Differential mobility spectrometry (DMS) of nitro-organic explosives and related compounds exhibited the expected product ions of M- or M x NO2- from atmospheric pressure chemical ionization reactions in purified air at 100 degrees C. Peaks in the differential mobility spectra for these ions were confined to a narrow range of compensation voltages between -1 to +3 V which arose through a low dependence of mobility for the ions in electric fields at E/N values between 0 and 120 Td (1 Td = 10(-17) V cm2). The field dependence of ions, described as an alpha parameter, ranged from -0.005 to 0.02 at a separation field of 100 Td. The alpha parameter could be controlled through the addition of organic vapors into the drift gas and was increased to 0.08-0.24 with 1000 ppm of methylene chloride in the drift gas. This modification of the drift gas resulted in compensation voltages of +3 to +21 V for peaks. The improved separation of peaks was consistent with a model of ion characterization by DeltaK or Kl - Kh, where Kl is the mobility coefficient of ions clustered with vapor neutrals during the low-field portion of the separation field waveform and Kh is for the same core ion when heated and declustered during the high-field portion of waveform.

The dependence of the mobilities of gas-phase ions on electric fields from 0 to 90 Td at ambient pressure was determined for protonated monomers [(MH+(H2O)n] and proton bound dimers [M2H+(H2O)n] for a homologous series of normal ketones, from acetone to decanone (M=C3H6O to C10H20O). This dependence was measured as the normalized function of mobility alpha (E/N) using a planar field asymmetric waveform ion mobility spectrometer (PFAIMS) and the ions were mass-identified using a PFAIMS drift tube coupled to a tandem mass spectrometer. Methods are described to obtain alpha (E/N) from the measurements of compensation voltage versus amplitude of an asymmetric waveform of any shape. Slopes of alpha for MH+ versus E/N were monotonic from 0 to 90 Td for acetone, butanone, and pentanone. Plots for ketones from hexanone to octanone exhibited plateaus at high fields. Nonanone and decanone showed plots with an inversion of slope above 70 Td. Proton bound dimers for ketones with carbon numbers greater than five exhibited slopes for alpha versus E/N, which decreased continuously with increasing E/N. These findings are the first alpha values for ions from a homologous series under atmosphere pressure and are preliminary to explanations of alpha (E/N) with ion structure.