Gas-phase Reaction Kinetics Research Articles

Ab Initio and Statistical Rate Theory Exploration of the CH (X2Π) + OCS Gas-Phase Reaction.

The first theoretical results regarding the gas-phase reaction mechanism and kinetics of the CH (X2Π) + OCS reaction are presented here. This reaction has a proposed importance in the removal of OCS in regions of the interstellar medium (ISM) and has the potential to form the recently observed HCS/HSC isomers, with both constitutional isomers having recently been observed in the L483 molecular cloud in a 40:1 ratio. Statistical rate theory simulations were performed on stationary points along the reaction potential energy surface (PES) obtained from ab initio calculations at the RO-CCSD(T)/aug-cc-pV(Q+d)Z//M06-2X-D3/aug-cc-pV(Q+d)Z level of theory over the temperature and total density range of 150-3000 K and 1011-1024 cm-3, respectively, using a Master Equation analysis. Exploration of the reaction potential energy surface revealed that all three pathways identified to create CS + HCO products required surmounting barriers of 16.5 kJ mol-1 or larger when CH approached the oxygen side of OCS, rendering this product formation negligible below 1000 K, and certainly under low-temperature ISM conditions. In contrast, when CH approaches the sulfur side of OCS, only submerged barriers are found along the reaction potential energy surface to create HCCO + S or CO + HCS, both of which are formed via a strongly bound OCC(H)S intermediate (-358.9 kJ mol-1). Conversion from HCS to HSC is possible via a barrier of 77.8 kJ mol-1, which is still -34.1 kJ mol-1 below the CH + OCS entrance channel. No direct route from CH + OCS to H + CO + CS was found from our ab initio calculations. Rate theory simulations suggest that the reaction has a strong negative temperature dependence, in accordance with the barrierless addition of CH to the sulfur side of OCS. Product branching fractions were also determined from MESMER simulations over the same temperature and total density range. The product branching fraction of CO + HCS reduces from 79% at 150 K to 0.0% at 800 K, while that of HCS dissociation to H + CS + CO increases from 22% at 150 K to 100% at 800 K. The finding of CO + HCS as the major product at the low temperatures relevant to the ISM, instead of H + CS + CO, is in opposition to the current supposition used in the KIDA database and should be adapted in astrochemical models as another source of the HCS isomer.

Protonation Isomer Specific Ion-Molecule Radical Reactions.

Through a combination of ion-mobility filtering and laser-equipped quadrupole ion-trap mass spectrometry, the gas-phase reaction kinetics of two protonation isomers of the distonic-radical quinazoline cation are independently measured with ethylene. For these radical addition reactions, protonation site variations drive significant changes in nearby radical reactivity, and this is primarily due to through-space electrostatic effects. Furthermore, quantum chemical methods specifically designed for calculating long-range interactions, such as double-hybrid density functional theory, are required to rationalize the experimentally measured difference in reactivity.

Development of a numerical method for the rapid prediction of ignition performance of biomass particles

Ignition is a critical step of the combustion process of biomass, due to its substantial impact on flame characteristics, process efficiency, and pollutant formation. This paper aims to develop a robust zero-dimensional ignition model as an effective tool to quickly estimate the ignition behaviour of biomass fuels. The numerical approach integrates an established devolatilization model with a well-tested mechanism for gas-phase reaction kinetics. The ignition delay time is determined from the sum of the devolatilization time and ignition time of the evolved gas species, as specified by the maximum in the OH radical concentration. The central premise of the modelling routine is that kinetics govern the ignition delay during biomass initial heating and thermochemical conversion which makes the elemental fuel composition the most important fuel property and heating rate the most important reactor condition. The predictions of the model are tested and verified against published experimentally measured ignition data for seven pulverized biomass fuels and are found to be in good agreement. The model for the first time can reasonably distinguish ignition behaviours of different biomass fuels, enabling its use in wider industrial applications.

OH Radical and Chlorine Atom Kinetics of Substituted Aromatic Compounds: 4-chlorobenzotrifluoride (p-ClC6H4CF3).

The mechanisms for the OH radical and Cl atom gas-phase reaction kinetics of substituted aromatic compounds remain a topic of atmospheric and combustion chemistry research. 4-Chlorobenzotrifluoride (p-chlorobenzotrifluoride, p-ClC6H4CF3, PCBTF) is a commonly used substituted aromatic volatile organic compound (VOC) in solvent-based coatings. As such, PCBTF is classified as a volatile chemical product (VCP) whose release into the atmosphere potentially impacts air quality. In this study, rate coefficients, k1, for the OH + PCBTF reaction were measured over the temperature ranges 275-340 and 385-940 K using low-pressure discharge flow-tube reactors coupled with a mass spectrometer detector in the ICARE/CNRS (Orléans, France) laboratory. k1(298-353 K) was also measured using a relative rate method in the thermally regulated atmospheric simulation chamber (THALAMOS; Douai, France). k1(T) displayed a non-Arrhenius temperature dependence with a negative temperature dependence between 275 and 385 K given by k1(275-385 K) = (1.50 ± 0.15) × 10-14 exp((705 ± 30)/T) cm3 molecule-1 s-1, where k1(298 K) = (1.63 ± 0.03) × 10-13 cm3 molecule-1 s-1 and a positive temperature dependence at elevated temperatures given by k1(470-950 K) = (5.42 ± 0.40) × 10-12 exp(-(2507 ± 45) /T) cm3 molecule-1 s-1. The present k1(298 K) results are in reasonable agreement with two previous 296 K (760 Torr, syn. air) relative rate measurements. The rate coefficient for the Cl-atom + PCBTF reaction, k2, was also measured in THALAMOS using a relative rate technique that yielded k2(298 K) = (7.8 ± 2) × 10-16 cm3 molecule-1 s-1. As part of this work, the UV and infrared absorption spectra of PCBTF were measured (NOAA; Boulder, CO, USA). On the basis of the UV absorption spectrum, the atmospheric instantaneous UV photolysis lifetime of PCBTF (ground level, midlatitude, Summer) was estimated to be 3-4 days, assuming a unit photolysis quantum yield. The non-Arrhenius behavior of the OH + PCBTF reaction over the temperature range 275 to 950 K is interpreted using a mechanism for the formation of an OH-PCBTF adduct and its thermochemical stability. The results from this study are included in a discussion of the OH radical and Cl atom kinetics of halogen substituted aromatic compounds for which only limited temperature-dependent kinetic data are available.

New Insight into the Gas Phase Reaction Dynamics in Pulsed Laser Deposition of Multi-Elemental Oxides.

The gas-phase reaction dynamics and kinetics in a laser induced plasma are very much dependent on the interactions of the evaporated target material and the background gas. For metal (M) and metal–oxygen (MO) species ablated in an Ar and O2 background, the expansion dynamics in O2 are similar to the expansion dynamics in Ar for M+ ions with an MO+ dissociation energy smaller than O2. This is different for metal ions with an MO+ dissociation energy larger than for O2. This study shows that the plume expansion in O2 differentiates itself from the expansion in Ar due to the formation of MO+ species. It also shows that at a high oxygen background pressure, the preferred kinetic energy range to form MO species as a result of chemical reactions in an expanding plasma, is up to 5 eV.

Gas-Phase Reaction Kinetics of the Ortho and Ipso Adducts 1,2,4,5-Tetramethylbenzene–OH with O2

The reversible reaction of OH radicals with 1,2,4,5-tetramethylbenzene (1245-TeMB, durene) leads to adducts at the substituted (ipso) and unsubstituted (ortho) positions of the ring. By the use of flash photolysis for production and resonance fluorescence for detection of OH, the gas-phase reactions of O2 with these adducts were investigated over the temperature range of 300–340 K in He at 200 mbar. The decay of OH, generated by pulsed vacuum-UV photolysis of H2O, was monitored under slow-flow conditions in the presence of 1245-TeMB and O2 at concentrations of up to 19 × 1012 cm–3 and 2 × 1016 cm–3, respectively. Triexponential OH decays resulted from the unimolecular decomposition of the two adducts, representing OH reservoirs with different stabilities. In the presence of O2, additional adduct loss pathways exist, leading to faster OH consumption. Triexponential functions fitted to these decays were analyzed to obtain rate constants for the reactions of O2 with both adducts. Rate constants in the range of (4–13) × 10–15 and (0.3–3) × 10–15 cm3 s–1 were obtained for the ortho and the ipso adducts, respectively, depending on temperature and assumptions regarding details of the underlying mechanism of adduct isomer formation and isomerization. At O2 concentrations exceeding about 1 × 1016 cm–3, deviations from a linear dependence of the adduct loss rates on the O2 concentration indicate an even more complex mechanism. The validity of the rate constants is therefore confined to O2 concentrations below 1 × 1016 cm–3. The adduct + O2 rate constants for 1245-TeMB are greater than the corresponding previously obtained rate constants for benzene, toluene, and p- and m-xylene but smaller than those for hexamethylbenzene. The results are discussed in terms of the current knowledge about the mechanism of OH-induced degradation of aromatic compounds in the presence of O2.

DLBFoam: An open-source dynamic load balancing model for fast reacting flow simulations in OpenFOAM

Computational load imbalance is a well-known performance issue in multiprocessor reacting flow simulations utilizing directly integrated chemical kinetics. We introduce an open-source dynamic load balancing model named DLBFoam to address this issue within OpenFOAM, an open-source C++ library for Computational Fluid Dynamics (CFD). Due to the commonly applied operator splitting practice in reactive flow solvers, chemistry can be treated as an independent stiff ordinary differential equation (ODE) system within each computational cell. As a result of the highly non-linear characteristics of chemical kinetics, a large variation in the convergence rates of the ODE integrator may occur, leading to a high load imbalance across multiprocessor configurations. However, the independent nature of chemistry ODE systems leads to a problem that can be parallelized easily (called an embarrassingly parallel problem in the literature) during the flow solution. The presented model takes advantage of this feature and balances the chemistry load across available resources. Additionally, a reference mapping model is utilized to further speed-up the simulations. When DLBFoam it utilized with both these features enabled, a speed-up by a factor of 10 is reported for reactive flow benchmark cases. To the best of our knowledge, this model is the first open-source implementation of chemistry load balancing in the literature. Program summaryProgram Title: DLBFoamCPC Library link to program files:https://doi.org/10.17632/bb9zjfzcmm.1Developer's repository link:https://github.com/blttkgl/DLBFoamLicensing provisions: GPLv3Programming language: C++Nature of problem: Solution of chemical kinetics in parallel reacting flow solvers raises a computational imbalance across multiprocessor architectures. DLBFoam balances the load distribution evenly, providing significant speed-up in reacting CFD applications.Solution method: The dynamic load balancing is implemented by distributing the point-wise chemistry problems from most loaded processes to less loaded ones using MPI communication protocol.Additional comments including restrictions and unusual features: The present model is designed to work with the standard chemistry model class available in OpenFOAM (versions 7 and 8). For the time being, the model does not support derived combustion models such as “TDAC” and covers gas-phase reaction kinetics only. In addition, the boundary surface chemistry problems are neglected by the model.

The gas-phase reaction kinetics of different structure of unsaturated alcohols and ketones with O3

Unsaturated alcohols and ketones are a category of oxygenated biogenic volatile organic compounds, which reacted with tropospheric ozone and then made a significant contribution to the formation of secondary organic aerosols (SOA). However, the chemical pathways of their reaction with O3 are poorly understood. Hence, the reactions of O3 with three unsaturated alcohols and ketones were conducted in 100 L FEP Teflon smog chamber and the rate constants were obtained by using the absolute rate method. The rate constant of 4-methyl-3-penten-2-one, 2-methyl-4-penten-2-ol, 4-penten-2-ol reacting with O3 at 298 K and 760 Torr was (7.68 ± 0.80) × 10−18, (4.27 ± 0.44) × 10−18 and (5.40 ± 0.57) × 10−18 cm3molecule−1s−1, respectively. Combining with theoretical calculation, the factors leading to the different rate constants of a series of similar structure compounds were analyzed, including the steric effect of methyl in specific position and the electron withdrawing effect of hydroxyl group in the gamma position for alcohols and carbonyl group in the beta position for ketones. Moreover, the major products of three unsaturated organics reacted with ozone were detected, and the reaction mechanisms were deduced by further supporting of theoretical calculation. The atmospheric lifetime of the target compounds and the environmental significant were explored.

Rate coefficients for reactions of OH with aromatic and aliphatic volatile organic compounds determined by the multivariate relative rate technique

Abstract. The multivariate relative rate method was applied to a range of volatile organic compound (VOC) reactions with OH. This previously published method (Shaw et al., 2018) was improved to increase the sensitivity towards more slowly reacting VOCs, broadening the range of compounds which can be examined. A total of 35 room temperature relative rate coefficients were determined, eight of which have not previously been reported. Five of the new reaction rate coefficients were for large alkyl substituted mono-aromatic species recently identified in urban air masses, likely with large ozone production potentials. The new results (with kOH (296 K) values in units of 10−12 cm3 molec.−1 s−1) were n-butylbenzene, 11 (±4); n-pentylbenzene, 7 (±2); 1,2-diethylbenzene, 14 (±4); 1,3-diethylbenzene, 22 (±4); and 1,4-diethylbenzene, 16 (±4). Interestingly, whilst results for smaller VOCs agreed well with available structure–activity relationship (SAR) calculations, the larger alkyl benzenes were found to be less reactive than the SAR prediction, indicating that our understanding of the oxidation chemistry of these compounds is still limited. kOH (296 K) rate coefficients (in units of 10−12 cm3 molec.−1 s−1) for reactions of three large alkanes with OH were also determined for the first time: 2-methylheptane, 9.1 (±0.3); 2-methylnonane, 11.0 (±0.3); and ethylcyclohexane, 14.4 (±0.3), all in reasonable agreement with SAR predictions. Rate coefficients for the 27 previously studied OH + VOC reactions agreed well with available literature values, lending confidence to the application of this method for the rapid and efficient simultaneous study of gas-phase reaction kinetics.

Gas-Phase Reaction Kinetics of Pyruvic Acid with OH Radicals: The Role of Tunneling, Complex Formation, and Conformational Structure.

The gas-phase reaction of pyruvic acid (PA) with the OH radical is studied theoretically using accurate quantum chemistry and transition state theory. Two chemically distinct H-atom abstraction reactions and two distinct OH addition reactions have been identified. The rate coefficients for these four processes were calculated. Quantum tunneling was included in each rate using the small curvature tunneling method. The influence of the conformational structure of PA was found to be particularly intriguing. While the trans-cis structure was found to dominantly react by H-atom abstraction from the methyl site, the trans-trans conformer was found to react mostly through H-atom abstraction from the acid site. A general formalism was developed to model the kinetics of the reactions that involve multiple conformers, interconverting prereactive complexes, and multiple transition states. Comparison of the results obtained with available experimental rate observations reveals agreement with the trans-trans conformer of PA but disagreement with the results obtained for a full statistical mixture of reagents. The role of these reactions in the atmospheric processing of PA is discussed.

A phenomenological modelling framework for particle emission simulation in a direct-injection gasoline engine

A phenomenological modelling framework is presented that allows the simulation of the engine-out particle emissions of direct-injection gasoline engines based on physical principles. It is applicable both at steady-state operating conditions and in transient driving cycles. Within the modelling framework, a multi-zone model with gas-phase reaction kinetics is coupled with a stochastic reactor model considering the soot formation dynamics. Both model parts are fed with inputs from an accompanying engine process simulation. Particle emissions from injector deposits and inhomgeneous gaseous mixture preparation are taken into account. Pyrolysis reactions are considered in a zone with remaining fuel film at the injector, whereas in gas-phase zones that arise from inhomogeneous mixture preparation, the reaction of the air–fuel mixture is calculated under sub-stoichiometric conditions. The setup of those mixture-induced zones is generated by an existing homogenisation sub-model. The modelling framework is evaluated by test bench measurements of the engine operating map, a variation of engine actuator settings and transient driving profiles. Hereby, an accuracy of less than 20% deviation for particle number and mass is achieved.

Particle-resolved simulation and modeling of the conversion rate of coal char in chemical looping with oxygen uncoupling

The high concentration of CO2 and low concentration of O2 at relatively low temperatures of 1123-1223 K are typical reactive atmospheres in the fuel reactor of a chemical looping with oxygen uncoupling (CLOU) unit. Char within this environment can be converted via lean-O2 oxidation and/or rich-CO2 gasification. Conventional models, which either considered the oxidation only or considered the oxidation and gasification contributions independently by simply adding the two individual conversion rates together, seem arbitrary. Therefore, it is necessary to quantitatively explore the contributions of the oxidation and the gasification reactions as well as their interactions in CLOU conditions through more detailed particle-resolved simulations.In this work, a single particle model which described a spherical reacting porous particle with its reacting boundary layer was developed to investigate the conversion characteristics of pulverized coal char in lean-O2 and/or rich-CO2 conditions (analogous CLOU conditions). The heterogeneous reaction kinetics developed by Tilghman and Mitchell [35] and the simplified GRI-Mech 3.0 gas-phase reaction kinetics were adopted. It was found that the char conversion rate in CLOU conditions could be basically modeled as the sum of the full oxidation consumption rate and the partial gasification consumption rate, i.e. rmix=φ1rgasi+roxid. The interactions between the oxidation and gasification reactions were elaborated in two aspects: on the one side, the oxidation of coal char in CLOU conditions is within the weak zone II burning region, where the oxidation reaction only happens peripherally and is nearly unaffected by the high concentration of CO2; on the other side, the gasification reaction within the external layer of the coal char particle is inhibited by the oxidation reaction, consequently the gasification reaction only happens inside the coal char particle where O2 cannot penetrate into. Based on these understandings, a correlation between the coefficient, φ1, and the effectiveness factor of the oxidation reaction, η, was proposed to describe the overall char conversion rate in CLOU conditions. Through fitting the simulation results under typical CLOU conditions, the quantitative relationship between φ1 and η was finally attained.

David Colin Phillips

David Colin Phillips, 77, died on Oct. 26, 2017, in North Wales. “Colin worked in the fields of laser chemistry, gas-phase reaction kinetics, electropolymerization, particulate chemistry, and isotope separation. He worked on NASA projects, including Project Apollo and the space shuttle’s fuel system; he also worked extensively on President Ronald Reagan’s Strategic Defense Initiative. He held over 50 patents. In 1975, through the Office of Naval Research, Colin patented a method for electrochemically depositing bone and collagen onto prostheses—a technique that enhanced bone repair and increased survival rates amongst Vietnam veterans with severe combat-sustained bone injuries. In 1976, he won the R&D 100 Award, along with J. D. B. Smith, for his organic particulate analysis instrument.”—Gareth Phillips, son Most recent title: Manager of physical chemistry research, Westinghouse Research Laboratories Education: B.Sc., chemistry, 1965, and Ph.D., physical chemistry, 1968, University College of Wales, Abery...

A detailed reaction mechanism for oxidative coupling of methane over Mn/Na2WO4/SiO2 catalyst for non-isothermal conditions

Direct production of ethylene from natural gas or other methane sources has proven to be challenging from catalytic, process design and economic perspectives, with no reports of a commercially viable process to date. Understanding of the underlying non-ideal homogeneous and heterogeneous reactions involved could lead to success, enabling utilization of vast natural gas resources as a replacement for petrochemicals. In this regards, an improved reaction mechanism and computational model, validated experimentally, for oxidative coupling of methane (OCM) over a Mn/Na2WO4/SiO2 catalyst is developed, taking into account the non-isothermal behavior exhibited by the gas and surface reactions. The reaction mechanism involves detailed gas-phase and surface elementary steps to describe the OCM chemistry and employing a reduced model for computational efficiency. The model uses laboratory-scale packed-bed reactor experiments for kinetic mechanism development. The modeling and simulation is particularly focused on a one-dimensional packed-bed reactor. The kinetic model is validated over a wide range of experimental conditions. The model-predicted results and their comparisons with the experimental data are presented wide temperature ranges and methane-to-oxygen feed ratios under adiabatic reactor conditions. The kinetic model is first of its kind in which non-isothermal OCM kinetic behavior is captured using detailed gas-phase and heterogeneous reaction kinetics.

Classical Trajectory Study of Collision Energy Transfer between Ne and C2H2 on a Full Dimensional Accurate Potential Energy Surface.

Collision energy transfer plays an important role in gas phase reaction kinetics and relaxation of excited molecules. However, empirical treatments are generally adopted for the collisional energy transfer in the master equation based approach. In this work, classical trajectory approach is employed to investigate the collision energy transfer dynamics in the C2H2-Ne system. The entire potential energy surface is described as the sum of the C2H2 potential and interaction potential between C2H2 and Ne. It is highlighted that both parts of the entire potential are highly accurate. In particular, the interaction potential is fit to ∼41 300 configurations determined at the level of CCSD(T)-F12a/cc-pCVTZ-F12 with the counterpoise correction. Collision energy transfer dynamics are then carried out on this benchmark potential and the widely used Lennard-Jones and Buckingham interaction potentials. Energy transfers and related probability densities at different collisional energies are reported and discussed.

A kinetic study of the gas-phase reactions of 1-methylsilacyclobutane in hot wire chemical vapor deposition.

The reaction kinetics of the decomposition of 1-methylsilacyclobutane (MSCB) in a hot wire chemical vapor deposition (HWCVD) reactor was investigated. The stable reaction products were monitored using vacuum ultraviolet laser single photon ionization in tandem with time-of-flight mass spectrometry. Steady-state approximation was used to determine the rate constants of three individual decomposition pathways of MSCB, i.e., cycloreversion to form ethene and methylsilene (R1), ring opening to form propene and methylsilylene (R2), and exocyclic Si-CH3 bond cleavage to form ˙CH3 radicals (R3). The activation energies (Ea) for R2 and R3 in a HWCVD reactor were determined to be 86.6 kJ mol-1 and 106 kJ mol-1, respectively. The fact that these Ea values are close to those obtained for the MSCB decomposition on metal surfaces under collision-free conditions indicates that the heterogeneous reactions on the hot wire surface govern the gas-phase reaction kinetics in the HWCVD reactor. In addition, the Ea values obtained from a theoretical study of the decomposition kinetics using ab initio calculations at the CCSD(T)/6-311++G(3d,2p)//MP2/6-311++G(d,p) level were 62.9 kcal mol-1 (i.e., 263 kJ mol-1), 62.0 kcal mol-1 (i.e., 259 kJ mol-1), and 86.2 kcal mol-1 (i.e., 361 kJ mol-1) for R1, R2, and R3, respectively. The much lower experimental Ea values compared with those from the theoretical calculations clearly suggest that the tungsten filament in the HWCVD reactor catalyzed the decomposition.

Reaction Kinetics of HBr with HO2: A New Channel for Isotope Scrambling Reactions.

The gas phase reaction kinetics of HBr with the HO2 radical are investigated over the temperature range of T = 200-1500 K using a theoretical approach based on transition state theory. The parameters for the potential energy surface are computed using density functional theory with the M11 exchange functional. The rate coefficient for the HBr + HO2 → Br + H2O2 abstraction channel is found to be somewhat larger than previous estimates at low temperatures due to quantum tunneling. The present study reveals the existence of a novel exchange pathway, HBr + H'O2 → H'Br + HO2, which exhibits a much lower reaction barrier than does the abstraction route. The transition state for this process is a symmetrical planar five-membered-ring-shaped structure. At low temperatures, this concerted double hydrogen transfer reaction is several orders of magnitude faster than the abstraction channel. The exchange process may be observed using isotope scrambling reactions; such reactions may contribute to observed isotope abundances in the atmosphere. The rate coefficients for the isotopically labeled reactions are computed.

Design and testing of temperature tunable de Laval nozzles for applications in gas-phase reaction kinetics

A series of three de Laval nozzles initially designed to generate uniform supersonic flows in helium at 23 and 36 K and in argon at 50 K have been used with either pure nitrogen or mixtures of nitrogen with helium or argon in order to make a sequence of pulsed supersonic flows working at different temperatures. For this, a computer homemade program has been used to design de Laval nozzles contours for gas mixtures in order to determine the theoretical pressure P and temperature T in these supersonic flows. Spatial evolution of T along the flow axis downstream of the nozzle exit has been characterized with a fast response Pitot tube instrument newly developed. Twenty-eight different gas mixture conditions have been tested, indicating a very good agreement with the corresponding calculated flow conditions. The length of uniformity ΔL of the supersonic flows have been found to be >30 cm in more than 80 % of the situations and >50 cm for more than 50 % of the tested conditions. Fine temperature tunability was achieved in the range 22–107 K with very small fluctuations of the mean temperature along ΔL. Advantages and limits of these new developments for studies of gas-phase reaction kinetics are discussed.

Experimental study on the axial mass transport of minced biomass (rape straw) into a pyrolysis rotating reactor working in the slipping regime

The paper presents an experimental study of the behavior of a minced biomass bed advancing into an inclined rotating drum to be used for biomass pyrolysis in the slipping regime. Minced rape straw was fed into the reactor with different feed rates, and its axial motion was examined at different slopes and cylinder rotating rates. By collecting and analysing images of the bed during the experimental runs, axial flow rates were determined; a mathematical model derived from mass and momentum balances was then applied, and the main parameter, the bed-wall friction factor, was obtained by regression of experimental data. Finally, in order to generalize bed dynamics, residence times and flow rates (mean values) were related to the experimental conditions by parametric semi-empirical and dimensionless correlations. Apart from its essential role in the future development of a whole chemical process model (including heat exchange, gas fluid dynamics, pyrolysis and gas phase reaction kinetics) to determine optimal working conditions, the dynamic model proposed here could also be of more general interest and be applied with other kinds of material and conditions on both an experimental and industrial scale.

Gas-phase reaction kinetics of 1,3-disilacyclobutane in a hot-wire chemical vapor deposition reactor

The reaction kinetics of the decomposition of 1,3-disilacyclobutane (DSCB) was investigated using a hot-wire chemical vapor deposition reactor. The reaction products were monitored using a vacuum ultraviolet laser single-photon ionization source coupled with a time-of-flight mass spectrometer. Steady-state approximation was used to determine the rate constants for three main decomposition pathways of DSCB: the exocyclic H2 elimination (k1), the cycloreversion (k2), and the ring-opening via 1,2-H shift (k3). Separate k2 and k3 were not obtained, but 2k2+k3 and k1 were determined. The activation energy (Ea) for the exocyclic H2 elimination reaction was determined to be 63.5kJ·mol−1. Compared to the Ea value of 43.6kJ·mol−1 previously obtained under collision-free conditions at much lower pressures, the value from this work is higher. This is attributed to the filament aging caused by the formation of silicon carbide (SiC) and tungsten sub-carbide (W2C) on the wire surface. The heterogeneous reactions on the metal surface also led to a much faster decay constant, koverall, for DSCB than those for each individual decomposition pathway, k1 and 2k2+k3.