Hydrogen bond redistribution effects in mixtures of protic ionic liquids sharing the same cation: non-ideal mixing with large negative mixing enthalpies

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F22%3A43924483" target="_blank" >RIV/60461373:22340/22:43924483 - isvavai.cz</a>

Výsledek na webu

<a href="https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP01209J" target="_blank" >https://pubs.rsc.org/en/content/articlelanding/2022/CP/D2CP01209J</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1039/d2cp01209j" target="_blank" >10.1039/d2cp01209j</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Hydrogen bond redistribution effects in mixtures of protic ionic liquids sharing the same cation: non-ideal mixing with large negative mixing enthalpies

Popis výsledku v původním jazyce

We report a joint experimental and theoretical study characterising the hydrogen bond (HB) redistribution in mixtures of two different protic ionic liquids (PILs) sharing the same cation: triethylammonium-methanesulfonate ([TEA][OMs]) and triethylammonium-trifluoromethanesulfonate ([TEA][OTf]). The mixing behaviour deviates strongly from ideality, exhibiting large negative energies of mixing. In the PIL, the [TEA] cation acts as a HB donor, being able to donate a single HB. Both, the [OMs] and the [OTf] anions can act as HB acceptors, which can accept multiple HBs via their respective SO3-groups. We use a combination of molecular dynamics (MD) simulations, calorimetry, and 1H-NMR chemical shift measurements to determine the difference in HB strength between the two species to be about 13 kJ mol−1, favouring the [TEA]-[OMs] interaction. Based on our MD simulations we are able to formulate 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 mixing energies by a simple relation, which is obeyed by both, MD-simulation as well as experimental calorimetry and 1H-NMR chemical shift data. © 2022 The Royal Society of Chemistry.

Název v anglickém jazyce

Hydrogen bond redistribution effects in mixtures of protic ionic liquids sharing the same cation: non-ideal mixing with large negative mixing enthalpies

Popis výsledku anglicky

We report a joint experimental and theoretical study characterising the hydrogen bond (HB) redistribution in mixtures of two different protic ionic liquids (PILs) sharing the same cation: triethylammonium-methanesulfonate ([TEA][OMs]) and triethylammonium-trifluoromethanesulfonate ([TEA][OTf]). The mixing behaviour deviates strongly from ideality, exhibiting large negative energies of mixing. In the PIL, the [TEA] cation acts as a HB donor, being able to donate a single HB. Both, the [OMs] and the [OTf] anions can act as HB acceptors, which can accept multiple HBs via their respective SO3-groups. We use a combination of molecular dynamics (MD) simulations, calorimetry, and 1H-NMR chemical shift measurements to determine the difference in HB strength between the two species to be about 13 kJ mol−1, favouring the [TEA]-[OMs] interaction. Based on our MD simulations we are able to formulate 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 mixing energies by a simple relation, which is obeyed by both, MD-simulation as well as experimental calorimetry and 1H-NMR chemical shift data. © 2022 The Royal Society of Chemistry.

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

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

—

Svazek periodika

24

Číslo periodika v rámci svazku

24

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

11

Strana od-do

14740-14750

Kód UT WoS článku

000797955800001

EID výsledku v databázi Scopus

2-s2.0-85132647190