Thermodynamic properties of the PMMA–acetonitrile–1,4-dioxane system

Katime, Issa; Ochoa, J. R.

doi:10.1039/f19878302289

Cited by 5 publications

(1 citation statement)

References 2 publications

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“…For example, such tuning could be achieved on the one hand, e.g., using acetonitrile (ε r = 37.5) and, on the other hand, for example, 1,4-dioxane (ε r = 2.2). Binary mixtures of two solvents can be produced at any ratio allowing to continuously adjust the dielectric constant as demonstrated in refs , . Assuming solvent mixing is happening also at the nanoscale, the VDEs of Np – could be tuned between 3.05 and 1.81 eV while those of Bp – could be tuned between 3.83 and 2.76 eV using binary mixtures of different ratios of acetonitrile and 1,4-dioxane.…”

Section: Discussionmentioning

confidence: 99%

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Nemirovich,

Young,

Brezina

et al. 2024

J. Am. Chem. Soc.

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We investigate the electronic structure of aromatic radical anions in the solution phase employing a combination of liquid-jet (LJ) photoelectron (PE) spectroscopy measurements and electronic structure calculations. By using recently developed protocols, we accurately determine the vertical ionization energies of valence electrons of both the solvent and the solute molecules. In particular, we first characterize the pure solvent of tetrahydrofuran (THF) by LJ-PE measurements in conjunction with ab initio molecular dynamics simulations and G 0 W 0 calculations. Next, we determine the electronic structure of neutral naphthalene (Np) and benzophenone (Bp) as well as their radical anion counterparts Np − and Bp − in THF. Wherever feasible, we performed orbital assignments of the measured PE features of the aromatic radical anions, with comparisons to UV−vis absorption spectra of the corresponding neutral molecules being instrumental in rationalizing the assignments. Analysis of the electronic structure differences between the neutral species and their anionic counterparts provides understanding of the primarily electrostatic stabilization of the radical anions in solution. Finally, we obtain a very good agreement of the reduction potentials extracted from the present LJ-PES measurements of Np − and Bp − in THF with previous electrochemical data from cyclic voltammetry measurements. In this context, we discuss how the choice of solvent holds significant implications for optimizing conditions for the Birch reduction process, wherein aromatic radical anions play crucial roles as reactive intermediates.

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Section: Discussionmentioning

confidence: 99%

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Nemirovich,

Young,

Brezina

et al. 2024

J. Am. Chem. Soc.

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Preferential interactions of poly(N‐vinyl‐2‐pyrrolidone) in the binary mixture water/CdCl₂

Gómez¹,

Blanco²,

Olmo³

et al. 1995

Polymer International

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The poly (N-vinyl-2-pyrrolidone)(PVP)(2)/water(1)/CdC1,(3) ternary system has been studied by viscometry, densimetry and atomic absorption spectrophotometry. In this system a preferential adsorption of CdZ+ at all solvent compositions studied and a conformational transition at 4 mM of salt, the concentration at which a preferential adsorption minimum of CdZ+ in exhibited, are observed. The PVP/Cd2+ bound molar ratio is 0.23. CdCl, behaves as a saltingin agent for the macromolecule. The binary solvent mixture is thermodynamically more favourable at salt concentrations greater than 10 mM of CdCl, . K e y words: viscometry, densimetry, unperturbed dimensions, preferential interactions, poly(N-vinyl-2-pyrrolidone), CdCl, .

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Anomalous behaviour of PMMA in the (methyl isobutyl ketone)/methanol system

Issa

Katime

García

et al. 1988

European Polymer Journal

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Thermodynamic properties of the PMMA–acetonitrile–1,4-dioxane system

Cited by 5 publications

References 2 publications

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Preferential interactions of poly(N‐vinyl‐2‐pyrrolidone) in the binary mixture water/CdCl₂

Anomalous behaviour of PMMA in the (methyl isobutyl ketone)/methanol system

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Thermodynamic properties of the PMMA–acetonitrile–1,4-dioxane system

Cited by 5 publications

References 2 publications

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Stability and Reactivity of Aromatic Radical Anions in Solution with Relevance to Birch Reduction

Preferential interactions of poly(N‐vinyl‐2‐pyrrolidone) in the binary mixture water/CdCl2

Anomalous behaviour of PMMA in the (methyl isobutyl ketone)/methanol system

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Preferential interactions of poly(N‐vinyl‐2‐pyrrolidone) in the binary mixture water/CdCl₂