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  • Chemistry  (7)
  • 1
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 21 (1989), S. 519-533 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of uncatalyzed and Ru(III) catalyzed oxidation of indigo carmine(IC) (disodium 3,3′-dioxobi-indolin-2,2′-ylidene-5,5′-disulphonate) by iodate ion in aqueous sulphuric acid solution is reported. The uncatalyzed reaction order was found to be four; one each with respect to IC and iodate ion and second order with H+ ion. The Ru(III) catalyzed reaction was of fifth order, second order with respect to H+ and first order with respect to reductant, oxidant, and catalyst. Stoichiometric ratios of both reactions were the same with a 3:2 reductant-oxidant ratio. In both uncatalyzed and catalyzed reactions isatin-5-monosulphonic acid (2,3-dioxoindoline-5-sulphonic acid) was observed as the oxidation product. Rate constants for both the reactions are reported. Reaction mechanisms consistent with the experimental data are suggested.Further, a fixed time method is described for the determination of Ru(III), based on its ability to catalyze the oxidation of IC by acidic iodate. Using [H+] 2.25M, [iodate] 1.00 × 10-3M and [IC] 5.0 × 10-5M, in presence of Ru(III), the reaction followed first order kinetics with respect to IC. The interference of various cations, neutral salts, and potassium iodide on the determination of Ru(III) was studied using synthetic mixtures. The selectivity of the method and the recommended procedure are described.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
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  • 2
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 30 (1998), S. 111-120 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The detailed kinetics of the reaction of toluidine blue {phenothiazine-5-ium, 3-amino-7(dimethylamino)-2-methyl chloride, tolonium chloride, TB+Cl-} with potassium bromate and with aqueous bromine reaction were studied. In most of the experiments, the kinetics were monitored by following the rate of consumption of TB+ at 590 nm with excess acid and bromate. The reaction exhibited complex kinetic behavior. Initial reaction was slow and after an induction time, the TB+ concentration decreased fast. It had first-order dependence on both TB+ and bromate, and second-order dependence on H+. Under excess bromate conditions, the stoichiometric ratio of TB+ to bromate was 1:1. Demethylated sulfoxides were found at the reaction products. Sharp increase in the overall potential synchronized with the increase in bromine levels and the fast depletion of [TB+]. The role of bromide ion and bromine in the reaction was established. A multi-step reaction mechanism is proposed consistent with the experimental results. © 1998 John Wiley & Sons, Inc. Int J Chem Kinet: 30: 111-120, 1998.
    Additional Material: 9 Ill.
    Type of Medium: Electronic Resource
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  • 3
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 999-1007 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the reaction of toluidine blue (tolonium chloride) (TB+ Cl-) with thiourea (TU) in aqueous hydrochloric acid solution is reported. The reaction was first order with respect to toluidine blue and the reductant and second order with respect to [H+]. Thiourea had a 2:1 stoichiometric ratio with TB+. Toluidine blue was reduced to a colorless base in two one-electron reduction steps and TU was oxidized to thioformamidinium ion, which dimerized rapidly to give stable dithioformamidinium ion. The energy parameters obtained for TB+-TU reaction were mean energy of activation (Ea′) = 26.7 ± 2.4 kJ M-1; enthalpy of activation (ΔH#) = 24.2 kJ M-1; frequency factor (A) = 1.04 × 104 M-3 s-1; and entropy of activation (ΔS#) = -176.35 J M-1 s-1. © John Wiley & Sons, Inc.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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  • 4
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 1113-1116 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Tab.
    Type of Medium: Electronic Resource
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  • 5
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 25 (1993), S. 745-753 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed kinetic study of the reaction between toluidine blue (tolonium chloride) (TB+Cl-) and stannous chloride is carried out in aqueous hydrochloric acid. The depletion kinetics of toluidine blue were spectrometrically monitored at 626 nm. The reaction had fractional order with respect to toluidine blue (one half), three halves with respect to Sn2+, and first-order dependence on H+ ion. Stoichiometric ratio between reductant and oxidant is 1:1. During the reaction Sn2+ is oxidized to Sn4+ and toluidine blue is reduced to colorless base in two univalent steps. © 1993 John Wiley & Sons, Inc.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 6
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 23 (1991), S. 113-125 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics and mechanism of the oxidation of 3,3′-dimethoxybenzidine (oda, o-dianisidine) by potassium bromate in aqueous acidic medium were studied by monitoring the formation rate of the reaction product, 3,3′-dimethoxy 4,4′-diphenoquinone at 447 nm. The reaction is, first order with respect to both the substrate and oxidant, and second order with respect to H+. The oda: bromate stoichiometric ratio is 1:1. Plausible mechanism and rate laws are proposed accounting the experimental findings. Computer simulations were done using the proposed mechanism.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
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  • 7
    Electronic Resource
    Electronic Resource
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 24 (1992), S. 41-49 
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The oxidation kinetics of malachite green (MG) with peroxydisulphate ion (PDS) were investigated by monitoring the absorbance change at 618 nm, in aqueous solutions under buffered and unbuffered conditions. Under both conditions, the reaction had first order dependence on reductant and a fractional order (one half) dependence on the oxidant. The stoichiometric ratio between MG and PDS was 1:2. The reaction had a negative salt effect. Reaction rates were enhanced under both high or low pH relative to neutral conditions. A plausible mechanism is proposed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
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