Computational simulation of redox reactions within a metal electrospray emitter

A computational simulation of the oxidation of chemical species inside a me tal emitter electrospray ion source, in the context of electrospray mass sp ectrometry (ES-MS), has been developed. The analysis code employs a boundar y integral method for the solution of the Laplace equation for the electric potential and current and incorporates standard activation and concentrati on polarization functions for the redox-active species in the system to def ine the boundary conditions. This paper provides a demonstration of the cap ability of this simulation method. Due to the approximate nature of some of the input data, and certain simplifying assumptions, the present results m ust be considered semiquantitative, The specific system modeled consisted o f a 100-mu m-i.d., inert metal capillary ES emitter and a spray solution co mposed of an analyte dissolved in CH3CN/H2O (90/10 v/v), Variable parameter s included the concentration (i.e., 5.0, 10, 20, and 50 mu M) of the easily oxidized analyte ferrocene (Fc, dicyclopentadienyl iron) in the solution, and solution conductivities of 1.9, 3.8, and 7.6 x 10(-7) Omega(-1)/cm, wit h an operational flow rate of 5.0 mu L/min and ES currents on the order of 0.05 mu A. Under these defined conditions, the two most prominent reactions at the emitter metal/ solution interface were assumed to be H2O oxidation (2H(2)O = O-2 + 4H(+-) + 4e(-)) and ferrocene oxidation (Fc Fc(+) + e(-)). Using this model, it was possible to predict the interfacial potentials, as well as the current density for each of the reactions, as a function of ax ial position from the emitter spray tip back upstream, under the various op erational conditions. The simulations show that the majority of the current from the redox reactions is generated within a 200-300-mu m region near th e spray tip. The lower the value of E-0 for a specific reaction, the furthe r upstream from the tip the reaction extends.