Gas phase reactions between hydrated protons H+(H2O)n 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+(H2O)n], rate constants k1 to form protonated monomer (MH+(H2O)x) and k2 to form proton bound dimer (M2H+(H2O)z), and diffusion constants. At 1 × 1010 cm-3 (0.4 ppb) for [H+(H2O)n] 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+(H2O)x and 7.8 μs to 46 ms for M2H+(H2O)z. Maximum yield for protonated monomer for a reaction time of 1 ms was ∼40% for k1 from 10-11 to 10-8 cm3·s-1, for k2/k1 = 0.8, and specific values of [M]. This model demonstrates that ion distributions could be shifted from [M2H+(H2O)z] to [MH+(H2O)x] using excessive levels of [H+(H2O)n], 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.
Keywords: atmospheric pressure chemical ionization; hydrated proton; proton bound dimer; protonated monomer; rate constant; reaction kinetics; vapor concentration.