A comparison of the most usual gas chromatographic methods for the calculation of partial molar enthalpies of solvation (@D"s"o"lH^o) has been carried out. Those methods based on the fitting of lnV"g or ln(k/T) vs. 1/T and ln(k/T) vs. (1/T and the temperature arrangement, T"a) are the most adequate ones for obtaining @D"s"o"lH^o values. However, the latter is the only reliable option for @D"s"o"lH^o estimation when commercial WCOT capillary columns are used, since in this case the estimation of some variables involved in the V"g determination is less accurate or even impossible. Consequently, in this paper, @D"s"o"lH^o obtained from ln(k/T) vs. (1/T+T"a) fitting at 373.15 and 298.15K for n-alkanes and n-alkylbenzenes on 12 commercial capillary columns coated with stationary phases covering the 203-3608 McReynolds polarity range are reported. Moreover, molar heat capacities of solvation at constant pressure (@D"s"o"lC"p^o) have also been calculated using this method. A clear influence on @D"s"o"lH^o of the type and content of the substitution group in the stationary phase was observed. In addition, a linear relationship of @D"s"o"lC"p^o with the van der Waals volume of the n-alkanes and the temperature gradient of density of the stationary phase was found. The effect of the size of the hydrocarbon on both thermodynamic variables was also investigated.
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