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Sonnleitner, Thomas ; Nikitina, Viktoriya ; Nazet, Andreas ; Buchner, Richard

Do H-Bonds Explain Strong Ion Aggregation in Ethylammonium Nitrate + Acetonitrile Mixtures?

Sonnleitner, Thomas, Nikitina, Viktoriya , Nazet, Andreas und Buchner, Richard (2013) Do H-Bonds Explain Strong Ion Aggregation in Ethylammonium Nitrate + Acetonitrile Mixtures? Physical Chemistry Chemical Physics 15 (42), S. 18445-18452.

Veröffentlichungsdatum dieses Volltextes: 14 Nov 2013 06:59
Artikel
DOI zum Zitieren dieses Dokuments: 10.5283/epub.29014


Zusammenfassung

Binary mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and acetonitrile (AN) were studied at 25 degrees C over the entire composition range by means of broadband dielectric spectroscopy covering 0.2 <= n/GHz <= 89. The dielectric spectra could be decomposed into two relaxation processes, both of which proved to be composite modes. For dilute solutions the higher-frequency Debye ...

Binary mixtures of the protic ionic liquid ethylammonium nitrate (EAN) and acetonitrile (AN) were studied at 25 degrees C over the entire composition range by means of broadband dielectric spectroscopy covering 0.2 <= n/GHz <= 89. The dielectric spectra could be decomposed into two relaxation processes, both of which proved to be composite modes. For dilute solutions the higher-frequency Debye relaxation centered at similar to 60 GHz is associated with the rotational diffusion of AN molecules, whereas at higher salt concentrations ultra-fast intermolecular vibrations and librations of EAN dominate the process. For EAN-rich solutions the lower-frequency relaxation is mainly due to jump reorientation of the ethylammonium cation, whereas contact ion pairs (CIPs) dominate this mode for dilute solutions. From the relaxation amplitudes effective solvation numbers and ion-pair concentrations were determined. For vanishing EAN mole fraction, x(EAN) -> 0, an effective cation solvation number of similar to 7 was found which steeply drops until x(EAN) approximate to 0.2 but shows only moderate decrease later on. The obtained association constant for EAN, K-A(0) = 970 L mol(-1), exceeds that of other 1 : 1 electrolytes in AN by a factor of similar to 30-50. This observation, as well as the fact that CIPs are formed despite strong cation solvation, indicates that ion pairing is mainly driven by the formation of strong hydrogen bonds between anions and cations.



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Details

DokumentenartArtikel
Titel eines Journals oder einer ZeitschriftPhysical Chemistry Chemical Physics
Verlag:ROYAL SOC CHEMISTRY
Ort der Veröffentlichung:CAMBRIDGE
Band:15
Nummer des Zeitschriftenheftes oder des Kapitels:42
Seitenbereich:S. 18445-18452
Datum2013
InstitutionenChemie und Pharmazie > Institut für Physikalische und Theoretische Chemie
Chemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Lehrstuhl für Chemie IV - Physikalische Chemie (Solution Chemistry)
Chemie und Pharmazie > Institut für Physikalische und Theoretische Chemie > Lehrstuhl für Chemie IV - Physikalische Chemie (Solution Chemistry) > PD Dr. Richard Buchner
Identifikationsnummer
WertTyp
10.1039/c3cp51773jDOI
Stichwörter / KeywordsDIELECTRIC-RELAXATION SPECTROSCOPY; AQUEOUS-ELECTROLYTE-SOLUTIONS; WATER MIXTURES; SOLVATION DYNAMICS; POLAR SOLVATION; BINARY-MIXTURES; LIQUIDS; SYSTEM; ASSOCIATION; SOLVENTS;
Dewey-Dezimal-Klassifikation500 Naturwissenschaften und Mathematik > 540 Chemie
StatusVeröffentlicht
BegutachtetJa, diese Version wurde begutachtet
An der Universität Regensburg entstandenJa
URN der UB Regensburgurn:nbn:de:bvb:355-epub-290140
Dokumenten-ID29014

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