Abstract
The gas chromatographic behaviour of C 1C 5 alcohols and chloroform on Carbowax 400 was studied in the range 58–88°. The specific retention volumes were determined, and the deviations from the expected order of elution were investigated by calculating the activity coefficients and the thermodynamic excess functions. The F lory-H uggins theory was used to evaluate the statistical contribution made by the mixing of molecules of different sizes, and the results were interpreted on the basis of the theory of associated ideal solutions. The difference between the order of elution of alcohols and the order of their boiling points was found to be due to differences in their molecular volumes. On the other hand, the nature of the association between the alcohols and Carbowax 400 is not very different from that of the associated species in the pure alcohol samples. The relative volatilities may therefore be predicted from the F lory-H uggins theory.
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