Predicting the Thermodynamics of Ionic Liquids: What to Expect from PC-SAFT and COSMO-RS?

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22340%2F22%3A43924909" target="_blank" >RIV/60461373:22340/22:43924909 - isvavai.cz</a>

Výsledek na webu

<a href="https://doi.org/10.1021/acs.jpcb.2c00685" target="_blank" >https://doi.org/10.1021/acs.jpcb.2c00685</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1021/acs.jpcb.2c00685" target="_blank" >10.1021/acs.jpcb.2c00685</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Predicting the Thermodynamics of Ionic Liquids: What to Expect from PC-SAFT and COSMO-RS?

Popis výsledku v původním jazyce

Two popular thermodynamic modeling frameworks, namely, the PC-SAFT equation of state and the COSMO-RS model, are benchmarked for their performance in predicting the thermodynamic properties of pure ionic liquids (ILs) and the solubility of CO2in ILs. The ultimate goal is to provide an illustration of what to expect from these frameworks when applied to ILs in a purely predictive way with established parametrization approaches, since the literature generally lacks their mutual comparisons. Two different modeling approaches with respect to the description of the molecular structure of ILs are tested within both models: a cation-anion pair as (i) a single electroneutral supermolecule and (ii) a pair of separately modeled counterions (ion-based approach). In general, we illustrate that special attention should be paid when estimating unknown thermodynamic data of ILs even with these two progressive thermodynamic frameworks. For both PC-SAFT and COSMO-RS, the supermolecule approach generally yields better results for the vapor pressure and the vaporization enthalpy of pure ILs, while the ion-based approach is found to be more suitable for the solubility of CO2. In spite of some shortcomings, COSMO-RS with the supermolecule approach shows the best overall predictive capabilities for the studied properties. The ion-based strategy within both models has significant limitations in the case of the vaporization properties of ILs. In COSMO-RS, these limitations can, to a certain extent, be surpassed by additional quantum mechanical calculations of the ion pairing in the gas phase, while the ion-based PC-SAFT approach still needs a sophisticated improvement to be developed. As an initiating point, we explore one possible and simple route considering a high degree of cross associations between the counterions in the gas phase. © 2022 American Chemical Society. All rights reserved.

Název v anglickém jazyce

Predicting the Thermodynamics of Ionic Liquids: What to Expect from PC-SAFT and COSMO-RS?

Popis výsledku anglicky

Two popular thermodynamic modeling frameworks, namely, the PC-SAFT equation of state and the COSMO-RS model, are benchmarked for their performance in predicting the thermodynamic properties of pure ionic liquids (ILs) and the solubility of CO2in ILs. The ultimate goal is to provide an illustration of what to expect from these frameworks when applied to ILs in a purely predictive way with established parametrization approaches, since the literature generally lacks their mutual comparisons. Two different modeling approaches with respect to the description of the molecular structure of ILs are tested within both models: a cation-anion pair as (i) a single electroneutral supermolecule and (ii) a pair of separately modeled counterions (ion-based approach). In general, we illustrate that special attention should be paid when estimating unknown thermodynamic data of ILs even with these two progressive thermodynamic frameworks. For both PC-SAFT and COSMO-RS, the supermolecule approach generally yields better results for the vapor pressure and the vaporization enthalpy of pure ILs, while the ion-based approach is found to be more suitable for the solubility of CO2. In spite of some shortcomings, COSMO-RS with the supermolecule approach shows the best overall predictive capabilities for the studied properties. The ion-based strategy within both models has significant limitations in the case of the vaporization properties of ILs. In COSMO-RS, these limitations can, to a certain extent, be surpassed by additional quantum mechanical calculations of the ion pairing in the gas phase, while the ion-based PC-SAFT approach still needs a sophisticated improvement to be developed. As an initiating point, we explore one possible and simple route considering a high degree of cross associations between the counterions in the gas phase. © 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

<a href="/cs/project/GJ19-04150Y" target="_blank" >GJ19-04150Y: Kohezní vlastnosti a fázové rovnováhy iontových kapalin studovány přesnými výpočty a experimenty</a><br>

Návaznosti

P - Projekt vyzkumu a vyvoje financovany z verejnych zdroju (s odkazem do CEP)

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 B

ISSN

1520-6106

e-ISSN

1520-5207

Svazek periodika

126

Číslo periodika v rámci svazku

20

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

20

Strana od-do

3717-3736

Kód UT WoS článku

000806447100010

EID výsledku v databázi Scopus

2-s2.0-85131043325