Reactivity Trends in the Gas Phase Addition of Acetylene to N-protonated Aryl Radical Cations

<div> <div> <div> <p>A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N- containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl) and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios and reaction efficiencies are reported. </p> </div> </div> </div>

Reactivity Trends in the Gas Phase Addition of Acetylene to N-protonated Aryl Radical Cations

<div> <div> <div> <p>A key step in gas-phase polycyclic aromatic hydrocarbon (PAH) formation involves the addition of acetylene (or other alkyne) to σ-type aromatic radicals, with successive additions yielding more complex PAHs. A similar process can happen for N- containing aromatics. In cold diffuse environments, such as the interstellar medium, rates of radical addition may be enhanced when the σ-type radical is charged. This paper investigates the gas-phase ion-molecule reactions of acetylene with nine aromatic distonic σ-type radical cations derived from pyridinium (Pyr), anilinium (Anl) and benzonitrilium (Bzn) ions. Three isomers are studied in each case (radical sites at the ortho, meta and para positions). Using a room temperature ion trap, second-order rate coefficients, product branching ratios and reaction efficiencies are reported. </p> </div> </div> </div>

Formation mechanism of aromatics during co-pyrolysis of coal and cotton stalk

Pyrolysis experiments were conducted in a tubular furnace from room temperature to 600 °C at 5 °C /min, and kept for 15 min. The light tar was then derived from the liquid products of pyrolysis by n-hexane supersonic extraction. Gas chromatography–mass spectrometry was employed to analyze the light tars from cotton stalk (CS) pyrolysis, Shenmu coal (SM) pyrolysis, and co-pyrolysis of CS/SM. Microcrystalline cellulose (MCC) was selected as a model compound, and the light tar from co-pyrolysis tar of MCC/SM was investigated for comparison. The results indicated that CS improved the yields and quality of phenols and benzenes in co-pyrolysis tar and that MCC had excellent performance in the formation of mononuclear aromatics during the co-pyrolysis of MCC/SM. Based on the pyrolytic behavior of CS and SM, the mechanisms of aromatic formation were further determined. It was shown that the free radicals that cracked from CS accelerated the formation of aromatics. The alkyl and mononuclear aromatic radicals of CS pyrolysis combined with the radicals from the SM aromatic structure, which then converted to benzenes and phenols. Finally, the most favorable reaction routes of mononuclear aromatics formation were proposed.

How the methyl group position influences the ultrafast deactivation in aromatic radicals

Excited xylyl (methyl–benzyl) radical isomers have been studied by femtosecond time-resolved photoelectron spectroscopy and mass spectrometry.