TY - JOUR
T1 - Experimental and theoretical vibrational spectroscopic evaluation of arsenate coordination in aqueous solutions, solids, and at mineral-water interfaces
AU - Myneni, Satish C.B.
AU - Traina, Samuel J.
AU - Waychunas, Glenn A.
AU - Logan, Terry J.
PY - 1998/10/1
Y1 - 1998/10/1
N2 - Arsenate (AsO43-) is a common species in oxidizing aquatic systems and hydrothermal fluids, and its solubility and partitioning into different mineral phases are determined by the nature of AsO43- coordination, solution pH, type of soluble cations, and H2O structure at the mineral-fluid interfaces. While the vibrational spectroscopy has been widely used in examining the AsO43- coordination chemistry, insufficient knowledge on the correlation of AsO43- molecular structure and its vibrational spectra impeded the complete spectral interpretation. In this paper, we evaluated the vibrational spectroscopy of AsO43- in solutions, crystals, and sorbed on mineral surfaces using theoretical (semiempirical, for aqueous species) and experimental studies, with emphasis on the protonation, hydration, and metal complexation influence on the As-O symmetric stretching vibrations. Theoretical predictions are in excellent agreement with the experimental studies and helped in the evaluation of vibrational modes of several arsenate-complexes and in the interpretation of experimental spectra. These vibrational spectroscopic studies (IR, Raman) suggest that the symmetry of AsO43- polyhedron is strongly distorted, and its As-O vibrations are affected by protonation and the relative influence on AsO43- structure decreases in the order: H+ >> cation ≥ H2O. For all AsO43- complexes, the As-OX symmetric stretching (X = metal, H+, H2O; ≤820 cm-1) shifted to lower wavenumbers when compared to that of uncomplexed AsO43-. In addition, the As-OH symmetric stretching of protonated arsenates in aqueous solutions shift to higher energies with increasing protonation (<720, <770, <790 cm-1 for HAsO42-, H2AsO4-, and H3AsO40, respectively). The protonated arsenates in crystalline solids show the same trend with little variation in As-OH symmetric stretching vibrations. Since metal complexation of protonated AsO43- does not influence the As-OH vibrations significantly, deducing symmetry information from their vibrational spectra is difficult. However, for metal unprotonated-AsO43- complexes, the shifts in As-OM (M = metal) vibrations are influenced only by the nature of complexing cation and the type of coordination, and hence the AsO43- coordination environment can be interpreted directly from the splitting of As-O degenerate vibrations and relative shifts in the As-OM modes. This information is critical in evaluating the structure of AsO43- sorption complexes at the solid-water interfaces. The vibrational spectra of other tetrahedral oxoanions are expected to be along similar lines.
AB - Arsenate (AsO43-) is a common species in oxidizing aquatic systems and hydrothermal fluids, and its solubility and partitioning into different mineral phases are determined by the nature of AsO43- coordination, solution pH, type of soluble cations, and H2O structure at the mineral-fluid interfaces. While the vibrational spectroscopy has been widely used in examining the AsO43- coordination chemistry, insufficient knowledge on the correlation of AsO43- molecular structure and its vibrational spectra impeded the complete spectral interpretation. In this paper, we evaluated the vibrational spectroscopy of AsO43- in solutions, crystals, and sorbed on mineral surfaces using theoretical (semiempirical, for aqueous species) and experimental studies, with emphasis on the protonation, hydration, and metal complexation influence on the As-O symmetric stretching vibrations. Theoretical predictions are in excellent agreement with the experimental studies and helped in the evaluation of vibrational modes of several arsenate-complexes and in the interpretation of experimental spectra. These vibrational spectroscopic studies (IR, Raman) suggest that the symmetry of AsO43- polyhedron is strongly distorted, and its As-O vibrations are affected by protonation and the relative influence on AsO43- structure decreases in the order: H+ >> cation ≥ H2O. For all AsO43- complexes, the As-OX symmetric stretching (X = metal, H+, H2O; ≤820 cm-1) shifted to lower wavenumbers when compared to that of uncomplexed AsO43-. In addition, the As-OH symmetric stretching of protonated arsenates in aqueous solutions shift to higher energies with increasing protonation (<720, <770, <790 cm-1 for HAsO42-, H2AsO4-, and H3AsO40, respectively). The protonated arsenates in crystalline solids show the same trend with little variation in As-OH symmetric stretching vibrations. Since metal complexation of protonated AsO43- does not influence the As-OH vibrations significantly, deducing symmetry information from their vibrational spectra is difficult. However, for metal unprotonated-AsO43- complexes, the shifts in As-OM (M = metal) vibrations are influenced only by the nature of complexing cation and the type of coordination, and hence the AsO43- coordination environment can be interpreted directly from the splitting of As-O degenerate vibrations and relative shifts in the As-OM modes. This information is critical in evaluating the structure of AsO43- sorption complexes at the solid-water interfaces. The vibrational spectra of other tetrahedral oxoanions are expected to be along similar lines.
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U2 - 10.1016/S0016-7037(98)00222-1
DO - 10.1016/S0016-7037(98)00222-1
M3 - Article
AN - SCOPUS:0032452745
VL - 62
SP - 3285
EP - 3300
JO - Geochmica et Cosmochimica Acta
JF - Geochmica et Cosmochimica Acta
SN - 0016-7037
IS - 19-20
ER -