Novel regimes of calcium carbonate dissolution in micron-scale confined spaces

Abstract

We report the discovery of novel regimes of calcium carbonate dissolution in micron-scale confined spaces through microfluidic experiments. In the experiments, hydrochloric acid is injected into a microfluidic chamber with pre-deposited calcium carbonate solids. As the acid flow rate is decreased, the dissolution of calcium carbonate transits from a liquid/solid single-phase reactive transport regime to a gas/liquid/solid two-phase one. The two-phase regime further splits into two different regimes, one with fluctuating and the other with nonfluctuating gaseous CO2 phase. We name the three regimes as “Nongaseous”, “Gaseous Breathing”, and “Gaseous Nonbreathing”. The experimental observations are reproduced and interpreted by mathematical modeling. Results show that the regimes are controlled by the ratio of H+ concentration and saturated CO2 concentration, the Peclet number and the second Damkohler number. Dimensionless diagrams distinguishing different regimes are presented and an empirical relationship is proposed. Our results offer insights into various engineering and natural processes, e.g., geological carbon storage, petroleum reservoir acidizing, Karst dissolution, and others that are governed by small scale multiphase reactive flow physics.