Due to possibility of visual observation of phase transformations and processes during solidification, the transparent binary alloy models are important in materials and metallurgical sciences. As such, phase diagram, linear velocity of crystallization, microstructure and spectral behaviour of binary organic systems of benzidine with resorcinol and catechol involving formation of addition compound with congruent melting point have been studied. While their phase diagrams show the formation of two eutectics and a 1:2 (B:RC, B:CT) addition compound in each case, the crystallization data obey the Hillig-Turnbull equation. The microstructural investigations give the characteristic morphology of the eutectics and the addition compounds, the spectral studies suggest intermolecular hydrogen bonding between two components forming the molecular complex.