LAUSR

Negative-ion mode electrospray ionization of solutions of ethanol (RF0OH), 2-fluoroethanol (RF1OH), 2,2-difluoroethanol (RF2OH), and/or 2,2,2-trifluoroethanol (RF3OH) produces anionic dimers of the types (RFnO)2H- and (RFnO)(RFn+1O)H-. The exchange reactions of these anionic dimers with the neutral alcohols are examined in a quadrupole-ion trap to extract kinetic data, from which the reaction Gibbs energies are obtained. In all cases, the formation of anionic dimers containing the more highly fluorinated alcohols is favored. Quantum chemical calculations confirm this trend and, besides affording structural data, also determine the dissociation energies of the anionic dimers. These dissociation energies are much higher than those of the corresponding neutral dimers and increase further for the more highly fluorinated alcohols due to the stronger hydrogen-bond donor ability of the latter. The present results on the interaction of individual alkoxide anions and neutral alcohol molecules contribute to a better understanding of the association of the fluorinated alcohols in solution.