Halogenation thermodynamics of pyrrolidinium-based ionic liquids

Halogenation thermodynamics of pyrrolidinium-based ionic liquids

Author Chaban, Vitaly Autor UNIFESP Google Scholar
Abstract Room-temperature ionic liquids (RTILs) exhibit a large difference between melting and boiling points. They are highly tunable thanks to numerous accessible combinations of the cation and the anion. On top of that, cations can be functionalized using methods of organic chemistry. This paper reports gas-phase thermodynamics (enthalpy, entropy, and Gibbs free energy) of the halogenation reactions (fluorination, chlorination, bromination) involving protonated pyrrolidine C4H10N+, protic N-ethylpyrrolidinium C4H9N(C2H5)(+), and aprotic N-ethyl-N-methylpyrrolidinium C4H8N(CH3)(C2H5)(+) cations. Substitution of all symmetrically nonequivalent hydrogen atoms was compared based of the thermodynamic favorability. Fluorination of all sites is much more favorable than chlorination, whereas chlorination is somewhat more favorable than bromination. This is not trivial, because electronegative fluorine and chlorine have to compete for the already insufficient number of electrons with other atoms belonging to the pyrrolidinium-based cations. The difference between different reaction sites within the cations is modest, although it often exceeds kT at simulated temperatures. The correlation between thermodynamics and electronic density distribution has been established, which allows new simple prediction of the reaction pathways. The reported results inspire further chemical modifications of the pyrrolidinium-based RTILs to achieve ever finer tunability of physical chemical properties.
Keywords Ternary Polymer Electrolytes
Language English
Sponsor CAPES (Brazil)
Date 2016
Published in Journal Of Chemical And Engineering Data. Washington, v. 61, n. 1, p. 228-233, 2016.
ISSN 0021-9568 (Sherpa/Romeo, impact factor)
Publisher Amer chemical soc
Extent 228-233
Origin http://dx.doi.org/10.1021/acs.jced.5b00505
Access rights Closed access
Type Article
Web of Science ID WOS:000368564600027
URI http://repositorio.unifesp.br/handle/11600/49643

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