Partitioning of a bimodal polymer mixture of different chain lengths into a
narrow slit has been examined by using lattice Monte Carlo simulations in
two approaches: the regular canonical ensemble simulation with a twin box a
nd the chain insertion method. The regular canonical ensemble simulation de
termines the partition coefficients of the two components directly from the
simulation. The results reveal that the short chains have an enhanced part
itioning and the long chains have a reduced partitioning into the pore in t
he bimodal mixture compared with the monodisperse systems at the same conce
ntration. In addition, the partition coefficients of the two components in
the bimodal mixture maximize their difference in the semidilute concentrati
on, substantiating the separation mechanism of the high osmotic pressure ch
romatography. The chain insertion method determines the chemical potentials
of the chains in the bimodal mixture in the bulk and in the slit. It was f
ound that the chemical potential depends strongly on the total volume fract
ion of the polymers but only weakly on the composition of the mixture in bo
th the confined and the bulk solutions. The partition coefficients in the b
imodal mixture were estimated from the chemical potentials by neglecting th
e dependence of the chemical potentials on the composition. The latter prod
uced a less pronounced enhancement and reduction in the partition coefficie
nts of the two components compared with those obtained from the simulations
using the twin box.