The configurational bias Monte Carlo (CBMC) technique has been used for computing the adsorption isotherms for linear and branched 2-methylalkanes on silicalite. The carbon numbers of the alkanes ranged from four to nine. For branched alkanes inflection behavior was observed for all carbon numbers studied. The inflection was found to occur at a loading of four molecules per unit cell. Below this loading the branched alkanes are seen to be located predominantly at the intersections of the straight and zigzag channels. To obtain loadings higher than four, the branched alkane must seek residence in the channel interiors which is energetically more demanding and therefore requires disproportionately higher pressures; this leads to the inflection behavior. Linear alkanes with six and more carbon atoms also were found to exhibit inflection behavior. Hexane and heptane show inflection due to commensurate "freezing"; the length of these molecules is commensurate with the length of the zigzag channels. This leads to a higher packing efficiency than for other linear alkanes. Available experimental data from the literature are used to confirm the accuracy of the predictions of the CBMC simulations. Furthermore, the temperature dependency of the isotherms are also properly modeled. For purposes of fitting the isotherms we found that the dual-site Langmuir model provides an excellent description of the simulated isotherms for linear and branched alkanes. In this model we distinguish between two sites with differing ease of adsorption: site A, representing the intersections between the straight and zigzag channels, and site B, representing the channel interiors. CBMC simulations of isotherms of 50-50 binary mixtures of C-5, C-6, and C-7 hydrocarbon isomers show some remarkable and hitherto unreported features. The loading of the branched isomer in all three binary mixtures reaches a maximum when the total mixture loading corresponds to four molecules per unit cell. Higher loadings are obtained by "squeezing out" of the branched alkane from the silicalite and replacing these with the linear alkane. This "squeezing out" effect is found to be entropic in nature; the linear alkanes have a higher packing efficiency and higher loadings are more easily achieved by replacing the branched alkanes with the linear alkanes. The mixture isotherms can be predicted quite accurately by applying the appropriate mixture rules to the dual-site Langmuir model. This model allows the mixture isotherm to be predicted purely on the basis of the parameters describing the isotherms of the pure components. The sorption selectivity exhibited by silicalite for the linear alkane in preference to the branched alkane in mixtures of Cg, C6, and C7 hydrocarbon isomers, provides a potential for the development of a novel separation technique based on entropy-driven sorption selectivity.