Reduction potential of the tert-butylperoxyl radical in aqueous solutions

Tomi Nath Das; T. Dhanasekaran; Z. B. Alfassi; P. Neta

doi:10.1021/jp972903t

Reduction potential of the tert-butylperoxyl radical in aqueous solutions

Tomi Nath Das, T. Dhanasekaran, Z. B. Alfassi, P. Neta

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Abstract

Rate constants for the oxidation of tert-butyl hydroperoxide anion by several oxidants were determined by pulse radiolysis. Since the reduction potentials of the oxidants are much higher than the t-BuO₂, the observed rate constants suggest that the self-exchange rate for t-BuO₂/r-BuO₂ is very slow and that it would be difficult to establish rapid equilibrium by pulse radiolysis with a suitable redox pair. Therefore, to determine the reduction potential for this peroxy radical, the forward and reverse rate constants for reaction, t-BuO₂^·+Fe(CN)₆^4- ⇔ t-BuO₂^-+Fe(CN)₆^3-, were measured independently. The forward rate constant was measured by kinetic spectrophotometric pulse radiolysis in N₂O-saturated solutions.

Original language	English
Pages (from-to)	280-284
Number of pages	5
Journal	Journal of Physical Chemistry A
Volume	102
Issue number	1
DOIs	https://doi.org/10.1021/jp972903t
State	Published - 1 Jan 1998
Externally published	Yes

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Physical and Theoretical Chemistry

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title = "Reduction potential of the tert-butylperoxyl radical in aqueous solutions",

abstract = "Rate constants for the oxidation of tert-butyl hydroperoxide anion by several oxidants were determined by pulse radiolysis. Since the reduction potentials of the oxidants are much higher than the t-BuO2, the observed rate constants suggest that the self-exchange rate for t-BuO2/r-BuO2 is very slow and that it would be difficult to establish rapid equilibrium by pulse radiolysis with a suitable redox pair. Therefore, to determine the reduction potential for this peroxy radical, the forward and reverse rate constants for reaction, t-BuO2·+Fe(CN)64- ⇔ t-BuO2-+Fe(CN)63-, were measured independently. The forward rate constant was measured by kinetic spectrophotometric pulse radiolysis in N2O-saturated solutions.",

author = "Das, {Tomi Nath} and T. Dhanasekaran and Alfassi, {Z. B.} and P. Neta",

year = "1998",

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T1 - Reduction potential of the tert-butylperoxyl radical in aqueous solutions

AU - Das, Tomi Nath

AU - Dhanasekaran, T.

AU - Alfassi, Z. B.

AU - Neta, P.

PY - 1998/1/1

Y1 - 1998/1/1

N2 - Rate constants for the oxidation of tert-butyl hydroperoxide anion by several oxidants were determined by pulse radiolysis. Since the reduction potentials of the oxidants are much higher than the t-BuO2, the observed rate constants suggest that the self-exchange rate for t-BuO2/r-BuO2 is very slow and that it would be difficult to establish rapid equilibrium by pulse radiolysis with a suitable redox pair. Therefore, to determine the reduction potential for this peroxy radical, the forward and reverse rate constants for reaction, t-BuO2·+Fe(CN)64- ⇔ t-BuO2-+Fe(CN)63-, were measured independently. The forward rate constant was measured by kinetic spectrophotometric pulse radiolysis in N2O-saturated solutions.

AB - Rate constants for the oxidation of tert-butyl hydroperoxide anion by several oxidants were determined by pulse radiolysis. Since the reduction potentials of the oxidants are much higher than the t-BuO2, the observed rate constants suggest that the self-exchange rate for t-BuO2/r-BuO2 is very slow and that it would be difficult to establish rapid equilibrium by pulse radiolysis with a suitable redox pair. Therefore, to determine the reduction potential for this peroxy radical, the forward and reverse rate constants for reaction, t-BuO2·+Fe(CN)64- ⇔ t-BuO2-+Fe(CN)63-, were measured independently. The forward rate constant was measured by kinetic spectrophotometric pulse radiolysis in N2O-saturated solutions.

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DO - 10.1021/jp972903t

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JO - Journal of Physical Chemistry A

JF - Journal of Physical Chemistry A

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Reduction potential of the tert-butylperoxyl radical in aqueous solutions

Abstract

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