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  • 1
    Electronic Resource
    Electronic Resource
    Kinetics and Mechanism of the Oxidation of 1,10-Phenanthroline by Diperiodatonickelate(IV)in Aqueous Alkaline Medium (2000)
    Springer
    Monatshefte für Chemie 131 (2000), S. 1129-1137 
    Details
    ISSN: 1434-4475
    Keywords: Keywords. Diperiodatonickelate(IV); 1 ; 10-Phenanthroline; Kinetics; Oxidation.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary.  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.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s007060070020
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  • 2
    Electronic Resource
    Electronic Resource
    Kinetic and Mechanistic Study of the Oxidative Deamination and Decarboxylation of L-Valine by Alkaline Permanganate (2000)
    Springer
    Monatshefte für Chemie 131 (2000), S. 739-748 
    Details
    ISSN: 1434-4475
    Keywords: Keywords. Kinetics; Oxidation; L-Valine; Activation parameters.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary.  The kinetics of the oxidation of L-valine, (L-Val) by permanganate in aqueous alkaline medium at a constant ionic strength of 0.50 molċdm−3 was studied spectrophotometrically. The reaction is of first order in [permanganate ion] and of fractional order in both [L-Val] and [alkali]. Addition of products has no significant effect on the reaction rate. However, increasing ionic strength and decreasing dielectric constant of the medium increase the rate. The oxidation process in alkaline medium has been shown to proceed via two paths, one involving the interaction of L-valine with permanganate ion in a slow step to yield the products, and the other path the interaction of alkali with permanganate ion to give manganate. Some reaction constants involved in the mechanism were determined; calculated and observed rate constants agree excellently. The activation parameters were computed with respect to the slow step of the mechanism.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/s007060070075
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  • 3
    Electronic Resource
    Electronic Resource
    Kinetics of the Oxidative Degradation of rac-Serine by Aqueous Alkaline Permanganate (2000)
    Springer
    Monatshefte für Chemie 131 (2000), S. 321-332 
    Details
    ISSN: 1434-4475
    Keywords: Keywords. rac-Serine; Alkaline permanganate; Oxidation; Kinetics.
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary.  The kinetics of the oxidation of rac-serine by permanganate in aqueous alkaline medium was studied spectrophotometrically. The reaction showed first order kinetics in permanganate ion concentration and an order less than unity in rac-serine and alkali concentration. Increasing ionic strength and decreasing dielectric constant of the medium increase the rate. The oxidation reaction proceeds via an alkali-permanganate species which forms a complex with rac-serine. The latter decomposes slowly, followed by a fast reaction between a free radical of rac-serine and another molecule of permanganate to give the products. There is a good agreement between the observed and the calculated rate constants under different experimental conditions. Investigations at different temperatures allowed the determination of the activation parameters with respect to the slow step of the proposed mechanism.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/
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  • 4
    Electronic Resource
    Electronic Resource
    Osmium(VIII) oxidation of arsenic(III) in aqueous sulphuric acid (1991)
    Springer
    Transition metal chemistry 16 (1991), S. 196-199 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The oxidation of AsIII by OsVIII or OsVI in aqueous H2SO4 follows the rate law: $$d[Os^{IV} ]/dt = k_a K_a [oxidant][As^{III} ]/(1 + K_a [As^{III} ]).$$ An oxidant−AsIII complex first forms (equilibrium constant Ka) followed by decomposition (rate constant ka) into products. The values of ka and Ka for the OsVIII−AsIII system were found to be 0.013±0.003 s−1 and 11.0±2.0 dm3 mol−1 respectively; in the OsVI−AsIII reaction, the values were 0.030±0.003 s−1 and 22.0±4.0 dm3 mol−1.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01032833
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  • 5
    Electronic Resource
    Electronic Resource
    Kinetics of oxidation of thallium(I) by permanganate in aqueous hydrochloric acid medium using the stopped-flow technique (1996)
    Springer
    Transition metal chemistry 21 (1996), S. 560-564 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The permanganate-TlI reaction in aqueous HCl was studied using the stopped-flow technique. The reaction rate increases as both [H+] and [Cl-] increase. It exhibits second-order kinetics and the rate law is given by Equation 1: $$rate = k\left[ {Mn^{III} } \right]^x \left[ {AA} \right]_0 \left[ {OAc^ - } \right]^x \left[ {H^ + } \right]^{ - x} $$ (1) where k is the rate constant of the slow step, and K 1 and K 4 are the respective formation constants of the active form of the reductant, TlCl, and the protonated species of the oxidant, HMnO4. A composite mechanism and rate law are proposed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00229713
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  • 6
    Electronic Resource
    Electronic Resource
    Permanganate oxidation of chromium(III) in aqueous alkaline medium: a kinetic study by the stopped-flow technique (1997)
    Springer
    Transition metal chemistry 22 (1997), S. 193-196 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract Permanganate oxidation of CrIII in aqueous medium (pH〉;12) at25°C has been studied by the stopped-flow technique, combined with a rapid scan spectrophotometry, and obeys the rate equation:¶ where K is the formation constant of the MnVII-CrIII adduct and k is the rate constant for its decomposition. The rate is independent of [OH−]. The active oxidant and reductant species are understood to be [MnO4]− and [Cr(OH)4]−, respectively.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1018487718591
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  • 7
    Electronic Resource
    Electronic Resource
    Ruthenium(III)-catalysed oxidation of thiocyanate by periodate in aqueous alkaline medium; autocatalysis in catalysis (2000)
    Springer
    Transition metal chemistry 25 (2000), S. 394-399 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Abstract The oxidation of thiocyanate by periodate has been studied in alkaline media. A micro quantity of RuIII is sufficient to catalyse the reaction. The active catalytic species and oxidant in the reaction are understood to be [Ru(H2O)5OH]2+ and IO− 4. The autocatalysis exhibited by one of the products, cyanate, is attributed to adduct formation between cyanate and periodate. A composite mechanism and rate law are proposed. The reaction constants involved in the mechanism are evaluated.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1023/A:1007084709817
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  • 8
    Electronic Resource
    Electronic Resource
    Oxidation of chromium(III) by alkaline hexacyanoferrate(III) (1991)
    Springer
    Transition metal chemistry 16 (1991), S. 335-338 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Alkaline hexacyanoferrate(III) oxidation of freshly prepared solutions of CrIII (pH〉12) at 27°C follows the rate law, Equation 1: 1 $$Rate = \frac{{kK_{OH} [Fe(CN)_6 ]^{3 - } [Cr^{III} ]_T [OH^ - ]_T }}{{(1 + K_{OH} [OH^ - ]_T )}}$$ [Fe(CN)6]3− and [Cr(OH)4]− are the active species. The values of KOH(1.62±0.02 dm3 mol−1) and k (2.5±0.2 dm3 mol−1s−1), the formation constant of [Cr(OH)4]− from soluble Cr(OH)3 and the rate constant respectively, were determined at 27.0°C. The solubility of CrIII at pH〉12 decreases with time, presumably due to slow formation of polynuclear CrIII species.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01024077
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  • 9
    Electronic Resource
    Electronic Resource
    Osmium(VIII)/palladium(II) catalysis of cerium(IV) oxidation of allyl alcohol in aqueous acid (1991)
    Springer
    Transition metal chemistry 16 (1991), S. 430-434 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary Catalysis of the CeIV-allyl alcohol (AA) reaction in acid solution depends both on the of rate enhancement and product distribution on the catalyst used: OsVIII results mainly in acrolein, whereas PdII 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 OsVIII-allyl alcohol complex and k1 is the rate constant of its oxidation by CeIV; K2 is the equilibrium constant for the formation of the CeIV-PdII-allyl alcohol complex and k2 is its rate constant of decomposition. Rate = K1k1[CeIV][AA][OsVIII]/(1+K1[AA]) (1) Rate = K1k1[CeIV][PdII]/(1+K2[CeIV]) (2) While OsVIII is effective in H2SO4 solution, aqueous HClO4 is needed for PdII. Both reactions proceed through formation of catalyst-allyl alcohol complexes with participation of free radicals. The details of these observations are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF01129458
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  • 10
    Electronic Resource
    Electronic Resource
    Kinetics of osmium(VIII) catalysis of periodate oxidation of DMF in aqueous alkaline medium (1994)
    Springer
    Transition metal chemistry 19 (1994), S. 215-217 
    Details
    ISSN: 1572-901X
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary The osmium(VIII) catalysed IO4 − oxidation of DMF in aqueous alkaline medium follows the rate law: $$ - {\text{d}}\left[ {{\text{IO}}_4^ - } \right]/{\text{d}}t = \frac{{kK_2 K_3 [{\text{DMF}}][{\text{OH}}^ - ][{\text{Os}}^{{\text{VIII}}} ]_T }}{{1 + K_2 K_3 [{\text{DMF}}][{\text{OH}}^ - ] + K_2 [{\text{OH}}^ - ]}}$$ where K 2 is the equilibrium constant of the reaction [OsO4(OH)2]2− + OH− ⇌ [OsO5(OH)]3− + H2O K 3 is the formation constant for the complex between DMF and [OsO5(OH)]3− and k is the decomposition rate constant. The data suggest that the oxidation of DMF proceeds via the formation of a complex between DMF and osmium(VIII) which decomposes slowly, followed by a fast reaction between the reduced osmium(VI) species and IO4 −. The reaction constants involved in the mechanism are derived.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00161893
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