Balance between contact and solvent-separated ion pairs in mixtures of the protic ionic liquid [et3nh][meso3] with water controlled by water content and temperature
The result's identifiers
Result code in IS VaVaI
<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F21%3A43922686" target="_blank" >RIV/60461373:22340/21:43922686 - isvavai.cz</a>
Result on the web
<a href="https://pubs.acs.org/doi/10.1021/acs.jpcb.1c01850" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpcb.1c01850</a>
DOI - Digital Object Identifier
<a href="http://dx.doi.org/10.1021/acs.jpcb.1c01850" target="_blank" >10.1021/acs.jpcb.1c01850</a>
Alternative languages
Result language
angličtina
Original language name
Balance between contact and solvent-separated ion pairs in mixtures of the protic ionic liquid [et3nh][meso3] with water controlled by water content and temperature
Original language description
The formation of aggregates of ionic species is a crucial process in liquids and solutions. Ion speciation is particularly interesting for the case of ionic liquids (ILs) since these Coulombic fluids consist solely of ions. Most of their unique properties, such as enthalpies of vaporization and conductivities, are strongly related to ion pair formation. Here, we show that the balance of hydrogen-bonded contact ion pairs (CIP) and solvent-separated (SIP) ion pairs in protic ionic liquids (PILs) and in their mixtures with water can be well understood by a combination of far-infrared (FIR) and mid-infrared (MIR) spectroscopy, density functional theory (DFT) calculations of PIL/water aggregates, and molecular dynamics (MD) simulations of PIL/water mixtures. This combined approach is applied to mixtures of triethylammonium methanesulfonate [Et3NH][MeSO3] with water. It is shown that ion speciation in this mixture depends on three parameters: The relative hydrogen bond acceptor strength of the counter ion and the molecular solvent, the solvent concentration, and the temperature. For selected PIL/water mixtures, the equilibrium constants for CIPs and SIPs were determined as a function of the solvent content and temperature. Finally, for the studied PIL/water mixtures, the transition from CIPs to SIPs could be understood on enthalpic and entropic grounds. A detailed picture of this interconversion process could be described at the molecular level by means of MD simulations. In addition, the concentration dependence of ion pair formation can be well understood with help of a simplified "cartoon-like" statistical model describing hydrogen bond redistribution. © 2021 American Chemical Society. All rights reserved.
Czech name
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Czech description
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Classification
Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10403 - Physical chemistry
Result continuities
Project
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Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace
Others
Publication year
2021
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů
Data specific for result type
Name of the periodical
Journal of Physical Chemistry B
ISSN
1520-6106
e-ISSN
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Volume of the periodical
125
Issue of the periodical within the volume
17
Country of publishing house
US - UNITED STATES
Number of pages
13
Pages from-to
4476-4488
UT code for WoS article
000648870900022
EID of the result in the Scopus database
2-s2.0-85105970619