Facilitated Ion Transfers at the Micro‐Water/1,2‐Dichloroethane Interface by Crown Ether Derivatives

Abstract

The transfers of potassium ion (K+) facilitated by 3,3′,6,6′‐tetrakis[p‐(n‐dodecyloxy)benzoyloxymethyl]dibenzo‐18‐crown‐6 (L1) and of sodium ion (Na+) facilitated by 3′,6′‐bis{3′′,4′′,5′′‐tris[p‐(n‐dodecyloxy)benzyloxy]benzoyloxymethyl}benzo‐15‐crown‐5 (L2) have been investigated at the micro‐water/1.2‐dichloroethane (micro‐W/DCE) interface supported at the tip of a micropipette by cyclic voltammetry and chronoamperometry. The experimental results demonstrate that the mechanisms of both facilitated ion transfer (FIT) processes correspond to the transfer by an interfacial complexation (TIC) and the transfer by an interfacial dissociation (TID) processes. Some thermodynamic parameters, such as, stoichiometry, diffusion coefficient and the association constants are evaluated by cyclic voltammetry. Furthermore, the chronoamperometry has been employed to explore the roughness of the interface supported at the micropipette by analysis of the current‐time curves based on the system of facilitated Na+ transfer by L2 at the water/DCE interface.

Preparation and crystal structure of tetraoctylphosphonium tetrakis(pentafluorophenyl)borate ionic liquid for electrochemistry at its interface with water

“…Conventional means of separation have been through physical mixing of the two phases [9,15]; however, as previously demonstrated [10][11][12]16], this process can also be investigated electrochemically using liquid|liquid electrochemistry performed at a polarizable interface between two immiscible electrolytic solutions (ITIES) [13,14,[17][18][19][20][21]. Furthermore, in order to reduce samples sizes and improve sensitivity, a micro-ITIES is often employed, such as at the tip of a pulled borosilicate glass capillary [11,16,[22][23][24]. In this way, facilitated ion transfer (FIT) can be studied through the three generalized mechanisms, including transfer through interfacial complexation (TIC), aqueous complexation followed by transfer, and transfer followed by complexation (TOC), and aqueous complexation followed by transfer (ACT) [13,14].…”

Electrochemical assessment of water|ionic liquid biphasic systems towards cesium extraction from nuclear waste

“…Electrochemistry at a micro-interface between two immiscible electrolytic solutions (micro-ITIES) offers a cost-effective technique for studying metal ion transfer (IT) and ligand assisted, or facilitated ion transfer (FIT) [12,14,[26][27][28], which are analogous to ion partitioning and interfacial complexation, respectively. These respective processes are shown in Eqs.…”

Recent developments in electrochemistry at the interface between two immiscible electrolyte solutions for ion sensing

“…Different fabrication strategies to prepare these µITIES exist and have been reviewed elsewhere. 20,22 ITIES of microscopic dimensions are now routinely used under the form of a single µITIES [43][44][45][46][47][48]37,[49][50][51] ( Figure 1D) or of an array of µITIES [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] ( Figure 1E) allowing to reach limits of detection in the range of tens of nM with an analysis time of a couple of minutes. Diffusion of ionic species at µITIES has shown an asymmetric profile.…”

“…31,32,86 This experimental set-up could be used for the calibration-free determination of ion Target analytes. The sensing of molecules of biological interest (small organic molecules, 52,53,28,87 carbohydrates, 88,29 and proteins 26,[54][55][56]30,[57][58][59][60] ), synthetic organic molecules (drug molecules, 61,43,[62][63][64]81,89 pollutants 44,45,27,42 ) and inorganic species (both cations 36,46,31,32,47,48,33,37,38,49,65,34,39,40,51,50,66,41 and anions 67,35,68 ) has been extensively studied in the 2010-2015 period covered in thi...…”

“…Different fabrica-tion strategies to prepare these µITIES exist and have been reviewed elsewhere. 20,22 ITIES of microscopic dimensions are now routinely used under the form of a single µITIES 37,[43][44][45][46][47][48][49][50][51] (Fig. 1D) or of an array of µITIES [52][53][54][55][56][57][58][59][60][61][62][63][64][65][66][67][68][69][70] (Fig.…”