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Kinetics of the electrochemical oxidation of organic compounds at BDD anodes: modelling of surface reactions

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Abstract

This paper presents the results of a numerical study of the kinetics of electrochemical oxidation of different organic substances at boron doped diamond (BDD).

It is well established that oxidation of organics at BDD anodes takes place in the potential region of oxygen evolution, through reaction steps in which OH radicals are involved: these radicals can react with organic compounds to give more oxidised substances, or with water to give oxygen. Because of the high reactivity of OH radicals these reactions are confined to a thin film adjacent to the electrode surface. A mathematical model was implemented, which accounts for chemical and electrochemical reactions, as well as for the transport phenomena involved in the process: the parameters of the model were derived from experimental data. The model allowed calculation of the trend with time of reactant concentration, reaction intermediates and oxidisable agents: their space profiles in the reactor were also obtained. The numerical predictions of the model were compared with experimental results obtained from galvanostatic electrolyses of different organic compounds: (a) 2,4,6-trihydroxy-1,3,5 triazine also known as cyanuric acid (CA), which is well known to be refractory to oxidation with OH; (b) atrazine (ATR) the most oxidisable precursor of CA, and (c) phenol which is considered as an OH scavenger because of its high reactivity. The agreement between experimental and model predicted data was good in all the examined conditions.

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Abbreviations

a :

Specific electrode area  \(a=\frac{A}{V}\) (m−1)

A :

Electrode area  (m2)

C i :

Concentration of the ith compound  (mol m−3)

d :

Nozzle diameter  (m)

D i :

Diffusivity of the ith compound  (m2 s−1)

F :

Faraday number  (C mol−1)

i :

Current density  (A m−2)

i lim :

Limiting current density  (A m−2)

k i :

OH-organic specific reaction rate  (dm3 mol−1 s−1)

k m :

Mass transfer coefficient  (m s−1)

k OH :

OH deactivation specific reaction rate  (s−1)

Re :

Reynolds number  \(Re=\frac{v d \rho}{\mu}\)

Sc :

Schmidt number  \(Sc=\frac{\mu }{\rho D_i}\)

Sh :

Sherwood number  \(Sh=\frac{k_{\rm m} d}{D_i}\)

V :

Volume of solution (m3)

δ:

Diffusion layer thickness  \(\delta =\frac{D_i}{k_{\rm m}}\) (m)

μ:

Viscosity of electrolyte  (kg m−1 s−1)

ν:

Linear velocity in the nozzle (m s−1)

ρ:

Density of electrolyte  (kg m3)

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Authors and Affiliations

  1. Dipartimento di Ingegneria Chimica e Materiali, Università degli Studi di Cagliari, Piazza d’Armi, 09123, Cagliari, Italy

    Michele Mascia, Annalisa Vacca, Simonetta Palmas & Anna Maria Polcaro

Authors
  1. Michele Mascia
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  2. Annalisa Vacca
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  3. Simonetta Palmas
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  4. Anna Maria Polcaro
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Correspondence to Michele Mascia.

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Mascia, M., Vacca, A., Palmas, S. et al. Kinetics of the electrochemical oxidation of organic compounds at BDD anodes: modelling of surface reactions. J Appl Electrochem 37, 71–76 (2007). https://doi.org/10.1007/s10800-006-9217-9

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  • DOI: https://doi.org/10.1007/s10800-006-9217-9

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