Selected ion flow tube studies of some gaseous ion-molecule reactions.

Type of content
Theses / Dissertations
Publisher's DOI/URI
Thesis discipline
Chemistry
Degree name
Doctor of Philosophy
Publisher
University of Canterbury. Chemistry
Journal Title
Journal ISSN
Volume Title
Language
Date
1986
Authors
Knight, J. S.
Abstract

The Selected Ion Flow Tube technique requires a mass spectrometer to select the mass of the ion studied in a flow tube measurement. The performance of the SIFT developed and used in this study is discussed and the rate coefficients and product distributions for a number of positive ion-molecule reactions have been measured. The relative proton affinity of cyanoacetylene (HC₃N) has been determined to be 751±2 kJ mol-¹. A number of reactions of HC₃N with ions of importance to interstellar chemistry as well as the reactions of HC₃N⁺ and C₃N⁺ with H₂ have also been investigated. The relevance of the results obtained are discussed with respect to the chemistry of HC₃N in interstellar clouds. The relative proton affinities of acetonitrile (CH₃CN) and methyl isocyanide (CH₃NC) have been determined to be 788±2 and 844±2 kJ mol-¹ respectively. Two distinct species were observed for the adduction C₂H₄N⁺ produced in the reaction of CH₃⁺ and HCN, CH₃CNH⁺ (85±8%) and CH₃NCH⁺ (15±8%). The former species was confirmed to have the same structure as protonated acetonitrile and the latter a protonated methyl isocyanide structure. The two C₂H₄N⁺ isomers were distinguished in the flow tube by their different reactivity. A lower limit to the internal energy required to convert CH₃NCH⁺ to CH₃CNH⁺ was measured as 132 kJ mol-¹. Two stable isomeric forms of the C₂N⁺ ion were identified in the flow tube on the basis of their markedly different reactivity with CH₄. HC₂N⁺ appeared to have one stable structure only at flow tube pressures. The relative proton affinity of diacetylene (C₄H₂ was estimated to be 738±3 kJ mol-¹. Rate coefficients and product distributions were determined for reactions of the neutrals C₂H₂, HCN, C₆H₆ and H₂ with a number of hydrocarbon ions. Some evidence for isomeric forms of the ions C₄H₄⁺, C₆H₄⁺ and C₆H₅⁺ is also presented.

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Copyright J. S. Knight