Tetrad effect in the adsorption of the lanthanides on zeolite Y

The adsorption of the lanthanides (except for Pm) on the zeolite Y was investigated under various solution conditions of nitrate ion concentration ([NO−3]: 0.001–2 mol/dm3) and total lanthanide concentration (from 0.0001 to 0.001 mol/dm3). The solutions of the lanthanide nitrates were equilibrated with the zeolite samples at 296 K. The concentrations of lanthanides in the initial and equilibrium solutions were determined by means of spectrophotometrical method with Arsenazo III reagent and distribution constants KdKd of the lanthanides between aqueous and zeolite phases were calculated. The evident concave tetrad effect in the change of logKdlogKd values (nitrate concentrations 0.4–2 mol/dm3) within the lanthanide series was noticed and an attempt at its explanation through the comparison of covalence in LnO bonds existing in AlO(1/3Ln1/3Ln)Si species in the zeolite phase and in Ln(NO3)2+ complexes forming in the aqueous phase was presented. The weak convex tetrad effect for equilibrium nitrate concentrations 0.001–0.32 mol/dm3, manifesting in the change of logKdlogKd values and in the alteration of logKlogK (adsorption constants), is evidence of the complexation of the tripositive lanthanide ions by the oxygens originating both from water molecules and from the zeolite framework.

Graphical abstractThe tetrad effect in the adsorption constants KdKd of the lanthanides on the zeolite Y was observed, manifesting in the deviations from the straightline relationship logKdlogKd vs 1/r1/r (where r is the ionic radius of the tripositive lanthanide ion) for different molar nitrates concentrations c in the aqueous phase. The effect was referred to the covalency in LnO bonds, in products and substrates of the adsorption.Figure optionsDownload full-size imageDownload as PowerPoint slide