Skip to main content Accessibility help
×
Home
Hostname: page-component-888d5979f-x5hg2 Total loading time: 0.943 Render date: 2021-10-27T09:36:06.759Z Has data issue: true Feature Flags: { "shouldUseShareProductTool": true, "shouldUseHypothesis": true, "isUnsiloEnabled": true, "metricsAbstractViews": false, "figures": true, "newCiteModal": false, "newCitedByModal": true, "newEcommerce": true, "newUsageEvents": true }

The Kinetics of Calcite Growth: Interpreting Chemical Affinity-Based Rate Laws Through the Lens of Direct Observation

Published online by Cambridge University Press:  14 March 2011

Henry H. Teng
Affiliation:
Department of Geology George Washington University, Washington, D.C. 20052
Patricia M. Dove
Affiliation:
Department of Geological Sciences Virginia Polytechnic Institute and State University Blacksburg, VA 24061
James J. De Yoreo
Affiliation:
Department of Chemistry and Materials Science Lawrence Livermore National Laboratory Livermore, CA 94550
Get access

Abstract

Chemical affinity-based rate laws are used across the geochemical and materials communities to quantify mineral/material corrosion and growth kinetics. These rate expressions are founded in assumptions regarding reaction mechanism with little evidence for surface processes. Using Atomic Force Microscopy (AFM), this study demonstrates the dependence of growth kinetics upon the structures of dislocation sources. In situ observations show that the dominant mode of growth occurs by hillock development initiated at complex sources. Derivations of surface process-based rate expressions show a complex dependence of rate on chemical affinity. This dependence is approximated by second order affinity-based rate laws only under the special conditions that 1) growth proceeds by development of single sourced spirals and 2) growth occurs at very near equilibrium conditions where spiral formation is the only operative mechanism. This suggests that growth experiments that measure temporal changes in solution chemistry yield a composite rate that arises from the contributions of the different hillock types. Hence, chemical affinity-based rate laws do not generally give meaningful interpretations of growth mechanism. By combining direct observations with macroscopic methods that monitor temporal changes in solution chemistry, rate laws with greater predictive capabilities may be possible.

Type
Research Article
Copyright
Copyright © Materials Research Society 2000

Access options

Get access to the full version of this content by using one of the access options below. (Log in options will check for institutional or personal access. Content may require purchase if you do not have access.)

References

1. Nancollas, G. H. and Reddy, M. M. (1971) The crystallization of calcium carbonate II: Calref growth mechanism. J. Colloid Interface Sci. 37, 843–830.CrossRefGoogle Scholar
2. Plummer, L. N., Wigley, T. M. L., and Parkhurst, D. L. (1978) The kinetics of calref dissolution in CO2-water systems at 5-60°C and 0.0-1.0 atm CO2 . Amer. J. Sci. 278, 179216.CrossRefGoogle Scholar
3. Busenberg, E. and Plummer, L. N. (1986) A comparison study of the dissolution and crystal growth kinetics of calref and aragonite. USGS Bull. 1578, 139168.Google Scholar
4. Christoffersen, J. and Christoffersen, M. R. (1990) Kinetics of spiral growth of calref crystals and determination of the absolute rate constant. J. Crystal. Growth 100, 203211.CrossRefGoogle Scholar
5. Shiraki, R. and Brantley, S. L. (1995) Kinetics of near-equilibrium calref precipitation at 1000C: An evaluation of elementary reaction-based and affinity based rate laws. Geochim. Cosmochim. Acta 59, 14571471.CrossRefGoogle Scholar
6. Nilsson, Ö and Sternbeck, J. (1998) A mechanistic model for calref crystal growth using surface speciation. Geochim. Cosmochim. Acta 63, 217226.CrossRefGoogle Scholar
7. Arakaki, T. and Mucci, A. (1995) A continuous and mechanistic representation of calref reaction-controlled kinetics in dilute solutions at 25°C and 1 Atm total pressure. Aquatic Geochemistry, 1, 105130.CrossRefGoogle Scholar
8. Smallwood, P. V. (1977) Some aspects of the surface chemistry of calref and aragonite. Colloid and Polyner Sci. 255, 9941000.CrossRefGoogle Scholar
9. Reddy, M. M. (1977) Crystallization of calcium carbonate in the presence of trace concentrations of phosphorous-containing anions. J. Crystal Growth 41, 287295.CrossRefGoogle Scholar
10. Reddy, M. M. and Gaillard, W. D. (1980) Kinetics of calcium carbonate (calref)-seeded crystallization: Influence of solid/solution ratio on the reaction rate constant. J. Colloid and Interface Science, 80, 171178.CrossRefGoogle Scholar
11. Reddy, M. M. (1988) Physical-Chemical mechanisms that affect regulation of crystallization. In Chemical Aspects of Regulation of Mineralization (eds. Sikes, C. S. and Wheeler, A. P.), 3-8, University of South Alabama Pub. Ser., Mobile, Alabama.Google Scholar
12. Compton, R. G. and Daly, P. J. (1987) The dissolution/precipitation kinetics of calcium carbonate: An assessment of various kinetic equations using a rotating disk method. J. Colloid. Interface Sci. 115, 493498.CrossRefGoogle Scholar
13. Reddy, M. M. and Nancollas, G. H. (1971) The crystallization of calcium carbonate I. Isotopic exchange and kinetics. J. Colloid and Interface Science, 36, 166172.CrossRefGoogle Scholar
14. Morse, J. W. (1978) Dissolution kinetics on calcium carbonate in sea water VI: The near equilibrium dissolution kinetics of calcium carbonate-rich deep sea sediments. Amer. J. Sci. 278, 344353.CrossRefGoogle Scholar
15. House, W. (1981) Kinetics of crystallisation of calref from calcium bicarbonate solutions. J. Chem. Soc. Faraday Trans. 77, 341359.CrossRefGoogle Scholar
16. Nielsen, A. E. (1983) Precipitates: formation, coprecipitation, and aging. In Treatise on Analytical Chemistry (eds. Kolthoff, I. M. and Elving, P. J.), 269374, Wiley, New York.Google Scholar
17. Mucci, A. (1983) The solubility of calref and aragonite in seawater at various salinities, temperatures, and one atmosphere total pressure. Amer. J. Sci. 283, 780799.CrossRefGoogle Scholar
18. Mucci, A. and Morse, J. W. (1983) The incorporation of Mg and Sr into calref overgrowths: Influences of growth rate and solution composition. Geochim. Cosmochim. Acta 47, 217233.CrossRefGoogle Scholar
19. Mucci, A. (1986) Growth kinetics and composition of magnesian calref overgrowths precipitated from seawater: Quantitative influence of orthophosphate ions. Geochim. Cosmochim. Acta 50, 22552265.CrossRefGoogle Scholar
20. Kazmierczak, T. F., Tomson, M. B., and Nancollas, G. H (1982) Crystal growth of calcium carbonate: A controlled composition kinetic study. J. Phys. Chem. 86, 103107.CrossRefGoogle Scholar
21. Lasaga, A. C. (1981) Transition state theory. In Kinetics of Geochemiscal Processes (eds. Lasaga, A. C. and Kirkpatrick, R. J.); Rev. Mineral., 135-169.Google Scholar
22. Blum, A. E. and Lasaga, A. C. (1987) Monte Carlo simulations of surface reaction rate laws. In Aquatic Surface Chemistry (ed. Stumm, W.), 255292, Wiley, New York.Google Scholar
23. Reddy, M. M. and Nancollas, G. H. (1973) Calref crystal growth inhibition by phosphates. Desalination 12, 6173.CrossRefGoogle Scholar
24. Inskeep, W. P. and Bloom, P. R. (1985) An evaluation of rate equations for calref precipitation kinetics at Pco2 less than 0.01 atm and pH greater than 8. Geochimica et Cosmochimica Acta 49, 21652180.CrossRefGoogle Scholar
25. Burton, W. K., Cabrera, N., and Frank, F. C. (1951) The growth of crystals and the equilibrium structure of their surfaces. Royal Soc. London Philos. Trans. A243, 299358.CrossRefGoogle Scholar
26. Rashkovich, L. N. (1991) KDP-family single crystals. 100165, IOP Pub., Norfold, England.Google Scholar
27. Vekilov, P. G. and Kuznetsov, Yu. G. (1992) Growth kinetics irregularities due to changed dislocation source activity: (101) ADP face. J. Crystal Growth, 119, 248260.CrossRefGoogle Scholar
28. Vekilov, P. G. and Rosenberger, F. (1996) Dependence of lysozyme growth kinetics on step sources and impurities. J. Crystal Growth, 158, 540551.CrossRefGoogle Scholar
29. Land, T. A., De Yoreo, J. J., and Lee, J. D. (1997) An in situ AFM investigation of canavalin crystallization kinetics. Surf. Sci. 384, 136155.CrossRefGoogle Scholar
30. Teng, H. H., Dove, P. M., Orme, C. A., and DeYoreo, J. J. (2000) Kinetics of calref growth: Surface processes and relationships to macroscopic rate laws. Geochimica et Cosmochimica Acta, 64, in press.CrossRefGoogle Scholar
31. Teng, H. H., Dove, P. M., Orme, C. A., and DeYoreo, J. J. (1998) Thermodynamics of calref growth: Baseline for understanding biomineral formation. Science, 282, 724727.CrossRefGoogle ScholarPubMed
32. Teng, H. H. and Dove, P. M. (1997) Surface site-specific interactions of aspartate with calref during dissolution: Implications for biomineralization. Amer. Mineral. 82, 878887.CrossRefGoogle Scholar
33. Stipp, S. L., Eggleston, C. M., and Nielsen, B. S. (1994) Calref surface structure observed at microtopographic and molecular scales with atomic force microscopy (AFM). Geochimica et Cosmochimica Acta, 58, 30233033.CrossRefGoogle Scholar
34. Teng, H. H., Dove, P. M., and DeYoreo, J. J. (1999) Reversed calcium carbonate morphologies induced by microscopic growth kinetics: Insight into biomineralization. Geochimica et Cosmochimica Acta, 63, 25072512.CrossRefGoogle Scholar
35. Chernov, A. A. (1961) The spiral growth of crystals. Soviet Phys. 4, 116148.CrossRefGoogle Scholar
36. Chernov, A. A. and Komatsu, H. (1995) Topics in crystal growth kinetics. In Science and Technology of Crystal Growth (eds. Eerden, J. P. van and Bruinsma, O. S. L.), 6780, Kluwer Acad. Pub., Amsterdam.CrossRefGoogle Scholar
37. Van der Eerden, J.P. (1993) Crystal Growth Mechanisms. In Handbook of Crystal Growth (ed. Hurle, D.J.T.) 1A, 307475.Google Scholar

Send article to Kindle

To send this article to your Kindle, first ensure no-reply@cambridge.org is added to your Approved Personal Document E-mail List under your Personal Document Settings on the Manage Your Content and Devices page of your Amazon account. Then enter the ‘name’ part of your Kindle email address below. Find out more about sending to your Kindle. Find out more about sending to your Kindle.

Note you can select to send to either the @free.kindle.com or @kindle.com variations. ‘@free.kindle.com’ emails are free but can only be sent to your device when it is connected to wi-fi. ‘@kindle.com’ emails can be delivered even when you are not connected to wi-fi, but note that service fees apply.

Find out more about the Kindle Personal Document Service.

The Kinetics of Calcite Growth: Interpreting Chemical Affinity-Based Rate Laws Through the Lens of Direct Observation
Available formats
×

Send article to Dropbox

To send this article to your Dropbox account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Dropbox.

The Kinetics of Calcite Growth: Interpreting Chemical Affinity-Based Rate Laws Through the Lens of Direct Observation
Available formats
×

Send article to Google Drive

To send this article to your Google Drive account, please select one or more formats and confirm that you agree to abide by our usage policies. If this is the first time you use this feature, you will be asked to authorise Cambridge Core to connect with your <service> account. Find out more about sending content to Google Drive.

The Kinetics of Calcite Growth: Interpreting Chemical Affinity-Based Rate Laws Through the Lens of Direct Observation
Available formats
×
×

Reply to: Submit a response

Please enter your response.

Your details

Please enter a valid email address.

Conflicting interests

Do you have any conflicting interests? *