Although short n-alkane chains are classic examples of hydrophobic solutes, mounting evidence points to a hydrophilic crossover for the hydration free energies (Delta G) of sufficiently long n-alkane chains. Experimental and simulation results for the hydration of n-alkanes from methane (Cl) to docosane (C22) are combined with fundamental thermodynamic relations to elucidate intermolecular contributions to A Delta G. Theoretical bounds on the influence of solute conformation on Delta G are inferred by considering the hydration of idealized linear (all-trans) and globular (spherical) model solutes. More detailed theoretical extrapolations of experimental and simulation results imply that the water-mediated free energy change associated with collapsing an all-trans C100 chain is on the order of -100 kJ/mol and thus that n-alkane chains of this length and longer may be hydrophilic (Delta G < 0).