The effect of alkyl-chain branching on the hydration and ion association of tetrabutylammonium cations

Moreno-Gomez, Nicolas and Vargas, Edgar F. and Buchner, Richard (2017) The effect of alkyl-chain branching on the hydration and ion association of tetrabutylammonium cations. JOURNAL OF MOLECULAR LIQUIDS, 248. pp. 586-594. ISSN 0167-7322, 1873-3166

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Abstract

Association constants and single-ion conductivities of the bromide salts of five isomeric tetrabutylammonium ions were determined with dilute-solution conductivity measurements for aqueous solutions at 298.15 K. In addition, for two of the isomers dielectric relaxation experiments were performed. It was found that, despite similar size of all cations, the hydrodynamic radii of the branched isomers were significantly smaller than that of the un-branched Bu4N(+) species. It appears that the more compact branched cations exert only a minor perturbation on the H-bond network of the surrounding solvent and easily strip off their hydration shell. This effect, and the-on average-closer approach between anions and cations in ion pairs of Bu-2 isoBu(2)NBr and isoBu(4)NBr probably explain the rather large association constants of the latter salts. (C) 2017 Elsevier B.V. All rights reserved.

Item Type: Article
Uncontrolled Keywords: QUATERNARY AMMONIUM-COMPOUNDS; DIELECTRIC-RELAXATION SPECTROSCOPY; AQUEOUS-SOLUTIONS; HYDROPHOBIC HYDRATION; ELECTROLYTE-SOLUTIONS; TETRAALKYLAMMONIUM HALIDES; NEUTRON-SCATTERING; WATER MIXTURES; DYNAMICS; CONDUCTANCE; Dielectric relaxation; Tetrabutylammonium bromide; Electrical molar conductivities; Ion solvation; Ion association; Isomers
Subjects: 500 Science > 540 Chemistry & allied sciences
Divisions: Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie
Chemistry and Pharmacy > Institut für Physikalische und Theoretische Chemie > Chair of Chemistry VI - Physical Chemistry (Solution Chemistry) > PD Dr. Richard Buchner
Depositing User: Dr. Gernot Deinzer
Date Deposited: 14 Dec 2018 13:19
Last Modified: 18 Feb 2019 12:23
URI: https://pred.uni-regensburg.de/id/eprint/1733

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