Kinetic Study of Di-Tert-Butyl Peroxide: Thermal Decomposition and Product Reaction Pathways

2015 ◽  
Vol 47 (3) ◽  
pp. 133-161 ◽  
Author(s):  
Nadia Sebbar ◽  
Joseph W. Bozzelli ◽  
Henning Bockhorn
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Study ◽  
Reaction Pathways ◽  
Tert Butyl ◽  
Butyl Peroxide

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.

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: A KINETIC STUDY OF THE THERMAL DECOMPOSITION OF (Z)-N-TERT.-BUTYL-ALPHA-PHENYLNITRONE

1975 ◽  
Vol 6 (11) ◽  
pp. no-no
Author(s):  
M. H. GOODROW ◽  
J. A. VILLARREAL ◽  
E. J. GRUBBS
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Study ◽  
Tert Butyl

scholarly journals Thermal Decomposition Analysis and Safety Study on Di-tert-butyl Peroxide

2012 ◽  
Vol 43 ◽  
pp. 312-317 ◽  
Author(s):  
Lv Jiayu ◽  
Chen Wanghua ◽  
Chen Liping ◽  
Tian Yingtao ◽  
Sun Xin
Keyword(s):  
Thermal Decomposition ◽  
Decomposition Analysis ◽  
Safety Study ◽  
Tert Butyl ◽  
Butyl Peroxide

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 decomposition of di-tert-butyl peroxide at high pressure

1968 ◽  
Vol 46 (16) ◽  
pp. 2721-2724 ◽  
Author(s):  
D. H. Shaw ◽  
H. O. Pritchard
Keyword(s):  
Carbon Dioxide ◽  
Thermal Decomposition ◽  
High Pressure ◽  
Shock Tube ◽  
Total Pressure ◽  
Order Rate Constant ◽  
Kcal Mole ◽  
First Order ◽  
Tert Butyl ◽  
Butyl Peroxide

The thermal decomposition of di-tert-butyl peroxide has been studied in the presence of carbon dioxide at total pressures from 0.05 to 15 atm and temperatures from 90–130 °C. The first-order rate constant for the decomposition is independent of total pressure in this range, with Arrhenius parameters E = 37.8 ± 0.3 kcal/mole and log A(s−1) = 15.8+0.2. A reevaluation of previous data on this reaction leads us to recommend E = 37.78 ± 0.06 kcal/mole and log A(s−1) = 15.80 ± 0.03 over the temperature range 90–350 °C; extension of this range to higher temperatures using a shock tube would be worthwhile.

Kinetic study of the thermal decomposition of (Z)-N-tert-butyl-.alpha.-phenylnitrone

1974 ◽  
Vol 39 (23) ◽  
pp. 3447-3449 ◽  
Author(s):  
Marvin H. Goodrow ◽  
Jose A. Villarreal ◽  
Edward J. Grubbs
Keyword(s):  
Thermal Decomposition ◽  
Kinetic Study ◽  
Tert Butyl

Thermal Decomposition of di-tert-Butyl Peroxide in Binary Mixtures near the Critical Point

1971 ◽  
Vol 49 (13) ◽  
pp. 2290-2296 ◽  
Author(s):  
C. K. Yip ◽  
H. O. Pritchard
Keyword(s):  
Thermal Decomposition ◽  
Critical Point ◽  
Rate Constant ◽  
High Pressures ◽  
Arrhenius Plot ◽  
Unequal Distribution ◽  
Temperature Range ◽  
Tert Butyl ◽  
Tert Butanol ◽  
Butyl Peroxide

The thermal decomposition of di-tert-butyl peroxide has been studied in the presence of high pressures of cyclopropane; the rate constant for the decomposition was determined from the sum of the rates of formation of tert-butanol and acetone. In the temperature range 125–160 °C, i.e. above the critical point of cyclopropane, concentrations of cyclopropane of between 2.6 and 3.6 mol/1 (60–80 amagats) were used; in the temperature range 100–124 °C, i.e. below the critical point of cyclopropane, an equivalent mean (liquid + gas) cyclopropane concentration was used. An Arrhenius plot of the rate constants for the peroxide decomposition is continuous through the critical point of the cyclopropane, and is indistinguishable from the best Arrhenius line representing all previous work on the reaction.However, an Arrhenius plot of the ratio of the rates of formation of tert-butanol and acetone shows a marked discontinuity at the critical point, but further investigation shows that this results from the unequal distribution of the reactant peroxide between the two phases which are present below the critical point of the cyclopropane.Less extensive series of experiments using propane, isobutane, cyanogen, and carbon dioxide as pressurizing gases confirm the pressure-independence of the rate of decomposition of di-tert-butyl peroxide: the experiments with propane and isobutane confirm the phase-independence of the rate; the propane experiments also exhibit the same apparent kinetic discontinuity at the critical point. Finally, rate-constant data are obtained for the reactions of the tert-butoxy radical with cyclopropane and isobutane, and for the addition of methyl radicals to cyanogen.

Sign in / Sign up

Export Citation Format

Share Document