Molar excess volumes, V-E and molar excess enthalpies, H-E of 1,3-dioxolane (D) (i) + propan-1-ol, 1,3-dioxolane (i) + butan-1-ol and 1,3-dioxolane (i) + butan-2-ol (j) binary mixtures have been measured as a function of composition at 308.15 K. The analysis of V-E data by graph, theoretical approach reveals that while propan-1-ol, butan-1-ol exist as associated entities in the pure state; 1,3-dioxolane and butanol exist as monomers in their pure state. These (i + j) binary mixtures are characterized by interactions between ethereal oxygen atom of D(i) and hydrogen atom of alkanols. The IR studies lend additional support to the proposed structure of molecular entitles in these mixtures. The energetics of the mixtures have also been studied. (C) 2003 Elsevier B.V. All rights reserved.