Calcite dissolution kinetics in view of Gibbs free energy, dislocation density, and pCO2

Xu, Jie; Fan, Chunfang; Teng, Hualiang

doi:10.1016/j.chemgeo.2012.04.019

Cited by 73 publications

(82 citation statements)

References 52 publications

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“…The "sawtooth" surface topography and the rapid emergence of a dynamic steady state dissolution behaviour suggest a layer-by-layer dissolution behaviour along the calcite surface. This supports the conclusions of Teng [36] that, at far-from-equilibrium conditions, initial defect density does not affect the calcite dissolution rate. The dissolution rate data and the activation energy parameters proposed in this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage.…”

Section: Discussionsupporting

confidence: 80%

“…The unassisted and spontaneous two-dimensional pit nucleation events outnumbered those formed from preexisting defect sites. As a result, when ΔG is less than -12 kJ·mol -1 , the effect of dislocation density on calcite dissolution rates is insignificant [36]. In this study, ΔG for all the conditions studied was between -20 kJ·mol -1 and -27 kJ·mol -1 after 20 min elapsed time.…”

Section: Impact Of Surface Morphology On Dissolution Ratementioning

confidence: 76%

“…However, the TST-derived rate laws are still preferred for implementation in geochemical modelling codes describing rock-fluid interaction, due to their simplicity and the large number of published rate constants data [41]. Additionally, Teng has recently proposed that the TST model is able to depict the relation between r and ΔG when the system ΔG falls from its extrema (-12 kJ·mol -1 ) [36]. Finally, the lack of integration on the number and the distribution of reactive sites into the TST-based kinetics model may be overcome by using crystal surface roughness as a proxy [41].…”

Section: Impact Of Co2 Pressure On Calcite Dissolution Ratementioning

confidence: 99%

“…The difference between the k2 value evaluated in this study and the one found by Chou et al could be attributed to the large uncertainty of the value obtained by Chou et al They suggested in their conclusions that the contribution of H2CO3* was not important under their experimental conditions. Teng [36] and Giudici [67] have recently measured dissolution rates for calcite on a microscopic scale using AFM under surface-reaction-controlled, far-from-equilibrium, conditions. Using equation (4) …”

Section: Impact Of Co2 Pressure On Calcite Dissolution Ratementioning

confidence: 99%

“…Holdren and Berner [34] proposed that defect-sites, such as dislocation and fractures, have a higher tendency to dissolve due to the existence of excess surface energy compared to a smooth surface. These observations were subsequently verified with the advent of atomicscale topographic techniques, such as Atomic Force Microscopy (AFM) and Vertical Scanning Interferometry (VSI) [35][36][37][38]. Calcite dissolution rate can be directly calculated from the realtime observation of the topographic changes by using step-retreat velocities and the step densities [39].…”

Section: Introductionmentioning

confidence: 99%

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Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

et al. 2015

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We report measurements of the calcite dissolution rate in CO2-saturated water at pressures ranging from (6.0 to 13.8) MPa and temperatures from (323 to 373) K. The rate of calcite dissolution in HCl(aq) at temperatures from (298 to 353) K was also measured at ambient pressure with pH between 2.0 and 3.3. A specially-designed batch reactor system, implementing a rotating disc technique, was used to obtain the dissolution rate at the solid/liquid interface of a single crystal, free of mass transfer effects. We used Vertical Scanning Interferometry to examine the texture of the calcite surface produced by the experiment and the results suggested that at far-from-equilibrium conditions, the measured calcite dissolution rate was independent of the initial defect density due to the development of a dynamic dissolution pattern which became steady-state shortly after the onset of dissolution. The results of this study indicate that the calcite dissolution rate under surface-reactioncontrolled conditions increases with increase of temperature from (323 to 373) K and CO2 partial pressure from (6.0 to 13.8) MPa. Fitting the conventional first order transition state kinetic model to the observed rate suggested that, although sufficient to describe calcite dissolution in CO2-free HCl(aq), this model clearly underestimate the calcite dissolution rate in the (CO2 + H2O) system over the range of conditions studied. A kinetic model incorporating both pH and the activity of CO2(aq) has been developed to represent the dissolution rates found in this study. We report correlations for the corresponding reaction rate coefficients based on the Arrhenius equation and compare the apparent activation energies with values from the literature. The results of this study should facilitate more rigorous modelling of mineral dissolution in deep saline aquifers used for CO2 storage.2

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Section: Discussionsupporting

confidence: 80%

Section: Impact Of Surface Morphology On Dissolution Ratementioning

confidence: 76%

Section: Impact Of Co2 Pressure On Calcite Dissolution Ratementioning

confidence: 99%

Section: Impact Of Co2 Pressure On Calcite Dissolution Ratementioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

et al. 2015

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First principles model of carbonate compaction creep

2016

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Rocks under compressional stress conditions are subject to long‐term creep deformation. From first principles we develop a simple micromechanical model of creep in rocks under compressional stress that combines microscopic fracturing and pressure solution. This model was then upscaled by a statistical mechanical approach to predict strain rate at core and reservoir scale. The model uses no fitting parameter and has few input parameters: effective stress, temperature, water saturation porosity, and material parameters. Material parameters are porosity, pore size distribution, Young's modulus, interfacial energy of wet calcite, the dissolution, and precipitation rates of calcite, and the diffusion rate of calcium carbonate, all of which are independently measurable without performing any type of deformation or creep test. Existing long‐term creep experiments were used to test the model which successfully predicts the magnitude of the resulting strain rate under very different effective stress, temperature, and water saturation conditions. The model was used to predict the observed compaction of a producing chalk reservoir.

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Mechanisms and Dynamics of Mineral Dissolution: A New Kinetic Monte Carlo Model

Martin

Manzano

Dolado

2019

Advcd Theory and Sims

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Mineral dissolution is a fundamental process in geochemistry and materials science. It is controlled by the complex interplay of atomic level mechanisms like adatoms and terraces removal, pit opening, and spontaneous vacancy creation that can be gradually activated at different energies. Though the development of a comprehensive atomistic model is key to go deeper into the understanding of this phenomenon, existing models have failed to reproduce the abrupt dependence of the dissolution rate with the Gibbs free energy ( G). Herein, a new atomistic kinetic Monte Carlo (KMC) model is presented, which, invoking the microscopic reversibility of chemical reactions, captures the experimentally observed sigmoid dependence of the dissolution rate and provides new insights on the concomitant dissolution mechanisms. As a salient result, the model predicts the possible existence of unreported close-to-equilibrium dissolution modes where spontaneous vacancies creation and pit opening can occur before adatom and terrace removal.

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Calcite dissolution kinetics in view of Gibbs free energy, dislocation density, and pCO2

Cited by 73 publications

References 52 publications

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

Kinetics of calcite dissolution in CO2-saturated water at temperatures between (323 and 373) K and pressures up to 13.8 MPa

First principles model of carbonate compaction creep

Mechanisms and Dynamics of Mineral Dissolution: A New Kinetic Monte Carlo Model

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