Corona discharge ion mobility spectrometry of aliphatic and aromatic hydrocarbons

Borsdorf, Helko; Schelhorn, H.; Flachowsky, J.; Doring, H.-R.; Stach, J.

doi:10.1016/s0003-2670(99)00567-x

Cited by 75 publications

(38 citation statements)

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“…It was found that O 2 ϩ• reacts mainly by dissociative or nondissociative charge transfer [17][18][19], NO ϩ by hydride abstraction [18 -22], and H 3 O ϩ by association [19,22]. Moreover, there are a few reports on the APCI-MS and ion mobility spectrometry (IMS) of alkanes, alkenes, and cycloalkanes in air [23,24]. However, to the best of our knowledge there are no comprehensive studies on the ion chemistry in a plasma generated by corona discharges in hydrocarbon-doped air.…”

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A mass spectrometry study of alkanes in air plasma at atmospheric pressure

Marotta

Paradisi

2008

J. Am. Soc. Mass Spectrom.

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The positive APCI-mass spectra in air of linear (n-pentane, n-hexane, n-heptane, n-octane), branched [2,4-dimethylpentane, 2,2-dimethylpentane and 2,2,4-trimethylpentane (i-octane)], and cyclic (cyclohexane) alkanes were analyzed at different mixing ratios and temperatures. The effect of air humidity was also investigated. Complex ion chemistry is observed as a result of the interplay of several different reagent ions, including atmospheric ions O 2 ϩ• , NO ϩ , H 3 O ϩ , and their hydrates, but also alkyl fragment ions derived from the alkanes. Some of these reactions are known from previous selected ion/molecule reaction studies; others are so far unreported. The major ion formed from most alkanes (M) is the species [M Ϫ H] ϩ , which is accompanied by M ϩ• only in the case of n-octane. Ionic fragments of C n H 2nϩ1 ϩ composition are also observed, particularly with branched alkanes: the relative abundance of such fragments with respect to that of [M Ϫ H] ϩ decreases with increasing concentration of M, thus suggesting that they react with M via hydride abstraction. The branched C 7 and C 8 alkanes react with NO ϩ to form a C 4 H 10 NO ϩ ion product, which upon collisional activation dissociates via HNO elimination. The structure of t-Bu ϩ (HNO) is proposed for such species, which is reasonably formed from the original NO ϩ (M) ion/molecule complex via hydride transfer and olefin elimination. . For air pollution control, different types of reactors and power supplies are being developed and tested for production of nonthermal plasmas by means of electrical discharges [3]. Following an initial phase devoted to prove the feasibility and competitiveness of the process in terms of energy and cost efficiency, research is presently focusing on the characterization of the chemistry-i.e., the products being released and the underlying chemical mechanisms-to develop a more efficient and cleaner process [5].In nonthermal plasmas, which are conveniently produced by electric corona discharges in air at atmospheric pressure, high-energy electrons induce ionization, excitation, and dissociation of the bulk gas molecules, N 2 and O 2 . The resulting reactive species, ionic and neutral as well as thermalized electrons, can attack molecules of organic pollutants present in the air, such as hydrocarbons and other volatile organic compounds (VOCs), and initiate a chain of reactions leading eventually to their oxidation. It is generally accepted that nonthermal plasma-induced VOC oxidation proceeds via VOC-derived organic radicals, R • , which are trapped by molecular oxygen and undergo further reactions as described for their tropospheric oxidation [6], leading eventually to CO 2 . As for the origin of such VOC-derived radicals, i.e., the nature of the initiation steps of nonthermal plasma-induced VOC decay, reactions of VOC molecules with neutrals and radicals, notably O( 3 P) and • OH, are usually envisioned. However, increasing numbers of literature reports suggest that in some cases ionic initiation steps might prevail [7][8][9...

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A mass spectrometry study of alkanes in air plasma at atmospheric pressure

Marotta

Paradisi

2008

J. Am. Soc. Mass Spectrom.

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“…N-alkanes provide well-defined ion mobility spectra using CD ionization while branched chain alkanes show complex spectra with series of product ion peaks due to their typical fragmentations [8]. It was not possible to attribute the product ion peaks to certain ionic structures.…”

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confidence: 99%

“…Gas-drying by silica gel and purification by charcoal yielded a relative humidity of about 2.0% (−25°C dew point ±3°C). The details of the sample introduction system used for IMS and its function has been described previously [8].…”

Section: Ion Mobility Measurementsmentioning

confidence: 99%

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Influence of structural features of isomeric hydrocarbons on ion formation at atmospheric pressure

Borsdorf

2008

Int. J. Ion Mobil. Spec.

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Ion mobility spectrometry (IMS) in combination with different techniques of atmospheric pressure ionization ( 63 Ni ionization, photoionization, Corona discharge ionization) was applied to determine the influence of structural features of aromatic and cyclic hydrocarbons on ion mobility spectra. For this purpose, different sets of isomeric hydrocarbons were investigated using the above-mentioned ionization techniques. We found different structural features of these isomeric non-polar compounds which cause distinct differences in ion mobility spectra. These differences result from the formation of different product ions or a different relative abundance of ions formed depending on the occurrence of certain structural features (position of the double bond, arrangement of double bonds within the carbon ring, configuration of aliphatic side chain in the space, position of aliphatic side chain on the carbon ring and the number of carbon atoms in the aliphatic side chain). The nature of product ions formed was determined using a coupling of IMS with mass spectrometry (MS).

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“…The details of the sample introduction system used for ion mobility measurements and its function are described elsewhere [24]. Series of measurements with increasing concentrations were detected for each compound in order to estimate any concentration-depen- Table 1.…”

Section: Ion Mobility Measurementsmentioning

confidence: 99%

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

Borsdorf

Nazarov

Eiceman

2002

J. Am. Soc. Mass Spectrom.

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The ionization pathways were determined for sets of isomeric non-polar hydrocarbons (structural isomers, cis/trans isomers) using ion mobility spectrometry and mass spectrometry with different techniques of atmospheric pressure chemical ionization to assess the influence of structural features on ion formation. Depending on the structural features, different ions were observed using mass spectrometry. Unsaturated hydrocarbons formed mostlywere found for saturated cis/trans isomers using photoionization and 63 Ni ionization. These ionization methods and corona discharge ionization were used for ion mobility measurements of these compounds. Different ions were detected for compounds with different structural features. 63 Ni ionization and photoionization provide comparable ions for every set of isomers. The product ions formed can be clearly attributed to the structures identified. However, differences in relative abundance of product ions were found. Although corona discharge ionization permits the most sensitive detection of non-polar hydrocarbons, the spectra detected are complex and differ from those obtained with 63 Ni ionization and photoionization. (J Am Soc

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Corona discharge ion mobility spectrometry of aliphatic and aromatic hydrocarbons

Cited by 75 publications

References 31 publications

A mass spectrometry study of alkanes in air plasma at atmospheric pressure

A mass spectrometry study of alkanes in air plasma at atmospheric pressure

Influence of structural features of isomeric hydrocarbons on ion formation at atmospheric pressure

Atmospheric pressure chemical ionization studies of non-polar isomeric hydrocarbons using ion mobility spectrometry and mass spectrometry with different ionization techniques

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