Kinetics and mechanism of the complex formation of the chlorite ion and iron (III) in aqueous solution

I. Fábián, Gilbert Gordon

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

On the basis of rapid-scan spectrophotometric and one-wavelength stopped-flow experiments, the formation of the FeClO22+ complex was confirmed in the iron(III)-chlorite ion system. The complex formation is associated with the appearance of a new charge-transfer band in the visible spectral region. The stability constant of FeClO22+ was calculated from the final absorbance value of stopped-flow traces recorded at 510 nm. log K = 1.14 ± 0.02 and ∈510 = 636 ± 10 M-1 cm-1 (I = 1.0 M (NaClO4), 25°C). It was demonstrated that the complex formation is kinetically coupled with catalytic decomposition of ClO2-. The proposed mechanism for the ligand substitution reaction includes the reactions of Fe3+ and Fe(OH)2+ and also a generalized pathway for the chlorite ion decomposition. The rate constant for the Fe3+ + ClO2- = FeClO22+ step, 269 ± 55 M-1 s-1, is consistent with an associative interchange mechanism predicted by previous kinetic data for complex formation reactions of Fe(III).

Original languageEnglish
Pages (from-to)3994-3999
Number of pages6
JournalInorganic Chemistry
Volume30
Issue number21
Publication statusPublished - 1991

Fingerprint

Iron
Ions
aqueous solutions
Decomposition
iron
Kinetics
kinetics
Interchanges
Charge transfer
Rate constants
ions
Substitution reactions
Ligands
decomposition
Wavelength
Experiments
charge transfer
substitutes
ligands
chlorite

ASJC Scopus subject areas

  • Inorganic Chemistry

Cite this

Kinetics and mechanism of the complex formation of the chlorite ion and iron (III) in aqueous solution. / Fábián, I.; Gordon, Gilbert.

In: Inorganic Chemistry, Vol. 30, No. 21, 1991, p. 3994-3999.

Research output: Contribution to journalArticle

@article{84df7dd06a154c4bb56b6b681f2d4b17,
title = "Kinetics and mechanism of the complex formation of the chlorite ion and iron (III) in aqueous solution",
abstract = "On the basis of rapid-scan spectrophotometric and one-wavelength stopped-flow experiments, the formation of the FeClO22+ complex was confirmed in the iron(III)-chlorite ion system. The complex formation is associated with the appearance of a new charge-transfer band in the visible spectral region. The stability constant of FeClO22+ was calculated from the final absorbance value of stopped-flow traces recorded at 510 nm. log K = 1.14 ± 0.02 and ∈510 = 636 ± 10 M-1 cm-1 (I = 1.0 M (NaClO4), 25°C). It was demonstrated that the complex formation is kinetically coupled with catalytic decomposition of ClO2-. The proposed mechanism for the ligand substitution reaction includes the reactions of Fe3+ and Fe(OH)2+ and also a generalized pathway for the chlorite ion decomposition. The rate constant for the Fe3+ + ClO2- = FeClO22+ step, 269 ± 55 M-1 s-1, is consistent with an associative interchange mechanism predicted by previous kinetic data for complex formation reactions of Fe(III).",
author = "I. F{\'a}bi{\'a}n and Gilbert Gordon",
year = "1991",
language = "English",
volume = "30",
pages = "3994--3999",
journal = "Inorganic Chemistry",
issn = "0020-1669",
publisher = "American Chemical Society",
number = "21",

}

TY - JOUR

T1 - Kinetics and mechanism of the complex formation of the chlorite ion and iron (III) in aqueous solution

AU - Fábián, I.

AU - Gordon, Gilbert

PY - 1991

Y1 - 1991

N2 - On the basis of rapid-scan spectrophotometric and one-wavelength stopped-flow experiments, the formation of the FeClO22+ complex was confirmed in the iron(III)-chlorite ion system. The complex formation is associated with the appearance of a new charge-transfer band in the visible spectral region. The stability constant of FeClO22+ was calculated from the final absorbance value of stopped-flow traces recorded at 510 nm. log K = 1.14 ± 0.02 and ∈510 = 636 ± 10 M-1 cm-1 (I = 1.0 M (NaClO4), 25°C). It was demonstrated that the complex formation is kinetically coupled with catalytic decomposition of ClO2-. The proposed mechanism for the ligand substitution reaction includes the reactions of Fe3+ and Fe(OH)2+ and also a generalized pathway for the chlorite ion decomposition. The rate constant for the Fe3+ + ClO2- = FeClO22+ step, 269 ± 55 M-1 s-1, is consistent with an associative interchange mechanism predicted by previous kinetic data for complex formation reactions of Fe(III).

AB - On the basis of rapid-scan spectrophotometric and one-wavelength stopped-flow experiments, the formation of the FeClO22+ complex was confirmed in the iron(III)-chlorite ion system. The complex formation is associated with the appearance of a new charge-transfer band in the visible spectral region. The stability constant of FeClO22+ was calculated from the final absorbance value of stopped-flow traces recorded at 510 nm. log K = 1.14 ± 0.02 and ∈510 = 636 ± 10 M-1 cm-1 (I = 1.0 M (NaClO4), 25°C). It was demonstrated that the complex formation is kinetically coupled with catalytic decomposition of ClO2-. The proposed mechanism for the ligand substitution reaction includes the reactions of Fe3+ and Fe(OH)2+ and also a generalized pathway for the chlorite ion decomposition. The rate constant for the Fe3+ + ClO2- = FeClO22+ step, 269 ± 55 M-1 s-1, is consistent with an associative interchange mechanism predicted by previous kinetic data for complex formation reactions of Fe(III).

UR - http://www.scopus.com/inward/record.url?scp=4243630196&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=4243630196&partnerID=8YFLogxK

M3 - Article

VL - 30

SP - 3994

EP - 3999

JO - Inorganic Chemistry

JF - Inorganic Chemistry

SN - 0020-1669

IS - 21

ER -