Perspective on electrospray ionization and its relation to electrochemistry.

The phenomenon of electrospraying of liquids is presented from the perspective of the electrochemistry involved. Basics of current and liquid flow in the capillary and spray tip are discussed, followed by specifics of charging and discharging of the sprayed liquid surface. Fundamental theories and numerical modeling relating electrospray current to solution and spray parameters are described and then compared with our own experimentally obtained data. The method of mapping potentials and currents inside the electrospray capillary by using an inserted electrically-isolated small wire probe electrode is discussed in detail with illustrations from new and published data. Based on these experimentally obtained results, a new mathematical model is derived. The introduced "nonlinear resistor electrospray capillary model" divides the electrospray capillary into small sections, adds their contributions, and then, by transition to infinitely small section thickness, produces analytical formulas that relate current and potential maps to other properties of the electrospraying liquid: primarily conductivity and current density. The presentation of the model is undertaken from an elementary standpoint, and it offers the possibility to obtain quantitative information regarding operating parameters from typical analytical systems subjected to electrospray. The model stresses simplicity and ease of use; examples applying experimental data are shown and some predictions of the model are also presented. The developed nonlinear resistor electrospray capillary model is intended to provide a new quantitative basis for improving the understanding of electrochemical transformations occurring in the electrospray emitter. A supplemental material section gives full derivation of the model and discusses other consequences.