THE PYROLYSIS OF DIALLYL (1,5-HEXADIENE)

1960 ◽  
Vol 38 (6) ◽  
pp. 827-834 ◽  
Author(s):  
D. J. Ruzicka ◽  
W. A. Bryce
Keyword(s):  
Activation Energy ◽  
Room Temperature ◽  
Hydrogen Abstraction ◽  
Radical Mechanism ◽  
Static System ◽  
Kcal Mole ◽  
Temperature Range ◽  
Gaseous Products ◽  
Mechanism Of Decomposition ◽  
Liquid Products

The mechanism of decomposition of diallyl has been studied in a static system in the temperature range 460–520 °C. The principal gaseous products (room temperature) were propylene, methane, ethylene, and 1-butene, and the liquid products were cyclopentene, cyclopentadiene, 1-hexene, and benzene. The over-all activation energy of decomposition was 31.3 ± 1.0 kcal/mole for an A factor of 107 sec−1. A mechanism of decomposition based on hydrogen abstraction by allyl and the addition of allyl to olefinic double bonds is proposed. Some decomposition by a non-radical mechanism may also occur.

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.

About the Electrical Activation of 1×1020 cm-3 Ion Implanted Al in 4H-SiC at Annealing Temperatures in the Range 1500 - 1950°C

2018 ◽  
Vol 924 ◽  
pp. 333-338 ◽  
Author(s):  
Roberta Nipoti ◽  
Alberto Carnera ◽  
Giovanni Alfieri ◽  
Lukas Kranz
Keyword(s):  
Activation Energy ◽  
Sheet Resistance ◽  
Annealing Time ◽  
Thermal Activation ◽  
Room Temperature ◽  
Annealing Temperature ◽  
Thermal Activation Energy ◽  
Electrical Activation ◽  
Temperature Range ◽  
Annealing Temperatures

The electrical activation of 1×1020cm-3implanted Al in 4H-SiC has been studied in the temperature range 1500 - 1950 °C by the analysis of the sheet resistance of the Al implanted layers, as measured at room temperature. The minimum annealing time for reaching stationary electrical at fixed annealing temperature has been found. The samples with stationary electrical activation have been used to estimate the thermal activation energy for the electrical activation of the implanted Al.

Aromatic oxidation by cobaltic acetate in acetic acid

1969 ◽  
Vol 47 (3) ◽  
pp. 387-392 ◽  
Author(s):  
Koichiro Sakota ◽  
Yoshio Kamiya ◽  
Nobuto Ohta
Keyword(s):  
Activation Energy ◽  
Electron Transfer ◽  
Acetic Acid ◽  
Bond Energy ◽  
Hydrogen Abstraction ◽  
Steric Factor ◽  
Benzyl Acetate ◽  
Kcal Mole ◽  
First Order ◽  
Reversible Electron Transfer

A detailed kinetic study of oxidation of toluene and its derivatives by cobaltic acetate in 95 vol% acetic acid is reported. The reaction was found to be profoundly affected by a steric factor and rather insensitive to the C—H bond energy. The order of reactivities of various alkylbenzenes is quite reversal to that of hydrogen abstraction reactions. The reaction was of first-order with respect to toluene, of second-order with respect to cobaltic ion and of inverse first-order with respect to cobaltous ion. The oxidation by cobaltic ion seems to proceed via an initial reversible electron transfer from toluene to cobaltic ion, yielding [Formula: see text] which is oxidized into benzyl acetate by another cobaltic ion. The apparent activation energy for toluene was found to be 25.3 kcal mole−1, and the same activation energy was found for ethylbenzene, cumene, diphenylmethane, and triphenylmethane.

The thermal decomposition of RDX at temperatures below the melting point. II. Activation energy

1970 ◽  
Vol 23 (4) ◽  
pp. 749 ◽  
Author(s):  
JJ Batten ◽  
DC Murdie
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Melting Point ◽  
Kinetic Parameter ◽  
Arrhenius Equation ◽  
Kcal Mole ◽  
Decomposition Products ◽  
Sample Geometry ◽  
Temperature Range ◽  
Definition Of

The activation energy has been determined in the temperature range 170-198�. If the sample was spread the activation energy was independent of the definition of the kinetic parameter substituted in the Arrhenius equation and was 63 kcal mole-1. In the case of the unspread samples the activation energies of the induction, acceleration, and maximum rates were 49, 43, and 62 kcal mole-1 respectively. The effect that sample geometry has on the activation energy is attributed to gaseous decomposition products influencing the reaction.

THE PHOTOLYSIS OF MERCURY DIMETHYL WITH DEUTERIUM

1954 ◽  
Vol 32 (2) ◽  
pp. 113-116 ◽  
Author(s):  
Richard E. Rebbert ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Satisfactory Agreement ◽  
Kcal Mole ◽  
Temperature Range ◽  
Work Done

Mercury dimethyl was photolyzed in the presence of deuterium in the temperature range from 27 °C. to 253 °C. The activation energy for the reaction[Formula: see text]was found to be 12.7 ± 0.5 kcal./mole. This is in satisfactory agreement with the work done with acetone and deuterium.

The adsorption of ethylene on silver(I) oxide. I. Rates of adsorption

1967 ◽  
Vol 20 (3) ◽  
pp. 399
Author(s):  
JA Allen ◽  
PH Scaife
Keyword(s):  
Activation Energy ◽  
Kinetic Data ◽  
Qualitative Explanation ◽  
Kcal Mole ◽  
Temperature Range ◽  
Elovich Equation

The rates of adsorption of ethylene on silver(I) oxide, Ag2O, have been measured in the temperature range 273-313�K. The kinetic data are analysed in terms of the generalized Elovich equation by methods developed and described in a previous paper.1 The activation energy derived from the rates at zero coverage is 15.6 kcal mole-1. The presence of isothermal anomalies is noted and the extent of each kinetic stage defined. A qualitative explanation of the existence of these stages is suggested.

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 REACTIONS OF PERFLUOROETHYL RADICALS WITH HYDROGEN AND METHANE

1960 ◽  
Vol 38 (11) ◽  
pp. 2128-2135 ◽  
Author(s):  
S. J. W. Price ◽  
K. O. Kutschke
Keyword(s):  
Activation Energy ◽  
Hydrogen Abstraction ◽  
Frequency Factor ◽  
Activation Energies ◽  
Recombination Reaction ◽  
Limited Data ◽  
Kcal Mole ◽  
Fluorinated Radical

The reactions of C2F5 radicals, produced by the photolysis of (C2F5)2CO, with methane and hydrogen have been studied. Assuming zero activation energy for 2C2F5 → C4F10 the activation energies for C2F5 + CH4 → C2F5H + CH3 and C2F5 + H2 → C2F5H + H are 10.6 kcal/mole and 11.9 kcal/mole respectively. The present results have been correlated with data on the reactions of CF3, C3F7, and CH3 radicals with H2, D2, CH4, and C2H6. Taking Erecombination ≈ 0 in all cases and assuming the frequency factor for the recombination reaction varies little from radical to radical, the order of ease of hydrogen abstraction from a given substrate is CF3 > C2F5 > C3F7 > CH3. Similarly the ease of hydrogen abstraction from a substrate by a given fluorinated radical is C2H6 > H2 > CH4 > D2. A calculation based on very limited data indicates the reaction CH3 + C2F5COC2F5 → CH3COC2F5 + C2F5 may occur with an activation energy of approximately 7 kcal/mole.

Kinetics of the oxidation of methyl methacrylate in the presence of phenolic compounds

1970 ◽  
Vol 23 (4) ◽  
pp. 765 ◽  
Author(s):  
SR Gun ◽  
US Nandi
Keyword(s):  
Activation Energy ◽  
Phenolic Compounds ◽  
Methyl Methacrylate ◽  
Chain Transfer ◽  
Hydrogen Abstraction ◽  
Experimental Results ◽  
Kcal Mole ◽  
Inhibited Oxidation ◽  
Presence And Absence ◽  
Kinetics Of

The kinetics of the reaction of methyl methacrylate with oxygen in the presence of 2,2'-azobisisobutyronitrile has been studied at 60-70� both in the presence and absence of phenol and 2,6-di-t-butyl-p-cresol. Retarded rates are proportional to the first power of the initiator concentrations, the first power of the methyl methacrylate concentrations, and the inverse first power of the phenol concentrations. The overall activation energy of the reaction in the absence of phenol is 31.51 kcal/mole and in the presence of phenol is 41.00 kcal/mole. The mechanism is discussed in the light of the experimental results and it is inferred that termination in inhibited oxidation proceeds through hydrogen abstraction and chain transfer.

THE PHOTOLYSIS OF AZOISOPROPANE

1953 ◽  
Vol 31 (4) ◽  
pp. 377-384 ◽  
Author(s):  
R. W. Durham ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Room Temperature ◽  
Excited Molecule ◽  
Energy Difference ◽  
Effect Of Pressure ◽  
Temperature Range ◽  
Excited Molecules

Azoisopropane has been photolyzed by 3600 Å radiation over the temperature range 30–120 °C. The effect of pressure indicates an excited molecule mechanism. Excited molecules which decompose give nitrogen and isopropyl radicals; the latter either combine, disproportionate, or react with azoisopropane. The activation energy difference between the two reactions[Formula: see text]has been found to be 6.5 ± 0.5 kcal. per mole.The difference in activation energy between the disproportionation and combination reactions is rendered ambiguous by the possibility of C3H7.N:N existing at the lower temperatures; but this is certainly small. The ratio of the rates of the two reactions is 0.5 at room temperature.

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