Dissolution or growth of soluble spherical oscillating bubbles: the effect of surfactants

A new theoretical formulation is developed for the effects of surfactants on mass transport across the dynamic interface of a bubble which undergoes spherically symmetric volume oscillations. Owing to the presence of surfactants, the Henry's law boundary condition is no longer applicable; it is replaced by a flux boundary condition that features an interfacial resistance that depends on the concentration of surfactant molecules on the interface. The driving force is the disequilibrium partitioning of the gas between free and dissolved states across the interface. As in the clean surface problem analysed recently (Fyrillas & Szeri 1994), the transport problem is split into two parts: the smooth problem and the oscillatory problem. The smooth problem is treated using the method of multiple scales. An asymptotic solution to the oscillatory problem, valid in the limit of large Péclet number, is developed using the method of matched asymptotic expansions. By requiring that the outer limit of the inner approximation match zero, the splitting into smooth and oscillatory problems is determined unambiguously in successive powers of [weierp ]−1/2, where [weierp ] is the Péclet number. To leading order, the clean surface solution is recovered. Continuing to higher order it is shown that the concentration field depends on RI[weierp ]−1/2, where RI is the (dimensionless) interfacial resistance associated with the presence of surfactants. Although the influence of surfactants appears at higher order in the small parameter, surfactants are shown to have a very significant effect on bubble growth rates owing to the fact that the magnitude of RI is approximately the same as the magnitude of [weierp ]1/2 at conditions of practical interest. Hence the higher-order ‘corrections’ happen numerically to be of the same magnitude as the leading-order, clean surface problem. This is the fundamental reason for major increases in the bubble growth rates associated with the addition of surfactants. This is in contrast to the case of a still, surfactant-covered bubble, in which the first-order correction to the growth rate is of order RI[weierp ]−1 and presents a [weierp ]−1/2 correction. Finally, although existing experimental results have shown only enhancement of bubble growth in the presence of a surfactant the present theory suggests that it is possible for a surfactant, characterized by weak dependence of interfacial resistance on surface concentration, to inhibit rather than enhance the growth of bubbles by rectified diffusion.