PHOTOLYSIS OF MERCURY DIMETHYL

1953 ◽  
Vol 31 (7) ◽  
pp. 631-637 ◽  
Author(s):  
Richard E. Rebbert ◽  
E. W. R. Steacie

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.


1959 ◽  
Vol 37 (4) ◽  
pp. 672-678 ◽  
Author(s):  
S. Toby ◽  
K. O. Kutschke

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.



1959 ◽  
Vol 37 (9) ◽  
pp. 1462-1468 ◽  
Author(s):  
A. R. Blake ◽  
K. O. Kutschke

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.



1970 ◽  
Vol 23 (4) ◽  
pp. 749 ◽  
Author(s):  
JJ Batten ◽  
DC Murdie

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.



1954 ◽  
Vol 32 (2) ◽  
pp. 113-116 ◽  
Author(s):  
Richard E. Rebbert ◽  
E. W. R. Steacie

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.



1967 ◽  
Vol 20 (3) ◽  
pp. 399
Author(s):  
JA Allen ◽  
PH Scaife

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.



1962 ◽  
Vol 15 (2) ◽  
pp. 181 ◽  
Author(s):  
JJ Batten

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.



1970 ◽  
Vol 55 (4) ◽  
pp. 451-466 ◽  
Author(s):  
F. L. Vieira ◽  
R. I. Sha'afi ◽  
A. K. Solomon

The apparent activation energy for the water diffusion permeability coefficient, Pd, across the red cell membrane has been found to be 4.9 ± 0.3 kcal/mole in the dog and 6.0 ± 0.2 kcal/mole in the human being over the temperature range, 7° to 37°C. The apparent activation energy for the hydraulic conductivity, Lp, in dog red cells has been found to be 3.7 ± 0.4 kcal/mole and in human red cells, 3.3 ± 0.4 kcal/mole over the same temperature range. The product of Lp and the bulk viscosity of water, η, was independent of temperature for both dog and man which indicates that the geometry of the red cell membrane is not temperature-sensitive over our experimental temperature range in either species. In the case of the dog, the apparent activation energy for diffusion is the same as that for self-diffusion of water, 4.6–4.8 kcal/mole, which indicates that the process of water diffusion across the dog red cell membrane is the same as that in free solution. The slightly, but significantly, higher activation energy for water diffusion in human red cells is consonant with water-membrane interaction in the narrower equivalent pores characteristic of these cells. The observation that the apparent activation energy for hydraulic conductivity is less than that for water diffusion across the red cell membrane is characteristic of viscous flow and suggests that the flow of water across the membranes of these red cells under an osmotic pressure gradient is a viscous process.



Author(s):  
J. D. C. McConnell ◽  
Duncan McKie

SummaryA kinetic analysis is presented of the data of MacKenzie (1957) on the hydrothermal treatment of NaAlSi3O8 under isobaric, isothermal conditions in the temperature range 450° C. to 1000° C.The analysis indicates the existence of a smeared polymorphic transformation in the temperature range around 600° C. The activation energy for the transformation is about 60 kcal. mole−1 and has been equated with the process of self-diffusion involved in Al-Si ordering in the structure. Some dry-heating experiments and the influence of varying water vapour pressure are discussed.



1960 ◽  
Vol 38 (6) ◽  
pp. 827-834 ◽  
Author(s):  
D. J. Ruzicka ◽  
W. A. Bryce

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.



1967 ◽  
Vol 20 (5) ◽  
pp. 837
Author(s):  
JA Allen ◽  
PH Scaife

The adsorption of ethylene oxide on stabilized silver(I) oxide in the temperature range 210-373% comprises two processes: (i) A non-activated process with a heat of adsorption from 10.7 to 6.9 kcal mole-l depending on the coverage, which persists over the entire temperature range; ��� (ii) an activated process with an activation energy at zero coverage of 22.7 kcal mole-1, which occurs at temperatures greater than 250�K. Reaction between adsorbate and adsorbent ensues above 323%. The generalized Elovich equation has been found to apply to the activated process at high coverage, and an explanation for this is proposed.



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