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A kinetic study of the oxidation of L‐ascorbic acid by chromium(VI)
Author(s) -
PerezBenito Joaquin F.,
Arias Conchita
Publication year - 1993
Publication title -
international journal of chemical kinetics
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.341
H-Index - 68
eISSN - 1097-4601
pISSN - 0538-8066
DOI - 10.1002/kin.550250402
Subject(s) - chemistry , ionic strength , reaction rate constant , chromium , redox , protonation , equilibrium constant , ascorbic acid , aqueous solution , inorganic chemistry , chromate conversion coating , reaction rate , ionic bonding , manganese , ion , reaction mechanism , kinetics , catalysis , organic chemistry , physics , food science , quantum mechanics
The reaction between chromium(VI) and L‐ascorbic acid has been studied by spectrophotometry in the presence of aqueous citrate buffers in the pH range 5.69–7.21. The reaction is slowed down by an increase of the ionic strength. At constant ionic strength, manganese(II) ion does not exert any appreciable inhibition effect on the reaction rate. The rate law found is\documentclass{article}\pagestyle{empty}\begin{document}$$ r = k_p k_r [Cr({\rm VI})][{\rm L - ascorbic\,acid][H}^{\rm + }]/(1 + k_p [H^ +]) $$\end{document}where K p is the equilibrium constant for protonation of chromate ion and k r is the rate constant for the redox reaction between the active forms of the oxidant (hydrogenchromate ion) and the reductant (L‐hydrogenascorbate ion). The activation parameters associated with rate constant k r are E a = 20.4 ± 0.9 kJ mol −1 , Δ H ≠ = 17.9 ± 0.9 kJ mol −1 , and Δ S ≠ =−152 ± 3 J K −1 mol −1 . The reaction thermodynamic magnitudes associated with equilibrium constant K p are Δ H 0 = 16.5 ± 1.1 kJ mol −1 and Δ S 0 = 167 ± 4 J K −1 mol −1 . A mechanism in accordance with the experimental data is proposed for the reaction. © 1993 John Wiley & Sons, Inc.