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Mass transfer at gas-evolving vertical electrodes

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Abstract

Various models have been proposed to describe the mass transfer of indicator ions to gas-evolving electrodes. For verification of the proposed models, the dependence of the mass transfer coefficient of indicator ions,k j, on the length,L e, of a gas-evolving electrode may be very useful. Experimental relations betweenk j andL e have been determined for oxygen-evolving as well as hydrogen-evolving vertical electrodes in a supporting electrolyte of 1 M KOH. Moreover, a modified hydrodynamic model, where a laminar solution flow is induced by rising bubbles, has been proposed in order to calculatek j. It has been found that this model is not useful for both types of gas-evolving electrodes. The experimental results support the earlier proposed convection-penetration model for the oxygen-evolving electrode. The solution flow near a vertical electrode, induced by rising bubbles, behaves in a turbulent manner.

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Abbreviations

A e :

electrode surface area

A 1 :

parameter defined by Equation 13

A 2 :

parameter defined by Equation 14

A 3 :

A 1/A 2

A 4 :

parameter defined by Equation 34

c :

concentration

c s :

concentration in bulk of solution

D :

diffusion coefficient

d e :

equivalent diameter of cell compartment at the level of the working electrode

F :

Faraday constant

F B :

buoyant force

F S :

shear force

g :

acceleration due to gravity

i :

current density

k j :

mass transfer coefficient of indicator ion j to an electrode

L c :

length of electrode

m :

parameter defined by Equation 13

m j :

quantity of speciesj

M :

momentum flow

ΔM :

change inM

n :

parameter defined by Equation 13

p :

parameter,x 3/4

υ:

velocity of solution flow

υs :

velocity of bulk solution flow

υ1 :

υ defined by Equation 2

V B :

volume of bubbles

w :

width of a volume element

x :

coordinate, distance from leading edge of electrode

y :

coordinate, distance to the electrode

z :

coordinate, width of electrode

δ:

boundary layer thickness

δb :

bubble layer thickness at the electrode

δn :

Nernst diffusion layer thickness

ε:

gas voidage

ϱ:

density

εav :

average density of a mixture of solution and bubbles in a volume element

εs :

density of bulk solution

εg :

density of gas

μ:

viscosity

μw :

viscosity of solution-gas bubble mixture at the electrode surface

ν:

kinematic viscosity, ν=μ/ϱ

ψ:

parameter defined by Equation 26

av:

average

b:

bubble layer at the surface of electrode

B:

bubble-induced convection

e:

electrode

F:

forced convection

fi:

Fe(CN) 3−6

fo:

Fe(CN) 4−6

FB:

combined forced and bubble-induced convection

g:

gas

max:

maximum

N:

natural convection

s:

bulk of solution

w:

on the electrode surface

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Authors and Affiliations

  1. Laboratory for Electrochemistry, Department of Chemical Technology, Eindhoven University of Technology, PO Box 513, 5600 MB, Eindhoven, The Netherlands

    L. J. J. Janssen

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Janssen, L.J.J. Mass transfer at gas-evolving vertical electrodes. J Appl Electrochem 17, 1177–1189 (1987). https://doi.org/10.1007/BF01023601

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  • DOI: https://doi.org/10.1007/BF01023601

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