Thermodynamics of the ion association of potassium cobalt(III) bis(1,2-dicarbollide) in acetonitrile, methanol and dimethyl sulfoxide

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F00216208%3A11310%2F23%3A10471106" target="_blank" >RIV/00216208:11310/23:10471106 - isvavai.cz</a>

Výsledek na webu

<a href="https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=wy6otDHvqJ" target="_blank" >https://verso.is.cuni.cz/pub/verso.fpl?fname=obd_publikace_handle&handle=wy6otDHvqJ</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.molliq.2023.123234" target="_blank" >10.1016/j.molliq.2023.123234</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Thermodynamics of the ion association of potassium cobalt(III) bis(1,2-dicarbollide) in acetonitrile, methanol and dimethyl sulfoxide

Popis výsledku v původním jazyce

The molar conductivities, Λ, of dilute solutions of potassium cobalt(III) bis(1,2-dicarbollide) (K[COSAN]) in methanol (MeOH), acetonitrile (MeCN) and dimethyl sulfoxide (DMSO) were determined at different temperature ranges. The data were analysed in the frame of Barthel&apos;s low-concentration chemical model (lcCM) to obtain the limiting molar conductivities,Λoo, and standard association constants, KAo, of K[COSAN]. To confirm the ion association of oppositely charged ions K+ and [COSAN]-, molecular dynamics (MD) simulations were performed, in which the values of KAo from the potential of the mean force between the pair of particles (ions) were determined. From temperature dependence of KAo, the thermodynamic parameters for ion association, namely standard free enthalpy ΔGAo, enthalpy ΔHAo, and entropy ΔSAo, were estimated. The dilution enthalpies of concentrated solutions of K[COSAN] in organic solvents were also determined by using isothermal titration calorimetry (ITC). Our experimental results show that K+ and [COSAN]- ions form ion pairs in all the investigated solvents. Ion association is most pronounced in MeOH and MeCN and the least expressed in DMSO, the process is endothermic and is accompanied by an increase in entropy. The agreement between the calculated values of KAo and the thermodynamic parameters obtained by conductivity and MD simulations follow the same trend.

Název v anglickém jazyce

Thermodynamics of the ion association of potassium cobalt(III) bis(1,2-dicarbollide) in acetonitrile, methanol and dimethyl sulfoxide

Popis výsledku anglicky

The molar conductivities, Λ, of dilute solutions of potassium cobalt(III) bis(1,2-dicarbollide) (K[COSAN]) in methanol (MeOH), acetonitrile (MeCN) and dimethyl sulfoxide (DMSO) were determined at different temperature ranges. The data were analysed in the frame of Barthel&apos;s low-concentration chemical model (lcCM) to obtain the limiting molar conductivities,Λoo, and standard association constants, KAo, of K[COSAN]. To confirm the ion association of oppositely charged ions K+ and [COSAN]-, molecular dynamics (MD) simulations were performed, in which the values of KAo from the potential of the mean force between the pair of particles (ions) were determined. From temperature dependence of KAo, the thermodynamic parameters for ion association, namely standard free enthalpy ΔGAo, enthalpy ΔHAo, and entropy ΔSAo, were estimated. The dilution enthalpies of concentrated solutions of K[COSAN] in organic solvents were also determined by using isothermal titration calorimetry (ITC). Our experimental results show that K+ and [COSAN]- ions form ion pairs in all the investigated solvents. Ion association is most pronounced in MeOH and MeCN and the least expressed in DMSO, the process is endothermic and is accompanied by an increase in entropy. The agreement between the calculated values of KAo and the thermodynamic parameters obtained by conductivity and MD simulations follow the same trend.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10403 - Physical chemistry

Projekt

<a href="/cs/project/GF21-20008K" target="_blank" >GF21-20008K: Metallakarboranové klastry pro přípravu funkčních nanostruktur a polymerních materiálů</a><br>

Návaznosti

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

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Journal of Molecular Liquids

ISSN

0167-7322

e-ISSN

1873-3166

Svazek periodika

391

Číslo periodika v rámci svazku

Part A, December

Stát vydavatele periodika

NL - Nizozemsko

Počet stran výsledku

7

Strana od-do

123234

Kód UT WoS článku

001103874800002

EID výsledku v databázi Scopus

2-s2.0-85173811682