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|a pubmed24n0530.xml
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|a (DE-627)NLM158914856
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|a (NLM)16285773
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|a DE-627
|b ger
|c DE-627
|e rakwb
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|a eng
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| 100 |
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|a Paul, Kristian W
|e verfasserin
|4 aut
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|a Effect of dehydration on sulfate coordination and speciation at the Fe-(hydr)oxide-water interface
|b a molecular orbital/density functional theory and Fourier transform infrared spectroscopic investigation
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|c 2005
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|a Text
|b txt
|2 rdacontent
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|a ohne Hilfsmittel zu benutzen
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|2 rdamedia
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|a Date Completed 05.04.2007
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|a Date Revised 15.11.2005
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|a published: Print
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|a Citation Status PubMed-not-MEDLINE
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|a The effect of dehydration on the coordination and speciation of sulfate at the Fe-(hydr)oxide-H2O interface was investigated using molecular orbital/density functional theory (MO/DFT) and Fourier transform infrared (FTIR) spectroscopy. IR frequency calculations were performed at the UB3LYP/6-31+G(d) level of theory for potential sulfate (bidentate bridging, monodentate, and H-bonded) and bisulfate (bidentate bridging and monodentate) surface complexes. MO/DFT calculated IR frequencies were compared to available IR literature results and attenuated total reflectance (ATR) FTIR spectra collected in our laboratory of sulfate adsorbed at the hematite-H2O interface. IR frequency calculations performed using the larger 6-311+G(d,p) basis set resulted in minor frequency shifts that did not dramatically alter the agreement with experiment. This investigation proposes that sulfate undergoes a speciation change as a function of surface dehydration. A generalized model for the speciation change is proposed as follows. (1) At the Fe-(hydr)oxide-H2O interface, sulfate adsorbs as a bidentate bridging or monodentate surface complex under most experimental conditions. (2) Upon surface dehydration, sulfate changes speciation to form bidentate bridging and/or monodentate bisulfate. However, surface dehydration does not yield 100% speciation change but leads to a mixture of sulfate and bisulfate. (3) The speciation change is reversible as a function of rehydration. The reversibility of the sulfate-bisulfate speciation change is chiefly determined by the local hydration environment of the O-H bond in bisulfate. Under dehydrated conditions, the O-H bond length is approximately 0.98 A. The bond length substantially increases (bond strength decreases) to approximately 1.03 A when the initial H-bond network is re-established through hydration, likely leading to deprotonation upon full mineral surface hydration
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|a Journal Article
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|a Borda, Michael J
|e verfasserin
|4 aut
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|a Kubicki, James D
|e verfasserin
|4 aut
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|a Sparks, Donald L
|e verfasserin
|4 aut
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|i Enthalten in
|t Langmuir : the ACS journal of surfaces and colloids
|d 1992
|g 21(2005), 24 vom: 22. Nov., Seite 11071-8
|w (DE-627)NLM098181009
|x 1520-5827
|7 nnns
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| 773 |
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|g volume:21
|g year:2005
|g number:24
|g day:22
|g month:11
|g pages:11071-8
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