Toward a conceptual model of the calcite surface: hydration,hydrolysis, and surface potential

Because of a recent increase in interest in the properties of the calcite surface, there has also been an increase in activity toward development of mathematical models to describe calcite’s surface behaviour, particularly with respect to adsorption and precipitation. For a mathematical model to be realistic, it must be based on a sound conceptual model of atomic structure at the interface. New observations from high resolution techniques have been combined with previously published data to resolve the apparent conflict with results from electrokinetic studies and to present a picture of what the calcite surface probably looks like at the atomic scale.In ultra-high vacuum (10^?10 mbar), a cleaved surface remains unreacted for at least an hour, but the unreacted surface does not remain as a termination of the bulk structure. X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED), and atomic force microscopy (AFM) show that the outer-most atomic layer relaxes and the surface slightly restructures. In air, dangling bonds are satisfied by hydrolysed water. XPS and time-of-flight secondary ion mass spectrometry (TOF-SIMS) reveal the presence of adsorbed OH and H. In AFM images, the features so typical of calcite, namely, alternate-row offset, pairing and height difference, as well as the consistent dependence of these features on the force and direction of tip scanning, are best explained by OH filling of the vacant O sites created during cleavage on the Ca octahedra. Thus there is solid evidence to indicate the presence of OH and H chemi-sorbed at the termination of the bulk calcite structure.Wet chemical studies, however, show that calcite’s pH_pzc (zero point of charge) varies with sample history and solution composition. Electrophoretic mobility measurements indicate that the potential-determining ions are not H⁺ and OH^?, but rather Ca²⁺ and CO₃^2? (or HCO₃^? or H₂CO₃⁰). This apparent conflict is resolved by a slight modification of the electrical double layer (EDL) model. At the bulk termination, hydrolysis species are chemi-bonded. At the Stern layer, adsorption attaches Ca²⁺ and CO₃^2? (or other carbonate species), but the hydrolysis layer keeps them in outer-sphere coordination to the surface. With dehydration, loss of the hydrolysis species results in direct contact between adsorbed ions and the bulk termination, therefore, inner-sphere sorption is equivalent to extension of the three dimensional bulk network, which is precipitation. Attachment of ions with size and charge compatible with Ca and CO₃ likewise results in coprecipitation and solid–solution formation.