Redox interactions between structurally different alkylresorcinols and iron(III) in aqueous media

Frozen-solution 57Fe Mössbauer spectroscopic studies, redox kinetics and quantum chemical evaluation of the alkylresorcinol reactivities

Alexander A. Kamnev, Roman L. Dykman, Krisztina Kovács, Alexei N. Pankratov, Anna V. Tugarova, Z. Homonnay, E. Kuzmann

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of 57Fe transmission Mössbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). Mössbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of Mössbauer spectroscopy: 4-n-HR 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR 5-n-PR > 5-MR resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure.

Original languageEnglish
Pages (from-to)649-657
Number of pages9
JournalStructural Chemistry
Volume25
Issue number2
DOIs
Publication statusPublished - 2014

Fingerprint

Hexylresorcinol
Iron
reactivity
iron
Kinetics
evaluation
kinetics
Density functional theory
interactions
Spectroscopy
density functional theory
Redox reactions
Kinetic parameters
spectroscopy
Rate constants
quadrupoles
analogs
aqueous solutions
Oxidation
oxidation

Keywords

  • Alkylresorcinols
  • DFT calculations
  • Iron(III) reduction
  • Redox kinetics

ASJC Scopus subject areas

  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Redox interactions between structurally different alkylresorcinols and iron(III) in aqueous media : Frozen-solution 57Fe Mössbauer spectroscopic studies, redox kinetics and quantum chemical evaluation of the alkylresorcinol reactivities. / Kamnev, Alexander A.; Dykman, Roman L.; Kovács, Krisztina; Pankratov, Alexei N.; Tugarova, Anna V.; Homonnay, Z.; Kuzmann, E.

In: Structural Chemistry, Vol. 25, No. 2, 2014, p. 649-657.

Research output: Contribution to journalArticle

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abstract = "Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of 57Fe transmission M{\"o}ssbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). M{\"o}ssbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of M{\"o}ssbauer spectroscopy: 4-n-HR 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR 5-n-PR > 5-MR resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure.",
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AU - Kamnev, Alexander A.

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AB - Iron(III)-containing aqueous solutions of 5-methylresorcinol (5-MR), 5-n-propylresorcinol (5-n-PR) and 4-n-hexylresorcinol (4-n-HR) at pH ~ 3 were studied by means of 57Fe transmission Mössbauer spectroscopy. Kinetic considerations were applied to the redox reactions. Density Functional Theory (DFT) calculations were performed for the alkylresorcinol (AR) molecules and their non-alkylated analogue (resorcinol). Mössbauer spectra consisted of quadrupole doublets assigned to high-spin Fe(III) and Fe(II) species. From changes in their relative spectral areas, a gradual reduction of Fe(III) by all the ARs studied was observed. However, significant differences were found for the reduction rates among the ARs. The following series of the reduction rates was established by means of Mössbauer spectroscopy: 4-n-HR 5-MR > 5-n-PR, supplemented by rate constants calculated using a kinetic model. DFT calculations resulted in the following series: 4-n-HR 5-n-PR > 5-MR resorcinol (the latter is not oxidised under the conditions applied). The reversed order of the experimentally observed 5-MR and 5-n-PR oxidation rates may be explained in terms of their different kinetic parameters related to their structure.

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