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Title: Role of trace iron(III) and equilibrium Fe(III) + Fe(CN) Fe(II) +Fe(CN) in the investigation on kinetics and mechanism of oxidation of hexacyanoferrate( II) by peroxodiphosphate in acid perchlorate solution
Authors: Mishra, Dilip Kumar
Amaladhas, T Peter
Bhargava, A P
Gupta, Y K
Issue Date: Mar-1993
Publisher: NISCAIR-CSIR, India
Abstract: Oxidation of hexacyanoferrate(ll) with peroxodiphosphate(pdp) in aqueous perchloric acid solutions occurs through the catalysis by Fe(III) present in traces in the reagents and distilled water involving the equilibrium. Fe(III) + Fe(CN) Fe(ll) + Fe(CN). Fe(ll) is oxidised back to Fe(III) by pdp in the fast step. The rate law is d[Fe(CN)]/dt =((k1 + kd/[H+]) [Fe(Ill)][Fe(CN)].The values of k1 and kd have been found to be 5.7 x 103dm3 mol-1 s-1 and 36 s-1 respectively at I = 0.5 mol dm- 3and 30°. The equilibrium constant for the above equilibrium determined spectrophotometrically is 34 ± 4 at 28°, I = 0.05 mol dm-3 and [H+] = 0.01 mol dm-3. Aquo copper(II) retards the rate of oxidation of Fe(CN) by pdp. Spectrophotometrically too the equilibrium is shifted to the left in the presence of Cu(II).
Page(s): 187-194
ISSN: 0975-0975(Online); 0376-4710(Print)
Appears in Collections:IJC-A Vol.32A(03) [March 1993]

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