We seek to explain 1) the effectiveness of substituting Sc with Dy, Er, Y and 2) the loss of properties when Sc is replaced with Yb, Gd and Sm . For a preliminary insight into the stability of structures we utilize the concept of Atomic Environment Type (AET) as pertaining to trialuminides. Electronic density functional total energy calculations at zero temperature are performed to obtain the enthalpy of mixing of quasi-binary Al-Sc-X structures. Estimates of the entropy are used to compute the stability regions of Al3Sc1-αXα L12 phase. We show that Sc is completely miscible with X=Dy, Er, Y and that there is a miscibility gap for X=Yb, Gd and Sm at temperatures near the aging temperature of Al-Sc alloys.