ADDITION OF ETHYL RADICALS TO ETHYLENE

1957 ◽  
Vol 35 (7) ◽  
pp. 588-594 ◽  
Author(s):  
J. A. Pinder ◽  
D. J. Le Roy

The addition of ethyl radicals to ethylene has been studied in the temperature range 58° to 123 °C. The radicals were produced by the mercury photosensitized decomposition of hydrogen in the presence of ethylene, and the rate of the addition reaction was measured in terms of the rate of formation of n-hexane by the combination of ethyl and butyl radicals. Corrections were made for the non-uniformity of radical concentrations in the reaction zone. Assuming a negligible activation energy for the combination of two ethyl radicals, the activation energy for the addition reaction is 5.5 kcal. per mole; the steric factor, relative to the square root of the steric factor for ethyl radical combination, is 5.0 × 10−5.


1958 ◽  
Vol 36 (2) ◽  
pp. 344-353 ◽  
Author(s):  
H. Cerfontain ◽  
K. O. Kutschke

The photolysis of azoethane at λ 3660 Å has been reinvestigated. The quantum yield of nitrogen formation was found to be dependent on the azoethane pressure and the temperature, indicating collisional deactivation of excited azoethane molecules.The results confirm the mechanism proposed by Ausloos and Steacie (1). For the activation energy of the addition reaction C2H5 + C2H5N2C2H5 a value of 6.0 ± 0.3 kcal./mole has been obtained, assuming a negligible activation energy for the combination reaction of two ethyl radicals.



1982 ◽  
Vol 18 ◽  
Author(s):  
L. R. Zheng ◽  
L. S. Hung ◽  
J. W. Mayer

Lateral diffusion couples formed by depositing platinum islands on silicon layers on Al2O3 were used in conjunction with scanning electron microprobe measurements to investigate the growth of platinum silicides in the temperature range 400–700 °C. The phase Pt2Si grows over a length of 4–30 μm with a rate proportional to the square root of time and an activation energy of approximately 1.3 eV. With samples containing 7 at.% Rh in the platinum, the growth rate of Pt2Si is reduced and the activation energy is increased to about 2.0 eV. In these Pt–7at.% Rh samples, electron-induced X-ray measurements indicate that rhodium remains in the original deposited region while both platinum and silicon diffuse in the formed Pt2Si region.



1949 ◽  
Vol 27b (8) ◽  
pp. 732-737
Author(s):  
C. A. Winkler ◽  
J. H. Greenblatt

Rate constants for the reaction between nitrogen atoms and ethylene have been obtained by diffusion flame technique over the temperature range 273° to 373 °C. An activation energy of about 3 kcal. has been obtained from the temperature coefficient of these rate constants, and using this value a steric factor of 10−2 has been calculated.



1966 ◽  
Vol 44 (4) ◽  
pp. 505-514 ◽  
Author(s):  
M C. Lin ◽  
M. H. Back

The rates of production of methane and butane in the pyrolysis of ethane have been measured over the temperature range 550–620 °C and at pressures of 40–600 mm. At high pressure the rates of formation of both products were first order in ethane, but below 200 mm the first-order rate coefficients decreased. The ratio of methane to butane was consistent with the interpretation that methane is a measure of the initiation reaction and that the combination and disproportionation of ethyl radicals is the main termination step. The order of the decomposition of the ethyl radical with respect to ethane varied between 0.38 and 0.59. The results are discussed in terms of the mechanism of the overall process.



1951 ◽  
Vol 29 (12) ◽  
pp. 1092-1103 ◽  
Author(s):  
M. H. J. Wijnen ◽  
E. W. R. Steacie

The photolysis of CH3CD2COCD2CH3 has been studied over a temperature range from 25°C. to 365°C. The results confirm several features of the mechanism, previously proposed for the photolysis of diethyl ketone. It is concluded that disproportionation of ethyl radicals occurs by a "head to tail" mechanism. As activation energy for the reaction[Formula: see text]a value E4 = 8.7 kcal. was found. As activation energy for Reaction (5)[Formula: see text]a value of E5 = 11.7 kcal. was found. An activation energy of ∼ 17 kcal. is estimated for the thermal decomposition of the pentanonyl radical



1955 ◽  
Vol 33 (10) ◽  
pp. 1530-1535 ◽  
Author(s):  
P. Ausloos ◽  
E. W. R. Steacie

The photolysis of acetic acid (CH3COOD) vapor has been investigated in the temperature range from room temperature to 285 °C. Since CH3D formation is independent of temperature, it is certain that the primary process[Formula: see text]occurs to the extent of about 10%. The results are complex and suggest that three other primary processes may occur, viz.[Formula: see text]The abstraction reaction[Formula: see text]is of importance, and the results indicate that it has an activation energy of 10.2 kcal., and a steric factor of the order of 10−3.



Metals ◽  
2021 ◽  
Vol 11 (4) ◽  
pp. 581
Author(s):  
Abdulhakim A. Almajid

This study is focused on the deformation mechanism and behavior of naturally aged 7010 aluminum alloy at elevated temperatures. The specimens were naturally aged for 60 days to reach a saturated hardness state. High-temperature tensile tests for the naturally aged sample were conducted at different temperatures of 573, 623, 673, and 723 K at various strain rates ranging from 5 × 10−5 to 10−2 s−1. The dependency of stress on the strain rate showed a stress exponent, n, of ~6.5 for the low two temperatures and ~4.5 for the high two temperatures. The apparent activation energies of 290 and 165 kJ/mol are observed at the low, and high-temperature range, respectively. These values of activation energies are greater than those of solute/solvent self-diffusion. The stress exponents, n, and activation energy observed are rather high and this indicates the presence of threshold stress. This behavior occurred as a result of the dislocation interaction with the second phase particles that are existed in the alloy at the testing temperatures. The threshold stress decreases in an exponential manner as temperature increases. The true activation energy was computed by incorporating the threshold stress in the power-law relation between the stress and the strain. The magnitude of the true activation energy, Qt dropped to 234 and 102 kJ/mol at the low and high-temperature range, respectively. These values are close to that of diffusion of Zinc in Aluminum and diffusion of Magnesium in Aluminum, respectively. The Zener–Hollomon parameter for the alloy was developed as a function of effective stress. The data in each region (low and high-temperature region) coalescence in a segment line in each region.



2018 ◽  
Vol 924 ◽  
pp. 333-338 ◽  
Author(s):  
Roberta Nipoti ◽  
Alberto Carnera ◽  
Giovanni Alfieri ◽  
Lukas Kranz

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.



2019 ◽  
Vol 85 (5) ◽  
pp. 60-68
Author(s):  
Yuliay Pogorenko ◽  
Anatoliy Omel’chuk ◽  
Roman Pshenichny ◽  
Anton Nagornyi

In the system RbF–PbF2–SnF2 are formed solid solutions of the heterovalent substitution RbxPb0,86‑xSn1,14F4-x (0 < x ≤ 0,2) with structure of β–PbSnF4. At x > 0,2 on the X-ray diffractograms, in addition to the basic structure, additional peaks are recorded that do not correspond to the reflexes of the individual fluorides and can indicate the formation of a mixture of solid solutions of different composition. For single-phase solid solutions, the calculated parameters of the crystal lattice are satisfactorily described by the Vegard rule. The introduction of ions of Rb+ into the initial structure leads to an increase in the parameter a of the elementary cell from 5.967 for x = 0 to 5.970 for x = 0.20. The replacement of a part of leads ions to rubium ions an increase in electrical conductivity compared with β–PbSnF4 and Pb0.86Sn1.14F4. Insignificant substitution (up to 3.0 mol%) of ions Pb2+ at Rb+ at T<500 K per order of magnitude reduces the conductivity of the samples obtained, while the nature of its temperature dependence is similar to the temperature dependence of the conductivity of the sample β-PbSnF4. By replacing 5 mol. % of ions with Pb2+ on Rb+, the fluoride ion conductivity at T> 450 K is higher than the conductivity of the initial sample Pb0,86Sn1,14F4 and at temperatures below 450 K by an order of magnitude smaller. With further increase in the content of RbF the electrical conductivity of the samples increases throughout the temperature range, reaching the maximum values at x≥0.15 (σ573 = 0.34–0.41 S/cm, Ea = 0.16 eV and σ373 = (5.34–8.16)•10-2 S/cm, Ea = 0.48–0.51 eV, respectively). In the general case, the replacement of a part of the ions of Pb2+ with Rb+ to an increase in the electrical conductivity of the samples throughout the temperature range. The activation energy of conductivity with an increase in the content of RbF in the low-temperature region in the general case increases, and at temperatures above 400 K is inversely proportional decreasing. The nature of the dependence of the activation energy on the concentration of the heterovalent substituent and its value indicate that the conductivity of the samples obtained increases with an increase in the vacancies of fluoride ions in the structure of the solid solutions.



1967 ◽  
Vol 6 (48) ◽  
pp. 911-915 ◽  
Author(s):  
M. P. Hochstein ◽  
G. F. Risk

The activation energy ϵe1 of polar firn samples determined by D.C. resistivity measurements is a function of temperature and density. In the temperature range −2° C. to −10° C. ϵe1 decreases with decreasing temperature reaching a nearly constant value for temperatures colder than −10°C.; in the temperature range −10°C. to −21°C. ϵe1 was found to decrease with increasing density and to lie between 0.7 eV. and 0.4 eV.



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