An evaluation of rate equations for calcite precipitation kinetics at pCO 2 less than 0.01 atm and pH greater than 8

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Scientific paper

We used a reproducible seeded growth technique with a pH-stat to study the kinetics of calcite precipitation at 25°C. We performed different experiments at initial Ca 2+ and HCO 3 - concentrations ranging from 0.7-2 and 4-7 mmol L -1 , pH values ranging from 8.25 to 8.70, pCO 2 values ranging from 0.0006 to 0.01 atm, and ionic strengths ranging from 0.015 to 0.10 mol L -1 . With this experimental data set, we used initial rate measurements and integral methods to test several precipitation rate equations. Rate equations that possess a disequilibrium functional dependence, such as the BURTON et al . (1951) dislocation model, forms of the Davies and Jones (1955) model, and the model used by and (1973), did not adequately describe the kinetics of calcite precipitation at pH greater than 8 and pCO 2 less than 0.01 atm. Rate equations that describe independent dissolution and precipitation mechanisms with elementary reactions, such as the equation presented by et al . (1978), and and (1971) were more successful. However, Plummer's model did not adequately describe the rate of all experiments due to the presence of an OH - surface term in the precipitation rate equation. The elementary reaction of the and model is written in terms of bulk Ca 2+ and CO 3 - concentrations, and appears to be the most successful model which describes calcite precipitation at pH > 8 and pCO 2 < 0.01 atm. The and model, altered to account for varying ionic strengths, adequately described the rate of all experiments and yielded a precipitation rate constant of 118.2 ± 13.9 dm 6 mol -1 m -2 s -1 , with an apparent Arrhenius activation energy of 48.1 kJ mol -1 .

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