Preparation of protic ionic liquids with minimal water content and (15)N NMR study of proton transfer.

Autor: Burrell GL; School of Chemistry, The University of Melbourne, Melbourne, VIC 3010, Australia., Burgar IM, Separovic F, Dunlop NF
Jazyk: angličtina
Zdroj: Physical chemistry chemical physics : PCCP [Phys Chem Chem Phys] 2010 Feb 21; Vol. 12 (7), pp. 1571-7. Date of Electronic Publication: 2010 Jan 12.
DOI: 10.1039/b921432a
Abstrakt: Low-molecular-weight Brønsted acids and amine bases were used to reproducibly prepare very dry, high-purity room-temperature protic ionic liquids (PILs). A series of eight amine bases and six Brønsted acids were combined to produce 48 mixtures, of which 18 were liquid at room temperature. The phase transitions and thermal decomposition temperatures were determined for each mixture; whereas viscosity, density and conductivity were determined for the room-temperature liquids. By utilising (15)N NMR it was possible to distinguish between neutral and ionised amine bases (ammonia vs. ammonium-type ion), which indicated that the protic ionic liquids were completely ionised when made as a stoichiometric mixture. However, a Walden plot comparison of fluidity and molar conductivity indicated the majority of PILs had much lower conductivity than predicted by viscosity unless the base contained excess proton-donating groups. This disparity is indicative of protic ionic molecules forming neutral aggregates or non-Newtonian fluid hydrogen-bonded networks with a secondary Grotthuss proton-hopping mechanism arising from polyprotic bases.
Databáze: MEDLINE