The interaction of H+- and Cu2+-ions with Ca-montmorillonite was inves
tigated in 0.1 mol/dm3 solutions of Ca(CIO4)2 at 298.2 K by potentiome
tric titrations using both glass electrodes (for H+) and ion specific
electrodes (for Cu2+). The experimental data were interpreted on the b
asis of the surface complexation model. The calculations were performe
d with the least-squares program FITEQL (Westall, 1982) using the cons
tant capacitance approximation. The best fit was obtained with a set o
f equilibria of the general form p H+ + q Cu2+ + = SOH double line arr
ow pointing left and right (H+)p(Cu2+)q(= SOH)(p+21)+ beta(p,q(int)s =
[H(p)Cu(q)(= SOH)(p+2q)]/[H+]p[Cu2+]q[= SOH] and the constants log be
ta1,0(int)s = 8.16 (+/- 0.04), log beta-1,0(int)s = -8.71 (+/- 0.08),
log beta0,1(int)s = 5.87 (+/- 0.06), log beta-1,1(int)s = -0.57 (+/- 0
.12), log beta-2,1(int)s = -6-76 (+/- 0.02). An appropriate modeling o
f the H+ adsorption data requires the introduction of a second surface
group = TOH with the acidity constant = TOH - H+ double line arrow po
inting left and right = TO- log beta-1,0(int)s = -5.77 (+/- 0.07). In
addition, the ion exchange equilibria Ca2+ - Cu2+ and Ca2+ - H+ had to
be taken into account. Arguments are presented to identify the groups
= SOH and = TOH as surface aluminol groups-Al(OH)(H2O) and surface si
lanol groups = Si-OH, respectively.