The relationship between molecular structure and ion adsorption on variable charge minerals

R.P.J.J. Rietra, T. Hiemstra, W.H. van Riemsdijk

Research output: Contribution to journalArticleAcademicpeer-review

121 Citations (Scopus)

Abstract

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.
Original languageEnglish
Pages (from-to)3009-3015
JournalGeochimica et Cosmochimica Acta
Volume63
Issue number19-20
DOIs
Publication statusPublished - 1999

Keywords

  • minerals
  • structure
  • adsorption

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