Chanda, M and O'Driscoll, KF and Rempel, GL (1981) Polymer supported metal complexes as catalysts for oxidation of thiosalts by molecular oxygen IV. Quaternised poly(4-vinyl pyridine) complexes with Cu2+ as template. In: Journal of Molecular Catalysis, 12 (2). pp. 197-211.
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Copper(II) complexes of quaternised poly(4-vinylpyridine) (PVP) of different degrees of quaternisation and copper content have been prepared by crosslinking the polymer with 1,2-dibromoethane in the presence of Cu2+ ion as template. The stability constant of the PVP---Cu(II) complexes is found to increase with the degree of crosslinking quaternisation of the resin, but the rate at which Cu2+ is adsorbed by the resin decreases. An optimum combination of both stability and rate can be achieved with a moderate degree (31%) of crosslinking. A kinetic study reveals that quaternisation increases significantly the catalytic activity of the complex for the oxidation of S2O2−3 by O2 compared with PVP----Cu(II) without quaternisation, but it deactivates the complex for the oxidation of both S3O2−6 and S4O2−6. The batch reactor oxidation kinetics at pH 2.16, where the rate is observed to be maximum, is well explained by the Langmuir—Hinshelwood model assuming the coordination of both O2 and thioanion to Cu(II) as a precursor to the oxidation reaction.
|Item Type:||Journal Article|
|Additional Information:||Copyright of this article belongs to Elsevier Science B. V|
|Department/Centre:||Division of Mechanical Sciences > Chemical Engineering|
|Date Deposited:||18 Jan 2010 10:05|
|Last Modified:||19 Sep 2010 05:45|
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