Kinetics and mechanism of the oxidation of thiosulfate ion by hexachloroiridate(IV)

Goyal, Bharti; Solanki, Sangeeta; Arora, Sumati; Prakash, Aditya; Mehrotra, Raj N.

doi:10.1039/dt9950003109

Cited by 14 publications

(16 citation statements)

References 30 publications

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“…It follows that the reaction sequence given by equation (14b) and (14c) describes the reaction of TCNQF 1À is described by equations ( 15) and (16). A related, two-step reaction has been proposed as part of the mechanism reported for oxidation of S 2 O 3 2À by [IrCl 6 ] 2À , [28] and [Fe(CN) 6 ] 3À , [29] although these reactions are more complex. [9,[29][30] TCNQF…”

Section: Equal or Excess Concentrations Of S 2 O 3 2àmentioning

confidence: 99%

Electrochemical Investigation of the Oxidation of Thiosulfate by 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane and Its Anion Radical

2021

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Section: Equal or Excess Concentrations Of S 2 O 3 2àmentioning

confidence: 99%

Electrochemical Investigation of the Oxidation of Thiosulfate by 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane and Its Anion Radical

2021

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“…, implicating a reaction process occurring via a single acid dependent pathway(Mshelia et al 2010;Onu et al 2015), thus the forward reaction in an equilibrium association of these active species becomes the rate determining step of the reaction in which an ion associate is formed (Equation 5). The concentration of the complex assuming a zero order with respect to the reaction, S2O3 2assuming a second order and the [H + ] taking up a first order was as a result of the equilibrium association of these species.…”

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confidence: 99%

Electron transfer reaction of Tris(1,10-phenanthroline) cobalt(III) complex [Co(phen)3]3+ and thiosulphate ion (S2O32âˆ’) in an aqueous acidic medium

Osunkwo

Nkole

Onu

et al. 2018

IJAC

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The electron transfer reaction of Tris (1,10-phenanthroline)cobalt(III) complex by thiosulphate ion has been studied in an aqueous acidic medium. Stoichiometric determination shows that for one mole of the oxidant that was reduced, one mole of the reductant was consumed; the reaction conforms to an overall equation: 2[Co(phen)3]3+ + 2S2O32− → 2[Co(phen)3]2+ + S4O62− Kinetics study carried out under pseudo-first order condition shows that the reaction proceeded via a one-way acid-dependent pathway and was third order overall; zero order with respect to the oxidant concentration, second order with respect to the reductant concentration and first order with respect to the hydrogen ion concentration. The empirical rate law conforms to the equation: − {Co(phen)3}3+] = a [H+] [S2O32−]2 ‘a’ = 128.26 dm6 mol−2 s−1: at [H+] = 2.0 × 10−2 mol dm−3, µ = 0.4 mol dm−3 (NaCl), T = 28 ± 1˚C and λmax = 495 nm.The rate of reaction increased at the increase in ionic strength and at the decrease in medium dielectric constant. Added cations and anions catalyzed and inhibited the reaction rates respectively. The Michaelis-Menten plot of 1/k1 versus 1/[S2O32−]2 started from the origin. Hence based on spectroscopic investigation, thermodynamic information from temperature dependence studies and kinetic evidence from Michaelis–Menten plots and the interactions with added ions, an outer-sphere mechanism has been rationalized for this reaction. The mechanistic scheme of the reaction was proposed via the stated mechanistic route.

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“…The acid dependence plot of k2 versus [H + ] starts from the origin (Fig. 4), and therefore signifies that the reaction occurs via a single acid dependence pathway [15,16,17], its slope of 0 78 infers a first-order dependence on the [acid] [18].…”

Section: Resultsmentioning

confidence: 92%

Reduction of tris(2,2’-bipyridine)cobalt(III) complex by thiosulphate ion in an aqueous acidic medium

Osunkwo¹,

Nkole

2021

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The reduction of tris(2,2-bipyridine)cobalt(III) complex by thiosulphate ion in an aqueous acidic medium gave a notable outcome. The stoichiometric evaluation indicates that one mole of the reducing agent has been consumed by one mole of the oxidant, and the reaction complies with an overall equation: 2[Co(bpy)3]3+ + 2S2O32− 2[Co(bpy)3]2+ + S4O62− The kinetics study conducted under a pseudo-first-order method shows that the rate of the reaction was acid-reliant and third-order overall; zero-order in the [oxidant], second-order in the [reductant], and first-order in the hydrogen ion concentration. The empirical rate expression complies with the equation:− [Co(bpy)33+] = a [H+][S2O32−]2‘a’ = 77.82 dm6 mol−2 s−1; at [H+] = 2.0 × 10−2 mol dm−3, µ = 0.4 mol dm−3 (NaCl), T = 28 ± 1˚C and λmax = 560 nm.With increased ionic strength and decreased medium dielectric constant, the reaction rate increased. The inclusion of cations and anions accelerate and constricted the reaction rates respectively. Spectroscopic examination and kinetic evidence indicate an outer sphere mechanism, and the mechanism was therefore proposed via an outer-sphere route.

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Kinetics and mechanism of the oxidation of thiosulfate ion by hexachloroiridate(IV)

Cited by 14 publications

References 30 publications

Electrochemical Investigation of the Oxidation of Thiosulfate by 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane and Its Anion Radical

Electrochemical Investigation of the Oxidation of Thiosulfate by 2,3,5,6‐tetrafluoro‐7,7,8,8‐tetracyanoquinodimethane and Its Anion Radical

Electron transfer reaction of Tris(1,10-phenanthroline) cobalt(III) complex [Co(phen)3]3+ and thiosulphate ion (S2O32âˆ’) in an aqueous acidic medium

Reduction of tris(2,2’-bipyridine)cobalt(III) complex by thiosulphate ion in an aqueous acidic medium

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