Kinetics and Mechanism of the Oxidation of 1,10-Phenanthroline by Diperiodatonickelate(IV)in Aqueous Alkaline Medium

 The title reaction was investigated in aqueous alkaline medium. A first order dependence on both [diperiodatonickelate(IV)] and [OH⁻] and an apparent fractional order in [1,10-Phenanthroline] was obtained. Addition of the reaction product has no effect on the reaction. The effects of dielectric constant, ionic strength, and temperature on the rate of the reaction were studied. A mechanism based on the experimental results is proposed, and the constants involved in the mechanism were evaluated. A good agreement between the observed and calculated rate constants at varying experimental conditions was obtained.     

Oxidation of chromium(III) by alkaline hexacyanoferrate(III)

Alkaline hexacyanoferrate(III) oxidation of freshly prepared solutions of Cr^III (pH>12) at 27°C follows the rate law, Equation 1:

Spectral and Mechanistic Investigation of the Osmium(VIII) Catalyzed Oxidation of Diclofenac Sodium by the Copper(III) Periodate Complex in Aqueous Alkaline Medium

The kinetics of the osmium(VIII) (Os(VIII)) catalyzed oxidation of diclofenac sodium (DFS) by diperiodatocuprate(III) (DPC) in aqueous alkaline medium has been studied spectrophotometrically at a constant ionic strength of 1.0 mol⋅dm⁻³. The reaction showed first order kinetics in [Os(VIII)] and [DPC] and less than unit order with respect to [DFS] and [alkali]. The rate decreased with increase in [periodate]. The reaction between DFS and DPC in alkaline medium exhibits 1:2 [DFS]:[DPC] stoichiometry. However, the order in [DFS] and [OH⁻] changes from first order to zero order as their concentration increases. Changes in the ionic strength and dielectric constant did not affect the rate of reaction. The oxidation products were identified by LC-ESI-MS, NMR, and IR spectroscopic studies. A possible mechanism is proposed. The reaction constants involved in the different steps of the mechanism were calculated. The catalytic constant (K _C) was also calculated for Os(VIII) catalysis at the studied temperatures. From plots of log ₁₀ K _C versus 1/T, values of activation parameters have been evaluated with respect to the catalytic reaction. The activation parameters with respect to the slow step of the mechanism were computed and discussed, and thermodynamic quantities were also determined. The active osmium(VIII) and copper(III) periodate species have been identified.     

A kinetic and mechanistic study of thallium(I) oxidation by quinolinium dichromate (QDC), a new oxidant

Quinolinium dichromate (QDC) oxidation of Tl^I in aqueous AcOH containing large concentrations of HCl is considerably accelerated both by H⁺ and Cl^– ions as well as by increasing the AcOH concentration in the medium; oxidation is made possible by altering the redox potentials. The reaction is first order in oxidant and in reductant but apparently less than unit order in [Cl^–] and nearly second order in [H⁺]. The active species of QDC and Tl^I are ClCrO₃ ^– and TlCl₂ ^– respectively. A possible mechanism is proposed and verified, and the reaction constants involved have been evaluated.     

Kinetics of oxidative degradation of pantothenic acid by cerium(IV) in aqueous perchloric acid

The kinetics of oxidation of pantothenic acid (PA), Me₂C(CH₂OH)CH(OH)C(O)NHCH₂CH₂CO₂H, by cerium(IV) in aqueous HClO₄ medium at constant ionic strength, 2.0 mol dm^–3, has been studied spectrophotometrically. The reaction showed first-order kinetics in Ce^IV concentration, an apparent less than unit order dependence in [PA] and an inverse fractional order in [H⁺]. Initial addition of products had no significant effect on the rate of the reaction. A possible mechanism is proposed, and the reaction constants involved in the mechanism have been computed. There is good agreement between the observed and calculated rate constants under different experimental conditions. The activation parameters were calculated with respect to the slow step of the proposed mechanism.     

Osmium(VIII)/palladium(II) catalysis of cerium(IV) oxidation of allyl alcohol in aqueous acid

Summary Catalysis of the Ce^IV-allyl alcohol (AA) reaction in acid solution depends both on the of rate enhancement and product distribution on the catalyst used: Os^VIII results mainly in acrolein, whereas Pd^II gives acrylic acid. The rate laws in the two cases also differ:viz., Equations 1 and 2K₁ is the equilibrium constant of formation of the Os^VIII-allyl alcohol complex and k₁ is the rate constant of its oxidation by Ce^IV; K₂ is the equilibrium constant for the formation of the Ce^IV-Pd^II-allyl alcohol complex and k₂ is its rate constant of decomposition. Rate = K₁k₁[Ce^IV][AA][Os^VIII]/(1+K₁[AA]) (1) Rate = K₁k₁[Ce^IV][Pd^II]/(1+K₂[Ce^IV]) (2)While Os^VIII is effective in H₂SO₄ solution, aqueous HClO₄ is needed for Pd^II. Both reactions proceed through formation of catalyst-allyl alcohol complexes with participation of free radicals. The details of these observations are discussed.     

A kinetic and mechanistic study of oxidation of arsenic(III) by hexacyanoferrate(III) in aqueous ethanoic acid

The kinetics of oxidation of As^IIIby Fe(CN)₆ ^3– has been studied spectrophotometrically in 60% AcOH–H₂O containing 4.0moldm^–3HCl. The oxidation is made possible by the difference in redox potentials. The reaction is first order each in [Fe(CN)₆ ^3–] and [As^III]. Amongst the initially added products, Fe(CN)₆ ^4– retards the reaction and As^Vdoes not. Increasing the acid concentration at constant chloride concentration accelerates the reaction. At constant acidity increasing chloride concentration increases the reaction rate, which reaches a maximum and then decreases. H₂Fe(CN)₆ ^–, is the active species of Fe(CN)₆ ^3–, while AsCl₅ ^2– in an ascending portion and AsCl₂ ⁺ in a descending portion are considered to be the active species of As^III. A suitable reaction mechanism is proposed and the reaction constants of the different steps involved have been evaluated.