Thermodynamic Analysis of Some Homologous Series

RTLn(V r(T)) - -nAG°(Methylene Group) -niAG (Methyl Group) 

AG (Methylene Group) is standard free energy of the methylene group, AG (Methyl group) is standard free energy of the methyl group, 

Marcel Dekker, 270 Madison Avenue, New York, New York 1C 

In fact, this procedure can be used for any aliphatic series such as alcohols, amines, etc. Consequently, before dealing with a specific homologous series, the validity of using the methylene group as the reference group needs to be established. The source of retention data that will be used to demonstrate this procedure is that published by Martire and his group [5-10] at Georgetown University and are included in the thesis of many of his students. The stationary phases used were all n-alkanes and there was extensive data available from the stationary phase n-octadecane. The specific data included the specific retention volumes of the different solutes at 0°C (V r(To)) thus, (V r(T)) was calculated for any temperature (Ti) as follows. 

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