The adsorption of Cu
2+ ions on MnO
2 was examined as a function of pH and concentrations of Cu
2+ and MnO
2. The adsorption isotherm shows that the surface concentration of adsorbed Cu
2+ increases with pH and concentration of Cu
2+ in solution, and that, at higher coverages, the surface concentration is lower than predicted by the Langmuir isotherm The behavior was characterized by considering the stoichiometry and equilibrium and concentration conditions of the adsorption. The surface acid hydroxyl groups, ≡MnOH(a), react with Cu
2+ ions to form the following two surface complexes.≡MnOH(a)+Cu
2++NO
-3_??_≡MnOCu
+·NO
-3+H
+, 2≡MnOH(a)+Cu
2+_??_(≡MnO)
2Cu+2H
+. The equilibrium conditlons of these surface complexations are given by.
K1int=
Q1eq exp (
B1[≡MnOCu
+·NO
-3]), β
2int=
Q2eq exp(
B2[(≡MnO)
2Cu]), where
K1int and β
2int are“intrinsic”stability constants of[1:1]and[1:2] surface complexes,
Q1eq and
Q2eq are concentration quotients at equilibrium, and
B1 and
B2 are constants expressing the extent of suppression of surface complexation by the respective complexes. The equations of equilibrium conditions and of concentration conditions for both solution and surface species were fitted to the adsorption isotherm, and the values of the constants were determined by the nonlinear leastsquares method. The values are:
K1int=8.15×10
-3m
3mol
-1, β
2int=2.41×10
3m
-1,
B1=3.81×10
6m
2mol
-1, and
B2=1.62×10
6m
2mol
-1 at an ionic strength of 0.1 (NaNO
3) and 25°C. These values well describe the observed adsorption behavior.
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