Phase diagram of the system CaSO4--K2SO4--KNO3--Ca(NO3)2--H2O

Potassium nitrate as a fertilizer suitable for greenhouse and hydroponic applications can be prepared by the reaction of potassium sulphate with calcium nitrate. However, it may happen that simultaneously with the precipitation of gypsum (CaSO[4]·[2]H[2]O) also two other binary salts, viz. syngenite (K[2]SO[4]·CaSO[4]·H[2]O) and görgeyite (K[2]SO[4]·[5]CaSO[4]·H[2]O) can crystallize. This would lower the yield of KNO[3]. For minimization of potassium loss we have to determine the conditions under which syngenite and görgeyite crystallize. As a useful tool for the quantitative determination of specific hydrates, simultaneous DTA/TG technique appeared. Each hydrate decomposes at a certain temperature. The loss of water at dehydration can be used for a quantitative determination of the amount of the hydrate in the precipitating solid phase. Based on the experimental data several conclusions can be drawn: (i) excess of calcium cations lowers the concentration of sulphate ions in the liquid phase together with lowering of contents of syngenite and görgeyite in the solid phase; (ii) higher content of water results in a higher solubility of sulphate ions; (iii) joint crystallization of syngenite and gypsum occurs in the composition area interesting from the point of KNO[3] production; (iv) area of the primary crystallization of görgeyite does not exist in the phase diagram at 80 °C. However, görgeyite crystallizes at the molar ratio Ca(NO[3])[2]:K[2]SO[4] = 1:1 by ternary crystallization; (v) area of crystallization of pure gypsum is shifted to lower ratio Ca(NO[3])[2]:K[2]SO[4] by the addition of water to the system.