Chronopotentiometry with Current Reversal.  Application to <i>p</i>-Benzoquinone Imine Hydrolysis

Testa, A. C.; Reinmuth, W. H.

doi:10.1021/ac60167a036

Cited by 88 publications

(54 citation statements)

References 18 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…9). Testa and Reinmuth concluded k1 to be 0.103 s -1 in 30˚C, 17 nearly twotimes the value obtained here. This is apparently reasonable since our experimental temperature was nearly 10˚C lower than that in chronopotentiometric experiment.…”

Section: Long-path-length Spectroelectrochemical Experiments On the Oxsupporting

confidence: 70%

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

2000

View full text Add to dashboard Cite

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...

show abstract

Section: Long-path-length Spectroelectrochemical Experiments On the Oxsupporting

confidence: 70%

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

2000

View full text Add to dashboard Cite

show abstract

“…Refs. [159][160][161]. However, since the general application of chronopotentiometry is severely limited for the study of anodic organic oxidations, as commented previously, this technique will not be further discussed.…”

Section: (I) Steady-state Methodsmentioning

confidence: 99%

“…166 At high methanol concentrations, the reaction rate for methanol oxidation was found to decrease with increasing CH 3 0H concentration.268.269 A further examination of the pressure effect can be made from a consideration of the reaction order for the unsaturated hydrocarbons. For the adsorption of large organic species a Langmuir-type isotherm can be written, as a first approximation, () (1 -()t = Kp (159) where n is the number of sites required for the adsorption of one organic molecule, i.e., 1/(1 -()t is the probability of finding n adjacent unoccupied sites. For the high coverages reported for ethylene adsorption (()C2H4 > 0.9), () will be essentially invariant with ethylene partial pressure (over the limited range of pressures considered); however, (1 -0) can change considerably.…”

mentioning

confidence: 99%

The Mechanism of Electrochemical Oxidation of Organic Fuels

Piersma¹,

Gileadi²

1966

Modern Aspects of Electrochemistry No. 4

View full text Add to dashboard Cite

“…21, 853 (1956). (21) Weber, J., Koutecky, J., Ibid., 20, 980 (1955). RECEIVED for review April 23, 1963. Accepted August 19,1963.…”

mentioning

confidence: 99%

Electrochemical Study of Kinetics of a Chemical Reaction Coupled between Two Charge Transfer Reactions. Potentiostatic Reduction of p-Nitrosophenol.

Alberts¹,

Shain²

1963

Anal. Chem.

157

View full text Add to dashboard Cite

b Theoretical relations were derived for electrolysis experiments at constant potential (potentiostatic method). The experiments describe an electrochemical system in which a homogeneous chemical reaction is coupled between two charge transfer reactions. Included were systelns with reversible and irreversible chemical reactions, for both plane and spherical electrodes. The method was used to investigate the coupled chemical reaction in the reduction of p-nitroso-

show abstract

Chronopotentiometry with Current Reversal. Application to p-Benzoquinone Imine Hydrolysis

Cited by 88 publications

References 18 publications

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

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

The Mechanism of Electrochemical Oxidation of Organic Fuels

Electrochemical Study of Kinetics of a Chemical Reaction Coupled between Two Charge Transfer Reactions. Potentiostatic Reduction of p-Nitrosophenol.

Contact Info

Product

Resources

About