-F-500-Water” microcapsule. DMC is dispersed in the water, which leads to the heat loss and the reduction of concentration and flammability. Moreover, the adsorption of F-500 molecules along the solid-liquid-gas three-phase contact line can reduce the interfacial tension of water and promote wetting process, which leads to the larger spreading area and speed of evaporation. During the application of the extinguishing agent, F-500 agent can improve the cooling efficiency of water. This work provides a reference for the design and development of novel extinguishing agent for LIB fires.

Comparative studies of the NOx impacts on the photooxidation mechanisms of isomeric monoterpenes of β-pinene and limonene

It is highly challenging to precisely compare the impacts of anthropogenic pollutants on the photooxidation of isomeric volatile organic compounds with respect to molecular compositions and particle number/mass concentrations of secondary organic aerosols (SOAs). In this study, we conducted a series of well-defined indoor chamber experiments to compare the effects of NOx (NO and NO2) on the photooxidation of isomeric monoterpenes of β-pinene and limonene. For the photooxidation of β-pinene with NOx, the increase of the initial concentrations of NO ([NO]0) shows a monotonous suppression of the particle mass concentration, whereas the increase of [NO2]0 shows a monotonous enhancement of the particle mass concentration. For the photooxidation of limonene with NOx, the increase of [NO]0 exhibits a monotonous suppression of the particle mass concentration, whereas the increase of [NO2]0 shows a parabolic trend of the particle mass concentration. Utilizing a newly developed vacuum ultraviolet free electron laser (VUV-FEL), the online threshold photoionization mass spectrometry reveals a series of novel compounds at molecular weight (MW) = 232 and 306 for the β-pinene + NOx system and MW = 187, 261, 280, and 306 for the limonene + NOx system. The molecular structures and formation pathways of these species were inferred, which led to the prediction of the diversity and difference of SOA products (i.e., ester and peroxide accretion products) formed from different monoterpene precursors. To improve the predictions of future air quality, it is recommended that climate models should incorporate the NOx-driven diurnal photooxidation of monoterpenes for SOA formation mechanisms.

Effect of methanol-water mixtures on the oxidation of n-heptane at low to intermediate temperatures: Experimental and numerical study

Methanol is widely recognized as a carbon-neutral fuel. This work used synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) to study the oxidation process of water/methanol/n-heptane mixes in a jet-stirred reactor (JSR) at a pressure of 1 atm, equivalence ratios (ϕ) of 1 and a temperature range of 500–1100 K. The results of the experiment indicate that the inhibition of n-heptane's oxidation at low temperatures (500–740K) is the primary manifestation of the action of methanol/water mixtures on n-heptane oxidation. The strong interactions among the components of water/methanol/n-heptane mixtures at low temperatures are primarily between methanol and n-heptane. The higher the methanol content, the greater the strength of inhibition of n-heptane oxidation. This inhibitory effect primarily results from the competition of methanol with ˙OH radicals. It is noteworthy that the chemical kinetic interactions between methanol-water mixtures and n-heptane not only manifest changes in the ˙OH radical pools but are also associated with the intermolecular chemical kinetic interactions between peroxyalkyl radicals (ROO˙) and CH3OH.

Thermal decomposition study of 1,3-dioxolane as a representative of battery solvent

As industrial compounds and organic solvent, 1,3-dioxolane (C3H6O2) is used in lithium-ion batteries arousing extensive interest. The pyrolysis of C3H6O2 at 150 torr pressure was conducted in the temperature range of 743–1013 K. In order to quantify the major products, experimental measurements of the photoionization cross-section (PICS) and photoionization efficiency (PIE) for C3H6O2 were carried out by using synchrotron radiation photoionization mass spectrometry (SR-PIMS). Twenty-three intermediates were detected in pyrolysis of C3H6O2 including the newly observed ketene, acetaldehyde, ethenol, ethanol, dimethyl ether, diacetylene and 2-propen-1-ol which played important roles in developing mechanism. The H-abstraction of C3H6O2 by H, CH3 and OH radicals were studied via high level ab initio calculations. EStokTP code was used to find and calculate optimal geometries, vibration frequencies and intrinsic reaction coordinate (IRC) at the theory level of M06–2X/6–311+G(d,p). Conventional transition state theory (TST) was used and Rice-Ramsperger-Kassel-Marcus/Master Equation (RRKM/ME) was solved to obtain rate coefficients. For H-abstraction by H and CH3, the rates are increasing versus temperature, and rates of H-abstraction by OH show different tendency. These rate parameters were used to update the model of C3H6O2, which could well predict the ignition delay times (IDTs) in shock tube and oxidation data in jet stirred reactor (JSR) from literature. For the pyrolysis, H-abstraction reactions by H, CH3 and OH and unimolecular reactions contribute to solvent decay. Detailed pathways of C3H6O2 decomposition were also given and analyzed through this experiment and previous literature. The findings, including the experimental data and the calculations will assist to better understand pyrolysis characteristics of C3H6O2 as well.

Recent Progress on the Involvement of Formaldehyde in the Methanol-to-Hydrocarbons Reaction.

The conversion of methanol-to-hydrocarbons (MTH) over zeolite catalysts has been the subject of intense research since its discovery. Great effort has been devoted to the investigation of four key topics: the initiation of C-C bonds, the establishment of hydrocarbon pool (HCP), the adjustment of product selectivity, and the deactivation process of catalysts. Despite 50 years of study, some mechanisms remain controversial. However, an intermediate species, formaldehyde (HCHO), has recently garnered considerable attention for its influence on the entire MTH process. The discovery of HCHO and its significant role in the MTH process has been facilitated by the application of in situ analytical techniques, such as synchrotron radiation photoionization mass spectrometry (SR-PIMS) and photoelectron photoion coincidence spectroscopy (PEPICO). It is now revealed that HCHO is involved in the initiation, propagation, and termination process of MTH reaction. Such mechanistic understanding of HCHO's involvement has provided valuable insights for optimizing the MTH process.

A Vacuum Ultraviolet Photoionization Mass Spectrometry and Density Functional Calculation Study of Formic Acid-Water Clusters.

The interaction between formic acid (FA) and water (W) holds significant importance in various chemical processes. Our study combines vacuum-ultraviolet photoionization mass spectrometry with density functional calculations to investigate formic acid water clusters generated in supersonic molecular beams. The mass spectra obtained reveal the formation of protonated clusters as the major product. Enhanced intensities are observed in the mass spectra for a number of clusters holding the following composition, FA1W5H+, FA2W4H+, FA3W3H+, FA4W2H+, FA5W1H+ and FA6W2H+ compared to their neighbors with one less or one more water component. Our calculations shed light on these potentially stable structures, highlighting cyclic arrangements with molecules enclosed within the ring as the most stable structures, and demonstrate a decrease in the stability upon the addition of a water molecule. Comparing experimental appearance energies with calculated ionization energies suggests that fragmentation can occur from clusters of various sizes.

Rapid differentiation of cystic fibrosis-related bacteria via reagentless atmospheric pressure photoionisation mass spectrometry

Breath analysis is an area of significant interest in medical research as it allows for non-invasive sampling with exceptional potential for disease monitoring and diagnosis. Volatile organic compounds (VOCs) found in breath can offer critical insight into a person’s lifestyle and/or disease/health state. To this end, the development of a rapid, sensitive, cost-effective and potentially portable method for the detection of key compounds in breath would mark a significant advancement. Herein, we have designed, built and tested a novel reagent-less atmospheric pressure photoionisation (APPI) source, coupled with mass spectrometry (MS), utilising a bespoke bias electrode within a custom 3D printed sampling chamber for direct analysis of VOCs. Optimal APPI-MS conditions were identified, including bias voltage, cone voltage and vaporisation temperature. Calibration curves were produced for ethanol, acetone, 2-butanone, ethyl acetate and eucalyptol, yielding R2 > 0.99 and limits of detection < 10 pg. As a pre-clinical proof of concept, this method was applied to bacterial headspace samples of Escherichia coli (EC), Pseudomonas aeruginosa (PSA) and Staphylococcus aureus (SA) collected in 1 L Tedlar bags. In particular, PSA and SA are commonly associated with lung infection in cystic fibrosis patients. The headspace samples were classified using principal component analysis with 86.9% of the total variance across the first three components and yielding 100% classification in a blind-sample study. All experiments conducted with the novel APPI arrangement were carried out directly in real-time with low-resolution MS, which opens up exciting possibilities in the future for on-site (e.g., in the clinic) analysis with a portable system.

Synchrotron vacuum ultraviolet photoionization mass spectrometry and modeling study of iso-octane low temperature oxidation at varied pressures

Because of its excellent anti-knock properties, iso-octane has been selected as the main component of gasoline surrogates, and a thorough understanding of its low temperature oxidation process is essential for the development of kinetic models. Although iso-octane has been studied for decades, a comprehensive understanding of its low temperature oxidation chemistry has not been realized, and kinetic models were not well developed. In this work, the previously developed, variable pressure jet-stirred reactor-synchrotron vacuum ultraviolet photoionization mass spectrometry system was used to study the low temperature oxidation of iso-octane at five bar, with an initial fuel mole fraction of 0.01, residence time of 2 s, and equivalence ratio of 0.25. Dozens of oxidation intermediates were qualitatively and quantitatively analyzed, helping to reveal the low temperature oxidation reaction processes of iso-octane and examine the kinetic models. Comparing iso-octane studies at high pressure in the literature, a highly detailed species pool was probed, which included H2O2, carbonyl acids, alkyl hydroperoxides, and keto-hydroperoxides (KHP). By combining the atmospheric pressure data in the literature, the recently developed model of iso-octane low temperature oxidation was examined. Further improvement of the kinetic model was achieved by carefully tuning the reaction rate constant of the KHP decomposition. Finally, according to the variation of mole fraction of products at different pressures, the pressure effects on key reaction pathways were discussed, and the selectivity of products at varied pressure conditions clarified.

Fulvenallenyl Radical (C7H5·)-Mediated Gas-Phase Synthesis of Bicyclic Aromatic C10H8 Isomers: Can Fulvenallenyl Efficiently React with Closed-Shell Hydrocarbons?

To understand the reactivity of resonantly stabilized radicals, often found in relevant concentrations in gaseous environments, it is important to determine their main reaction pathways. Here, it is investigated whether the fulvenallenyl radical (C7H5·) reacts preferentially with closed-shell molecules or radicals. Electronic structure calculations on the C10H9 potential energy surface accessed by the reactions of C7H5· with methylacetylene (CH3CCH) and allene (H2CCCH2) were combined with RRKM-ME calculations of temperature- and pressure-dependent rate constants using the automated EStokTP software suite and kinetic modeling to assess the reactivity of C7H5· with closed-shell unsaturated hydrocarbons. Experimentally, the reactions were attempted in a chemical microreactor heated to 998 ± 10 K by preparing fulvenallenyl radicals via pyrolysis of trichloromethylbenzene (C7H5Cl3) and seeding the radicals in methylacetylene or allene carrier gas, with product identification by means of photoionization mass spectrometry. The measured photoionization efficiency curve of m/z = 128 was assigned to a linear combination of the reference curves of two C10H8 isomers, azulene (minor) and naphthalene (major), presumably resulting from the C7H5· plus C3H4 reactions. However, the calculations demonstrated that these reactions are too slow, and kinetic modeling of processes in the reactor allowed us to conclude that the observation of naphthalene and azulene is due to the C7H5· plus C3H3· reaction, where propargyl is produced by direct hydrogen atom abstraction by chlorine (Cl) atoms from allene or methylacetylene and Cl stem from the pyrolysis of C7H5Cl3. Modeling results under the copyrolysis conditions of toluene and methylacetylene in high-temperature shock tube experiments confirmed the prevalence of the fulvenallenyl reaction with propargyl over its reactions with C3H4 even when the concentrations of allene and methylacetylene largely exceed that of propargyl. Overall, the reactions of fulvenallenyl with both allene and methylacetylene were found to be noncompetitive in the formation of naphthalene and azulene thus attesting the inefficiency of the fulvenallenyl radical reactions with the prototype closed-shell hydrocarbon species. In the meantime, the new reaction pathways revealed, including H-assisted isomerizations between C10H8 isomers and decomposition reactions of various C10H9 isomers, emerge as relevant and are recommended for inclusion in combustion kinetic models for naphthalene formation.

Ultrafine particles formation from ozonolysis of gas- and particle-phases of cigarette smoke

Cigarette smoke and ozone (O3) are two main pollutants in indoor environments and their mutual reaction can generate substantial detrimental substances having synergistic influences on the environment and human health. The aging process of cigarette smoke in the atmosphere is mainly gone through ozonolysis reaction attracting increasing attention in recent years. Herein, the ozonolysis reaction of cigarette smoke with indoor O3 concentrations has been investigated in a Teflon chamber. The gas- and particle-phases of cigarette smoke are divided and their individual ozonolysis process can generate ultrafine particles (UFPs) with high number concentrations. The chemical compositions of the gas- and particle-phases of cigarette smoke as well as their nascent UFPs are measured and their differences during the ozonolysis have been clearly observed with vacuum ultraviolet (VUV) photoionization mass spectrometry. In particular, several representative key species of cigarette smoke, i.e., the gas-phase furan and 2,5-dimethylfuran and the particle-phase nicotine, as well as their ozonolysis products are definitely identified and play an important role in the nucleation formation of UFPs. Their ozonolysis reaction mechanisms are also discussed. In addition, this work demonstrates that the ozonolysis of the particle-phase of cigarette smoke contributes more UFPs than that of the gas-phase.

Thermal decomposition study of 4-methyloxybenzyl-glycoside by TG/DTA and on-line pyrolysis-photoionization mass spectrometry

A flavor precursor of 4-methyloxybenzyl-2, 3, 4, 6-tetra-O-acetyl-β-d-glucopyranoside (MBGL) was synthesized via a modified Koenigs–Knorr reaction. The thermal decomposition behaviour and pyrolysis intermediate products of the glycoside were studied by simultaneous thermogravimetric/differential thermal analysis (TG/DTA) and synchrotron vacuum ultraviolet (VUV) photoionization mass spectrometry (PIMS). TG/DTA results showed that the largest mass loss rate appeared at a Tp of 246.7 °C. PIMS was used to identify the pyrolysis products of MBGL at 300 °C, 500 °C and 700 °C, respectively. The experimental apparatus had some advantages in real-time analysis and fewer secondary reactions. Some important pyrolysis intermediates, such as the ions of the 4-methyloxybenzyl group at m/z 121 and the glycone moiety at m/z 347, were detected by PIMS. The results indicate that the MBGL was probably showed a different pyrolysis way compared with the other glycosides. This work reports a useful application of synchrotron VUV PIMS in a thermal decomposition study of glycoside flavor precursors.