Activation Energy of Methyl Radical Decay in Methane Hydrate

2005 ◽  
Vol 109 (44) ◽  
pp. 21086-21088 ◽  
Author(s):  
Kei Takeya ◽  
Kouhei Nango ◽  
Takeshi Sugahara ◽  
Kazunari Ohgaki ◽  
Atsushi Tani
1972 ◽  
Vol 50 (8) ◽  
pp. 1123-1128 ◽  
Author(s):  
E. Furimsky ◽  
K. J. Laidler

The results of Part I are further analyzed with reference to certain of the elementary free-radical processes occurring. A fall-off in the methyl radical combination is observed at low pressures. Comparison of this process with the CH3 + neopentane abstraction yields for the latter an activation energy of 11.5 kcal/mol and a frequency factor of 4.9 × 1011 cc mol−1 s−1. The relative importance of CH3 + neopentyl and neopentyl + neopentyl is compared. The decomposition of the neopentyl radical into i-C4H8 + CH3 shows a fall-off at low pressures; the limiting activation energy at high pressures is 29.0 kcal/mol, while that at low pressure is 17.1 kcal/mol. The former value leads to 6.7 kcal/mol for the heat of formation of the neopentyl radical at 25 °C, to 21.3 kcal/mol for the heat of its dissociation into i-C4H8 + CH3, and to 98.5 kcal/mol for the heat of dissociation of neopentane into neopentyl + H. Entropy values are also calculated in an approximate manner.


1949 ◽  
Vol 27b (8) ◽  
pp. 721-731
Author(s):  
C. A. Winkler ◽  
J. H. Greenblatt

Reaction of nitrogen atoms with ethylene has been found to produce hydrogen cyanide, ethane, and a polymerizable material. The yield of hydrogen cyanide was approximately 70% of the ethylene consumed by nitrogen atoms, while the amount of polymerizable material averaged about 16% by weight of the hydrogen cyanide produced. The yield of ethane increased as the excess of ethylene over nitrogen atoms was increased. The reaction was found to proceed by "clean-up of nitrogen atoms. An activation energy of 6.9 kcal. was calculated from collision yields, a steric factor of 0.1 being assumed. A mechanism for the reaction has been proposed, involving rupture of the ethylene double bond with formation of hydrogen cyanide and a methyl radical, the methyl radical then reacting further with nitrogen atoms.


Molecules ◽  
2020 ◽  
Vol 25 (5) ◽  
pp. 1224 ◽  
Author(s):  
Mong-Feng Chiou ◽  
Haigen Xiong ◽  
Yajun Li ◽  
Hongli Bao ◽  
Xinhao Zhang

We describe here a mechanistic study of the iron-catalyzed carboazidation of alkenes involving an intriguing metal-assisted β-methyl scission process. Although t-BuO radical has frequently been observed in experiments, the β-methyl scission from a t-BuO radical into a methyl radical and acetone is still broadly believed to be thermodynamically spontaneous and difficult to control. An iron-catalyzed β-methyl scission of t-BuO is investigated in this work. Compared to a free t-BuO radical, the coordination at the iron atom reduces the activation energy for the scission from 9.3 to 3.9 ~ 5.2 kcal/mol. The low activation energy makes the iron-catalyzed β-methyl scission of t-BuO radicals almost an incomparably facile process and explains the selective formation of methyl radicals at low temperature in the presence of some iron catalysts. In addition, a radical relay process and an outer-sphere radical azidation process in the iron-catalyzed carboazidation of alkenes are suggested by density functional theory (DFT) calculations.


1969 ◽  
Vol 47 (10) ◽  
pp. 1627-1631 ◽  
Author(s):  
R. Srinivasan ◽  
F. I. Sonntag

Photolysis of acetone has been used as a source of methyl radicals to study the abstraction of hydrogen atoms from bicyclo[2.1.1]hexane by methyl radicals. The reaction was found to have an activation energy of 10.3 kcal/mole and a pre-exponential factor that is typical of other abstraction reactions. The absolute rate of abstraction of hydrogen atoms from bicyclo[2.1.1]hexane by chlorine atoms at room temperature was measured to be 8.1 × 1010 l mole−1 s−1. The photochlorination of 1-methylbicyclo-[2.1.1]hexane in solution gave both the 1-chloromethyl and 2- or 3-chloro-1-methylbicyclohexanes. The relative rates of attack at the methyl and the 2- or 3- position were determined to be 1:2.1. It is pointed out that the rate parameters for the abstraction of an H atom from bicyclo[2.1.1]hexane by a methyl radical are slower than for cyclopentane, as would be expected for a highly strained hydrocarbon, whereas the abstraction by chlorine is slightly faster than the rate for cyclopentane.


1992 ◽  
Vol 96 (15) ◽  
pp. 6395-6398 ◽  
Author(s):  
Mingting Xu ◽  
Chunlei Shi ◽  
Xuemin Yang ◽  
Michael P. Rosynek ◽  
Jack H. Lunsford

The photolysis of 3-pentanone- d 10 has been studied over a temperature range from 25 to 314°C, and the kinetic results agree closely with those observed with 2, 2, 4, 4-(3-pentanone)- d 4 . The reaction Et ⋅ + Me ⋅CD 2 ⋅CO.CD 2 ⋅ Me → Et ⋅D + Me ⋅CD⋅CO⋅CD 2 ⋅ Me is common to both systems and no significant difference was found between the two possible values, either of the energy of activation or of the frequency factor. A value of 1⋅6 kcal/mole was found for the mean difference in activation energy for the abstraction of D or H, respectively, by the ethyl radical from the α -methylene group of 3-pentanone (- d 10 , - d 4 or - d 0 ). This agrees well with the corresponding value of 1⋅6 kcal/mole for the abstraction of D or H by the methyl radical from acetone (- d 6 or - d 0 ). All five reactions share the same value of the frequency factor within the limits of experimental error. We may conclude that an appreciable isotopic effect is observed only when the substitution of D for H has increased the strength of the bond to be broken, and that this effect is an increase in the activation energy alone, the frequency factor remaining unaltered.


2003 ◽  
Vol 762 ◽  
Author(s):  
A. Gordijn ◽  
J.K. Rath ◽  
R.E.I. Schropp

AbstractDue to the high temperatures used for high deposition rate microcrystalline (μc-Si:H) and polycrystalline silicon, there is a need for compact and temperature-stable doped layers. In this study we report on films grown by the layer-by-layer method (LbL) using VHF PECVD. Growth of an amorphous silicon layer is alternated by a hydrogen plasma treatment. In LbL, the surface reactions are separated time-wise from the nucleation in the bulk. We observed that it is possible to incorporate dopant atoms in the layer, without disturbing the nucleation. Even at high substrate temperatures (up to 400°C) doped layers can be made microcrystalline. At these temperatures, in the continuous wave case, crystallinity is hindered, which is generally attributed to the out-diffusion of hydrogen from the surface and the presence of impurities (dopants).We observe that the parameter window for the treatment time for p-layers is smaller compared to n-layers. Moreover we observe that for high temperatures, the nucleation of p-layers is more adversely affected than for n-layers. Thin, doped layers have been structurally, optically and electrically characterized. The best n-layer made at 400°C, with a thickness of only 31 nm, had an activation energy of 0.056 eV and a dark conductivity of 2.7 S/cm, while the best p-layer made at 350°C, with a thickness of 29 nm, had an activation energy of 0.11 V and a dark conductivity of 0.1 S/cm. The suitability of these high temperature n-layers has been demonstrated in an n-i-p microcrystalline silicon solar cell with an unoptimized μc-Si:H i-layer deposited at 250°C and without buffer. The Voc of the cell is 0.48 V and the fill factor is 70 %.


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