Comparative study of the kinetics and mechanisms of dissolution of carbonate minerals

The influence of pH on the rate of dissolution of various carbonates (calcite, aragonite, witherite, magnesite and dolomite) has been investigated at 25°C using a continuous fluidized bed reactor. The general rate dependence on pH observed for the simple carbonates is very similar and is in agreement with the results observed for calcite and aragonite by L.N. Plummer and coworkers. However, the rate of dissolution of magnesite is approximately four orders of magnitude lower than calcite.

For simple carbonates, the elementary steps involved in the dissolution reaction are:

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where M represents the metal ion which can be Ca, Mg and Ba. According to the stoichiometry of the three reaction steps and the thermodynamic constraints, the total forward and backward rates can be expressed as:

R_f=k₁a_H+k₂a_H2CO3^*+K₃

r_b=k_-1^aM²+^aHCO₃^-+k_-2^aHCO3^-+k_{-3^aM²+^aCO3^2-}

The rate constants (k₁, k₂, k₃ and k₋₃) determined with our experimental results for calcite, aragonite and witherite show that the dissolution rates are similar for these three minerals and that the nature of the cations does not play a significant role. The good agreement between the K_sp calculated from the measured k₃/k₋₃ ratio and the theromodynamic value suggests that our dissolution mechanism is coherent.

The rate dependence on pH of the dissolution of dolomite obeys a fractional order at low pH's and confirms previously published observations therein. However, the two-step reaction mechanism proposed does not explain the fractional reaction order observed, which is likely due to a more complex surface reaction.