Determination of the rate of tetraethylammonium ion transfer across the water/1,2-DCE interface with steady-state voltammetry at a nano-ITIES. Theory and experiment

Silver, Barry R.; Holub, Karel; Mareček, Vladimı́r

doi:10.1016/j.jelechem.2016.11.022

Cited by 6 publications

(4 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…An interesting value is also the magnitude of the ion transfer rate which can be concluded from the equilibration experiment. Using the geometry values for our setup, one finds 1.65 × 10 –3 cm/s, which is at the lower end of values discussed in the literature for other ions. , …”

Section: Discussionmentioning

confidence: 46%

“…Using the geometry values for our setup, one finds 1.65 × 10 −3 cm/s, which is at the lower end of values discussed in the literature for other ions. 12,18 The clear preference of electron transfer over ion transfer might be explained by kinetic and energetic arguments. There is the dramatically higher mass of the ions (5 orders of magnitude) in comparison to electrons which lowers the transfer rates as one could conclude from transition rate theory (see e.g., ref 19).…”

Section: Discussionmentioning

confidence: 99%

See 1 more Smart Citation

Electrochemical Impedance Spectroscopy at Redox-Type Liquid|Liquid Interfaces: The Capacitance Lag

Akilavasan

Marlow

2020

J. Phys. Chem. C

View full text Add to dashboard Cite

Liquid|liquid interfaces (LLIs) between redox-type electrolytes are investigated with a 2-electrode technique by the subtraction of the volume effects of the adjacent bulk phases and a correction of equipment errors. In this system, the electron transfer through the LLI turns out to overdominate the ion transfer. Surprisingly, no indication for a barrier in the charge transfer was found. The measured resistances assignable to the LLI are extremely low. The efficient charge transfer through the LLI is ascribed to an ionic adsorption layer acting as a buffer for the electrons and opening a new channel for the charge transport. The impedance spectra show a specific peculiarity: a "capacitance lag" at high frequencies. This lag is interpreted using a new model of delayed transport. Microscopically, such a kind of transport is explained with an adsorbed ion layer with variable charge. It acts as a buffer and causes a time delay in the charge transfer.

show abstract

Section: Discussionmentioning

confidence: 46%

Section: Discussionmentioning

confidence: 99%

Electrochemical Impedance Spectroscopy at Redox-Type Liquid|Liquid Interfaces: The Capacitance Lag

Akilavasan

Marlow

2020

J. Phys. Chem. C

View full text Add to dashboard Cite

show abstract

“…An interface between two immiscible electrolyte solutions (ITIES) is a unique electrode, capable of detecting a wide range of electroactive chemical species regardless of their classification as redox-active or redox-inactive. − ITIES electrodes have become more prevalent in analytical science due to their sensitivity beyond redox-active analytes and their ease of fabrication down to the nanoscale, , allowing for high spatial resolution which enables single-entity and nanostructure studies. − Electrochemistry at the ITIES has enabled researchers to probe fundamental mechanistic processes ,,− and a wide range of applications, including catalysis, − cellular studies, − ,,,,− heavy metal detection, − pharmacological studies, ,− …”

Section: Introductionmentioning

confidence: 99%

Interface between Two Immiscible Electrolyte Solutions Electrodes for Chemical Analysis

et al. 2022

View full text Add to dashboard Cite

The interface between two immiscible electrolyte solutions (ITIES) plays vital roles in various fields, such as neuroscience, environmental science, analytical chemistry, separation, catalysis, and nanoparticle synthesis. ITIES emerges as a unique approach in chemical analysis due to its sensitivity to both redox-active and redox-inactive analytes. Neurotransmitters, metal ions, drug molecules, and other complex molecules such as proteins have been detected using ITIES. The detection of redox-inactive species at the ITIES has opened a door to understanding a wide range of complex systems that are less suited to probing by solid electrodes. In this feature article, we present the history of electrochemistry at the ITIES; charge transfer reactions, thermodynamics, and kinetics at the ITIES; electrode−solution interfacial structure; and a diverse range of applications enabled by ITIES.

show abstract

“…According to eq ( D i is the diffusion coefficient of ionic species i ), m 0 is inversely proportional to the pipette radius r , implying that the maximum measurable value of k 0 increases linearly with 1/ r . Therefore, it is obvious that nano-L/L interfaces enable fundamental studies of the kinetics of rapid IT reactions at such interfaces. Scanning electrochemical microscopy and steady-state voltammetry are usually applied to measure the kinetic parameters of electrochemical processes taking place at nanointerfaces. − The three-point method proposed by Mirkin and Bard is a way to obtain kinetic parameters from steady-state voltammograms in quasi-reversible systems . Three potential values ( E 1/2 , E 1/4 , E 3/4 ) are extracted from the voltammogram to determine k 0 and α .…”

mentioning

confidence: 99%

Electrostatic-Gated Kinetics of Rapid Ion Transfers at a Nano-liquid/Liquid Interface

Shao

et al. 2022

Anal. Chem.

View full text Add to dashboard Cite

Charge (ion and electron)-transfer reactions at a liquid/ liquid interface are critical processes in many important biological and chemical systems. An ion-transfer (IT) process is usually very fast, making it difficult to accurately measure its kinetic parameters. Nanoliquid/liquid interfaces supported at nanopipettes are advantageous approaches to study the kinetics of such ultrafast IT processes due to their high mass transport rate. However, correct measurements of IT kinetic parameters at nanointerfaces supported at nanopipettes are inhibited by a lack of knowledge of the nanometer-sized interface geometry, influence of the electric double layer, wall charge polarity, etc. Herein, we propose a new electrochemical characterization equation for nanopipettes and make a suggestion on the shape of a nano-water/1,2-dichloroethane (nano-W/DCE) interface based on the characterization and calculation results. A theoretical model based on the Poisson−Nernst−Planck equation was applied to systematically study how the electric double layer influences the IT process of cations (TMA + , TEA + , TPrA + , ACh + ) and anions (ClO 4 − , SCN − , PF 6 − , BF 4 − ) at the nano-W/DCE interface. The relationships between the wall charge conditions and distribution of concentration and potential inside the nanopipette revealed that the measured standard rate constant (k 0 ) was enhanced when the polarity of the ionic species was opposite to the pipette wall charge and reduced when the same. This work lays the right foundation to obtain the kinetics at the nano-liquid/liquid interfaces.

show abstract

Determination of the rate of tetraethylammonium ion transfer across the water/1,2-DCE interface with steady-state voltammetry at a nano-ITIES. Theory and experiment

Cited by 6 publications

References 18 publications

Electrochemical Impedance Spectroscopy at Redox-Type Liquid|Liquid Interfaces: The Capacitance Lag

Electrochemical Impedance Spectroscopy at Redox-Type Liquid|Liquid Interfaces: The Capacitance Lag

Interface between Two Immiscible Electrolyte Solutions Electrodes for Chemical Analysis

Electrostatic-Gated Kinetics of Rapid Ion Transfers at a Nano-liquid/Liquid Interface

Contact Info

Product

Resources

About