1974 The Leaching of Chalcopyrite PDF

THE LEACHING OF CHALCOPYRITE
by
DAVID L. JONES
B.Sc. University of B r i t i s h Columbia, 1965
M.Sc. University of B r i t i s h Columbia, 1970
A THESIS SUBMITTED IN PARTIAL FULFILMENT

OF THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
in the Department
of
Metallurgy
'We accept this thesis as conforming to the

/) a requited standard
THE UNIVERSITY OF BRITISH COLUMBIA
May, 1974
In presenting this thesis in partial fulfilment of the requirements for
an advanced degree at the University of British Columbia, I agree that
the Library shall make it freely available for reference and study.
I further agree that permission for extensive copying of this thesis
for scholarly purposes may be granted by the Head of my Department or
by his representatives. It is understood that copying or publication
of this thesis for financial gain shall not be allowed without my
written permission.
Department of Metallurgy
The University of British Columbia

Vancouver 8, Canada
Date July 29, 1974

ABSTRACT
The a n o d i c d i s s o l u t i o n o f c h a l c o p y r i t e has been examined i n c h l o r i d e
and s u l p h a t e s o l u t i o n s from 20°C t o 175°C. In c h l o r i d e the y i e l d o f elemen-
t a l s u l p h u r i s n e a r l y 100%, whereas i n s u l p h a t e s o l u t i o n s i t i s 75% o r l e s s ,
the remainder b e i n g o x i d i z e d .
It i s p o s t u l a t e d t h a t i n s u l p h a t e s o l u t i o n s the copper d i s s o l v e s as
a t h i o s u l p h a t e complex, which can decompose e i t h e r t o a s o l u b l e f o r m , o r t o
c u p r i c s u l p h i d e and a n o t h e r s u l p h u r s p e c i e s , p r o b a b l y d i t h i o n a t e .
The a n o d i c p o l a r i z a t i o n o f c h a l c o p y r i t e d i s p l a y s two i m p o r t a n t r e g i o n s :
f i r s t a d i f f u s i o n r e g i o n i n which the c u r r e n t i s h i g h l y time-dependent, but
p o t e n t i a l independent and second a h i g h e r c u r r e n t r e g i o n , a t t r i b u t e d t o the
b u i l d up o f a space-charge i n the m i n e r a l . T h i s space-charge c u r r e n t is
l a r g e l y time independent but i s l i n e a r l y dependent on p o t e n t i a l .
At low temperatures c h l o r i d e s o l u t i o n s and s u l p h a t e s o l u t i o n s g i v e
s i m i l a r p o l a r i z a t i o n curves but at 90°C and above, the space-charge region
i n c h l o r i d e s o l u t i o n s s t a r t s at much lower p o t e n t i a l s (500 mV) whereas i n
s u l p h a t e s o l u t i o n s i t does n o t . Sulphuric acid solutions passivate the
m i n e r a l at h i g h temperatures and p o t e n t i a l s .
The e l e c t r o c h e m i c a l r e s u l t s c o r r e l a t e w e l l w i t h l e a c h i n g experiments
u s i n g f e r r i c s u l p h a t e and f e r r i c c h l o r i d e , and t h e r e i s every r e a s o n t o b e -
l i e v e t h a t f o r c h a l c o p y r i t e an e l e c t r o c h e m i c a l mechanism i s o p e r a t i v e d u r i n g
leaching.
F e r r i c c h l o r i d e i s an e q u a l o r more e f f e c t i v e o x i d i z i n g agent t h a n
f e r r i c sulphate; i t s (ferric chloride) e f f e c t i v e n e s s i s i n c r e a s e d by f i n e
p a r t i c l e s i z e , high [ F e + + +
]. F e r r i c sulphate leaching i s relatively
-ii-
unaffected by these f a c t o r s , but decreased by [ F e ] . + +

Linear k i n e t i c s are
normally observed with both reagents, but under optimum conditions with
f e r r i c c h l o r i d e a r a p i d i n i t i a l d i s s o l u t i o n precedes the l i n e a r stage.
F e r r i c sulphate appears to s e l e c t i v e l y attack the mineral along
grain boundaries, whereas f e r r i c c h l o r i d e does not.
Mixed p o t e n t i a l measurements i n d i c a t e that i n f e r r i c sulphate the
r e a c t i o n i s undei" mixed c o n t r o l , and that both anodic and cathodic reactions
are quite i r r e v e r s i b l e . In cupric chloride the leaching r e a c t i o n i s under
anodic c o n t r o l , and the cathodic r e a c t i o n i s h i g h l y r e v e r s i b l e . F e r r i c
chloride leaching appears to be cupric chloride leaching i n r e a l i t y ; the
f e r r i c ions serve the purpose of depressing the [ C u ] , thus r a i s i n g the

+
p o t e n t i a l of the C u / C u
++ +
couple. Thus, f e r r i c c h l o r i d e leaching i s also
under anodic c o n t r o l .
-iii-
LIST OF CONTENTS
Page
A. INTRODUCTION 1
I. General 1
II. Some P r o p e r t i e s of C h a l c o p y r i t e 4
(a) Phase R e l a t i o n s 4
(b) Thermodynamics 7
(c) C r y s t a l S t r u c t u r e and Bonding 10
III. The L e a c h i n g o f Copper S u l p h i d e s 14
(a) An Overview 14
(b) L e a c h i n g o f S i m p l e Copper S u l p h i d e s 15
(c) E l e c t r o c h e m i c a l S t u d i e s of Simple Copper
Sulphides 18
(d) A Note on the L e a c h i n g o f B o r n i t e , Cubanite,
Idaite 22
(e) L e a c h i n g of C h a l c o p y r i t e 23
(i) F e r r i c Sulphate 23
(ii) Ferric Chloride 25
(iii) Other O x i d a n t s 31
(f) E l e c t r o c h e m i c a l S t u d i e s on C h a l c o p y r i t e .... 32
IV. E l e c t r o c h e m i c a l E x p e r i m e n t s i n Aqueous S o l u t i o n s
Above 100°C 35
(a) S t a t e of the A r t 36
(b) A p p l i c a t i o n to Sulphide Minerals 38
B. EXPERIMENTAL 39
I. Apparatus 39
(a) Pressure Vessel Design 42

(b) Electrode Design (for Sulphide Minerals) ... 48
(c) Reference E l e c t r o d e 49
-iv-
Page
II. Chemicals 50
III. Instrumentation 50
IV. Analysis 50
V. Source o f C h a l c o p y r i t e Used 51
C. RESULTS 53
I. P r e l i m i n a r y Experiments 53
(a) The Meaning of C u r r e n t E f f i c i e n c y 53

(b) P o t e n t i o s t a t i c Scans 54
(c) Constant P o t e n t i a l Experiments 59
(d) S u r f a c e of C h a l c o p y r i t e A f t e r A n o d i z i n g .... 66
(e) Summary 66
II. Anodic P o l a r i z a t i o n s 72
(a) E a s t Scans 72
(b) Summary 74
(c) Slow Scans 86
(d) Summary 88
III. Constant P o t e n t i a l Experiments 102
(a) Without S o l u t i o n A n a l y s i s 102

(b) With Solution A n a l y s i s Ill
(i) D i l u t e C h l o r i d e S o l u t i o n s (90°C) ... 112
(ii) S t r o n g C h l o r i d e S o l u t i o n s (90°C) ... 113
(iii) S u l p h a t e C h l o r i d e S o l u t i o n s (90°C) . 114
(iv) Sulphate/Bisulphate Solutions
(125°C) 122
(v) Sulphate/Bisulphate S o l u t i o n s (125-
175°C) 132
(vi) Chloride/Bisulphate Solutions - A
Comparison 133
(vii) Sundry E f f e c t s 134
(viii) Summary 135
-V-
Page
IV. Leaching Experiments 147
(a) The M o t i v e 147

(b) L e a c h i n g E x p e r i m e n t s on M a s s i v e CuFeS2 148
(i) P r e l i m i n a r y Experiments 148
(ii) Morphology 149
(iii) A Comparison of C h e m i c a l and E l e c t r o -
chemical D i s s o l u t i o n 157
(iv) Chemistry of D i s s o l u t i o n 159
(c) Powder L e a c h i n g 160
(i) Shape of L e a c h i n g Curve 166
(ii) E f f e c t of P a r t i c l e S i z e 166
(iii) Fe /Cu R a t i o Produced D u r i n g
Leaching 172
(iv) E f f e c t of F e r r i c C o n c e n t r a t i o n 172
(v) E f f e c t of Added C h l o r i d e 172
(vi) E f f e c t of F e r r o u s C o n c e n t r a t i o n 172
(vii) E f f e c t of Acid 176
(viii) E f f e c t of S t i r r i n g Mode 176
(ix) E f f e c t of Temperature 176
(x) E f f e c t of G r a i n S i z e i n F e r r i c Sulphate
Leaching 176
(xi) Comparison o f F e r r i c C h l o r i d e and F e r r i c
Sulphate Leaching 177
(d) Concentrate Leaching 181
(e) Summary 184
V. Mixed P o t e n t i a l E x p e r i m e n t s 189
(a) Motive 1 8 9
(b) Results 190

(i) F e r r i c Sulphate Leaching 190
(ii) Cupric C h l o r i d e Leaching 195
(iii) F e r r i c C h l o r i d e Leaching 196
(iv) Summary 205
-vi-
Page
(c) Discussion 205

(i) Calculated Potentials 206
(ii) F e r r i c Sulphate Leaching 209
(iii) Cupric C h l o r i d e Leaching 211
(iv) F e r r i c C h l o r i d e Leaching 214
(v) Summary 216
D. DISCUSSION 217
I. The C h e m i s t r y of the A n o d i c D i s s o l u t i o n of
Chalcopyrite 217
(a) C h l o r i d e System 217
(b) S u l p h a t e System 218
(i) T h i o s u l p h a t e Mechanism 222
(ii) Sulphur D i s p r o p o r t i o n a t i o n Mechanism . 228
(iii) Hydrogen S u l p h i d e Mechanism 229
II. The A n o d i c P o l a r i z a t i o n Curve o f C h a l c o p y r i t e ... 230
(a) The D i f f u s i o n a l P r o c e s s i n C h a l c o p y r i t e .... 231
(b) The E f f e c t of S o l u t i o n 235
E. CONCLUSION 238
REFERENCES 239
APPENDIX A 249
APPENDIX B 263
-vii-
LIST OF TABLES
Page
I D i s s o l u t i o n of C o v e l l i t e i n F e r r i c Sulphate
S o l u t i o n s a t 35°C; E f f e c t o f P a r t i c l e S i z e
Ifrom S u l l i v a n (106)]. 17
II R e s t P o t e n t i a l s of Copper S u l p h i d e s v s . Cu
M e t a l at 25°C Measured By V a r i o u s A u t h o r s . 19
III Data on Mechanism o f D i s s o l u t i o n o f C h a l c o p y r i t e

i n F e r r i c Sulphate (at 35°C) I f r o m S u l l i v a n ( 1 3 0 ) ] . 23
IVA A n a l y s i s of S o l u t i o n s A f t e r C o n s t a n t Potential
E x p e r i m e n t s on C u F e S 2 i n 0.1M HCIO^. 63
IVB A n a l y s i s of S o l u t i o n s A f t e r C o n s t a n t P o t e n t i a l
E x p e r i m e n t s on CuFeS2 i n 0.1M I^SO^. 64
V A n a l y s i s of S o l u t i o n s A f t e r H e a t i n g E x p e r i m e n t s
on C u F e S 2 i n 0.1M HCIO^. 64
VI S u c c e s s i v e A n o d i c Scans a t R a p i d Scanning R a t e s ;
Specimen #200. 84,85
VII S u c c e s s i v e A n o d i c Scans a t Slow Scanning Rates;

Specimen #202 and #207. 100,101
-viii-
FIGURE CAPTIONS
Fig. 1 Cu-Fe-S system a t 200°C (from Yund and K u l l e r u d ^ ^ ) . 1 0
Fig. 2 C r y s t a l s t r u c t u r e o f CuFeS2>
Fig. 3 L e a c h i n g of c h a l c o p y r i t e c o n c e n t r a t e i n f e r r i c c h l o r i d e ,
e f f e c t of temperature (from Haver and Wong (-^37)^
Fig. 4 L e a c h i n g of c h a l c o p y r i t e c o n c e n t r a t e i n f e r r i c c h l o r i d e ,
e f f e c t of p a r t i c l e s i z e (as g r i n d i n g t i m e ) . (From Haver
and Wong^ - )). 1 37
Fig. 5 A n o d i c d i s s o l u t i o n of c h a l c o p y r i t e . Solution analysis

from Z e v g o l i s ^
Fig. 6 A p p a r a t u s f o r l e a c h i n g powdered c h a l c o p y r i t e .
Fig. 7 Apparatus f o r l e a c h i n g massive specimens.
Fig. 8 Pressure vessel
F i g . 10 Electrochemical cell
F i g . 11 E3.ectrode mounting
Fig. 12 P o t e n t i o s t a t i c scans i n p e r c h l o r i c a c i d a t v a r i o u s
temperatures.
F i g . 13 P o t e n t i o s t a t i c scans i n s u l p h u r i c a c i d a t various
temperatures.
F i g . 14 E f f e c t of s c a n n i n g r a t e on p o t e n t i o s t a t i c s c a n .
F i g . 15 The l i n e a r c u r r e n t / p o t e n t i a l r e l a t i o n s h i p i n p o t e n t i o -
s t a t i c scans.
F i g . 16 P o t e n t i o s t a t i c scans i n p e r c h l o r i c a c i d .
F i g . 17 C u r r e n t decay d u r i n g c o n s t a n t p o t e n t i a l e x p e r i m e n t s
a t 125°C.
F i g . 18 C u r r e n t decay d u r i n g c o n s t a n t p o t e n t i a l e x p e r i m e n t s
a t 150°C.
-ix-
F i g . 19 Scanning e l e c t r o n m i c r o g r a p h of c h a l c o p y r i t e a n o d i z e d
a t 1500 mV f o r 3 hours i n 0.1M HC10 , 1 7 5 ° C 4
F i g . 20 Scanning e l e c t r o n m i c r o g r a p h o f c h a l c o p y r i t e a f t e r
a n o d i z i n g (16 h o u r s , 700 mV, 0.IM HC10 , 150°C). 4
F i g . 21 Scanning e l e c t r o n m i c r o g r a p h o f CuFeS2 specimen a f t e r

a n o d i z i n g (7 h o u r s , 615 mV, 0.1M HCIO4, 175°C).
F i g . 22 Scanning e l e c t r o n m i c r o g r a p h s o f CuFeS2 specimen a f t e r

a n o d i z i n g (11 h o u r s , 615 mV, 0.1M HCIO4, 175°C).
F i g . 23 Scanning e l e c t r o n m i c r o g r a p h s of CuFeS specimen a f t e r

2
a n o d i z i n g Oh h o u r s , 690 mV, 0.1M HCTO4, 175°C).
F i g . 24 P o t e n t i o s t a t i c scans on GuFeS2 i n v a r i o u s s o l u t i o n s a t
300 mV/min., 20°C.
F i g . 25 P o t e n t i o s t a t i c scans i n c h l o r i d e s o l u t i o n s a t 300 mV/

m i n . , 20°C.
F i g . 26 P o t e n t i o s t a t i c scans i n 0.1M H C l , 20°C a t v a r i o u s s c a n -

ning r a t e s .
F i g . 27 P o t e n t i o s t a t i c scans i n s u l p h a t e s o l u t i o n , 20°C, a t
various scanning r a t e s .
F i g . 28 P o t e n t i o s t a t i c scans i n IM H C l , 20°C.
F i g . 29 S u c c e s s i v e p o t e n t i o s t a t i c scans i n 0.1M H C l a t 20°C,

300 mV/min.
F i g . 30 P o t e n t i o s t a t i c scans a t 20°C.
F i g . 31 P o t e n t i o s t a t i c scans i n s u l p h a t e s o l u t i o n a t 300 mV,

and v a r i o u s t e m p e r a t u r e s .
F i g . 32 P o t e n t i o s t a t i c scans i n 0.1M H C l a t 95°C, and v a r i o u s

scanning r a t e s .
F i g . 3 3 , 34 Slow scans a t 20°C i n v a r i o u s s o l u t i o n s .
F i g . 35 Slow scans a t 20°C i n s u l p h a t e s o l u t i o n s .
F i g . 36 Slow scans a t 20°C i n c h l o r i d e s o l u t i o n s .
F i g . 37 Slow scans i n 0.1M HCIO^ a t v a r i o u s t e m p e r a t u r e s .
F i g . 38 Slow scans a t 90°C i n v a r i o u s s o l u t i o n s .

-X-
F i g . 39 Slow scans a t 90°C i n IM H C l and IM H ^ O ^ .
F i g . 40 Slow scans a t 90°C i n sodium s u l p h a t e s o l u t i o n s .
F i g . 41 Slow scans a t 90°C i n c h l o r i d e s o l u t i o n s .
F i g . 42 Slow scans a t 90°C i n 4M H C l a t pH 1 and pH 3 . 5 .
F i g . 43 C u r r e n t decay a t 700 mV, 20°C i n v a r i o u s s o l u t i o n s .
F i g . 47 E f f e c t of temperature on c u r r e n t a t 700 mV, i n 0.1M

H S0 .
2 4
F i g . 48 A r r h e n i u s diagram f o r c u r r e n t a t 700 mV i n 0.1M HCIO^.
F i g . 49 A r r h e n i u s diagram f o r c u r r e n t a t 700 mV i n 0.1M KC1

and IM KC1-.
F i g . 50 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n 0.3M N a C l , 0.2M H C l
a t 90°C, and v a r i o u s p o t e n t i a l s .
F i g . 51 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n 3.0M N a C l , 0.2M H C l
a t 90°C, and v a r i o u s p o t e n t i a l s .
F i g . 52 C u r r e n t o s c i l l a t i o n s produced a f t e r s e v e r a l hours a t
900 mV, 90°C i n 3M N a C l , 0.2M H C l . E f f e c t of t e m p e r a -
t u r e and p o t e n t i a l .
F i g . 53 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n 0.4M Na2S0^, 0.1M

H2SO4 a t 90°C, and v a r i o u s p o t e n t i a l s .
F i g . 54 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n 0.3M Na2S0^, 0.2M

H2S
O 4 at 90°C and 735 mV.
F i g . 55 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n s u l p h a t e and b i s u l p h -
a t e s o l u t i o n s a t 125°C, 735 mV.
F i g . 56 C o n s t a n t p o t e n t i a l e x p e r i m e n t s i n s u l p h a t e and b i s u l p h -
a t e s o l u t i o n s a t 125°C -> 175°C, 735 mV.
F i g . 57 C o n s t a n t p o t e n t i a l experiments a t 735 mV i n 0.4M N a C l ,

0.1M HCl a t 175°C, 150°C and 125°C.
-xi-
F i g . 58 C o n s t a n t p o t e n t i a l e x p e r i m e n t s a t 735 mV i n 0.4M NaHSO^,

0.1M H S O a t 125°C and 175°C.
2 A
Fig. 59 A r r h e n i u s diagram f o r c u r r e n t a t 735 mV i n 0.4M N a C l ,

0.1M H C l .
F i g . 60 S u c c e s s i v e c o n s t a n t p o t e n t i a l e x p e r i m e n t s a t 90°C, 735
mV i n b i s u l p h a t e and c h l o r i d e s o l u t i o n s .
F i g . 61 E f f e c t of d e c r e a s e d a c i d on c o n s t a n t p o t e n t i a l e x p e r i -
ment i n d i l u t e c h l o r i d e s o l u t i o n a t 735 mV, 90°C.
F i g . 62 E f f e c t o f no a c i d on c o n s t a n t p o t e n t i a l e x p e r i m e n t in
s t r o n g c h l o r i d e s o l u t i o n a t 535 mV, 90°C.
F i g . 63 Scanning e l e c t r o n m i c r o g r a p h s of c h a l c o p y r i t e after
l e a c h i n g (5 d a y s , 9 5 ° C ) .
F i g . 64 Scanning e l e c t r o n m i c r o g r a p h s of c h a l c o p y r i t e after
l e a c h i n g (11 h o u r s , 95°C, IM F e C l ) . 3
Fig. 65 Scanning e l e c t r o n m i c r o g r a p h of c h a l c o p y r i t e after

l e a c h i n g i n IM F e C S O ^ at 9 5 ° C
5
Fig. 66 Scanning e l e c t r o n m i c r o g r a p h s of c h a l c o p y r i t e after

l e a c h i n g i n IM Fe(S04> a t 95°C.
F i g . 67 T h e o r e t i c a l r e l a t i o n s h i p between p e r c e n t s u l p h u r as S°
and F e / C u
+ + + +
r a t i o i n equation (20).
Fig. 68 L e a c h i n g of m a s s i v e c h a l c o p y r i t e i n IM F e ( S 0 A ) 1 ,., 90°C.
F i g . 69 Comparison o f l e a c h i n g i n 0.1M and IM F e ( S 0 ) ^ 4 ...
F i g . 70 Comparison of l e a c h i n g i n s u l p h a t e , p e r c h l o r a t e and
chloride solutions.
Fig. 71 E f f e c t of s u r f a c e p r e p a r a t i o n on F e C l 3 l e a c h i n g .
F i g . 72 The l e a c h i n g o f powdered c h a l c o p y r i t e w i t h f e r r i c sulph-

ate.
F i g . 73 Comparison of l i n e a r and p a r a b o l i c k i n e t i c s i n the l e a c h -

i n g of powdered c h a l c o p y r i t e w i t h f e r r i c s u l p h a t e .
Fig. 74 L e a c h i n g of powdered c h a l c o p y r i t e w i t h f e r r i c chloride.
F i g . 75 E f f e c t of p a r t i c l e s i z e i n f e r r i c s u l p h a t e l e a c h i n g .
i i i
Fig. 76 E f f e c t of [Fe ] i n f e r r i c sulphate l e a c h i n g .
-xii-
Fig. 77 Effect of [Fe '] i n f e r r i c chloride leaching.

11
Fig. 78 Effect of [Fe"""*"] i n f e r r i c sulphate and chloride leach-

1
ing.
Fig. 79 Effect of s t i r r i n g mode i n f e r r i c sulphate and chloride

leaching.
Fig. 80 Effect of temperature on f e r r i c chloride leaching.

Fig. 81 Effect of grain size on f e r r i c sulphate leaching.
Fig. 82 Leaching of various concentrates with f e r r i c chloride.

Fig. 83 Effect of particle size on concentrate leaching.
Fig. 84 Optimum leaching of various concentrates.
Fig. 85 Mixed potential of chalcopyrite i n f e r r i c sulphate.

Effect of [ F e ] . + + +
Fig. 86 Mixed potential of chalcopyrite i n f e r r i c sulphate.

Effect of [ F e ] . ++
Fig. 87 Mixed potential of chalcopyrite i n dilute f e r r i c sulph-

ate. Effect of iFe" "*] . 1
Fig. 88 Mixed potential of chalcopyrite i n cupric chloride.

Effect of [ C u ] . ++

Effect of [Cu ]. +

Effect of [ C l ] .

Effect of [Cl] i n absence of:cuprous chloride.
Fig. 92 Mixed potential of chalcopyrite i n f e r r i c chloride.
Effect of [ F e ] . + + +

Effect of [ F e ] . ++

Effect of iFe "^] when l F e ] i s low.
4 + + +

Effect of [Cl""].-

Effect of [CU++].
-xiii-
AC KNOWLED GEMENT S
The a u t h o r w i s h e s t o e x p r e s s h i s s i n c e r e thanks to D r . E.
P e t e r s f o r h i s s u p p o r t and encouragement d u r i n g t h i s p r o j e c t . The
numerous c r i t i c a l d i s c u s s i o n s t h a t he has provoked have been a most
welcome s o u r c e of s t i m u l a t i o n .
The i n t e r a c t i o n w i t h o t h e r g r a d u a t e s t u d e n t s has a l s o been
v e r y r e w a r d i n g ; p a r t i c u l a r thanks a r e due t o D r . K. J i b i k i f o r h i s h e l p
w i t h the p r e p a r a t i o n of the f i n a l m a n u s c r i p t .
The t e c h n i c a l s t a f f o f t h e Department o f M e t a l l u r g y have
g i v e n i n v a l u a b l e h e l p i n overcoming a s e r i e s o f e x p e r i m e n t a l d i f f i c u l t i e s .
The a u t h o r i s a l s o k e e n l y a p p r e c i a t i v e of t h e open door p o l i c y
of the Department o f M e t a l l u r g y , and i t s Head, D r . E. T e g h t s o o n i a n , w h i c h
has g r e a t l y f a c i l i t a t e d a c c e s s to m a t e r i a l s and equipment.
Finally, the a u t h o r would l i k e t o thank h i s w i f e , Susan, and
o t h e r f a m i l y members f o r t h e i r e x c e p t i o n a l p a t i e n c e and s u p p o r t , w h i c h
enabled t h i s work to be c a r r i e d t o c o m p l e t i o n .
A. INTRODUCTION
I General
Copper i s the twenty-fifth most abundant element i n the earth's crust,
with an average concentration of only 70 ppm (1). In useful ore bodies the
concentration i s t y p i c a l l y 1% (10,000 ppm) present as sulphide minerals or
t h e i r oxidation products. The most important sulphide mineral of copper i s
chalcopyrite, CuFeS2.
Sulphide ores can readily be upgraded by f l o t a t i o n methods to elimin-
ate most of the associated gangue minerals, and achieve a t y p i c a l l y 30%
copper concentrate. The extraction of the copper from the sulphide mineral
has t r a d i t i o n a l l y been carried out by melting and converting: the concen-
trate i s slowly melted and partly oxidized i n a large reverbatory furnace,
to remove remaining gangue and some of the iron and sulphur; the r e s u l t i n g
l i q u i d copper-iron sulphide, or matte, i s then blown with a i r to oxidize the
remaining iron and sulphur, which are respectively slagged o f f and vented
as SO2 gas.
This process, which i s now nearly 100 years o l d (4), was an outstanding
achievement of the early metallurgists. I t depends f o r i t s success on the
remarkable n o b i l i t y of l i q u i d copper at converting temperatures (1100°C),
such that a i r may be blown through the l i q u i d metal, oxidizing the iron
and sulphur s e l e c t i v e l y . This s i t u a t i o n may be compared to that existing
in a n i c k e l or t i n smelter, where the a f f i n i t y f o r oxygen i s much greater,
and separation from iron i s consequently not achieved.
The main drawback to the copper smelting process i s the production of
large quantities of S02-containing gas, which can cause serious p o l l u t i o n
-1-
-2-
problems when i t i s vented to the atmosphere. The economical c o n v e r s i o n of
t h i s gas into sulphuric a c i d may be a c h i e v e d i f the SO,, content o f the gas is
h i g h enough, but l a c k o f nearby markets f o r the sulphuric a c i d produced
can p r e s e n t a problem.
It has long been r e c o g n i z e d t h a t an a l t e r n a t i v e method o f extracting
copper from i t s ores might be found i n h y d r o m e t a l l u r g y ; some types o f ore,
p a r t i c u l a r l y o x i d e s , have been p r o c e s s e d by aqueous methods f o r y e a r s , but
no generally a p p l i c a b l e process f o r sulphide c o n c e n t r a t e s has yet been proven
on a plant scale. However, t h i s problem has r e c e n t l y been the subject of
intensive research by numerous o r g a n i z a t i o n s and i n d i v i d u a l s ; i t seems v e r y
l i k e l y that at l e a s t one economic p r o c e s s w i l l be demonstrated i n the
near future.
The v a r i e t y o f p r o c e s s e s t h a t have been or are b e i n g i n v e s t i g a t e d is
quite l a r g e , and a number o f e x c e l l e n t review a r t i c l e s have r e c e n t l y appeared
(2-5) . The various p r o c e s s e s can be c l a s s i f i e d a c c o r d i n g t o the n a t u r e of
the leaching step ( i n which the copper i s d i s s o l v e d ) , for i t is usually the
most d i f f i c u l t and f u r t h e r m o r e , i t determines the possible c h o i c e s i n sub-
sequent s t e p s . The most i n e r t m i n e r a l to t r e a t i s almost i n v a r i a b l y c h a l -
c o p y r i t e , which i s a l s o the most common. T h e r e f o r e the problem i s one of
extracting copper from c h a l c o p y r i t e . T h i s may be a c h i e v e d w i t h a number o f
r e a g e n t s , but economics d i c t a t e s t h a t o n l y a few are p r a c t i c a b l e - these are
all o x i d i z i n g agents:
Ferric Sulphate
in acid solutions
Ferric Chloride
Oxygen i n s u l p h u r i c acid
Oxygen i n ammoniacal solutions
Nitric Acid
-3-
There are o t h e r t e c h n i c a l l y f e a s i b l e o x i d a n t s , but they do not seem t o
be r e c e i v i n g much a t t e n t i o n r e c e n t l y . In a d d i t i o n , c o n s i d e r a b l e e f f o r t has
been d i r e c t e d towards the p o s s i b i l i t y o f ' a c t i v a t i n g ' the c h a l c o p y r i t e be-
f o r e the l e a c h , i . e . s u b j e c t i n g i t t o some form o f p r e - t r e a t m e n t such as
h e a t i n g which w i l l enhance i t s r e a c t i v i t y These p r o c e s s e s , which u s u a l l y
i n v o l v e s u b s t a n t i a l chemical change, show much promise, but do not fall
w i t h i n the scope o f t h i s work, which i s d i r e c t e d o n l y at the d i s s o l u t i o n of
chalcopyrite i n i t s natural form.
Although t h e r e are s e v e r a l p u b l i c a t i o n s d e a l i n g with the l e a c h i n g o f
c h a l c o p y r i t e with each o f these o x i d a n t s , t h e r e i s l i t t l e p u b l i s h e d informa-
t i o n on the fundamental b e h a v i o u r o f c h a l c o p y r i t e under o x i d i z i n g aqueous
conditions. A u n i f i e d u n d e r s t a n d i n g o f the v a r i o u s l e a c h i n g c o n d i t i o n s might
be gained through c o n s i d e r i n g such r e a c t i o n s as b e i n g e l e c t r o c h e m i c a l i n
n a t u r e ; then the (anodic) d i s s o l u t i o n o f the m i n e r a l can be s t u d i e d i n d e -
pendently o f the c h e m i s t r y o f r e d u c t i o n o f the o x i d a n t .
The theory that c h a l c o p y r i t e , l i k e other s u l p h i d e s , leaches electro-
c h e m i c a l l y , i s f r e q u e n t l y mentioned i n the l i t e r a t u r e (5) ; however, i n s p i t e
of the l o g i c and c o n s i s t e n c y o f such a mechanism t h e r e appears t o be little
d i r e c t e x p e r i m e n t a l evidence t o support i t .
The aim o f t h i s work i s t o f u r t h e r our u n d e r s t a n d i n g o f the l e a c h i n g of
c h a l c o p y r i t e under o x i d i z i n g c o n d i t i o n s , and t o demonstrate t h a t such l e a c h -
ing may indeed be e l e c t r o c h e m i c a l . To achieve t h i s , both e l e c t r o c h e m i c a l
and chemical experiments have been c a r r i e d out; i n p a r t i c u l a r , l e a c h i n g with
f e r r i c s u l p h a t e and f e r r i c c h l o r i d e has been s t u d i e d , f o r these are two
of the most important oxidants i n d u s t r i a l l y available.
An additional i n c e n t i v e f o r examining the e l e c t r o c h e m i c a l d i s s o l u t i o n of
chalcopyrite lies i n the p o s s i b i l i t y of direct e l e c t r o l y t i c r e f i n i n g of
copper concentrates. Such a p r o c e s s has been o p e r a t e d commercially on

-4-
n i c k e l s u l p h i d e mattes f o r some y e a r s (183,4) and s e v e r a l investigators
have s t u d i e d the comparable p r o c e s s on copper m a t t e . There i s , however,
l i t t l e known about the a n o d i c b e h a v i o u r o f c h a l c o p y r i t e .
II Some P r o p e r t i e s o f C h a l c o p y r i t e
a) Phase R e l a t i o n s
The Cu-Fe-S system has p r o b a b l y r e c e i v e d more a t t e n t i o n than any o t h e r
t e r n a r y m i n e r a l system (6-44) and y e t t h e r e are s t i l l some i m p o r t a n t features
which are u n c l e a r . Yund and K u l l e r u d ( 1 0 ) , u s i n g pure m a t e r i a l s annealed
t o g e t h e r f o r long p e r i o d s t o form s y n t h e t i c m i n e r a l assemblages, constructed
phase diagrams f o r temperatures from 700°C down t o 200°C. At 200°C, many
r e a c t i o n s i n t h i s system are a l r e a d y v e r y s l o w , r e q u i r i n g up t o 500 days
f o r e q u i l i b r a t i o n , and below t h i s t e m p e r a t u r e , r e s u l t s are u n r e l i a b l e . This
has been a major h u r d l e t o i n v e s t i g a t o r s i n t h i s field.
It appears from F i g u r e 1 t h a t t h e r e i s o n l y a s i n g l e phase w i t h the
CuFeS2 c o m p o s i t i o n , and t h a t the s t o i c h i o m e t r i c v a r i a t i o n o f t h i s phase
i s v e r y s m a l l , and d e c r e a s i n g w i t h t e m p e r a t u r e . F u r t h e r , the p o s s i b l e two
phase assemblages i n v o l v i n g c h a l c o p y r i t e are:
1) C h a l c o p y r i t e - b o r n i t e
2) C h a l c o p y r i t e - p y r i t e
3) C h a l c o p y r i t e - p y r r h o t i t e (and/or cubanite)
These a s s o c i a t i o n s are the same as those found i n n a t u r e : the f i r s t two
are t y p i c a l o f a p o r p h y r y copper d e p o s i t i n B r i t i s h C o l u m b i a , whereas the
l a s t i s found w i t h n i c k e l m i n e r a l s i n the Sudbury Basin.
Yund and K u l l e r u d a l s o showed t h a t at h i g h t e m p e r a t u r e s the 'CuFeS^'
phase a c t u a l l y c o n t a i n e d l e s s s u l p h u r t h a n r e q u i r e d by t h e s t o i c h i o m e t r i c
formula. At 500°C, t h i s might be w r i t t e n as CuFeS^ g. This implies that
c h a l c o p y r i t e formed at h i g h temperatures w i l l be d e f i c i e n t i n s u l p h u r , if
not annealed f o r s u f f i c i e n t l y l o n g t i m e s , i n the presence o f s u l p h u r .

-5-
Fig.I Cu-Fe-S system at 2 0 0 ° C .
Fig. 1 Cu-Fe-S system a t 200°C (from Yund and Kullerud^ ^).

1 0
bn bornite Cu FeS, c
cc chalcocite Cu S 2
cn carbonite CuFe S 2 3
cp chalcopyrite CuFeS 2
cv covellite CuS
dg digenite
1.8
C U S
id idaite Cu FeS,
5.5 6 .5
c c
po pyrrhotite Fe S
1-x
1
py pyrite FeS 2
-6-
Tn the main, Yund and Kullerud's r e s u l t s were i n agreement with the
e a r l i e r study by Merwin and Lombard (6) although the l a t t e r postulated a
new phase Cu,Fe.S, (which was not observed by Yund and Kullerud), and a
low temperature composition of CuFeS for chalcopyrite, (as opposed to

1.97
stoichiometric CuFeS2 proposed by. Yund and Kullerud). Perhaps the most
important conclusion from the point of view of the extractive metallurgist,
was that a large s o l i d solution f i e l d (iss) existed at high temperatures
(but did not include the CuFeS2 stoichiometric composition) and gradually
shrank to the stoichiometric CuFeS2 composition at ambient temperatures,
where the range was very small. Although low temperature (<200°C)
e q u i l i b r i a could not be observed, i t was inferred that the same pattern
would continue to ambient temperatures.
These conclusions have been placed i n doubt, by recent r e s u l t s of other
workers (20-29) , and i t now appears that the Cu-Fe-S phase diagram i s far
more complicated at 25-100°C than as indicated above. Shortly a f t e r the pub-
l i c a t i o n of Yund and Kullerud's work a new copper-iron sulphide, talnakhite,
was discovered in the Soviet Union(21), and this was soon followed by two
others (26). Thus four phases in the 'CuFeS2' region are now known as well
as cubanite, which i s also included in the ' i s s ' at high temperatures:
chalcopyrite
talnakhite
mooihoekite
Cu Fe S
4 5 1 6 haycocknte
cubanite
The s i t u a t i o n i s summarized by Cabri (27):
... the central area of the Cu-Fe-S system i s character-

ized by.a large s o l i d solution f i e l d at elevated temperatures
which breaks up into f i v e distant phases at low temperatures.
-7-
The picture i s complicated by numerous phase transformations,

unquenchable phases and phases with closely related c r y s t a l chem-
i s t r y , r e s u l t i n g i n t h e i r having s i m i l a r physical appearance and
X-ray d i f f r a c t i o n powder patterns. The slow rate of most of the
reactions at low temperatures also makes i t d i f f i c u l t (in some
cases impossible) to achieve equilibrium i n the laboratory.
Chalcopyrite, talnakhite and mooihoekite were synthesized, while
attempts to synthesize cubanite and haycockite were unsuccessful.
In addition to the new data on the central portion of the Cu^-Fe-S
system, there have been several other recent developments:
Idaite, long a subject of controversy, was given the formula Cu,. cjFeS^ ^
by Yund and Kullerud (10) and Cu FeS 3 4 by Cabri. (27)
Digenite, Cu S, an 'accepted' mineral f o r several years i n the Cu-S

1. o
system (36), has recently been considered as an iron-containing mineral
(30-32), and a new mineral a n i l i t e Cu^S^ proposed, which unlike i t s predeces-
sor has a very limited range of composition. Furthermore a n i l i t e may be con-
verted into a metastable digenite phase by grinding.
Although Yund and Kullerud (10) showed no copper-containing phase
that was more sulphur-rich than c o v e l l i t e , CuS, a copper disulphide phase
has been synthesized under high pressure (33), and a new mineral, f u k u c h i l i t e
Cu^FeSg discovered (34) and synthesized (35). The importance of these d i s -
coveries to hydrometallurgy i s that oxidation of c o v e l l i t e or chalcopyrite
could conceivably result in the formation of such a phase, even i f meta-
stable, instead of elemental sulphur.
b) Thermodynamics
The most useful thermodynamic quantities pertaining to chalcopyrite
are naturally the free energy AF° and entropy, S°. Unfortunately, at the
present time there appear to be no r e l i a b l e experimental values published
for the quantities (nor f o r any other ternary Cu-Fe-S mineral). This
deficiency, which w i l l hopefully be remedied soon, has in part been overcome

-8-
by calculation based on mineral assemblages, and decomposition pressures
(37-44). Kelley (39), published some calculations of Maier (which were
based on Joly's observation (41) that the decomposition temperature of
chalcopyrite was 743°K) and gave -AF°^g = -41.3 kcal./mole.
Golomzik (38) however, measured the sulphur vapour pressures at three
temperatures (500, 600 and 700°C) and calculated A F ° g g = -51.5 kcal./mole.
Young made a more detailed study of the problem (42,43) and evaluated
the little-known work of Bartholome (40), who calculated the equilibrium
p a r t i a l pressures of sulphur vapour over the various ternary associations.
This method depends on having a r e l i a b l e phase diagram, from which one can
predict reactions. Bartholome, with less experimental data than was avail-
able to Young, calculated AF°gg =

~ ^5.0 ^ ^ l / ° l -
c m e
Young used McKinstry's
(44) and Yund and Kullerud's (10) data and calculated AF = -45.5 kcal/mole.
Young also u t i l i z e d Merwin and Lombard's data f o r the decomposition pressure
of chalcopyrite (6) and calculated AF°gg =

-41.8 kcal./mole. These c a l -
culations are discussed i n more d e t a i l i n Appendix A .
Experimentally one may determine the free energy of a mineral i n
several ways, for instance:
1) Rest Potential Measurements i n a C e l l
2) Bomb Calorimetry (enthalpy only)
3) Solution Calorimetry (enthalpy only)
4) Low temperature heat capacity measurements
5) Sulphur a c t i v i t y measurements.
The f i r s t of these methods depends on having a reversible electrode
reaction, involving the mineral, i n which the free energies of the other
products and reagents are known and t h e i r a c t i v i t i e s measurable. This i s
quite possible with simple copper sulphides, as discussed l a t e r , but does

-9-
not appear to have been attempted with a ternary mineral. This was attempted
unsuccessfully i n the present work.
Bomb calorimetry can y i e l d a value f o r the enthalpy of a mineral i f
i t can be combusted to products (oxides) whose heat contents are a c c u r a t e l y
known. This method has been used extensively i n some f i e l d s and some o f the
oft quoted values for sulphides were obtained i n this way. Thus von Warten-
berg (45) measured A H ^ g of Cu^S and CuS, Zeumer and Roth (46) measured
AH°gg of FeS, and Lipin et a l . (47) measured AH°gg of o y r i t e and marcasite.
This method was also attempted i n the present work (Appendix A); no previous
attempt appears i n the l i t e r a t u r e .
Solution calorimetry can also y i e l d a value f o r AH^gg i f the mineral
can dissolve reasonably rapidly (about an hour, maximum) i n a solution where
the product has a known heat content. This method also has been applied to
binary sulphides (48,49) but not ternary sulphides as f a r as can be determined.
The d i f f i c u l t y of dissolving chalcopyrite r a p i d l y , except i n hot solutions,
has probably not encouraged work i n t h i s d i r e c t i o n .
Heat capacity measurements appear to o f f e r the best chance o f obtaining
r e l i a b l e AF°gg values. Kelley (50) has given a useful summary of the r e s t r i c -
tions on this method, which depends c h i e f l y on the a p p l i c a b i l i t y o f the t h i r d
law of thermodynamics. Numerous binary sulphides and oxides have been studied
by t h i s method (51-61) but not ternary minerals. Pankratz and King (62)
measured the high temperature ( 2 9 8 1 0 5 0 ° K ) enthalpies of bornite and
chalcopyrite i n 1970 and low temperature measurements were said to be
i n progress. A recent compilation by the same authors (63) does give stan-
dard free energy and enthalpy values f o r bornite and chalcopyrite (AH^gg =
-45.50 kcal/mole; ^ F ^ g g =
~45-S5 kcal./mole) based on low temperature
measurements. However the source o f the data i s a private communication

-10-
(Stuves, U.S. Bureau of Mines, 1971) which so far (1974) does not appear
to have been published.
By measurement of the p a r t i a l pressure ratio P C /Pu i n

equilibrium
2 2
with a sulphide at a temperature T, one may measure the standard free
energy of formation of the sulphide at that temperature. However, such
measurements can only be c a r r i e d out at high temperatures, and values
at 298°K can only be obtained by extrapolation, using r e l i a b l e values f o r
the s p e c i f i c heat. Although this method has been used extensively for binary
sulphides (64-66), extrapolation to low temperatures i s unreliable (67).
High temperature studies have been made on the Cu-Fe-S system (68) and other
ternary systems (69).
c) Crystal Structure and Bonding
Chalcopyrite has the zincblende structure (70-72), i n which alternate
Zn atoms are replaced by Cu and Fe Atoms. The zincblende structure itself
i s derived from the diamond structure; each Zn atom i s tetrahedrally co-
ordinated to four S atoms, and vice versa. The S l a t t i c e has the fee struc-
ture with the metal atoms i n alternate tetrahedral holes. Due to the s l i g h t
asymmetry caused by alternating Cu and Fe, the unit c e l l i n chalcopyrite i s

o o
twice as large as i n zincblende, and i s tetragonal (a = 5.24 A, c = 10.30 A),
rather than c u b i c However, at 547°C, chalcopyrite undergoes a transform-
ation to a cubic form, presumably due to disordering of the Cu and Fe atoms.
The magnetic structure of chalcopyrite was determined by Donnay et a l .
(73) using neutron d i f f r a c t i o n , i n a pioneering experiment (75). The two
Fe atoms connected to a common S atom were found to be a n t i - p a r a l l e l , re-
sulting i n antiferro-magnetism.
Mbssbauer spectra of chalcopyrite have been reported many times, but
with varying r e s u l t s .
-11-
O Cu ©Fe OS
Fig. 2 Crystal structure of CuFeS

-12-
Vaughan (74) r e p o r t e d a s i x - l i n e h y p e r f i n e magnetic spectrum, which
was i n t e r p r e t e d as o r i g i n a t i n g from m a g n e t i c a l l y o r d e r e d i r o n i n one t y p e o f
site. The observed v a l u e s i n the spectrum s u g g e s t e d m a g n e t i c a l l y c o u p l e d
high spin F e 3 +
in tetrahedral sites. T h i s c o n c l u s i o n i s s u p p o r t e d by o t h e r
work i n the l i t e r a t u r e (76-79), but i n disagreement w i t h t h a t o f C a b r i and
Goodman (80) and p a r t i c u l a r l y t h a t o f Aramu (81), who reported a two-line
spectrum which was i n t e r p r e t e d as o r i g i n a t i n g from the r e s o n a n t c o n f i g u r a -
tion:
Cu Fe S2
+ 3 +
•*-+ Cu^Fe'S**.
T h i s work has been d i s c u s s e d by Hefzenberg (82) and Frank (83) who suggest
"that t h e r e may be two forms o f c h a l c o p y r i t e , one o f which i s p a r a m a g n e t i c .
The bonding i n c h a l c o p y r i t e has been d i s c u s s e d by Vaughan (74) ; i t may
be c o n s i d e r e d i n i o n i c , c o v a l e n t o r m o l e c u l a r o r b i t a l terms. In t h e ionic
i i i O d e l , thfe f e e l a t t i c e o f 3 anions lias a l L e r n a L e "cbtrahedral xioies fillea

3+ +
w i t h e i t h e r Fe o r Cu atoms. In c o v a l e n t terms, the S and m e t a l atoms
3
may be viewed as forming sp bonds, which a r e t e t r a h e d r a l l y d i r e c t e d . The
bond l e n g t h s which are sometimes used as a c r i t e r i o n o f degree o f c o v a l e n c y
are (7):
Cu-S 2.34 A
Fe-S 2.22 A
whereas t h e
„ sum
+ o f the i o n i c r a d i i are ( 1 ) :
Cu + S =
2 .80 o
A
_ ++ o
Cu + S =
2 .56 A
„ ++
Fe + s =
2 .58 X
o
Fe 3 +
+ s =
2 .48 A
In the m o l e c u l a r o r b i t a l approach, t h e r e i s a f i l l e d set of valence
bonds formed by o v e r l a p p i n g s and p o r b i t a l s from metal and s u l p h u r atoms, .
and a h i g h e r energy s e t o f empty a n t i b o n d i n g o r b i t a l s (the c o n d u c t i o n ba n d ) .

-13-
Th e d levels of Cu and Fe may contribute to s d hybridization and create

J
new energy levels between the f i l l e d valence and empty conduction bands,
thus reducing the band gap.
Frueh (84-86), considered that the semi-metallic c h a r a c t e r i s t i c s of
the sulphide minerals j u s t i f i e d a limited application of zone theory, and
determined the important B r i l l o u i n zones of digenite, bornite and chalcopy-
rite. These three minerals have the same basic structure, i . e . cubic clos-
packed sulphur atoms with the i n t e r s t i t i a l tetrahedral holes being i n part
occupied by the metal atoms. Assuming that a l l the outer s h e l l electrons
of each element can contribute free electrons, (Cu one, Fe three, and S s i x
electrons) then the electron/atom r a t i o of the minerals would be:
chalcopyrite 4
bornite 3.2
digenite 2.8
chalcocite 2.7
covellite 3.5.
The p r i n c i p a l B r i l l o u i n zones of these minerals were then calculated
and the electron/atom ratios necessary to f i l l these zones. The electrons
of the f i r s t three minerals just f i l l e d one of the important Brillouin
zones, and i n each instance, the B r i l l o u i n zone just f i l l e d was that con-
structed from the same basic r e f l e c t i o n s . However chalcocite and c o v e l l i t e
did not f i t i n any zone. Frueh concluded that i n the f i e l d from digenite
to chalcopyrite the structural type i s maintained, despite the increase i n
the Fe/Cu r a t i o by the omission of s u f f i c i e n t metal atoms to avoid increasing
the e /atom r a t i o beyond the capacity of the f i l l e d zone.
Vaughan (74) has noted the high s t a b i l i t y of the zincblende structure
is to be expected from such a network of tetrahedrally directed covalent bonds

-14-
similar to those in diamond, and that such a structure is favoured by tran-
sition metal cations with the symmetrical d*' ( F e +++

) and d ^ (Cu ) electron,
+
configurations.
Chalcopyrite is a semiconductor and is reported always to be n^.type
(74,86-88), due to a stoichiometric excess of cations (86). Frueh (86)
studied the resistivity of chalcopyrite, and found that i t increased slowly
with temperature, up to 310°C, at which point it f e l l rapidly. This behaviour
is contrary to the usual semiconductor pattern, in which resistivity declines
with temperature as more electrons are excited across the band gap. In this
case, the conductivity evidently arises from an extra band of electrons,
which are derived from the excess cations; they lie just below the con-
duction band and can be excited into i t with l i t t l e or no activation,
energy. The mineral thus behaves like a metal with a vastly reduced number
of electrons in the conduction band, whose conductivity is inversely airected
by temperature, due to increased thermal vibrations of the lattice. The
rapid decrease in resistivity at 310°C is due to decomposition with sulphur
loss; thus Frueh concluded that i t is impossible to reach the intrinsic
region before the mineral decomposes.
The use of 'chalcopyrite-like' compounds is very widespread in the
electronics industry, and a considerable literature exists on the subject,
particularly in the Soviet sector, due to the work of Poplavnoi (e.g. (87)).
I l l The Leaching of Copper Sulphides
a) An Overview
Despite the impressive array of proposed processes for extracting copper
from chalcopyrite (over forty may be counted in a recent review (4)), there
is comparatively l i t t l e published literature on the fundamental behaviour of
the mineral under oxidizing aqueous conditions. However, there is consider-

-15-
ably more information on the corresponding processes with the binary copper
sulphides - chalcocite (Cu S), digenite (Cu, S)

0 Q and c o v e l l i t e (CuS).
Furthermore, there i s far more known about the electrochemical behaviour
of these minerals, and i t i s useful to consider t h i s information f i r s t . All
of the copper sulphide minerals are semiconductors with conductivities
ranging from 10 ^tt ^cm ^ to lO^fi ^cm ^ , and t h e i r d i s s o l u t i o n reactions
are often considered to be electrochemical i n nature. However, evidence to
support this proposition i s invariably i n d i r e c t , and usually consists of
demonstrating that the anodic reaction driven by an appropriate external emf
w i l l give the same r e s u l t s as the leaching reaction (90). This evidence can,
however, be quite convincing: thus Needes and Nicol (91) showed that the
dissolution rate of UT^ in a v a r i e t y of oxidants corresponded c l o s e l y with
the rate of the anodic reaction r e s u l t i n g from imposing an external emf
appropriate to each oxidant.
Some other evidence for electrochemical reactions on sulphides has come
from studies of the leaching of p y r i t e (92-94), which i s attacked at certain
s i t e s , causing p i t t i n g . These are interpreted as anodic s i t e s . Other work-
ers (95) have demonstrated that the leaching of sphalerite i s catalyzed by
certain metal cations which was accounted for by an electrochemical mechan-
ism. However, Peters and Majima (96) demonstrated that the anodic d i s s o l u -
tion of p y r i t e produced 100% sulphate whereas pressure leaching can produce
up to 50% elemental sulphur (185).
Several reviews of this subject have been published (92,98-101,186).
b) Leaching of Simple Copper Sulphides
Sullivan (102) studied the leaching of natural chalcocite i n powdered
form, with a c i d i f i e d f e r r i c sulphate solutions. The d i s s o l u t i o n occurred i n
two stages: the f i r s t , which was rapid, involved d i s s o l u t i o n of copper to

-16-
form a CuS p h a s e , and the s e c o n d , much s l o w e r , r e s u l t e d i n e l e m e n t a l s u l p h u r
formation:
C^S + Fe (S0 )
2 4 3 -+ CuS + CuS0 4 + 2 FeS0 4 (1)
CuS + Fe (S0 )
2 4 3 -+ C u S 0 4 + S° + 2 FeS0 4 (2)
The r e a c t i o n r a t e was found t o be independent o f [ F e + + +

] above 0.01M
and a l s o l a r g e l y independent o f pH and [Fe + +

].
S u l l i v a n a l s o examined the e f f e c t o f p a r t i c l e s i z e , and c o n c l u d e d t h a t
the d i s s o l u t i o n r a t e was v i r t u a l l y the same f o r s i z e s (-10+28) t o (-150+200).
F o r p a r t i c l e s l a r g e r t h a n t h i s , t h e d i s s o l u t i o n was much s l o w e r , although
t h i s f a c t seems t o have been o v e r l o o k e d . In f a c t , the much s l o w e r leaching
r a t e s o f Thomas et a l (103) (approx. 2%/hour, compared t o 3 0 % / h r . ) can
o n l y be e x p l a i n e d t h i s way.
L a t e r s t u d i e s on the d i s s o l u t i o n o f c h a l c o c i t e and d i g e n i t e have agreed
w i t h the r e s u l t s o f S u l l i v a n ; the mechanism has been r e f i n e d t o i n c l u d e
d i g e n i t e , Cu S, as an i n t e r m e d i a t e p h a s e . Thomas et a l (103), using

1. o
r o t a t i n g s i n t e r e d d i s k s o f s y n t h e t i c c h a l c o c i t e , found t h a t the d i s s o l u t i o n
+++ 0
r a t e was l i n e a r l y dependent on [Fe ] up t o about 0.1M (at 95 rpm and 25 C ) ,
and then appeared t o l e v e l o f f somewhat. A s i m i l a r dependence o f d i s s o l u -
t i o n r a t e upon r o t a t i o n speed was f o u n d . These f i n d i n g s , t o g e t h e r w i t h an
a c t i v a t i o n energy o f 5 k c a l / m o l e , were t a k e n as an i n d i c a t i o n o f a p r o c e s s
c o n t r o l l e d by mass t r a n s p o r t o f r e a g e n t s a c r o s s t h e boundary layer.
Sullivan (102) a l s o examined the l e a c h i n g o f n a t u r a l c h a l c o c i t e powder
w i t h f e r r i c c h l o r i d e s o l u t i o n s , and r e p o r t e d s i m i l a r d i s s o l u t i o n r a t e s (as
with f e r r i c sulphate) at 35°C, but v e r y r a p i d d i s s o l u t i o n at b o i l i n g temp-
eratures. K i n g (104) and B u r k i n (105) a l s o s t u d i e d t h i s r e a c t i o n and found
t h a t the f i r s t stage (50% Cu e x t r a c t e d ) was complete i n 3-4 minutes at 40°C,
but the second r e q u i r e d two hours at 70°C. They found an a c t i v a t i o n energy

-17-
o£ 0.8 kcal for the f i r s t stage and proposed that s o l i d state diffusion of
_ + . ....
Cu ions was rate limiting.
Sullivan (106) and Thomas et a l (107) also studied the leaching of
covellite with f e r r i c sulphate. The stoichiometry of the reaction was found
to be the same as the second stage of chalcocite leaching (equation (2)),
i.e. 100% elemental sulphur formation. The rate, however, was considerably
slower. An activation energy of 22-25 kcal./mole was found, implying that
the process was controlled by a surface reaction. Sullivan found the rate
was unaffected by pH or [ F e + + +
] , but was dependent on particle size, though
not proportionately (see Table 1).
TABLE 1 [from Sullivan (106)]
Dissolution of Covellite i n Ferric Sulphate Solutions at 35°C
-Effect of Particle Size
. Mineral Calculated Area % Dissolved After

(cm / g)
2
5 days 24 days
Butte
- 3+ 10 26 6 9
- 10+ 28 65 10 13
-100+200 385 16 25
-200 4,575 40 56
Kennecott
- 3+ 10 26 14 25
- 10+ 28 65 20 31
-100+200 385 27 41
-200 3,867 42 62
-18-
Sullivan also compared the rates o f c o v e l l i t e leaching i n f e r r i c
chloride and ferric sulphate. At 35°C, leaching was f a s t e r i n f e r r i c sulphate
than i n f e r r i c chloride, but at 98°C, the leaching rates were i d e n t i c a l .
In a l l cases the [Fe ] was unimportant i n the range covered.
This s i t u a t i o n i s to be compared with that o f chalcocite, where the
rate i s f a s t e r i n f e r r i c chloride (102).
Jackson and Strickland (108) studied the leaching o f chalcocite and
c o v e l l i t e by chlorine i n acid chloride solutions; they found exclusive
elemental sulphur formation and a reaction controlled by d i f f u s i o n of chlorine
in the s o l u t i o n .
Oxygen pressure leaching of copper sulphides produces some sulphate,
depending inversely on the a c i d i t y (109-111). Tkachenko and Tseft (112)
studied the f e r r i c chloride leaching of massive chalcocite and found an a c t i -
vation ev.eray nf 4 kcal./mole, i n d i c a t i v e of a d i f f u s i o n process. The reaction
slowed down with time, but was unaffected by changing the s t i r r i n g speed from
100 to 500 rpm. The authors concluded that the rate c o n t r o l l i n g step was
d i f f u s i o n of reagent through the sulphur f i l m .
c) Electrochemical Studies of Simple Copper Sulphides
(i) Thermodynamic measurements
Several authors have measured the rest potentials of the various copper
sulphides (90,113-118). Most o f the early work was done at ambient temper-
ature on natural minerals, but there i s s u r p r i s i n g l y l i t t l e scatter i n the
results. There have been several studies recently using synthetic minerals,
which nevertheless give as much scatter as the former experiments. Etienne
(90), using synthetic stoichiometric mineral mixtures, sintered into disks at
400°C, obtained quite r e v e r s i b l e electrodes above 45°C, with c o v e l l i t e -
digenite and digenite - d j u r l e i t e mixtures. Precise rest p o t e n t i a l s

-19-
(+ 0.35 mV) were o b t a i n e d from these e l e c t r o d e s , but c h a l c o c i t e - djurleite
and c o v e l l i t e - s u l p h u r mixtures d i d not g i v e such r e l i a b l e r e s u l t s . Rick-
ert. and Matheu (117) u s i n g vacuum d e p o s i t e d t h i n f i l m s and a c o u l o m e t r i c
t i t r a t i o n method a r r i v e d at s i g n i f i c a n t l y lower v a l u e s . C o l e (118) , on the
o t h e r hand, u s i n g s y n t h e t i c m i n e r a l s f u s e d i n t o d i s k s at 950°C f o r 30
minutes, and the c o u l o m e t r i c t i t r a t i o n method, o b t a i n e d v a l u e s t h a t were
s i g n i f i c a n t l y h i g h e r than E t i e n n e ' s . The reason f o r these d i f f e r e n c e s
i s not apparent.
TABLE I I
Rest P o t e n t i a l s o f Copper S u l p h i d e s v s . Cu Metal at 25°C
Measured by V a r i o u s Authors
Phases *Etienne (90) Rickert (117) Cole (118) Others
(45-90°C) (15-90°C) (25°C) ( 25°C)
47 (116)
Chalcocite Metastability 127 mV +145 mV 166 (115)
+ Djurleite, Problem ( *5) 134 (113)
Djurleite + 163(± .35)mV 144 +180(±5)mV *
+ Digenite 150 m V
Digenite + 178(± .45)mV 165 mV +200(±5)mV

+ Covellite
Covellite Irreversible 251 mV — 340 (113)

+ Sulphur Electrode
* E x t r a p o l a t e d t o 25°C
-20-
(ii) Stoichiometry
Several workers have studied the anodic dissolution of C^S and CuS,
using either synthetic material (90,116,118,119), natural minerals or matte
anodes (120-126). Most are agreed that the anodic reactions are the same as
found in leaching (equations (1) and (2)). However, Venkatachalam et al and
Loshkarev (120,121) indicated that a significant amount (up to 55%) of sul-
phur was oxidized to sulphate. Other workers generally found 3% or less.
Another important feature observed by several authors is the high CuS con-
tent in the anode slime, which would be a severe drawback to any process u t i l -
izing direct electrolytic refining of copper matte anodes.
( i i i ) Leaching Mechanism
Kuxmann and Biallass (116) studied the anodic dissolution of fused
synthetic chalcocite in acidified copper sulphate solutions, under galvan-
osta.T-i c conditions. They found the dissolution behavi OUT similar to that in
the leaching experiments described above, but the polarization underwent
a sharp increase of about one volt after a certain time, which depended i n -
versely on the current density. Etienne (90) obtained similar results with
synthetic digenite and covellite anodes, and showed the transition time, x ,
was related to the current density, I.

j2 _ _ 2 -4 -1
I T =2.5 amp cm sec .
At the transition, the normal anodic dissolution of CuS is no longer
capable of maintaining the imposed current. A second, higher potential
reaction, probably oxygen evolution or sulphate formation, then takes over.
Kuxmann and Biallass attributed this to the surpassing of the maximum diffu-
sion rate of Cu ions in the solid, because the internal diffusion layer is
+
too deep. This assumes that the Cu ions move through the covellite layer
+
by solid state diffusion as proposed by King and Burkin (104,105).

-21-
Etienne (90), however, considered that the s o l i d state d i f f u s i o n of Cu +
in c o v e l l i t e i s too slow to account for the observed d i s s o l u t i o n rate, and
therefore proposed that there must be aqueous d i f f u s i o n through the shrink-
age pores of the p a r t i a l l y reacted c o v e l l i t e , which are f i l l e d with solution.
At high current densities, or after s u f f i c i e n t l y long times, these pores
would saturate with and p r e c i p i t a t e CuSO^, thus stopping the reaction, and
causing a r i s e i n p o t e n t i a l .
The aqueous pore d i f f u s i o n model resulted from another experiment of
Etienne's, i n which a copper sulphide scale was 'grown' on a copper anode
in an H^S saturated solution, and the i o n i c conductivity of Cu +

ion measured.
In digenite, at 55°C, this was 7.5x10 ^Q, âa \ and i n chalcocite 3.5x10 ^Q. ^cm
In comparison, the observed d i s s o l u t i o n rate of a digenite anode resulted i n
a flux of Cu +
ions through the c o v e l l i t e (product) layer equivalent to an
-4 -1 -1
i o n i c conductivity of 8x10 Q. cm . Since there was no reason to believe
that c o v e l l i t e would have such a high ionic conductivity, i t was concluded
that some other mechanism must account f o r the high flux of Cu +

ions: due
to the decrease in molar volume i n passing from digenite to c o v e l l i t e , there
i s 19.7% of the cross-sectional area occupied by aqueous e l e c t r o l y t e .

This view of the d i f f u s i o n a l processes in the copper sulphides has
been contested by Cole (118), who subjected synthetic chalcocite anodes to
coulometric t i t r a t i o n s , and estimated d i f f u s i o n c o e f f i c i e n t s of Cu +

ion
-8 2
(1.8x10 cm /sec at 25°C) that are 1000 times larger than those calculated
-11 2
by Etienne (2.5x10 cm /sec at 25°C). He therefore concluded that the
s o l i d state d i f f u s i o n of Cu +
ions is_ capable of generating a s u f f i c i e n t flux
to account for the observed d i f f u s i o n rate.

-22-
d) A Note on the Leaching of Bornite, Cubanite and Idaite
Although bornite i s an important copper mineral, e s p e c i a l l y i n B.C., it
w i l l not be considered here, for i t apparently leaches r a p i d l y compared
with chalcopyrite (127,128) and w i l l not therefore be a l i m i t i n g factor
in a process. Furthermore, i t s d i s s o l u t i o n behaviour i s d i f f e r e n t from
that of chalcopyrite, i n that copper dissolves p r e f e r e n t i a l l y . There appears
to be no electrochemical work on bornite, published i n the literature.
Cubanite (CuFe S ) i s reported to leach even slower than chalcopyrite

2 3
(129); fortunately i t i s a comparatively rare mineral.
Nothing i s known about the leaching of i d a i t e (Cu^FeS^) and the very
formula of this rare.mineral i s s t i l l under controversy. However, i t i s re-
portedly the product of bornite leaching (127).
e) Leaching of Chalcopyrite
This reaction i s best treated by covering:each reagent separately,
(i) F e r r i c Sulphate
This reagent has great importance as the active agent i n dump leaching,
as i s practised i n the South Western United States and elsewhere. It was
f i r s t investigated by Sullivan (130) , who showed that hot solutions dissolved
appreciable amounts of copper from f i n e l y divided material, but the rate
appeared to decrease rapidly with time. A s i g n i f i c a n t amount of sulphur
was oxidized to sulphate, and two equations for the leaching reaction were
given:
CuFeS 2 + 2Fe (S0 )2 4 3 + CuS0 4 + 5FeS0 4 + 2S° (3)
CuFeS 2 + 30 2 + 2H 0 + 2 F e ( S 0 ) +
2 2 4 3 CuS0 4 + 5FeS0 4 + 2H S0
2 4 (4)
This observation, that sulphate i s formed, appears to have been missed
by later workers, possibly because of the i n c l u s i o n of oxygen i n the second
equation, instead of:

-23-
CuFeS 2 + 8Fe (S0 )

2 4 3 +-8H 0
2 CuS0 4 + 17FeS0 + 8H S0
4 2 4 (5)
From Sullivan's data,(Table I I I ) , i t can be seen that the r a t i o o f
Cu:Fe:S i n the residue remained nearly constant, i n that there was no
s e l e c t i v e d i s s o l u t i o n ; since more copper was extracted than pure sulphur
liberated some sulphur was undoubtedly oxidized (about 25-35%). The poss-
i b i l i t y that oxygen can contribute to the reaction cannot of course be
ruled out, but appears u n l i k e l y from the general experience that oxygen
reacts extremely slowly under such conditions.
Table I I I [from S u l l i v a n (130)]
Data on Mechanism of Dissolution of Chalcopyrite
i n F e r r i c Sulphate (at 35°C)
Time Copper Dissolved Total Sulphur i n O r i g i n a l Atomic Ratio of

(days) Sample E x i s t i n g i n Cu:Fe:S i n Resi-
Residue i n a form due a f t e r CS
2
Soluble i n CS (%) 2
Treatmemt
(Free Sulphur)
0 - - 1.00:1.18:2.20
1 8.2 5.4 1.00:1.17:2.27
7 14.8 10.4 1.00:1.16:2.23
14 21.8 15.8 1:00:1.17:2.25
21 25.5 19.1 1.00:1.17:2.25
42 30.1 22.6 1.00:1.17:2.17

-24-
Dutrizac et a l . (131) also studied the r e a c t i o n of c h a l c o p y r i t e with
f e r r i c sulphate. To avoid the complications of i m p u r i t i e s and an i n d e f i n -
i t e surface area, they used s y n t h e t i c c h a l c o p y r i t e which was pressed i n t o
disks. The d i s s o l u t i o n r e a c t i o n found was equation ( 3 ) , i . e . no sulphate
formation. The basis f o r t h i s conclusion was a statement that the r a t i o
Fe +++
/ C u ^ produced was
+
close to 5 (as required by equation ( 3 ) ) , r a t h e r
than 17 (equation ( 5 ) ) , and S°/Cu ++

was approximately 2:1. However, no o-
ther experimental data were given.
Dutrizac et a l . found the leaching rate to decrease with time, t ,
according to a p a r a b o l i c rate law:
Cu d i s s o l v e d = -K/t or Rate = K^/tT (6)
This r e s u l t was a t t r i b u t e d to a thickening f i l m of elemental sulphur
on the surface, which retarded the r e a c t i o n . The r e a c t i o n was found to be
independent of pll, l o t a t i o n speed and [Fc . ] above ? very low l e v e l (0,005 M)
but sharply dependent on [ F e ] . + +

I t was concluded that the rate determining
++ o
step was the d i f f u s i o n of Fe ions away from the surface through the S
film. An a c t i v a t i o n energy of 17.3 kcal./mole was determined. This in-
t e r p r e t a t i o n has been c r i t i c i z e d by Roman and Brenner (3) who concluded
that such a high a c t i v a t i o n energy must be due to chemical c o n t r o l , and
Peters (132) who suggested that the p a r a b o l i c d i s s o l u t i o n r a t e could be due
to the d i f f u s i o n of s o l i d s t a t e defects out to the surface of the mineral.
Dutrizac et a l . also found that n a t u r a l massive c h a l c o p y r i t e leached
about 15 times slower than s y n t h e t i c m a t e r i a l . They claimed that the same
p a r a b o l i c rate law applied however, but the data appear to be i n s u f f i c i e n t
t© v e r i f y t h i s . The slower leaching rate was a t t r i b u t e d to the reduced
p o r o s i t y of the n a t u r a l m a t e r i a l .
This postulate has been affirmed i n another p u b l i c a t i o n by the same
-25-
authors (133) i n which natural chalcopyrite was crushed and then pressed
into a disk l i k e the synthetic mineral. The r e s u l t s showed that the presse
disk of natural mineral also reacted r a p i d l y . This same paper also showed
that impurities can s i g n i f i c a n t l y affect the rate presumably due to gal-
vanic e f f e c t s . More noble sulphides (or rather more passive) such as p y r i t
and molybdenite accelerated the rate, whereas less noble ones (galena)
decreased i t .
Lowe (134) also examined the k i n e t i c s of f e r r i c sulphate leaching of
chalcopyrite and found the reaction to be independent of pH and [Fe + + +

],
and therefore concluded that the r a t e - c o n t r o l l i n g step was a surface elec-
trode reaction involving chemisorbed f e r r i c ions. An a c t i v a t i o n energy of
17.8 Kcal was calculated. The experimental data for these calculations
consisted only of F e + + +
ion consumption; the stoichiometry was assumed to
be that of equation (3).
( i i ) F e r r i c Chloride
F e r r i c chloride has been u t i l i z e d for leaching chalcopyrite for many
years, for i t was recognized that i t was a f a r stronger reagent than f e r r i c
sulphate. Forward and Warren (135) have summarized the early work. How-
ever, there i s l i t t l e i n the way of published data comparing the two rea-
gents except for a few results of S u l l i v a n (130), and Pike et a l . (136).
Most of the investigators seemed s a t i s f i e d with the a b i l i t y of f e r r i c chlor-
ide to extract the copper from chalcopyrite and concentrated on the diffi-
cult problems of the rest of the process, such as reagent regeneration and
copper recovery.
Sullivan (130) reported that stronger solutions ( i . e . more con-
centrated i n [ F e + + +
] ) were b e n e f i c i a l , which was not true in f e r r i c s u l -
phate leaching. Fine grinding and high temperatures also increased the
-26-
rate of extraction, as expected.
A more complete examination of the leaching reaction was undertaken
by Haver and Wong (137); they reported excellent d i s s o l u t i o n rates (essen-
t i a l l y 100% extraction i n one hour) on f i n e l y ground material with strong
([Fe + + +
] ) solutions at reflux temperatures (106°C). The stoichiometry of
the reaction was found to be
CuFeS 2 + 3FeCl 3 4FeCl 2 + CuCl (7)
rather than
CuFeS 2 + 4FeCl 3 5FeCl 2 + CuCl 2 + 2S° (8)
By using a constant volume of solution (212 g/1 F e + + +

) the s t o i c h i -
ometry was revealed by varying the quantity of concentrate. Thus i t was
found that 2.7 pounds of F e C l 3 were needed per pound of concentrate (equa-
tion (7)) rather than 3.5 pounds (equation (8)). Since the reaction
FeCl 3 + CuCl + CuCl 2 + FeCl 2 (9)
goes r e a d i l y i t i s apparent that the actual leaching agent i n the l a t t e r
part of the leach (when F e C l 3 i s used up), must be CuCl,,, i . e . :
CuFeS 2 + 3CuCl + 4CuCl + F e C l

2 2 + 2S° (10)
Haver and Wong reported that agitation s l i g h t l y decreased the disso-
lution rate; Roman (3) commenting on this unexpected r e s u l t , suggested
that a reaction product such as CuCl 2 might have a c a t a l y t i c e f f e c t . This
had been reported on work on chalcocite (138,139). This suggestion i s
supported by the results described herein.
A large temperature dependence was demonstrated by Haver and Wong,
but appreciable d i s s o l u t i o n did not take place below 80°C.
The leaching curves (Figure 3) also show that for a l l temperatures
a very high proportion of the t o t a l copper that i s extracted (within 2
hours) actually dissolves by the time of the f i r s t sample ( f i f t e e n

LEACH T I M E , min
Fig. 3 L e a c h i n g of c h a l c o p y r i t e c o n c e n t r a t e i n f e r r i c c h l o r i d e ; e f f e c t o f temperature,
showing t h e change i n r a t e a f t e r 15 minutes (from Haver and Wong^ ' ). 137 )
-28-
minutes).*
Thus the d i s s o l u t i o n i s extremely rapid i n i t i a l l y , and then slows
down by an order of magnitude. P r a c t i c a l leaching therefore must aim
at extracting the copper almost e n t i r e l y i n the f i r s t period. The
reason for t h i s slower rate may be the buildup of a sulphur f i l m .
Ermilov (140) investigated the leaching of massive specimens i n
f e r r i c chloride and reported that the d i s s o l u t i o n rate depended l i n e a r l y
on [Fe + + +
] i n the range 50 -+ 150 g/1. This i s contrary to the findings of
Klets and Serikov (141), who reported that the [ F e + + +

] was not important
i n the d i s s o l u t i o n of Ni-Cu concentrates. Ermilov also found that the
sulphur f i l m produced during the reaction did not slow down the d i s s o l u -
t i o n which was l i n e a r with time. This r e s u l t i s not necessarily i n con-
f l i c t with the above i n t e r p r e t a t i o n of Haver and Wong's two-part leaching
curve. In the l a t t e r case the p a r t i c l e s were ground to an average size
of only 3 p; and larger p a r t i c l e s exhibited a much reduced i n i t i a l d i s -
solution.
Hence the i n i t i a l d i s s o l u t i o n on a massive specimen might well be
n e g l i g i b l e and the actual d i s s o l u t i o n measured by Ermilov would then cor-
respond to the slow second part of Haver and Wong's leaching curves.
The production of sulphate i n f e r r i c chloride leaching i s reported
to be small (137) f2-4%) but s i g n i f i c a n t when one considers:that 3% s u l -
phate r e s u l t s i n a 12% higher consumption o f f e r r i c chloride:
CuFeS 2 + 3.36.FeCl '+' 0.24 H'0 -*• CuCl + 4.36 F e C l

3 2 2 + 1.94 S° + .36 HCl
+ .06 l^SO^ ' (11)
This phenomenon i s masked somewhat by the authors' decision to draw

the d i s s o l u t i o n curve from 15 minutes instead of zero time.
to
LEACH T I M E , min
Fig. 4 L e a c h i n g o f c h a l c o p y r i t e c o n c e n t r a t e i n f e r r i c c h l o r i d e , e f f e c t of p a r t i c l e size
(as g r i n d i n g t i m e ) . (From Haver and W o n g ^ 137

^).
-30-
However, i t i s possible that the sulphate arises from p r i o r oxidation
of the concentrate, during grinding, f l o t a t i o n , shipping or storage.
In addition to many early i n d u s t r i a l attempts to use f e r r i c chloride
(135), two recent patents haye been issued Which u t i l i z e the reagent (142,
143). In the Cominco process (142) a single leach at atmospheric pressure
(106°G) i s used, and complete extraction i s obtained i n only 9-12 hours,
using strong solutions (200 g./l.) and reground concentrates. In agree-
ment with the work of Haver and Wong, less FeCl^ i s required than needed
by equation (8), thus f i n i s h i n g up with some cuprous (approximately 50%
of t o t a l Cu) i n the f i n a l solution; beyond t h i s point leaching with CuC^
apparently became too slow.
The process proposed by Duval (143), i s also i n agreement on this
point. However the extractions obtained by them at atmospheric pressures
(106°C) were considerably lower than those of Cominco (142) or Haver and
Wong (137). Because of t h i s , Duval chose a two-stage counter-current
leach: j
'. Fresh Concentrate

— v.
I CuCl., Leach i Pregnant Solution (50% Cu ,50% C u )

+ ++
j " 106°C | — " " • —

I , ._. • Tp Stripping
1
i
V i
'Partially
Cu Soln. .Leached
j. ' Concentrate
j FeCl, Leach I Regenerated

| 140°C <
[ _ _ _ _j and Stripped Solution
-31-
The strong FeCl^ leach, which s t r i p s the remaining Cu values out of
the p a r t i a l l y leached concentrates, i s conducted at 140°C, because the
106°C leach required 12 hours. The CuCl^ leach has two purposes:
1) Reduces the quantity o f FeCl^ required
2) P a r t i a l l y reduces the cupric solution to cuprous i n preparation
for e l e c t r o l y s i s .
The requirement that the FeCl^ leach (Duval) be conducted i n a pressure
vessel i s a s i g n i f i c a n t escalation i n cost, which the Cominco process i n -
dicates i s not required. The reason f o r this c o n f l i c t i n g result l i e s prob-
ably i n the type of concentrate leached and i t s p a r t i c l e size. At any
rate the extremely fast reactions obtained by Haver and Wong (on a Nevada
concentrate) may not be obtainable on a l l chalcopyrite concentrates.
( i i i ) Other Oxidants
Several other oxidizing agents have been extensively studied, but
w i l l not be considered i n d e t a i l here except as they contribute to a gen-
eral understanding of the anodic d i s s o l u t i o n of chalcopyrite. This does
not r e f l e c t a preference for f e r r i c solutions as reagents; however, the
emphasis of the present work has been on understanding the leaching by
f e r r i c solutions as a matter of convenience, i n l i n k i n g electrochemical
results with p r a c t i c a l leaching conditions.
At s u f f i c i e n t l y high temperatures and pressures, oxygen w i l l dissolve
chalcopyrite at p r a c t i c a l rates. In strongly acid solutions, iron and
copper both go into solution, and the y i e l d of elemental sulphur i s high (144).
At higher pH, iron i s hydrolyzed and sulphur i s largely oxidized to sulphate
(145). In ammoniacal solutions, intermediate sulphur species, p a r t i c u l a r l y
thiosulphate, 5^0^ , are formed. Sherritt-Gordon u t i l i z e s the NH^-02
system to dissolve chalcopyrite-pentlandite concentrates (146) and the new

-32-
Arbiter process (147) also uses NH^-O^.
N i t r i c acid i s an e f f e c t i v e oxidizing agent for chalcopyrite (148-
150) but the chemistry of the d i s s o l u t i o n reaction i s complex. In addition
to the p o s s i b i l i t y of sulphate formation, there i s a complicated dependence
on n i t r i c acid concentration. Both NO., and NO may be produced i n the
reaction, but NO^ can further react with the sulphide, or react with water
to form more n i t r i c acid and NO. At high acid strengths, NO,, i s lost by
evolution and elemental sulphur i s oxidized to sulphate; thus the effi-
ciency of the reaction, i n terms of copper extracted, i s decreased a l -
though the rate of reaction i s increased. In d i l u t e acid the NO and N0 2
may be trapped within the s o l u t i o n , and re-oxidized by 0 , the n i t r i c

2
acid thus acting as a catalyst.
f) Electrochemical Studies on Chalcopyrite
Springer (151) examined the semiconducting properties of chalco-

2
pyrite by measuring the anodic p o l a r i z a t i o n up to 10 mA/cm and found no
saturation current, as expected for an n-type semiconductor (152). Zevgolis
(89) also measured anodic p o l a r i z a t i o n s , at much higher voltages, and found

2
a saturation current at about 50 mA/cm above 3 volts (vs. S.C.E.). He
concluded that the hole density in chalcopyrite determines the value of
the l i m i t i n g anodic current. This conclusion was supported by an i l l u m -
ination experiment which increased the current, presumably due to the
increased concentration of holes (152). However, the 200 watt illuminator
used shone d i r e c t l y on the mineral specimen, and raised the bath_ temper-
ature by 4°C. The r e s u l t i n g heat effect was not corrected for.
Zevgolis also examined the stoichiometry of the anodic d i s s o l u t i o n
reaction (in 1.5M l^SO^ at 30°C) and claimed 100% current e f f i c i e n c y for
the reaction:
-33-
CuFeS 2 - 4e ->• C u + +
+ Fe + + + 2 S
(12)
However, the author a p p a r e n t l y made an e r r o r in calculating current
e f f i c i e n c y , f o r o n l y 50% o f the c u r r e n t i s a c t u a l l y accounted f o r by
reaction (12). T h i s may be seen by examining F i g u r e 5, r e p r o d u c e d from
r e f e r e n c e (89).
0.8
I (ma)
Fig. 5 Anodic d i s s o l u t i o n of c h a l c o p y r i t e . Solution
analysis from Zevgolis^^.
-34-
The solid lines are theoretical lines generated from Faraday's Laws
A.
1
Ix
i " F
8. = Electrochemical conversion at an electrode of suhstance i (grams)

l
A^ = Equivalent weight of substance i
= Molecular weight/number of.electrons in reaction
I
= M../n
F = Faraday's constant (96,500 coulombs/equivalent)
I = Current (amps)
T = Time (seconds)
h ( i\ I
M
T \ nF /
If the reaction is equation (12), then n = 4. For Cu:
mi 1liprams
I
i
ix I
Q j . i ' r J
= 1.53x10' / amp = 9.2x10 m i _ ^
n u t e
T \4x96,500/
Thus the expected shope will be :
0.0092 mg/min-mA for CU
0.0081 mg/min-mA for Fe
i f n = 4.
•In Zevgolis' figures the actual slopes are: 0.0050 (Cu)
0.0042 (Fe).
Therefore n must be approximately 8, instead of 4, and half of the
electrons are unaccounted for. This may also be seen from other data in
Zevgolis' work, e.g. 3 hours at 160 mAmps produced 148 mg of Cu (Figure
26 (89)). From.this, n = 7.8.

-35-
Oki. and co-workers (126,154,155) have s t u d i e d the anodic reactions
o f CuS and CuFeS2 at h i g h current d e n s i t i e s . The CuS e l e c t r o d e suffered
a very l a r g e p o t e n t i a l (40 v o l t s ! ) i n c r e a s e a f t e r a c e r t a i n time, which
was a t t r i b u t e d t o CuSO^ p r e c i p i t a t i o n i n agreement w i t h Etienne (90).
However, up t o t h i s p o i n t the r e a c t i o n went smoothly, p r o d u c i n g elemental
sulphur:
CuS - 2e" -y C u + +
+ S° (13)
as noted b e f o r e . The CuFeS 2 e l e c t r o d e p o t e n t i a l ( i n IM H S 0 2 4 > 25°C) was
shown t o be dependent on [Fe ] , [Cu ] and [Fe ] i n dilute solutions
o f these ions (10~ 3

-> 1 0 " M) .
2
Anodic p o l a r i z a t i o n s o f CuFeS 2 were c a r r i e d out at 10 -> lOOmA/cm ,
r e s u l t i n g mainly i n the r e a c t i o n
CuFeS 2 - 5e" -»• C u + +

+ Fe 3 +
+ 2S° . (14)
Seventy-five percent c u r r e n t e f f i c i e n c y was r e p o r t e d f o rthis reac-
t i o n , independent o f c u r r e n t density. [Fe ]+ +

was low compared t o [ F e + + +
].
IV Electrochemical Experiments i n Aqueous S o l u t i o n s above 100°C
In the e x i s t i n g l i t e r a t u r e on the e l e c t r o c h e m i c a l b e h a v i o u r o f s u l -
phides, there i s an e v i d e n t d i s t i n c t i o n between those m i n e r a l s which e q u i l -
i b r a t e under normal l a b o r a t o r y c o n d i t i o n s and those which do not. Thus
i n the b i n a r y copper s u l p h i d e system i n v e s t i g a t e d by E t i e n n e (90), Cole (11
and o t h e r s , u s e f u l thermodynamic data can be o b t a i n e d from r e s t p o t e n t i a l s
i n the range 25 - 85°C, w h i l e i n the i r o n s u l p h i d e system o n l y mixed
p o t e n t i a l s are o b t a i n e d (153) and p a s s i v i t y i s p r e s e n t (96). The copper-
i r o n sulphur system, as i n v e s t i g a t e d h e r e , u n f o r t u n a t e l y falls rather
w i t h i n the l a t t e r c l a s s o f m i n e r a l s and i t i s p a r t l y f o r t h i s reason t h a t
h i g h temperature s t u d i e s have been c a r r i e d o u t , i n hope t h a t diffusion

-36-
processes can be speeded up and equilibrium more nearly attained,
a) State of the Art
High temperature electrochemistry i s a r a p i d l y developing s u b - f i e l d
with i t s own s p e c i a l i z e d technology. A recent conference (156) and review
article (157) have summarized the state of the a r t . Three p a r t i c u l a r ex-
perimental d i f f i c u l t i e s arise when attempting to make electrochemical
measurements at high temperature:
1) The pressure vessel design and the nature o f the l i n e r , to prevent
contamination.
2) The design of the insulated e l e c t r i c a l connections.
3) The reference electrode.
Pressure vessels have sometimes been used f o r electrochemical experi-
ments without l i n e r s , but the a p p l i c a t i o n s are generally l i m i t e d to non-
chloride solutions, f o r the high n i c k e l a l l o y s are known to be subject to
stress corrosion cracking i n chloride solutions.
Liners are generally made of m e t a l l i c , ceramic or p l a s t i c (fluoro-
carbon) materials. The precious metals have high corrosion resistance and
are commonly used (161,162) but place economic l i m i t s on the s i z e o f the
autoclave. S i l i c a t e materials are s i g n i f i c a n t l y soluble i n many high
temperature solutions and can give misleading r e s u l t s (163). T e f l o n and
other fluorocarbons appear to give o f f f l u o r i d e s above 200°C (158,159)
but t h i s problem can be reduced by pre-heating (160).
Electrode leads can be s e a l e d i n t o pressure vessel walls by several
methods but mainly the choice l i e s between a m e t a l l i z e d ceramic s e a l , such
as a spark plug, and a compression seal. Compression seals, which are the
most widely used and are commercially a v a i l a b l e , form a pressure-tight
connection by compressing an i n s u l a t i n g material around the electrode lead

-37-
Teflon or soapstone are generally used f o r the i n s u l a t i n g material. The
Aminco seal (164), the Conaxseal (165) which can carry multiple leads, the
Bridgeman seal (166) and mineral insulated cable (167) have a l l been used.
Teflon tends to extrude under high pressure and temperature (about 250°C)
and specialized designs (160) or a i r cooling f164) may be necessary to
exceed this limit.
Reference electrodes may be used i n t e r n a l l y or e x t e r n a l l y , with re-
spect to the autoclave. The disadvantage of an internal electrode i s that
i t must be calibrated f o r high temperatures; external electrodes require
either a pressure-reducing device (168) to connect them to the c e l l or a
method of containing the pressure externally (165).
Internal reference electrodes can either be primary (hydrogen electrode)
or secondary. The use of a platinum/hydrogen electrode does not seem to
have serious drawbacks (169,170), other than the inconvenience of main-
taining a given p a r t i a l pressure of hydrogen, and a s l i g h t s o l u b i l i t y of
platinum in high temperature aqueous solutions (157).
Lietzke and coworkers have carried out an extensive series of re-
ference electrode evaluations, some of which have been summarized (171).
The following electrodes have been used :
Ag/AgCl
Ag/AgBr
Ag/AgI
Ag/Ag S0 2 4
Hg/Hg Cl 2 2
Hg/Hg S0 2 4
Pb0 /PbS0
2 4
-38-
The AgCl electrode has been widely used and calibrated up to 275°C
(160,170); i t has the disadvantage of s i g n i f i c a n t s o l u b i l i t y above 100°C.
To overcome this the AgBr (172) and Agl (173) electrodes have been used.
The former i s reported to be less r e l i a b l e than AgCl (174). AgÔ^
electrodes appear to be suitable for use i n s u l f u r i c acid up to 200°C
(175). Ph^Cl^ (calomel) and hk^SO^ electrodes are reported to be un-
stable at high temperature (175,176).
A comprehensive review of this subject has been published by Ives
and Janz (177), and also by Jones and Masterson (157).
b) Application to Sulphide Minerals
Electrochemical studies on sulphide minerals appear to have been
limited to solutions below the b o i l i n g point. The p a r t i c u l a r problem that
arises when studying sulphides i s that of the connecting leads to the min-
e r a l . Due to the semiconducting properties, care must be exercised to avoid
a r e c t i f y i n g junction; this can be done by having a low current density
at the connection interface, or by using two leads, one f o r current and
one for p o t e n t i a l . Primarily, previous workers have used the f i r s t a l -
ternative (90,153) and this may be accomplished by a mercury contact,
s i l v e r solder, graphite-impregnated glue or other means. Mercury contacts
were found to be unsuitable, f o r the mercury penetrates the pores of the
mineral at high temperatures, whereas S i l v e r solder i s l i a b l e to con-
taminate the electrode with Ag +

ions. Epoxy cement remained i n s u f f i c i e n t l y
conductive despite l i b e r a l doses of graphite. The problem was solyed using
pressed Pt wires in holes d r i l l e d c a r e f u l l y to a p r e s s - f i t size.

-39-
B. EXPERIMENTAL
Four types of experiments were carried out on chalcopyrite:
1) Leaching experiments - on powder and massive specimens
2) Anodic Polarizations - current/voltage scans
3) Constant Potential experiments
4) Mixed Potential experiments.
The leaching experiments were carried out in f e r r i c sulphate and f e r r i c
chloride solutions, primarily at 90°C, to determine reaction rates, s t o i c h i -
ometry and possible mechanisms. Mainly high grade chalcopyrite was used,
but some experiments were done with a variety of commercial copper concen-
trates, from various mines.
The anodic polarizations were done in order to determine the shape
of the current/voltage curve for chalcopyrite and i t s dependence on the
major variables such as scanning speed, temperature and solution.
The constant potential experiments were of two kinds: One in which
the current/time relationship f o r chalcopyrite at a given potential was
determined, and the second, more involved, i n which the chemistry of d i s -
solution of chalcopyrite was determined.
Mixed potential experiments simply consisted of measuring the e l e c t -
rode potential of chalcopyrite while under leaching conditions. These
experiments provide the link between the leaching and electrochemical
experiments.
I Apparatus
Leaching experiments on powder were carried out i n an apparatus as
shown in Figure 6, using either mechanical or magnetic stirring.

4
I 2 3 5
i 7 *
1 Heaters
2 T h e r m i s t o r probe
8 3 Sampling tube, w i t h frit
4 Gas o u t l e t
5 Gas inlet
6 Stirrer
7 Meoprene Bung i
O '
8 Water b a t h , 12 l i t r e , pyrex I
9 Leaching v e s s e l , 1 l i t r e , pyrex
10 Magnetic stirrer
10
o
Fig. 6 Apparatus f o r leaching powdered c h a l c o p y r i t e .
-41-
Leaching with mechanical s t i r r i n g was performed with s i m i l a r appara-
tus except that the sample tube was removed and a mechanical s t i r r e r (glass
rod) i n s t a l l e d above the leaching vessel.
Leaching experiments on massive chalcopyrite were performed in appara-
tus as shown i n Figure 7.
1 Heater
2 Specimen mounted i n epoxy
(as F i g . 11)
3 Gas outlet
4 Gas inlet
5 Thermistor probe
6 ' Leaching vessel, pyrex (750 ml)
Magnetic s t i r r i n g bar
Magnetic s t i r r e r
38
Fig. 7 Apparatus f o r leaching massive specimens.

-42-
A l l electrochemical experiments were done i n large H - c e l l s , construct-
ed of two 1 - l i t r e Berzeli.us beakers joined by a short tube containing a
f i t t e d disk, 30 mm O.D. Magnetic s t i r r i n g was used f o r both compartments,
but temperature and atmospheric control was maintained only i n the anode
cell. Two such c e l l s were used, one exclusively f o r low temperature
(<100°C) experiments and one for a l l temperatures -6°C -»- 190°C. In the
low temperature c e l l neoprene bungs served as c e l l l i d s ; i n the high temp-
erature c e l l s i l i c o n e rubber was used i n the (unheated) cathode cell,
whereas a s o l i d Teflon bung was used i n the anode compartment. A thin
(3/8") plate of s i l i c o n e rubber on top of the Teflon served to hold the
various electrodes, etc.
For experiments at atmospheric pressures only one heater was employed,
and a gas bubbler i n s t a l l e d (not shown). For high temperature experiments,
(ins?Hf? P T^ sssi ?
r iv
v p c c p i two heaters v ere used, and the inert ?.tmosph-re
T
supplied by the pressure vessel atmosphere.
Mixed potential experiments (measurement of electrode p o t e n t i a l under
leaching conditions) were carried out i n the large H-cell (Figure 10).
a) Pressure Vessel Design
A large pressure vessel (Figures 8, 9 ) was designed and b u i l t to do
the electrochemical experiments at high temperatures, using the duplex
system, i . e . with an i n t e r n a l pyrex c e l l (shown in Figure 10). A c y l i n -
d r i c a l shape was used with the inside dimensions, 12" (diameter) x 18"
(high). The walls were constructed of a single welded s h e l l of type 304
s t a i n l e s s s t e e l , (3/8" thick x 12" I.D. x 18"). The base-plate and top-
plate were s i m i l a r l y constructed of 304 s t a i n l e s s s t e e l (1/2" thick x 14"
<j>) . Steel backing plates (1" thick) were added f o r extra r i g i d i t y . The
-43-
1
/
/
/
z z z i •fez ZZZ7J | / / / / / | ] [ k m
•
1 Gas i n l e t 5 Base (and t o p ) p l a t e
2 P r e s s u r e 'Gauge 6 C o n a x p r e s s u r e s e a l s (3)
3 Cylindrical shell 7 Backing plates
4 Bolts (8) 7/8" O.D. 3 Gas o u t l e t

Fig. 10 Electrochemical c e l l
-46-
1 Potential-scanning lead i
° Platinum
2 Current-carrying lead ' .025"
3 Teflon insulation
4 Pyrex tube
5 M i n e r a l specimen
6 Epoxy
F i g . 11 E l e c t r o d e mounting
-47-
whole p r e s s u r e v e s s e l was b o l t e d t o g e t h e r by long b o l t s (7/8" <|>) p a s s i n g
through both b a c k i n g p l a t e s . The p r e s s u r e s e a l was m a i n t a i n e d by rubber
O-rings s e t i n grooves at the top and bottom o f the s h e l l .
The p r e s s u r e v e s s e l was designed t o be used up t o 250 p s i , w i t h a
safety factor of f i v e . Tbe main l i m i t a t i o n t o the p r e s s u r e i s the bending
of the e n d - p l a t e s , c a u s i n g leakage around the O - r i n g s . So f a r t h i s was
never encountered.
The p r e s s u r e v e s s e l was b o l t e d t o g e t h e r i n such a way t h a t , when the
bottom nuts were unscrewed, the t o p - p l a t e s c o u l d be l i f t e d c l e a r o f the
base, t o g e t h e r with the b o l t s and s h e l l , l e a v i n g the bottom p l a t e s f r e e
and clear.
T h i s f a c i l i t a t e d adjustments t o the c e l l and e l e c t r i c a l connections.
The H - c e l l s a t on the magnetic s t i r r e r s on the base p l a t e and was
h e l d i n p l a c e by a clamp and a s m a l l s t r u c t u r a l p i e c e l i g h t l y screwed into
the base.
All electrical c o n n e c t i o n s were made through t h r e e Conax s e a l s which
were screwed i n t o the base p l a t e , (holes were cut i n t o the b a c k i n g plate).
T h i s enabled the top assembly t o be l i f t e d c l e a r , with no e l e c t r i c a l leads
attached. One Conax s e a l (PL-16-6) c a r r i e d the power l e a d s (two h e a t e r s
and two s t i r r e r s ) , another (PL-16-2) c a r r i e d the two p o t e n t i a l s e n s i n g leads
to the p o t e n t i o s t a t (working and r e f e r e n c e e l e c t r o d e s ) . The l a s t (Pl-16-6)
c a r r i e d two c u r r e n t - c a r r y i n g leads t o the p o t e n t i o s t a t (working and a u x i l i -
ary e l e c t r o d e s ) two thermocouple l e a d s , and two t h e r m i s t o r l e a d s .
All these leads were 16 gauge copper wires encased i n Teflon f o r i n -
s u l a t i o n and p r e s s u r e s e a l i n g , (as s u p p l i e d by t h e m a n u f a c t u r e r ) , with
the e x c e p t i o n o f the thermocouple leads which were chromel and alumel.
These were encased i n "Heat-Shrink" ( t e f l o n ) and s u b s t i t u t e d f o r the

-48-
copper leads i n the Conax s e a l , which was modified s l i g h t l y to accept the
s l i g h t l y larger diameter of these wires.
P u r i f i e d nitrogen (Canadian Liquid A i r L-grade, 20 ppm 0 ) was

2 ad-
mitted through a one-way valve i n the top plate and released through a one-
way valve i n the s h e l l . A pressure gauge was attached to the i n l e t pipe.
An inert atmosphere was achieved by flushing the autoclave at least s i x
times with L-grade N , 2 i . e . pressurizing to 50 psig and releasing. This
expensive method was adopted after abandoning attempts to evacuate the
autoclave with an oil-pump, which frequently and unpredictably resulted in
flushing of the c e l l solution. The work described in preliminary experi-
ments was, however, carried out i n this way.
b) Electrode Design (For Sulphide Minerals)
Small pieces of chalcopyrite, cut to approximately 1/2 x 1 x 1 cm.,
were used as specimens. Two holes, each 0.025" i n diameter and 3/32" deep
were d r i l l e d into the back and 0.025" Pt wires (10" long) pressed into them.
Teflon spaghetti tubing was s l i d over each wire and the specimen placed
face down i n a 1" cf) s i l i c o n e rubber mold. An epoxy cement, consisting of
100:20 Epon 828: Shell Curing Agent Z, was poured i n to a depth of at
least 1/2" and cured at 80°C for at least four hours. A fresh surface of
chalcopyrite was obtained by cutting a thin s l i c e o f f the front of the
specimen with a thin blade (0.020") diamond saw. To prevent excess wear
on the diamond saw blade, unnecessary epoxy on the sides of the specimen
was removed with the belt sander.
In e a r l i e r work a fresh surface was obtained by grinding o f f the
epoxy with a polishing wheel, but polishing appeared to affect the prop-
e r t i e s of the specimen.
Other electrode designs were t r i e d . A two-part Teflon assembly that

-49-
screwed together was desirable because i t would allow ready examination of
the specimen, but at 2oo°C no design could be found which would r e l i a b l y
prevent leakage of the solution into the i n t e r i o r of the holder. Silicone
cement was t r i e d , but i t dissolved at 200°C i n d i l u t e HCl. 'Sauereisen'
cement lost i t s adhesive properties under these conditions. Mercury con-
tacts were t r i e d , but the mercury rapidly leaked through the fissures
in the specimen.
The epoxy used was capable of withstanding IM HCl at 200°C for several
hours; a normal epoxy using DETA as curing agent did not stand up. No
chemical dissolution or wear of the epoxy electrodes as used was observed.
c) Reference Electrode
The Ag/AgCl electrode was used as a reference electrode; i t has the
advantages of ease of construction, wide range of temperature a p p l i c a t i o n
and well established properties. The major disadvantages were that i n
strong chloride solutions i t dissolved at high temperatures, and i n cath-
odic experiments i t acted as an oxidizing agent. For the l a t t e r a p p l i -
cation, the Agl electrode was calibrated but more complete work was later
discovered i n the l i t e r a t u r e (173).
The work of Greeley (178) c a r e f u l l y documents the properties of the
AgCl electrode, and his methods of preparation were followed. A mixture
of s i l v e r oxide, (Ag20) with s i l v e r chlorate (AgClO^) (20%) was made into
a paste with water, and a platinum s p i r a l (0.015" thick, and approximately
1/8" (j)) coated with i t . This was f i r e d at 650°C f o r f i v e minutes. The
procedure was repeated twice more. Several.such electrodes gave i d e n t i -
cal potentials, within the precision required i n this work (+ 0.5 mV), and
the predicted potential versus a freshly prepared calomel electrode.

-50-
II Chemicals
Double-distilled water was used i n a l l cases. A l l chemicals (reagent

/
grade) were used as received from the manufacturer with the exception of
barium chloranilate, (used i n the sulphate analysis) which was freshly
prepared, as described by Agterdenbos and Martinius (181) .
III Instrumentation
Two potentiostats were used: Wenking 68TS10 and Wenking 70HV1/90.
For scanning experiments, a Wenking SMP 66 scanning motor potentiometer
was used. Working electrode potentials were measured with a Wenking Poten-
tiometer PPT 69. Total coulombs passed i n an experiment were monitored
by a Varitech Coulometer; Sargent SR recorders were used to record potential
or current as a function of time.
Heating of the electrochemical c e l l was achieved by internal 'Glo-
quartz' heaters (410 watt), and controlled by thermistors set i n a pyrex
well connected to a Yellow Springs Temperature Controller. The tempera-
ture of the c e l l was independently monitored by a Chrome1-Alumel therm-
couple set i n another pyrex well. The thermistor leads (thermistor i t -
s e l f + guard wire) were cut in order to pass through the Conax seal, and
joined up on the other side. This did not appear to have a detrimental
effect.
IV Analysis
Copper i n solution was o r i g i n a l l y measured by the Cuproin method (179)
(Section I) but this was soon abandoned i n favour of atomic absorption.
However the Cuproin method was used f o r simultaneous [Cu ] and+

[Cu ]
++
-51-
determination. The O-Phenanthroline method (179) was used to determine
[Fe ] and [Fe ], (with or without hydroxylamine hydrochloride). Sul-
phate concentrations were measured by the Barium Chloranilate method, using
the UV band at 332 my (180) and modifications suggested i n reference (181) ;
Dowex 50-W r e s i n , in a v e r t i c a l column, was used to remove cations.
Spectrophotometric measurements were made on a Beckman DV instrument,
equipped with a photomultiplier and voltage stabilizer.
Atomic absorption measurements were made on a Unicam SP90 instrument.
Corrections were made for iron, chloride and sulphate contained i n the
solution. The quantity of ferrous ions produced during f e r r i c sulphate/
chloride leaching was measured by the eerie sulphate t i t r a t i o n method (182)
using Ferroin (1,10 O-phenathroline ferrous sulphate) as i n d i c a t o r .
V Source of Chalcopyrite used ^
A l l electrochemical experiments and most of the leaching experiments
were done using specimens of chalcopyrite cut from the same rock, a high
grade lump about 4" in diameter obtained from the Craigmont Mine, through
the courtesy of G. Bacon. The p u r i t y of this specimen was exceptionally
good: X-ray, microprobe, chemical and microscopic analysis revealed no
sulphides other than chalcopyrite which had the stoichiometric composition
(34.9% S, 34.6% Cu, 30.5% Fe). Occasionally small quantities of three
other minerals were evident, which were i d e n t i f i e d by x-ray and microscopic
analysis as calcium carbonate, hematite and an insoluble Ca ,Mg,Fe s i l i c a t e
probably actinolite. These impurities occurred i n well defined veins,
generally together, which could be e a s i l y avoided i n most cases when cutting
a specimen. However, small quantities of hematite did occasionally find
their way into a specimen and thereby cause high iron extractions.
-52-
Powdef samples f o r leaching were either crushed (in a mortar) from
above specimens, or commercial concentrates, used as received or, as noted,
further crushed. A few experiments were done on single crystals from
Baxter Springs, Kansas obtained through Ward's Museum.

-53-
C. •RESULTS
I Preliminary Experiments
Two types of anodic experiments were carried out, p o t e n t i o s t a t i c scans
and constant potential experiments; i n the former the r e l a t i v e rates of
dissolution at each potential were measured, and i n the l a t t e r the chem-
i s t r y of dissolution at each potential was determined.
A l l potentials quoted i n this work are on the standard hydrogen
electrode (S.H.E.) scale.
a) The Meaning of Current E f f i c i e n c y
Current e f f i c i e n c y as used i n r e l a t i v e l y simple electrochemical pro-
cesses, such as metal r e f i n i n g , i s usually defined as the percentage of
the t o t a l current which i s used in the dissolution (or p l a t i n g out) of
the metal concerned. In a complex process such as the d i s s o l u t i o n of
chalcopyrite, where each of three elements has more than one possible
valence state in solution, and not a l l of the elements go into solution,
the meaning of the term i s not obvious. There i s considerable confusion on
this simple point in the l i t e r a t u r e ; usually authors f i r s t postulate a
p a r t i c u l a r reaction and then state the current e f f i c i e n c y f o r each element,
as i f that reaction were the only one involved i n the anodic process. Here
the current e f f i c i e n c y f o r each element i s defined as the
Total equivalents ( i ) dissolved

C.E. (i) = 100 x —
Total faradays passed
Moles (i)
= 100 x x n
Coulombs/F
where n = valence state of (i) in solution.

-54-
Th e procedure then i s to calculate the current e f f i c i e n c y of each
element, and then postulate a reaction.
The current e f f i c i e n c y of sulphate was not always determined experi-
mentally, (as i n sulphate s o l u t i o n s ) ; however, as a f i r s t approximation
the quantity (100 - C.E.„ „ ) can be used as a measure o f C.E...

n J
Cu + Fe SO.
4
b) Potentiostatic Scans
Anodic behaviour was studied i n 0.1M HCIO^ and 0.1M H^SO^, at temp-
eratures from 7°C to 175°C. At low temperatures (up to 85°C) p o l a r i z a t i o n
curves i n the two acids are very s i m i l a r , but at higher temperatures the
r e a c t i v i t y of chalcopyrite suddenly drops i n H^SO^, whereas i n HCIO^ i t
continues to increase steadily with temperature (Figures 12, 13). At 95°C
and above, i n l^SO^, the current density at low potentials continues to
increase with temperature, but at higher potentials (above 1 v o l t ) i t
'passivates' - that i s the current f a i l s to increase i n the usual '<>ay.
It i s evident that there are two regions on the p o l a r i z a t i o n curves,
the f i r s t being quite f l a t and the second, s t a r t i n g around 800 mV, ex-
h i b i t i n g a sharp increase of current with p o t e n t i a l . The boundary between
the two regions i s not always clear from a graph, but experimentally, i t
can be seen because the current i n the f i r s t region f a l l s back between
each increment of potential but not i n the second region.
This can be also seen from Figure 14, where the scanning rate affects
the current i n the f i r s t region, but not i n the second; these regions
may be characterized as time-dependent and time-independent respectively.
A specimen whose potential was raised well into the second region
exhibited a linear dependence of current on voltage (Figure 15); thus the
current appeared to be controlled by an ohmic resistance.
Some specimens were prepared with the potential-scanning lead pressed

-55-
POTENTIAL (V).vs.SHE
Fig. 12 P o t e n t i o s t a t i c scans i n p e r c h l o r i c acid
at v a r i o u s temperatures.
-56-
POTENTIAL (V) vs.SHE
F i g . 13 Potentiostatic scans i n sulphuric acid

at various temperatures.
-57-
POTENTIAL (V) vs.SHE
F i g . 14 E f f e c t of scanning rate on potentiostatic scan.

-58-
100
O.IM HCIQ
T
75 ° (
300mV/min
25 °C
150 °C
co
e
<
E
50h
>-
CO
-z.
UJ
Q
h-
UJ
cn
0i
0.2
POTENTIAL (V) vs. SHE

F i g . 15 The linear current/potential relationship
i n potentiostatic scans.
-59-
in very close to the surface, whilst the current-carrying lead was put in
at the back as before. However, no difference was observed i n the polar-
i z a t i o n behaviour of a given specimen, using t h i s side lead, and i n f a c t
reversing the leads made no difference e i t h e r . Evidently the ohmic drop
through the bulk of the specimen was not important.
The exposure of a specimen to hot sulphuric acid for prolonged periods
appeared to adversely a f f e c t the r e a c t i v i t y ; the conditions required
varied, but generally a few hours at 150°C lowered the r e a c t i v i t y . The
loss i n r e a c t i v i t y was also accompanied by a reduction in conductivity,
which sometimes dropped to 10 0

0, - cm. or l e s s . Perchloric acid never
had t h i s e f f e c t , and i t seems more than coincidental that hot sulphuric
acid has a depressant e f f e c t on the current achieved at high p o t e n t i a l s .
c) Constant Potential Experiments
A f t e r performing the p o l a r i z a t i o n s shown i n Figure 16, the specimen
was held at constant p o t e n t i a l , as indicated by the c i r c l e s on the curve,
to determine the time dependence and stoichiometry of the d i s s o l u t i o n .
The time dependence i s seen most c l e a r l y in comparing current-decay curves
(for constant p o t e n t i a l ) . In Figure 17 there i s a drop of 35% i n current
at 710 mV (in the f l a t region) but at 785 mV at the beginning of the high
current region, the current stays nearly constant, a f t e r an i n i t i a l rise.
The e f f e c t of s t i r r i n g was studied i n 0.1 M HCIO^ at 20°C and was observed
to have no appreciable e f f e c t even on the high-current region, where the
current appears to be l i m i t e d by some ohmic drop (see above). Similarly
the a c i d i t y was varied up to IM HCIO^ without e f f e c t .
A f t e r these constant p o t e n t i a l experiments (in 0.1 M HCIO^), solution
analysis was c a r r i e d out; t h i s data are l i s t e d i n Table IVa, along with some
-60-
100
F i g . 16 Potentiostatic scans i n perchloric acid, showing

potentials of constant potential experiments.
-61-
2.0| > 1 -> 1 —•— i —i
1 2 5 °C
O.IM HCI0 4
7 8 5 mV
L
1.5
9 3 5 mV
2 10
71 0 mV
0.5
I . I . I
0 4 8 12
TIME ( min. )
F i g . 17 Current decay during constant potential....

experiments at 125°C
-62-
0'
0 4 8 12
T I M E ( min.)
Fig. 18 Current decay during constant potential

experiments at 150°C.
TABLE IVA
ANALYSIS OF SOLUTIONS AFTER CONSTANT POTENTIAL EXPERIMENTS

ON CuFeS 2 IN 0.1M HCK> 4
Coulombs Current E f f i c i e n c y (%)

Temp Potential Time % S as
Passed/
(cm ) 2
(°C) (mV)--- (hrs) Cu SO.
Fe SO. Total 4
4
234 85 970 16 30.0 30.0 44.8 105 25
215 125 710 42 23.0 35 52.1 110 30
125 125 785 6 32.2 40.8 47.4 120 22
I
300 125 935 2 34.3 34.0 49.8 118 24
ON
OJ
I
145 150 700 16 17.4 38.9 67.8 123 40

295 150 . 935. 3 34.6 36 46.1 116 22
93 175 615 7 29 77.6 189 295 59
115 175 690 6 338 62.8 232 328 80
125 175 765 16 32 46.6 202 280 86
680 175 1500 24 30.5 33.8
-64-
TABLE IVB
ANALYSIS OF SOLUTIONS AFTER CONSTANT POTENTIAL

EXPERIMENTS ON CuFeS 0 IN 0.1M H S0, o
Coulombs Temp Potential Time -Current. E f f i c i e n c y

2
(°C) (mV) (hrs) . Cu Fe
Passed/cm
440 85 1100 47 28.3 28.8
335 7 1500 6 29.4. -
1240 37 1500 10 30.0 -

*
240 67 1500 -
5 7.7
455 97 1500 25 32.0 -
320 125 1500 18 33.8 -
180 175 1500 3 32.2 -
*
There was a s i g n i f i c a n t amount of pyrite i n the specimen.
TABLE V
ANALYSIS OF SOLUTIONS AFTER HEATING EXPERIMENTS

ON CuFeS„ IN 0.1M HC10.
1 4
Area of Moles Dissolved x 10" 4
Temp Hours Specimen

(°C) (cm )
2
Cu Fe so 4
=
125 12 1.0 Undetectable 0.56 0.08
150 12 1.95 2.9 2.9
175 6 2.7 3.8 3.8

-65-
other experiments at 85°C and 175°C.
The current e f f i c i e n c y f o r copper was f a i r l y constant, f o r potentials
i n the second region, at about 32%. At lower potentials (125°C, 710 mV
and 150°C, 700 mV), lower values were found.
Iron current e f f i c i e n c i e s were also f a i r l y constant at about 35%, up
to 150°C; but at 175°C very high values were recorded except at high po-
tentials.
The current e f f i c i e n c y f o r sulphate was approximately 47% up to 150°C,
except f o r the two experiments i n the low potential region where higher
values were observed. At 175°C, unreasonably high values indicated that
some chemical oxidation of sulphur was taking place, possibly by per-
chlorate.
The t o t a l current e f f i c i e n c i e s are seen to be i n the 110-120% range,
except f o r 175°C experiments.
Similar experiments were also carried out i n 0.1 M ^SO^ (Table I.Vb)
At high potentials (1.5 v ) , the copper current e f f i c i e n c y seems quite
constant, over a large temperature range, at about 31% +_ 3%. The presence
of pyrite i n the specimen severely lowered the copper current e f f i c i e n c y .
The anomalously large quantities of iron and sulphate produced at
175°C, can be attributed to a direct d i s s o l u t i o n of chalcopyrite i n acid:
CuFeS 2 + 2H +
•+ CuS + F e + +
.+ H S
2 (15)
To test this hypothesis, blank runs were carried out on fresh specimens
at 125°C, 150°C and 175°C i n 0.1 M HC10 4 (Table V), and i t was found that
while copper did not dissolve at a l l , iron and sulphur did, and i n some
manner the sulphur was completely oxidized to sulphate at 150°C and 175°C.
The oxidizing agent f o r this reaction i s unknown, but the f a m i l i a r i n e r t -
ness of perchloric acid i s known to disappear at high temperature. There

-66-
is also the p o s s i b i l i t y that not a l l the oxygen was removed from the pres-
sure vessel by the evacuation procedure.
d) Surface of Chalcopyrite After Anodizing
Various s o l i d products were observed on the surface of the mineral,
depending on conditions. At low temperatures, i t was possible to produce
a 'clean' chalcopyrite surface with only a loosely adherent sulphur
film.
Increasing the temperature caused the deposition of hematite, Fe20 3> and
depending on the potential i t may occur i n p i t s and cracks (low potential)
or i t may cover the surface (high p o t e n t i a l ) . Removal of the FeÔ^ with
a b r i e f oxalate leach (190) revealed the deeply p i t t e d chalcopyrite matrix,
(Figure 19). This hematite may be a secondary oxidation product, due to
the action of perchlorate.
At low p o t e n t i a l s , i . e . i n the f i r s t region of the p o l a r i z a t i o n
curve another s o l i d phase, c o v e l l i t e , CuS, appeared, corresponding to the
p r e f e r e n t i a l d i s s o l u t i o n of iron. At low temperatures (125°C) the co-
v e l l i t e appeared as a f i n e l y c r y s t a l l i n e material, but at high tempera-
tures (175°C), large well-defined c r y s t a l s were v i s i b l e , Figures 21-23,
and i n the cracks of the specimens e s p e c i a l l y large plates of CuS were
formed.
e) Summary
In 0.1 M HC10. and 0.1 M HLSO. the anodic p o l a r i z a t i o n curve of

4 2 4 F
CuFeS^ i s composed of two regions, the f i r s t (up to 800 mV) being
time-dependent and the second time-independent. Furthermore the second
region i s characterized by a l i n e a r dependence of current upon p o t e n t i a l .
The anodic behaviour i n the two acids i s s i m i l a r up to 85°C, but beyond

-67-
that s u l f u r i c acid has a passivating effect i n the second region, whereas
perchloric acid does not.
Up to 150°C, the current e f f i c i e n c i e s f o r copper and iron are about
30-35% i n both acids independent of p o t e n t i a l , except that i n the lower
potential region (<700 mV), copper current e f f i c i e n c y i s lower. About
25-30% of the sulphur i s oxidized to sulphate, independent of p o t e n t i a l ,
and temperature (up to 150°C).
At 175°C, chemical dissolution of iron becomes important, with, ex-
cessively high current e f f i c i e n c y for iron at low potentials. Copper
current e f f i c i e n c y remains constant, however.

F i g . 19 Scanning e l e c t r o n micrograph of chalcopyrite 20 Scanning electron micrograph of chalcopyrite
anodized at 1500 mV for 3 hours i n 0.1M a f t e r anodizing (16 hours, 700 mV, 0.1M
HCIO4, 175°C; showing deep p i t t i n g attack. HCIO4, 150°C). 'Clean' CuFeS surface show-
2
Surface f i l m s of sulphur and Fe203 were pre- ing c r y s t a l structure. Other s o l i d phases
viously removed with CS2 and an oxalate solu- have presumably been swept away by s t i r r i n g
t i o n (190), respectively. action.
F i g . 21 Scanning electron micrograph of CuFeS2 specimen a f t e r anodizing
(7 hours, 615 mV, O.IM HCIO4, 175°C). Fine c r y s t a l s and large
plates of CuS.
F i g . 22 Scanning electron micrographs of CuFeS2 specimen after anodizing
(11 hours, 615 mV, O.IM HC10 , 175°C). Ordered matrix of CuS
4
crystals overlaying unreacted CuFeS2 l a t t i c e .

F i g . 23 Scanning electron micrographs of CuFeS2 specimen a f t e r anodizing
(3% hours, 690 mV, 0.1M HC10 , 175°C). Large c r y s t a l s of CuS on
4
top of CuFeS2.
-72-
II Anodic Polarizations
The polarizations shown i n Section I were conducted only i n 0.1 M
H^SO^ and 0.1 M HCIO^, primarily as a function of temperature, with only
two scanning speeds, 300 and 30 mV/min., both of which are 'fast' compared
with steady state. The object of the experiments i n this section i s to
investigate more thoroughly the e f f e c t of solution composition and slower
scan rates. The temperature range f o r these experiments i s 20-95°C.
Such experiments are more useful i n interpreting leaching reactions, which
may be considered steady state anodizations, i n which the main variables
are oxidant strength (potential) temperature (generally near 100°C) and
solution composition.
Four variables we examined here were:
1. [Chloride]
2. [Sulphate]
3. pH
4. Scan Rate,
a) Fast Scans
It was shown i n the previous section that at low temperatures (<80°C),
similar p o l a r i z a t i o n curves were obtained i n 0.1 M HC10. and 0.1 M H„S0..

^ 4 2 4
However, at high temperatures, the electrode 'passivated' i n the high
potential region i n sulphate solutions, but not i n perchlorate.
The term 'passivation' normally implies a decrease i n current (with
an increase i n p o t e n t i a l ) , whereas ' i n h i b i t i o n ' refers to a constant
current, which does not increase with p o t e n t i a l . In this work, however,
passivation w i l l be used to describe a p o l a r i z a t i o n in which the current
either decreases with potential or stays constant.

-73-
It can be seen from Figure 24 that p o l a r i z a t i o n s at low temperature
in 0.1 M HCl are also similar to those i n 0.1 M H^SO^; furthermore
additions of Na2S0^ have l i t t l e e f f e c t . However, additions of KC1 p a s s i -
vate the mineral at high p o t e n t i a l (Figure 25).
The two regions of the p o l a r i z a t i o n curves are c l e a r l y seen i n com-
paring the log I and linear I plots. The f i r s t region which extends
from 500-1000 mV (at 20°C) i s time-dependent, and represents some kind
of l i m i t i n g current. Variation of scanning rate (Figures 26-28) demon-
strates this time-dependence.
The second region (1000 mV ->• ) c l e a r l y i s less time-dependent, and
the current i s proportional to the p o t e n t i a l , but largely independent of
solution composition. Except i n strong KC1 solutions, the slope of the
I/V plot was approximately constant, independent of solution or scanning
rate. Furthermore the onset of this region i s c l e a r l y marked and repro-
ducible at 1000 mV (20°C) (Table VI).
The actual slope of t h i s region decreased about 50% or less, i n
passing from 300 to 3 mV/min. (scan rates) as seen i n Table VI.
Polarizations i n strong KC1 solutions affect subsequent p o l a r i z a t i o n s
in solutions not containing high [KC1]. This effect can be p a r t l y removed
by polishing or completely by heating to 95°C (Figure 29).
A brown deposit was noticed on the surface of the mineral a f t e r polar-
izations i n strong chloride. This was not further investigated but i s
possibly cuprous chloride or basic cupric chloride, Cu(OH)^ 5 ^ 1 Q re-
polarizations i n 1 M HCl do not passivate the mineral i n the same
way as those in (1 M KCl, 0.1 M HCl). The t r a n s i t i o n point i s s h i f t e d
to higher potential (1150 mV), but the slope of the second region i s
-74-
approximately the same, or higher, (Figure 30) (in contrast to the reduced
slope produced i n strong KC1 s o l u t i o n s ) . This supports the idea of a basic
salt p r e c i p i t a t i n g out, for i t would be more soluble i n HCl than KC1.
There does appear to be a small difference between p o l a r i z a t i o n s i n
0.1 M H^SO^ and i n 0.1 M HCl; although the slopes of the second region are
indistinguishable, the t r a n s i t i o n point i s 50 mV lower i n the case of
0.1 M H S0
2 4 (Figures 24, 30).
The effect of increasing the temperature on p o l a r i z a t i o n i n a sulphate
solution i s again i l l u s t r a t e d i n Figure 31 - an increased current i n the
f i r s t region and a passivating e f f e c t i n the second region. The t r a n s i t i o n
point however remains f a i r l y constant. No such e f f e c t s are seen at 95°C
in 0.1 M HCl (Figure 32).
b) Summary
At low temperatures, a two-stage anodic p o l a r i z a t i o n curve i s ob-
tained f o r chalcopyrite. The f i r s t region, extending from the rest poten-
tial (500 mV) to about 1000 mV, appears to have a l i m i t i n g current, which
i s markedly dependent upon scanning rate, and to some extent solution
composition. This region w i l l be referred as the d i f f u s i o n region.
The current i n the second region beginning at 1000 mV i s largely independ-
ent of scanning rate, and solution composition and i s proportional to
potential. It w i l l be referred to as the space-charge region.
Sulphate, perchlorate and chloride solutions a l l give s i m i l a r p o l a r i -
zation curves except for strong KC1 solutions which at high potential
appears to form a p r e c i p i t a t e on the surface, possibly Cu(OH)^ 5^1^ ^, and
passivate.
At higher temperatures this feature i s absent, but sulphate solutions
passivate instead.
-75-
0.5 1.0 1.5

F i g . 24 Potentiostatic scans on CuFeS2 i n various solutions

at 300 mV/min., 20°C.
-76-
P O T E N T I A L (V) vs. SHE
F i g . 25 Potentiostatic scans i n chloride solutions

at 300 mV/min., 20°C.
-77-
F i g . 26 Potentiostatic scans i n 0.1M HCl, 20°C at

various scanning rates.
-78-
0.5 0.75 1.0

F i g . 27 Potentiostatic scans i n sulphate solution, 20°C,

at various scanning rates.
-80-
F i g . .29 Successive potentiostatic scans i n 0.1M HCl at 20°C,

300 mV/min., showing passivating e f f e c t of KC1 on
subsequent experiments.
(A) I n i t i a l scan
(B) After a scan i n IM KC1
(C) After polishing specimen.
-81-
F i g . 30 P o t e n t i o s t a t i c scans a t 20°C, showing e f f e c t of

c h l o r i d e and s u l p h a t e s o l u t i o n s on t r a n s i t i o n
potential.
-82-

F i g . 31 Potentiostatic scans i n sulphate solution at 300 mV,
and various temperatures; showing passivating e f f e c t
of sulphate at 95°C.
-83-
100
Fig. 32 Potentiostatic scans i n O.IM HCl at 95°C, and

various scanning rates; an unreactive specimen.
-84-
TABLE VI
S u c c e s s i v e A n o d i c Scans A t R a p i d Scanning Rates
Specimen #200
1st .., 2nd

Temp. Scan Trans-
S1 ope Slope
(°C) Rate Solution ition Other
Number uA/mV u A/mV .
f 0
CmV)
(
(mV/min ) v
cm J
^ cm
201-1,2 20 300 0. IM HCl 0 1000 116
220 300 0 IM H S 0 0 950 116

201-3 2 4
300 p IM H S 0 IM Na SO 970 92
201-4,5 20 2 4 + 2
4 °
201-6 20 300 0 IM H S 0 ^ 0 1060 87

2
.+ IM KC1
4
1 0M N a S 0 2 4
20 300 0. IM H S 0 ' 0 1160 45

201-7 2 4
+ IM KC1
1. OM N.a S0 2 4
20 300 0. IM HCl 0 990 45

201-8
300 0 IM HCl 0 1000 108 Repolished

201-9 20
IM KC1 + 0.1M HCl 0 1230 53 Repolished

201-11 20 300
4M KC1 + 6.1M HCl -1350 22 Repolished

201-12 20 300
4M KC1 + 0.1M HCl Indefinite Repolished

201-13 20 300
201-17 20 300 0 .IM HCl 1000 150
20 30 0 .IM HCl 1000 125

201-18
20 3 0 .IM HCl 1000 85

201-20
-85-
TABLE VI (Cont.)
Specimen #201
1st 2nd
Temp. Scan Trans-
Slope Slope
Number (°C) Rate Solution ition Plateau
yA/mV yA/mV
(mV/min.) OV)
cm v
cm
201-1 95 300 0 IM HCl — 5 890 300
201-2 95 30 0 IM HCl 0 880 300
201-3 95 3 0 IM HCl —14 835 120
201-6 20 300 1040 600

0
IM HCl
201-7 20 30 0 2M H S 0 990 410
2 4
201-9 20 3 0 8M N a S 02 4 960 —200
201-8 20 300 0 1025 420
0 IM HCl 2
201-11 43 300 0 1090 540 1.5 mV/cm
0 2M H S 0
2 4
201-10 95 3000 0 8M Na S02 4

25, 1070 15.5 2
5 mV/cm
2
201-12 95 3 ' —10" — 7.5
J
1.5 mV/cm
2
201-13 20 300 IM HCl 1175 390 1.5 mV/cm
201-14 20 3 IM HCl 1135 36Q
201-15 20 300 0. IM HCl 1050 220
201-17 20 300 0 IM H SO,

? 1000 250
-86-
Th e t r a n s i t i o n point between d i f f u s i o n and space-charge region i s
remarkably constant (1000 mV) decreasing somewhat for sulphate solutions,
and increasing with [ C l ] .
The slope of the l i n e i n the space-charge region i s t y p i c a l l y 100-K500

2
uA/cm -mV at 20°C f o r fast scans; this value varies considerably from one
specimen to another, but i s r e l a t i v e l y independent of solution and scan
rates i n the range 3 - 300 mV/min.
c) Slow Scans
Slow scanning i n t h i s context i s defined as 0.3 mV/minute. This
figure was used, because i t i s a reasonable approximation to steady state,
and slower rates are impractical.
At 0.3 mV/min., a t y p i c a l 600 mV scan takes over 30 hours. Lower
scan rates would reduce the number of experiments possible, and lead to
such extensive mineral decomposition as to destroy the specimen before
the scan i s complete i n many cases.
(i) Low Temperature (20°C)
At 20°C, slow polarizations i n 0.1 M and 1 M HCl, H S 0 2 4 and HC1C> are

4
very s i m i l a r (Figures 33,34) except as noted above; the t r a n s i t i o n point
moves to higher p o t e n t i a l with increasing [ C l ] , and i n the d i f f u s i o n region
the current increases with increasing strength of s o l u t i o n . However the
r e l a t i o n s h i p i n the space-charge region i s s t i l l l i n e a r , and the slopes
s i m i l a r (7.S + 2.5 ^ f f P ) f o r each of these s i x solutions. These slopes

cm -mV
/ r
are much smaller than those obtained with fast scan rates. A relation-
ship between t r a n s i t i o n point and d i f f u s i o n region current may be noted,
i . e . the higher the d i f f u s i o n current, the higher the p o t e n t i a l needed
to s t a r t the space-charge region, but the sharper the slope i n the space-
charge region.
-87-
Increasing the pH (at 20°C) has l i t t l e effect on polarizations i n
sulphate solutions, but a more severe effect on those i n chloride solutions,
as noted i n the previous section (Figure 35,36), although the d i f f u s i o n
current i s lower i n each case.
Increasing the temperature has a drastic effect on the d i f f u s i o n
current, as shown i n Figure 37 f o r 0.1 M HCIO^ solutions. However, the
space-charge region current i s remarkably constant over the range 20, 40,
60°C but i s about s i x times higher at 90°C.
( i i ) High Temperature (90°C)
Shown i n Figure 38 i s the effect of solution composition on 90°C scans.
There i s such a large change i n passing from 0.1 M HCIO^ to 0.1 M. HCl that
i t i s not obvious that the same features are present. The t r a n s i t i o n
point i n HCl has s h i f t e d about 500 mV towards lower potentials, and the
d i f f u s i o n current region i s ' l o s t ' , due to the high rest p o t e n t i a l .
Furthermore, the slope of the line i s the space-charge region i s nearly
doubled (17.5 ->- 32 /mV) i n passing from 0.1 M HCl to 1 M HCl.
The actual values of the space-charge slopes (at 90°C) are (Table
uA
VII) i n the range 17.5 -»• 75 /mV, an order of magnitude higher than at
20°C.
The v a r i a t i o n i n these values i s due not only to solution, but also
to the d i f f e r i n g behaviour of individual specimens.
The passivating e f f e c t of I^SO^ noted above i s again seen i n Figure
38; evidently the space-charge region i s not accessible in this solution
at reasonable potentials.
The maxima i n the HCl polarizations appear to be the cumulative
effect of the slow scan rate and high dissolution rates.

Additional confirmation of. the d i f f e r i n g behaviour i n HCl, H S0 9 /1
-88-
i s provided by Figure 59, i n which the ^SO^ s c a n w a s

performed first,
on a fresh mineral. The potential of the t r a n s i t i o n point, from d i f f u s i o n
to space-charge region, i s lowered by the addition of KC1, although the
slope of the l i n e i n the space-charge region i s l i t t l e affected (Figure
40). •
Approximately 100 mV less potential i s needed f o r the onset of the
space-charge region i n 4M KC1 than i n 0.1M KC1.
It i s possible to consider the f i r s t part of the d i f f u s i o n region
as an a c t i v a t i o n - c o n t r o l l e d process, f o r i n some experiments there i s
an approximate T a f e l r e l a t i o n s h i p at the s t a r t o f the p o l a r i z a t i o n (a
l i n e a r r e l a t i o n s h i p on the log I p l o t s ) . Thus, i n the experiments shown
i n Figure 4 l (variation of [KC1]) a T a f e l slope of 85 mV/current decade
i s evident from the f i r s t 200 mV. In most experiments (e.g. Figure 38)
tha rest potential i s too high to observe this feature.
Anodizations (at 90°C) i n IM NaÔ^ solutions do not appear to p a s s i -
vate as r e a d i l y as those i n IM ^SO^ (Figure 41). It i s i n t e r e s t i n g
to compare the log I and l i n e a r I p l o t s i n t h i s f i g u r e . The log I p l o t
appears to indicate a l i n e a r (Tafel) r e l a t i o n s h i p with slope 95 mV. where-
as the l i n e a r I plot indicates two stages, i . e . d i f f u s i o n - space charge
regions. The same comments apply to the following figure.
Lowering the pH from 3.5 to 1.05 i n a 4M KC1 solution had v i r t u a l l y
no e f f e c t on the p o l a r i z a t i o n (Figure 42) .
d) Summary
At 20°C, steady state currents are r e l a t i v e l y independent of solution
composition; and the boundary between the d i f f u s i o n region and the space-
charge region i s c l e a r l y marked, at about 1000 mV.
Increasing the temperature to 60°C has l i t t l e e f f e c t except to increase

-89-
the d i f f u s i o n current, which i s s t i l l very low.
At 90°C the d i f f u s i o n current i n HCIO^ and H^SO^ i s greatly increase
and adding chloride to a perchlorate solution allows the space-charge
region to start 500 mV lower. Thus the current i s strongly p o t e n t i a l -
dependent i n the region 500-800 mV, for chloride solutions.
The steady-state space-charge slope i s increased by an order of
magnitude from 20°C to 90°C (5 -* 50 /mV) i n chloride solutions.
In H^SO^ (IM), the electrode passivates at 90°C, and the sDaceTcharg
region i s not achieved; thus the current i n t h i s solution i s largely
potential-independent. This passivating effect disappears at higher pH.
pH has no effect on p o l a r i z a t i o n s i n 4M KC1 (from pH 1 -* 3), at
90°C.
The p o l a r i z a t i o n curve may be considered as a three-part curve:
1) An a c t i v a t i o n controlled region
2) A d i f f u s i o n - c o n t r o l l e d region
3) A space-charge region.
The f i r s t region i s often obscured by high rest p o t e n t i a l s .

-91-
-92-
showing effect of pH.

-93-
I M HCl
POTENTI A L (V) vs. SHE

F i g . 36 Slow scans a t 20°C i n c h l o r i d e solutions,
showing e f f e c t of pH.
Fig. 37 Slow scans i n O.IM HCIO, a t v a r i o u s temperatures.
-95-
tOr " —

F i g . 38 Slow scans a t 90°C i n v a r i o u s solutions.
-96-
Fig. 39 Slow scans at 90°C in IM HCl and IM H SO0

-97-
F i g . 40 Slow scans a t 90°C i n sodium s u l p h a t e solutions.

-99-
-100-
TABLE VII
Successive Anodic Scans At Slow Scanning Rates
Specimen #202 $ #207
1st „, 2nd
Temp. Scan Trans
Slope
C 1
. . Slope
Number C°c) Rate Solution A /™ir ,i t i o n uA/mV Plateau
,uA/mV oV
(mV/min.) C 2J (mV) ^ cm
v
cm K J
2
202-1 20° 0.3 IM HCl 0 1110 9.2
0.08 mA/cm
2
202-2 20° 0.3 0.IM HCl 0.1 985 5.7 0.02 mA/cm
202-3 20° 0.3 0. IM H S0 2 4 0.1 935 6.4 0.02 mA/cm 2
202-4 20° 0.3 0.IM HC10 4

885 5.2 0.015 mA/cm 2
, 2
202-5 20° 0.3 IM H S0 2 4
1015 10.8 0.05 mA/cm
2
202-6 20° 0.3 IM HC10 980 6.4
4
0.035 mA/cm
, 2
202-7 20° 0.3 0.,2M H SO 915 5.9 0.01 mA/cm
0.,8M Na S0 2 4
2
202-8 20° 0.3 0.. IM HCl O 1000 1.7
0.025 mA/cm
1..OM NaCl
2
202-9 20° 0.3 0., IMHC10 4
0. 890 5.0 0.025 mA/cm
207-3 20 0.3 0,. IM HC10 4

0.03 920 5.9
207-2 43 0.3 0,.IM HC10 4

0.68 965 5.9
207-4 60 0.3 0.. IM HC10 4

1.10 1040 8.55
207-6 90 0.3 0.. IM HC10 4

16.3 520 3.73
1057 48.7
207-7 90 0.3 0.IM HCl 10.3 580 17.5
207-8 90 0.3 IM HCl 525 32

2
207-9 90 0.3 IM 17.3 542 decreasing
H
2 °4S
J 0.73 mA/cm
-101-
TABLE VII (Cont.)
Specimen #208 $ #210
Temp. Scan l s
. Trans-
t 2 n
Tafel
d
Number (°C) Rate Solution „°Pf, i t i o n 7° f, Slope p
(mV/min.) ( 2)(mV) (^
yA/mV
2) A/mV
^ cm cm .
208-1 90 0.3 IM H SO —3.4 650 0 '

900 4.0
208-2 90 0.3 IM HCl 1.2 535 25.4
210-1 90 0.3 IM KC1 2.4 385 12.0 —85

0.1M HCl 510 56
210-2 90 0.3 4M KC1 4.8 488 68 —85

0.1M HCl
210-3 90 0.3 IM KC1 4.8 510 74 —85

0.1M HCl
210-4 90 0.3 4M KC1 -~2.5 460 45 88

0.1M HCl
210-5 90 0.3 0.1M KC1 < 1 . 560 34.3 88

0.1M HCl
210-6 90 0.3 0.1M Na SO .50 570 16 95

0.1M H S0
2 4
210-7 90 0.3 IM Na^SO, 0.36 525 24 95

2 4
0.1M H„50. 625 •+ decreasing
700 + 0
725 negative
210-8 90 0.3 4M KC1 (No 0.06 525 58 —130

acid)
(pH 3.5)
210-9 90 0.3 4M KC1 + 0.05 528 58 —130

0.03 HCl
. (pH 1.0)
-102-
III Constant Potential Experiments
The main object of these experiments i s to examine the chemistry of
the anodic dissolution of the mineral, CuFeS2, as a function of p o t e n t i a l ,
temperature and solution. However, a secondary aim i s to observe the
current/time relationship at a fixed p o t e n t i a l ; such experiments are
quickly performed, i f not encumbered with solution analysis.
a) Without Solution Analysis
Current decay curves at 20°C,(700 mV) i n (O.IM and IM) HCl, H S0 2 4
and HCIO^ solutions are shown i n Figure 43. Amongst the O.IM solutions,
H^SO^ c l e a r l y gives a higher current, whereas HCl and HCIO^ are s i m i l a r .
Adding H^SO^ to the HCIO^ solution confirms t h i s . However, f o r the IM
solutions, HCl gives the highest current, although i n ^SO^ i t i s also
increased, i . e .
O.IM HC10 4 * HCl < H S0

2 4
IM HC10 4 < H S0 < HCl

2 4
In the case of HC10 4 and H S0 , the current approximately doubles from

2 4
O.IM to IM, but f o r HCl i t quadruples.
At 60°C (and 700 mV) the d i s t i n c t i o n between HCl and HC10 /H So 4 2 4 (IM)
i s much greater (Figure 44); the current i s three times higher after three
hours, and f i v e times higher after twelve hours. This figure also shows
that i n HCl the current increases with time, a f t e r an i n i t i a l decline,
(while i n HC10 or H S0
4 2 4 i t continues to d e c l i n e ) . This behaviour i n d i -
cates that i n HCl, the mineral i s i n the space-charge region under these
conditions, while i n HC10. or H S0. i t i s s t i l l i n the d i f f u s i o n region.

o
> 4 2 4 6
Additions of KC1 further increase the current, and again demonstrate the
time-independence.
-103-
In (0.2M H S0 2 4 + 0.8M Na S0 ) the behaviour under the above conditions

2 4
(60°C, 700 mV) i s very s i m i l a r to that i n IM H S0 2 4 (Figure 45).
At 90°C and 700 mV, s i m i l a r differences are observed (Figure 46), be-
tween chloride and sulphate, though not as pronounced.
In Figure 47 i s shown the e f f e c t of temperature on the current at
700 mV i n 0.1M H SO.. There i s a marked difference between the increasing

. 2 4 6
temperature curve and the decreasing temperature curve. Although the
values are close at 20°, 30°, 60° and 90°C, there i s an order of magnitude
difference at 40°C. Other current/temperature curves are shown i n Figures
48, 49 and activation energies were calculated:
16..9 kcal/mole 0.1M HC10 4
0.1M HC10,
14., 1 kcal/mole 4
0. IM KC1
0.1M HC10.
14. 1 kcal/mole 4
IM KC1
b) Summary
At 700 mV, which i s a t y p i c a l potential (vs S.H.E.) one might expect
in f e r r i c leaching (E° = 770 mV), current densities (at 20°C) are s i m i l a r
in chloride and sulphate solutions. At 60°C, current densities are much
higher i n chloride than i n sulphate and time independent; additions of KC1
accentuate t h i s . At 90°C, this difference i s lessened, but s t i l l appreci-
able. An activation energy of 14.1 kcal was calculated for the current
in chloride solutions at 700 mV.

-104-
-105-
IM HCI0 4
7 0 0 mV , 6 0 °C
0 4 8 12
T I M E (hrs)
F i g . 44 Current decay at 700 mV, 60°C i n various solutions.

F i g . 45 Current decay at 700 mV, 60°C i n various solutions.
-107-
-108-
T E M P E R A T U R E (°C)
90 75 60 50 40 30 20
1 0 0 0 / T ( ° K )
F i g . 47 Effect of temperature on current at 700 mV, i n O.IM
H-SO,, showing hysteresis.
-109-
Fig. 48 Arrhenius diagram for current at 700 mV in O.IM HCIO

-110-
T E M P E R A T U R E ( °C )
90 75 60 50 40 30 20
I i i i !
i i r~
I 0 0 0 / T (°K )
F i g . 49 Arrhenius diagram for current at 700 mV i n O.IM KC1

and IM KC1.
-111-
c) With Solution Analysis •
In the preliminary experiments, Section I, the chemistry of dissolu-
tion i n O.IM HCIO^ and O.IM t^SO^ was examined, primarily at high temper-
atures 125 175°C. It was found that the current e f f i c i e n c y f o r copper
rarely rose above 32% and was less at low potentials. The extra current
was used up i n sulphur oxidation. However, the iron current e f f i c i e n c y
was often improbably high, possibly due to the chemical dissolution of
iron:
CuFeS 2 + 2H +
• -> CuS + H S2 + Fe + +
(15)
The object of the experiments i n this section was to examine the
chemistry of anodic d i s s o l u t i o n , in p a r t i c u l a r i n chloride and sulphate
solutions at leaching temperatures (90°C). Considerable scatter was evi-
dent i n some preliminary experiments, and i t was evident that i n s u f f i c i e n t
consideration had been given to the time dependence of the reaction.
Therefore experiments are described herein which were carried out f o r
extended periods of time, with frequent solution analysis. A new specimen
was used for each experiment (at a given p o t e n t i a l ) .
The meaning of the term current e f f i c i e n c y , as i t i s used i n this work,
has been defined i n Section I. An exception to this d e f i n i t i o n i s the
current e f f i c i e n c y of iron.
To f a c i l i t a t e computations, the current e f f i c i e n c y of iron i s calcu-
lated as though i t were a l l F e + +

, and then the extra current e f f i c i e n c y
of F e + + +
present ( i f any) calculated at 1/3 of i t s actual value.
In this section sulphate produced during anodization was not deter-
mined d i r e c t l y , for the a n a l y t i c a l method used i n the previous section
does not apply to strong chloride or sulphate solutions. Consequently
t o t a l current e f f i c i e n c y , as used here, means t o t a l metal current e f f i c i e n c y :
C.E. T = C.E._ + C.E.„ + C.E. C 3 +
Total Cu Fe Fe- * 3
-112-
but the real C.E.p 3 e + i s three times that quoted.
The quantity (100 - ^ • • p t l - ' ^

0 a
s a m e a s u r e
°f ^•^'S0 '
= a S a
^^ rst
approximation.
(i) Dilute Chloride Solutions f90°C)
In Figure 50 i s shown the results of anodizing separate specimens i n
-0.2M HCl , at 90°C at the following p o t e n t i a l s :

•0.3M NaCl J
535
635
735 mV vs. S.H.E.
935
1185
These conditions were chosen to approximate leaching i n d i l u t e chloride
solutions.
The current density (CD.) plot shows a marked increase of current with
time, (for a l l except the lowest p o t e n t i a l ) , and a steady increase of
current with p o t e n t i a l , up to 935 mV.
The current e f f i c i e n c y for copper (C.E.^) for a l l potentials i s 40 -
45%, after an i n i t i a l period, i n which i t i s generally lower, except for
535 mV. This plot i l l u s t r a t e s the danger of taking only one solution analy-
s i s as was done i n the preliminary experiments, for a f t e r ten hours the
average C.E.^ i s only 30 - 35%.
For most p o t e n t i a l s , iron current e f f i c i e n c i e s are approximately the
same as those of copper a f t e r 100 hours, (40 - 50%), but the trend i s
the down instead of up, and there i s more scatter to the r e s u l t s . This
plot p a r t l y explains the e r r a t i c C.E.p e i n Section I - iron d i s s o l u t i o n
rates are strongly time independent, i n some cases.
The Fe/Cu r a t i o plot shows that p r e f e r e n t i a l iron d i s s o l u t i o n extends
for about 50 hours, and then the r a t i o i s close to unity; however, at 535
mV the r a t i o never reaches 1.0, probably because the d i s s o l u t i o n rate i s

-113-
so low, and iron current e f f i c i e n c i e s are so high that chemical d i s s o l u t i o n
must be occurring.
The t o t a l current e f f i c i e n c y for a l l experiments i s close to 90%,
(after 30 hours) with the exception of the highest potential (1185), where
i t i s 80%. Therefore sulphate production i s c e r t a i n l y quite low, f o r 10%
C.E. = requires only 3.3% sulphur oxidation.

i)U
4
+++ +
Analysis f o r [Fe ] or [Cu ] was not carried out i n these experiments
due to errors of both judgment and analysis. However, i t i s l i k e l y that
this i s not a serious omission as w i l l be demonstrated,
( i i ) Strong Chloride Solutions (90°C)
In Figure 51 are shown the results of anodizing separate specimens

in 3.0M NaCl, at 90°C at the following potentials:
r
0.2M HCl
L
535 mV
635
735 (twice)
935
1085
1185
Current densities again increase markedly with potential (up to 935 mV),
and time (after an i n i t i a l decrease). Overall, the values are about double
those obtained i n dilute chloride, although the increase i s greatest at
lowest p o t e n t i a l , 535 mV.
Copper current e f f i c i e n c i e s are again in the 40 - 45% range (lower at
the start) except for the 535 and 635 mV experiments, where i t i s 50 - 60%.
[Cu ] analysis was carried out only on one experiment

+
(P-36) at 535 mV, and
a constant percentage 12.5% (+ 1.5%) of the t o t a l Cu was found to be Cu .

+
This, however, i s only a small correction to the copper current e f f i c i e n c y ,
which i s decreased from 61% to 57%. For higher potentials therefore, the
formation of Cu as Cu +
i s l i k e l y to be n e g l i g i b l e .
-114-
Iron current e f f i c i e n c i e s were s i m i l a r l y 40 - 50%, except at low po-
t e n t i a l s ; t o t a l current e f f i c i e n c i e s were mostly near 90% , but rose to
near 120% for 535 and 635 mV.
Fe/Cu ratios were close to 1.0 eventually, and again were higher at
the beginning. [Fe + + +

] was determined for the high potential experiments,
and found to be 10 - 20% of the t o t a l iron.
The high current e f f i c i e n c i e s found at low potentials are probably
caused by the chemical dissolution of iron (equation 15).
At high potentials, the electrodes developed a peculiar o s c i l l a t i n g
behaviour a f t e r a certain time (a couple of days). This i s i l l u s t r a t e d
in Figure 52. It was found that this was quite reproducible; the height
of the o s c i l l a t i o n s depended upon potential (935 mV being a threshold),
whereas the frequency depended on temperature (80°C being a threshold).
This behaviour was not observed at the beginning of the experiment,
however. Once established, though, i t appeared to go on i n d e f i n i t e l y , (for
the l i f e of the specimen).
No s a t i s f a c t o r y explanation of this phenomenon can be advanced at
this time; i t seems appropriate nevertheless to record the observation
in the hope that i t may prove useful at some l a t e r date. It i s possible,
however, that sulphur chloride, S2CI2, i s being formed under these condi-
tions.
( i i i ) Sulphate Solutions (90°C)
The previous experiments i n chloride solution were repeated with
0.4M Na S0
2 :
0.1M H SO J
535 mV
635
735 (4 times)
935
1185
as shown i n Figure 53.

-115-
_ 1 2
T I M E ( hrs)
F i g . 50 Constant potential experiments i n 0.3M NaCl, 0.2M HCl

at 90°C, and various potentials.
(a), (b) Current density and Fe/Cu r a t i o .
-116-
TOTAL
120
100
A t>
=4
o 80 -d
z
UJ
_ 6Qk
o
[735
u.
u.
Ul
, © d
3
I-
z
UJ -o—•
o -a
or
or
IRON
O
50 ^ 53 5 mV
735
COPPER
50 100
T I M E ( hrs )
Fig. 50 (c),(d),(e) Current e f f i c i e n c y .

-117-
F i g . 51 Constant potential experiments i n 3.0M NaCl, 0.2M HCl

at 90°C, and various potentials.
(a),(b),(c) Current density and r a t i o s .
-118-
I80i T
I TOTAL <
%
5 3 5 mV
„ 140
^SL.
635
o
100
Ul -0
o
1185
LL. ,SL
u_ COPPER
•^-•UPV
60
50
.ô—^^<DC^--—— 0
or 40
f
cc
o RON "m
80
••-^
v—•
60
-A—
40
cr
_i 1 1 1—i 1 1 1 i l i i .J i l i i_
0 50 100 150 200
T I M E ( hrs)
F i g . 51 (d), (e) , (f) Current e f f i c i e n c y .

-119-
F l g . 52 Current o s c i l l a t i o n s produced a f t e r several hours at 900 mV,

90°C i n 3M NaCl, 0.2M HCl. E f f e c t of temperature and p o t e n t i a l .
-120-
C u r r e n t d e n s i t i e s were g e n e r a l l y lower than i n c h l o r i d e s o l u t i o n s ,
p a r t i c u l a r l y a t lower p o t e n t i a l s , and decrease s l i g h t l y w i t h time. An
e x c e p t i o n t o t h i s r u l e was found i n one experiment a t 735 mV w h i c h i n c r e a s e d
w i t h time. T h i s was t h e r e f o r e r e p e a t e d t h r e e t i m e s . The r e s u l t was i n -
c o n c l u s i v e - i n two experiments (P 18, P30) t h e c u r r e n t went up, and i n
the o t h e r two (P 31, P 26) i t went down ( F i g u r e 5 4 ) .
735 mV appears t o be a t h r e s h o l d v a l u e f o r t h e c u r r e n t d e n s i t y :
mV CD. ( a f t e r 70 h o u r s ) (mA/cm ) 2
535 0.2
635 0.4
735 0.4; 1.9; 1.8; 0:5
935 1.9 -
1185 4.5
In c o n t r a s t , i n c h l o r i d e s o l u t i o n , t h e c u r r e n t i n c r e a s e d s t e a d i l y from
535 t o 935, and then l e v e l l e d o f f .
Copper c u r r e n t e f f i c i e n c i e s were n e a r 27% except f o r t h e lowest
potentials:
Potential C.E.^
Cu
535 mV 11.5 %
635 19.5
735 29, 26, 27, 20
935 29
1185 26
These r e s u l t s c o n f i r m those i n t h e p r e l i m i n a r y e x p e r i m e n t s , Section I.
The v a l u e s a r e a l s o r e l a t i v e l y c o n s t a n t over t h e l e n g t h o f t h e experiment.
In c o n t r a s t , t h e i r o n c u r r e n t e f f i c i e n c y showed a v e r y s t r o n g t i m e -
dependence. T h i s was shown t o be p a r t l y due t o c h e m i c a l d i s s o l u t i o n o f

-121-
of i r o n , for 'blank' runs were carried out i n some experiments, before the
s t a r t , i . e . the specimens were held i n the s o l u t i o n , with no applied poten-
t i a l , u n t i l iron d i s s o l u t i o n stopped (usually about two days). This iron
was then subtracted from the t o t a l i n solution, and separately plotted,
as "after subtracting blank".
This greatly reduced the time-dependence of C.E.p , which can be seene
as about 25%.
The Fe/Cu r a t i o , greater than 1.0 at the s t a r t , declined s t e a d i l y
towards that value. After subtracting blank, values of about 0.8 were
obtained.
Considerable Fe dissolved, and Fe /Fe^ values were about 0.8.
However, no F e + + +
dissolved i n the blank runs, and i n i t i a l Fe /Fe^, values ++
after subtracting blank were often quite low: 0.1 ->- 0.4.
This means that 60 -90% of the iron dissolved, as F e + + +

, initially,
e.g. P 21 Experiment (635 mV) averaged about 65% Fe as Fe + + +

.
Total current e f f i c i e n c y p l o t s , r e f l e c t i n g the complex iron behaviour,
show considerable scatter; a f t e r 100 hours a mean value of about 70% i s
evident, except for low potentials where the amount of d i s s o l u t i o n i s
still low. After subtracting the blank, 50 -60% t o t a l current e f f i c i e n c y
is obtained near the s t a r t .
The 735 mV experiment was carried out four times, as mentioned, to
determine the r e p r o d u c i b i l i t y , using a fresh specimen each time (Figure
54). The current densities, as noted, varied considerably as did the
iron current e f f i c i e n c i e s (16 - 36% a f t e r 150 hours); but the Cu and Fe 3 +
current e f f i c i e n c i e s were quite reproducible (28% and 5% r e s p e c t i v e l y ) .
The Fe/Cu r a t i o was generally above 1.0, but f e l l below i t a f t e r a
s u f f i c i e n t l y long time (100 - 200 hours) or a f t e r subtracting the blank.

-122-
The F e / F e + +
T r a t i o varied greatly (0.5 - 0.85), but i n any case showed
that s i g n i f i c a n t F e + + +
was produced. The t o t a l current e f f i c i e n c y showed
an interesting correlation with current density and F e / F e : ++
i 1
Experiment j CD. j C.E.„ ^ , Fe /Fe
+ +
| i Total T
1
- i
. P18 1 1.6 + 3.1 j 90+72 .70 + .80

. . ! i
P30 | 1.3+2.4 110 + 87 .82 + .84
!
P31 | 0.4 +0.7 78 + 53 .52 + .60

1
P2 6 j 0.6+0.5 80 + 50 .75 +.73
, P26 i 77 + 44 .10 + .65

A.S.B.
( }
!
Thus a high C D . i s associated with high C E . and low f r a c t i o n of

+++
Fe dissolved as Fe
(iv) Sulphate/Bisulphate Solutions (125°C)
The experiment described above v i z . 735 mV, 90°C,,0.4M Na~S0..

{
o . m H soJ
2
J
were repeated three times at 125°C (P 22, 27, 28) i n

similar solutions. I t was also repeated at 125°C i n bisulphate, i . e .
,0.4M NaHSO., (P 29); at the end of t h i s experiment, the solution was

0.1M H S0
l
2 4
J
changed, back to sulphate again (P 29A). The results are shown i n Figure 55.
Again there i s a f a i r range of current densities from one experiment
to another. Of the three sulphate experiments, one increased sharply
(100%), one decreased (35%) and the last stayed f a i r l y l e v e l . On the
average, the current density at 125°C (and 735 mV) was about double that
at 90°C (^2.5 mA/cm vs.^1.2 mA/cm ). 2 2

-123-
0.4 Na S0
12
2 4
0 . I H Sp
\ 9 0 °C
z 4
CM
\
\
E
u
^ 8
E
\
1185 m V
2
UJ
or
a:
,5t
"~--*~ 9 3 5mV
-^-^5
or
_—-<zr 73 5
- 0 1
I I I l_ 3.
50 100 150 200
T I M E ( hrs)
Fig. 53 Constant potential experiments i n 0.4M Na S0^, O.IM 2
I^SO^ at 90°C, and various p o t e n t i a l s .

(a),(b) Current density.
-124-
COPPER
50
40
\ 73 5 mV
>-
o
30
A-
l£5 ^ ^ - ^ t ' f - S l . .
^ <zr~~^*
Z 20 • •••
UJ
•6-3^-
o -o
10 o- -o- -o
535
u.
0- -I I I L. —1 I I L. J I I '
LU F E R R I C
0C
0C
20
O
15
•—..
10
5h
100 150 200

T I M E ( hrs )
F i g . 53 (c) Copper current efficiency.

Cd) Ferric ion current efficiency.
F i g . 53 (e) Iron current e f f i c i e n c y .
(f) Iron current e f f i c i e n c y a f t e r subtracting
blank.
-126-
20 h
AFTER SUBTRACTING BLANK

01 i i, i i I i i i i _j i i i i i — i ' '
0 50 100 150 200

T I M E (hrs)
Fig. 53 (g) Total current efficiency.

(h) Total current e f f i c i e n c y a f t e r subtracting
blank.
-127-
0
\ 53 5 mV
•V
635
——^.
O 2 ^935 X
-
W , ^ ^ ^ *T"r—®
< ^ ^ ' ^ Z
= = L
^ ^ ~ ^ z ^ ^ = ^ ^ ^
rr
0 -J 1 1 1 1 L _ 1 1 1 I I l i l I l l i i
<r
UJ
Q_
Q.
O AFTER SUBTRACTING BLANK
O 2.5
O
2.0
rr
1.5
.0
- - v
0.5
0 I i i i i L_ J — i — i — i i i i i ' i i i i
0 50 100 150 200
T I M E ( hrs )
F i g . 53 ( i ) Fe/Cu r a t i o .
(j) Fe/Cu r a t i o after subtracting blank.
-128-
.0
1185 mV
635 C ^ ^ - ^ - ^ 3 5 ,
* ' —•- ~ ^ —M "
"O O—<£.
935 735 535
0.5
<
tr
0 J 1 i i_ J i i i_ _| 1 1 L.
O
o
AFTER SUBTRACTING BLANK
u_
+
CM 1.0
53— -V-
v-
0.5
• V" .On
JD O"
•
_L J_ i . i, i
0
' i i ' 1_
0 50 100 150 200

T I M E ( hrs )
F i g . 53 (k) Fe /Fe T o f c a l ratio.

(1) Fe /Fe^ .. r a t i o after subtracting blank.
Total
-129-
(P26) AFTER SUTRACTING

100
BLANK
>•
o
z: 80
UJ
o
Lu
U_
UJ
(P26) A
tr
<
•A.
I-
O
40L ' i I—i 1 i — i I- i i i i I I 1 1 L.
CM
E 3.0
u
<
E
0.4M Na S0
>- 2 4
tCO 2.0^ 0. I M H S 0 2 4
9 0 °C
Q
7 3 5 mV
Z
LU
cr
cr
O
50 100 150 200

T I M E (hrs)
Fig. 54 Constant p o t e n t i a l experiments i n 0.3M ^2^0^, 0.2M

H^SO^ at 90°C and 735 mV; various specimens.
(a) Current density.
(b) Total current e f f i c i e n c y .
-130-
50h
PI8 •
30 •a— P26
>•
o COPPER _J I I , ,1 I I L_ 1 1_ _l I l_
z 10 i i i i_
UJ
o
u_
u.
ii-
Ul
100
UJ
60
rr
rr -•^.Q^'f
a P3i \.
A _ ; ^ * - , - D
20 A B ^ s . ^ r c r ^-==R — A - ^ —1
(P26) ——> & J
IRON
i ' • I l i I 1 1 1—^-i 1 L 1 ' 1 1
10 - ^
P3I X . ^ P26
V
FM8
-P30 62fc^
5 h ' ^ ^ ^ ' ^ • • ^ ^ f _ r n
: FE RR1 C j i i i > • ' • J — i — i — i — i —

• i ' ' 1 i—
50 100 150 200
T I M E ( h rs )
Fig. 54 (c) Copper current efficiency.

Cd) Iron current efficiency.
(e) Ferric ion current efficiency.
-131-
Fe +
2
Fe total
1.0
P30 PI8
,!>-•-
-^^...^..^L *—
_ P3I
0.5
(P26)
- 0' I I I I I I l_ _i . L • i I J I I I L
50 100 150 200

T I M E ( hrs)
Fig. 54 (f) F e 7 F e T o t a l ratio,

(g) Fe/Cu r a t i o .
-132-
The current density i n the bisulphate experiment was much lower

2 2
(0.7 mA/cm ), t h i s being supported by P 29A (sulphate solution; 3.1 mA/cm ).
It would appear that current density r i s e s with pH. Current e f f i c i e n c i e s ,
however, declined with pH (based on one experiment).
Copper C.E. for sulphate solutions was about 22% (+4%), whereas i n
bisulphate i t was 30% (+1.5%). Again P 29A supports t h i s .
Iron and t o t a l C.E. show the same trend: after 50 hours the iron
C.E. i n sulphate solutions f e l l to about 18%, whereas i n bisulphate,
a constant 40% value was found. Total C.E. was about 35 - 50% (sulphate)
after 50 hours, as against 75 - 67% (bisulphate).
Iron C.E. i s probably lowered by hydrolysis i n sulphate solutions
at 125°C, i f any F e + + +
ions are present. However the copper C.E. i s
not affected and i t appears that increasing temperature and pH decreases
t o t a l (metal) C.E. This implies increasing oxidation o f sulphur,
(v) Bisulphate/Sulphate Solutions (125°C + 175°C)
Specimen #P 32 was anodized successively (at 735 mV) at 125, 150 and
175°C i n 0.4M NaHSO then at 125 and 175°C i n 0.4M Na S0 . (Figure

?
0.1M H SO
l J
'•O.IM H SO J
56), 1 4 1 4
In bisulphate solution, the current density approximately trebled
with each 25°C increment. Iron C.E. dropped somewhat (45, 38 and 34%)
but copper C.E. dropped to near zero (27.5, 16.5 and 2.0%). Considering
that these current e f f i c i e n c i e s are cumulative, the incremental C.E. of
the 175°C experiment i s actually negative. (The same solution was kept i n
the c e l l ) . That i s , the t o t a l copper i n solution at the end of the 175°C
experiment was less than 1/3 of that e x i s t i n g i n solution at the s t a r t
(i.e. after the 150°C experiment).

-133-
Blue CuS powder was scattered through the c e l l . Evidently some
reducing agent had removed copper from solution, even more quickly than
i t was dissolved.
In sulphate solution, (at 125°C) the copper C.E. was nearly the
same as i n bisulphate (28%), but the iron was lower (23%). At 175°C
2
very large currents were recorded, (52 mA/cm ), but this may have been
due to a short c i r c u i t . The (cumulative) copper C.E. was reduced (10%)
but not as severely as i n the bisulphate case. The bisulphate experiment
was repeated with a fresh electrode (P 33), at 150°C and 175°C (Figure
2 2
56). Current densities were 6 mA/cm and 12 ->• 24 mA/cm r e s p e c t i v e l y ,
while copper C.E. was 13% (150°C) and 5% (175°C). Iron C.E. remained
high at 62% and 52%, and t o t a l C.E. was 75% and 58%. These results
confirmed that above 125°C, some reducing agent was produced, capable
of p r e c i p i t a t i n g copper from solution as CuS.
(vi) Chloride/Bisulphate Solutions - A Comparison
Electrode P 34 was anodized in.0.4M NaCl. successively (at 735 mV)

O.IM HCl )
at 175°C, 150°C and 125°C (Figure 57). Then a bisulphate solution

,0.4M NaHSO... was put i n the c e l l and the experiment repeated, f i r s t at
0.1M H SO
l j
125°C, fhen 175°C (Figure 28).
Very high current densities were recorded i n chloride solutions;
a plot of C D . vs. Temperature i s shown i n Figure 59. An a c t i v a t i o n
energy of 13.1 kcal/mole was calculated. Current e f f i c i e n c i e s were also
high.
CUMULATIVE C.E.
(Chloride)
Temp. Cu Fe Total (Fe )
. 175°C 41.2 47.0 90.1 2.6

150°C 41.2 45.6 92.1 2.0
125°C • 45.6 49.2 96.5 2.3
-134-
CUMULATIVE C.E.
(Bisulphate)
Temp. Cu Fe Total (Fe )
125°C 29.9 46.0 77.1 1.2

175°C 1.3 27.4 29.3 0.5
This experiment demonstrates conclusively the difference between
chloride and sulphate systems. In chloride solution v i r t u a l l y a l l the cur-
rent may be accounted f o r by metal dissolution at each temperature; but
in bisulphate solution approximately 1/2 the current i s used up by sulphur
oxidation at 125°C, and at higher temperatures some sulphur species actu-
a l l y reduces copper from solution.
In Figure 60 the difference between sulphate and chloride i s again
demonstrated. Specimen P 31 was f i r s t anodized at 90°C in ,0.4M Na S0.. ?
•-O.IM H SO }
at 735 mV. Then the solution was changed to ,0.4M NaCl-. and
'•O.IM HCl J
the experiment repeated.
Current Density Current Density

2
Cu Fe Fe Total
mA/cm
Sulphate 1.5 29 21 4 53
Chloride 3.8 •> 5.8 43 54 2 97
( v i i ) Effect of Acid
The effect of acid strength on anodizing CuFeS2 (at 90°C and 735 mV)
in 0.5M C l solution was examined i n experiments P 3 and P 12.
.P 3 0.3M NaCl
0.2M HCl
P 12 0.46M NaCl
0.04M HCl
-135-
In Figure 61, i t can be seen that there i s no appreciable difference
to the current e f f i c i e n c i e s , copper or iron, but the current density i s
about 50% higher i n P 12.
In P 5 and P 16 a similar comparison was made, this time at 535 mV
in 3M NaCl (90°C) :
P 5 3M NaCl (pH =3.5)
P 16 3M NaCl (pH = 0.5)

0.2M HCl
In Figure 76, i t i s shown that without any added acid, the current
steadily declined, instead of increasing, and the current e f f i c i e n c y for
iron or copper was only 10 - 15% (instead of 80 and 60%).
The effect of electrode surface preparation was also examined, P 6, 7
and 11 were prepared by p o l i s h i n g whereas P 8, 9 and 13 were prepared by
saw-cut. No sytematic difference could be observed. A l l other electrodes
were prepared by saw-cut.
( v i i i ) Summary
In dilute chloride solutions at 90°C, the probable anodic reaction
for chalcopyrite i s (in the p o t e n t i a l range 535 - 1185 mV):
CuFeS 2 - 4.4 e" + .266 H 02 + Cu + +

+ Fe + +
+ 1.933 S° + 0.066 SO^ + 0.533 H +
(16)
The above stoichiometry i s reached only after considerable time
(100 hours), before which iron i s dissolved p r e f e r e n t i a l l y .
The current density increases with time, and potential up to 935 mV.
In strong chloride solutions at 90°C, the probable anodic reaction
i s similar to that found in dilute solution (equation 16). However, at
low potentials (535 - 635 mV) some Cu +

i s produced:
CuFeS 2 - (4-x) e" -> x Cu +

+ (1-x) C u + +
+ Fe + +
+ 2 S° (17)
where x = 0.-12 at 535 mV and lower at 635 mV.

-136-
and considerable chemical d i s s o l u t i o n of iron occurs:
CuFeS 2 + 2 H +
•+ CuS + F e + +
+ HS
2 (15)
The percentage of sulphur oxidized to sulphate, omitted i n equation
(17) for c l a r i t y , i s small, as i n d i l u t e solutions, probably not exceeding
3%.
The s i t u a t i o n i s further complicated by the fact that at higher po-
t e n t i a l s (935-1185) approximately 10 - 20% of the iron dissolved appears
in solution as F e + + +
. Anodic current densities i n strong chloride solutions
again increase with time, and p o t e n t i a l , p a r t i c u l a r l y at lower potentials.
The chemistry of the anodic dissolution of chalcopyrite i n ,0.4M Na~S0.

'•O.IM H SOj
solutions at 90°C may be approximated:
CuFeS 2 - 7.2 e~ + 2 H 0 + C u 2
+ +
+ 0.8 F e + +
+ 0.2 F e + + +
+ 1.5 S°
+ 0.5 SO^ + 4 H +
(18)
This equation, which implies 27.8% current e f f i c i e n c y f o r copper,
f i t s the data reasonably well i n the potential range 735 - 1185 mV. At
lower potentials, the current e f f i c i e n c y f o r copper i s considerably reduced
(to 10 - 20%), but the percentage of sulphur oxidized to sulphate continues
to be about 25%.
The current densities i n sulphate solution are much lower than i n
chloride, p a r t i c u l a r l y at 735 mV or below. Furthermore, they usually de-
crease slowly with time, (as opposed to the increasing currents observed
in chloride solutions).
CURRENT DENSITY AFTER 50 HOURS ANODIZING
Potential 0.5M 3M 0.5M
[Cl] [Cl] [S0 ) 4
535 0.1 0.8 - 1.4 0.2

635 2 2.8 0.4
735 2.5 7.8 0.5;1.8
935 8.2 8.8 1.95
1085 7.0
1185 6.6 5.6 5.3
-137-
Th e chemical d i s s o l u t i o n of iron, which again complicates the s t o i c h -
iometry of the anodic d i s s o l u t i o n , occurs only as F e + +

dissolution.
The current density obtainable upon anodizing a given specimen varies
widely from one specimen to another, but i s r e l a t e d to 1) amount of iron
dissolved chemically, and 2) the f r a c t i o n of iron dissolved anodically as
Fe .
+ +
At 125°C - 175°C, anodizations i n chloride solutions are l i t t l e dif-
ferent from those at 90°C, except for an increased current density. At
735 mV, an activation energy of 13.1 kcal/mole was determined for the
current density.
In the sulphate system, however, r a i s i n g the temperature changes the
chemistry of anodic d i s s o l u t i o n , as well as increasing the current density.
At 125°C i n sulphate solutions ,0.4M Na„SO.. copper and iron current

'•O.IM H S 0
2
4J
e f f i c i e n c i e s f a l l to near 20%, i n d i c a t i n g increasing oxidation of sulphur.
However, i n bisulphate,0.4M NaHSO.. current e f f i c i e n c i e s remain nearly

'•O.IM H SO 2
}
constant, at 27 - 30% (Cu) and 35 - 40% (Fe).
Above 125°C, the current e f f i c i e n c y for copper f a l l s even i n bisulphate
solutions, and at 175°C copper i s actually removed from solution during
anodization, i n d i c a t i n g a negative current e f f i c i e n c y .

-138-
80
P29 (BISULPHATE)
60
>-
o
E ,29 A (SULPHATE)
40 --Ct-r———O
LU
LU
tr
OC
o
20
I , I I 1_ JL_ I I i -I I I l_ _l ' • •
0.4 M Na S0 2 4
1= 0.1 M H S 0 2 4
o I 2 5 °C
< 7 3 5 mV
E
/P28
>-
CO
29A
z p X p 2 7
UJ
Q v (j) o
I
LU
tr P22
OC
I
o I
P29
4 I _i i i i_
150 200
100
T I M E ( hrs )
F i g . 55 Constant p o t e n t i a l experiments i n sulphate and

bisulphate solutions at 125°C, 735 mV.
(a) Current density.
.(b) Total current e f f i c i e n c y .
-139-
COPPER
50
,P27
P29
>- X • o
25
o
x>—v P22
-f—•
z O —O
UJ
P28 29A
u. J 1 1 I I I I I -j i i i
u.
UJ
I R O N
\
UJ
\
rr \ P27
50 \
or
3 \ P29
O
- \ 0-—^ J2L
Nsx
25
P2SX P22 29A
0 o
'X •
01 -i i i i i i_
1 1 i i L _i i • '
i i
50 100 150 200

0
T I M E ( hrs )
F i g . 55 (c) Copper current e f f i c i e n c y .

(d) Iron current e f f i c i e n c y .
-140-
E , ( h r s )
F i g . 56 Constant potential experiments i n sulphate and

bisulphate solutions at 125°C -> 175°C, 735 mV.
Left: Successive experiments at 125°C, 150°C
and 175°C i n bisulphate; then at 125°C
i n sulphate solution.
Right: Successive experiments at 150°C and 175°C
i n bisulphate solution.
(Current e f f i c i e n c i e s are cumulative f o r each
bisulphate solution.)
-141-
lOOr
90- o TOTAL 0.4M NaCl
0. I M HCl
50|
I^RO N 7 3 5 mV
M-
o
40 - t " ^ CO PP E R
-
UJ
o
u. 30 •
li.
UJ
2 20-
Ul
LX
10 -
o
! FERRIC
D-H —,—O— r-, T ••
L-L 1 I I J L
F i g . 57 Constant potential experiments at 735 mV i n 0.4M NaCl,

O.IM HCl at 175°C, 150°C and 125°C.
-142-
F i g . 58 Constant potential experiments at 735 mV i n 0.4M NaHSO^,

O.IM H SO at 125°C and 175°C. Same specimen as used
2 Zf
for l a s t experiment (Fig. 57).

-143-
F i g . 59 Arrhenius diagram f o r current at 735 mV i n 0.4M NaCl,

O.IM HCl.
-144-
O—O TOTAL
120 h A—-A IRON
COPPER
a—a FERRIC
80
>-
o
z
UJ
o 'A
V 57..
UJ 40
X
Ul
cn
cc
• —
3
<_>
•-o — a 1 • i
_J L_ 1- • i I I I 1 L- 1 X _
L
7 3 5 mV , 9 0 °C
<M 6
E
o
>-
co
z 0.4 M NaCl
UJ
0. I M HCl
o
z 2
UJ
0. 4 M Na S0 2 4
cc 0.1 M H S 0
cc 2 4
3
o
J i—i—i— _L
50 100 150 200
T I M E (hrs)
60 Successive constant potential experiments at 90°C, 735

mV i n bisulphate and chloride solutions.
-145-
F i g . 61 Effect of decreased acid on constant p o t e n t i a l experi-

ment i n d i l u t e chloride solution at 735 mV, 90°C.
-146-
O O TOTA L
A—-A IRON
v—COPPER
200
>-
o
150
UJ
LZ I00f
LU
UJ 50f
tr
tr
o
i
0
J ' i I , I L J 1 _l |_
1 _i l 1_
E
5 3 5 mV , 9 0 °C
3 M NaCl
E
£ 2
NO ACID
to
0.2 M HCl
UJ
I F
tr
tr
O
_L
0 -I 1 I ,-L. J I 1 1
— _l I I l_
0 50 100 150 200

T I M E (hrs)
Fig. 62 Effect of no acid on constant potential experiment in

strong chloride solution at 535 mV, 90°C.
-147-
IV Leaching
a) The Motive
The electrochemical experiments of the preceding sections showed that
there i s considerable difference i n the anodic d i s s o l u t i o n of chalcopyrite
in chloride and sulphate. In p a r t i c u l a r , the d i s s o l u t i o n rate i s consider-
ably faster at low potentials i n chloride than i n sulphate, and the oxida-
tion of sulphur i s s i g n i f i c a n t (25%) i n sulphate solutions but not i n
chloride.
The available data i n the l i t e r a t u r e bn the chemistry of leaching .
chalcopyrite are not very large, as outlined i n the introduction, but they
indicates l i t t l e difference i n the d i s s o l u t i o n stoichiometry of f e r r i c
sulphate and f e r r i c chloride leaching (130,131). A l l workers agree that
f e r r i c chloride leaching produces l i t t l e or no sulphate, i n agreement with
the anodic d i s s o l u t i o n i n chloride solutions shown here.
However, Dutrizac (131) also claimed i n s i g n i f i c a n t sulphate formation
for f e r r i c sulphate leaching, and this r e s u l t has been frequently stated
by other writers, reviewing hydrometallurgical processes f o r chalcopyrite
concentrates (2,3,5,132).
The r e s u l t s of the electrochemical experiments described i n t h i s
work do not appear to be compatible with Dutrizac's experiments, by reason
of the sulphate formation observed here. This suggests that the e l e c t r o -
chemical d i s s o l u t i o n of chalcopyrite may have d i f f e r e n t stoichiometry than
the chemical d i s s o l u t i o n ; such a r e s u l t would place serious doubt on the
postulate that chalcopyrite leaches electrochemically, and would m a t e r i a l l y
reduce the value of these electrochemical experiments.
In order to resolve t h i s problem, leaching experiments were undertaken,
primarily to determine once more the chemistry of d i s s o l u t i o n of chalco^

-148-
pyrite i n f e r r i c sulphate and f e r r i c chloride.
b) Leaching Experiments on Massive CuFeS.,
(i) Preliminary experiments
Preliminary experiments were carried out using small pieces of CuFeS
placed i n u n s t i r r e d solutions for one day.
Cu Dissplvec Equivalent
Specimen Solution Temp. Atmosphere day-cm^ Current
Control (mmoles) Density
(mA/cm )2
I-l IM KC1 90°C 0 0

N
2
0-1 IM KC1 90 C
U
Open 15 0.07
1 Beaker
F-l IM FeCl 85°C Covered
0.2M HCl Beaker 100 0.43
F-2 0.5M FeCl 100°C 130 0.60 "
Narrow-
0.2M HCl
necked
F-3 ' 0.5M FeCl 100°C 143 0.67
flask
0.2M HCl
with
F-4 IM F e ( S 0 ) 100°C 22 0.10
Condenser
4 1
0.2M H SO
? k
The equivalent current was calculated by assuming that the anodic
dissolution produces only C u + +

and F e + +
(n = 4).
Then from Faraday's Laws: 1 mA = 213 ymole Cu/day
100 ymole Cu/day =0.47 mA •
It can be seen that no copper dissolves from chalcopyrite i n a chloride
solution, without an oxidizing agent, and that a small amount dissolves
when there i s free 'access to a i r . F e r r i c chloride dissolves f a r more copper
than f e r r i c sulphate (6 times) but the equivalent current densities are
s t i l l quite low (see Figures 50, 53), and correspond to low applied poten-
tials .
-149-
( i i ) Morphology
Specimens were mounted i n epoxy and fresh faces revealed by p o l i s h i n
The leaching vessel was a round bottom flask f i t t e d with a condenser and
heated by a mantle; the specimen was placed i n the bottom of the f l a s k ,
face up, with no s t i r r i n g .
In Figure 63 i s shown scanning electron micrographs of specimens
leached for five days at 95°C. In 1.0M f e r r i c sulphate (F-6) , attack
appears to be primarily along f i s s u r e s , as evidenced by sulphur deposits,
whereas i n IM f e r r i c chloride (F-5) there i s overall attack.
Leaching for shorter periods i n FeCl^ s t i l l produces o v e r a l l attack
fFigure 64) (11 hours, 100°C, IM F e C l ) . 3
A more detailed examination of the surface of chalcopyrite during
f e r r i c sulphate leaching showed progressive attack along grain boundaries
In Figure 65 i s shown the surface of chalcopyrite after 11 hours leaching
at 98°C i n IM F e ( S 0 )
4 1 5 (+ 0.2M H S0 ).
2 4 The appearance of the surface
is unchanged from the o r i g i n a l , unleached condition, and p o l i s h i n g marks
are c l e a r l y in evidence. In the same figure i s shown the appearance of
one small area, adjacent to a f i s s u r e , after 305 hours leaching. This
i l l u s t r a t e s what a leached surface can look l i k e .
Three separate areas are shown, i n Figure 66, as a function of
leaching time. The area shown i n Figure 66(a) i s s t i l l apparently un-
attacked after 305 hours, (at least according to the c r i t e r i a of the
polishing marks and the flattened, polished face). Figures 66(b) and (c)
however, show substantial attack along f i s s u r e s , (which were not v i s i b l e
on the specimen before leaching) after 71 hours. These fissures are
widened after 135 hours, but s t i l l there i s l i t t l e or no attack on the
o r i g i n a l nolished surface.
-150-
F i g . 63 Scanning e l e c t r o n micrographs of c h a l c o p y r i t e a f t e r l e a c h i n g
(5 days, 9 5 ° C ) .
Top: IM FeC±3 The whole s u r f a c e i s covered w i t h e l e m e n t a l s u l p h u r .
Bottom: IM F e ( S 0 4 > 5 C h a l c o p y r i t e i s l a r g e l y unchanged. Sulphur i s
1
d e p o s i t e d a l o n g the g r a i n boundaries ( w h i t e ) .
-151-
JFig. 64 Scanning electron micrographs of chalcopyrite a f t e r leaching

(11 hours, 95°C, IM F e C l ) .
3
The entire surface has the 'woolly' appearance of a sulphur

coating.
-152-
Fig. 65 Scanning electron micrograph of chalcopyrite after leaching

i n IM F e ( S 0 ) at 95°C.
4 1 # 5
Top and bottom l e f t : 11 hours leaching; surface s t i l l has the

polished appearance.
Bottom right: 305 hours leaching. Area adjacent to
fissure; fresh crystal facets of chalcopy-
rite visible.
-153-
-154-
F i g . 66 (b) An area that has been attacked.

Top: 71 hours. Fissures formed with elemental sulphur deposit.
No attack on surrounding area (polishing marks v i s i b l e ) .
Bottom: 305 hours. Fissures largely unchanged, but surrounding area
has been attacked; fresh c r y s t a l facets are v i s i b l e .
-155-
F i g . 66 (c) Another attacked area. Top ; 71 hours

Bottom: 305 hours
-156-
F i g . 67 Theoretical relationship between percent sulphur as S°

,|..j„ ||
and Fe /Cu r a t i o i n equation (20).
-157-
After 305 hours the surface i t s e l f i s attacked, and polishing marks
are eliminated; fresh crystal facets are evident.
During this time copper dissolved at a f a i r l y constant rate; quanti-
tative data on this aspect i s given i n the next section.
( i i i ) A Comparison of Chemical and Electrochemical Dissolution
Specimens were mounted i n epoxy as i n the electrochemical experiments
and the leaching carried out i n an apparatus described i n Figure 7, with
nitrogen passing into the leaching vessel.
A t y p i c a l leaching experiment i n f e r r i c sulphate -1.0M Fe(S0.) r-,

"-0.2M H S0 2 4
J
gave the following r e s u l t :
Specimen Dissolved Metals

Temp. Area Time (mmoles) Fe /Cu++
S° S°
(cm )
2
(days) Cu Fe^ (mmoles) 2 • Cu
90°C 0.96 38 1.45 10.36 7.15 2.10 0.72
(S° analysis was by CS extraction). ?
If the only products of CuFeS^ leaching are C u , F e , S° and SO^ , ++ + +
then the d i s s o l u t i o n reaction may be written:
CuFeS 2 + (4+6x) F e 3 +
-+ C u + +
+ (5+6x)Fe ++
+ (2-x)S° + x SCfj (19)
where x/2 = f r a c t i o n of sulphur oxidized to sulphate.
Then the relationship between the percent sulphur as elemental sulphur
(%S°) and Fe /Cu r a t i o i s :

++
%S° = 100/12(17 - F e / C u ) ++ ++
(20)
or F e / C u
+ + + +
= 17 - 12/100(%S°).
From t h i s r e l a t i o n s h i p (plotted i n Figure 67) a F e / C u + + + +

r a t i o of
7.15 should correspond with 82% S°. The actual value of S ?

extracted i s
-158-
72%.*
2
The rate o f d i s s o l u t i o n o f Cu i s 40.0 mmoles/day-cm . This may
be translated into equivalent current density, by choosing a value f o r n,
the number of electrons i n the anodic reaction, which may be calculated
from F e / C u + + + +
ratio:
n = Fe /Cu + + + +
- 1 (= 4+6x)
or from percent sulphur produced as S ° (%S°)J
n = 4 + 12/100(100-%S°)
In the above case:
n = 6.15 by F e / C u + + + +
produced.
n = 7.35 by S ° analysis.
Then the equivalent current density i s :
(n = 6.15) 0.29 mA/cm 2
(n = 7.35) 0.345 mA/cm 2
These currents correspond to an applied p o t e n t i a l (Figure 53) of
635 - 735 mV, a reasonable value for f e r r i c sulphate leaching (see Section
V).
The current e f f i c i e n c y for copper in the anodic d i s s o l u t i o n experiments
(in sulphate) was t y p i c a l l y 27%, although smaller at lower p o t e n t i a l s . From
the values f o r n, above, we may calculate current e f f i c i e n c y for copper,
(C.E. ): C u
C.E. Cu = 100 (2/n) = 32.6% (by F e / C u

+ + + +
27.2% (by S°).
There i s reasonable agreement then between t h i s leaching experiment
i n sulphate solution and electrochemical r e s u l t s , i n two areas: the
equivalent current density and the chemistry of d i s s o l u t i o n .

7t
Only rhombic and monoclinic sulphur are soluble i n CS , 9 amorphous

sulphur i s not (196). 1
-159-
The results f o r a t y p i c a l f e r r i c chloride IM FeCl leach at 90°C

'•0.2M HCV
were:
2
Dissolved Metals
(mmoles/cm )
Temp. Time Fe /Cu S°
(°C) (Hrs.) Cu + +
Fe + +
2.Cu
90 140 2.97 14.9 5.02
212 3.75 18.2 4.83 .895

, 1
Thus the F e / C u
+ + + +
r a t i o was very close to 5.0, which corresponds
to 100% elemental sulphur production; S° analysis by CS^ extraction yielded
89.5% S°. The corresponding current e f f i c i e n c i e s f o r copper are 50% and

2
39%, and the equivalent current densities (at 140 hours) 2.4 mA/cm and
2
3.1 mA/cm .
Such current densities i n strong chloride solutions (Figure 51) cor-
respond to a potential o f 635 mV; copper current e f f i c i e n c y at t h i s poten-
t i a l was 55%.
There i s then reasonable agreement between chemical and electrochemi-
cal experiments i n chloride solutions as well as sulphate.
(iv) Chemistry of Dissolution (at 90°C)(using apparatus i n Figure 7)
The results of f e r r i c sulphate leaching are shown i n Figures 68, 69.
After an i n i t i a l period, the rate of d i s s o l u t i o n of copper was constant,
even up to 57 days. When the solution was IM i n [ F e + + +

] , an induction
period (100 hours) was noticeable, during which leaching rates were about
one t h i r d of the l a t e r values. Aside from this phenomenon, s i m i l a r leach-
ing rates were observed i n IM and 0.1M F e + + +

. The r a t i o F e / C u
+ + + +
produced
during leaching o r i g i n a l l y had high values (>10) at the beginning o f a
leach. This slowly declined to about 6.5 a f t e r about 10 days, and s t a b i l i z e d .

-160-
Leaching with f e r r i c perchlorate gave s i m i l a r d i s s o l u t i o n rates, but
the F e / C u
+ + + +
r a t i o declined s t e a d i l y to very low values (<3) with no
stable value. This was evidently due to oxidation of ferrous ions by per-
chlorate.
Leaching with f e r r i c chloride resulted in greatly increased d i s s o l u -
t i o n rates (Figure 70), which depended strongly on the [Fe + + +

].
The i n i t i a l leaching period (50 hours) i n d i l u t e f e r r i c chloride
(O.IM) appeared to be influenced by the surface treatment of the mineral
(Figure 71). Polishing or exposure to a i r for a few days, lowered the
rate of d i s s o l u t i o n of copper i n this period, compared to a fresh saw-
cut surface, by a factor of f i v e or more. No such effect was found in
either IM FeCl^ or f e r r i c sulphate leaching.
After this i n i t i a l period, approximately l i n e a r rates of d i s s o l u t i o n
were observed in d i l u t e f e r r i c chloride, which were approximately five
times as high as in f e r r i c sulphate.
In strong f e r r i c chloride (Figure 70), leaching was very rapid for
the f i r s t day or two, then l e v e l l e d o f f .
Fe /Cu
++ ++
r a t i o s produced during f e r r i c chloride leaching again
started at high values (>10) but l e v e l l e d o f f a f t e r two days (5M Fe + + +

)
or seven days (O.IM Fe + + +

) at about 5.5.
c) Powder Leaching
In the previous section i t was shown that the d i s s o l u t i o n of massive
specimens of chalcopyrite in f e r r i c sulphate/chloride i s in accord with the
electrochemical results obtained e a r l i e r . However, the hydrometallurgical
processing of chalcopyrite concentrates i s u n l i k e l y to be carried out on

-161-
T I M E (days)
Fig. 68 Leaching of massive chalcopyrite i n IM Fe(SO.) , 90°C.

-162-
0 100 200 300
T I M E (hrs)
Fig. 69 Comparison of leaching in O.IM and IM Fe(SO.)

-163-
T I M E (hrs)
Fig. 70 Comparison of leaching i n sulphate, perchlorate and

chloride solutions.
-164-
T I M E (hrs)
F i g . 71 Effect of surface preparation on FeCl^ leaching.

-165-
massive specimens (except perhaps i n heap or dump leaching) and given the
peculiar morphology o f leaching observed i n Figures 63-66, i t i s quite
possible that the leaching of f i n e l y ground material has e n t i r e l y d i f f e r e n t
characteristics. The factors a f f e c t i n g the d i s s o l u t i o n of powdered mater-
i a l are the subject o f study i n this section.
Powdered material was obtained by crushing chalcopyrite (from the
same source as before, a high grade lump of Craigmont ore); t h i s was done
with a mortar and pestle, i n a i r . Chalcopyrite crushes very e a s i l y , and
actually shatters on l i g h t impact; thus reasonably f i n e material was ob-
tained without grinding. 1
Size reduction below about 200 mesh required grinding, however,
which was undesirable due to the danger of oxidation. A significant
f r a c t i o n of shattered material was s u f f i c i e n t l y f i n e , however, that grind-
ing was not necessary unless a complete piece was to be reduced. The use
of such a f r a c t i o n assumes that i t has the same properties as the rest
of the material.
In order to conserve material, the p u r i t y of chalcopyrite used i n
t h i s part of the work was not as high as i t was earlier. Several analyses
were c a r r i e d out (using the method outlined i n Scott (182), involving
decomposition of the ore with Br^/CCl^, followed by HNO^) and an average
p u r i t y of 93% was calculated. However, t h i s w i l l vary somewhat from
one sample to another, owing to the desire not to homogenize the s i z e d i s -
t r i b u t i o n , as noted above.
-166-
(i) Shape of Leaching Curve
Sullivan (130) showed that i n f e r r i c sulphate leaching of powdered
CuFeS2, the rate of extraction of copper f e l l o f f very r a p i d l y ; s i m i l a r -
l y , Dutrizac et a l (131) reported that i n f e r r i c sulphate leaching of
massive sintered disks of synthetic CuFeS2, a parabolic leaching curve
was obtained. However, the results reported here c l e a r l y showed l i n e a r
dissolution rates of massive, natural CuFeS2 (even a f t e r 57 days), i n
accord with the anodic studies i n sulphate solution.
The results of a t y p i c a l leaching experiment i n f e r r i c sulphate are
shown i n Figure 72. A declining rate of d i s s o l u t i o n i s evident, as the
reaction proceeds; p l o t t i n g the extraction of copper vs. /time, gives
a nearly linear relationship up to 60% extraction, but not beyond that
(Figure 73).
If one assumes that the mineral p a r t i c l e s are spheres, then the de-
cline i n available mineral surface area during a reaction may be corrected

1/3
for by p l o t t i n g [l-(l-R) ], (instead of % Cu extracted) where R = f r a c t i o n
of Cu extracted (199). Such a plot i s also shown i n Figure 73.
It can be seen that a nearly l i n e a r r e l a t i o n s h i p exists up to a
certain point (36% extraction).
The extraction of copper, as shown i n this experiment, evidently
stops at 70%; the reason i s not apparent.

Other experiments, using O.IM FeCl^, and a variety of p a r t i c l e sizes
1/3
are shown i n Figure 74, where l - ( l - R ) i s plotted. Linear relationships
were also found.
( i i ) Effect of P a r t i c l e Size
As seen i n Figure 74, increasing p a r t i c l e size decreases the rate of the
Cu extraction i n f e r r i c chloride. The slopes of the leaching curves are

-167-
in the following r a t i o s :
Relative Approximate
Size Slope Mean
Radius
-12+ 16 0.40 720 \i
-50+100 1.00 100 vi
-400 4.5 <17 \i
Since the area/gram of a mineral p a r t i c l e declines l i n e a r l y with i n -
creasing values:
Area 1
a
gram r
i t can be seen that the r i s e in d i s s o l u t i o n rates i s not proportional to
the r i s e in area for smaller p a r t i c l e s . This assumes a constant roughness
factor. However, the increase i n rate i s c e r t a i n l y substantial, and i t
indicates that the area of the p a r t i c l e exposed to the solution i s an
important factor. The actual size of the p a r t i c l e s i n the larger size
ranges may have been reduced considerably by the magnetic s t i r r i n g action
(see below).
Not shown i n Figure 74 i s the fact that the leaching stops after 80
hours at 95% extraction (for -400 mesh p a r t i c l e s ) , and 150 hours at 73%
extraction (for -50+100 mesh p a r t i c l e s ) .
In f e r r i c sulphate p a r t i c l e size seems to be less important, Figure
75. Increasing dissolution rates are evident in going from (-^12+16) to
(^50+100), with no change thereafter, even at -400 mesh. Dissolution stop-
ped at about 70% extraction. The reason for t h i s phenomenon i s not apparent.
-168-
Fe (mmole)
O 1
1 1 i I 1
0 4 8 12
T I M E (hrs)
72 The leaching of powdered chalcopyrite with f e r r i c sulphate.

-169-
T I M E (days)
«/T I M E ( hrs)
F i g . 73 Comparison of linear and parabolic k i n e t i c s i n the leaching
of powdered chalcopyrite with f e r r i c sulphate.
-170-
0.5
T I M E (days)
F i g . 74 Leaching of powdered chalcopyrite with f e r r i c chloride.

-171-
T I M E ( hrs )
F i g . 75 Effect of p a r t i c l e size i n f e r r i c sulphate leaching.

-172-
(iii) Fe /Cu+ + + +
Ratios Produced During Leaching
In Figure 68, an approximately constant r a t i o of 7.5 i s established
after the f i r s t day; the dip i n the curve seems to be spurious. This ex-
periment was done i n f e r r i c sulphate, and s i m i l a r experiments produced
Fe /Cu
+ + + +
r a t i o s close to 7.5 (Figure 76).
In f e r r i c chloride, ratios were close to 6.0 (Figure 77)
These values are approximately i n agreement with those obtained i n
leaching of massive specimens, although somewhat higher i n each case.
The reason for this may be connected with the cessation of the reaction.
(iv) Effect of F e r r i c Concentration
In chloride solutions, increasing the [ F e + + +

] increases the rate of
extraction of copper (Figure 77). The increase, however, i s by no means
proportionate to [ F e + + +
] , as reported by Ermilov et a l (140), on massive
specimens.
In sulphate solutions, the d i s s o l u t i o n rate does not improve for
[Fe " ] above O.IM

J ++
(Figure 76).
These results are again i n agreement with e a r l i e r work here and in
the l i t e r a t u r e ,(131), on massive specimens.
(v) E f f e c t of Added Chloride
In 0.03M FeCl^, the d i s s o l u t i o n rate was increased 50% by adding IM
NaCl, but the e f f e c t was n e g l i g i b l e i n O.IM FeCl^.
(vi) E f f e c t of [ F e ] ++
In chloride solutions, addition of 0-1M [ F e ] had no e f f e c t on the

++
dissolution rate; however in sulphate solutions, a d r a s t i c reduction
in rate was noted between 0.01M [Fe ] and O.IM [Fe ] (Figure 78).
With O.IM FeS0 , leaching v i r t u a l l y stopped at 4% Cu extraction, whereas

4
-173-
F i g . 76 Effect of [Fe J i n f e r r i c sulphate leaching.

F i g . 77 E f f e c t of TFe ] i n f e r r i c chloride leaching.
-175-
Effect of i F e ] i n f e r r i c sulphate and chloride leaching.

-176-
in 0.01M FeSO^ the rate i s the same as i n a solution with no added
FeS0 4>
( v i i ) Effect of Acid
In chloride solutions, the d i s s o l u t i o n rate appears to be at a mini-
mum with 0.24M HCl with small increases observed at higher or lower pH.
In sulphate solutions, rates are similar i n 0.018M and 0.18M H S0 . 2 4
( v i i i ) Effect of S t i r r i n g Mode
Using (-50+100) mesh p a r t i c l e s , a s i g n i f i c a n t increase i n rate of
dissolution i s realized by changing from mechanical to magnetic s t i r r i n g ,
(Figure 79), i n f e r r i c chloride s o l u t i o n .
However, i n f e r r i c sulphate s o l u t i o n , a very much greater increase
is realized (with magnetic s t i r r i n g ) .
The reason for this increased rate i s almost c e r t a i n l y the grinding
action of the magnetic s t i r r e r bar, which can cause size reduction of the
p a r t i c l e s or create some other b e n e f i c i a l e f f e c t , such as higher defect
concentrations i n the s o l i d .
(ix) Effect of Temperature
The effect of temperature on leaching with IM FeCl^ i s displayed i n
Figure 80. Using the amount of copper after 5 hours, an a c t i v a t i o n energy
of 17.3 kcal/mole was calculated. This i s somewhat higher than values
calculated e a r l i e r for anodic d i s s o l u t i o n (Figures 47-49, 59), but i n
agreement with values i n the l i t e r a t u r e for f e r r i c chloride (Ermilov (140)
12.3 kcal.) and f e r r i c sulphate (Dutrizac (131), 17.3 k c a l ) .
(x) Effect of Grain Size i n F e r r i c Sulphate Leaching
Some single crystals of chalcopyrite, obtained from Ward's Museum,
were v e r i f i e d by Laue photographs. Their size was approximately i n the
(-12+16) range.
-177-
It was of i n t e r e s t to study the leaching of this material because the
e a r l i e r work (Section IV - (b)) had indicated that CuFeS2 dissolved prefer-
e n t i a l l y i n f e r r i c sulphate along f i s s u r e s , which presumably were grain
boundaries.
A comparison of the leaching of these single c r y s t a l s with that of
'normal' ( p o l y c r y s t a l l i n e ) CuFeS2 i s shown i n Figure 81. Unfortunately
the only data f o r p o l y c r y s t a l l i n e material were obtained using magnetic
s t i r r i n g , whereas the single c r y s t a l s were leached with a mechanical
stirrer. However the rate i s faster with the single c r y s t a l s , even though
the mechanical s t i r r i n g produces slower extraction rates (see above).
This unexpected r e s u l t seems to disprove the theory that f e r r i c s u l -
phate leaches p r i m a r i l y at grain boundaries. However, there i s the p o s s i -
b i l i t y of sub-grain boundaries playing an important r o l e .
material by v i r t u e of not having been ground or crushed i n any way.

++ ++
It may be s i g n i f i c a n t that the Fe /Cu r a t i o produced on leaching
single c r y s t a l s i s abnormally high (Figure 81).
(xi) Summary: Comparison of F e r r i c Chloride and F e r r i c Sulphate
Leaching
In Figure 79, the rate of d i s s o l u t i o n of (-50+100) mesh CuFeS^ i s
shown as being approximately equal i n O.IM FeCl^ and 0:iM Fe2(S0^)2,
using magnetic s t i r r i n g . These conditions are optimum f o r f e r r i c sulphate
leaching, f o r increasing [ F e + + +
] , or f i n e r p a r t i c l e s do not increase the
rate. However, FeCl- leaching i s benefitted greatly by these two f a c t o r s ;
furthermore high [ F e ] depresses the rate of f e r r i c sulphate

++
leaching,
but not f e r r i c chloride leaching.
Therefore i t must be concluded that f e r r i c chloride leaching i s i n gen-
e r a l f a s t e r than f e r r i c sulphate leaching, the difference depending on

-178-
Fig. 79 E f f e c t of s t i r r i n g mode i n f e r r i c sulphate and chloride leaching.

-179-
T I M E (hrs)
R A T E = Cu EXTRACTION / 5 hrs
I OOO / T(°K)
F i g . 80 Effect of temperature on f e r r i c chloride leaching.

-181-
[Fe + + +
], [ F e ] and the size of the p a r t i c l e s ,
++
d) Concentrate Leaching
In the experiments described i n the previous section, i t was demon-
strated that chalcopyrite leaching i n f e r r i c solutions i s f a c i l i t a t e d by
the following conditions:
Chloride Solution
High [Fe + + +
]
High Temperature
Small P a r t i c l e Size.
However, i n a l l these experiments, extractions were slow compared to
i n d u s t r i a l requirements: e.g. 80 hours required to extract 90% of
contained copper i n O.IM FeCl^ from -400 mesh powder, 90°C.

+++
It may be argued that r a i s i n g the [Fe ] or temperature, or lowering
the p a r t i c l e size w i l l improve this extraction rate s i g n i f i c a n t l y , but
i t i s d i f f i c u l t to v i s u a l i z e how 99% extractions could be obtained within
an hour, as reported by Haver and Wong (137); e.g. i n Figure 77 i t i s seen
that only a 50% increase i n rate i s achieved i n leaching (-50+100) material
in lM.FeClj rather than 0.1M.
The answer to this dilemma i s to be found i n the shape of the leaching
curves, as mentioned i n the introduction. This i s demonstrated i n t h i s
section, using actual concentrates from f i v e separate mines:
Concentrate % Cu % Fe
Craigmont (B.C.) 26 .0 52 .5
Ruttan Lake (Man.) 31 .9 31 •?
Phoenix (B.C.) 27 .5 31 .5
Valley Copper (B.C.) 43 .3 19 .1
Granisle (B.C.) 39 .1 20 .0
(analysis carried out by author).

-182-
The f i r s t three concentrates were (supposedly) primarily chalcopyrite,
but the last two contained some bornite (Cu^FeS^). The high iron content
of the Craigmont concentrate may indicate the presence of some bornite
also.
In Figure 82, the leaching of three of these concentrates i n IM FeCl^
at 90°C i s shown; a d i s t i n c t l y faster rate i s evident at the start of
each experiment, compared to that p r e v a i l i n g after the f i r s t three hours.
In fact, the slow, second stage seemed to have a similar rate i n a l l three
experiments, and the distinguishing feature i s the rate of the f i r s t stage.
Using Craigmont concentrate only, the same conclusion may be drawn
about the effect of p a r t i c l e size or [ F e + + +

] (Figure 83), i . e . decreasing
the p a r t i c l e size from 200 u to 30 u increases the rate of the f i r s t
stage by 50% (O.IM FeCl ) or nearly 100%

3 (IM F e C i p . Increasing the
[Fe + + +
] from 0.1M to IM increases the rate of the f i r s t stage by 60%
(-400 mesh) or 45% ((-50+100) mesh). In a l l these cases, the second stage
leaching rates were approximately equal.
This phenomenon has great importance i n an i n d u s t r i a l process, for
leaching rates are not as important as extraction times. Due to the slow
rate of the second stage, i t i s important to achieve the desired extraction
within the f i r s t stage. Thus i n Figure 83 (0.1M FeCl^ leaching) only five
hours are required to extract 36% of the copper i n a (-400) mesh sample
whereas 15 hours were required f o r a (-50+100) mesh sample. The
extraction time (to 36%) was decreased by a factor of three; however the
second stage leaching rate was hardly affected.
High extractions i n short residence times are therefore consistent
only with the persistence of stage 1 leaching e s s e n t i a l l y to completion;
the effects of the above variables on stage 2 are so small that i f the
t r a n s i t i o n occurs before acceptable extraction, very long residence times

-183-
become mandatory.
The maximum extraction rates for the d i f f e r e n t concentrates was de-
tenained by leaching the finest f r a c t i o n of each, i n 4M FeCl 3 at r e f l u x
temperature, 109°C.
Concentrate Finest Max. Extraction 90% Extraction

Fraction Extent Time Time Ratio
Craigmont -400 100% 4 hrs. 2 hrs. 8
Ruttan -325 86% 5 OO CO
Phoenix . -270 90% 3 3 12

+325
Valley Copper -400 100% 1 1/4 1
Granisle -400 97% 2 1 4
These data are shown i n Figure 84, where the very fast rate of d i s s o l u -
tion of Valley Copper concentrate i s evident, the rate i n the f i r s t stage
i s 2 - 3 times as, fast as i t i s for Craigmont, Phoenix, or Ruttan concen-
trates. The 90% extraction times are i n the r a t i o 1:4:8:12:°° .
The difference between the various concentrates may be mineralogical
or average p a r t i c l e size. It was d i f f i c u l t to reduce the Ruttan and
Phoenix concentrates to -400 mesh, using a mortar and pestle - the
b r i t t l e n e s s that characterizes large pieces of chalcopyrite does not
extend past about 200 mesh. Therefore each of the three less reactive con-
centrates was ground several hours i n a small porcelain j a r m i l l , and
the -400 f r a c t i o n leached as before, under optimum conditions.
The results of this extra grinding were not b e n e f i c i a l - i n each
case the extractions were s l i g h t l y reduced.

++ ++
The Fe /Cu ratios produced during leaching were also determined
(Figures 82, 84). For Craigmont concentrate values were close to 5.0
-184-
(1M Fe C l 3 90°C) or 4.5 (4M F e C l 3 109°C). Values below 5.0 can be the
result of bornite present i n the sample, or p r i o r oxidation. For the known
bornite concentrates, Granisle and Valley Copper, values were near 3.2
(4M F e C l , 109 C); for Pho enix and Ruttan r a t i o s were 5 -

3 5.5.
e) Summary
Leaching chalcopyrite with f e r r i c chloride i s much more e f f e c t i v e than
leaching with f e r r i c sulphate. At 90°C, i n d i l u t e ( f e r r i c ) solutions, the
leaching rates are approximately equal, for p a r t i c l e s larger than 100 mesh.
However, in f e r r i c chloride leaching, the reaction rate i s greatly increased
by using f i n e r p a r t i c l e s and higher [Fe + + +

] , these factors having n e g l i g i b l e
effect i n f e r r i c sulphate. Furthermore, i n f e r r i c sulphate, the leaching
rate i s severely depressed by high [Fe '], whereas this has no e f f e c t i n
f e r r i c chloride leaching.
The chemistry of the leaching reaction i n f e r r i c sulphate and ferric
chloride i s s i m i l a r to that found i n electrochemical experiments, i . e . there
i s a greater degree of sulphur oxidation i n sulphate solutions than i n
chloride,(approximately 25%),and iron dissolves before copper does.
The observed leaching rate i n f e r r i c sulphate or f e r r i c chloride also
correlated with the anodic current densities obtained i n the electrochemical
experiments. Therefore the leaching of chalcopyrite appears to be an
electrochemical reaction.
The morphology of leaching appears to be d i f f e r e n t i n f e r r i c sulphate
from that i n f e r r i c chloride. In the former case, p r e f e r e n t i a l attack
along fissures was noted, whereas i n the l a t t e r o v e r a l l attack on the min-
eral surface was observed.
Similar d i s s o l u t i o n chemistry was observed i n the leaching of massive
specimens and powdered material. Linear k i n e t i c s were observed with massive

-185-
specimens, but on powdered material a more complex behaviour was noted.
In f e r r i c sulphate and under 'gentle' conditions i n f e r r i c chloride
(i.e. large p a r t i c l e s , low [Fe + + +

] , low temperature) l i n e a r k i n e t i c s were
observed up to a certain point (generally 50 -80% d i s s o l u t i o n ) , and then
the reaction slowed down and stopped. Under optimum conditions in f e r r i c
chloride (small p a r t i c l e s , high [ F e + + +

] , high temperature), a non-linear
behaviour was evident; at the s t a r t of the reaction there was a very fast
dissolution rate, whose extent depended on these same variables. After
this stage, the second slow d i s s o l u t i o n rate prevailed. This phenomenon
leads to a d r a s t i c reduction i n extraction times, which are no longer prop-
ortional to the (inverse of the) leaching rate, as in the l i n e a r case.

-186-
Fig. 82 Leaching of various concentrates with f e r r i c chloride.

-187-
F i g . 83 E f f e c t of p a r t i c l e size on concentrate leaching.

-188-
100 rrr»—A-
10 9 °C , 4 M FeCI 3
CONCENTRATES
RUTTAN ,-325mesh
a
PHOENIX, (-270.+325) . <j
5 /> - r ^ ^ Q -
<
cr CRAIGMONT,(-400)
+
(VI
o
+
a> n
Ll_
VALLEY COPPER ,(-400)

-O
—A GRANISLE,(-400)
0
( hrs )
F i g . 84 Optimum leaching of various concentrates.

-189-
V Mixed Potential Measurements
a) Motive
The mixed potential of a mineral i s that potential which results from
the mineral being placed i n a corroding environment. It d i f f e r s from a true
rest potential i n that the combination of anodic and cathodic processes that
take place i n the mineral are no longer symmetrical, and a net corrosion
current i s present.
A t y p i c a l mixed potential i s obtained when a sulphide i s placed i n an
oxygenated acid solution; here one cafhodic process i s the reduction of
oxygen, probably strongly polarized, while the anodic process i s the
dissolution of the mineral:

-190-
In the figure i s the mixed p o t e n t i a l , and 1^ i s the corrosion cur-
rent, which i s related to the leaching rate by the stoichiometry of the
reaction.
The purpose of measuring mixed potentials i n this work i s two-fold:
1) To determine what t y p i c a l values are
2) To determine how these values are affected by solution composition.
Mixed potentials provide a useful link between the chemical and electro-
chemical r e s u l t s ; by knowing both the p o t e n t i a l that a mineral assumes and
the resulting current and chemistry associated with that p o t e n t i a l , one may
predict the leaching rates of the mineral, and compare these predictions with
the observed chemical leaching r e s u l t s . I f favourable, this comparison i s
substantial evidence for an electrochemical mechanism; i t has been used suc-
c e s s f u l l y by Etienne (90) on copper sulphides, and Needes and Nicol (91)
on uranium dioxide leaching.
b) Results
(i) F e r r i c Sulphate Leaching
Mixed potentials were measured using one-lead electrodes, against a
Ag/AgCl electrode i n IM KC1, a l l at 90°C. This reference electrode was fre-
quently checked, and when using a strong leaching s o l u t i o n , a 4M KC1 solution
was used i n the Luggin c a p i l l a r y , although l i q u i d - j u n c t i o n potentials appeared
to be n e g l i g i b l e . The apparatus' was that shown i n Figure 7, and a l l experi-
ments were done at 90°C.
Duplicate electrodes were used i n a l l the experiments to be described;
they were freshly prepared by saw-cutting.
Starting with a solution ,0.2M H„S0 . where F e i s present as

+ + +
0.005M [ F e ]
l + + + J
f e r r i c sulphate, the [Fe ] was increased i n stages to 1,0M. Additions of

-191-
f e r r i c sulphate were only made a f t e r a stable p o t e n t i a l was reached; the
t o t a l time required f o r t h i s experiment (10 days) was 30 hours, including
a 15 hour break. The r e s u l t s are shown i n Figure 85.
As can be seen, a l i n e a r r e l a t i o n s h i p of p o t e n t i a l vs. log [ F e + + +

]
was obtained. The two electrodes were approximately 20 mV apart. The slope
of the l i n e i s 62 mV. At T = 90°C (363°K), the c o e f f i c i e n t i n the Nernst
equation i s 72 mV:
T, 3+ - „ 2+
e.g. Fe + e -> Fe
P P o 2. 3RT , a
Fe 2 +
„ c n , 0 , a
Fe 2 +
n h a
Fe3+ a
Fe3+
where E i s potential
E° i s standard p o t e n t i a l , and R, F have the usual

meaning.
After completion of the experiment described above, successive additions
~,-C -C~ ~,. ^ r*- „ *-x* ~ ~.—,^ r, ^ i - ~—"\ - n r-n: ^
A t o t a l time of 24 hours was required f o r t h i s experiment (5 additions).
Small additions, up to 0.05M [ F e ] had l i t t l e e f f e c t , but thereafter

+ +
a substantial drop i n potential was observed. The electrodes were s t i l l
20 mV apart. A t o t a l drop of 45 mV was obtained between ,1M F e + + +

.
+ + + .001M F e l + + J
and ,1M Fe . .
0.5M F e
l + + J
This experiment was repeated on a d i l u t e solution of f e r r i c sulphate
(O.IM) (Figure 87). Adding O.IM [ F e ] raised one potential and dropped the
++
other, adding 0.5M [ F e ] dropped both potentials by about 80

++
mV.
In every case a f t e r the perturbation caused by the addition o f ferrous
or f e r r i c sulphate, the p o t e n t i a l was slow to s t a b i l i z e , about an hour being
required. This phenomenon, and the persistent large difference between
the two electrodes, indicates a s i g n i f i c a n t degree of i r r e v e r s i b i l i t y of the
reactions taking place on the chalcopyrite surface, during f e r r i c sulphate

-192-
F i g . 85 Mixed p o t e n t i a l of chalcopyrite i n f e r r i c sulphate.

E f f e c t of i F e ^ ] .
4 4
Fig. 86 Mixed potential of chalcopyrite in ferric sulphate.
Effect of iFe"*""] .
1
-194-
650
6
T I M E (hrs)
F i g . 87 Mixed potential of chalcopyrite i n d i l u t e f e r r i c sulphate.

Effect of TFe**].
-195-
leaching.
Typical mixed potentials to be expected during f e r r i c sulphate
leaching are about 610 mV ( [ F e ] / [ F e ] = 1 ) .

3 + 2 +
( i i ) Cupric Chloride Leaching
Two new electrodes were prepared, and used for the balance of the
experiments described.
Starting with a solution ..3M NaCl . (at 90°C) successive additions of

0.2M HCl-'
l
CuCl^ were made, from 0.005M - IM (Figure 88). An excellent l i n e a r r e l a t i o n -
ship with slope 55 mV was obtained, the two electrodes d i f f e r i n g by a constant
5 mV.
A remarkable feature of this experiment was the r a p i d i t y with which
the electrode re-equilibrated a f t e r each addition of CuC^. The potential
adjusted i t s e l f as quickly as the crystals dissolved, with no d r i f t i n g
whatever. This behaviour was i n marked contrast to the previous experiment
with f e r r i c sulphate, where e q u i l i b r a t i o n required about an hour, instead
of a few seconds.
Adding CuCl to the solution obtained at the end of the last experiment,
decreased the potential (Figure 89), with a slope of 65 mV. At the conclu-
sion of this experiment, the solution contained IM CuC^, IM CuCl, 3M NaCl
and 0.2M HCl.
CaC^ was then added to this solution, up to 2M C a C ^ (Figure 90) .
This had the effect of increasing the potential again, with a slope of 138
mV.
This experiment was repeated, using as s t a r t i n g solution O.IM CuCl ?
O.IM CuCl
0.2M HCl
0.5M CaCl .
-196-
The p o t e n t i a l of the CuFeS2 electrodes again displayed a l i n e a r
relationship with log [ C l ] , slope 137 mV.
In each of these four experiments (Figures 87 - 90), the r e - e q u i l i -
bration was very fast as noted above, and the p o t e n t i a l s of the two electrodes
were indistinguishable a f t e r the addition of 0.0.1M CuCl. This behaviour
indicates that the reactions occurring on the chalcopyrite surface are
s u b s t a n t i a l l y r e v e r s i b l e , during C u C l 2 leaching.
The effect of [Cl] on CuCl,, p o t e n t i a l s i s diminished by low [Cu ]+
levels. Adding C a C l 9 to a s o l u t i o n containing no (added) Cu , i.e.,1.0 C u C l .

+
?
1
0.2M HCl e J
increased the p o t e n t i a l , as shown i n Figure 91. The slope i s reduced to
65 mV, from 137 mV (Cu /Cu++ +

= 1). S i m i l a r l y , adding [Cu ] on to s o l u t i o n
+
already high i n [ C l ] , did not depress the p o t e n t i a l as much as when [Cl]
i s low (not shown).
( i i i ) F e r r i c Chloride Leaching
+++
The e f f e c t of [Fe ] on the mixed p o t e n t i a l s i n chloride s o l u t i o n i s
shown i n Figure 92; the (positive) slope i s 75 mV. The mixed p o t e n t i a l s
(IM F e C l ) were 685/700 mV,

3 compared with 674/688 mV (IM [ F e + + +
] as F e r r i c
Sulphate) and 731/736 mV (IM C u C l ) .

2
The e f f e c t of Fe C l 2 on the mixed p o t e n t i a l of chalcopyrite i n IM
FeClj i s n e g l i g i b l e below O.IM [ F e ] , and only drops about 15 mV

+ +
at IM
[Fe ]++
(Figure 93) .
Even less e f f e c t i s observed with O.IM FeCl^ (Figure 9 4 ) .
Additions of C a C l 2 have no e f f e c t at a l l on the mixed p o t e n t i a l i n
0.15M FeCl 3 s o l u t i o n (Figure 95).
Additions of C u C l , however, do have a s i g n i f i c a n t p o s i t i v e e f f e c t ,

2
t h i s being more evident i n d i l u t e F e C l than concentrated (Figure 96).

3
The r a p i d i t y with which the CuFeS- electrodes r e - e q u i l i b r a t e d i n F e C l 3

-197-
Flg. 88 Mixed potential of chalcopyrite in cupric chloride.

Effect of iCu"*"*].
-198-
F i g . 89 Mixed potential of chalcopyrite i n cupric c h l o r i d e .

E f f e c t of I C u ] .
+
-199-
9 0
I 3 8 mV/DECADE
600
I 3 7 m V/ DECADE
0.2 M HCl , 0.1 M CuCI 2
0.1 M CuCl, CaCI 2
5 50
500" 1 I I I
2 3 7 8 9 10
( Cf ) total - 2( CuCl ) (M )
F i g . 90 Mixed potential of chalcopyrite i n cupric c h l o r i d e .

Effect of IC1].
-200-
F i g . 91 Mixed potential pf chalcopyrite i n cupric chloride.

Effect of IC1] i n absence of cuprous c h l o r i d e .
-201-

E f f e c t of [Te^l.
-202-
UJ
X
to
<» 600tV XL XL O £2
—A A
>
E
9 0 °C
UJ
0.2 M HCl , 0.1 M F e C I 3
Q_
550 FeCI
s j l—l ! l.ll,
2
III ' i i i i i i
j i—1_
X
10
,-3
10'
,-2
10"
( Fe ) 2+
( M)
UJ
X
CO 700
co
>
>
E
9 O °C
UJ
0.2 M HCl ,1 M F e C I
650 3
Fe C L
Q
Ul
X
i i i i i i i i i I I I i i i i ' i i i i i i
1 0 -3 10" 10"
( Fe 2 +
) (M )
Figs. 93, 94 Mixed potential of chalcopyrite i n f e r r i c chloride.

E f f e c t of i F e * ] . 4
-203-
< C R
'TOTAL ( M )
Fig. 95 Mixed potential of chalcopyrite in ferric chloride.

E f f e c t of I C l " ] .
-204-
F i g . 96 Mixed potential of chalcopyrite i n f e r r i c chloride.

Effect of ICu"""] .
1 4
-205-
solutions was again noticeable, though not as much as i n CuC^ leaching,
(iv) Summary
The mixed potential of chalcopyrite i s responsive to [ F e + + +

] and
[ F e ] i n sulphate solutions, though the reactions appear to be i r r e v e r -

++
sible. In f e r r i c chloride solutions, the mixed potential i s s i m i l a r l y
responsive to [Fe ], but not [Fe ].
In cupric chloride solutions, the mixed potentials respond immediately

++ +
to changes i n [Cu ] and [Cu ], and also [ C l ] . The magnitude of the
effects of [Cu ] and [Cl] are i n t e r r e l a t e d v i z . when [Cl] i s high, the

+
effect of [Cu ] i s reduced; and when [Cu ] i s high, the effect of [Cl] i s
+ +
increased.
In chloride solutions, both cupric and f e r r i c , the reactions exhibit
a high degree of r e v e r s i b i l i t y .
Higher potentials can be achieved i n IM CuC^ solutions than i n
1.0M FeCl^ or 1.0M FefSO^)^ solutions, i n which the mixed potentials
are approximately equal.
c) Discussion
An electrochemical reaction may be said to be under anodic, cathodic
or mixed control; this term refers to the r e l a t i v e degrees of p o l a r i z a t i o n
of the anodic and cathodic reactions. Thus i n the figure on page 189
the cathodic reaction i s highly polarized, and the o v e r a l l reaction may
be said to be under cathodic control.
The mixed potential of a mineral i n a leaching environment may be used
as an indicator of the control of the leaching reaction, i f the Nernst
potentials of the anodic and cathodic reactions can be calculated.

-206-
(i) Calculated Potentials
The standard potentials, E°, of the following h a l f - c e l l s at 298°K
were calculated using the free-energy data given below:
c o AF°
= " ~nF
where AF° i s the standard free energy change of the reaction
n i s the number of electrons
F = Faraday = 23.06 k c a l / v o l t
Cathodic Reactions
+++ - ++
C-1 Fe + e -»- Fe
C-2 Cu + +
+ e~ -> Cu +
C-3 Cu + +
+ e" + C l " ->• CuCl
Anodic Reactions
A-l CuFeS 2 - 4 e" -> C u + +

+ Fe + +
+ 2 S°
A-2 CuFeS 2 - 16 e''+ 8 H 0 2 -> C u + +

+ Fe + +
+ 16 H +
+ 2 SO^
A-3 CuFeS 2 - 3 e" + 2 C l " -> CuCl" + F e + +

+ 2 S°
A-4 CuFeS 2 - 3 e" + C l " + CuCl + F e + +

+ 2 S°
A-5 CuFe S 2 - 7 1/4 e" + 2 H 0 2 •+ C u + +

+ 3/4 F e + +
+ 1/4 Fe + + +
+ 3/2 S° + 1/2 SOj + 4 H +
A-6 CuFeS 2 - 6 e" + 3/2 H 0 2 + 3/4 C u + +

+ 1/4 C u C S ^ ) ^ + 3/4 Fe + +
+ 1/4 F e + + +
+ 3 H +
+ S°
A-7 CuFeS 2 - 7 3/4 e" + 3 H 0 2 -> 1/2 C u + +

+ 1/2 C u ( S 0 ) 2 3
5
+ 3/4 Fe + + +
+ 1/4 F e + +
+ 6 H +
-207-
AF
°298
Reaction E°
kcal/mole (mV)
C-1 - 17.78 770
C-2 - 3.53 153
C-3 - 12.38 536
A-l 40.78 442
A-2 139.62 379
A-3 30.05 435
A-4 28.40 411
A-5 69.94 419
A-6 63.60 460
A-7 82.35 461
AF°
Reference
.ur 2 g g
kcal/mole
CuFeS ? - 45 55 63
CuS - 11 7 187
Cu + +
15 53 187
Cu +
12 0 187
CuCl - 28 2 187
. CuCl - - 57 9 187
Cu(-S|0_)| -250 3 This work
Fe + + 6
- 20 30 187
F e +++ - . 2 53 187
ci- - 31 35 187
SO4 -177 34 187
HO - 56 69 187"
-208-
AF°
Reference
298
kcal/mole
-116.1 . 187
s
2°; -124.0 187
• S
2°6 = -231 187
S
2°4 -143.4 187
S
4°6 -244.3 187
The above data can only be applied to the present work with the follow-
ing approximations in mind:
1) Free energy values are v a l i d only at 25°C. The mixed potential and
other experiments were largely carried out at 90°C.
2) The free energy values are mainly taken from an older reference
(187) .
3) Potential values for reaction C-1 in f e r r i c chloride and sulphate
are l i k e l y to be lower than 770 mV, due to complexing.
4) Potential values for reaction A-3 i s l i k e l y to be lower at 90°C,
due to increased s t a b i l i t y of the CuC^ complex at t h i s temperature
(188) .
5) The free-energy value for CuFeS2 as used here, has not been supported
by published experimental evidence.
6) The free energy value f o r C u ^ O ^ ) " was calculated from Latimer's
(187) data:
-209-
AF
298
Ag(S 0 )^ 2 3 -247.6
Ag(CN)~ +72.05
Cu(CN)~ +69.3
/. Cu(S 0 )= 2 3 -250.3
Six possible anodic reactions have been written, but these f a l l
within a range of only 81 mV (379 - 460 mV) . The mixed potential experiments
showed that electrode potentials during f e r r i c and cupric leaching were
generally 520 - 720 mV. Therefore none of these anodic reactions can be
excluded on thermodynamic grounds.
The f i r s t two of these reactions represent 100% S° and 100% SO^
formation respectively; the l a t t e r i s actually favoured thermodynamically.
Reactions A-3, A-4 can be expected during chloride leaching (both are
included, because the potential of A-3 seems u n r e a l i s t i c a l l y high). It
can be seen that these reactions, which produce Cu +

species, are only
s l i g h t l y favoured over A - l , which produces C u + +

(e.g. i n sulphate s o l u t i o n ) .
Reactions A-5, A-6 are two possible reactions which can be postu-
lated from data on sulphate solutions presented i n Section III ( i i ) . They
incorporate a F e / F e
+ + + + +
r a t i o of 3.0, and a 25% oxidation of sulphur.
The potential of reaction A-5 i s very s i m i l a r to that of A-4 (chloride solu-
t i o n s ) , whereas A-6 i s 40 mV higher.
( i i ) F e r r i c Sulphate Leaching
The above calculations indicate that the standard potential of the
anodic d i s s o l u t i o n of chalcopyrite i n sulphate solutions i s 420 mV + 40 mV

-210-
at 25°C. The actual mixed potential during f e r r i c sulphate leaching i s

typically 200 mV higher than this (Figure 86); therefore there appears
to be a significant degree of anodic polarization.
The Fe^ /Fe^ couple has a standard potential of 770 mV, which i n -
+ +
creases with temperature; i t has been found to react reasonably reversibly

on a platinum surface, with a r e l a t i v e l y small degree of activation polar-
ization (189) . Etienne u t i l i z e d these data (90) to correlate electrochemical
work on digenite with f e r r i c sulphate leaching, with the implicit assumption
that the charge transfer characteristics of the Fe /Fe^ couple on digenite
3+ +
were similar to those on platinum. The correlation appeared to be reasonable
However, the mixed potentials of chalcopyrite indicate that, i n sulphat

solutions at least, the Fe^ /Fe^ couple is not reversible on the chalco-
+ +
pyrite surface. In a 0.1M F e + + +

, 0.1M F e ++
solution (Figure 87), a polar-
ization of about 200 mV i s apparent, since the mixed potential i s near 600
mV, compared to a standard potential of 770 mV or higher.
With approximately equal amounts of cathodic and anodic polarization,

the leaching of chalcopyrite i n f e r r i c sulphate solution may be said to be
under mixed control.
This calculation may be refined by correction for (a) temperature and

(b) complex formation. Using a method outlined below, the following correct-
ions were calculated:
Reaction A E° (25 •* 90°C)
C-1 + 77 mV
A-l . + 8 mV
A-2 ' . -121 mV

-211-
Furthermore, i n sulphate solution, E° for the Fe^ /Fe^ + +

couple (C-1)
i s reduced by 80 mV (1). Thus the overall effect of these corrections i s
n e g l i g i b l e , (except to note that the sulphate reaction (A-2) becomes pro-
gressively more favourable with higher temperature); mixed control i s s t i l l
indicated.
( i i i ) Cupric Chloride Leaching
The standard potential of the anodic dissolution of chalcopyrite in
chloride solutions was calculated (above) to be 411 mV. Actual mixed po-
t e n t i a l s were at least 200 mV above t h i s ; s i g n i f i c a n t anodic polarization
is again indicated.
The cathodic reaction may be written in more than one way, depending
on the incorporation of chloride ions i n the equation (C-2 or C-3).

_ ++ - _ +
Cu + e -* Cu
Cu +
+ 2 C l " •> CuCl^ K = 1.76 x 10 4
[Cu ] = +
[CuCl~]
K^Cl"] 2
+-,
2.3RT . [Cu ]
E
cu + +
/cu + =
" - p - l o g
TCu^T
= 153 + 59 log K + 118 log [Cl] + 59 logJ^^JjL

[Cu ]
++
= .404 + 118 log [Cl] + 59 log ^ C u C 1

2^
[Cu ] ++
(at 25°C)
At 90°C, t h i s equation changes s i g n i f i c a n t l y . In order to calculate
the temperature c o e f f i c i e n t of E° , i t i s necessary to use the van't Hoff
Isochore (rather than the Criss and Cobble approach (200)). This choice*
*A calculation based on the Criss and Cobble method yields, a s i m i l a r

result i n this case.
-212-
i s dictated by the p o t e n t i a l scale used i n t h i s work, which i s based on the
standard hydrogen electrode having a zero p o t e n t i a l at each temperature,
by d e f i n i t i o n . This follows from the use of Greeley's (178) values f o r
the Ag°/AgCl reference electrode which were determined empirically from
the cell:
Pt; H ( g ) , HCl, AgCl; Ag.

2
Thus
dE\ AS° 2 9 8
dt/298 nF
A H
298 ~ A F
298
298 ' nF
For Cu + +
+ 2 C l " + e~ -*• CuCl"
AH 2 Q 8 15.39 -80.05 -66.1 + -1.44
AF 2 g 8 15.53 -62.7 -57.9 •* -10.73
Therefore
U*) = 9 2 9 0
= 1.352 mV
\ dt/298 298 x 23.06 *K
Assuming that this temperature c o e f f i c i e n t remains constant up to
90°C
then AE,,_ = 88 mV.
Hence: E C u
+ +
/ C u + (363°K)'= 492 mV + 144 log [Cl] + 72 log ^ C u C 1
2^
[Cu ]
In Figure 90, where the solution i s j 0.1M CuCl ] + CaCl„, the mixed
0.1M CuCl
• 0..2M HCl /
-213-
p o t e n t i a l of CuFeS v a r i e s from 520 mV

2 (0.5M C a C l ) to 620 mV
2 (3.5M CaCl ) 2
with a slope of 137 mV. As discussed below the [Cl] of the 0.5M CaCl 2
s o l u t i o n i s considered to be 1.3M. Thus the c a l c u l a t e d value i s :
E„ ++. + = 492 + 144 log (1.3)

Cu /Cu
= 508 mV (90°C).
This i s very close to the experimental mixed p o t e n t i a l of 520 mV (which
was found f o r both e l e c t r o d e s ) . Therefore the degree of cathodic p o l a r -
i z a t i o n must be q u i t e small and the leaching of c h a l c o p y r i t e i n c u p r i c
chloride can be s a i d to be under anodic c o n t r o l .
The dependence of the mixed p o t e n t i a l upon [ C u ] , (Cu ] and [Cl ] + + +
i s v e r i f i c a t i o n of t h i s statement. The a c t u a l slopes observed f o r each
variable:
[Cu ] ++
+55 mV
[Cu ]
+
-65 mV
[Cl"] +137 mV
are somewhat lower (72 or 144) than p r e d i c t e d by the Nernst equation, but
t h i s may be due to the use of concentrations instead of a c t i v i t i e s , or to
a s l i g h t amount of cathodic p o l a r i z a t i o n .
The dependence of [Cl] as shown i n Figure 90 i s p l o t t e d against [Cl] :
[ C l ] * = [Cl] - 2 [CuCl]
f o r i t i s assumed (187) that each Cu +

ion i s complexed as C u C l , and that2
therefore these C l ions are no longer a v a i l a b l e . I t i s i n t e r e s t i n g that
the slopes of the l i n e s i n Figure 90 only coincide when t h i s d e f i n i t i o n i s
used. The v a r i a t i o n between them i s considerable (20% or more) i f t o t a l
[Cl] i s used.
However, Helgeson (188) has c a l c u l a t e d that i n strong b r i n e s , the
predominant Cu +
species i s CuCl^ , and the C u + +
ions are also complexed as
-214-
CuCl .
+
This would not change the expected slope of the line i n Figure 90, v i z .
CuCl +
+ 2 C l " + e" CuCl 3
=
Since two Cl ions are involved the slope should be 144 mV again, but
_ *
the experimental slope, based on [Cl ] would change:
[ C l ] * = [Cl ] - [Cu ] - 3
- - ++
[Cu ].
+
The experimental slopes would now be 90 and 126 mV, in Figure 90.
These values are obviously less s a t i s f a c t o r y in the present context, but
cannot be e n t i r e l y discounted, without an evaluation of Helgespn's calcu-
lations.
If the anodic reaction i s at a l l r e v e r s i b l e , then i t s dependence on
[Cl] w i l l tend to lower the mixed p o t e n t i a l , thus providing a rationale
for the reduced slope found experimentally.
The temperature dependence of the standard potential of the anodic
reaction (A-3) was also calculated i n the above manner. E° was found to
decrease by 80 mV, from 25°C to 90°C. Thus the anodic p o l a r i z a t i o n i s even
greater than indicated, r e i n f o r c i n g the concept of anodic control during
cupric chloride leaching.
d) Ferric Chloride Leaching
Similar mixed potentials are obtained in IM FeCl^ as in IM FefSO^)^
therefore the conclusion may also be drawn that the reaction i s s i m i l a r l y
under mixed control. However, there are two important differences:
1) [ F e ] has ++
l i t t l e effect on the mixed potential in chloride solutions
2) The reaction appears f a r more reversible in chloride solutions.
The lack of effect of [ F e ] on the mixed potential can be

++
explained
by postulating that the active leaching agents i n f e r r i c chloride solutions
are not F e + + +
ions but C u + +
ions. Since the C u / C u ++ +
couple has been
-215-
shown to be r e v e r s i b l e on chalcopyrite, i t i s possible that t h i s reaction
w i l l proceed much q u i c k e r than the Fe^ /Fe^

+ +
cpuple.
3+
The r o l e o f Fe ions in ferric c h l o r i d e l e a c h i n g would then be to
suppress the [Cu ],

+
f o r the reaction:
3+ „ + ++ „ ++
Fe + Cu -> Fe + Cu
K = 3.5 x 10 8
tends s t r o n g l y to the r i g h t .
[Cu ] +
= [Fe + +
][Cu + +
] x 2.9 x 10~ 9
[Fe + + +
]
I f t h i s r e a c t i o n was at e q u i l i b r i u m then the mixed p o t e n t i a l s h o u l d
depend on [Fe ]. However, the important [Cu ] i s t h a t at the surface of
the m i n e r a l , [Cu ] ,
+
s where i t i s b e i n g produced. The [Cu*]^ i s probably
l i m i t e d by the speed with which the F e + + +

ions can d i f f u s e from the bulk
o f the s o l u t i o n to the surface from which C u +

is introduced.
Since the [Cu ] +

w i l l be v e r y low i n a strong Fe + + +
solution, the
complexing power o f C l i o n s , observed i n c u p r i c c h l o r i d e l e a c h i n g , will
be unimportant; i t i s to be expected t h e r e f o r e that [Cl ] w i l l not affect
the mixed p o t e n t i a l i n f e r r i c chloride leaching (Figure 95).
The effect of [ C u ] i n r a i s i n g the mixed p o t e n t i a l o f

+ +
chalcopyrite
in f e r r i c chloride solutions i s supporting evidence f o r t h i s t h e o r y . It i s
i n t e r e s t i n g to compare the p o t e n t i a l s o f the following solutions: (Figures
88, 96)
IM FeCl 678
685
IM FeCl 738
IM C u C l ^ 738
IM CuCl 731
3M NaCl' 736
-216-
Thus IM F e C l ^ has the same e f f e c t as 3M NaCl, when used with IM CpC^-
Presumably, both the FeCl and NaCl suppress the [Cu ],

+
possibly in differ-
ent ways.
e) Summary
F e r r i c sulphate leaching of c h a l c o p y r i t e e x h i b i t s both anodic and
cathodic p o l a r i z a t i o n , and i s under mixed c o n t r o l .
Cupric chloride leaching e x h i b i t s only anodic p o l a r i z a t i o n and the
reaction i s therefore anodically controlled. The cathodic process i s
highly reversible.
Ferric chloride leaching appears to be cupric chloride l e a c h i n g in,
reality, i n which the [Cu ]+

i s suppressed by the h i g h [Fe^ ] .+
The reaction
is therefore a l s o under anodic c o n t r o l . However, simple f e r r i c leaching,
u n c a t a l y z e d by Cu + +
, p r o b a b l y a l s o o c c u r s , though more slowly.
The a c t u a l mixed p o t e n t i a l t h a t chalcopyrite attains during ferric
sulphate leaching i s increased by h i g h [Fe + + +

] , but decreased by h i g h [Fe + +
];
typically i t would be about 600 m'V.
In f e r r i c chloride leachine, the mixed p o t e n t i a l depends only on
[Fe + + +
], and (to a l e s s e r e x t e n t ) [Cu ]. + +
T y p i c a l mixed p o t e n t i a l s should
be i n the range 680 - 720 mV in practical solutions.
In c u p r i c c h l o r i d e leaching, the mixed p o t e n t i a l s are increased
by h i g h [ C u ] and
+ +
[Cl] but decreased by Cu +
ions. Actual potentials
attained during a l e a c h would decrease w i t h time, as [ C u ] decreases

+ +
and [Cu ] increases. In a s t r o n g c h l o r i d e s o l u t i o n , the p o t e n t i a l would
p r o b a b l y s t a r t around 750 mV and finish at 600 mV, when the leaching
becomes i m p r a c t i c a l l y slow.
-217-
D. DISCUSSION
I The Chemistry of the Anodic Dissolution of Chalcopyrite
a) Chloride System
In chloride solutions the d i s s o l u t i o n reaction appears to be quite
straightforward:
CuFeS 2 - 4.4 e" + 0.266 H 0 2 Cu* " + Fe^

4
+ 1.933 S° + 0.066 S 0 + 0.533 H
4
= +
(DI)
The amount of sulphur oxidation i s c e r t a i n l y small and of no great
importance. However, at low potentials i n strong chloride s o l u t i o n , much
higher copper and iron current e f f i c i e n c i e s (60 - 70%) are encountered than
is allowed by this equation. Iron current e f f i c i e n c i e s of greater than 50%
may be achieved by chemical dissolution:
CuFeS 2 + 2 H +
'+ CuS + F e + +
+ HS 2 (D2)
However, the corresponding process for copper was found not to occur
to a detectable extent.
Copper current e f f i c i e n c i e s of more than 50% are possible i f the copper
dissolves as cuprous, but even at the lowest p o t e n t i a l only 12% of the
copper was found as Cu . +

Two explanations can be offered to resolve this
problem:
1) Some of the Cu +
was oxidized by atmospheric oxygen d i f f u s i n g into
the c e l l .
2) Some of the Cu +
was oxidized by Fe^ +
ions, simultaneously produced
on anodizing.
The f i r s t p o s s i b i l i t y seems u n l i k e l y in view of the constant C u / C u + ++
r a t i o with time.
-218-
Th e second p o s s i b i l i t y draws credence from the observation i n
sulphate solutions that an approximately constant proportion (1:4) of F e + + +

:
Fe + +
i s dissolved at a l l potentials, and indeed at higher potentials i n
chloride solutions also.
I f 20% of the iron then dissolves as F e + + +

i t would l i k e l y react im-
mediately with an equivalent quantity of Cu , probably on or near the mineral
surface. Thus the actual y i e l d of Cu would be 32% of the t o t a l Cu.

+
„ + „ +++ „ + + „ + +
Cu + Fe ->- Cu + Fe (D3)
This would reduce the current e f f i c i e n c y f o r copper to 50%, (at 535 mV),
and the extra current e f f i c i e n c y f o r iron can be accounted for by chemical
d i s s o l u t i o n , as stated.
b) Sulphate System (and Perchlorate)
In the sulphate system, the d i s s o l u t i o n i s not complicated by cuprous
formation, but instead by sulphur oxidation. In the preliminary experiments
i t was shown that i n O.IM FLSO. and O.IM HC10., current e f f i c i e n c i e s o f

2 4 4'
near 30% are obtained f o r copper and iron at a l l temperatures and potentials
with two exceptions:

1) At low potentials (below 700 mV) less copper i s dissolved
2) At high temperature (175°C), the chemical d i s s o l u t i o n of iron
becomes dominant.
With these two exceptions i n mind the d i s s o l u t i o n reaction (in 0.1M
H^SO^ and 0.1M HCIO^) i s (ignoring F e + + +

formation f o r the moment):
CuFeS 2 - 7 e" + 2 H 0 -> C u

2
+ +
+ Fe + +
+ 1.5 S° + 0.5 S 0 4
=
+ 4 H +
(D4)
The predicted y i e l d of sulphate (25% of the t o t a l sulphur) was actually
found by spectrophotometric analysis i n perchlorate solutions.

-219-
However, i n l a t e r experiments (Section III (b)) the sulphate solu-
t i o n s used were 0.4M N a S 0 . and

o O.IM H S 0 „ , and
o 0.4M NaHSO. and O.IM H-SO,.
2 4 2 4 4 2 4
At 90°C, the anodic d i s s o l u t i o n r e a c t i o n was s i m i l a r to t h a t i n O.IM H^SO^,
based on copper and i r o n current efficiencies.
At 125°C, though, lower c u r r e n t efficiencies (20%) were observed i n
the sulphate s o l u t i o n , (but not in bisulphate). This i n d i c a t e s that an
increased proportion of sulphur i s o x i d i z e d under these c o n d i t i o n s : (90°C):
CuFeS 2 - 7 e" + 2 Cu + +
+ Fe + +
+ 1.5 S° + 0.5 S0 4
=
+ 4 H +
(D4)
(125°C; 0.4M Na SO only):

O.IM H SOj
CuFeS 2 - 10 e" + 4 H O + Cu + +
+ Fe + +
+ S° + S 0 4
=
+ 8 H +
(D5)
At 150°C the copper c u r r e n t e f f i c i e n c y was a l s o lower i n b i s u l p h a t e
s o l u t i o n , and at 175°C i t was negative.
This l a s t r e s u l t cannot be r a t i o n a l i z e d i n terms o f i n c r e a s e d sulphur
o x i d a t i o n , and i s i n d i c a t i v e o f a more complex p r o c e s s . It i s rather
s u r p r i s i n g i n view o f the constant stoichiometry observed i n O.IM HC10 , 4
O.IM H S0
2 4 and c h l o r i d e s o l u t i o n s , at a l l temperatures as noted.
In oxygen p r e s s u r e leaching of chalcopyrite (in sulphuric acid solu-
t i o n s ) i t has been observed (144) t h a t the y i e l d o f e l e m e n t a l s u l p h u r in-
creases with [H ],+

the remainder o f the s u l p h u r being oxidized. At low
pH. t h i s o x i d i z e d sulphur i s sulphate, whereas at h i g h e r pH (neutral or
a l k a l i n e regions) intermediate sulphur species such as t h i o s u l p h a t e are
found (146) .
I t i s thus r e a s o n a b l e to suppose t h a t i n the anodic d i s s o l u t i o n o f
c h a l c o p y r i t e , the d e c r e a s i n g copper c u r r e n t e f f i c i e n c y can be a t t r i b u t e d
to i n c r e a s i n g s u l p h u r o x i d a t i o n , which i n t u r n can be a t t r i b u t e d to
-220-
higher pH.
The pH of a O.IM H S0 solution (and O.IM HCIO^ will probably stay

2 4
nearly constant over the range 25 - 175°C since the equilibrium
H S0
2 4 t H + HS'0 "
+
4 (D6)
s t i l l has a positive log K value even at 300°C (188).
The pH of a 0.4M Na_S0. solution rises with temperature due to the

O.IM H SO 2
shift in the equilibrium (188):
HSO." -y H + SO.
+ =
(D7)
Temp °C log K
25 -1.99
60 -2.40
100 -2.99
150 -3.74
200 -4.49
Thus the pH will probably rise from 1.25 (25°C, experimentally) to
over 3 at 175°C, the increase being moderated by the equilibrium:
NaSO~ t Na + S0
+
4
=
(D8)
Values for the corresponding potassium salt are given by Helgeson (188)
Temp °C log K
25 -0.84
60 -1.06
100 -1.30
150 -1.60
200 -1.94
-221-
In a bisulphate buffered solution on the other hand, the pH i s less
affected by the s h i f t i n the equilibrium of equation (D7). Experimental
values of pH at 175°C were not obtained but the trend at 90°C can be ex-
pected to continue:
EXPERIMENTAL pH VALUES
0.4M NaHSO. 0.4M Na S0 2 4
O.IM H S0
2 4 O.IM H S02 4 O.IM H S0
2 4
pH (20°C) 0.80 0.30 1.25
pH (90°C) 0-90 0.75 2.15
Therefore the results up to 150°C can be explained i n terms of
increased sulphur oxidation at higher temperatures, due to the r i s e i n
pH.
The d e t a i l s of the sulphur oxidation leave room f o r much speculation;
the surface photomicrographs i n Section I, obtained i n 0.1M HC10 4 at 175°C,
show that CuS crystals have been deposited from solution. Furthermore,
the low current e f f i c i e n c i e s found i n bisulphate solutions at high temper-
atures also are associated with CuS deposition. Frequently, a thin f i l m
of CuS was deposited a l l over the epoxy mounting of the specimen, during
a high temperature run.
Therefore, i n postulating a mechanism f o r sulphur oxidation, the mass
transfer of copper from the sulphide mineral to another s i t e , v i a the solu-
t i o n , must be considered.
-222-
At least three mechanisms can be suggested:
i ) Thiosulphate
i i ) Sulphur Disportionation
i i i ) Hydrogen Sulphide.
i ) Thiosulphate Mechanism
It has been well established that thiosulphate i s an important inter-
mediate i n the oxidation of sulphide minerals at neutral or higher pH (e.g.
the ammonia leach of Sherritt-Gordon) (193). However, thiosulphate i s known
to be unstable at lower pH (approximately pH 5 (196)) p a r t i c u l a r l y when the
solution i s hot and o x i d i z i n g , and i t s existence under these conditions, i s
not usually considered.
Nevertheless, there i s an extra complication i n t h i s s i t u a t i o n , and
that i s the presence of copper i n the s o l u t i o n .
Cuprous ions form a series of complexes with thiosulphate: (194)
Cu +
+ x (S 0 ) 2 3
=
t Cu(S 0 )^"
2 3
2 x
(D9)
The analogous s i l v e r complex Ag(S <J ) ~ i s l i s t e d by Latimer

2 3 2 (187) as
one of the strongest complexes known of that metal, being exceeded only by
the cyanide.
COMPLEX LOG K (25°C) REFERENCE
AgCl - 2
- 5.25 188
Ag(NH ) 3 2
+
- 7.77 187
Ag(S 0 ) 2 3 2
=
-13.78 187
Ag(CN) " 2 -18.75 187
Gu(CN) " 2 -16.00 187

-223-
The strength of this cuprous thiosulphate complex s t a b i l i z e s both
cuprous and thiosulphate ions, the former being usually unstable i n sulphate
solutions (with respect to disproportionation: 2 Cu +

-»- Cu° + C u ) ,
+ +
and
the l a t t e r being unstable i n acid solutions (also with respect to disprop-
ortionation: s o -> S° + s o )
2 3
=
3
=
.
In fact, some b r i e f experiments i n this work indicated that some of
the a n a l y t i c a l techniques employed f o r copper analysis do not detect copper
i f i t i s present as the thiosulphate complex. For instance, the Cuproin
method depends on the extraction of cuprous from the aqueous phase to
an organic phase; i f the cuprous i s very strongly complexed i n the aqueous
phase, then i t i s possible that an unfavourable extraction r a t i o w i l l be
encountered.
The strength of this complex notwithstanding however, i t s s t a b i l i t y
at elevated temperatures i s limited by the reaction:
Cu(S 0 ) 2 3
_
-> CuS + {S0 ">.
3
The exact stoichiometry of this reaction i s uncertain, and probably
varies with conditions, but i t i s certain that a copper sulphide (either
CuS or Cu S) and an oxidized sulphur species are formed.

2 This fact i s used
in Sherritt-Gordon's 'copper b o i l ' step to remove copper from s o l u t i o n ,
a f t e r the leaching operation. The reactions have been written (191):
Cu + +
+ S 0 2 3
=
+ H02 + CuS+ + 2 H +
+ S0 4
=
(D10)
2 Cu +
+ S 0 2 3
=
+ H0 2 -> Cu S4- + 2 H
2
+
+ S0 4
=
(Dll)
In this work we have clear evidence that copper has been transported
v i a solution from one s o l i d s i t e to another. It i s plausible therefore
that at least some copper dissolves anodically as a cuprous thiosulphate
complex which may either decompose to form soluble copper or a copper
sulphide:
-224-
CuFeS - 7 e
2 +3^0 -> Cu(S C> )~ + F e
2 3
++
+ 6 H +
(D12)
then
Cu(S 0 )" + 2 H
2 3
+
-»• C u ++
+ 1/2 S 0 4
=
+ 3/2 S°4- + H 0 2 (D13)
or:
Cu(S 0 )
2 3 + 1/2 H 07 -»• CuSi + 1/2 S 0 3
=
+ 1/2 S0 4 + H (D14)
This reaction may go through an intermediate step involving dithion-
ate:
Cu(S 0 )"
2 3 CuSI + 1/2 S 0 2 6 (-0.7) (D14a)
1/2 S 0 2 6
=
+ 1/2 H 02 -»• 1/2 S0 " + 1/2 S 0
3 4
=
+ H +
(-2.85) (D14b)
which is reported to decompose rapidly into S0 ~ and S0 ~ in acid solution 3 4
(187).
The production of S0 3 allows more thiosulphate to be formed by reaction
with elemental sulphur on the mineral surface:
S0 3
=
+ S° + S 0 2 3
=
(D15)
and thereby permit more copper to be removed from solution, i . e . negative
current efficiency.
The sum of equations D12 and D13 i s :
CuFeS - 7 e" + 2 H 0 +
2 2 Cu ++
+ Fe ++
+ 1/2 S 0 4
=
+ 3/2 S° + H +
(D4)
which is the observed stoichiometry of the anodic dissolution under most
conditions in sulphate solutions. It is interesting that equation (D13),
dissolution of copper, is favoured by acid solutions, whereas equation (D14),
precipitation of copper, is not. This conforms to the observed pattern
of lower copper current efficiencies at higher pH.
Alternatively, other equations may be written, particularly for the
copper precipitation reaction, the details of which are not known, other
than the fact that cupric sulphide is formed (195), (although some authors
-225-
reported a mixture of cupric and cuprous sulphides). The dithiosulphate
complex may be formed, e.g.

CuFeS - 7 1/2 e~ + 3 IkO + 1/2 C u ( S 0 ) | + 1/2. C u
2 2 3
++
+ Fe ++
+ 6 H +
(D16)
then either:
1/2 Cu(S 0 )= + 1/2 e" + 2 H -> 1/2 Cu '
2 3
+ + K
+ 1/2 S 0 + 3/2 S ° i + ILO
4 (U17)
or:
1/2 Cu(S 0 ) 2 3 2 + •*• 1/2 .CuS + -+ 1/4 S 0 4 6 + 1/2 SO" (D18)
This last equation seems possible for tetrathionate, SÔ", is a common
oxidation product of thiosulphate, and also because the production of sulphite,
S0 3 , allows more copper to be precipitated, as described above.
The reaction of sulphite, S 0 ~ , and elemental sulphur could well be3
favoured under conditions where the sulphur is in a metastable high energy
form, as i t may be after anodizing chalcopyrite.
S t i l l another decomposition reaction for the thiosulphate complex
can be written, involving hyposulphite:

Cu(S 0 ) "
2 3 2 -> CuSi + 3/2 S 0 -, AF = +23.7 kcal (187)
2
=
(D19a)
This reaction appears to be thermodynamically unfavourable. Hyposul-
phite however decomposes rapidly in acid solution to regenerate thiosulphate:
3/2 S 0 2 4
=
+ 3/4 H 0 2 •+ 3/4 S ^ " + 3/2 SC> + 3/2 H =
3
+
(D19b)
This reaction is favoured by 24.4 kcal (187). Thus the overall
reaction is slightly favoured:
Cu(S 0 )= + 3/4 H 0
2 3 2 -> CuS+ + 3/4 S C> + 3/2 S 0
2 3
=
3
=
+ 3/2 H +
, (D19)
AF = -0.7 kcal. •
Again, the production of S 0 ~ and S0 ~ both permit the formation of more

2 3 3
cuprous thiosulphate complexes, and hence a reduction in the level of copper
in the solution, as noted above.

-226-
Hyposulphite can enter into several other reactions (192): copper
dissolved as the sulphate reportedly i s reduced to the reddish-brown hydride,
CuH. This compound, which might e a s i l y be mistaken f o r hematite, FeÔ^,
readily decomposes to a sponge of m e t a l l i c copper.
The various decomposition reactions described can be evaluated thermo-
dynamically: *
298
AF Expected Effect of Increased
(kcal) pH on Reaction
DISSOLUTION OF COPPER
D13 (mono-complex) - 3.8 Slower
PRECIPITATION OF COPPER
(i) D14a s
2 ° ~ 6 formation 0.7
D14b S0 /S0 3
=
4
=
formation 2.88 Faster
D14 Overall 3.55 Faster
( i i ) D18 S CLT/SO =
formation - 5.7
( i i i ) D19a s
2
0
4
_
formation +23.7
D19b S 0 /S0 2 3
=
3
=
formation -24.4 Faster
D19 Overall -.0.7 Faster
* The value of AF^gg used f o r C u ^ O ^ i s -250.3 k c a l . ; the derivation

of this value i s described i n the l a s t section. For Cu(S203)" a reasonable
figure i s arrived at simply by assuming that this complex i s equally as
stable as the di-complex. Then
298 " - 3 kcal.AF = 1 2 6
It appears from the e x i s t i n g l i t e r a t u r e on t h i s subject (194) that t h i s i s

a reasonable approximation.
-227-
In evaluating these reactions, i t must be recognized that paths
( i i ) and ( i i i ) are derived from the di-complex, whereas ( i ) i s derived from
the mono-complex. The l a t t e r seems more l i k e l y , since there w i l l not be
an excess of thiosulphate i n solution, and i t apparently has a bridged
structure (194):
-
-0
as opposed to the linear structure of the di-complex:
One can v i s u a l i z e the formation of the bridged structure being favoured
on a mineral surface.
Thermodynamically, the production of hyposulphite, S2<J ~, seems un-4
l i k e l y at best although the overall reaction D19 i s possible.
Reaction D18, producing tetrathionate cannot be ruled out on thermo-
dynamic grounds, but i t has three unfavourable characteristics:
a) It i s derived from the di-complex rather than the mono-thiosulphate
b) It requires two new species to be nucleated
c) It i s not favoured by high pH.
Reaction D14 involving dithionate S20^~, on the other hand, has none
of these disadvantages, and appears to be the most l i k e l y reaction.
The competition between a s o l u b i l i z i n g reaction D13 and D14 may simply
b o i l down to a pH problem. The free energies are very similar (-3.8 vs.
-3.55 kcal) but the pH dependence i s opposite.
In summary, the thiosulphate mechanism postulates that copper dissolves
as a cuprous thiosulphate complex which may either 1) decompose to give
soluble copper, or 2) decompose to form a copper sulphide p r e c i p i t a t e .
The choice between these two paths i s l i k e l y to be influenced by pH, with

-228-
the f i r s t being favoured at lower pH.
( i i ) Sulphur Disproportionation Mechanism
The enhanced r e a c t i v i t y which elemental sulphur may have when produced
under the non-equilibrium conditions e x i s t i n g on a chalcopyrite anode plays
an important role i n this mechanism.
It i s well known that at s u f f i c i e n t l y high temperatures elemental
sulphur can be made from H,,S gas (196) :
2 H S + S0
2 2 -> 3 S° + 2 H 0 2
However i t i s also possible f o r t h i s reaction to be reversed, i f
1) the a c t i v i t y of sulphur can be raised
2) the a c t i v i t y of H S can be depressed.

2
Under the conditions e x i s t i n g on a chalcopyrite anode, the f r e s h l y
formed elemental sulphur w i l l i k e l y not be i n i t s most stable form. Further-
more the a c t i v i t y of H S i s depressed greatly by the copper content of the

2
solution. Therefore the disproportionation reaction:
Cu + +
+ 4/3 S° +' 4/3 H 0 2 -> CuS + 1/3 SC> =
4 + 8/3 H +
(D20)
i s possible (producing SO^ rather than SO^").

-
Combined with the 'normal' chalcopyrite d i s s o l u t i o n :
CuFeS 2 - 4 e" + Cu + +
+ Fe + +
+ 2S° (D21)
CuFeS 2 - 4 e" + 4/3 H 0 2 -»• CuS + 2/3 S° + 1/3 S 0 4

=
+ Fe + +
+ 8/3 H +
This equation f i t s the data reasonably w e l l , f o r i t predicts a 16.7%
sulphur oxidation, and a 33.2% current e f f i c i e n c y f o r copper, (presuming
that the CuS i s formed on the specimen, where i t can be anodized:)
CuS - 2 e" -> C u + +

+ 2 S°
However, i t would be expected that the disproportionation would increase
with temperature, but t h i s does not seem to be the case, generally.
A l t e r n a t i v e l y , i t can be postulated that the two reactions (D20, D21)

-229-
occur almost simultaneously, so that the copper never a c t u a l l y dissolves,
(except as CuS). This idea i s supported by the regular array of CuS
crystals on the CuFeS^ l a t t i c e i n some cases (Figures 22-23). The CuS
which has obviously D r e c i p i t a t e d from solution (Figure 21) may then be
due to:
1) Actual separation of reactions as postulated i n i t i a l l y , or
2) Some H^S p r e c i p i t a t i o n as discussed below.
( i i i ) Hydrogen Sulphide Mechanism
It i s observed that some iron dissolves chemically from CuFeS^ even
at 90°C. Presumably the reaction i s :
CuFeS 2 + 2 H +
-> F e + +
+ H St + CuS
2
When combined with anodic d i s s o l u t i o n , and H S p r e c i p i t a t i o n :

2
CuS - 2 e" •+ C u + +
+ S°
H S + Cu
2
+ +
•*• CuS4- + 2 H +
i t i s possible that CuS could be transported 'through' the solution. This
mechanism does not, however, predict sulphate formation nor d o e s i t agree
with the temperature and pH data.
The l i m i t i n g quantity would presumably be amount of H S evolved since 2
there i s an excess of copper i n s o l u t i o n . This evolution w i l l increase
with temperature but not pH; i n fact the CuS formation does not (always)
increase with temperature but does increase with pH.
However, some H S evolution may occur, and cause some CuS p r e c i p i t a -

2
t i o n , as a side reaction.
-230-
II The Anodic Polarization Curve of Chalcopyrite
Three main forms of p o l a r i z a t i o n are commonly encountered i n electro-
chemical processes: activation, concentration and ohmic. Each form affects
the shape of the current/voltage (I/V) curve i n a p a r t i c u l a r manner:
Activation: I = ae^ where a,b are constants
Concentration: Limiting Current (I independent of V)
Ohmic: I = V/R where R i s a resistance.
In order to gain an understanding of the anodic process on chalco-
p y r i t e , i t may be necessary to consider forms of p o l a r i z a t i o n which are
peculiar to a compound semiconductor. A detailed analysis of such a system
i s beyond the scope of the present work, however, and only an outline can
be attempted. Furthermore, where possible c l a s s i c a l electrochemical concepts
w i l l be invoked, for i n understanding new phenomena i t i s h e l p f u l to r e l a t e
them to established concepts.
The anodic p o l a r i z a t i o n curves of chalcopyrite as shown i n Sections
I and II contain two stages which d i f f e r p r i n c i p a l l y i n t h e i r time-dependence.
The f i r s t stage i s highly time dependent and the second i s not; these have
been labelled the d i f f u s i o n region and the space charge region respectively.
An activation-controlled region must of course exist at the start of
the p o l a r i z a t i o n . In most cases, however, i t has a very small range of
potential.
In the d i f f u s i o n region the current i s nearly independent of p o t e n t i a l ;
this region i s c l e a r l y i n evidence at low temperatures (20°C), f o r about
500 mV. However, the current i n this region decays rapidly with time, and
increases with temperature: i t has an activation energy of 14 kcal. These
observations suggest that a l i m i t i n g current has been reached, which i s

-231-
related to a d i f f u s i o n a l process i n the electrode.
In the space charge region the time-dependence of the current i s much
smaller, but the potential dependence i s much greater, and i s i n fact
linear:
I = V/R.
It i s therefore postulated that at t h i s stage there i s a region within
the semiconductor, across which there i s a substantial drop i n potential
i . e . a space-charge region. Across t h i s gap a s i g n i f i c a n t e l e c t r i c field
w i l l exist, which can force the migrating cations out of the l a t t i c e . The
flux of these cations w i l l depend on the strength of the f i e l d , and w i l l
not decay with time.
The t r a n s i t i o n between the two regions i s c l e a r l y marked on most
occasions, and reproducible. There i s a s i g n i f i c a n t correlation (at a given
temperature) between the size of the d i f f u s i o n current and the potential
of the t r a n s i t i o n point. For instance (at 20°C) in IM HCIO^, the d i f f u s i o n
current i s higher than i n O.IM HC10 , but the t r a n s i t i o n potential i s

4
also higher. However, the slopes i n the space-charge region are s i m i l a r
(Figure 34).
It appears then that the d i f f u s i o n current i s a leakage phenomenon,
draining away the effect of increased potential so as to delay the start
of the space-charge region. Therefore a higher leakage or d i f f u s i o n current
corresponds to a higher t r a n s i t i o n potential.
a) The Diffusional Process i n Chalcopyrite
It has been well established by Wagner (201) and others that Cu +

ions
have an unusually high ionic d i f f u s i v i t y , being exceeded i n this respect
only by Ag .+
More highly charged species such as C u , F e , F e ++ + + + + +
are
-232-
more strongly held i n the l a t t i c e , and anions such as sulphide, S~, are
considered v i r t u a l l y immobile i n the temperatures range considered here.
The flux of ions across a charged i n t e r f a c e may be expressed as the
sum of a purely d i f f u s i o n a l term and a potential-dependent term:
j = _D IpL _ [ c ] d*
dx L J
dx
2
where J -sec.)
= flux of ions (mole/cm
D = dissusion c o e f f i c i e n t (cm^/sec)
3
[C] = concentration of ions (mole/cm )
x = distance (cm)
u = mobility of ions
+ •= p o t e n t i a l ( v o l t s ) .
By the Nernst-Einstein equation:
D-q
u =
KT
-19
where q = electron charge = 1.6 x 10 coulombs
-23
K = Boltzmann's Constant = 1.3S x 10 Joule
K-molecule
T = temperature °K
Therefore:
+
The concentration of Cu ions i n chalcopyrite may be calculated from
o
the c e l l dimensions (118) (a = 5.24 A):
[C] = 2.5 x 10" 2

mole
cm-*
At 50°C: . '
sM = o.go *°f
KT cnw-joule
-233-
0 90 ° l '
m : e s e c
cm-^-coul-ft
0.90 m
° l e
cm 4
volt/cm
Therefore:
J - -DD*M + 0.9 C 5 0
° C
^
L dx dx _|
Therefore the current across an anode (which i s related to the f l u x 3
by the stoichiometry of the reaction) i s dependent upon two terms. In
order to evaluate the r e l a t i v e magnitudes of these terms, i t i s necessary
to know the p o t e n t i a l gradient and the concentration gradient. However, only
very rough estimates of these quantities can be made:

-4
The space-charge region on germanium i s reported to be 10 cm.(198),
while the available p o t e n t i a l may be of the order of 200 mV. Therefore:

^ = 2 x 10 volt/cm. 3
dx
-2 3
The maximum concentration difference i s [C] = 2.5 x 10 mole/cm ,
while the boundary layer for s o l i d state d i f f u s i o n o f Cu +

ions might be
guessed at O.lu (10 cm). Therefore:

d[C] = 2.5 x 10" mole/cm 3 3
dx
On the basis of these rough estimates, i t appears that these terms
have approximately equal magnitudes.
It follows then that the d i f f u s i o n current dominates the low p o t e n t i a l
region, whilst the space-charge region takes over l a t e r .
Estimates of the d i f f u s i o n c o e f f i c i e n t , D, i n chalcopyrite maybe
taken from the works of Etienne (90) and Cole (118), who studies the copper
sulphides. As described i n the Introduction, Frueh has pointed out that
the structure of chalcopyrite i s s i m i l a r to that of d i g e n i t e , Cu^ gS, except

-234-
that the l a t t i c e i s t i g h t e r (see p. 13 ). We may assume therefore that
the d i f f u s i o n c o e f f i c i e n t of C u ions i n digenite represents

+
an upper bound
for that i n chalcopyrite.
-10 2 -7 2
At 50°C, Etienne found 2.4 x 10 cm /sec and Cole 1.7 x 10 cm /sec
(after extrapolation from 25°C, with an a c t i v a t i o n energy of 13 k c a l ) .
Then the f l u x may be calculated:

c n m 13 moles
-
. -
J = 6.0 x 10 ? (Etienne)
sec-cm^
. „ m"10 moles ~ ,
J = 4.2 x 10 2 r r
(Cole)
sec-cm^ v
I f the anodic reaction i s ( i n c h l o r i d e ) :
CuFeS. - 4 e" -»• F e

2
+ +
+ Cu + +
+ 2 S°
Then 1 mA/cm = 2
2.5 x 10~ mole 9
(Cu ) ++
sec-cm2
and the calculated current density that can be achieved i s :

-4 2
I = 2.4 . 10 mA/cm (Etienne)
I = 1.7 x 10" mA/cm 1

(Cole). 2
The actual current densities that are attained on anodizing chalco-

2
p y r i t e at 50°C (Figure 50) are about 0.50 mA/cm ( i n cnloride s o l u t i o n at
735 mV).
Thus the d i f f u s i o n c o e f f i c i e n t estimated using Cole's data, provides
an approximately s u f f i c i e n t f l u x of C u ions, whilst Etienne's value i s

+
1000 times too low.
However, Etienne also found that the anodic d i s s o l u t i o n of digenite
was too fast to be accounted f o r by her own experimental values f o r D;
she therefore concluded that the actual d i f f u s i o n a l process i n that case
was aqueous d i f f u s i o n , i n the shrinkage pores, rather than s o l i d state
diffusion.
-235-
In the present work such a conclusion i s s t i l l possible. In f a c t ,
i t i s observed that iron dissolves out of chalcopyrite f i r s t , and there-
fore the matrix through the Cu +

ions are d i f f u s i n g may be very d i f f e r e n t
from chalcopyrite. It may be a metastable iron-depleted l a t t i c e , or an
actual CuS l a t t i c e . In any case, there i s a strong p o s s i b i l i t y of (aqueous)
pore d i f f u s i o n .
It i s i n t e r e s t i n g to note that th° a c t i v a t i o n energies expected from
equation (D22) , are nearly independent of the r e l a t i v e magnitudes of the
two terms (diffusional and potential-dependent), since the a c t i v a t i o n energy
i s associated with the common factor, the d i f f u s i o n c o e f f i c i e n t .
Thus activation energies can be determined over a temperature range
which includes regions where either term i s dominant.
Experimentally this i s confirmed by the l i n e a r i t y of the Arrhenius
plots. For instance, at 735 mV i n chloride solutions the d i f f u s i o n current
i s dominant at low temperatures (20°C) (Figure 33), but the space-charge
current i s dominant at 90°C (Figure 39) . The Arrhenius plot i s l i n e a r
(Figure 63) •
Furthermore the various a c t i v a t i o n energies are s i m i l a r i n d i f f e r e n t
solutions (13.1 -> 14 k c a l ) , and also s i m i l a r to Etienne's: 12.1 kcal f o r
digenite.
b) Effect of Solution
At 20°C, the d i f f u s i o n region current i s increased by increasing the
strength of the solution, This can be r a t i o n a l i z e d by considering that the
dissolution of the metal ions i s aided, thus increasing the concentration
gradient i n equation (D22).
The space charge current, (at 20°C) i n contrast, i s almost unaffected

-236-
by the solution, and this also follows from equation (D22).
However, at 90°C, there i s a great difference between chloride, per-
chlorate and sulphate solutions v i z . the space-charge region s t a r t s around
500 mV i n hydrochloric acid, 900 mV i n perchloric acid and never i n s u l -
phuric acid.
Thus, i n some manner, at 90°C, the onset of the space-charge region
i s affected by the solution. No r e a l l y s a t i s f a c t o r y explanation of this
effect can be offered.
The 'passivity' of sulphuric acid may be due to the formation of a
basic s a l t on the surface, but this seems u n l i k e l y i n view of the fact that
sodium sulphate solutions (at a higher pH) do not passivate the mineral
to the same extent. The explanation may l i e i n the fact that the con-
d u c t i v i t y of a mineral specimen i s rapidly decreased by anodizing i n s u l -
phuric acid. This loss i n conductivity i s apparently an inter-granular
effect. This phenomenon correlates with the observation that i n f e r r i c
sulphate leaching, dissolution occurs p r e f e r e n t i a l l y along f i s s u r e s , which
presumably are grain boundaries.
The positive effect of chloride ions of r a i s i n g the space-charge
current (and also lowering the t r a n s i t i o n potential) i s hard to r a t i o n a l i z e .
It i s possible that chloride ions catalyze the closing of the Sg rings,
a necessary step i n the formation of elemental sulphur i n i t s rhombic
or monoclinic v a r i e t i e s . This postulate comes from the observation that
chlorine reacts readily with sulphur at low temperatures to form S2CI2,
and thus must be capable of opening the Sg ring. It i s therefore conceivable
that a low energy t r a n s i t i o n state i s formed with chloride ions that permits
an easy transformation to or from an S R ring.

-237-
Another explanation for the b e n e f i c i a l effect of chloride ions l i e s i n
the shrinkage pore model of Etienne, described above. I f i t i s true that
the d i f f u s i o n a l process takes place i n an aqueous environment, then cer-
t a i n l y increasing [Cl] w i l l aid d i s s o l u t i o n .
As a f i n a l speculation, i t i s worthwhile considering that space-
charge currents are related to overall attack on the mineral (as evidenced
by f e r r i c chloride leaching), whereas d i f f u s i o n currents are s o l e l y the
product of grain-boundary attack ( f e r r i c sulphate leaching).

-238-
E. CONCLUSION
The leaching of chalcopyrite can be interpreted as an e l e c t r o -
chemical reaction. F e r r i c chloride leaching i s faster than f e r r i c s u l -
phate leaching for four reasons:
1) In chloride solutions at t y p i c a l leaching temperatures (90°C) , the
anodic current i s potential dependent, whereas i n sulphate solu-
tions i t i s not.
2) The cathodic reduction of f e r r i c sulphate i s quite i r r e v e r s i b l e ,
and the reaction i s under mixed control. F e r r i c chloride leaching
actually proceeds v i a the cupric/cuprous couple which i s highly
reversible on chalcopyrite. The reaction i s thus under anodic
control.
3) F e r r i c sulphate attacks the mineral only along grain boundaries,
whereas f e r r i c chloride exhibits o v e r a l l attack.
4) The current e f f i c i e n c y for copper in the anodic d i s s o l u t i o n i s near
45% i n chloride solutions, but only 28% in sulphate solutions.
The balance of the current i s used up i n sulphur oxidation.

-239-
REFERENCES
1. Handbook of Chemistry and Physics, C.R.L. Press, 53rd Edition,

1973, Ed. R.C. Weast, p. F-167.
2. K.N. Subramanian and P.H. Jennings, Can. Met. Quart., 11, 387
(1972).
3. R.J. Roman and B.R. Brenner, Mineral Science and Engineering, 5_,
3 (1973).
4. (a) D.G. Treilhard, Eng. and Mining Journal, A p r i l (1973).
(b) J . Dasher, C.I.M. B u l l . , 48 (1973).
5. M.E. Wadsworth, Mineral Science and Engineering, 4, 36 (1972).
6. H.E. Merwin and R.H. Lombard, Econ. Geol., 32, 203 (1937).
7. J.E. H i l l e r and K. Probstain, Zeitschr. K r i s t a l l o g r a p h i e , 108,

108 (1956).
8. G. Donnay and G. Kullerud, Carn.Inst. Washington Year Book, 57,

246 (1958).
9. E.H. Roseboom and G. Kullerud, Carn. Inst. Washington Year Book,

57, 222 (1958).
10. R.A. Yund and G. Kullerud, J . Petrology, 454 (1966).
11. G. Kullerud, R.A. Yund and G.H. Mah, Econ. Geol. Mon., 4-, 323
(1969).
12. H. Mukaiyama and E. Izawa, i n "Volcanism and Ore Genesis", T.

Tatsumi ed., p. 339 (1970).
13. P.B. Barton, J r . , Econ. Geol., £8, 455 (1973).
14. Hiromi Shima, Ganseki Kobutso Kosho Gakkaishi, 47, 123-33 (1962).
15. P.B. Barton, J r . and P r i e s t l e y Toulomin, Econ. Geol., 54, 747

(1964).
16. M. Nambu and S. Kano, Gansehi Kobutso Kosho Gakkaishi, 60, 127
(1968).
17. R. Adams, R. Beaulieu, M. V a s s i l i a d i s and A. Wold, Mat. Res. B u l l . ,

7_, 87 (1972).
18. R. Adams, P. Russo, R. Arnott and A. Wold, Mat. Res. B u l l , 7_, 93

(1972).
-240-
19. J.H. Kim and T.R. Middleton, paper presented at AIME Annual Meet-
ing, San Francisco (1972).
20. P.B. Barton and B.J. Skinner, i n "Geochemistry of Hydrothermal Ore

Deposits", ed. H.L. Barnes, p. 236 (1967).
21. L. Cabri, Econ. Geol., 62, 910 (1967).
22. W.H. Maclean, L.J. Cabri and J.E. G i l l , Can. J . Earth S c i . , %

1305 (1972).
23. S.R. H a l l and E.J. Gabe, Am. Mineralogist, 57, 368 (1972).
24. A.H. Clark, Econ. Geol., 65, 590 (1970).
25. L.J. Cabri and D.C. Harris, Econ. Geol., 6^5, 673 (1971).
26. L.J. Cabri and S.R. H a l l , Am. Mineralogist, 57, 689 (1972).
27. L.J. Cabri, Econ. Geol., 68, 443 (1973).
28. S.R. H a l l and J.F. Rowland, i n preparation (1973)(ref. 27).
29. J.R. Rowland and S.R. H a l l , i n preparation (1973)(ref. 27).
30. N. Morimoto and K. Koto, Am. Mineralogist, 54, 1256 (1969).
31. N. Morimoto and K. Koto, Am. Mineralogist, \5_5_, 106 (1970).
32. N. Morimoto and A. Gyobu, Am. Mineralogist, _56, 1889 (1971).
33. R.A. Munson, Inorg. Chem., 5_, 1296 (1966).
34. Y.Kajiwara, Mineral.'J. (Tokyo), 5_, 399 (1969).
35. H. Shimazaki and L.A. Clark, Can. Mineralogist, 9_, 648 (1970).
36. E.H. Roseboom, Econ. Geol., 61, 641 (1966).
37. R.M. Garrels and C. Christ, "Solutions, Minerals and E q u i l i b r i a " ,

Harper and Row, New York (1965).
38. A. Golomzik, Izv. Vysshikh. Ucheba. Zavedni. Tsveta. Met., 7_, 2

(47).
39. K.K. Kelley, U.S. Bureau of Mines B u l l . 406 (1937).
40. P. Bartholome, "On the Paragenesis of Copper Ores", Studia Univer-

s i t a t i s "Lovanium" (1958) (Leopoldville, Belgian Congo).
41. J . Joly, P h i l . Mag. 25, 856 (1913).
42. R. Townend, P.K. Schultz, H.W. Funder and P.A. Young, B u l l . Aust.
Min. Dev. Lab., 2, 1-11, 76-77 (1966).
-241-
43. P.A. Young, B u l l . Aust. Min. Dev. Lab., 3_, 1-19 (1967).
44. H. McKinstry, Econ. Geol., 54, 975 (1959).
45. H. von Wartenberg, Z. Physik. Chem., 67_, 446 (1909).
46. H. Zeumer and W.A. Roth, Z. Physik. Chem. A, 173, 365 (1935).
47. S.V. L i p i n , V.S. Uskov and V.R. Klokman, Zhurnal Poikladavi Khimii,
15, 411 (1942).
48. L.H. Adami and E.G. King, U.S. Bureau of Mines, Rept. Invest. 6495
(1964).
49. J.C. Southard, Ind. and Eng. Chem., 32, 442 (1940).
50. K.K. Kelley, U.S. Bureau of Mines B u l l . , 592 (1961).
51. R.W. M i l l a r , J . Am. Chem. S o c , 5_0, 1875 (1928).
52. C.T. Anderson, J . Am. Chem. S o c , 52_, 2296 (1930).
54. C.T. Anderson, J . Am. Chem. S o c , 54, 107 (1932).
56. J-H. Hu and H.L. Johnson, J . Am. Chem. S o c , 75_, 2471 (1953).
57. E.F. Westrum, J r . , J.B. Hatcher and D.W. Osborne, J . Chem. Phys.,
21, 419 (1953).
58. F. Gronvold, E.F. Westrum, J r . and Chien Chou, J . Chem. Phys., 30,
528 (1959).
59. E.F. Westrum, J r . and A.F. Beale, J r . , J . Phys. Chem., 65, 353
(1961).
60. E.G. King and W.W. Weller, U.S. Bureau of Mines, R.I. 5590 (1959).
61. W.W. Weller, U.S. Bureau of Mines, R.I. 6669 (1965).
62. L.B. Pankratz and E.G. King, U.S. Bureau of Mines, R.I. 7435 (1970).
63. "Thermodynamic Properties of Copper and i t s Compounds", I.N.C.R.A.

Monograph I I , ed. E.B. King, Mah, L.B. Pankratz, International
Copper Research Association, Cambridge, Mass. (1973).
64. T. Rosenquist, Metals Trans., 185, 451 (1949).
65. A.A. Brooks, J . Am. Chem. S o c , 75_, 2464 (1953).

-242-
66. F.D. Richardson and J.E. A n t i l l , Trans. Farad. S o c , 51, 22 (1955).
67. H.H. Kellogg, Can. Met. Quart., 8_, 3 (1969).
68. W.A. Krivsky and R. Schumann, J r . , Metals Trans. AIME, 982 (1957).
69. J.R. Craig and W.R. Lees, Econ. Geol., 67_, 373 (1972).
70. L. Pauling and CO. Brockway, Z e i t s . K r i s t . , 82^, 188 (1932).
71. " C r y s t a l Structures of Minerals", L. Bragg, G.F. C l a r i n g b u l l and

W.H. Taylor, B e l l and Sons, Ltd., London (1965).
72. "Structural Inorganic Chemistry", A.F. Wells, Clarendon Press,

Oxford (1960).
73. G. Donnay, L.M. C a r l i s s , J.D.H. Donnay, N. E l l i o t t and J.M. Hastings,

Phys. Rev., 112, 1917-1923 (1958).
74. D.J. Vaughan, Ph.D. Thesis, Oxford (1971).
75. S.J. Pickart, Mineral. Soc. Amer. Spec Pap., 3_, 145 (1970).
76. A.S. Marfunia and A.R. Mkrtychan, Geokhimiya, 10, 1094 (1968).
77. B.V. Borshagorskii, A.S. Marfunia, A.R. Mkrtychan, R.A. Stukan and
G.N. Nadzharyan, Izv. Akad. Nauk., U.S.S.R., Ser. Khim. 1968 (6)
1267.
78. N.N. Greenwood and H.J. Whitfield, J . Chem. S o c A, 1697 (1968).
79. J . Piekoszewski, J . Suwalski and S. Ligenza, Phys. Stabus. S o l i d i ,

K99 (1969).
80. L.J. Cabri and R.H. Goodman, Geokhimya 636 (1969).
81. F. Aramu, T. Bressani and P. Manca, Nuovo Cimento, B51, 370 (1967).
82. C L . Herzenberg, Nuovo Cimento, 53, 516 (1968).
83. E. Frank, Nuovo Cimento, 58, 407 (1968).
84. A.J. Frueh, Geochimica et Cosmochimica Acta., 6^, 79 (1954).
85. A.J. Frueh, Z e i t . K r i s t . , 106, 299 (1955).
86. A.J. Frueh, Am. Mineral., 44, 1010 (1959).
87. G.F. Karavaev, A.S. Poplavnoi and V.G. Tyuterev, Izv. Vyssh. Ucheb.
Zaved. F i z . , 13, 42 (1970).
88. M. Telkes, Am. Mineralogist, 25, 536 (1950).

-243-
89. E.N. Zevgolis, Ph.D. Thesis, Univ. Minnesota (1971).
90. A. Etienne, Ph.D. Thesis, Univ. B r i t . Col. (1970).
91. C.R.S. Needes, M.J. Nicol, Nat. Inst. Met. (Johannesburg) Report
#1380 (1972).
92. J.T. Woodcock, Proc. Aust. Inst. Min. Met., No. 198, 47 (1961).
93. R.J. Cornelius and J.T. Woodcock, Proc. Aust. Inst. Min. Met., No.
185, 65 (1958).
94. I.H. Warren, Aust. J . App. S c i . , 7_, 346 (1956).
95. T.R. Scott and N.F. Dyson, Trans. Am. Inst. Min. Engrs., 242, 1815
(1968).
96. E. Peters and H. Majima, Can. Met. Quart., 7_, 111 (1968).
97. J . Wright, Amdel B u l l . #12, 47 (1971).

#13, 27 (1972).
98. R. Woods, Proc. Aust. Inst. Min. Met., #241, 53 (1972).
99. A.P. Prosser, IX Commonwealth Mining and M e t a l l u r g i c a l Congress,

London, 1969, V o l . 3.
100. M. Majima and E. Peters, VIII Int. Min. Proc. Cong., Leningrad, E l
(1968).
101. E. Habashi, Min. S c i . Eng., 3_, 3 (1971).
102. J . Sullivan, U.S. Bureau Mines, Tech. Pap., 473 (1930).
103. G. Thomas, T.R. Ingraham and R.J.L. MacDonald, Can. Met. Quart., J5,
281 (1967).
104. J.A. King, Ph.D. Thesis, Univ. London (1966).
105. A.R. Burkin, Min. S c i . Eng., 1/ 4 (1969).
106. J . Sullivan, U.S. Bureau Mines, Tech. Paper, 487 (1930).
107. G. Thomas and T.R. Ingraham, Can. Met. Quart., 6_, 153 (1967).
108. K.J. Jackson and J.D.H. Strickland, Trans. Met. Soc. AIME, 212,
373 (1958).
109. I.H. Warren, Aust. J . App. S c i . , % 36 (1956).
110. F. Loewen, M.A. Sc. Thesis, Univ. B r i t . C o l . (1967).

-244-
111. J . Dahms, J . Gerlach and F. Pawlek, Erzmetall, 20, 203 (1967).
112. O.B. Tkachenko and A.L. Tseft, Tr. Inst. Met. Obogaskeh. Akad.
Nauk. Kaz. S.S.S.R., 30, 15 (1969).
113. K. Wrabetz and W. Noddack, Z. Elektrochem., 5_9, 96 (1955).

59, 752 (1955).
60, 722 (1956).
114. B.Z. U s t i n s k i i and D.M. Chlzikov, Zb. Prik. Khimii., 22^ 1249
(1949).
115. M. Sato, Econ. Geol., 55_, 1202 (I960).
116. V. Kuxmann and H. B i a l l a s s , Enzmetall, 22_, 53 (1969).
117. H.J. Matheu and H. Rickert, Z e i t . Phys. Chem. Neue Folge Bd. 7_9,
S315 (1972).
118. S. Cole, Ph.D. Thesis, Univ. Columbia (1972).
119. P. Brennet, S. J a f f e r a l i , J.M. Vanseveren, J . Verecken and R. Winrad,

Met. Trans. AIME, 5_, 127 (1974).
120. S. Venkatachalam, R. Mallikarjunan, Inst. Min. Met. Trans., 7_7, 45

(1968).
121. A.G. Losharev, A.F. Vozinar, Zh. P r i k l . Khimii, 26^, 49 (1953).
122. D.M. Chizikov and B.Z. U s t i n s k i i , Izvest. Akad. Nauk. S.S.S.R.,

Otdel Tekh. Nauk., 229 (1948).
123. L.S. Renzoni, R.C. McQuire and W.V. Barker, J . Metals, 10_, 414
(1958).
124. F. Habashi and N. Torres-Acuna, Tr. AIME, 242, 780 (1968).
125. T. Kato and T. Oki, Denki Kagaku, 40, 670 (1972).
126. T. Kato and T. Oki, Japan Inst. Metals. Journal, 36, 947 (1972).
127. J.D. Sullivan, U.S. Bureau of Mines, Tech. Pap., 486 (1930).
128. J.E. Dutrizac, R.J.C. MacDonald and T.R. Ingraham, Met. Trans., 1,
225 (1970).
129. J.E. Dutrizac, R.J.C. MacDonald and T.R. Ingraham, Met. Trans., 1,
3083 (1970).
130. J.D. Sullivan, Trans. AIME, 106, 515 (1933).
131. J.E. Dutrizac, R.J.C. MacDonald and T.R. Ingraham, Trans. Met. Soc.
AIME, 245, 955 (1969).
-245-
132. E. P e t e r s , "The P h y s i c a l Chemistry of H y d r o m e t a l l u r g y " , ATME I n t .

Symposium on Hydrometallurgy, Chicago (1973) .
133. J . E . D u t r i z a c , R.J.C. MacDonald, Can. Met. Quart., 12, 409 (1973).
134. F. Lowe, Ph.D. T h e s i s , U n i v . of A r i z o n a (1970).
135. F.A. Forward and I.H. Warren, M e t a l l . Rev., _5, 137 (1960).
136. R.0. P i k e , G.H. West, L.V. Steck, R. Cummings and B.P. Little,
T r a n s . AIME, 90, 311 (1930).
137. F.P. Haver and M.M. Wong, U.S. Bureau of Mines, R.I. 7474 (1971).
138. P.A. Pazdnikov and Yu-M. P o t a s h i n i k o v , Sb Nauch-Tekh. T r . Trudov

Nauch. I s s l e d . I n s t . M e t a l l . C h e l y b . Sovet. Narod. Khoz., #2, 121
(1960).
139. W. Mulak and J . Niemec, Rocz. Chemmii, 42, 775 (1968).
140. V.V. E r m i l o v , O.B. Tkachenko and A.L. T s e f t , T r . I n s t . Met. Obogasch.,

Akad. Nauk. Kaz. S.S.S.R., 30, 3 (1969).
141. V.E. K l e t s and A.P. S e r i k o v , T r . I r t u t s k . P o l i t e k h . I n s t . , 18, 31

(1963).
142. Can. P a t e n t #938793, Cominco L t d . (1973).
143. U.S. Patent #3,785,944, D u v a l Corp. (1974).
144. A . I . V i z s o l y i , J . M e t a l s , 19, 52 (1967).
145. P.H. Yu, Ph.D. T h e s i s , U n i v . of Utah (1972).
146. F. Forward, J . M e t a l s , ]_, 457 (1955).
147. M. Kuhn, paper p r e s e n t e d a t 3rd C.I.M. H y d r o m e t a l l u r g y C o n f e r e n c e ,

Edmonton (1973).
148. J.D. P o r t e r , P.B. Queneau and T . J . Hudson, paper p r e s e n t e d a t AIME

Annual Meeting, San F r a n c i s c o (1972).
149. F. Habashi, T r a n s . S.M.E.-AIME, 254, 224 (1973).
150. G. B j o r l i n g and G.A. K o l t a , P r o c . I n t e r n . M i n e r a l P r o c e s s i n g Cong.

7th, New York (1965).
151. G. S p r i n g e r , T r a n s . I n s t . Min. Met., C l l (1970).
152. W.H. B r a t t a i n and C.G.B. G a r r e t t , B e l l System Techn. J o u r n a l , 34,

129 (1955).
153. K. J i b i k i , M.Sc. T h e s i s , U.B.C. (1971).

-246-
154. T. Oki and S. Ono, Japan Inst. Min. Met. Journal, 83, 1159 (1967).
155. H. Sawamoto, T. Oki and A. Nishina, Nagoya Univ., Fac. Eng. Memoirs,
14, 197 (1962).
156. Internat. Symp. on High Temperature Electrochemistry, Guildford,

U.K. (1973).
157. D. de G. Jones and H.G. Masterson, "Techniques f o r the Measurement

of Electrode Processes at Temperatures above 100°C", i n Adv. Corros.
Science and Tech., ed. M.G. Fontana and R.W. Staehle, V o l . I (1970).
158. W.C. Waggener and A.M. Tripp, Rev. S c i . Instr., 3 £ , 677 (1959).
159. R.H. Krenz, A.S.T.M., Spec. Tech. Pub., 368 (1963).
160. M.H. Lietzke, R.S. Greeley, W.T. Smith and R.W. Stoughton, J . Phys.
Chem., 64, 652 (1960).
161. E.V. Franck, J.E. Savolainen and W.L. Marshall, Rev. S c i . Instr.,
33, 115 (1962).
162. A.J. E l l i s , J . Chem. S o c , 2299, 4300 (1963).
163. G. Kennedy, Econ. Geology, 45_, 629 (1960).
164. A.L. Bacarella and A.L. Sutton, J . Electrochem. S o c , 112, 546

(1965).
165. M.W. Connell, U.S. Patent #2,625,573 (1953).
166. P.W. Bridgeman, "The Physics of High Pressure", B e l l and Sons (1949).
167. A. Disteche, Rev. S c i . Inst., 30, 474 (1959).
168. V.V. Gerasimov, Corrosion of Reactor Materials, A C o l l e c t i o n of

A r t i c l e s , A.E.C. Transl. 5219, p.13 (1962).
169. J . Giner, J . Electrochem. S o c , 111, 376 (1966).
170. S. Stene, Rec. Trans. Chim. Pays-Bas, 49, 1133 (1930).
171. M.H. Lietzke and R.W. Stoughton, i n "Encyclopaedia of Electrochemis-

try", C A . Hampel, Ed. Reinhold, N.Y., p. 505 (1964).
172. M.H. Lietzke and R.W. Stoughton, J . Phys. Chem., 67_, 2573 (1963).
173. G. Kortum and W. Hausserman, Ber. Bunsenges. Physikchem., 69, 594

(1965).
174. R.W. Lietzke and R.W. Stoughton, J . Phys. Chem., 68, 3043 (1964).
175. M.H. Lietzke and R.W. Stoughton, J . Am. Chem. S o c , 75_, 5226 (1953).
-247-
176. M.H. L i e t z k e and J.V. Vaughan, J . Am. Chem. Soc.,i '77, 876 (1954).
177. D.G. I v e s and G.J. J a n z , "Reference E l e c t r o d e s " , Academic P r e s s ,

N.Y. (1961).
178. R. G r e e l e y , Ph.D. T h e s i s , U n i v . o f Tennessee (1960).
179. E.B. S a n d e l l , " C o l o r i m e t r i c D e t e r m i n a t i o n o f T r a c e Amounts o f M e t a l s " ,

I n t e r s c i e n c e P u b l i s h e r s , New Y o r k , 3 r d Ed. (1959).
180. R.J. B e r t o l a c i n i and J.E. Barney I I , A n a l . Chem., 30, 202 (1958).
181. J . Agterdenbos and N. M a r t i n i u s , T a l a n t a , 11, 875 (1964).
182. "Standard Methods of C h e m i c a l A n a l y s i s " , N.H. Furman ed., V o l . I ,

p. 544, S i x t h e d i t i o n , D. Van N o s t r a n d Co., I n c . , P r i n c e t o n , N.J.
(1962).
183. L.S. R e n z o n i , R.C. McQuire and W.V. B a r k e r , J . of M e t a l s , 10, 414

(1958).
184. Symposium on t h e Thompson O p e r a t i o n , C.I.M. B u l l e n t i n , 57, 1181

(1964).
185. J . G e r l a c h , H . HShne and F. Pawlek, Z. E r z b e r g a n Metallhlittenw.,

i 9 ( 2 ) 66 (1966).
186. H. Majima and E. P e t e r s , V I I I I n t e r n a t . M i n e r a l P r o c e s s i n g C o n g r e s s ,

L e n i n g r a d , E l (1968).
187. W. L a t i m e r , " O x i d a t i o n P o t e n t i a l s " , 2nd e d i t i o n , P r e n t i c e - H a l l , N.J.

(1950).
188. H. H e l g e s o n , "The Thermodynamics of H y d r o t h e r m a l Systems a t E l e v a t e d

Temperatures and P r e s s u r e s " , Amer. J . S c i e n c e , 247, 729 (summer 1969).
189. K . J . V e t t e r , E l e c t r o c h e m i c a l K i n e t i c s , T h e o r e t i c a l and Experimental

A s p e c t s , Academic P r e s s , N.J. (1967).
190. E. D e v u y s t , Ph.D. T h e s i s , U n i v . o f B.C. (1973).
191. "The W i n n i n g of N i c k e l " , J.R. B o l d t and P. Queneau, Longmans, T o r o n t o ,

p. 306 (1967).
192. T. N g o i and E. P e t e r s , P r i v a t e c o m m u n i c a t i o n .
193. F.A. Forward and V.N. Mackiw, J . M e t a l s , 461 (1965).
194. D.I. Ryabchikov and V.G. S i l ' n i c h e n k o (Moscow R e g i o n a l Ped. Inst.)

B u l l . a c a d . s c i . U.R.S.S., C l a s s e s c i . chim. 19-26 (1947).
-248-
195. "A Comprehensive T r e a t i s e on I n o r g a n i c and T h e o r e t i c a l C h e m i s t r y " ,

J.W. M e l l o r , W i l e y (N.Y.)(1922).
196. " M e l l o r ' s Modern I n o r g a n i c C h e m i s t r y " , Rev. Ed., G.D. P a r t e e s ,

Longmans, London (1967).
197. V.F. Toropova, I.A. S i r o t i n a and T . I . L i s o v a , Uchenye Z a p i s k i

Kazan. G o s u d a r s t . U n i v . im. V. I . U l ' y a n o v a - L e n i n a , Khim. 115,
No. 3, 43-52 (1955).
198. S.M. Ahmed and D. Maksimov, Mines Branch R e s e a r c h R e p o r t , R196,

Ottawa (1968).
199. R. M c E l r o y , Ph.D. T h e s i s , U.B.C. (1972).
200. C M . C r i s s and J.W. Cobble, J . Amer. Chem. S o c , 816, 5385 (1964).
201. C. Wagner, " C o n d u c t i o n and D i f f u s i o n i n I o n i c C r y s t a l s " , i n "The

M o l e c u l a r D e s i g n i n g o f M a t e r i a l s and D e v i c e s " , ed. A. Von H i p p e l ,
MIT P r e s s (1965).
-249-
APPENDIX A
A THERMOCHEMICAL STUDY OF THE Cu-Fe-S MINERALS*
Introduction
The Cu-Fe-S system has been extensively investigated by
Yund and Kullerud"*" at temperatures as low as 200°C and their
i n t e r p r e t a t i o n of the stable assemblages at t h i s temperature i s given i n
Figure 1. It can be seen that, i n addition to the usual binary sulphides,
there are four stable ternary sulphides:
Chalcopyrite CuFeS 2 (cp)
Bornite Cu FeS.
c (bn)
Cubanite CuFe^ (cb)
Kdaite Cu FeS- (id)

5.5
c c
6.5
Of these, the f i r s t two minerals are very commonly encountered
i n nature, and are the major sources of copper i n Canada, whilst cubanite
i s comparatively uncommon and i d a i t e i s r a r e l y reported. However, i n
contrast to the r e l i a b l e thermochemical data available on the binary

2 3
sulphides ' few such studies are reported on the ternary sulphides and
Young^ has summarized the work to date (1967).
'Maier'"' using a value of 743°C (?) f o r the decomposition
temperature of CuFeS a r r i v e s at the values:

9
AH° 9 g = -41.59 AG 2 9 g = -41.33 Kcal/mole
Bartholome^ using the assemblages shown i n Figure 2, and
available data on equilibrium p a r t i a l pressures of sulphur over these
*Taken from report submitted for INCRA Grant #160, by D. Jones and E.
Peters (1970).
-250-
Fig.l Cu-Fe-S system at 2 0 0 ° C .

(Yund S Kullerud)
Fig.2 Cu-Fe-S system at 2 5 ° C .

(Bartholome)
-251-
assemblages (at 25°C) deduces:

-AG°
298
CuFeS 2 -45.0 ± 3 . 5 kcal/mole
Cu FeS. -89.0 ± 6.0

5c
4
CuFe S 2 3 -69.0 ± 3.0
His work suffers from the fact that his ternary diagram i s
probably not correct^ and the large error l i m i t s imposed by the lack of
data.
Golomzik'' reports some sulphur pressures at 500, 600 and
700°C over chalcopyrite, quoted from a source so obscure as to be
suspicious, and calculates:
AG° 9 g (CuFeS ) = -51.49 Kcal/Mole

2
This calculation i s subject to serious errors due to the
heat of transformation, s p e c i f i c heat changes and presence i n the sulphur
vapor of species other than diatomic.

4
Young s i m i l a r l y made some calculations, u t i l i z i n g the
8
sulphur vapor pressures for each mineral tabulated by Merwin and Lombard ;
to do t h i s , as i n the above calculations, i t was necessary to assume what the
decomposition products are, and this i s never an unambiguous choice.
Thus, f o r example, one may write four d i f f e r e n t reactions for CuFeS : 2
- °298 AG
9CuFeS 9 y Cu FeS. + 4CuFe S„ + 2S ^

c 0 40.8
^ 5 4 2 3 • rh
5CuFeS 2 > J C u e S
4 + 4 F e S + 2 S
r h 3 9 , 5
-252-
4CuFeS 2 • 2Cu S + 4FeS + 2 S

2 r h 39.8
CuFeS 2 • Cu + Fe + 2S r h 38.7
Similarly f o r CuFe,^:
" 298 AG
CuFe S 2 3 y Cu + 2FeS + S 3 r h 64.9
CuFe S 2 3 y Cu + 2Fe + 3 S a r h 62.8
and Cu^FeS^:
Cu FeS
5 A y / C u + l/ CuFe S + / S
9
2 2 2 3
5
2 r h 79.6
Cu FeS
5 4 y 5Cu + Fe^ + 4 S r h 75.1
Young considers these valu&s to be rough estimates at best.
He also does some separate c a l c u l a t i o n s based on mineral assemblages
alone. Following the arrow i n F i g . l , he writes the set of reactions as
each t i e - l i n e i s crossed:
Fe + S 2 y 2FeS
l 0
/ C u + / FeS + S
3
2
3 2 • /3Cu FeS
2
5 4
Cu-FeS. + 9FeS + S„ »• 5CuFe„S_ etc.

5 4 2 2 3
(Each reaction i s written with one mole S ) 2
Then, using the fact that the free energy change f o r each
successive reaction i s smaller ( i . e . less negative) than the one
preceding i t , he writes the appropriate set of i n e q u a l i t i e s .

-253-
2/ AG°(FeS) " / 2
3 AG°(Cu^-FeS^) * "2 AG°(FeS)
AG°(Cu FeS ) + 9AG° (FeS) - 5AG° (CuFegS ) < /

5 4
2
3 AG° (FeS) - / A G ° ( C u F e S )
2
3 5 4
etc.
Then, knowing AG°(FeS), the i n e q u a l i t i e s may be solved,
giving lower l i m i t s for the free energies of each mineral. So f a r the
calculation appears acceptable, but then the author goes on to obtain
upper l i m i t s by using Bartholome's estimate for digenite;
AG°(Cu S ) = -101.0 ± 8.0

9 5 Kcal/mole
and putting the values for the lower l i m i t s back into the i n e q u a l i t i e s .
2
F i r s t l y , we now have a very r e l i a b l e digenite value from Etienne's work
AG° 9 g (Cu S ) = -90.7

9 5 ± 3.0 Kcal/mole
and secondly, the algebra of this step appears to be incorrect. Upper
l i m i t s may be obtained, but they do not approach the lower l i m i t s as
closely as Young suggested. However, they are s t i l l useful and together
with the previous results are given i n Table 1.

-254-
Table 1. Calculated Free Energies of Minerals: AG°29 8 (Kcal./mole)
Mineral 1) 2) 3) 4) 5)
CuFeS 2 45.3 ± 0.2 43.5 ± 2.1 45.0 ± 4.5 40.8 38.7
CuFe S2 3 68.2 ± 0.2 66.2 ± 2.2 69.0 ± 4.5 64.9. 62.8
Cu FeS. 85.9 ± 6.1 84.9 ± 5.2 89.0 ± 8.0 79.4 75.1

5
r
4
Cu FeS.
c 100.8 ± 3.8 102.3 ± 2.4 97.5 -
J 0
1) Young's calculations from mineral assemblages.
2) Our modification of 1) as outlined above.
3) Bartholomg calculations from sulphur pressures.
4) Young's calculations based on Merwin and Lombard's decomposition

pressures and Bartholome (low-T) assemblages.
5) Repeat of 4) with Kullerud's (high-T) assemblages.
The formula f o r i d a i t e used i n a l l these e f f o r t s i s Cu FeS,; according to

c
5 D
1
Kullerud , the correct one i s Cu c-FeS, •
-255-
Combustion Experiments
The p r i n c i p l e of bomb calorimetry i s that the heat of
formation, AH° of a substance may be determined from i t s combustion to
a product of known heat content. For organic materials this i s very
convenient because most of them are very e a s i l y ignited, under high oxygen
pressure, to what i s e s s e n t i a l l y water and carbon dioxide. However, f o r
inorganic substances, combustion i s not so simple, for a v a r i e t y of
products are possible and often their heat content i s unknown.
Previous combustion work on sulphides goes back a long way,
but appears to have gone out of fashion f o r some time now, i n favor of
other techniques such as measuring the equilibrium gas pressures and
composition as a function of temperature. The reason for this decline i n
interest appears to be two-fold: F i r s t l y , values of AH° obtained from
combustion are often caught i n an 'error-limits squeeze' i . e . a small
difference between two large numbers, such that a small error i n the heat
of combustion results i n a large error i n the heat of formation. Secondly,
the exact nature of the product of combustion i s not e a s i l y determined,
and a 95% combustion i s not good enough.
For this reason, i t was intended that the product of a
combustion of CuFeS„ and Cu FeS. should be converted to a soluble

r form,
2 5 4
which presumably would be a known species.
-256-
Experj.mental Results
Using a Parr adiabatic bomb calorimeter with 30 atm. 0^,
CuFeS^ samples could be ignited to form SO^ and a s o l i d oxide product.
Several attempts were made to quantitatively convert the SO^ to S0^ and
dissolve the gas i n a basic solution within the bomb; however, there i s
d i f f i c u l t y i n oxidizing the SO^ completely, and since this o v e r a l l reaction:
%0 o + S0 o + 20H~ y S07 +
H_0
2 2 4 2
i s strongly exothermic, a large error i s introduced by any unoxidized
SO2. Therefore i t appeared more accurate to leave the sulphur i n i t s
S0^ form and keep SO3 formation to a minimum; t h i s necessitated using a
dry bomb. Any SO^ present can e a s i l y be detected by i t s fuming i n a i r .
The nature of the s o l i d oxide product constituted the most
difficult problem;it was extremely insoluble i n cold a c i d , and only
dissolved slowly i n b o i l i n g sulphuric - f a r slower than the s t a i n l e s s
s t e e l capsule. Evidently there was no ordinary s o l u t i o n which could
dissolve the oxide i n a reasonable length of time (say one hour) without
attacking the bomb i t s e l f .
Experiments were conducted to see i f the oxide could be reduced
by a zinc amalgam covered d i l u t e sulphuric acid. This was partially
successful, but the reaction was f a r too slow and by no means complete.
Other amalgams were t r i e d with s i m i l a r r e s u l t s .
Another approach that was t r i e d was i g n i t i n g CuFeS2 with
NH^Cl and/or NH^CIO^, i n the hope a soluble s a l t would be formed. Again
there was p a r t i a l success, but never 100% conversion, due to the
incomplete combustion.
-257-
Therefore i t was decided to abandon a l l attempts to
s o l u b i l i z e the oxide product, and instead to determine i t s heat content
indirectly. No AH values for 'CuFeO,,' could be found i n the l i t e r a t u r e ,
and so this had to be determined experimentally. A one-to-one mixture of
copper and i r o n powder can be ignited to give a heat of combustion AH^ of
114.3 kcal./mole
°2
Cu + Fe • 'CuFeO ' AH = -114.3 Kcal./mole.
z c
Iron powder alone can be ignited, but copper powder' can not.
°2
Fe —=-*• 'FeO' AH = -86.8 Kcal./mole,
c
However, assuming that CuO and 'FeO' mix with no significant
interactions•one obtains:
°2
Cu — — * • CuO AH = -27.5 Kcal./mole.
c
This assumption, which gives a value for CuO that i s 10 Kcal.
lower than the l i t e r a t u r e value, nevertheless gave some apparently
consistent results, as follows;
CuS, C^S FeS, and FeS,, were a l l i g n i t e d , and literature
values of AH 0
of these substances were only obtained by using the values
of AH c of CuO and FeO, determined experimentally. Thus i t appeared
that the AH C value for single 'CuFeO' was a useful one.
The i g n i t i o n of CuFeS,, gave however a very low value:
°2
CuFeS —=-+ 2 2S0 + 'CuFe0 '
2 2 AH c = -169.8 Kcal./mole.
-258-
Using the l i t e r a t u r e value f o r SO^ (AH^° = -71.0 Kcal./mole)
and the experimental value f o r CuFe02 of-114.3, we obtain:
AH °(CuFeS )
f 2 = -86.5 Kcal./mole
This i s an impossibly large f i g u r e , and would imply several
unknown reactions and mineral associations. Estimates based on mineral
associations and gas pressures are about half this value.
However, combustion of a (CuS and FeS) mixture gave i d e n t i c a l
results which was extremely puzzling.
(CuS + FeS) + r
CuFeO ' + 2S0 2
AH = - 221.8 Kcal/mole
c
This leads to: AH (CuFeS ) = -86.9
f 2 Kcal./mole
Therefore the r e s u l t s were i n t e r n a l l y self-consistent, but
wrong! The way out of the dilemma was f i n a l l y found however, by
re-investigating the combustion of CuS. In order to get more accurate
data larger samples were ignited and i t was found that the heat of
combustion was dependent upon the s i z e of the sample.
Weight of sample (g) AH (CuS)(Kcal./mole)

c
Earlier results 0.91 84.0

0.96 84.1
1.52 89.8
2.13 86.2
2.38 88.2
3.28 94.1
6.30 98.4
Theoretical r e s u l t : 96.0 ± 1.3

-259-
E v i d e n t l y , the o r i g i n a l v a l u e AH^(CuO) of -27.5 kcal.
was i n c o r r e c t , and a p p l i e d o n l y t o samples i n a narrow s i z e range. With
s m a l l e r samples too much heat i s l o s t to the s u r r o u n d i n g s and the
sample i s never t o t a l l y combusted. S i m i l a r but more d r a m a t i c results
were found f o r (CuS and FeS) m i x t u r e :
Weight of sample (g) -. AH (CuS + FeS) (Kcal/mole)
1.08 221.8
3.04 135.2
5.06 120
The low heat of combustion CuFeS^ was f i n a l l y made c l e a r

when the combustion products were examined upon the m i c r o p r o b e . T h i s
instrument showed t h a t w h i l e the combustion product of CuS and FeS
( s e p a r a t e l y ) c o n t a i n e d no s u l p h u r , the C u F e S 2 combustion product certainly
d i d . DTA work on the l a t e r substance i n d i c a t e d the presence of copper
ferrite CuFe„0..
2 4
Owing to the u n s a t i s f a c t o r y n a t u r e of t h e s e experiments,
c o r r e s p o n d i n g work on b o r n i t e was not advanced beyond the p r e l i m i n a r y s t a g e .

-260-
CONCLUSIONS
Combustion experiments upon CuFeS^ with pure 0^ gave a
mixed product containing some r e s i d u a l sulphur, whose heat content
was not known.
Attempts to s o l u b i l i z e this product f a i l e d and so d i d
efforts to determine i t s heat content experimentally.
Experiments designed to oxidize CuFeS^ with other oxidants
which would give a soluble product were also unsuccessful.
Combustion of simple copper and iron sulphides gives a
heat of combustion which i s dependent upon the s i z e of the sample.
Corrections to Young's calculations
1) The 'descending' column i n Table 4 has the inequality sign backwards;
therefore these are lower limits.
2) The value f o r digenite (from Bartholome) 101.8 kcal. (w.r.t. S ^)
can be replaced by Etienne's value of 90.7 ± 3.0.
3) Upper l i m i t s cannot be obtained i n any way by using the lower
l i m i t s (shown i n table 4).
4) Upper l i m i t s may be obtained by intorducing values for (dg) and (py)
(as well as (po)) into i n e q u a l i t i e s (28), (29),(30) and (32) (not 27,
28, 29,31, as suggested). These may be reduced to:
cn £ po + cp (28)
2bn £ dg + cn (29)
7cp + 2dg <_' 5bn + 2py (30)
4id <_ dg + 4py + l l c v (32)
-261-
Substituting (28) and (29) into (30) gives a value for (cp),
which may then be used i n (28) to obtain (cn), etc.
5) Known values used were:

(dg) = -90.7
(py) = -42.0
(po) = -37.37
(cv) = -22.5
-262-
References
1. R.A. Yund and G. Kullerud, J . P e t r o l . , 7_, 454, (1966).
2. A. Etienne, Ph.D. Thesis, U.B.C., 1970.
3. K.K. K e l l y , U.S. Bureau of Mines B u l l . , 584, 592.
4. P.A. Young, AMDEL B u l l e t i n , A p r i l 1967.
5. Maier, quoted i n K.K. K e l l y , U.S. Bur. Min. B u l l . , 406
6. P. Bartholomew Studia Univ. Lovan. Faculte des Sciences.

(Leopoldville) 4, 1, (1958)
7. A. Golomzik, Izv. Vysshikh. Uchebn. Zavednii, Tsvetn. Met.7_(2) 47(1964)
8. M.E. Merwin and R.H. Lombard, Econ. Geol., (1937) 32,203.
9. D.W. McGlashan, A.D. Rovig, and D.M. Podbnik, Trans. S.M.E.,

244,446,(1969).
10. S. Venkatachalan and R. Mallikarjunan, Trans. Inst. Min. Metal.,

C, 181, (1970).
11. P. Ruetschi and R.F. Amlie, J . Electrochem. S o c , 112, 665 (1965).
12. K. J i b i k i , M.Sc Thesis, U.B.C, 1971.
13. E.Peters, and H. Majima, Can. Met. Quart. , ]_, 111, (1968).
14. G.M. Swinkels and A.L. Mular, AIME Meeting, Denver, 1970.
15. Brodie, M.Sc. Thesis, U.B.C, 1969.
16. G. Thomas and T.R. Ingraham, Can. Met. Quart, 6, 153 (1967).
16. C Thomas and T.R. Ingraham, Can. Met. Quart., 6, 153, (1967).
17. G. Thomas, T.R. Ingraham, and R.J.C. MacDonald, Can. Met. Quart.,
6, 281, (1967).
18. J.E. Dutrizac, R.J.C MacDonald, and T.R. Ingraham, Trans.TMS-AIME,

245 , 995 (1969).
19. J.E. Dutrizac, R.J.C MacDonald, and T.R. Ingraham., Met. Trans.
1 225, (1970).
-263-
APPENDIX B
The data from some of the constant-potential experiments
(Figs. 50, 51) i n Section 111(b) are included here f o r greater c l a r i t y .
The l a t e r experiments i n sulphate solutions are more adequately repre-
sented i n the f i g u r e s .
Dilute Strong
Potential Chloride Solution.... Chloride Solution
535 (SHE) p.2, p.3 p.5, p.16
635 p.l P.17
735 p.12, p.14 p.4
935 p.7, p.8 p.6, p.9
1085 P-15
1185 p.10 p.11, P.13

-264-
SUMMARY OF PI
Potential =450 mV (AgCl) = 635 mV (S.H.E.) Electrode Area = 0.64 cm 2
Temperature = 90°C Solution: 0.3M NaCl

Saw Cut Electrode 0.2M HCl
, ......
1 %
i
l i Current Efficiency
Time Current C.D | Cu Ferp Fe/Cu
>2
(Hr.) (mA) (mA/cm )'i(mmoles) (mmoles) Ratio Cu Fe Total Coulombs
•
1
.25 .38 .59 f

2.00 .39 .61
3.00 .41 .64
5.00 .50 .78
11.00 .79 1.23 .0335 34 19
21.00 .91 1.41 .089 .150 1.69 35.7 60.3 96.0 48.1
35.00 1.12 1.75 . 190 .244 1.28 39.1 50.0 89.1 94.0
43.00 1.2 1.97
57.0 1.44 2.25 .453 .573 1.265 43.1 54.6 97.8 203.1
81.00 1.65 2.58 .748 .84 1.12 43.1 48.4 91.5 335
106.00 1.87 2.92 1.10 1.19 1.08 42.6 46.1 88.7 499.3
136.00 1.87
153.00 2.81 1.994 2.145 1.075 47.5 51 98.5 810. 7
180.00 1.90 2.97 2.17 2.38 1.10 43.3 47.5 90.8 968
i
SUMMARY OF P2
Potential = 350 mV (AgCl) = 535 mV (S.H.E.) Electrode Area = 1.2 cm 2

Current Efficiency
Time Current C.D Cu
2 F e x • Fe/Cu
(Hr.) (mA) (mA/cm ) (mmoles) (mmoles )j Ratio Cu Fe ! Total Coulombs
|
i
.08 .84 .69
i t
i
.50 .50 .42 i
• 1
i
1.50 .35 .29 j I
5.50 .25 .21 . •
•
i
j
20 .175 .15 .0374 | .210 ! 5.62 51.1 288 340 14.1
30 .175 .15 ! i 1 j
53 .165 •14 | .0772 j .352 • 4.55 42.8 195- | 238 34.8
73 .14 .12 j .0942 ! .370 ! 4.70 39.4 154 i 194 46.2
100 .12 .10 | .1142 j .457 i 4.00 38.5 154 i 193 57.3
126 i
•
.075 .063 I
137 .078 .065 j .149 !I .4945 3.32 40.1 133 ! 173.1 71.7
!
\
{ •
-265-
SUMMARY OF P3
Potential = 350 mV (AgCl) = 535 mV (S.H.E.) Electrode Area = 1.25 cm

Current Efficiency
Time Current C.D 2 Cu Fe/Cu %
(Hr.) (mA) T F e
[mA/cm ) (mmoles) (mmoles) Ratio Cu Fe Total Coulombs
.08 2.3 1.8

.50 1.5 1.2
1.50 1.25 1
5.50 1.35 1.08 .04 .10 2.5 30.0 74 10.4 26
7.25 1.52 1.21
10 1.75 1.40
18 2.4 1.91 .193 .251 1.3 33.3 43.3 76.6 112
23 2.7 2.15
31 3.0 2.4 .490 .58 1.182 40.6 48.0 88.6 233
52 3.9 3.1 1.10 1.15 1.045 42.7 44.6 87.3 498
73 5.15 4.1 1.93 1.81 .937 44.9 42.1 87.0 830
126 6.0 4.8 4.82 4.56 .945 48.1 45.5 93.6 1935
137 6.0 4.8 5.07 5.50 .922 45.3 49.1 94.4 2160
SUMMARY OF P4
Potential = 550 mV (AgCl) 735 mV (S.H.E.) Electrode Area = 0.60 cm

Temperature = 90°C Solution: 3M NaCl
Current Efficiency
Time Current CD. Cu Fe,, Fe/Cu
T
(Hr.) (mA) Ratio Cu Fe Total Coulombs
mA/cnO l(mmoles) l(mmoles)
.08 0.9 1.5
.50 0.65 1.1
1 0.63 1.05
3.50 0.71 1.2
5 0.80 1.35
1.05 1.7
12 1.65 2.75
17 2.6 4.3
20 3.2 5.3 .193 .250 1.30 41.4 53.6 95.0 90
30 4.4 . 7.3 .520 .690 1.32 43.6 58.0 101.6 230
44 4.7 7.8 1.042 1.215 1.16 43.5 50.7 94.2 463
53 4.7 7.8
66 4.4 7.3 1.878 1.975 1.05 44.4 46.7 91.1 817
79 4.2 7.0
93 3.9 6.5 2.90 3.02 1.05 45.4 47.2 92.6 1235
114 3.7 16
123 3.6 0 3.80 4.07 1.07 45.1 48.2 93.3 1627
-266-
SUMMARY OF P5

Saw Cut Electrode No Acid
Current E f f i c i e n c y
Time Current CD. Cu Fe j Fe/Cu ?-
(Hr.) PA) JnA/cm ) (mmoles) (mmoles) Ratio Cu Fe Total Coulombs
.08 1 .77
1.00 1 ..77
2 1.15 .89
4 1.50 1.15
6.50 1.9 1.46 .03 .074 2.20
12 1.9 1.46
20 1.72 1.32 .091 .144 1.58 14.1 22.3 36.4 124.7
30 1.55 1.19
41.5 1.17 0.90 .123 .130 1.06 10.3 10.9 21.2 231
54.5 .65 0.50
68 .45 0.35 .173 .191 1.11 11.4 12.6 24.0 293
SUMMARY OF P6

Polishec Electrode 0. 2M HCl
Time Current CD. Cu Fe Fe/Cu
T %
(Hr.) (mA) ;mA/cm ) (mmoles) (mmoles) Ratio Cu Fe Total Coulomb
.08 2.2 3.1

.25 2.1 2.95
2.50 2.0 2.80
4 2.05 2.90
6 2.35 3.3
8 3.0 4.2
10 3.9 5.5
18.50 8.6 12.1 .501 .728 1.45 34.2 49.6 83.8 283
28 10.0 14.1 1.10 1.63 1.48 35.4 52.4 87.8 601
35 10.0 14.1
40 9.5 13.4.
48 8.9 12.5 2.77 3.29 1.18 40.9 48.5 89.4 1309
54 8.75 12.3
78 7.4 10.4
94 7.7 10.8 5.93 6.41 1.08 44.2 47.9 92.1 2586
-267-
SUMMARY OF P7
Potential = 750 mV (AgCl) = 935 mV (S.H.E.) Electrode Area = 1.3 cm*

Polished Electrode 0.2M HCl
Time Current C.D Cu Fe/Cu %
T
2 F e
(Hr.) (mA) (mA/cm ) (mmoles) (mmoles) Ratio Cu Fe Total Coulomb
.17 2.6 2.05

.42 2.4 1.90
1.00 1.9 1.50
2.00 1.5 1.18
4 1.0 .79
10 1.0 .79
17 1.12 .88
19 1.27 1.00 .318 .210 .66 81.9 54 136 75
24 1.47 1.16
30 1.65 1.30
37 2.1 1.60 .379 .405 1.07 41.8 44.7 86.5 175
SUMMARY OF P8

Saw Cut Electrode 0 2M HCl
Time Current CD. Cu Fe Fe/Cu T
(Hr.) (mA) (mA/cm2) (mmoles^ (mmoles) Ratio Cu Fe Total Coulombs
.10 4.2 6.0

.66 3.6 5.1
1.17 2.95 4.2
2 2.2 3.15
6 1.63 2.33
10 1.75 2.50
15 2.03 2.90
22 2.95 4.2 .286 .582 2.04 34.1 69.3 103.4 162
41 4.95 7.1 .843 1.245 1.48 33.5 55.1 88.6 436
65 6.3 9.0 2.05 2.40 1.17 42.0 49.25 91.25 942
72 6.2 8.9
88 4.8 6.9 3.23 3.86 1.195 43.9 52.5 96.4 1420
97 7.3 , 10.5
100 11.5 16.5 3.86 4.52 1.17 44.9 52.6 97.5 1660
-268-
SUMMARY OF P9

„ ++
Current Efficiency
Time Current Cu Fe Fe/Cu %
(Hr.) (mA)
T
Fe
(mmoles) (mmoles) Ratio
(mmoles) Cu Fe Fe Total Coulombs
.08 2.4
.34 1.95
1 1.62
3 1.65
6 2.25
9 3.20
15 5.10
17 5.5 .337 .474 1.40 33.4 46.9 80.3 195
21 6.65
25 7.5
29.5 8.0 .875 1.010 1.15 35.6 41.1 76.7 474
40 8.4
50 8.1 2.13 2.20 1.03 38.3 39.5 77.8 1075
67 8.25 3.45 3.60 1.04 2.70 40.7 42.5 6.6 89.8 1635
80 7.8
93 7.1 5.15 5.08 .99 4.15 42.4 41.8 5.8 89.4 2342
117 7.6 6.25 6.28 1.005 5.88 _ 40.7 40.9 2.! 84.5 2965
SUMMARY OF P10
Potential = 1000 mV (AgCl) = 1185 m V

(S.H.E.) Electrode Area = 1.06 cm^
Saw Cut Electrode 1
0.2M HCl
Current Efficiency
Time Current Cu Fe^ Fe/Cu Fe
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles) Cu Fe Total Coulombs
.17 4.7
.50 3.6
1 3.3
3 2.4
7 2.2
9 2.3 .139 .182 1.31 31.9 41.8 73.7 84
12 2.5
15 2.75
20 3.1
28 3.9 .556 .545 0.98 .542 37.1 36.3 73.4 290
35 4.9
40 5.5
54 7.4 1.665 1.665 1.00 1.665 39.1 39.1 78.2 823
60 7.8
65 8.25
70 8.5
78 9.1 3.05 3.05 1.00 3.05 39.4 39.4 78.8 1535
-269-
SUMMARY OF P l l

Time Current Cu Fe. Fe/Cu Fe 0.
TFT
(Hr.) (mA) (mmoles)(mmoles) Ratio (mmoles)! Cu Fe Coulombs
Fe Total
.08 3.7
1.00 2.9
5 2.35
10 3.2
20 5.0
Beginning to o s c i l l a t e
5.3 .633 | .810 | 1.28 | .421 36.2 46.2 11.1 93.5 338
O s c i l l a t i n g strongly
1.60 1.725 1.075 1.34 42.5 45.8 5.0 93.3 728
SUMMARY OF P12
Potential = 550 mV (AgCl) = 735 mV (S.H.E.) Electrode Area =1.00 cm

Time Current Cu Fe Fe + +
%
T
(Hr.) (mA) (mmoles) (mmoles" (mmoles) Cu Fe Fe Total Coulombs
.107 3.0
.08 1.6
1.00 1.35
3 1.45
10 2.00
22 2.95 .34 .358 .350 40.3 41.5 81.8 163
43.5 4.1 1.01 .93 1.05 44.8 46.6 91.4 435
61 4.95 1.595 1.52 1.82 42.8 48.9 91.7 720
75 5.3
87 5.5 2.75 2.56 2.73 43.7 43.3 87.0 1215
112 5.1 3.89 3.43 3.92 44.5 44.9 89.4 1685
140 4.5 4.36 4.86 4.77 38.9 43.2 .4 82.5 2170
159 4.3 5.03 5.50 5.36 39.3 43.2 .6 83.1 2472
-270-
SUMMARY OF PI3
Potential = 1000 mV (AgCl) = 1185 mV (S.H.E.) Electrode Area = 1.50 cm 2

Time Current Cu Fe T Fe/Cu Fe + +
n
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles; Cu Fe Fe Total Coulombs
.08 4.5
1 2.7
3 1.9
5 2.05
8 2.5
12 3.5
16 4.6 .292 .415 1.43 .42 34.2 49 83.2 163
Oscillating
23 6.2
25 5.8
O s c i l l a t i n g strongly
30 6.2
42 5.7 1.53 1.58 0.83 1.26 41.1 42.4 4.3 88.8 720
67 5.5 2.60 2.440 0.78 2.03 40.6 38.2 3.2 82.0 1235
95 3.5 3.75 3.33 0.95 3.57 42.1 37.4 79.5 1720
117 3.2 4.45 4.66 0.96 4.27 42.4 44.4 1.9 88.7 2027
SUMMARY OF P14
Potential = 550 mV (AgCl) = 735 mV (S.H.E.) Electrode Area =0.78 cm 2
Temperature = 90°C Solution: 0.5M HCl

Saw Cut Electrode
%
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles; Cu Fe c " +
Total
M
Coulombs
Fe
.17 0.90
4 .70
19 1.22 54
24 1.90
25 1.57 .165 .25 1.51 39.4 59.6 99.0 81
43 2.1 .4.6 .556 1.33 .42 40.1 53.6 6.5 100.2 200
50 2.2
70 3.1 .957 1.072 1.12 .84 42.0 47.1 5.0 94.1 440
95 3.75 1.650 1.78 1.08 1.40 42.8 46.1 4.9 93.8 745
113 4.0 2.075 2.37 1.14 1.82 40.5 46.2 5.4 92.1 990
141 4.5 3.09 3.40 1.10 3.325 42.4 46.6 0.5 89.5 1408
165 5.05 3.99 4.25 1.07 3.76 42.7 45.6 2.6 90.9 1792
-271-
SUMMARY OF P15
Potential = 900 mV (AgCl) = 1085 mV (S.H.E.)

Electrode Area =0.80 cn/
Temperature = 90°C
Solution: 3M NaCl
Saw Cut Electrode
0.2M HCl
Current Efficiency
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles] Cu .+++

Fe Fe Total Coulombs
.17 2.7
2 2.15
4 2.05
9 3.0
75
O s c i l l a t i o n s begin
12 3.8
110
O s c i l l a t i n g strcsngly
18 5.0 .393 .5705 1.45 .42 36. 1 52.5 6.9 95.5 210
24 5.2
43 5.5 1.537 1.882 1.225 1.815 41. 0 50.2 .9 92.1 724
70 5.8 2.66 3.30 1.237 3.05 41. 2 51.1 2.6 94.0 1270
95 4.9 3.66 4.55 1.242 4.00 40.6 50.5 3.0 94.1 1775
113 4.9 4.26 5.27 1.235 4.38 39. 8 49.2 4.1 93.1 2130
141 3.7 5.36 6.44 1.202 5.37 41. 3 49.6 4.0 93.9 2580
SUMMARY OF P16
Potential = 350 mV (AgCl) = 535 mV (S.H.E.) Electrode Area = 0.94 cm z

Current Efficiency
Time Current Cu Fe T Fe/Cu Fe
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles Cu | Fe |Fe +++
Total Coulombs
.17 0.78
.50 0.61
12 0.61
24 0.57
37 0.58 .271 .462 1.70 66.6 114 180.6 78.5
64 0.75 .471 .705 1.50 60.1 89.8 149.9 151.4
108 0.65 1.00 1.189 1.12 73.5 87.3 160.8 263.8
134 0.71
180 0.75 1.50 1.88 25 1.625 62.0 77.5 5.4 144.9 468
230 0.65 1.98 2.36 19 2.11 63.5 75.7 4.0 143.2 601
256 0.65 2.20 2.60 1.18 2.19 63.5 75.0 5.8 144.3 670
-272-
SUMMARY OF PI7
Potential = 450 mV (AgCl) 635 mV (S.H.E.) Electrode Area = 0.65 cm^

Time Current Cu Fe T Fe/Cu Fe + + 0,
(Hr.) (mA) (mmoles) (mmoles) Ratio (mmoles] Cu Fe Fe Total Coulombs
.17 1.05
1 .75
12 1.45
23 1.78
37 1.8 .532 .580 1.09 52.8 57.6 110.4 194.5
64 2.0 .964 1.060 1.10 52.7 58.0 110.7 353
108 2.7 2.005 2.02 1.01 57.4 57.8 115.2 675
134 3.0
180 3.0 3.4 3.75 1.10 3.40 51.4 56.6 2.6 110.6 1278
230 2.5 4.25 4.68 1.10 4.15 52.8 55.9 3.3 112.0 1615
256 2.45 4.62 5.19 1.12 4.50 49.9 56.0 3.7 109.6 1787
SUMMARY OF P18

Temperature = 90°C Solution: 0.4M Na SO
Saw Cut Electrode 0.1M H SO
Time Current Cu FeT Fe/Cu Fe + +
.17 1.65
10 1.60
35 1.80 .251 .738 2.94 22.9 68.1 90.9 212
60 2.0
83 2.2 .850 1.27 1.49 .876 29.5 44.1 7.0 80.6 555
108 2.45 1.145 1.555 1.36 1.325 29.7 40.4 2.8 72.9 754
141 2.8
180 3.1 2.60 2.76 1.06 2.08 33.4 35.5 3.5 72.4 1500
-273-
SUMMARY OF P19
Potential = 350 mV (AgCl") = 535 mV (S.H.E.) Electrode Area = 1.62 cm

Temperature = 90°C Solution: 0.4M Na SO.
Saw Cut Electrode O.IM H^SO
Time Current Cu FeT Fe/Cu Fe + +
.17 0.80
1 0.65
6 0.65
7 0.64
10 0.60
15 0.52
20 0.47
25 0.44
30 0.41
35 0.38 .0394 .565 14.3 11.7 170 182 64
60 0.35
83 0.32 .0742 .65 8.75 .495 11.7 102 12.3 126 122.6
108 0.29 .0813 .702 8.64 .48 10.5 93.5 14.7 118.7 144.8
180 0.19 .145 .825 5.69 .638 12.5 71.1 12.4 96.0 218

1974 The Leaching of Chalcopyrite PDF

Uploaded by

Document Information

Original Title

Copyright

Available Formats

Share this document

Share or Embed Document

Sharing Options

Did you find this document useful?

Is this content inappropriate?

Copyright:

Available Formats

1974 The Leaching of Chalcopyrite PDF

Uploaded by

Copyright:

Available Formats

THE LEACHING OF CHALCOPYRITE

B.Sc. University of B r i t i s h Columbia, 1965

M.Sc. University of B r i t i s h Columbia, 1970

A THESIS SUBMITTED IN PARTIAL FULFILMENT

'We accept this thesis as conforming to the

THE UNIVERSITY OF BRITISH COLUMBIA

an advanced degree at the University of British Columbia, I agree that

I further agree that permission for extensive copying of this thesis

for scholarly purposes may be granted by the Head of my Department or

by his representatives. It is understood that copying or publication

of this thesis for financial gain shall not be allowed without my

The University of British Columbia

Date July 29, 1974

The a n o d i c d i s s o l u t i o n o f c h a l c o p y r i t e has been examined i n c h l o r i d e

and s u l p h a t e s o l u t i o n s from 20°C t o 175°C. In c h l o r i d e the y i e l d o f elemen-

t a l s u l p h u r i s n e a r l y 100%, whereas i n s u l p h a t e s o l u t i o n s i t i s 75% o r l e s s ,

a t h i o s u l p h a t e complex, which can decompose e i t h e r t o a s o l u b l e f o r m , o r t o

f i r s t a d i f f u s i o n r e g i o n i n which the c u r r e n t i s h i g h l y time-dependent, but

p o t e n t i a l independent and second a h i g h e r c u r r e n t r e g i o n , a t t r i b u t e d t o the

b u i l d up o f a space-charge i n the m i n e r a l . T h i s space-charge c u r r e n t is

l a r g e l y time independent but i s l i n e a r l y dependent on p o t e n t i a l .

At low temperatures c h l o r i d e s o l u t i o n s and s u l p h a t e s o l u t i o n s g i v e

s i m i l a r p o l a r i z a t i o n curves but at 90°C and above, the space-charge region

i n c h l o r i d e s o l u t i o n s s t a r t s at much lower p o t e n t i a l s (500 mV) whereas i n

s u l p h a t e s o l u t i o n s i t does n o t . Sulphuric acid solutions passivate the

u s i n g f e r r i c s u l p h a t e and f e r r i c c h l o r i d e , and t h e r e i s every r e a s o n t o b e -

f e r r i c sulphate; i t s (ferric chloride) e f f e c t i v e n e s s i s i n c r e a s e d by f i n e

unaffected by these f a c t o r s , but decreased by [ F e ] . + +

f e r r i c c h l o r i d e a r a p i d i n i t i a l d i s s o l u t i o n precedes the l i n e a r stage.

F e r r i c sulphate appears to s e l e c t i v e l y attack the mineral along

grain boundaries, whereas f e r r i c c h l o r i d e does not.

Mixed p o t e n t i a l measurements i n d i c a t e that i n f e r r i c sulphate the

r e a c t i o n i s undei" mixed c o n t r o l , and that both anodic and cathodic reactions

are quite i r r e v e r s i b l e . In cupric chloride the leaching r e a c t i o n i s under

anodic c o n t r o l , and the cathodic r e a c t i o n i s h i g h l y r e v e r s i b l e . F e r r i c

chloride leaching appears to be cupric chloride leaching i n r e a l i t y ; the

f e r r i c ions serve the purpose of depressing the [ C u ] , thus r a i s i n g the

(c) C r y s t a l S t r u c t u r e and Bonding 10

III. The L e a c h i n g o f Copper S u l p h i d e s 14

(a) Pressure Vessel Design 42

(a) The Meaning of C u r r e n t E f f i c i e n c y 53

III. Constant P o t e n t i a l Experiments 102

(a) Without S o l u t i o n A n a l y s i s 102

IV. Leaching Experiments 147

(a) The M o t i v e 147

(b) Results 190

(c) Discussion 205

III Data on Mechanism o f D i s s o l u t i o n o f C h a l c o p y r i t e

VII S u c c e s s i v e A n o d i c Scans a t Slow Scanning Rates;

Fig. 1 Cu-Fe-S system a t 200°C (from Yund and K u l l e r u d ^ ^ ) . 1 0

Fig. 5 A n o d i c d i s s o l u t i o n of c h a l c o p y r i t e . Solution analysis

Fig. 7 Apparatus f o r l e a c h i n g massive specimens.

Fig. 8 Pressure vessel

Fig. 9 Pressure vessel

F i g . 21 Scanning e l e c t r o n m i c r o g r a p h o f CuFeS2 specimen a f t e r

F i g . 22 Scanning e l e c t r o n m i c r o g r a p h s o f CuFeS2 specimen a f t e r

F i g . 23 Scanning e l e c t r o n m i c r o g r a p h s of CuFeS specimen a f t e r

a n o d i z i n g Oh h o u r s , 690 mV, 0.1M HCTO4, 175°C).

F i g . 25 P o t e n t i o s t a t i c scans i n c h l o r i d e s o l u t i o n s a t 300 mV/

F i g . 26 P o t e n t i o s t a t i c scans i n 0.1M H C l , 20°C a t v a r i o u s s c a n -

F i g . 29 S u c c e s s i v e p o t e n t i o s t a t i c scans i n 0.1M H C l a t 20°C,

F i g . 31 P o t e n t i o s t a t i c scans i n s u l p h a t e s o l u t i o n a t 300 mV,

F i g . 32 P o t e n t i o s t a t i c scans i n 0.1M H C l a t 95°C, and v a r i o u s