Excess volumes, V(E), have been determined from density measurements using a vibrating tube densimeter (DMA 60/602) at 303.15 K for ten binary mixtures of ethyl acetate, ethyl propionate, ethyl butyrate, amyl acetate, decyl acetate, dodecyl acetate, ethyl-2-bromopropionate, ethyl-3-bromopropionate, ethyl-2-bromobutyrate and ethyl-4-bromobutyrate with n-hexane. The molecular size of alkanoate and the position of the bromine atom in bromoalkanoate has the predominant effect on V(E). The experimental results have also been analysed using the Prigogine-Flory-Patterson theory employing both the van der Waals and the Lennard-Jones energy models.