Interpreting the gas chromatographic retention of n-alkanes.

Non-linear regressions were applied to n-alkanes retention data for the determination of gas hold-up in a preceding paper. It was found that at temperatures over 100 degrees C the reduced partial molar free energy of solution, deltaG/RT, tends to be negligible for the solute methane in poly(dimethylsiloxane) stationary phases. A consequence of interest can be inferred from this fact. The C-H bonds from terminal methyl groups of n-alkane solute molecules should not contribute significantly to deltaG/RT in these conditions. The analysis of data confirms that, within the chromatographic experimental error, the contributions of n-alkane end C-H bonds are also negligible in this temperature range. Consequently, the regression parameter that contains the phase ratio of the column only includes the gas hold-up as the accompanying factor.