Mechanism and rate of anomalous extraction of chloride salts from water to 1,2-dichloroethane

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F24%3A00587478" target="_blank" >RIV/61388955:_____/24:00587478 - isvavai.cz</a>

Výsledek na webu

<a href="https://www.sciencedirect.com/science/article/pii/S001346862400882X" target="_blank" >https://www.sciencedirect.com/science/article/pii/S001346862400882X</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1016/j.electacta.2024.144642" target="_blank" >10.1016/j.electacta.2024.144642</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Mechanism and rate of anomalous extraction of chloride salts from water to 1,2-dichloroethane

Popis výsledku v původním jazyce

Open circuit potential (OCP) measurements, potentiostatic pulse (PP) amperometry and cyclic voltammetry (CV), were used to investigate and to sort by rate the anomalous extraction of the chloride salts RCl of the cations R+ = tetrabutylammonium (TBA+), tetrapentylammonium (TPeA+), tetrahexylammonium (THexA+), tetraheptylammonium (THepA+) and bis(triphenyl-phosphoranylidene)ammonium (BA+) from water to 1,2-dichloroethane (DCE). A tentative mechanism is proposed comprising (a) the diffusion-controlled transport of the ion-pairs (RCl)ip from the aqueous to the organic solvent phase providing a major contribution to the chloride extraction, (b) decomposition of the multiple ion-pairs or clusters (RCl)ipx, which are formed by agglomeration of the single ion-pairs (RCl)ip in the aqueous phase (w), and (c) the exponential decay of the ion-pairs (RCl)ip accumulated on the organic solvent side of the interface at the beginning of the OCP measurements. This model enables to simulate successfully the experimental time dependence of the chloride concentration. A conclusion is made that the effect of the composition of the organic solvent electrolyte RX, where X- = tetraphenylborate (TPB-) or tetrakis(pentafluorophenyl) borate (TB-), on the rate and extent of the anomalous accumulation of the chloride anion in the phase (o) of the two-phase liquid system LiCl(w)/RX(o) can be related to the hydrophobicity of the electrolytes RCl and RX. The latter property can be characterized by the standard Gibbs energy of transfer from the aqueous (w) to the organic solvent (o) phase. The accumulation of the chloride anion in the phase (o) appears to be promoted by the decreasing value of the transfer Gibbs energy of RCl in the sequence TBACl > TPeACl > THexACl > THepACl > BACl, while the decreasing value of the transfer Gibbs energy of RX in the sequence TBATPB > TPeATPB > THexATPB > THepATPB > BATPB > BATB starts to block the cycle combining the energetically unfavorable extraction of RX from the phase (o) to the phase (w) with the energetically favorable extraction of RCl in the opposite direction. IR spectroscopy provides evidence of the formation of the water clusters in the organic solvent phase equilibrated with the aqueous phase in the presence of the tetraalkylammonium cation in both phases, which are supposed to drive the anomalous accumulation of the chloride anion in the phase (o).

Název v anglickém jazyce

Mechanism and rate of anomalous extraction of chloride salts from water to 1,2-dichloroethane

Popis výsledku anglicky

Open circuit potential (OCP) measurements, potentiostatic pulse (PP) amperometry and cyclic voltammetry (CV), were used to investigate and to sort by rate the anomalous extraction of the chloride salts RCl of the cations R+ = tetrabutylammonium (TBA+), tetrapentylammonium (TPeA+), tetrahexylammonium (THexA+), tetraheptylammonium (THepA+) and bis(triphenyl-phosphoranylidene)ammonium (BA+) from water to 1,2-dichloroethane (DCE). A tentative mechanism is proposed comprising (a) the diffusion-controlled transport of the ion-pairs (RCl)ip from the aqueous to the organic solvent phase providing a major contribution to the chloride extraction, (b) decomposition of the multiple ion-pairs or clusters (RCl)ipx, which are formed by agglomeration of the single ion-pairs (RCl)ip in the aqueous phase (w), and (c) the exponential decay of the ion-pairs (RCl)ip accumulated on the organic solvent side of the interface at the beginning of the OCP measurements. This model enables to simulate successfully the experimental time dependence of the chloride concentration. A conclusion is made that the effect of the composition of the organic solvent electrolyte RX, where X- = tetraphenylborate (TPB-) or tetrakis(pentafluorophenyl) borate (TB-), on the rate and extent of the anomalous accumulation of the chloride anion in the phase (o) of the two-phase liquid system LiCl(w)/RX(o) can be related to the hydrophobicity of the electrolytes RCl and RX. The latter property can be characterized by the standard Gibbs energy of transfer from the aqueous (w) to the organic solvent (o) phase. The accumulation of the chloride anion in the phase (o) appears to be promoted by the decreasing value of the transfer Gibbs energy of RCl in the sequence TBACl > TPeACl > THexACl > THepACl > BACl, while the decreasing value of the transfer Gibbs energy of RX in the sequence TBATPB > TPeATPB > THexATPB > THepATPB > BATPB > BATB starts to block the cycle combining the energetically unfavorable extraction of RX from the phase (o) to the phase (w) with the energetically favorable extraction of RCl in the opposite direction. IR spectroscopy provides evidence of the formation of the water clusters in the organic solvent phase equilibrated with the aqueous phase in the presence of the tetraalkylammonium cation in both phases, which are supposed to drive the anomalous accumulation of the chloride anion in the phase (o).

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

<a href="/cs/project/GA22-32631S" target="_blank" >GA22-32631S: Anomální extrakce solí z vody do organického rozpouštědla: Nový mechanismus spontánní emulzifikace a praktická aplikace</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2024

Kód důvěrnosti údajů

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

Název periodika

Electrochimica acta

ISSN

0013-4686

e-ISSN

1873-3859

Svazek periodika

498

Číslo periodika v rámci svazku

SEP 2024

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

9

Strana od-do

144642

Kód UT WoS článku

001267414700001

EID výsledku v databázi Scopus

2-s2.0-85197652311