Dissolution kinetics of dolomite: Effects of lithology and fluid flow velocity

The dissolution kinetics of three stoichiometric dolomite specimens (hydrothermal single crystal, microcrystalline sedimentary rock, coarse-grained marble) were studied in aqueous carbonate solutions. Hydrodynamic conditions were controlled through use of a rotating dolomite disk in which one face was exposed to solution and fluid flow regime was defined by spinning rate. The resulting mass transfer properties were uniform across the disk surface. The dissolution experiments were begun at an initially undersaturated condition set by CO₂ at ~ 1 atm dissolved in deionized water. The reaction was followed by measuring concentrations of Ca²⁺, Mg²⁺, HCO₃^?, and pH over time in a free-drift type of experiment at 0, 15, and 25°C.Dissolution rates for all three samples were similar in form and value; grain size effects were insignificant. Ca/Mg was constant throughout each run at 0.81–0.96. From initial conditions, the dissolution rate decreased as the solution became more saturated. At solution conditions still far from equilibrium (ion activity product = 10^?19), rate dropped off sharply to a very low value. Surface morphology, determined by SEM, showed deep narrow holes in the single crystal, while the rocks dissolved along grain boundaries. These features suggested preferential dissolution of energetically favored sites and surface reaction rate control. Initial rates were used to calculate an apparent activation energy of 32 kJ mol^?1 (sedimentary dolomite) and 27 kJ mol^?1 (single crystal).Initial dissolution rates at 25°C and pH ~ 4 for all samples varied with spinning speed and ranged from 1–3 μmol m^?2 s^?1 for laminar flow conditions to almost 3–6 μmol m^?2 s^?1 as the transition to turbulence began. At lower temperatures, the rate was lower, and increasing spinning velocity had less effect. The strongest spinning rate dependence occurred far from equilibrium, and it became a less important factor as the saturation state increased.