Experimental studies were performed on two difficult model mixtures; o
ne (bovine/horse heart cytochrome c) exhibiting converging and the oth
er (ribonuclease A /alpha-chymotrypsinogen A) diverging log capacity f
actor(k')-log salt plots. While step gradient chromatography proved no
t suited for these classes of separations, both overloaded linear grad
ient and displacement were efficacious. Induced sample displacement wa
s observed for the convergent case in linear gradient improving perfor
mance.