Mechanism for sonochemical reduction of Au(III) in aqueous butanol solution under Ar based on the analysis of gaseous and water-soluble products

When an aqueous Au(III) solution containing 1-butanol was sonicated under Ar, Au(III) was reduced to Au(0) to form Au particles. This is because various reducing species are formed during sonication, but the reactivity of these species has not yet been evaluated in detail. Therefore, in this study, we analyzed the effects of Au(III) on the rates of the formation of gaseous and water-soluble compounds (CH₄, C₂H₆, C₂H₄, C₂H₂, CO, CO₂, H₂, H₂O₂, and aldehydes), and the rate of Au(III) reduction as a function of 1-butanol concentration. The following facts were recognized: 1) for Au(III) reduction, the contribution of the radicals formed by the pyrolysis of 1-butanol was higher than that of the secondary radicals formed by the abstraction reactions of 1-butanol with ·OH, 2) ·CH₃ and CO acted as reductants, 3) the contribution of ·H to Au(III) reduction was small in the presence of 1-butanol, 4) aldehydes and H₂ did not act as reductants, and 5) the types of species that reduced Au(III) changed with 1-butanol concentration.     

Detailed and simplified kinetic models of n-dodecane oxidation: The role of fuel cracking in aliphatic hydrocarbon combustion

A detailed kinetic model is proposed for the combustion of normal alkanes up to n-dodecane above 850 K. The model was validated against experimental data, including fuel pyrolysis in plug flow and jet-stirred reactors, laminar flame speeds, and ignition delay times behind reflected shock waves, with n-dodecane being the emphasis. Analysis of the computational results reveal that for a wide range of combustion conditions, the kinetics of fuel cracking to form smaller molecular fragments is fast and may be decoupled from the oxidation kinetics of the fragments. Subsequently, a simplified model containing a minimal set of 4 species and 20 reaction steps was developed to predict the fuel pyrolysis rate and product distribution. Combined with the base C₁-C₄ model, the simplified model predicts fuel pyrolysis rate and product distribution, laminar flame speeds, and ignition delays as close as the detailed reaction model.     

Optical properties of natural quantum-well compounds (C6H5-CnH2n-NH3)2PbBr4 (n=1-4)

This paper describes the synthesis and characterization of self-assembled organic-inorganic layered perovskite compounds, (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-4). the effect of the number of carbon atoms of the alkyl chain length (n) on optical properties has been studied. (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ films fabricated by spin-coating are microcrystalline form, single phase and oriented with the c-axis. Crystallinity, the maximum PL intensity and the lifetime of exciton emissions varied with the number of carbon atoms. the lowest-energy exciton splits into a few fine-structure levels at low temperatures. Time-resolved photoluminescence spectra reveal that (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ shows both singlet and triplet excitons. with decreasing temperature, triplet exciton emissions become dominant for (C₆H₅-C_nH_2n-NH₃)₂PbBr₄ (n=1-3), while (C₆H₅-C₄H₈-NH₃)₂PbBr₄ shows mainly singlet exciton emissions. The intersystem crossing from excited singlet state to triplet state plays an important role in the relaxation process of excitons.     

Fuel dependence of benzene pathways

The relative importance of formation pathways for benzene, an important precursor to soot formation, was determined from the simulation of 22 premixed flames for a wide range of equivalence ratios (1.0-3.06), fuels (C₁-C₁₂), and pressures (20-760 torr). The maximum benzene concentrations in 15 out of these flames were well reproduced within 30% of the experimental data. Fuel structural properties were found to be critical for benzene production. Cyclohexanes and C₃ and C₄ fuels were found to be among the most productive in benzene formation; and long-chain normal paraffins produce the least amount of benzene. Other properties, such as equivalence ratio and combustion temperatures, were also found to be important in determining the amount of benzene produced in flames. Reaction pathways for benzene formation were examined critically in four premixed flames of structurally different fuels of acetylene, n-decane, butadiene, and cyclohexane. Reactions involving precursors, such as C₃ and C₄ species, were examined. Combination reactions of C₃ species were identified to be the major benzene formation routes with the exception of the cyclohexane flame, in which benzene is formed exclusively from cascading fuel dehydrogenation via cyclohexene and cyclohexadiene intermediates. Acetylene addition makes a minor contribution to benzene formation, except in the butadiene flame where C₄H₅ radicals are produced directly from the fuel, and in the n-decane flame where C₄H₅ radicals are produced from large alkyl radical decomposition and H atom abstraction from the resulting large olefins.     

Low- and high-temperature study of n-heptane combustion chemistry

n-Heptane has been used extensively in various fundamental combustion experiments as a prototypical hydrocarbon fuel. While the formation of polycyclic aromatic hydrocarbon (PAH) in n-heptane combustion has been studied preferably in premixed flames, this study aims to investigate the combustion chemistry of n-heptane in less-studied diffusion flame and highly rich high-temperature homogeneous oxidation configurations by using a counterflow burner and a flow reactor, respectively. This work addresses the formation of higher-molecular species in the mass range up to about 160 u in both configurations. Samples are analyzed by time-of-flight (TOF) molecular beam mass spectrometry (MBMS) using electron-impact (EI) and single-photon ionization (PI). Highly resolved speciation data are reported. Laminar flow reactor experiments cover a wide temperature range. Especially the measurements at low temperatures provide speciation data of large oxygenates produced in the low-temperature oxidation of n-heptane, which are scarce in the literature. Important precursor molecules for PAH and soot formation, such as C₉H₈, C₁₀H₈, C₁₁H_10, and C₁₂H₈, are formed during the high-temperature combustion process in the counterflow flame, while oxygenated growth species are observed under low-temperature conditions, even at the fuel-rich equivalence ratio of ?=4.00.Numerical modeling for both conditions is performed by using a newly developed kinetic model of n-heptane, which includes the n-heptane and PAH formation chemistry with state-of-the-art kinetic knowledge. Good agreement between model predictions and experimental data of counterflow flame and flow reactor is observed for the major species and some intermediates of n-heptane oxidation. While the concentrations of benzene and toluene measured in the counterflow burner are well-reproduced, the numerical results for flow reactor data are not satisfactory. Differences are found between the formation pathways of fulvene, from whose isomerization benzene is produced in diffusion flame and flow reactor.     

Polycyclic aromatic hydrocarbons production from the supercritical pyrolysis of n-decane,ethylcyclohexane, and n-decane/ethylcyclohexane blends

To investigate the effects of fuel composition on the production and growth of polycyclic aromatic hydrocarbons (PAH) at conditions relevant to the pre-combustion environment of fuels in future high-speed aircraft, we have conducted supercritical pyrolysis experiments in an isothermal, silica-lined stainless-steel flow reactor at 568 °C, 94.6 atm, and 133 s, with the model fuels n-decane and ethylcyclohexane—as well as n-decane/ethylcyclohexane blends in which the fraction of fuel carbon coming from ethylcyclohexane is 0.25, 0.50, and 0.75. High-pressure liquid-chromatographic analyses of the reaction products have led to the isomer-specific identification and quantification of 169 three- to nine-ring PAH—159 of which have never before been reported as products of a cyclic-alkane fuel. Quantification of the aliphatic products by gas chromatographic techniques reveals that n-decane produces mostly 1-alkenes and n-alkanes, whose radicals generate more radicals; whereas ethylcyclohexane produces mostly C₅-ring and C₆-ring alkanes and alkenes, whose radicals show a propensity for ring dehydrogenation. These contrasts in the aliphatic-product distributions have major impacts on PAH growth, which, in this reaction environment, occurs chiefly through the reactions of resonance-stabilized arylmethyl radicals with the C₂-C₄ 1-alkenes. For fuel compositions rich in n-decane, all the ingredients necessary for these PAH-growth reactions to thrive are in place: methyl-substituted PAH, as sources of arylmethyl radicals; a radical-rich environment that fosters H abstraction and arylmethyl-radical formation; and C₂-C₄ 1-alkenes, as growth species. However, an increase in the level of ethylcyclohexane in the fuel brings about substantial reductions in the levels of H-abstracting radicals and C₂-C₄ 1-alkenes as well as an increase in the supply of “donated” hydrogen for stabilizing radicals. These factors combine to bring about marked reductions in PAH growth at fuel compositions rich in ethylcyclohexane, resulting in much lower production of the high-ring-number PAH that are the precursors to solids in the supercritical fuel-pyrolysis environment.     

Skeletal mechanism generation and analysis for n-heptane with CSP

We use a procedure based on the decomposition into fast and slow dynamical components offered by the Computational Singular Perturbation (CSP) method to generate automatically skeletal kinetic mechanisms for the simplification of the kinetics of n-heptane oxidation. The detailed mechanism of the n-heptane oxidation here considered has been proposed by Curran et al. and involves 561 species and 2538 reactions. After carrying out a critical assessment of important aspects of this procedure, we show that the comprehensive skeletal kinetic mechanisms so generated are able to reproduce the main features of n-heptane ignition at various initial pressures and temperatures and equivalence ratios. A by-product of the algorithm that generates the skeletal mechanisms is the identification of the network of important species and reactions at a given state of the kinetic system. The analysis of this network is carried out by resorting to a visual representation of the pathways at selected time instants of the ignition process. Visual inspection of the pathways enables the identification and comparison of the relevant kinetic processes as obtained at different ignition regimes. The graphs are generated by interfacing the model reduction procedure with the open-source package graphviz.     

Insight into STM image contrast of n-tetradecane and n-hexadecane molecules on highly oriented pyrolytic graphite

Two-dimensional ordered patterns of n-tetradecane (n-C₁₄H₃₀) and n-hexadecane (n-C₁₆H₃₄) molecules at liquid/graphite interface have been directly imaged using scanning tunneling microscope (STM) under ambient conditions. STM images reveal that the two different kinds of molecules self-organize into ordered lamellar structures in which alkane chains of the molecules extend along one of three equivalent lattice axes of highly oriented pyrolytic graphite (HOPG) basal plane. For n-C₁₄H₃₀ molecules, the molecular axes are observed to tilt by 60° with respect to inter-lamellar trough lines and the carbon backbones of the alkane chains are perpendicular to the HOPG basal plane in an all-trans conformation. However, for n-C₁₆H₃₄ molecules, the molecular axes are perpendicular to lamellar borders (90°) and the planes of the all-trans carbon skeletons are parallel to the graphite basal plane. The results clearly indicate that outmost hydrogen atoms of the alkane chains dominate atom-scaled features of the STM images. That is, in the case of long-chain alkane molecules, topographic effects dominantly determine STM image contrast of the methylene regions of the alkane chains that are adsorbed on HOPG.     

Structural impact on the methano bridge in norbornadiene, norbornene and norbornane

An electronic structural study of the ground electronic states for the chemically similar bicyclic norbornadiene (NBD, C₇H₈, X¹A₁), norbornene (NBN, C₇H₁₀, X¹A′) and norbornane (NBA, C₇H₁₂, X¹A₁) molecules is provided quantum mechanically. Initially, the unique orbital imaging capability of electron momentum spectroscopy is used to validate which of the quantum mechanical models available to us for these calculations best represents these species. Thereafter, individual molecular point group symmetry is incorporated in the calculations with energy minimization in the search for equilibrium geometries of the species using MP2/TZVP and B3LYP/TZVP models. The optimized geometries compare favourably with available crystallographic results and also build confidence in cases where the crystallographic results are ambiguous. The present study aims to reveal the particular subtle structural deviation of the species, which results in significant molecular property differences among these organic compounds. This work intends to probe bonding information of the species and the impact, on the seven member carbon skeleton, as the CC double bonds of NBD are progressively saturated by hydrogen atoms to give NBN and NBA. Significant changes observed through the present work include: (i) the seven member carbon skeleton tends to relax the strain whenever possible and (ii) the ethano ring experiences greater structural changes than the methano bridge. The methano bridge (C₍₁₎-C₍₇₎-C₍₄₎) of the less symmetric NBN molecule (C_s) tilts to the single C-C bond side of the ethano ring of the molecule (rather than the CC side), producing a dihedral angle of 8.7° between plane H-C₍₁₎-C₍₄₎ (the yz-plane) and plane C₍₁₎-C₍₇₎-C₍₄₎. Our work suggests that it is this unique dihedral angle in NBN which causes the molecules exo-reactivity and is also responsible for the extra activity of its CC bond.     

Chemical reactivity of solid [PtnC60] towards carbon monoxide

Evidence of chemical reactivity of solid platinum-fullerene [Pt_nC₆₀] compounds towards carbon monoxide is presented. The interaction was systematically studied by means of infrared spectroscopy, X-ray powder diffraction and thermogravimetric analysis. The interaction of carbon monoxide, even under low pressure, is confirmed by the appearance of infrared absorption bands in the CO stretching region at 2064, 2014 and 1991 cm⁻¹ for the carbonylation products. The exceptions were those products with low Pt:C₆₀ ratios, which also displayed bands at 1870 and 1830 cm⁻¹. The data suggest that the CO coordination depends on the specific morphology of the solids, the original Pt:C₆₀ ratio, and the carbon monoxide nominal pressure. Therefore, these results indicate the formation of [(CO)_xPt]_m species supported in a fullerene matrix mixed with [Pt_n−mC₆₀] compounds. As there is a competition between carbon monoxide and fullerene molecules for the electronic density at the platinum centers, the nature of the CO interaction with [Pt_nC₆₀] was found to be destructive, leading to the displacement of the latter. Nevertheless, the platinum-carbonyl species formed presents relatively high stability, as shown by desorption tests.     

A statistical model for the product energy distribution in reactions leading to prompt dissociation

Direct dynamics calculations have been performed for three reactions: C₃H₈ + H → i-C₃H₇ + H₂, C₃H₈ + H → n-C₃H₇ + H₂, and C₂H₃ + O₂ → HCO + CH₂O. The fraction of the population for the radical products that promptly dissociates is computed. The results for C₃H₈ + H are qualitatively similar to previous results for C₃H₈ + OH, but the new results exhibit a slightly higher branching fraction for prompt dissociation products, owing to the fact that a greater fraction of the internal energy in the transition state ends up in the radical. For C₂H₃ + O₂ → HCO + CH₂O, the fraction of HCO that promptly dissociates is in excess of 99%. Consequently, the main product for C₂H₃ + O₂ at lower temperatures should be written as H + CO + CH₂O and not HCO + CH₂O. These results are then compared with four previous systems: CH₂O + H → HCO + H₂, CH₂O + OH → HCO + H₂O, C₃H₈ + OH → i-C₃H₇ + H₂O, and C₃H₈ + OH → n-C₃H₇ + H₂O. Based upon these seven system, several statistical models are presented. The goal of these statistical models is to predict the fraction of the transition state energy that ends up in the rovibrationally excited radical. On average, these statistical models provide an excellent prediction of product energy distribution. Consequently, these models can be used instead of costly trajectory simulations for predicting prompt radical dissociation for larger species.     

An experimental study on the formation of polycyclic aromatic hydrocarbons in laminar coflow non-premixed methane/air flames doped with four isomeric butanols

Experimental measurements were conducted for temperatures and mole fractions of C1–C16 combustion intermediates in laminar coflow non-premixed methane/air flames doped with 3.9% (in volume) 1-butanol, 2-butanol, iso-butanol and tert-butanol, respectively. Synchrotron vacuum ultraviolet photoionization mass spectrometry (SVUV-PIMS) technique was utilized in the measurements of species mole fractions. The results show that the variant molecular structures of butyl alcohols have led to different efficiencies in the formation of polycyclic aromatic hydrocarbons (PAHs) that may cause the variations in sooting tendency. Detailed species information suggests that the presence of allene and propyne promotes benzene formation through the C₃H₃ + C₃H₄ reactions and consequently PAH formation through the additions of C2 and C3 species to benzyl or phenyl radicals. As a matter of fact, PAHs formed from the 1-butanol doped flame are the lowest among the four investigated flames, because 1-butanol mainly decomposes to ethylene and oxygenates rather than C3 hydrocarbon species. Meanwhile, the tert-butanol doped flame generates the largest quantities of allene and propyne among the four flames and therefore is the sootiest one.     

Ignition behavior of pure and blended methyl octanoate,n-nonane,and methylcyclohexane

Excited-state species profiles and ignition delay times were obtained under dilute conditions (99% Ar) using a heated shock tube for methyl octanoate (C₉H₁₈O₂), n-nonane (n-C₉H₂₀), and methylcyclohexane (MCH) over a broad range of temperature and equivalence ratio (? = 0.5, 1.0, 2.0) at pressures near 1 and 10 atm. Measurements were then extended to include two ternary blends of the fuels using 5% and 20% (vol.) of the methyl ester under stoichiometric conditions. Using three independently validated chemical kinetics mechanisms, a model was compiled to assess the influence of methyl ester concentration on ignition delay times of the ternary blends. Under near-atmospheric pressure, ignition delay times were of the following order for the pure fuels: methyl octanoate < n-nonane < methylcyclohexane. Experimental results indicate that the ignition behavior of the higher-order methyl ester approaches that of the higher-order linear alkane with increased pressure regardless of equivalence ratio. Methyl octanoate also displayed significantly lower pressure dependence relative to the linear alkane and the cycloalkane species. Both of these results are supported by model calculations. Blending of methyl octanoate with n-nonane and methylcyclohexane impacted ignition delay time results more strongly at 1.5 atm, yet had only a small effect near 10 atm for temperatures above 1400 K. The study provides the first shock-tube data for a ternary blend of a linear alkane, a cycloalkane, and a methyl ester. Ignition delay time measurements for the C₉:0 methyl ester were also measured for the first time.     

Methyl concentration time-histories during iso-octane and n-heptane oxidation and pyrolysis

Methyl radical concentration time-histories were measured during the oxidation and pyrolysis of iso-octane and n-heptane behind reflected shock waves. Initial reflected shock conditions covered temperatures of 1100-1560 K, pressures of 1.6-2.0 atm and initial fuel concentrations of 100-500 ppm. Methyl radicals were detected using cw UV laser absorption near 216 nm; three wavelengths were used to compensate for time- and wavelength-dependent interference absorption. Methyl time-histories were compared to the predictions of several current oxidation models. While some agreement was found between modeling and measurement in the early rise, peak and plateau values of methyl, and in the ignition time, none of the current mechanisms accurately recover all of these features. Sensitivity analysis of the ignition times for both iso-octane and n-heptane showed a strong dependence on the reaction C₃H₅ + H = C₃H₄ + H₂, and a recommended rate was found for this reaction. Sensitivity analysis of the initial rate of CH₃ production during pyrolysis indicated that for both iso-octane and n-heptane, reaction rates for the initial decomposition channels are well isolated, and overall values for these rates were obtained. The present concentration time-history data provide strong constraints on the reaction mechanisms of both iso-octane and n-heptane oxidation, and in conjunction with OH concentration time-histories and ignition delay times, recently measured in our laboratory, should provide a self-consistent set of kinetic targets for the validation and refinement of iso-octane and n-heptane reaction mechanisms.     

Ignition limit and shock-to-detonation transition mode of n-heptane/air mixture in high-speed wedge flows

In this work, oblique detonation of n-heptane/air mixture in high-speed wedge flows is simulated by solving the reactive Euler equations with a two-dimensional (2D) configuration. This is a first attempt to model complicated hydrocarbon fuel oblique detonation waves (ODWs) with a detailed chemistry (44 species and 112 reactions). Effects of freestream equivalence ratios and velocities are considered, and the abrupt and smooth transition from oblique shock to detonation are predicted. Ignition limit, ODW characteristics, and predictability of the transition mode are discussed. Firstly, homogeneous constant-volume ignition calculations are performed for both fuel-lean and stoichiometric mixtures. The results show that the ignition delay generally increases with the wedge angle. However, a negative wedge angle dependence is observed, due to the negative temperature coefficient effects. The wedge angle range for successful ignition of n-heptane/air mixtures decreases when the wedge length is reduced. From two-dimensional simulations of stationary ODWs, the initiation length generally decreases with the freestream equivalence ratio, but the transition length exhibits weakly non-monotonic dependence. Smooth ODW typically occurs for lean conditions (equivalence ratio < 0.4). The interactions between shock/compression waves and chemical reaction inside the induction zone are also studied with the chemical explosive mode analysis. Moreover, the predictability of the shock-to-detonation transition mode is explored through quantifying the relation between ignition delay and chemical excitation time. It is demonstrated that the ignition delay (the elapsed time of the heat release rate, HRR, reaches the maximum) increases, but the excitation time (the time duration from the instant of 5% maximum HRR to that of the maximum) decreases with the freestream equivalence ratio for the three studied oncoming flow velocities. Smaller excitation time corresponds to stronger pressure waves from the ignition location behind the oblique shock. When the ratio of excitation time to ignition delay is high (e.g., > 0.5 for n-C₇H₁₆, > 0.3 for C₂H₂ and > 0.2 for H₂, based on the existing data compilation in this work), smooth transition is more likely to occur.     

Experimental and kinetic modeling study on auto-ignition properties of ammonia/ethanol blends at intermediate temperatures and high pressures

The auto-ignition properties of ammonia (NH₃)/ethanol (C₂H₅OH) blends close to engine operating conditions were investigated for the first time. Specifically, the ignition delay times (IDT) of ammonia/ethanol blends were measured in a rapid compression machine (RCM) at elevated pressures of 20 and 40 bar, five C₂H₅OH mole fractions from 0% to 100%, three equivalence ratios (ϕ) of 0.5, 1.0 and 2.0, and intermediate temperatures between 820 and 1120 K. The measurements reveal that ethanol can drastically promote the reactivity of ammonia, e.g., the auto-ignition temperature with merely 1% C₂H₅OH in fuel decreases accordingly around 110 K at 40 bar as compared to that of neat ammonia. Moreover, the promotion efficiency of ethanol is higher than hydrogen and methane with a factor of 5 and 10 under the same condition. Different dependences of IDT on the equivalence ratio were observed with different ethanol fractions in the blends, i.e., the IDTs of the 5%, 10% and 100% C₂H₅OH in fuel decrease with an increase of ϕ, but an opposite trend was observed in the mixture with 1% C₂H₅OH. A new chemical kinetic mechanism for NH₃/C₂H₅OH mixtures was developed and it is highlighted that the addition of cross-reactions between the two fuels is necessary to obtain reasonable simulations. Basically, the newly developed mechanism can reproduce the measurements of IDT very well, whereas it overestimates the reactivity of the stoichiometric and fuel-rich mixture with 1% C₂H₅OH in fuel. The sensitivity, reaction pathway, as well as rate of production analysis indicated that the ethanol addition to ammonia fuel blends provides key interaction pathways and enriches the O/H radical pool which further promotes the auto-ignition process.     

Effective, fast, and low temperature encapsulation of fullerene derivatives in single wall carbon nanotubes

High filling of single wall nanotubes (SWCNTs) with the typical exohedrally functionalized fullerene derivative of C₆₀N-methyl-3,4-fulleropyrrolidine C₆₀-C₃NH₇ is reported at the temperature of refluxing hexane. The new peapod material is characterized by STM (scanning tunneling microscopy), TEM (transmission electron microscopy) and Raman spectroscopy. Atomically resolved STM scans on SWCNT show no excessive defects or sidewall functionalization as a result of this treatment. The radial breathing mode (RBM) mode of SWCNT at 165 cm⁻¹ becomes weaker and shifted to 169 cm⁻¹ indicating filled nanotubes. TEM studies show bundles of SWCNT are highly filled with derivative C₆₀-C₃NH₇ and form the (C₆₀-C₃NH₇)_n peapods. Individual pyrrolidine-type functional groups attached to the fullerene cages are unambiguously visualized by a lower-dose observation.     

Rotational spectra of gauche perfluoro-n-butane, C4F10; perfluoro-iso-butane, (CF3)3CF; and tris(trifluoromethyl)methane, (CF3)3CH

The microwave spectra of the gauche conformer of perfluoro-n-butane, n-C₄F₁₀, of perfluoro-iso-butane, (CF₃)₃CF, and of tris(trifluoromethyl)methane, (CF₃)₃CH, have been observed and assigned. The rotational and centrifugal distortion constants for gauche n-C₄F₁₀ are: A = 1058.11750(7) MHz, B = 617.6832(1) MHz, C = 552.18794(1) MHz, Δ_J = 0.0257(5) kHz, δ_J = 0.0052(3) kHz. A C-C-C-C dihedral angle, ω, of ∼55° has been determined. These values agree well with those obtained from a coupled cluster (CCSD/cc-PVTZ) calculation. The rotational and centrifugal distortion constants for iso-C₄F₁₀ and iso-C₄HF₉ are: B_o = 816.4519(4) MHz, D_J = 0.023(2) kHz, and B_o = 903.6985(25) MHz, D_J = 0.043(4) kHz, respectively. The dipole moment of iso-C₄F₁₀ and iso-C₄HF₉ have been measured and found to be 0.0338(8) and 1.69(9) D, respectively.     

Skeletal mechanism generation with CSP and validation for premixed n-heptane flames

An automated procedure has been previously developed to generate simplified skeletal reaction mechanisms for the combustion of n-heptane/air mixtures at equivalence ratios between 0.5 and 2.0 and different pressures. The algorithm is based on a Computational Singular Perturbation (CSP)-generated database of importance indices computed from homogeneous n-heptane/air ignition solutions. In this paper, we examine the accuracy of these simplified mechanisms when they are used for modeling laminar n-heptane/air premixed flames. The objective is to evaluate the accuracy of the simplified models when transport processes lead to local mixture compositions that are not necessarily part of the comprehensive homogeneous ignition databases. The detailed mechanism was developed by Curran et al. and involves 560 species and 2538 reactions. The smallest skeletal mechanism considered consists of 66 species and 326 reactions. We show that these skeletal mechanisms yield good agreement with the detailed model for premixed n-heptane flames, over a wide range of equivalence ratios and pressures, for global flame properties. They also exhibit good accuracy in predicting certain elements of internal flame structure, especially the profiles of temperature and major chemical species. On the other hand, we find larger errors in the concentrations of many minor/radical species, particularly in the region where low-temperature chemistry plays a significant role. We also observe that the low-temperature chemistry of n-heptane can play an important role at very lean or very rich mixtures, reaching these limits first at high pressure. This has implications to numerical simulations of non-premixed flames where these lean and rich regions occur naturally.     

Infrared crystal spectra of C2H4, C2D4, and as-C2H2D2 and the general harmonic force field of ethylene

Carbon-13 frequency shifts for C₂H₄, C₂D₄, and as-C₂H₂D₂ have been measured in isotopic solid solutions in crystalline films at 60 K. All but two of the shifts (for as-C₂H₂D₂) are compatible with recently determined ζ data for C₂H₄, with ¹³C frequency shifts for C₂H₄ and C₂D₄ in the gas phase and with conventional frequency data. Together, these data completely determine with precision all 18 parameters of the GHFF for ethylene, the previous ambiguity in choice between two sets of A_g species force constants being removed. The force field reproduces closely the observed centrifugal distortion constants for C₂H₄, a ζ constant observed for trans-C₂H₂D₂, and the inertia defects for C₂H₄, C₂D₄, and as-C₂H₂D₂. Vibration and rotation constants for all isotopically deuterated ethylenes are calculated.Possible explanations for the two anomalous crystal shifts in as-C₂H₂D₂ involve the effects of the crystal field, and failure of the use of Dennison's rule for making anharmonic corrections to the shifts. The former explanation is preferred as a result of thorough analysis of the anharmonicity constants for as-C₂H₂D₂ determined from many overtone and combination bands in the gas and crystal spectra.