Pseudo‐polymorphic Behavior of Precipitated Calcium Oxalate

Abstract

AbstractThe precipitation of calcium oxalate pseudo‐polymorphs was studied in a Y‐mixer in series with a reaction tube. Experiments were performed with the aim to identify the decisive variables influencing the phase composition of the precipitate. Initial supersaturation, stoichiometric ratio of the lattice ions, ionic strength and pH were varied. The resulting phase distribution was determined with the help of DSC measurements. Mixing conditions were chosen such that mixing of the reactants had no influence on the experiments. Increasing supersaturation, ionic strength and pH each favor formation of the metastable calcium oxalate dihydrate over the thermodynamic stable monohydrate, although the influence of the two latter parameters is comparatively weak. If the ratio from calcium to oxalate activities was increased in the experiments a steep change in the phase composition from approximately 50 mass percent of the monohydrate to pure monohydrate was observed. Modeling of the experimental results is successful using a combination of classical nucleation theory with an equation that relates the adsorption of potential determining ions to the interfacial tension. The interfacial tension for the uncharged particles was obtained by regression from the experimental determined dependence of the phase distribution on the supersaturation.