Estimation of Medium Effects for Single Ions in Non-Aqueous Solvents

Popovych, Orest; Bates, Roger G.

doi:10.1080/10408347008542592

Cited by 31 publications

(9 citation statements)

References 52 publications

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“…Establishing these anchor points can be carried out by different methods75—all based on extra thermodynamic assumptions—and a sizable number of which has been collected by Marcus 76. 77…”

Section: The Absolute Redox Potentialmentioning

confidence: 99%

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The Protoelectric Potential Map (PPM): An Absolute Two‐Dimensional Chemical Potential Scale for a Global Understanding of Chemistry

Radtke

Himmel

Pütz

et al. 2014

Chemistry A European J

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We introduce the protoelectric potential map (PPM) as a novel, two-dimensional plot of the absolute reduction potential (peabs scale) combined with the absolute protochemical potential (Brønsted acidity: pHabs scale). The validity of this thermodynamically derived PPM is solvent-independent due to the scale zero points, which were chosen as the ideal electron gas and the ideal proton gas at standard conditions. To tie a chemical environment to these reference states, the standard Gibbs energies for the transfer of the gaseous electrons/protons to the medium are needed as anchor points. Thereby, the thermodynamics of any redox, acid-base or combined system in any medium can be related to any other, resulting in a predictability of reactions even over different media or phase boundaries. Instruction is given on how to construct the PPM from the anchor points derived and tabulated with this work. Since efforts to establish "absolute" reduction potential scales and also "absolute" pH scales already exist, a short review in this field is given and brought into relation to the PPM. Some comments on the electrochemical validation and realization conclude this concept article.

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Section: The Absolute Redox Potentialmentioning

confidence: 99%

“…In the literature, the discussion of the physical significance of single ion activities is still ongoing 115–119. An older, but nevertheless substantial and still valid overview can be found by Popovych 75…”

Section: Appendix With Auxiliary Relationsmentioning

confidence: 99%

The Protoelectric Potential Map (PPM): An Absolute Two‐Dimensional Chemical Potential Scale for a Global Understanding of Chemistry

Radtke

Himmel

Pütz

et al. 2014

Chemistry A European J

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“…[23] Several extrathermodynamic assumptions have been applied to determine the transfer thermodynamics of individual ions. [24][25][26][27] Quantum chemical approaches to calculate Brønsted acidity in the liquid phase: According to Scheme 1, the thermodynamic relation between acidity in the gas phase and in solution is expressed by the Gibbs solvation energies of the acid, its conjugate base, and the proton. For the well-established gas-phase acidity scale the agreement between experiment and theory is within some kJ mol…”

mentioning

confidence: 99%

Anchor Points for the Unified Brønsted Acidity Scale: The rCCC Model for the Calculation of Standard Gibbs Energies of Proton Solvation in Eleven Representative Liquid Media

Himmel

Goll

Leito

et al. 2011

Chemistry A European J

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The COSMO cluster-continuum (CCC) solvation model is introduced for the calculation of standard Gibbs solvation energies of protons. The solvation sphere of the proton is divided into an inner proton-solvent cluster with covalent interactions and an outer solvation sphere that interacts electrostatically with the cluster. Thus, the solvation of the proton is divided into two steps that are calculated separately: 1) The interaction of the proton with one or more solvent molecules is calculated in the gas phase with high-level quantum-chemical methods (modified G3 method). 2) The Gibbs solvation energy of the proton-solvent cluster is calculated by using the conductor-like screening model (COSMO). For every solvent, the solvation of the proton in at least two (and up to 11) proton-solvent clusters was calculated. The resulting Gibbs solvation energies of the proton were weighted by using Boltzmann statistics. The model was evaluated for the calculation of Gibbs solvation energies by using experimental data of water, MeCN, and DMSO as a reference. Allowing structural relaxation of the proton-solvent clusters and the use of structurally relaxed Gibbs solvation energies improved the accordance with experimental data especially for larger clusters. This variation is denoted as the relaxed COSMO cluster-continuum (rCCC) model, for which we estimate a 1σ error bar of 10 kJ mol(-1) . Gibbs solvation energies of protons in the following representative solvents were calculated: Water, acetonitrile, sulfur dioxide, dimethyl sulfoxide, benzene, diethyl ether, methylene chloride, 1,2-dichloroethane, sulfuric acid, fluorosulfonic acid, and hydrogen fluoride. The obtained values are absolute chemical standard potentials of the proton (pH=0 in this solvent). They are used to anchor the individual solvent specific acidity (pH) scales to our recently introduced absolute acidity scale.

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“…[15][16][17][18][19] In recent years, commercialization of some of these processes has been initiated by major chemical companies as well as by new, IL-focused startups, with several pilot plants already constructed. While there is a significant body of work concerning Brønsted acids in nonaqueous solvents, [22][23][24] the behavior of acids in ILs and how that behavior may vary with the identity of the acid and/or the IL has been difficult to predict. While there is a significant body of work concerning Brønsted acids in nonaqueous solvents, [22][23][24] the behavior of acids in ILs and how that behavior may vary with the identity of the acid and/or the IL has been difficult to predict.…”

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confidence: 99%

Spectroscopic determination of relative Brønsted acidity as a predictor of reactivity in aprotic ionic liquids

2015

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Estimation of Medium Effects for Single Ions in Non-Aqueous Solvents

Cited by 31 publications

References 52 publications

The Protoelectric Potential Map (PPM): An Absolute Two‐Dimensional Chemical Potential Scale for a Global Understanding of Chemistry

The Protoelectric Potential Map (PPM): An Absolute Two‐Dimensional Chemical Potential Scale for a Global Understanding of Chemistry

Anchor Points for the Unified Brønsted Acidity Scale: The rCCC Model for the Calculation of Standard Gibbs Energies of Proton Solvation in Eleven Representative Liquid Media

Spectroscopic determination of relative Brønsted acidity as a predictor of reactivity in aprotic ionic liquids

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