304

ELECTROCH EMICAL REACTIONS AN D SOLUTION CHEM ISTRY

ELECTROCHEMICAL PROCESSES

IN THE LEACHING OF METAL SULFIDES AND oXTDES

Wadsworth

J. .Brent Hiskey and Milton E.

J.. .Brent. Hiskey is Senior Scientist, Kennecott Minerals Company Process Technology M.E. Wadsworth is Professor of Metallurgy and Metal'lurgical Engineeiing, University ofUtah

'

Sa'l

Lake

City,

Utah

INTRODUCTION

understanding the mechanisms of underlying electrode reactions. Impressive as these advances are, there is stilI a growing need for electrochemica'l research of mineral systems and electrochemical engineering

Fifteen years ago a distinguished electrochemist referred to electrochglslfX as an "underdeveloped science. " In=JE-;;T;IEJ question, Professor Bockris (1) stated that many areas of natural phenomena and applied technology are not perceived as being electrochemically based. At that time" this was especially true for much of non-ferrous extractive netallurgy and was a particularly accurate description of hydrometal1urgy. During the Iast decade, there has been considerable advancement in applying the theory of electrochemistry to our knowledge of hydrometaiTurgTGTpieses and in

such that back reacticn kinetics normally are unimportant. Build up on ions in solution, however, may markedly affect the kinetics by influencing the potential at the mineral (electrode) solut'ion
i

nterface.

Properties

of

some

sulfide and ox'ide minerals

to appiy thisrv',ork in practicai situations.

electrodics. Ionics is restricted to the of ions in so'lutions, examples being many familiar redox processes. E'lectrodics represents the main part of electrochemistry, and is the study of
and

Bockris and Reddy (2) refer to elerctrochemigry as being divided into two fundanreTT-ii6IiITonics
behavior

In a broad sense electrochemistry is defined as the physical chemist[Tr-i-Tn-!o-1 ution and of phenomena which occur at the electrified interface.

minerals. Metal sulfides have received the most attention because they are recognized as va'luable sources of non-ferrous metal. Koch (3) has reviewed the e'lectrochemistry of sulfide ininerals and Shuey (4) has reviewed the e'lectronic properties of both oxide and sulfide minerals. Included in Table I are resistivities, electronic, and structural information for se'lected sulfide and oxide minerals. The cova'lent character of most sulfides provides non-localization of charge resulting in appreciable intrinsic electronic conductivity. The ability of many suifides to form non-stoichiometric compounds results in increased conduction via electron holes or excess electrons. Oxides in general are more ionic in nature and usually have h'igher resistivities compared to sulfide minera'ls.
'is the characteristic "rest" potential. For interfacia'l electrode processes, the "rest" potential coresponds to the equilibrium (no net anod'ic or
A fundamental property

Several investigators have presented information on the electrchemical behavior of su'lfide and oxide

of

semiconducting minerals

charged interfaces and the conditions governing charge transfer reactions across them. Considering hydrometal lurgical applications, electrodics suggests

the following relationship for a conducting solid (bulk or surface)

Electrodics: Solid Ions in solution + Electrons in solid

An exce'llent example

of the field of electrodics is the study of metal corrosion in aqueous solution.

galvanic couples are read'ily established in aqueous systems. This is true for p-type, n-type or metallic

The electronic properties of most metal sulfides and of certain oxides are such that corrosion and

tain equi'librium potentiai that depends not only on the solution composition but also on the composition of the solid phase. Figure 'l illustrates results for the e'lectrochemical oxjdation of Cu2S to CuS in an acid solution (10). The steps in the data have been explained on the basis of the sequential formation of a series of CUS compounds with corresponding rest ootentials as follows:
CutS

cathodic current) electrode potential. Rest potentials for severa'l hetal slfides qre shown in Table II. It is important to remember that a mineral electrode system will establish and maintain a cer-

Crl.93S

Crl.83S

Cr.l.67 + Cu.,.OS + CuS

electronic transport numbei. As a resuli of their electronic conductivity, certain minerals can participate in coupled charge transfer processes ana'logous to a metal corroding in an electrolyte, and the kinetics of leaching can be related to the potential of the solid in contact with the aqueous electrolyte. From a thermodynamic point of view most hydrornetal'lurgical dissolution reactions are strongly favored

Iike

compounds

for which ta =

l.

where

t. is the

were

calculated. At 25"C, the standard free energy of formation values are

aG"rrr"*(Cu.,.9SS)

From the work of Etienne and Peters (ll), the standard free energy of formation of Cu-93S and Cu1.g3S

-1g,2BZ

t640 cal mole-l