Abstract
The kinetics of the anodic oxidation of benzyl alcohol in the two-phase system involving both, the redox mediator, OCl−/Cl−, and a phase transfer catalyst were investigated. The reaction order of the anodic oxidation of chloride ion in the aqueous phase was unity. The charge-transfer parameters, α,k 02 and the exchange current density,i 0, of the anodic oxidation of chloride ion in the aqueous phase were obtained. The theoretical model calculations correlated well with experimental data. The fractions of anodic surface covered by the aqueous phase were evaluated to be 0.89, 0.61, and 0.23 when the organic-to-aqueous volume ratios were 0.5, 1.0, and 2.0, respectively.
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Abbreviations
- A :
-
area of the anode (cm2)
- F :
-
Faraday constant (C)
- f :
-
the fraction of the anodic surface covered by the aqueous phase in the two-phase system
- I :
-
total current (A)
- i :
-
current density (A cm−2)
- K 1 :
-
equilibrium adsorption constant of choloride ion on the anodic surface
- k 2 :
-
reaction rate constant of the anodic oxidation of Cl− (dm min−1)
- k 02 :
-
reaction rate constant of the anodic oxidation of Cl− at η=0 (cm s−1)
- K 3 :
-
equilibrium constant of the hydrolysis of Cl2 (M2)
- K 4 :
-
dissociative constant of HOCl (M)
- K 5,K 7 :
-
associative constants of (Q+OCl−)aq and (Q+Cl−)aq (M−1)
- K 6,K 8 :
-
distribution ratio of ion pairs between organic and aqueous
- k 9 :
-
reaction rate constant of the oxidation of benzyl alcohol (M−1 min−1)
- m:
-
reaction order of quaternary ammonium hypochlorite ion pair in the organic phase
- n:
-
reaction order of benzyl alcohol in the organic phase
- N 0 :
-
initial total moles of phase transfer catalyst (mol)
- N cl :
-
total moles of chloride ion (mol)
- Q+ :
-
quaternary ammonium cation
- r:
-
reaction rate of benzyl alcohol (M min−1)
- R v :
-
organic-to-aqueous volume ratio
- t :
-
time (min)
- V :
-
volume of solution (lm3)
- aq:
-
aqueous phase
- org:
-
organic phase
- 0:
-
initial state
- α:
-
charge-transfer coefficient
- η:
-
overpotential
- θ:
-
fraction of the anodic surface covered by the adsorbed chloride ion
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Do, J.S., Chou, T.C. Kinetics of the anodic oxidation of benzyl alcohol in dichloromethane in the presence of redox mediator and phase transfer catalyst. J Appl Electrochem 20, 978–985 (1990). https://doi.org/10.1007/BF01019575
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DOI: https://doi.org/10.1007/BF01019575