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.

Explosive Thermal Decomposition Mechanism of NTO

1995 ◽  
Vol 418 ◽  
Author(s):  
David J. Beardall ◽  
Tod R. Botcher ◽  
Charles A. Wight
Keyword(s):  
Thin Films ◽  
Thermal Decomposition ◽  
Fourier Transform ◽  
Infrared Spectroscopy ◽  
Condensed Phase ◽  
Decomposition Product ◽  
Rapid Heating ◽  
Initial Step ◽  
Thermal Decomposition Mechanism ◽  
Decomposition Products

AbstractThe initial step of the thermal decomposition of NTO (5-nitro-2,4-dihydro-3H-1,2,4- triazol-3-one) is determined by pulsed infrared laser pyrolysis of thin films. Rapid heating of the film and quenching to 77 K allows one to trap the initial decomposition products in the condensed phase and analyze them using transmission Fourier-transform infrared spectroscopy. The initial decomposition product is CO2; NO2 and HONO are not observed. We propose a new mechanism for NTO decomposition in which CO2 is formed.

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

Oxidative Stress Relaxation of Natural Rubber Vulcanized with Di-Tertiary-Butyl Peroxide

1956 ◽  
Vol 29 (3) ◽  
pp. 1043-1046 ◽  
Author(s):  
Svein Ore
Keyword(s):  
Oxidative Stress ◽  
Stress Relaxation ◽  
Carbon Black ◽  
Natural Rubber ◽  
First Grade ◽  
Main Reaction ◽  
Reaction Products ◽  
Hydrogen Atoms ◽  
Tertiary Butyl ◽  
Butyl Peroxide

Abstract It has been shown by Farmer and Moore that natural rubber can be vulcanized with di-tert.-butyl peroxide (DTBP), Presumably the free radicals formed by the unimolecular decomposition of the peroxide abstract some of the more labile (e.g., α-methylenic) hydrogen atoms, leading to direct C—C crosslinks between the rubber molecules, with tert.-butanol and acetone as the main reaction products. This preliminary communication presents some of the results of an investigation of the oxidative stress relaxation of the following types of DTBP vulcanizates. (A) First grade pale crepe, DTBP, and carbon black (MPC) mixed on the mill and vulcanized in a press. The carbon black was added to minimize the deleterious effect of impurities. (B) Purified rubber vulcanized: (1) in aqueous heating media; (2) in the press; (3) in DTBP vapor.

Influence of some heavy foreign gases on the thermal decomposition of di-tertiary butyl peroxide

1958 ◽  
Vol 247 (1250) ◽  
pp. 381-389 ◽  
Keyword(s):  
Thermal Decomposition ◽  
Nitrous Oxide ◽  
Pressure Range ◽  
Order Rate Constant ◽  
Chemical Effect ◽  
Sulphur Hexafluoride ◽  
Tertiary Butyl ◽  
First Order ◽  
Butyl Peroxide ◽  
Limiting Value

The first-order rate constant for the thermal decomposition of di-tertiary butyl peroxide in the pressure range 0 to 600 mm follows an equation of the form k = A 1 n /(1+ A' 1 n + A 2 n , where n is the peroxide pressure. For a given value of n additions of sulphur hexafluoride (which appears from analysis to have no chemical effect) raise k to a limiting value, k n ,∞. This value is itself a function of the peroxide pressure approximately of the form k n , ∞ = An /(1+A' n )+B. In the light of previous work on nitrous oxide and on paraffins, these results are tentatively explained in terms of a scheme in which energized molecules go reversibly to special activated states from which decomposition follows either spontaneously or when induced by collisions.

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.

Catalytic influence of certain foreign gases on the thermal decomposition of di-tertiary butyl peroxide

1959 ◽  
Vol 249 (1257) ◽  
pp. 173-179 ◽  
Keyword(s):  
Activation Energy ◽  
Thermal Decomposition ◽  
Carbon Tetrachloride ◽  
Rate Constant ◽  
Tertiary Butyl ◽  
Extended Theory ◽  
Uncatalyzed Reaction ◽  
Butyl Peroxide ◽  
Limiting Value ◽  
Induced Reaction

Silicon tetrafluoride accelerates the decomposition of di-tertiary butyl peroxide, the rate constant k n,x for a given pressure, n , of the peroxide rising with the fluoride pressure, x , to a limiting value k n ,∞ . This value is different for different values of n . The activation energy of the induced reaction is 27 ± 1 kcal compared with 37 kcal for the uncatalyzed reaction. The products are little different from those of the normal decomposition except that the ratio of methane to ethane is slightly increased. The order of effectiveness of fluorides is SiF 4 > SF 6 > CF 4 , the inverse order of the ease with which they should release fluorine atoms. Carbon tetrachloride causes acceleration comparable with that caused by the silicon fluoride with a much more drastic shift in the product ratios. The mechanism of these actions is discussed in relation to the extended theory of unimolecular reactions.

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.

Thermal reactions of leadhillite Pb4SO4(CO3)2(OH)2

Clay Minerals ◽  
1984 ◽  
Vol 19 (5) ◽  
pp. 825-841 ◽  
Author(s):  
A. E. Milodowski ◽  
D. J. Morgan
Keyword(s):  
Evolved Gas Analysis ◽  
Gas Analysis ◽  
Continuous Heating ◽  
Original Structure ◽  
Reaction Products ◽  
Decomposition Products ◽  
Evolved Gas ◽  
Thermal Reactions ◽  
Decomposition Reactions ◽  
Higher Temperature

AbstractReactions undergone by leadhillite from the type locality on heating to 1000°C have been followed by DTA, TG, DSC, evolved gas analysis, continuous-heating XRD and IR, and hot-stage microscopy. Intermediate decomposition products were identified by X-ray powder photography. At 80°C, biaxial leadhillite inverts to a uniaxial phase with properties similar to those of susannite, a naturally occurring polymorph of leadhillite, but this higher-temperature modification only partially reverts to the original structure on cooling (up to 24 hours at room temperature is required for complete reversion). Between 250 and 600°C the mineral undergoes two decomposition reactions: PbO.PbCO3 and PbO.PbSO4 form during the first reaction (PbCO3 may form in the initial stages) and 4PbO.PbSO4 during the second. α-2PbO.PbSO4 appears at 650°C due to solid-state reaction between the other lead oxysulphate products. Melting occurs above 850°C. The reaction products are discussed in relation to the phase diagrams for the systems PbO-CO2 and PbO-PbSO4.

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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