The copper-catalysed oxidation of ascorbic acid by dioxygen. Part 4. The effect of chloride ions on the kinetics and mechanism

Reginald F. Jameson, Ninian Blackburn

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24 Citations (Scopus)

Abstract

The effect of chloride ions on the kinetics and mechanism of the copper-catalysed oxidation of ascorbic acid by dissolved oxygen has been examined over the pH range 2.0-3.5 and chloride concentrations up to 0.2 mol dm-3. The empirical rate law has been established as - d[O2]/dt = kobs.[O2]1/2 over the whole range. At constant total ascorbate, total copper, and hydrogen ion concentrations, the general relationship (1) was obtained. The constants kobs. = A + B[Cl-]/C + D[Cl-] + E[Cl-]2 (1) A to E were evaluated using data obtained in pure nitrate media to fix A and C, and the dependence of all the constants on pH, total copper concentration, and total ascorbate concentrations established experimentally. It is also pointed out that a mechanism based on the involvement of copper(I) rather than the copper(III) invoked by us cannot be entirely ruled out.

Original languageEnglish (US)
Pages (from-to)9-13
Number of pages5
JournalJournal of the Chemical Society, Dalton Transactions
Issue number1
DOIs
StatePublished - 1982
Externally publishedYes

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Ascorbic Acid
Chlorides
Copper
Ions
Oxygen
Oxidation
Kinetics
pH
Dissolved oxygen
Nitrates

ASJC Scopus subject areas

  • Chemistry(all)

Cite this

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abstract = "The effect of chloride ions on the kinetics and mechanism of the copper-catalysed oxidation of ascorbic acid by dissolved oxygen has been examined over the pH range 2.0-3.5 and chloride concentrations up to 0.2 mol dm-3. The empirical rate law has been established as - d[O2]/dt = kobs.[O2]1/2 over the whole range. At constant total ascorbate, total copper, and hydrogen ion concentrations, the general relationship (1) was obtained. The constants kobs. = A + B[Cl-]/C + D[Cl-] + E[Cl-]2 (1) A to E were evaluated using data obtained in pure nitrate media to fix A and C, and the dependence of all the constants on pH, total copper concentration, and total ascorbate concentrations established experimentally. It is also pointed out that a mechanism based on the involvement of copper(I) rather than the copper(III) invoked by us cannot be entirely ruled out.",
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AU - Jameson, Reginald F.

AU - Blackburn, Ninian

PY - 1982

Y1 - 1982

N2 - The effect of chloride ions on the kinetics and mechanism of the copper-catalysed oxidation of ascorbic acid by dissolved oxygen has been examined over the pH range 2.0-3.5 and chloride concentrations up to 0.2 mol dm-3. The empirical rate law has been established as - d[O2]/dt = kobs.[O2]1/2 over the whole range. At constant total ascorbate, total copper, and hydrogen ion concentrations, the general relationship (1) was obtained. The constants kobs. = A + B[Cl-]/C + D[Cl-] + E[Cl-]2 (1) A to E were evaluated using data obtained in pure nitrate media to fix A and C, and the dependence of all the constants on pH, total copper concentration, and total ascorbate concentrations established experimentally. It is also pointed out that a mechanism based on the involvement of copper(I) rather than the copper(III) invoked by us cannot be entirely ruled out.

AB - The effect of chloride ions on the kinetics and mechanism of the copper-catalysed oxidation of ascorbic acid by dissolved oxygen has been examined over the pH range 2.0-3.5 and chloride concentrations up to 0.2 mol dm-3. The empirical rate law has been established as - d[O2]/dt = kobs.[O2]1/2 over the whole range. At constant total ascorbate, total copper, and hydrogen ion concentrations, the general relationship (1) was obtained. The constants kobs. = A + B[Cl-]/C + D[Cl-] + E[Cl-]2 (1) A to E were evaluated using data obtained in pure nitrate media to fix A and C, and the dependence of all the constants on pH, total copper concentration, and total ascorbate concentrations established experimentally. It is also pointed out that a mechanism based on the involvement of copper(I) rather than the copper(III) invoked by us cannot be entirely ruled out.

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