320

ELECTROCHEMICAL REACTIONS AND SOLT'TION CHEMISTRY

CATHODIC CONVERSION OF CHALCOPYRITE

Shirts et al. (36) have denrcnstrated that chalcopyrite will react cathodically by bringing it into physical contact with a metal having a 'lower potential. Three metals, Cu, Fe, and Pb. were used. The reactions observed wei^e
CuFeS,

Cu

2H+

CuzS

+ Fe2*
2Fe2+

*
+ +

HzS

(as

welds and establishes good electrical contact. It was found that at lower temperatures, stirring disrupted the bond and retarded the reaction. At 90"C stirring had less effect on the overall kinetics. Figure 24 illustrates results obtained for an itimate mixture of copper powder and chalcopyrite concentrates.

Hiskey and l,ladsworth (37) measured the kinetics of the galvanic conversion of CuFeS2 using copoer. Figure 23 illustrates the galvanic CuFeS2-Cu couple. Both the cathodic and anodic reactions produce CUZS ,hich

2CuFeS, 2CuFeS,

+ Fe + 4H+ *
Pb +.6tt+

Cu

+
+

2HZS

(e0 )

B
F
,

r.o

lrl
CuzS ?FeZ+ Pb?+

+ 3H2S (9f)
(e?)

> 0.8

cuFes, + pb + 4H+

cu

FeZ*

PbZ*

2H2S

Galvanic couples are readily established because of

The

o .0.6 -.4 Uo 3 o.+

z o

the exce'llent electronic conductivity of a1l principal cathodic reaction is

2CuFeS,

phases.

o G325l+4OO) o l-?oot+2701 (-roo/+r5o) I''.tI Lu r o a (-60l+65) o (- 35/1481

6H+

+ 2e' =

cuzs

2Fe2+

3H2S

(e3)

30
FIGURE

TIME (MINUTES)

60

90
for

r20

of

by copper. The half-cell reaction rnvolvlng tne copper 1s

CuFeS2

'is a large driving force for the cathodic conversion

It is

evident from Figure 3(h), )ine d-e, that there

24.

to

Cu2S

ieduction of c.halcopyrite by various sizes of

Fraction reacted versus time

copper.

cathodic

rrtallic

CurS+2H++2-=2Cu+HzS

(e4)

Several s'izes

Reaction (94),. having a rnre negative potential than reaction (9), wlll react anodically. It is also evident from Figure 3(b) that metallic iron wilI
reduce CuFeS2

chalcopyrite with excess copper, molar Cu/CuFeS2 ratio of '1.5. The extent of the reaction was rBasured by the fraction o, indicated by the amount of iron released to the so'lution. The curves of Figure 24
surface

of

copper were used

with

3251400 mesh

in acid chloride golutions.

to retallic

copper as

wi'll metallic

Pb

predominantly anodically controlled. As the chalcopyrite reacts, its area becomes smaller and the kinetics shift from predominant'ly anodic control to predominantly cathodic control. The Ievelling off below a = 1.0 was attributed to'lack of perfect mixing of the initial solid phases. Carefu'l blending increased the extent of reaction. In a galvanic system it is necessary to nonnalize the data in terms of the anodic (Ar) and cathodic (A.) surface areas by the relationships I = iA and I. = i6A. where I and Is refer to the total anodic and cathodic currents respectively. Additional tests showed the rate of reaction to be essentia'lly independent of tFe III in solution. The experimental activation energy was approximately ll.5 kcal/mole. Figure 25 depicts the initia'l rate versus initial hydrogen ion concentration. The rate order for hydrogen ion is in the range 0.480.52 or essentially one-half. Assuming single charge transfer in the activated state, the net cathodic and anodic electrode processes may be represented by the
equati ons

area. Initially the chalcopyrite surface area is larger than that of the copper and the rate is

il'lustrate the importance of the copper,

anodic

I.
FIGURE

= A.k.2F

-(r-B^)rE^ B-FEexptl#t - A.kiar*2F exp-nff

(95)

23,

Schematic representation of the CuFeS"-Cuo galvanic couple in sulfuric acld. '

and