| The role of solvation of several types of ionic reactions was investigated at well-defined thermal conditions. Research carried out in this thesis was performed on a variable temperature fast-flow reactor. Reaction mechanisms of protonated water clusters [D3O+(D2O) n] with hydrogen bromide (HBr) and nitric acid (DNO3) were elucidated over a temperature range of 143 K to 173 K. The dissolution of these acid species is found to occur at critical cluster sizes. Rate coefficients of the thermal energy reactions of DNO3 and D3O +(D2O)n were investigated and found to display a dependence on cluster size. The minimum cluster size necessary for the first uptake of nitric acid and hydrogen chloride by hydrated sodium and potassium cluster ions was investigated, and compared with the uptake studies of protonated water clusters.;Potential reaction mechanisms of D+(D2O) n with chlorine nitrate (ClONO2) were investigated. Chemical reactions are not observed to occur between D+(D 2O)n and chlorine nitrate. Instead, through studies employing the heavy isotope of hydrogen, nitric acid was observed in the product ion spectrum which arises from a nitric acid impurity that is usually present to some degree in the methods employed to synthesize ClONO 2 reactant gas. The results from this study serve to explain other conflicting reaction mechanisms reported in the literature. Reactions of ClONO2 with deuterium chloride doped deuterated water were investigated over a temperature range of 148 K to 158 K; deuterated species were employed in place of light hydrogen containing molecules to facilitate the determination of reaction mechanisms. Chemical reactions were found to occur between water clusters and chlorine nitrate only under conditions where dissolved deuterium chloride was present.;Associative ionization reactions of excited sodium species with water, acetonitrile (CH3CN), benzene (C6H6), acetone [(CH3)2CO], diethylether (Et2O), ethanol (CH3CH2OH), methanol (CH3OH), ammonia (NH 3), 1-propanol (CH3CH2CH2OH), n-butyl alcohol (CH3CH2CH2CH 2OH), and dimethyloxyethane (DME) were investigated. This is the first reported heteronuclear associative ionization reaction of excited sodium species with these ligands. These measurements allow for an assessment of the relative extent of interaction of sodium ions with benzene compared to the above mentioned ligands. |
