Silver-Catalyzed Oxidation of Ethylene to Ethylene Oxide in a Microreaction System

2002 ◽  
Vol 41 (4) ◽  
pp. 710-719 ◽  
Author(s):  
Harry Kestenbaum ◽  
Armin Lange de Oliveira ◽  
Wolfgang Schmidt ◽  
Ferdi Schüth ◽  
Wolfgang Ehrfeld ◽  
...  
Keyword(s):  
Ethylene Oxide ◽  
Catalyzed Oxidation

THE SILVER CATALYZED OXIDATION OF ETHYLENE: IV. REACTION MECHANISM

1954 ◽  
Vol 32 (4) ◽  
pp. 443-451 ◽  
Author(s):  
A. Orzechowski ◽  
K. E. MacCormack
Keyword(s):  
Reaction Mechanism ◽  
Ethylene Oxide ◽  
Temperature Dependent ◽  
Heterogeneous Oxidation ◽  
Initial Oxidation ◽  
Partial Pressures ◽  
Parallel Reactions ◽  
Single Oxygen ◽  
Catalyzed Oxidation ◽  
Adsorbed Ethylene

A reaction mechanism for the silver catalyzed oxidation of C2H4 by oxygen has been formulated which is consistent with kinetic data for this system. It is suggested that both ethylene oxide and CO2 formation involve interaction of single gaseous C2H4 molecules with single oxygen adatoms. This may be a system of two parallel reactions of different activation energy requirements or a common initiation step to form adsorbed ethylene oxide which may then desorb immediately or isomerize to acetaldehyde followed by rapid oxidation to CO2 and H2O. Account is taken of the known adsorption characteristics of O2 on silver to deduce expressions for initial rates of ethylene oxide and CO2 formation as a function of reactant partial pressures. The generalized form of the equation is r = k(1 + a/pE + b/pO)−1, where k, a, and b are temperature dependent constants and pE and pO are partial pressures of ethylene and of oxygen respectively.A mechanism is also suggested for the heterogeneous oxidation of ethylene oxide which involves interaction between a gas phase ethylene oxide molecule and a single oxygen adatom to form an intermediate (probably formaldehyde) which is rapidly oxidized to CO2 and H2O. A similar expression to that above for the initial oxidation rate is deduced. These expressions have been fitted successfully to experimental data.

THE SILVER CATALYZED OXIDATION OF ETHYLENE: III. KINETICS OF ETHYLENE OXIDE OXIDATION

1954 ◽  
Vol 32 (4) ◽  
pp. 432-442 ◽  
Author(s):  
A. Orzechowski ◽  
K. E. MacCormack
Keyword(s):  
Ethylene Oxide ◽  
Initial Rate ◽  
Oxidation Mechanism ◽  
Kinetic Studies ◽  
Main Step ◽  
Direct Oxidation ◽  
Flow Rates ◽  
Rate Determining Step ◽  
Kinetics Of ◽  
Catalyzed Oxidation

A flow type apparatus was used for kinetic studies of the silver catalyzed oxidation of ethylene oxide (EtO) by oxygen at 274 °C. Using N2 as diluent the concentrations of O2 and ethylene oxide were varied independently from 9.9 to 79% and 2.35 to 9.4% respectively while a total pressure of 1 atmosphere was maintained. Flow rates were varied to give a range of contact times varying from 0.06 to 0.25 sec. It was shown that EtO is oxidized without previous dissociation into C2H4 and O2. The dependence of the initial rate of oxidation of EtO on reactant concentrations excludes isomerization of EtO (to acetalde hyde) as a main step in its oxidation, and a direct oxidation mechanism is suggested. The results of a few experiments to determine the extent of isomerization of EtO to acetaldehyde in the absence of oxygen are presented. No steady state could be achieved but the results may be used semiquantitatively to support the belief that isomerization is not the rate determining step in the oxidation of ethylene oxide.

THE SILVER CATALYZED OXIDATION OF ETHYLENE: I. SLOW PROCESSES ON THE CATALYST SURFACE

1954 ◽  
Vol 32 (4) ◽  
pp. 388-398 ◽  
Author(s):  
A. Orzechowski ◽  
K. E. MacCormack
Keyword(s):  
Ethylene Oxide ◽  
Reaction Temperature ◽  
Catalyst Surface ◽  
Flow System ◽  
Catalyst Activity ◽  
Reference State ◽  
Silver Catalyst ◽  
Kinetic Measurements ◽  
Catalyzed Oxidation ◽  
Oxygen Atoms

In the silver catalyzed oxidation of ethylene or ethylene oxide (EtO), the silver catalyst activity measured under constant standard conditions in a flow system was found to be dependent on the conditions of previous catalyst treatment such as reaction temperature and reactant composition. The results are explained on the basis of slow establishment of equilibrium respecting fixation of stably sorbed oxygen atoms and surface products of oxidation. It is emphasized that in view of the slow processes observed, the kinetic measurements must be punctuated by frequent stabilizing check runs in order to maintain the catalyst in the same reference state.

THE ROLE OF REACTION PRODUCTS IN THE SILVER-CATALYZED OXIDATION OF ETHYLENE

1960 ◽  
Vol 38 (11) ◽  
pp. 2256-2268 ◽  
Author(s):  
Kenneth E. Hayes
Keyword(s):  
Carbon Dioxide ◽  
Ethylene Oxide ◽  
Initial Rate ◽  
Flow System ◽  
Oxygen Exchange ◽  
Reaction Products ◽  
Exchange Reactions ◽  
Kinetics Of ◽  
Catalyzed Oxidation

Initial-rate studies of the kinetics of the silver-catalyzed oxidation of ethylene oxide and carbon dioxide in a flow system have been made. It was found that, using carefully purified reactants, the effect of added carbon dioxide was to suppress the formation of ethylene oxide only. The initial rate of the formation of ethylene oxide is given by the equation[Formula: see text]where r0 is the initial rate in the absence of CO2; m, n, and k are constants with m + n = 1.These results together with the results of oxygen exchange reactions between O18 and C2H4O16, CO216 and H2O16 are interpreted mechanistically.

Renilla Bioluminescence: A Morphologic Approach to the Location of Photocytes

1974 ◽  
Vol 32 ◽  
pp. 208-209
Author(s):  
Ben O. Spurlock ◽  
Milton J. Cormier
Keyword(s):  
Excited State ◽  
Ground State ◽  
Molecular Basis ◽  
Light Emission ◽  
Chemical Basis ◽  
Electronic Excited State ◽  
Colonial Form ◽  
The Common ◽  
Eighteenth And Nineteenth Centuries ◽  
Catalyzed Oxidation

The phenomenon of bioluminescence has fascinated layman and scientist alike for many centuries. During the eighteenth and nineteenth centuries a number of observations were reported on the physiology of bioluminescence in Renilla, the common sea pansy. More recently biochemists have directed their attention to the molecular basis of luminosity in this colonial form. These studies have centered primarily on defining the chemical basis for bioluminescence and its control. It is now established that bioluminescence in Renilla arises due to the luciferase-catalyzed oxidation of luciferin. This results in the creation of a product (oxyluciferin) in an electronic excited state. The transition of oxyluciferin from its excited state to the ground state leads to light emission.

The Structure of Radiation Cross-Linked Poly (ethylene oxide) Gels

1971 ◽  
Vol 29 ◽  
pp. 76-77
Author(s):  
C. E. Cluthe ◽  
G. G. Cocks
Keyword(s):  
Molecular Weight ◽  
Ethylene Oxide ◽  
Parallel Plate ◽  
Average Molecular Weight ◽  
Radical Reaction ◽  
Free Radical Reaction ◽  
Nitrogen Gas ◽  
Poly Ethylene Oxide ◽  
Poly Ethylene ◽  
Initial Viscosity

Aqueous solutions of a 1 weight-per cent poly (ethylene oxide) (PEO) were degassed under vacuum, transferred to a parallel plate viscometer under a nitrogen gas blanket, and exposed to Co60 gamma radiation. The Co60 source was rated at 4000 curies, and the dose ratewas 3.8x105 rads/hr. The poly (ethylene oxide) employed in the irradiations had an initial viscosity average molecular weight of 2.1 x 106.The solutions were gelled by a free radical reaction with dosages ranging from 5x104 rads to 4.8x106 rads.

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