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Kinetics and mechanistic investigation of persulfate anion-mediated oxidation of hexacyanoruthenate(II) in aqueous medium

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Title Kinetics and mechanistic investigation of persulfate anion-mediated oxidation of hexacyanoruthenate(II) in aqueous medium
 
Creator Singh, Ruchi
Srivastava, Abhishek
Yadav, Rupal
Gangwar, Chinki
Yaseen, Bushra
Kumar, Indresh
Naik, Radhey Mohan
 
Subject Persulfate
Oxidation
Hexacyanoruthenate(II)
Kinetics and Mechanism
Ion-pair, Salt effect
 
Description 1282-1288
The proposed study aimed to explore the kinetics of [Ru(CN)6]4– oxidation in an aqueous media by persulfate anion
(S2O8
2–). The increment in absorbance at 460 nm, which is indicative of the concentration of [Ru(CN)6]3–, was measured to
determine the reaction rate. Applying the pseudo-first-order state, the reaction's progression was analyzed as an indicator of
[Ru(CN)6
4–], temperature, [S2O8
2–], ionic strength, and pH. The findings indicate that the pH of the medium is the crucial
factor that significantly affects the rate of the reaction. The [Ru(CN)6]4– undergoes a 2:1 stoichiometric interaction with
S2O8
2–. The observed reaction exhibits first-order kinetics with regard to [Ru(CN)6
4–], and [S2O8
2–], within the range of
concentrations investigated. The observed invariance in reaction rate upon electrolyte’s introduction is suggestive of a zero
salt effect. The electron transfer from [Ru(CN)6]4– to S2O8
2– proceeds via the formation of ion-pair, which leads to the
formation of [Ru(CN)6]3, sulfate ion, and sulfate radical ion. The formation of ion-pair is strengthened by the zero salt
effect, while, the comparatively low activation energy and free radical test supports the formation of sulfate radical ion
during the course of the reaction. The outer-sphere electron transfer pathway, via the formation of ion-pair as proposed by
us, is further supported by the negative entropy of activation value.
 
Date 2023-12-20T09:38:17Z
2023-12-20T09:38:17Z
2023-12
 
Type Article
 
Identifier 2583-1321 (Online); 0019-5103 (Print)
http://nopr.niscpr.res.in/handle/123456789/63021
https://doi.org/10.56042/ijc.v62i12.5814
 
Language en
 
Publisher NIScPR-CSIR, India
 
Source IJC Vol.62(12) [December 2023]