Tube Experiments Research Articles

Numerical simulation of shock attenuation with real gas effects and a turbulent boundary layer in the expansion tube

AbstractThe influence of real gas effects and a turbulent boundary layer on shock wave attenuation in the expansion tube is studied by numerically solving the axisymmetric compressible Navier–Stokes equations with an adaptive mesh refinement technique. Numerical simulation results reveal that the ideal gas assumption is not applicable to the expansion tube, and the turbulent boundary layer plays a major role in decreasing the shock wave speed in the acceleration tube of the expansion tube. Shock wave attenuation is attributed to the turbulent boundary layer decreasing the pressure behind the shock wave. The numerical simulations that include the real gas effects and the development of turbulent boundary layers qualitatively agree with analytical solutions in the shock tube, and they show good agreement with the experimental results, especially for the shock speed in the acceleration tube of the expansion tube. Both effects should be considered in the numerical simulation model aimed to support experiments in expansion tubes.

Analysis of Low-Frequency Sound Absorption Performance and Optimization of Structural Parameters for Acoustic Metamaterials for Spatial Double Helix Resonators

Low-frequency noise absorbers often require large structural dimensions, constraining their development in practical applications. In order to improve space utilization, an acoustic metamaterial with a spatial double helix, called a spatial double helix resonator (SDHR), is proposed in this paper. An analytical model of the spatial double-helix resonator is established and verified by numerical simulations and impedance tube experiments. By comparing the acoustic absorption coefficients of the spatial double-helix resonator, it is shown that the results of the analytical model, the numerical model, and the experiments are in good agreement, proving the accuracy of the theoretical model. The effects of different structural parameters on the peak sound absorption coefficient and resonance frequency are quantitatively revealed. The impedance variation law of the model is obtained, and the resistance and reactance distributions at the resonance frequency are analyzed. In the optimization model, the Back Propagation (BP) network is used to construct the mapping between the structural parameters and the resonance frequency and sound absorption coefficient, and this is used as the constraints of the equation, which is combined with Wild Horse Optimization (WHO) to establish the BP-WHO optimization model to minimize the volume of the spatial double helix resonator. The results show that, for a given noise frequency, the optimized structural parameters enhance the space utilization without affecting the performance of the space double helix resonator.

Efficient and broadband sound absorption properties of slotted aluminum foam

To enhance the sound absorption performance of aluminum foam, a slotted structure was developed. Firstly, the theoretical model of sound absorption for the slotted aluminum foam was established by the transfer matrix method. Secondly, the finite element model was established using COMSOL software to predict the sound absorption coefficient. The reliability of the theoretical and finite element models was validated through impedance tube experiments. The sound absorption mechanism is investigated by analyzing the internal sound field. Finally, the sound absorption properties of aluminum foam with other slot patterns are investigated. Additionally, the factors that influence sound absorption properties are investigated. The results indicate that the slots alter the sound pressure distribution within the material, inducing a pressure diffusion effect. When sound waves enter the interior of the material through the narrow slots, they are absorbed and dissipated by the matrix material on the sides of the slots. The sound absorption coefficient can be improved by increasing the thickness, slot scale, and slot depth of the slotted aluminum foam. Specifically, when the slot depth is 15 mm, and the slot width is 5 mm, the average sound absorption coefficient of incompletely slotted aluminum foam in the frequency range of 1000 ∼ 6300 Hz is 0.86, which can realize broadband sound absorption. With the increase of slot depth, the sound absorption peak becomes more pronounced.

Formation of Nitrosamines from the Heterogeneous Reaction of Nitrous Acid and Organic Amines in Indoor Environments.

Carcinogenic nitrosamines have been widely studied due to their risk to human health. However, the universality and evolutionary processes of their generation, particularly concerning their secondary sources, remain unclear at present. We demonstrated through laboratory flow tube experiments that corresponding nitrosamines were generated from heterogeneous reactions of nitrous acid (HONO) with five structurally diverse amines commonly found indoors, including diphenylamine (DPhA), dibenzylamine (DBzA), dioctylamine (DOtA), N-(1,3-dimethylbutyl)-N'-phenyl-p-phenylenediamine (6PPD), and N-phenyl-1-naphthylamine (PANA). The heterogeneous reaction rate constants of DBzA and DOtA with HONO (∼70 ppb) were 1.21 × 10-3 and 2.13 × 10-3 min-1 at 30% relative humidity (RH), resulting in a lifetime of 13.8 and 7.8 h. As compared to higher RH (∼80%), more nitrosamines were produced from the reaction of HONO with surface-sorbed DBzA, DOtA, 6PPD, and PANA at lower RH (30%), with product yields ranging from <0.1% to 0.5%. Furthermore, we observed the formation of nitroso-6PPDs and nitro-6PPDs during room air exposure of 6PPD in a genuine indoor environment, in addition to various other transformation products indicative of reactions of 6PPD with HONO, NOx, and ozone indoors. This study confirmed the universality of the heterogeneous reaction of surface-sorbed amine with HONO as a source of nitrosamines indoors.

Evaluation of a reduced-pressure chemical ion reactor utilizing adduct ionization for the detection of gaseous organic and inorganic species

Abstract. Volatile organic compounds (VOCs) and volatile inorganic compounds (VICs) provide critical information across many scientific fields including atmospheric chemistry and soil and biological processes. Chemical ionization (CI) mass spectrometry has become a powerful tool for tracking these chemically complex and temporally variable compounds in a variety of laboratory and field environments. It is particularly powerful with time-of-flight mass spectrometers, which can measure hundreds of compounds in a fraction of a second and have enabled entirely new branches of VOC and/or VIC research in atmospheric and biological chemistry. To accurately describe each step of these chemical, physical, and biological processes, measurements across the entire range of gaseous products is crucial. Recently, chemically comprehensive gas-phase measurements have been performed using many CI mass spectrometers deployed in parallel, each utilizing a different ionization method to cover a broad range of compounds. Here we introduce the recently developed Vocus AIM (adduct ionization mechanism) ion–molecule reactor (IMR), which samples trace vapors in air and ionizes them via chemical ionization at medium pressures. The Vocus AIM supports the use of many different reagent ions of positive and negative polarity and is largely independent of changes in the sample humidity. Within the present study, we present the performance and explore the capabilities of the Vocus AIM using various chemical ionization schemes, including chloride (Cl−), bromide (Br−), iodide (I−), nitrate (NO3-), benzene cations (C6H6+), acetone dimers ((C3H6O)2H+), and ammonium (NH4+) reagent ions, primarily in laboratory and flow tube experiments. We report the technical characteristics and operational principles, and compare its performance in terms of time response, humidity dependence, and sensitivity to that of previous chemical ionization approaches. This work demonstrates the benefits of the Vocus AIM reactor, which provides a versatile platform to characterize VOCs and VICs in real time at trace concentrations.

Decontamination of Bacterial Spores Using a Bio-reaction System

This report describes the test results of decontamination of Bacillus atrophaeus spores. The spore solution at 109 cfu/mL concentration was treated with chemical decontaminants, hydrogen peroxide, DF-200, sodium dichloroisocyanurate(NaDCC), and perasasfe. DF-200 was not suitable for decontamination of the spore solution. Among them, the optimal decontamination reaction conditions of perasafe and NaDCC were established from test tube experiments in a mL-scale, and they were validated in a bio-reaction system in a L-scale. The optimal conditions of perasafe and NaDCC were 1.0 % of concentration with 5 minutes of reaction time and 0.3 % of concentration with 10 minutes of reaction time, respectively. Also, both decontaminants required adequate agitation for decontamination. The results in the bio-reaction system were similar with the results from the smaller scale using test tubes, showing that the optimal conditions from the smaller scale experiments can be applied to the larger scale.

Validation of an absorption coefficient measurement technique using two cardioid microphones in any impedance tube

We have proposed a technique for measuring sound pressure and particle velocity using a combination of cardioid microphones and then applied it to obtain the acoustic absorption coefficient in a tube. So far, we have revealed that either using one cardioid microphone measured twice or using a pair of cardioid microphones measured once are both suitable for the measurement and that the calibration of the cardioid microphones is required. If the technique works correctly, this technique holds promise for measuring the acoustic absorption coefficient of various specimens in any tube and with any cardioid microphones. To validate the technique's effectiveness, we conducted experiments in multiple square-section wooden or round-section steel tubes, with specimens of glass wool and polyester terephthalate (PET) wool. As a result, this technique can provide accurate absorption coefficient measurements in any tube configuration.

The universal gaseous detonation dynamics

The present communication proposes a new scaling approach to unify the dynamics of gaseous detonations subject to wall losses in both the narrow channels and small tubes, by compiling the published experimental data of detonations in 23 different mixtures with a very large range of cellular instabilities. A kinetic induction length Δi,loss can be determined from the detonation velocity deficit and detailed chemistry. In order to take into account the sensitivity of the latter length to post-shock temperature fluctuations (through the reduced activation energy θ), which is a partial and indirect marker of the cellular structure, and to bring out energetics (through the Chapman–Jouguet detonation Mach number MCJ), an effective kinetic length of Δi,loss(MCJ4/θ3) was built and has been shown to collapse the different detonation dynamics of various gaseous mixtures, subjected to wall losses, into a single universal curve for detonation velocity deficits.Novelty and Significance: Scaling analysis of large sets of published data of gaseous detonation experiments in narrow channels and small tubes has been made for 23 different mixtures with varied cellular instabilities and activation energies. The universal dynamics of gaseous detonations subject to wall losses in different mixtures has been achieved, for the first time, by adopting an effective kinetic length by taking into account the effect of both the activation energy and the energetics.

Experimental study on the acoustic properties of monofilament fabrics

The traditional machining perforated sound absorption structure has high processing cost and inconvenient installation and disassembly, so that how to efficiently and economically manufacture submillimeter micropores still remains a challenge. In this study, a kind of flexible microporous sound absorbing material was obtained by weaving a polymer artificial fiber covered with ethylene polyester fiber, and the relationship between the sound absorption performance of the curtain and the porosity of the pass and fabric was obtained through the finite element simulation model and impedance tube experiment. The mechanism parameters of wide-band flexible microporous material with high sound absorption performance are obtained, which guide the design of a kind of sound absorption material with lower production cost and easy installation and disassembly.

Decomposition of CH3NH2${\rm CH}_3{\rm NH}_2$: Implications for CHx/NHy${\rm CH}_{\rm {\it x}}/{\rm NH}_{\rm {\it y}}$ radical–radical reactions

AbstractExperiments on methylamine () decomposition in shock tubes, flow reactors, and batch reactors have been re‐examined to improve the understanding of hydrocarbon/amine interactions and constrain rate constants for + reactions. In high‐temperature shock tube experiments, the rapid thermal dissociation of provides a fairly clean source of and radicals, allowing an assessment of reactions of with and NH. At the lower temperatures in batch and flow reactors, is mostly consumed by reaction with H to form + ; these results are useful in determining the fate of the radical. Interpretation of these data, along with flow reactor data for the /H system at lower temperature, indicates that at temperatures up to about 1400 K at atmospheric pressure and above 2000 K at 100 atm, the + reaction forms mainly methylamine. At sufficiently high temperature, H‐abstraction to form + NH and addition–elimination to form + H become competitive. The + NH reaction, with a rate constant close to collision frequency, forms + H, also leading into the hydrocarbon amine pool. Thus, methylamine can be expected to be an important intermediate in co‐combustion of natural gas and ammonia, and more work on the chemistry of is desirable.

Experimental study on the thermal performance of a high-temperature finned latent heat storage system

The primary objective of this study is to develop and evaluate the performance of a latent heat storage (LHS) system. A tube-in-tube heat exchanger configuration was used to design the LHS system. Sodium nitrate and air were employed as the phase change material (PCM) and heat transfer fluid (HTF), respectively. To mitigate the low thermal conductivity of the PCM, six circular fins were integrated on the HTF tube surface and experiments were conducted in an in-house experimental facility. Temperature plots from the charging-discharging experiments revealed that the HTF flow direction governs the heat transfer along the axis of the system. The sensible heat gain by the PCM in the range of 270–330 °C, led to an additional ⁓0.4 MJ of heat storage beyond the storage capacity of 1 MJ. Furthermore, increasing the inlet temperature from 400 °C to 440 °C reduced the charging time by 39.6 %, while reducing the inlet temperature from 210 °C to 170 °C decreased the discharging time by 18.2 %. Despite improved heat transfer, higher inlet temperatures adversely affected the thermal uniformity whereas, the increase in inlet air velocity enhanced both the dynamics of heat transfer and the thermal uniformity within the storage system.

Kinetic insights into double-branched acyclic ether: Methyl tert-butyl ether and 2,2-dimethoxypropane

This study presents the first kinetic mechanism for methyl tert-butyl ether (MTBE) containing low-temperature chemistry, as well as the first mechanism for 2,2-dimethoxypropane (DMP). The mechanisms have been validated against ignition delay time experiments conducted in a high-pressure shock tube and rapid compression machine. The rapid compression machine conditions were set to 20 and 40 bar for MTBE, and 10 and 20 bar for DMP in a temperature range of 584 to 946 K. Shock tube experiments have been performed for DMP at 20 and 40 bar for stoichiometric and fuel-lean conditions in air at temperatures ranging from 913 to 1173 K. A pronounced negative temperature coefficient regime with two-stage ignition has been observed for both fuels. The developed mechanism consists of reaction rate constants that were primarily modeled in analogy to iso-octane and dimethoxymethane, and calculated thermodata on the G4//B3LYP-D3BJ/def2-TZVP level of theory. Simulations have been performed to analyze the fuel oxidation at different temperatures. Over the full temperature range, H-atom abstraction occurs mainly on the α-side for DMP and on the β-side for MTBE. At low temperatures, both fuels isomerize to the peroxy radical. The dominant MTBE radicals then tend to produce cyclic ether, while the DMP radicals react with O2, enabling significant chain branching and explaining the higher reactivity of DMP. With rising temperature, β-scission of the fuel radicals and unimolecular elimination reactions start to dominate the oxidation process.Novelty and Significance StatementThe novelty of this research is the first observation of a two-stage ignition of methyl-tert butyl ether (MTBE) in an RCM and a discussion of its fundamental ignition chemistry, which is based on a developed detailed kinetic mechanism. In addition, 2,2-dimethoxypropane (DMP) has been investigated experimentally and theoretically to explain the difference in reactivity to MTBE despite their strong molecular similarity. The experiments include RCM and shock tube experiments. The kinetic model is based on rate constant analogies and newly calculated thermo data on the G4//B3LYP-D3BJ/def2-TZVP level of theory. This work is significant, as MTBE is still a widely used octane booster and the developed model could help to improve engine simulations. Furthermore, the findings of DMP provide insights into future fuel design.

Maximum likelihood estimators for colony-forming units.

Measuring the abundance of microbes in a sample is a common procedure with a long history, but best practices are not well-conserved across microbiological fields. Serial dilution methods are commonly used to dilute bacterial cultures to produce countable numbers of colonies, and from these counts, to infer bacterial concentrations measured in colony-forming units (CFUs). The most common methods to generate data for CFU point estimates involve plating bacteria on (or in) a solid growth medium and counting their resulting colonies or counting the number of tubes at a given dilution that have growth. Traditionally, these types of data have been analyzed separately using different analytic methods. Here, we build a direct correspondence between these approaches, which allows one to extend the use of the most probable number method from the liquid tubes experiments, for which it was developed, to the growth plates by viewing colony-sized patches of a plate as equivalent to individual tubes. We also discuss how to combine measurements taken at different dilutions, and we review several ways of analyzing colony counts, including the Poisson and truncated Poisson methods. We test all point estimate methods computationally using simulated data. For all methods, we discuss their relevant error bounds, assumptions, strengths, and weaknesses. We provide an online calculator for these estimators.Estimation of the number of microbes in a sample is an important problem with a long history. Yet common practices, such as combining results from different measurements, remain sub-optimal. We provide a comparison of methods for estimating abundance of microbes and detail a mapping between different methods, which allows to extend their range of applicability. This mapping enables higher precision estimates of colony-forming units (CFUs) using the same data already collected for traditional CFU estimation methods. Furthermore, we provide recommendations for how to combine measurements of colony counts taken across dilutions, correcting several misconceptions in the literature.

An improved prediction model for miscibility characterization and optimization of CO2 and associated gas co-injection

Insufficient reservoir pressure and gas source problems seriously limit effective applications of CO2 flooding in hydrocarbon reservoirs. An attractive strategy is to co-inject the produced associated hydrocarbon gas with CO2 to achieve miscible/near-miscible flooding to enhance oil recovery. However, the composition of the injected mixture and the in-situ spatio-temporal composition evolution of the displacing/displaced fluids significantly affect the CO2-oil miscibility and the overall hydrocarbon recovery performance. In this work, based on slim tube simulation results, a prediction model of minimum miscible pressure (MMP)/minimum near-miscible pressure (MNMP) is established. This model takes into account the effects of CO2 concentration distribution, oil composition and temperature changes to achieve accurate spatiotemporal characterization of miscibility in the reservoir. In addition, the distribution law of the phase and components front for the impure CO2 injection process was also investigated. The miscible volume factor and recovery efficiency were used as the basis for judging the minimum injection concentration limit of CO2. The simulation results of slim tube experiment indicate that the MMP and MNMP obtained are 16.74 MPa and 12.35 MPa, respectively. Furthermore, the error caused by the traditional slim tube experiment can be reduced by using the CO2 produced fraction. It is found that CO2 injection concentration and reservoir temperature are the main factors affecting miscibility, but injection rate has less effect. Moreover, the fast migration of CH4 front leads to the shrinkage of miscible/near-miscible zone, which is not conducive to CO2 flooding. Finally, the CO2 injection concentration of non-breakthrough stage, breakthrough stage and large-scale breakthrough stage was determined to be 78.3%, 61.5% and 29.2%, respectively. This work provides strong evidence for the treatment of associated gas reinjection, which is beneficial for optimization of carbon capture, EOR-utilization and storage (CCUS-EOR) projects.

Quasi-one-dimensional non-equilibrium method for shock tube and stagnation line flows

Shock tube experiments are used to investigate non-equilibrium thermochemistry and radiative processes in reacting gas hypersonic flows. Boundary layer and shock structure are known to influence the spatial variation of the test slug state properties. This work derives and validates a novel method for viscous, quasi-one-dimensional, non-equilibrium flow in a shock tube assuming constant shock speed. The proposed method fully resolves the shock structure. Mirels' estimate for boundary layer growth around the test slug determines the dilation rate at the centerline. This, along with relevant boundary conditions, appropriately models core flow in a shock tube. The flow equations are discretized by finite differences on a staggered grid. The resulting highly non-linear set of algebraic equations is solved by Newton iterations. The Jacobian matrix is block tridiagonal with a Schur complement, allowing efficient inversion. This culminates in a unique and computationally efficient quasi-one-dimensional method offering improved modeling of the physical characteristics of shock tube experiments. Results of a 3 km/s, 66.6 Pa argon test case solved by a viscous, axisymmetric Navier–Stokes solution had agreement with the proposed method in temperature and pressure profiles to within 2% and post-shock velocity to within 15%. Reacting gas shock tube experiments in synthetic air and synthetic Titan atmospheres were analyzed. Radiance values in the non-equilibrium and equilibrium regions were compared under various assumptions for the shock structure and radial velocity distribution. These results highlight the necessity of a dedicated shock tube solver when analyzing shock tube thermochemistry, particularly when determining reaction rates and relaxation parameters.

Rhythmidia: A modern tool for circadian period analysis of filamentous fungi.

Circadian rhythms are ubiquitous across the kingdoms of life and serve important roles in regulating physiology and behavior at many levels. These rhythms occur in ~24-hour cycles and are driven by a core molecular oscillator. Circadian timekeeping enables organisms to anticipate daily changes by timing their growth and internal processes. Neurospora crassa is a model organism with a long history in circadian biology, having conserved eukaryotic clock properties and observable circadian phenotypes. A core approach for measuring circadian function in Neurospora is to follow daily oscillations in the direction of growth and spore formation along a thin glass tube (race tube). While leveraging robust phenotypic readouts is useful, interpreting the outputs of large-scale race tube experiments by hand can be time-consuming and prone to human error. To provide the field with an efficient tool for analyzing race tubes, we present Rhythmidia, a graphical user interface (GUI) tool written in Python for calculating circadian periods and growth rates of Neurospora. Rhythmidia is open source, has been benchmarked against the current state-of-the-art, and is easily accessible on GitHub.

A comprehensive experimental and theoretical study of thermal response mechanisms of TKX-50 and HMX

TKX-50 and HMX, as two highly promising energetic materials, are widely used in rocket propellants. TKX-50/HMX cocrystal can also improve the defects of TKX-50 and HMX and vastly expand their application scope. Their response mechanisms to the same thermal stimulation, including reactivity and decomposition and combustion behavior, are important in understanding their combustion characteristics and engine performance. This study systematically investigates the thermal response mechanisms of TKX-50 and HMX under the same thermal stimulations based on experimental measurements and theoretical analysis. Ignition delay times and burn times of TKX-50 and HMX with different particle sizes at various temperatures and pressures are measured in shock tube experiments. ReaxFF MD simulations are performed to analyze the thermal decomposition of TKX-50 and HMX in terms of potential energy evolution, intermediate and final products, and possible reaction pathways. Ab initio kinetics of hydrogen atom abstraction reactions of TKX-50 and HMX with three highly active species, Ḣ, ȮH, and NO2, are studied. The barrier heights, reaction enthalpies and rate coefficients for all reactions are further analyzed. The results show that: (1) the ignition delay time and burn time of TKX-50 (128, 138, and 55 µm) are measured to be 200–600 µs and 40–400 µs respectively, which are almost the same as those of HMX (6 and 0.8 µm) in the same temperature range; (2) the burn time of TKX-50 is less affected by pressure but more affected by particle size, whereas both pressure and particle size have a significant effect on the burn time of HMX; (3) TKX-50 is shown to be readily decomposed and less affected by temperature changes than HMX under the same conditions; (4) ȮH is generated more rapidly in the TKX-50 system, but more persistently in the HMX system; (5) H atom abstraction reactions from TKX-50 by all species are less endothermic but more exothermic than those from HMX.

Robotic exploration of Martian caves: Evaluating operational concepts through analog experiments in lava tubes

Caves on Mars are a tantalizing target for exploration, as they could harbor evidence of extinct or extant life, clues to the planet’s geological history, and even potential future human habitation. However, the inherent challenges of navigating unknown and challenging terrain, coupled with limited communication capabilities, pose significant obstacles for robotic exploration in these caves. This paper presents the results of an effort to evaluate different operational concepts for a mission dedicated to exploration of caves on Mars. We conducted a series of analog exploration experiments in lava tubes on Earth, testing two hypotheses: (1) that two robots are more effective than one, and (2) that high levels of autonomy are more effective than low levels of autonomy. Our findings suggest that two robots are indeed more effective, except in low autonomy cases, where more operational resources are required. We also found that full autonomy is more efficient than low autonomy, as it enables quicker exploration and detection of targets of interest. However, the low autonomy cases benefited from the operator input to acquire higher quality data, an area of autonomy requiring further development. This paper provides insight into the design of our experiments, as well as detailing the results and implications for the design of future missions to explore caves on Mars. By shedding light on the operational concepts tested and their corresponding outcomes, we contribute to the knowledge base required to formulate optimal strategies for the realization of successful cave exploration missions on the Red Planet.

A multifunctional heterogeneous structure inspired by shell brick-mud structure: Balancing noise reduction and mechanical performance

Electric armoured vehicles, which are crucial for strategic operations, must possess superior mechanical properties and noise reduction to maintain normal functionality. However, achieving high energy absorption and noise reduction performance simultaneously is challenging with a single uniform material or structure. This study introduces heterogeneous structures with metal lattice skeletons filled with polymer materials. The skeleton, known as the bionic mantis shrimp structure (BMS), is filled with polyurethane and epoxy. Impedance tube experiments revealed that the sound absorption coefficients of Heterostructure-polyurethane foam (HS-PU) and Heterostructure-epoxy (HS-EP) are significantly higher than BMS. HS-PU achieved an average sound insulation of 33.6 dB, marking a 739 % improvement over BMS. Compression tests show that polymer filling can inhibit the destructive collapse of BMS and enhance its mechanical performance. HS-EP exhibits specific strength and specific energy absorption values of 57 MPa/(g·cm−3) and 30.75 J/g, respectively, representing an increase of 67.6 % and 315 % compared to BMS. Additionally, as the volume fraction of BMS increased in the heterogeneous structure, the elastic modulus and compressive strength increase while the specific energy absorption decreased. This research suggest that the design of metal/polymer heterogeneous structures offers a promising approach for developing high-strength and noise-reducing protective structures.

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.