Shock Tube Data Research Articles

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.

Studies on the Kinetics of the CH + H2 Reaction and Implications for the Reverse Reaction, 3CH2 + H.

The reaction of CH radicals with H2 has been studied by the use of laser flash photolysis, probing CH decays under pseudo-first-order conditions using laser-induced fluorescence (LIF) over the temperature range 298-748 K at pressures of ∼5-100 Torr. Careful data analysis was required to separate the CH LIF signal at ∼428 nm from broad background fluorescence, and this interference increased with temperature. We believe that this interference may have been the source of anomalous pressure behavior reported previously in the literature (Brownsword, R. A.; J. Chem. Phys. 1997, 106, 7662-7677). The rate coefficient k1 shows complex behavior: at low pressures, the main route for the CH3* formed from the insertion of CH into H2 is the formation of 3CH2 + H, and as the pressure is increased, CH3* is increasingly stabilized to CH3. The kinetic data on CH + H2 have been combined with experimental shock tube data on methyl decomposition and literature thermochemistry within a master equation program to precisely determine the rate coefficient of the reverse reaction, 3CH2 + H → CH + H2. The resulting parametrization is kCH2+H(T) = (1.69 ± 0.11) × 10-10 × (T/298 K)(0.05±0.010) cm3 molecule-1 s-1, where the errors are 1σ.

Experimental and modeling study of acetone combustion

The pyrolysis and oxidation of acetone were studied using three complementary experimental setups. Jet-stirred reactor experiments were performed at four equivalence ratios (ϕ = 0.5, 1, 2, and ∞), at pressure of 1.067 bar (800 Torr) and over the temperature range of 700–1200 K for pyrolysis and 600–1150 K for oxidation. The decomposition of acetone starts around 800 K with a conversion rate of 50% obtained around 1000 K in both pyrolysis and oxidation studies. The main stable products detected in both conditions are small hydrocarbons (methane, ethane, and ethylene), with also acetaldehyde, CO and CO2 for oxidation. Oscillation behavior was detected beyond 1000 K under oxidation conditions and the products were followed with on-line mass spectrometry. Ignition delay times were measured using a rapid compression machine at pressures of 20 and 40 bar under non-diluted stoichiometric conditions over the temperature range 850–1100 K. The ignition delay times measured in the present study, combined with shock tube data of literature, exhibit a slight inflexion to the Arrhenius behavior, but no negative temperature coefficient. Laminar burning velocities were measured using a flat flame burner at atmospheric pressure for three fresh gas temperatures: ambient temperature, 358 and 398 K. A detailed kinetic model of the combustion of acetone including 852 species and 3265 reactions was developed. This new kinetic mechanism predicts relatively well the experimental measurements of ignition delay times, the mole fraction of the products in the jet-stirred reactor including oscillations and laminar burning velocities. Related flow rate and sensitivity analysis are also presented providing new insights into the acetone reaction network.

Numerical study of real gas effects during bubble collapse using a disequilibrium multiphase model

An explicit density-based solver of the Euler equations for inviscid and immiscible gas–liquid flow media is coupled with real-fluid thermodynamic equations of state supporting mild dissociation and calibrated with shock tube data up to 5000 K and 28 GPa. The present work expands the original 6-equation disequilibrium method by generalising the numerical approach required for estimating the equilibrium pressure in computational cells where both gas and liquid phases co-exist while enforcing energy conservation for all media. An iterative numerical procedure is suggested for taking into account the properties of the gas content as derived from highly non-linear real gas equations of state and implemented in a tabulated form during the numerical solution. The developed method is subsequently used to investigate gaseous bubble collapse cases considering both spherical and 2D asymmetric arrangements as induced by the presence of a rigid wall. It is demonstrated that the predicted maximum temperatures are strongly influenced by the equations of state used; the real gas model predicts a temperature reduction in the bubble interior up to 41% space-averaged and 50% locally during the collapse phase compared to the predictions obtained with the aid of the widely used ideal gas approximation.

Vibrational relaxation and triggering of the non-equilibrium vibrational decomposition of CO2 in gas discharges

Non-equilibrium vibrational dissociation CO2 → CO + O at translational–rotational temperatures T ⩽ 1200 K is investigated with semi-empiric and computational models. The governing parameter has been introduced, where Q is the specific volumetric power coupled into vibrational states and n 0 is the initial number density of CO2. It has been shown that the non-equilibrium vibrational process can only be triggered when exceeds some critical value determined by the speed of vibrational relaxation. Simple semi-empiric calculations are backed by the state-to-state simulations of the CO2 vibrational kinetics in two-modes approximation performed for conditions of microwave sustained gas discharges. The vibrational kinetics model is benchmarked against the experimental vibrational relaxation times as well as the shock tube data on the rate of the process CO2 + M → CO + O + M for M = Ar and literature data for M = CO2. At T = 300 K the estimated W m3 or 35 W (m− 3 Pa− 2) (p is the gas pressure). is found to always increase with increased T.

A numerical investigation of methane ignition in supercritical CO2

The supercritical CO2 power cycle (sCO2) is a relatively new technology, which promises to reduce CO2 emissions with potentially higher efficiencies. However, due to challenging conditions posed by supercritical pressures, the ignition phenomena in sCO2 combustion are relatively less understood and studied. The primary objective of the current study is to elucidate ignition processes using homogeneous ignition calculations (HMI) and two-dimensional direct numerical simulations (DNS). To accurately model the supercritical conditions, the employed formulation includes the cubic Peng–Robinson equation of state, mass, and heat flux vectors derived from nonequilibrium thermodynamics and compressible form of governing equations. For selection of a suitable chemical mechanism, HMI calculations are employed to investigate the performance of existing skeletal mechanisms against shock-tube experimental data. The chemical characteristics of ignition are further studied using path flux and sensitivity analysis, with CH3O2 chemistry exhibiting the largest effect on accelerating the ignition process. Different chemical pathways of fuel breakdown are also discussed to aid in interpretation of subsequent DNS case. In the DNS case, autoignition of a two-dimensional mixing layer perturbed with pseudoturbulence is simulated. The ignition is found to be delayed compared to the HMI case, with the ignition kernels forming in a spotty manner. The two phenomena are primarily attributed to variation of scalar dissipation within the mixing layer. The ignition kernels expand and evolve into a tribrachial edge flame propagating along the stoichiometric isosurface. Further investigation on the structure of edge flame revealed an asymmetrical structure, with CH4 molecules being entirely consumed in the triple point region of the flame along the stoichiometric isosurface, and more stable fuels like CO burning in the non-premixed branch of the edge flame. The edge flame propagation speeds are also calculated, with variations found to be correlated with scalar dissipation and upstream progress variable of the reacting mixture.

Vibrational-Specific Model of Simultaneous and Relaxation Under Postshock Conditions

The present paper discusses the development of an aerothermochemistry model that can be efficiently coupled with fluid dynamics simulations and retains the accuracy of the quantum-mechanical and molecular dynamic principles from which it is derived. The present model allows simulations of thermochemical nonequilibrium in nitrogen without relying on the existence of a vibrational temperature. A series of verification tests suggest that the vibrational-specific master equation model is sufficiently accurate and computationally efficient when applied to the modeling of dissociating nitrogen flows under adiabatic conditions. Toward this end, a kinetic dataset describing vibrational energy transfer and dissociation in and collisions is obtained on a high-fidelity potential energy surface, and curve fit coefficients are reported. Validation against shock-tube data indicates that the inclusion of electronically excited and ionic species is potentially required when computing and comparing relaxation parameters with the experimental data derived from the radiative signatures of nitrogen shock flows.

An Experimental Kinetics Study of Isopropanol Pyrolysis and Oxidation behind Reflected Shock Waves

Isopropanol has potential as a future bio-derived fuel and is a promising substitute for ethanol in gasoline blends. Even so, little has been done in terms of high-temperature chemical kinetic speciation studies of this molecule. To this end, experiments were conducted in a shock tube using simultaneous CO and H2O laser absorption measurements. Water and CO formation during isopropanol pyrolysis was also examined at temperatures between 1127 and 2162 K at an average pressure of 1.42 atm. Species profiles were collected at temperatures between 1332 and 1728 K and at an average pressure of 1.26 atm for equivalence ratios of 0.5, 1.0, and 2.0 in highly diluted mixtures of 20% helium and 79.5% argon. Species profiles were also compared to four modern C3 alcohol mechanisms, including the impact of recent rate constant measurements. The Li et al. (2019) and Saggese et al. (2021) models both best predict CO and water production under pyrolysis conditions, while the AramcoMech 3.0 and Capriolo and Konnov models better predict the oxidation experimental profiles. Additionally, previous studies have collected ignition delay time (τign) data for isopropanol but are limited to low pressures in highly dilute mixtures. Therefore, real fuel–air experiments were conducted in a heated shock tube with isopropanol for stoichiometric and lean conditions at 10 and 25 atm between 942 and 1428 K. Comparisons to previous experimental results highlight the need for real fuel–air experiments and proper interpretation of shock-tube data. The AramcoMech 3.0 model over predicts τign values, while the Li et al. model severely under predicts τign. The models by Capriolo and Konnov and Saggese et al. show good agreement with experimental τign values. A sensitivity analysis using these two models highlights the underlying chemistry for isopropanol combustion at 25 atm. Additionally, modifying the Li et al. model with a recently measured reaction rate shows improvement in the model’s ability to predict CO and water profiles during dilute oxidation. Finally, a regression analysis was performed to quantify τign results from this study.

Oxidation and pyrolysis of methyl propyl ether

AbstractThe ignition, oxidation, and pyrolysis chemistry of methyl propyl ether (MPE) was probed experimentally at several different conditions, and a comprehensive chemical kinetic model was constructed to help understand the observations, with many of the key parameters computed using quantum chemistry and transition state theory. Experiments were carried out in a shock tube measuring time variation of CO concentrations, in a flow tube measuring product concentrations, and in a rapid compression machine (RCM) measuring ignition delay times. The detailed reaction mechanism was constructed using the Reaction Mechanism Generator software. Sensitivity and flux analyses were used to identify key rate and thermochemical parameters, which were then computed using quantum chemistry to improve the mechanism. Validation of the final model against the 1–20 bar 600–1500 K experimental data is presented with a discussion of the kinetics. The model is in excellent agreement with most of the shock tube and RCM data. Strong non‐monotonic variation in conversion and product distribution is observed in the flow‐tube experiments as the temperature is increased, and unusually strong pressure dependence and significant heat release during the compression stroke is observed in the RCM experiments. These observations are largely explained by a close competition between radical decomposition and addition to at different sites in MPE; this causes small shifts in conditions to lead to big shifts in the dominant reaction pathways. The validated mechanism was used to study the chemistry occurring during ignition in a diesel engine, simulated using Ignition Quality Test (IQT) conditions. At the IQT conditions, where the MPE concentration is higher, bimolecular reactions of peroxy radicals are much more important than in the RCM.

Modification of chemical-kinetic parameters for 11-air species in re-entry flows

The chemical-kinetic parameters for the two-temperature model for 11-air species are modified to increase the accuracy of the thermochemical nonequilibrium model for high temperature gases in Earth re-entry flows. In the present work, a set of modified chemical-kinetic parameters, for the vibrational relaxation time with high temperature correction, the Arrhenius rate coefficients for dissociation, the vibrational energy removal ratio due to chemical reaction, the equilibrium constant to evaluate the reverse rate coefficients, and collision integrals for high temperature gases are proposed, based on the results of recent state-to-state kinetic calculations and shock-tube experimental data. These modified chemical-kinetic parameters are utilized to reproduce the measured NO, N2, and N2+ VUV and UV spectrum of the high-enthalpy shock-tube experiments performed at the EAST facility, and the existing flight and ground experimental data from BSUV-2, the Mars-entry spacecraft model, RAM C-II, and FIRE-II. The proposed chemical-kinetic parameters more accurately reproduce the measured molecular spectra in the VUV and UV ranges, and the surface heat flux and electron number density on the surface of the re-entry modules, than the previous chemical-kinetic parameters in the Park model, except for the super orbital re-entry speed of the Fire-II experiments. In the Fire-II experimental case, the influence of the modified chemical-kinetic parameters in the present work are less effective because of the fast dissociation of the molecules.

A chemically consistent rate constant for the reaction of nitrogen dioxide with the oxygen atom.

In the present study, a chemically consistent rate constant for the reaction between nitrogen dioxide and the oxygen atom has been obtained by combining low-temperature experimental data from the literature and new high-temperature quantum chemical calculations. The expression for our rate constant is kNO2+O=NO+O2= 2.589 × 1015T-1.035 exp(-226/RT) + 4.242 × 1016T-0.861exp(-50 917/RT) cm3 mol-1 s-1, where R = 8.314 J mol-1 K-1, and is valid over the temperature range T = 221 to 3000 K. The effect of the inclusion of the new rate constant on the prediction of three detailed reaction models from the literature has been studied using (i) new experimental oxygen atom profiles obtained in a shock tube during nitrogen dioxide pyrolysis, and (ii) published shock tube and jet-stirred reactor data for H2-NOx mixtures with and without dioxygen. The impact of the new rate constant on the sensitivity coefficients and reaction pathways has also been analyzed under some conditions. Overall, the predictive capability of the reaction models were improved. The present study suggests that our chemically consistent rate constant should be included in detailed reaction models for combustion applications.

Shock tube data processing tools using open source hardware and software platforms

AbstractTo cater the need of specific shock‐tube data acquisition and processing system, a low cost open‐source alternative has been developed and presented in this paper. Using easily available open‐source hardware and software platforms such as ARDUINO, a robust 5.3 MHz speed data acquisition system along with optimized shock tube data processing software is designed and an indigenous shock tube data processing tool has been developed. This has been found to be 10 times less cost than the general‐purpose computing equipment available on the market, with a substantial reduction in shockwave data processing time and effort. The setup has been tested with the different diaphragms producing shockwaves of different Mach numbers. The experimental results are compared with the theoretical values obtained using normal shock relations and are found to be consistent with admissible error limits. This validates the design and construction of the device for scientific experiments.

Experimental and kinetic modeling studies on the auto-ignition of methyl crotonate at high pressures and intermediate temperatures

Biofuels, including biodiesel have the potential to partially replace the conventional diesel fuels for low-temperature combustion engine applications to reduce the CO2 emission. Due to the long chain lengths and high molecular weights of the biodiesel components, it is quite challenging to study the biodiesel combustion experimentally and computationally. Methyl crotonate, a short unsaturated fatty acid methyl ester (FAME) is chosen for this chemical kinetic study as it is considered as a model biodiesel fuel. Auto-ignition experiments were performed in a rapid compression machine (RCM) at pressures of 20 and 40 bar under diluted conditions over a temperature range between 900 and 1074 K, and at different equivalence ratios (ϕ = 0.25, 0.5 and 1.0). A chemical kinetic mechanism is chosen from literature (Gaïl et al. 2008) and is modified to incorporate the low-temperature pathways. The mechanism is validated against existing shock tube data (Bennadji et al. 2009) and the present RCM data. The updated mechanism shows satisfactory agreement with the experimental data with significant improvements in low-temperature ignition behavior. The key reactions at various combustion conditions and the improved reactivity of the modified mechanism are analyzed by performing sensitivity and path flux analysis. This study depicts the importance of low-temperature pathways in predicting the ignition behavior of methyl crotonate at intermediate and low temperatures.

Shock tube measurement of NO time-histories in nitromethane pyrolysis using a quantum cascade laser at 5.26 µm

The pyrolysis of nitromethane, CH3NO2, was studied at ∼3.5 atm and 1013 K–1418 K in a heated shock tube by measuring the key product nitric oxide (NO) using mid-infrared laser absorption spectroscopy. We used a quantum cascade laser (QCL) at 5.26 µm to exploit the strong NO absorption at 1900.08 cm−1. With the NO absorption cross-section data characterized at 1006 K–1789 K and 2.7 atm–3.5 atm behind reflected shock waves, we measured the NO concentration time-histories during the pyrolysis of nitromethane at two different concentrations (1.05% and 0.6%). The absorption interference from other major products such as CO and H2O was analyzed to be negligible, leading to an interference-free NO diagnostic in nitromethane pyrolysis. A recent kinetic model of Shang et al. (2019) was adopted to interpret the shock tube data. All the NO time-histories measured over the entire temperature range 1013 K–1418 K were well-predicted by this model in terms of the initial NO formation rate and the final plateau level. The rate-of-production, sensitivity, and reaction flux analyses were performed to identify four important reactions (CH3NO2 = CH3 + NO2, CH3NO2 ↔ CH3ONO = CH3O + NO, CH3 + NO2 = CH3O + NO, and NO2 + H = NO + OH) that determine the NO formation during CH3NO2 pyrolysis. The satisfactory agreement between the simulation and shock tube/laser absorption measurement further validated the kinetic mechanism of nitromethane decomposition. The developed mid-infrared NO absorption sensor provides a promising diagnostic tool for studying fuel-nitrogen chemical kinetics in the shock tube experiments.

Probing the Effects of NOx and SOx Impurities on Oxy-Fuel Combustion in Supercritical CO2: Shock Tube Experiments and Chemical Kinetic Modeling

Abstract The direct-fired supercritical carbon dioxide cycles are one of the most promising power generation methods in terms of their efficiency and environmental friendliness. Two important challenges in implementing these cycles are the high pressure (300 bar) and high CO2 dilution (>80%) in the combustor. The design and development of supercritical oxy-combustors for natural gas require accurate reaction kinetic models to predict the combustion outcomes. The presence of a small amount of impurities in natural gas and other feed streams to oxy-combustors makes these predictions even more complex. During oxy-combustion, trace amounts of nitrogen present in the oxidizer is converted to NOx and gets into the combustion chamber along with the recirculated CO2. Similarly, natural gas can contain a trace amount of ammonia and sulfurous impurities that get converted to NOx and SOx and get back into the combustion chamber with recirculated CO2. In this work, a reaction model is developed for predicting the effect of impurities such as NOx and SOx on supercritical methane combustion. The base mechanism used in this work is GRI Mech 3.0. H2S combustion chemistry is obtained from Bongartz et al. while NOx chemistry is from Konnov. The reaction model is then optimized for a pressure range of 30–300 bar using high-pressure shock tube data from the literature. It is then validated with data obtained from the literature for methane combustion, H2S oxidation, and NOx effects on ignition delay. The effect of impurities on CH4 combustion up to 16 atm is validated using NOx-doped methane studies obtained from the literature. In order to validate the model for high-pressure conditions, experiments are conducted at the UCF shock tube facility using natural gas identical mixtures with N2O as an impurity at ∼100 bar. Current results show that there is a significant change in ignition delay with the presence of impurities. A comparison is made with experimental data using the developed model and predictions are found to be in good agreement. The model developed was used to study the effect of impurities on CO formation from sCO2 combustors. It was found that NOx helps in reducing CO formation while the presence of H2S results in the formation of more CO. The reaction mechanism developed herein can also be used as a base mechanism to develop reduced mechanisms for use in CFD simulations.

Effects of High Fuel Loading and CO2 Dilution on Oxy-Methane Ignition Inside a Shock Tube at High Pressure

Abstract Ignition delay times were measured for methane/O2 mixtures in a high dilution environment of either CO2 or N2 using a shock tube facility. Experiments were performed between 1044 K and 1356 K at pressures near 16 ± 2 atm. Test mixtures had an equivalence ratio of 1.0 with 16.67% CH4, 33.33% O2, and 50% diluent. Ignition delay times were measured using OH* emission and pressure time-histories. Data were compared to the predictions of two literature kinetic mechanisms (ARAMCO MECH 2.0 and GRI Mech 3.0). Most experiments showed inhomogeneous (mild) ignition which was deduced from five time-of-arrival pressure transducers placed along the driven section of the shock tube. Further analysis included determination of blast wave velocities and locations away from the end wall of initial detonations. Blast velocities were 60–80% of CJ-Detonation calculations. A narrow high temperature region within the range was identified as showing homogenous (strong) ignition which showed generally good agreement with model predictions. Model comparisons with mild ignition cases should not be used to further refine kinetic mechanisms, though at these conditions, insight was gained into various ignition behavior. To the best of our knowledge, we present first shock tube data during ignition of high fuel loading CH4/O2 mixtures diluted with CO2 and N2.

The Reaction NCN + H2: Quantum Chemical Calculations, Role of 1NCN Chemistry, and 3NCN Absorption Cross Section.

The NCN radical plays a key role for modeling prompt-NO formation in hydrocarbon flames. Recently, in a combined shock tube and flame modeling study, the so far neglected reaction NCN + H2 and the related chemistry of the main product HNCN turned out to be significant for NO modeling under fuel-rich conditions. In this study, the reaction has been thoroughly revisited by detailed quantum chemical rate constant calculations both for the singlet 1NCN and triplet 3NCN pathways. Optimized geometries and vibrational frequencies of reactants, products, and transition states were calculated on B3LYP/aug-cc-pVQZ level with single-point energy calculations carried out against the optimized structures using CASPT2/aug-cc-pVQZ. The determined rate constants for the 1NCN + H2 reaction as well as the newly measured high temperature absorption cross section of 3NCN made a reevaluation of the shock tube data of the previous work necessary, finally revealing quantitative agreement between experiment and theory. Moreover, the new directly measured Doppler-limited absorption cross section data, σ(3NCN, λ = 329.1302 nm) = 2.63 × 109 × exp(-1.96 × 10-3 × T/K) cm2/mol (±23%, p = 0 bar, T = 870-1700 K), are in agreement with previously reported values based on detailed spectroscopic simulations. Hence, a long-standing debate about a reliable high temperature 3NCN absorption cross section has been resolved. Whereas 3NCN + H2 resembles a simple abstraction type reaction with the exclusive products HNCN + H, the singlet radical reaction is initiated by the insertion into the H-H bond. Up to pressures of 100 bar, the main products of the subsequent decomposition of the H2NCN intermediate are HNCN + H as well, with minor contributions of CN + NH2 toward higher temperatures. Although much faster than the triplet reaction, the singlet radical insertion is actually rather slow, due to the necessary reorganization of the HOMO electron density in 1NCN that is equally distributed over the two N atom sites. In general, the distinct reactivity differences call for a separate treatment of 1NCN and 3NCN chemistry. However, as the main reaction products in case of the H2 reaction are the same and as the population of the 1NCN in thermal equilibrium remains low, a properly weighted effective rate constant k(NCN + H2 → HNCN + H) = 2.62 × 104 × (T/K)2.78 × exp(-97.6 kJ/mol/RT) cm3 mol-1s-1(±30%, 800 K < T < 3000 K, p < 100 bar) is recommended for inclusion into flame models that, as yet, do not explicitly account for 1NCN chemistry.

Reevaluation of the reaction rate of H + O2 (+M) = HO2 (+M) at elevated pressures

The rate coefficients for H + O2 (+M) = HO2 (+M) at high-pressure conditions were re-evaluated using the reported experimental shock tube data of Davidson et al. (1996), Bates et al. (2001), Shao et al. (2019) and Choudhary et al. (2019), and based on an updated mechanism of Hong et al. (2011). The major updates of the Hong et al. Mechanism compared to the originally used GRI-Mech in the works of Davidson et al. (1996) and Bates et al. (2001) were the interfering reactions of H + O2, H + HO2 and OH + HO2 as well as NOx-related reactions. After applying the updates of the elementary reaction kinetics, the revised rates of H + O2 (+M) = HO2 (+M) for Davidson et al. (1996) and Bates et al. (2001) showed improved agreement with each other, and consequently led to a more reliable Troe formula of H + O2 (+M) = HO2 (+M) with M = Ar and N2 covering the pressure range of 1–150 bar and temperature range of 300–1800 K. The new Troe formula is expected to facilitate kinetic model development and high-pressure combustion studies.

Fuel molecular structure effect on autoignition of highly branched iso-alkanes at low-to-intermediate temperatures: Iso-octane versus iso-dodecane

Highly branched iso-alkanes are an important class of hydrocarbons found in conventional petroleum-derived and alternative renewable fuels used for combustion applications. Recognizing that chemical kinetics for most of these iso-alkanes, especially at low-to-intermediate temperatures, has not been well studied, an experimental and modeling investigation of two selected iso-alkanes, iso-octane (2,2,4-trimethylpentane, iC8) and iso-dodecane (2,2,4,6,6-pentamethylheptane, iC12), is conducted to understand the fuel molecular structure effect on their autoignition characteristics. Using a rapid compression machine (RCM), the ignition responses of iC8 and iC12 at varying pressures, temperatures, and equivalence ratios are characterized and compared. The newly-acquired experimental ignition delay times have been compared with the literature RCM and shock tube data, demonstrating the complementary nature of the current dataset. Further comparison of the experimental pressure traces and ignition delay times illustrates the reactivity crossover between iC8 and iC12. Namely, there exists a temperature window in the negative temperature coefficient regime within which iC12 is less reactive than iC8, but iC12 becomes more reactive outside this temperature window. Furthermore, a chemical kinetic model of iso-alkanes including both iC8 and iC12 is developed. Simulated results using this model are then compared to the experimental data obtained in this study and available in the literature, showing its ability to predict the experimental trends. Chemical kinetic analyses have also been conducted to identify the important reaction pathways controlling autoignition at varying conditions, and to elucidate the underlying mechanism leading to different reactivity trends between iC8 and iC12.

Thermochemical nonequilibrium modeling of oxygen in hypersonic air flows

The thermochemical nonequilibrium model for oxygen, O2, in collisions with atmospheric gas species, is modified in the present work. The vibrational relaxation time with high temperature corrections, dissociation reaction rates, equilibrium constants for the reverse reactions, the vibrational energy loss ratio due to chemical reaction, and the collision integrals for nonequilibrium transport properties are proposed to describe the thermochemical nonequilibrium of O2. The proposed set of thermochemical nonequilibrium parameters for O2 successfully reproduces existing shock-tube experimental data and the flight and ground experimental data of the ELECTRE vehicle, orbital reentry experiments (OREX) flight modules, and double-cone geometry in the LENS-XX facility. In post-shock and hypersonic flow calculations, it is found that the vibrational relaxation and coupled chemical reactions calculated using the present parameters occur more slowly than using the previous parameters. The delayed nonequilibrium chemical reactions contribute to the extension of the shock stand-off distance, and drastically change the reverse reaction near the wall of the hypersonic vehicle.