On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents - Publication - MOST Wiedzy

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On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents

Abstract

The structures of the N,N-dimethylformamide (dmf), N,N-dimethylacetamide (dma), and N,N-dimethylpropionamide (dmp) solvated strontium and barium ions have been determined in solution using large angle X-ray scattering and EXAFS spectroscopy. The strontium ion has a mean coordination number (CN) between 6.2 and 6.8, and the barium ion has a mean CN between 7.1 and 7.8 in these amide solvents. The non-integer numbers indicates that equilibria between different coordination numbers and geometries exist in these systems. Structural information of the alkali, alkaline earth, and selected transition metal and lanthanoid(III) ions, and the halide ions in water, methanol, ethanol, dimethylsulfoxide, formamide, dmf and dma has been combined with previously reported standard partial molar volumes, V0. The ionic radii and charge densities (charge/ionic volume), and corresponding V0 values have been used to gain information on the relationship between structural and volumetric properties. For the structure-breaking ions, i.e. the alkali metal and halide ions, there is an almost linear relationship between the ionic radius and V0. On the other hand, for the structure-making ions, here the alkaline earth, transition metal and lanthanoid(III) ions, a linear relationship is observed between the charge density and V0. Solvents with a well-defined bulk structure through hydrogen bonding, specifically, water, methanol and ethanol, will be more contracted through solvation than aprotic solvents, as the space between the solvent molecules is lost as a result of the hydrogen bonding. In this respect, methanol stands out as the most compressed solvent participating in solvation compared to its bulk structure.

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Details

Category:
Articles
Type:
artykuł w czasopiśmie wyróżnionym w JCR
Published in:
PHYSICAL CHEMISTRY CHEMICAL PHYSICS no. 20, edition 21, pages 14525 - 14536,
ISSN: 1463-9076
Publication year:
2018
Bibliographic description:
Lundberg D., Warmińska D., Fuchs A., Persson I.: On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents// PHYSICAL CHEMISTRY CHEMICAL PHYSICS. -Vol. 20, iss. 21 (2018), s.14525-14536
DOI:
Digital Object Identifier (open in new tab) 10.1039/c8cp02244e
Verified by:
Gdańsk University of Technology

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