Kinetics of Oxidation of Some Aliphatic Alcohols by Vanadium (V)

A spectrocoulometric macrocell with a direct-view optical probe was designed and constructed, where the optical signal is transferred by light-conducting glass or quartz fibres permitting to work at wavelengths above 410 or 300 nm. The method of measurement on the proposed equipment is described; it was tested in the study of the mechanism and kinetics of oxidation of Fe(bipy)32+ ions (bipy = 2,2'-bipyridyl) with the use of potentiostatic coulometric electrolysis with open-circuit relaxation at a suitable time. The primary product of electrolysis, Fe(bipy)33+, undergoes a follow-up hydrolytic reaction with the formation of a binuclear complex. The rate constant of the reaction of the first order involves the contributions, kBi, from all bases present in solution; the corresponding values for H2O, OH-, bipy, and CH3COO- ions at a ionic strength 0·5 mol dm-3 and 25 °C were determined as kOH = (5·0 ± 0·6) . 105 mol-1 dm3 s-1, kbipy = (1·3 ± 0·2) . 10-1 mol-1 dm3 s-1, kAc = (5·8 ± 1·0) . 10-2 mol-1 dm3 s-1, and kH2O is not significant with respect to experimental errors.

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Effects of salts on the kinetics of oxidation of alkenes by thallic salts in aqueous solutions

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19810693 ◽

1981 ◽

Vol 46 (3) ◽

pp. 693-700 ◽

Cited By ~ 1

Author(s):

Milan Strašák ◽

Jaroslav Majer

Keyword(s):

Aqueous Solutions ◽

Phase Transfer ◽

Heterogeneous Reaction ◽

Qualitative Model ◽

Kinetic Effect ◽

Tetraalkylammonium Salts ◽

Reaction Conditions ◽

Kinetics Of Oxidation ◽

Kinetics Of ◽

Heterogeneous Reaction Conditions

The kinetics of oxidation of alkenes by thallic sulphate in aqueous solutions, involving the two reaction steps-the hydroxythallation and the dethallation - was studied, and the effect of salts on the kinetics was examined; this made it possible to specify more precisely the reaction mechanism and to suggest a qualitative model of the reaction coordinate. It was found that in homogeneous as well as in heterogeneous reaction conditions, the reaction can be accelerated appreciably by adding tetraalkylammonium salts. These salts not only operate as catalysts of the phase transfer, but also exert a significant kinetic effect, which can be explained with a simplification in terms of a stabilization of the transition state of the reaction.

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Kinetics of oxidation of ammonia on cobalt catalyst I model of the reactor with catalytically active wall

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19822087 ◽

1982 ◽

Vol 47 (8) ◽

pp. 2087-2096 ◽

Cited By ~ 3

Author(s):

Bohumil Bernauer ◽

Antonín Šimeček ◽

Jan Vosolsobě

Keyword(s):

Parabolic Equations ◽

Cobalt Catalyst ◽

Nonlinear Parabolic Equations ◽

Catalytic Reactions ◽

Temperature Profiles ◽

Dimensional Model ◽

Kinetics Of Oxidation ◽

Nonlinear Parabolic ◽

Catalytically Active ◽

Kinetics Of

A two dimensional model of a tabular reactor with the catalytically active wall has been proposed in which several exothermic catalytic reactions take place. The derived dimensionless equations enable evaluation of concentration and temperature profiles on the surface of the active component. The resulting nonlinear parabolic equations have been solved by the method of orthogonal collocations.

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Thermodynamic and Kinetic Investigation of the Solvent Effect on the Oxidation of [Co(en)2SCH2COO]+ with S2O82- In Water-Methanol and Water-tert-Butyl Alcohol Mixtures

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc19931001 ◽

1993 ◽

Vol 58 (5) ◽

pp. 1001-1006 ◽

Cited By ~ 1

Author(s):

Oľga Vollárová ◽

Ján Benko

Keyword(s):

Transfer Functions ◽

Activation Parameters ◽

Butyl Alcohol ◽

Oxidation Of Co ◽

Kinetics Of Oxidation ◽

Tert Butyl ◽

Tert Butyl Alcohol ◽

Alcohol Mixtures ◽

Kinetics Of

The kinetics of oxidation of [Co(en)2SCH2COO]+ with S2O82- was studied in water-methanol and water-tert-butyl alcohol mixtures. Changes in the reaction activation parameters ∆H≠ and ∆S≠ with varying concentration of the co-solvent depend on the kind of the latter, which points to a significant role of salvation effects. The solvation effect on the reaction is discussed based on a comparison of the transfer functions ∆Ht0, ∆St0 and ∆Gt0 for the initial and transition states with the changes in the activation parameters accompanying changes in the CO-solvent concentration. The transfer enthalpies of the reactant were obtained from calorimetric measurements.

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