Photolysis of Di-tert-butyl Peroxide in Solution

1974 ◽  
Vol 52 (13) ◽  
pp. 2491-2492 ◽  
Author(s):  
Eduardo Lissi
Keyword(s):  
Carbon Tetrachloride ◽  
Quantum Yield ◽  
Gas Phase ◽  
Hydrocarbon Concentration ◽  
Tert Butyl ◽  
Carbon Tetrachloride Solution ◽  
Butyl Peroxide ◽  
Peroxide Molecule

Di-tert-butyl peroxide has been photolyzed at 3130 Å in carbon tetrachloride solution in the presence of cyclohexane. The quantum yield of free tert-butoxy radicals was 1.9 ± 0.1, independent of the hydrocarbon concentration. Unlike results obtained in the gas phase at 2537 Å, no evidence for the quenching of the excited peroxide molecule could be detected.

Photolysis of Di-tert-butyl Peroxide at High Pressure

1972 ◽  
Vol 50 (10) ◽  
pp. 1531-1534 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Gaseous Phase ◽  
Chemical Reactivity ◽  
Hydrocarbon Concentration ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Butoxy Radical ◽  
Peroxide Molecule

Di-tert-butyl peroxide has been photolyzed at 2537 Å in the gaseous phase in the presence of up to 47 amagats (2.10 mol/l) of propane and of cyclopropane. It was confirmed that no acetone is formed in the limit of infinite hydrocarbon concentration and therefore that the primary chemical act leading to the eventual formation of acetone is the formation of two tert-butoxy radicals from the excited peroxide molecule; in addition, some crude information was obtained concerning relative rates of photochemical vs. deactivation processes. It was also found that at these densities the tert-butoxy radical formed in the photolysis of di-tert-butyl peroxide did not appear to differ in chemical reactivity from the tert-butoxy radical formed in the thermal decomposition of di-tert-butyl peroxide.

Kinetics of the gas phase decomposition of di-tert-butyl peroxide

1967 ◽  
Vol 44 (9) ◽  
pp. 514 ◽  
Author(s):  
William A. Guillory
Keyword(s):  
Gas Phase ◽  
Phase Decomposition ◽  
Tert Butyl ◽  
Butyl Peroxide ◽  
Kinetics Of

Di-tert-butyl peroxide: can its photolysis be quenched by carbon tetrachloride and why is it stable at room temperature?

1984 ◽  
Vol 49 (18) ◽  
pp. 3415-3416 ◽  
Author(s):  
S. A. Davis ◽  
B. C. Gilbert ◽  
D. Griller ◽  
A. S. Nazran
Keyword(s):  
Carbon Tetrachloride ◽  
Room Temperature ◽  
Tert Butyl ◽  
Butyl Peroxide

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.

ChemInform Abstract: DI-TERT-BUTYL PEROXIDE: CAN ITS PHOTOLYSIS BE QUENCHED BY CARBON TETRACHLORIDE AND WHY IS IT STABLE AT ROOM TEMPERATURE?

1985 ◽  
Vol 16 (9) ◽  
Author(s):  
S. A. DAVIS ◽  
B. C. GILBERT ◽  
D. GRILLER ◽  
A. S. NAZRAN
Keyword(s):  
Carbon Tetrachloride ◽  
Room Temperature ◽  
Tert Butyl ◽  
Butyl Peroxide

THE PHOTODECOMPOSITION OF CHLORINE DIOXIDE IN CARBON TETRACHLORIDE SOLUTION

1937 ◽  
Vol 15b (12) ◽  
pp. 499-524 ◽  
Author(s):  
J. W. T. Spinks ◽  
H. Taube
Keyword(s):  
Thermal Decomposition ◽  
Carbon Tetrachloride ◽  
Quantum Yield ◽  
Light Intensity ◽  
Quantum Efficiency ◽  
Chlorine Dioxide ◽  
Concentration Effects ◽  
Low Light ◽  
Carbon Tetrachloride Solution ◽  
Chlorine Monoxide

Insolation of carbon tetrachloride solutions of chlorine dioxide initiates a thermal decomposition, the magnitude of which may exceed that for the photoreaction with low light intensity. This thermal decomposition is inhibited by keeping the solutions at 3 °C. or by adding water.In contradiction to the findings of other investigators, it is found that chlorine and oxygen are not the only products of photodecomposition. As products of the photodecomposition of chlorine dioxide at the wave-lengths 3650 and 4360 Å, the oxides Cl2O, Cl2O6, and Cl2O7 as well as chlorine and oxygen appear. The quantum efficiency at λ 3650 Å is 2, and at 4360 Å, 1.In the unsensitized decomposition, concentration effects are observed which are greatly decreased when the solutions are stirred.In the bromine sensitized decomposition with 5460 Å, there is less chlorine monoxide but relatively as much Cl2O6 and Cl2O7 formed as in the unsensitized reaction.In the sensitized decomposition the quantum yield is independent of the concentration of chlorine dioxide, but depends on the light intensity. The observed quantum yield for the sensitized reaction is 0.2 to 0.3.Mechanisms for the photo-reactions have been proposed.

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.

Complex formation in the gas-phase reaction of hydrogen bromide with di-tert-butyl peroxide

1967 ◽  
Vol 71 (6) ◽  
pp. 1836-1838 ◽  
Author(s):  
Leslie Batt ◽  
Frank R. Cruickshank
Keyword(s):  
Complex Formation ◽  
Gas Phase ◽  
Hydrogen Bromide ◽  
Phase Reaction ◽  
Gas Phase Reaction ◽  
Tert Butyl ◽  
Butyl Peroxide

THE INFRARED FREQUENCIES AND INTENSITIES OF THE HYDROXYL GROUP IN 2,6-DI-tert-BUTYL-4-SUBSTITUTED PHENOLS

1960 ◽  
Vol 38 (7) ◽  
pp. 1092-1098 ◽  
Author(s):  
K. U. Ingold
Keyword(s):  
Carbon Tetrachloride ◽  
Benzene Ring ◽  
Hydroxyl Group ◽  
Steric Repulsion ◽  
Substituted Phenols ◽  
Tert Butyl ◽  
Carbon Tetrachloride Solution ◽  
Butyl Group ◽  
Tert Butyl Group ◽  
Infrared Frequencies

The infrared frequencies, intensities, and apparent half band widths of the O—H stretching band of a series of 2,6-di-tert-butyl-4-substituted phenols have been measured in carbon tetrachloride solution and compared with the corresponding 4-substituted phenols. The frequencies of the former are 36 cm−1 higher than the latter and the intensities are also slightly higher. Both the frequency and intensity follow a Hammett ρσ relation. It is shown that the O—H bond lies in the plane of the benzene ring, the increase in frequency and intensity being ascribed to a steric repulsion of the phenolic hydrogen by the adjacent tert-butyl group.

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