Why Do Liquids Mix? the Mixing of Protic Ionic Liquids Sharing the Same Cation Is Apparently Driven by Enthalpy, Not Entropy

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F22%3A43924482" target="_blank" >RIV/60461373:22340/22:43924482 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.acs.org/doi/10.1021/acs.jpclett.2c00634" target="_blank" >https://pubs.acs.org/doi/10.1021/acs.jpclett.2c00634</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpclett.2c00634" target="_blank" >10.1021/acs.jpclett.2c00634</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Why Do Liquids Mix? the Mixing of Protic Ionic Liquids Sharing the Same Cation Is Apparently Driven by Enthalpy, Not Entropy

Popis výsledku v původním jazyce

We study hydrogen bond (HB) redistribution in mixtures of two protic ionic liquids (PILs) sharing the same cation: triethylammonium methanesulfonate ([TEA][OMs]) and triethylammonium trifluoromethanesulfonate ([TEA][OTf]). The mixtures exhibit large negative energies of mixing. Based on results obtained from atomic detail molecular dynamics (MD) simulations, we derive a lattice model, discriminating between HB and nonspecific intermolecular interactions. We demonstrate that due to the ordered structure of the PILs, mostly the HB interactions contribute to the mixing energy. This allows to us to connect the equilibrium of HBs to each of the two anion species with the corresponding excess energies and entropies. The entropy associated with HB redistribution is shown to be negative, and even overcompensating the positive entropy associated with a statistical distribution of the ions in the mixture. This is strongly suggesting that the mixing process is driven by enthalpy, not entropy. © 2022 American Chemical Society. All rights reserved.

Název v anglickém jazyce

Why Do Liquids Mix? the Mixing of Protic Ionic Liquids Sharing the Same Cation Is Apparently Driven by Enthalpy, Not Entropy

Popis výsledku anglicky

We study hydrogen bond (HB) redistribution in mixtures of two protic ionic liquids (PILs) sharing the same cation: triethylammonium methanesulfonate ([TEA][OMs]) and triethylammonium trifluoromethanesulfonate ([TEA][OTf]). The mixtures exhibit large negative energies of mixing. Based on results obtained from atomic detail molecular dynamics (MD) simulations, we derive a lattice model, discriminating between HB and nonspecific intermolecular interactions. We demonstrate that due to the ordered structure of the PILs, mostly the HB interactions contribute to the mixing energy. This allows to us to connect the equilibrium of HBs to each of the two anion species with the corresponding excess energies and entropies. The entropy associated with HB redistribution is shown to be negative, and even overcompensating the positive entropy associated with a statistical distribution of the ions in the mixture. This is strongly suggesting that the mixing process is driven by enthalpy, not entropy. © 2022 American Chemical Society. All rights reserved.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

—

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2022

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

Journal of Physical Chemistry Letters

ISSN

1948-7185

e-ISSN

—

Svazek periodika

13

Číslo periodika v rámci svazku

16

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

6

Strana od-do

3556-3561

Kód UT WoS článku

000795879200005

EID výsledku v databázi Scopus

2-s2.0-85129091654