The cation exchange properties of cell walls isolated from collard (Bassia okracea var acephala D.C.) leaves were investipted. Cation sorption on cell walls was described by mass-action expressions of ion exchange, rather than by the traditional Donnan equilibrium. The massaction expressions enable the selectivity of the wail for one cation over another to be determined unambiguously from ion exchange isotherms. We found that: (a) the cation composition of the wall varied as a function of the solution cation concentration, solution cation composition, and pH in a way predicted by mass action; (b) the affinity of the wall for divalent cations increased as the equivalent fraction of divalent cation on the wall increased, and as the concentration of divalent cations in solution increased; (c) the selectivity of the wall for any metal cation pair was not altered by the concentration of HZ in solution or on the wall; (d) H' sorption on the wail may be treated as a cation exchange reaction making it possible to calculate the relative affinity of the wall for metal cation pairs from HI-metal (Me) titration curves; and (e) the relative affinity of the wall for the cations we studied was: HI >> (K -Ca2+) > Mg2+. A cation-exchange model including surface complexes is consistent with observed cation selectivity. We conclude that metal cations interact with the wall to minimiz or eliminate long-range electrostatic interactions and suggest that this may be due to the formation of site-specific cationwall surface complexes.Cation binding to plant cell walls has been implicated as a crucial step in a wide range of physiological processes including cell elongation (13), heavy metal tolerance (15), and ion uptake (9). The cation composition of the higher plant cell wall cannot be easily measured, and therefore attempts have been made to model its cation composition as a function of the cation composition of the surrounding solution. The traditional approach to developing these models treats the wall as a Donnan system (3-7, 9, 16). A serious drawback to this approach, however, is that the resultant equations involve ionic molalities that cannot be directly measured. In this paper we use the mass-action description ofion exchange to describe cation binding to isolated cell walls ofcollard leaves and thereby avoid ambiguities inherent in previous approaches.The total cation mass ofthe cell wall is divisible into two parts: '