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

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

doi:10.1002/chem.201603080

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

Christian van der Linde, Wai-Kit Tang, Chi-Kit Siu^*, Martin K. Beyer^*

^*Corresponding author for this work

Research output: Journal Publications and Reviews › RGC 21 - Publication in refereed journal › peer-review

15 Citations (Scopus)

Abstract

Gas-phase reactions of CO₃ ^.− with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF₆ to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O₂, which in turn transfer the electron to O₃. O₃ ^.− reacts with CO₂ to form CO₃ ^.−. The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

Original language	English
Pages (from-to)	12684-12687
Journal	Chemistry - A European Journal
Volume	22
Issue number	36
DOIs	https://doi.org/10.1002/chem.201603080
Publication status	Published - 26 Aug 2016

Research Keywords

electron
gas-phase reactions
radical ions
reaction mechanisms
reactive intermediates

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title = "Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone",

abstract = "Gas-phase reactions of CO3 .− with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2, which in turn transfer the electron to O3. O3 .− reacts with CO2 to form CO3 .−. The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.",

keywords = "electron, gas-phase reactions, radical ions, reaction mechanisms, reactive intermediates",

author = "{van der Linde}, Christian and Wai-Kit Tang and Chi-Kit Siu and Beyer, {Martin K.}",

year = "2016",

month = aug,

day = "26",

doi = "10.1002/chem.201603080",

language = "English",

volume = "22",

pages = "12684--12687",

journal = "Chemistry - A European Journal",

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publisher = "John Wiley & Sons",

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}

TY - JOUR

T1 - Electrons Mediate the Gas-Phase Oxidation of Formic Acid with Ozone

AU - van der Linde, Christian

AU - Tang, Wai-Kit

AU - Siu, Chi-Kit

AU - Beyer, Martin K.

PY - 2016/8/26

Y1 - 2016/8/26

N2 - Gas-phase reactions of CO3 .− with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2, which in turn transfer the electron to O3. O3 .− reacts with CO2 to form CO3 .−. The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

AB - Gas-phase reactions of CO3 .− with formic acid are studied using Fourier transform ion cyclotron resonance (FT-ICR) mass spectrometry. Signal loss indicates the release of a free electron, with the formation of neutral reaction products. This is corroborated by adding traces of SF6 to the reaction gas, which scavenges 38 % of the electrons. Quantum chemical calculations of the reaction potential energy surface provide a reaction path for the formation of neutral carbon dioxide and water as the thermochemically favored products. From the literature, it is known that free electrons in the troposphere attach to O2, which in turn transfer the electron to O3. O3 .− reacts with CO2 to form CO3 .−. The reaction reported here formally closes the catalytic cycle for the oxidation of formic acid with ozone, catalyzed by free electrons.

KW - electron

KW - gas-phase reactions

KW - radical ions

KW - reaction mechanisms

KW - reactive intermediates

UR - http://www.scopus.com/inward/record.url?scp=84983320517&partnerID=8YFLogxK

UR - https://www.scopus.com/record/pubmetrics.uri?eid=2-s2.0-84983320517&origin=recordpage

U2 - 10.1002/chem.201603080

DO - 10.1002/chem.201603080

M3 - RGC 21 - Publication in refereed journal

SN - 0947-6539

VL - 22

SP - 12684

EP - 12687

JO - Chemistry - A European Journal

JF - Chemistry - A European Journal

IS - 36

ER -

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

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