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Cathodic behaviour of antimony (III) species in chloride solutions

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Abstract

Cathodic copper is easily contaminated by antimony in copper electrowinning from chloride solutions even when the antimony concentration in the electrolyte is as low as 2 p.p.m. Reduction potential measurements of copper and antimony species indicate that electrodeposition of antimony is unlikely unless copper concentration polarization exists near the cathode surface. A.c. impedance measurements and the effect of the rotation speed of the disc electrode indicate that the cathodic process mechanism for antimony is complicated. Both diffusion and chemical reactions occurring on the cathode surface supply the electrochemical active antimony species for the cathodic process. Reaction orders of the cathodic process with respect to antimony chloride, hydrogen and chloride ion concentrations are 2, −1 and −1, respectively. A proposed reaction mechanism for the process explains the experimental findings satisfactorily.

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Abbreviations

A :

surface area (cm2)

ao1, a1 :

constants

C :

concentration (mol cm−3)

D :

diffusion coefficient (cm2 s−1)

E :

potential (V)

F :

Faraday constant (Cmol−1)

f :

frequency (s−1)

I :

current (A)

i :

current density (A cm−2)

i d 8 :

limiting diffusion current density due to the diffusion of species O from bulk to the electrode surface and then the subsequent Reac tions 1 and 2 (A cm−2)

i d o :

limiting diffusion current density of species O (A CM−2)

K :

chemical equilibrium constant

k :

rate constant (s−1)

n :

number of electrons involved in the reaction

Q :

charge (C)

Q dl :

charge devoted to double layer capacitance (C)

Q f :

total charge in the forward step of potential step chronocoulometry (C)

Q r :

total charge in reverse step of potential step chronocoulometry (C)

t :

time (s)

υ:

sweep rate (V s−1)

Γ:

amount of species adsorbed per unit area (mol cm−2)

θ:

fraction of adsorption sites on the surface occupied by adsorbate.

σ:

ratio of rate constant defined in Equation 1

δc :

thickness of reaction layer (cm)

δd :

thickness of diffusion layer (cm)

τ:

time (s)

τ′:

modified time (s1/2)

ν:

kinematic viscosity (cm2 s−1)

ω:

angular velocity (s−1)

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Authors and Affiliations

  1. Mineral Industry Research Laboratory, University of Alaska Fairbanks, 99775-7240, Fairbanks, Alaska

    H. K. Lin, X. Wu & P. D. Rao

Authors
  1. H. K. Lin
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  2. X. Wu
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  3. P. D. Rao
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Lin, H.K., Wu, X. & Rao, P.D. Cathodic behaviour of antimony (III) species in chloride solutions. J Appl Electrochem 24, 758–766 (1994). https://doi.org/10.1007/BF00578091

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  • DOI: https://doi.org/10.1007/BF00578091

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