THE REACTION OF METHYL RADICALS WITH FORMALDEHYDE

1959 ◽  
Vol 37 (4) ◽  
pp. 672-678 ◽  
Author(s):  
S. Toby ◽  
K. O. Kutschke
Keyword(s):  
Activation Energy ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Formyl Radical ◽  
Temperature Range ◽  
Abstraction Reaction

Azomethane was photolyzed in the presence of up to 30 mole per cent formaldehyde and formaldehyde-d2 at temperatures from 80 °C to 180 °C. The value of the activation energy for the abstraction reaction with methyl radicals was found to be 6.2 kcal mole−1 for CH2O and 7.9 kcal mole−1 for CD2O. The results indicated that the formyl radical was stable over the temperature range studied.

THE REACTION OF METHYL RADICALS WITH FORMALDEHYDE

1959 ◽  
Vol 37 (9) ◽  
pp. 1462-1468 ◽  
Author(s):  
A. R. Blake ◽  
K. O. Kutschke
Keyword(s):  
Activation Energy ◽  
Kinetic Analysis ◽  
Addition Reactions ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
A Value ◽  
Abstraction Reaction ◽  
Butyl Peroxide

The pyrolysis of di-t-butyl peroxide has been reinvestigated and used as a source of methyl radicals to study the abstraction reaction between methyl radicals and formaldehyde. At low [HCHO]/[peroxide] ratios the system was simple enough for kinetic analysis, and a value of 6.6 kcal/mole was obtained for the activation energy. At higher [HCHO]/[peroxide] ratios the system became very complicated, possibly due to the increased importance of addition reactions.

PHOTOLYSIS OF MERCURY DIMETHYL

1953 ◽  
Vol 31 (7) ◽  
pp. 631-637 ◽  
Author(s):  
Richard E. Rebbert ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Kcal Mole ◽  
Temperature Range ◽  
Abstraction Reaction

The photolysis of mercury dimethyl was investigated over the temperature range from 125° to 250 °C. The results indicate that methane is formed only by an abstraction reaction and ethane is formed only by recombination, at least under the conditions used in these experiments. It is concluded that the activation energy of the reaction[Formula: see text]is 10.8 ± 0.3 kcal./mole.

THE PHOTOLYSIS OF DIMETHYL MERCURY IN HEXANE SOLUTION AT LOW TEMPERATURES

1954 ◽  
Vol 32 (5) ◽  
pp. 457-464 ◽  
Author(s):  
D. H. Derbyshire ◽  
E. W. R. Steacie
Keyword(s):  
Low Temperatures ◽  
Methyl Radicals ◽  
Temperature Range ◽  
Abstraction Reaction ◽  
Hexane Solution ◽  
Mechanism Of The Reaction

The photolysis of dimethyl mercury in solution in n-hexane has been studied over the temperature range +25 °C. to −80 °C. The results indicate that methane is produced by an abstraction reaction involving the solvent, and ethane is produced by dimerization of methyl radicals. The mechanism of the reaction is discussed, and it is concluded that the abstraction reaction involves radicals possessing considerable energy carried over from the photodissociation.

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 VAPOR PHASE PHOTOLYSIS OF HEXAFLUOROACETONE IN THE PRESENCE OF METHANE AND ETHANE

1955 ◽  
Vol 33 (5) ◽  
pp. 743-749 ◽  
Author(s):  
P. B. Ayscough ◽  
J. C. Polanyi ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Vapor Phase ◽  
Activation Energies ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Photolytic Decomposition

The photolytic decomposition of hexafluoroacetone by light of wavelength 3130 Å has been used to produce trifluoromethyl radicals for a study of their reactions with methane and ethane. It has been shown that these radicals abstract hydrogen with greater facility than do methyl radicals. The activation energies for the two reactions[Formula: see text]and[Formula: see text]are found to be 10.3 ± 0.5 kcal./mole and 7.5 ±0.5 kcal./mole respectively, if one can assume zero activation energy for the recombination of trifluoromethyl radicals.

THE GAS PHASE REACTION OF METHYL RADICALS WITH HEXAFLUOROACETONE

1957 ◽  
Vol 35 (10) ◽  
pp. 1216-1224 ◽  
Author(s):  
G. O. Pritchard ◽  
E. W. R. Steacie
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Gas Phase ◽  
Steric Factor ◽  
Phase Reaction ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Gas Phase Reaction

The photolytic and thermal decomposition of azomethane in the presence of hexafluoroacetone produces small amounts of fluorinated products, mainly fluoroform. The mechanism of this and related reactions is discussed. It is concluded that the proposed reaction.[Formula: see text]has an activation energy of about 6 kcal./mole, with a steric factor of about 10−5.

THE PYROLYSIS OF TRIMETHYLTHALLIUM

1965 ◽  
Vol 43 (7) ◽  
pp. 1961-1967 ◽  
Author(s):  
M. G. Jacko ◽  
S. J. W. Price
Keyword(s):  
Activation Energy ◽  
Rate Constant ◽  
Total Pressure ◽  
Flow System ◽  
Total Darkness ◽  
Methyl Radicals ◽  
Kcal Mole ◽  
Homogeneous Process ◽  
Carrier Flow ◽  
Reaction Proceeds

The pyrolysis of trimethylthallium has been studied in a toluene carrier flow system from 458 to 591 °K using total pressures from 5.6 to 33.0 mm. The progress of the reaction was followed by measuring the amount of methane, ethane, ethylene, and ethylbenzene formed and, in 21 runs, by direct thallium analysis. All preparative and kinetic work was carried out in total darkness where possible. A shielded 10 W lamp was used when some illumination was necessary.The decomposition is approximately 80% heterogeneous in an unconditioned vessel and 14–27% heterogeneous in a vessel pretreated with hot 50% HF for 10 min. The reaction proceeds by the simple consecutive release of three methyl radicals. The rate constant depends only slightly on the total pressure in the system so that the activation energy of the homogeneous process, 27.4 kcal/mole, may be equated to D[(CH3)2Tl—CH3].

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