Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

Wulf, Alexander; Ludwig, Ralf

doi:10.1002/cphc.200500425

Cited by 51 publications

(39 citation statements)

References 52 publications

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“…The hard double-charged cation is preferably solvated by water (the hardest of the solvents under consideration), and as its fraction in solution decreases, the nickel halide is salted out. The same result follows also from the formation of stable heteromolecular associates of water with organic solvent, which was confirmed by thermodynamic methods [15][16][17][18][19][20]. Similar effect is also observed for the other systems considered in this work.…”

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confidence: 89%

Solubility of d-element salts in organic and aqueous–organic solvents: II. Effect of halocomplex formation on solubility of cobalt bromide and chloride and nickel chloride

et al. 2016

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Solubility of salts in the systems MCl 2 -H 2 O-Solv (M = Co, Ni) and CoBr 2 -H 2 O-Solv (Solv = dimethyl sulfoxide, dimethyl formamide, and dimethyl acetamide) at 25°C was measured experimentally. Dominating species of cobalt and nickel halides existing in various concentration regions were identified by analysis of electron absorption spectra. It was shown that the major factor defining solubility is the interaction of halocomplexes of metal ions with solvent molecules. 1 For communication I, see [1].In absence of complexation with anions (in the systems with cobalt, cadmium and copper sulfates in organic and mixed aqueous-organic solvents) ionic association is the dominating process in concentrated solutions and, as a consequence, solubility is determined mainly by the solvent dielectric permittivity [1]. This paper presents results of studying systems consisting of cobalt and nickel halides in aqueous-organic mixtures with various content of non-aqueous oxygendonor solvents: dimethyl sulfoxide (DMSO), dimethyl acetamide (DMA), and dimethyl formamide (DMF). All organic solvents used in the work are miscible continuously with water, values of their dielectric permittivity and donor ability [2] (Table 1) decrease in rather broad ranges, which makes it possible to reveal the influence of these factors on solubility of salts in the systems under study.The formation of several coordination compounds (rather stable halocomplexes in solution and various solid crystal solvates) makes the behavior of aqueousorganic solutions of such salts more diverse than that of the systems containing sulfates of d-elements, where ionic association is the dominating process [1]. The study of solubility in the systems copper(II) halideaqueous-organic solvent [3] has shown that the formation of halocomplexes along with resolvation leads to the fact that the stability of formed halocomplexes [4, 5], but not dielectric permittivity of a solvent, becomes the major factor defining the solubility.The formation of halocomplexes in ternary systems leads to the increase in the number of species present in the solution. In this case the solubility should be influenced by not so much by macroparameters of separate components (properties of salt and solvents) as by a combination of reactions proceeding between a solute and a solvent.We have carried out the following research to check this hypothesis. Solubility of cobalt and nickel salts in aqueous-organic solutions was measured experimentally, and compositions of the equilibrium

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confidence: 89%

Solubility of d-element salts in organic and aqueous–organic solvents: II. Effect of halocomplex formation on solubility of cobalt bromide and chloride and nickel chloride

et al. 2016

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“…[42,43] (Figure 3). [35,[56][57][58][59] simulations agree very well over almost the whole concentration range, we used the simulated diffusion data of the alcohol in the mixtures with the IL for checking the validity of the SE relation (see Figure 6). [35,[56][57][58][59] simulations agree very well over almost the whole concentration range, we used the simulated diffusion data of the alcohol in the mixtures with the IL for checking the validity of the SE relation (see Figure 6).…”

Section: Reorientational Correlation Times T Od Of Methanol In Ilsmentioning

confidence: 98%

Dynamics of Methanol in Ionic Liquids: Validity of the Stokes–Einstein and Stokes–Einstein–Debye Relations

et al. 2014

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The validity of Stokes-Einstein (SE) and Stokes-Einstein-Debye (SED) relations for methanol in the physical environment of the ionic liquid (IL) 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide is studied by means of nuclear magnetic resonance (NMR) relaxation time experiments, viscosity measurements and molecular dynamics (MD) simulations. The reorientational correlation times of the hydroxyl groups of pure methanol and of methanol in the IL/methanol mixtures were determined. For that purpose an approach for estimating NMR deuteron quadrupole coupling constants, presented by Wendt and Farrar (Mol. Phys. 1998, 95, 1077-1081), was confirmed. The self-diffusion coefficients of methanol were taken from the MD simulations. The viscosities of all systems were then measured and the SE and SED relations validated. For pure methanol both relations are valid, whereas they become increasingly invalid with increasing IL concentration, as indicated by effective volumes and radii that are too low. The deviation from the SE and SED relations could be related to dynamical heterogeneities described by the non-Gaussian parameter α(t) obtained from MD simulations. For pure methanol, α(t) is close to zero in accord with the validity of both relations. With increasing IL concentration the dynamical heterogeneities of methanol increase strongly. The times t* at the maximum of α(t) increase linearly with the relative number of methanol monomers in the mixtures. Thus, the dynamical heterogeneities are largest for single methanol molecules fully embedded in the IL environment. In their own environment methanol molecules are highly mobile, whereas in the IL-rich region the mobility is strongly reduced leading to the non-validity of SE and SED relations.

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“…[11][12][13] Along with the mentioned nonideal mixing behavior, a local heterogeneity of DMSO/ water mixtures has been discovered by both experimental techniques [14] and molecular dynamics simulation methods. [15][16][17] Aside from the molecular formations of DMSO molecules, the origin of inter-and intramolecular interactions leadThe effects of hydrogen bonding between dimethyl sulfoxide (DMSO) and the co-solvents water, methanol, and ethanol on the symmetric and antisymmetric CSC stretching vibrations of DMSO are investigated by means of Raman spectroscopy. The Raman spectra are recorded as a function of co-solvent concentration and reflect changes in structure and polarizability as well as hydrogen-bond donor and acceptor ability.…”

Section: Introductionmentioning

confidence: 99%

Concentration‐Dependent Hydrogen‐Bonding Effects on the Dimethyl Sulfoxide Vibrational Structure in the Presence of Water, Methanol, and Ethanol

Noack¹,

Kiefer²,

Leipertz³

2010

ChemPhysChem

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The effects of hydrogen bonding between dimethyl sulfoxide (DMSO) and the co-solvents water, methanol, and ethanol on the symmetric and antisymmetric CSC stretching vibrations of DMSO are investigated by means of Raman spectroscopy. The Raman spectra are recorded as a function of co-solvent concentration and reflect changes in structure and polarizability as well as hydrogen-bond donor and acceptor ability. In all cases studied a nonideal mixing behavior is observed. The spectra of the DMSO/water system show blue-shifted CSC stretching modes. The antisymmetric frequencies are always further blue-shifted than the symmetric stretching ones. The DMSO/methanol system also features blue-shifted CSC stretching frequencies but at high mole fractions a pronounced red shifting is observed. In the binary DMSO/ethanol system, the co-solvent also gives rise to blue shifts of the CSC stretching frequencies but restricted to mole fractions between x=0.38 and 0.45. The different magnitudes and occurrences of both blue- and red-shifted spectral lines are comprehensively and critically discussed with respect to the existing literature concerning wavenumbers and Raman intensities in both absolute and normalized values. In particular, the normalized Raman intensities show a higher sensitivity for the nonideal mixing behavior because they are independent of the mole fraction.

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Structure and Dynamics of Water Confined in Dimethyl Sulfoxide

Cited by 51 publications

References 52 publications

Solubility of d-element salts in organic and aqueous–organic solvents: II. Effect of halocomplex formation on solubility of cobalt bromide and chloride and nickel chloride

Solubility of d-element salts in organic and aqueous–organic solvents: II. Effect of halocomplex formation on solubility of cobalt bromide and chloride and nickel chloride

Dynamics of Methanol in Ionic Liquids: Validity of the Stokes–Einstein and Stokes–Einstein–Debye Relations

Concentration‐Dependent Hydrogen‐Bonding Effects on the Dimethyl Sulfoxide Vibrational Structure in the Presence of Water, Methanol, and Ethanol

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