Abstract A more exact thermodynamic interpretation of the empirical correlations between retention parameters of solutes (i.e. the relative retention times: τ (s)) and their boiling points ( T B) was established using Trouton–Hildebrandt–Everett’s rule (the extension of Trouton’s rule). These empirical correlations are known for C 6–C 12 alkylbenzenes for low and medium polar stationary phases. A statistical analysis has been made to compare the description by the old and newly developed models. The exponential relation suggested earlier [ Chromatographia, 44 (1997) 179–186] can be extended into a form consisting of two variables T M, T B: τ (i) corr. =AT M(i) exp(BT B(i) ) where: τ ( i)corr. =( t R( i) − t 0)/ t R(st) , A=( t 0 Φ/ t R(st) ) exp(−4.0), T M( i) = T B( i) ( T B( i) / T−1) , B=4.0/ T, t 0 is the column dead time, Φ is the phase ratio, t R(st) is the retention time of the standard compound, R is the gas constant, T is the column temperature, and subscript ‘( i)’ refers to the ith alkylbenzene. High correlation coefficients and small residual error indicate the superiority of the developed equation. Moreover, the residua show normal behavior, whereas curvature can be seen in the residua for earlier models. Validity of the approach proposed was confirmed through a comparison of the numerical values obtained from our computation (fitted values) with those stemming from theory.