Kinetics and mechanism of the redox reaction of thallic sulphate with acroleine

1980 ◽  
Vol 45 (4) ◽  
pp. 1173-1181 ◽  
Author(s):  
Ľudovít Treindl ◽  
Milan Melicherčík
Keyword(s):  
Sulphuric Acid ◽  
Rate Equation ◽  
Redox Reaction ◽  
Reaction Order ◽  
Kinetics And Mechanism ◽  
Aqueous Dioxane ◽  
Rate Determining Step

The stoichiometry, kinetics and mechanism of the redox reaction of thallic sulphate with acroleine in aqueous sulphuric acid or in aqueous dioxane solutions were studied. The acroleine molecule is oxidised with Tl(III) ions in two consecutive one-electron steps to glyceraldehyde. The corresponding rate equation is -d[Tl(III)]/dt = k[Tl(III)]n [A], where n = 0-2. The zeroth reaction order with respect to thallic ions is attributed to a slow enolization of the hydrated acroleine, which is the rate-determining step preceding the redox reaction proper.

Kinetics and mechanism of oxidation of Cr(II) ions by tetrachloromethane

1980 ◽  
Vol 45 (1) ◽  
pp. 21-25 ◽  
Author(s):  
Peter Ševčík ◽  
Miroslav Khír
Keyword(s):  
Rate Constants ◽  
Redox Reaction ◽  
Second Order ◽  
Kinetics And Mechanism ◽  
Bridge Structure ◽  
Order Rate ◽  
Rate Determining Step ◽  
Inner Sphere ◽  
Mechanism Of Oxidation ◽  
Kinetics Of

Kinetics of the redox reaction of Cr(II) ions with tetrachloromethane has been studied in H2O-CH3OH-HClO4 and H2O-CH3COOH-HClO4. In the redox reaction 2 moles of Cr(II) are consumed per one mol of CCl4, and CrCl2+ and CrCCL2+3 ions are formed in the same amounts. Second order rate constants (k293 = 2.31 mol-1 s -1 in 50% CH3OH, k293 = 1.66 l . mol-1 s-1 in 50% CH3COOH) are independent of H+ ions concentration.The rate determining step is an inner sphere transfer of the halogen from CCl4 to Cr(II), the Cr-Cl-C bridge structure being retained in both media.

scholarly journals Kinetics and Mechanism of Oxidation of Aliphatic Aldehydes by Benzyltrimethylammonium tribromide

1999 ◽  
Vol 23 (3) ◽  
pp. 176-177
Author(s):  
Garima Goswami ◽  
Seema Kothari ◽  
Kalyan K. Banerji
Keyword(s):  
Carboxylic Acid ◽  
Kinetics And Mechanism ◽  
Intermediate Complex ◽  
Aliphatic Aldehydes ◽  
Rate Determining Step ◽  
Mechanism Of Oxidation ◽  
Subsequent Decomposition

The oxidation of aliphatic aldehydes by benzyltrimethylammonium tribromide involves the formation of an intermediate complex and its subsequent decomposition in the rate-determining step to the corresponding carboxylic acid.

Kinetics and mechanism of the reduction of CrVI to CrIII by D-ribose and 2-deoxy-D-ribose

1999 ◽  
Vol 77 (1) ◽  
pp. 57-64 ◽  
Author(s):  
Verónica Daier ◽  
Sandra Signorella ◽  
Marcela Rizzotto ◽  
María Inés Frascaroli ◽  
Claudia Palopoli ◽  
...  
Keyword(s):  
Redox Reaction ◽  
Kinetics And Mechanism ◽  
Epr Spectra ◽  
Oxidation Reactions ◽  
Redox Mechanism ◽  
Rate Laws ◽  
Aldonic Acid

The oxidation of D-ribose and 2-deoxy-D-ribose by CrVI yields the aldonic acid and Cr3+ as final products when an excess of sugar over CrVI is used. The redox reaction occurs through CrVI–>CrIII and CrVI–>CrV–>CrIII paths. The complete rate laws for the CrVI oxidation reactions are expressed by -d[CrVI]/dt = kH[H+]2 [ribose][CrVI], where kH = (5.9 ± 0.1) × 10-2 mol-3 dm9 s-1, and -d[CrVI]/dt = (k0 + kH'[H+]2) [2-deoxyribose][CrVI], where k0 = (1.3 ± 0.5) × 10-3 mol-1 dm3 s-1 and kH' = (4.2 ± 0.1) × 10-2 mol-3 dm9 s-1, at 33°C. An intermediate sugar alkoxide radical could be trapped with DMPO and observed by EPR as a multiline signal at g = 2.003. CrV is formed in a rapid step by reaction of the sugar radical with CrVI. CrV reacts with the substrate faster than CrVI does. The EPR spectra show that five- and six-coordinate oxochromate(V) intermediates are formed, and the distribution of these CrV species in the reaction mixture essentially depends on the solution acidity.Key words: ribose, 2-deoxyribose, chromium, redox, mechanism, kinetics.

scholarly journals The kinetics of the hydrogen chloride oxidation

2013 ◽  
Vol 78 (12) ◽  
pp. 2115-2130 ◽  
Author(s):  
Martinez Gonzalez ◽  
Tanja Vidakovic-Koch ◽  
Rafael Kuwertz ◽  
Ulrich Kunz ◽  
Thomas Turek ◽  
...  
Keyword(s):  
Kinetic Parameters ◽  
Gas Phase ◽  
Hydrogen Chloride ◽  
Reaction Order ◽  
Membrane Electrode ◽  
Polarization Data ◽  
Rate Determining Step ◽  
Electrode Assemblies ◽  
Apparent Kinetic Parameters ◽  
Kinetics Of

Hydrogen chloride (HCl) oxidation has been investigated on technical membrane electrode assemblies in a cyclone flow cell. Influence of Nafion loading, temperature and hydrogen chloride mole fraction in the gas phase has been studied. The apparent kinetic parameters like reaction order with respect to HCl, Tafel slope and activation energy have been determined from polarization data. The apparent kinetic parameters suggest that the recombination of adsorbed Cl intermediate is the rate determining step.

scholarly journals Kinetics and mechanism of cetyltrimethylammonium bromide catalyzed oxidation of diethylene glycol by chloramine-T in acidic medium

2003 ◽  
Vol 68 (7) ◽  
pp. 535-542 ◽  
Author(s):  
V.W. Bhagwat ◽  
J. Tiwari ◽  
A. Choube ◽  
B. Pare
Keyword(s):  
Diethylene Glycol ◽  
Acidic Medium ◽  
Cetyltrimethylammonium Bromide ◽  
Reaction Rate ◽  
Chloride Ions ◽  
Kinetics And Mechanism ◽  
Product Analysis ◽  
Rate Determining Step ◽  
Chloramine T ◽  
Catalyzed Oxidation

The kinetics and mechanism of the C16TABcatalyzed oxidation of diethylene glycol (2,2?-oxydiethanol) by chloramine-T in acidic medium has been studied. The reaction has a first-order dependence on chloramine-T. With excess concentrations of other reactants, the reaction rate follows fractional order kinetics with respect to [diethylene glycol]. The micellar effect due to cetyltrimethylammonium bromide, a cationic surfactant, has been studied. The reaction is catalyzed by chloride ions as well. The small salt effect and increase in the reaction rate with increasing dielectric constant suggest the involvement of neutral molecules in the rate determining step. Addition of p-toluenesulfonamide retards the reaction rate. On the basis of product analysis, a pertinent mechanism is proposed.

Kinetics and Mechanism of Redox Reaction between Tetrachloroaurate(III) Ions and Hydrazine

2014 ◽  
Vol 46 (6) ◽  
pp. 328-337 ◽  
Author(s):  
Bartłomiej Streszewski ◽  
Wiktor Jaworski ◽  
Konrad Szaciłowski ◽  
Krzysztof Pacławski
Keyword(s):  
Redox Reaction ◽  
Kinetics And Mechanism

scholarly journals Kinetics and mechanism of the Oxidative regeneration of Carbonyl Compounds from Phenylhydrazones by Tetramminecopper(2+) Bis (Permanganate)

2003 ◽  
Vol 2003 (4) ◽  
pp. 184-185
Author(s):  
Raghvendra Shukla ◽  
László Kótai ◽  
Pradeep K. Sharma ◽  
Kalyan K. Banerji
Keyword(s):  
Acetic Acid ◽  
Carbonyl Compounds ◽  
Kinetics And Mechanism ◽  
Aqueous Acetic Acid ◽  
Acid Proceeds ◽  
Oxidative Regeneration ◽  
Rate Determining Step ◽  
Activated Complex

The oxidation of aldo- and keto-phenylhydrazones by tetraamminecopper(2+) bis(permanganate) (TACP), in aqueous acetic acid, proceeds through a mechanism involving the formation of a cyclic activated complex, in the rate-determining step.

Modeling of Gas Turbine Combustors—A Convenient Reaction Rate Equation

1972 ◽  
Vol 94 (3) ◽  
pp. 173-180 ◽  
Author(s):  
D. Kretschmer ◽  
J. Odgers
Keyword(s):  
Rate Equation ◽  
Reaction Rate ◽  
Reaction Order ◽  
Bimolecular Reaction ◽  
Rate Equations ◽  
Combustion System ◽  
Wide Range ◽  
Simple Mass ◽  
Rich Mixtures ◽  
Reaction Rate Equation

In order to model a practical combustion system successfully, it is necessary to develop one or more reaction rate equations which will describe performance over a wide range of conditions. The equations should be kept as simple as possible and commensurate with the accuracy needed. In this paper a bimolecular reaction is assumed, based upon a simple mass balance. Temperatures derived from the latter are related to measured practical ones such that, if required, an evaluation of the partly burned product composition can be made. A convenient reaction rate equation is given which describes a wide range of blow-out data for spherical reactors at weak mixture conditions. NVP2φ={1.29×1010(m+1)[5(1−yε)]φ[φ−yε]φe−C/(Ti+εΔT)}/{0.082062φyε[5(m+1)+φ+yε]2φ[Ti+εΔT]2φ−0.5} Analysis of the components used in the above equation (especially the variation of activation energy) clearly shows its empirical nature but does not detract from its engineering value. Rich mixtures are considered also, but lack of data precludes a reliable analysis. One of the major results obtained is the variation of the reaction order (n) with equivalence ratio (φ): weak mixtures, n = 2φ; rich mixtures, n = 2/φ. Some support for this variation has been noticed in published literature of other workers.

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