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On metal ion chelates and conditional stability constant determination: Method development and selective ion flotation of chelating surfactants
Mid Sweden University, Faculty of Science, Technology and Media, Department of Chemical Engineering.
2014 (English)Licentiate thesis, comprehensive summary (Other academic)
Place, publisher, year, edition, pages
Sundsvall: Mid Sweden University , 2014. , 36 p.
Series
Mid Sweden University licentiate thesis, ISSN 1652-8948 ; 111
National Category
Chemical Sciences
Identifiers
URN: urn:nbn:se:miun:diva-24029ISBN: 978-91-87557-59-0 (print)OAI: oai:DiVA.org:miun-24029DiVA: diva2:775415
Supervisors
Available from: 2015-01-02 Created: 2015-01-02 Last updated: 2015-03-13Bibliographically approved
List of papers
1. Determination of conditional stability constants for some divalent transition metal ion-EDTA complexes by electrospray ionization mass spectrometry
Open this publication in new window or tab >>Determination of conditional stability constants for some divalent transition metal ion-EDTA complexes by electrospray ionization mass spectrometry
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2014 (English)In: Journal of Mass Spectrometry, ISSN 1076-5174, E-ISSN 1096-9888, Vol. 49, no 7, 550-556 p.Article in journal (Refereed) Published
Abstract [en]

Conditional stability constants of coordination complexes comprising divalent transition metals, Cu2+, Ni2+, Zn2+, Co2+, and ethylenediaminetetraacetic acid (EDTA) were determined utilizing electrospray ionization mass spectrometry. The deviation of signal response of a reference complex was monitored at addition of a second metal ion. The conditional stability constant for the competing metal was then determined through solution equilibria equations. The method showed to be applicable to a system where Co2+ and Zn2+ competed for EDTA at pH 5. When Cu2+ and Ni2+ competed for EDTA, the equilibrium changed over time. This change was shown to be affected in rate and size by the type of organic solvent added. In this work, 30% of either methanol or acetonitrile was used. It was found that if calibration curves are prepared for both metal complexes in solution and the measurements are repeated with sufficient time space, any change in equilibrium of sample solutions will be discovered. Copyright © 2014 John Wiley & Sons, Ltd. Copyright © 2014 John Wiley & Sons, Ltd.

Keyword
chelating agent, conditional stability constant, EDTA, electrospray ionization mass spectrometry, mixed solvent
National Category
Chemical Sciences
Identifiers
urn:nbn:se:miun:diva-22614 (URN)10.1002/jms.3372 (DOI)000339614300002 ()2-s2.0-84904184855 (Scopus ID)
Note

Correspondence Address: Norgren, M.; Fibre Science and Communication Network (FSCN), Mid Sweden University, SE-851 70 Sundsvall, Sweden; email: Magnus.Norgren@miun.se

Available from: 2014-10-10 Created: 2014-08-20 Last updated: 2016-09-29Bibliographically approved
2. Metal Ion Coordination, Conditional Stability Constants and Solution Behavior of Chelating Surfactant Metal Complexes
Open this publication in new window or tab >>Metal Ion Coordination, Conditional Stability Constants and Solution Behavior of Chelating Surfactant Metal Complexes
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2014 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 16, 4605-4612 p.Article in journal (Refereed) Published
Abstract [en]

Coordination complexes of some divalent metal ions with the DTPA (diethylenetriaminepentaacetic acid)-based chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C12-DTPA) have been examined in terms of chelation and solution behavior. The headgroup of 4-C 12-DTPA contains eight donor atoms that can participate in the coordination of a metal ion. Conditional stability constants for five transition metal complexes with 4-C12-DTPA were determined by competition measurements between 4-C12-DTPA and DTPA, using electrospray ionization mass spectrometry (ESI-MS). Small differences in the relative strength between the coordination complexes of DTPA and 4-C12-DTPA indicated that the hydrocarbon tail only affected the chelating ability of the headgroup to a limited extent. The coordination of Cu2+ ions was investigated in particular, using UV-visible spectroscopy. By constructing Job's plots, it was found that 4-C12-DTPA could coordinate up to two Cu2+ ions. Surface tension measurements and NMR diffusometry showed that the coordination of metal ions affected the solution behavior of 4-C 12-DTPA, but there were no specific trends between the studied divalent metal complexes. Generally, the effects of the metal ion coordination could be linked to the neutralization of the headgroup charge of 4-C 12-DTPA, and the resulting reduced electrostatic repulsions between adjacent surfactants in micelles and monolayers. The pH vs concentration plots, on the other hand, showed a distinct difference between 4-C12-DTPA complexes of the alkaline earth metals and the transition metals. This was explained by the difference in coordination between the two groups of metal ions, as predicted by the hard and soft acid and base (HSAB) theory.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:miun:diva-21401 (URN)10.1021/la5002336 (DOI)000335297300011 ()2-s2.0-84899622360 (Scopus ID)
Available from: 2014-02-20 Created: 2014-02-20 Last updated: 2016-09-29Bibliographically approved
3. Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents and divalent metal ions
Open this publication in new window or tab >>Headgroup interactions and ion flotation efficiency in mixtures of a chelating surfactant, different foaming agents and divalent metal ions
2014 (English)In: Langmuir, ISSN 0743-7463, E-ISSN 1520-5827, Vol. 30, no 22, 6331-6338 p.Article in journal (Refereed) Published
Abstract [en]

The correlation between interaction parameters and ion flotation efficiency in mixtures of chelating surfactant metal complexes and different foaming agents was investigated. We have recently shown that chelating surfactant 2-dodecyldiethylenetriaminepentaacetic acid (4-C-12-DTPA) forms strong coordination complexes with divalent metal ions, and this can be utilized in ion flotation. Interaction parameters for mixed micelles and mixed monolayer formation for Mg2+ and Ni2+ complexes with the chelating surfactant 4-C-12-DTPA and different foaming agents were calculated by Rubingh's regular solution theory. Parameters for the calculations were extracted from surface tension measurements and NMR diffusometry. The effects of metal ion coordination on the interactions between 4-C-12-DTPA and the foaming agents could be linked to a previously established difference in coordination chemistry between the examined metal ions. As can be expected from mixtures of amphoteric surfactants, the interactions were strongly pH-dependent. Strong correlation was found between interaction parameter beta(sigma)for mixed monolayer formation and the phase-transfer efficiency of Ni2+ complexes with 4-C-12-DTPA during flotation in a customized flotation cell. In a mixture of Cu(2+)and Zn2+, the significant difference in conditional stability constants (log K) between the metal complexes was utilized to selectively recover the metal complex with the highest log K (Cu2+) by ion flotation. Flotation experiments in an excess concentration of metal ions confirmed the coordination of more than one metal ion to the headgroup of 4-C-12-DTPA.

National Category
Physical Chemistry
Identifiers
urn:nbn:se:miun:diva-21402 (URN)10.1021/la500689n (DOI)000337198900004 ()2-s2.0-84902190309 (Scopus ID)
Available from: 2014-02-20 Created: 2014-02-20 Last updated: 2015-01-02Bibliographically approved

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