Addition of Methyl Radicals to Vinyl Chloride and Catalysis of Di-t-butyl Peroxide Decomposition by Chlorinated Compounds

1964 ◽  
Vol 86 (21) ◽  
pp. 4558-4562 ◽  
Author(s):  
A. M. Hogg ◽  
Paul. Kebarle
Keyword(s):  
Vinyl Chloride ◽  
Methyl Radicals ◽  
Chlorinated Compounds ◽  
Peroxide Decomposition ◽  
Butyl Peroxide

Pyrolysis of trifluoroacetaldehyde, initiated by di-tertiary-butyl peroxide decomposition

1979 ◽  
Vol 57 (17) ◽  
pp. 2201-2210 ◽  
Author(s):  
Leon F. Loucks ◽  
Michael T. H. Liu ◽  
David G. Hooper
Keyword(s):  
Thermal Decomposition ◽  
Decomposition Product ◽  
Reaction Order ◽  
Methyl Radicals ◽  
Reaction Products ◽  
Decomposition Products ◽  
Tertiary Butyl ◽  
Decomposition Reactions ◽  
Peroxide Decomposition ◽  
Butyl Peroxide

The thermal decomposition of 95:5 mixtures of trifluoroacetaldehyde (TFA) and di-tert-butyl peroxide (DTBP) has been studied at 100 Torr over the temperature range of 390 to 440 K. The major decomposition products included CO, CF3H, CH3COCH3, and CH4 while C2F6, CF3CHOHCH3, CF3CH3, CF3COCH3, C2H6, (CF3)2CHOH, and H2 were also found. In addition to the usual reactions for TFA thermal decomposition, reactions of methyl radicals with TFA to form isopropoxyl radicals were found. The alcohol products result from H atom abstraction reactions of the isopropoxyl radicals while CF3COCH3 is a decomposition product. Arrhenius parameters for several reactions were determined: for DTBP decomposition, log k = 15.82 − 37.73/2.303RT; for H abstraction from TFA by CH3, log k = 8.30 − 7.37/2.303RT; for H abstraction from TFA by CF3, log k = 8.98 − 8.61/2.303RT. Consideration has also been given to several rate constant ratios for the formation and decomposition of isopropoxyl radicals.A study of the reaction order for the formation of CF3H, C2F6, and CH4 showed that the orders were 3/2, 1, and 1 respectively for these three products. A reaction mechanism involving 14 individual steps is proposed to explain the reaction products and the observed orders of reaction.

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.

Di-tertiary-butyl Peroxide Decomposition and Combustion with Air: Reaction Mechanism, Ignition, Flame Structures, and Laminar Flame Velocities

2016 ◽  
Vol 31 (3) ◽  
pp. 2260-2273 ◽  
Author(s):  
N. Sebbar ◽  
P. Habisreuther ◽  
H. Bockhorn ◽  
I. Auzmendi-Murua ◽  
J. W. Bozzelli
Keyword(s):  
Reaction Mechanism ◽  
Laminar Flame ◽  
Tertiary Butyl ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
Flame Structures

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.

scholarly journals The free radical polymerization of the vapours of certain vinyl derivatives

1946 ◽  
Vol 187 (1008) ◽  
pp. 37-53 ◽  
Keyword(s):  
Free Radical ◽  
Radical Polymerization ◽  
Vinyl Chloride ◽  
Free Radical Polymerization ◽  
Radical Mechanism ◽  
Methyl Radicals ◽  
Kinetic Methods ◽  
Free Radical Mechanism ◽  
Vinyl Derivatives ◽  
Styrene Butadiene

The free radical polymerization of the vapours of vinyl chloride, acrylic nitrile, styrene, butadiene and methyl isopropenyl ketone has been investigated using methyl radicals from photo-decomposing acetone. Although all the reactions do not exhibit ideal behaviour it is possible by the application of kinetic methods to measure the ratio of the propagation to the termination coefficients for these polymerization reactions. In this way relative values of the quantitative tendency for a molecule to polymerize by a free radical mechanism can be computed.

Di-tert-butyl peroxide decomposition behind shock waves

1976 ◽  
Vol 54 (4) ◽  
pp. 581-585 ◽  
Author(s):  
David K. Lewis
Keyword(s):  
Thermal Decomposition ◽  
Gas Phase ◽  
Single Pulse ◽  
First Order ◽  
Tert Butyl ◽  
First Order Kinetics ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
Temperature Work ◽  
Lower Temperature

The homogeneous, gas phase thermal decomposition of di-tert-butyl peroxide has been studied in a single pulse shock tube. Samples containing 0.05% to 0.5% reactant in argon were heated to 528–677 K at total pressures of about 1 atm. Acetone and ethane were the only significant products. The reaction obeyed first order kinetics. The Arrhenius parameters, log A (s−1) = 15.33 ± 0.50, Eact (kJ/mol) = 152.3 ± 5.8, are in agreement with the bulk of the earlier reported results of lower temperature work, and with a recently reported result obtained via the very low pressure pyrolysis technique. Indications from some of the earlier work that the A factor may decline at high temperatures are not supported by the present study.

Isolation of the initial step in the thermal decomposition of di-tert-butyl peroxide

1969 ◽  
Vol 47 (24) ◽  
pp. 4808-4809 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Initial Step ◽  
Butyl Alcohol ◽  
Major Product ◽  
Tert Butyl ◽  
Tert Butyl Alcohol ◽  
Peroxide Decomposition ◽  
Butyl Peroxide

The thermal decomposition of di-tert-butyl peroxide in the presence of propane has been studied at total pressures up to 100 atm. At the highest propane concentrations, the major product of the decomposition is tert-butyl alcohol, and extrapolation to infinite propane pressure indicates that the initial step in the peroxide decomposition is exclusively the formation of two tert-butoxy radicals. The activation energy for the abstraction of hydrogen from propane by t-BuO radicals is discussed.

Inhibition phenomena in the decomposition of di- t -butyl peroxide

1961 ◽  
Vol 261 (1306) ◽  
pp. 293-302 ◽  
Keyword(s):  
Carbon Tetrachloride ◽  
Gas Phase ◽  
Methyl Chloride ◽  
Major Product ◽  
Sulphur Hexafluoride ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
A Chain ◽  
Catalytic Effects ◽  
Limiting Value

Carbon tetrachloride vapour accelerates the gas phase decomposition of di- t -butyl peroxide, the rate constant k n, z , for a given pressure, n , of the peroxide rising with the chloride pressure, x , to a limiting value k n, ∞ . The normal products of the reaction are somewhat changed, acetone being still a major product but methane largely replacing ethane while methyl chloride and probably iso -butene oxide also appear. The effects of the carbon tetrachloride can be largely inhibited by the addition of ammonia, propylene or iso -butene. Similar phenomena are observed with certain other chlorine compounds, and the accelerations are now interpreted in terms of a chain reaction involving chlorine atoms. Acceleration of the peroxide decomposition is also caused by silicon tetrafluoride, sulphur hexafluoride or fluoroform. Propylene considerably inhibits the actions of these compounds and ammonia slightly. Although the interpretation is less certain, it seems likely that the catalytic effects of the fluorides are at least partly due to chemical chain processes.

Die Kinetik des Zerfalls von Ditertiärbutylperoxid bei hohen Drücken und Temperaturen / The Kinetic of the Decomposition of Di-tertiary-butyl-peroxide up to High Pressures and Temperatures

1979 ◽  
Vol 34 (12) ◽  
pp. 1482-1488 ◽  
Author(s):  
M. Buback ◽  
H. Lendle
Keyword(s):  
Activation Energy ◽  
High Pressures ◽  
Activation Volume ◽  
Tertiary Butyl ◽  
Rate Law ◽  
First Order ◽  
Order Rate ◽  
Peroxide Decomposition ◽  
Butyl Peroxide ◽  
High Pressures And Temperatures

AbstractThe decomposition of di-tertiary-butyl-peroxide dissolved in n-heptane has been measured ir-spectroscopically up to pressures of 2300 bar at temperatures between 140 °C and 200 °C. The reaction follows a first order rate law with an activation energy Ea = 151.4 ± 1.6 kJ mol-1 and an activation volume ΔV ǂ = 10.1 ± 1.1 cm3 mol-1. The effectivity of the peroxide decomposition is discussed.

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