A Spectrophotometric Study of the Hydrolysis of Iron(III) Ion. II. Polynuclear Species<sup>1</sup>

Milburn, Ronald M.; Vosburgh, W. C.

doi:10.1021/ja01610a084

Cited by 184 publications

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“…It is worth noting here that this figure, which is in fact much larger than that obtained for the solution of Fig. 1 a, is very close to the relative concentration of dihydroxo dimers in 10~2M aqueous solu tions of (C104)3Fe for a pH = 2.5 derived by Milburn and Vosburgh [26]. This fact outlines the ability of water (or of OH-ions produced by the hydrolysis) for replacing the isopropanol as ligand of Fe3+ [7], This feature has also been noticed for solutions of Al3+ and Be2+ in non-aqueous solvents [8,9], Anyway, the results shown on Fig.…”

Section: Applicationssupporting

confidence: 71%

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Rodríguez

Moreno

Sal

1984

Zeitschrift Für Naturforschung A

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M a g n e tiz a tio n M e a s u r e m e n ts o n I r o n ( I I I ) S o l u t i o n s fo r D e te c tin g O lig o m e r F o r m a tio n F. Rodríguez, M. Moreno, and J. C. Gómez Sal Departamento de Optica y Estructura de la Materia. Facultad de Ciencias, Universidad de Santander, Santander, Spain Z. Naturforsch. 39a, 617-622 (1984); received February 29, 1984 By measuring the magnetization at low temperatures (near 1 K) and intense magnetic fields 100 KG), information about oligomer formation in ferric salts solutions can be obtained. It is shown that, under rather general conditions, the magnetic moment per ferric ion of a given ferric solution measured in the saturation regime should be equal to 5 ß if all the complexes involved in the solution are high-spin monomers. Moreover, if the solution is mainly composed by monomeric species and antiferromagnetic dimers, the relative concentration of monomeric and dimeric species can easily be determined. This techniques has been applied to solutions of Cl3Fe and (N03)3Fe9H20 in isopropanol as solvent containing about 0.4 M of water. In the first case the present measurements are consistent with the existence of dihydroxo ferric dimers suggested by previous Mössbauer and Optical Absorption data. The relative concentration of these dimers increases from 25% to 50% when the water content increases from 0.4 M to ~ 10 M. In the second case it is confirmed that the solution is mainly composed by oligomers, the relative concentration of monomeric species being less than 30%.

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Section: Applicationssupporting

confidence: 71%

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Rodríguez

Moreno

Sal

1984

Zeitschrift Für Naturforschung A

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“…T h e principal hydrolyzed species present in solution are FeOH2+ and UOH3+ (15,17,13), which exist in equilibrium with the parent fully hydrated ions according to:…”

Section: Effect Of Hydrogen-ion Concentrationmentioning

confidence: 99%

Kinetics of the Oxidation of Uranium (Iv) by Iron (Iii) in Aqueous Solutions of Perchloric Acid

Betts¹

1955

Can. J. Chem.

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The kinetics of oxidation of uranium (IV) b y iron (111) in aqueous solutions of perchloric acid have been investigated a t four temperatures between 3.1°C. and 24.8"C. The reaction was followed by measurement of the amount of ferrous ion formed. For the conditions (Il+) = 0.1-1.0 iM, ionic strength = 1.02, (FelII) = 10-'-10-5 hf, and (UIV) = lO-'-lO-6 ill, the observed rate law is d(FeZ+)/dt = -2d(UIV) /dt -K1 and Kn are the first hydrolysis constants for Fe3+ and U4+, respectively, and K'and K" are pseudo rate constants. At 24.8"C., K' = 2.98 sec.-I, and K" = 10.6 mole liter-' sec-'. The corresponding temperature coefficients are AH' = 22.5 kcal./mole and AH" = 24.2 kcal./mole. The kinetics of the process are consistent with a mechanism which involves, as a rate-controlling step, electron transfer between hydrolyzed ions. INTRODUCTIONOxidation-reduction reactions between cations in aqueous solution have been thought until recently t o proceed very rapidly, and the term "instantaneous" has frequently been used to characterize their rates. However recent studies with radioactive tracers have shown that even such elementary reactions as electron transfer between iron (11) and iron (I 11), or between Ce (I 11) and Ce (IV), do not proceed instantaneously (18,8). Such results have reawakened interest in the whole subject of both isotopic and ilo~lisotopic electron transfer reactioils between cations in solution. Some kinetic information is now available relating to the reactioils between the nonisotopic pairs Sn (11) -Fe (111) (5), T1 (111) -Fe (11) (2), and N p (IV) -Fe (111) (10).Several review articles have recently appeared in which the current status of theory and experiment have been summarized for both isotopic and nonisotopic clcctron transfer reactioils (1,14,19). The proceedings of a symposium held in 1954 on this subject have also been published (12).As a further example of this type of reaction, the present paper describes experiments relating to the kinetics of the oxidatioil of uranium (IV) by iron (111) in aqueous acidic media. Perchloric acid and sodium perchlorate were chosen as the principal electrolytes, since amongst the common inorganic anions, perchlorate has the least tendency to form ion-pairs with cations. T o bring the rate of reaction into a range suitable for study, it has been necessary to work with solutions to 10-5 M in uranium (IV) and iron (111). T h e course of the reaction has been followecl by measurement of the rate of formatioil of iron (11). Such measurements, in conju~lction with a knowledge of the stoichiometry of the reaction, were sufficient to enable a kinetic analysis of the results to be made. I t would have been useful, as confirmatory evidence, lMa?zz~script

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“…A known concentration of (0.1 mol dm Ϫ3 ) iron(III) in aqueous perchloric acid medium was prepared and standardized according to the method described elsewhere [10,11]. Fluka sample of sodium dodecyl sulphate (SDS) has been used in the preparation of 0.1 mol dm Ϫ3 solution.…”

Section: Methodsmentioning

confidence: 99%

Kinetics of some electron-transfer reactions of iron (III)-2,2?-bipyridyl complex. Micellar effect of sodium dodecyl sulphate

Rao

Ramakrishna

et al. 1997

Int. J. Chem. Kinet.

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Iron(III)-2,2Ј-bipyridyl complex obtained, in situ, by direct mixing of iron(III) and 2,2Ј-bipyridyl, oxidizes aniline, thiourea, and ascorbic acid. The reaction is markedly accelerated by sodium dodecyl sulphate. The rate-[surfactant] profile exhibits a maximum. The kinetic analysis of the micellar effect has been carried out using Berezin's approach. The binding constants of 2,2Ј-bipyridyl, aniline, thiourea, and ascorbic acid have been determined.

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A Spectrophotometric Study of the Hydrolysis of Iron(III) Ion. II. Polynuclear Species¹

Cited by 184 publications

References 1 publication

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Kinetics of the Oxidation of Uranium (Iv) by Iron (Iii) in Aqueous Solutions of Perchloric Acid

Kinetics of some electron-transfer reactions of iron (III)-2,2?-bipyridyl complex. Micellar effect of sodium dodecyl sulphate

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A Spectrophotometric Study of the Hydrolysis of Iron(III) Ion. II. Polynuclear Species1

Cited by 184 publications

References 1 publication

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Magnetization Measurements on Iron (III)Solutions for Detecting Oligomer Formation

Kinetics of the Oxidation of Uranium (Iv) by Iron (Iii) in Aqueous Solutions of Perchloric Acid

Kinetics of some electron-transfer reactions of iron (III)-2,2?-bipyridyl complex. Micellar effect of sodium dodecyl sulphate

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A Spectrophotometric Study of the Hydrolysis of Iron(III) Ion. II. Polynuclear Species¹