Oxidation of Hydrocarbons. III. Kinetics and Mechanism of the Oxidation of Arenes by Aqueous Sodium Dichromate

1971 ◽  
Vol 49 (17) ◽  
pp. 2763-2769 ◽  
Author(s):  
Donald G. Lee ◽  
Udo A. Spitzer
Keyword(s):  
Free Radical ◽  
Kinetics And Mechanism ◽  
Sodium Dichromate ◽  
Radical Process ◽  
Aqueous Sodium ◽  
Oxidation Of Hydrocarbons ◽  
Acidic Conditions ◽  
Kinetics Of ◽  
Chromate Ion ◽  
Free Radical Process

The kinetics of the Oxidation of several sodium p-alkylbenzenesulfonates by aqueous dichromate have been studied under slightly acidic conditions (pH = 7.0 to 5.4). The results indicate that the only active oxidant under these conditions is the acid chromate ion, HCrO4−, and that the reaction probably involves a free radical process.

Absolute rate constants for hydrocarbon autoxidation. 32. On the self-reaction of 1,1-diphenylethylperoxyl in solution

1982 ◽  
Vol 60 (20) ◽  
pp. 2566-2572 ◽  
Author(s):  
J. A. Howard ◽  
J. H. B. Chenier ◽  
T. Yamada
Keyword(s):  
Free Radical ◽  
Rate Constants ◽  
The Self ◽  
Absolute Rate ◽  
Radical Process ◽  
First Order ◽  
Hydroperoxide Decomposition ◽  
Solvent Cage ◽  
Induced Decomposition ◽  
Free Radical Process

The major products of the self-reaction of 1,1-diphenylethylperoxyl have been determined from product studies of the autoxidation of 1,1-diphenylethane, induced decomposition of 1,1-diphenylethyl hydroperoxide, and decomposition of 2,2,3,3-tetraphenylbutane under an atmosphere of oxygen. Overall self-reaction is a complex free-radical process involving the intermediacy of 1,1-diphenylethoxyl and 1-phenyl-1-phenoxyethoxyl which undergo H-atom abstraction, β-scission and, in the case of the former radical, rearrangement. Hydroperoxide decomposition under an atmosphere of 36O2 has shown that 1,1-diphenylethylperoxyl undergoes β-scission faster than α-cumylperoxyl at 303 K in solution. The values of the rate constants for self-reaction of Ph2C(Me)O2• relative to those for tert-butylperoxyl are, however, not affected by this reaction. Furthermore they are not affected to any appreciable extent by the efficiency with which Ph2C(Me)O•, formed in nonterminating self-reactions, escape from the solvent cage. They are influenced principally by the first-order rate of decomposition of Ph2C(Me)OOOOC(Me)Ph2.

Hydrogels based on pullulan derivatives crosslinked via a “living” free-radical process

2002 ◽  
Vol 203 (10-11) ◽  
pp. 1285-1291 ◽  
Author(s):  
Vittorio Crescenzi ◽  
Mariella Dentini ◽  
Debora Bontempo ◽  
Giancarlo Masci
Keyword(s):  
Free Radical ◽  
Radical Process ◽  
Free Radical Process

Oxidative addition to iridium(I). Free-radical process

1972 ◽  
Vol 94 (11) ◽  
pp. 4043-4044 ◽  
Author(s):  
John S. Bradley ◽  
Dan E. Connor ◽  
David Dolphin ◽  
Jay A. Labinger ◽  
John A. Osborn
Keyword(s):  
Free Radical ◽  
Oxidative Addition ◽  
Radical Process ◽  
Free Radical Process
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