Article ID Journal Published Year Pages File Type
6438677 Geochimica et Cosmochimica Acta 2014 16 Pages PDF
Abstract
Measured dissolution rates were initially rapid and decreased over time as the saturation state of solution relative to chlorite increased. Temperature had the strongest effect on dissolution rate, with an apparent activation energy of 16 ± 0.5 kJ mol−1 and rate constant of log k0 = −9.56 ± 0.07 mol m−2 s−1 assuming a rate law of the form: rate = k0exp(−EA/RT). The apparent activation energy is lower than previously accepted values, but is consistent with a study of chlorite dissolution using flow through techniques (Smith et al., 2013). Mineral dissolution rates are typically proton enhanced, but the lack of a significant pH effect or pCO2 effect on chlorite dissolution rate in this study suggests that the use of NaHCO3 to buffer the pH of CO2 saturated solutions led to an inhibition of mineral dissolution in competition with the expected pH effect. This is supported by the observed dissolution rate increasing dramatically (half a log unit) with the use of an organic acid buffer (KHpthalate) under CO2 free conditions. The effect of chloride (NaCl ∼5 to 50 g/L) was found not to affect the dissolution rate of chlorite. Various empirical rate laws are proposed and fit to the data and lead to the development of a surface complex model describing proton promoted dissolution and bicarbonate inhibition of chlorite dissolution rates. The model can be applied to predict the rate of chlorite dissolution under elevated pCO2 conditions relevant to the storage of CO2 in reservoirs from 50 to 275 °C in contact with fluids ranging in pH from 3.4 to 5.4.
Related Topics
Physical Sciences and Engineering Earth and Planetary Sciences Geochemistry and Petrology
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