Change search
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf
Sulfur X-ray absorption and vibrational spectroscopic study of sulfite, sulfur dioxide and sulfonate solutions, and of the substituted sulfonate ions X3CSO3- (X = H, Cl, F)
Stockholm University, Faculty of Science, Department of Physical, Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Materials and Environmental Chemistry (MMK), Inorganic and Structural Chemistry.
Stockholm University, Faculty of Science, Department of Physics.
Show others and affiliations
2007 (English)In: Inorganic Chemistry, ISSN 0020-1669, E-ISSN 1520-510X, Vol. 46, no 20, 8332-8348 p.Article in journal (Refereed) Published
Abstract [en]

Sulfur K-edge X-ray absorption near-edge structure (XANES) spectra have been recorded and the S(1s) electron excitations evaluated by means of density functional theory−transition potential (DFT−TP) calculations to provide insight into the coordination, bonding, and electronic structure. The XANES spectra for the various species in sulfur dioxide and aqueous sodium sulfite solutions show considerable differences at different pH values in the environmentally important sulfite(IV) system. In strongly acidic (pH < 1) aqueous sulfite solution the XANES spectra confirm that the hydrated sulfur dioxide molecule, SO2(aq), dominates. The theoretical spectra are consistent with an OSO angle of 119° in gas phase and acetonitrile solution, while in aqueous solution hydrogen bonding reduces the angle to 116°. The hydration affects the XANES spectra also for the sulfite ion, SO32-. At intermediate pH (4) the two coordination isomers, the sulfonate (HSO3-) and hydrogen sulfite (SO3H-) ions with the hydrogen atom coordinated to sulfur and oxygen, respectively, could be distinguished with the ratio HSO3-:SO3H- about 0.28:0.72 at 298 K. The relative amount of HSO3- increased with increasing temperature in the investigated range from 275 to 343 K. XANES spectra of sulfonate, methanesulfonate, trichloromethanesulfonate, and trifluoromethanesulfonate compounds, all with closely similar S−O bond distances in tetrahedral configuration around the sulfur atom, were interpreted by DFT−TP computations. The energy of their main electronic transition from the sulfur K-shell is about 2478 eV. The additional absorption features are similar when a hydrogen atom or an electron-donating methyl group is bonded to the −SO3 group. Significant changes occur for the electronegative trichloromethyl (Cl3C−) and trifluoromethyl (F3C−) groups, which strongly affect the distribution especially of the π electrons around the sulfur atom. The S−D bond distance 1.38(2) Å was obtained for the deuterated sulfonate (DSO3-) ion by Rietveld analysis of neutron powder diffraction data of CsDSO3. Raman and infrared absorption spectra of the CsHSO3, CsDSO3, H3CSO3Na, and Cl3CSO3Na·H2O compounds and Raman spectra of the sulfite solutions have been interpreted by normal coordinate calculations. The C−S stretching force constant for the trichloromethanesulfonate ion obtains an anomalously low value due to steric repulsion between the Cl3C− and −SO3 groups. The S−O stretching force constants were correlated with corresponding S−O bond distances for several oxosulfur species.

Place, publisher, year, edition, pages
2007. Vol. 46, no 20, 8332-8348 p.
National Category
Inorganic Chemistry
Identifiers
URN: urn:nbn:se:su:diva-24303DOI: 10.1021/ic062440iISI: 000249698700033OAI: oai:DiVA.org:su-24303DiVA: diva2:197185
Available from: 2007-05-15 Created: 2007-05-04 Last updated: 2017-12-13Bibliographically approved
In thesis
1. Structure and bonding of sulfur-containing molecules and complexes
Open this publication in new window or tab >>Structure and bonding of sulfur-containing molecules and complexes
2007 (English)Doctoral thesis, comprehensive summary (Other academic)
Abstract [en]

Synchrotron-based spectroscopic techniques enable investigations of the many important biological and environmental functions of the ubiquitous element sulfur. In this thesis the methods for interpreting sulfur K-edge X-ray absorption near edge structure (XANES) spectra are developed and applied for analyses of functional sulfur groups. The influence of coordination, pH, hydrogen bonding, etc., on the sulfur 1s electronic excitations is evaluated by transition potential density functional theory. Analyses have been performed of reduced sulfur compounds in marine-archaeological wood from historical shipwrecks, including the Vasa, Stockholm, Sweden and the Mary Rose, Portsmouth, U.K.. The accumulation of sulfur as thiols in lignin-rich parts of the wood on the seabed is also a probable pathway in the natural sulfur cycle for how reduced sulfur enters fossil fuels via humic matter in anaerobic marine sediments. Sulfur K-edge XANES spectra for several biochemical model compounds and for coexisting isomeric sulfur species in cysteine and sulfite(IV) aqueous solutions have been analyzed with the aid of theoretical calculations. Cysteine derivatives are important for biochemical detoxification, and mercury(II) cysteine complexes in solution have been structurally characterized by means of Extended X-ray Absorption Fine Structure (EXAFS), Raman and 199Hg NMR spectroscopy. Lanthanoid(III) ions were found to coordinate eight dimethyl sulfoxide oxygen atoms in a distorted square antiprism in the solid state and in solution, by combining crystallography, EXAFS, XANES and vibrational spectroscopy. The mean M-O bond distances for the disordered crystal structures are in good agreement with those from the lattice-independent EXAFS studies. The different sulfur K-edge XANES spectra for the dimethyl sulfoxide ligands in the hexasolvated complexes of the trivalent group 13 metal ions, Tl(III), In(III), Ga(III) and Al(III), were interpreted by theoretical calculations.

Place, publisher, year, edition, pages
Stockholm: Institutionen för fysikalisk kemi, oorganisk kemi och strukturkemi, 2007. 105 p.
Keyword
Sulfur species, x-ray absorption and vibrational spectroscopy, TP-DFT calculations
National Category
Chemical Sciences
Research subject
Structural Chemistry
Identifiers
urn:nbn:se:su:diva-6843 (URN)978-91-7155-423-9 (ISBN)
Public defence
2007-06-05, Magnélisalen, Kemiska övningslaboratoriet, Svante Arrhenius väg 12 A, Stockholm, 10:00 (English)
Opponent
Supervisors
Available from: 2007-05-15 Created: 2007-05-04 Last updated: 2010-01-15Bibliographically approved

Open Access in DiVA

No full text

Other links

Publisher's full text

Search in DiVA

By author/editor
Eriksson, LarsMink, JanosPettersson, Lars G. M.Sandström, Magnus
By organisation
Department of Physical, Inorganic and Structural ChemistryInorganic and Structural ChemistryDepartment of Physics
In the same journal
Inorganic Chemistry
Inorganic Chemistry

Search outside of DiVA

GoogleGoogle Scholar

doi
urn-nbn

Altmetric score

doi
urn-nbn
Total: 92 hits
CiteExportLink to record
Permanent link

Direct link
Cite
Citation style
  • apa
  • ieee
  • modern-language-association-8th-edition
  • vancouver
  • Other style
More styles
Language
  • de-DE
  • en-GB
  • en-US
  • fi-FI
  • nn-NO
  • nn-NB
  • sv-SE
  • Other locale
More languages
Output format
  • html
  • text
  • asciidoc
  • rtf