Ion evaporation from Taylor cones of propylene carbonate mixed with ionic liquids

Abstract

A combined experimental and numerical approach is used to extract information on the kinetics of ion evaporation from the region of high electric field around the tip of a Taylor cone of the neutral solvent propylene carbonate (PC) mixed with two ionic liquids. On the numerical side, the electric field on the surface of the liquid is computed in the absence of evaporation by solving the electrohydrodynamic problem in this region within the framework of the leaky dielectric model. These computations justify the approximate (2% max error) scaling Emax = β Ek for the maximum electric field on the surface, with Ek = γ1/2 ϵ0−2/3 (K/Q)1/6 for 0.111 < K < 0.888 S m−1 and a numerical value of β ≈ 0.76. Here γ is the surface tension of PC, ϵ0 is the electrical permittivity of vacuum, and K and Q are the liquid electrical conductivity and flow rate. On the experimental side, 16 different propylene carbonate solutions with either of the ionic liquids 1-ethyl-3-methylimidazolium tetrafluoroborate (EMI-BF4) or EMI-bis(trifluoro-methylsulfonyl)imide (EMI-Im) are electrosprayed in a vacuum from a single Taylor cone, and their emissions of charged drops and ions are analysed by time-of-flight mass spectrometry at varying liquid flow rates Q. The sprays contain exclusively drops at large Q, both for small and for large electrical conductivities K, but enter a mixed ion–drop regime at sufficiently large K and small Q. Interestingly, the mixtures containing 10% and 15% (vol) EMI-Im exhibit no measurable ion currents at high Q, but approach a purely ionic regime (almost no drops) at small Q. The charge/mass ratio for the drops produced in these two mixtures increases continuously with decreasing Q, and gets very close to ionic values. Measured ion currents are represented versus computed maximum electric fields Emax on the liquid surface to infer ion evaporation kinetics. Comparison of measured ion currents with predictions from ion evaporation theory yields an anomalously low activation energy (~1.1 eV). This paradox appears to be due to alteration of the pure conj–eet electric field in the scaling laws used for the pure cone–jet regime, due to the substantial ion current density arising even when the ion current is relatively small. Elimination of this interference would require future ion current measurements in the 10–100 pA level. The electrical propulsion characteristics of the emissions from these liquids are determined and found to be excellent, particularly for 10% and 15% (vol) EMI-Im.