Application of a Theory of Irreversible Polarographic Waves to the Reduction of Nitroalkanes in Non-aqueous Solvents<sup>1</sup>

Findeis, A. F.; Vries, Thos. De

doi:10.1021/ja01537a011

Cited by 4 publications

(6 citation statements)

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“…Thus, plots of (ilia) vs. (hl/2/ ho 1/2) would be expected to give a series of lines of ever increasing slope as the limiting current is approached. Although good experimental verification has been obtained in the few cases tested, anomalies have been observed for nitromethane and 2-methyl-2-nitropropane in methanol (15). 2 Since the planar electrode theory prediction of the fl function is in accord with that of the expanding spherical electrode, both theories will be in accord regarding current dependence on the mercury head.…”

Section: Electrochemical Processes Involving One Electrochemical Reac...mentioning

confidence: 92%

“…[2] and [4] become identical, and the slopes of plots of (i/io) vs. (hl/S/ho l/s) would be expected to be nearly constant at 0.87 at all points along the wave. Although good experimental verification has been obtained in the few cases tested, anomalies have been observed for nitromethane and 2-methyl-2-nitropropane in methanol (15). For irreversible waves, planar electrode theory predicts current-independence of h at the beginning of the wave and direct proportionality to h 1/2 at the limiting current (13).…”

Section: Electrochemical Processes Involving One Electrochemical Reacmentioning

confidence: 92%

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Polarographic Reduction of the Phenyl-Substituted Ethenes

Grodzka

Elving²

1963

J. Electrochem. Soc.

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The theoretically expected variations of the criteria of reversibility for electrochemical reduction, which have been proposed for inorganic systems on the basis of direct current polarography, have been developed for the various possible mechanisms, which might be expected for the reduction of the phenylsubstituted ethenes at the dropping mercury electrode. These criteria of reversibility include the beta function (ratio of mean current to instantaneous current), the dependence of the current on the drop-time (mercury column ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.210.126.199 Downloaded on 2015-05-29 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.210.126.199 Downloaded on 2015-05-29 to IP ) unless CC License in place (see abstract). ecsdl.org/site/terms_use address. Redistribution subject to ECS terms of use (see 128.210.126.199 Downloaded on 2015-05-29 to IP

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Section: Electrochemical Processes Involving One Electrochemical Reac...mentioning

confidence: 92%

Section: Electrochemical Processes Involving One Electrochemical Reacmentioning

confidence: 92%

Polarographic Reduction of the Phenyl-Substituted Ethenes

Grodzka

Elving²

1963

J. Electrochem. Soc.

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“…Diffusion of the resulting carbanion into the bulk solution, where R- § H + --> RH--) dimerization or disproportionation [ 14] 2. Interfacial neutralization and reduction: R-+ H + -~ RH [15] RH + e--) RH- [16] RH-+ H + ~ RH2 [17] 3. Immediate reversible reduction, R-+ e<-~-R = [18] followed by diffusion of the doubly charged carbanion into the bulk solution, where R = + 2H + -~ RH2 [19] or…”

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confidence: 99%

Polarographic Reduction of the Phenyl-Substituted Ethenes

Grodzka

Elving

1963

J. Electrochem. Soc.

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The polarographic behavior of the five phenyl-substituted ethenes (styrene, stilbene, 1,1-diphenylethylene, triphenylethylene, and tetraphenylethylene) at the dropping mercury electrode has been examined in dimethylformamide (DMF) and DMF-water solution containing 0.2M tetra-n-butylammonium iodide as background electrolyte on the basis of the various criteria for reversibility based on direct current polarography. Heterogeneous rate constants and ana values have been calculated on the basis of the spherical expanding electrode theory.None of the reversibility criteria predictions for the various possible mechanisms are entirely in accord with the experimental results. Although polar0graphic reduction of the phenyl-substituted ethenes is indicated to occur by processes which involved a change of electron transfer mechanisms, a definite decision regarding the actual mechanisms cannot be reached because of the lack of adequate theoretical bases for such a mechanism change and for the effects of variation in double layer structure on any given mechanism.

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“…In other work, the catalysis of hydrogen evolution by organic compounds a t the dropping mercury electrode has been investigated (592) and found t o be characteristic only of nitrogen and sulfur-containing materials (592). ammetric membrane electrode (56) and was used with other compounds to test the behavior of impregnated graphite electrodes in classical polarography (155,455) and in anodic chronopotentiometry (156). I n the last study the ease of oxidation of the isomeric dihydroxybenzenes R as compared.…”

Section: Stanley Wawzonekmentioning

confidence: 99%

“…Nitro Compounds. Polarographic studies are reported for nitromethane and 2-methyl-2-nitropropane in various alcohols (155), for 2-nitropropane in glycerol (298), and for 1-nitro-lpentene in acid medium (411). The last compound is reduced stepwise to valeraldoxime and n-amylhydroxylamine.…”

Section: Ch¿hcooh XVIImentioning

confidence: 99%