Essyllt Louarn

Oxygen anion (O−) and hydroxide anion (HO−) reactivity with a series of old and new refrigerants

The reactivity of a series of commonly used halogenated compounds (trihalomethanes, chlorofluorocarbon, hydrochlorofluorocarbon, fluorocarbons, and hydrofluoroolefin) with hydroxide and oxygen anion is studied in a compact Fourier transform ion cyclotron resonance. O- is formed by dissociative electron attachment to N2 O and HO- by a further ion-molecule reaction with ammonia. Kinetic experiments are performed by increasing duration of introduction of the studied molecule at a constant pressure. Hydroxide anion reactions mainly proceed by proton transfer for all the acidic compounds. However, nucleophilic substitution is observed for chlorinated and brominated compounds. For fluorinated compounds, a specific elimination of a neutral fluorinated alkene is observed in our results in parallel with the proton transfer reaction. Oxygen anion reacts rapidly and extensively with all compounds. Main reaction channels result from nucleophilic substitution, proton transfer, and formal H2+ transfer. We highlight the importance of transfer processes (atom or ion) in the intermediate ion-neutral complex, explaining part of the observed reactivity and formed ions. In this paper, we present the first reactivity study of anions with HFO 1234yf. Finally, the potential of O- and HO- as chemical ionization reagents for trace analysis is discussed.

Compact FTICR Mass Spectrometry for Real Time Monitoring of Volatile Organic Compounds

In this paper, we present a compact Fourier transform ion cyclotron resonance mass spectrometer (FTICR-MS) designed for real time analysis of volatile organic compounds (VOCs) in air or in water. The spectrometer is based on a structured permanent magnet made with NdFeB segments. Chemical ionization is implemented inside the ICR cell. The most widely used reaction is the proton transfer reaction using H3O+ precursor ions, but other ionic precursors can be used to extend the range of species that can be detected. Complex mixtures are studied by switching automatically from one precursor to another. The accuracy obtained on the mass to charge ratio (Δm/z 5 × 10−3), allows a precise identification of the VOCs present and the limit of detection is 200 ppb without accumulation. The time resolution is a few seconds, mainly limited by the time necessary to come back to background pressure after the gas pulses. The real time measurement will be illustrated by the monitoring of VOCs produced during the thermal degradation of a polymer and by an example where three different precursor ions are used alternatively to monitor a gas sample.

Gas Analysis by Electron Ionization Combined with Chemical Ionization in a Compact FTICR Mass Spectrometer

In this Article, a compact Fourier transform ion cyclotron resonance (FTICR) mass spectrometer based on a permanent magnet is presented. This instrument has been developed for real-time analysis of gas emissions. The instrument is well-suited to industrial applications or analysis of toxic and complex samples where the concentrations can vary rapidly on a wide range. The novelty of this instrument is the ability to use either electron ionization (EI) or chemical ionization (CI) individually or both of them alternatively. Also in CI mode, different precursor ions can be used alternatively. Volatile organic compounds (VOCs) from the ppb level to very high concentrations (% level) can be detected by CI or EI. The magnet is composed of three Halbach arrays, and the nominal field achieved is 1.5 T. The ICR cell is a 3 cm side length cubic cell. The mass range is 12-200 u with a broad band detection. The mass accuracy of 0.005 u and the resolving power allow the separation of isobaric ions such as C3H8+ and CO2+. Gas introduction via controlled gas pulses, electron ionization, ion-molecule reactions, ion selection, and detection are all performed in the ICR cell. The potential of the instrument will be illustrated by an analysis of a gas mixture containing trace components at ppm level (VOCs) and components in the 0.5-100% range (N2, alkanes, and CO2).

FT-ICR studies of anionic reactions for the chemistry of planetary ionospheres

The rate constants of several ion-molecule reactions involving CN− and C3N− anions and HC3N molecules have been measured in a FT-ICR spectrometer. These measurements are of particular importance for the chemistry of Titans ionosphere and interstellar medium.