Jump to ContentJump to Main Navigation
Show Summary Details
More options …

Radiochimica Acta

International Journal for chemical aspects of nuclear science and technology

Editor-in-Chief: Qaim, Syed M.

IMPACT FACTOR 2018: 1.339

CiteScore 2018: 1.20

SCImago Journal Rank (SJR) 2018: 0.333
Source Normalized Impact per Paper (SNIP) 2018: 0.720

See all formats and pricing
More options …
Volume 96, Issue 7


Formation and hydrolysis of polynuclear Th(IV) complexes – a nano-electrospray mass-spectrometry study

C. Walther / M. Fuss / S. Büchner
Published Online: 2009-09-25 | DOI: https://doi.org/10.1524/ract.2008.1509

Polynuclear hydroxide complexes play an important role for the hydrolysis of tetravalent thorium ions in aqueous solution, in particular for Th(IV) concentrations exceeding some [Th(IV)]=10−4 M. Consequently, these polymers must be considered when describing hydrolysis of Th(IV) or dissolution processes of Th(IV) solids. In the past, considerable efforts were made to obtain equilibrium formation constants of these polymers and different stoichiometries for dimers, tetramers and hexamers have been suggested. However, most information was obtained from indirect methods, in particular, from potentiometric titrations. In the present work, we present an approach of directly quantifying polymeric metal hydroxide complexes in solution. By nano-electrospray mass-spectrometry the degrees of polymerization, i.e. the numbers of Th4+ ions and the numbers of hydroxide ligands, and as a consequence, also the charges of the complexes are measured. All mono- and polynuclear species which are present in solution are quantified simultaneously down to species contributing less than 0.1% of the total [Th(IV)] concentration. Solutions of [Th(IV)]=6×10−6–10−1 M are investigated in HCl at [H+]=10−4–0.1 M. More than 30 different polymeric complexes are observed with the general trend of increasing number of hydroxide ligands with decreasing acidity. A surprising finding is the presence of the pentamer Th5(OH)yz +, which was not described in the literature before. With decreasing Th(IV) concentration the stability field of polymers narrows continuously until polymers can no longer be detected below [Th(IV)]=10−5 M.

Keywords: Thorium; Hydrolysis; Polymerization; Nano-electrospray

About the article

Received: 2008-01-08

Accepted: 2008-01-11

Published Online: 2009-09-25

Published in Print: 2008-07-01

Citation Information: Radiochimica Acta, Volume 96, Issue 7, Pages 411–425, ISSN (Online) 2193-3405, ISSN (Print) 0033-8230, DOI: https://doi.org/10.1524/ract.2008.1509.

Export Citation

© Oldenbourg Wissenschaftsverlag.Get Permission

Citing Articles

Here you can find all Crossref-listed publications in which this article is cited. If you would like to receive automatic email messages as soon as this article is cited in other publications, simply activate the “Citation Alert” on the top of this page.

Kathryn George, Julie Muller, Laurence Berthon, Claude Berthon, Dominique Guillaumont, Iñigo J. Vitorica-Yrezabal, H. Victoria Stafford, Louise S. Natrajan, and Christelle Tamain
Inorganic Chemistry, 2019
Peng Li, Xingjie Wang, Ken-ichi Otake, Jiafei Lyu, Sylvia L. Hanna, Timur Islamoglu, and Omar K. Farha
ACS Applied Nano Materials, 2019
Peng Li, Subhadip Goswami, Ken-ichi Otake, Xingjie Wang, Zhijie Chen, Sylvia L. Hanna, and Omar K. Farha
Inorganic Chemistry, 2019
Rémi Marsac, Florent Réal, Nidhu Lal Banik, Mathieu Pédrot, Olivier Pourret, and Valérie Vallet
Dalton Trans., 2017
E. Myllykylä, T. Lavonen, L. Koivula, K. Ollila, and M. Siitari-Kauppi
Journal of Radioanalytical and Nuclear Chemistry, 2017, Volume 311, Number 1, Page 225
M. Felipe-Sotelo, J. Hinchliff, L.P. Field, A.E. Milodowski, O. Preedy, and D. Read
Chemosphere, 2017, Volume 179, Page 127
P. L. Zanonato, P. Di Bernardo, Z. Zhang, Y. Gong, G. Tian, J. K. Gibson, and L. Rao
Dalton Trans., 2016, Volume 45, Number 32, Page 12763
Harald Zänker, Stephan Weiss, Christoph Hennig, Vinzenz Brendler, and Atsushi Ikeda-Ohno
ChemistryOpen, 2016, Volume 5, Number 3, Page 174
J. A. Drader, N. P. Martin, N. Boubals, N. Zorz, P. Guilbaud, and L. Berthon
Journal of Radioanalytical and Nuclear Chemistry, 2016, Volume 310, Number 1, Page 441
Björn Drobot, Anne Bauer, Robin Steudtner, Satoru Tsushima, Frank Bok, Michael Patzschke, Johannes Raff, and Vinzenz Brendler
Analytical Chemistry, 2016, Volume 88, Number 7, Page 3548
N. Priyadarshini, M. Sampath, Shekhar Kumar, and U. Kamachi Mudali
Journal of Radioanalytical and Nuclear Chemistry, 2016, Volume 307, Number 1, Page 25
Björn Drobot, Robin Steudtner, Johannes Raff, Gerhard Geipel, Vinzenz Brendler, and Satoru Tsushima
Chem. Sci., 2015, Volume 6, Number 2, Page 964
N. Priyadarshini, M. Sampath, Shekhar Kumar, U. Kamachi Mudali, and R. Natarajan
Journal of Nuclear Chemistry, 2014, Volume 2014, Page 1
Rémi Marsac, Nidhu Lal Banik, Christian Michael Marquardt, and Jens Volker Kratz
Geochimica et Cosmochimica Acta, 2014, Volume 131, Page 290
Harald Zänker and Christoph Hennig
Journal of Contaminant Hydrology, 2014, Volume 157, Page 87
Luther W. McDonald, James A. Campbell, and Sue B. Clark
Analytical Chemistry, 2014, Volume 86, Number 2, Page 1023
Michael Steppert and Clemens Walther
Radiochimica Acta, 2013, Volume 101, Number 5, Page 307
Olga N. Batuk, D. Vinga Szabó, Melissa A. Denecke, Tonya Vitova, and Stepan N. Kalmykov
Radiochimica Acta, 2013, Volume 101, Number 4, Page 233
Philip X. Rutkowski, Maria del Carmen Michelini, and John K. Gibson
The Journal of Physical Chemistry A, 2013, Volume 117, Number 2, Page 451
Christoph Hennig, Stephan Weiss, Dipanjan Banerjee, Erica Brendler, Veijo Honkimäki, Gabriel Cuello, Atsushi Ikeda-Ohno, Andreas C. Scheinost, and Harald Zänker
Geochimica et Cosmochimica Acta, 2013, Volume 103, Page 197
Clemens Walther, Jörg Rothe, Bernd Schimmelpfennig, and Markus Fuss
Dalton Transactions, 2012, Volume 41, Number 36, Page 10941
Daniel S. Alessi, Benjamin Uster, Harish Veeramani, Elena I. Suvorova, Juan S. Lezama-Pacheco, Joanne E. Stubbs, John R. Bargar, and Rizlan Bernier-Latmani
Environmental Science & Technology, 2012, Volume 46, Number 11, Page 6150
Detlef Schröder
Physical Chemistry Chemical Physics, 2012, Volume 14, Number 18, Page 6382
Isabell Dreissig, Stephan Weiss, Christoph Hennig, Gert Bernhard, and Harald Zänker
Geochimica et Cosmochimica Acta, 2011, Volume 75, Number 2, Page 352
M. Schmidt, S.S. Lee, R.E. Wilson, L. Soderholm, and P. Fenter
Geochimica et Cosmochimica Acta, 2012, Volume 88, Page 66
Karah E. Knope, Monica Vasiliu, David A. Dixon, and L. Soderholm
Inorganic Chemistry, 2012, Volume 51, Number 7, Page 4239
M. Steppert, C. Walther, M. Fuss, and S. Büchner
Rapid Communications in Mass Spectrometry, 2012, Volume 26, Number 6, Page 583
J. Lützenkirchen, T. Kupcik, M. Fuss, C. Walther, A. Sarpola, and O. Sundman
Applied Surface Science, 2010, Volume 256, Number 17, Page 5406
Michael Steppert, Ivana Císařová, Thomas Fanghänel, Andreas Geist, Patric Lindqvist-Reis, Petra Panak, Petr Štěpnička, Sascha Trumm, and Clemens Walther
Inorganic Chemistry, 2012, Volume 51, Number 1, Page 591
Vojtěch Šádek, Detlef Schröder, and Nikos G. Tsierkezos
International Journal of Mass Spectrometry, 2011, Volume 304, Number 1, Page 9
Ágnes Révész, Detlef Schröder, Jan Svec, Michaela Wimmerová, and Vladimir Sindelar
The Journal of Physical Chemistry A, 2011, Volume 115, Number 41, Page 11378
Karah E. Knope, Richard E. Wilson, Monica Vasiliu, David A. Dixon, and L. Soderholm
Inorganic Chemistry, 2011, Volume 50, Number 19, Page 9696
Jana Paterová, Jan Heyda, Pavel Jungwirth, Christopher J. Shaffer, Ágnes Révész, Emilie L. Zins, and Detlef Schröder
The Journal of Physical Chemistry A, 2011, Volume 115, Number 25, Page 6813
Jana Jaklová Dytrtová, Michal Jakl, Ivana Šestáková, Emilie-Laure Zins, Detlef Schröder, and Tomáš Navrátil
Analytica Chimica Acta, 2011, Volume 693, Number 1-2, Page 100
Clemens Walther, Markus Fuss, Sebastian Büchner, and Horst Geckeis
Journal of Radioanalytical and Nuclear Chemistry, 2009, Volume 282, Number 3, Page 1003
Michael Steppert, Clemens Walther, Andreas Geist, and Thomas Fanghänel
New Journal of Chemistry, 2009, Volume 33, Number 12, Page 2437
Journal of Mass Spectrometry, 2009, Volume 44, Number 1, Page 151

Comments (0)

Please log in or register to comment.
Log in