Minimum in the temperature dependence of the Kovats retention indices of nitroalkanes and alkanenitriles on an apolar phase

The Kovats retention indices (I) of 1-nitroalkanes and alkanenitriles were determined on polydimethylsiloxane and Innowax (polyethylene glycol) columns in a wide temperature range. The temperature dependence of the retention indices exhibits a definite minimum for the early members of the homologous series. The position of the minimum shifts to lower temperatures with increasing carbon atom number of the solute. The thermodynamic explanation of an extreme in the I vs. T function is the higher solvation heat capacities of nitroalkanes and alkanenitriles relative to those of the reference n-alkanes, owing to the deviation from the ideal state in the solution. A novel equation was derived which describes the minimum in the I vs. T function, too. (C) 2002 Elsevier Science B.V. All rights reserved.