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Chlorate electrosynthesis current efficiency equations based on dimensionless groups

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Abstract

Various mathematical models for the electrosynthesis of chlorate are analysed taking into account that the current efficiency is mainly affected by the distribution of the two competing reactions forming chlorate, i.e. the anodic oxidation and the autoxidation of hypochlorite. It is shown that the current efficiency is determined by four dimensionless groups one of which is commonly negligible. Results are compared with a known current efficiency equation. Two new current efficiency equations, representing the limiting operating conditions of chlorate systems, are proposed for industrial application.

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Abbreviations

a :

activity (−)

A :

electrode surface are (m2)

c :

concentration of hypochlorite (mol m−3)

C, C′ :

numerical constants, Equations 19 and 45

F :

Faraday constant (F=96 487 A s mol−1)

H :

electrode height (m)

I :

total current (A)

I 1,I 2 :

partial currents of chloride oxidation (A)

I a :

partial current of hypochlorite oxidation (A)

I v :

loss currents (A)

K * :

equilibrium constant of Reaction 6 (−)

K a :

anodic oxidation number (−)

k d :

mass transfer coefficient (m s−1)

k r :

reaction rate constant of chemical hypochlorite oxidation (m6 mol−2 s−1)

K rC :

autoxidation number of cell (−)

K rR :

autoxidation number of chemical reactor (−)

\(N^\blacksquare \) :

flux of total hypochlorite (mol s−1)

Re :

Reynolds number (−)

S :

cross-sectional area of fluid flow (m2)

Sc :

Schmidt number (−)

Sh :

Sherwood number (−)

St :

Stanton number, Equation 32 (−)

t :

time (s)

V :

volume (m3)

\(V_L ^\blacksquare \) :

liquid flow rate (m3 s−1)

x:

coordinate in flow direction (m)

ε:

current efficiency (−)

a:

anodic oxidation of hypochlorite

C:

cell

i:

entrance cell

o:

exit cell

r:

autoxidation of hypochlorite

R:

chemical reactor

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Authors and Affiliations

  1. Fachbereich Verfahrens und Umwelttechnik, Technische Fachhochschule Berlin, D-1000, Berlin 65, Germany

    H. Vogt

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  1. H. Vogt
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Vogt, H. Chlorate electrosynthesis current efficiency equations based on dimensionless groups. J Appl Electrochem 22, 1185–1191 (1992). https://doi.org/10.1007/BF01297422

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  • DOI: https://doi.org/10.1007/BF01297422

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