Calcium oxalate hydrate, dehydration

At low and medium supersaturations, hydrophilic cations form different crystal hydrates by heterogeneous nucleation and subsequent crystal growth and phase transformation. Dehydration curves give information on the modes of water incorporation resulting from different modes of crystallization. A useful application of thermal analysis is the analytical approach by determining the mass loss due to dehydration, it was possible to quantitatively determine the proportion of different calcium oxalate hydrates in mixtures, which have been qualitatively analyzed by other techniques (X-ray powder diffraction, IR spectroscopy, etc.). The method yielded excellent results in studies of the kinetics of phase transformation and has been successfully used to demonstrate the potential of surfactant micelles to control the nature of the crystallizing phase. 

Similar discontinuities in Arrhenius plots are observed in thermal analysis (TA) as well, in particular, in the dehydration of crystalline hydrates performed in humid air. For illustration. Fig. 3.2 reproduces an Arrhenius plot for the dehydration of calcium oxalate monohydrate in an air flow, carried out under non-isothermal conditions by Dollimore et al. [28]. The equilibrium pressure of water vapour Pgqp measured at temperatures of up to 400 K and comparatively moderate decomposition rates turns out to be lower than its partial pressure in air which implies that the decomposition occurs in the isobaric mode. Above 400 K, the equilibrium pressure of H2O becomes higher than p with the process becoming equimolar. The slope of the plot decreases to one half of its former value in full agreement with theory (see Sect. 3.7). 

FIG. 4 Partial TG curves (dehydration only) showing the loss of water from (1) compact and dendritic crystals of COM and (2) microcrystaUine aggregates with the structure of COD, dmi and dm2 are the total mass loss (i.e., loss of hydration water) corresponding to 1 mol of HjO (rfm, for COM) and 2.5 mol of HjO dm2 Irom microcrystalline aggregates) per mole of calcium oxalate. (Adapted from Ref. 44.)... 

By determining the mass loss due to dehydration (rfwi and dm2 in Fig. 4), it is possible to quantitatively determine the phase composition of mixtures of crystal hydrates provided it was qualitatively ascertained by some other method (for instance, by X-ray powder diffraction). This method has been used to determine the influence of various experimental parameters on the phase composition of calcium oxalate precipitates. Several examples are given in Figs. 5-9. 

Decomposition of model substances method The third method of calibration is by carrying out an experimental run using certain well studied model substances such as copper sulfate pentahydrate, calcium carbonate, calcium oxalate mono hydrate, potassium carbonate, sodium hydroxide, zinc oxalate dihydrate, and benzoic acid. These model substances show well resolved dehydration and decomposition temperatures over a wide temperature range. 

A classic example of a solid—fluid ceramic powder synthesis reaction is that of calcination and dehydration of natural or synthetic raw materials. Calcination reactions are common for the production of many oxides from carbonates, hydrates, sulfates, nitrates, acetates, oxalates, citrates, and so forth. In general, the reactions produce an oxide and a volatile gaseous reaction product, such as CO2, SOg, or HgO. The most extensively studied reactions of this type are the decompositions of magnesium hydroxide, magnesium carbonate, and calcium carbonate. Depending on the particular conditions of time, temperature, ambient pressure of CO2, relative humidity, particle size, and so on, the process may be controlled by a surface reaction, gas diffusion to the reacting... 

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