scholarly journals Oxidation of Sodium Hypophosphite by Oxygen in Alcoholic Solutions of Ferrum (III)

2016 ◽  
Vol 7 (1) ◽  
pp. 33
Author(s):  
G.S. Polimbetova ◽  
M.M. Aleshkova ◽  
G.O. Bugubaeva ◽  
Zh.U. Ibraimova ◽  
A.K. Borangazieva
Keyword(s):  
Organophosphorus Compounds ◽  
Activation Parameters ◽  
Reduction Reaction ◽  
Coordination Mechanism ◽  
Sodium Hypophosphite ◽  
Optimum Conditions ◽  
Redox Potentiometry ◽  
Protection Coating ◽  
Metal Protection ◽  
Mechanism Of The Reaction

<p>Hypophosphites are widely used as reducers in the metal protection coating, as reagents in the synthesis of various organophosphorus compounds, in analytical chemistry, and in many other fields. NaH<sub>2</sub>PO<sub>2</sub> difficultly reacts with many oxidizers without catalysts despite of the significant reduction potential. The kinetics and the mechanism of hypophosphite oxidation in aqueous acid solution of the metal and nonmetal salts are studied in detail. The reactivity of hypophosphite in the organic solvents was not almost studied. In this work the basic possibility of synthesis dialkylphosphites from cheap, accessible and harmless NaH<sub>2</sub>PO<sub>2</sub> and alcohols is shown. Sodium hypophosphite is oxidized by oxygen in alcoholic solutions of FeCl<sub>3</sub> at 50-80 °С to dialkylphosphites. Kinetic and mechanism of the reaction are investigated by methods of volumetry, redox-potentiometry, GC, IR-, UV-, EPR-, Mössbauer- and NMR <sup>31</sup>Р-spectroscopy and X-ray powder diffraction analysis, optimum conditions are found, kinetic and activation parameters of the reaction are calculated. It is shown, that the process follows redox-mechanism and consists of two key stages: reduction of Fe (III) by hypophosphite with formation of dialkylphosphite and reoxidation of Fe (II) by oxygen. The coordination mechanism of reduction reaction of Fe (III) by hypophosphite is proposed. According to this mechanism the dialkylphosphite forms through innersphere redox-decomposition of intermediate alcoxyhypophosphite complex of Fe (III). The coordination mechanism of the process is confirmed by low values of Е<sup>≠</sup> and negative activation entropies ∆S<sup>≠</sup>. The availability in an inner sphere of Fe (III) bromide, low-molecular alcohols, water, characterized by high acidity, increases the reaction rate of oxidative alcoxylation of hypophosphite and promotes the further transformation of dialkylphosphite to di- and trialkylphosphate.</p>

Kinetics and mechanism of the reaction of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione

1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco
Keyword(s):  
Aqueous Solution ◽  
Metal Ion ◽  
Activation Parameters ◽  
Enol Form ◽  
Kinetics And Mechanism ◽  
Kinetic Constants ◽  
Steric Factors ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reactions of iron(III) with 6-methyl-2,4-heptanedione and 3,5-heptanedione to form the corresponding monocomplexes have been studied spectrophotometrically in the range 5 °C to 16 °C at I 25 mol l-1 in aqueous solution. In the proposed mechanism for the two complexes, the enol form reacts with the metal ion by parallel acid-independent and inverse-acid paths. The kinetic constants for both pathways have been calculated at five temperatures. Activation parameters have also been calculated. The results are consistent with an associative activation for Fe(H2O)63+ and dissociative activation for Fe(H2O)5(OH)2+. The differences in the results for the complexes of heptanediones studied are interpreted in terms of steric factors.

In-situ stabilization of silver nanoparticles in polymer hydrogels for enhanced catalytic reduction of macro and micro pollutants

2020 ◽  
Vol 0 (0) ◽  
Author(s):  
Luqman Ali Shah ◽  
Rida Javed ◽  
Mohammad Siddiq ◽  
Iram BiBi ◽  
Ishrat Jamil ◽  
...  
Keyword(s):  
Catalytic Reduction ◽  
Thermo Gravimetric Analysis ◽  
Activation Parameters ◽  
Reduction Reaction ◽  
Gravimetric Analysis ◽  
X Ray Diffraction ◽  
In Situ Stabilization ◽  
Hybrid Hydrogels ◽  
Kinetics Of

AbstractThe in-situ stabilization of Ag nanoparticles is carried out by the use of reducing agent and synthesized three different types of hydrogen (anionic, cationic, and neutral) template. The morphology, constitution and thermal stability of the synthesized pure and Ag-entrapped hybrid hydrogels were efficiently confirmed using scanning electron microscopy (SEM), Fourier transform infrared (FTIR) spectroscopy, X-ray diffraction (XRD) and thermo gravimetric analysis (TGA). The prepared hybrid hydrogels were used in the decolorization of methylene blue (MB) and azo dyes congo red (CR), methyl Orange (MO), and reduction of 4-nitrophenol (4-NP) and nitrobenzene (NB) by an electron donor NaBH4. The kinetics of the reduction reaction was also assessed to determine the activation parameters. The hybrid hydrogen catalysts were recovered by filtration and used continuously up to six times with 98% conversion of pollutants without substantial loss in catalytic activity. It was observed that these types of hydrogel systems can be used for the conversion of pollutants from waste water into useful products.

The kinetics, isotope effects, and mechanism of the reaction of 2,2-di(4-nitrophenyl)-1,1,1-trifluoroethane with alkoxide bases in alcohol solvents

1985 ◽  
Vol 63 (3) ◽  
pp. 576-580 ◽  
Author(s):  
Arnold Jarczewski ◽  
Grzegorz Schroeder ◽  
Wlodzimierz Galezowski ◽  
Kenneth T. Leffek ◽  
Urszula Maciejewska
Keyword(s):  
Rate Constants ◽  
Isotope Effects ◽  
Activation Parameters ◽  
Tert Butanol ◽  
Deuterium Isotope Effects ◽  
Alcohol Solvents ◽  
Multistep Reaction ◽  
Mechanism Of The Reaction

The reaction between 2,2-di(4-nitrophenyl)-1,1,1-trifluoroethane and the alkoxide bases ŌCH3, ŌC2H5, ŌnC4H9, ŌCH(CH3)2, and ŌC(CH3)3 in their corresponding alcohol solvents is a multistep reaction with several intermediates: 2,2-di(4-nitrophenyl)-1,1-difluoro-1-alkoxyethane (A), 2,2-di(4-nitrophenyl)-1-fluoro-1-alkoxyethene (B), 2,2-di(4-nitrophenyl)-1,1-dialkoxyethene (C), 2,2-di(4-nitrophenyl)-1,1-difluoroethene (D), and 4,4′-dinitrobenzophene (E). Rate constants and activation parameters have been measured for the appearance of the two stable products B and C. The kinetic deuterium isotope effects for the appearance of B fell in the range of kH/kD = 1 to 2 at 25 °C for the primary and secondary alkoxides, whereas kH/kD = 5.4 at 30 °C for the appearance of D with tert-butoxide. Exchange experiments showed that H/D exchange took place between the substrate and solvent to the extent of 100% with methoxide, 50% with ethoxide and isopropoxide, and 0% with tert-butoxide. It is concluded the HF elimination from the substrate follows an (ElcB)R mechanism with methoxide/methanol, changing to (ElcB)I or E2 with tert-butoxide/tert-butanol.

Kinetics and Mechanism of the Reaction of Dichlorotetraaquaruthenium(III) and Thiols

2012 ◽  
Vol 65 (2) ◽  
pp. 113 ◽  
Author(s):  
Suprava Nayak ◽  
Gouri Sankhar Brahma ◽  
K. Venugopal Reddy
Keyword(s):  
Electron Transfer ◽  
Ionic Strength ◽  
Equilibrium Constants ◽  
Activation Parameters ◽  
Kinetics And Mechanism ◽  
Intermediate Complex ◽  
Mechanism Of Formation ◽  
Temperature Range ◽  
Temperature Reduction ◽  
Mechanism Of The Reaction

The formation of an intermediate ruthenium(iii) thiolate complex by the interaction of thiols, RSH (R = glutathione and l-cysteine) and dichlorotetraaquaruthenium(iii), [RuIIICl2(H2O)4]+, is reported in the temperature range 25–40°C. The kinetics and mechanism of formation of the intermediate complex were studied as a function of [RuIIICl2(H2O)4]+, [RSH], pH, ionic strength and temperature. Reduction of the intermediate complex takes place slowly and results in the corresponding disulfides RSSR and [RuIICl2(H2O)4]+. The results are interpreted in terms of a mechanism involving a rate-determining inner-sphere one-electron transfer from RSH to the oxidant used in the present investigation and a comparison of rate and equilibrium constants is presented with activation parameters.

scholarly journals Temperature dependence of the kinetics of oxygen reduction on carbon-supported pt nanoparticles

2008 ◽  
Vol 73 (6) ◽  
pp. 641-654 ◽  
Author(s):  
Nevenka Elezovic ◽  
Biljana Babic ◽  
Nedeljko Krstajic ◽  
Snezana Gojkovic ◽  
Ljiljana Vracar
Keyword(s):  
Temperature Dependence ◽  
Oxygen Reduction ◽  
Current Density ◽  
Pt Nanoparticles ◽  
Reduction Reaction ◽  
Hydrogen Electrode ◽  
Rate Determining Step ◽  
Current Densities ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The temperature dependence of oxygen reduction reaction (ORR) was studied on highly dispersed Pt nanoparticles supported on a carbon cryo-gel. The specific surface area of the support was 517 m2 g-1, the Pt particles diameter was about 2.7 nm and the loading of the catalyst was 20 wt.%. The kinetics of the ORR at the Pt/C electrode was examined in 0.50 mol dm-3 HClO4 solution in the temperature range from 274 to 318 K. At all temperatures, two distinct E-log j regions were observed; at low current densities with a slope of -2.3RT/F and at high current densities with a slope of -2.3?2RT/F. In order to confirm the mechanism of oxygen reduction previously suggested at a polycrystalline Pt and a Pt/Ebonex nanostructured electrode, the apparent enthalpies of activation at selected potentials vs. the reversible hydrogen electrode were calculated in both current density regions. Although ?H ?a,1 > ?H ?a,h , it was a,1 a, h found that the enthalpies of activation at the zero Galvani potential difference were the same and hence it could be concluded that the rate-determining step of the ORR was the same in both current density regions. The synthesized Pt/C catalyst showed a small enhancement in the catalytic activity for ORR in comparison to the polycrystalline Pt, but no change in the mechanism of the reaction.

Aromatic Substitutions with Carbanion Nucleophiles. II. The Kinetics and Mechanism of the Reaction of 1-Fluoro-2,4-dinitrobenzene with the Diethyl Malonate Anion

1973 ◽  
Vol 51 (10) ◽  
pp. 1659-1664 ◽  
Author(s):  
Kenneth T. Leffek ◽  
Paul H. Tremaine
Keyword(s):  
Dimethyl Sulfoxide ◽  
Sodium Salt ◽  
Rate Constants ◽  
Activation Parameters ◽  
Diethyl Malonate ◽  
Kinetics And Mechanism ◽  
Reaction Solution ◽  
Red Color ◽  
Unstable Intermediate ◽  
Mechanism Of The Reaction

The reaction of fluoro-2,4-dinitrobenzene with the sodium salt of diethyl malonate to form diethyl (2,4-dinitrophenyl)malonate is fast in dimethyl sulfoxide solvent. The stable red color of the reaction solution is due to the anion of the product, although the initially formed unstable intermediate between the substrate and the anion nucleophile is also red and can be observed at times less than 200 ms after mixing.The rate constants for all the steps in the reaction have been measured and the activation parameters for the three processes involved in the nucleophile substitution have been calculated.

scholarly journals Kinetics and Mechanism Study of Oxidation of Ethylenediamine and Ethanolamine by Potassium Ferrate (VI) in Alkaline Media

2018 ◽  
Vol 10 (3) ◽  
pp. 53
Author(s):  
Chaochao Chen ◽  
Jinhuan Shan ◽  
Xiaofang Li ◽  
Dan Su
Keyword(s):  
Activation Parameters ◽  
Reduction Reaction ◽  
Alkaline Media ◽  
Rate Equations ◽  
Potassium Ferrate ◽  
Mechanism Study ◽  
Oxidation Reduction ◽  
Oxidation Reduction Reaction ◽  
Kinetics Of ◽  
Rate Controlling Step

In this work, the kinetics of oxidation of Ethylenediamine and Ethanolamine by Potassium Ferrate (VI) has been studied by using stop –flow spectrometer under alkaline media. The results show that the oxidation-reduction reaction is a first-order to reactant and a negative fraction order to [OH-]. A convincing mechanism involving a slow response as the rate-controlling step is proposed and the rate equations derived from the mechanism was shown to fit all the experimental observations. The rate constants of the rate-controlling step and the thermodynamic activation parameters were calculated.

scholarly journals Kinetic analysis of metsulphmyoglobin and metmyoglobin reduction by Fe(EDTA)2-

1985 ◽  
Vol 229 (3) ◽  
pp. 765-769 ◽  
Author(s):  
A R Lim ◽  
A G Mauk
Keyword(s):  
Electron Transfer ◽  
Ph Dependence ◽  
Activation Parameters ◽  
Reduction Reaction ◽  
Exchange Chromatography ◽  
Central Metal Atom ◽  
Central Metal ◽  
Prosthetic Group ◽  
Point Reduction ◽  
Relative Electron

Metsulphmyoglobin prepared from horse heart myoglobin was purified by ion-exchange chromatography to yield a product that on reduction with Fe(EDTA)2- has an A617/A561 ratio greater than 3.5:1. The kinetics of reduction of this purified metsulphmyoglobin and of native metmyoglobin by Fe(EDTA)2- were studied under various conditions of pH, ionic strength and temperature to compare the relative electron-transfer reactivities of a metallochlorin and a metalloporphyrin in identical protein environments. Although the rate of metsulphmyoglobin reduction is 2-7 times that of metmyoglobin under a variety of conditions, this difference can be more than compensated for by the reported difference in mid-point reduction potential between the two forms of the protein. The electrostatic and activation parameters observed for native metmyoglobin and metsulphmyoglobin are essentially identical, and small differences are found in the pH-dependence of the reduction reaction. These findings lead us to conclude that conversion of the porphyrin prosthetic group into a chlorin has relatively little effect on the electron-transfer reactivity of the central metal atom.

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