Kinetics and mechanisms of the reaction between carbon monoxide and copper(II) in aqueous solution

1969 ◽  
Vol 47 (2) ◽  
pp. 313-321 ◽  
Author(s):  
J. J. Byerley ◽  
E. Peters
Keyword(s):  
Aqueous Solution ◽  
Carbon Monoxide ◽  
Reaction Path ◽  
Carbonyl Complex ◽  
Cupric Ion ◽  
Inhibiting Effect ◽  
Rate Determining Step ◽  
Ph Dependent ◽  
A Minor ◽  
Kinetics Of

The kinetics of the reduction of copper(II) to copper(I) by carbon monoxide in aqueous solutions have been investigated at 120 °C and carbon monoxide pressures up to 1360 atm. The reaction is homogeneous and proceeds by two paths, one of which is virtually independent of carbon monoxide pressure due to the formation of a stable cuprous carbonyl complex Cu(CO)+. The second reaction path contains both a pH-dependent and pH-independent component. The rate-determining step in both paths appears to be the decomposition of a carbon monoxide insertion complex by a cupric ion. Complexing ligands such as acetate were observed to have a minor inhibiting effect on the overall reaction.

Kinetics of carbon monoxide methanation on a Ni/SiO2 catalyst

1990 ◽  
Vol 55 (7) ◽  
pp. 1678-1685
Author(s):  
Vladimír Stuchlý ◽  
Karel Klusáček
Keyword(s):  
Carbon Monoxide ◽  
Reaction Rate ◽  
Catalyst Activity ◽  
Adsorbed Hydrogen ◽  
Reaction Products ◽  
Co Methanation ◽  
Molar Ratios ◽  
Rate Determining Step ◽  
Higher Temperature ◽  
Kinetics Of

Kinetics of CO methanation on a commercial Ni/SiO2 catalyst was evaluated at atmospheric pressure, between 528 and 550 K and for hydrogen to carbon monoxide molar ratios ranging from 3 : 1 to 200 : 1. The effect of reaction products on the reaction rate was also examined. Below 550 K, only methane was selectively formed. Above this temperature, the formation of carbon dioxide was also observed. The experimental data could be described by two modified Langmuir-Hinshelwood kinetic models, based on hydrogenation of surface CO by molecularly or by dissociatively adsorbed hydrogen in the rate-determining step. Water reversibly lowered catalyst activity and its effect was more pronounced at higher temperature.

Kinetics of the Decomposition of Sulphur Dicyanide in Aqueous Solution

1962 ◽  
Vol 15 (2) ◽  
pp. 211 ◽  
Author(s):  
W Kitching ◽  
RH Smith ◽  
IR Wilson
Keyword(s):  
Aqueous Solution ◽  
Aqueous Solutions ◽  
Nucleophilic Substitution ◽  
Perchloric Acid ◽  
Reaction Path ◽  
Acid Solutions ◽  
Kinetics Of

The kinetics and stoicheiometry of the decomposition of aqueous solutions of sulphur dicyanide have been studied at temperatures between 0-70 �C and in media ranging from dilute perchloric acid to pH 7. The predominant reaction is nucleophilic substitution at carbon, but in perchloric acid solutions an alternative reaction path has been revealed.

Metal complex catalyzed reactions of anils. III. Kinetic and mechanistic studies

1977 ◽  
Vol 55 (12) ◽  
pp. 2432-2441 ◽  
Author(s):  
A. R. Boate ◽  
D. R. Eaton
Keyword(s):  
Aqueous Solution ◽  
Metal Complex ◽  
Metal Atom ◽  
Nucleophilic Attack ◽  
Mechanistic Studies ◽  
Acetone Molecule ◽  
Rate Determining Step ◽  
Catalyzed Reactions ◽  
Kinetics Of ◽  
Hydrolysis Of

The kinetics of the homogeneously catalyzed formation and hydrolysis of anils in non-aqueous solution have been studied. The catalysts used are zinc complexes of thiourea. It is shown that all the evidence obtained, kinetic and otherwise, is consistent with a model in which the rate determining step for anil formation is nucleophilic attack by an aniline held in the second coordination sphere of the metal complex on an acetone molecule directly bound to the metal atom. Analogous mechanisms are suggested for anil hydrolysis and for transimination.

Fast time-resolved i.r. spectroscopy of biological molecules in aqueous solution: The reaction kinetics of myoglobin with carbon monoxide

1988 ◽  
Vol 44 (12) ◽  
pp. 1309-1314 ◽  
Author(s):  
Andrew J. Dixon ◽  
Paul Glyn ◽  
Michael A. Healy ◽  
P.Michael Hodges ◽  
Timothy Jenkins ◽  
...  
Keyword(s):  
Aqueous Solution ◽  
Carbon Monoxide ◽  
Reaction Kinetics ◽  
Biological Molecules ◽  
Fast Time ◽  
Time Resolved ◽  
Kinetics Of

The thermally induced rearrangements of 2-vinyloxirane

1976 ◽  
Vol 54 (21) ◽  
pp. 3364-3376 ◽  
Author(s):  
Robert J. Crawford ◽  
Stuart B. Lutener ◽  
Robert D. Cockcroft
Keyword(s):  
Carbon Monoxide ◽  
Gas Phase ◽  
Isotope Effects ◽  
Kinetic Isotope Effects ◽  
Thermally Induced ◽  
Rate Determining Step ◽  
Kinetic Isotope ◽  
Carbonyl Ylide ◽  
Structural Isomerization ◽  
Kinetics Of

The kinetics of the gas phase thermolysis of 2-vinyloxirane (4) have been studied over the temperature range 270–310 °C. The racemization of chiral 4 occurs six times faster than the structural isomerization to 2,3-dihydrofuran, (E)- and (Z)-2-butenal, and 3-butenal. The butenals undergo a slow thermolysis to propene and carbon monoxide. cis-Deuterio- and trans-3-deuterio-vinyloxirane have been synthesized and their interconversion is slow. Deuterium kinetic isotope effects on mono- and dideuterio-4 suggest that for the formation of the butenals the rate determining step involves rupture of the oxirane C—O bond. The dihydrofuran is produced by thermolysis of the oxirane C—C bond. The preferred mechanistic interpretation is that a carbon–oxygen diradical serves as an intermediate for butenal formation, and that a carbonyl-ylide is involved in the formation of the dihydrofuran.The relative rates, at 307.4 °C, of cis–trans-5-isomerization:dihydrofuran formation:racemization: butenal formation for 3-deuterio-2-vinyloxirane are 1.0:0.88:40.2:5.94, respectively.

Copper(II)-catalyzed oxidation of carbon monoxide by molecular oxygen

1967 ◽  
Vol 45 (24) ◽  
pp. 3025-3030 ◽  
Author(s):  
J. J. Byerley ◽  
Jolland Y. H. Lee
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Aqueous Solutions ◽  
Molecular Oxygen ◽  
Rate Determining Step ◽  
Oxidation By Molecular Oxygen ◽  
Kinetics Of ◽  
Equilibrium Step ◽  
Catalyzed Oxidation ◽  
Oxidation Of Carbon Monoxide

The kinetics of the copper (II)-catalyzed oxidation of carbon monoxide by molecular oxygen, i.e. [Formula: see text] have been investigated in aqueous solutions at 120 °C. The rate law was found to be of the form −d[O2]/dt = kexpt[O2][CO][Cu(II)]/[H+], where kexpt = 7.88 × 10−6 M−1 s−1 in 0.25 M acetate solutions. The apparent activation energy is 29 600 cal/mole. The rate-determining step of the reaction appears to be the oxidation by molecular oxygen of a carbon monoxide insertion complex [Formula: see text] formed in the pre-equilibrium step.

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