314

ELECTROCHEMICAL REACTIONS AND SOLUTION CHEMISTRY

PbCl2 and PbS04 formed from suggested a mechanism

From

the respective solutions.

the study described above Paul et al. (28) for the dissolution of galena in acidic perchlorate solutjons. The overall anodic reaction is given in Eq. (39). Tafel slopes fail to support this simple two electron-transfer reaction. Therefore, the oxidation of galena is assumed to transfer steps,
take place according

is foned as an intermediate and is subsequently oxidized to the sulfate (43). Beckstead and Miller (qe) foun the kinetics to be approxinately half order with respect to hydroxy) and cupric ions and oxygen at low pressures. At high pressures the rate becare zero order with respect to oxygen. Sigmoida'l reaction curves were explained on the basis of
Thiosulfate

to distinguishab'le

one-electron(42)
(+s

pbsrpb2++S-+e

postulated. Figure 14 illustrates typical rate data obtained showing the effect of cupric ion on the rate

the autocatalytic effect of cupric ion. Two parallel reactions, one of which involves cupric ion, were
The

of reaction.
^LO B
o.s o.g

kinetic data were we]I comelated

S-*S'+e
The "S

" sulfur interrediate has been proposed elsewhere (23). The Butler-Volmer treatement for steady
state conditions (dtS-l/dt = 0) yields the following equation for the net anodic current
+ 'l=

tJ

,a

a,

o1
o.e

& o

I (44)

lnriol

Cue Conc

where tPb2+1,

is thq concqntration of lead ions at the electrode surface, k and li are the respective forward and reverse rate constants for reaction (42), k' is the specific rate of reaction (43), and the other terms are analogous to those previously defined. At
sufficiently poiitive values f E or ai lo* tPb2*r, since the first term of the denominator of Eq. (a4) is small compared to the second term, the expression
FIGURE

o
l-

02
o.l
o.o

o 30 gpl o lO Spl olspl a no initiol

Cu'+

ot?14
Time, hours Fraction reacted versus time plots for different .ll initial cupric lon concentrations at 90oC, solids, 1.8 t1 (NHI + NH1), pH = 1.02, 325 x 400

foria

14.

reduces to

mesh

iu = 2rexp
second term

(l-Ba)FEIRT)

particles,2JlB atospheres 0,

(4s )

ressure.

Conversely, when

the tPb2+l'is high and E is low the in the denominator can be neglected and
exP t(2-B;)rElRrr
(46
)

over brrcad ranges of temperature, pressure, and cupric ion concentration by the rate equations
Low Pressure (Pn

"2

<I

atmosohere)

iu

fl#5

Both cases cited alove along w'ith an additional condition when Pbz+1" appraches zero have been verified experimentalTy. Therefore, the proposed mechanism involving consecutive one-electron-transfer reactions is an accurate description of the anodic

# =P o

rcu-t' tort' (kr * kz tcu}*t)% (1-,\2/3

1P02

(48)

High Pressur.

atmosphere)

dissolution of galena.

0xidation of chalcopyrite in armoniacal solutions

Beckstead and Mi'l'ler (42) have explained the kinetics of the oxidation of chalcopyrite in oxygenated armoniacal solution on the basis of an electrochemical model. The stoichiometry of the reactions

f+ =

roH-r% (kr

+ k2) rcu2+r 'ft q't'o72/3

(4e )

involved were established by Forward and Mackiw (43) and npre recent)y Kuhn et al. (aa) have described the Arbiter process based upon the anrnoniacal dissolution of copper sulfides using oxygen. The overal'l reaction f_or chal copyri te i s
CuFeS,

CuFeS,

1991-

4NH, +

lhz*

cr2*
zOttH2o

\Fero, + 2so1- *

$zo + l7ethe

(50)

cu(uH4)2+

+'eFeror+ zso; +

(47

and two

parallel cathodic reactions involving