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.

Blocking of the silver catalyst surface in the conversion of ethylene to ethylene oxide

1977 ◽  
Vol 6 (3) ◽  
pp. 409-415 ◽  
Author(s):  
Sh. L. Guseinov ◽  
I. T. Frolkina ◽  
L. A. Vasilevich ◽  
A. K. Avetisov ◽  
A. I. Gel'bstein
Keyword(s):  
Ethylene Oxide ◽  
Catalyst Surface ◽  
Silver Catalyst

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.

Physicochemical and Catalytic Properties of Spinels Formed by Solid-Solid Interaction Between Fe2O3and V2O5

1996 ◽  
Vol 61 (8) ◽  
pp. 1131-1140 ◽  
Author(s):  
Abd El-Aziz Ahmed Said
Keyword(s):  
Vanadium Oxide ◽  
Active Sites ◽  
Catalyst Surface ◽  
Catalytic Properties ◽  
Flow System ◽  
Oxide Catalysts ◽  
X Ray Diffraction ◽  
Selective Catalyst ◽  
X Ray ◽  
Solid Catalysts

Vanadium oxide catalysts doped or mixed with 1-50 mole % Fe3+ ions were prepared. The structure of the original samples and those calcined from 200 up to 500 °C were characterized by TG, DTA, IR and X-ray diffraction. The SBET values and texture of the solid catalysts were investigated. The catalytic dehydration-dehydrogenation of isopropanol was carried out at 200 °C using a flow system. The results obtained showed an observable decrease in the activity of V2O5 on the addition of Fe3+ ions. Moreover, Fe2V4O13 is the more active and selective catalyst than FeVO4 spinels. The results were correlated with the active sites created on the catalyst surface.

Origin of enhanced ethylene oxide selectivity by Cs-promoted silver catalyst

2017 ◽  
Vol 441 ◽  
pp. 92-99 ◽  
Author(s):  
Dongmei Ren ◽  
Haoxiang Xu ◽  
Jianwei Li ◽  
Jinbing Li ◽  
Daojian Cheng
Keyword(s):  
Ethylene Oxide ◽  
Silver Catalyst

Active surface centres in vanadium pentoxide/alkali metal sulphate heterogeneous catalysts for 2-propanol decomposition

1979 ◽  
Vol 57 (18) ◽  
pp. 2464-2469 ◽  
Author(s):  
David Victor Fikis ◽  
William John Murphy ◽  
Robert Anderson Ross
Keyword(s):  
Alkali Metal ◽  
Surface Area ◽  
Vanadium Pentoxide ◽  
Heterogeneous Catalysts ◽  
Catalyst Activity ◽  
Active Surface ◽  
Hydroxyl Groups ◽  
Kinetic Measurements ◽  
The Stability ◽  
The Individual

Infrared spectra of the surfaces of vanadium pentoxide and vanadium pentoxide containing 9.09 mol% caesium and potassium, as sulphates, have been determined after exposure to 2-propanol for various times. Interpretation of the spectra leads to the proposal that the principal source of catalyst activity may be associated with surface hydrogen and hydroxyl groups on V5+ and V4+ sites. The "stability" of the catalysts towards reduction by the alcohol was consistent with the activity series derived from kinetic measurements: V2O5 (pure) < V2O5 (Cs) < V2O5 (K). The degree of sample reduction has also been assessed qualitatively by measurements of the ratio of surface area before to that after reaction and the same catalyst sequence was established. The trend in surface area ratios was similar to that shown by the surface "Tammann" temperatures of vanadium pentoxide and alkali metal sulphates which has been taken to imply that the ease and (or) extent with which the sulphates enter into inter-solid reactions with the oxide in the preparation stage may exert influence on the subsequent reducibility of the individual members of the catalyst series.

Microreactors as tools in kinetic investigations: Ethylene oxide formation on silver catalyst

2013 ◽  
Vol 87 ◽  
pp. 306-314 ◽  
Author(s):  
Tapio Salmi ◽  
José Hernández Carucci ◽  
Mauricio Roche ◽  
Kari Eränen ◽  
Johan Wärnå ◽  
...  
Keyword(s):  
Ethylene Oxide ◽  
Silver Catalyst ◽  
Oxide Formation ◽  
Kinetic Investigations

Die Reaktion eines gemischten Doppelylids mit Ethylenoxid / Reaction of a Mixed Double Ylide with Ethylene Oxide

1978 ◽  
Vol 33 (5) ◽  
pp. 572-573 ◽  
Author(s):  
Hubert Schmidbaur ◽  
Peter Holl
Keyword(s):  
Ethylene Oxide ◽  
Nmr Spectra ◽  
Trigonal Bipyramidal ◽  
Bipyramidal Structure ◽  
Oxygen Atoms

Abstract Dimethyl-trimethylphosphinimino-methylene-phosphorane, (CH3)3P=N-P(CH3)2 = CH2 was found to react with ethylene oxide to form a 1:1 adduct, that was identified as 2,2-dimethyl-2-trimethylphosphinimino -1,2λ5 -oxaphospholane. According to its 1H, 13C, 31P NMR spectra it is assigned a rigid trigonal bipyramidal structure with nitrogen and oxygen atoms in axial positions.

Rate constants for reactions of horseradish peroxidase compounds I and II with 4-substituted arylboronic acids

1994 ◽  
Vol 72 (10) ◽  
pp. 2159-2162 ◽  
Author(s):  
Weimei Sun ◽  
Xiaoying Ji ◽  
Larry J. Kricka ◽  
H. Brian Dunford
Keyword(s):  
Horseradish Peroxidase ◽  
Rate Constants ◽  
Compound I ◽  
Arylboronic Acid ◽  
Experimental Conditions ◽  
Kinetic Measurements ◽  
Arylboronic Acids ◽  
Total Ionic Strength ◽  
Compound Ii ◽  
Catalyzed Oxidation

The rate constants for the reactions of horseradish peroxidase compound I (k1) and compound II (k2) with three 4-substituted arylboronic acids, which enhance chemiluminescence in the horseradish peroxidase catalyzed oxidation of luminol by hydrogen peroxide, were determined at pH 8.6, total ionic strength 0.11 M, using stopped-flow kinetic measurements. For comparison, the rate constants of the reactions of 4-iodophenol with compounds I and II were also determined under the same experimental conditions. The three arylboronic acid derivatives and their rate constants are: 4-biphenylboronic acid, k1 = (1.21 ± 0.08) × 106 M−1 s−1, k2 = (4.6 ± 0.2) × 105 M−1 s−1; 4-bromophenylboronic acid, k1 = (5.5 ± 0.2) × 104 M−1 s−1, k2 = (3.6 ± 0.2) × 104 M−1 s−1; and 4-iodophenylboronic acid, k1 = (1.1 ± 0.2) × 105 M−1 s−1, k2 = (1.3 ± 0.1) × 104 M−1 s−1. 4-Biphenylboronic acid, which shows comparable luminescent enhancement to 4-iodophenol, has the highest reactivity in the reduction of both compounds I and II among the three arylboronic acid derivatives tested.

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.

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