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

Alberts, G. S.; Shain, Irving.

doi:10.1021/ac60205a019

Cited by 157 publications

(54 citation statements)

References 30 publications

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“…It could be deduced that the lifetime of the reduction intermediate is too short to detect on the RRDE with a collection coefficient of 0.239. Nicholson and Alberts researched the ECE mechanism by use of experiments and by mathematical modeling [11][12][13].…”

Section: Voltammetric Behavior On Rrdementioning

confidence: 99%

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

Chen

Zheng

2011

Res Chem Intermed

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The reduction of 6-amino-5-nitroso-1,3-dimethyluracil (ANDMU) is a key step in caffeine synthesis. Electroreduction technology is a promising green chemical process. The voltammetric behavior of ANDMU at polycrystalline platinum and nickel cathodes was studied. The Nicholson theory was used to resolve the reduction process semi-quantitatively. The results show that ANDMU mainly undergoes an ECE (electron transfer, chemical reaction, electron transfer) process involving four electrons on the platinum and nickel cathodes in which the two electron-transfer steps occur at almost the same potential and the rate of the coupling chemical reaction between two electron-transfer steps is very fast. Apparent kinetic data and diffusion coefficient were determined for the platinum rotating-disk electrode.

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Section: Voltammetric Behavior On Rrdementioning

confidence: 99%

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

Chen

Zheng

2011

Res Chem Intermed

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“…(23) and (27), and the ordinary eigenvectors are all linearly independent. This is expected for sufficiently sparse matrices K. In fact, it seems that all published literature examples of the IEs for homogeneous reaction-diffusion systems at planar electrodes, including Refs.…”

Section: The Effect Of Matrix K On the Eigenvalues Of B(s)mentioning

confidence: 99%

“…[16][17][18][19][20][21][22][23][24][25][26][27]), it is still not clear whether the limitation to linear PDEs is the only limitation of the method. Furthermore, the literature does not seem to contain any general discussion of what kinds of integral transformation kernels are actually expected to occur in the IEs, depending on various reaction mechanisms and other conditions.…”

Section: Introductionmentioning

confidence: 99%

Analysis of the applicability of the integral equation method in the theory of transient electroanalytical experiments for homogeneous reaction–diffusion systems: The case of planar electrodes

Bieniasz

2011

Journal of Electroanalytical Chemistry

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“…Several authors have investigated these mechanisms under heuristic or limiting conditions. Alberts and Shain (1963) solved an ECE problem analytically assuming a diffusion limited electrode process (A = C = 0 at the surface). Nicholson and Shain (1965) assumed a forward process only in step (ii) (B -► C) and converted the ECE problem into an integral formulation and solved that numerically.…”

Section: + E~ -> D (At the Electrode) (Iii) B + C ^ A + D (Throughomentioning

confidence: 99%

ECE versus DISP electrochemical competition

Cole¹,

Wilder²

1989

Quart. Appl. Math.

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Abstract. The ECE (Electrochemical, Chemical, Electrochemical) and DISP (DISProportionation) mechanisms describe electrochemical reactions between four species in a diffusive solution. The general set of reactions which encompass both mechanisms is modelled by:in the case when the applied overpotential is large enough that only the forward steps in (i) and (iii) are present. The ECE mechanism follows the pathway (i), (ii), (iii). The DISP mechanism follows the pathway (i), (ii), (iv). These electrochemical mechanisms play an important role in many organic reactions such as cleavage processes and in inorganic reactions such as the production of forms of technicium used as a radiopharmaceutical. It is important to understand these mechanisms in order to better predict product synthesis and performance. This paper uses asymptotic expansion and perturbation techniques to provide rigorous, relatively simple analytic/numerical solutions for the (linear) ECE mechanism, the (weakly nonlinear) DISP mechanism and a (weakly nonlinear) "competition" mechanism involving all four pathway steps. It is shown that for large dimensionless time, the ECE mechanism evolves to a state with only two species present in order one quantities. Yet, the DISP mechanism retains all four species in order one amounts when step (iv) is reversible. The competition mechanism behaves like the ECE mechanism for small time yet evolves for large time to a form more similar to the DISP mechanism showing that nonlinear effects eventually dominate the mechanistic behavior.

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

Cited by 157 publications

References 30 publications

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

Electroreduction of 6-amino-5-nitroso-1,3-dimethyluracil on polycrystalline platinum and nickel cathodes in acid aqueous solution

Analysis of the applicability of the integral equation method in the theory of transient electroanalytical experiments for homogeneous reaction–diffusion systems: The case of planar electrodes

ECE versus DISP electrochemical competition

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