Experimental and Modeling Investigation of the Low-Temperature Oxidation of Dimethyl Ether

The oxidation of dimethyl ether (DME) was studied using a jet-stirred reactor over a wide range of conditions: temperatures from 500 to 1100 K; equivalence ratios of 0.25, 1, and 2; residence time of 2 s; pressure of 106.7 kPa (close to the atmospheric pressure); and an inlet fuel mole fraction of 0.02 (with high dilution in helium). Reaction products were quantified using two analysis methods: gas chromatography and continuous wave cavity ring-down spectroscopy (cw-CRDS). cw-CRDS enabled the quantification of formaldehyde, which is one of the major products from DME oxidation, as well as that of hydrogen peroxide, which is an important branching agent in low-temperature oxidation chemistry. Experimental data were compared with data computed using models from the literature with important deviations being observed for the reactivity at low-temperature. A new detailed kinetic model for the oxidation of DME was developed in this study. Kinetic parameters used in this model were taken from literature or calculated in the present work using quantum calculations. This new model enables a better prediction of the reactivity in the low-temperature region. Under the present JSR conditions, error bars on predictions were given. Simulations were also successfully compared with experimental flow reactor, jet-stirred reactor, shock tube, rapid compression machine, and flame data from literature. The kinetic analysis of the model enabled the highlighting of some specificities of the oxidation chemistry of DME: (1) the early reactivity which is observed at very low-temperature (e.g., compared to propane) is explained by the absence of inhibiting reaction of the radical directly obtained from the fuel (by H atom abstraction) with oxygen yielding an olefin + HO₂·; (2) the low-temperature reactivity is driven by the relative importance of the second addition to O₂ (promoting the reactivity through branching chain) and the competitive decomposition reactions with an inhibiting effect

Hydroperoxide Measurements During Low-Temperature Gas-Phase Oxidation of <i>n-</i>Heptane and <i>n-</i>Decane

A wide range of hydroperoxides (C₁–C₃ alkyl hydroperoxides, C₃–C₇ alkenyl hydroperoxides, C₇ ketohydroperoxides, and hydrogen peroxide (H₂O₂)), as well as ketene and diones, have been quantified during the gas-phase oxidation of <i>n-</i>heptane. Some of these species, as well as C₁₀ alkenyl hydroperoxides and ketohydroperoxides, were also measured during the oxidation of <i>n-</i>decane. These experiments were performed using an atmospheric-pressure jet-stirred reactor at temperatures from 500 to 1100 K and one of three analytical methods, time-of-flight mass spectrometry combined with tunable synchrotron photoionization with a molecular beam sampling: time-of-flight mass spectrometry combined with laser photoionization with a capillary tube sampling, continuous wave cavity ring-down spectroscopy with sonic probe sampling. The experimental temperature at which the maximum mole fraction is observed increases significantly for alkyl hydroperoxides, alkenyl hydroperoxides, and then more so again for hydrogen peroxide, compared to ketohydroperoxides. The influence of the equivalence ratio from 0.25 to 4 on the formation of these peroxides has been studied during <i>n-</i>heptane oxidation. The up-to-date detailed kinetic oxidation models for <i>n-</i>heptane and for <i>n-</i>decane found in the literature have been used to discuss the possible pathways by which these peroxides, ketene, and diones are formed. In general, the model predicts well the reactivity of the two fuels, as well as the formation of major intermediates

Products from the Oxidation of Linear Isomers of Hexene

The experimental study of the oxidation of the three linear isomers of hexene was performed in a quartz isothermal jet-stirred reactor (JSR) at temperatures ranging from 500 to 1100 K including the negative temperature coefficient (NTC) zone, at quasi-atmospheric pressure (1.07 bar), at a residence time of 2 s and with dilute stoichiometric mixtures. The fuel and reaction product mole fractions were measured using online gas chromatography. In the case of 1-hexene, the JSR has also been coupled through a molecular-beam sampling system to a reflectron time-of-flight mass spectrometer combined with tunable synchrotron vacuum ultraviolet photoionization. A difference of reactivity between the three fuels, which varies with the temperature range has been observed and is discussed according to the changes in the possible reaction pathways when the double bond is displaced. An enhanced importance of the reactions via the Waddington mechanism and of those of allylic radicals with HO₂ radicals can be noted for 2- and 3-hexenes compared to 1-hexene

Elliptical micropillars for efficient generation and detection of coherent acoustic phonons

Coherent acoustic phonon generation and detection assisted by optical resonances are at the core of efficient optophononic transduction processes. However, when dealing with a single optical resonance, the optimum generation and detection conditions take place at different laser wavelengths, i.e. different detunings from the cavity mode. In this work, we theoretically propose and experimentally demonstrate the use of elliptical micropillars to reach these conditions simultaneously at a single wavelength. Elliptical micropillar optophononic resonators present two optical modes with orthogonal polarizations at different wavelengths. By employing a cross-polarized scheme pump-probe experiment, we exploit the mode splitting and couple the pump beam to one mode while the probe is detuned from the other one. In this way, at a particular micropillar ellipticity, both phonon generation and detection processes are enhanced. We report an enhancement of a factor of ~3.1 when comparing the signals from elliptical and circular micropillars. Our findings constitute a step forward in tailoring the light-matter interaction for more efficient ultrahigh-frequency optophononic devices