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Title: 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,more » 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.« less

Authors:
ORCiD logo [1]; ORCiD logo [2];  [1]; ORCiD logo [1]
  1. Department of Molecular Science, Swedish University of Agricultural Sciences, SE-750 07 Uppsala, Sweden
  2. Department of Physical Chemistry, Chemical Faculty, Gdańsk University of Technology, PL-80-233 Gdańsk, Poland
Publication Date:
Research Org.:
Stanford Univ., CA (United States); SLAC National Accelerator Lab., Menlo Park, CA (United States). Stanford Synchrotron Radiation Lightsource (SSRL)
Sponsoring Org.:
USDOE Office of Science (SC), Biological and Environmental Research (BER); USDOE Office of Science (SC), Basic Energy Sciences (BES); The Swedish Institute; Swedish Research Council (VR); The Knut and Alice Wallenbergs Foundation; National Institutes of Health (NIH); National Institute of General Medical Sciences (NIGMS)
OSTI Identifier:
1437319
Alternate Identifier(s):
OSTI ID: 1624957
Grant/Contract Number:  
AC02-76SF00515
Resource Type:
Published Article
Journal Name:
Physical Chemistry Chemical Physics. PCCP (Print)
Additional Journal Information:
Journal Name: Physical Chemistry Chemical Physics. PCCP (Print) Journal Volume: 20 Journal Issue: 21; Journal ID: ISSN 1463-9076
Publisher:
Royal Society of Chemistry
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry; Physics

Citation Formats

Lundberg, Daniel, Warmińska, Dorota, Fuchs, Anna, and Persson, Ingmar. On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents. United Kingdom: N. p., 2018. Web. doi:10.1039/C8CP02244E.
Lundberg, Daniel, Warmińska, Dorota, Fuchs, Anna, & Persson, Ingmar. On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents. United Kingdom. doi:10.1039/C8CP02244E.
Lundberg, Daniel, Warmińska, Dorota, Fuchs, Anna, and Persson, Ingmar. Mon . "On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents". United Kingdom. doi:10.1039/C8CP02244E.
@article{osti_1437319,
title = {On the relationship between the structural and volumetric properties of solvated metal ions in O-donor solvents using new structural data in amide solvents},
author = {Lundberg, Daniel and Warmińska, Dorota and Fuchs, Anna and Persson, Ingmar},
abstractNote = {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.},
doi = {10.1039/C8CP02244E},
journal = {Physical Chemistry Chemical Physics. PCCP (Print)},
number = 21,
volume = 20,
place = {United Kingdom},
year = {2018},
month = {4}
}

Journal Article:
Free Publicly Available Full Text
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DOI: 10.1039/C8CP02244E

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