A SIFT study of the reactions of H 2ONO + ions with several types of organic molecules

Abstract

A selected ion flow tube (SIFT) study has been carried out of the reactions of hydrated nitrosonium ions, NO +H 2O, which theory has equated to protonated nitrous acid ions, H 2ONO +. One objective of this study was to investigate if this ion exhibits the properties of both a cluster ion and a protonated acid in their reactions with a variety of organic molecules. The chosen reactant molecules comprise two each of the following types—amines, terpenes, aromatic hydrocarbons, esters, carboxylic acids, ketones, aldehydes and alcohols. The reactant H 2ONO + (NO +H 2O) ions are formed in a discharge ion source and injected into helium carrier gas where they are partially vibrationally excited and partially dissociated to NO + ions. Hence, the reactions of the H 2ONO + ions had to be studies simultaneously with NO + ions, the reactions of the latter ions readily being studied by selectively injecting NO + ions into the carrier gas. The results of this study indicate that the H 2ONO + ions undergo a wide variety of reaction processes that depend on the properties of the reactant molecules such as their ionisation energies and proton affinities. These processes include charge transfer with compounds, M, that have low ionisation energies (producing M +), proton transfer with compounds possessing large proton affinities (MH +), hydride ion transfer (MH +), alkyl radical (MR +), alkoxide radical transfer (MOR +), ion–molecule association (NO +H 2OM) and ligand switching (NO +M), producing the ions given in parentheses.