Solution chemistry and secondary ion emission from amine-glycerol solutions

Analytical Chemistry Division, Oak Ridge National Laboratory, Oak Ridge, Tennessee, USA Secondary ion mass spectra were obtained from a series of C₄-C₁₀ n-alkylamines introduced via the gas phase onto glycerol. It was found that the amine-characteristic secondary ion intensity varied linearly with amine partial pressure. Henry's law constants and surface activity constants for each of the amines in glycerol solution were measured. A linear correlation was found between amine-characteristic secondary ion intensity and Henry's law concentrations. The concentrations calculated from Henry's law were too low to yield the intensities observed, indicating that secondary ion precursors were not free-base amine molecules but ions in solution. Explicit kinetic equations describing glycerol and amine protonation and deprotonation as a result of primary ion damage to the solutions are derived to rationalize the observed spectra.