Abstract This paper evaluates the effect of a microsecond pulsed plasma (MPP) on the stabilization and emission characteristics of non-premixed biogas/air flames with various CO2 contents. The MPP is generated by a unique DC-pulsed power generator providing high voltage (HV) pulses over a wide range of pulse repetition frequencies (PRFs). The burner configuration is made up of two concentric tubes in which a swirler is placed inside the annular part, ensuring the oxidizer's rotation. The central tube delivers the fuel through an injector placed close to the burner exit. Electrical diagnostics, including voltage, were performed. OH* chemiluminescence measurements were done to describe the structure and stability of the flame. Results showed that plasma generated by microsecond HV pulses can improve flame stability. In this regard, the distribution of key active species in the burner was studied via optical emission spectroscopy (OES). The results revealed that the pulsed plasma generates chemically active species such as excited N2*, CH*, OH* molecules, and H* and O* atoms, thereby improving flame stability. The dependence of the emitted species intensities on plasma parameters was investigated in detail. It is demonstrated that MPP can drastically enhance the dynamic flame stability of swirling non-premixed biogas flames, especially at lean operating conditions. In addition, NOx and CO emissions were studied over a wide range of pulse repetition frequencies. It is seen that the pulsed plasma increases NOx emission slightly and significantly reduces CO concentration in the flue gases.

As dienes contain two C[double bond, length as m-dash]C bonds, theoretically, they are much more chemically reactive with hydroxyl radical (˙OH) than alkenes and alkanes, and the reaction with ˙OH is one of the main atmospheric degradation routes of dienes during the daytime. In our work, rate coefficients of three types of acyclic dienes: conjugated as 3-methyl-1,3-pentadiene (3M13PD), isolated as 1,4-hexadiene (14HD), and cumulated as 1,2-pentadiene (12PD) reaction with ˙OH were measured in the temperature range of 273-318 K and 1 atm using the relative rate method. At 298 ± 3 K, the rate coefficients for those reactions were determined to be k3M13PD+OH = (15.09 ± 0.72) × 10-11, k14HD+OH = (9.13 ± 0.62) × 10-11, k12PD+OH = (3.34 ± 0.40) × 10-11 (as units of cm3 per molecule per s), in the excellent agreement with values of previously reported. The first measured temperature dependence for 3M13PD, 14HD and 12PD reaction with ˙OH can be expressed by the following Arrhenius expressions in units of cm3 per molecule per s: k3M13PD+OH = (8.10 ± 2.23) × 10-11 exp[(173 ± 71)/T]; k14HD+OH = (9.82 ± 5.10) × 10-12 exp[(666 ± 123)/T]; k12PD+OH = (1.13 ± 0.87) × 10-12 exp[(1038 ± 167)/T] (as units of cm3 per molecule per s). The kinetic discussion revealed that the relative position between these two C[double bond, length as m-dash]C could significantly affect the reactivity of acyclic dienes toward ˙OH. A simple structure-activity relationship (SAR) method was proposed to estimate the reaction rate coefficients of acyclic dienes with ˙OH.

Abstract Stratospheric aerosols are greatly influenced by medium-to-large volcanic eruptions. Over the last few years, extreme wildfires have been identified as new sources of stratospheric particles, in the form of carbonaceous aerosols injected by pyrocumulonimbus (pyroCb) events in the upper troposphere and lower stratosphere, associated with significant impacts on climate and ozone chemistry. To assess the impact of wildfires and volcanic eruptions on stratospheric aerosol loadings in the Northern Hemisphere, the Rapid Balloon Experiments for Sudden Aerosol Injection in the Stratosphere (REAS) project has been initiated. REAS is an international initiative that aims to respond to sudden events impacting stratospheric aerosol composition. Seventeen balloons were launched from Reims, eastern France, between November 2021 and January 2022 to quantify the atmospheric content for both aerosols and trace/greenhouse gases from the ground up to stratospheric levels. The main measurements concerned trace gases (CO/CO2 as tracers of smoke) and aerosol together with ozone using instruments such as a gas collector, optical particle counters, backscatter sondes, an aerosol sampler, an aerosol impactor, and ozonesondes. The Groupe de Spectrométrie Moléculaire et Atmosphérique (GSMA) launch facility provided unique possibilities of combining multiple measurements in one flight thanks to medium flights (corresponding to a 6 kg payload). While no major event impacted the stratosphere during the campaign, we particularly discuss the influence of the aged volcanic plume from La Soufrière volcano (Saint Vincent island) and smoke particles from series of pyroCb events that took place in North America. The burden as well as the optical and microphysical properties of the observed aerosols are quantified from these in situ observations in association with various satellite data.

Structure–activity relationships are an increasingly necessary tool to assess the reactivity of chemicals within the environment. We present a new, automated approach for estimating unknown rate coefficients based on the electrotopological state.

AbstractCyclopentane (C5H10) and tetrahydrofuran (C4H8O) are both five‐membered ring compounds. The present study compares the auto‐ignition of cyclopentane and tetrahydrofuran in a high‐pressure shock‐tube (20 atm). Twelve different mixtures were investigated at two different fuel initial mole fractions (1% and 2%): at Xfuel = 1%, three equivalence ratios, kept constant between cyclopentane and tetrahydrofuran, were studied (0.5, 1, and 2), whereas three Xfuel/XO2 were investigated when Xfuel = 2%. A detailed kinetic mechanism was developed to reproduce cyclopentane and tetrahydrofuran auto‐ignition. The agreement between our experimental results and the modeling is very good. This mechanism was used to explain the similarities and differences observed between cyclopentane and tetrahydrofuran auto‐ignition.

Hydrofluoroolefins are being adopted as sustainable alternatives to long-lived fluorine- and chlorine-containing gases and are finding current or potential mass-market applications as refrigerants, among a myriad of other uses. Their olefinic bond affords relatively rapid reaction with hydroxyl radicals present in the atmosphere, leading to short lifetimes and proportionally small global warming potentials. However, this type of functionality also allows reaction with ozone, and whilst these reactions are slow, we show that the products of these reactions can be extremely long-lived. Our chamber measurements show that several industrially important hydrofluoroolefins produce CHF3 (fluoroform, HFC-23), a potent, long-lived greenhouse gas. When this process is accounted for in atmospheric chemical and transport modeling simulations, we find that the total radiative effect of certain compounds can be several times that of the direct radiative effect currently recommended by the World Meteorological Organization. Our supporting quantum chemical calculations indicate that a large range of exothermicity is exhibited in the initial stages of ozonolysis, which has a powerful influence on the CHF3 yield. Furthermore, we identify certain molecular configurations that preclude the formation of long-lived greenhouse gases. This demonstrates the importance of product quantification and ozonolysis kinetics in determining the overall environmental impact of hydrofluoroolefin emissions.

This study employed numerical modeling to investigate the reactivity and kinetics involved in the slow pyrolysis of lignocellulosic biomass. The model integrates a biomass multi-step kinetics scheme with heat, momentum, and mass transfer, and it was based on the transport of species and flow in a porous medium approach. To develop the multi-step kinetics model, two samples of biomass, avocado stone (AS) with a high hemicellulose content and α-cellulose (CEL), were subjected to TGA experiments in an inert atmosphere. Furthermore, several experimental data in the literature on the evolution of slow pyrolysis products and data obtained by TGA experiments were considered to refine and validate the proposed kinetic mechanism. The temperature range, from 25 to 700 °C, was explored using different heating rates (10, 20, and 40 °C/min). Experimental results showed that CO and CO2 are the predominant gases during primary devolatilization, whereas H2 and CH4 result from secondary reactions at temperatures above 400 °C. The proposed mechanism involves computational fluid dynamic (CFD) simulations of laboratory-scale biomass pyrolysis, comparing temperature and species concentrations with experimental data. The predicted results for individual non-condensable gas mass yields showed an average relative error of below 6.90 % and 11.59 % for CEL and AS, respectively. In the case of biochar, the error was 6.41 % and 9.74 % for AS and CEL, respectively. The developed kinetic model can be applied to simulate the slow pyrolytic degradation of biomass based on its chemical composition.

Measurements of ion speed in the plume of a pulsed high-current vacuum arc thruster were performed by means of electrostatic probes. The probes were designed to provide direct speed measurements with minimum disturbance on the plasma jet. Typical mean values of vi for Ti and Cu cathodes are determined at different locations downstream of the electrodes, in the far field region. From one VAT discharge to another, the mean ion speed strongly varies which leads to a large statistical dispersion. Single-shot analysis allows the observation of the plume anisotropy and its high divergence as well as the existence of several ion groups of different speeds throughout a discharge.

AbstractA first access to mono‐, di‐ and tri‐(Het)arylated pyrazolo[5,1‐b]oxazoles is reported. The series were generated from a library of 3‐(Het)arylpyrazolo[5,1‐b]oxazole platforms selectively functionalized through regioselective arylation procedures. The regioselective functionalization in C‐2 and C‐7 positions was investigated. Each Palladium‐catalyzed cross‐coupling condition was optimized and a representative library of the scope and limitations of the reactions was studied.

A discharge-flow reactor combined with modulated molecular beam mass spectrometry technique was employed to determine the rate constants of H-atom reactions with hydrogen sulfide and thiirane. The rate constants for both reactions were determined at a total pressure of 2 Torr from 220 to 950 K under pseudo-first-order conditions by monitoring either consumption of H atoms in excess of H2S (C4H4S) or the molecular species in excess of atomic hydrogen. For H + H2S reaction, a suggested previously strong curvature of the Arrhenius plot was confirmed: kl = 8.7 × 10−13 × (T/298)2.87 × exp(−125/T) cm3 molecule−1 s−1 with a conservative uncertainty of 15% at all temperatures. Non-Arrhenius behavior was also observed for the reaction of H-atom with C2H4S, with the experimental rate constant data being best fitted to a sum of two exponential functions: k2 = 1.85 × 10−10 exp(−1410/T) + 4.17 × 10−12 exp(−242/T) cm3 molecule−1 s−1 with an independent of temperature uncertainty of 15%.