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Title: Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.

Abstract

Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.

Authors:
; ;  [1];  [2];  [2]
  1. (Chemical Sciences and Engineering Division)
  2. (
Publication Date:
Research Org.:
Argonne National Lab. (ANL), Argonne, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1020683
Report Number(s):
ANL/CSE/JA-69428
Journal ID: 1520-6106; TRN: US1103765
DOE Contract Number:  
DE-AC02-06CH11357
Resource Type:
Journal Article
Resource Relation:
Journal Name: J. Phys. Chem. B; Journal Volume: 115; Journal Issue: 14 ; Apr. 14, 2011
Country of Publication:
United States
Language:
ENGLISH
Subject:
11 NUCLEAR FUEL CYCLE AND FUEL MATERIALS; AQUEOUS SOLUTIONS; CHLOROFORM; CROWN ETHERS; ION EXCHANGE; IONIZATION; MOLTEN SALTS; NITRIC ACID; NUCLEAR FUELS; NUCLEAR MAGNETIC RESONANCE; PROTONS; REPROCESSING; SPECTROSCOPY; WATER

Citation Formats

Marin, T., Shkrob, I., Dietz, M., Benedictine Univ.), and Univ. of Wisconsin at Milwaukee). Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.. United States: N. p., 2011. Web. doi:10.1021/jp201193f.
Marin, T., Shkrob, I., Dietz, M., Benedictine Univ.), & Univ. of Wisconsin at Milwaukee). Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.. United States. doi:10.1021/jp201193f.
Marin, T., Shkrob, I., Dietz, M., Benedictine Univ.), and Univ. of Wisconsin at Milwaukee). Thu . "Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.". United States. doi:10.1021/jp201193f.
@article{osti_1020683,
title = {Hydrogen-bonding interactions and protic equilibria in room-temperature ionic liquids containing crown ethers.},
author = {Marin, T. and Shkrob, I. and Dietz, M. and Benedictine Univ.) and Univ. of Wisconsin at Milwaukee)},
abstractNote = {Nuclear magnetic resonance (NMR) spectroscopy has been used to study hydrogen-bonding interactions between water, associated and dissociated acids (i.e., nitric and methanesulfonic acids), and the constituent ions of several water-immiscible room-temperature ionic liquids (ILs). In chloroform solutions also containing a crown ether (CE), water molecules strongly associate with the IL ions, and there is rapid proton exchange between these bound water molecules and hydronium associated with the CE. In neat ILs, the acids form clusters differing in their degree of association and ionization, and their interactions with the CEs are weak. The CE can either promote proton exchange between different clusters in IL solution when their association is weak or inhibit such exchange when the association is strong. Even strongly hydrophobic ILs are shown to readily extract nitric acid from aqueous solution, typically via the formation of a 1:1:1 {l_brace}H{sub 3}O{sup +} {center_dot} CE{r_brace}NO{sub 3}{sup -} complex. In contrast, the extraction of methanesulfonic acid is less extensive and proceeds mainly by IL cation-hydronium ion exchange. The relationship of these protic equilibria to the practical application of hydrophobic ILs (e.g., in spent nuclear fuel reprocessing) is discussed.},
doi = {10.1021/jp201193f},
journal = {J. Phys. Chem. B},
number = 14 ; Apr. 14, 2011,
volume = 115,
place = {United States},
year = {Thu Apr 14 00:00:00 EDT 2011},
month = {Thu Apr 14 00:00:00 EDT 2011}
}