Ac impedance analysis of tetraethylammonium ion transfer at liquid/liquid microinterfaces

Lhotský, Alexandr; Holub, Karel; Neužil, Pavel; Mareček, Vladimı́r

doi:10.1039/ft9969203851

Cited by 36 publications

(21 citation statements)

References 15 publications

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“…On the other hand, while with the microelectrodes the charge transfer resistance is considerably increased and can become comparable with the solution resistance, new problems can also arise; 77 parasitic impedances 6 and currents at the edges and corresponding disturbance of the interface. 78 Conclusions presently inferred from studies using 6,13 microsized liquid/liquid interfaces differ from each other and remain to be resolved.…”

Section: 11mentioning

confidence: 99%

“…78 Conclusions presently inferred from studies using 6,13 microsized liquid/liquid interfaces differ from each other and remain to be resolved.…”

Section: 11mentioning

confidence: 99%

“…4,8 Under conditions of small driving force ͑i.e., kХk 0 ͒ the slope of the Tafel plot is universally around 0.5. 2,3,4,7,8,11 However, it has been pointed out 6,13 that some of the measurements are near the diffusion-control limit. We comment later on several results obtained using ac impedance of microinterfaces, which reduce the possibility of diffusion control.…”

Section: Introductionmentioning

confidence: 99%

“…The reported experimental results [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] include the absolute values of the rate constants k 0 for the ''exchange'' current ͑current at zero electrochemical Gibbs energy of ion transfer͒, which are apparently usually about 0.01-0.1 cm s Ϫ1 . These values are of the order of 1000-fold less than those expected from a bulk diffusion constant for crossing the interface.…”

Section: Introductionmentioning

confidence: 99%

“…Experimental results [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] on rates of ion transfer across liquid/liquid interfaces have been obtained by various methods, including AC impedance, potential-step chronofluorometry, 8 chronoabsorptometry, 9 and potential modulated reflectance, 9 the spectroscopic methods being limited to fluorescent or light absorbing ions. The reported experimental results [1][2][3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18] include the absolute values of the rate constants k 0 for the ''exchange'' current ͑current at zero electrochemical Gibbs energy of ion transfer͒, which are apparently usually about 0.01-0.1 cm s Ϫ1 .…”

Section: Introductionmentioning

confidence: 99%

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On the theory of ion transfer rates across the interface of two immiscible liquids

Marcus

2000

The Journal of Chemical Physics

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Ion transfer across the interface of two immiscible liquids involves a mechanism for initiating desolvation from the first liquid, A, and concerted solvation by the second, B. In the present article a mechanism is considered in which this initiation is facilitated by the ion attaching itself to the tip of a solvent protrusion of B into A. ͑Protrusions have been observed in computer simulations and termed ''fingers'' or ''cones.''͒ It is presumed that the most effective protrusion represents a balance between two opposing effects: the more convex the protrusion the less probable the ion/ protrusion formation but also the less the resistance to extrusion of the intervening liquid between the ion and the surface. An analogy of the latter to hydrodynamics is noted, namely, the more convex the surface the less the frictional force it exerts on the approaching ion. After diffusion in coordinate and solvation space across the interfacial region, the final detachment of the ion from solvent A is assumed to occur from a protrusion of A into B. Existing data on ion transfer rates are discussed, including the question of diffusion vs kinetic control. Computer simulations that correspond to the experimental conditions in realistic liquids for measurement of the electrochemical exchange current rate constant k 0 are suggested. They can be used to test specific theoretical features. With a suitable choice of systems the need ͑and a major barrier to the simulations͒ for having a base electrolyte in such simulations can be bypassed. An experiment for the real-time observation of an ion leaving the interface is also suggested.

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Section: 11mentioning

confidence: 99%

“…78 Conclusions presently inferred from studies using 6,13 microsized liquid/liquid interfaces differ from each other and remain to be resolved.…”

Section: 11mentioning

confidence: 99%