The Measurement of the Molal Ferric-Ferrous Electrode Potential

Schumb, Walter C.; Sherrill, Miles S.; Sweetser, Sumner B.

doi:10.1021/ja01290a079

Cited by 39 publications

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“…Ici par contre, le ClO2 est un produit de la reaction globale et [9] est un quasiCquilibre. On retrouve la loi [5] [I21 HCIOz + C1 + HClO + CIO La rupture peut Ctre [I31 ou [14] D'autre part nous savons (1) que le HCIO form6 rtagit trks rapidement avec le chlorite suivant [15] et [16].…”

Section: Interpretation Des Resultatsunclassified

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Mécanisme des réactions du chlorite et du dioxyde de chlore. 3. La dismutation du chlorite

Schmitz¹,

Rooze²

1985

Can. J. Chem.

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R e p le 20 juin 1984 GUY SCHMITZ et HENRI ROOZE. Can. J. Chem. 63, 975 (1985).La dismutation du chlorite a CtC CtudiCe en solutions d'acide perchlorique 0,Ol M a I M, a 25°C et pour une force ionique de 1 M. Les rCsultats impliquent au moins trois processus rCactionnels. Le premier est catalysC par les ions C1-, le second donne une loi d'ordre deux et le troisitme est catalysC par le fer. Sa loi cinCtique est Elle peut Ctre interprktee par la rkaction riversible CIO; + Fe3+ C102 + Fe" suivie de deux Ctapes dkterminantes Few + HCIOz -. produits et Fe" + C10, -. produits. Nous dCduisons de cette etude et de la prCcCdente faite en prCsence d'orrho-tolidine, que la reaction d'ordre deux correspond a un mkcanisme radicalaire en chaine.GUY SCHMITZ and HENRI ROOZE. Can. J. Chem. 63, 975 (1985).The disproportionation of chlorite was studied in 0.01 to I M perchloric acid solutions at 25°C and an ionic strength of 1 M. The results suggest at least three reaction paths. The first is catalysed by C1-ions, the second gives a second-order rate law, and the third is catalysed by iron. Its rate law is' This can be interpreted by the reversible reaction ClOi + Fe3' g C102 + Fe" followed by two rate-determining reactions Few + HCIOz -. products, Fez+ + C101 -. products. From this study and the former, made with added orrho-tolidine, we conclude that the second-order reaction proceeds by a radical chain mechanism.

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Section: Interpretation Des Resultatsunclassified

“…Avec [14], du fait de la prtpondtrance de [15] par rapport a [16], on prevoit une formation relative de CIOz beaucoup plus importante que celle obt'enue expCrimentalement pour la reaction catalyste par le fer. Nous admettons donc que, dans nos conditions, la rupture est [13].…”

Section: Interpretation Des Resultatsunclassified

Mécanisme des réactions du chlorite et du dioxyde de chlore. 3. La dismutation du chlorite

Schmitz¹,

Rooze²

1985

Can. J. Chem.

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“…50 In the determination of the standard potential of highly charged cations such as Fe 3+ , obtaining accurate extrapolations to infinite dilution requires additional corrections for chemical effects such as hydrolysis of a first-shell water molecule coordinated to the Fe 3+ ion, as well as accounting for non-unit activity coefficients of Fe 3+ , Fe 2+ , and H + under measurement conditions. 51 Most aqueous experimental reduction potentials have been extrapolated to infinite dilution and therefore these may be directly compared with theoretical calculations in which activity effects are ignored by assuming infinite dilution.…”

Section: Definition Of the Standard Reduction Potentialmentioning

confidence: 99%

Computational electrochemistry: prediction of liquid-phase reduction potentials

Marenich

Coote

et al. 2014

Phys. Chem. Chem. Phys.

445

563

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This article reviews recent developments and applications in the area of computational electrochemistry. Our focus is on predicting the reduction potentials of electron transfer and other electrochemical reactions and half-reactions in both aqueous and nonaqueous solutions. Topics covered include various computational protocols that combine quantum mechanical electronic structure methods (such as density functional theory) with implicit-solvent models, explicit-solvent protocols that employ Monte Carlo or molecular dynamics simulations (for example, Car-Parrinello molecular dynamics using the grand canonical ensemble formalism), and the Marcus theory of electronic charge transfer. We also review computational approaches based on empirical relationships between molecular and electronic structure and electron transfer reactivity. The scope of the implicit-solvent protocols is emphasized, and the present status of the theory and future directions are outlined.

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“…where E 0 Fe 3þ !Fe 2þ ¼ 0:77V is the standard reduction potential of Fe 3+ (Schumb et al, 1937) and K i is the stability constant of the complex i.…”

Section: Evaluation Of Rate Constants In the Context Of Marcus Theorymentioning

confidence: 99%

Influence of phosphate on the oxidation kinetics of nanomolar Fe(II) in aqueous solution at circumneutral pH

Mao

Pham

Rose

et al. 2011

Geochimica et Cosmochimica Acta

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The Measurement of the Molal Ferric-Ferrous Electrode Potential

Abstract: this determination exceeded 99.99 mole per cent. been determined and the observed value for the The phase equilibrium diagram for the con-eutectic point was -160.2 f 0.5'. densed system 2-methylpentane-n-heptane has NORWOOD, PENNA.

Cited by 39 publications

References 0 publications

Mécanisme des réactions du chlorite et du dioxyde de chlore. 3. La dismutation du chlorite

Mécanisme des réactions du chlorite et du dioxyde de chlore. 3. La dismutation du chlorite

Computational electrochemistry: prediction of liquid-phase reduction potentials

Influence of phosphate on the oxidation kinetics of nanomolar Fe(II) in aqueous solution at circumneutral pH

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