Effect of column temperature on elution order in gas chromatography

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Virginia Tech


This study concerns the effect of column temperature on selectivity in gas chromatography (GC). Reversal of peak elution order at different temperatures is observed when selectivity is sufficiently changed by changing the temperature.

A study of homologous functional groups and the elution order of a test mixture was made at several temperatures, by keeping constant operating chromatographic parameters such as column head pressure, split ratio, sample concentration, injector and detector temperature. The homologous series studied were esters, carboxylic acids, ketones and alkanes. The stationary phases used were Carbowax (Supelcowax 10), and 5% diphenyl and 95% dimethyl silicone ( HP Ultra 2). The identification of each compound was confirmed by two methods : comparing retention times, and spiking the sample.

The results of an investigation for accurately determining the dead time is also presented. The experimental results of using 10% methane in helium and the results of a theoretical model based on Poiseuille's equation were studied and compared. It is concluded that dead time calculations are a major source of error for the calculations in this work.

In addition, a derived thermodynamic equation based on the Van't Hoff equation was obtained and used to calculate the molar enthalpy and entropy of compounds over a range of temperatures. The experimental thermodynamic values were compared with the theoretical values obtained from the Clausius- Clapeyron equation.

From the data obtained, a graph of In k' (retention factor) versus 1/ temperature for a homologous series, known as a Van't Hoff plot, predicts a reversal of elution order where an intersection of two lines occur. Selectivity of the stationary phase has changed solely due to temperature effects. This can only occur when different solute/solvent interactions are present.

This work is an attempt to predict when peak inversion should occur based on the Van Hoff's plot. Experimental result are presented that confirm the prediction.