Oxidation kinetics of trans-aqua-bis(ethylenediamine)-isothiocyanatocobalt(III) ion with peroxodisulphate

1979 ◽  
Vol 44 (4) ◽  
pp. 1052-1059 ◽  
Author(s):  
Olga Volárová ◽  
Vladislav Holba
Keyword(s):  
Ionic Strength ◽  
Temperature Dependence ◽  
Rate Constants ◽  
Oxidation Kinetics ◽  
Salt Effect ◽  
Activation Parameters ◽  
Thermodynamic Activation Parameters ◽  
Ionic Reactions ◽  
Kinetics Of

Oxidation kinetics of trans-aqua-bis(ethylenediamine)cobalt(III) ion with peroxodisulphate have been investigated in 0.01M-HClO4 medium within the ionic strength and temperature intervals 0.0411 to 0.4415M and 315.5 to 336.9 K, respectively. From the temperature dependence of the rate constants extrapolated to zero ionic strength the extrapolated values of thermodynamic activation parameters have been calculated. The data obtained by investigation of the primary salt effect have been confronted with relations valid for ionic reactions.

Kinetics of oxidation of cis-bis(ethylenediamine)isothiocyanatonitrocobalt(III) ion with peroxodisulphate

1979 ◽  
Vol 44 (12) ◽  
pp. 3588-3594 ◽  
Author(s):  
Vladislav Holba ◽  
Olga Volárová
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Oxidation Kinetics ◽  
Reaction Rate ◽  
Salt Effect ◽  
Activation Parameters ◽  
Reaction Products ◽  
Kinetics Of Oxidation ◽  
Thermodynamic Activation Parameters ◽  
Kinetics Of

The oxidation kinetics of cis-bis(ethylenediamine)isothiocyanonitrocobalt(III) ion with peroxodisulphate was investigated in the medium of 0.01 M-HClO4 in dependence on the ionic strength and temperature and the reaction products were identified. Extrapolated values of thermodynamic activation parameters were determined from the temperature dependence of the rate constants extrapolated to zero ionic strength. The distance of the closest approach was estimated for the reacting ions by evaluating the primary salt effect. To elucidate the mechanism, the influence of the cyclic polyether 18-crown-6 on the reaction rate was followed.

Kinetic Study of the Oxidation of Alcohols with Quaternary Ammonium Permanganates

1993 ◽  
Vol 58 (8) ◽  
pp. 1777-1781 ◽  
Author(s):  
Robert Šumichrast ◽  
Vladislav Holba
Keyword(s):  
Kinetic Study ◽  
Catalytic Reaction ◽  
Rate Constants ◽  
Quaternary Ammonium ◽  
Iterative Procedure ◽  
Activation Parameters ◽  
Reaction Products ◽  
Thermodynamic Activation Parameters ◽  
Oxidation Of Alcohols ◽  
Kinetics Of

Kinetics of the oxidation of 2-propanol, 1-butanol, and 1-pentanol with tetraalkylammonium permanganates have been investigated as function of temperature. The studied reactions are partly autocatalytic, colloidal manganese dioxide as one of the reaction products has been identified as the autocatalyst.A computerized iterative procedure has been used in order to obtained the rate constants of both non-catalytic and catalytic reaction steps together with the thermodynamic activation parameters.

Fast disproportionation of hexacyanomanganate(III) in acidic solution. Formation of hexacyanomanganate(IV) and kinetics of its decomposition

1986 ◽  
Vol 64 (12) ◽  
pp. 2301-2304 ◽  
Author(s):  
Guillermo López-Cueto ◽  
Carlos Ubide
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Acidic Solution ◽  
Activation Parameters ◽  
Rate Law ◽  
First Order ◽  
Experimental Rate ◽  
Parallel Pathways ◽  
Solution Formation ◽  
Kinetics Of

When potassium hexacyanomanganate(III) dissolves in acidic solution it rapidly disproportionates into hexacyanomanganate(IV) and Mn(II). Hexacyanomanganate(IV) then slowly decomposes to yield Mn(II) and (CN)2. Kinetics of the latter reaction has been studied. The reaction is found to be first order with respect to [Formula: see text], H+, and Mn(II) concentrations and the experimental rate law has the form v = kobs[Mn(IV)] = (ka + kb[H+] + kc[Mn(II)])[Mn(IV)]. At 40 °C and ionic strength 2.0, ka, kb, and kc values are (1.78 ± 0.01) × 10−4 s−1, (5.97 ± 0.05) × 10−5 s−1 M−1, and (3.40 ± 0.18) × 10−3 s−1 M−1, respectively. A mechanism with three parallel pathways is proposed, the deduced rate law being similar to the experimental one. Activation parameters, ΔH≠and ΔS≠ for the rate constants ka, kb, and kc are also reported.

Kinetics of hydrolysis of peroxodisulphate ions in acidic medium to peroxomonosulphuric acid

1981 ◽  
Vol 46 (5) ◽  
pp. 1229-1236 ◽  
Author(s):  
Jan Balej ◽  
Milada Thumová
Keyword(s):  
Ionic Strength ◽  
Rate Constants ◽  
Acidic Medium ◽  
Measured Data ◽  
Molar Ratios ◽  
Starting Solution ◽  
Kinetics Of Hydrolysis ◽  
Rate Of Hydrolysis ◽  
Kinetics Of ◽  
Hydrolysis Of

The rate of hydrolysis of S2O82- ions in acidic medium to peroxomonosulphuric acid was measured at 20 and 30 °C. The composition of the starting solution corresponded to the anolyte flowing out from an electrolyser for production of this acid or its ammonium salt at various degrees of conversion and starting molar ratios of sulphuric acid to ammonium sulphate. The measured data served to calculate the rate constants at both temperatures on the basis of the earlier proposed mechanism of the hydrolysis, and their dependence on the ionic strength was studied.

Salt effect in hydrolysis of 3-acyl-1,3-diphenyltriazenes

1981 ◽  
Vol 46 (12) ◽  
pp. 3104-3109 ◽  
Author(s):  
Miroslav Ludwig ◽  
Oldřich Pytela ◽  
Miroslav Večeřa
Keyword(s):  
Sodium Chloride ◽  
Temperature Dependence ◽  
Potassium Chloride ◽  
Rate Constants ◽  
Zinc Sulphate ◽  
Salt Effect ◽  
Sodium Sulphate ◽  
Potassium Sulphate ◽  
Lithium Sulphate ◽  
Hydrolysis Of

Rate constants of non-catalyzed hydrolysis of 3-acetyl-1,3-diphenyltriazene (I) and 3-(N-methylcarbamoyl)-1,3-diphenyltriazene (II) have been measured in the presence of salts (ammonium chloride, potassium chloride, lithium chloride, sodium chloride and bromide, ammonium sulphate, potassium sulphate, lithium sulphate, sodium sulphate and zinc sulphate) within broad concentration ranges. Temperature dependence of the hydrolysis of the substrates studied has been measured in the presence of lithium sulphate within temperature range 20° to 55 °C. The results obtained have been interpreted by mechanisms of hydrolysis of the studied substances.

Kinetics and Mechanism of Hexachloroiridate(IV) Oxidation of Arsenic(III) in Acidic Perchlorate Solutions

1992 ◽  
Vol 57 (7) ◽  
pp. 1451-1458 ◽  
Author(s):  
Refat M. Hassan
Keyword(s):  
Ionic Strength ◽  
Fractional Order ◽  
Activation Parameters ◽  
Order Reaction ◽  
First Order Reaction ◽  
Intermediate Complex ◽  
Constant Ionic Strength ◽  
Kinetics Of Oxidation ◽  
First Order ◽  
Kinetics Of

The kinetics of oxidation of arsenic(III) by hexachloroiridate(IV) at lower acid concentrations and at constant ionic strength of 1.0 mol dm-3 have been investigated spectrophotometrically. A first-order reaction in [IrCl62-] and fractional order with respect to arsenic(III) have been observed. A kinetic evidence for the formation of an intermediate complex between the hydrolyzed arsenic(III) species and the oxidant was presented. The results showed that decreasing the [H+] is accompanied by an appreciable acceleration of the rate of oxidation. The activation parameters have been evaluated and a mechanism consistent with the kinetic results was suggested.

scholarly journals KINETICS OF OZONE REACTIONS WITH ADENINE AND CYTOSINE IN AQUEOUS SOLUTIONS

2020 ◽  
Vol 63 (10) ◽  
pp. 17-22
Author(s):  
Aigul A. Maksyutova ◽  
Elvina R. Khaynasova ◽  
Yuriy S. Zimin
Keyword(s):  
Aqueous Solutions ◽  
Rate Constants ◽  
Correlation Coefficients ◽  
Activation Parameters ◽  
Second Order ◽  
Order Kinetic ◽  
Temperature Dependences ◽  
Ozone Reactivity ◽  
Kinetics Of ◽  
Ozone Reactions

The ultraviolet spectroscopy method has been applied to study the kinetics of the ozone reactions with nitrogenous bases (NB), namely adenine and cytosine in aqueous solutions. At the first research stage, the range of NB working concentrations has been determined. It was found that linear dependences between optical densities and concentrations of nitrogenous bases aqueous solutions are quite reliable, with correlation coefficients r ≥ 0.998, are satisfied up to [NB] = 2.3 ∙ 10–4 mol/l. According to the Bouguer-Lambert-Beer law, adenine and cytosine extinction coefficients in aqueous solutions were determined and subsequently used to calculate their residual concentrations. At the next stage, the kinetics of nitrogenous bases ozonized oxidation was studied with equal initial concentrations of the starting substances ([NB]0 = [О3]0). The results revealed that the kinetic consumption curves of the starting reagents are fairly well linearized (r ≥ 0.996) in the second-order reaction equation coordinates. As found with the bubbling installation, 1 mol of the absorbed ozone falls on 1 mol of the used NB. Thus, the reactions of ozone with adenine and cytosine explicitly proceed according to the second-order kinetic laws (the first – according to О3 and the first – according to NB). The rate constants were calculated by the integral reaction equations, the values of which indicate a higher ozone reactivity in relation to nitrogen bases. The temperature dependences of the second-order rate constants was studied ranging 285-309 K, and the activation parameters (pre-exponential factors and activation energies) of the ozone reactions with adenine and cytosine in aqueous solutions were determined.

Kinetik der Reaktion von 2.4-Dinitrofluorbenzol mit Imidazol-, SH- und Imidazol-SH-Verbindungen / Kinetics of the Reaction of 2,4-dinitro-1-fluorobenzene with Imidazole-, SH- and Imidazole-SH-compounds

1971 ◽  
Vol 26 (10) ◽  
pp. 1010-1016 ◽  
Author(s):  
Renate Voigt ◽  
Helmut Wenck ◽  
Friedhelm Schneider
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Reaction Rate ◽  
Ph Dependence ◽  
First Order ◽  
Molecular Transfer ◽  
Thiolate Anion ◽  
Nucleophilic Reactivity ◽  
Kinetics Of ◽  
Lindley Equation

First order rate constants of the reaction of a series of SH-, imidazole- and imidazole/SH-compounds with FDNB as well as their pH- and temperature dependence were determined. Some of the tested imidazole/SH-compounds exhibit a higher nucleophilic reactivity as is expected on the basis of their pKSH-values. This enhanced reactivity is caused by an activation of the SH-groups by a neighbouring imidazole residue. The pH-independent rate constants were calculated using the Lindley equation.The kinetics of DNP-transfer from DNP-imidazole to SH-compounds were investigated. The pH-dependence of the reaction displays a maximum curve. Donor in this reaction is the DNP-imidazolecation and acceptor the thiolate anion.The reaction rate of FDNB with imidazole derivatives is two to three orders of magnitude slower than with SH-compounds.No inter- or intra-molecular transfer of the DNP-residue from sulfure to imidazole takes place.

Annealing experiments on CO2-bearing jadeite glass: an insight into the true temperature dependence of CO2 speciation in silicate melts

2001 ◽  
Vol 65 (6) ◽  
pp. 701-707 ◽  
Author(s):  
Y. Morizet ◽  
S. C. Kohn ◽  
R. A. Brooker
Keyword(s):  
Temperature Dependence ◽  
Rate Constants ◽  
Negative Charge ◽  
Silicate Melts ◽  
True Temperature ◽  
Carbonate Group ◽  
Image Position ◽  
Kinetics Of ◽  
Annealing Experiments ◽  
Insight Into

AbstractThe thermodynamics and kinetics of CO2 speciation in silicate melts have been studied by measuring the concentration of CO2mol and carbonate in jadeite glass annealed at 575, 450 and 400°C. Assuming that the reaction is1where CO2mol..Obr represents a CO2 molecule weakly bonded to a bridging oxygen in the network and CO3 represents a bridging carbonate group with no net negative charge, ΔH for the reaction is –17 (+4/–8) kJ mol−1 and ΔS is –24 (+6/–9) J K−1 mol−1. The rate of equilibration of the species was measured at each temperature and the rate constants were deduced. The temperature dependence of the rate constants was used to determine the activation energy of the forward and reverse reactions which are 68 (+3/–31) kJ mol−1 and 86 (+1/–69) kJ mol−1 respectively. The data suggest that CO2mol may be much more abundant in silicate melts than previously assumed on the basis of studies of CO2-bearing glasses. Models of solubility, diffusion, and isotope fractionation should take this into account.

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