Kinetics and mechanism of the oxidation of formaldehyde by hexacyanoferrate(III) ion

Singh, Vir; Gangwar, M. C.; Saxena, B.B.L.; Singh, M. P.

doi:10.1139/v69-165

Cited by 38 publications

(24 citation statements)

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“…Tests to establish the formation of a free radical intermediate using vinyl acetate were negative. This is in agreement with previous ferricyanide oxidations of similar functional groups, where it is concluded that the free radical had no independent existence [7].…”

Section: Resultssupporting

confidence: 93%

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A kinetic study of the oxidation of formaldehyde by the octacyanomolybdate(V) ion in aqueous alkaline medium

Dennis

Potgieter

Basson

2011

Reac Kinet Mech Cat

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The kinetics of the oxidation of formaldehyde by octacyanomolybdate(V) ions has been studied in aqueous alkaline medium. A formaldehydedependent and -independent reaction has been observed. The HCHO-dependent reaction displays first order kinetics in [Mo(CN) 83-], [HCHO], [OH -] and alkali metal ion catalysis was observed. The rate law is consistent with:Activation parameters for both the formaldehyde-dependent and -independent reaction have been obtained. The activation parameters for the HCHO-independent reaction provide evidence for the identification of the reaction. A reaction mechanism is proposed.

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Section: Resultssupporting

confidence: 93%

“…Kinetic studies of the oxidation of formaldehyde (HCHO) with ferricyanide (Fe(CN) 6 3-) [7] and octacyanotungstate(V) (W(CN) 8 3-) [8] have been reported. In both studies, the reactions are first order with respect to the metal cyanide complex, formaldehyde and the hydroxide ion and correspond to the rate law:…”

Section: Introductionmentioning

confidence: 99%

A kinetic study of the oxidation of formaldehyde by the octacyanomolybdate(V) ion in aqueous alkaline medium

Dennis

Potgieter

Basson

2011

Reac Kinet Mech Cat

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“…1), by plotting −dc/dt values against [hexacyanoferrate(III)] (Fig. 2), by calculating the firstorder rate constant k 1 …”

Section: Resultsmentioning

confidence: 99%

“…Transition metals like osmium [1], iridium [2], tungsten [3], etc. have successfully been used as homogeneous catalysts.…”

Section: Introductionmentioning

confidence: 99%

Cocatalysis by ruthenium(III) in hydrogen ions catalyzed oxidation of iodide ions: A kinetic study

Tandon

Mehrotra

Singh

et al. 2004

Int J of Chemical Kinetics

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RuCl 3 further catalyzes the oxidation of iodide ion by K 3 Fe(CN) 6 , already catalyzed by hydrogen ions. The rate of reaction, when catalyzed only by hydrogen ions, was separated graphically from the rate when both Ru(III) and H + ions catalyzed the reaction. Reactions studied separately in the presence as well as absence of RuCl 3 under similar conditions were found to follow second-order kinetics with respect to [I − ], while the rate showed direct proportionality with respect to [Fe(CN) 6 ] 4− ions retards the reaction velocity, while changing the ionic strength of the medium has no effect on the rate. With the help of the intercept of the catalyst graph, the extent of the reaction that takes place without adding Ru(III) was calculated and it was in accordance with the values obtained from the reaction in which only H + ions catalyzed the reaction. It is proposed that ruthenium forms a complex, which slowly disproportionates into the rate-determining step. Arrhenius parameters at four different temperatures were also calculated. C

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“…However, Speakman and Waters [3] have suggested different paths of oxidation of aldehydes, ketones and nitroparaffins. Singh and coworkers [4,5], while discussing the oxidations of formaldehyde, acetone and ethyl methyl ketone have suggested that the oxidation takes place via an electron transfer process resulting in the formation of a free radical intermediate.…”

Section: Introductionmentioning

confidence: 99%

Mechanistic Studies of Osmium(VIII) Catalysed Oxidation of Sulfanilic Acid by Hexacyanoferrate (III) in Alkaline Medium

Farokhi

Nandibewoor

2008

Catal Lett

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The kinetics of osmium(VIII) catalyzed oxidation of sulfanilic acid (p-aminobenzenesulfonic acid) by hexacyanoferrate(III) (HCF(III)) in alkaline medium was studied spectrophotometrically. The reaction showed first order kinetics in hexacyanoferrate(III) and osmium concentrations and an order of less than unity in sulfanilic acid (SAA) and alkali concentrations. The rate of reaction increased with increase in alkali concentration. Increasing ionic strength and dielectric constant of the medium increased the rate of the reaction. A retarding effect was observed by one of the products i.e. hexacyanoferrate(II) (HCF(II)). A mechanism involving the formation of a complex between sulfanilic acid and osmium(VIII) species, [(OsO 5 (OH)] 3-(in presence of high OH -concentrations), has been proposed. The main products were identified by spectral studies. The reaction constants involved in the mechanism are evaluated.

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Kinetics and mechanism of the oxidation of formaldehyde by hexacyanoferrate(III) ion

Cited by 38 publications

References 0 publications

A kinetic study of the oxidation of formaldehyde by the octacyanomolybdate(V) ion in aqueous alkaline medium

A kinetic study of the oxidation of formaldehyde by the octacyanomolybdate(V) ion in aqueous alkaline medium

Cocatalysis by ruthenium(III) in hydrogen ions catalyzed oxidation of iodide ions: A kinetic study

Mechanistic Studies of Osmium(VIII) Catalysed Oxidation of Sulfanilic Acid by Hexacyanoferrate (III) in Alkaline Medium

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