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Hydrometallurgy 144145 (2014) 148150

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Hydrometallurgy
journal homepage: www.elsevier.com/locate/hydromet

Technical note

Evidence of the existence of cathodic and anodic zones during the


leaching of minerals and metals
Fathi Habashi, Ahmet Deniz Bas
Department of Mining, Metallurgy, and Materials Engineering, Laval University, Quebec City, Canada

a r t i c l e i n f o a b s t r a c t

Available online 15 February 2014 It is accepted worldwide that the dissolution of minerals in some cases, is an electrochemical process where an-
odic and cathodic reactions take place. There are many parameters, such as agent concentration, that directly af-
Keywords: fect the dissolution process. The rate of leaching of minerals may differ depending on the oxygen concentration.
Leaching In this paper, the existence of anodic and cathodic zones on the mineral surface during the dissolution/leaching of
Minerals
minerals and metals has been presented with some different works. It is worth mentioning that a good number of
Anodic and cathodic zones
published papers have experimentally demonstrated the existence of anodic and cathodic areas on the mineral
Dissolution
Corrosion
surface.
2014 Elsevier B.V. All rights reserved.

We read with interest the recent paper entitled The Dissolution and The experiment of Thornber (1975) on the dissolution of pyrite:
Leaching of Minerals. Mechanisms, Myths, and Misunderstandings, by pyrite embedded in an agar gel to which phenolphthalein was added;
F.K. Crundwell, published in Hydrometallurgy Volume 139, July 2013, after some days a red colour appeared on the surface of the gel due to
pages 132148. We agree with the author that the rate of leaching of the liberation of OH ions at the cathodic zone (Fig. 5).
minerals may have an order 1 or with respect to oxygen as seen in The model for the formation of anodic and cathodic zones during
Figs. 1 and 2 but we reject his argument and his conclusions regarding dissolution of minerals (Fig. 6) permitted the establishment of a kinetic
the non-existence of anodic and cathodic zones on the mineral surface. equation:
We believe that the existence of anodic and cathodic zones during
the dissolution of conducting and semiconducting minerals is real. It k1 k2 A D C 
Rate of dissolution
has been experimentally demonstrated in a number of cases. k1 D k2 C 
The educational lm Corrosion in Action (LaQue et al., 1955), pro-
duced by the International Nickel Company some years ago, shows where [D] is the concentration of depolarizer, [C] the concentration of
many experiments with an iron nail embedded in a gel containing phe- complexing agent, A = area of mineral exposed in the leaching agent,
nolphthalein and potassium ferricyanide. After some time, a region of
the nail becomes coloured pink (the cathodic zone) due to the reduction
of oxygen to OH ions, while another region of the nail becomes
coloured blue due to the liberation of ferrous ion which forms Prussian
blue (the anodic zone) (Fig. 3):


O2 H2 O e 2OH
2
FeFe e :

Thompson (1947) embedded gold particle in a gel of cyanide solu-


tion to which air was completely excluded. When oxygen was allowed
to ow in one direction he observed the dissolution of the particle by
means of a microscope. He found that gold dissolved through only one
region (Fig. 4).

Corresponding author.
E-mail addresses: Fathi.Habashi@arul.ulaval.ca (F. Habashi),
ahmet-deniz.bas.1@ulaval.ca (A.D. Bas). Fig. 1. Leaching of ZnS in sulfuric acid at different oxygen pressures (Habashi, 1966).

http://dx.doi.org/10.1016/j.hydromet.2014.02.002
0304-386X/ 2014 Elsevier B.V. All rights reserved.
F. Habashi, A.D. Bas / Hydrometallurgy 144145 (2014) 148150 149

Fig. 5. Formation of cathodic zone during the dissolution of pyrite (Thornber, 1975).
Fig. 2. Leaching of UO2 in sulfuric acid at different oxygen pressures (Habashi and
Thurston, 1967).

Fig. 3. The pink colour developed around the shank of the nail indicated the formation of a
cathode. Blue areas developed around the cold worked head where the iron went into so-
lution indicating that these areas are the anodes (LaQue et al., 1955).

and k1 and k2 are constants. This theoretical equation coincided with


experiment (Fig. 7):
Fig. 6. Model for dissolution of minerals (Habashi, 2012).
At low concentrations of C, the second term in the denominator may
be neglected in comparison with the rst, and the rate equation
simplies to:

Rate = k1A[D]

i.e., the rate of dissolution in this case is only a function of the


complexing agent concentration. D
Rate of dissolution

Concentration of leaching agent C


Fig. 4. Dissolution of gold in cyanide gel when air was introduced from one direction
(Thompson, 1947). Fig. 7. Experimental data obtained on dissolution of minerals (Habashi, 2007).
150 F. Habashi, A.D. Bas / Hydrometallurgy 144145 (2014) 148150

At high concentrations of C, the rst term in the denominator may be expanded form as Kinetics of Metallurgical Processes, Mtallurgie Extractive Qubec,
Qubec City, Canada 1999, distributed by Laval University Bookstore www.zone.ul.ca).
neglected in comparison with the second, and the velocity equation Habashi, F., 1970. Principles of extractive metallurgy. Hydrometallurgy, vol. 2. Gordon &
simplies to: Breach, New YorkLondonParis (1970 (reprinted 1980). Published later in an ex-
panded form as Textbook of Hydrometallurgy, Mtallurgie Extractive Qubec, Qubec
Rate k2 AC City, Canada 1993, second edition 1999, distributed by Laval University Bookstore
www.zone.ul.ca).
i.e., the rate of dissolution under these conditions depends only on the Habashi, F., 2007. A Generalized Kinetic Model for Hydrometallurgical Processes.
Manuscript 1047. The Berkeley Electronic Press, California.
concentration of the depolarizer.
Habashi, F., 2012. Leaching mechanism of semiconducting minerals. A historical note.
J. Miner. Metall. Sect. B-Metall. 48 (3), 477481.
This has been discussed in a number of publications (Habashi, 1969,
Habashi, F., Thurston, G.A., 1967. Kinetics and mechanism of uranium dioxide dissolution.
1970, 2007, 2012). Energ. Nucl. 14, 238244.
LaQue, F.L., May, T.P., Uhlig, H.H., 1955. Corrosion in action, The International Nickel Com-
References pany. Toronto, Canada, Book accompanying the lm.
Thompson, P.F., 1947. The dissolution of gold in cyanide solutions. J. Electrochem. Soc. 91
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