A vector model is developed for separations using combinations of two
or more stationary phase chemistries. The model is useful for the deve
lopment of separation optimization strategies for methods involving se
ries-coupled columns, parallel columns, or mixed stationary phases. In
the model, each mixture component occupies a single point in a multid
imensional vector space, with each orthogonal axis representing the re
tention on a particular stationary phase. For every pair of points, a
separation vector is defined. The length and direction of the separati
on vector give all the necessary information on the separation of this
binary mixture. The ensemble of separation vectors for the entire mix
ture is used to describe the multiphase separation. For the case of a
separation using series-coupled columns or mixed stationary phases, th
e multidimensional space collapses by orthogonal projections onto a li
near separation axis. The orientation of this axis defines the fractio
nal contributions of the various phases to the overall separation sele
ctivity. An example of the use of the vector model in establishing the
optimal separation axis and thus phase fraction in a two-phase separa
tion is presented.