Ligand-Catalyzed Polarographic Reduction of Indium(III) for Determination of Halides and Certain Organic Sulfur and Nitrogen Compounds.

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

doi:10.1021/ac60221a007

Cited by 54 publications

(24 citation statements)

References 22 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The complexes of Zn(II) ions with a catalyzing substance are probably formed only when the hydration sphere of Zn(II) ions is partially degenerated, i.e., close to the Helmholtz outside plane. Labilization of the hydration sphere plays a key role in all ligand catalyzed reductions of metal ions [24]. Introduction of catalytic substances to the coordination sphere of the aquo-ion increases the rate of displacement of the remaining water molecules.…”

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Zn(II) Ions Electroreduction Catalyzed by Organic Compounds

Dalmata

2005

Electroanalysis

View full text Add to dashboard Cite

The paper describes the results of the studies of organic substances catalytic activity on Zn(II) ions electroreduction on mercury in perchlorate solutions. Zn(II) ions electroreduction in the presence of catalyzing substance proceeds in two one-electron stages. The first electron transfer is the stage determining the process rate. All catalyzing substances increase the rate of first electron transfer. The acceleration effect is connected with the stability of active complexes formed on the electrode surface. The rate of the second electron transfer depends mainly on the adsorption of the catalyzing substance on the electrode surface -of the surface excess and the structure of the adsorption layer. Hence the second electron transfer can be inhibited or catalyzed. The mechanism of the organic substance catalytic activity is also given.

show abstract

Section: Resultsmentioning

confidence: 99%

Kinetics and Mechanism of Zn(II) Ions Electroreduction Catalyzed by Organic Compounds

Dalmata

2005

Electroanalysis

View full text Add to dashboard Cite

show abstract

“…Introduction of the foreign ligand (such as thiourea) into the coordination sphere of an aquo-ion increases the rate of displacement of the remaining water molecules. Hence labilization of the hydration sphere probably plays a key role in all ligand catalyzed reduction of metal ions [21]. This reaction occurs preferentially at the electrode surface because the significant local thiourea concentration existing as a result of adsorption of thiourea on the mercury electrode [36] creates favorable conditions for formation of indium-thiourea complexes.…”

Section: Resultsmentioning

confidence: 99%

“…In view of the small rate of the exchange of coordinated water molecule [20] one can observe a poorly developed, irreversible wave of indium (III) while an addition of halides, pseudohalides or some organic substances to the supporting electrolyte accelerates the reduction of In(III) [21,22].…”

Section: Introductionmentioning

confidence: 99%

Studies of the Effect of Thiourea on the Electroreduction of In(III) Ions in Perchloric Acid

Nosal‐Wiercińska¹,

Dalmata²

2002

Electroanalysis

View full text Add to dashboard Cite

“…For this later study, indium(II1) seemed very promising. Polarographic studies of the thiocyanate of indium(II1) appear in the literature (4)(5)(6)(7)(8)(9)(10)(11)(12), whereas the electrochemical behavior of the corresponding isosteric azide complex remains practically unexplored. The pseudo-halides of both the thiocyanate and azide are isosteric and thus the purpose of the present work is the search for and verification of such similarities.…”

Section: Introductionmentioning

confidence: 99%

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

Tokoro¹,

Bertotti²,

Angnes³

1995

Can. J. Chem.

View full text Add to dashboard Cite

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).

show abstract

Ligand-Catalyzed Polarographic Reduction of Indium(III) for Determination of Halides and Certain Organic Sulfur and Nitrogen Compounds.

Cited by 54 publications

References 22 publications

Kinetics and Mechanism of Zn(II) Ions Electroreduction Catalyzed by Organic Compounds

Kinetics and Mechanism of Zn(II) Ions Electroreduction Catalyzed by Organic Compounds

Studies of the Effect of Thiourea on the Electroreduction of In(III) Ions in Perchloric Acid

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

Contact Info

Product

Resources

About