Dipole Effects on Hydrogen Atom Transfer in Ion-Molecule Reactions

Abstract

Proton and hydrogen atom transfer has been investigated in the methanol-acetaldehyde system. Combinations of CH3OH, CD3OH, CH3CHO, CD3CDO, CD3CHO, and CH3CDO were employed to allow evaluation of the position from which the transfer occurs, and the ratio plot method (variation of ionizing voltage near the onset of methanol-ion formation) was used to distinguish between proton and hydrogen atom transfer. Proton transfer appears to be determined chiefly by the energetics of the competitive processes, while hydrogen atom transfer is favored from the acetyl and hydroxyl groups by a factor of 3.