Hydration of the cations aluminum(3+) and copper. A theoretical study

Veillard, H.

doi:10.1021/ja00464a016

Cited by 29 publications

(9 citation statements)

References 10 publications

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“…On the basis of the XAFS results, , a distorted trigonal pyramid of surface oxygen atoms is the most likely coordination environment of adsorbed Pb 2+ . However, three water molecules in the vicinity of adsorbed Pb 2+ probably will also act as ligands (Pb–OH 2 bond distances ≥2.59 Å) to stabilize the trigonal pyramid geometry, since three short Pb–O bonds (2.2–2.3 Å) are not sufficient to fulfill the bonding requirements of the Pb 2+ alone. , Therefore, the adsorbed Pb 2+ is considered as 6-fold coordinated, as done in the literature, , but, the effect of the difference in Pb–O bond distances on the charge distribution of Pb 2+ over the surface is not considered. The calculated n 0 CD-values for the bidentate and tridentate adsorption geometry based on Pauling bond valences are, respectively, 0.67 and 1; by correcting them for water dipole orientation effects the values are further refined, see SI.…”

Section: Resultsmentioning

confidence: 99%

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

Zhao

Tan

Wang

et al. 2018

Environ. Sci. Technol.

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The surface complexation modeling of metal adsorption to birnessites is in its infancy compared to the charge-distribution multisite ion complexation (CD-MUSIC) models for iron/aluminum (hydr)oxides. Therefore, using X-ray diffraction with Rietveld refinement to obtain the reactive sites and their densities, a CD-MUSIC model combined with a Stern-Gouy-Chapman electrical double layer (EDL) model for the external surface and a Donnan model for the interlayer surface is developed for birnessites with different Mn average oxidation state (MnAOS). Proton affinity constants and the charge distributions of Pb surface complexes were calculated a priori. By fitting Pb adsorption data to the model the obtained equilibrium constants (log K) of Pb complexes were 6.9-10.9 for the double-corner-sharing and double-edge-sharing Pb complexes on the edge sites and 2.2-6.5 for the triple-corner-sharing Pb complex on the vacancies. The larger log K value was obtained for higher MnAOS. Speciation calculations showed that with increasing MnAOS from 3.67 to 3.92 the interlayer surface contribution to the total Pb adsorption increased from 43.2% to 48.6%, and the vacancy contribution increased from 43.9% to 54.7%. The vacancy contribution from interlayer surface was predominant. The present CD-MUSIC-EDL model contributes to understand better the difference in metal adsorption mechanism between birnessite and iron/aluminum (hydr)oxides.

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Section: Resultsmentioning

confidence: 99%

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

Zhao

Tan

Wang

et al. 2018

Environ. Sci. Technol.

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“…Because of its widespread and important role in condensed phase chemistry and biochemistry − numerous experimental and theoretical − investigations have focused on the structural properties of hydrated cupric ion, Cu 2+ . The most powerful experimental methods for structural elucidation are X-ray and neutron diffraction, together with NMR and quasielastic neutron scattering. − Such studies on various copper(II) salts have provided considerable insight into the surroundings of Cu 2+ in water. − There is strong experimental evidence for a JT distortion of the hexaaquo complex which is best represented by a model where two bonds are elongated, leading to a tetragonal bipyramidal structure with four closer equatorial and two more distant axial ligands.…”

Section: Introductionmentioning

confidence: 99%

Investigation of Cu²⁺ Hydration and the Jahn−Teller Effect in Solution by QM/MM Monte Carlo Simulations

1999

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The Cu2+ hydration shell structure has been studied by a combined ab initio quantum mechanical/molecular mechanical (QM/MM) Monte Carlo simulation, in which the ion and its first hydration sphere are treated at the Born−Oppenheimer ab initio quantum mechanical level, while classical pair and three-body potentials are employed for the remaining system. Whereas traditional simulations based on MM potentials are not able to predict higher-body effects such as the Jahn−Teller (JT) distorted octahedral structure of the first hydration shell of Cu2+, the combined QM/MM approach reproduces correctly this experimentally confirmed property and delivers more accurate hydration energy values as well.

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“…Furthermore, (1) contains two extra water molecules while (2) only contains one of them. The average Al-O bond lengths are 1.880 and 1.884 Å for (1) and (2), respectively, which is slightly shorter than the literature average distance of 1.90 Å (Hay & Myneni, 2008;Veillard, 1977). Structures of aluminium sulfate, Al 2 (SO 4 ) 3 , and derivatives thereof have been reported with different amounts of additional structural water and varying connectivities.…”

Section: Tablementioning

confidence: 70%

Synthesis and crystal structures of [Al(H₂O)₆](SO₄)NO₃·2H₂O and [Al(H₂O)₆](SO₄)Cl·H₂O

Svensson

2021

Acta Cryst E

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Two novel aluminium double salts, [Al(H2O)6](SO4)NO3·2H2O, hexaquaaluminium sulfate nitrate dihydrate, (1), and [Al(H2O)6](SO4)Cl·H2O, hexaquaaluminium sulfate chloride hydrate, (2), were obtained in the form of single crystals. Their crystal structures are each based on an octahedral [Al(H2O)6]3+ unit and both structures have in common one charge-balancing SO4 2− anion. The final positive charge from the aluminium(III) cation is balanced by an NO3 − or a Cl− anion for (1) and (2), respectively. Compound (1) further contains two unligated water molecules while compound (2) only contains one unligated water molecule. In the crystal structures, all components are spatially separated and interactions are mediated via medium–strong hydrogen bonding, compared to many other reported aluminium sulfates where corner-sharing of the building units is common. The two compounds represent rare cases where one aluminium(III) cation is charge-balanced by two different anions.

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Hydration of the cations aluminum(3+) and copper. A theoretical study

Cited by 29 publications

References 10 publications

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

Investigation of Cu²⁺ Hydration and the Jahn−Teller Effect in Solution by QM/MM Monte Carlo Simulations

Synthesis and crystal structures of [Al(H₂O)₆](SO₄)NO₃·2H₂O and [Al(H₂O)₆](SO₄)Cl·H₂O

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Hydration of the cations aluminum(3+) and copper. A theoretical study

Cited by 29 publications

References 10 publications

CD-MUSIC-EDL Modeling of Pb2+ Adsorption on Birnessites: Role of Vacant and Edge Sites

CD-MUSIC-EDL Modeling of Pb2+ Adsorption on Birnessites: Role of Vacant and Edge Sites

Investigation of Cu2+ Hydration and the Jahn−Teller Effect in Solution by QM/MM Monte Carlo Simulations

Synthesis and crystal structures of [Al(H2O)6](SO4)NO3·2H2O and [Al(H2O)6](SO4)Cl·H2O

Contact Info

Product

Resources

About

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

CD-MUSIC-EDL Modeling of Pb²⁺ Adsorption on Birnessites: Role of Vacant and Edge Sites

Investigation of Cu²⁺ Hydration and the Jahn−Teller Effect in Solution by QM/MM Monte Carlo Simulations

Synthesis and crystal structures of [Al(H₂O)₆](SO₄)NO₃·2H₂O and [Al(H₂O)₆](SO₄)Cl·H₂O