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Electrochemical oxidation of sulphite ions at graphite electrodes

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Abstract

The electrochemical oxidation of sodium sulphite has been studied in aqueous sodium sulphate solution at two different graphite electrodes, one being of natural graphite (EC) and the other impregnated with phenol (ECK). The objective of the present work was to obtain some insight into the direct oxidation as well as the indirect oxidation, via produced oxygen radical species, of sulphite on non-metal electrodes. For this reason a study of the oxidation of sulphite in the concentration range between 0–0.10m in aqueous sodium sulphate using a batch electrochemical reactor, operating potentiostatically, was undertaken. The potential range was chosen between 1.0 to 2.5 V/SCE, and the concentration of the supporting electrolyte, sodium sulphate, was kept constant at 0.5m. A kinetic Tafel type law, considering irreversible behaviour for the direct sulphite oxidation and the mass transfer performance in regards to the experimental conditions were applied to predict the time variations of the sulphite conversion.

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Abbreviations

A e :

area of electrode (m2)

a e :

specific area of electrode (m−1)

c i :

concentration of speciesi (M or mol m−3)

D :

diameter of impeller (m)

D :

diffusion coefficient (m2 s−1)

E :

electrode potential (V)

e :

distance between the two eccentric tubes (m)

E 0 :

equilibrium potential (V)

E 00 :

standard potential (V)

F :

Faraday constant (=96485 A s mol−1)

f :

ratio (F/RT) (V−1)

i :

current density averaged on the geometrical electrode surface (A m−2)

I :

total current (A)

i k :

kinetically limited current density (A m−2)

i lim :

limiting current density (A m−2)

i 0 :

exchange current density (A m−2)

i 00 :

specific exchange current density defined by Equation 11

k d :

average mass transfer coefficient (m s−1)

K w :

ionic product of water (M2)

L :

characteristical length (m)

m :

molality (mol kg−1)

n :

order of the electrochemical reaction, defined by Equation 11

n :

number of moles

N :

stirring rate (r.p.s.)

Q′ :

heat flow rate (W)

Q i :

charge passed for time segment i (A s)

Q max :

maximal charge consummable during electrolysis (A s)

R :

gas constant (8.314 J mol−1 K−1)

S :

form factor defined by Equation 17

r 1,r 2 :

radius of electrodes

T :

temperature (K)

X A :

conversion term of species A

V 1 :

liquid volume of the reactor (L or m3)

Re:

Reynolds number, defined as (ND 2/ν)

Sc:

Schmidt number, defined as (ν/D)

Sh:

Sherwood number, defined as (k d D/D)

α:

charge transfer coefficient

β:

exponent used in Equation 21

γ:

activity coefficient

η:

overpotential (V)

κ:

specific conductivity (Ω-1 m-1)

λ:

thermal conductivity (W m−1 K−1)

μ:

dynamic viscosity (Pa s)

ν:

kinematic viscosity (m2 s−1)

νe :

number of electrons involved

ρ:

specific gravity (kg m−3)

Фe :

current efficiency

A:

compound A

b:

bulk

e:

electrode

ferri:

relative to ferri/ferro system

sulphite:

relative to the sulphite/sulphate system

0:

initial condition

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Authors and Affiliations

  1. Laboratoire des Sciences du Génie Chimique, CNRS-ENSIC-INPL 1, rue Grandville, B.P. 451, F-54001, Nancy Cedex, France

    T. Hunger, F. Lapicque & A. Storck

Authors
  1. T. Hunger
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  2. F. Lapicque
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  3. A. Storck
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Hunger, T., Lapicque, F. & Storck, A. Electrochemical oxidation of sulphite ions at graphite electrodes. J Appl Electrochem 21, 588–596 (1991). https://doi.org/10.1007/BF01024846

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