TY - JOUR
T1 - Kinetics of near-equilibrium calcite precipitation at 100°C
T2 - An evaluation of elementary reaction-based and affinity-based rate laws
AU - Shiraki, Ryoji
AU - Brantley, Susan L.
N1 - Funding Information:
Acknowledgments-We would like to thank N. Plummer and L. Walter for their critical reading of the manuscript and invaluable comments. We also would like to thank to D. Voigt, I. MacInnis, L. Stillings, and Y. Chen for help and discussion. C. Perry observed run products with SEM microscopy. This research was supported by Gas Research Institute contract 5088-260-1746. S.L.B. acknowledges support from grant EAR-86-57868 from the National Science Foundation and support from the David and Lucile Packard Foundation. Acknowledgment is made to the donor of The Petroleum Research Fund, administered by the ACS, for partial support of this research.
Copyright:
Copyright 2015 Elsevier B.V., All rights reserved.
PY - 1995/4
Y1 - 1995/4
N2 - Three affinity-based rate models based upon physical growth mechanisms were used to fit surface-controlled precipitation rate data for calcite using a continuously stirred tank reactor in NaOHCaCl2CO2H2O solutions at 100°C and 100 bars total pressure between pH 6.38 and 6.98. At higher stirring speeds, when aH2CO3* was smaller than 2.33 × 10-3, rate showed a parabolic dependence upon exp(Δ G RT) for exp(Δ G RT) < 1.72. However, the rate increased exponentially for exp(Δ DG RT) > 1.72 and followed a rate law based upon the assumption that surface nucleation is rate-limiting. When αH2CO3* was greater than 5.07 × 10-3, the rate showed a linear dependence upon exp(Δ G RT), suggesting growth by a simple surface adsorption mechanism. The rate of these three mechanisms at 100°C can be expressed by the following equations: (spiral growth) Rppt = 10-9.00±0.15exp ΔG RT- 11.93±0.14, (adsorption) Rppt = 10-8.64±0.07exp ΔG RT- 11.09±0.10, (surface nucleation) Rppt = 10-7.28±0.49exp- 2.36±0.21 ΔG/RT. The mechanistic model of Plummer et al. (1978) given by Rnet = k1aH+ + k2aH2CO3* + k3aH2O - k4aCa2+aHCO-3. also describes the precipitation rate when growth followed the spiral growth equation. The rate constant for precipitation, k4, ranges between 7.08 × 10-4 to 1.01 × 10-3 moles cm-2 s-1 in the aH2CO3* range studied. This work shows that precipitation at 100°C in the spiral growth regime is well fit by both the mechanistic model of Plummer et al. (1978), based on multiple elementary reactions, and by a model derived for growth at screw dislocations. Outside of the regime of spiral growth, however, the model of Plummer et al. (1978) fails, suggesting that different elementary reactions control growth in the adsorption or two-dimensional nucleation regimes. However, the model of Plummer et al. (1978), based upon individual elementary reactions, accurately predicts both dissolution and precipitation of calcite under certain conditions; tests of the affinity based models reveal that none of these models accurately predict dissolution. Therefore, although affinity-based models may yield insights concerning the physical mechanism of growth, they may not be as useful in modelling dissolution and growth over the full range of ΔG.
AB - Three affinity-based rate models based upon physical growth mechanisms were used to fit surface-controlled precipitation rate data for calcite using a continuously stirred tank reactor in NaOHCaCl2CO2H2O solutions at 100°C and 100 bars total pressure between pH 6.38 and 6.98. At higher stirring speeds, when aH2CO3* was smaller than 2.33 × 10-3, rate showed a parabolic dependence upon exp(Δ G RT) for exp(Δ G RT) < 1.72. However, the rate increased exponentially for exp(Δ DG RT) > 1.72 and followed a rate law based upon the assumption that surface nucleation is rate-limiting. When αH2CO3* was greater than 5.07 × 10-3, the rate showed a linear dependence upon exp(Δ G RT), suggesting growth by a simple surface adsorption mechanism. The rate of these three mechanisms at 100°C can be expressed by the following equations: (spiral growth) Rppt = 10-9.00±0.15exp ΔG RT- 11.93±0.14, (adsorption) Rppt = 10-8.64±0.07exp ΔG RT- 11.09±0.10, (surface nucleation) Rppt = 10-7.28±0.49exp- 2.36±0.21 ΔG/RT. The mechanistic model of Plummer et al. (1978) given by Rnet = k1aH+ + k2aH2CO3* + k3aH2O - k4aCa2+aHCO-3. also describes the precipitation rate when growth followed the spiral growth equation. The rate constant for precipitation, k4, ranges between 7.08 × 10-4 to 1.01 × 10-3 moles cm-2 s-1 in the aH2CO3* range studied. This work shows that precipitation at 100°C in the spiral growth regime is well fit by both the mechanistic model of Plummer et al. (1978), based on multiple elementary reactions, and by a model derived for growth at screw dislocations. Outside of the regime of spiral growth, however, the model of Plummer et al. (1978) fails, suggesting that different elementary reactions control growth in the adsorption or two-dimensional nucleation regimes. However, the model of Plummer et al. (1978), based upon individual elementary reactions, accurately predicts both dissolution and precipitation of calcite under certain conditions; tests of the affinity based models reveal that none of these models accurately predict dissolution. Therefore, although affinity-based models may yield insights concerning the physical mechanism of growth, they may not be as useful in modelling dissolution and growth over the full range of ΔG.
UR - http://www.scopus.com/inward/record.url?scp=0028794374&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0028794374&partnerID=8YFLogxK
U2 - 10.1016/0016-7037(95)00055-5
DO - 10.1016/0016-7037(95)00055-5
M3 - Article
AN - SCOPUS:0028794374
SN - 0016-7037
VL - 59
SP - 1457
EP - 1471
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
IS - 8
ER -