Since chromatography of ions is a widely used technique in analytical chemi
stry a basic understanding of the retention mechanism is important. The pri
nciples of the different retention models that have been proposed are exami
ned in this paper. The focus is on those models that are derived from the p
hysical chemistry of charged surfaces immersed in an electrolyte solution.
In the first two sections the theory for the electrical double layer and th
e Donnan potential are presented together with experimental results from su
rface and colloid chemistry. In Section 3 a comparison between stoichiometr
ic and non-stoichiometric models is made. In this section the physical mean
ing of the retention factor is also examined. The Donnan model and the diff
erent double layer models developed for ion exchange chromatography of smal
l ions are discussed in Section 4. The next section presents the correspond
ing models that have been developed for ion pair chromatography and compare
s them with the experimental findings. The theoretical modifications needed
when going from small ions to ionic macromolecules are discussed in the la
st section and the developed models are compared with the experimental resu
lts. (C) 1999 Elsevier Science B.V. All rights reserved.