Kinetics and mechanism of the reaction of chlorous acid with chlorate in aqueous sulfuric acid

1992 ◽  
Vol 31 (1) ◽  
pp. 137-145 ◽  
Author(s):  
M. Fazlul Hoq ◽  
Bhart Indu ◽  
William R. Ernst
Keyword(s):  
Sulfuric Acid ◽  
Kinetics And Mechanism ◽  
Aqueous Sulfuric Acid ◽  
Chlorous Acid ◽  
Mechanism Of The Reaction

THE WALLACH REARRANGEMENT: PART II. KINETICS AND MECHANISM OF THE ACID-CATALYZED REARRANGEMENT OF AZOXYBENZENE

1965 ◽  
Vol 43 (4) ◽  
pp. 862-875 ◽  
Author(s):  
E. Buncel ◽  
B. T. Lawton
Keyword(s):  
Sulfuric Acid ◽  
Proton Transfer ◽  
Acid Concentration ◽  
Entire Range ◽  
Kinetics And Mechanism ◽  
The Other ◽  
Rate Data ◽  
Spectrophotometric Methods ◽  
Aqueous Sulfuric Acid ◽  
Acid Catalyzed

The rate of rearrangement of azoxybenzene to p-hydroxyazobenzene has been measured in 75.3–96.4% sulfuric acid at 25° and in 65.0–90.4% sulfuric acid at 75.5° by spectrophotometric methods. The pKa of azoxybenzene in aqueous sulfuric acid has also been determined. It is found that although azoxybesssnzene is almost completely protonated over the entire range of acid concentration studied, the rate increases by more than 1 000-fold. A two-proton process is therefore indicated and mechanisms are proposed involving a dication (II) as the key intermediate. The rate data do not allow differentiation between two proposed mechanisms, one involving two equilibrium protonations, and the other a single equilibrium protonation followed by rate-determining proton transfer. Past mechanisms of the Wallach rearrangement are discussed.

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