Mechanism and thermodynamics of the polarographic deposition of aquo in (III)

Lawson, Joan C.; Aikens, D. A.

doi:10.1016/0022-0728(67)85023-x

Cited by 24 publications

(6 citation statements)

References 26 publications

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“…This EO' agrees fairly well with the values from Lawson and Aikens (16) and Naruzawa et al (46). Good results are also obtained by calculation of this formal potential using the global constants for the system, determined by Bertotti and Tokoro (14), Avsar (49), and Momoki and Ogawa (53) (see Table 3).…”

Section: Discussionsupporting

confidence: 90%

Polarographic studies of indium(III) in aqueous medium of sodium azide

Tokoro¹,

Bertotti²,

Angnes³

1995

Can. J. Chem.

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Abstract:In this paper, some aspects of the polarography of indium(II1) in azidelhydrazoic acid buffer are presented. The electrode process is mostly governed by diffusion in the complexing medium. Nevertheless, for controlled-potential coulometry (involving a large time window) a catalytic process was observed, ascribed to the reaction of the hydrazoic acid and indium amalgam. The stability of azide complexes of In(II1) was studied polarographically, and the formation of four mononuclear species was confirmed by computational analysis of data obtained from polarograms of In(II1) in different azide concentrations. The values of the global constants obtained are: PI = 3.7 x 10' M-', P2 = 8.6 x lo5 M -~, P3 = 5.0 x lo7 M -~, P4 = 2.1 x lo9 MA, in a constant ionic strength medium held at 2.0 M with NaC10,. These data are in good agreement with those obtained by potentiometry. The value found for E ' of the In(III)/In couple was -5 12.2 mV vs. calomel electrode (3 M NaCl), the mean diffusion coefficient of the complex being (6.1 ? 0.2) x 10-~cm' s-I in perchlorate medium (T = 25OC).Key words: polarography, indium(II1). azide, stability constants, catalytic wave Resum6 : Dans ce travail, on prCsente quelques aspects de la polarographie de l'indium(II1) dans un tampon d'azoturelacide hydrazoi'que. Le processus B 1'Clectrode est principalement dCterminC par la diffusion dans le milieu complexant. Toutefois, pour la coulomCtrie B potentiel contr61C (impliquant une large fenstre de temps), on a observt un processus catalytique attribuC B la rCaction de I'acide hydrazoi'que avec l'amalgame d'indium.Faisant appel a la polarographie, on a CtudiC la stabilitC des complexes d'azoture avec le In(II1) et on a confirm6 la formation de quatre espbces mononuclCaires par une analyse mathkmatique des donnCes obtenues B partir de polarogrammes du In(II1) B diverses concentrations d'azoture. Les valeurs des constantes globales obtenues sont : p = 3.7 x 10' M-I, P, = 8,6 x 10" M-', P, = 5,O x lo7 M-? el P, = 2,l x lo9 MA, B une force ionique constante maintenue B 2,O M par du NaCIO,. Ces donnCes sont en bon accord avec celles obtenues par potentiomCtrie. La valeur trouvCe pour EO' dans le couple In(II1)IIn est de -5 12,2 mV vs. Clectrode au calomel (3 M NaCI) alors que le coefficient moyen de diffusion du complexe est (6,l ? 0.2) x 10" cm2 s-I dans un milieu de perchlorate (T = 25OC).

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Section: Discussionsupporting

confidence: 90%

Polarographic studies of indium(III) in aqueous medium of sodium azide

Tokoro¹,

Bertotti²,

Angnes³

1995

Can. J. Chem.

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“…10 -1 m 3 mol -1 for each of the In(III) species [39], enables the rate constant for loss of a proton from a given In(III) species to be estimated as ca. 510 5 s -1 [6]. This value confirms that there will be rapid interchange between H2O and OHin the inner-hydration sphere, whilst the equilibrium concentrations of the various In(III) species derive from the hydrolysis constants.…”

Section: Reaction Layer and Lability Considerations For The Aqueous In(iii) Systemsupporting

confidence: 55%

“…Literature from the 1960s evidences that voltammetric waves recorded for free 3 26 In(H O) + with a dropping mercury electrode at a pH sufficiently low to suppress hydrolysis, show a drawn-out electrochemically irreversible wave for the 3 26 In(H O) + species with halfwave potential, E1/2, of -0.95 V (vs. saturated calomel electrode (SCE)); as the pH is increased an electrochemically reversible diffusion-controlled wave with E1/2 of -0.55 V (vs. SCE) is observed [2][3][4]. These observations suggest that In(III) hydroxy species are the predominant electroactive contributors to the electrodic reduction current [5][6][7].…”

Section: Introductionmentioning

confidence: 95%

Electrochemical activity of various types of aqueous In(III) species at a mercury electrode

Town

Duval

Leeuwen

2020

J Solid State Electrochem

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An interpretation framework is presented which provides a straightforward means to characterise the electrochemical reactivity of aqueous ions together with their various hydrolysed counterparts. Our novel approach bypasses the more laborious strategy of solving rigorously, for all relevant species, the complete set of Butler Volmer equations coupled to diffusion differential equations. Specifically we consider the spatial variable via a Koutecky-Koryta type of differentiation between nonlabile and labile zones adjacent to the electrode. The theory is illustrated by an assessment of the electrochemical reactivity of aqueous In(III) species based upon proper comparison between relevant time scales of the involved interfacial processes, i.e. diffusion, (de)protonation of inner-sphere water, dissociation/release of H2O and OH -, and electron transfer.The analysis reveals that whilst all In(III) species are labile on the experimental timescale with respect to (de)protonation and (de)hydration, there are large differences in the rates of electron transfer between 3 26In(H O) + and the various hydroxy species. Specifically, in the case of 3 26In(H O) + the rate of electron transfer is so slow that it replaces the traditional Eigen rate-limiting water release step in the overall passage from hydrated In 3+ to its reduced metallic form; in contrast the In(III) hydroxy species display electrochemically reversible behaviour.

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“…Indium oxide (III) is applied in the modification of electrodes used to study kinetics in bioelectric systems with: ferredoxin [10], cytochrome c [11] or mioglobin [12,13]. According to Molodov [14], Lawson [15] and Armstrong [16] [17,[18][19][20][21]. Using the NMR method, Cannon, Fratiello and co-workers [22,23] proved that in acidic solutions of non-complexing electrolytes the In(III) ions exist in the form of [In(H 2 O) 6 ] 3+ .…”

Section: Introductionmentioning

confidence: 99%

Catalytic activity of thiourea and its selected derivatives on electroreduction of In(III) in chlorates(VII)

Nosal‐Wiercińska

2010

Open Chemistry

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It was found that thiourea, N-methylthiourea, N,N'-dimethylthiourea and N-allylthiourea accelerate the electroreduction process of In(III) ions in chlorates(VII). These substances are adsorbed on mercury from chlorates(VII). The relative surface excesses of thiourea and its derivatives increase with the increase of their concentrations and electrode charge. After adding thiourea, N-methylthiourea, N,N'-dimethylthiourea and N-allylthiourea to the solution an acceleration of the electroreduction process of In(III) ions occurs. This process depends on two factors: the adsorption of an accelerating substance on mercury and on the formation of complexes between a depolarizer and an accelerating substance on the electrode surface. The equilibrium of this complexing reaction determines the magnitude of the catalytic effect.© Versita Warsaw and Springer-Verlag Berlin Heidelberg.

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Mechanism and thermodynamics of the polarographic deposition of aquo in (III)

Cited by 24 publications

References 26 publications

Polarographic studies of indium(III) in aqueous medium of sodium azide

Polarographic studies of indium(III) in aqueous medium of sodium azide

Electrochemical activity of various types of aqueous In(III) species at a mercury electrode

Catalytic activity of thiourea and its selected derivatives on electroreduction of In(III) in chlorates(VII)

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