A completely analytical equation of state for pure hard chain fluids, derived on the basis of perturbation theory and reported in our previous work, is applied for the calculation of pVT properties and the prediction of vapour-liquid equilibria of n-alkanes and n-perfluoroalkanes. The molecules are treated as a chain formed from freely joined spheres which interact via an extended site-site square-well potential. The molecular parameters of compounds are obtained from the experimental compressibility factor data above the critical temperature. These parameters are capable of relatively satisfactory prediction of the vapour-liquid equilibrium coexistence curves of compounds. Linear relationships have been found between the potential parameters of fluids and their molecular weight, which make it possible to predict the pVT data and vapour-liquid phase equilibria of heavier compounds. (C) 2010 Elsevier B.V. All rights reserved.