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

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.

1955 ◽  
Vol 33 (2) ◽  
pp. 356-364 ◽  
Author(s):  
E. Peters ◽  
J. Halpern

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.


1959 ◽  
Vol 37 (9) ◽  
pp. 1446-1450 ◽  
Author(s):  
J. Halpern ◽  
J. F. Harrod ◽  
P. E. Potter

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.


1976 ◽  
Vol 31 (12) ◽  
pp. 1735-1738 ◽  
Author(s):  
T. S. Rao ◽  
S. I. Mali

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.


1986 ◽  
Vol 51 (4) ◽  
pp. 763-773 ◽  
Author(s):  
Vladimír Morávek ◽  
Miloš Kraus

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.


1990 ◽  
Vol 55 (8) ◽  
pp. 1984-1990 ◽  
Author(s):  
José M. Hernando ◽  
Olimpio Montero ◽  
Carlos Blanco

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.


1989 ◽  
Vol 54 (5) ◽  
pp. 1311-1317
Author(s):  
Miroslav Magura ◽  
Ján Vojtko ◽  
Ján Ilavský

The kinetics of liquid-phase isothermal esterification of POCl3 with 2-isopropylphenol and 4-isopropylphenol have been studied within the temperature intervals of 110 to 130 and 90 to 110 °C, respectively. The rate constants and activation energies of the individual steps of this three-step reaction have been calculated from the values measured. The reaction rates of the two isomers markedly differ: at 110 °C 4-isopropylphenol reacts faster by the factors of about 7 and 20 for k1 and k3, respectively. This finding can be utilized in preparation of mixed triaryl phosphates, since the alkylation mixture after reaction of phenol with propene contains an excess of 2-isopropylphenol over 4-isopropylphenol.


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