New Approaches to the Study of Electrochemical Decarboxylation and the Kolbe Reaction: Part Iii. Quantitative Analysis of Decay and Discharge Transients and the Role of Adsorbed Intermediates

Conway, B. E.; Dzieciuch, Matthew A.

doi:10.1139/v63-007

Cited by 41 publications

(8 citation statements)

References 8 publications

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“…Thus, it is assumed that the coverage of the metal (oxide) surface with alkoxy and alkyl radicals inhibits the oxygen evolution reaction or solvent oxidation, while the Kolbe electrolysis is promoted. [36][37][38][39][40][41][42] After the adsorption, an irreversible single electron transfer from the carboxylate to the anode takes place, whereas the simultaneous decarboxylation leads to the formation of an alkyl radical and CO 2 . 36,37 Subsequently, the formed alkyl radicals can follow four different reaction pathways depending on the applied reaction conditions:…”

Section: Background Of (Non-)kolbe Electrolysismentioning

confidence: 99%

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

2020

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Section: Background Of (Non-)kolbe Electrolysismentioning

confidence: 99%

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

2020

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“…Equation [13] call be written for P = 0.5 as For steady-state, rather than quasi-equilibrium conditions, the maximum in the C-V plot occurs a t a potential given from the steady-state "Langmuir" equation the rate constant ratio kg/kb, which determines the relative "extent" to which the discharge step is not in true equilibrium. Results of these calculations are shown in Fig.…”

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confidence: 99%

“…In another paper (lo), we have shown how these theoretical considerations can be applied to the elucidation of the adsorption behavior of intermediates involved in electrochemical decarboxj~lation reactions reported elsewhere (11)(12)(13).…”

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“…T h e kinetic sequence of steps in these reactions may be written: Analogous steps to I and I1 occur in the oxygen evolution reaction (9). Evidence has been given that the pathway I and I1 is the mechanism of the hydrogen evolution reaction from aqueous acids a t a number of transition metals (14)(15)(16)(17), while 111-IV is the mechanism of formate decarboxylation a t high anodic potentials (10)(11)(12)(13). In the above reactions, the pseudocapacitance is associated with H' adsorption in 1-11 and with HCOO' adsorption in 111-IV (10).…”

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Steady-State Theory of Adsorption Pseudocapacitance in Electrochemical Radical-Ion Reactions

Conway¹,

Gileadi²

1964

Can. J. Chem.

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The theory of adsorption pseudocapacity behavior is developed for a sequence of electrochemical reactions involving an ion discharge step which produces an adsorbed radical, followed by a n "ion-atom" recombination reaction with or without desorption of the product of this step. The adsorption pseudocapacity behavior is deduced analytically particularly for the steadystate case and distinguished from the results obtained for assumed quasi-equilibrium in the ion discharge step when the succeeding step is rate-controlling. The effect of variation of the relative values of the rate constants of the discharge and of succeeding steps is investigated. I t is shown that the capacity-potential behavior is sensitively dependent 011 the ratio of these rate constants, particularly for the case of adsorption isotherms involving a large value for the "heterogeneity parameter", r , defining the variation of energy of adsorption of the intermediates with coverage. Under the latter conditions, limiting coverages of the electrode by the adsorbed species are reached with increasing potential, depending on the relative valiles of the rate constants and the value of r.Alost electrochemical reactions not involving simple metal-ion redox reactions proceed by two or more consecutive steps. Under these circumstances, adsorbed inter~nediates are involved, the surface concentrations of which are usually potential dependent. Since Faradaic charge is involved in the formation of the layer of intermediates, the potential dependence of the coverage leads to an adsorption pseudocapacitance (1, 2).2 The importance of studies of charging curves was already recognized by Bowden and Rideal(3) with regard to the ionic double-layer and the method was developed by Slygin and Frumlrin (4-6) for the study of H atom adsorption in the hydrogen evolution reaction; a t about the same time, Butler and Drever (7) used this method for the study of oxide films and Pearson and Butler ( 8 ) examined electrochemical hydrogen adsorption a t the platinum metals by means of charging curves. Studies of charging curves and the corresponding adsorption pseudocapacitance can provide an important method, complementary to direct kinetic current-potential studies, for elucidation of electrode reaction mechanisms. 3Iuch contemporary interest in electrochemical kinetics centers around the study of charging curves and the measurement of electrode capacitance, but further work is required in the interpretation of such data.In a previously published paper (9), we have shown how studies of the dependence of adsorption pseudocapacitance upon potential can lead to information on the type of isotherm governing the adsorption of reaction intermediates, and to information about the potential dependence of coverage by such intermediates in two or multistep electrochelnical reactions. In another paper (lo), we have shown how these theoretical considerations can be applied to the elucidation of the adsorption behavior of intermediates involved in electrochemical decarboxj~lation react...

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“…5 It was concluded that these intermediates were carboxyl radicals, the ratedetermining step being either the decarboxylation following electrochemical discharge, or else an electrochemical desorption step involving a carboxyl radical and a carboxylate ion. 5 It was concluded that these intermediates were carboxyl radicals, the ratedetermining step being either the decarboxylation following electrochemical discharge, or else an electrochemical desorption step involving a carboxyl radical and a carboxylate ion.…”

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Kinetic study of the Hofer-Moest reaction

Atherton¹,

Fleischmann²,

Goodridge³

1967

Trans. Faraday Soc.

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The anodic decarboxylation of acetate ions has been studied potentiostatically, using both a conventional steady-state method, and a novel non-steady state square d.c. pulse technique. The products observed were carbon dioxide, oxygen, ethane, and methanol. Most of the steady state and non-steady state data are explained by a rapid discharge of acetate ions to form methyl radicals which replace an adsorbed intermediate in the oxygen evolution reaction. The methyl radicals are common to tlze formation of ethane and methyl alcohol. As it is not possible to simulate all the observations by analogue computation, it is suggested that the progressive formation of oxide films with time have also to be taken into account.

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New Approaches to the Study of Electrochemical Decarboxylation and the Kolbe Reaction: Part Iii. Quantitative Analysis of Decay and Discharge Transients and the Role of Adsorbed Intermediates

Cited by 41 publications

References 8 publications

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

(Non-)Kolbe electrolysis in biomass valorization – a discussion of potential applications

Steady-State Theory of Adsorption Pseudocapacitance in Electrochemical Radical-Ion Reactions

Kinetic study of the Hofer-Moest reaction

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