Thin-layer electrochemical cell for long optical pathlength observation of solution species

Żak, Jerzy; Porter, Marc D.; Kuwana, Theodore

doi:10.1021/ac00264a004

“…Another advantage is that, as in reflection spectroscopy, there is no requirement for the electrode to be transparent. Since that time many other designs have been presented in the literature [186,187]. The electrode may be mounted vertically or horizontally, but vertically seems more sensible for matching modern spectrometer slits.…”

Section: Long Optical Path-length Thinlayer Cell (Loptlc)mentioning

confidence: 99%

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

Crayston

¹

2003

Encyclopedia of Electrochemistry

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The sections in this article are Introduction and Principles Introductory Remarks Theory and Techniques: Steady State Measurement Cell Transmission for a Simple Electron Transfer Reaction: Determination of E and n Effect of Follow‐up Reactions in OTTLE Cells Theory and Techniques: Kinetic Measurements Chronoabsorptometry Instrumentation for Chronoabsorptometry Slow Heterogeneous Kinetics Effect of Follow‐up Reactions Derivative Cyclic Voltabsorptometry ( DCVA ) Galvanostatic Conditions Adsorption Cell Geometries, Design, Techniques, and Instrumentation General Considerations Transmission under Thin‐layer Conditions: OTTLEs and Flow‐cells Variations on and Alternatives to the Basic OTTLE Design OTTLE Cells Intended for Both UV ‐visible and FTIR Use OTTLE Cell Electrochemical and Spectroscopic Response Semi‐infinite Cells: Optically Transparent Electrodes ( OTEs ) Reflection from Electrodes and Liquid–Liquid Interfaces Glancing Incidence Reflection, Near‐parallel or Parallel Reflection, and Diffraction Liquid–Liquid Interface and Attenuated Total Reflection Long Optical Path‐length Thin‐layer Cell ( LOPTLC ) Forced Convection, RDE and Channel Flow UV ‐vis Combined with Other Spectroscopic Techniques Applications Solution Studies of Inorganic Species Solution Studies of Organic Species Molten Salts Spectroelectrochemistry Studies of Species of Biological Interest Inorganic Thin Films and Modified Electrodes Conducting Polymers and Oligomer Models Conclusions

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“…The LOPLTLE cell is modeled, in general, after that described by Zak [22], however modifications were made to the cell to accommodate an ITO/glass electrode. The side and front views of the LOPLTLE cell are shown in Figures 1a and 1b, respectively.…”

mentioning

confidence: 99%

“…The performance of a LOPTLE as a thin-layer cell is usually evaluated through chronoamperometry/chronoabsorptometry [22] and/or voltammetry [10,23] of a wellstudied electrochemical probe. The voltammogram of 0.0415 mM ferricyanide in 0.5 M KCl using the LOPLTLE is shown in Figure 2.…”

mentioning

confidence: 99%

“…TRIS buffer is used because it doesnt readily bind to dissolved iron. The large formation constant (b 3 ¼ 5 Â 10 22 ) of the tris-1,10-phenanthroline complex (ferroin) favors a high degree of reaction completeness and the large extinction coefficient of the complex affords measurable absorbances for small concentrations of released iron. The moles of iron released from a layer were calculated from a calibration curve using ferroin in the LOPLTLE, and the volume of the LOPLTLE cell described above.…”

mentioning

confidence: 99%

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Electrochemically Induced Iron Release of Adsorbed Horse Spleen Ferritin: Quantitation of Iron Using Long Optical Path Length Thin‐Layer Spectroelectrochemistry

Kreutzian

¹

,

Seraj

²

,

Anderson

³

et al. 2007

Electroanalysis

3

0

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In this work, long optical path length thin-layer electrochemical cell was constructed using indium-tin oxide on glass as the electrode material. Iron release from ferritin adsorbed on the electrode was induced by applying a negative potential sweep in the presence of 1,10-phenanthroline. The usefulness of spectroelectrochemistry as a means of determining the quantity of iron released from an adsorbed layer of ferritin is demonstrated.

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“…5 Compared with OTE, the long-path-length spectroelectrochemical technique has been applied in researching electrochemical mechanisms and evaluating the kinetic parameters B → C k 1 A → B ±ne theoretically and experimentally for higher sensitivity. [6][7][8][9][10][11][12] In this work, the long-path-length spectroelectrochemical technique was utilized to study the EC mechanism. Not only were A-t curves with different values of molar absorptivities of species B and C analyzed, but also the effects of the molar absorptivity of species A, the first-order rate constant and the diffusion coefficients on the shapes of the A-t curves were investigated in detail by a digital simulation.…”

mentioning

confidence: 99%

Evaluation of the Kinetic Parameters of First-Order Reactions Following Charge Transfer by Applying a Long-Path-Length Spectroelectrochemical Technique

Zhang

¹

,

Yao

²

,

Wei

³

2000

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It is well known that electrochemical mechanisms and parameters can be studied by the spectroelectrochemical technique. (1) (2) by applying transmission spectroscopy using optically transparent electrodes (OTE). They studied the shapes of the chronoabsorbance vs. time (A-t) curves when species A did not absorb, and found that the first-order rate constant could be calculated from the maximum absorbance (A t max ), which did not require a tedious curve-fitting procedure for εB/εC≥5. This OTE method had been applied to the solvolytic reaction of the 9,10-diphenylanthracene cation radical (DPA + ) in aqueous acetonitrile.2 McCreery established a thin-layer spectroelectrochemical technique for monitoring the electrogenerated reactive intermediates involved in the irreversible pseudo-first-order hydrolysis of quinone imine electrogenerated from p-aminophenol to form p-quinone. 3 Heineman et al. demonstrated the applicability of thin-layer optically transparent electrodes for monitoring homogeneous chemical reactions of electrogenerated species using the benzidene rearrangement as a model system. 4 Besides, Dong et al. had given a valuable discussion on investigating the EC mechanism by the spectroelectrochemical technique. 5 Compared with OTE, the long-path-length spectroelectrochemical technique has been applied in researching electrochemical mechanisms and evaluating the kinetic parameterstheoretically and experimentally for higher sensitivity. [6][7][8][9][10][11][12] In this work, the long-path-length spectroelectrochemical technique was utilized to study the EC mechanism. Not only were A-t curves with different values of molar absorptivities of species B and C analyzed, but also the effects of the molar absorptivity of species A, the first-order rate constant and the diffusion coefficients on the shapes of the A-t curves were investigated in detail by a digital simulation. The experimental result concerning the electrooxidation of p-aminophenol in an acid aqua solution was compared with the simulated curve. TheoryConcerning a reaction of Eqs. (1) and (2), if a sufficient potential step is applied to transform species A to species B completely on the surface of the working electrode, the concentration distributions of three species follow Fick's laws of diffusion to a plane modified by the appropriate kinetic terms: 13,14 (3) (4) (5) where CA, CB, CC and DA, DB, DC are the concentration distributions and the diffusion coefficients of species A, B and C respectively.The initial and semi-infinite boundary conditions are: College of Chemistry and Chemical Engineering, Hunan University, Changsha 410082, P. R. ChinaA long-path-length spectroelectrochemical technique was developed for investigating the EC mechanism and evaluating the kinetic parameters under a semi-infinite condition. The chronoabsorbances were obtained by a digital simulation method. Simulated results showed that the shapes of A-t curves are markedly dependent upon the relative values of the molar absorptivities of spieces A, B and C. When εA=0, εB/ε...

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Thin-layer electrochemical cell for long optical pathlength observation of solution species

Cited by 86 publications

References 20 publications

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

Spectroelectrochemistry: In s itu UV ‐visible Spectroscopy

Electrochemically Induced Iron Release of Adsorbed Horse Spleen Ferritin: Quantitation of Iron Using Long Optical Path Length Thin‐Layer Spectroelectrochemistry

Evaluation of the Kinetic Parameters of First-Order Reactions Following Charge Transfer by Applying a Long-Path-Length Spectroelectrochemical Technique

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