CCL.—The reaction between phosphorous acid and iodine

Mitchell, Alec Duncan

doi:10.1039/ct9232302241

Cited by 20 publications

(12 citation statements)

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“…Results are given in Table 2. Calculated k' values were obtained by substituting the values of the constants k , = 16.6 dm3 mol-' s-', K , = 37.6 dm3 mol-', K2 = 175 dm3 rnol and K3 = 130 dm3 mol-' at 45 "C in rate equation (15).…”

Section: Resultsmentioning

confidence: 99%

Kinetics and mechanism of the oxidation of hypophosphite with N-chlorotoluene-p-sulphonamide (chloramine T) catalysed by osmium (VIII) in alkaline solution

Hussain¹,

Mishra²,

Sharma³

1991

J. Chem. Soc., Dalton Trans.

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Section: Resultsmentioning

confidence: 99%

Kinetics and mechanism of the oxidation of hypophosphite with N-chlorotoluene-p-sulphonamide (chloramine T) catalysed by osmium (VIII) in alkaline solution

Hussain¹,

Mishra²,

Sharma³

1991

J. Chem. Soc., Dalton Trans.

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“…The fact that 3k6[MnVi1]/kw = 265 and 3k7Kl[MnV"]/kH = 44 or 3k9K2[Mnv1']/kH = 3.9 x lo3 establishes that phosphorous acid is oxidised (by permanganate ion) in its inactive form (A). Support for this conclusion can be obtained by comparing the values of 3k7[MnV"] or 3k9[MnV1'] with that of k, which is, however, not known, but a useful guess could be made from equation (10) by making the following assumptions: (a) when k2 x k3 then kl = 2kH;…”

Section: Ai€(k9)smentioning

confidence: 99%

Kinetics and mechanisms of redox reactions in aqueous solution. Part 9. Permanganate oxidation of phosphorous acid in perchlorate solution

Mehrotra¹

1984

J. Chem. Soc., Dalton Trans.

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The reaction between phosphorous acid and permanganate exhibits a first-order dependence both on [MnVI1] and [H,P03] and the dependence of kobs. on [H+] is of the form (i) at constant ionic strength; kobs. is independent of ionic strength. The most probable mechanism in which the ' inactive ' form of phosphorous acid, H-P=O(OH)*, is the reactive species is discussed and the values of the rate-limiting constants together with their associated thermodynamic parameters are reported. The duality of H + catalysis is also discussed in an alternative mechanism.The oxidation of phosphorous acid by several metal 2-7 and non-metal ions 8-11 has been studied. All these oxidations could be classified in two broad groups: those first order with respect to oxidant concentration and those with a zero-order dependence on the oxidant. The latter dependence is invariably explained by assuming that the rate-limiting step involves the transformation of the ' inactive form' into the ' active form ' which then reacts rapidly with the oxidant.It is surprising that the oxidation of phosphorous acid by permanganate ion has not yet been reported. The present study is thus an attempt to characterise the kinetics of this reaction, to suggest the most probable mechanism, and to discuss the nature of the reactive tautomer of phosphorous acid, a problem which has not been tackled well in most previous studies.

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“…The solution was titrated iodometrically to check its concentration. However, if the osmium (VIII) solution is kept in bottles blackened on the outside, and containing [NaOH] > 0.3 mol dm -3 at a refrigerated temperature, the solution exhibits [15] much longer stability. All other solutions of various reagents were prepared in doubly distilled water; the second distillation was from alkaline KMnO 4 solution in an all-glass assembly.…”

Section: Introductionmentioning

confidence: 99%

Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium

Sharma

Agrawal

et al. 2005

Transition Met Chem

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The kinetics of electron transfer from mannitol to hexacyanoferrate(III), catalyzed by osmium(VIII), has been studied in alkaline medium. The substrate order is complex, whereas it is one with respect to the catalyst. The rate is independent of the concentration of oxidant. Also, the rate increases with increasing concentration of hydroxide ion in a complex manner. A kinetic rate law corresponding to the proposed mechanism has been suggested as follows:À 1 2 d½FeðCNÞ 3À 6 dt

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CCL.—The reaction between phosphorous acid and iodine

Cited by 20 publications

References 0 publications

Kinetics and mechanism of the oxidation of hypophosphite with N-chlorotoluene-p-sulphonamide (chloramine T) catalysed by osmium (VIII) in alkaline solution

Kinetics and mechanism of the oxidation of hypophosphite with N-chlorotoluene-p-sulphonamide (chloramine T) catalysed by osmium (VIII) in alkaline solution

Kinetics and mechanisms of redox reactions in aqueous solution. Part 9. Permanganate oxidation of phosphorous acid in perchlorate solution

Kinetics and mechanism of electron transfer reactions. Osmium(VIII) catalyzed oxidation of mannitol by hexacyanoferrate(III) in aqueous alkaline medium

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