High-pressure studies. VIII. Thermal decomposition of isomeric tert-butyl vinyl peresters in solution

1971 ◽  
Vol 93 (17) ◽  
pp. 4242-4246 ◽  
Author(s):  
Robert C. Neuman ◽  
Gary D. Holmes
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Tert Butyl ◽  
High Pressure Studies

High pressure studies. XVIII. One-bond and two-bond homolytic scission of tert-butyl p-nitrophenylperacetate

1975 ◽  
Vol 40 (21) ◽  
pp. 3147-3149 ◽  
Author(s):  
Robert C. Neuman ◽  
Richard Wolfe
Keyword(s):  
High Pressure ◽  
Tert Butyl ◽  
High Pressure Studies

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.

ChemInform Abstract: HIGH PRESSURE STUDIES PART 17, THERMAL DECOMPOSITION OF CYCLIC AZO COMPOUNDS

1975 ◽  
Vol 6 (33) ◽  
Author(s):  
ROBERT C. JUN. NEUMAN ◽  
ERNEST W. ERTLEY
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Azo Compounds ◽  
High Pressure Studies

High pressure studies. VII. Pressure dependence of cage effects. Products from substituted tert-butyl phenylperacetates

1971 ◽  
Vol 36 (5) ◽  
pp. 657-661 ◽  
Author(s):  
Robert C. Neuman ◽  
Joseph V. Behar
Keyword(s):  
High Pressure ◽  
Pressure Dependence ◽  
Tert Butyl ◽  
High Pressure Studies ◽  
Cage Effects

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.

High pressure studies. XVII. Thermal decomposition of cyclic azo compounds

1975 ◽  
Vol 97 (11) ◽  
pp. 3130-3137 ◽  
Author(s):  
Robert C. Neuman ◽  
Ernest W. Ertley
Keyword(s):  
Thermal Decomposition ◽  
High Pressure ◽  
Azo Compounds ◽  
High Pressure Studies
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