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Speciation and the structure of lead(II) in hyperalkaline aqueous solution

Bajnóczi, Éva G. and Pálinkó, István and Körtvélyesi, Tamás and Bálint, Szabolcs and Bakó, Imre and Sipos, Pál and Persson, Ingmar (2014). Speciation and the structure of lead(II) in hyperalkaline aqueous solution. Dalton Transactions: an international journal of inorganic chemistry [incorporating Acta Chemica Scandinavica]. 43, 17971 - 17979
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Official URL: http://dx.doi.org/10.1039/c4dt02757d

Abstract

The identity of the predominating lead(II) species in hyper-alkaline aqueous solution has been determined by Raman spectroscopy, and ab initio quantum chemical calculations and its structure has been determined by EXAFS. The observed and calculated Raman spectra for the [Pb(OH)(3)](-) complex are in agreement while they are different for two-coordinated complexes and complexes containing Pb=O double bonds. Predicted bond lengths are also consistent with the presence of [Pb(OH)(3)](-) and exclude the formation of Pb=O double bond(s). These observations together with experimentally established analogies between lead(II) and tin(II) in hyper-alkaline aqueous solutions suggest that the last stepwise hydroxido complex of lead(II) is [Pb(OH)(3)](-). The Pb-O bond distance in the [Pb(OH)(3)](-) complex as determined is remarkably short, 2.216 angstrom, and has low symmetry as no multiple back-scattering is observed. The [Pb(OH)(3)](-) complex has most likely trigonal pyramidal geometry as all reported three-coordinated lead(II) complexes in the solid state. From single crystal X-ray data, the bond lengths for O-coordinated lead(II) complexes with low coordination numbers are spread over an unusually wide interval, 2.216-2.464 angstrom for N = 3. The Pb-O bond distance is at the short side and within the range of three coordinated complexes, as also observed for the trihydroxidostannate(II) complex indicating that the hydroxide ion forms short bonds with d(10)s(2) metal ions with occupied anti-bonding orbitals.

Authors/Creators:Bajnóczi, Éva G. and Pálinkó, István and Körtvélyesi, Tamás and Bálint, Szabolcs and Bakó, Imre and Sipos, Pál and Persson, Ingmar
Title:Speciation and the structure of lead(II) in hyperalkaline aqueous solution
Series/Journal:Dalton Transactions: an international journal of inorganic chemistry [incorporating Acta Chemica Scandinavica] (1477-9226)
Year of publishing :2014
Depositing date:10 February 2015
Volume:43
Page range:17971 - 17979
Number of Pages:5
Publisher:Royal Society of Chemistry
ISSN:1477-9226
Language:English
Publication Type:Journal article
Refereed:Yes
Article category:Scientific peer reviewed
Version:Accepted version
Full Text Status:Public
Agris subject categories.:X Agricola extesions > X50 Chemistry
Subjects:(A) Swedish standard research categories 2011 > 1 Natural sciences > 104 Chemical Sciences > Inorganic Chemistry
Agrovoc terms:chemistry, calculation, potentiometry, solutions, chemicophysical properties
Keywords:hyper-alkaline aqueous solution, lead(II), speciation, structure, tin(II)-hydroxid complex, potentiometric titrations, spectoscopy, quantum chemical calculations, thermodynamic studies
URN:NBN:urn:nbn:se:slu:epsilon-e-2392
Permanent URL:
http://urn.kb.se/resolve?urn=urn:nbn:se:slu:epsilon-e-2392
Additional ID:
Type of IDID
Web of Science (WoS)000344598200037
DOI10.1039/c4dt02757d
ID Code:11768
Faculty:NJ - Fakulteten för naturresurser och jordbruksvetenskap
Department:(NL, NJ) > Department of Chemistry and Biotechnology (140101-161231)
Deposited By: SLUpub Connector
Deposited On:10 Feb 2015 11:28
Metadata Last Modified:09 Oct 2015 12:21

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