TY - JOUR
T1 - The relationship between molecular structure and ion adsorption on variable charge minerals
AU - Rietra, R.P.J.J.
AU - Hiemstra, T.
AU - van Riemsdijk, W.H.
PY - 1999
Y1 - 1999
N2 - Ion adsorption modeling is influenced by the presumed binding structure of surface complexes. Ideally, surface complexes determined by modeling should correspond with those derived from spectroscopy, thereby assuring that the mechanistic description of ion binding scales from the nanoscopic molecular structure to the macroscopic adsorption behavior. Here we show that the structure of adsorbed species is a major factor controlling the pH dependency of adsorption. An important aspect of the pH dependency is the macroscopic proton-ion adsorption stoichiometry. A simple and accurate experimental method was developed to determine this stoichiometry. With this method, proton-ion stoichiometry ratios for vanadate, phosphate, arsenate, chromate, molybdate, tungstate, selenate and sulfate have been characterized at 1 or 2 pH values. Modeling of these data shows that the macroscopic proton-ion adsorption stoichiometry is almost solely determined by the interfacial charge distribution of adsorbed complexes. The bond valence concept of Pauling can be used to estimate this charge distribution from spectroscopic data. Conversely, the experimentally determined proton-ion adsorption stoichiometry allows us to successfully predict the spectroscopically identified structures of, for example, selenite and arsenate on goethite. Consequently, we have demonstrated a direct relationship between molecular surface structure and macroscopic adsorption phenomena.
AB - Ion adsorption modeling is influenced by the presumed binding structure of surface complexes. Ideally, surface complexes determined by modeling should correspond with those derived from spectroscopy, thereby assuring that the mechanistic description of ion binding scales from the nanoscopic molecular structure to the macroscopic adsorption behavior. Here we show that the structure of adsorbed species is a major factor controlling the pH dependency of adsorption. An important aspect of the pH dependency is the macroscopic proton-ion adsorption stoichiometry. A simple and accurate experimental method was developed to determine this stoichiometry. With this method, proton-ion stoichiometry ratios for vanadate, phosphate, arsenate, chromate, molybdate, tungstate, selenate and sulfate have been characterized at 1 or 2 pH values. Modeling of these data shows that the macroscopic proton-ion adsorption stoichiometry is almost solely determined by the interfacial charge distribution of adsorbed complexes. The bond valence concept of Pauling can be used to estimate this charge distribution from spectroscopic data. Conversely, the experimentally determined proton-ion adsorption stoichiometry allows us to successfully predict the spectroscopically identified structures of, for example, selenite and arsenate on goethite. Consequently, we have demonstrated a direct relationship between molecular surface structure and macroscopic adsorption phenomena.
KW - mineralen
KW - structuur
KW - adsorptie
KW - minerals
KW - structure
KW - adsorption
U2 - 10.1016/S0016-7037(99)00228-8
DO - 10.1016/S0016-7037(99)00228-8
M3 - Article
VL - 63
SP - 3009
EP - 3015
JO - Geochimica et Cosmochimica Acta
JF - Geochimica et Cosmochimica Acta
SN - 0016-7037
IS - 19-20
ER -