Using computational chemistry to explore experimental solvent parameters – solvent basicity, acidity and polarity/polarizability
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W. Earle Waghorne
Abstract
Solvent basicity and polarity/polarizability parameters are analysed using molecular properties of solvents derived from computational chemistry. The results show that Kamlet and Taft’s measure of hydrogen bond basicity, β, is essentially identical to Gutmann’s donor number, a measure of Lewis basicity, both being determined by the charge on the most negative atom of the solvent molecule and the energy of the electron donor orbital. It is also found that, for both parameters, the calculated values for alcohols and N–H containing bases deviate systematically from those for aprotic solvents. This mirrors Kamlet and Taft’s earlier observation that different solvatochromic probes yield different β values in amphiprotic solvents. Reichardt’s E T (30) and Kamlet, Abboud and Taft’s π * both show direct dependences on the dipole moments and quadrupolar amplitudes of the solvent molecules and, surprisingly, an inverse dependence on the molecular polarizability. Additionally, E T (30) has a strong dependence on the charge on the most positive hydrogen atom of the solvent molecule, reflecting its sensitivity to hydrogen bonding. Unexpectedly, π * shows a dependence on the energy of the electron donor orbital. Kammet and Taaft’s hydrogen bond acidity parameter, α, is discussed in light of the results for π * and E T (30).
Article note
A collection of invited papers based on presentations at the 36th International Conference of Solution Chemistry (ICSC-36), held in Xining, China, 4–8 August 2019.
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Artikel in diesem Heft
- Frontmatter
- In this issue
- Preface
- Selected papers from the 36th International Conference on Solution Chemistry (ICSC-36)
- Conference papers
- Using computational chemistry to explore experimental solvent parameters – solvent basicity, acidity and polarity/polarizability
- Solution chemistry in the surface region of aqueous solutions
- Water confined in solutions of biological relevance
- Real-time in-situ 1H NMR of reactions in peptide solution: preaggregation of amyloid-β fragments prior to fibril formation
- Free energy profile of permeation of Entecavir through Hepatitis B virus capsid studied by molecular dynamics calculation
- Dielectric relaxation spectroscopy: an old-but-new technique for the investigation of electrolyte solutions
- Excess spectroscopy and its applications in the study of solution chemistry
- Structure of aqueous sodium acetate solutions by X-Ray scattering and density functional theory
- Desymmetrization in geometry optimization: application to an ab initio study of copper(I) hydration
- Interactions between adsorbents and adsorbates in aqueous solutions
- Modeling vapor-liquid-liquid-solid equilibrium for acetone-water-salt system
- Apparent molar volumes of sodium arsenate aqueous solution from 283.15 K to 363.15 K at ambient pressure: an experimental and thermodynamic modeling study
- Extraction of various metal ions by open-chain crown ether bridged diphosphates in supercritical carbon dioxide
- Solvation heterogeneity in ionic liquids as demonstrated by photo-chemical reactions
- The structure and composition of solid complexes comprising of Nd(III), Ca(II) and D-gluconate isolated from solutions relevant to radioactive waste disposal
- Separation of phenols from oils using deep eutectic solvents and ionic liquids
Artikel in diesem Heft
- Frontmatter
- In this issue
- Preface
- Selected papers from the 36th International Conference on Solution Chemistry (ICSC-36)
- Conference papers
- Using computational chemistry to explore experimental solvent parameters – solvent basicity, acidity and polarity/polarizability
- Solution chemistry in the surface region of aqueous solutions
- Water confined in solutions of biological relevance
- Real-time in-situ 1H NMR of reactions in peptide solution: preaggregation of amyloid-β fragments prior to fibril formation
- Free energy profile of permeation of Entecavir through Hepatitis B virus capsid studied by molecular dynamics calculation
- Dielectric relaxation spectroscopy: an old-but-new technique for the investigation of electrolyte solutions
- Excess spectroscopy and its applications in the study of solution chemistry
- Structure of aqueous sodium acetate solutions by X-Ray scattering and density functional theory
- Desymmetrization in geometry optimization: application to an ab initio study of copper(I) hydration
- Interactions between adsorbents and adsorbates in aqueous solutions
- Modeling vapor-liquid-liquid-solid equilibrium for acetone-water-salt system
- Apparent molar volumes of sodium arsenate aqueous solution from 283.15 K to 363.15 K at ambient pressure: an experimental and thermodynamic modeling study
- Extraction of various metal ions by open-chain crown ether bridged diphosphates in supercritical carbon dioxide
- Solvation heterogeneity in ionic liquids as demonstrated by photo-chemical reactions
- The structure and composition of solid complexes comprising of Nd(III), Ca(II) and D-gluconate isolated from solutions relevant to radioactive waste disposal
- Separation of phenols from oils using deep eutectic solvents and ionic liquids
