Determination of ion association constants by means of IR absorption band intensities of the molecules forming the first coordination spheres of the cations

Solovieva, L.A.; Akopyan, S. Kh.; Vilaseca, Eudald

doi:10.1016/0584-8539(94)80004-9

Cited by 14 publications

(9 citation statements)

References 9 publications

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“…[64] Extensive concentration-dependent ion-pairing was also found for weak coordinating counterions, such as in LiBF 4 [30] and LiClO 4 , [62] by studying the CN vibration. [65] These findings for the coordination number are in good agreement with published X-ray structures. [66][67][68] However, Sajeevkumar and Singh found the average coordination number to be 4.7, [69] whereas Megyes et al found up to six acetonitrile molecules surrounding the Li + ion in the gas phase by means of mass spectrometry.…”

supporting

confidence: 92%

Ligand‐Exchange Processes on Solvated Lithium Cations: Acetonitrile and Hydrogen Cyanide

et al. 2007

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supporting

confidence: 92%

Ligand‐Exchange Processes on Solvated Lithium Cations: Acetonitrile and Hydrogen Cyanide

et al. 2007

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“…coordination seems to be the most stable at dilute concentrations, moving to Li(N)3.1(F)1.8 for the concentrated systems, and progressing to a much higher anion content, Li(N)1.9(F)2.5, for the highly concentrated electrolytes. The total coordination number, however, remains close to 4.5 for all cases, larger than the 4-fold coordination reported experimentally by different techniques [43,[46][47][48], suggesting the PM7 method to slightly overestimate the coordination number, the cut-off to be set to high, or possibly that the solvent exchange affects the experimental data. As noted above for both the ACN and the PC based electrolytes an increased salt concentration promotes a substitution of solvent molecules by anions in the first solvation shell, as expected [28].…”

Section: Cn and Cn Variancementioning

confidence: 52%

Solvation structure in dilute to highly concentrated electrolytes for lithium-ion and sodium-ion batteries

Flores

Åvall

Jeschke

et al. 2017

Electrochimica Acta

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The solvation structure of several lithium and sodium based electrolytes are explored as a function of salt concentration over a wide range via a detailed PM7 computational study.The cation coordination shells are found to be well-defined and solvent rich for dilute electrolytes, while disordered and anion rich for the more concentrated electrolytes. The Nabased electrolytes display larger cation coordination shells with a more pronounced presence of fluorine as compared to the Li-based electrolytes. The origins of the structural differences are discussed as well as their consequences for properties of battery electrolytes and battery usage -especially targeting the current large interest in highly concentrated electrolytes.

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“…Hence, it seems that, to some extent, aspects of both the solvent insensitivity and solvent independence models must apply. Strong evidence supporting this conclusion comes also from studies of electrolytes dissolved in ACN, in which both “free” and “cation-bound” ACN molecules are similarly identified. , …”

Section: Rationalizing the Solvent Shift On The Basis Of The Solvent ...mentioning

confidence: 81%

“…c Δ E is given as the raw energy, that as corrected for basis-set-superposition error (BSSE), and that with both BSSE and zero-point energy correction (ZPT). d Calculations for T d ACN 4 Li + , energies are per ACN, obs is for Li + in ACN …”

Section: Shaping a Quantitative Theorymentioning

confidence: 99%

“…However, the calculated shifts in ν 2 are comparable only for linear hydrogen-bonding configurations. To estimate the errors in our calculated frequency shifts for complexes of this type, we consider solutions of Li + dissolved in acetonitrile . The observed CN frequency shift is +20 cm -1 , and ACN is found to have a coordination number of 4 around Li + .…”

Section: Shaping a Quantitative Theorymentioning

confidence: 99%

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The Solvation of Acetonitrile

1999

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Acetonitrile is an extremely important solvent and cosolvent. Despite this, we have no general picture of the nature of mixed liquids containing acetonitrile applicable across-solvent families. We consider the properties of acetonitrile dissolved in 33 solvents, focusing on interpretation of the environment-sensitive solvent shift, Δν, of its CN stretch frequency, ν2. The two major models (dispersive and specific solvation) which have been proposed to interpret Δν are based on diverse experiments with incompatible conclusions. We ascertain the robust features of these models and combine them into a new one in which solvent−solvent and solvent−solute forces compete to determine the structure of the solution and hence Δν. First, Δν is analyzed in terms of solvent repulsive and dielectric effects combined with specific solvation effects. To interpret this specific solvation, 95 MP2 or B3LYP calculations are performed to evaluate structures and CN frequency shifts for CH3CN complexed with one molecule of either water, methanol, ethanol, 2-propanol, tert-butyl alcohol, phenol, benzyl alcohol, acetic acid, trifluoroacetic acid, 2,2,2-trifluoroethanol, 1,1,1,3,3,3-hexafluoro-2-propanol, acetonitrile, chloroform, carbon tetrachloride, tetrahydrofuran, formamide, pyridine, or Cl-, as well as 45 parallel calculations for the solvent monomers or dimers. The results are then convolved using known structural properties of the various solutions and/or related neat liquids, leading to an interpretation of the observed solvent shifts. Also, we measure Δν for acetonitrile in aqueous solution using Fourier transform Raman spectroscopy and show that the results are consistent with, but require modification of, microheterogeneity theories for the structure of acetonitrile−water solutions. Although such theories are still in their infancy, we suggest that microheterogeneity could also account for most known properties of acetonitrile−alcohol solutions and, in fact, be a quite general phenomenon.

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Determination of ion association constants by means of IR absorption band intensities of the molecules forming the first coordination spheres of the cations

Cited by 14 publications

References 9 publications

Ligand‐Exchange Processes on Solvated Lithium Cations: Acetonitrile and Hydrogen Cyanide

Ligand‐Exchange Processes on Solvated Lithium Cations: Acetonitrile and Hydrogen Cyanide

Solvation structure in dilute to highly concentrated electrolytes for lithium-ion and sodium-ion batteries

The Solvation of Acetonitrile

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