RES³T - Rossendorf Expert System for Surface and Sorption Thermodynamics

A multisite surface complexation (MUSIC) model for ferrihydrite (Fh) has been developed. The surface structure and composition of Fh nanoparticles are described in relation to ion binding and surface charge development. The site densities of the various reactive surface groups, the molar mass, the mass density, the specific surface area, and the particle size are quantified. As derived theoretically, molecular mass and mass density of nanoparticles will depend on the types of surface groups and the corresponding site densities and will vary with particle size and surface area because of a relatively large contribution of the surface groups in comparison to the mineral core of nanoparticles. The nano-sized (∼2.6 nm) particles of freshly prepared 2-line Fh as a whole have an increased molar mass of M ∼ 101 ± 2 g/mol Fe, a reduced mass density of ∼3.5 ± 0.1 g/cm³, both relatively to the mineral core. The specific surface area is ∼650 m²/g. Six-line Fh (5–6 nm) has a molar mass of M ∼ 94 ± 2 g/mol, a mass density of ∼3.9 ± 0.1 g/cm³, and a surface area of ∼280 ± 30 m²/g. Data analysis shows that the mineral core of Fh has an average chemical composition very close to FeOOH with M ∼ 89 g/mol. The mineral core has a mass density around ∼4.15 ± 0.1 g/cm³, which is between that of feroxyhyte, goethite, and lepidocrocite. These results can be used to constrain structural models for Fh. Singly-coordinated surface groups dominate the surface of ferrihydrite (∼6.0 ± 0.5 nm⁻²). These groups can be present in two structural configurations. In pairs, the groups either form the edge of a single Fe-octahedron (∼2.5 nm⁻²) or are present at a single corner (∼3.5 nm⁻²) of two adjacent Fe octahedra. These configurations can form bidentate surface complexes by edge- and double-corner sharing, respectively, and may therefore respond differently to the binding of ions such as uranyl, carbonate, arsenite, phosphate, and others. The relatively low PZC of ferrihydrite can be rationalized based on the estimated proton affinity constant for singly-coordinated surface groups. Nanoparticles have an enhanced surface charge. The charging behavior of Fh nanoparticles can be described satisfactory using the capacitance of a spherical Stern layer condenser in combination with a diffuse double layer for flat plates.