Tandem flowing afterglow-SIFT-Drift: developments and applications to gas phase ion chemistry
This thesis describes the detailed design of the Tandem Flowing Afterglow-SIFT-Drift and applications of this technique and other flow tube techniques to gas phase ion chemistry. The versatile ion source and high sensitivity and resolution of the instrument allows generation and study of a variety of ions including highly reactive ions (CH/sub 2//sup -/), solvated ions (HO/sup -/(H/sub 2/O)), ions which must be synthesized by a series of ion molecule reactions (C/sub 3/H/sub 3/N/sub 2//sup -/) as well as isotopically labelled ions (/sup 37/Cl, /sup 34/S, /sup 13/C, /sup 18/O) from unenriched precursors. The acidities of a series of ..beta..-branched and polycyclic hydrocarbons are probed using the kinetic acidity method developed by DePuy, et al. (1984). A preliminary investigation of a more sensitive extension of this method is also presented. The chemistry of diazomethyl anion is described. Addition with loss of nitrogen is a common reaction. The acidity of diazomethane is bracketted as 373 +/- 4 kcal/mol and the electron affinity of diazomethyl radical is estimated to be approx. 48 kcal/mol. The product ion of the O/sub 2//sup +/ + CH/sub 4/ room temperature reaction is identified as methylene hydroperoxide. A comprehensive study of the chemistry of this cation is discussed. A qualitative and semi-quantitative model for the reaction mechanism for O/sub 2//sup +/ + CH/sub 4/ at room temperature is prepared.
- Research Organization:
- Colorado Univ., Boulder (USA)
- OSTI ID:
- 7200871
- Resource Relation:
- Other Information: Thesis (Ph. D.)
- Country of Publication:
- United States
- Language:
- English
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ORGANIC
PHYSICAL AND ANALYTICAL CHEMISTRY
ALKANES
CHEMICAL REACTIONS
CARBON 13
ISOTOPIC EXCHANGE
LABELLED COMPOUNDS
CHLORINE 37
IONS
OXYGEN 18
SULFUR 34
FLUID FLOW
SOLVATION
CARBON ISOTOPES
CHARGED PARTICLES
CHLORINE ISOTOPES
EVEN-EVEN NUCLEI
EVEN-ODD NUCLEI
HYDROCARBONS
ISOTOPES
LIGHT NUCLEI
NUCLEI
ODD-EVEN NUCLEI
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OXYGEN ISOTOPES
STABLE ISOTOPES
SULFUR ISOTOPES
400201* - Chemical & Physicochemical Properties
400202 - Isotope Effects
Isotope Exchange
& Isotope Separation