A quantitative explanation for the apparent anomalous temperature dependence of OH + HO2 = H2O + O2 through multi-scale modeling

Kinetic models for complex chemical mechanisms are comprised of tens to thousands of reactions with rate constants informed by data from a wide variety of sources – rate constant measurements, global combustion experiments, and theoretical kinetics calculations. In order to integrate information from distinct data types in a self-consistent manner, a framework for combustion model development is presented that encapsulates behavior across a wide range of chemically relevant scales from fundamental molecular interactions to global combustion phenomena. The resulting kinetic model consists of a set of theoretical kinetics parameters (with constrained uncertainties), which are related through kinetics calculations to temperature/pressure/bath-gas-dependent rate constants (with propagated uncertainties), which in turn are related through physical models to combustion behavior (with propagated uncertainties). Direct incorporation of theory in combustion model development is expected to yield more reliable extrapolation of limited data to conditions outside the validation set, which is particularly useful for extrapolating to engine-relevant conditions where relatively limited data are available. Several key features of the approach are demonstrated for the H₂O₂ decomposition mechanism, where a number of its constituent reactions continue to have large uncertainties in their temperature and pressure dependence despite their relevance to high-pressure, low-temperature combustion of a variety of fuels. Here, we use the approach to provide a quantitative explanation for the apparent anomalous temperature dependence of OH + HO₂ = H₂O + O₂ – in a manner consistent with experimental data from the entire temperature range and ab initio transition-state theory within their associated uncertainties. Interestingly, we do find a rate minimum near 1200 K, although the temperature dependence is substantially less pronounced than previously suggested.     

An experimental and modeling study of the autoignition of 3-methylheptane

An experimental and kinetic modeling study of the autoignition of 3-methylheptane, a compound representative of the high molecular weight lightly branched alkanes found in large quantities in conventional and synthetic aviation kerosene and diesel fuels, is reported. Shock tube and rapid compression machine ignition delay time measurements are reported over a wide range of conditions of relevance to combustion engine applications: temperatures from 678 to 1356 K; pressures of 6.5, 10, 20, and 50 atm; and equivalence ratios of 0.5, 1.0, and 2.0. The wide range of temperatures examined provides observation of autoignition in three reactivity regimes, including the negative temperature coefficient (NTC) regime characteristic of paraffinic fuels. Comparisons made between the current ignition delay measurements for 3-methylheptane and previous results for n-octane and 2-methylheptane quantifies the influence of a single methyl substitution and its location on the reactivity of alkanes. It is found that the three C₈ alkane isomers have indistinguishable high-temperature ignition delay but their ignition delay times deviate in the NTC and low-temperature regimes in correlation with their research octane numbers. The experimental results are compared with the predictions of a proposed kinetic model that includes both high- and low-temperature oxidation chemistry. The model mechanistically explains the differences in reactivity for n-octane, 2-methylheptane, and 3-methylheptane in the NTC through the influence of the methyl substitution on the rates of isomerization reactions in the low-temperature chain branching pathway, that ultimately leads to ketohydroperoxide species, and the competition between low-temperature chain branching and the formation of cyclic ethers, in a chain propagating pathway.     

Low-temperature combustion chemistry of biofuels: Pathways in the low-temperature (550–700 K) oxidation chemistry of isobutanol and tert-butanol

Butanol isomers are promising next-generation biofuels. Their use in internal combustion applications, especially those relying on low-temperature autoignition, requires an understanding of their low-temperature combustion chemistry. Whereas the high-temperature oxidation chemistry of all four butanol isomers has been the subject of substantial experimental and theoretical efforts, their low-temperature oxidation chemistry remains underexplored. In this work we report an experimental study on the fundamental low-temperature oxidation chemistry of two butanol isomers, tert-butanol and isobutanol, in low-pressure (4–5.1 Torr) experiments at 550 and 700 K. We use pulsed-photolytic chlorine atom initiation to generate hydroxyalkyl radicals derived from tert-butanol and isobutanol, and probe the chemistry of these radicals in the presence of an excess of O₂ by multiplexed time-resolved tunable synchrotron photoionization mass spectrometry. Isomer-resolved yields of stable products are determined, providing insight into the chemistry of the different hydroxyalkyl radicals. In isobutanol oxidation, we find that the reaction of the α-hydroxyalkyl radical with O₂ is predominantly linked to chain-terminating formation of HO₂. The Waddington mechanism, associated with chain-propagating formation of OH, is the main product channel in the reactions of O₂ with β-hydroxyalkyl radicals derived from both tert-butanol and isobutanol. In the tert-butanol case, direct HO₂ elimination is not possible in the β-hydroxyalkyl + O₂ reaction because of the absence of a beta C–H bond; this channel is available in the β-hydroxyalkyl + O₂ reaction for isobutanol, but we find that it is strongly suppressed. Observed evolution of the main products from 550 to 700 K can be qualitatively explained by an increasing role of hydroxyalkyl radical decomposition at 700 K.     

Soot low-temperature combustion on Cu–Zr/ZSM-5 catalysts in O2/He and NO/O2/He atmospheres

Zirconium doped Cu/ZSM-5 catalysts were prepared and characterized in this investigation. Catalytic activity during soot combustion was determined in both O₂/He and NO/O₂/He atmospheres by temperature-programmed oxidation. The use of zirconium reduces the temperature of maximum soot oxidation rate by 229 °C in O₂/He atmosphere and 270 °C in NO/O₂/He atmosphere. The promoting effect of zirconium is discussed in terms of surface dispersion, enrichment of active components, and creation of oxygen vacancies where molecular oxygen or NO_x is adsorbed forming basic surface oxygen species active for soot oxidation. The NO₂ formed at the copper–zirconium interface sites leads to the ignition temperature being significantly decreased to 93 °C, which is inside the exhaust temperature range of diesel engines. To understand the combustion reaction kinetics, the activation energy and reaction order of soot combustion were evaluated. According to the Redhead method, the activation energy for non-catalyzed reaction is 164 kJ/mol under the O₂/He atmosphere. For the Cu/ZSM-5 and Cu–Zr/ZSM-5, the activation energies under the O₂/He atmosphere (134–151 kJ/mol) are slightly higher than those under the NO/O₂/He atmosphere (128–135 kJ/mol). The Freeman–Carroll method is suitable to describe the soot combustion in the NO/O₂/He atmosphere, with the activation energies for the catalysts in the range of 97–112 kJ/mol and the average value of reaction order equal to 1.36.     

Stabilized flames in hybrid aluminum-methane-air mixtures

A premixed methane–air bunsen-type flame is seeded with micron-sized (d₃₂ = 5.6 μm) atomized aluminum powder over a wide range of solid fuel concentrations. The burning velocities of the resulting two-phase hybrid flame are determined using the total surface area of the inner flame cone and the known volumetric flow rate, and spatially resolved flame spectra are obtained with a spectral scanning system. Flame temperatures are derived through polychromatic fitting of Planck’s law to the continuous part of the spectrum. It is found that an increase in the solid fuel concentration changes the aluminum combustion regime from low temperature oxidation to full-fledged flame front propagation. For stoichiometric methane–air mixtures, the transition occurs in the aluminum concentration range of 140–220 g/m³ and is manifested by the appearance of AlO sub-oxide bands and an increase in the flame temperature to 2500 K. The flame burning velocity is found to decrease only slightly with an increase in aluminum concentration, in contrast to the rapid decrease in flame speed, followed by quenching, that is observed for flames seeded with inert SiC particles. The observed behavior of the burning velocity and flame temperature leads to the conclusion that intense aluminum combustion in a hybrid flame only occurs when the flame front propagating through the aluminum suspension is coupled to the methane–air flame.     

High-pressure shock-tube investigation of the impact of 3-pentanone on the ignition properties of primary reference fuels

Ignition-delay times for pure 3-pentanone, 3-pentanone/iso-octane (10/90% by volume) and 3-pentanone/n-Heptane mixtures (10/90% by volume) have been determined in a high-pressure shock tube under engine-relevant conditions (p₅ = 10, 20, and 40 bar) for equivalence ratios ? = 0.5 and 1.0 and over a wide temperature range 690 K < T₅ < 1270 K. The results were compared to ignition delay times of primary reference fuels under identical conditions. A detailed kinetics model is proposed for the ignition of all fuel mixtures. The model predicts well the ignition delay times for pure 3-pentanone for a wide range of pressure and temperature and equivalence ratios in argon dilution as well as in air. Ignition delay times for 3-pentanone-doped mixtures, especially in the low-temperature range are overpredicted by approx. a factor of 0.5 (at 800 K, 40 bar, ? = 1.0) by the calculation but the model still reproduces the overall trend of the experimental data. For lean conditions, 10% 3-pentanone reduces the reactivity of n-Heptane below 1000 K while for stoichiometric conditions it does not alter the ignition delay by more than 11% at 850 K and 20 bar. In iso-octane the effect is inverse, leading to acceleration of the main ignition. Based on the model, the influence of 3-pentanone on the main heat release in a n-Heptane-fueled HCCI engine cycle is simulated.     

Oxygen species on the silver surface oxidized by MW-discharge: Study by photoelectron spectroscopy and DFT model calculations

A polycrystalline silver surface has been studied by synchrotron radiation photoelectron spectroscopy after deep oxidation by microwave discharge in an O₂ atmosphere. Oxidized structures with high oxygen content, AgO_x with x > 1, have been found on the silver surface after oxidation at 300–400 K. The line shapes observed in the O1s spectra were decomposed into five components and indicated that complex oxidized species were formed. An analysis of the oxidized structures with binding energies, Е_b(O1s), greater than 530 eV pointed to the presence of both Ag–O and O–O bonds. We have carried out a detailed experimental study of the valence band spectra in a wide spectral range (up to 35 eV), which has allowed us to register the multicomponent structure of spectra below Ag4d band. These features were assigned to the formation of Ag–O and O–O bonds composed of molecular (associative) oxygen species. DFT model calculations showed that saturation of the defect oxidized silver surface with oxygen leads to the formation of associative oxygen species, such as superoxides, with electrophilic properties and covalent bonding. The high stability of oxygen-rich silver structures, AgO_x, can be explained by the formation of small silver particles during the intensive MW oxidation, which can stabilize such oxygen species.     

Admittance of metal–insulator–semiconductor structures based on graded-gap HgCdTe grown by molecular-beam epitaxy on GaAs substrates

Metal–insulator–semiconductor structures based on n-Hg_1−xCd_xTe (x = 0.19–0.25) were grown by molecular-beam epitaxy on the GaAs (0 1 3) substrates. Near-surface graded-gap layers with high CdTe content were formed on both sides of the epitaxial HgCdTe. Admittance of these structures was studied experimentally in a wide temperature range (8–150) K. It is shown that an increase in the composition of the working layer and a decrease in temperature lead to a decrease in the frequency of transition to high-frequency behavior of the capacitance–voltage characteristics. The differential resistance of space charge region in the strong inversion increases with the composition of the working layer and for x = 0.22 and 0.25, the differential resistance is limited by the Shockley-Read generation. The values of the differential resistance of space charge region at different frequencies and temperatures were found.     

Study of the competing chemical reactions in the initiation and spread of smouldering combustion in peat

Smouldering combustion of natural fuel layers such as peatlands leads to the largest fires on Earth and posses a possible positive feedback mechanism to climate change. In this paper, we use an experimental methodology to study the smouldering combustion of samples of peat under a wide range burning conditions. Vertical samples (30 mm deep and 125 mm in diameter) are ignited by radiation on the top free surface and the smouldering front propagates downward against a forced flow of oxidizer. By varying the oxygen concentration ([O₂]) and the ignition conditions we investigate the competing pyrolysis and oxidation reactions. A reaction framework with two regimes is consistently observed. The measurements show that a char species is formed by the competing pyrolysis and oxidation reactions in the first regime resulting in net char production and in the second regime char oxidation results in conversion of the char to ash. Lower mass loss rates and the larger residual mass at lower [O₂] suggest that a wider smouldering front is required to sustain combustion as the [O₂] is decreased. These results improve our understanding of smouldering phenomena and the role of the competing chemical reactions.     

Experimental and semi-detailed kinetic modeling study of decalin oxidation and pyrolysis over a wide range of conditions

Decalin is the simplest polycyclic alkane (polynaphtenic hydrocarbon) found in liquid fuels (jet fuels, Diesel). In order to better understand the combustion characteristics of decalin, this study provides new experimental data for its oxidation in a jet-stirred reactor. For the first time, stable species concentration profiles were measured in a jet-stirred reactor at a constant mean residence time of 0.1 s and 0.5 s at respectively 1 and 10 atm, over a range of equivalence ratios (? = 0.5–1.5) and temperatures (750–1350 K). The oxidation of decalin under these experimental conditions was modeled using a semi-detailed chemical kinetic reaction mechanism (11,000 reactions involving 360 species) derived from a previously proposed scheme for the ignition of the same fuel in a shock-tube. The proposed mechanism that includes both low- and high-temperature chemistry shows reasonably good agreement with the present experimental data set. It can also represent well decalin pyrolysis and oxidation data available in the literature. Reaction path analyses and sensitivity analyses were conducted to interpret the results.     

Structural,magnetic and superconducting phase transitions in CaFe2As2 under ambient and applied pressure

At ambient pressure CaFe₂As₂ has been found to undergo a first order phase transition from a high temperature, tetragonal phase to a low-temperature orthorhombic/antiferromagnetic phase upon cooling through T ～ 170 K. With the application of pressure this phase transition is rapidly suppressed and by ～0.35 GPa it is replaced by a first order phase transition to a low-temperature collapsed tetragonal, non-magnetic phase. Further application of pressure leads to an increase of the tetragonal to collapsed tetragonal phase transition temperature, with it crossing room temperature by ～1.7 GPa. Given the exceptionally large and anisotropic change in unit cell dimensions associated with the collapsed tetragonal phase, the state of the pressure medium (liquid or solid) at the transition temperature has profound effects on the low-temperature state of the sample. For He-gas cells the pressure is as close to hydrostatic as possible and the transitions are sharp and the sample appears to be single phase at low temperatures. For liquid media cells at temperatures below media freezing, the CaFe₂As₂ transforms when it is encased by a frozen media and enters into a low-temperature multi-crystallographic-phase state, leading to what appears to be a strain stabilized superconducting state at low temperatures.     

Transport and magnetic properties of La1.48Nd0.4Sr0.12CuO4/La0.67Sr0.33MnO3 bilayer

We have grown La_1.48Nd_0.4Sr_0.12CuO₄/La_0.67Sr_0.33MnO₃ (LNSCO/LSMO) bilayer structure on SrTiO₃ (0 0 1) substrate. Both temperature dependences of resistivity and magnetization curves show anomalies between 60 < T < 80 K, where a low-temperature orthorhombic (LTO) to low-temperature tetragonal (LTT) structural transition is observed in LNSCO bulk crystal. It is suggested that the formation of domains in LSMO layer can relax the strains caused by the LTO–LTT transition in LNSCO layer.     

Structure sensitivity of propene oxidation over Co-Mn spinels

Single-phase cobalt–manganese spinel oxides (Co_3?nMn_nO₄, CMO) were studied for the catalytic oxidation of propene in a systematic optimization strategy. CMO films were synthesized by pulsed-spray evaporation chemical vapor deposition (PSE–CVD) and characterized by X-ray diffraction (XRD), Fourier transform infrared (FTIR), Raman and Ultraviolet–Visible (UV–Vis) spectroscopy. The effect of Co/Mn ratio in the mixed oxide systems on their catalytic activity was investigated in a fixed-bed reactor at T = 100–800 °C, with a space velocity of 90,000 mL/g_cat h and a feed of 2% C₃H₆/20% O₂/78% Ar. XRD patterns, FTIR and Raman spectroscopy reveal that a cubic single-phase spinel structure is obtained for n ? 1.23, while a tetragonal spinel structure is observed for n > 1.23. With increasing of the manganese content, the temperature–programmed analysis demonstrates a lower reducibility, a general decrease of the temperature required for the reduced samples to be re-oxidized and increasing thermal stability. The catalytic tests show that the involvement of cobalt–manganese oxides in propene oxidation suppresses the formation of reaction intermediates, favoring the selectivity toward CO₂ at low temperatures. Co_2.35Mn_0.65O₄ exhibits the best catalytic performance, which follows in line with its better reducibility compared with the other compositions in the series of CMO oxides. These results show the great potential of CMO for future industrial application as a low-temperature catalytic system which does not rely on precious metals.     

In situ XPS and MS study of methanol decomposition and oxidation on Pd(111) under millibar pressure range

The methanol decomposition and oxidation on a Pd(111) single crystal have been investigated in situ using ambient-pressure X-ray photoelectron spectroscopy (XPS) and mass-spectrometry (MS) in the temperature range of 300–600 K. It was found that even in the oxygen presence the methanol decomposition on palladium proceeds through two competitive routes: fast dehydrogenation to CO and H₂, and slow decomposition of methanol via the C–O bond scission. The rate of the second route is significant even in the millibar pressure range, which leads to a blocking of the palladium surface by carbon and to a prevention of the further methanol conversion. As a result, no gas phase products of methanol decomposition were detected by mass-spectrometry at 0.1 mbar CH₃OH in the whole temperature range. The methanol C–O bond scission produces CH_x species, which fast dehydrogenate to atomic carbon even at room temperature and further partially dissolve in the palladium bulk at 400 K with the formation of the PdC_x phase. According to in situ XPS data, the PdC_x phase forms even in the oxygen excess. The application of an in situ XPS–MS technique unambiguously shows a good correlation between a decrease in the surface concentration of all carbon-containing species and the rate of methanol conversion. Since these carbon species have a high reactivity towards oxygen, heating of Pd(111) above 450 K in a methanol–oxygen mixture yields CO, CO₂, and water. The product distribution indicates that the main route of methanol conversion is the dehydrogenation of methanol to CO and hydrogen. However, under the experimental conditions used, hydrogen is completely oxidized to water, while CO is partially oxidized to CO₂. No palladium oxide was detected by XPS in these conditions.     

Oxygen non-stoichiometry and electrical conductivity of Pr2−xSrxNiO4±δ with x = 0–0.5

Oxygen non-stoichiometry and electrical conductivity of the Pr_2−xSr_xNiO_4±δ series with x = 0.0–0.5 were investigated in Ar/O₂ (pO₂ = 2.5 to 21 000 Pa) within a temperature range of 20–1000 °C. The equilibrium values of oxygen non-stoichiometry and electrical conductivity of these nickelates were determined as functions of temperature and oxygen partial pressure (pO₂). The nickelates with x = 0–0.5 appear to be p-type semiconductors in the investigated temperature and pO₂ ranges. The nickelates with x = 0.3–0.5 show very feebly marked pO₂ dependencies of the conductivity. Pr_1.7Sr_0.3NiO_4±δ shows the anomalies of the conductivity versus oxygen partial pressure which can be related to the orthorhombic–tetragonal crystal structure transformations. The conductivity of the Pr_2−xSr_xNiO_4±δ samples correlates with the average oxidation state of the nickel cations. The samples with x = 0.5 have the highest nickel oxidation state (≈ 2.5+), the highest [Ni³⁺]/[Ni²⁺] ratio close to 1 and show the highest conductivity (≈ 120 S/cm) in the whole pO₂ and temperature ranges investigated.     

New experimental evidence and modeling study of the ethylbenzene oxidation

A study of the oxidation of ethylbenzene has been performed in a jet-stirred reactor (JSR) at quasi-atmospheric pressure (800 Torr), at temperatures ranging 750–1100 K, at a mean residence time of 2 s and at three equivalence ratios ? (0.25, 1, and 2). Reactants and 25 reaction products were analyzed online by gas chromatography after sampling in the outlet gas. A new mechanism for the oxidation of ethylbenzene was proposed whose predictions were in satisfactory agreement with the measured species profiles obtained in JSR and with flow reactor data from the literature. A flow rate analysis has been performed at 900 K showing the important role of the combinations with HO₂ radicals of resonance stabilized radicals obtained from ethylbenzene by H-atom abstractions. Other important reactions of ethylbenzene are the ipso-additions of H- and O-atoms and of methyl radicals to the aromatic ring.     

Reversible and irreversible reactions of three oxygen precursors on InAs(0 0 1)-(4 × 2)/c(8 × 2)

The substrate reactions of three common oxygen sources for gate oxide deposition on the group III rich InAs(0 0 1)-(4 × 2)/c(8 × 2) surface are compared: water, hydrogen peroxide (HOOH), and isopropyl alcohol (IPA). Scanning tunneling microscopy reveals that surface atom displacement occurs in all cases, but via different mechanisms for each oxygen precursor. The reactions are examined as a function of post-deposition annealing temperature. Water reaction shows displacement of surface As atoms, but it does not fully oxidize the As; the reaction is reversed by high temperature (450 °C) annealing. Exposure to IPA and subsequent low-temperature annealing (100 °C) show the preferential reaction on the row features of InAs(0 0 1)-(4 × 2)/c(8 × 2), but higher temperature anneals result in permanent surface atom displacement/etching. Etching of the substrate is observed with HOOH exposure for all annealing temperatures. While nearly all oxidation reactions on group IV semiconductors are irreversible, the group III rich surface of InAs(0 0 1) shows that oxidation displacement reactions can be reversible at low temperature, thereby providing a mechanism of self-healing during oxidation reactions.     

Rate limiting steps of the porous La0.6Sr0.4Co0.8Fe0.2O3−δ electrode material

The electrode reaction of porous La_0.6Sr_0.4Co_0.8Fe_0.2O_3?δ films deposited onto Ce_0.9Gd_0.1O_1.95 (CGO) was investigated by impedance spectroscopy within the temperature and oxygen partial pressure (pO₂) ranges of 500 ≤ T ≤ 700 °C and 10^? 4 < pO₂ < 1 atm, respectively, using Ar and He as gas carriers. The electrochemical impedance spectroscopy (EIS) measurements reveal a high frequency (HF) and a low frequency (LF) regions in the Nyquist plane. The high frequency (HF) region was fitted with a Warburg-type impedance element, and the low frequency (LF) region was reproduced with a resistance in parallel to a constant phase element. Both, the slight dependence of the polarization resistance (R_W) and the small variation of the apex frequency (f_v) of the HF Warburg-type element, on pO₂, suggest that this contribution corresponds to the oxygen diffusion in the bulk of the La_0.6Sr_0.4Co_0.8Fe_0.2O_3?δ electrode material. The variation of the polarization resistance of the LF region (R_rcpe) with pO₂ indicates that as T increases, the limiting step evolves from dissociative oxygen adsorption to oxygen gas diffusion in the pores of the mixed ionic/electronic conductor (MIEC) electrode.     

Effect of CuI on the formation and properties of Te-based far infrared transmitting chalcogenide glasses

A series of Ge–Te–CuI far infrared transmitting chalcohalide glasses were prepared by traditional melt-quenching method and the glass-forming region was determined. Properties measurements include density, DTA, XRD, SEM, Vis–NIR and infrared (IR) transmission spectra. The results show that with the addition of CuI, the glass-forming ability is improved and nearly 30 mol% CuI can be dissolved into the Ge₂₀Te_80?x(CuI)_x glass system. The density and glass transition temperature of Ge–Te–CuI chalcohalide glasses are within the range 5.459–5.960 g cm^?3 and 150–184 °C, respectively. These glasses all have wide optical transmission window from 1.8 to 25 μm and offer an alternative solution for far infrared transmitting materials.     

Reactivity of the Cu2O(1 0 0) surface: Insights from first principles calculations

We present a summary of results of systematic first principles calculations of the electronic and geometric structures of the Cu₂O(1 0 0) surface and the process of CO oxidation on this surface (energetics and pathways of adsorption, diffusion and reactions of CO and O₂ on the surface). The (p, T) phase diagram of the Cu₂O(1 0 0) in equilibrium of with gas phase O₂ built using the ab initio thermodynamics approach suggests that the O-terminated surface is preferred over the Cu-terminated one within the entire ranges of pressures and temperatures in which the compound exists. Metastable Cu-terminated Cu₂O(1 0 0) is found to undergo a surface reconstruction in agreement with experiment. We find CO to oxidize spontaneously on the O-terminated Cu₂O(1 0 0) surface by consuming surface O atoms. Our calculations also show that the surface O-vacancies left in the course of the CO oxidation can be easily filled with dissociative adsorption of the gas phase O₂ molecules, which are usually present in reaction environment.