Parametric Sensitivity in a Generalized Model for Atmospheric Pressure Chemical Ionization Reactions.

Gas phase reactions between hydrated protons H(HO) and a substance M, as seen in atmospheric pressure chemical ionization (APCI) with mass spectrometry (MS) and ion mobility spectrometry (IMS), were modeled computationally using initial amounts of [M] and [H(HO)], rate constants to form protonated monomer (MH(HO)) and to form proton bound dimer (MH(HO)), and diffusion constants. At 1 × 10 cm (0.4 ppb) for [H(HO)] and vapor concentrations for M from 10 ppb to 10 ppm, a maximum signal was reached at 4.5 μs to 4.6 ms for MH(HO) and 7.8 μs to 46 ms for MH(HO). Maximum yield for protonated monomer for a reaction time of 1 ms was ∼40% for from 10 to 10 cm·s, for / = 0.8, and specific values of [M]. This model demonstrates that ion distributions could be shifted from [MH(HO)] to [MH(HO)] using excessive levels of [H(HO)], even for [M] > 10 ppb, as commonly found in APCI MS and IMS measurements. Ion losses by collisions on surfaces were insignificant with losses of <0.5% for protonated monomer and <0.1% for proton bound dimer of dimethyl methylphosphonate (DMMP) at 5 ms. In this model, ion production in an APCI environment is treated over ranges of parameters important in mass spectrometric measurements. The models establish a foundation for detailed computations on response with mixtures of neutral substances.