The principal material in the phosphate ores is composed of calcium fluorapatite Ca 10 (PO 4 ) 6 F 2 , in which the various components have been partially substituted by magnesium, sodium, carbonate, and hydroxyl ions. These substitutions affect the stability of the material and its reactivity toward the acid attack. The present chapter reports the influence of carbonates and magnesium on these properties. Using different calorimeters, dissolution experiments of carbonated and noncarbonated Ca and Ca/Mg apatites were carried out in acid solutions leading to thermochemical quantities. The results show that substitution of carbonate for F ions in the channel (to get A-type carbonate F-apatites) results in increasing the stability of the edifice, while substitution of CO 3 for PO 4 in fluor-or hydroxyapatites (to get B-type apatites) leads to a decrease in stability. The latter phenomenon was also observed when substituting magnesium for calcium in F-apatites. The presence of the former in the apatite structure results in an increase of the speed of dissolution in acid solution that is enhanced when carbonate is also replacing phosphate groups. Dissolution mechanism of synthesized Ca/Mg F-apatites seems to be a one-step process, while dissolution of a Gafsa (TN) natural phosphate to get superphosphate fertilizer is more complex.