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National Repository of Grey Literature
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Mechanism of the Water Clusters Formation in the Organic Phase in the Presence of Hydrated Ions
Holub, Karel
;
Samec, Zdeněk
;
Mareček, Vladimír
A two-electrode cell comprising a liquid/liquid interface is used to study the water clusters formation in the organic solvent phase following the extraction of tetraalkylammonium chloride (TAACl) from the aqueous phase. The change in the concentration of the common TAA+ ion on the aqueous side of the interface is monitored by the open circuit potential measurements. It is shown that the amount of TAACl extracted into the organic phase exceeds considerably the limit determined by the concentration of Cl- in the organic phase at a given interfacial potential difference and the electroneutrality condition. A mechanism is proposed including an accumulation of the excess TAACl in the water clusters formed from the hydration shell of the Cl- ions, water already dissolved in the organic phase, and additional water extracted from the aqueous phase. At higher concentration of TAACl in the aqueous phase this process leads to the formation of emulsion in the organic phase.
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Electrochemical Monitoring of the Water Clusters Formation in an Organic Solvent in the Presence of Hydrated Ions
Mareček, Vladimír
An electrochemical method has been developed that makes it possible to monitor the\ndynamics of the co-extraction of water with hydrated chloride ions at the interface between\ntwo immiscible electrolyte solutions (ITIES). The interfacial potential was controlled by the\ndistribution of a common tetralkylammonium (TAA+) ion. Changes in the TAA+\nconcentration at the interface were monitored by measuring the open circuit potential (OCP).\nTransfer of hydrated chloride ions is accompanied by the transfer of TAA+, decreasing its\nconcentration on the aqueous side of the interface. This process involves the co-extraction of\nwater molecules with the hydrated chloride ions and the formation of water clusters in the\norganic solvent phase. The ability to monitor the process from the very beginning of interface\nformation allowed us to obtain important kinetic data.
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Determination of the Rate of Tetraethylammonium Ion Transfer across the\nWater/1,2-DCE Interface with Steady-State Voltammetry at a Nano-ITIES
Silver, Barry Richard
;
Holub, Karel
;
Mareček, Vladimír
The rate of TEA+ ion transfer across the water/1,2-dichloroethane interface has been\nmeasured using steady-state cyclic voltammetry at a capillary with an orifice of nano-sized\ndimension. It was found that the average rate constant for TEA+ transfer from water to oil and\nfrom oil to water is 0.64 cm/s. The results are repeatable using the same capillary. This value\nis similar to that measured previously using electrochemical impedance spectroscopy and\nfluctuation analysis at the micro-interface.
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