Kinetics of the thermal reactions of ethylene. Part I

1968 ◽  
Vol 46 (14) ◽  
pp. 2415-2426 ◽  
Author(s):  
M. L. Boyd ◽  
T-M. Wu ◽  
M. H. Back
Keyword(s):  
Activation Energy ◽  
Molecular Weight ◽  
Free Radical ◽  
Induction Period ◽  
Pressure Range ◽  
Kcal Mole ◽  
Radical Chain ◽  
Thermal Reactions ◽  
Chain Polymerization ◽  
Kinetics Of

The pyrolysis of ethylene has been studied in the temperature range 500–600 °C and the pressure range 15–60 cm. The main products were ethane, propylene, butene, butadiene, and a polymer of molecular weight corresponding to C8 or higher. Small amounts of methane, butane, unsaturated C5, unsaturated C6, and benzene were also measured. Of the main products, propylene, butene, and butadiene showed an induction period, as long as several minutes at the lowest temperature. The order with respect to ethylene of ethane, propylene, and butene was close to two and the activation energy of the rates was approximately 40 kcal/mole. The results have been interpreted in terms of a free radical chain polymerization. It is suggested that the polymer formed is unstable and decomposes to yield the products for which an induction period was observed.

Kinetics of the thermal reactions of ethylene. Part II. Ethylene–ethane mixtures

1968 ◽  
Vol 46 (14) ◽  
pp. 2427-2433 ◽  
Author(s):  
M. L. Boyd ◽  
M. H. Back
Keyword(s):  
Free Radical ◽  
Product Formation ◽  
Radical Chain ◽  
Thermal Reactions ◽  
Temperature Range ◽  
Initiation Step ◽  
Chain Polymerization ◽  
Main Effects ◽  
Kinetics Of ◽  
Simplified Mechanism

Mixtures of ethane and ethylene have been pyrolyzed in the temperature range 563–600 °C and at pressures from 30–60 cm. The products were similar to those obtained from the pyrolysis of ethylene by itself, described m Part I, with a marked increase in the yields of the saturated products. The initial rates of product formation and the dependence of these rates on the concentration of ethane suggest that the initiation step is the same as that proposed in the pyrolysis of ethylene alone, viz.[Formula: see text]and that the reaction[Formula: see text]is not an important source of radicals. A simplified mechanism is outlined to account for the main effects of ethane on the free radical chain polymerization.

Kinetics of the Reaction between Silver and Nitric Acid

1962 ◽  
Vol 15 (2) ◽  
pp. 181 ◽  
Author(s):  
JJ Batten
Keyword(s):  
Activation Energy ◽  
Nitric Acid ◽  
Induction Period ◽  
Acid Concentration ◽  
Maximum Rate ◽  
Kcal Mole ◽  
Temperature Range ◽  
Induction Rate ◽  
Rate Of Dissolution ◽  
Kinetics Of

The rate of dissolution of silver gauze in nitric acid at various concentrations and temperatures was measured in a static system. The solution process was measured by the weight of silver dissolved in various time intervals. In general, induction periods were observed, but after this period the dissolution proceeded with an appreciable velocity. To examine the influence of acid concentration and temperature on the kinetics of the reaction, the duration of the induction period, the rate of dissolution during this period, and the subsequent maximum rate were taken as kinetic parameters of the reaction. The induction rate was found to be highly dependent on the initial acid concentration (approx. seventh power), whereas over most of the concentration range accessible to study, the maximum rate was proportional to the square of the concentration. It was also observed that increase in temperature sharply increases the induction rate, but has little effect upon the subsequent maximum rate over most of the temperature range studied. The activation energy of the induction rate was greater than 20 kcal/mole, whereas that of the maximum rate was about 4 kcal/mole over most of the temperature range studied. This difference in the activation energy during and after the induction period is explained by a shift in the mechanism controlling the rate of the process from a chemical reaction at the surface to a diffusion process.

THE KINETICS OF THE DECOMPOSITION REACTIONS OF THE LOWER PARAFFINS: VII. THE NITRIC OXIDE INHIBITED DECOMPOSITION OF ETHANE

1940 ◽  
Vol 18b (11) ◽  
pp. 351-357 ◽  
Author(s):  
E. W. R. Steacie ◽  
Gerald Shane
Keyword(s):  
Nitric Oxide ◽  
Activation Energy ◽  
Thermal Decomposition ◽  
Free Radical ◽  
Radical Chain ◽  
Decomposition Reactions ◽  
Rearrangement Mechanism ◽  
Chain Lengths ◽  
Kinetics Of

An investigation has been made of the nitric oxide inhibited thermal decomposition of ethane. Apparent chain lengths of 2.4 to 5 are found at temperatures from 640° to 565 °C. The activation energy of the inhibited reaction is found to be 77.3 Kcal. The results are discussed and it is concluded that the thermal decomposition of ethane proceeds mainly by a rearrangement mechanism and that free-radical chain mechanisms for the ethane decomposition are untenable.

THE KINETICS OF THE THERMAL REACTIONS OF ETHYLENE OXIDE

1963 ◽  
Vol 41 (12) ◽  
pp. 2956-2961 ◽  
Author(s):  
M. Lynne Neufeld ◽  
Arthur T. Blades
Keyword(s):  
Free Radicals ◽  
Free Radical ◽  
Ethylene Oxide ◽  
Thermal Reactions ◽  
Kinetics Of

The thermal reactions of ethylene oxide in the presence of an excess of propylene have been studied as a function of pressure and it has been found that there are two sets of products, acetaldehyde and free radicals, presumably methyl and formyl. These products are believed to arise from an excited acetaldehyde intermediate. Some evidence has been obtained for the occurrence of a surface-catalyzed rearrangement to acetaldehyde but the free radical products are uninfluenced by surface.

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.

The slow oxidation of methane

1956 ◽  
Vol 235 (1201) ◽  
pp. 158-173 ◽  
Keyword(s):  
Activation Energy ◽  
Hydrogen Peroxide ◽  
Induction Period ◽  
Hydrofluoric Acid ◽  
Pressure Rise ◽  
Pressure Change ◽  
Kcal Mole ◽  
Gaseous Products ◽  
Oxidation Of Methane ◽  
Reproducible Manner

Mixtures of methane and oxygen behave in a reproducible manner at temperatures of 440 to 520°C and initial pressures of 100 to 350 mm when reacting in Pyrex vessels freshly cleaned with hydrofluoric acid. The apparent order of the reaction ranged from 2∙3 to 2∙6 and the overall activation energy from 29 to 41 kcal/mole. Analyses of the products formed have been made, together with measurements of pressure change. Formaldehyde is formed from the commencement of the reaction including the induction period, but its concentra­tion reaches a maximum near the stage where the pressure rise is a maximum, and then falls off. Hydrogen peroxide is also formed, less rapidly in the earliest stage, but its rate of formation overtakes that of formaldehyde and it reaches an even higher concentration. No other peroxides were detected, nor was methanol found. Hydrogen was present in the gaseous products. These observations are not in full accord with some of the conclusions derived from earlier investigations.

The Kinetics of Free-Radical Polymerization: Fundamental Aspects

2002 ◽  
Vol 55 (7) ◽  
pp. 399 ◽  
Author(s):  
G. T. Russell
Keyword(s):  
Molecular Weight ◽  
Steady State ◽  
Free Radical ◽  
Radical Polymerization ◽  
Chain Length ◽  
Free Radical Polymerization ◽  
Length Dependence ◽  
Model Independent ◽  
Living Free Radical Polymerization ◽  
Kinetics Of

Some fundamental aspects of the kinetics of free-radical polymerization are reviewed. So-called classical results for rate and molecular-weight distribution are first of all presented. It is shown how this approach can be built upon when chain-length-dependent termination is allowed, which it always should be. Various termination models are considered, and it is illustrated that although the models are different, rather remarkably they give common, model-independent behaviour. Some leading experimental results regarding the chain-length dependence of termination are summarized, before the chain-length dependence of other reactivities, the variation of reactivities with conversion, and non-steady state experiments are briefly discussed. Finally, living free-radical polymerization as effected by a reversible termination agent is considered. An outline of the kinetics of these systems is given, with the oft-neglected importance of conventional termination being stressed.

Insect blood-brain barrier: a radioisotope study of the kinetics of exchange of a liposoluble molecule (n-butanol)

1976 ◽  
Vol 64 (1) ◽  
pp. 119-130
Author(s):  
M. V. Thomas
Keyword(s):  
Activation Energy ◽  
Temperature Sensitivity ◽  
Nerve Cord ◽  
Previous Investigation ◽  
Time Course ◽  
Kcal Mole ◽  
Similar Time ◽  
Kinetics Of ◽  
Butanol Concentration ◽  
Good Agreement

About 90% of the butanol uptake by the cockroach abdominal nerve cord washed out with half-times of a few seconds, in good agreement with an electrophysiological estimate, and the temperature sensitivity suggested an activation energy of 3 Kcal mole-1. The remaining activity washed out far more slowly, with a similar time course to that observed in a previous investigation which had not detected the fast fraction. Its size was similar to the non-volatile uptake, and was considerably affected by the butanol concentration and incubation period. It apparently consisted of butanol metabolites, which could be detected by chromatography.

Kinetics of the pyrolysis of propylene. Part I

1970 ◽  
Vol 48 (2) ◽  
pp. 317-325 ◽  
Author(s):  
M. Simon ◽  
M. H. Back
Keyword(s):  
Molecular Weight ◽  
Chain Length ◽  
Sharp Increase ◽  
Pressure Range ◽  
Pressure Change ◽  
Short Chain ◽  
Short Chain Length ◽  
Radical Process ◽  
Initiation Step ◽  
Kinetics Of

The kinetics of the pyrolysis of propylene have been studied over the temperature range 743–873 °K and the pressure range 200–600 Torr. At the lower temperatures initial rates of formation of methane, propane, and C6 products were measured and shown to be formed by a radical process of very short chain length. The orders and activation energies of the rates were consistent with the occurrence of the bimolecular initiation step[Formula: see text]Measurement of the pressure change showed that products of molecular weight higher than C7 and not measured by the analysis were formed in the initial stages of the reaction at the lower temperatures. As these higher molecular weight compounds, which are more unstable than propylene, accumulated in the system their dissociation increased the concentration of radicals and caused a sharp increase in the rates of formation of the lower molecular weight stable products.

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