Thermochemical study of some inorganic and organic salts of cobalt, nickel and copper

Differential enthalpy analysis has been carried out on a certain number of inorganic (halides, halide oxy-acid salts, nitrates and sulfates) and organic (alkanoates, and dicarboxylates) of cobalt, nickel and copper using a Tian-Calvet high-temperature microcalorimeter. Other investigational methods such as thermo-crystallography, thermogravimetry, spectroscopy and gas-phase chromatography have been used to complete this work. An intrinsic study of the microcalorimeter covering thermal leakage, the sensitivity and the aging of the batteries, the deviation of the experimental zero, has been carried out. A satisfactory experimental device has been developed which corresponds to optimum conditions of analysis. We have shown which are the most important factors affecting differential thermal analysis and have detected certain phenomena; we have also demonstrated that intermediate hydrates exist and shown the possibilities of thermal recrystallization. Various enthalpies of transformation have been evaluated. The various possible reaction mechanisms are discussed. The normal formation enthalpies of several series of alkanoates and dicarboxylates have been measured. A graphical method has been devised for evaluating the kinetic parameters of heterogeneous dissociations from the thermograms obtained. Finally, we have developed a simple method for estimating the normal formation enthalpies of carboxylates and oxy-acid salts, both anhydrous and hydrated. The agreement with available experimental data is satisfactory. (author)