A selected ion flow tube study of the reactions of H₃O⁺, NO⁺ and O₂ ⁺ with methyl vinyl ketone and some atmospherically importan

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• 作者：Michel ; E. ; Schoon ; N. ; Amelynck ; C. ; Guimbaud ; C. ; Catoire ; V. ; Arijs ; E.
• 关键词：SIFT ; Ion/molecule reactions ; Aldehydes ; Methyl vinyl ketone ; Proton transfer ; Charge transfer ; Hydride ion transfer
• 刊名：International Journal of Mass Spectrometry
• 出版年：2005
• 出版时间：June 15, 2005
• 年：2005
• 卷：244
• 期：1
• 页码：50-59
• 全文大小：183 K

文摘

The rate constant and product ion distribution of the reactions of H₃O⁺, NO⁺ and O₂⁺ with methyl vinyl ketone (MVK), methacrolein (MaCR), pivaldehyde, 2-methyl-butanal, glyoxal, o-, m- and p-tolualdehyde have been investigated at 150 Pa and 297 K using a selected ion flow tube (SIFT). All reactions, except the NO⁺/glyoxal reaction, proceed at a rate close to the collisional rate, calculated with the Su and Chesnavich model, using the polarizability and electric dipole moment of the compounds derived from quantum chemical calculations.

All H₃O⁺ reactions proceed by proton transfer, non-dissociative for all compounds, except for 2-methyl-butanal, where two minor channels resulting from fragmentation after protonation are observed.

Association is the only pathway in the NO⁺/MVK and NO⁺/glyoxal reaction. Hydride ion transfer is the major process occurring in all the other NO⁺ reactions. Elimination of CHO for pivaldehyde and association for MaCR are also non-negligible channels in their reaction with NO⁺.

All O₂⁺ reactions result in the parent cation by charge transfer and in at least one fragment ion.

Hydration of the product ions has been investigated by adding water vapor in the reaction zone. A method is proposed to derive the three-body association rate constants of the product ions with water and to estimate the rate constants of the reactions of the hydrated precursor ions H₃O⁺·H₂O and NO⁺·H₂O with the reactants.