Combustion involves chemical reactions that are often highly exothermic. Combustion systems utilize the energy of chemical compounds released during this reactive process for transportation, to generate electric power, or to provide heat for various applications. Chemistry and combustion are interlinked in several ways. The outcome of a combustion process in terms of its energy and material balance, regarding the delivery of useful work as well as the generation of harmful emissions, depends sensitively on the molecular nature of the respective fuel. The design of efficient, low-emission combustion processes in compliance with air quality and climate goals suggests a closer inspection of the molecular properties and reactions of conventional, bio-derived, and synthetic fuels. Information about flammability, reaction intensity, and potentially hazardous combustion by-products is important also for safety considerations. Moreover, some of the compounds that serve as fuels can assume important roles in chemical energy storage and conversion. Combustion processes can furthermore be used to synthesize materials with attractive properties. A systematic understanding of the combustion behavior thus demands chemical knowledge. Desirable information includes properties of the thermodynamic states before and after the combustion reactions and relevant details about the dynamic processes that occur during the reactive transformations from the fuel and oxidizer to the products under the given boundary conditions. Combustion systems can be described, tailored, and improved by taking chemical knowledge into account. Combining theory, experiment, model development, simulation, and a systematic analysis of uncertainties enables qualitative or even quantitative predictions for many combustion situations of practical relevance. This article can highlight only a few of the numerous investigations on chemical processes for combustion and combustion-related science and applications, with a main focus on gas-phase reaction systems. It attempts to provide a snapshot of recent progress and a guide to exciting opportunities that drive such research beyond fossil combustion.

The oxidation of two blends, benzene/-decane and toluene/-decane, was studied in a jet-stirred reactor with gas chromatography analysis (temperatures from 500 to 1100 K, atmospheric pressure, stoichiometric mixtures). The studied hydrocarbon mixtures contained 75% of aromatics in order to highlight the chemistry of the low-temperature oxidation of these two aromatic compounds which have a very low reactivity compared to large alkanes. The difference of behavior between the two aromatic reactants is highly pronounced concerning the formation of derived aromatic products below 800 K. In the case of benzene, only phenol could be quantified. In the case of toluene, significant amounts of benzaldehyde, benzene, and cresols were also formed, as well as several heavy aromatic products such as bibenzyl, phenylbenzylether, methylphenylbenzylether, and ethylphenylphenol. A comparison with results obtained with neat -decane showed that the reactivity of the alkane is inhibited by the presence of benzene and, to a larger extent, toluene. An improved model for the oxidation of toluene was developed based on recent theoretical studies of the elementary steps involved in the low-temperature chemistry of this molecule. Simulations using this model were successfully compared with the obtained experimental results.

An experimental ignition delay time study for the promising biofuel 2-methyl furan (2MF) was performed at equivalence ratios of 0.5, 1.0 and 2.0 for mixtures of 1% fuel in argon in the temperature range 1200-1800 K at atmospheric pressure. Laminar burning velocities were determined using the heat-flux method for mixtures of 2MF in air at equivalence ratios of 0.55-1.65, initial temperatures of 298-398 K and atmospheric pressure. A detailed chemical kinetic mechanism consisting of 2059 reactions and 391 species has been constructed to describe the oxidation of 2MF and is used to simulate experiment. Accurate reproduction of the experimental data has been obtained over all conditions with the developed mechanism. Rate of production and sensitivity analyses have been carried out to identify important consumption pathways of the fuel and key kinetic parameters under these conditions. The reactions of hydrogen atom with the fuel are highlighted as important under all experimental conditions studied, with abstraction by the hydrogen atom promoting reactivity and hydrogen atom addition to the furan ring inhibiting reactivity. This work, to the authors knowledge, is the first to combine theoretical and experimental work to describe the oxidation of any of the alkylated furans. The mechanism developed herein to describe 2MF combustion should also function as a sub-mechanism to describe the oxidation of 2,5-dimethyl furan whilst also providing key insights into the oxidation of this similar biofuel candidate.

The formation of hydroperoxides postulated in all the kinetic models for the low temperature oxidation of alkanes have been experimentally proved thanks to a new type of apparatus associating a quartz jet-stirred reactor through a molecular-beam sampling system to a reflectron time-of-flight mass spectrometer combined with tunable synchrotron vacuum ultraviolet photoionization. This apparatus has been used to investigate the low-temperature oxidation of -butane and has allowed demonstrating the formation of different types of alkylhydroperoxides, namely methylhydroperoxide, ethylhydroperoxide and butylhydroperoxide, and of C alkylhydroperoxides including a carbonyl function (ketohydroperoxides). In addition, the formation of products deriving from these ketohydroperoxides, such as C molecules including either two carbonyl groups or one carbonyl and one alcohol functions, has been observed. Simulations using a detailed kinetic model have been performed to support some of the assumptions made in this work.

An improved chemical kinetic model for the toluene oxidation based on experimental data obtained in a premixed laminar low-pressure flame with vacuum ultraviolet (VUV) photoionization and molecular beam mass spectrometry (MBMS) techniques has been proposed. The present mechanism consists of 273 species up to chrysene and 1740 reactions. The rate constants of reactions of toluene decomposition, reaction with oxygen, ipso-additions and metatheses with abstraction of phenylic H-atom are updated; new pathways of C + C species giving benzene and fulvene are added. Based on the experimental observations, combustion intermediates such as fulvenallene, naphtol, methylnaphthalene, acenaphthylene, 2-ethynylnaphthalene, phenanthrene, anthracene, 1-methylphenanthrene, pyrene and chrysene are involved in the present mechanism. The final toluene model leads to an overall satisfactory agreement between the experimentally observed and predicted mole fraction profiles for the major products and most combustion intermediates. The toluene depletion is governed by metathese giving benzyl radicals, ipso-addition forming benzene and metatheses leading to CHCH radicals. A sensitivity analysis indicates that the unimolecular decomposition via the cleavage of a methyl C-H bond has a strong inhibiting effect, while decomposition via C-C bond breaking, ipso-addition of H-atom to toluene, decomposition of benzyl radicals and reactions related to CHCH radicals have promoting effect for the consumption of toluene. Moreover, flow rate analysis is performed to illustrate the formation pathways of mono- and polycyclic aromatics.

The modeling of the low temperature oxidation of large saturated methyl esters really representative of those found in biodiesel fuels has been investigated. Models have been developed for these species and then detailed kinetic mechanisms have been automatically generated using a new extended version of software EXGAS, which includes reactions specific to the chemistry of esters. A model generated for a binary mixture of n-decane and methyl palmitate was used to simulate experimental results obtained in a jet-stirred reactor for this fuel. This model predicts very well the reactivity of the fuel and the mole fraction profiles of most reaction products. This work also shows that a model for a middle size methyl ester such as methyl decanoate predicts fairly well the reactivity and the mole fractions of most species with a substantial decrease in computational time. Large n-alkanes such as n-hexadecane are also good surrogates for reproducing the reactivity of methyl esters, with an important gain in computational time, but they cannot account for the formation of specific products such as unsaturated esters or cyclic ethers with an ester function.

We demonstrate that stable and relatively unreactive "environmentally persistent free radicals (PFRs)" can be readily formed in the post-flame and cool-zone regions of combustion systems and other thermal processes. These resonance-stabilized radicals, including semiquinones, phenoxyls, and cyclopentadienyls, can be formed by the thermal decomposition of molecular precursors including catechols, hydroquinones and phenols. Association with the surfaces of fine particles imparts additional stabilization to these radicals such that they can persist almost indefinitely in the environment. A mechanism of chemisorption and electron transfer from the molecular adsorbate to a redox-active transition metal or other receptor is shown through experiment, and supported by molecular orbital calculations, to result in PFR formation. Both oxygen-centered and carbon-centered PFRs are possible that can significantly affect their environmental and biological reactivity.

While it is well documented iron oxide can reduce soot through burnout in the oxidative regions of flames, it may also impact molecular growth and particle inception. The role of FeO nanoparticles in mass growth of soot from 1-methylnapthalene (1-MN) was studied in a dual-zone, high-temperature flow reactor. An iron substituted, dendrimer template was oxidized in the first zone to generate ~5 nm FeO nanoparticles, which were seeded into the second zone of the flow reactor containing 1-MN at 1100°C and = 1.4-5.0. Enhanced molecular growth in the presence of FeO nanoparticles resulted in increased yields of polycyclic aromatic hydrocarbons (PAH) and soot compared to purely gas-phase reactions of 1-MN at identical fuel-air equivalence ratios. This also resulted in an increase in soot-number concentration and a slight shift to smaller particles with increasing addition (from no addition to 3 mM) of FeO. Introduction of FeO nanoparticles resulted in the formation of stabilization of environmentally persistent free radicals (EPFRs), including benzyl, phenoxyl, or semiquinone-type radicals as well as carbon-centered radicals, such as cyclopentadienyl or a delocalized electron in a carbon matrix. At the high concentrations in the flow reactor, these resonance-stabilized free radicals can undergo surface-mediated, radical-radical, molecular growth reactions which may contribute to molecular growth and soot particle inception.

Pulverized bituminous coal was burned in a 10W externally heated entrained flow furnace under air-combustion and three oxy-combustion inlet oxygen conditions (28, 32, and 36%). Experiments were designed to produce flames with practically relevant stoichiometric ratios (SR=1.2-1.4) and constant residence times (2.3s). Size-classified fly ash samples were collected, and measurements focused on the soot, elemental carbon (EC), and organic carbon (OC) composition of the total and ultrafine (<0.6μm) fly ash. Results indicate that although the total fly ash carbon, as measured by loss on ignition, was always acceptably low (<2%) with all three oxycombustion conditions lower than air-combustion, the ultrafine fly ash for both air-fired and oxy-fired combustion conditions consists primarily of carbonaceous material (50-95%). Carbonaceous components on particles <0.6μm measured by a thermal optical method showed that large fractions (52-93%) consisted of OC rather than EC, as expected. This observation was supported by thermogravimetric analysis indicating that for the air, 28% oxy, and 32% oxy conditions, 14-71% of this material may be OC volatilizing between 100 and 550°C with the remaining 29-86% being EC/soot. However, for the 36% oxy condition, OC may comprise over 90% of the ultrafine carbon with a much smaller EC/soot contribution. These data were interpreted by considering the effects of oxy-combustion on flame attachment, ignition delay, and soot oxidation of a bituminous coal, and the effects of these processes on OC and EC emissions. Flame aerodynamics and inlet oxidant composition may influence emissions of organic hazardous air pollutants (HAPs) from a bituminous coal. During oxy-coal combustion, judicious control of inlet oxygen concentration and placement may be used to minimize organic HAP and soot emissions.

Firebrands are a significant source leading to structures ignited and lost in large outdoor fires, such as Wildland-Urban Interface (WUI) fires, a large international problem, and urban fires, common in Japan. Sadly, hardly any information is available with regard to firebrand production from burning structures or actual large outdoor fires in general. To this end, an experimental database is being generated from firebrand generation from structure combustion. This paper will focus on how these detailed database results are being used to generate firebrand showers using a redesigned firebrand generator experimental apparatus installed in a full-scale wind tunnel, with the intent to experimentally simulate firebrand showers produced from structure combustion in large outdoor fires.

The flammability of combustible materials in spacecraft environments is of importance for fire safety applications because the environmental conditions can greatly differ from those on earth, and a fire in a spacecraft could be catastrophic. Moreover, experimental testing in spacecraft environments can be difficult and expensive, so using ground-based tests to inform microgravity tests is vital. Reducing buoyancy effects by decreasing ambient pressure is a possible approach to simulate a spacecraft environment on earth. The objective of this work is to study the effect of pressure on material flammability, and by comparison with microgravity data, determine the extent to which reducing pressure can be used to simulate reduced gravity. Specifically, this work studies the effect of pressure and microgravity on upward/concurrent flame spread rates and flame appearance of a burning thin composite fabric made of 75% cotton and 25% fiberglass (Sibal). Experiments in normal gravity were conducted using pressures ranging between 100 and 30 kPa and a forced flow velocity of 20 cm/s. Microgravity experiments were conducted during NASA's Spacecraft Fire Experiment (Saffire), on board of the Orbital Corporation Cygnus spacecraft at 100 kPa and an air flow velocity of 20 cm/s. Results show that reductions of ambient pressure slow the flame spread over the fabric. As pressure is reduced, flame intensity is also reduced. Comparison with the concurrent flame spread rates in microgravity show that similar flame spread rates are obtained at around 30 kPa. The normal gravity and microgravity data is correlated in terms of a mixed convection non-dimensional parameter that describes the heat transferred from the flame to the solid surface. The correlation provides information about the similitudes of the flame spread process in variable pressure and reduced gravity environments, providing guidance for potential on-earth testing for fire safety design in spacecraft and space habitats.

Compared to current refrigerants, next-generation refrigerants are more environmentally benign but more flammable. The laminar burning velocity is being used by industry as a metric to screen refrigerants for fire risk, and it is also used for kinetic model development and validation. This study reports measurements of difluoromethane/air flame burning velocities for equivalence ratios from 0.9 to 1.4 in a spherical, constant volume device. Experimental burning velocities produced with the aid of an optically thin radiation model are about 17 % greater than those obtained with an adiabatic model. Characterization of flame stretch based on the product of Markstein and Karlovitz numbers indicates that while many experimental data are nearly stretch-free, those for slower burning velocities, smaller flame radii, and leaner conditions may not be. Limiting the data to regions estimated to be stretch-free requires extrapolation away from the experimental conditions to extract burning velocities near ambient conditions, e.g., at (298 K, 101 kPa). Lower uncertainty, desirable for kinetic model validation, is obtained by interpolating between experimental conditions, e.g., at (400 K, 304 kPa). Since thermal radiation and flame stretch were found to affect the inferred burning velocities of difluoromethane/air constant volume spherical flames, they should also be considered during data reduction of other mildly flammable refrigerants.

The effects of phosphorus-containing compounds (PCCs) on the extinguishment and structure of methane-air coflow diffusion flames, in the cup-burner configuration, is studied computationally. Dimethyl methylphosphonate (DMMP), trimethyl phosphate (TMP), or phosphoric acid is added to either the air or fuel flow. Time-dependent axisymmetric computation is performed with full gas-phase chemistry and transport to reveal the flame structure and inhibition process. A detailed chemical-kinetics model (77 species and 886 reactions) is constructed by combining the methane-oxygen combustion and phosphorus inhibition chemistry. A simple model for radiation from CH, CO, CO, HO, and soot based on the optically thin-media assumption is incorporated into the energy equation. The inhibitor effectiveness is calculated as the minimum extinguishing concentrations (MECs) of CO (added to the oxidizer) as a function of the PCC loading (added to the oxidizer or fuel stream). The calculated MEC of CO without an inhibitor is in good agreement with the measured value. For moderate DMMP loading to the air (<1 %), the measured value becomes significantly smaller, presumably due to particle formation in the experiment. An inhibitor in the oxidizer flow is an order of magnitude more effective compared to that in the fuel flow in gas-phase inhibition of co-flow diffusion flames. The three PCCs studied behave similarly with regard to flame inhibition, lowering radical concentrations and the heat-release rate at the flame-stabilizing peak reactivity spot (i.e., reaction kernel) in the base, promoting flame blow-off. The three compounds behave differently, however, with regard to the trailing flame. While all three raise the maximum temperature in the trailing flame, DMMP and TMP, which contain three methyl groups, result in higher maximum flame temperature and combustion enhancement there, with a unique two-zone flame structure, whereas phosphoric acid does not.

Molecules constituting nascent soot particles have been analyzed by two-step laser desorption laser ionization mass spectrometry. Three samples have been collected from a slightly sooting ethylene/air premixed flame with the aim to investigate soot composition in the transition from nucleated to just-grown soot particles. Sampling locations have been selected based on the evolution of the particle size distribution along the flame axis. The mass spectrometric results point to a strong evolution of the molecular composition. Just-nucleated soot is rich in polycyclic aromatic hydrocarbons (PAHs) dominated by medium sizes from 18 to 40 carbon atoms but containing sizes as large as 90 carbon atoms. Most abundant PAHs are in the form of -condensed structures. The presence of a large fraction of odd numbered carbon species shows that pentagonal cycles are a common feature of the detected population. Increasing the distance from the burner outlet, i.e., the particle residence time in flame, leads to an evolution of the chemical composition of this population with a major contribution of carbon clusters including also fullerenes up to about 160 carbon atoms. Our data support a scenario in which large PAHs containing pentagonal rings evolve very efficiently upon thermal processing by a series of dehydrogenation and isomerization processes to form fullerenes. This chemistry happens in the early steps of soot growth showing that carbonization is already active at this stage. © 2020 The Authors. Published by Elsevier Inc. on behalf of The Combustion Institute. This is an open access article under the CC BY-NC-ND license (http://creativecommons.org/licenses/by-nc-nd/4.0/).

Bi-directional probes are utilized throughout fire science to measure fire-induced flows due to their ability to measure flow which changes direction, and to withstand hostile environments. However, they are not available commercially and researchers must take it upon themselves to make and manufacture them. S-type pitot probes (S-probes) work on the same principle as bi-directional probes, measuring the differential pressure between two openings, thereby offering the same benefits. However, S-probes also feature reliable manufacturing and calibration standards. In this study, the performance of bi-directional and S-probes is characterized against pitot-static probes in two scenarios. First, measurements of a steady, smooth flow in a well-characterized wind tunnel are examined. Second, the probes are used to measure the velocity profile across a turbulent jet from a blower fan. In both scenarios, the S-probe performed comparable to or better than the bi-directional probe in terms of accuracy. It is found that S-probes have similar performance to bi-directional probes in well conditioned flows. In the turbulent jet flow measurements, S-probe measurements are within 2% of pitot-static measurements in the core region of the jet, while bi-directional probes are within 6%.