KINETICS OF THE CUPRIC ACETATE CATALYZED HYDROGENATION OF DICHROMATE IN AQUEOUS SOLUTION

1955 ◽  
Vol 33 (2) ◽  
pp. 356-364 ◽  
Author(s):  
E. Peters ◽  
J. Halpern
Keyword(s):  
Activation Energy ◽  
Aqueous Solution ◽  
Partial Pressure ◽  
Kinetic Study ◽  
Reaction Rates ◽  
Homogeneous Catalyst ◽  
Cupric Acetate ◽  
Partial Pressures ◽  
Kinetics Of

In aqueous solution, cupric acetate was found to act as a homogeneous catalyst for the reduction of dichromate by hydrogen, i.e.[Formula: see text] The paper describes a kinetic study of this reaction. Rates were determined at temperatures between 80° and 140 °C. and hydrogen partial pressures up to 27 atmospheres. The rate is independent of the dichromate concentration but varies directly with the partial pressure of hydrogen and is nearly proportional to the concentration of cupric acetate. The activation energy is 24,600 calories per mole. Cupric acetate, apparently acting as a true catalyst, activates the hydrogen through formation of a complex with it. An extension of the mechanism proposed earlier for the reaction of cupric acetate itself with hydrogen also accounts for the kinetics of the dichromate reaction.

KINETICS OF THE HOMOGENEOUS REACTION BETWEEN CUPRIC ACETATE AND MOLECULAR HYDROGEN IN AQUEOUS SOLUTION

1954 ◽  
Vol 32 (10) ◽  
pp. 969-978 ◽  
Author(s):  
R. G. Dakers ◽  
J. Halpern
Keyword(s):  
Aqueous Solution ◽  
Cuprous Oxide ◽  
Molecular Hydrogen ◽  
Sodium Acetate ◽  
Reaction Rates ◽  
Reaction Vessel ◽  
Homogeneous Reaction ◽  
Cupric Acetate ◽  
Partial Pressures ◽  
Kinetics Of

Cupric acetate was found to react homogeneously with molecular hydrogen in aqueous solution according to the following equation:[Formula: see text]The paper describes a kinetic study of this reaction. Rates were determined at temperatures between 80 and 140 °C and hydrogen partial pressures between 6.8 and 34.0 atm. The reaction was found to be of second order, the rate being proportional to the concentrations of cupric acetate and molecular hydrogen. It was established that the rate was independent of the surface of the reaction vessel, the cuprous oxide product and of the concentrations of sodium acetate and acetic acid in the solution. The reaction has an activation energy of 24200 cal. per mole. The kinetic results are discussed and a mechanism is proposed. This appears to be one of the few known homogeneous reactions of molecular hydrogen in solution.

Ferricyanide Oxidation of Butanol Homogeneously Catalysed by Chlororuthenium Complexes

1979 ◽  
Vol 32 (9) ◽  
pp. 1905 ◽  
Author(s):  
AF Godfrey ◽  
JK Beattie
Keyword(s):  
Aqueous Solution ◽  
Complex Formation ◽  
Linear Dependence ◽  
Rate Constants ◽  
Homogeneous Catalyst ◽  
Basic Solution ◽  
Rate Law ◽  
Kinetics Of ◽  
Solution Estimates ◽  
Butanol Concentration

The oxidation of butan-1-ol by ferricyanide ion in alkaline aqueous solution is catalysed by solutions of ruthenium trichloride hydrate. The kinetics of the reaction has been reinvestigated and the data are consistent with the rate law -d[FeIII]/dt = [Ru](2k1k2 [BuOH] [FeIII])/(2k1 [BuOH]+k2 [FeIII]) This rate law is interpreted by a mechanism involving oxidation of butanol by the catalyst (k1) followed by reoxidation of the catalyst by ferricyanide (k2). The non-linear dependence of the rate on the butanol concentration is ascribed to the rate-determining, butanol-independent reoxidation of the catalyst, rather than to the saturation of complex formation between butanol and the catalyst as previously claimed. Absolute values of the rate constants could not be determined, because some of the ruthenium precipitates from basic solution. With K3RuCl6 as the source of a homogeneous catalyst solution, estimates were obtained at 30�0�C of k1 = 191. mol-1 s-1 and k2 = 1�4 × 103 l. mol-1 s-1.

CATALYTIC ACTIVATION OF HYDROGEN IN AQUEOUS SOLUTION BY THE CHLOROPALLADATE(II) ION

1959 ◽  
Vol 37 (9) ◽  
pp. 1446-1450 ◽  
Author(s):  
J. Halpern ◽  
J. F. Harrod ◽  
P. E. Potter
Keyword(s):  
Aqueous Solution ◽  
Ferric Chloride ◽  
Molecular Hydrogen ◽  
Homogeneous Catalyst ◽  
Rate Law ◽  
Catalytic Activation ◽  
Kinetics Of ◽  
Mechanism Of The Reaction

The kinetics of the reduction of ferric chloride by molecular hydrogen in aqueous solution, in the presence of chloropalladate(II), were examined. The latter acts as a homogeneous catalyst for the reaction. The rate-law was found to be,[Formula: see text]where[Formula: see text]The mechanism of the reaction is discussed.

scholarly journals Polyethylene Glycol Mediated Kinetic Study of Nitro Decarboxylation ofα,β-Unsaturated Acids by Blau’s Fe(III) Phen Complex

2013 ◽  
Vol 2013 ◽  
pp. 1-10
Author(s):  
K. Ramesh ◽  
S. Shylaja ◽  
K. C. Rajanna ◽  
P. Giridhar Reddy ◽  
P. K. Saiprakash
Keyword(s):  
Polyethylene Glycol ◽  
Kinetic Study ◽  
Structural Variation ◽  
Negative Charge ◽  
Reaction Rates ◽  
Cationic Form ◽  
Rate Law ◽  
Structural Resemblance ◽  
Kinetics Of ◽  
Acetonitrile Medium

Polyethylene glycol (PEG) mediated kinetic study of nitro decarboxylation ofα,β-unsaturated acids (USA) has been taken up by Blau’s [Fe(III) nitrate-Phen] yellow complex in acetonitrile medium. Kinetics of the reactions indicated Michaelis-Menton type of mechanism and rate law. Reaction rates are significantly influenced by the structural variation and concentration of PEG. Catalysis of PEG was explained on the lines of nonionic micelles such as TX-100 because of their structural resemblance and also due to a slight negative charge developed on polyoxyethylene and cationic form(s) of Fe(III) chelates in the intermediate stages.

Kinetics of Fast Brominations by the Use of Rotating Platinum Electrode

1976 ◽  
Vol 31 (12) ◽  
pp. 1735-1738 ◽  
Author(s):  
T. S. Rao ◽  
S. I. Mali
Keyword(s):  
Aqueous Solution ◽  
Platinum Electrode ◽  
Reaction Rates ◽  
Specific Reaction ◽  
Fast Reactions ◽  
Kinetics Of

AbstractThe utility of the rotating platinum electrode for the study of fast reactions has been shown by evaluating the specific reaction rates of brominations of m-acetotoluidide, acetanilide and o-acetotoluidide in aqueous solution.

Kinetics of individual steps in reaction network ethanol-diethyl ether-ethylene-water on alumina

1986 ◽  
Vol 51 (4) ◽  
pp. 763-773 ◽  
Author(s):  
Vladimír Morávek ◽  
Miloš Kraus
Keyword(s):  
Diethyl Ether ◽  
Reaction Network ◽  
Reaction Rates ◽  
Rate Equations ◽  
Initial Reaction ◽  
Ethanol Dehydration ◽  
Partial Pressures ◽  
Type Rate ◽  
Kinetics Of ◽  
Hydrolysis Of

The rates of single reactions have been measured at 250 °C in the complex reaction of ethanol dehydration to ethylene and to diethyl ether involving also hydrolysis of the ether, its disproportionation to ethanol and ethylene and its dehydration to ethylene. The found dependences of the initial reaction rates on partial pressures of the reactants were correlated by semiempirical Langmuir-Hinshelwood type rate equations.

THE NON-ENZYMATIC HYDROLYSIS OF ADENOSINE DIPHOSPHATE

1957 ◽  
Vol 35 (12) ◽  
pp. 1496-1503 ◽  
Author(s):  
K. A. Holbrook ◽  
Ludovic Ouellet
Keyword(s):  
Activation Energy ◽  
Aqueous Solution ◽  
Enzymatic Hydrolysis ◽  
Inorganic Phosphate ◽  
Adenosine Diphosphate ◽  
Hydrogen Ions ◽  
Kcal Mole ◽  
First Order ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of the non-enzymatic hydrolysis of adenosine diphosphate in aqueous solution have been studied at pH 3.5 to 10.5 and temperatures from 80° to 95 °C. The reaction has been followed by measuring colorimetrically the inorganic phosphate liberated according to the over-all reaction[Formula: see text]The reaction has been found to be first order with respect to ADP concentration and to be catalyzed by hydrogen ions. From rate studies at pH 8.0 an activation energy of 24.2 kcal./mole was derived. A mechanism is proposed to account for the observed facts and the mechanism for the hydrolysis of adenosine triphosphate is also discussed.

scholarly journals Kinetics of stibnite (Sb2S3) oxidation at roasting temperatures

2014 ◽  
Vol 50 (2) ◽  
pp. 127-132 ◽  
Author(s):  
R. Padilla ◽  
A. Aracena ◽  
M.C. Ruiz
Keyword(s):  
Partial Pressure ◽  
Intrinsic Rate ◽  
Analysis Method ◽  
Surface Chemical Reaction ◽  
Partial Pressures ◽  
Rate Of Reaction ◽  
Detectable Rate ◽  
Shrinking Core ◽  
One Step ◽  
Kinetics Of

Experimental work on the oxidation of stibnite (Sb2S3) was carried out at temperatures between 350 and 500?C and oxygen partial pressures between 1.01 and 21.28 kPa by using a thermogravimetric analysis method. The oxidation rate of stibnite was significantly influenced by both temperature and partial pressure of oxygen. Stibnite oxidized in one step to valentinite (Sb2O3) and neither stibnite nor valentinite showed a detectable rate of volatilization at these low temperatures. The oxidation reaction of stibnite was analyzed by using the shrinking core model and it was found that the rate of reaction was controlled by the surface chemical reaction and it was of 3/5 order with respect to the oxygen partial pressure. The intrinsic rate constants were determined and an activation energy value of 90.3 kJ/mol was obtained for the range of temperature studied.

Kinetics of Reactions Between Silica and Carbon and the Formation of Silicon Carbide

1995 ◽  
Vol 410 ◽  
Author(s):  
Kjell Wiik ◽  
Ketil Motzfeldt
Keyword(s):  
Silicon Carbide ◽  
Reaction Mechanism ◽  
Partial Pressure ◽  
Diffusion Path ◽  
Reaction Rates ◽  
Coarse Grained ◽  
Continuous Formation ◽  
Thermogravimetric Investigation ◽  
Kinetics Of

ABSTRACTThe reactions taking place between coarse grained mixtures of silica (cristobalite) and carbon (graphite) at 1558°C in pure CO as well as mixtures of CO and Ar, have been subjected to a thermogravimetric investigation. A model is developed in the regime where the formation of SiC does not take place. The primary steps are assumed to be: Reaction betweefn SiO2 and CO to give SiO(g) and CO2 followed by the reaction between CO2 and C to give CO. The model predicts the prevailing partial pressure of SiO throughout the charge, and the correlation between observations and model strongly supports the above given reaction mechanism.Enhanced and accelerating reaction rates were observed when the formation of β-SiC took place. It is suggested that this is due to the continuous formation of stable SiC-nucleus on the Csurface and the subsequent shortening of the diffusion path for SiO.

scholarly journals Temperature and pH effects on the kinetics of 2-aminophenol auto-oxidation in aqueous solution

2003 ◽  
Vol 1 (3) ◽  
pp. 233-241 ◽  
Author(s):  
Dumitru Oancea ◽  
Mihaela Puiu
Keyword(s):  
Experimental Data ◽  
Activation Energy ◽  
Aqueous Solution ◽  
Ph Effects ◽  
Influence Of Temperature ◽  
First Order ◽  
Incremental Methods ◽  
First Order Kinetics ◽  
Ph Range ◽  
Kinetics Of

AbstractThe kinetics of the auto-oxidation of 2-aminophenol (OAP) to 2-amino-phenoxazin-3-one (APX) was followed in air-saturated aqueous solutions and the influence of temperature and pH on the auto-oxidation rate was studied. The kinetic analysis was based on a spectrophotometric method following the increase of the absorbance of APX. The process follows first order kinetics according to the rate law—d[OAP]/dt=k′[OAP]. The experimental data, within the pH range 4–9.85, were analyzed using both differential and incremental methods. The temperature variation of the overall rate constant was studied at pH=9.85 within the range 25–50°C and the corresponding activation energy was evaluated.

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