Electrons Mediate the Gas‐Phase Oxidation of Formic Acid with Ozone

Linde, Christian van der; Tang, Wai Kit; Siu, Chi‐Kit; Beyer, Martin K.

doi:10.1002/chem.201603080

Cited by 15 publications

(16 citation statements)

References 36 publications

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“…Despite its reactive radical character, only a small number of gas-phase reactions of CO 3 •– has been reported, − in particular the reactions with nitrogen oxides that lead to the formation of nitrate NO 3 – . − In a recent study of CO 3 •– with HCOOH, we observed a quite efficient reaction with a rate constant of 3.6 ± 0.9 × 10 –10 cm 3 s –1 , which starts with a proton transfer from the acid molecule to CO 3 •– . Also nitric acid − and methanesulfonic acid react with CO 3 •– , while no products could be identified in reactions with HCl by Dotan et al, who established an upper limit of 3 × 10 –11 cm 3 s –1 for the rate constant.…”

Section: Introductionmentioning

confidence: 72%

Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

et al. 2016

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The carbonate radical anion CO is a key intermediate in tropospheric anion chemistry. Despite its radical character, only a small number of reactions have been reported in the literature. Here we investigate the gas-phase reactions of CO and CO(HO) with HCl under ultrahigh vacuum conditions. Bare CO forms OHCl with a rate constant of 4.2 × 10 cm s, which corresponds to an efficiency of only 0.4%. Hydration accelerates the reaction, and ligand exchange of HO against HCl proceeds with a rate of 2.7 × 10 cm s. Quantum chemical calculations reveal that OHCl is best described as an OH hydrogen bonded to Cl, while the ligand exchange product is Cl(HCO). Under tropospheric conditions, where CO(HO) is the dominant species, Cl(HCO) is efficiently formed. These reactions must be included in models of tropospheric anion chemistry.

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Section: Introductionmentioning

confidence: 72%

Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

et al. 2016

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“…The photochemistry of formic acid was investigated in rare gas matrices and dissociation channels of H 2 +CO 2 and H 2 O+CO were identified. We recently showed that formic acid is oxidized by the carbonate radical anion CO 3 .− to CO 2 and H 2 O, and the detached electron is available for the formation of a new CO 3 .− molecular ion …”

Section: Introductionmentioning

confidence: 99%

Photodissociation of Sodium Iodide Clusters Doped with Small Hydrocarbons

Bersenkowitsch

Ončák

Heller

et al. 2018

Chemistry A European J

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Marine aerosols consist of a variety of compounds and play an important role in many atmospheric processes. In the present study, sodium iodide clusters with their simple isotope pattern serve as model systems for laboratory studies to investigate the role of iodide in the photochemical processing of sea‐salt aerosols. Salt clusters doped with camphor, formate and pyruvate are studied in a Fourier transform ion cyclotron resonance mass spectrometer (FT‐ICR MS) coupled to a tunable laser system in both UV and IR range. The analysis is supported by ab initio calculations of absorption spectra and energetics of dissociative channels. We provide quantitative analysis of IRMPD measurements by reconstructing one‐photon spectra and comparing them with the calculated ones. While neutral camphor is adsorbed on the cluster surface, the formate and pyruvate ions replace an iodide ion. The photodissociation spectra revealed several wavelength‐specific fragmentation pathways, including the carbon dioxide radical anion formed by photolysis of pyruvate. Camphor and pyruvate doped clusters absorb in the spectral region above 290 nm, which is relevant for tropospheric photochemistry, leading to internal conversion followed by intramolecular vibrational redistribution, which leads to decomposition of the cluster. Potential photodissociation products of pyruvate in the actinic region may be formed with a cross section of <2×10−20 cm2, determined by the experimental noise level.

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“…3 ) Fehsenfeld et al 4 ) and van der Linde et al 5 ) reported that CO 3 −• reacted with HNO 3 via a proton transfer reaction to form NO 3 − and HCO 3 • . In addition, van der Linde et al 6 ) studied gas-phase reactions of CO 3 −• with formic acid (HCOOH) to form [HCOO − ····OH • ] using FT-ICR mass spectrometry. Ninomiya et al 3 ) predicted that CO 3 −• reacts with H 2 O 2 to form the cluster ion, O 2 −• ····H 2 CO 3 .…”

Section: Introductionmentioning

confidence: 99%

Corona Discharge and Field Electron Emission in Ambient Air Using a Sharp Metal Needle: Formation and Reactivity of CO3−• and O2−•

et al. 2021

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CO 3 −• and O 2 −• are known to be strong oxidizing reagents in biological systems. CO 3 −• in particular can cause serious damage to DNA and proteins by H • abstraction reactions. However, H • abstraction of CO 3 −• in the gas phase has not yet been reported. In this work we report on gas-phase ion/molecule reactions of CO 3 −• and O 2 −• with various molecules. CO 3 −• was generated by the corona discharge of an O 2 reagent gas using a cylindrical tube ion source. O 2 −• was generated by the application of a 15 kHz high frequency voltage to a sharp needle in ambient air at the threshold voltage for the appearance of an ion signal. In the reactions of CO 3 −• , a decrease in signal intensities of CO 3 −• accompanied by the simultaneous increase of that of HCO 3 − was observed when organic compounds with H–C bond energies lower than ∼100 kcal mol −1 such as n -hexane, cyclohexane, methanol, ethanol, 1-propanol, 2-propanol, and toluene were introduced into the ion source. This clearly indicates the occurrence of H • abstraction. O 2 −• abstracts H + from acid molecules such as formic, acetic, trifluoroacetic, nitric and amino acids. Gas-phase CO 3 −• may play a role as a strong oxidizing reagent as it does in the condensed phase. The major discharge product CO 3 −• in addition to O 2 −• , O 3 , and NO x • that are formed in ambient air may cause damage to biological systems.

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Electrons Mediate the Gas‐Phase Oxidation of Formic Acid with Ozone

Cited by 15 publications

References 36 publications

Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

Hydration Leads to Efficient Reactions of the Carbonate Radical Anion with Hydrogen Chloride in the Gas Phase

Photodissociation of Sodium Iodide Clusters Doped with Small Hydrocarbons

Corona Discharge and Field Electron Emission in Ambient Air Using a Sharp Metal Needle: Formation and Reactivity of CO<sub>3</sub><sup>−•</sup> and O<sub>2</sub><sup>−•</sup>

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