Reaction of methyl radicals with cis-butene-2

1969 ◽  
Vol 47 (16) ◽  
pp. 2987-3001 ◽  
Author(s):  
Nobuo Yokoyama ◽  
R. K. Brinton
Keyword(s):  
Gas Phase ◽  
Equilibrium Distribution ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Radical Concentration ◽  
Radical Decomposition ◽  
Similar Temperature ◽  
Carbonyl Radical

Methyl radicals generated by di-t-butylperoxide pyrolysis interact at comparable rates with cis-butene-2 in the gas phase by both addition and hydrogen atom abstraction. The determination of the rate of these reactions was simplified by the addition of a large concentration of acetaldehyde to the system. The additive, a source of low activation energy abstractable hydrogen atoms, was effective in suppressing polymerization reactions, and in addition, maintained a high steady state methyl radical concentration as a result of the carbonyl radical decomposition. The rate constants, k5 and k6 for the reactions [5] and [6], were determined to be 4.5 × 1010exp (−7000/RT)and 1.8 × 1010exp (−7300/RT)[Formula: see text]cm3 mole−1 s−1, respectively, over the temperature range 126–163 °C. The butenyl radical formed in reaction [6] isomerizes much faster than its interaction with other species in the system, and the distribution of the various conformations is similar to the equilibrium distribution of the butenes at a similar temperature.

Reactions of free radicals with aromatic compounds in the gaseous phase. I. Kinetics of the reaction of methyl radicals with toluene

1964 ◽  
Vol 17 (12) ◽  
pp. 1329 ◽  
Author(s):  
MFR Mulcahy ◽  
DJ Williams ◽  
JR Wilmshurst
Keyword(s):  
Flow System ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Methyl Group ◽  
Benzyl Radical ◽  
Toluene Molecule ◽  
Benzyl Radicals ◽  
Butyl Peroxide ◽  
Kinetics Of

The kinetics of abstraction of hydrogen atoms from the methyl group of the toluene molecule by methyl radicals at 430-540�K have been determined. The methyl radicals were produced by pyrolysis of di-t-butyl peroxide in a stirred-flow system. The kinetics ,agree substantially with those obtained by previous authors using photolytic methods for generating the methyl radicals. At toluene and methyl-radical concentrations of about 5 x 10-7 and 10-11 mole cm-3 respectively the benzyl radicals resulting from the abstraction disappear almost entirely by combination with methyl radicals at the methylenic position. In this respect the benzyl radical behaves differently from the iso-electronic phenoxy radical, which previous work has shown to combine with a methyl radical mainly at ring positions. The investigation illustrates the application of stirred-flow technique to the study of the kinetics of free-radical reactions.

The reaction of hydrogen atoms with ethylene

1970 ◽  
Vol 316 (1527) ◽  
pp. 575-591 ◽  
Keyword(s):  
Hydrogen Atom ◽  
Rate Constant ◽  
Recombination Reaction ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Ethyl Radical ◽  
Cracking Reaction ◽  
Computer Calculations ◽  
First Time

A detailed study has been made of the products from the reaction between hydrogen atoms and ethylene in a discharge-flow system at 290 ± 3 K. Total pressures in the range 8 to 16 Torr (1100 to 2200 Nm -2 ) of argon were used and the hydrogen atom and ethylene flow rates were in the ranges 5 to 10 and 0 to 20 μ mol s -1 , respectively. In agreement with previous work, the main products are methane and ethane ( ~ 95%) together with small amounts of propane and n -butane, measurements of which are reported for the first time. A detailed mechanism leading to formation of all the products is proposed. It is shown that the predominant source of ethane is the recombination of two methyl radicals, the rate of recombination of a hydrogen atom with an ethyl radical being negligible in comparison with the alternative, cracking reaction which produces two methyl radicals. A set of rate constants for the elementary steps in this mechanism has been derived with the aid of computer calculations, which gives an excellent fit with the experimental results. In this set, the values of the rate constant for the addition of a hydrogen atom to ethylene are at the low end of the range of previously measured values but are shown to lead to a more reasonable value for the rate constant of the cracking reaction of a hydrogen atom with an ethyl radical. It is shown that the recombination reaction of a hydrogen atom with a methyl radical, the source of methane, is close to its third-order region.

THE REACTION OF HYDROGEN ATOMS WITH METHYL CYANIDE

1955 ◽  
Vol 33 (12) ◽  
pp. 1814-1818 ◽  
Author(s):  
W. Forst ◽  
C. A. Winkler
Keyword(s):  
Discharge Tube ◽  
Hydrogen Cyanide ◽  
Main Product ◽  
Initial Step ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Hydrogen Atoms ◽  
Methyl Cyanide ◽  
Secondary Reactions

Hydrogen atoms produced in a discharge tube were found to react with methyl cyanide to produce hydrogen cyanide as the main product, together with smaller amounts of methane and ethane. The proposed mechanism involves the formation of hydrogen cyanide and a methyl radical in the initial step; methane and ethane are attributed to secondary reactions of the methyl radicals.

Reactions in Omcvd: Detection of Gas Phase Radicals In Gaas Deposition Under Single Gas-Surface Collision Conditions

1987 ◽  
Vol 101 ◽  
Author(s):  
D.W. Squire ◽  
C.S. Dulcey ◽  
M.C. Lin
Keyword(s):  
Gas Phase ◽  
Ionization Mass ◽  
Laser Ionization ◽  
Methyl Radicals ◽  
Methyl Radical ◽  
Arrhenius Activation Energy ◽  
Gallium Atom ◽  
Surface Collision ◽  
Low Pressures ◽  
Radical Yield

ABSTRACTLaser ionization mass spectrometry has been used to study the deposition of gallium from trimethylgallium with and without AsH3. The apparent Arrhenius activation energy for the production of gas-phase methyl radicals from trimethylgallium is measured to be 28 ± 2 kcal/mol in the presence of AsH3, about the same value as measured in the absence of AsH3. At a substrate temperature of 1150 K where gallium desorption is substantial, addition of AsH3 is found to increase methyl radical yield but drastically decrease gallium atom desorption. A mechanism is presented to describe the deposition of GaAs at low pressures under single gas-surface collision conditions.

Photosensitization by Cd(3P0,1) atoms. III. Gas phase decomposition of cyclopentane

1976 ◽  
Vol 54 (1) ◽  
pp. 77-84 ◽  
Author(s):  
Bansi L. Kalra ◽  
Arthur R. Knight
Keyword(s):  
Gas Phase ◽  
Vapor Phase ◽  
Product Formation ◽  
Time Dependent ◽  
Primary Process ◽  
Phase Decomposition ◽  
Unimolecular Decomposition ◽  
Hydrogen Atoms ◽  
Volatile Products ◽  
Radical Decomposition

The triplet cadmium photosensitized decomposition of cyclopentane in the vapor phase has been studied at 355 °C and has been shown to give rise to cyclopentyl radicals and hydrogen atoms with close to unit efficiency in the primary process. Subsequent reactions of these species, including an important contribution from unimolecular decomposition of cyclopentyl radicals, yield the observed volatile products, hydrogen, methane, ethylene, ethane, propylene, and cyclopentene. As a result of significant olefin scavenging of H-atoms product yields are strongly time dependent. The system has been shown to be unaffected by addends. The temperature dependence of the rate of product formation is consistent with the known energetics of cyclopentyl radical decomposition.

A method for the direct determination of the rate constants for radical-radical interactions in the gas phase II. The rate constant for the recombination of methyl radicals

1957 ◽  
Vol 243 (1232) ◽  
pp. 130-142 ◽  
Keyword(s):  
Gas Phase ◽  
Rate Constant ◽  
Room Temperature ◽  
Direct Determination ◽  
Theoretical Interpretation ◽  
Methyl Radicals ◽  
Gas Phase Reactions ◽  
A Value ◽  
Acetone Vapour

The technique outlined in part I of this paper has been employed to study the photo­sensitized decomposition of acetone vapour. A theoretical interpretation of the non-stationary state applied to non-chain photochemical gas phase reactions with second-order termination has been given and the effects of non-homogeneous absorption of radiation have been considered. A value has been obtained for the rate constant for the recombination of methyl radicals in the gas phase at room temperature.

Gas phase photolysis of 1-pentene and 1-pentene-d10 at 7.1 and 7.6 eV. Kinetic considerations

1978 ◽  
Vol 56 (10) ◽  
pp. 1435-1441 ◽  
Author(s):  
Andrzej Więckowski ◽  
Guy J. Collin
Keyword(s):  
Gas Phase ◽  
Isotope Effects ◽  
Distribution Functions ◽  
Static System ◽  
Hydrogen Atoms ◽  
Photochemical Process ◽  
Radical Decomposition ◽  
Energy Distribution Functions ◽  
Kinetics Of ◽  
Non Equilibrium

The gas phase photolysis of n-pentene was carried out in a static system using nitrogen resonance lines at [Formula: see text] and the bromine line at [Formula: see text] The mechanism for the photolysis was proposed and compared to what was concluded at 8.4 eV (147 nm, the xenon resonance line). The kinetics of the decomposition of the excited C3H5* radicals formed in the primary photochemical process and the C5H11* radicals formed by the addition of hydrogen atoms to the parent molecules were discussed. The investigations were extended to the n-C5D10 photolytic System. The observed decomposition rate constants of the excited pentyl radicals as well as the secondary non-equilibrium isotope effects agree with the data published earlier. It is concluded from these experiments that, at least at 7.6 eV, hot hydrogen atoms are produced.Only a small fraction of the C3H5* radicals décompose and yield aliène. At the same time the combined primary–secondary non-equilibrium isotope effects are much less than those calculated for the 'pure' primary isotope effects. To account for these observations, it is assumed that the C3H5* radicals are formed with a wide spread in the internal energies. Since the threshold of the decomposition of the excited C3H5* radical lies above its mean excess energy (calculated on the statistical basis), an analogy in the energy-distribution functions on the radicals activated photochemically and thermally may be suggested. If so, an inverse secondary isotope effect may contribute to the gross effect involved in the C3H5* radical decomposition.

Abstraction of hydrogen atoms from bicyclo[2.1.1]hexane by methyl radicals and chlorine atoms: photochlorination of 1-methylbicyclo[2.1.1]hexane

1969 ◽  
Vol 47 (10) ◽  
pp. 1627-1631 ◽  
Author(s):  
R. Srinivasan ◽  
F. I. Sonntag
Keyword(s):  
Activation Energy ◽  
Room Temperature ◽  
Methyl Radicals ◽  
Absolute Rate ◽  
Methyl Radical ◽  
Kcal Mole ◽  
Hydrogen Atoms ◽  
Chlorine Atoms ◽  
Exponential Factor ◽  
Highly Strained

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.

Ab Initio Determination of a New Complex Structure (55 Non-Hydrogen Atoms) from Synchrotron Powder Data: An Uncommon Nickel Succinate, Ni7(C4H4O4)4(OH)6(H2O)3•7H2O

2004 ◽  
Vol 443-444 ◽  
pp. 333-336
Author(s):  
N. Guillou ◽  
C. Livage ◽  
W. van Beek ◽  
G. Férey
Keyword(s):  
Ab Initio ◽  
Complex Structure ◽  
Three Dimensional ◽  
Free Water ◽  
Hydrogen Atoms ◽  
Monoclinic System ◽  
Synchrotron Powder Diffraction ◽  
Chloride Hexahydrate ◽  
Autogenous Pressure

Ni7(C4H4O4)4(OH)6(H2O)3. 7H2O, a new layered nickel(II) succinate, was prepared hydrothermally (180°C, 48 h, autogenous pressure) from a 1:1.5:4.1:120 mixture of nickel (II) chloride hexahydrate, succinic acid, potassium hydroxide and water. It crystallizes in the monoclinic system (space group P21/c, Z = 4) with the following parameters a = 7.8597(1) Å, b = 18.8154(3)Å, c = 23.4377(4) Å,ϐ = 92.0288(9)°, and V = 3463.9(2) Å3. Its structure, which contains 55 non-hydrogen atoms, was solved ab initio from synchrotron powder diffraction data. It can be described from hybrid organic-inorganic layers, constructed from nickel oxide corrugated chains. These chains are built up from NiO6hexameric units connected via a seventh octahedron. Half of the succinates decorate the chains, and the others connect them to form the layers. The three dimensional arrangement is ensured by hydrogen bonds directly between two adjacent layers and via free water molecules.

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