THE KINETICS OF CUPRENE GROWTH

1950 ◽  
Vol 28b (7) ◽  
pp. 358-372
Author(s):  
Cyrias Ouellet ◽  
Adrien E. Léger
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Carbon Monoxide ◽  
Apparent Activation Energy ◽  
Copper Catalyst ◽  
Maximum Velocity ◽  
Static System ◽  
Reaction Velocity ◽  
First Order ◽  
Kinetics Of

The kinetics of the polymerization of acetylene to cuprene on a copper catalyst between 200° and 300 °C. have been studied manometrically in a static system. The maximum velocity of the autocatalytic reaction shows a first-order dependence upon acetylene pressure. The reaction is retarded in the presence of small amounts of oxygen but accelerated by preoxidation of the catalyst. The apparent activation energy, of about 10 kcal. per mole for cuprene growth between 210° and 280 °C., changes to about 40 kcal. per mole above 280 °C. at which temperature a second reaction seems to set in. Hydrogen, carbon monoxide, or nitric oxide has no effect on the reaction velocity. Series of five successive seedings have been obtained with cuprene originally grown on cuprite, and show an effect of aging of the cuprene.

scholarly journals The combination of carbon monoxide–haem with apoperoxidase

1969 ◽  
Vol 114 (4) ◽  
pp. 719-724 ◽  
Author(s):  
Charles Phelps ◽  
Eraldo Antonini
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Rate Constant ◽  
Binding Sites ◽  
Order Process ◽  
First Order ◽  
Effects Of Ph ◽  
Kinetics Of

1. Static titrations reveal an exact stoicheiometry between various haem derivatives and apoperoxidase prepared from one isoenzyme of the horseradish enzyme. 2. Carbon monoxide–protohaem reacts rapidly with apoperoxidase and the kinetics can be accounted for by a mechanism already applied to the reaction of carbon monoxide–haem derivatives with apomyoglobin and apohaemoglobin. 3. According to this mechanism a complex is formed first whose combination and dissociation velocity constants are 5×108m−1sec.−1 and 103sec.−1 at pH9·1 and 20°. The complex is converted into carbon monoxide–haemoprotein in a first-order process with a rate constant of 235sec.−1 for peroxidase and 364sec.−1 for myoglobin at pH9·1 and 20°. 4. The effects of pH and temperature were examined. The activation energy for the process of complex-isomerization is about 13kcal./mole. 5. The similarity in the kinetics of the reactions of carbon monoxide–haem with apoperoxidase and with apomyoglobin suggests structural similarities at the haem-binding sites of the two proteins.

THE THERMAL DECOMPOSITION OF PHENYLACETIC ACID

1960 ◽  
Vol 38 (8) ◽  
pp. 1261-1270 ◽  
Author(s):  
Margaret H. Back ◽  
A. H. Sehon
Keyword(s):  
Carbon Dioxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Rate Constant ◽  
Phenylacetic Acid ◽  
Order Process ◽  
First Order ◽  
Kinetics Of ◽  
Dissociation Step

The thermal decomposition of phenylacetic acid was investigated by the toluene-carrier technique over the temperature range 587 to 722 °C. The products of the pyrolysis were carbon dioxide, carbon monoxide, hydrogen, methane, dibenzyl, and phenylketene. From the kinetics of the decomposition it was concluded that the reaction[Formula: see text]was a homogeneous, first-order process and that the rate constant of this dissociation step was represented by the expression k = 8 × 1012.e−55,000/RT sec−1. The activation energy of this reaction may be identified with D(C6H5CH2—COOH). The possible reactions of carboxyl radicals are discussed.

The kinetics of the thermal decomposition of branched-chain paraffin hydrocarbons - II. The isomeric hexanes

1952 ◽  
Vol 214 (1118) ◽  
pp. 339-343 ◽  
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Order Transition ◽  
First Order ◽  
Single Transition ◽  
Branched Chain ◽  
Kinetics Of ◽  
Constant Activation Energy ◽  
Methyl Pentane

In the study of the thermal decomposition of paraffins the contrast of iso -butane with n -butane and of the branched pentanes with normal pentane has led to the investigation of the isomeric hexanes. The nitric oxide-inhibited reaction of neo -hexane possesses a constant, activation energy at different initial pressures and shows a single transition from second to first order with increasing pressure. The reactions of 2:3-dimethyl-butane, 2-methyl-pentane and 3-methyl-pentane show a double-order transition and a rise in activation energy at lower initial pressures, as previously found for the higher normal paraffins.

Kinetics of catalytic reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst

1983 ◽  
Vol 48 (11) ◽  
pp. 3202-3208 ◽  
Author(s):  
Zdeněk Musil ◽  
Vladimír Pour
Keyword(s):  
Carbon Monoxide ◽  
Nitrogen Oxide ◽  
Rate Equation ◽  
Catalytic Reduction ◽  
Zero Order ◽  
Spectroscopic Measurements ◽  
First Order ◽  
Ir Spectroscopic ◽  
Kinetics Of ◽  
Al2o3 Catalyst

The kinetics of the reduction of nitrogen oxide by carbon monoxide on CuO/Al2O3 catalyst (8.36 mass % CuO) were determined at temperatures between 413 and 473 K. The reaction was found to be first order in NO and zero order in CO. The observed kinetics are consistent with a rate equation derived from a mechanism proposed on the basis of IR spectroscopic measurements.

Vulcanization of Elastomers. 23. The Chemical Kinetics of Vulcanization Reactions and The Physical Properties of The Vulcanizates. I

1960 ◽  
Vol 33 (2) ◽  
pp. 335-341
Author(s):  
Walter Scheele ◽  
Karl-Heinz Hillmer
Keyword(s):  
Activation Energy ◽  
Physical Properties ◽  
Chemical Kinetics ◽  
Kcal Mole ◽  
First Order ◽  
Equilibrium Swelling ◽  
Kinetics Of ◽  
Kinetics Of Vulcanization ◽  
Limiting Value ◽  
Good Agreement

Abstract As a complement to earlier investigations, and in order to examine more closely the connection between the chemical kinetics and the changes with vulcanization time of the physical properties in the case of vulcanization reactions, we used thiuram vulcanizations as an example, and concerned ourselves with the dependence of stress values (moduli) at different degrees of elongation and different vulcanization temperatures. We found: 1. Stress values attain a limiting value, dependent on the degree of elongation, but independent of the vulcanization temperature at constant elongation. 2. The rise in stress values with the vulcanization time is characterized by an initial delay, which, however, is practically nonexistent at higher temperatures. 3. The kinetics of the increase in stress values with vulcanization time are both qualitatively and quantitatively in accord with the dependence of the reciprocal equilibrium swelling on the vulcanization time; both processes, after a retardation, go according to the first order law and at the same rate. 4. From the temperature dependence of the rate constants of reciprocal equilibrium swelling, as well as of the increase in stress, an activation energy of 22 kcal/mole can be calculated, in good agreement with the activation energy of dithiocarbamate formation in thiuram vulcanizations.

STUDIES ON HOMOGENEOUS FIRST ORDER GAS REACTIONS: VII. THE DECOMPOSITION OF ETHYLIDENE DIBUTYRATE AND HEPTYLIDENE DIACETATE

1937 ◽  
Vol 15b (6) ◽  
pp. 247-253 ◽  
Author(s):  
C. C. Coffin ◽  
J. R. Dacey ◽  
N. A. D. Parlee
Keyword(s):  
Activation Energy ◽  
Homologous Series ◽  
Reaction Velocity ◽  
Vapor State ◽  
Specific Reaction ◽  
First Order ◽  
Gas Reactions

Ethylidene dibutyrate and heptylidene diacetate decompose in the vapor state at temperatures between 200° and 300 °C. to form an aldehyde and an anhydride. The reactions are homogeneous, unimolecular, and complete. The activation energy is the same as that previously found for other members of this homologous series. Ethylidene dibutyrate decomposes at the same rate as ethylidene diacetate, and thus provides further evidence that the specific reaction velocity is independent of the size of the anhydride radicals. Heptylidene diacetate decomposes at the same rate as butylidene diacetate. This indicates that after the aldehyde radical has attained a certain size (three or four carbon atoms) the addition of –CH2− groups leaves the specific reaction velocity unchanged. The velocity constants are given by the equations[Formula: see text]

Methanation on exfoliated and supported MoS2

1989 ◽  
Vol 67 (5) ◽  
pp. 862-866 ◽  
Author(s):  
Guenter A. Scholz ◽  
S. Roy Morrison
Keyword(s):  
Activation Energy ◽  
Carbon Monoxide ◽  
Transition Metal Catalysts ◽  
Surface Species ◽  
Reaction Products ◽  
Third Order ◽  
Ammonium Heptamolybdate ◽  
First Order ◽  
Methanation Reaction ◽  
Improved Performance

The methanation reaction on MoS2 exfoliated to a thickness of a few layers or less and adsorbed onto alumina is found to be very small. However, by calcining and resulfiding the exfoliated MoS2 catalysts, greatly improved performance is achieved that is at least equal to the commercial catalysts based on ammonium heptamolybdate. The creation of molybdenum oxysulflde surface species therefore appears to be a necessary step toward producing significant methanation rates with exfoliated and supported MoS2. The methanation products are almost exclusively CO2 and CH4, their mole ratios near unity, with otherwise only very much smaller amounts of longer chain hydrocarbons. The activation energy for methanation is generally observed to be near 100 kJ/mol, with the overall reaction being first order in the carbon monoxide concentration and third order in the hydrogen concentration. In contrast to the transition-metal catalysts, no water could be detected in the reaction products of the molybdenum based catalyst. Keywords: methanation reaction on MoS2, exfoliated and supported MoS2 as catalyst.

scholarly journals Improvement of recovered activity and stability of the Aspergillus oryzae β-galactosidase immobilized on duolite A568 by combination of immobilization methods

2017 ◽  
Vol 23 (4) ◽  
pp. 495-506 ◽  
Author(s):  
Larissa Falleiros ◽  
Bruna Cabral ◽  
Janaína Fischer ◽  
Carla Guidini ◽  
Vicelma Cardoso ◽  
...  
Keyword(s):  
Activation Energy ◽  
Aspergillus Oryzae ◽  
Physical Adsorption ◽  
Cross Linking ◽  
Thermal Deactivation ◽  
Order Model ◽  
First Order ◽  
Immobilized Biocatalyst ◽  
The Stability ◽  
Kinetics Of

The immobilization and stabilization of Aspergillus oryzae ?-galactosidase on Duolite??A568 was achieved using a combination of physical adsorption, incubation step in buffer at pH 9.0 and cross-linking with glutaraldehyde and in this sequence promoted a 44% increase in enzymatic activity as compared with the biocatalyst obtained after a two-step immobilization process (adsorption and cross-linking). The stability of the biocatalyst obtained by three-step immobilization process (adsorption, incubation in buffer at pH 9.0 and cross-linking) was higher than that obtained by two-steps (adsorption and cross-linking) and for free enzyme in relation to pH, storage and reusability. The immobilized biocatalyst was characterized with respect to thermal stability in the range 55-65 ?C. The kinetics of thermal deactivation was well described by the first-order model, which resulted in the immobilized biocatalyst activation energy of thermal deactivation of 71.03 kcal/mol and 5.48 h half-life at 55.0 ?C.

Kinetics and Activation Parameters for the Alkaline Aqueous Rearrangement of Trichorfon [O,O-Dimethyl-(2,2,2-Trichloro-1-Hydroxyethyl) Phosphonate] to Dichlorvos [O,O-Dimethyl-O-(2,2-Dichloroethenyl)Phosphate]

2001 ◽  
Vol 36 (3) ◽  
pp. 589-604 ◽  
Author(s):  
Julian M. Dust ◽  
Christopher S. Warren
Keyword(s):  
Activation Energy ◽  
High Pressure ◽  
Activation Parameters ◽  
Base Catalysis ◽  
Rearrangement Product ◽  
Exponential Factor ◽  
First Order ◽  
Pseudo First Order ◽  
Order Plot ◽  
Kinetics Of

Abstract The kinetics of the alkaline rearrangement of O,O-dimethyl-(2,2,2-trichloro-1- hydroxyethyl)phosphonate, (trichlorfon, 1), the active insecticidal component in such formulations as Dylox, was followed at 25±0.5°C by high pressure liquid chromatography (UV-vis detector, 210 nm). The rearrangement product, O,Odimethyl- O-(2,2-dichloroethenyl)phosphate (dichlorovos, 2), which is a more potent biocide than trichlorfon, undergoes further reaction, and the kinetics, consequently, cannot be treated by a standard pseudo-first-order plot. A two-point van't Hoff (initial rates) method was used to obtain pseudo-first-order rate constants (kѱ) at 25, 35 and 45°C: 2.6 × 10-6, 7.4 × 10-6 and 2.5 × 10-5 s-1, respectively. Arrhenius treatment of this data gave an activation energy (Ea) of 88 kJ·mol-1 with a pre-exponential factor (A) of 5.5 × 109 s-1. Kinetic trials at pH 8.0 using phosphate and tris buffer systems show no buffer catalysis in this reaction and indicate that the rearrangement is subject to specific base catalysis. Estimates are reported for pseudo-first-order half-lives for trichlorfon at pH 8.0 for environmental conditions in aqueous systems in the Corner Brook region of western Newfoundland, part of the site of a recent trichlorfon aerial spray program.

The gas-phase photochemistry and thermal decomposition of glyoxylic acid

1985 ◽  
Vol 63 (2) ◽  
pp. 542-548 ◽  
Author(s):  
R. A. Back ◽  
S. Yamamoto
Keyword(s):  
Thermal Decomposition ◽  
Carbon Monoxide ◽  
Absorption Spectrum ◽  
Gas Phase ◽  
Singlet State ◽  
Glyoxylic Acid ◽  
Static System ◽  
First Order ◽  
Increasing Temperature ◽  
Homogeneous Formation

The photolysis of glyoxylic acid vapour has been studied at five wavelengths, 382, 366, 346, 275, and 239 nm, and pressures from about 1 to 6 Torr, at a temperature of 355 K. Major products were CO2 and CH2O, initially formed in almost equal amounts, while minor products were CO and H2. Except at 382 nm, the system was complicated by the rapid secondary photolysis of CH2O. Three primary processes are suggested, each involving internal H-atom transfer followed by dissociation.The absorption spectrum is reported and shows the three distinct absorption systems. A finely-structured spectrum from about 320 to 400 nm is attributed to a transition to the first excited π* ← n+ singlet state; a more diffuse absorption ranging from about 290 nm to a maximum at 239 nm is assigned to the π* ← n− state, while a much stronger absorption beginning below 230 nm is attributed to the π* ← π transition. Product ratios vary with wavelength and depend on which excited state is involved.The thermal decomposition was studied briefly in a static system at temperatures from 470 to 710 K and pressures from 0.4 to 8 Torr. Major products were again CO2 and CH2O, but the latter was always less than stoichiometric. First-order rate constants for the apparently homogeneous formation of CO2 are described by Arrhenius parameters log A (s−1) = 7.80 and E = 30.8 kcal/mol. Carbon monoxide and H2 were minor products, and the CO/CO2 ratio increased with increasing temperature and showed some surface enhancement at lower temperatures. The SF6-sensitized thermal decomposition of glyoxylic acid, induced by a pulsed CO2 laser, was briefly studied, with temperatures estimated to be in the 1100–1600 K range, and the CO/CO2 ratio increased with increasing temperature, continuing the trend observed in the static system.

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