Oxidation of β-Cyclodextrin by Hexacyanoferrate(III) in Aqueous Alkaline Medium: a Kinetic and Mechanistic Study

M.B. Bolattin¹ , A.S. Kulkarni² , N.M. Mulla³ , S.S. Badiger⁴ , M.S. Gurav⁵ , N.B. Banashetti⁶

1. P.G. Department of Studies in Chemistry, D.M.S. Mandal’s, Bhaurao Kakatkar College, Belgaum, India.
2. P.G. Department of Studies in Chemistry, D.M.S. Mandal’s, Bhaurao Kakatkar College, Belgaum, India.
3. P.G. Department of Studies in Chemistry, D.M.S. Mandal’s, Bhaurao Kakatkar College, Belgaum, India.
4. P.G. Department of Studies in Chemistry, D.M.S. Mandal’s, Bhaurao Kakatkar College, Belgaum, India.
5. P.G. Department of Studies in Chemistry, D.M.S. Mandal’s, Bhaurao Kakatkar College, Belgaum, India.
6. P.G..

Section:Research Paper, Product Type: Isroset-Journal
Vol.5 , Issue.5 , pp.1-7, Oct-2018

Online published on Oct 31, 2018

Copyright © M.B. Bolattin, A.S. Kulkarni, N.M. Mulla, S.S. Badiger, M.S. Gurav, N.B. Banashetti . This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.
 

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Abstract :
The kinetics of redox reaction between β-cyclodextrin (β-CD) and hexacyanoferrate(III) has been studied spectrophotometrically in alkaline medium at 25oC and at an ionic strength of 1.10 mol dm–3. The order with respect to [Fe(CN)6]3- was found to be unity and order with respect to alkali and [β-CD] was found to be less than unity. Increasing alkali and ionic strength concentration accelerates the rate of the reaction. The reaction between β-CD and hexacyanoferrate(III) involves 1:2 stoichiometry. Oxidised products are confirmed by FT-IR and 1H-NMR spectral technique. The main reaction product is identified as (3S,4R,5S,6S)-4,5-dihydroxy-3,6-dimethoxy-tetrahydro-2H-pyran-2-carbaldehyde. Based on the experimental results a suitable mechanism is proposed and the rate law is derived. The reaction in alkaline medium proceeds through the formation of oxidant–reductant complex that decomposes slowly in a rate determining step followed by fast step to give the product. The activation parameters with respect to the slow step of the mechanism are calculated. The reaction constants involved in the mechanism have been computed. There is a good agreement between the experimental and calculated rate constants under different experimental conditions.

Key-Words / Index Term :
Kinetics; Oxidation; β-cyclodextrin; Hexacyanoferrate(III); Mechanism

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