Chemical ionization using CF3+: Efficient detection of small alkanes and fluorocarbons

Dehon, Christophe; Lemaire, Joël; Héninger, Michel; Chaput, Aurélie; Mestdagh, H.

doi:10.1016/j.ijms.2010.09.033

Cited by 21 publications

(33 citation statements)

References 49 publications

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“…Pentane exhibited some fragmentation in contrast to the results of Dehon et al 20 who reported that while they observed complete fragmentation in pentane, there were weak signs of hydride transfer in hexane. Kinetic studies of the possible reaction mechanisms by the same group (Latappy et al 25 ) showed that apart from direct hydride transfer which was not favoured, an alternative two-stage reaction scheme was possible in which a C3H7 + fragment rather than CF3 + initiated the hydride transfer with the alkane molecule.…”

Section: Resultscontrasting

confidence: 91%

“…They found minimal fragmentation in the reaction products and demonstrated the potential of CF3 + and CF2H + ions as CI reagents for alkane measurement. The observed rate constants with some common n-alkanes as reported by Lias et al 18 and Dehon et al 20 showed good agreement with each other.…”

Section: Introductionsupporting

confidence: 85%

“…While contributions from such two-stage reaction processes would be small in low pressure working, at higher working pressures contributions from this route could become significant. Discussions with Mestdagh 26 confirmed from a re-examination of the original data 20 showed traces of hydride transfer were also observed in pentane and hexane. The secondary effect would be expected to be more prominent at higher working pressures and a characteristic would be the yield of the hydride transfer ion showing a positive deviation from linearity with increases in analyte concentration.…”

Section: Resultsmentioning

confidence: 84%

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CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

Blake

Ouheda

Evans

et al. 2016

Analyst

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SummaryAlkanes provide a particular analytical challenge to commonly used chemical ionisation methods such as proton-transfer from water owing to their basicity. It is demonstrated that the fluorocarbon ions CF3 + and CF2H + , generated from CF4, as reagents provide an effective means of detecting light n-alkanes in the range C2-C6 using direct chemical ionisation mass spectrometry. The present work assesses the applicability of the reagents in a Chemical Ionisation Mass Spectrometric (CI-TOF-MS) environments with factors such as high moisture content, operating pressures of 1-10 Torr, accelerating electric fields (E/N) and long-lived intermediate complex formation. Of the commonly used chemical ionisation reagents, H3O + and NO + only react with hexane and higher while O2 + reacts with all the target samples, but creates significant fragmentation. By contrast, CF3 + and CF2H + acting together were found to produce little or no fragmentation. In dry conditions with E/N = 100 Td or higher the relative intensity of CF2H + to CF3 + was mostly less than 1% but always less than 3%, making CF3 + the main reagent ion. Using O2 + in a parallel series of experiments, a substantially greater degree of fragmentation was observed. The detection sensitivities of the alkanes with CF3 + and CF2H + , while relatively low, were found to be better than those observed with O2 + . Experiments using alkane mixtures in the ppm range have shown the ionisation technique based on CF3 + and CF2H + to be particularly useful for measurements of alkane/air mixtures found in polluted environments. As a demonstration of the technique's effectiveness in complex mixtures, the detection of n-alkanes in smoker's breath is demonstrated

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Section: Resultscontrasting

confidence: 91%

Section: Introductionsupporting

confidence: 85%

Section: Resultsmentioning

confidence: 84%

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CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

Blake

Ouheda

Evans

et al. 2016

Analyst

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“…The mobile ICR analyzer MS and its use for ion‐molecule reaction study and quantification of pollutants have been described extensively elsewhere . In short, it is a transportable compact FT‐ICR MS based on a permanent magnet.…”

Section: Methodsmentioning

confidence: 99%

“…Due to its high mass accuracy, FT‐ICR spectrometry makes identification of the molecular formulae possible. Experimental masses are obtained from the observed frequencies using a 2‐parameter calibration law as explained in a previous work . In the present work, mass calibration is conveniently carried out using the precursor ion HO − ( m/z 17.003) or O − ( m/z 15.995) and a known ion in the spectrum.…”

Section: Methodsmentioning

confidence: 99%

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

et al. 2018

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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 N 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 H 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.

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Rapid online analysis of n-alkanes in gaseous streams via APCI mass spectrometry

Wentrup,

Bösing,

Dülcks

et al. 2024

Anal Bioanal Chem

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Online monitoring of dynamic chemical processes involving a wide volatility range of hydrocarbon species is challenging due to long chromatographic measurement times. Mass spectrometry (MS) overcomes chromatographic delays. However, the analysis of n-alkane mixtures by MS is difficult because many fragment ions are formed, which leads to overlapping signals of the homologous series. Atmospheric pressure chemical ionization (APCI) is suitable for the analysis of saturated hydrocarbons and is the subject of current research. Still, although APCI is a “soft ionization” technique, fragmentation is typically inevitable. Moreover, it is usually applied for liquid samples, while an application for online gas-phase monitoring is widely unexplored. Here, we present an automated APCI-MS method for an online gas-phase analysis of volatile and semi-volatile n-alkanes. Mass spectra for n-heptane and n-decane reveal [M-H]+, [M-3H]+ and [M-3H+H2O]+ as abundant ions. While [M-H]+ and [M-3H]+ show an excessive fragmentation pattern to smaller CnH2n+1+ and CnH2n-1+ cations, [M-3H+H2O]+ is the only relevant signal within the CnH2n+1O+ ion group, i.e., no chain cleavage is observed. This makes [M-3H+H2O]+ an analyte-specific ion that is suitable for the quantification of n-alkane mixtures. A calibration confirms the linearity of C7 and C10 signals up to concentrations of ~1000–1500 ppm. Moreover, validated concentration profiles are measured for a binary C7/C10 mixture and a five-alkane C7/C10/C12/C14/C20 mixture. Compared to the 40-min sampling interval of the reference gas chromatograph, MS sampling is performed within 5 min and allows dynamic changes to be monitored. Graphical Abstract

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Chemical ionization using CF3+: Efficient detection of small alkanes and fluorocarbons

Cited by 21 publications

References 49 publications

CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

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

Rapid online analysis of n-alkanes in gaseous streams via APCI mass spectrometry

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Chemical ionization using CF3+: Efficient detection of small alkanes and fluorocarbons

Cited by 21 publications

References 49 publications

CF3+and CF2H+: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

CF3+and CF2H+: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

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

Rapid online analysis of n-alkanes in gaseous streams via APCI mass spectrometry

Contact Info

Product

Resources

About

CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

CF₃⁺and CF₂H⁺: new reagents for n-alkane determination in chemical ionisation reaction mass spectrometry

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