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Laser ionization of H2S and ion-molecule reactions of H3S+ in laser-based ion mobility spectrometry and drift cell time-of-flight mass spectrometry

  • The detection of hydrogen sulfide (H2S) by 2 + 1 resonance-enhanced multi-photon ionization (REMPI) and the application of H2S as a laser dopant for the detection of polar compounds in laser ion mobility (IM) spectrometry at atmospheric pressure were investigated. Underlying ionization mechanisms were elucidated by additional studies employing a drift cell interfaced to a time-of-flight mass spectrometer. Depending on the pressure, the primary ions H2S+, HS+, S+, and secondary ions, such as H3S+, were observed. The 2 + 1 REMPI spectrum of H2S near lambda = 302.5 nm was recorded at atmospheric pressure. Furthermore, the limit of detection and the linear range were established. In the second part of the work, H2S was investigated as an H2O analogous laser dopant for the ionization of polar substances by proton transfer. H2S exhibits a proton affinity (PA) similar to that of H2O, but a significantly lower ionization energy facilitating laser ionization. Ion-molecule reactions (IMR) of H3S+ with a variety of polar substances with PAThe detection of hydrogen sulfide (H2S) by 2 + 1 resonance-enhanced multi-photon ionization (REMPI) and the application of H2S as a laser dopant for the detection of polar compounds in laser ion mobility (IM) spectrometry at atmospheric pressure were investigated. Underlying ionization mechanisms were elucidated by additional studies employing a drift cell interfaced to a time-of-flight mass spectrometer. Depending on the pressure, the primary ions H2S+, HS+, S+, and secondary ions, such as H3S+, were observed. The 2 + 1 REMPI spectrum of H2S near lambda = 302.5 nm was recorded at atmospheric pressure. Furthermore, the limit of detection and the linear range were established. In the second part of the work, H2S was investigated as an H2O analogous laser dopant for the ionization of polar substances by proton transfer. H2S exhibits a proton affinity (PA) similar to that of H2O, but a significantly lower ionization energy facilitating laser ionization. Ion-molecule reactions (IMR) of H3S+ with a variety of polar substances with PA between 754.6 and 841.6 kJ/mol were investigated. Representatives of different compound classes, including alcohols, ketones, esters, and nitroaromatics were analyzed. The IM spectra resulting from IMR of H3S+ and H3O+ with these substances are similar in structure, i.e., protonated monomer and dimer ion peaks are found depending on the analyte concentration.show moreshow less

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Metadaten
Author:Daniel Riebe, Robert Laudien, Christian Brendler, Toralf Beitz, Hans-Gerd LöhmannsröbenGND
DOI:https://doi.org/10.1007/s00216-013-7186-5
ISSN:1618-2642 (print)
Parent Title (English):Analytical & bioanalytical chemistry
Publisher:Springer
Place of publication:Heidelberg
Document Type:Article
Language:English
Year of first Publication:2013
Year of Completion:2013
Release Date:2017/03/26
Tag:Hydrogen sulfide; Ion mobility spectrometry; Mass spectrometry; Proton transfer reaction; REMPI
Volume:405
Issue:22
Pagenumber:9
First Page:7031
Last Page:7039
Funder:German Federal Ministry of Education and Research (BMBF); ForMaT project
Organizational units:Mathematisch-Naturwissenschaftliche Fakultät / Institut für Chemie
Peer Review:Referiert