Structure and reactivity of the calcite–water interface
Abstract
The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO2 partial pressure. Changes in pH have only a weak effect in non–equilibrium solutions. The surface structure of (104) faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ~4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 ± 0.05 Å above surface calcium ions and the second layer at 3.24 ± 0.06 Å above the surface associated with surface carbonate ions. A Basic Stern surface complexation model is developed to model observed zetapotentials, while only considering outer–sphere complexes of ions other than protons and hydroxide. The Basic Sternmore »
- Authors:
-
- Karlsruher Inst. für Technologie, Karlsruhe (Germany)
- Univ. of Alaskan, Fairbanks, AK (United States)
- Univ. of Chicago, IL (United States). GeoSoilEnviroCars
- Forschungszentrum Julich (Germany). Inst. für Energieforschung
- Publication Date:
- Research Org.:
- Univ. of Chicago, IL (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences, and Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1509824
- Grant/Contract Number:
- FG02-94ER14466; AC02-06CH11357
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Colloid and Interface Science
- Additional Journal Information:
- Journal Volume: 354; Journal Issue: 2; Journal ID: ISSN 0021-9797
- Publisher:
- Elsevier
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 58 GEOSCIENCES; Synchrotron radiation; Calcite; Zetapotential; Surface diffraction; Crystal truncation rod; Surface complexation model
Citation Formats
Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., and Bosbach, Dirk. Structure and reactivity of the calcite–water interface. United States: N. p., 2010.
Web. doi:10.1016/j.jcis.2010.10.047.
Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., & Bosbach, Dirk. Structure and reactivity of the calcite–water interface. United States. https://doi.org/10.1016/j.jcis.2010.10.047
Heberling, Frank, Trainor, Thomas P., Lützenkirchen, Johannes, Eng, Peter, Denecke, Melissa A., and Bosbach, Dirk. Tue .
"Structure and reactivity of the calcite–water interface". United States. https://doi.org/10.1016/j.jcis.2010.10.047. https://www.osti.gov/servlets/purl/1509824.
@article{osti_1509824,
title = {Structure and reactivity of the calcite–water interface},
author = {Heberling, Frank and Trainor, Thomas P. and Lützenkirchen, Johannes and Eng, Peter and Denecke, Melissa A. and Bosbach, Dirk},
abstractNote = {The zetapotential of calcite in contact with aqueous solutions of varying composition is determined for pre-equilibrated suspensions by means of electrophoretic measurements and for non-equilibrium solutions by means of streaming potential measurements. Carbonate and calcium are identified as charge determining ions. Studies of the equilibrium solutions show a shift of isoelectric point with changing CO2 partial pressure. Changes in pH have only a weak effect in non–equilibrium solutions. The surface structure of (104) faces of single crystal calcite in contact to solutions corresponding to those of the zetapotential investigations is determined from surface diffraction measurements. The results reveal no direct indication of calcium or carbonate inner-sphere surface species. The surface ions are found to relax only slightly from their bulk positions; the most significant relaxation is a ~4° tilt of the surface carbonate ions towards the surface. Two ordered layers of water molecules are identified, the first at 2.35 ± 0.05 Å above surface calcium ions and the second layer at 3.24 ± 0.06 Å above the surface associated with surface carbonate ions. A Basic Stern surface complexation model is developed to model observed zetapotentials, while only considering outer–sphere complexes of ions other than protons and hydroxide. The Basic Stern SCM successfully reproduces the zetapotential data and gives reasonable values for the inner Helmholtz capacitance, which are in line with the Stern layer thickness estimated from surface diffraction results.},
doi = {10.1016/j.jcis.2010.10.047},
journal = {Journal of Colloid and Interface Science},
number = 2,
volume = 354,
place = {United States},
year = {Tue Oct 26 00:00:00 EDT 2010},
month = {Tue Oct 26 00:00:00 EDT 2010}
}
Web of Science
Figures / Tables:
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