Hydrotalcites are used in technology as catalysts and anion exchangers and are important sinks for environmental contaminants. Their compositional variability makes it important, but difficult, to estimate their aqueous solubility. We report calorimetric measurements of the heats of formation of cobalt-aluminum hydrotalcite phases. The heat and free energy of formation from the elements are equal to those of mechanical mixtures of binary compounds, namely hydroxides and carbonates. The interlayer anion is much more important than the cation in determining the solubility of the hydrotalcite phase and its ability to contain or release heavy metals to the environment. Because hydrotalcites do not have an unreactive polymer as a structural core, their aqueous stability will change dramatically with composition, particularly with anion content. This simple mechanical mixture model allows prediction of aqueous solubilities and trace metal retention in a variety of geochemical settings.

The formation of mixed-metal-Al layered double hydroxide (LDH) phases similar to hydrotalcite has been identified as a significant mechanism for immobilization of trace metals in some environmental systems. These precipitate phases become increasingly stable as they age, and their formation may therefore be an important pathway for sequestration of toxic metals in contaminated soils. However, the lack of thermodynamic data for LDH phases makes it difficult to model their behavior in natural systems. In this work, enthalpies of formation for Ni LDH phases with nitrate and sulfate interlayers were determined and compared to recently published data on carbonate interlayer LDHs. Differences in the identity of the anion interlayer resulted in substantial changes in the enthalpies of formation of the LDH phases, in the order of increasing enthalpy carbonate<sulfate<nitrate. Substitution of silica for carbonate resulted in an even more exothermic enthalpy of formation, confirming that silica substitution increases the stability of LDH precipitates. Both mechanical mixture and solid-solution models could be used to predict the thermodynamic properties of the LDH phases. Modeling results based on these thermodynamic data indicated that the formation of LDH phases on soil mineral substrates decreased Ni solubility compared to Ni(OH)2 over pH 5–9 when soluble Al is present in the soil substrate. Over time, both of these precipitate phases will transform to more stable Ni phyllosilicates.

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The enthalpies of formation of hydrotalcite-like phases containing Mg and Al and intercalated with NO3 -, Cl-, I-, ReO4 -, or CO3 2- were determined using high-temperature oxide melt and room-temperature acid solution calorimetry. The relative stability of phases bearing the various anions was gauged by comparing the enthalpy of formation from the single-cation components (Δf H scc). Trends relating Δf H scc to the nature of intercalating anions (halides, NO3 -, and CO3 2-) show small stabilization from the mechanical mixtures of single-cation components. The aim of this study was to relate the enthalpy of formation to the nature of interlayer bonding in hydrotalcite-like compounds (HTLCs) bearing various anions, to uncover trends in the relative aqueous solubilities of these phases. The entropy of formation of these compounds was estimated using an approximation based on third-law entropy measurements for the compound Mg0.74Al0.26(OH)2(CO3)0.13·0.39H2O which were performed in a previous study. This approximation for the third-law entropy was combined with the enthalpy data from our calorimetric measurements performed in this work in order to calculate the standard-state free energy of formation for the HTLCs. The solubility products for the compounds investigated in this study were calculated from these free energies of formation and were used in geochemical calculations. The results of these calculations support our previous hypothesis that carbonate-intercalated HTLCs are less soluble than phases bearing other anions such as nitrates and halides. We suspect that the solubilities of HTLCs bearing anions other than carbonate may correspond to the solubilities of single-cation phases bearing the same anions.