Mass transport at gas-evolving electrodes

Abstract

Direct numerical simulations are utilised to investigate mass-transfer processes at gas-evolving electrodes that experience successive formation and detachment of bubbles. The gas–liquid interface is modelled employing an immersed boundary method. We simulate the growth phase of the bubbles followed by their departure from the electrode surface in order to study the mixing induced by these processes. We find that the growth of the bubbles switches from a diffusion-limited mode at low to moderate fractional bubble coverages of the electrode to a reaction-limited growth dynamics at high coverages. Furthermore, our results indicate that the net transport within the system is governed by the effective buoyancy driving induced by the rising bubbles and that mechanisms commonly subsumed under the term ‘microconvection’ do not significantly affect the mass transport. Consequently, the resulting gas transport for different bubble sizes, current densities and electrode coverages can be collapsed onto one single curve and only depends on an effective Grashof number. The same holds for the mixing of the electrolyte when additionally taking the effect of surface blockage by attached bubbles into account. For the gas transport to the bubble, we find that the relevant Sherwood numbers also collapse onto a single curve when accounting for the driving force of bubble growth, incorporated in an effective Jakob number. Finally, linking the hydrogen transfer rates at the electrode and the bubble interface, an approximate correlation for the gas-evolution efficiency has been established. Taken together, these findings enable us to deduce parametrisations for all response parameters of the systems.