Excess molar volumes V E , excess molar enthalpies H E , speeds of sound, u and vapour–liquid equilibrium data of 1,3-dioxolane (i)+aniline or N-methyl aniline or o-toluidine (j) binary mixtures have been measured as a function of composition at 308.15K. Speeds of sound and vapour–liquid equilibrium data of (i+j) binary mixtures have been utilized to determine isentropic compressibilities changes of mixing, κSE and excess Gibb's free energy G E . The observed data have been analyzed in term of Graph theory which involves the topology of the mixture constituents. It has been observed V E , H E , κSE and G E values predicted by Graph theory compare well with their corresponding experimental values.