Theoretical and 27Al CPMAS NMR investigation of aluminum coordination changes during aluminosilicate dissolution

Louise J. Criscenti, Susan Louise Brantley, Karl Todd Mueller, Natia Tsomaia, James D. Kubicki

Research output: Contribution to journalArticle

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Abstract

Ab initio molecular orbital calculations were performed, and 27Al CP MAS-NMR spectra were evaluated in order to investigate the possible tetrahedral to octahedral coordination change of Al at the feldspar-water interface under acidic conditions. Aluminum coordination is octahedral in solution, and tetrahedral in feldspar crystals. Whether this change in coordination can occur on feldspar surfaces as part of the dissolution mechanism has been debated. Molecular orbital calculations were performed on aluminosilicate clusters with a few surrounding water molecules to partially account for solvation effects at the feldspar-water interface. The calculations on both fully-relaxed and partially-constrained clusters suggest that the energy difference between [4]Al and [6]Al where both are linked to three Si-tetrahedra (i.e., Q3Al) in the feldspar structure, is small enough to allow for the conversion of Q3 [4]Al to Q3 [6]Al in a hydrated layer of feldspar, prior to the release of Al ions to the aqueous solution. The introduction of a few water molecules to the clusters introduced the possibility of multiple optimized geometries for each Al coordination, with energy differences on the order of several hydrogen bonds. The calculation of activation energies and transition states between Q3 [4]Al, Q3 [5]Al, and Q3 [6]Al was complicated by the introduction of water molecules and the use of fully-relaxed aluminosilicate clusters. Calculated isotropic shifts for Q1 [6]Al, Q2 [6]Al, and Q3 [6]Al suggest that the [6]Al observed on aluminosilicate glass surfaces using 27Al CP MAS-NMR is Q1 [6]Al and therefore formed as part of the dissolution process. The formation of [6]Al in situ on a feldspar surface (as opposed to re-precipitation from solution) has significant implications for the dissolution mechanism and surface chemistry of feldspars.

Original languageEnglish (US)
Pages (from-to)2205-2220
Number of pages16
JournalGeochimica et Cosmochimica Acta
Volume69
Issue number9
DOIs
StatePublished - May 1 2005

Fingerprint

aluminosilicate
Aluminum
nuclear magnetic resonance
feldspar
Dissolution
aluminum
dissolution
Nuclear magnetic resonance
Water
Orbital calculations
MAS
Molecular orbitals
Molecules
water
Solvation
co-ordination
Surface chemistry
activation energy
energy
Hydrogen bonds

All Science Journal Classification (ASJC) codes

  • Geochemistry and Petrology

Cite this

Criscenti, Louise J. ; Brantley, Susan Louise ; Mueller, Karl Todd ; Tsomaia, Natia ; Kubicki, James D. / Theoretical and 27Al CPMAS NMR investigation of aluminum coordination changes during aluminosilicate dissolution. In: Geochimica et Cosmochimica Acta. 2005 ; Vol. 69, No. 9. pp. 2205-2220.
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Theoretical and 27Al CPMAS NMR investigation of aluminum coordination changes during aluminosilicate dissolution. / Criscenti, Louise J.; Brantley, Susan Louise; Mueller, Karl Todd; Tsomaia, Natia; Kubicki, James D.

In: Geochimica et Cosmochimica Acta, Vol. 69, No. 9, 01.05.2005, p. 2205-2220.

Research output: Contribution to journalArticle

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T1 - Theoretical and 27Al CPMAS NMR investigation of aluminum coordination changes during aluminosilicate dissolution

AU - Criscenti, Louise J.

AU - Brantley, Susan Louise

AU - Mueller, Karl Todd

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AU - Kubicki, James D.

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AB - Ab initio molecular orbital calculations were performed, and 27Al CP MAS-NMR spectra were evaluated in order to investigate the possible tetrahedral to octahedral coordination change of Al at the feldspar-water interface under acidic conditions. Aluminum coordination is octahedral in solution, and tetrahedral in feldspar crystals. Whether this change in coordination can occur on feldspar surfaces as part of the dissolution mechanism has been debated. Molecular orbital calculations were performed on aluminosilicate clusters with a few surrounding water molecules to partially account for solvation effects at the feldspar-water interface. The calculations on both fully-relaxed and partially-constrained clusters suggest that the energy difference between [4]Al and [6]Al where both are linked to three Si-tetrahedra (i.e., Q3Al) in the feldspar structure, is small enough to allow for the conversion of Q3 [4]Al to Q3 [6]Al in a hydrated layer of feldspar, prior to the release of Al ions to the aqueous solution. The introduction of a few water molecules to the clusters introduced the possibility of multiple optimized geometries for each Al coordination, with energy differences on the order of several hydrogen bonds. The calculation of activation energies and transition states between Q3 [4]Al, Q3 [5]Al, and Q3 [6]Al was complicated by the introduction of water molecules and the use of fully-relaxed aluminosilicate clusters. Calculated isotropic shifts for Q1 [6]Al, Q2 [6]Al, and Q3 [6]Al suggest that the [6]Al observed on aluminosilicate glass surfaces using 27Al CP MAS-NMR is Q1 [6]Al and therefore formed as part of the dissolution process. The formation of [6]Al in situ on a feldspar surface (as opposed to re-precipitation from solution) has significant implications for the dissolution mechanism and surface chemistry of feldspars.

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