Direct measurement of ion evaporation kinetics from electrified liquid surfaces

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When concentrated solutions of NaI in formamide with electrical conductivities K larger than 1.1 S/m are electrosprayed from a Taylor cone-jet in a vacuum, ions are evaporated at substantial rates from the surface of the meniscus and the drops. This constitutes a new source of ions and nanoparticles, where the relative importance of these two contributions is adjustable. The currents of ions are measured independently from those associated with drops by a combination of stopping voltage analysis and preferential scattering in a gas background. The magnitude E of the electric field at the surface of the drops and at the apex of the cone-jet is controlled through the electrical conductivity K of the liquid and its flow rate Q through the jet. E is related through available scaling laws for Taylor cone-jets to the ratios K/Q or I/Q, where I is the current of drops emitted by the jet. Ion currents are very small or null at typical K/Q values used in the past. A relatively small initial ion current is attributed to a few particularly sharp features present, perhaps associated with small satellite drops. At still higher K/Q this first ionization source saturates, and ion evaporation from the main drops begins to dominate (E∼1 V/nm). E can then be determined with little ambiguity, and the associated ion current is also measured over a broad enough range of electric fields to determine the ionization kinetics. At still higher K/Q the ion current from the drops approaches saturation, and ion evaporation directly from the meniscus becomes dominant. The total spray current then presents the anomaly of increasing rapidly at decreasing liquid flow rate. The ion current from the meniscus can also be measured in this regime over a broad range of K/Q, with qualitative agreement with the ionization measurements from the drops. But the relation established between K/Q and E becomes suspect because ion and drop currents are now comparable. A third approach to infer the ionization rate is based on the related disappearance of Coulomb explosions of the drops above a critical K/Q. These results are congruent with the model of Iribarne and Thomson, with an activation barrier for ion evaporation equal to 1.7 eV−(e3E/4πε0)1/2.