Excess Volumes of Mixtures of Cycloalkanes and Methylcycloalkanes

Abstract Excess volumes vE have been obtained for mixtures of cyclopentane, methylcyclopentane, methylcyclohexane + n‐heptane, n‐decane, n‐tetradecane, carbon tetrachloride: methylcyclopentane + benzene, cyclopentane, cyclohexane, methylcyclohexane and methylcyclo‐hexane + cyclopentane at 293.15 K and 313.15 K, and cyclohexane + benzene at 293.15 K. The excess volumes of cyclopentane mixtures are much smaller than those of cyclohexane mixtures. Addition of a methyl group to cyclopentane enhances vE, to cyclohexane decreases vE. This behaviour seems to be caused by packing effects due to molecular structure, as yet not sufficiently accounted for by theories of mixtures.