Journal article
In Situ 27 Al NMR Spectroscopy of Aluminate in Sodium Hydroxide Solutions above and below Saturation with Respect to Gibbsite
Inorganic chemistry, Vol.57(19), pp.11864-11873
07/23/2018
Handle:
https://hdl.handle.net/2376/107421
PMID: 30036042
Abstract
Aluminum hydroxide (Al(OH)
, gibbsite) dissolution and precipitation processes in alkaline environments play a commanding role in aluminum refining and nuclear waste processing, yet mechanistic aspects underlying sluggish kinetics during crystallization have remained obscured due to a lack of in situ probes capable of isolating incipient ion pairs. At a molecular level Al is cycling between tetrahedral ( T
) coordination in solution to octahedral ( O
) in the solid. We explored dissolution of Al(OH)
that was used to produce variably saturated aluminate (Al(OH)
)-containing solutions under alkaline conditions (pH >13) with in situ
Al magic angle spinning (MAS)-nuclear magnetic resonance (NMR) spectroscopy, and interrogated the results with ab initio molecular dynamics (AIMD) simulations complemented with chemical shift calculations based on high-level theory. The collective results highlight the overall stability of the solvation structure for T
Al in the Al(OH)
oxyanion as a function of both temperature and Al concentration. The observed chemical shift did not change significantly even when the Al concentration in solution became supersaturated upon cooling and limited precipitation of the octahedral Al(OH)
phase occurred. However, subtle changes in Al(OH)
speciation correlated with the dissolution/precipitation reaction were found. AIMD-informed chemical shift calculations indicate that measurable perturbations should begin when the Al(OH)
···Na
distance is less than 6 Å, increasing dramatically at shorter distances, coinciding with appreciable changes to the electrostatic interaction and reorganization of the Al(OH)
solvation shell. The integrated findings thus suggest that, under conditions incipient to and concurrent with gibbsite crystallization, nominally expected contact ion pairs are insignificant and instead medium-range (4-6 Å) solvent-separated Al(OH)
···Na
pairs predominate. Moreover, the fact that these medium-range interactions bear directly on resulting gibbsite characteristics was demonstrated by detailed microscopic and X-ray diffraction analysis and by progressive changes in the fwhm of the O
resonance, as measured by in situ NMR. Sluggish gibbsite crystallization may arise from the activation energy associated with disrupting this robust medium-range ion pair interaction.
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Details
- Title
- In Situ 27 Al NMR Spectroscopy of Aluminate in Sodium Hydroxide Solutions above and below Saturation with Respect to Gibbsite
- Creators
- Trent R Graham - The Voiland School of Chemical and Biological Engineering , Washington State University , Pullman , Washington 99164 , United StatesMateusz Dembowski - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesErnesto Martinez-Baez - Department of Chemistry , Washington State University , Pullman , Washington 99164 , United StatesXin Zhang - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesNicholas R Jaegers - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesJianzhi Hu - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesMiroslaw S Gruszkiewicz - Oak Ridge National Laboratory , Oak Ridge , Tennessee 37831 , United StatesHsiu-Wen Wang - Oak Ridge National Laboratory , Oak Ridge , Tennessee 37831 , United StatesAndrew G Stack - Oak Ridge National Laboratory , Oak Ridge , Tennessee 37831 , United StatesMark E Bowden - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesCalvin H Delegard - TradeWind Services LLC , Richland , Washington 99352 , United StatesGregory K Schenter - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesAurora E Clark - Department of Chemistry , Washington State University , Pullman , Washington 99164 , United StatesSue B Clark - Department of Chemistry , Washington State University , Pullman , Washington 99164 , United StatesAndrew R Felmy - Department of Chemistry , Washington State University , Pullman , Washington 99164 , United StatesKevin M Rosso - Pacific Northwest National Laboratory , Richland , Washington 99352 , United StatesCarolyn I Pearce - Pacific Northwest National Laboratory , Richland , Washington 99352 , United States
- Publication Details
- Inorganic chemistry, Vol.57(19), pp.11864-11873
- Academic Unit
- Chemistry, Department of
- Publisher
- United States
- Identifiers
- 99900547398401842
- Language
- English
- Resource Type
- Journal article