Bismuth is an element obtained as a sub-product in lead production; Mexico occupies the second position in the world in production of this element. Bismuth is used as iron, aluminum and copper alloying, in the pharmaceutical industry, in the cosmetics industry, etc. Bismuth is separated from lead by the Kroll-Betterton Process in which a Ca-Mg alloy is added to the melting lead to form the intermetallic compounds Ca3Bi2, Mg3Bi2 and Ca2MgBi2 which float to the surface of the bath. Unfortunately, there is little thermodynamical information of the compounds of the system Ca-Mg-Bi which can be used to study and optimize the Kroll-Betterton process in a theoretical way. In this work there were synthesized the compounds Ca3Bi2, Mg3Bi2 and CaMg2Bi2 using powders of pure elements (Ca, Mg and Bi) in the required amounts and melted under an inert atmosphere. After synthesis, the samples were characterized by X-Ray Diffraction to ensure the formation of the desire compounds. Later, calorimetric technique was used to determine the thermodynamical properties of the compounds. The results obtained by X-Ray Diffraction show the formation of Mg3Bi2 and Mg2CaBi2 species; however, there is no crystallographic information of the compound Ca3Bi2. The heating curves obtained by calorimetry show endothermic peaks, due to the presence of phases changes as is indicated in the Ca-Bi, Mg-Bi and Ca-Mg-Bi phases diagrams.