BUBBLE DYNAMICS AT GAS-EVOLVING ELECTRODES

Nucleation of bubbles, their growth by diffusion of dissolved gas to the bubble surface and by coalescence, and their detachment from the electrode are all very fast phenomena; furthermore, electrolytically generated bubbles range in size from ten to a few hundred microns; therefore, magnification and high speed cinematography are required to observe bubbles and the phenomena of their growth on the electrode surface. Viewing the action from the front side (the surface on which the bubbles form) is complicated because the most important events occur close to the surface and are obscured by other bubbles passing between the camera and the electrode; therefore, oxygen was evolved on a transparent tin oxide "window" electrode and the events were viewed from the backside. The movies showed that coalescence of bubbles is very important for determining the size of bubbles and in the chain of transport processes; growth by diffusion and by coalescence proceeds in series and parallel; coalescing bubbles cause significant fluid motion close to the electrode; bubbles can leave and reattach; and bubbles evolve in a cycle of growth by diffusion and different modes of coalescence. An analytical solution for the primary potential and current distribution around a spherical bubble in contact with a plane electrode is presented. Zero at the contact point, the current density reaches only one percent of its undisturbed value at 30 percent of the radius from that point and goes through a shallow maximum two radii away. The solution obtained for spherical bubbles is shown to apply for the small bubbles of electrolytic processes. The incremental resistance in ohms caused by sparse arrays of bubbles is given by {Delta}R = 1.352 af/kS where f is the void fraction of gas in the bubble layer, a is the bubble layer thickness, k is the conductivity of gas free electrolyte, and S is the electrode area. A densely populated gas bubble layer on an electrode was modeled as a hexagonal array of dielectric spheres. Accurately machined lucite spheres were placed one at a time in one end of a hexagonal cell which simulated the unit cell of such an array. The resistance as a function of gas bubble layer packing density sharply increased as close packing was approached. Because the interaction of the fields around bubbles closely spaced in the direction perpendicular to the current dominates the added resistance, and because there is a tri-modal distribution of bubble sizes in a bubble layer, the Distribution Model of Meredith and Tobias (16), derived for three dimensional gas dispersions, approximately predicted the conductivity of a bubble layer at void fractions greater than 0.3. At moderate-to-high current densities, the bubble layer in a cell having an interelectrode gap of half a centimeter could increase the ohmic resistance by as much as 20 percent