Copper Electrowinning From Cyanide Solutions by Lu Jianming PDF

COPPER ELECTROWINNING FROM CYANIDE SOLUTIONS
by
Jianming L u
B . E n g . , N o r t h e a s t e r n U n i v e r s i t y , P . R . C h i n a , 1983
M . E n g . , S h a n g h a i U n i v e r s i t y , P . R . C h i n a , 1990
M . A . S c . , U n i v e r s i t y o f B r i t i s h C o l u m b i a , 1996
A THESIS SUBMITTED IN PARTIAL F U L F I L L M E N T OF
THE REQUIREMENTS FOR T H E DEGREE OF
D O C T O R OF PHILOSOPHY
in
THE F A C U L T Y OF G R A D U A T E STUDIES
D e p a r t m e n t o f M e t a l s and M a t e r i a l s E n g i n e e r i n g
W e accept this thesis as c o n f o r m i n g
to the r e q u i r e d standard
THE UNIVERSITY OF BRITISH C O L U M B I A
O c t o b e r 1999
J i a n m i n g L u , 1999
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
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Department of
The University of British Columbia

Vancouver, Canada
DE-6 (2/88)
ABSTRACT
T h e objective o f this research w a s to e x p l o r e a n efficient process to r e c o v e r c y a n i d e
a n d c o p p e r f r o m barren g o l d c y a n i d e s o l u t i o n . T h e research w o r k d e s c r i b e d here c o n c e r n s a n
i n v e s t i g a t i o n into fundamental and p r a c t i c a l aspects o f t w o options for e l e c t r o w i n n i n g c o p p e r
f r o m c y a n i d e s o l u t i o n . These t w o options are: (a) the use o f a n alternative anode r e a c t i o n to
limit the e l e c t r o - o x i d a t i o n o f c y a n i d e i n concentrated c y a n i d e solutions a n d (b) the use o f a
graphite fibre cathode to e l e c t r o w i n copper f r o m dilute c y a n i d e s o l u t i o n .
(1) A c r i t i c a l literature survey w a s c o n d u c t e d to e x a m i n e the s t a b i l i t y constants o f
c o p p e r c y a n i d e species. T h e distributions and the e q u i l i b r i u m r e d o x potentials o f c o p p e r
cyanide species were c a l c u l a t e d u s i n g the most r e l i a b l e stability constants. They are
dependent o n the m o l e ratio o f c y a n i d e to copper, total c y a n i d e c o n c e n t r a t i o n , p H a n d
temperature. P o t e n t i a l measurements have c o n f i r m e d the v a l i d i t y o f the c a l c u l a t e d results.
T h e p H - p o t e n t i a l d i a g r a m w a s d r a w n u s i n g the G i b b s free energy data d e r i v e d b y s e l e c t i n g
the most r e l i a b l e stability constants.
(2) D i r e c t copper e l e c t r o w i n n i n g f r o m dilute c y a n i d e solutions w a s c o n d u c t e d i n a
m e m b r a n e c e l l . T h e a c c u m u l a t i o n o f deposited copper o n the graphite felt as the p l a t i n g
proceeds s i g n i f i c a n t l y i m p r o v e s the c o n d u c t i v i t y o f the graphite felt, increases the s p e c i f i c
surface area a n d benefits copper d e p o s i t i o n . C o p p e r c a n be deposited o n the graphite felt
f r o m l o w c o n c e n t r a t i o n solutions (1-2 g L " C u a n d C N : C u m o l e ratio = 3-4) w i t h 5 0 - 8 0 %

1
current e f f i c i e n c y , the r e m o v a l o f a r o u n d 4 0 % C u a n d an energy c o n s u m p t i o n o f 1 -2 k W h / k g
C u i n the s u p e r f i c i a l current density range 30 - 100 A m " at 40 C .2
(3) C o p p e r e l e c t r o w i n n i n g f r o m concentrated copper c y a n i d e s o l u t i o n (70 g L " C u ) 1
w a s c o n d u c t e d u s i n g four s a c r i f i c i a l species (sulphite, m e t h a n o l , thiocyanate a n d a m m o n i a )
at 4 0 to 60 C . O n l y sulphite c a n decrease the a n o d i c current e f f i c i e n c y o f c y a n i d e o x i d a t i o n
f r o m ~ 100 to 10-20 % o v e r the current density range o f 2 5 0 - 5 0 0 A m " . W i t h i n c r e a s i n g2
C N : C u m o l e ratio f r o m 3 to 4.5, the a n o d i c current e f f i c i e n c y o f c y a n i d e o x i d a t i o n i n c r e a s e d
a n d the c o p p e r d e p o s i t i o n current e f f i c i e n c y decreased. A s regards the r e c o v e r y o f c o p p e r
f r o m barren g o l d c y a n i d e s o l u t i o n , it has been s h o w n that u s i n g sulphite o x i d a t i o n as a n
alternative anode reaction, copper c a n be e l e c t r o w o n f r o m a c y a n i d e electrolyte c o n t a i n i n g

Ill
about 70 gL~' C u ( C N : C u = about 3) a n d 0.5 M N a S 0 2 3 at a cathode current e f f i c i e n c y o f
about 9 5 % w i t h a energy c o n s u m p t i o n o f about 0.8 k W h / k g C u at 2 5 0 A m " . 2
(4) I n a l k a l i n e solutions, sulphite is o x i d i z e d to sulphate o n the graphite anode i n a
t w o - e l e c t r o n reaction. T h e reaction order w i t h respect to sulphite i o n s is b e l o w 1 at l o w
potentials(< 0.4 V v s . S C E ) a n d 1 at h i g h potentials. T h e r e a c t i o n order for h y d r o x i d e i o n s is
c l o s e to z e r o . T w o T a f e l slopes were observed, 0.060 - 0.64 V decade"' at l o w potentials a n d
0.19-0.20 V decade" 1
at h i g h potentials i n the temperature range 4 0 - 60 C . S u l p h i t e
o x i d a t i o n i n a l k a l i n e s o l u t i o n appears to undergo a n e l e c t r o n - r a d i c a l m e c h a n i s m .
(5) T h e a n o d i c o x i d a t i o n o f copper c y a n i d e has been studied u s i n g a graphite r o t a t i n g
disk with reference to cyanide concentration (0.05-4 M), CN:Cu mole ratio (3-12),
temperature (25-60 C ) a n d h y d r o x i d e c o n c e n t r a t i o n (0.01-0.25 M ) . C o p p e r h a d a s i g n i f i c a n t
c a t a l y t i c effect o n c y a n i d e o x i d a t i o n . I n the l o w p o l a r i z a t i o n r e g i o n (< about 0.4 V v s . S C E ) ,
c u p r o u s c y a n i d e is o x i d i z e d to c u p r i c c y a n i d e c o m p l e x e s w h i c h further react to f o r m cyanate.
A t a C N : C u ratio o f 3 a n d [OH"] = 0.25 M , the T a f e l slope w a s about 0.12 V decade"'.
C u ( C N ) " w a s d i s c h a r g e d o n the electrode surface. W i t h i n c r e a s i n g C N : C u m o l e ratio a n d

3
2
decreasing p H , the d o m i n a n t d i s c h a r g e d species shifted to C u ( C N ) " . I n the h i g h p o l a r i z a t i o n

4
3
r e g i o n (about 0.4 -0.6 V v s . S C E ) , cuprous c y a n i d e c o m p l e x e s were o x i d i z e d to c o p p e r o x i d e
and cyanate. W h e n the concentration o f c y a n i d e w a s h i g h and the p H l o w , c y a n o g e n w a s
f o r m e d , but n o copper o x i d e .
(6) S u l p h i t e o x i d a t i o n is enhanced b y the presence o f copper c y a n i d e . T h e effect o f
sulphite o n l i m i t i n g the o x i d a t i o n o f copper c y a n i d e decreases w i t h i n c r e a s i n g m o l e ratio o f
c y a n i d e to copper. T h i s is related to the shift i n the d i s c h a r g e d species f r o m C u ( C N ) " to 3

2
C u ( C N ) " w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. S u l p h i t e is o x i d i z e d to sulphate.

4
3
A t [ C u ] = a r o u n d 1 M , C N : C u = 3 -3.2, [OH"] = 0.05-0.25 M , [ S 0 " ] = 0.4-0.6 M a n d the 3

2
temperature = 50 - 60 C , the anode current e f f i c i e n c y o f sulphite o x i d a t i o n r e a c h e d 80-90%)
as the a n o d i c current e f f i c i e n c y o f c y a n i d e f e l l to 20 to 10 % .
iv
TABLE OF CONTENTS
Abstract. ii
Table o f Contents iv
List o f Tables ix
List o f Figures xi
Acknowledgments XXJS
Nomenclature xxv:
1. I n t r o d u c t i o n 1
2. Literature R e v i e w 8
2.1 A q u e o u s C h e m i s t r y o f the C o p p e r - C y a n i d e S y s t e m 8
2.2 D e p o s i t i o n o f C o p p e r f r o m C o p p e r - C y a n i d e S o l u t i o n 12
2.2.1 P r a c t i c e o f C o p p e r D e p o s i t i o n f r o m C y a n i d e S o l u t i o n 12
2.2.2 E f f e c t o f Parameters o n C o p p e r D e p o s i t i o n 13
2.2.3 K i n e t i c s a n d M e c h a n i s m o f C o p p e r D e p o s i t i o n 15
2.3 E l e c t r o c h e m i c a l O x i d a t i o n o f C y a n i d e 16
2.3.1 Cyanide Oxidation in Alkaline Solution 17
2.3.2 C y a n i d e O x i d a t i o n i n W e a k l y A c i d i c , or A l k a l i n e or N e u t r a l S o l u t i o n s 17
2.3.3 A n o d i c O x i d a t i o n o f C o p p e r C y a n i d e 18
2.4 E l e c t r o c h e m i c a l O x i d a t i o n o f T h i o c y a n a t e 21
2.5 E l e c t r o c h e m i c a l O x i d a t i o n o f Sulphite 23
2.6 E l e c t r o c h e m i c a l O x i d a t i o n o f M e t h a n o l 26
2.7 E l e c t r o c h e m i c a l O x i d a t i o n o f A m m o n i a 27
2.8 S u m m a r y 27
V
3. T h e r m o d y n a m i c s o f C o p p e r C y a n i d e 30
3.1 D i s t r i b u t i o n o f C o p p e r C y a n i d e Species 30
3.2 E q u i l i b r i u m P o t e n t i a l M e a s u r e m e n t o f C o p p e r C y a n i d e 37
3.2.1 Experimental 37
3.2.2 R e s u l t s a n d D i s c u s s i o n s 38
3.3 P o t e n t i a l - p H D i a g r a m s for C o p p e r C y a n i d e S y s t e m 41
3.4 S u m m a r y 45
4. E l e c t r o d e p o s i t i o n o f C o p p e r o n G r a p h i t e F e l t f r o m D i l u t e C y a n i d e S o l u t i o n s 46
4.1 S o m e F u n d a m e n t a l A s p e c t s o f G r a p h i t e F i b r e E l e c t r o d e s 46
4.2 E x p e r i m e n t a l 50
4.2.1 E l e c t r o l y t i c C e l l a n d E x p e r i m e n t a l Set-up 50
4.2.2 M a t e r i a l s 52
4.3 R e s u l t s a n d D i s c u s s i o n s 52
4.4 S u m m a r y 61
5. E l e c t r o w i n n i n g f r o m C o p p e r C y a n i d e S o l u t i o n s U s i n g A l t e r n a t i v e A n o d e 62
Reactions
5.1 E x p e r i m e n t a l A p p a r a t u s and Set-up for E l e c t r o w i n n i n g 62
5.2 S e l e c t i o n o f S a c r i f i c i a l M a t e r i a l s 63
5.2.1 Thiocyanate 64
5.2.2 M e t h a n o l 65
5.2.3 A m m o n i a 65
5.2.3 Sulphite 66
5.3 E f f e c t o f S o m e Parameters o n the A n o d i c and C a t h o d i c Processes i n the 67

Presence o f Sulphite
vi
5.3.1 Effect o f C u r r e n t D e n s i t y 67
5.3.2 Effect o f S u l p h i t e C o n c e n t r a t i o n 68
5.3.3 Effect o f T h i o c y a n a t e and M o l e R a t i o o f C y a n i d e to C o p p e r 68
5.3.4 Effect o f Temperature 73
5.4 S u m m a r y 74
6. A n o d i c O x i d a t i o n o f Sulphite o n the G r a p h i t e A n o d e i n A l k a l i n e S o l u t i o n 75
6.1 Some Fundamental Aspects o f Rotating D i s k Electrodes 75
6.2 T h e r m o d y n a m i c s o f Sulphite O x i d a t i o n 79
6.3 E x p e r i m e n t a l A p p a r a t u s and Set-up 80
6.4 P o l a r i z a t i o n M e a s u r e m e n t s 82
6.5 C o u l o m e t r i c M e a s u r e m e n t s 88
6.6 R e a c t i o n O r d e r 89
6.7 E f f e c t o f p H 95
6.8 C a l c u l a t i o n o f A c t i v a t i o n E n e r g y for the K i n e t i c C u r r e n t 97
6.9 D i f f u s i o n C o e f f i c i e n t E s t i m a t i o n 97
6.10 P o t e n t i a l S w e e p S t u d y 99
6.11 P o s s i b l e R e a c t i o n M e c h a n i s m 101
6.12 S u m m a r y 103
7. A n o d i c O x i d a t i o n o f C o p p e r C y a n i d e o n a G r a p h i t e A n o d e i n A l k a l i n e S o l u t i o n 104
7.2 P o l a r i z a t i o n M e a s u r e m e n t s and Identification o f the Precipitate 105
7.2.1 A n o d i c B e h a v i o u r for D i l u t e C o p p e r C y a n i d e S o l u t i o n 105
7.2.2 A n o d i c B e h a v i o r o f Concentrated C o p p e r C y a n i d e S o l u t i o n 111

vii
7.3 C o u l o m e t r i c M e a s u r e m e n t 120
7.4 E f f e c t o f C N : C u M o l e R a t i o 122
7.5 E f f e c t o f p H 129
7.6 R e a c t i o n O r d e r 140
7.7 R e a c t i o n b e t w e e n C y a n i d e and Copper(II) 144
7.8 C y c l i c V o l t a m m e t r y 147
7.9 P o s s i b l e R e a c t i o n M e c h a n i s m 148
7.10 D i f f u s i o n C o e f f i c i e n t E s t i m a t i o n 154
7.11 A c t i v a t i o n E n e r g y C a l c u l a t i o n for the K i n e t i c Current 156
7.12 S u m m a r y 157
8. A n o d i c O x i d a t i o n o f M i x e d C o p p e r C y a n i d e a n d Sulphite i n A l k a l i n e S o l u t i o n 158
8.2 A n o d i c B e h a v i o u r o f M i x e d Sulphite and C o p p e r C y a n i d e S o l u t i o n 159
8.2.1 A n o d i c Behaviour o f Dilute Copper Cyanide Solution w i t h Sulphite 159
8.2.2 A n o d i c B e h a v i o u r o f Concentrated C o p p e r C y a n i d e S o l u t i o n w i t h 167

Sulphite
8.3 C o u l o m e t r i c M e a s u r e m e n t s 178
8.4 P o s s i b l e A n o d i c R e a c t i o n s 183
8.5 Summary 184
9. C o n c l u s i o n s 186
10. R e c o m m e n d a t i o n s 190
11. References 191
A p p e n d i x 1 Initial E c o n o m i c Assessment 211
Appendix 2 Total Cyanide Analysis 219

viii
A p p e n d i x 3 Copper Titration U s i n g E D T A 227
A p p e n d i x 4 D e t e r m i n a t i o n o f Sulphite Ions b y the I o d i m e t r i c M e t h o d 229
A p p e n d i x 5 Calculation o f A c t i v i t y Coefficient U s i n g Pitzer's M e t h o d 232
A p p e n d i x 6 M e a s u r e m e n t o f the K i n e m a t i c V i s c o s i t y 235
A p p e n d i x 7 C a l c u l a t i o n o f L i q u i d J u n c t i o n Potential 237
A p p e n d i x 8 Figures 239
ix
LIST of TABLES
T a b l e 2-1 A s s o c i a t i o n constants for copper c y a n i d e c o m p l e x e s 8
T a b l e 2-2 C o p p e r c y a n i d e bath c o m p o s i t i o n s a n d c o n d i t i o n s 13
T a b l e 3-1 E q u i l i b r i u m constants for copper c y a n i d e system 30
T a b l e 3-2 G i b b s free energy data for copper and c y a n i d e species 41
T a b l e 4-1 C o n d u c t i v i t i e s o f copper c y a n i d e solutions w i t h different c y a n i d e 53

concentrations at f i x e d copper c o n c e n t r a t i o n
T a b l e 4-2 C o p p e r c a t h o d i c current e f f i c i e n c y and p o w e r c o n s u m p t i o n at 40 C and 54

i n i t i a l [ C u ] = 1 g L " for experiments w i t h o x y g e n e v o l u t i o n at a n anode
1
T a b l e 4-3 C o p p e r c a t h o d i c current e f f i c i e n c y and p o w e r c o n s u m p t i o n at 40 C and 54

i n i t i a l [Cu] = 2 g L " for experiments w i t h o x y g e n e v o l u t i o n at a n anode
1
T a b l e 4-4 D i s t r i b u t i o n and potentials o f copper c y a n i d e s o l u t i o n at [OH"] = 0.01 M 55

at 40 C
T a b l e 4-5 R e s u l t s o f c y c l e r u n at 40 C (an i n i t i a l C N : C u ratio o f 3) 60
T a b l e 5-1 R e s u l t s for the selection o f s a c r i f i c i a l species at 60 C 64
T a b l e 5-2 E f f e c t o f current density o n the a n o d i c current e f f i c i e n c y o f c y a n i d e and 68

the c a t h o d i c current e f f i c i e n c y o f copper at 60 C . E l e c t r o l y t e : 70 g L " 1
C u , C N : C u m o l e ratio = 3, 10 g L " N a O H and 113 g L "

1 1
Na S02 3
T a b l e 5-3 E f f e c t o f sulphite concentration o n the a n o d i c current e f f i c i e n c y o f 68

c y a n i d e and the c a t h o d i c current e f f i c i e n c y o f copper at 60 C a n d 2 5 0 A
m" . E l e c t r o l y t e : 70 g L
2 1
C u , C N : C u m o l e ratio = 3, 10 g L " 1
NaOH
T a b l e 5-4 R e s u l t s o f copper e l e c t r o w i n n i n g at 250 A m " and 60 C . E l e c t r o l y t e : 70

2
69
g L " C u , C N : C u m o l e ratio = 3-4.5, 63 g L
1 1
Na S0
2 3 a n d 10 g L " 1
NaOH
i n the presence and absence o f S C N "
T a b l e 5-5 R e s u l t s o f copper e l e c t r o w i n n i n g at 2 5 0 A m " a n d different

2
74
temperatures. E l e c t r o l y t e s : 70 g L " C u , C N : C u m o l e ratio = 3, 63 g L "
1 1
Na S0 2 3 and 10 g L " N a O H i n the presence and absence o f S C N "

1
T a b l e 6-1 T h e activities and a c t i v i t y coefficients for 0.1 M N a S 0 , 0.25 M N a O H ,

2 3 80
1 M Na S0 2 4 at 2 5 , 4 0 , 50 and 60 C
X
T a b l e 6-2 N u m b e r o f the electrons transferred for the a n o d i c o x i d a t i o n o f sulphite 88
T a b l e 6-3 R e a c t i o n order and the k i n e t i c current c a l c u l a t e d u s i n g different 90

m e t h o d s for 0.1 M N a , S 0 3
T a b l e 6-4 R e a c t i o n order and the k i n e t i c current c a l c u l a t e d u s i n g different 90

m e t h o d s for 0.4 M N a S 0 2 3
T a b l e 6-5 T a f e l slopes ( V decade" ) for the different potential ranges at 2 5 , 4 0 , 50

1
94
a n d 60 C
T a b l e 7-1 A m o u n t o f c y a n i d e and copper (I) o x i d i z e d per F a r a d a y at 100 r p m a n d 121

different C N : C u m o l e ratios and h y d r o x i d e concentrations
T a b l e 7-2 A m o u n t o f c y a n i d e and copper (I) o x i d i z e d per F a r a d a y at 4 0 0 A m " , 2

122
100 r p m , different C N : C u m o l e ratios and h y d r o x i d e concentrations
T a b l e 8-1 C u r r e n t efficiencies f r o m copper c y a n i d e u s i n g c o n t r o l l e d p o t e n t i a l 179

c o u l o m e t r i c measurements
T a b l e 8-2 C u r r e n t efficiencies f r o m copper c y a n i d e u s i n g c o n t r o l l e d current 180

c o u l o m e t r i c measurements
T a b l e 8-3 C u r r e n t efficiencies f r o m copper c y a n i d e u s i n g c o n t r o l l e d current 181

c o u l o m e t r i c measurements at 100 r p m
T a b l e 8-4 C u r r e n t e f f i c i e n c y for copper c y a n i d e a n d sulphite u s i n g c o n t r o l l e d 182

current c o u l o m e t r i c measurements at 100 r p m
T a b l e 8-5 C u r r e n t e f f i c i e n c y for copper c y a n i d e a n d sulphite u s i n g c o n t r o l l e d 183

potential c o u l o m e t r i c measurements at 100 r p m
xi
LIST OF FIGURES
F i g u r e 1-1 F l o w s h e e t for solvent extraction - e l e c t r o w i n n i n g process for the 6

r e c o v e r y o f copper c y a n i d e
F i g u r e 1-2 F l o w s h e e t for direct e l e c t r o w i n n i n g o f copper f r o m c y a n i d e solutions 7
F i g u r e 3-1 C o p p e r c y a n i d e species d i s t r i b u t i o n a n d E ( C u ( I ) / C u ) v s . m o l e ratio o f 32

c y a n i d e to copper for v a r i o u s solutions at 25 C a n d p H 9
F i g u r e 3-2 C o p p e r c y a n i d e species d i s t r i b u t i o n a n d E ( C u ( I ) / C u ) v s . m o l e ratio o f 33

c y a n i d e to copper for v a r i o u s solutions at 25 C and p H 12
F i g u r e 3-3 C o p p e r c y a n i d e species d i s t r i b u t i o n and E ( C u ( I ) / C u ) v s . m o l e ratio o f 34

c y a n i d e to copper for v a r i o u s solutions at 60 C and p H 12
F i g u r e 3-4 (a) E ( C u ( I ) / C u ) v s . m o l e ratio o f c y a n i d e to copper at 25 C , p H 12 35

a n d different C u concentrations a n d (b) E ( C u ( I ) / C u ) v s . p H at 25 C ,
0.1 M C u and different m o l e ratios o f c y a n i d e to copper
F i g u r e 3-5 C o p p e r concentrations i n the f o r m o f copper c o m p l e x e s a n d the 36

e q u i l i b r i u m potential vs. total copper c o n c e n t r a t i o n at [ C N " ] = 2.455 g
L " and [OH"] = 0.01 M
]
F i g u r e 3-6 C o p p e r concentrations i n the f o r m o f copper c o m p l e x e s and the 36

e q u i l i b r i u m potential v s . total copper c o n c e n t r a t i o n at [ C N ] = 1.227 g
L " a n d [ O H ] = 0.01 M
1
F i g u r e 3-7 E x p e r i m e n t a l set-up for the e q u i l i b r i u m potential measurement 38
F i g u r e 3-8 E l e c t r o d e potential vs. t i m e at 25 C , C N : C u = 3 a n d [ C u ] total = 0.1 M 39
F i g u r e 3-9 E l e c t r o d e potential vs. the m o l e ratio o f c y a n i d e to c o p p e r at 2 5 , 4 0 , 40

50 and 60 C , [ C u ] total = 0.1 M and [OH"] = 0.01 M
F i g u r e 3-10 E l e c t r o d e potential v s . the m o l e ratio o f c y a n i d e to c o p p e r at 2 5 , 4 0 , 40

50 a n d 60 C , [ C u ] total = 0.01 M and [OH"] = 0.01 M
F i g u r e 3-11 C N - H 0 p o t e n t i a l - p H d i a g r a m at a l l solute species a c t i v i t i e s o f 1 a n d

2 42
P ( C N ) 2 = 1 a t m a n d 25 C . (a) a s s u m i n g H C N O and C N O are stable and
(b) a s s u m i n g ( C N ) is stable
2
F i g u r e 3-12 P o t e n t i a l - p H diagrams for C u - C N - H 0 s y s t e m at 25 C and the

2 43
a c t i v i t i e s o f a l l solute species = 1, 10" , 10" a n d 10" c o n s i d e r i n g C u O
2 4 6
as a stable species. H C N O , C N O " and ( C N ) are not c o n s i d e r e d

2
F i g u r e 3-13 P o t e n t i a l - p H diagrams for C u - C N - H 0 s y s t e m at 25 C and the
2 44
a c t i v i t i e s o f a l l solute species = 1, 10" , 10" and 10" c o n s i d e r i n g
2 4 6
C u ( O H ) as a stable species. H C N O , C N O " a n d ( C N ) are not

2 2
considered
F i g u r e 3-14 P o t e n t i a l - p H d i a g r a m for C u - C N - H 0 system at 25 C and solute

2 45
copper species activities o f 0.01 a n d c y a n i d e species" a c t i v i t i e s o f 0.1
c o n s i d e r i n g C u ( O H ) as a stable species. H C N O , C N O " a n d ( C N ) are
2 2
not c o n s i d e r e d
F i g u r e 4-1 S c h e m a t i c d i a g r a m o f porous electrode 47
F i g u r e 4-2 Schematic diagram o f electrolytic cell 51
F i g u r e 4-3 S c h e m a t i c d i a g r a m o f e x p e r i m e n t a l set-up 51
F i g u r e 4-4 C u r r e n t e f f i c i e n c y a n d the p o w e r c o n s u m p t i o n o f c o p p e r d e p o s i t i o n 56
v s . the m o l e ratio o f c y a n i d e to copper at different c a t h o d i c current
densities a n d 40 C . T h e electrolyte: (a) 1 g L " ' C u , 0.01 M N a O H a n d
0.00862 M N a S C N , a n d (b): 2 g L " C u , 0.01 M N a O H a n d 0.01724 M
1
N a S C N . T h e f l o w v e l o c i t y : 2.97, 5.93 a n d 9.83 c m m i n . " r e s p e c t i v e l y

1
for 3 0 , 60 and 100 A m " . 2
F i g u r e 4-5 C o n v e r s i o n o f C u ( I ) to C u vs. the m o l e ratio o f c y a n i d e to c o p p e r at 56

different cathodic current densities and 40 C . T h e electrolyte: (a) 1 g
L" 1
C u , 0.01 M N a O H and 0.00862 M N a S C N , a n d (b): 2 g L " C u , 1
0.01 M N a O H a n d 0.01724 M N a S C N . T h e f l o w v e l o c i t y : 2.97, 5.93

and 9.83 c m m i n . ' r e s p e c t i v e l y for 30, 60 and 100 A m" .
1 2
F i g u r e 4-6 C e l l voltage v s . t i m e at the c a t h o d i c current density = 30 A m " a n d 4 0 2

57
C . T h e electrolyte: l g L " C u , C N : C u = 3, 0.01 M N a O H a n d 0.00862
1
M N a S C N and the f l o w v e l o c i t y : 2.97 c m m i n . " . 1
F i g u r e 4-7 C e l l v o l t a g e v s . the m o l e ratio o f c y a n i d e to c o p p e r at different 58

c a t h o d i c current densities a n d 40 C . T h e electrolyte: 2 g L " C u , 0.01 1
M N a O H a n d 0.00862 M N a S C N , the f l o w v e l o c i t y : 2.97, 5.93 a n d

9.83 c m min." r e s p e c t i v e l y for 30, 60 and 100 A m" .
1 2
F i g u r e 4-8 G r a p h i t e fibre felt o n w h i c h copper has been deposited. 59
F i g u r e 4-9 C r o s s - s e c t i o n o f the graphite fibre felt o n w h i c h c o p p e r has b e e n 59

deposited.
F i g u r e 4-10 C o n c e n t r a t i o n o f copper v s . the n u m b e r o f the s o l u t i o n passes t h r o u g h 61

the graphite felt at [ C u ] inital = 1 and 2 g L " a n d 40 C . T h e e l e c t r o l y t e :
1
xiii
(1) l g L " C u , C N : C u = 3, 0.01 M N a O H and 0.00862 M N a S C N a n d

1
(2) 2 g L " C u , C N : C u =3, 0.01 M N a O H and 0.01724 M N a S C N , and

1
the f l o w v e l o c i t y : 2.97 c m min."'.
F i g u r e 5-1 S c h e m a t i c d i a g r a m o f the e x p e r i m e n t a l set-up 63
F i g u r e 5-2 C o n c e n t r a t i o n o f c y a n i d e v s . the e l e c t r o l y s i s t i m e for o b t a i n i n g the 63

current e f f i c i e n c y o f c y a n i d e o x i d a t i o n at 60 C . E l e c t r o l y t e : 70 g L " '
C u , C N : C u = 3, 113 g L " ' N a S 0 , 10 g L " ' N a O H
2 3
F i g u r e 5-3 C e l l voltage v s . the t i m e o f e l e c t r o l y s i s i n the presence o f a m m o n i a 67

a n d sulphite as a s a c r i f i c i a l species at 500 A m" a n d 60 C . 2
E l e c t r o l y t e : 70 g L " ' C u , C N : C u = 3, a n d 10 g L " '
F i g u r e 5-4 C a t h o d i c current e f f i c i e n c y o f copper d e p o s i t i o n a n d p o w e r 71

c o n s u m p t i o n v s . the m o l e ratio o f c y a n i d e to c o p p e r at 60 C and 2 5 0
A m" . E l e c t r o l y t e : 7 0 g L " ' C u , 63 g L " N a S 0 , 10 g L " ' N a O H , a n d
2 1
2 3
different c y a n i d e concentrations i n the presence and absence o f 4 0 g L "

1
SCN" 1
F i g u r e 5-5 A n o d i c current e f f i c i e n c y for c y a n i d e o x i d a t i o n v s . the m o l e ratio o f 71

c y a n i d e to copper at 2 5 0 A m " and 60 C . E l e c t r o l y t e : 7 0 g L " ' C u , 63
2
g L " N a S 0 , 10 g L " N a O H , and different c y a n i d e concentrations i n

1
2 3
1
the presence a n d absence o f 40 g L " S C N " 1 1
F i g u r e 5-6 C e l l voltage v s . t i m e o f e l e c t r o l y s i s at 2 5 0 A m " and 60 C . 2

73
E l e c t r o l y t e : 7 0 g L " C u , 63 g L - l N a S 0 , 10 g L " N a O H , a n d
1
2 3
1
different c y a n i d e concentrations i n the absence o f S C N " 1
F i g u r e 6-1 R o t a t i n g d i s k coordinate system used i n c a l c u l a t i o n s o f l i q u i d f l o w 76

near the rotating d i s k
F i g u r e 6-2 S c h e m a t i c d i a g r a m o f rotating d i s k 81
F i g u r e 6-3 S c h e m a t i c d i a g r a m o f the e x p e r i m e n t a l set-up 82
F i g u r e 6-4 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 84

50 a n d 60 C . E l e c t r o l y t e : 0.1 M N a S 0 , 0.25 M N a O H and 1 M
2 3
Na S0
2 4
F i g u r e 6-5 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 87

2 3
Na S0
2 4
F i g u r e 6-6 C o m p a r i s o n o f the p o l a r i z a t i o n curves w i t h different sulphite a n d 88

h y d r o x i d e concentrations at 25 C a n d 4 0 0 r p m
xiv
F i g u r e 6-7 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 25 C . 90

E l e c t r o l y t e : 0.1 M N a S 0 , 0.25 M N a O H and 1 M N a S 0
2 3 2 4
F i g u r e 6-8 L o g i v s . L o g ( l - i / i , ) at constant potentials a n d 25 C . E l e c t r o l y t e : 0.1 91

M N a S 0 , 1 M N a S 0 and 0.25 M N a O H
2 3 2 4
F i g u r e 6-9 1/i v s . 1/i, at constant potentials ( V vs. S C E ) 25 C . E l e c t r o l y t e : 0.1 M 91

N a S 0 , I M N a S 0 and 0.25 M N a O H
2 3 2 4
F i g u r e 6-10 L o g i v s . L o g ( l - i / i , ) at constant potentials and 25 C . E l e c t r o l y t e : 0.4 92

2 3 2 4
F i g u r e 6-11 1/i v s . 1/i, at constant potentials ( V v s . S C E ) and 25 C . E l e c t r o l y t e : 92

0.4 M N a S 0 , I M N a S 0 a n d 0.25 M N a O H
2 3 2 4
F i g u r e 6-12 L o g i v s . l o g [SO, "] at 25 C and 4 9 0 0 r p m . E l e c t r o l y t e : I M N a S 0

2
2 4 93
a n d 0.25 M N a O H
F i g u r e 6-13 P o t e n t i a l v s . l o g ( ( i / ( l - i / i , ) ) at different temperatures. E l e c t r o l y t e : 0.1 95

2 3 2 4
F i g u r e 6-14 P o l a r i z a t i o n curves at different h y d r o x i d e concentrations and 25 C . 96

E l e c t r o l y t e : 0.1 M N a S 0 a n d 1 M N a S 0
2 3 2 4
F i g u r e 6-15 E f f e c t o f p H o n sulphite o x i d a t i o n at different potentials and 25 C . 96

E l e c t r o l y t e : 0.1 M N a S 0 , 1 M N a S 0 at variable p H
2 3 2 4
F i g u r e 6-16 L o g i v s . l / T at different potentials ( V v s . S C E ) . E l e c t r o l y t e : 0.1 M

k 97
N a S 0 , 1 M N a S 0 and 0.25 M N a O H
2 3 2 4
F i g u r e 6-17 D i f f u s i o n current density v s . the square root o f rotational speed at 98

different temperatures. E l e c t r o l y t e : 0.05 M N a S 0 , l M N a S 0 , 0.25
2 3 2 4
M NaOH
F i g u r e 6-18 L o g p l o t o f d i f f u s i o n coefficient v s . 1/T 99
F i g u r e 6-19 V o l t a m m o g r a m s at different scan rates at 25 C . E l e c t r o l y t e : 0.1 M 100

N a S 0 , 1 M N a S 0 , 0.25 M N a O H
2 3 2 4
F i g u r e 6-20 P e a k current v s . potential scan rate at 25 C . E l e c t r o l y t e : 0.1 M 101

N a S 0 , 1 M N a S 0 a n d 0.25 M N a O H
2 3 2 4
F i g u r e 7-1 S c h e m a t i c d i a g r a m for detection o f c u p r i c c y a n i d e species 105
F i g u r e 7-2 P o l a r i z a t i o n curves at different rotational speeds and temperatures. 109

XV
E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1

M Na S02 4
F i g u r e 7-3 C y c l i c v o l t a m m e t r y at 25 and 40 C . E l e c t r o l y t e : 0.05 M C N " , C N : C u 110

m o l e ratio = 3, 0.25 M N a S 0 2 4 and 1 M N a S 0 2 4

E l e c t r o l y t e : 3 M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H and 1 M
Na S0
2 4

E l e c t r o l y t e : 3.5 M C N " , C N : C u m o l e ratio = 3.5, 0.25 M N a O H a n d
0.5 M N a S 0 2 4

E l e c t r o l y t e : 4 M C N " , C N : C u m o l e ratio = 4, 0.25 M N a O H a n d 0.5 M
Na S0
2 4

E l e c t r o l y t e : 3 M C N " , C N : C u m o l e ratio = 3, 0.05 M N a O H a n d 0.5 M
Na S0
2 4
F i g u r e 7-8 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. 118

E l e c t r o l y t e : 4 M C N " , C N : C u m o l e ratio = 1, 0.05 M N a O H and 0.5 M
Na S0
2 4

E l e c t r o l y t e : 4 M C N " , C N : C u m o l e ratio = 1, 0.50 M N a O H and 0.5 M
Na S0
2 4
F i g u r e 7-10 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n - 125

current v s . potential o n a graphite rotating d i s k at 4 9 0 0 r p m a n d
different temperatures. E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio =
3, 4, 6, 12 a n d no copper, 0.25 M N a O H and 1 M N a S 0 2 4

p o t e n t i a l v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0
r p m (25 a n d 6 0 C ) . E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio = 3,
4, 6, 12 a n d no copper, 0.25 M N a O H and 1 M N a S 0 2 4

p o t e n t i a l v s . l o g current density o n a p y r o l y t i c graphite rotating
electrode at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : 0.05 M C N " , C N : C u
m o l e ratio = 3, 4, 6, 12 and 0.25 M N a O H and 1 M N a S 0 2 4

xvi
potential vs. l o g (current density) o n a graphite rotating d i s k at 4 9 0 0

r p m (25 a n d 60 C ) . E l e c t r o l y t e s : [ C u ] = 0 . 0 0 8 3 3 , [CN"] = 0.025,
+
0.05, 0.1, 0.2 and 0.4 M , 0.25 M N a O H and 1 M N a S 0 2 4

p o t e n t i a l v s . l o g (current density) o n a p y r o l y t i c graphite rotating d i s k
at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : [ C u ] = 0.00833 M , [ C N " ] =
+
0.025, 0.05, 0.1, 0.2 and 0.4 M , 0.25 M N a O H and 1 M N a S 0 2 4

current v s . potential o n a graphite rotating d i s k at 4 9 0 0 r p m a n d 60 C .
E l e c t r o l y t e s : 1 M C u , [CN"] = 3, 3.5 and 4, 0.25 M N a O H a n d 0.5 M
+
Na S0
2 4

potential v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0
r p m and 60 C . E l e c t r o l y t e s : 1 M C u , [CN"] = 3, 3.5 a n d 4, 0.25 M
+
N a O H and 0.5 M N a S 0 2 4
F i g u r e 7-17 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - current v s . p o t e n t i a l o n a graphite 131

rotating d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 3, [OH"] = 0.25, 0.05 a n d 0 . 0 1 M a n d
1 M Na S0 2 4
F i g u r e 7-18 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current density) 132

o n a graphite rotating d i s k at 4 9 0 0 r p m (25 and 6 0 C ) . E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 3, [OH"] = 0.25, 0.125, 0.05, 0.025
a n d 0 . 0 I M and 1 M N a S 0 2 4
F i g u r e 7-19 E f f e c t o f o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current 132

density) o n a p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C .
E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio = 3, [OH"] = 0.25, 0.125,
0.05, 0.025 and 0 . 0 1 M and 1 M N a S 0 2 4

rotating d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 4, [OH"] = 0.25, 0.05, a n d 0 . 0 I M and
1 M Na S0 2 4

o n a graphite rotating d i s k 4 9 0 0 r p m (25 and 60 C ) . E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 4, [OH"] = 0.25, 0.05, a n d 0 . 0 1 M and
1 M Na S0 2 4

o n a p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m and 25 C .
XVII
E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio = 4, [OH"] = 0.25, 0.05,

a n d 0 . 0 I M and 1 M N a S 0 2 4

rotating d i s k at 4 9 0 0 r p m and different temperatures. E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 12, [OH"] = 0.25, 0.05, a n d 0 . 0 1 M
and 1 M N a S 0 2 4

o n a graphite rotating d i s k at 4 9 0 0 r p m (25 and 6 0 C ) . E l e c t r o l y t e s :
0.05 M C N " , C N : C u m o l e ratio = 12, [OH"] = 0.25, 0.05 a n d 0 . 0 1 M
and 1 M N a ^ O ,

o n a p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C .
E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio = 12, [OH"] = 0.25,
0.125, 0.05, 0.025 a n d O . O l M a n d 1 M N a S 0 2 4
F i g u r e 7-26 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - the p l o t o f the current v s . the 137

p o t e n t i a l o n a graphite rotating d i s k at 4 9 0 0 r p m a n d different
temperatures. E l e c t r o l y t e s : 3 M C N " , C N : C u m o l e ratio = 3, [OH"] =
0.5, 0.25 and 0.05 M and 0.5 M N a S 0 2 4

o n a graphite rotating d i s k at 4 9 0 0 r p m and 60 C . E l e c t r o l y t e s : 3 M
C N , C N : C u m o l e ratio = 3, [ O H ] = 0.5, 0.25, a n d 0.05 M a n d 0.6 M
Na S0
2 4

rotating d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : 4
M C N " , C N : C u m o l e ratio = 4, [OH"] = 0.5 a n d 0.25 and 0.05 M a n d
0.5 M N a S 0 2 4

o n a graphite rotating d i s k at 60 C . E l e c t r o l y t e s : 4 M C N , C N : C u
m o l e ratio = 4, [OH"] = 0.50, 0.25 a n d 0.05 M a n d 0.5 M N a S 0 2 4
F i g u r e 7-30 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a graphite

3
2
141
rotating d i s k at 4 9 0 0 r p m (25 and 6 0 C ) . E l e c t r o l y t e s : [CN"] = 0.025,
0.05, 0.1 a n d 0.20 M , C N : C u m o l e ratio = 3, [OH"] = 0.25 M and 1 M
Na S0
2 4
F i g u r e 7-31 P l o t s o f l o g (current density) vs. l o g ( [ C u ( C N ) " ] ) o n a graphite

4
2
141
rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : [CN"] = 0.05, 0 . 1 ,
0.20 a n d 0.40 M , [ C u ] = 0.00833 M , [OH"] = 0.25 M a n d 1 M N a S 0
+
2 4
XVlll
F i g u r e 7-32 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a p y r o l y t i c

3
2
142
graphite rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : [CN"] =
0.05, 0.10, 0.20 a n d 0.40 M , [ C u ] = 0.0833 M , [OH"] = 0.25 M a n d 1
+
M Na S02 4
F i g u r e 7-33 P l o t s o f l o g (current density) vs. l o g ( [ C u ( C N ) " ] ) o n a graphite

3
2
143
rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : [CN"] = 0.40 M ,
[ C u ] = 0.0167, 0.00833, 0.00417, 0.00208, 0.00104 M , [OH"] = 0.25
+
M and 1 M N a S 0 2 4
F i g u r e 7-34 A b s o r b a n c e vs. t i m e w h e n 2.5 c m o f 0.05 M c y a n i d e s o l u t i o n w i t h

3
144
0.25 M O H " w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r sulphate
3
s o l u t i o n at 25 C
F i g u r e 7-35 A b s o r b a n c e v s . time w h e n 2.5 c m o f 0.05 M c y a n i d e s o l u t i o n w i t h

3
145
0.05 M O H " w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r sulphate
3
s o l u t i o n at 25 C
F i g u r e 7-36 A b s o r b a n c e v s . time w h e n 2.5 c m o f 1 M c y a n i d e s o l u t i o n w i t h 0.25

3
145
M O H " w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r sulphate s o l u t i o n at
3
25 C
F i g u r e 7-37 T h e plot o f (Absorbance)"' vs. time w h e n 2.5 c m o f 1 M c y a n i d e 3

146
s o l u t i o n w i t h 0.25 M O H " w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r
3
sulphate s o l u t i o n at 25 C
F i g u r e 7-38 C y c l i c v o l t a m m e t r y at 25 C . E l e c t r o l y t e : 0.025 M C N " , C N : C u m o l e 148

ratio =3, 0.25 M N a O H and 1 M N a S 0 2 4
F i g u r e 7-39 P l o t s o f potential vs. l o g (current density) u s i n g data m e a s u r e d and 154

predicted u s i n g E q u a t i o n 7-12 at 25 C . E l e c t r o l y t e : 0.1 M C N " ,
C N : C u m o l e ratio = 12, 0.25 M N a O H and 1 M N a S 0 2 4
F i g u r e 7-40 L i m i t i n g current v s . rotational speed at 4 0 , 50 a n d 60 C . E l e c t r o l y t e : 155

0.05 M C N " , C N : C u m o l e ratio= 3, 0.25 M N a O H a n d 1 M N a S 0 2 4
F i g u r e 7-41 A c t i v a t i o n energy c a l c u l a t i o n - p l o t o f l o g (current density) v s . 1 / T a t 156

constant potentials. E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3,
0.25 M N a O H and 1 M N a S 0 2 4
F i g u r e 8-1 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 0.05 M C N " , 162

0.0167 M C u ( C N : C u m o l e ratio = 3), 0.25 M N a O H , 0.4 M N a S 0
+
2 3
and 1 M N a S 0 2 4
F i g u r e 8-2 E f f e c t o f potential scanning rate o n the anodic b e h a v i o u r o f m i x e d 163

sulphite and copper c y a n i d e at 4 9 0 0 r p m and 60 C . E l e c t r o l y t e : 0.05
XIX
M C N " , 0.0167 M C u ( C N : C u m o l e ratio = 3), 0.25 M N a O H , 0.4 M

+
Na S0
2 3 and 1 M N a S 0 2 4
F i g u r e 8-3 P o l a r i z a t i o n curves for for (1) 0.05 M C N " , 0.0167 M C u a n d 0.4 M +

163
N a S 0 , (2) the same c o m p o s i t i o n as (1), o n the electrode coated w i t h
2 3
c o p p e r o x i d e at 0.5 V v s . S C E for 10 m i n u t e s i n the same s o l u t i o n . (3)

0.4 M N a S 0 , (4) 0.4 M N a S 0 o n the electrode coated w i t h c o p p e r
2 3 2 3
o x i d e i n the same s o l u t i o n as (1), and (5) 0.4 M N a S 0 o n the 2 3
electrode coated w i t h c o p p e r o x i d e f r o m 0.05 M C N " a n d 0.0167 M

C u . S u p p o r t i n g electrolyte: 0.25 M N a O H a n d 1 M N a S 0
+
2 4
F i g u r e 8-4 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0167 M C u ( C N : C u m o l e +

164
ratio = 3) a n d 0.4 M N a S 0 , (2) 0.4 M N a S 0 and (3) 0.05 M C N "
2 3 2 3
a n d 0.0167 M C u at 4 0 0 r p m a n d 60 C . S u p p o r t i n g electrolyte: 0.25

+
M N a O H and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 2 4
F i g u r e 8-6 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0167 M C u ( C N : C u m o l e +

166
ratio = 3) a n d 0.4 M N a S 0 , (2) 0.4 M N a 2 S 0 a n d (3) 0.05 M C N "
2 3 3
a n d 0.0167 M C u at 4 0 0 r p m a n d 60 C . S u p p o r t i n g electrolyte: 0.05

+
M N a O H and 1 M N a S 0 2 4
F i g u r e 8-7 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0125 M C u a n d 0.4 M +

166
N a S 0 , (2) 0.4 M N a S 0 , (3) 0.05 M C N " , 0.0125 M C u a n d 0.2 M
2 3 2 3
+
N a S 0 , (4) 0.2 M N a S 0 and (5) 0.05 M C N " a n d 0.0125 M C u

2 3 2 3
+
at
4 0 0 r p m and 60 C . S u p p o r t i n g electrolyte: 0.05 M N a O H a n d 1 M
Na S0 .
2 4
F i g u r e 8-8 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 3 M C N " , 1 170

M C u , 0.25 M N a O H , 0.5 M N a S 0
+
2 3
F i g u r e 8-9 C u r r e n t density vs. t i m e at constant potentials, 4 0 0 r p m a n d different 171

temperatures. E l e c t r o l y t e : 3 M C N " , 1 M C u , 0.25 M N a O H , 0.5 M +
Na S0
2 3

M C u \ 0.1 M N a O H , 0.5 M N a S O 2

M C u , 0.05 M N a O H , 0.5 M N a S 0
+
2 3
F i g u r e 8-12 P o l a r i z a t i o n curves for (1) 3 M C N " , 1 M C u ( C N : C u m o l e ratio = 3), +

174
0.25 M N a O H and 0.5 M N a S 0 , (2) 0.5 M N a S 0 , 0.25 M N a O H 2 3 2 3
XX
a n d 1 M N a S 0 and (3) 3 M C N " , 1 M C u , 0.25 M N a O H a n d 0.5 M

2 4
+
Na S0
2 4 at 4 0 0 r p m and 60 C
F i g u r e 8-13 P o l a r i z a t i o n curves at 4 0 0 r p m and 25 C for (1) 3 M C N " + 1 M C u + +

174
0.4 M N a S 0 + 0.1 M N a S 0 (2) 3 M C N " + 1 M C u + 0.2 M
2 3 2 4
+
Na S0
2 3 + 0.3 M N a , S 0 , (3) 0.4 M N a S 0 + 1 M N a ^ O , , (4) 0.2 M
4 2 3
Na S0
2 3 + 1 M N a j S C ^ (5) 3 M C N " + 1 M C u + 0.5 M N a S 0 +
2 4 at
[ N a O H ] = 0.05 M N a O H

1 M C u , 0.25 M N a O H , 0.5 M N a S 0
+
2 3
F i g u r e 8-15 P o l a r i z a t i o n curves for (1) 3.5 M C N " , 1 M C u ( C N : C u m o l e ratio = +

176
3), 0.25 M N a O H and 0.5 M N a S 0 , (2) 3 M C N " , 1 M C u , 0.25 M
2 3
+
N a O H and 0.5 M N a S 0 and (3) 0.5 M N a S 0 , 0.25 M N a O H at 4 0 0

2 4 2 3
r p m and 60 C

M C u , 0.25 M N a O H , 0.5 M N a S 0
+
2 3
F i g u r e 8-17 P o l a r i z a t i o n curves for (1)4 M C N " , 1 M C u ( C N : C u m o l e ratio = 3), +

178
0.25 M N a O H and 0.5 M N a S 0 , (2) 0.5 M N a S 0 , 0.25 M N a O H
2 3 2 3
a n d 1 M N a S 0 and (3) 4 M C N " , 1 M C u , 0.25 M N a O H and 0.5 M

2 4
+
Na S0
2 4 at 4 0 0 r p m and 60 C
Figure A - l P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 239

50 and 60 C . E l e c t r o l y t e : 0.05 M N a S 0 , 0.25 M N a O H and 1 M 2 3
Na S0
2 4
Figure A - 2 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 240

50 a n d 60 C . E l e c t r o l y t e : 0.2 M N a S 0 , 0.25 M N a O H a n d 1 M
2 3
Na S0
2 4

2 3
Na S0
2 4
Figure A - 4 P o l a r i z a t i o n c u r v e s o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 242

50 a n d 60 C . E l e c t r o l y t e : 0.5 M N a S 0 , 0.25 M N a O H a n d 1 M 2 3
Na S0
2 4
Figure A - 5 B a c k g r o u n d current density v s . potential o n graphite rotating d i s k at 243

2 5 , 4 0 , 50 a n d 60 C . E l e c t r o l y t e : 0.25 M N a O H a n d 1 M N a S 0 2 4

2 3
XXI
Na S02 4

2 3
Na S0
2 4
Figure A - 8 L o g (i) v s . L o g (1-1/i,) (a) a n d 1/i v s . 1/i, (b) at 40 (1), 50 (2) a n d 60 246
(3) C a n d the c o r r e s p o n d i n g fitted function (y v s . x ) are i n the
d i a g r a m . E l e c t r o y t e : 0.1 M N a S 0 , 0.25 M N a O H and 1 M N a S 0 .
2 3 2 4
Figure A - 9 C o m p a r i s o n o f the effects o f C u O - c o a t e d graphite and c o p p e r i o n s i n 247

the s o l u t i o n at 100 r p m and different temperatures. E l e c t r o l y t e : 0 . 2 5 M
N a O H and 1 M N a S 0 2 4
Figure A - 1 0 X P S s p e c t r u m o f the precipitate prepared at 25 C and 0.5 V v s . S C E . 248

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d
1 M Na S0 2 4
Figure A - l 1 X P S s p e c t r u m o f the precipitate prepared at 60 C a n d 0.5 V v s . S C E . 248

1 MNa S0 2 4
Figure A - 1 2 X P S s p e c t r u m o f the precipitate prepared at 25 C and 0.5 V v s . S C E . 249

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H and
1 M Na S0 2 4
Figure A - 1 3 X P S s p e c t r u m o f the precipitate prepared at 60 C a n d 0.5 V v s . S C E . 249

1 M Na S0 2 4
Figure A - 1 4 P o l a r i z a t i o n curves o n the graphite coated w i t h C u O a n d no C u O i n 250

the absence o f c y a n i d e and copper at different temperatures.
E l e c t r o l y t e : 0.25 M N a O H and 1 M N a S 0 2 4
Figure A - 1 5 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. 251

E l e c t r o l y t e : 0.05 M C N ' , C N : C u m o l e ratio = 3.5, 0.25 M N a O H a n d 1
M N a S 0 . K e y s : 1 - no p r e c i p i t a t i o n o f c o p p e r o x i d e , 2 - p r e c i p i t a t i o n
2 4
o f c o p p e r o x i d e and 3 - e v o l u t i o n o f o x y g e n

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3.5, 0.25 M N a O H a n d 1
2 4

xxn
2 4
o f copper o x i d e , 3 - e v o l u t i o n o f o x y g e n a n d 2+3 - c o p p e r o x i d e a n d
o x y g e n appeared almost at the same potential
Figure A - 1 8 P o l a r i z a t i o n curves at different rotational speeds and temperatures. 254

M N a S 0 . K e y s : 1 - no p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n
2 4
o f copper o x i d e , 3 - e v o l u t i o n o f o x y g e n a n d 2+3 - c o p p e r o x i d e a n d
o x y g e n appeared almost at the same potential

2 4
o f copper o x i d e and 3 - e v o l u t i o n o f o x y g e n

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 4, 0.05 M - N a O H a n d 1
2 4
Figure A-21 P o l a r i z a t i o n curves at different rotational speeds and temperatures. 257

2 4

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3, 0.01 M N a O H and 1
2 4

2 4

2 4

E l e c t r o l y t e : 0.5 M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M
N a S 0 . K e y s : 1 - no p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f
2 4
copper o x i d e a n d 3 - e v o l u t i o n o f o x y g e n
Figure A - 2 6 X - r a y d i f f r a c t i o n pattern o f the a n o d i c precipitate prepared under the 262

c o n d i t i o n s : 3 M C N " , 1 M C u (I), 0.25 M N a O H , 0.5 M N a S 0 , 25 2 4
XX111
C , 0.5 V v s . S C E , and 100 r p m
Figure A - 2 7 X - r a y d i f f r a c t i o n pattern o f the a n o d i c precipitate prepared under the 262

c o n d i t i o n s : 3 M C N " , 1 M C u (I), 0.25 M N a O H , 0.5 M N a S 0 , 60 2 4
C , 0.5 V v s . S C E , and 100 r p m
Figure A - 2 8 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n - 263

p o t e n t i a l v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0
r p m (40 and 50 C ) . E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio - 3,
4, 6, 12 and n o copper, 0.25 M N a O H and 1 M N a S 0 2 4
Figure A - 2 9 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n - 263

potential vs. l o g (current density) o n a graphite rotating d i s k at 4 9 0 0
r p m (40 and 50 C ) . E l e c t r o l y t e s : [ C u ] = 0.00833 M , [ C N ] = 0 . 0 2 5 ,
+
0.05, 0.1, 0.2 a n d 0.4 M , 0.25 M N a O H a n d 1 M N a S 0 2 4
Figure A - 3 0 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current density) 264

o n a graphite rotating d i s k at 4 9 0 0 r p m (40 a n d 5 0 C ) . E l e c t r o l y t e s :
0.05 M " C N " , a C N : C u m o l e ratio o f 3, [ O H ] = 0.25, 0.125, 0.05,
0.025 and 0 . 0 I M and 1 M N a S 0 2 4

o n a P t graphite rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s :
0.05 M " C N " , a C N : C u m o l e ratio o f 3, [OH"] = 0.25, 0.125, 0.05,
0.025 a n d 0 . 0 I M and 1 M N a S 0 2 4
Figure A - 3 2 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - p o t e n t i a l v s . l o g (current density) 265

o n a graphite rotating d i s k 4 9 0 0 r p m (40 and 50 C ) . E l e c t r o l y t e s :
0.05 M " C N " , a C N : C u m o l e ratio o f 4, [OH"] = 0.25, 0.05, a n d 0 . 0 1 M
and 1 M N a S 0 2 4

o n a graphite rotating d i s k at 4 9 0 0 r p m (40 and 50 C ) . E l e c t r o l y t e s :
0.05 M " C N , a C N : C u m o l e ratio o f 12, [OH"] = 0.25, 0.05 a n d 0 . 0 I M
and 1 M N a S 0 2 4
Figure A - 3 4 P l o t s o f potential v s . l o g (current density) o n a graphite rotating d i s k at 266

4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : [ C N ] = 0.025,
0.05, 0.1 a n d 0.20 M , a C N : C u m o l e ratio - 3, [OH"] = 0.25 M a n d 1
M Na S02 4
Figure A - 3 5 P l o t s o f the potential v s . l o g (current density) o n a p y r o l y t i c graphite 267

rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [CN"] = 0.025,
0.05, 0.1 a n d 0.20 M , a C N : C u m o l e ratio = 3, [OH"] = 0.25 M a n d 1
M Na S0 2 4
xxiv
Figure A - 3 6 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a p y r o l y t i c

3
2
267
graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [CN"] =
0.025, 0.05, 0.1 and 0.20 M , a C N : C u m o l e ratio = 3, [OH"] = 0.25 M
and 1 M N a ^ O ,
Figure A - 3 7 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 0.05 M C N " , 268

+
2 3
and 1 M N a S 0 .
2 4

+
2 3
and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 2 4
Figure A-41 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 0.05 M C N " , 272

+
2 3
and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 2 4

+
2 3
and 1 M N a S 0 .
2 4

0.0125 M C u ( C N : C u m o l e ratio = 4), 0.05 M N a O H , 0.1 M
+
N a ^
and 1 M N a j S O , .
Nomenclature
Lists o f symbols
a s p e c i f i c area (m" )1
aj a c t i v i t y o f species i
C c o n c e n t r a t i o n ( m o i dm" )
3
C b b u l k c o n c e n t r a t i o n ( m o i dm" ) 3
C s surface concentration ( m o l e dm" ) 3
C. E. current e f f i c i e n c y
D d i f f u s i o n coefficient ( m 2
s" )
1
d diameter o f graphite fibre
E p o t e n t i a l o f the electrode ( V )
e porosity o f matrix
e 0 initial porosity o f matrix
E standard potential ( V )
E P peak potential i n l i n e a r potential sweep ( V )
E P / 2 p o t e n t i a l where i = i / 2 i n linear p o t e n t i a l sweep ( V )

p
E. C. energy c o n s u m p t i o n ( k W h r kg" ) 1
EDTA ethylenediaminetetra-acetic a c i d
en ethylenediamine
F F a r a d a y constant = 9 6 4 8 7 A s m o i " 1
G e x
excess G i b b s free energy
I current ( A ) or i o n i c strength
I, current i n the l i q u i d phase ( A )

xxvi
I s current i n the s o l i d phase ( A )
i current density, ( A m" ) 2
i C u current density o f copper d e p o s i t i o n ( A m" ) 2
i d d i f f u s i o n current density ( A m " ) 2
i H current density o f h y d r o g e n e v o l u t i o n ( A m" ) 2
i k k i n e t i c a l l y c o n t r o l l e d current density ( A m" ) 2
i, l i m i t i n g current density ( A m " ) 2
i p p e a k current density ( A m" ) 2
k heterogeneous rate constant ( m s" ) 1
K a constant o f H C N d i s s o c i a t i o n
K s p solubility product o f C u C N
k m mass transfer coefficient ( m s" ) 2 1
K, e q u i l i b r i u m constant between S 0 ( a q . ) and H S 0 "

2 3
K 2 e q u i l i b r i u m constant between H S 0 " a n d S 0 " 3 3

2
K 2 3 e q u i l i b r i u m constant for C u ( C N ) " + C N " - > C u ( C N ) "

2 3
2
K 3 4 e q u i l i b r i u m constant for C u ( C N ) " + C N " - C u ( C N ) "

3
2
4
3
M m o l a r i t y ( m o i dm" )
3
m f m o l a l i t y o f species i , ( m o i kg"')
n n u m b e r o f electrons transferred or m o l e s o f solutes i , j or k
n r r e a c t i o n order
n w k i l o g r a m s o f solvent
pH negative l o g a r i t h m to base 10 o f the a c t i v i t y o f h y d r o g e n i o n
R gas constant (8.314 J K " ' moi"')

xxvii
Re Reynolds number
S Siemens (Q" ) 1
SCE saturated c a l o m e l electrode
Sh Sherwood number
SHE standard h y d r o g e n electrode
T absolute temperature, ( K )
u v e l o c i t y o f the l i q u i d ( m s" )
1
U * a c t i v a t i o n energy at the potential = 0 (J moi" ) 1
U* (E) a c t i v a t i o n energy at potential ( E ) (J moi" ) 1
v scan rate o f potential sweep ( V s" ) 1
Z, i o n i c charge
Lists o f Greek Symbols
a charge transfer coefficent
a a a n o d i c charge transfer coefficient
a, P i t z e r ' s parameters (= 2.0 for 1-1, 2 - 1 , 1-2,3-1, 4-1 electrolyte)
a 2 P i t z e r ' s parameters (= 0.0 for 1-1, 2 - 1 , 1-2,3-1, 4-1 electrolyte)
P 0 P i t z e r ' s parameter
(3, P i t z e r ' s parameter
P 2 P i t z e r ' s parameter for 2-2 electrolyte or the a s s o c i a t i o n constant for

Cu(CN) " 2
Yi a c t i v i t y coefficient o f species i
0 P i t z e r ' s interaction parameter for l i k e charged i o n s
X n t e r m for d e s c r i b i n g the short-range i n t e r i o n i c effects as a f u n c t i o n o f i o n i c

xxi:
strength to d i s p l a y the type o f b e h a v i o u r caused b y the h a r d core effect
p f c h e m i c a l potential o f the solute ( m o l a l i t y )
u, c h e m i c a l potential i n the solute ( m o l a l i t y ) standard state
Li ijk t e r m for t r i p l e i o n interactions w h i c h ignores any i o n i c strength dependence
8 d thickness o f the d i f f u s i o n l a y e r (m)
r) overpotential ( V )
v kinematic viscosity ( m 2
s" )
1
Q o h m or n u m b e r o f m o l e s o f solvent i n a k i l o g r a m (55.51 for water)
co angular v e l o c i t y (s" )
1
K effective c o n d u c t i v i t y o f the l i q u i d (solution) phase (S m" )1
a effective c o n d u c t i v i t y o f the s o l i d (graphite fibre) phase (S m"')
c3> potential difference bewteen the s o l i d phase and the l i q u i d ( V )
, potential o f the l i q u i d phase ( V )
O s potential o f the s o l i d phase ( V )
(j) o s m o t i c coefficient
\\i P i t z e r ' s ternary parameter

XXI X
ACKNOWLEDGEMENTS
I w o u l d l i k e to express m y sincere a p p r e c i a t i o n to D r . D . B . D r e i s i n g e r for h i s
thoughtful s u p e r v i s i o n a n d constructive d i s c u s s i o n s and r e v i e w i n g a n d e d i t i n g this thesis. I
a m v e r y grateful to D r . W . C . C o o p e r for r e v i e w i n g and e d i t i n g this thesis. I w o u l d also l i k e
to a c k n o w l e d g e D r . D . T r o m a n s , D r . G . H . K e l s a l l a n d Prof. C . O l o m a n for p r o v i d i n g
constructive ideas. D r . B . W a s s i n k ' s k i n d help e s p e c i a l l y i n c h e m i c a l a n a l y s i s is v e r y m u c h
appreciated..
Thanks are extended to my fellow graduate students and the staff of the
h y d r o m e t a l l u r g y g r o u p and w i t h w h o m I have enjoyed w o r k i n g .
T h e f i n a n c i a l support f r o m the F a c u l t y o f Graduate Studies i n the f o r m o f a U B C
Graduate F e l l o w s h i p is greatly appreciated.
F i n a l l y , I w o u l d l i k e to thank m y w i f e , m y parents, brothers a n d sisters for g i v i n g m e
m o r a l support.
1
1. INTRODUCTION
C y a n i d e l e a c h i n g has been w i d e l y accepted as a n e x c e l l e n t i n d u s t r i a l m e t h o d to
r e c o v e r g o l d a n d s i l v e r [1, 2 ] . H o w e v e r , the c y a n i d a t i o n o f c o p p e r - g o l d ores c o n t a i n i n g the
common o x i d e and secondary sulfide copper minerals e.g. chalcocite (Cu S),2 bornite
( C u F e S ) , malachite ( C u C 0 ,
5 4 3 C u ( O H ) ) , c o v e l l i t e ( C u S ) and cuprite ( C u 0 ) results
2 2 in
cyanide degradation and copper solubilization as cuprous cyanide complexes. In
c o n v e n t i o n a l g o l d p r o c e s s i n g , the copper a n d c o m p l e x e d c y a n i d e are not r e c o v e r e d after the
g o l d is r e m o v e d f r o m s o l u t i o n . T h i s leads to a s i g n i f i c a n t e c o n o m i c penalty i n excess c y a n i d e
c o n s u m p t i o n , loss o f a v a l u a b l e copper b y - p r o d u c t a n d s i g n i f i c a n t cost i n c y a n i d e d e s t r u c t i o n
d u r i n g effluent treatment.
S e v e r a l w a y s have been p r o p o s e d to s o l v e the above p r o b l e m s . F o r e x a m p l e , (1)
pretreating ores to r e m o v e copper etc. before c y a n i d a t i o n s u c h as pressure o x i d a t i o n l e a c h i n g
[3], r o a s t i n g - l e a c h i n g [4-6], and b i o l e a c h i n g [7, 8 ] ; (2) the a p p l i c a t i o n o f alternative l i x i v i a n t s
to r e c o v e r g o l d s u c h as thiourea [9], a m m o n i u m thiosufate [10], c h l o r i d e [2], a n d b r o m i d e [2,
11]; (3) the a d d i t i o n o f other reagents s u c h as a m m o n i a to decrease the c o n s u m p t i o n o f
c y a n i d e [12]. H o w e v e r , the above methods have their o w n d r a w b a c k s or a p p l i c a t i o n l i m i t s
a n d so i n m o s t cases c y a n i d e is still used to l e a c h g o l d ores c o n t a i n i n g copper.
Therefore the r e c o v e r y o f copper a n d associated c o m p l e x e d c y a n i d e f r o m l e a c h
solutions has been approached i n a v a r i e t y o f w a y s s u c h as a c i d i f i c a t i o n - v o l a t i l i z a t i o n -
regeneration ( A V R ) , i o n exchange and electrolysis [13-25]. T h e b a s i c A V R process consists
o f the f o l l o w i n g steps: (1) a c i d i f y i n g the barren s o l u t i o n to p H 2-3 w i t h s u l p h u r i c a c i d to
dissociate c o p p e r c y a n i d e c o m p l e x e s to f o r m H C N and precipitate c o p p e r as C u C N or a
m i x t u r e o f C u C N and C u S C N , i f there is S C N " i n the s o l u t i o n ; (2) v o l a t i l i z i n g H C N f r o m the
s o l u t i o n b y intense air sparging, a n d (3) r e c o v e r i n g the H C N b y a b s o r p t i o n i n a n a l k a l i n e
s o l u t i o n ( N a O H or C a ( O H ) ) [13 - 18]. I n order to r e c o v e r c y a n i d e f r o m the

2 precipitates,
oxidants s u c h as H 0 2 2 and 0 3 have been tested to convert C u C N and C u S C N to C u 2 +

and
H C N i n the A V R process [15, 17]. N a H S w a s tested to precipitate c o p p e r as C u S 2 and
r e c o v e r a l l o f the c y a n i d e i n the A V R process [18]. S e v e r a l i o n - e x c h a n g e process has b e e n
p r o p o s e d to i m p r o v e the r e c o v e r y o f c y a n i d e i n a c o m b i n a t i o n w i t h the A V R process [15, 19,
20].
2
E l e c t r o w i n n i n g w a s u s e d to r e c o v e r c o p p e r as m e t a l and c y a n i d e [21-25]. D u r i n g
e l e c t r o w i n n i n g , c y a n i d e is o x i d i z e d to cyanate, decreasing the r e c o v e r y o f c y a n i d e , a n d
c o p p e r d e p o s i t i o n current e f f i c i e n c y w a s l o w due to the l o w c o p p e r c o n c e n t r a t i o n . S e v e r a l
m e t h o d s have b e e n p r o p o s e d to solve the above p r o b l e m s . T o increase the c o p p e r d e p o s i t i o n
current e f f i c i e n c y , p o r o u s electrodes were u s e d to deposit c o p p e r [22-25]. O r o c o n Inc. [22]
reported that the thiocyanate i n the s o l u t i o n c o u l d be o x i d i z e d to C N " a n d S 0 " to decrease 4

2
the c o n s u m p t i o n o f c y a n i d e . H o w e v e r , the a n o d i c current e f f i c i e n c y o f t h i o c y a n a t e w a s not
g i v e n . T o prevent the c y a n i d e o x i d a t i o n at the anode, a n i o n - e x c h a n g e m e m b r a n e w a s u s e d to
separate the anode a n d the cathode [25]. R e c e n t l y a process w a s p r o p o s e d w h i c h c o m b i n e s
i o n exchange, A V R , m e m b r a n e c e l l e l e c t r o l y s i s a n d i m p r o v e s the e f f i c i e n c y for r e c o v e r i n g
c o p p e r a n d c y a n i d e [26, 2 7 ] .
H o w e v e r , g e n e r a l l y these processes suffer f r o m the f o l l o w i n g d r a w b a c k s : i n c o m p l e t e
r e c o v e r y o f c y a n i d e , i n c o m p l e t e r e c o v e r y o f copper, l o w - v a l u e c o p p e r products (e.g. C u C N ,
C u S C N a n d C u S ) a n d c o m p l i c a t e d flowsheets. I n order to o v e r c o m e the a b o v e d r a w b a c k s , a

2
solvent e x t r a c t i o n - e l e c t r o w i n n i n g process has been d e v e l o p e d to r e c o v e r c o p p e r a n d c y a n i d e
f r o m g o l d m i n i n g effluents [28]. I n s u m m a r y , c o p p e r c y a n i d e is extracted u s i n g a g u a n i d i n e -
based extractant ( X I 7 9 5 0 ) or a m i x e d strong base extractant with nonylphenol (XI78),
stripped w i t h strong a l k a l i n e electrolyte and f i n a l l y e l e c t r o l y z e d i n a m e m b r a n e c e l l to
p r o d u c e c o p p e r m e t a l and a b l e e d stream for A V R to r e c o v e r c y a n i d e . T h e c h e m i s t r y o f the
process is s h o w n b e l o w :
Copper extraction:
Na Cu(CN)
2 3 + 2 R + 2 H 0 -> R H C u ( C N )
2 2 2 3 + 2NaOH (1-1)
w h e r e R species refers to the g u a n i d i n e solvent extractant.
Copper stripping:
R H Cu(CN)
2 2 3 +2NaOH->2R + Na Cu(CN) 2 3 +H 0
2 (1-2)
Copper electrowinning (in a membrane cell):
Na Cu(CN)
2 3 + N a O H - > C u + 3NaCN + l / 4 0 2 +1/2H 02 (1-3)
T h e use o f a m e m b r a n e ( N a t i o n ) c e l l i n the c o p p e r e l e c t r o w i n n i n g c e l l is necessary to
prevent c y a n i d e o x i d a t i o n at the anode. H o w e v e r , the N a f i o n m e m b r a n e is e x p e n s i v e a n d
m a y be subject to m e c h a n i c a l damage b y the g r o w i n g m e t a l deposit. I n order to e l i m i n a t e the
use o f a m e m b r a n e c e l l , a n alternative anode r e a c t i o n is u s e d to prevent the o x i d a t i o n o f

3
c y a n i d e . T h i s w i l l result i n a s i m p l e r c e l l d e s i g n (no m e m b r a n e ) w i t h r e d u c e d c a p i t a l cost a n d
l o w c e l l voltage ( l o w energy c o n s u m p t i o n ) . A l t e r n a t i v e anode reactions w h i c h h a v e been
suggested a n d tested are: (1) the o x i d a t i o n o f thiocyanate to c y a n i d e a n d sulphate, (2) the
o x i d a t i o n o f m e t h a n o l to C O , a n d H 0 , (3) the o x i d a t i o n o f sulphite to sulphate a n d (4) the

2
o x i d a t i o n o f a m m o n i a to N 2 and H 0 . T h e i n c l u s i o n o f the above s a c r i f i c i a l species

2 was
tested i n some p r o o f - o f - c o n c e p t e l e c t r o w i n n i n g experiments i n our lab a n d w a s s h o w n to be
p r o m i s i n g o n l y for sulphite. W i t h sulphite a d d i t i o n , the c e l l c h e m i s t r y b e c o m e s :
Na Cu(CN)
2 3 +l/2Na S0 2 3 + N a O H = C u + 3 N a C N + 112Na S0 2 4 + 1/2H 0 2 (1-4)
Therefore a process has been p r o p o s e d b y the H y d r o m e t a l l u r g y G r o u p at U B C u s i n g
the flowsheet s h o w n i n F i g u r e 1-1 to recover copper and c y a n i d e . I n the first step ( l o a d i n g ) ,
barren c y a n i d e s o l u t i o n (0.5 -2 g L " ' C u , C N : C u m o l e ratio = 3-4) is m i x e d w i t h o r g a n i c
phase (extractant and solvent) a n d copper c y a n i d e is extracted to the o r g a n i c phase. I n the
s e c o n d step (stripping), the organic phase l o a d e d w i t h copper c y a n i d e is m i x e d w i t h strong
a l k a l i n e electrolyte (60 g L " ' C u , C N : C u = about 3, 4 - 1 0 g L " N a O H a n d 5 0 - 6 0 g L " N a S 0 )

1 1
2 3
a n d c o p p e r c y a n i d e is transferred to the electrolyte and the copper c o n c e n t r a t i o n o f the
electrolyte increases to about 70 g L " ' . I n the t h i r d step ( e l e c t r o w i n n i n g ) , the electrolyte is
returned to the e l e c t r o w i n n i n g c e l l a n d copper is deposited o n the cathode. I n the f o u r t h step
( a c i d i f i c a t i o n ) , a b l e e d stream o f electrolyte is t a k e n out and m i x e d w i t h H S 0 2 4 and copper
c y a n i d e is d i s s o c i a t e d to f o r m H C N a n d C u C N at p H 2 - 3 . C u C N w a s returned to the
e l e c t r o w i n n i n g c e l l and H C N is r e m o v e d b y sparging air and f i n a l l y absorbed i n a l k a l i n e
s o l u t i o n ( N a O H or C a ( O H ) ) .
2
T h e direct e l e c t r o w i n n i n g o f copper f r o m a barren c y a n i d e l e a c h s o l u t i o n m a y be
preferred i n some cases for the r e c o v e r y o f copper a n d r e c y c l e o f c y a n i d e . H o w e v e r , careful
study o f this process has not been reported. Therefore, the efficient d e p o s i t i o n o f c o p p e r f r o m
a b a r r e n c y a n i d e s o l u t i o n is a p r o m i s i n g alternative a p p r o a c h to the r e c o v e r y o f c y a n i d e a n d
copper. T h e process for the direct e l e c t r o w i n n i n g process has been d e v e l o p e d a n d consists o f
the f o l l o w i n g steps: (1) barren c y a n i d e s o l u t i o n ( 1-2 g L " C u and C N : C u m o l e ratio = 3-4)

1
enters the m e m b r a n e c e l l a n d f l o w s t h r o u g h the graphite felt cathode o n w h i c h c o p p e r is
deposited a n d the copper depleted c y a n i d e s o l u t i o n returns to g o l d l e a c h i n g a n d (2) c o p p e r is
deposited o n a m e t a l sheet and then refined i n a second e l e c t r o r e f i n i n g c e l l c o n t a i n i n g c o p p e r
sulphate s o l u t i o n . T h e flowsheet is s h o w n i n F i g u r e 1-2.

A n i n i t i a l e c o n o m i c assessment has been p e r f o r m e d o n direct e l e c t r o w i n n i n g a n d o n
the S X - E W system(see A p p e n d i x 1). T h e assessment has been m a d e u s i n g a n a s s u m e d ore
grade. T h e a n a l y s i s indicates that a s i g n i f i c a n t benefit m a y be a v a i l a b l e b y a p p l y i n g one o f
these processes.
In order to i m p r o v e the above processes, the t w o e l e c t r o w i n n i n g processes s h o u l d be
studied as regards b o t h the p r a c t i c a l and fundamental aspects. Therefore the present research
w a s undertaken w i t h the f o l l o w i n g objectives:
(1) T o study the aqueous c h e m i s t r y o f copper c y a n i d e solutions i n the temperature range 25 -
60 C w i t h reference to copper concentration, C N : C u m o l e ratio a n d p H . T h e results c o u l d be
generated b y c a l c u l a t i o n u s i n g the e q u i l i b r i u m copper c y a n i d e constants a n d then c o n f i r m e d
by p o t e n t i a l measurement. It was expected that this study w o u l d l e a d to a n i m p r o v e d
understanding o f the d i s t r i b u t i o n o f copper c y a n i d e c o m p l e x e s under p r a c t i c a l c o n d i t i o n s a n d
their role i n the e l e c t r o d e p o s i t i o n and the a n o d i c o x i d a t i o n o f copper c y a n i d e .
(2) T o study the e l e c t r o w i n n i n g o f copper f r o m concentrated c y a n i d e s o l u t i o n s u s i n g a n
alternative anode r e a c t i o n so as to l i m i t the o x i d a t i o n o f c y a n i d e . T h e study w o u l d be
c o n d u c t e d w i t h reference to C N : C u m o l e ratio (3-4.5), temperature (40-60 C ) a n d the
c o n c e n t r a t i o n o f s a c r i f i c i a l species (for sulphite 50 - 1 2 0 g L " ' ) . T h e s e parameters will
significantly affect the cathode a n d anode processes. Copper concentration should be
c o n t r o l l e d at 6 0 - 7 0 g L " to get a reasonable copper d e p o s i t i o n current e f f i c i e n c y a n d to

1
simulate the c o p p e r content o f the strong electrolyte i n the e l e c t r o w i n n i n g process.
(3) T o study the e l e c t r o w i n n i n g o f copper o n a graphite felt cathode w i t h reference to c o p p e r
c o n c e n t r a t i o n (1-2 g L " ) , m o l e ratio o f c y a n i d e to copper (3-4.5) a n d f l o w rate a n d current

1
density ( 3 0 - 1 0 0 A m" ) at a n ambient temperature (25-40 C ) f r o m v i e w p o i n t o f i n d u s t r i a l

2
practice.
(4) T o study the o x i d a t i o n o f sulphite o n graphite w i t h reference to temperature (25 - 6 0 C ) ,
Na S02 3 c o n c e n t r a t i o n (0.05-0.5 M ) a n d h y d r o x i d e c o n c e n t r a t i o n (0.05-0.25 M ) u s i n g r o t a t i n g
d i s k technique a n d linear p o t e n t i a l sweep. T h e a n o d i c b e h a v i o u r o f sulphite o n the graphite
( T a f e l slope a n d rate constant) a n d the mass transfer ( d i f f u s i o n coefficient) c a n be o b t a i n e d
a n d c o m p a r e d to those o f copper c y a n i d e to decrease the a n o d i c o x i d a t i o n o f c y a n i d e .
(5) T o study the o x i d a t i o n o f copper c y a n i d e o n graphite w i t h reference to temperature ( 2 5 -
60 C ) , m o l e ratio o f c y a n i d e to copper (3-12), c y a n i d e c o n c e n t r a t i o n (0.05-4 M ) a n d

5
h y d r o x i d e c o n c e n t r a t i o n (0.01-0.25 M ) u s i n g the rotating d i s k technique. T h i s research c o u l d
lead to k n o w i n g h o w these parameters affect the a n o d i c b e h a v i o u r o f c o p p e r c y a n i d e .
(6) T o study the a n o d i c o x i d a t i o n o f copper c y a n i d e and sulphite s o l u t i o n s w i t h reference to
their concentrations, C N : C u m o l e ratio, temperature (25-60 C ) , h y d r o x i d e c o n c e n t r a t i o n
(0.05-0.25 M ) and the current density u s i n g the rotating d i s k technique. T h e a n o d i c b e h a v i o u r
o f m i x e d sulphite a n d c o p p e r c y a n i d e m a y not be the same as w h e n they are present
separately i n the s o l u t i o n . Therefore it is necessary to k n o w the a n o d i c b e h a v i o u r o f the
mixture.
T h e results o f this study s h o u l d h e l p to increase the e f f i c i e n c y o f r e c o v e r i n g c o p p e r
a n d c y a n i d e f r o m a barren g o l d s o l u t i o n and to decrease the cost.
T h i s thesis consists o f seven major chapters: C h a p t e r 2 deals w i t h a r e v i e w o f the
literature, p r o v i d i n g a s u m m a r y o f current ideas about the d e p o s i t i o n o f c o p p e r f r o m c y a n i d e
s o l u t i o n , the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e a n d the a n o d i c o x i d a t i o n o f sulphite,
thiocyanate, m e t h a n o l and a m m o n i a . C h a p t e r 3 considers the t h e r m o d y a n i c s o f c o p p e r
c y a n i d e . Chapters 4 - 8 present the e x p e r i m e n t a l aspects, results a n d d i s c u s s i o n o f the direct
copper electrowinning from a dilute c y a n i d e s o l u t i o n , c o p p e r e l e c t r o w i n n i n g u s i n g a n
alternative a n o d i c r e a c t i o n , the a n o d i c o x i d a t i o n o f sulphite, a n o d i c o x i d a t i o n o f c o p p e r
cyanide and the anodic oxidation o f mixed sulphite and copper cyanide solutions
respectively. Chapter 9 summarizes the research work and Chapter 10 gives some
suggestions for future studies.

6
Barren cyanide solution
H S0
2 4 a Loading ->Raffinate
Organic Organic
phase phase
NaOH- a Stripping
Electrolyte Electrolyte
NaOH- Cu
Electrowinning
Na2S03- -> Barren solution
Bleed CuCN
H 2 S O 4 - Acidification
HCN
CaO- Neutralization Ca(CN)2
Figure 1-1 Flowsheet for solvent extraction - electrowinning process for the recovery of
copper cyanide
7
Water
Heap leaching U
Gold Gold recovery Solution storage < Reagent
Cu Electrowinning
Barren solution Cu depleted solution
Impure Cu
Cu electrorefining
Pure Cu
Figure 1 -2 Flowsheet for direct electrowinning of copper from cyanide solutions

8
2. LITERATURE REVIEW
2.1 Aqueous Chemistry of the Copper-Cyanide System
Copper cyanide c a n be d i s s o l v e d i n the presence o f excess c y a n i d e to form
cyanocuprate ions, C u ( C N ) " , C u ( C N ) " a n d C u ( C N ) " i n aqueous s o l u t i o n . T h i s d i s s o l u t i o n

2 3
2
4
3
has been studied by various methods [29-59]. These species undergo the following
s u c c e s s i v e e q u i l i b r i u m steps i n r e a c t i o n w i t h free c y a n i d e a n d u n d i s s o c i a t e d h y d r o c y a n i c
acid.
CuCN = Cu +
+ CAT Ksp (2-1)
CuCN + CN- =Cu(CN)~ Ki, 2

(2-2)
Cu +
+2CN' = Cu(CNy 2 (2-3)
Cu(CN) ~ 2 + CN~ = Cu(CN) ~ 3

2
K , 2 3
(2-4)
Cu(CN) - 3
2
+CN~ = Cu(CN) ~ 4
3
K ,4
3
(2-5)
HCN =H +
+ CAT K a
(2-6)
T a b l e 2-1 T h e a s s o c i a t i o n constants for copper c y a n i d e c o m p l e x e s
Method Temperature Concentration log P 2 log K 2 3 log K 3 4
Potentiometry [32] 25 C 10" - 1 0 " M C N -

1 7
23.72 - -
Potentiometry [42] 20 C 0.5 -5 M C N 21.7+ 1.0 4.6 0 . 3 0 2.3 0 . 1 5
Potentiometry [46] 22 C 0. 01 M C u 21.7 + 0.2 5.1 0 . 2 1.1 0 . 2
Potentiometry [47] 25 C 0.15 M C u 24 0.23 4.8 2.25
Potentiometric titration [59] 25 C 1 M NaCl 23.97 0.01 5.43 + 0.04 2.38 +
Infrared spectroscopy [33] 25 C 0.1 -0.2 M C u - 4.89 1.72
Ultraviolet spectroscopy [58] 25 C ionic strength: 0.01M - 5.34 1.74
Ultraviolet spectroscopy [39] 25 C 0.001 M Cu - 4.1 -
Calorimetry 25 C 1.0 M C u - 5.0 2.6
Calorimetry [38] 25 C ionic strength 0 - 5.3 +0.01 1.5 0 . 2
T h e s o l u b i l i t y p r o d u c t (IC^) o f cuprous c y a n i d e differs s l i g h t l y b e t w e e n authors, a
v a l u e o f 10" 20
at 2 5 C b e i n g generally accepted [44]. There is g o o d agreement for the H C N
d i s s o c i a t i o n constant ( K J amongst the p u b l i s h e d data. T h e r e c o m m e n d e d v a l u e for K at 25 a
C is 1 0 " 921
w h i c h w a s obtained b y e x t r a p o l a t i o n to the i o n i c strength = 0 or b y c a l c u l a t i o n
u s i n g a n extended f o r m o f the D e b y e - H i i c k e l equation [44, 5 2 ] . T h e d i s s o c i a t i o n constant i n
aqueous s o l u t i o n c o n t a i n i n g different i o n i c m e d i a has also been reported [52, 5 4 - 5 7 ] .

9
T h e e q u i l i b r i u m constants for copper c y a n i d e c o m p l e x e s ( T a b l e 2-1) differ b e t w e e n
authors due to the different methods o f measurement a n d the p r o c e s s i n g o f the data.
Vladimirova and Kakovsky [32] obtained a value of 10 23 7 2

for (3 2 using potential
measurements w i t h pure copper and copper a m a l g a m at p H 4.2. T h i s w a s consistent w i t h the
v a l u e estimated f r o m the e q u i l i b r i u m constant b e t w e e n C u C N S a n d C u ( C N ) \ T h i s v a l u e w a s 2
corrected to 1 0 24
b y some authors [33, 38, 39, 44] u s i n g the D e b y e - H i i c k e l e q u a t i o n a n d a
m o r e r e l i a b l e d i s s o c i a t i o n constant for H C N . R o t h b a u m [42] reported a v a l u e o f 1 0 2 1 , 7

for P 2
at 2 0 C b y m e a s u r i n g the copper potential i n a s o l u t i o n o f h i g h c o p p e r c y a n i d e c o n c e n t r a t i o n
i n the presence o f air a n d s i m p l i f y i n g the copper c y a n i d e species for c a l c u l a t i o n w i t h o u t
c o n s i d e r i n g the a c t i v i t y coefficient, l e a d i n g to some error. H a n c o c k et a l . [46] o b t a i n e d a
value o f 1 0 2 1 7
for P u s i n g potential measurement i n solutions c o n t a i n i n g 0.01 M C u ( I ) a n d
2
0.025 - 0.1 M C N " at p H 11 a n d 22 C under a n A r atmosphere. H o w e v e r , p 2 c o u l d be
underestimated because some o f the potential data u s e d for the c a l c u l a t i o n o f p 2 were
m e a s u r e d at a C N : C u m o l e ratio > 4 a n d were w e l l b e l o w the h y d r o g e n e q u i l i b r i u m p o t e n t i a l .
The measured potentials were m i x e d potentials and higher than the corresponding
e q u i l i b r i u m potentials. B e k a n d Z h u k o v [47] reported a v a l u e for 1 0 24

for P u s i n g p o t e n t i a l
2
measurements i n s o l u t i o n s w i t h 0.15 M C u ( I ) , C N : C u = 4, a n d 0.1 M N a O H a n d a n e x t e n d e d
f o r m o f the D e b y e - H i i c k e l equation. K a p p e n s t e i n and H u g e l [48] o b t a i n e d a v a l u e o f 1 0 1 6 7
for p u s i n g U V spectroscopy, c h a n g i n g the p H and a s s u m i n g C u ( C N ) " w a s the o n l y c o p p e r

2 2
c o m p l e x i n the s o l u t i o n . H o w e v e r , this v a l u e is m u c h l o w e r than the f o r m a t i o n constant
( 1 / K s p ) for C u C N a n d C u ( C N ) " w a s not d o m i n a n t under s u c h c o n d i t i o n s a c c o r d i n g to its P

2 2
v a l u e . R e c e n t l y Hefter et a l . [59] reported a v a l u e o f 1 0 2 3 9 7

for P w h i c h w a s o b t a i n e d b y
2
p o t e n t i o m e t r i c titration u s i n g a C u s o l u t i o n p r o d u c e d b y r e d u c t i o n o f C u
+ 2 +
w i t h a n excess o f
c o p p e r a n d s t a b i l i z e d b y c h l o r i d e . S o the most r e l i a b l e v a l u e for p appears to be 1 0 .2

24
T h e differences a m o n g the reported values o f K , a n d K 23 34 are r e l a t i v e l y s m a l l . T h e
most reliable values o f K 2 3 and K 3 4 are those reported b y Izatt et a l . [38]. T h e y w e r e o b t a i n e d
under w e l l - d e f i n e d c o n d i t i o n s u s i n g p H measurements and c a l o r i m e t r y a n d the Debye-
H i i c k e l equation.
A 6 3
C u and 6 5
C u m a g n e t i c resonance study s h o w e d that C u ( C N ) " retains a tetrahedral 4
3
symmetry and Cu(CN) " 3

2
has a distorted tetrahedral rather than a plane triangular
c o n f i g u r a t i o n [43]. C u p r o u s ions f o r m m i x e d c o m p l e x e s w i t h the c y a n i d e l i g a n d a n d other

10
ligands such as thiourea, thiocyanate, iodide, ammonia and chloride, for example,
C u ( C N ) S C N - a n d C u ( C N ) S C N " [43]. T h e c o m p l e x e d c y a n i d e r a p i d l y exchanges

3
3
4
4
with
aqueous free c y a n i d e [29]. W h e n the m o l e ratio o f c y a n i d e to c o p p e r is less than 3, the c o p p e r
c y a n i d e is r e a d i l y o x i d i z e d b y air, suggesting that C u ( C N ) " is less stable [60]. 2
C u p r i c i o n s react w i t h C N " and f o r m c u p r i c c o m p l e x e s , w h i c h are unstable and
d e c o m p o s e r a p i d l y [29, 5 8 ] . It w a s reported that w h e n the m o l e ratio o f C N : C u is not h i g h ,
c u p r i c i o n s react w i t h the c y a n i d e i n aqueous s o l u t i o n to g i v e c u p r i c c y a n i d e as a y e l l o w i s h -
b r o w n precipitate, w h i c h d e c o m p o s e s into c u p r i c c y a n i d e a n d c y a n o g e n a c c o r d i n g to the
f o l l o w i n g equations [61, 6 2 ] :
Cu 2 +
+ 2 C N " -> C u 1 1
(CN) 2 (2-7)
2Cu (CN) n
2 2Cu'CN + (CN) 2 (2-8)
T h e c y a n o g e n thus f o r m e d is e v o l v e d as a gas f r o m a c i d i c s o l u t i o n , or it is d e c o m p o s e d i n
a l k a l i n e s o l u t i o n as f o l l o w s :
(CN) 2 + 2 0 F T -> C N " + C N O " + H 0 2 (2-9)
W h e n the m o l e ratio o f c y a n i d e to copper is h i g h , not copper(II) d i c y a n i d e but a
p u r p l e intermediate is f o r m e d w h i c h r a p i d l y d e c o m p o s e s into c y a n o g e n a n d a c o p p e r species.
E v e n at o r d i n a r y temperature a transient v i o l e t c o l o u r m a y be n o t e d i n neutral or s l i g h t l y
a l k a l i n e m e d i a [29, 6 3 , 6 4 ] . T h e k i n e t i c s studies p r o v i d e d the first strong e v i d e n c e for the
f o r m a t i o n o f C u ( C N ) " i n reactions b e t w e e n C u
4
2 2 +
or its E D T A c o m p l e x a n d C N " [29, 5 8 , 6 5 ,
66]. Longo and Bush [67] conducted the Cu 2 +

- C N " reaction in methanol or
d i m e t h y l f o r m a m i d e f r o m -60 to -30 C a n d c o n c l u d e d that the unstable p u r p l e species is a
square p l a n a r c o m p l e x C u ( C N ) " . M o n s t e d a n d B j e r r u m [68] studied the r e a c t i o n b e t w e e n

4
2
Cu 2 +
a n d C N " i n aqueous m e t h a n o l at - 70 C a n d reported that the a b s o r p t i o n m a x i m u m at
535 n m w a s n e a r l y i n the same p o s i t i o n as that for C u ( e n ) 2

2 +
, suggesting a distorted
tetrahedral structure. N e i t h e r the electron s p i n resonance n o r the optical spectrum is
i n f l u e n c e d b y the presence o f excess o f c y a n i d e , s h o w i n g that n o pentacyano c o m p l e x is
formed.
T h e r e are t w o reports about the f o r m a t i o n constant o f c u p r i c tetracyanide [69, 7 0 ] .
Paterson a n d B j e r r u m [69] estimated the f o r m a t i o n constant o f C u ( C N ) " as

4
2
10 2 6 7
by
p o t e n t i o m e t r i c e x p e r i m e n t i n water-methanol s o l u t i o n ( m o l e fraction o f m e t h a n o l = 0.45) at -
45 C , w i t h the i o n i c strength v a r y i n g b e t w e e n 0.05 a n d 0.1 M ( N a C N ) . K a t a g i r i et a l . [70,

11
71] o x i d i z e d C u ( C N ) " o n a p l a t i n u m electrode to generate C u ( C N ) " a n d m e a s u r e d

4
3
4
2
the
r e d o x p o t e n t i a l for the C u ( C N ) 7 C u ( C N ) " c o u p l e . T h e y reported that the standard p o t e n t i a l

4
2
4
3
for the C u ( C N ) 7 C u ( C N ) " r e d o x c o u p l e w a s 0.54 V v s . S H E a n d the o v e r a l l f o r m a t i o n

4
2
4
3
constant for C u ( C N ) ' w a s 1 0 . 4

2 24
B a x e n d a l e a n d W e s t c o t t [58] studied the r e a c t i o n b e t w e e n C u 2 +

and C N " i n w e a k l y
a c i d i c s o l u t i o n to keep the concentration o f free c y a n i d e i o n l o w a n d decrease the r e a c t i o n
rate. T h e y f o u n d that the reaction w a s s e c o n d order i n C u 2 +

and 6th order i n C N " f r o m the
change i n the c o n c e n t r a t i o n o f the reaction product, C u ( C N ) " u s i n g a U V spectrophotometer. 2
T h e y p r o p o s e d the f o l l o w i n g m e c h a n i s m :
Cu 2 +
+ 3 C N " <^ C u ( C N V (2-10)
2 C u ( C N ) ~ -> 2 C u ( C N ) " + ( C N )
3 2 2 (2-11)
N o r d a n d M a t t h e s [72] u s e d the stopped - f l o w technique to study the r e a c t i o n b e t w e e n C u 2 +
and C N " i n aqueous solutions at 0 to 25 C and f o u n d that the r e a c t i o n w a s s e c o n d order w i t h
respect to C u ( C N ) " a n d i n v e r s e l y p r o p o r t i o n a l to the c o n c e n t r a t i o n o f the free c y a n i d e . O n

4
2
the basis o f these results, they p r o p o s e d the f o l l o w i n g r e a c t i o n m e c h a n i s m :
Cu(CN) " 4
2
Cu(CN) " + C N " 3 (2-12)
C u ( C N ) " + C u ( C N ) " -> C u ( C N ) " + C u ( C N ) " + ( C N )

4
2
3 3
2
2 2 (2-13)
R e a c t i o n 2-13 is c o n s i d e r e d to be the r a t e - c o n t r o l l i n g step. K a t a g i r i et a l . [70, 73] s t u d i e d the
k i n e t i c s a n d m e c h a n i s m o f the d e c o m p o s i t i o n o f C u ( C N ) " generated b y the a n o d i c o x i d a t i o n

4
2
o f C u ( C N ) " a n d f o u n d that the rate o f the d e c o m p o s i t i o n w a s s e c o n d order w i t h respect to

4
3
C u ( C N ) " a n d i n v e r s e l y p r o p o r t i o n a l to the square o f the c o n c e n t r a t i o n o f the free c y a n i d e

4
2
concentration. The f o l l o w i n g decomposition mechanism was proposed:
2Cu(CN) ~ 2
4 <=> Cu (CN)l 2 + 2CN~ (2-14)
Cu (CN) -
2
2
-> 2Cu(CN) ~ 2 +(CN) 2 (2-15)
R e a c t i o n 2-15 is p r o p o s e d as the rate-determining step.
T h e r a p i d d e c o m p o s i t i o n o f c u p r i c c y a n i d e results i n the o x i d a t i o n o f c y a n i d e w h i c h
has l e d to the use o f c u p r i c ions as a catalyst to destroy c y a n i d e i n waste water [74 - 7 6 ] .

12
2.2 The Electrodeposition of Copper from Copper-Cyanide Solution
2.2 A Practice of C o p p e r Deposition from C y a n i d e Solution
T h e e l e c t r o d e p o s i t i o n o f copper f r o m c y a n i d e s o l u t i o n has been w i d e l y reported [21-
2 9 , 3 1 , 7 7 - 1 2 8 ] . H o w e v e r , there are v e r y f e w reports o n c o p p e r e l e c t r o w i n n i n g f r o m c o p p e r
c y a n i d e s o l u t i o n and m o s t reports deal w i t h copper p l a t i n g . A n early c o p p e r e l e c t r o w i n n i n g
o p e r a t i o n w a s c a r r i e d out at the S a n Sebastian M i n e i n 1904 [79]. C l e v e n g e r [84, 85]
reported that copper w a s r e c o v e r e d i n N e v a d a a n d M e x i c o , but c y a n i d e c o n s u m p t i o n w a s
h i g h ( 3 0 % o f c y a n i d e w a s destroyed) and the current e f f i c i e n c y for c o p p e r d e p o s i t i o n w a s
l o w . L o w e r [21] reported that the direct e l e c t r o w i n n i n g o f copper f r o m a l e a c h s o l u t i o n
c o n t a i n i n g 13.7 - 24 g L " C u at ambient temperatures gave about 70 %> current e f f i c i e n c y a n d

1
a energy c o n s u m p t i o n o f about 1.3 k W h / k g C u at 47-93 A r n . S h a n t z a n d R e i c h [77] ran

2
l o c k e d l e a c h i n g - e l e c t r o w i n n i n g tests o n a copper rougher concentrate a n d o b t a i n e d 62 %
current e f f i c i e n c y a n d a energy c o n s u m p t i o n o f 0.7 k W h / k g C u at 70-80 A m " . C o p p e r 2
e l e c t r o w i n n i n g f r o m dilute barren copper c y a n i d e solutions w a s c a r r i e d out w i t h a h i g h
surface area cathode [22-25], but no details s u c h as copper d e p o s i t i o n current e f f i c i e n c y ,
c y a n i d e c o n s u m p t i o n a n d energy c o n s u m p t i o n are reported. D u P o n t [26] has patented a
process for the r e c o v e r y o f c y a n i d e and copper b y e l e c t r o w i n n i n g f r o m c y a n i d e s o l u t i o n s i n a
c e l l i n w h i c h the anolyte is separated f r o m the catholyte b y a m e m b r a n e to a v o i d the a n o d i c
oxidation o f cyanide. Acidification, i o n exchange or c a r b o n adsorption was used to
concentrate the c o p p e r c y a n i d e solutions a n d adjust the ratio o f c y a n i d e to c o p p e r to b e l o w
3.0 - 4.0. C o p p e r e l e c t r o w i n n i n g has been c o n d u c t e d at U B C u s i n g m e m b r a n e c e l l s w i t h the
effects o f temperature, c o m p o s i t i o n , current density b e i n g studied [28]. S o l v e n t e x t r a c t i o n
w a s u s e d to concentrate copper c y a n i d e . S o l v e n t e x t r a c t i o n is m o r e effective i n the e x t r a c t i o n
o f c o p p e r c y a n i d e f r o m dilute copper c y a n i d e solutions than the use o f a c i d i f i c a t i o n , i o n
exchange or c a r b o n adsorption. T h e U B C S X - E W process m a y have advantages o v e r the D u
P o n t process.
C o p p e r p l a t i n g f r o m c y a n i d e solutions has been used throughout the m e t a l f i n i s h i n g
industry since E l k i n g t o n d i s c o v e r e d this t e c h n o l o g y in 1840 [80]. U n d e r the proper
c o n d i t i o n s , the m e t a l d i s t r i b u t i o n o v e r i r r e g u l a r l y shaped articles is e x c e l l e n t because o f the
g o o d t h r o w i n g p o w e r . T y p i c a l copper c y a n i d e bath c o m p o s i t i o n s a n d c o n d i t i o n s are l i s t e d i n
T a b l e 2-2. C u r r e n t e f f i c i e n c y is a f u n c t i o n o f c o m p o s i t i o n , temperature a n d current density.

13
C o p p e r c y a n i d e s o l u t i o n w a s used to plate copper o n p o r o u s materials [121] or c a r b o n
fibres i n the presence o f s u p p o r t i n g electrolyte [125].
T a b l e 2-2 C o p p e r c y a n i d e bath c o m p o s i t i o n s and c o n d i t i o n s [82]
Bath Type Strike Rochelle H i g h Efficiency

C u (g/1) 11.0 15-30 34-89
F r e e c y a n i d e (g/1) 6.0 4-9 11 - 19
N a 2 C 0 or N a O H (g/1)
3 15(Na C0 ) 2 3 15-60 ( N a C 0 ) 2 3 22-27(Na0H)
Temperature ( C ) 41-60 55-70 60-80
Cathode Current ( A / m ) 2
1 0 0 - 320 160 - 650 1 0 0 - 1110
C a t h o d e current e f f i c i e n c y (%) 10-60 30-70 >99
2 . 2 . 2 T h e Effect of Parameters on C o p p e r Deposition
T h e c o p p e r current e f f i c i e n c y decreases w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to
copper [91, 92, 124]. W i t h i n c r e a s i n g ratio o f c y a n i d e to copper, the e q u i l i b r i u m p o t e n t i a l
decreases. B y L e C h a t e l i e r ' s p r i n c i p l e w e s h o u l d expect i n c r e a s i n g c y a n i d e to i n h i b i t the
d i s s o c i a t i o n o f copper c y a n i d e c o m p l e x e s and to retard the discharge reactions. H o w e v e r , it
has a m o r e important effect i n shifting the c o m p l e x d i s t r i b u t i o n t o w a r d s the less active
c o m p l e x state ( C u ( C N ) " -> 2 C u ( C N ) " C u ( C N ) " ) . Therefore

3
2
4
3
the copper discharge
p o t e n t i a l decreases r e s u l t i n g i n m o r e h y d r o g e n e v o l u t i o n . T h e ratio o f c y a n i d e to c o p p e r
c l o s e to 3 is o p t i m u m for the h i g h e f f i c i e n c y electrolyte.
T h e e q u i l i b r i u m potential for H 0 / H
2 2 (expressed as E ( H 7 H ) = -0.0591 p H V v s . S H E )
decreases w i t h i n c r e a s i n g p H , but p H has a r e l a t i v e l y s m a l l effect o n the r e d o x p o t e n t i a l for
C u V C u at a p H a b o v e 9. I n a l k a l i n e s o l u t i o n H 0 is d i s c h a r g e d o n the electrode a n d so the

2
current o f h y d r o g e n e v o l u t i o n at a f i x e d potential m a y not be dependent o n p H as e x p e c t e d
f r o m the change i n the e q u i l i b r i u m potential for H 0 / H . T h e copper current e f f i c i e n c y m a y

2 2
not s i g n i f i c a n t l y increase w i t h i n c r e a s i n g p H . H y d r o x i d e or carbonate salts have to be a d d e d
to get a h i g h e r p H . H o w e v e r , a d d i t i o n o f carbonate a n d h y d r o x i d e i o n s is also associated w i t h
a r e d u c t i o n i n the current for copper d e p o s i t i o n , w i t h the r e l a t i o n s h i p b e i n g a p p r o x i m a t e l y
linear [92, 124]. T h e s e effects are not o n l y due to the presence o f C 0 " a n d O H " i o n s , but 3
2
p r o b a b l y to the c o n c o m i t a n t increase i n the a l k a l i m e t a l i o n c o n c e n t r a t i o n a n d surface
adsorption.
14
The current e f f i c i e n c y decreases w i t h i n c r e a s i n g current density. O b v i o u s l y , at a
h i g h e r current density a n d a h i g h e r p o l a r i z a t i o n p o t e n t i a l [87, 88, 9 1 , 9 2 ] , the ratio o f c y a n i d e
to c o p p e r i n the s o l u t i o n near the cathode surface is h i g h e r due to a l i m i t e d d i f f u s i o n rate a n d
h y d r o g e n e v o l u t i o n increases faster than c o p p e r d e p o s i t i o n .
The c a t h o d i c current e f f i c i e n c y increases w i t h i n c r e a s i n g temperature. A t higher
temperatures, the c o p p e r - c y a n i d e d i s s o c i a t i o n constant is larger a n d the b a l a n c e shifts to the
f o r m a t i o n o f l o w l y c o o r d i n a t e d c o p p e r c o m p l e x e s ( C u ( C N ) " ) , w h i c h w i l l be d i s c u s s e d i n the
2
next chapter, and cuprous c o m p l e x e s diffuse faster to the cathode surface a n d are more
r e a d i l y r e d u c e d . H o w e v e r , w i t h i n c r e a s i n g temperature, the h y d r o l y t i c d e c o m p o s i t i o n o f
c y a n i d e increases [91].
A g i t a t i o n increases the c a t h o d i c current e f f i c i e n c y [92]. D u e to the r e d u c t i o n o f
c u p r o u s i o n s at the cathode, the ratio o f c o p p e r to c y a n i d e i n the cathode b o u n d a r y l a y e r
decreases r e s u l t i n g i n a l o w e r current e f f i c i e n c y . A g i t a t i o n accelerates the rate o f c u p r o u s i o n
m o v e m e n t to the cathode surface and c y a n i d e m o v e m e n t a w a y f r o m the cathode. T h e r e f o r e
the c o n c e n t r a t i o n o f cuprous ions near the cathode surface increases, r e s u l t i n g i n a h i g h e r
current e f f i c i e n c y .
I r o n a n d c h r o m i u m i n the c o p p e r - c y a n i d e s o l u t i o n decrease the current efficiency
[92]. B i s m u t h , z i n c , a n t i m o n y a n d other metals w i l l cause a r o u g h deposit at t i m e s [89].
The i n c o r p o r a t i o n o f thiocyanate and s p e c i f i c surface-active agents p e r m i t s the
d e p o s i t i o n o f bright, s m o o t h deposits [90-98, 101-104]. T h i o c y a n a t e also increases the
c a t h o d i c current e f f i c i e n c y [92, 9 4 - 9 6 , 9 8 ] . It is p o s s i b l e that the a d s o r p t i o n o f S C N " at the
c o p p e r cathode suppresses the discharge o f H +

(or H 0 ) a n d therefore increases the c o p p e r
2
c a t h o d i c current e f f i c i e n c y . S h i v i r i n et a l [99, 100] reported that the a d d i t i o n o f t h i o c y a n a t e
h a d little effect o n the overpotential o f h y d r o g e n e v o l u t i o n . It w a s reported that t h i o c y a n a t e
c o u l d be u s e d i n p l a c e o f c y a n i d e for copper p l a t i n g [105].
S o d i u m sulphite a n d b i s u l p h i t e have been r e c o m m e n d e d as a d d i t i o n s to copper
c y a n i d e baths to i m p r o v e the brightness o f the deposits [90].

15
2.2.3 T h e Kinetics and M e c h a n i s m of C o p p e r Deposition
T h e k i n e t i c s a n d m e c h a n i s m o f copper d e p o s i t i o n f r o m c o p p e r - c y a n i d e s o l u t i o n h a v e
not been w i d e l y studied. B l a n c [108] reported that the species d i s c h a r g e d c o u l d not be free
Cu +
a c c o r d i n g to his w o r k o n the effect o f alternating current. G l a s s t o n e [32] p r o p o s e d the
direction reduction o f copper from C u ( C N ) " . 2
C o s t a [110] studied 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 c o p p e r - c y a n i d e s o l u t i o n s ( 0 . 0 1 -
0.08 M C u C l a n d 0.06-0.93 M K C N ) and p r o p o s e d the f o l l o w i n g m e c h a n i s m :
Cu(CN) ~ 3
2
-> CuCN + 2C7V" (2-16)
CuCN +e^Cu + CN~ (2-17)
T h e transfer coefficient w a s 0.38 0.04 and the exchange current density was
p r o p o r t i o n a l to C u concentration. T h e c u r v e o f l o g I, as a f u n c t i o n o f l o g [ C N " ] e x h i b i t s a
+
c h a n g i n g slope for a free C N " c o n c e n t r a t i o n greater than 0.21 M . T h e v a r y i n g slope is
c o n s i d e r e d to be a result o f the v a r i a t i o n i n the p h y s i c a l surface o f the electrode rather than a
change i n the e l e c t r o c h e m i c a l process.
L o w e n h e i m [111] thought that the direct discharge o f C u ( C N ) " w a s m o r e p o s s i b l e4

3
than the two-step discharge m e c h a n i s m
0<C/V) 4
3
- - Cu+
+ 4CAT +
" >Cu (2-18)
R a u b a n d M u l l e r [112] thought that the reaction m e c h a n i s m is:
Cu(CN) - 3
2
-> Cu(CN) 2 + CAT - ^ ^ C u (2-19)
B e k a n d Z h u k o v [113-116] studied the d e p o s i t i o n o f copper f r o m a s o l u t i o n w i t h 0.1
M Cu +
a n d a C N : C u m o l e ratio o f 2.8-3.2 at p H 13 and thought that c o p p e r d e p o s i t i o n
+
results i n a s i g n i f i c a n t v a r i a t i o n i n the d i s t r i b u t i o n o f the c o p p e r - c y a n i d e species a n d a
s i g n i f i c a n t c o n c e n t r a t i o n p o l a r i z a t i o n . T h e y f o u n d that C u ( C N ) " w a s the d i s c h a r g e d species

2
a n d the charge transfer coefficient w a s 0.1 after c o r r e c t i n g for the c o n c e n t r a t i o n change. T h e y
p r o p o s e d the f o l l o w i n g reaction m e c h a n i s m :
Cu(CN) - 3
2
-> Cu{CN) 2 + CN~ at C N : C u ratio < 3 (2-20)
Cu(CN) - 4
3
-> Cu(CN) 2 + 2C7V" at C N : C u ratio > 4 (2-21)
16
Cu{CN) ~ 2 + e -> Cu + 2CN~ (2-22)
S i n i t s k i et a l . [118] reported that a distinct l i m i t i n g current c o u l d be o b t a i n e d i n dilute
c o p p e r c y a n i d e solutions at p H 4.95. T h e T a f e l slopes ranged f r o m 0.130-0.165 V decade" 1
a n d the transfer coefficient w a s 0.40 0.03.
C h u and F e d k i w [122] have used the v o l t a m m e t r i c a n d steady-state p o l a r i z a t i o n
response o f a c o p p e r - d i s k electrode to study the k i n e t i c s o f copper d e p o s i t i o n f r o m a c y a n i d e
bath u s i n g the s o l u t i o n : 0.1 M N a C 02 3 + 0.2 M C u C N + 0.6 M N a C N a n d p H 12. T h e m a j o r
species d i s c h a r g e d w a s c o n s i d e r e d to be C u ( C N ) " , a l t h o u g h C u ( C N ) " is the

3
2
4
3
predominant
c o m p l e x . T h e c y a n i d e released d u r i n g d e p o s i t i o n shifts the d i s t r i b u t i o n o f the c o m p l e x e s at
the surface to the c o o r d i n a t e l y saturated state and results i n a decreased c o p p e r d e p o s i t i o n
rate since the discharge o f C u ( C N ) " is c o n s i d e r a b l y s l o w e r than that o f C u ( C N ) " .

4
3
3
2
H a t h e r l e y et a l . [124] measured the p o l a r i z a t i o n curves o f c o p p e r d e p o s i t i o n f r o m
c y a n i d e s o l u t i o n . It w a s c o n c l u d e d that C u ( C N ) " w a s first d i s c h a r g e d a n d

2 subsequently
C u ( C N ) " . C u ( C N ) " does not seem to take part i n the d e p o s i t i o n process. A t a c e r t a i n

3
2
4
3
l i m i t i n g current density these processes break d o w n and there is a loss o f cathode current
efficiency.
S t e p o n a v i c i u s et a l . [127] studied the m e c h a n i s m o f c o p p e r d e p o s i t i o n u s i n g l i n e a r
potential sweep, linear current scan and single galvanostatic p u l s e m e t h o d s a n d f o u n d that the
p r e c e d i n g r e a c t i o n for copper d e p o s i t i o n is the d i s s o c i a t i o n o f C u ( C N ) " into C u ( C N ) " a n d

3
2
2
C N " and then C u ( C N ) " is d i s c h a r g e d o n the cathode.

2
H s u a n d T r a n [129] studied the r e d u c t i o n o f copper c y a n i d e u s i n g a rotating d i s c a n d
f o u n d that the e l e c t r o c h e m i c a l active species is C u ( C N ) " . 2
2.3 Electrochemical Oxidation of Cyanide
G r e a t attention has been p a i d to the study o f the e l e c t r o c h e m i c a l o x i d a t i o n o f C N " i n
order to m i n i m i z e the destruction o f c y a n i d e i n m e t a l e l e c t r o w i n n i n g f r o m c y a n i d e s o l u t i o n
a n d m a x i m i z e the e f f i c i e n c y o f the destruction o f c y a n i d e i n effluent streams to meet
e n v i r o n m e n t a l requirements [21-24, 85, 130 - 168]. T h e products a n d m e c h a n i s m o f c y a n i d e

17
o x i d a t i o n d e p e n d m a i n l y o n p H , potential a n d concentration. F r o m the f o l l o w i n g redox
reactions, h y d r o c y a n i c a c i d i s m o r e d i f f i c u l t to o x i d i z e a n d is m u c h less electro-active [138].
2HCN = (CN) 2 + 2H+

+2e E = 0.373 V v s . S H E (2-23)
2CN~ = (CAT) +2e 2 E = - 0.176 V v s . S H E (2-24)
2.3.1 C y a n i d e Oxidation in Alkaline Solution
U n d e r a l k a l i n e c o n d i t i o n s , the r e a c t i o n for the o x i d a t i o n o f c y a n i d e i s [ 1 3 1 , 132, 149,
150, 1 5 8 ] :
CN~ + 20H~ = CNO' +H 0 2 + 2e E = - 0.97 V v s . S H E (2-25)
C y a n a t e c a n be further o x i d i z e d at h i g h e r potentials to C 0 " a n d N 3

2
2 [ 1 3 1 , 137, 1 5 8 ] ,
but its current e f f i c i e n c y has not been reported.
2CNO~ + %OH~ = 2C0 ~ 2

+ N + 4H 0
2 2 + 6e E = - 0.95 V v s . S H E (2-26)
A r i k a d o et a l . [143] reported that the T a f e l slope for c y a n i d e o x i d a t i o n o n a graphite
electrode w a s about 0.12 V decade" a n d the r e a c t i o n orders were u n i t y a n d zero f o r C N " a n d

1
O H " r e s p e c t i v e l y . C y a n i d e i s not o x i d i z e d b y a t o m i c o x y g e n f o r m e d b y w a y o f o x y g e n
evolution. T h e f o l l o w i n g mechanism was proposed:
OH~ + CN~ "2e

) HOCN + Q / r
> CNO~ + H 0 2 (2-27)
T h e rate o f c y a n i d e o x i d a t i o n increases w i t h i n c r e a s i n g c y a n i d e c o n c e n t r a t i o n a n d i s
independent o f O H " c o n c e n t r a t i o n (> 0.01 M ) . T h e discharge o f c y a n i d e i o n determines the
o v e r a l l r e a c t i o n rate. T h e apparent n u m b e r o f electrons p a r t i c i p a t i n g i n the r e a c t i o n decreases
f r o m 2 to 1 w i t h decreasing O H " concentration (1 to 10" M ) [143]. 4
T h e current e f f i c i e n c y o f c y a n i d e o x i d a t i o n depends o n the anode m a t e r i a l s , current
density a n d c o n c e n t r a t i o n [156].
2.3.2 C y a n i d e Oxidation in W e a k l y Acidic, or Alkaline or Neutral Solutions
In neutral a n d w e a k l y a l k a l i n e solutions ( p H 7.0 - 11.7), c y a n o g e n is the m a i n c y a n i d e
o x i d a t i o n p r o d u c t a c c o r d i n g to R e a c t i o n 2 - 2 4 [138, 143, 149, 150, 1 6 3 ] . T h i s c o n d i t i o n i s
referred to as h y d r o x i d e - s t a r v e d o x i d a t i o n o f c y a n i d e . C y a n o g e n c a n react subsequently w i t h
h y d r o x i d e i n s o l u t i o n to g i v e cyanate a n d c y a n i d e :
18
(CJV) + 20H~ = CNO~ + CN~ + H 0

2 2 (2-28)
T h e c y a n i d e r a d i c a l c a n also p o l y m e r i z e to f o r m p a r a c y a n o g e n ( C N ) . n
Azulmin, (HCN) n is f o r m e d due to the p o l y m e r i z a t i o n o f aqueous h y d r o c y a n i c a c i d
[136, 149,156, 157]. H i n e et a l . [156] reported that a z u l m i n f o r m a t i o n is c l o s e l y related to the
ratio o f CNT to O H " .
In neutral or s l i g h t l y a l k a l i n e solutions ( p H 7.0 - 8.6) [157] or i n w e a k l y a l k a l i n e
carbonate-buffer solutions ( p H 9.3) [149], the cyanate ion may continuously undergo
h y d r o l y s i s to p r o d u c e a m m o n i u m and carbonate i o n s ( C N O + 2 H 0 > N H -

2 4
+
+ C0 ").
3
2
In w e a k l y a c i d i c s o l u t i o n ( p H 5.2-6.8), (CN) 2 is h y d r o l y z e d to f o r m oxamide,
(CONH ) 2 2 a n d oxalate, C 0 " and N H

2 4
2
4
+
:
(CN) 2 +2H 0 2 = (CONH ) 2 2 (2-29)
(CN) 2 +4H 0 2 = C0- + 2 M

2
2
4
+
(2-30)
2.3.3 T h e A n o d i c Oxidation of C o p p e r C y a n i d e
There are some reports o n the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e , but m o s t o f t h e m
are about the products a n d p h e n o m e n a o f the e l e c t r o l y t i c o x i d a t i o n a n d are i n c o m p l e t e [ 1 3 5 ,
139-142, 144, 145, 147, 149-152, 156, 157, 160]. Sperry a n d C a l d w e l l [135], D a r t et a l .
[139], a n d E a s t o n [141] thought that copper d e p o s i t i o n releases free c y a n i d e at the cathode
a n d then the free c y a n i d e is o x i d i z e d to cyanate at the anode. D r o g e n a n d P a s e k [140] a n d
D a u b a r a s [151] p r o p o s e d a direct o x i d a t i o n route (copper c y a n i d e c o m p l e x e s are d i r e c t l y
o x i d i z e d to cyanate a n d cuprous i o n s . T a n et a l . [160] b e l i e v e d that c o p p e r cyanide
c o m p l e x e s are first o x i d i z e d to cyanate releasing cuprous ions, w h i c h are o x i d i z e d to c o p p e r
h y d r o x i d e a c c o r d i n g to their e l e c t r o l y t i c products.
B y e r l e y et a l . [142] o b s e r v e d that cuprous i o n s sufficient to c o m p l e x 10 - 3 0 % o f total
c y a n i d e e x h i b i t e d the best catalytic effect o n c y a n i d e o x i d a t i o n at p H 10 - 11. H o f s e t h a n d
C h a p m a n [168] reported that the c y a n i d e c o n c e n t r a t i o n c a n be r e d u c e d f r o m 100 to 1 p p m i n
a p o r o u s f l o w - t h r o u g h reticulated vitreous c a r b o n c a t a l y z e d b y c o p p e r i o n s . Y o s h i m u r a a n d
K a t a g i r i et a l . [144, 145, 147, 149, 150] measured the steady-state p o l a r i z a t i o n c u r v e s at a

19
p l a t i n u m anode i n c y a n i d e solutions c o n t a i n i n g a v e r y s m a l l amount o f copper ( C N : C u > 5)
a n d 0.5 M K S 0 2 4 as supporting electrolyte, and f o u n d that the T a f e l slope w a s about 0.158 V
decade -1
i n a l o w potential r e g i o n , suggesting that a s i m p l e o n e - e l e c t r o n r e a c t i o n was
o c c u r r i n g at the electrode. T h e current at a constant potential w a s p r o p o r t i o n a l to the total
c u p r o u s i o n c o n c e n t r a t i o n but it w a s almost independent o f the total c y a n i d e c o n c e n t r a t i o n . It
w a s a s s u m e d that a l l o f the copper exists i n the f o r m o f C u ( C N ) " w i t h o u t c h e c k i n g the 4

3
d i s t r i b u t i o n o f copper species. I n fact, i n the ranges o f c y a n i d e a n d c o p p e r c o n c e n t r a t i o n
studied b y these authors, a significant amount o f copper exists i n the f o r m o f C u ( C N ) " a n d 3

2
their a s s u m p t i o n is not appropriate. T h e c a l c u l a t e d r e a c t i o n order w i t h respect to C u ( C N ) " 4

3
(actually C u ( I ) ) w a s 0.9. C u ( C N ) 4
2 _
w a s detected b y E S R spectroscopy. It w a s thought that
C u ( C N ) ~ is o x i d i z e d to C u ( C N )
4
3
4
2 _
, w h i c h is the rate-determining step. T h e following
m e c h a n i s m w a s p r o p o s e d [150]:
Cu(CN) ' 3
4 -> Cu(CN) ~ 4
2
+e (2-31)
2Cu(CN) - 2
<=> Cu (CN) ;
2
2
+ 2CN~ (2-32)
Cu (CN) -
2
2
2Cu(CN) 2 + (CN) 2 (2-33)
Cu(CN) 2 + 2CN~ -> Cu(CN)/- (2-34)
(CN) 2 + 20H~ -> C A T + OCN~ + H0 2 (2-35)
H o w e v e r , no k i n e t i c data are g i v e n for a l k a l i n e copper c y a n i d e s o l u t i o n s except for a
p o l a r i z a t i o n c u r v e i n 1 M K O H s o l u t i o n . T h e r e a c t i o n products o f the a n o d i c o x i d a t i o n o f
c y a n i d e at 0.6 a n d 1.2 V v s . S C E were determined. I n a l k a l i n e s o l u t i o n s ( p H 11.8-14), the
r e a c t i o n c a n be expressed b y E q u a t i o n 2-25 and cyanate i o n w a s not o x i d i z e d further.
H i n e et a l . [156] studied the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e o n a P b 0 2 -coated
anode a n d f o u n d that o n l y copper e x h i b i t e d a c a t a l y t i c effect o n c y a n i d e o x i d a t i o n . T h e T a f e l
slope for the o x i d a t i o n o f the s o l u t i o n c o n t a i n i n g 1 M N a C N a n d 0.3 M c o p p e r w a s 0.070 -
0.110 V d e c a d e -1
i n the current density range o f 50 - 1 0 0 0 A m . T h e current e f f i c i e n c y o f
- 2
c y a n i d e o x i d a t i o n decreased w i t h decreasing total c y a n i d e c o n c e n t r a t i o n at constant c o p p e r
c o n c e n t r a t i o n . It w a s thought that the f o l l o w i n g r e a c t i o n w a s o c c u r r i n g :
Cu(CN) - + 2 0 H " = Cu(OH)

3
2
2 + 3CN" + e (2-36)
H w a n g et a l . [157] studied the e l e c t r o l y t i c o x i d a t i o n o f c o p p e r c y a n i d e s o l u t i o n w i t h
C N : C u m o l e ratios o f 2.8 to 20 a n d at different p H ' s u s i n g a p l a t i n u m anode. I n s t r o n g l y

20
a l k a l i n e s o l u t i o n ( p H > 12), the c o p p e r - c y a n i d e c o m p l e x i s o x i d i z e d d i r e c t l y to cyanate a n d
copper o x i d e . T h e f o l l o w i n g r e a c t i o n sequence w a s p r o p o s e d :
Cu(CN) ;- ( iy
+ 2nOH~ = Of + nCNO~ + nH 0 + 2ne 2 (2-37)
2 C V + 20H~ = Cu 0 + H 0 2 2 (2-38)
Cu 0 + 20H'
2 = CuO + 2H 0 2 + 2e (2-39)
H o w e v e r , the potential w a s c o n t r o l l e d at 0.71 a n d 1.2 V v s . S C E a n d so the o x y g e n
e v o l u t i o n m a y have affected the c o u l o m e t r i c measurement. A l s o , i n their e x p e r i m e n t , the
cathode a n d the anode were not separated. Therefore copper d e p o s i t i o n m a y h a v e affected
s i g n i f i c a n t l y the m o l e ratio o f c y a n i d e to copper d u r i n g the course o f the e x p e r i m e n t . I n
neutral o r w e a k l y a l k a l i n e or a c i d i c solutions, the c o m p l e x does not u n d e r g o the direct
o x i d a t i o n , but dissociates to free c y a n i d e due to copper d e p o s i t i o n a n d t h e n free c y a n i d e i s
o x i d i z e d o n the anode. A p p a r e n t l y the above o x i d a t i o n procedure i s not reasonable. I f the
anode a n d the cathode are separated, the a n o d i c o x i d a t i o n w i l l not happen. E v e n i f the anode
a n d the cathode are not separated, at l o w C N : C u m o l e ratios (e.g. 3 ) , the free cyanide
released f r o m the cathode w i l l i m m e d i a t e l y b o n d to the l o w l y c o o r d i n a t e d c o p p e r c y a n i d e
c o m p l e x e s ( C u ( C N ) " a n d C u ( C N ) " ) . F u r t h e r m o r e i f o n l y free c y a n i d e i s o x i d i z e d , at C N : C u

3
2
2
< 3, the c o n c e n t r a t i o n o f free c y a n i d e i s so l o w (less than 1/1000 o f the total c y a n i d e ) that the
c y a n i d e o x i d a t i o n c a n be neglected.
L a t e r H w a n g et a l . [166] adopted the direct o x i d a t i o n m e c h a n i s m reported b y their
g r o u p [157] a n d the c a t a l y t i c m e c h a n i s m b y K a t a g i r i et a l . [147, 150] a n d reported that the
T a f e l slope i n c r e a s e d f r o m 0.040 V decadent C N : C u = 3 to 0.120 V d e c a d e 1

at C N : C u > 10.
T h e a n o d i c o x i d a t i o n o f copper c y a n i d e undergoes b o t h direct o x i d a t i o n a n d c a t a l y t i c
o x i d a t i o n . A t C N : C u < 3, there is o n l y the direct o x i d a t i o n a n d at C N : C u > 10, there i s o n l y
the c a t a l y t i c o x i d a t i o n .
T h e a n o d i c o x i d a t i o n o f copper c y a n i d e resulted i n the f o r m a t i o n o f c o p p e r o x i d e ,
w h i c h c a t a l y z e d the o x i d a t i o n o f free c y a n i d e [159, 163, 165, 1 6 7 ] .
F r o m the above d i s c u s s i o n , there are i n c o m p l e t e a n d c o n f l i c t i n g results o n the a n o d i c
o x i d a t i o n o f c o p p e r c y a n i d e i n a l k a l i n e s o l u t i o n a n d the i n f o r m a t i o n f r o m the literature i s
insufficient f o r the present research, especially with respect to the design o f an
e l e c t r o c h e m i c a l process for C u - C N e l e c t r o w i n n i n g .
21
2.4 The Electrochemical Oxidation of Thiocyanate
T h i o c y a n i c a c i d exists i n t w o i s o m e r i c forms, H - S -C = N or H - N = C = S i n
equilibrium with each other and thiocyanate ions exist in two tautomeric forms,
" S - C ss TV (I) and S = C = N' (II) [169]. T h e r e d o x r e a c t i o n i s :
2SCN- = (SCN) 2 +2e E = 0.77 V v s . S H E (2-40)
T h e structure o f t h i o c y a n o g e n i s N = C - S - S - C = N . (SCN) 2 undergoes r a p i d
h y d r o l y s i s i n water to g i v e S 0 " , H C N , and H .

4
2 +
T h e e l e c t r o c h e m i c a l o x i d a t i o n o f thiocyanate has been studied for a l o n g t i m e b o t h i n
aqueous a n d non-aqueous m e d i a [130, 131, 170-204]. T h e products o f the o x i d a t i o n o f
thiocyanate i n aqueous s o l u t i o n are sulphate and either c y a n i d e or cyanate or, further,
a m m o n i u m a n d carbonate or n i t r o g e n d e p e n d i n g o n the p H o f the s o l u t i o n a n d the a n o d i c
potential.
T h e o x i d a t i o n o f thiocyanate is i r r e v e r s i b l e . I n a c i d solutions, the r e a c t i o n c a n be
expressed m a i n l y b y the f o l l o w i n g equation [174, 177-180, 185, 192-195, 198, 199, 2 0 3 ] :
SCN~ + 4H 02 = SOl' + HCN + 7H +

+ 6e E = 0.515 V v s . S H E (2-41)
Other products are also f o r m e d , e.g. p a r a t h i c y a n o g e n ( S C N ) , [177-179], a p a s s i v a t i o n f i l m

X
C N S , a n d ( S C N ) " [192]. T h e i n i t i a l step o f the a n o d i c o x i d a t i o n m a y be the r e m o v a l o f a n

6 4 4 3
e l e c t r o n f r o m one thiocyanate i o n [185, 192]. H o w e v e r , L o u c k a et a l . [203] reported that the
first step is the d e c o m p o s i t i o n into sulfur and c y a n i d e a n d then the sulfur is o x i d i z e d to
sulphate a n d the o x i d a t i o n o f thiocyanate o c c u r s at potentials h i g h e r than 0.7 V v s . S H E .
I n basic solutions, the o x i d a t i o n reaction c a n be expressed as: [133, 170]:
SCN' + WH' = SO]' + C N

~ +4H 0 2 + 6e E = - 0.61 V v s . S H E (2-42)
Gauguin [174-176] gave the following expressions for the potential of SCN"
o x i d a t i o n : E = 0.57 - 0.058 l o g [ S C N ] f r o m p H 0 to 7 a n d E = 1.17 + (0.058/6) log
( [ H ] / [ S C N " ] ) f r o m p H 9 to p H 14. T h e potential for C N " o x i d a t i o n is E = 0.10 - 0.058 l o g

+ 8 6
[ C N ] f r o m p H 0 to 13 and E = 0.88 + (0.058/2) l o g ( [ H ] / [ C N " ] ) above p H 13. + 2

22
T h e e l e c t r o l y t i c c o n v e r s i o n o f thiocyanate to c y a n i d e has been studied as a m e a n s o f
regenerating c y a n i d e a n d m i n i m i z i n g the c o n s u m p t i o n o f c y a n i d e i n h y d r o m e t a l l u r g y [23, 87,
130, 170-172, 189-191, 193-195]. T h e c o n v e r s i o n o f thiocyanate to c y a n i d e is never
c o m p l e t e and depends o n c y a n i d e a n d thiocyanate concentrations, p H , p o t e n t i a l , a n d anode
materials. I n 1911, C l e n n e l l [78, 170] reported that the p r o d u c t i o n o f c y a n i d e rose to a
m a x i m u m a n d then ceased. I f the e l e c t r o l y s i s w a s c o n t i n u e d , the c y a n i d e p r o d u c e d f r o m
thiocyanate o x i d a t i o n g r a d u a l l y d i m i n i s h e d and f i n a l l y disappeared.
C r o o k et a l . [171] investigated the e l e c t r o l y s i s o f thiocyanate o n graphite anodes a n d
gave results at different current densities. W i t h o u t the a d d i t i o n o f K O H , no C N " w a s detected.
T h i s w a s p r o b a b l y because H C N w a s f o r m e d a n d v o l a t i l i z e d at l o w p H . T h e increase i n C N "
w a s p r o p o r t i o n a l to the decrease i n S C N " and K O H .
K e r n [172] f o u n d that thiocyanate i n c y a n i d e solutions r e d u c e d the c o n s u m p t i o n o f
c y a n i d e i n the e l e c t r o l y s i s and w a s converted into c y a n i d e to some extent.
Varentsov and Belyakova [189-191] studied the electrochemical oxidation of
thiocyanate a n d c y a n i d e at a r u t h e n i u m o x i d e or c o b a l t o x i d e coated t i t a n i u m anode a n d
graphite. T h e y f o u n d that the relative rates o f thiocyanate a n d c y a n i d e o x i d a t i o n d e p e n d e d o n
their concentrations a n d at h i g h e r concentrations o f thiocyanate, m o r e thiocyanate was
oxidized and less c y a n i d e . T h e graphite anode f a v o r e d the oxidation o f thiocyanate.
H o w e v e r , the graphite broke d o w n l e a d i n g to c o n t a m i n a t i o n o f the s o l u t i o n .
O r o c o n Inc. reported that thiocyanate f r o m barren l e a c h solutions c a n be o x i d i z e d to
C N ' a n d sulphate o n graphite fibre [23]. N o current e f f i c i e n c y o f the a n o d i c o x i d a t i o n o f
thiocyanate w a s g i v e n .
B y e r l e y and E n n s [193-195] studied the e l e c t r o c h e m i c a l regeneration o f c y a n i d e f r o m
thiocyanate at graphite anodes a n d f o u n d that the r e c o v e r y o f C N " f r o m thiocyanate i n c r e a s e d
w i t h decreasing p H . A t l o w p H thiocyanate is e l e c t r o o x i d i z e d to p r o d u c e c y a n i d e i o n w h i c h
is i m m e d i a t e l y protonated b y H . T h e a c i d i c anode b o u n d a r y l a y e r functions to

+
preserve
c y a n i d e f r o m r a p i d e l e c t r o o x i d a t i o n at the anode b y c o n v e r t i n g the c y a n i d e i o n into H C N , the
m u c h m o r e d i f f i c u l t l y o x i d i z e d neutral protonated f o r m . T h e p H s h o u l d be kept b e l o w 4 to
r e a l i z e the better c o n v e r s i o n o f thiocyanate into c y a n i d e .

23
2.5 The Electrochemical Oxidation of Sulphite
T h e a n o d i c o x i d a t i o n o f sulphite has been studied o v e r a w i d e range o f p H . T h e
a n o d i c b e h a v i o u r changes w i t h p H due to the change i n the s p e c i a t i o n o f sulphite. It i s
important to k n o w the d i s t r i b u t i o n o f the sulphite species w i t h p H i n order to understand the
anodic oxidation o f S 0 3
2
\
I n s o l u t i o n , sulphite exists i n the f o r m o f S 0 2 (aq), H S 0 ~ a n d S 0

3 3
2
' w i t h the
f o l l o w i n g e q u i l i b r i a b e t w e e n these species [205]:
S0 (aq)
2 +H0 2 = HSO; +H +
K, = 1.6 x 10" (25 C ) 2
(2-43)
HSO; +H 0 2 = SO ' 2
+H +
K = 1.0 x 10" (25 C )
2
7
(2-44)
S0 2 (aq), H S 0 ' a n d S 0 3 3
2
' species are p r e d i c t e d to p r e d o m i n a t e o v e r the p H ranges < 1.8, 1.8
- 7 and > 7, r e s p e c t i v e l y . A t p H > 12, the d o m i n a n t species i n s o l u t i o n i s S 0 ' . 3

2
T h e r e d o x r e a c t i o n o f sulphite -sulphate o n graphite c a n be expressed b y the f o l l o w i n g
equations:
SO '+2e
2
+ 4H = +
H S0 +H 0
2 3 2 E = 0.158 V v s . S H E (2-45)
SOl~ +2e + H 0 2 = SO ' 2

+ 20H~ E = -0.936 V v s . S H E (2-46)
S02
2
' +2e = 2S0 ' 2
E = 0.037 V v s . S H E (2-47)
S0 3
2
' cannot be r e d u c e d c a t h o d i c a l l y , w h i l e H S 0 ' ( p H 6-3) m a y be r e d u c e d to
3
dithionite S 0 2 4
2
' [206]. T h e sulphite-sulphate r e d o x systems are i r r e v e r s i b l e .
T h e e l e c t r o c h e m i c a l o x i d a t i o n o f sulphur d i o x i d e o r sulphite has been s t u d i e d a n d
t r i e d as a n anode depolariser to reduce the o v e r a l l c e l l v o l t a g e i n the p r o d u c t i o n o f h y d r o g e n
a n d i n c o p p e r e l e c t r o w i n n i n g i n a c i d sulphate m e d i u m [ 2 0 7 - 2 5 2 ] . H o w e v e r , there are o n l y a
f e w reports o n the e l e c t r o c h e m i c a l o x i d a t i o n o f sulphite i n a l k a l i n e s o l u t i o n s [243, 2 5 3 - 2 5 5 ] .
Sulphate a n d dithionate are f o r m e d d u r i n g the o x i d a t i o n o f sulphite i n a l k a l i n e a n d
neutral solutions. T h e amount o f dithionate p r o d u c e d at the a n o d i c surface w a s s h o w n to
depend o n operating c o n d i t i o n s , n a m e l y the anode m a t e r i a l , its preparation, current density,
s o l u t i o n p H , a n d the presence o f additives i n the electrolyte. F r i e s s n e r et a l . [207,208] s t u d i e d
the o x i d a t i o n o f sulphite earlier a n d c o n c l u d e d that the f o r m a t i o n o f dithionate takes p l a c e at
h i g h e r potentials than that o f sulphate. E s s i n [209] reported that the a d d i t i o n o f N H F 4
increases the a n o d i c potential a n d this benefits the f o r m a t i o n o f dithionate. T h e a n n e a l i n g o f
p l a t i n u m leads to the f o r m a t i o n o f p l a t i n u m o x i d e w h i c h favours the f o r m a t i o n o f dithionate.

24
G l a s s t o n e et a l . [210, 211] investigated the effect o f e l e c t r o l y s i s c o n d i t i o n s o n the y i e l d o f
dithionate a n d f o u n d that dithionate y i e l d s o f up to 30 % c a n be o b t a i n e d o n n i c k e l or g o l d
electrodes, whereas the y i e l d d i d not e x c e e d 3 % for graphite electrodes. P r e l i m i n a r y a n o d i c
p o l a r i z a t i o n increases dithionate y i e l d f r o m 22 to 3 3 % . I n the current density range f r o m 10
to 30 A / m , the dithionate f o r m a t i o n rate does not change, but it decreases n o t i c e a b l y at

2
b e l o w 10 A / m . D i t h i o n a t e does not f o r m at current densities above 3 0 0 A / m . I n c r e a s i n g

2 2
temperature i n the range o f 18 - 60 C h a d a little negative effect o n dithionate f o r m a t i o n .
T h e sulphite c o n c e n t r a t i o n has no effect o n the dithionate y i e l d . T h e o p t i m a l p H v a l u e for the
f o r m a t i o n o f dithionate is f r o m 7 to 9.
R o z e n t a l et a l . [216] reported that the o x i d a t i o n o f sulphite i n a c i d m e d i a takes p l a c e
at m u c h s m a l l e r p o s i t i v e potentials (about 0.7 V v s . S H E ) than the e v o l u t i o n o f o x y g e n a n d
c o n c l u d e d that the o x i d a t i o n takes place v i a the surface o x i d e s o f p l a t i n u m .
L e z h n e v a et a l . [219] investigated the rate o f the o x i d a t i o n o f s u l p h u r d i o x i d e o n g o l d
a n d p l a t i n u m - g o l d a l l o y s and f o u n d that the presence o f water, cations, a n d a n i o n s near the
m e t a l surface sharply changes the properties o f the surface o x y g e n c o m p o u n d s . Therefore,
data o n the properties o f surface o x y g e n c o m p o u n d s obtained b y e l e c t r o c h e m i c a l m e t h o d s
cannot a l w a y s be used i n s t u d y i n g the m e c h a n i s m o f sulphite o x i d a t i o n .
S h l y g i n et a l . [220, 221] studied the o x i d a t i o n o f sulphur d i o x i d e a n d sulphite at a
p l a t i n u m electrode a n d c o n c l u d e d that the a n o d i c o x i d a t i o n o f s u l p h u r d i o x i d e i n a c i d a n d
neutral solutions takes place at l o w potentials ( 0.65-1.2 V S H E ) b y a r e v e r s i b l e e l e c t r o n -
radical mechanism:
S0 + AH 0<^ H SO + 2H 0
2 2 2 A }
+
+ 2e (2-48)
T h e appearance o f adsorbed o x y g e n c a n c o m p l e t e l y stop the o x i d a t i o n b y the e l e c t r o n - r a d i c a l
m e c h a n i s m at above 1.2 V v s . S H E . T h e e l e c t r o c h e m i c a l o x i d a t i o n o f S 0 " a n d H S 0 " b e g i n s

3
2
3
at 1.2 V v s . S H E a n d is i r r e v e r s i b l e . T h e ions cannot be o x i d i z e d b y the e l e c t r o n - r a d i c a l
m e c h a n i s m . T h e i r o x i d a t i o n m e c h a n i s m consists i n the a d d i t i o n o f a n O H r a d i c a l at r e l a t i v e l y
h i g h a n o d i c potentials a n d the m e c h a n i s m m a y be expressed b y the f o l l o w i n g reactions:
2H 0^> 2H 0 + 2e
2 2
+
(2-49)
25
2H 0 + 2H 0 -> 20H + 2H 0
2
+
2 3 (2-50)
S0 ~ + 20H
3 -> SO, ' + H 0
2
2 (2-51)
T a r a s e v i c h et a l . [239-240, 243] studied the o x i d a t i o n o f sulphite o n p l a t i n u m a n d
c a r b o n materials at 2 2 C . T h e a n c h o r i n g o f the a c i d i c o x i d e s o n the surface o f the c a r b o n
materials decreases the r e a c t i o n rate. T h e r e a c t i o n order o f the e l e c t r o c h e m i c a l o x i d a t i o n
depends o n the sulphite concentration, b e i n g i n a l l cases less than 1. T h i s b e h a v i o u r m a y be
due to a d s o r p t i o n effects. A t l o w concentrations o f sulphite, the coverage is l o w a n d the
r e a c t i o n rate is p r o p o r t i o n a l to the concentration o f sulphite i n the b u l k s o l u t i o n . A t h i g h
concentrations, the current is p r o p o r t i o n a l to the c o n c e n t r a t i o n to a f r a c t i o n a l p o w e r . I n
a l k a l i n e solutions, sulphite seems to be adsorbed to a lesser extent than i n a c i d s o l u t i o n a n d
the r e a c t i o n is first-order up to 0.1 M . T h e dependence o f the r e a c t i o n rate o n p H p l a y s a n
essential r o l e . T h e dE/dpH v a l u e for b o t h p y r o g r a p h i t e a n d activated c a r b o n is c l o s e to -40
m V i n the range o f p H 0 - 7 and b e c o m e s zero i n the r e g i o n o f h i g h e r p H v a l u e s . T h e
3E/31ogi v a l u e i n the case o f pyrographite amounts to ca. 150 m v decade"' for p H < 7, a n d
increases u p to c a . 2 8 0 m v decade" for p H > 7. T h e shape o f the p o l a r i z a t i o n c u r v e s o n the

1
activated c a r b o n is w e a k l y dependent o n the type o f a n i o n .
I n the r e g i o n o f intermediate p H values, the curves e x h i b i t t w o or e v e n three T a f e l
slopes. T h e first slope i n the a c i d i c and neutral p H r e g i o n is 35 to 50 m V decade" , whereas i n 1
a l k a l i n e s o l u t i o n s it is 60 - 70 m v decade" . T h e e l e c t r o c h e m i c a l o x i d a t i o n o f sulphite to
1
s u l p h u r i c a c i d proceeds m o s t l i k e l y v i a the m e c h a n i s m i n v o l v i n g the direct loss o f a n
e l e c t r o n f r o m the o x i d i z e d species. T h e dependence o f the r e a c t i o n rate o n p H for c a r b o n
materials is due to a v a r i a t i o n i n the c o m p o s i t i o n o f the species w h i c h are subject to o x i d a t i o n
(at p H < 1.8 H S 0 , H S 0 \ at p H 1.8-7, H S 0 " , S 0 " a n d at p H > 7, S 0 " ) . T h e a d s o r b e d

2 3 3 3 3
2
3
2
species that are subject to o x i d a t i o n undergo deprotonation ( p H < 7):
H S0 -> HS0
2 3 3 ADS + H + (2-52)
+
HSO; -so - + H~ 3
2
ads
(2-53)
T h e s l o w step m a y i n v o l v e the transfer o f the first a n d the s e c o n d e l e c t r o n f r o m the
a d s o r b e d species:
26
HSO; ads -> HSOf +e (2-54)
S0 ~+
3
2
H 0-+H SQ -+e
2 2 4 (2-55)
H u n g e r et a l . [253, 254] studied the e l e c t r o c h e m i c a l o x i d a t i o n o f sulphite (0.012 M -
0.09 M ) o n a graphite electrode at p H 9 a n d 25 C a n d o b s e r v e d that the current g r a d u a l l y
i n c r e a s e d at about 0.2 V v s . S C E w i t h i n c r e a s i n g electrode p o t e n t i a l . A p o o r l y d e f i n e d
current density plateau w a s o b s e r v e d i n the range 0.5-0.7 V v s . S C E . T h e onset o f o x y g e n
started at 1.5 V v s . S C E . B a s e d o n the K o u t e c k y - L e v i c h equation, they c a l c u l a t e d the k i n e t i c
current at different sulphite concentrations a n d f i n a l l y obtained r e a c t i o n rate constants,
r e a c t i o n orders o f 0.68 a n d 1.34, a n d charge transfer coefficients o f 0.058 and 0.048
r e s p e c t i v e l y for natural graphite and graphite i m p r e g n a t e d w i t h p h e n o l . It s h o u l d be n o t e d
that the K o u t e c k y - L e v i c h equation is v a l i d o n l y for the first order r e a c t i o n a n d therefore their
results are not c o n v i n c i n g .
B r e v e t t a n d J o h n s o n [255] studied the a n o d i c o x i d a t i o n o f sulphite (0.02-0.18 M ) o n
pure a n d d o p e d P b 0 2 f i l m electrodes at 25 a n d 65 C i n a N a H C 0 / N a C 0 3 2 3 buffer ( p H 10).
T h e y o b t a i n e d a r e a c t i o n order o f -0.2 u s i n g the same m e t h o d as H u n g e r et a l . [253, 2 5 4 ] .
T h e reason for their o b t a i n i n g negative r e a c t i o n order m a y be that the current w a s c o r r e c t e d
b y subtracting the b a c k g r o u n d i n the absence o f sulphite w h i c h w a s m u c h s m a l l e r than that i n
the presence o f sulphite a n d the K o u t e c k y - L e v i c h equation w a s not v a l i d for their c a l c u l a t i o n
o f the k i n e t i c current.
S t a n k o v i c et a l . [256] reported that the c o n c e n t r a t i o n o f sulphite i o n s a n d temperature
greatly i n f l u e n c e the r e a c t i o n rate. T h e n u m b e r o f transferred electrons for the s l o w step w a s
n e a r l y one.
2.6 The Electrochemical Oxidation of Methanol
T h e c a t a l y t i c e l e c t r o c h e m i c a l o x i d a t i o n o f m e t h a n o l has b e e n w i d e l y s t u d i e d for
about 70 years [257-280]. T h e r e a c t i o n i n a l k a l i n e solutions c a n be w r i t t e n as:
CH OH+WH-
3 = CO ' 2
+6H 0
2 + 6e E = - 0.895 V v s . S H E (2-56)
27
T h e best c a t a l y t i c anode materials are p l a t i n u m metals a n d their a l l o y s [258, 2 5 9 , 2 7 0 - 2 7 5 ] .
T h e o x i d a t i o n o f m e t h a n o l is m a i n l y used i n fuel c e l l s . M e t h a n o l has been s t u d i e d for use i n
m e t a l e l e c t r o w i n n i n g for d e p o l a r i z a t i o n [275-280]. A m o n g s o l u b l e fuels, m e t h a n o l is the
m o s t p r a c t i c a l to use i n a n e l e c t r o w i n n i n g c e l l . V e r e e c k e n et a l . [275] u s e d m e t h a n o l for z i n c
e l e c t r o w i n n i n g a n d o b s e r v e d its o x i d a t i o n at a l o w p o t e n t i a l o n a p l a t i n u m - a c t i v a t e d graphite
anode. T h e electrode potential, h o w e v e r , started to drift u p w a r d s after some t i m e , a n d
e v e n t u a l l y the r e a c t i o n shifted to o x y g e n e v o l u t i o n . V i n i n g et a l . [276, 277] p r o p o s e d the use
o f a p r e c i o u s m e t a l coated t i t a n i u m anode to extend the c a t a l y t i c a c t i v i t y o f the electrode. T h e
anode materials for a n a c i d i c electrolyte are m a i n l y p l a t i n u m - b a s e d a n d a Ru0 -based

2
c a t a l y t i c f i l m o n t i t a n i u m . There is no report o n the a p p l i c a t i o n o f m e t h a n o l e l e c t r o c h e m i c a l
o x i d a t i o n i n a l k a l i n e solutions i n e l e c t r o m e t a l l u r g y .
2.7 The Electrochemical Oxidation of Ammonia
I n aqueous solutions the o x i d a t i o n o f a m m o n i a to n i t r o g e n is o n l y p o s s i b l e i n a l k a l i n e
solutions a n d is dependent o n the electrode materials and their pretreatment [281]. T h e r e f o r e
the study o f a m m o n i a o x i d a t i o n w a s c o n d u c t e d i n concentrated h y d r o x i d e s o l u t i o n s [282-
2 9 1 ] . T h e r e a c t i o n c a n be expressed as:
2NH 3 + 60H~ = 6H 0 +N +6e 2 2 E = -0.74 V v s . S H E (2-57)
T h e best catalysts are p l a t i n u m metals a n d their a l l o y s a n d these materials were
studied for fuel c e l l a p p l i c a t i o n [281-289]. T h e a n o d i c o x i d a t i o n o f a m m o n i a w a s also
conducted on a T i / T i 0 / R u 0 2 2 electrode [291]. D u e to the s l o w k i n e t i c s for ammonia
o x i d a t i o n , c h l o r i d e i o n w a s used as a catalyst to o x i d i z e a m m o n i a [292, 2 9 3 ] .
2.8 Summary
C o p p e r a n d c y a n i d e c a n f o r m three stable cuprous c o m p l e x e s ( d i c y a n i d e , t r i c y a n i d e
a n d tetracyanide) a n d their d i s t r i b u t i o n depends o n the concentrations o f c o p p e r a n d c y a n i d e
a n d the m o l e ratio o f c y a n i d e to copper. C u p r i c c y a n i d e c o m p l e x e s are not stable a n d r a p i d l y
d e c o m p o s e a n d c y a n i d e is o x i d i z e d . C o p p e r has a c a t a l y t i c effect o n the a n o d i c o x i d a t i o n o f

28
c y a n i d e . I n a l k a l i n e solutions, c y a n i d e is m o r e r e a d i l y o x i d i z e d than thiocyanate a n d the
relative o x i d a t i o n rates are dependent o n the ratio o f c y a n i d e to thiocyanate concentration,
current density, temperature and anode materials. H o w e v e r , the situation c o u l d be different i n
a copper c y a n i d e s o l u t i o n . T h e a n o d i c o x i d a t i o n o f sulphite a n d c y a n i d e b e g i n s at an
a p p r o x i m a t e l y potential. H o w e v e r , there are no data w h i c h afford a direct c o m p a r i s o n . F o r
m e t h a n o l , a n anode w i t h a p l a t i n u m - b a s e d f i l m has to be used to decrease the o v e r p o t e n t i a l
for m e t h a n o l o x i d a t i o n . T h e anode w i l l p r o b a b l y lose its c a t a l y t i c effect w i t h t i m e . A m m o n i a
c a n be r e a d i l y o x i d i z e d i n strongly a l k a l i n e s o l u t i o n at a p l a t i n u m electrode. H o w e v e r , s u c h a
h i g h h y d r o x i d e c o n c e n t r a t i o n is not suitable for the c o p p e r - c y a n i d e system.
T h e copper d e p o s i t i o n f r o m c y a n i d e s o l u t i o n has b e e n w i d e l y reported. H o w e v e r ,
m o s t o f these reports focus o n copper p l a t i n g . T h e copper e l e c t r o w i n n i n g f r o m c y a n i d e
s o l u t i o n has not been studied e x t e n s i v e l y a n d the operating c o n d i t i o n s s h o u l d be o p t i m i z e d .
H o w e v e r , some c o n d i t i o n s used for p l a t i n g c a n be a p p l i e d to i m p r o v e the e f f i c i e n c y o f
copper e l e c t r o w i n n i n g . I n order to o b t a i n a h i g h current e f f i c i e n c y o f c o p p e r d e p o s i t i o n , the
temperature s h o u l d be above 4 0 C , the copper c o n c e n t r a t i o n s h o u l d be a b o v e 50 g L " a n d 1
the C N : C u m o l e ratio s h o u l d be a r o u n d at 3. T h e a d d i t i o n o f thiocyanate c a n i m p r o v e the
c o p p e r c a t h o d i c current e f f i c i e n c y .
T h e r e is v e r y little i n f o r m a t i o n o n copper e l e c t r o d e p o s i t i o n f r o m d i l u t e c y a n i d e
solutions. I n order to get a reasonable current e f f i c i e n c y o f c o p p e r d e p o s i t i o n , p o r o u s h i g h
surface area electrodes have to be used. T h e graphite fibre has a large surface area a n d has
been used to r e m o v e m e t a l ions f r o m waste effluent e f f i c i e n t l y . It is p o s s i b l e to use graphite
fibre felt to deposit c o p p e r f r o m dilute c y a n i d e e f f i c i e n t l y . T o prevent c y a n i d e o x i d a t i o n , a
m e m b r a n e c e l l s h o u l d be used.
F r o m the above d i s c u s s i o n s , the i n f o r m a t i o n a v a i l a b l e i n the literature is i n s u f f i c i e n t
for this project and the further study must be done to d e v e l o p a successful process.
T h e a n o d i c a n d cathodic b e h a v i o u r o f copper c y a n i d e is dependent o n the d i s t r i b u t i o n
o f the concentrations o f copper c y a n i d e species. T h e first step t o w a r d u n d e r s t a n d i n g the
a n o d i c a n d c a t h o d i c b e h a v i o u r o f copper c y a n i d e is to k n o w the d i s t r i b u t i o n o f c o p p e r
c y a n i d e species at different concentrations, p H ' s , and temperatures. T h e d i s t r i b u t i o n o f
copper cyanide species can be calculated using reliable complex constants. Copper
e l e c t r o w i n n i n g u s i n g a n alternative anode r e a c t i o n i n a n u n d i v i d e d c e l l s h o u l d be c o n d u c t e d
29
i n a m i n i - c e l l to select the best s a c r i f i c i a l species. F i n a l l y u s i n g the best s a c r i f i c i a l species,
c o p p e r e l e c t r o w i n n i n g c a n be i m p r o v e d b y c h a n g i n g the temperature a n d the c o m p o s i t i o n s o f
the electrolyte. Therefore the a n o d i c o x i d a t i o n o f the s a c r i f i c i a l species, c o p p e r c y a n i d e a n d
their m i x t u r e s h o u l d be studied to (a) understand h o w the s a c r i f i c i a l species l i m i t s the a n o d i c
o x i d a t i o n o f c y a n i d e and (b) p r o v i d e some fundamental i n f o r m a t i o n to further i m p r o v e the
c o p p e r e l e c t r o w i n n i n g process.
A l t h o u g h the graphite fibre felt c a n be u s e d e f f e c t i v e l y to deposit c o p p e r f r o m v e r y
dilute s o l u t i o n , c o p p e r is m o r e d i f f i c u l t to deposit f r o m c y a n i d e s o l u t i o n . A f e a s i b i l i t y test
s h o u l d first be done a n d then further research c a n be c o n d u c t e d to investigate the direct
e l e c t r o w i n n i n g o n a graphite felt cathode w i t h reference to c o p p e r c o n c e n t r a t i o n , m o l e ratio
o f c y a n i d e to c o p p e r and f l o w rate.
30
3. THERMODYNAMICS OF COPPER CYANIDE
3.1 Distribution of Copper Cyanide Species
C o p p e r c y a n i d e species establish a n e q u i l i b r i u m s p e c i a t i o n ( R e a c t i o n s 2-1 to 2-6).
T h e c o r r e s p o n d i n g e q u i l i b r i u m constants selected for 25 C are l i s t e d i n T a b l e 3-1 [38, 4 4 ,
49]. I n some cases, w e have to k n o w the d i s t r i b u t i o n o f copper c y a n i d e species a n d the
e q u i l i b r i u m potentials for C u ( I ) / C u to understand copper d e p o s i t i o n a n d c y a n i d e o x i d a t i o n at
h i g h e r temperatures. H o w e v e r , so far the p u b l i s h e d data are inadequate for s u c h a study.
Therefore a d d i t i o n a l data must be generated b y c a l c u l a t i o n . T h e A H v a l u e s for R e a c t i o n s 2-1
a n d 2-3 to 2-6 are 128, -121.8, -46.4, -46.9 a n d 43.6 k J m o i ' r e s p e c t i v e l y , the absolute v a l u e s1
o f w h i c h are larger than 40 k J / m o l e . A s s u m i n g that A H is a p p r o x i m a t e l y constant i n the
range o f 25 - 60 C , w e c a n calculate the e q u i l i b r i u m constant u s i n g the equation: d l n K / d T =
AH/RT 2
[294]. S o m e c a l c u l a t e d constants are listed i n T a b l e 3-1.
T a b l e 3-1 E q u i l i b r i u m constants for copper c y a n i d e s y s t e m [38, 44, 4 9 , 57]
Temperature(C) K a K s p P2 K ,3
2
K 3 j 4
25 6.17xl0- 1 0
l.OxlO' 2 0
l.OxlO 2 4
2.00xl0 5
31.63
40 1.43X10" 09
8.44x10' 20
9.47x10 22
8.14xl0 4
12.77
50 2.40x10" 09
5.33xl0" 19
2.22x10 2 2
4.69xl0 4
7.317
60 3.91xl0' 9
2.27xl0' 1 8
5.61xl0 2 1
2.79xl0 4
4.333
T h e c o n c e n t r a t i o n distributions o f these species are dependent o n p H , temperature a n d
the total concentrations o f copper a n d c y a n i d e . T h e m a s s balances o f the c o p p e r a n d c y a n i d e
species are d e s c r i b e d b y the f o l l o w i n g equations:
[Cu(I)] Total = [Cu ] + [Cu(CN) -] + [Cu(CN) -]

+
2 3
2
+ [Cu(CN) -] 4
3
(3-1)
[CN] T o f t l l = [ C N - ]+ [HCN] + 2[Cu(CN) -] + 3[Cu(CN) -] + 4[Cu(CN) -]

2 3
2
4
3
(3-2)
31
B y c o n s i d e r i n g the e q u i l i b r i a (Reactions 2-1 to 2-6) a n d s o l v i n g the above equations for the
mass balance o f these species, the d i s t r i b u t i o n o f copper c y a n i d e species has been c a l c u l a t e d .
S i n c e the exact v a l u e s o f the e q u i l i b r i u m constants used to calculate the concentration
d i s t r i b u t i o n are not s u f f i c i e n t l y accurate a n d the parameters to calculate the a c t i v i t y
coefficients o f a l l the species are not a v a i l a b l e , the a c t i v i t y coefficients h a v e not been
c o n s i d e r e d i n this study. Therefore the c a l c u l a t e d values s h o u l d be interpreted as i n d i c a t i n g
trends rather than absolute values. H o w e v e r , the v a l i d i t y o f the p r e d i c t i o n is c o n f i r m e d b y the
e x p e r i m e n t a l potential measurements reported i n the next section. F i g u r e s 3-1 a n d 3-2 s h o w
the cyanocuprate d i s t r i b u t i o n and the redox potential for C u ( I ) / C u v s . m o l e ratio o f total
c y a n i d e to copper at p H 9 a n d 12. There is the f o l l o w i n g r e l a t i o n b e t w e e n the p o t e n t i a l a n d
the a c t i v i t y o f cuprous i o n s :
E(Cu(I) / Cu) = E(Cu(I) / Cu) + Y " l n ( a C u + ) (3-3)
w h e r e E ( C u ( I ) / C u ) is the e q u i l i b r i u m potential for the C u ( I ) / C u c o u p l e , E ( C u ( I ) / C u ) the
standard potential ( 0 . 5 2 1 , 0.520, 0.5195, a n d 0.519 V v s . S H E r e s p e c t i v e l y for 2 5 , 4 0 , 50 a n d
60 C , w h i c h were c a l c u l a t e d u s i n g the data f r o m the literature [295]). T h e other s y m b o l s
have their c o m m o n m e a n i n g s . Therefore the potential reveals the a c t i v i t y (or concentration)
o f cuprous i o n s . T h e d i s t r i b u t i o n o f the copper c y a n i d e species depends m a i n l y o n the m o l e
ratio o f total c y a n i d e to copper a n d also o n the concentration o f total c o p p e r a n d the p H . A t
C N : C u m o l e ratio < 3, the d i s t r i b u t i o n o f the cyanocuprate species depends o n the C N : C u
m o l e ratio, a n d less o n the concentration o f copper at p H > 9. T h e d o m i n a n t species are
copper t r i c y a n i d e and d i c y a n i d e , and copper tetracyanide c a n be neglected. A t a m o l e ratio o f
c y a n i d e to c o p p e r = 3, copper t r i c y a n i d e dominates and m o s t o f copper exists i n the f o r m o f
t r i c y a n i d e . A t a m o l e ratio o f c y a n i d e to copper > 3, the d i s t r i b u t i o n o f the c o p p e r - c y a n i d e
species depends o n the C N : C u m o l e ratio, the total copper c o n c e n t r a t i o n a n d p H . F o r
example, A t [Cu(I)] Xotal = 0.001 M , copper t r i c y a n i d e dominates a n d s l o w l y decreases w i t h
i n c r e a s i n g C N : C u m o l e ratio a n d p H . A t [ C u ( I ) ] Xota , = I M a n d C N : C u m o l e ratio = 3-4,
t r i c y a n i d e dominates a n d decreases greatly w i t h i n c r e a s i n g C N : C u m o l e ratio a n d s l o w l y

32
w i t h i n c r e a s i n g p H . W i t h further increase i n the m o l e ratio o f c y a n i d e to c o p p e r , tetracyanide
is d o m i n a n t .
0.0010 T
0.0
0.0009 - j. -0.1
0.0008 -. -0.2 >

2 0.0007 -- -0.3 LU
c X
o 0.0006 .= -0.4 V)
re 0.0005 --
c
a> 0.0004 -0.6 o
o
c
o 0.0003 - -0.7 |
o
0.0002 -, -0.8 Si
LU
0.0001 -I 0.9
0.0000 - i -1.0
14 12 14
Mole ratio of cyanide to copper Mole ratio of cyanide to copper
(a)[Cu(I)] T o t a l = 0.001M,pH9 (b) [ C u ( I ) ] Total = 0.01M,pH9
F i g u r e 3-1 C o p p e r c y a n i d e species d i s t r i b u t i o n a n d E ( C u ( I ) / C u ) v s . m o l e ratio o f c y a n i d e to

c o p p e r for v a r i o u s s o l u t i o n s at 25 C a n d p H 9
33
0.10 -, r 0.0
2 4 6 8 10 12 14 2 4 6 8 10 12 14
Mole ratio of cyanide to copper Mole ratio of cyanide to C o p p e r
(c) [ C u ( I ) ] Total = 0.1M,pH12 (d) [ C u ( I ) ] T o t a ] = l M , p H 12
F i g u r e 3-2 C o p p e r - c y a n i d e species d i s t r i b u t i o n and E ( C u ( I ) / C u ) v s . m o l e ratio o f c y a n i d e to

c o p p e r for v a r i o u s solutions at 25 C and p H 12.
F i g u r e 3-3 s h o w s the d i s t r i b u t i o n o f copper c y a n i d e species v s . the m o l e ratio o f
c y a n i d e to copper at 60 C . C o m p a r e d to F i g u r e 3-2b and d (25 C ) , at C N : C u m o l e ratio < 3,
the d i s t r i b u t i o n o f c o p p e r c y a n i d e a l m o s t does not change. A t a C N : C u m o l e ratio > 3, the
distribution shifts to lowly coordinated complexes to some extent with increasing
temperature due to the decrease i n the stability constants o f copper c y a n i d e c o m p l e x e s .

34
0.010 , ,- 0.0 1.0 -, r 0.0
Mole ratio of cyanide to copper Mole ratio of cyanide to copper
(a) [Cu(IVJ = 0.01 M a n d p H 12 (b) [Cu(I)] = 1 M a n d p H 12
F i g u r e 3-3 C o p p e r c y a n i d e species d i s t r i b u t i o n and E ( C u ( I ) / C u ) v s . m o l e ratio o f c y a n i d e to

copper for v a r i o u s solutions at 60 C and p H 12
T h e r e d o x potential for C u ( I ) / C u decreases w i t h i n c r e a s i n g ratio o f total c y a n i d e to
c o p p e r a n d to some extent w i t h i n c r e a s i n g p H . F r o m F i g u r e 3-4 a, w i t h i n c r e a s i n g C N : C u
m o l e ratio, the r e d o x potential for C u 7 C u decreases greatly at a C N : C u m o l e ratio < 4 a n d
decreases r e l a t i v e l y s l o w l y at a C N : C u m o l e ratio > 4. A t a C N : C u m o l e ratio < about 3, the
h i g h e r the total c o p p e r concentration, the h i g h e r the r e d o x potential for C u ( I ) / C u . A t a C N :
C u ratio = 3, the r e d o x potential is almost independent o f the total c o p p e r c o n c e n t r a t i o n . A t a
C N : C u m o l e ratio > about 3, the h i g h e r the total C u +

c o n c e n t r a t i o n , the l o w e r the r e d o x
p o t e n t i a l . F i g u r e 3-4 b s h o w s the r e d o x potential for C u ( I ) / C u v s . p H at [ C u ( I ) ] Tota , = 0.1 M
a n d different C N : C u m o l e ratios. T h e effect o f p H o n the r e d o x p o t e n t i a l depends o n the
C N : C u m o l e ratio and p H range.
I n c r e a s i n g p H is s i m i l a r to i n c r e a s i n g free c y a n i d e concentration, because at a h i g h e r
p H , less h y d r o g e n i o n s compete for C N ' w i t h copper to f o r m H C N .

35
F i g u r e 3-4 (a) E ( C u ( I ) / C u ) vs. m o l e ratio o f c y a n i d e to copper at 25 C , p H 12 a n d different

copper c o n c e n t r a t i o n and (b) E ( C u ( I ) / C u ) v s . p H at 25 C , 0.1 M C u and different m o l e ratios
o f c y a n i d e to copper
I n the direct e l e c t r o w i n n i n g process for copper d e p l e t i o n f r o m s o l u t i o n s , the c y a n i d e
c o n c e n t r a t i o n is m a i n t a i n e d at a constant v a l u e a n d the copper c o n c e n t r a t i o n changes due to
c o p p e r c a t h o d i c d e p o s i t i o n . F o r e x a m p l e , copper c o n c e n t r a t i o n decreases f r o m 2 g L " (or 1 g

1
L " ) to 1 g L " (or 0.5 g L " ) due to copper d e p o s i t i o n o n the graphite felt electrode a n d the
1 1 1
c y a n i d e c o n c e n t r a t i o n is kept at 2.445 g L " (or 1.228 g L " ) . Therefore it is necessary to k n o w

1 1
the d i s t r i b u t i o n o f copper c y a n i d e species at a constant c y a n i d e c o n c e n t r a t i o n a n d different
c o p p e r concentrations. F i g u r e s 3-5 and 6 s h o w the c o n c e n t r a t i o n d i s t r i b u t i o n o f c o p p e r
c y a n i d e species at [CN"] = 0.09442 M (2.455 g L " ) a n d 0.04721 M (1.228 g L " ) r e s p e c t i v e l y .

1 1
F r o m F i g u r e 3-5, w i t h decreasing total copper c o n c e n t r a t i o n f r o m 2 to 1.2 g L " , the1
concentrations o f d i c y a n i d e a n d t r i c y a n i d e decrease. H o w e v e r , the tetracyanide c o n c e n t r a t i o n
increases. T h e c a l c u l a t e d r e d o x potential for C u ( I ) / C u decreases q u i c k l y . W i t h further
decrease i n the total copper concentration, a l l copper c y a n i d e species decrease a n d the r e d o x
p o t e n t i a l for C u ( I ) / C u decreases. A s i m i l a r trend is s h o w n i n F i g u r e 3-6.
T h e stability o f the c o p p e r - c y a n i d e s o l u t i o n depends not o n l y o n the ratio o f t o t a l
c y a n i d e to copper, but also o n the concentrations o f total copper, p H a n d temperature. F o r
e x a m p l e , the c r i t i c a l c y a n i d e concentrations for stable solutions c o n t a i n i n g I M C u ( I ) are 2.8,
2.7, 2.6 a n d 2.5 M for 2 5 , 4 0 , 50 and 60 C r e s p e c t i v e l y , and i f the c y a n i d e concentrations are

36
l o w e r than the above values, the p r o d u c t o f the e q u i l i b r i u m [ C N ] a n d [ C u ] w i l l be larger

+
than the K s p o f C u C N a n d C u C N w o u l d precipitate. T h e p r o d u c t o f [ C u ] a n d [ C N ' ] for

+
0.0021 M c y a n i d e a n d 0.001 M copper s o l u t i o n is less than the K s p o f C u C N . Therefore the
s o l u t i o n is stable. T h e l o w e r the total c y a n i d e concentration, the l o w e r the c r i t i c a l m o l e ratio
o f c y a n i d e to copper.
Total copper concentration / g L" Total copper concentration / g l -
(a) 25 C ib) 40 C
F i g u r e 3-5 C o p p e r concentrations i n the f o r m o f copper c o m p l e x e s a n d the e q u i l i b r i u m

p o t e n t i a l v s . total c o p p e r concentration at [CN"] = 2.455 g L " a n d [ O H ' ] = 0.01 M .
1
(a) 25 C (b) 40 C
F i g u r e 3-6 C o p p e r concentrations i n the f o r m o f copper c o m p l e x e s a n d the e q u i l i b r i u m

p o t e n t i a l v s . total copper c o n c e n t r a t i o n at [CN"] = 1.227 g L " a n d [OH"] = 0.01 M .
1
37
3.2 The Equilibrium Potential Measurement of Copper Cyanide
T h e c u p r o u s e q u i l i b r i u m potential c a n be expressed b y E q u a t i o n 3-3. T h e a c t i v i t y o f
the c u p r o u s i o n depends o n the d i s t r i b u t i o n o f the c y a n i d e c o p p e r species. Therefore
E ( C u ( I ) / C u ) is a f u n c t i o n o f the c o p p e r c y a n i d e a s s o c i a t i o n constants at constant temperature,
p H , a n d the c o p p e r a n d c y a n i d e concentrations. W e c a n evaluate the v a l i d i t y o f the c a l c u l a t e d
v a l u e u s i n g t h e r m o d y n a m i c constants b y c o m p a r i n g the c a l c u l a t e d e q u i l i b r i u m potentials to
the measured v a l u e s for different c o m p o s i t i o n s . It is v e r y i m p o r t a n t to conduct the
m e a s u r e m e n t o f the e q u i l i b r i u m potentials. T h e r e are m a n y v a r i e d reports o n the p o t e n t i a l
measurement for the C u ( I ) / C u c o u p l e i n c o p p e r c y a n i d e s o l u t i o n [31, 3 2 , 4 2 , 4 6 , 47] w i t h
different m e a s u r i n g methods a n d c o n d i t i o n s . I n this thesis, a f e w measurements o f c o p p e r
c y a n i d e e q u i l i b r i u m potentials w e r e m a d e to c o n f i r m the c a l c u l a t e d v a l u e s i n S e c t i o n 3.1.
3.2.1 Experimental
E q u i p m e n t : T h e c o p p e r c y a n i d e solutions w e r e p l a c e d i n a 1 0 0 - m L airtight w a t e r - j a c k e t e d
e l e c t r o l y t i c c e l l w h o s e temperature w a s m a i n t a i n e d at constant ( 0.2 C ) u s i n g a water b a t h
c i r c u l a t o r . T h e solutions w e r e rendered free o f o x y g e n b y b u b b l i n g w i t h h i g h l y pure a r g o n
gas w h i c h passed a F I S H E R O X I C L E A R gas p u r i f i e r to reduce o x y g e n to b e l o w 5 p p b . T h e
c o p p e r electrode w a s a 2 - m m diameter 9 9 . 9 9 9 % pure c o p p e r w i r e w h i c h w a s first p o l i s h e d
b y s i l i c o n carbide sand, then w a s h e d w i t h acetone a n d f i n a l l y put i n 0.01 M pure s o d i u m
c y a n i d e s o l u t i o n s at p H 10 a w a i t i n g for use. A S o l a r t r o n 1286 e l e c t r o c h e m i c a l interface w a s
u s e d to measure the potential b e t w e e n the c o p p e r w i r e a n d the saturated c a l o m e l reference
electrode a n d the p o t e n t i a l data o v e r t i m e w e r e r e c o r d e d b y a c o m p u t e r . T h e e x p e r i m e n t set-
u p is s h o w n i n F i g u r e 3-7. T h e l i q u i d j u n c t i o n p o t e n t i a l , estimated b y the H e n d e r s o n e q u a t i o n
( A p p e n d i x 7), is less than 2 m V and n e g l i g i b l e .
Reagents: 99.99%) s o d i u m c y a n i d e , 9 9 . 9 9 % c o p p e r c y a n i d e , standard 1 M NaOH
s o l u t i o n a n d ultrapure d e i o n i z e d water w e r e u s e d to prepare the r e q u i r e d c o p p e r c y a n i d e
s o l u t i o n s c o n t a i n i n g 0.01 M N a O H .
38
Computer
Oxyclear Solatron
gas purifier voltmeter
F i g u r e 3-7 E x p e r i m e n t a l set-up for the e q u i l i b r i u m p o t e n t i a l measurement
3.2.2 Results and Discussion
A n y o x y g e n i n the s o l u t i o n has a s i g n i f i c a n t effect o n the p o t e n t i a l measurement.
F i g u r e 3-8 s h o w s the electrode potential decreasing w i t h c o n t i n u e d A r gas b u b b l i n g a n d
s t a b i l i z i n g after 3 hours. I n general, 3 hours were r e q u i r e d to s t a b i l i z e the p o t e n t i a l a n d so the
f i n a l v a l u e w a s t a k e n after 3 hours. F i g u r e s 3-9 a n d 3-10 s h o w b o t h the c a l c u l a t e d a n d
m e a s u r e d potentials v s . the m o l e ratio o f copper to c y a n i d e at 2 5 , 4 0 , 50 a n d 60 C for the
solutions c o n t a i n i n g 0.1 M and 0 . 0 I M copper. A t a C N : C u m o l e ratio < 4, the measured
potentials are a little h i g h e r than the c a l c u l a t e d v a l u e s and the differences b e t w e e n the
m e a s u r e d a n d c a l c u l a t e d potentials are i n the range o f 5-20 m V for 0.1 M a n d 1 0 - 2 5 m v for
0.01 M C u . T h i s difference m i g h t be caused b y a trace amount o f o x y g e n a n d the s o l u t i o n
i o n i c strength or change i n the concentration e q u i l i b r i u m constant. T h e e x c h a n g e current for
the l o w e r c o n c e n t r a t i o n is l o w e r than that for the h i g h e r c o n c e n t r a t i o n a n d m a y be e a s i l y
affected b y s o m e factors s u c h as o x y g e n and h y d r o g e n ions. Therefore the difference for the
s o l u t i o n c o n t a i n i n g 0.01 M C u is larger than that for the s o l u t i o n c o n t a i n i n g 0.1 M C u . A t a
C N : C u m o l e ratio > 4, the difference b e t w e e n the c a l c u l a t e d a n d m e a s u r e d potentials b e c a m e
larger. T h e reason c o u l d be that at 0.01 M O H , the h y d r o g e n p o t e n t i a l is about 0.70 V v s .

-
S H E a n d m u c h h i g h e r than the potential for C u ( I ) / C u . Therefore the m e a s u r e d potential

39
m i g h t be a m i x e d p o t e n t i a l . S o u s i n g the m e a s u r e d potentials to evaluate or c a l c u l a t e the
e q u i l i b r i u m constants m a y be inappropriate.
T h e e q u i l i b r i u m constants obtained b y R o t h b a u m [42] a n d H a n c o c k [46] u s i n g the
potentials measured at C N : C u m o l e ratio > 4 are less r e l i a b l e i n spite o f the high
o v e r p o t e n t i a l o f h y d r o g e n o n copper. T h e potential trend w i t h C N : C u m o l e ratio, total c o p p e r
c o n c e n t r a t i o n a n d temperature is the same as that p r e d i c t e d b y c a l c u l a t i o n . F o r e x a m p l e , at a
C N : C u m o l e ratio < 3, the potential decreases w i t h i n c r e a s i n g temperature a n d increases w i t h
i n c r e a s i n g c o p p e r concentration. A t a C N : C u m o l e ratio = 3-4, the p o t e n t i a l is less dependent
o n the temperature and concentration. A t a C N : C u m o l e ratio > 4, the p o t e n t i a l increases w i t h
i n c r e a s i n g temperature a n d decreases w i t h i n c r e a s i n g copper c o n c e n t r a t i o n .
T h e above dependence o f the e q u i l i b r i u m potential for C u ( I ) / C u o n the temperature
a n d C N : C u m o l e ratio is s i m i l a r to those measured i n 0.5 to 0.4 M C u s o l u t i o n s w i t h C N : C u

+
m o l e ratio = 2.4 - 4 0 at 20 a n d 80 C [42] and i n 0.15 M C u s o l u t i o n s w i t h C N : C u m o l e

+
ratio = 2.9 - 4.03 i n the temperature range 10 to 50 C [47]. F r o m the a b o v e statements, it
w o u l d appear that the use o f the c i t e d e q u i l i b r i u m constants to calculate the d i s t r i b u t i o n o f
copper c y a n i d e species w i l l not result i n a significant error.
F i g u r e 3-8 E l e c t r o d e p o t e n t i a l v s . t i m e at 25 C , C N : C u m o l e ratio = 3 a n d [ C u ] tota] = 0.1 M

40
Mole ratio of cyanide to copper
F i g u r e 3-9 E l e c t r o d e potential v s . the m o l e ratio o f c y a n i d e to c o p p e r at 2 5 , 4 0 , 50 a n d 60

C, [Cu] total = 0.1 M and [OH"] = 0.01 M .
F i g u r e 3-10 E l e c t r o d e potential v s . the m o l e ratio o f c y a n i d e to copper at 2 5 , 4 0 , 50 a n d 60

C, [Cu] total = 0.01 M a n d [OH"] = 0.01 M .
41
3.3 Potential-pH Diagrams for Copper Cyanide
In S e c t i o n 3 . 1 , the d i s t r i b u t i o n o f c o p p e r c y a n i d e species has b e e n discussed.
H o w e v e r , since the s t a b i l i t y o f the c o p p e r c y a n i d e species i s related to the p o t e n t i a l a n d p H ,
p o t e n t i a l - p H d i a g r a m s are r e q u i r e d to discuss the s t a b i l i t y o f the c o p p e r c y a n i d e species.
P o t e n t i a l - p H d i a g r a m s s h o w w h i c h species are stable at a f i x e d species c o n c e n t r a t i o n ,
p o t e n t i a l a n d p H . B e c a u s e the s t a b i l i t y o f copper c y a n i d e changes w i t h c o n c e n t r a t i o n , the
p o t e n t i a l - p H d i a g r a m s for the different species concentrations s h o u l d be u s e d . T h e free
energy data p r o v i d e d b y B a r d et a l . [296] are thought to be the m o s t r e l i a b l e a n d therefore the
free energy data f o r c o p p e r a n d c y a n i d e are c i t e d f r o m this source. H o w e v e r , the data f o r
c o p p e r d i c y a n i d e are questionable because its free energy w a s c a l c u l a t e d f r o m the s t a b i l i t y
constant ((3 ) reported b y K a p p e n s t e i n a n d H u g e l [48] w h i c h i s o n l y 1 0

2
1 6 7
and m u c h smaller
t h a n the f o r m a t i o n constant ( K ^ ' X I O ) o f C u C N . T h i s v a l u e w a s d i s c u s s e d i n C h a p t e r 2 a n d

2 0
c o n s i d e r e d to be u n r e l i a b l e . A c c o r d i n g to the free energy data o f d i c y a n i d e a n d t r i c y a n i d e
reported b y B a r d et a l . [296], K 2 3 i s 1 0 ' , m u c h larger than 1 0

11 7 5 3
the v a l u e w h i c h i s
c o n s i d e r e d to be m o s t r e l i a b l e . Therefore i n this study, the free energy data f o r d i c y a n i d e ,
t r i c y a n i d e a n d tetracyanide have b e e n c a l c u l a t e d f r o m the free energy data f o r C u , C N " a n d +
e q u i l i b r i u m constants ( P = 1 0 , K = 1 0
2
24
3
5 3
a n d K = 1 0 ) o f the c o p p e r c y a n i d e c o m p l e x e s .
4
1 5
T h e free energy data f o r a l l species are listed i n T a b l e 3-2.
T a b l e 3-2 G i b b s free energy data f o r copper a n d c y a n i d e species ( J moi" ) at 25 C [38, 4 4 , 1
49,284]
Cu Cu+ Cu^+ Cu 0 2 CuO Cu(OH) 2 HCu0 - 2
0 50,300 65,700 -148,100 -134,000 -359,500 -258,900

Cu02 " 2
H 0
2 H+ H 2
02
CN" HCN
-183900 -237178 0 0 0 166,000 113,423
CNO- HCNO (CN)2
CuCN Cu(CN) - 2
Cu(CN) ^- 3 Cu(CN)4^"
-98700 -12,100 296,300 102,126 245,291 381,035 538,471
O n the basis o f the change i n G i b b s free energy, C u O i s m o r e stable t h a n C u ( O H ) . 2
However, C u ( O H ) 2 m a y exist o r c o e x i s t w i t h C u O . Therefore b o t h C u O a n d C u ( O H ) 2 are
c o n s i d e r e d i n p o t e n t i a l - p H diagrams. F i g u r e 3-11 s h o w s the p o t e n t i a l - p H d i a g r a m f o r the
C N - H 0 s y s t e m a s s u m i n g that C N " , C N O " , H C N , H C N O a n d ( C N )

2 2 are stable, a l t h o u g h a l l o f
t h e m are not stable. I n the h i g h potential range, C N " a n d H C N are not stable a n d are o x i d i z e d
42
i n accordance with thermodynamics. H o w e v e r , H C N and C N " are metastable and the
potentials for the o x i d a t i o n o f H C N a n d C N " are m u c h h i g h e r (1.0-1.2 V ) than those s h o w n i n
F i g u r e 3 - 1 1 . Therefore C N " a n d H C N are c o n s i d e r e d to be stable i n the Cu-CN-H 0 2
p o t e n t i a l - p H d i a g r a m . F i g u r e s 3-12 a n d 13 s h o w the C u - C N - H 0 p o t e n t i a l - p H d i a g r a m s at
2
the a c t i v i t i e s o f a l l o f the solute species = 1, 10" , 10" a n d 10" a s s u m i n g C u O , C u ( O H )

2 4 6
2 and
C N " are stable. F r o m these t w o d i a g r a m s , at the activities o f a l l o f the solute species = 1,
C u C N , C u ( C N ) " a n d C u ( C N ) " are stable i n the three regions. A t the a c t i v i t i e s o f a l l o f the

3
2
4
2
solute species = 0.01 and 0.0001, C u C N , C u ( C N ) " and C u ( C N ) " are stable i n the three p H
2 3
2
regions. A t the activities o f a l l o f the solute species = 0 . 0 0 0 0 0 1 , o n l y C u C N a n d C u ( C N ) " are 2
stable. F r o m F i g u r e 3-14, at the activities o f the copper solute species = 0.01 a n d the
activities o f cyanide species = 0.1, a l l copper cyanide species are stable in their
c o r r e s p o n d i n g p H regions. C o p p e r c y a n i d e species are stable i n certain p o t e n t i a l a n d p H
r e g i o n s . W i t h i n c r e a s i n g potential, copper c y a n i d e w i l l be o x i d i z e d to C u , C u O ( C u ( O H ) )
2 +
2
a n d C u 0 " . C y a n i d e c a n also be o x i d i z e d to cyanate f r o m F i g u r e 3 - 1 1 . C o p p e r c y a n i d e

2
c o m p l e x e s c a n be o x i d i z e d to copper o x i d e a n d cyanate f r o m the point o f v i e w of
thermodynamics.
F i g u r e 3-11 C N - H 0 p o t e n t i a l - p H d i a g r a m at a l l solute species a c t i v i t i e s o f 1 a n d P

2 ( C N ) 2 = 1
a t m a n d 25 C . (a) a s s u m i n g H C N O and C N O " are stable and (b) a s s u m i n g ( C N ) is stable. 2
43
F i g u r e 3-12 P o t e n t i a l - p H d i a g r a m s for C u - C N - H 0 system at 25 C a n d the a c t i v i t i e s o f a l l

2
solute species = 1, 10" , 1 0 2 -4

and 10" c o n s i d e r i n g C u O as a stable species. H C N O , C N O " a n d
6
( C N ) are not c o n s i d e r e d .
2
44
F i g u r e 3-13 P o t e n t i a l - p H d i a g r a m s for C u - C N - H 0 s y s t e m at 25 C a n d the a c t i v i t i e s o f a l l

2
solute species = 1, 10" , 10" a n d 10" c o n s i d e r i n g C u ( O H )

2 4 6
2 as a stable species. H C N O , C N O "
a n d ( C N ) are not c o n s i d e r e d .
2
45
PH
F i g u r e 3-14 P o t e n t i a l - p H d i a g r a m for C u - C N - H 0 s y s t e m at 25 C a n d solute c o p p e r species

2
a c t i v i t i e s o f 0.01 a n d c y a n i d e species activities o f 0.1 c o n s i d e r i n g C u ( O H ) 2 as a stable

species. H C N O , C N O " a n d ( C N ) are not c o n s i d e r e d .
2
3.4 Summary
T h e d i s t r i b u t i o n s a n d e q u i l i b r i u m potentials o f copper c y a n i d e species are functions
o f the m o l e ratio o f c y a n i d e to copper, total c y a n i d e concentration, p H a n d temperature. W i t h
increasing CN:Cu m o l e ratio, the d i s t r i b u t i o n o f copper cyanide species shifts more
c o m p l e t e l y to the h i g h l y c o o r d i n a t e d c o m p l e x ( C u ( C N ) " ) at a h i g h c y a n i d e c o n c e n t r a t i o n
4
3
than that at a l o w c y a n i d e concentration. T h e e q u i l i b r i u m p o t e n t i a l for C u ( I ) / C u decreases
w i t h i n c r e a s i n g C N : C u m o l e ratio. Increasing p H is s i m i l a r to i n c r e a s i n g free cyanide
c o n c e n t r a t i o n . I n c r e a s i n g temperature results i n decreasing s t a b i l i t y constants. Therefore the
d i s t r i b u t i o n o f c o p p e r c y a n i d e shifts to the l o w l y c o o r d i n a t e d c o m p l e x e s . T h e p o t e n t i a l
measurements have c o n f i r m e d the v a l i d i t y o f the c a l c u l a t e d results. I n the p H - p o t e n t i a l
d i a g r a m s , C u C N , C u ( C N ) " , C u ( C N ) " a n d C u ( C N ) " c a n p r e d o m i n a t e i n the different p H

2 3
2
4
3
r e g i o n s . F r o m the above d i s c u s s i o n , it is expected that C u d e p o s i t i o n current e f f i c i e n c y
decreases w i t h i n c r e a s i n g C N : C u m o l e ratio a n d increases w i t h i n c r e a s i n g temperature. The
change i n the d i s t r i b u t i o n o f copper c y a n i d e m a y affect its a n o d i c b e h a v i o u r .

46
4. ELECTRODEPOSITION OF COPPER ON GRAPHITE FELT FROM

DILUTE CYANIDE SOLUTIONS
P o r o u s 3 - d i m e n s i o n a l electrodes s u c h as c a r b o n felt a n d c l o t h , r e t i c u l a t e d v i t r e o u s
c a r b o n a n d m e t a l m e s h are b e i n g used i n c r e a s i n g l y i n e l e c t r o c h e m i c a l p r o c e s s i n g due to t h e i r
h i g h area per unit electrode v o l u m e a n d their m o d e r a t e l y h i g h m a s s transport characteristics.
O n e o f their a p p l i c a t i o n s is to recover and r e m o v e metals f r o m dilute waste water because 2 -
d i m e n s i o n a l electrodes (e. g. planar) are inefficient for this a p p l i c a t i o n [ 2 9 7 - 3 1 5 ] . N o careful
study o n the e l e c t r o d e p o s i t i o n o f copper f r o m dilute c y a n i d e s o l u t i o n has been reported [22-
25].
I n this chapter, a careful study o f direct e l e c t r o w i n n i n g o f C u o n a graphite fibre
electrode is reported. C o p p e r c o m p l e x e d w i t h c y a n i d e is m u c h m o r e d i f f i c u l t to deposit f r o m
dilute s o l u t i o n . E s p e c i a l l y w h e n the C N : C u m o l e ratio is h i g h , the e q u i l i b r i u m p o t e n t i a l for
the C u ( I ) / C u c o u p l e is m u c h l o w e r than the e q u i l i b r i u m p o t e n t i a l for H 7 H 2 a n d so h y d r o g e n
e v o l u t i o n w i l l s i g n i f i c a n t l y decrease the current e f f i c i e n c y . G r a p h i t e fibre has a h i g h surface
area, g i v i n g a m a x i m u m p l a t i n g area for copper d e p o s i t i o n and m i n i m i z i n g the o v e r p o t e n t i a l
for copper p l a t i n g a n d the c o n c e n t r a t i o n p o l a r i z a t i o n . G r a p h i t e also has a r e l a t i v e l y h i g h
o v e r p o t e n t i a l for h y d r o g e n e v o l u t i o n w h i c h s h o u l d m a x i m i z e the current e f f i c i e n c y o f c o p p e r
d e p o s i t i o n i n the i n i t i a l d e p o s i t i o n stage. Therefore i n this study, graphite fibre felt w a s u s e d
as the p o r o u s cathode.
4.1 Some Fundamental Aspects of Graphite Fibre Electrodes
F i g u r e 4-1 s h o w s the schematic d i a g r a m o f a o n e - d i m e n s i o n a l p o r o u s electrode. T h e
electrochemical reaction takes places in the porous electrode. A consequence of
electroneutrality is that the charge is c o n s e r v e d b e t w e e n the p o r o u s electrode m a t r i x a n d
p o r e - s o l u t i o n phases. T h e f o l l o w i n g equation must be a p p l i e d :
I +I,=0
s (4-1)
w h e r e I is the m a t r i x current density and I, the s o l u t i o n current density.

s
47
Metal^backing Porous electrode Metal backing

I I
x=0 x =L x=0 x=L

(a) (b)
F i g u r e 4-1 S c h e m a t i c d i a g r a m o f porous electrode
I n the p o r o u s electrode, at x = x , the potential difference ( O ) b e t w e e n the s o l i d phase
(<P ) a n d the s o l u t i o n phase (O,) is O - O , . T h e increase i n O ( d O ) due to the increase i n the

S s
distance (dx) is:
dO = d(<$> -O,) s = d<$> -d<b, =

s dx--dx (4-2)
cr K
where a is the effective c o n d u c t i v i t y o f the s o l i d phase and K the effective c o n d u c t i v i t y o f the
s o l u t i o n . F r o m E q u a t i o n 4 - 2 , the f o l l o w i n g equation c a n be d e r i v e d :
Is /, JO
--- = -r (4-3)
a K dx
T h e increase i n the s o l i d phase ( d l ) or the l i q u i d phase (dl,) is due to the e l e c t r o c h e m i c a l

s
r e a c t i o n o n the interface between the s o l i d phase and the s o l u t i o n . T h e r e f o r e w e have:
dl = -di,
s = Taidx (4-4)
where a is the specific area (m /m ), 2 3

i the local Faradaic current density of the
e l e c t r o c h e m i c a l r e a c t i o n o n the surface ( A m" ) (negative 2

for the c a t h o d i c process and
p o s i t i v e for the a n o d i c process) a n d the s i g n - for F i g u r e 4 - l a a n d the s i g n + for F i g u r e 4 - l b .
F r o m E q u a t i o n 4-4, the f o l l o w i n g equation c a n be d e r i v e d :

(4-5)
dx dx
F r o m E q u a t i o n s 4-3 a n d 4 - 5 , w e have the f o l l o w i n g equation:
d G>
2
1 1
= +a( + )i
dx 22
~ V K' J (4
"> 6
I n the case o f c o p p e r d e p o s i t i o n f r o m c y a n i d e s o l u t i o n s , the f o l l o w i n g e q u a t i o n c a n be
applied:
48
H (4-7)
dC,Cu ai,Cu
dx = + F
(4-8)
w h e r e i the l o c a l F a r a d a i c current density o n the electrode surface, i C u copper deposition
current density ( A m" ), i the h y d r o g e n e v o l u t i o n current density ( A m" ) a n d C

2
H
2
C u the c o p p e r
c o n c e n t r a t i o n ( M ) . T h e overpotential ( n ) c a n replace <3> because O c a n be expressed as ( n +
const.).
F r o m the a b o v e equations, the distributions o f the potential a n d current are n o n -
u n i f o r m due to the resistivities o f the fibre and the electrolyte. I n the case o f the c o p p e r
d e p o s i t i o n , the d r i v i n g force (I <t - O , I) o f copper d e p o s i t i o n decreases l o c a l l y to a v a l u e so

s
l o w that c o p p e r d e p o s i t i o n stops. I n order to r e m o v e m o r e copper, the p o t e n t i a l difference
must be increased. H o w e v e r , this m a y result i n m o r e h y d r o g e n e v o l u t i o n a n d l o w e r c o p p e r
current e f f i c i e n c y . S i g n i f i c a n t h y d r o g e n e v o l u t i o n c a n b l o c k the electrolyte f r o m the fibre,
stop copper d e p o s i t i o n a n d d r a m a t i c a l l y increase the effective r e s i s t i v i t y o f the e l e c t r o l y t e .
Z a m y a t i n a n d B e k [310] studied the effect o f h y d r o g e n e v o l u t i o n o n g o l d d e p o s i t i o n
i n graphite fibre felt a n d f o u n d that the current e f f i c i e n c y decreased w i t h i n c r e a s i n g total
current (potential difference) and the d e p o s i t i o n rate o f g o l d first increased to a m a x i m u m
value a n d decreased with i n c r e a s i n g current due to hydrogen evolution. The copper
d e p o s i t i o n also depends o n the electrolyte c o m p o s i t i o n , temperature a n d f l o w rate (mass
transfer). T h e m a x i m u m potential difference b e t w e e n the fibre a n d the electrolyte or- the
m a x i m u m current is selected b y e x p e r i m e n t w i t h reference to the electrolyte c o m p o s i t i o n a n d
temperature. T h e thickness o f the fibre electrode is d e t e r m i n e d b y the d e s i r e d extent o f
c o p p e r r e m o v a l f r o m the electrolyte a n d the m a x i m u m p o t e n t i a l difference b e t w e e n the fibre
a n d the electrolyte [297]. B e y o n d a certain thickness, the electrode s i m p l y adds a b a r r e n z o n e
where no c o p p e r d e p o s i t i o n w i l l take p l a c e .
I n the case o f p l a t i n g , supporting electrolytes are u s e d to increase the c o n d u c t i v i t y to
o b t a i n a u n i f o r m copper d e p o s i t i o n . F o r e x a m p l e , B e k and Z e r e b i l o v [125] d e p o s i t e d a t h i n
l a y e r o f c o p p e r o n c a r b o n fibres u s i n g 0.01 M C u + 0.03 M C N " s o l u t i o n c o n t a i n i n g 1 M

+
N a j S C ^ a n d 0.5 M N a S 0 2 3 as supporting electrolytes.
M a s s transfer i n graphite fibre felt is important to be able to p r e d i c t the effect o f f l o w
rate ( v e l o c i t y ) o n copper d e p o s i t i o n e f f i c i e n c y . T h e r e are several reports o n the m a s s transfer

49
i n graphite fibre [316-320]. B e k and Z a m y a t i n [316] reported the f o l l o w i n g relations for
f l o w - t h r o u g h fibre w i t h 10 u m diameter:
k m = 1.90x10- u 2 3 5 2
( 0.02 < R e < 0.15) (4-9)
where k m is the m a s s transfer c o e f f i c i e n t ( c m s" ), u the v e l o c i t y o f the l i q u i d ( c m s" ), R e the

1 1
R e y n o l d s n u m b e r ( u d / v ) , d the fibre diameter ( c m ) a n d v the k i n e m a t i c v i s c o s i t y ( c m s). 2
T r a n s f o r m e d into d i m e n s i o n l e s s f o r m , E q u a t i o n 4-7 reads
Sh=6.1Re 0 3 5 2
(0.02 < R e < 0.15) (4-10)
w h e r e S h is the S h e r w o o d n u m b e r ( k m d / D ) and D the d i f f u s i o n coefficient.
S c h m a l et a l . [318] gave the f o l l o w i n g r e l a t i o n for the single fibre w i t h 8 - u m diameter:
Sh=7Re 0 4
(0.04 < R e < 0.2) (4-11)
T h e a b o v e r e l a t i o n w a s consistent w i t h the results d e r i v e d f r o m heat transfer. T h e S h v a l u e
for f l o w p a r a l l e l to the fibre is 40 % l o w e r than that for f l o w p e r p e n d i c u l a r to the fibre.
K i n o s h i t a a n d L e a c h [317], V a t i s t a s et a l . [319] a n d C a r t a et a l . [320] studied the
m a s s transfer for f l o w - b y fibre felts a n d their S h n u m b e r s are s m a l l e r than that for the f l o w -
t h r o u g h fibre reported b y B e k and Z a m y a t i n [316].
The compression o f fibre felt also s i g n i f i c a n t l y changes its c o n d u c t i v i t y w h i c h
depends primarily on the contact resistance between fibres. The degree of matrix
c o m p r e s s i o n is a c c o u n t e d for b y the change i n p o r o s i t y a n d the m a t r i x c o n d u c t i v i t y c a n be
c a l c u l a t e d a p p r o x i m a t e l y b y the c o r r e l a t i o n [321]:
o - = 10 + 2800(1 -e/e ) 0
155
(S m" ) (0.68 < e/e < 1 at 20 C )
1
0 (2-12)
where e is the p o r o s i t y o f the m a t r i x a n d e the i n i t i a l p o r o s i t y o f the m a t r i x .

0
T h e c o n d u c t i v i t y o f a t y p i c a l aqueous electrolyte falls i n the range 1 - 100 S m " . 1
Therefore the degree o f m a t r i x c o m p r e s s i o n has a s i g n i f i c a n t effect o n the potential
d i s t r i b u t i o n . M a t r i x c o m p r e s s i o n also changes the s p e c i f i c electrode surface, a n d w h e n the
r e a c t i o n is mass-transfer c o n t r o l l e d , the c o m p r e s s i o n affects the l o c a l current density b y the
r e l a t i o n o f the mass transfer coefficient to the p o r o s i t y [317].
M e t a l d e p o s i t i o n also s i g n i f i c a n t l y increases the c o n d u c t i v i t y a n d the s p e c i f i c surface
area o f the fibre m a t r i x and decreases the p o r o s i t y o f the fibre m a t r i x . T h e current and
potential d i s t r i b u t i o n s change w i t h t i m e .
50
4.2 Experimental
4.2.1 Electrolytic C e l l a n d Experimental Set-up
G e n e r a l l y the m a i n types o f f l o w for p o r o u s electrodes are flow-through and flow-by.
F l o w - t h r o u g h w a s e m p l o y e d for this study, i.e. the f l o w i n the fibre felt is p a r a l l e l to the
current flow. T h e graphite fibre felt s u p p l i e d b y the N a t i o n a l E l e c t r i c C a r b o n C o . has a
specific surface area o f 0.7 m 2

g" a n d a p o r o s i t y o f 96.5 % . S S 3 1 6 stainless steel m e s h w a s
1
u s e d to fix the fibre felt o n t w o sides a n d c o n d u c t e l e c t r i c i t y to the fibre. E x c e p t for e l e c t r i c a l
contact parts, the stainless steel m e s h w a s painted. T h e s u p e r f i c i a l cathode surface area w a s
12 c m . T h e catholyte w a s separated f r o m the anolyte b y a D u P o n t N a t i o n 4 5 0 m e m b r a n e to

2
prevent the a n o d i c o x i d a t i o n o f c y a n i d e . T h e anodes w e r e n i c k e l sheet for o x y g e n e v o l u t i o n
and T I R 2 0 0 0 (Ir a n d T a coated t i t a n i u m ) for c h l o r i n e e v o l u t i o n a n d their surfaces w e r e 6 c m . 2
The e l e c t r o l y t i c c e l l c o n s i s t e d o f t w o parts o f p o l y c a r b o n a t e w h i c h w e r e c o n n e c t e d b y s c r e w s
and sealed b y rubber. F i g u r e 4-2 s h o w s the schematic d i a g r a m o f c e l l .
To start a n e x p e r i m e n t , a p p r o x i m a t e l y 18 liters o f electrolyte i n a container w e r e
preheated to about 4 0 C u s i n g a water bath a n d then p u m p e d to the e l e c t r o l y t i c c e l l u s i n g a
C o l e - P a r m e r p u m p M o d e l 7 5 1 9 - 2 0 A e q u i p p e d w i t h a d i g i t a l v a r i a b l e - s p e e d c o n s o l e d r i v e for
precise u n i f o r m f l o w rate c o n t r o l . T h e e l e c t r o l y t i c c e l l w a s put i n a water bath to m a i n t a i n the
electrolyte temperature at 4 0 C . A f t e r the electrolyte h a d passed t h r o u g h the c e l l , it w a s
p u m p e d to a container i n order to m a i n t a i n a u n i f o r m f l o w rate. T w o tubes a n d p u m p s w e r e
u s e d to a d d N a O H a n d N a C l a n d circulate the anolyte. F i g u r e 4-3 s h o w s the s c h e m a t i c
d i a g r a m o f electrolyte flow. A c o u l o m e t e r w a s u s e d to r e c o r d the a m o u n t o f charge
c o n s u m e d . I n the case o f c h l o r i n e e v o l u t i o n , a B a c h - S i m p s o n L t d . P H M 8 2 standard p H meter
w a s u s e d to m o n i t o r the p H o f the anolyte, k e e p i n g it above 4 a n d a v o i d i n g the s i g n i f i c a n t
m i g r a t i o n o f h y d r o g e n ions t h r o u g h the m e m b r a n e .
A J e n w a y M o d e l 5 3 1 0 c o n d u c t i v i t y meter w a s u s e d to measure the c o n d u c t i v i t y o f the
electrolyte w h i c h w a s p l a c e d i n a 100 m L tube w h o s e temperature w a s c o n t r o l l e d b y a water
bath. T h e c o p p e r c o n c e n t r a t i o n i n the s o l u t i o n w a s a n a l y z e d b y a t o m i c a b s o r p t i o n a n d the
cyanide concentration was analyzed using distillation-absorption-titration method (see

51
Appendix 2). The copper deposited in the graphite felt was dissolved in nitric acid and
analyzed by atomic absorption.
Copper conductor
Figure 4-2 Schematic diagram of electrolytic cell (size: 1 8 ( H ) x l 3 ( L ) x l 2 ( W ) cm)
Figure 4-3 Schematic diagram of experimental set-up

52
4.2.2 Materials
Reagent grade sodium cyanide, copper cyanide, sodium hydroxide, sodium thiocyanate
and sodium chloride were used to prepare the required synthetic solutions. Solid sodium
cyanide and copper cyanide were analyzed prior to preparation of the solutions to ensure that
the required compositions were achieved.
4.3 Results and Discussion
The conductivity of dilute copper cyanide solutions is expected to be low and this
low conductivity significantly affects the potential and current distribution. The conductivity
was therefore measured. The results are listed in Table 4-1. The conductivity is very low and
will affect the potential distribution resulting in nonuniform copper deposition. From
Equation 4-12, the approximate conductivities of graphite fibre felt are 10, 37, 89, 158, 241,
336 and 443 S m"' respectively for 0. 5, 10, 15, 20, 25, 30 % compression. In order to
increase the conductivities of the graphite felt and decrease the potential difference in the
graphite felt, the compression of the graphite felt should be increased. The compression of
the graphite felt also increases the specific surface area. However, when the graphite felt is
compressed to some degree, the conductivity of the graphite felt is much larger than that of
the solution and the further compression will not significantly affect the potential and current
distribution according to Equation 4-12. If the compression is too high, the porosity becomes
low and the amount of the deposited copper per unit volume becomes low. The compression
mainly affects the deposition of copper when the deposition begins. When a certain amount
of copper is deposited in the graphite felt, the contact resistivity between the fibres becomes
negligible and the conductivity of the graphite felt becomes much higher. Therefore the
selection of the degree of the compression is important. In the preliminary test, at a low mole
ratio of cyanide to copper (e.g. 3), the compression had less effect on the current efficiency.
At a high mole ratio of cyanide to copper, the compression had a significant effect on the
current efficiency.
The reasons are: at a low mole ratio of cyanide to copper, copper is easily deposited
on the graphite and then significantly increases the conductivity of the graphite and improves
the surface condition. At a high mole ratio of cyanide to copper, copper is difficult to deposit
53
o n the graphite and h y d r o g e n e v o l u t i o n is d o m i n a n t a n d the c o n d u c t i v i t y o f the graphite felt
does not i m p r o v e s greatly w i t h t i m e . F r o m these tests, 2 5 % o f c o m p r e s s i o n is r e q u i r e d to get
a n acceptable a n d r e p r o d u c i b l e current e f f i c i e n c y . Therefore, 25%o o f c o m p r e s s i o n w a s u s e d
for a l l the experiments. I n the dilute solutions discussed, the m i g r a t i o n o f c o p p e r c y a n i d e
c o m p l e x e s is important, r e s u l t i n g i n a decrease i n the mass transfer t o w a r d the cathode. A l s o
the effect o f the diffuse d o u b l e layer c a n decrease the r e d u c t i o n o f c o p p e r c o m p l e x e s due to
their negative charge w h e n the potential is w e l l b e l o w the zero-charge p o t e n t i a l .
T a b l e 4-1 C o n d u c t i v i t i e s o f copper c y a n i d e solutions w i t h different C N : C u m o l e ratios at

f i x e d C u concentrations (unit: S m ) * - 1
[Cu]/gL-' Temp. (C) CN:Cu = 3 C N : C u = 3.5 CN:Cu=4 CN:Cu=4.5

2 25 1.105 1.241 1.375 1.512
2 40 1.410 1.588 1.769 1.955
1 25 0.703 0.788 0.873 0.952
1 40 0.902 1.002 1.121 1.220
* [ N a O H ] = 0.01 M , [ N a C N S ] = 0.01724 and 0.00862 M r e s p e c t i v e l y for 2 a n d 1 g L " C u . 1
C o p p e r d e p o s i t i o n o n graphite fibre w a s first c o n d u c t e d i n a n u n d i v i d e d c e l l i n a n
attempt to use the a n o d i c o x i d a t i o n o f thiocyanate to prevent the c y a n i d e o x i d a t i o n . H o w e v e r ,
the thiocyanate d i d not protect against the a n o d i c o x i d a t i o n o f c y a n i d e a n d the anodic
o x i d a t i o n current e f f i c i e n c y w a s a r o u n d 1 0 0 % . Therefore the catholyte w a s separated f r o m
the anolyte b y a D u P o n t N a f i o n 4 5 0 m e m b r a n e . T h e anolytes w e r e 5 M N a O H a n d 5 M
N a C l r e s p e c t i v e l y for the o x y g e n and c h l o r i n e e v o l u t i o n experiments. T h e current e f f i c i e n c y
o f c o p p e r d e p o s i t i o n and the c o n d u c t i v i t i e s o f the s o l u t i o n are expected to increase w i t h
i n c r e a s i n g s o l u t i o n temperature. O p e r a t i n g copper d e p o s i t i o n at elevated temperatures needs
heating a large v o l u m e o f dilute s o l u t i o n , r e s u l t i n g i n s i g n i f i c a n t energy consumption.
H o w e v e r , operating at a l o w temperature results i n a l o w current e f f i c i e n c y w h i c h increases
the p o w e r c o n s u m p t i o n . A temperature range o f 2 5 - 4 0 C w a s selected for the i n v e s t i g a t i o n .
T h e v e l o c i t y o f f l o w used, w a s i n the range 3-10 c m m i n / and the estimated m a s s transfer

1
coefficient is i n the range 0.55 to 1.01 x l O " 2

cm s a c c o r d i n g to E q u a t i o n 4 - 1 0 . I n a l l the
experiments, the total c y a n i d e concentration d i d not change after e l e c t r o w i n n i n g a n d the
amount o f the deposited copper m a t c h e d c l o s e l y the change o f the c o p p e r c o n c e n t r a t i o n i n
the s o l u t i o n .
54
The results o f copper d e p o s i t i o n a n d energy c o n s u m p t i o n f o r o x y g e n e v o l u t i o n as
anode r e a c t i o n are l i s t e d i n T a b l e 4 - 2 ( i n i t i a l copper c o n c e n t r a t i o n = 1 g L ) a n d T a b l e 4-3

_ 1
( i n i t i a l copper concentration = 2 g L " ) . I n the case o f c h l o r i n e e v o l u t i o n , the c e l l voltages are

1
0.78, 0.57 a n d 0.41 V h i g h e r than those i n the case o f o x y g e n e v o l u t i o n r e s p e c t i v e l y f o r 3 0 ,
60 a n d 100 A m " and the other results are the same.

2
T a b l e 4 - 2 C o p p e r c a t h o d i c current e f f i c i e n c y a n d energy c o n s u m p t i o n at 4 0 C a n d i n i t i a l
[Cu] = 1 g L " for experiments w i t h o x y g e n e v o l u t i o n at anode
1
CN:Cu 3 3.5 4 4.5 3 3.5 4 4.5 3 3.5 4 4.5
Current Density / Am" 2

30 30 30 30 60 60 60 60 100 100 100 100
Flow velocity / cm min." 1
2.97 2.97 2.97 2.97 5.93 5.93 5.93 5.93 9.83 9.83 9.83 9.83
[Cul/gL'O)* 0.713 0.837 0.905 0.925 0.740 0.877 0.950 0.978 0.778 0.902 0.956 0.980
[Cu ] / g L" (2)**
+ 1
0.686 0.767 0.868 0.900 0.725 0.823 0.919 0.970 0.751 0.864 0.948 0.975
C.E. / % (average) 64.2 40.0 22.4 22.0 57.4 38.6 23.2 19.6 47.0 30.8 11.7 7.5
Cell voltage / V 2.64 2.65 2.63 2.56 3.66 3.64 3.52 3.42 5.01 4.85 4.62 4.60
* T h e samples were taken after the s o l u t i o n passed the c e l l i n the m i d d l e course o f the
experiments.
** T h e samples were taken after the s o l u t i o n passed the c e l l at the e n d o f the e x p e r i m e n t s .
T a b l e 4-3 C o p p e r cathodic current e f f i c i e n c y a n d energy c o n s u m p t i o n at 4 0 C a n d i n i t i a l

[Cu] = 2 g L " f o r experiments w i t h o x y g e n e v o l u t i o n at anode
1
CN:Cu 3 3.5 4 4.5 3 3.5 4 4.5 3 3.5 4 4.5
Current Density / Am" 30 2

30 30 30 60 60 60 60 100 100 100 100
Flow velocity / cm min." 2.97 2.97 2.97 2.97 5.93 5.93 5.93 5.93 9.83 9.83 9.83 9.83
1
[Cul/gL/'O)* 1.663 1.703 1.845 1.849 1.667 1.708 1.810 1.856 1.672 1.788 1.920 1.950
[Cu ] / g L" (2)**

+ 1
1.612 1.658 1.712 1.741 1.633 1.661 1.767 1.800 1.642 1.708 1.82 1.86
C.E. / % (average) 88.6 69.4 42.9 37.6 84.4 58.4 38.0 31.6 80.6 47.4 23.2 18.0
Cell voltage / V 2.17 2.28 2.30 2.15 2.91 2.94 2.89 2.82 3.81 3.64 3.63 3.56
* T h e samples w e r e taken after the s o l u t i o n passed the c e l l i n the m i d d l e course o f the

experiments.
** T h e samples w e r e t a k e n after the s o l u t i o n passed the c e l l at the e n d o f the e x p e r i m e n t s .
F r o m F i g u r e 4 - 4 , w i t h i n c r e a s i n g C N : C u m o l e ratio, the current e f f i c i e n c y decreases
s i g n i f i c a n t l y a n d the energy c o n s u m p t i o n increases s i g n i f i c a n t l y . T h i s i s due to the fact that
the l o w l y c o o r d i n a t e d copper c y a n i d e c o m p l e x e s ( d i c y a n i d e or t r i c y a n i d e i s electroactive
species) a n d the c a l c u l a t e d e q u i l i b r i u m potential for C u ( I ) / C u r e d o x c o u p l e decreased w i t h
i n c r e a s i n g C N : C u m o l e ratio (see T a b l e 4-4). T h e exchange current i s e x p e c t e d to decrease

55
w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. T h e l o w c o n c e n t r a t i o n o f e l e c t r o a c t i v e
species a n d the l o w exchange current result i n a h i g h p o l a r i z a t i o n at a f i x e d current.
Therefore at a h i g h m o l e ratio o f c y a n i d e to copper, h y d r o g e n e v o l u t i o n is d o m i n a n t a n d
decreases the current e f f i c i e n c y s i g n i f i c a n t l y .
T a b l e 4-4 D i s t r i b u t i o n a n d potentials o f c o p p e r c y a n i d e at [OH"] = 0.01 M at 4 0 C

[Cu]/gL-l Species & potential CN:Cu = 3 C N : C u = 3.5 CN:Cu = 4 C N : C u = 4.5
Cu(CN) " 2 3.00 % 0.17% 0.08 % 0.05 %

1 Cu(CN) - 3
2
96.51 % 92.01 % 85.30 % 79.34 %
Cu(CN) " 4
3
0.49 % 7.82 % 14.62 % 20.61 %
E C u ( n / C u vs. SHE/V -0.632 -0.851 -0.907 -0.941
Cu(CN) " 2 2.30 % 0.09 % 0.04 % 0.02 %
2 Cu(CN) - 3
2
97.06 % 86.95 % 76.47 % 67.86 %
Cu(CN) " 4
3
0.64 % 12.96 % 23.49 % 32.11 %
Ecudvcu vs. S H E / V -0.656 -0.878 -0.937 -0.974
W h e n the ratio o f the current to the f l o w rate w a s m a i n t a i n e d constant, the current
e f f i c i e n c y decreased w i t h i n c r e a s i n g current and f l o w rate, suggesting that the effect o f f l o w
rate o n mass transfer and o n current e f f i c i e n c y w a s l o w e r than that o f the current density.
T h i s p h e n o m e n o n b e c o m e s m o r e apparent w h e n the ratio o f c y a n i d e to c o p p e r is h i g h . T h e
reasons are: (1) the mass transfer coefficient i n graphite felt is o n l y p r o p o r t i o n a l to ( f l o w
rate) 04
f r o m E q u a t i o n s 4-9 to 4 - 1 1 . Therefore the increase i n the mass transfer does not m a t c h
the increase i n the current density, r e s u l t i n g i n h i g h e r c o n c e n t r a t i o n p o l a r i z a t i o n a n d hence
l o w current e f f i c i e n c y ; (2) the charge transfer coefficient for h y d r o g e n e v o l u t i o n (e.g. about
0.45 [113]) is larger than that for c o p p e r d e p o s i t i o n (0.1 [116] or 0.38 [110]). T h e r e f o r e the
increase i n the current density p o s s i b l y results i n m o r e increase i n the current d e n s i t y for
h y d r o g e n e v o l u t i o n than that for copper d e p o s i t i o n . A t a h i g h m o l e ratio o f c y a n i d e to
copper, the h y d r o g e n e v o l u t i o n is a d o m i n a n t r e a c t i o n a n d the mass transfer has less effect o n
the current e f f i c i e n c y o f c o p p e r d e p o s i t i o n . T h e increase i n the current results i n s i g n i f i c a n t
h y d r o g e n e v o l u t i o n a n d h y d r o g e n bubbles c o u l d b l o c k the s o l u t i o n f r o m c o n t a c t i n g the
graphite, r e s u l t i n g i n a significant decrease i n the current e f f i c i e n c y a n d the effective
c o n d u c t i v i t y o f the s o l u t i o n , g i v i n g a h i g h energy c o n s u m p t i o n .
56
D u e to the above dependence o f current e f f i c i e n c y o n C N : C u m o l e ratio a n d current
density, the c o n v e r s i o n o f C u (I) to C u decreases w i t h i n c r e a s i n g C N : C u m o l e ratio a n d
i n c r e a s i n g current density at a fixed ratio o f current density to f l o w v e l o c i t y ( F i g u r e 4-5).
(a) 1 g L " C u 1
(b) 2 g L " ' C u
F i g u r e 4-4 C u r r e n t e f f i c i e n c y ( C . E . ) and the energy c o n s u m p t i o n ( E . C . ) o f c o p p e r d e p o s i t i o n

v s . the m o l e ratio o f c y a n i d e to copper at different c a t h o d i c current densities a n d 4 0 C . T h e
electrolyte: (a) 1 g L " C u , 0.01 M N a O H and 0.00862 M N a S C N , a n d (b): 2 g L " C u , 0.01 M
1 1
N a O H a n d 0.01724 M N a S C N . T h e flow v e l o c i t y : 2 . 9 7 , 5.93 a n d 9.83 c m m i n . " r e s p e c t i v e l y

1
for 30, 60 a n d 100 A m " . 2
Mole ratio of c y a n i d e to c o p p e r Mole ratio of c y a n i d e to c o p p e r
(a) 1 g L " C u 1
(b) 2 g L " C u1
F i g u r e 4-5 C o n v e r s i o n o f C u ( I ) to C u v s . the m o l e ratio o f c y a n i d e to c o p p e r at different

c a t h o d i c current densities a n d 40 C . T h e electrolyte: (a) 1 g L " C u , 0.01 M N a O H a n d
1
0.00862 M N a S C N , a n d (b): 2 g L " C u , 0.01 M N a O H and 0.01724 M N a S C N . T h e f l o w

1
v e l o c i t y : 2.97, 5.93 and 9.83 c m min." r e s p e c t i v e l y for 3 0 , 60 and 100 A m " .

1 2
57
From Figure 4-6, the cell voltage decreased with increasing time. This is due to the
increasing amount of copper deposited on the graphite fibre electrode giving improved
conductivity of the graphite fibre electrode with time.
2.85 -r
2.80 -
Time / hours
Figure 4-6 Cell voltage vs. time at the cathodic current density = 30 A m" and 40 C. The
2
electrolyte: l g L ' Cu, CN:Cu = 3, 0.01 M NaOH and 0.00862 M NaSCN and the flow
1
velocity: 2.97 cm min." .1
From Figures 4-7, the relation between the cell voltage and the mole ratio of cyanide
to copper is dependent on the current density and the copper concentration. The cell voltage
is the sum of the anode potential drop, the anolyte IR drop, the membrane IR drop, the
catholyte IR drop, the cathode potential drop and the hardware IR drop. At a constant
potential, only the cathode potential drop and the catholyte IR drop change with CN:Cu mole
ratio. According to Table 4-1, with increasing CN:Cu mole ratio, the solution conductivity
increases, resulting in a decrease in the cell voltage. From Table 4-4, with increasing CN:Cu
mole ratio, the redox potential for Cu(I)/Cu decreases, the concentration of dicyanide or
triycyanide decreases, leading to a lower exchange current for copper reduction. Also the
potential for hydrogen evolution moves negatively due to the inhibiting effect of cyanide ions
on hydrogen evolution [113]. The above factors result in a decrease (more negative) in the
cathode potential (i.e. an increase in the cathode potential drop) and an increase in the cell
voltage at a fixed current density. Therefore the relation between the cell voltage and CN:Cu
58
m o l e ratio depends o n w h i c h one (the changes i n the s o l u t i o n I R d r o p a n d the cathode
potential) is p r e d o m i n a n t .
3 3.5 4 4.5 3 3.5 4 4.5

Mole ratio of c y a n i d e to c o p p e r Mole ratio of c y a n i d e to c o p p e r
(a) 1 g L " C u1
(b) 2 g L " C u1
F i g u r e 4-7 C e l l v o l t a g e v s . the m o l e ratio o f c y a n i d e to c o p p e r at different c a t h o d i c current

densities a n d 4 0 C . T h e electrolyte: (a) 1 g L " C u , 0.01 M N a O H a n d 0 . 0 0 8 6 2 M N a S C N ,
1
(b) 2 g L " C u , 0.01 M N a O H and 0.01724 M N a S C N , the f l o w v e l o c i t y : 2 . 9 7 , 5.93 a n d 9.83

1
c m m i n . " r e s p e c t i v e l y for 30, 60 and 100 A m" .

1 2
F i g u r e s 4-8 a n d 4-9 s h o w the graphite fibre felt after the d e p o s i t i o n o f c o p p e r f r o m
c o p p e r c y a n i d e s o l u t i o n . L e s s copper w a s deposited w h e r e the graphite felt contacted the
stainless steel m e s h p r o b a b l y due to the s h i e l d i n g effect o f stainless steel a n d the p o o r m a s s
transfer because m o s t o f the s o l u t i o n d i d not pass this area. T h e a m o u n t o f d e p o s i t e d c o p p e r
decreased w i t h i n c r e a s i n g distance f r o m the surface to the i n s i d e o f the graphite due to the
n o n - u n i f o r m p o t e n t i a l d i s t r i b u t i o n caused b y the l o w c o n d u c t i v i t i e s o f the s o l u t i o n a n d the
graphite fibre felt. H e n c e there w a s a decrease i n the d r i v i n g force ( p o l a r i z a t i o n ) o f c o p p e r
d e p o s i t i o n . A t a m o l e ratio o f c y a n i d e to c o p p e r > 4, c o p p e r w a s m a i n l y d e p o s i t e d i n a v e r y
n a r r o w area near the surface o f the graphite felt. T h i s m a y be c a u s e d b y the s i g n i f i c a n t
h y d r o g e n e v o l u t i o n w h i c h greatly decreased the effective c o n d u c t i v i t y o f the s o l u t i o n a n d
e v e n b l o c k e d the s o l u t i o n f r o m c o n t a c t i n g the graphite fibre. D u e to the fact that n o c o p p e r
w a s deposited i n s i d e the graphite felt, the c o n d u c t i v i t y o f the graphite felt w a s not i m p r o v e d .

F i g u r e 4-9 C r o s s - s e c t i o n o f graphite fibre felt o n w h i c h c o p p e r has been deposited
60
F r o m T a b l e s 4-2 a n d 4 - 3 , after the s o l u t i o n passed t h r o u g h the c e l l , the copper
c o n c e n t r a t i o n i n the s o l u t i o n taken at the e n d o f the e x p e r i m e n t w a s l o w e r than that i n the
m i d d l e o f the experiment. T h i s means the current e f f i c i e n c y i n c r e a s e d w i t h t i m e . T h i s
p h e n o m e n o n is due to the i n c r e a s i n g amount o f copper deposited o n the graphite giving
i m p r o v e d c o n d u c t i v i t y o f the graphite fibre electrode, the s p e c i f i c surface area a n d the
surface c o n d i t i o n . Therefore the effect o f deposited copper o n the current e f f i c i e n c y w a s
tested u s i n g c y a n i d e solutions w i t h a h i g h m o l e ratio o f c y a n i d e to copper. T h e e x p e r i m e n t s
w e r e c o n d u c t e d b y three-cycle runs w i t h l g I / and 2 g L " C u s o l u t i o n w i t h a n i n i t i a l C N : C u

1 1
m o l e ratio o f 3. T h e results are g i v e n i n T a b l e 4 - 5 .
T a b l e 4-5 R e s u l t s o f c y c l e r u n at 4 0 C (the i n i t i a l C N : C u ratio = 3)
No. of 1 2 3 Average Energy

cycle [Cu]/C.E. [Cu]/C.E. [Cu]/C.E. C.E. consumption
1 g L' Cu1
0.76 g L 1
/ 0.53 g L" /1
0.34 g L " ' / 57.5 % 1.8kWh/kg Cu
61 % 58% 53%
2 g L"' C u 1.67 g L" / 1
1.38 g L" /1
1.12 g L " / 1
78.7 % 1.15kWh/kg Cu
86% 73 % 68%
A f t e r three-cycle runs, copper concentrations decreased f r o m 1 g L " to 0.34 g L " ' w i t h a n 1
average current e f f i c i e n c y o f 57.5 % a n d a energy c o n s u m p t i o n o f 1.8 k W h / k g C u a n d f r o m
2 g L _ 1
to 1.1 g L' ]
w i t h a n average current e f f i c i e n c y o f 78.7 % a n d a energy c o n s u m p t i o n o f
1.15 k W h / k g C u . F r o m F i g u r e 4 - 1 0 , the copper c o n c e n t r a t i o n decreased approximately
l i n e a r l y after e v e r y single s o l u t i o n pass t h r o u g h the graphite felt a n d the current e f f i c i e n c y
decreased v e r y little. T h e m o l e ratio o f c y a n i d e to c o p p e r increased f r o m 3 to 9.4 a n d 5.5
r e s p e c t i v e l y for the i n i t i a l concentrations o f 1 g L _ 1

a n d 2 g L . A p p a r e n t l y for the first s i n g l e
1
pass, the current e f f i c i e n c y w a s h i g h because copper w a s ready to deposit. F o r the s e c o n d a n d
t h i r d passes, the current efficiencies were still h i g h because a certain a m o u n t o f c o p p e r w a s
deposited o n the graphite felt, i m p r o v i n g the c o n d u c t i v i t y o f the graphite felt a n d i n c r e a s i n g
the s p e c i f i c surface. F r o m F i g u r e s 3-5 b and 3-6 b , as expected, after the first s i n g l e passes
t h r o u g h the graphite felt, the e q u i l i b r i u m potential for the C u ( I ) / C u c h a n g e d s i g n i f i c a n t l y .
A f t e r the s e c o n d a n d t h i r d passes, the e q u i l i b r i u m potential c h a n g e d m o d e s t l y , w i t h the
c o p p e r t r i c y a n i d e species b e i n g a l w a y s d o m i n a n t . C o p p e r d e p o s i t i o n releases free c y a n i d e
w h i c h not o n l y suppresses the c a t h o d i c r e d u c t i o n o f copper (I), but also the hydrogen

61
e v o l u t i o n [113]. Therefore copper c a n be r e m o v e d e f f i c i e n t l y f r o m c y a n i d e s o l u t i o n e v e n
w i t h a h i g h C N : C u m o l e ratio.
2.0 r 10
o
4- 1
0.2 -
0.0
0 1 2
Number of cycle runs
F i g u r e 4 - 1 0 C o n c e n t r a t i o n o f copper vs. the n u m b e r o f the s o l u t i o n passes t h r o u g h the

graphite felt at [ C u ] i n i t a l = 1 a n d 2 g L " a n d 40 C . T h e electrolyte: (1) l g I /
1 1
C u , C N : C u = 3,
0.01 M N a O H a n d 0.00862 M N a S C N and (2) 2 g L " C u , C N : C u =3, 0.01 M N a O H a n d
1
0.01724 M N a S C N , and the f l o w v e l o c i t y : 2.97 c m m i n . " . 1
4.4 Summary
T h e current e f f i c i e n c y o f copper d e p o s i t i o n o n a graphite felt electrode decreases w i t h
i n c r e a s i n g C N : C u m o l e ratio and current density. D u e to the l o w c o n d u c t i v i t i e s o f the
s o l u t i o n a n d the graphite felt, the potential a n d current d i s t r i b u t i o n o f c o p p e r t h r o u g h the 3-
d i m e n s i o n a l electrode are not u n i f o r m . T h e a c c u m u l a t i o n o f deposited c o p p e r w i t h the
graphite felt as the p l a t i n g proceeds, s i g n i f i c a n t l y i m p r o v e s the c o n d u c t i v i t y o f the graphite
felt i n c r e a s i n g the specific surface area and benefiting copper d e p o s i t i o n . C o p p e r c a n be
deposited e f f i c i e n t l y o n the graphite felt f r o m l o w c o n c e n t r a t i o n solutions event at a h i g h
C N : C u m o l e ratio. U p to 60 % o f the C u c a n be r e m o v e d e f f i c i e n t l y f r o m the s o l u t i o n . T h e
energy requirement for copper deposition was as l o w as 1-2 kWh/kg C u (1000-2000
k W h / t o n n e C u ) i n the current range 3 0 - 1 0 0 A m " , w h i c h c o m p a r e s f a v o r a b l y w i t h the v a l u e

2
obtained in conventional copper electrowinning from sulphuric acid-copper sulphate
solutions. T h e obtained results meet the requirement for i n d u s t r i a l practice.

62
5. ELECTROWINNING FROM COPPER CYANIDE SOLUTION USING

ALTERNATIVE ANODE REACTIONS
A s d i s c u s s e d , copper c y a n i d e c a n be extracted f r o m dilute solutions u s i n g solvent
e x t r a c t i o n to p r o d u c e a concentrated copper c y a n i d e s o l u t i o n f r o m w h i c h c o p p e r c a n be
r e c o v e r e d u s i n g the copper e l e c t r o w i n n i n g process. U s i n g a n alternative a n o d i c r e a c t i o n w a s
selected as a w a y to prevent the a n o d i c o x i d a t i o n o f c y a n i d e a n d e l i m i n a t e the use o f a
m e m b r a n e c e l l . T h i o c y a n a t e , m e t h a n o l , sulphite, a n d a m m o n i a were selected as s a c r i f i c i a l
species for a d d i t i o n to the electrolyte.
5.1 Experimental Apparatus and Set-up for Electrowinning
E l e c t r o w i n n i n g w a s c a r r i e d out i n a 1.5-L m i n i - c e l l m a d e f r o m p o l y c a r b o n a t e . T h e
electrolyte w a s c i r c u l a t e d u s i n g a C O L E - P A R M E R peristaltic p u m p at a f l o w rate o f 0.18 L
m i n " . T h e electrolyte w a s a l l o w e d to o v e r f l o w into a 2 5 0 - m l E r l e n m e y e r flask f r o m w h i c h a

1
b l e e d w a s t a k e n p e r i o d i c a l l y to r e m o v e free c y a n i d e . C u C N , N a O H a n d s a c r i f i c i a l species
w e r e added p e r i o d i c a l l y to m a i n t a i n their respective concentrations due to c o p p e r d e p o s i t i o n
and the a n o d i c c o n s u m p t i o n o f N a O H and the s a c r i f i c i a l species. A m a g n e t i c stirrer w a s u s e d
to accelerate the d i s s o l u t i o n a n d the m i x i n g o f C u C N , N a O H a n d the s a c r i f i c i a l species. I n
order to keep a constant v o l u m e o f the electrolyte, d e i o n i z e d water w a s a d d e d as r e q u i r e d .
The electrolyte was heated with quartz-shielded immersion heaters connected to a
temperature c o n t r o l l e r . A p o w e r s u p p l y w a s used to s u p p l y the current and a c o u l o m e t e r w a s
u s e d to measure the amount o f e l e c t r i c i t y passed. T h e anode materials selected for study w e r e
T I R 2 0 0 0 D S A ( t i t a n i u m coated w i t h i r i d i u m a n d tantalum o x i d e ) for S C N " , C H O H , N H 3 3
a n d S 0 " a n d graphite o n l y for S 0 " and S C N " . S S 3 1 6 stainless steel w a s used as the cathode
3
2
3
2
m a t e r i a l . I n the case o f the o x i d a t i o n o f S 0 " , n i t r o g e n gas w a s used to prevent a i r o x i d a t i o n .

3
2
T h e e x p e r i m e n t a l set-up is s h o w n i n F i g u r e 5-1.
T h e d e p o s i t e d copper w a s recovered, w a s h e d , d r i e d a n d w e i g h e d to determine the
cathodic current efficiency. The current efficiencies for the oxidation o f thiocyanate,
m e t h a n o l , a m m o n i a a n d sulphite were based o n the c y a n i d e a n a l y s i s ( A p p e n d i x 2).
R e a g e n t grade c h e m i c a l s were used i n a l l experiments.

63
Erlenmeyer flask
Power supply
Stirrer
I
Coulometer 1
Stirring plate
ft Pump
Heater Temperature
3-rri controller
ft Pump
F i g u r e 5-1 S c h e m a t i c d i a g r a m o f the e x p e r i m e n t a l set-up
5.2 Selection of Sacrificial Materials
T h e a n o d i c current e f f i c i e n c y w a s obtained u s i n g least-squares f i t t i n g a c c o r d i n g to the
concentrations o f the supposed o x i d i z e d species i n every b l e e d s a m p l e a n d the m a s s balance:
the amount taken out for the b l e e d , the amount added, a n d the a m o u n t i n the e l e c t r o l y t i c c e l l
for a f i x e d v o l u m e o f the electrolyte. A s s u m i n g a p a r t i c u l a r a n o d i c current e f f i c i e n c y o f
c y a n i d e , the c y a n i d e c o n c e n t r a t i o n i n the electrolyte c a n be p r e d i c t e d a n d least-squares c a n be
u s e d to fit the current e f f i c i e n c y to the m e a s u r e d concentration. F i g u r e 5-2 s h o w s the d i a g r a m
o f the fitted a n d m e a s u r e d concentrations o f c y a n i d e .
86
Analyzed
85 Fitted
C.E. for cyanide = 14.4 %
4 6 8
Time / Hours
F i g u r e 5-2 C o n c e n t r a t i o n o f c y a n i d e vs. the e l e c t r o l y s i s t i m e for o b t a i n i n g the current

e f f i c i e n c y o f c y a n i d e o x i d a t i o n at 60 C . E l e c t r o l y t e : 70 g L " C u , C N : C u = 3, 113 g L "
1 1
N a S 0 , 10 g L
2 3
1
NaOH.
T a b l e 5-1 R e s u l t s for selection o f s a c r i f i c i a l species at 6 0 C
Additive Anodes current Time / Average Anodic Copper Anode surface cathode copper
density hours cell voltage C.E. / % C. E. /% condition condition
/Am" 2
/V
SCN" Graphite 500 13 2.26 9.10 94.6 some black dendrite
30 g L- 1
coating
SCN" Graphite 1000 13 2.42 6.3 95.2 some black sponge dendrite
30 g L- 1
coating
SCN" TIR2000 500 12 2.32 12.98 94.96 some black sponge dendrite
40 g L" 1
coating
SCN" TIR2000 1000 8 2.68 10.54 94.82 some black sponge dendrite
40 g L" 1
coating
CH OH3 TIR2000 500 12 4.00 9.2 91.4 thick black sponge-like
22.4 g L" 1
coating dendrite
CH3OH TIR2000 1000 8 4.16 ? 88.1 thick black strong dendrite
22.4 g L" 1
108 for CN- coating
NH 3 TIR2000 500 12 3.67 12.2 91.5 thick black coral-like strong
54.2 g L" 1
coating and dendrite
some foam
NH 3 TIR2000 1000 6 8.74 ? 82.7 thick black coral-like strong
54.2 g L" 1
110 for CN" coating and a lot dendrite
of foam
Na S02 3 TIR2000 500 12 2.18 84.5 91.7 a very little coral-like strong
113 gL" 1
black coating dendrite
Na S02 3 TIR2000 1000 6 3.57 40 91.3 a very little coral-like strong
113 g L" 1
black coating dendrite
Na S02 3 TIR2000 250 14 1.85 87.5 91.9 a very little small dendrite
113 gL" 1
black coating
Na S02 3 Graphite 500 12 2.20 84.5 91.9 a very little dendrite
H3gL-' black coating
Na S02 3 Graphite 250 14 1.90 86.5 92.1 a very little small dendrite
113gL-' black coating
5.2.1 Thiocyanate
I n the case o f thiocyanate as a s a c r i f i c i a l species, f r o m T a b l e 5-1, the a n o d i c current
e f f i c i e n c y o f t h i o c y a n a t e o x i d a t i o n w a s v e r y l o w o n the graphite anode a n d a little h i g h e r o n
the T I R 2 0 0 0 anode. T h i s means that thiocyanate w a s m o r e d i f f i c u l t to o x i d i z e o n the a b o v e
t w o anodes t h a n c o p p e r c y a n i d e . B o t h the graphite anode a n d the T I R 2 0 0 0 anode w e r e
coated w i t h a b l a c k s o l i d substance, w h i c h w a s r e a d i l y d i s s o l v e d i n c y a n i d e s o l u t i o n o r H C 1
s o l u t i o n . A f t e r d i s s o l u t i o n o f the b l a c k substance, the H C 1 s o l u t i o n b e c a m e b l u e . A n a l y s i s
s h o w e d that c o p p e r w a s i n b o t h the c y a n i d e a n d H C 1 solutions. T h e r e f o r e the b l a c k substance
w a s p r e s u m e d to be c u p r i c o x i d e or a m i x t u r e o f c u p r i c o x i d e a n d h y d r o x i d e . N o gas
e v o l u t i o n w a s o b s e r v e d o n the graphite anode, m e a n i n g there w a s no o x y g e n e v o l u t i o n o r n o

65
o x i d a t i o n o f cyanate to carbonate and n i t r o g e n gas. A t 500 A m* , o n the cathode, v e r y tight

2
s m a l l dendrites were o b s e r v e d a n d at 1000 A m" , large dendrites l i k e sponge c o r a l w e r e

2
f o r m e d o n the cathode. T h e current e f f i c i e n c y w a s h i g h p o s s i b l y due to the f o r m a t i o n o f
c o r a l - l i k e c o p p e r w h i c h m a d e the r e a l surface area m u c h larger than the apparent cathode
surface area and the s p e c i f i c current density m u c h l o w e r than the o b s e r v e d v a l u e . A n o t h e r
r e a s o n is that thiocyanate suppresses h y d r o g e n e v o l u t i o n and increases the current e f f i c i e n c y
as reported i n the literature [92, 9 4 - 9 6 , 98].
5.2.2 Methanol
I n the case o f m e t h a n o l as a s a c r i f i c i a l species, at 500 A m " the a n o d i c current

2
e f f i c i e n c y for m e t h a n o l w a s about 9.2 % based o n the c y a n i d e a n a l y s i s , but at 1000 A m " the 2
a n o d i c current e f f i c i e n c y w a s negative and the a n o d i c current e f f i c i e n c y for c y a n i d e w a s
about 1 0 8 % . T h e a n o d i c o x i d a t i o n current for c y a n i d e w a s o v e r 1 0 0 % p r o b a b l y due to
c h e m i c a l o x i d a t i o n b y air i n the presence o f m e t h a n o l . A little gas e v o l u t i o n w a s o b s e r v e d
a n d s o m e gas b u b b l e s adhered to the anode surface. T h e gas w a s p r o b a b l y o x y g e n or n i t r o g e n
due either to o x y g e n e v o l u t i o n or the o x i d a t i o n o f cyanate to n i t r o g e n gas. T h e anode w a s
coated w i t h a v e r y t h i c k layer o f a b l a c k substance w h i c h dissolved readily i n H C 1 solution
w h i c h b e c a m e b l u e . Therefore the substance w a s a g a i n thought to be c o p p e r o x i d e . D u e to
the t h i c k b l a c k c o a t i n g a n d gas bubble effects, the c e l l v o l t a g e b e c a m e v e r y h i g h (4 V at the
s h u t d o w n o f the experiment. T h e f o r m a t i o n o f c u p r i c o x i d e c o u l d contribute to the l o w
c o n s u m p t i o n o f c y a n i d e a n d so the a n o d i c current e f f i c i e n c y for m e t h a n o l m a y be l o w e r t h a n
the v a l u e based o n a n a l y s i s .
5.2.3 Ammonia
I n the case o f a m m o n i a as a s a c r i f i c i a l species, at 500 A m " the a n o d i c 2

current
e f f i c i e n c y for a m m o n i a o x i d a t i o n w a s 12.2 % based o n the c y a n i d e a n a l y s i s . H o w e v e r , at
1000 A m" , the a n o d i c current e f f i c i e n c y was about zero a n d the a n o d i c current e f f i c i e n c y for
2
c y a n i d e w a s about 120 % . W h i t e f o a m f o r m e d a r o u n d the anode a n d the h i g h e r the current
density, the greater the f o a m . A b l a c k a n d b r o w n substance h e a v i l y coated the anode surface
a n d f o r m e d the p a s s i v a t i n g f i l m . F r o m F i g u r e 5-3, the c e l l v o l t a g e increased w i t h i n c r e a s i n g

66
t i m e o f e l e c t r o l y s i s f r o m 2.22 to 5.41 V at 500 A m " due to i n c r e a s i n g f o r m a t i o n o f c o p p e r

2
o x i d e . T h e c e l l v o l t a g e increased f r o m 2.89 to 19.0 V for 1000 A m " at s h u t - d o w n . T h e b l a c k

2
substance d i s s o l v e d i n c y a n i d e a n d H C 1 solutions. H o w e v e r , the w h i t e b r o w n substance d i d
not d i s s o l v e . T h i s substance and w h i t e f o a m w e r e p r o b a b l y p r o d u c e d b y the r e a c t i o n o f
a m m o n i a a n d c y a n i d e at the anode resulting i n the h i g h c o n s u m p t i o n o f c y a n i d e ( C . E . for
c y a n i d e is o v e r 1 0 0 % ) . A t 500 A m" the c u p r i c o x i d e f o r m a t i o n c o u l d contribute to the l o w

2
c o n s u m p t i o n o f c y a n i d e . Therefore the a n o d i c current e f f i c i e n c y o f a m m o n i a w a s l o w e r than
the above v a l u e based o n the c y a n i d e analysis.
5.2.4 Sulphite
I n the case o f sulphite as a s a c r i f i c i a l species, at 5 0 0 A m " 2

the a n o d i c current
e f f i c i e n c y for sulphite o x i d a t i o n w a s about 8 5 % b o t h o n graphite a n d T I R 2 0 0 0 based o n the
c y a n i d e a n a l y s i s . H o w e v e r , at 1000 A m" the current e f f i c i e n c y decreased to 4 0 % at T I R

2
2 0 0 0 . T h i s means that i n c r e a s i n g the current results i n the o x i d a t i o n o f m o r e c y a n i d e . T h i s
m a y be due to a change i n the e l e c t r o c h e m i c a l k i n e t i c s o f the t w o anode reactions at h i g h
current density. W i t h a n i n c r e a s i n g c i r c u l a t i n g f l o w rate o f electrolyte, the c e l l voltage
decreased due to i m p r o v e d m a s s transfer o f b o t h copper i o n s to the cathode a n d sulphite i o n s
to the anode. O n l y a v e r y s m a l l amount o f b l a c k m a t e r i a l coated the upper side o f the anode
near the surface o f the electrolyte. Therefore sulphite a d d i t i o n c a n e f f e c t i v e l y prevent or
decrease the f o r m a t i o n o f copper o x i d e at the anode. F r o m F i g u r e 5-3, the c e l l v o l t a g e first
i n c r e a s e d a little a n d then decreased slightly with increasing time o f electrolysis. The
decrease i n the c e l l voltage m a y be caused b y the g r o w i n g cathode and i n c r e a s i n g r e a l surface
area due to the f o r m a t i o n o f the dendritic copper deposit. N o gas e v o l u t i o n w a s o b s e r v e d o n
the anodes.
F r o m the a b o v e d i s c u s s i o n , thiocyanate, m e t h a n o l a n d a m m o n i a d i d not e f f e c t i v e l y
protect against c y a n i d e o x i d a t i o n and the anode surface b e c a m e coated w i t h b l a c k c o p p e r
o x i d e a n d lost its c a t a l y t i c a c t i v i t y . O n l y sulphite o x i d a t i o n w a s f o u n d to e f f e c t i v e l y l i m i t the
o x i d a t i o n o f c y a n i d e . T h e a n o d i c current e f f i c i e n c y o f sulphite w a s the same o n T I R 2 0 0 0 a n d
graphite anodes. Therefore sulphite o x i d a t i o n a n d graphite were selected as the sacrificial
a d d i t i v e a n d the anode m a t e r i a l r e s p e c t i v e l y for further tests.

67
0 2 4 6 8 10 12
Time / hours
F i g u r e 5-3 C e l l v o l t a g e v s . the t i m e o f e l e c t r o l y s i s i n the presence o f a m m o n i a a n d sulphite

as a s a c r i f i c i a l species at 500 A m" a n d 60 C . E l e c t r o l y t e : 70 g L " C u , C N : C u = 3, a n d 10 g
2 1
L" .
1
5.3 Effect of Some Parameters on the Anodic and Cathodic Processes in the
Presence of Sulphite
5.3.1 Effect of Current Density
The current density u s u a l l y affects the a n o d i c a n d c a t h o d i c processes significantly.
T h u s e x p e r i m e n t s were c o n d u c t e d to determine the effect o f current density. T h r e e current
densities were tested a n d the results are l i s t e d i n T a b l e 5-2. T h e a n o d i c current e f f i c i e n c y o f
c y a n i d e decreases s i g n i f i c a n t l y w i t h decreasing current density f r o m 1000 to 500 A m " , but 2
decreases s l i g h t l y f r o m 500 to 2 5 0 A m" . T h e c a t h o d i c current e f f i c i e n c y

2
was almost
independent o f the current density. T h i s p h e n o m e n o n is p r o b a b l y related to the m o r p h o l o g y
o f the c o p p e r deposits. A t a h i g h current density, m o r e a n d larger dendrites w e r e p r o d u c e d
a n d at a l o w current density, fewer and s m a l l e r dendrites w e r e o b t a i n e d , r e s u l t i n g i n
a p p r o x i m a t e l y the same real current density.

68
T a b l e 5-2 E f f e c t o f current density o n the a n o d i c current e f f i c i e n c y o f c y a n i d e a n d the

c a t h o d i c current e f f i c i e n c y o f copper at 60 C . E l e c t r o l y t e : 70 g L " C u , C N : C u m o l e ratio =3,
1
10 g L " N a O H a n d 113 g I /
1 1
Na S0 .
2 3
C u r r e n t density / A m " 2
1000 500 250
C . E . for c y a n i d e o x i d a t i o n / % 59.9 14.4 12.8 3
C . E . for copper d e p o s i t i o n / % 92.2 92.0 92.1 1
5.3.2 Effect of sulphite concentration
A t 2 5 0 A m ' solutions w i t h 50, 63 a n d 113 g L " N a S 0

2 1
2 3 w e r e tested w i t h the results
b e i n g l i s t e d i n T a b l e 5-3. I n this range o f sulphite concentration, the a n o d i c current e f f i c i e n c y
o f c y a n i d e w a s not affected v e r y m u c h b y sulphite c o n c e n t r a t i o n a n d the c a t h o d i c current
e f f i c i e n c y o f c o p p e r d e p o s i t i o n w a s almost independent o f the sulphite c o n c e n t r a t i o n . T h e
sulphite c o n c e n t r a t i o n d i d not affect the m o r p h o l o g y o f the c a t h o d i c deposit. T h e r e f o r e the
use o f 5 0 - 6 0 g L " N a 2 S 0 1
3 is sufficient to get a reasonable a n o d i c current efficiency
( m i n i m u m c o n s u m p t i o n o f sulphite).
T a b l e 5-3 E f f e c t o f sulphite concentration o n the a n o d i c current e f f i c i e n c y o f c y a n i d e a n d the

c a t h o d i c current e f f i c i e n c y o f copper at 60 C a n d 2 5 0 A m " . E l e c t r o l y t e : 70 g L " ' C u , C N : C u
2
m o l e ratio =3, 10 g L " N a O H . 1
[Na S0 ] / g L
2 3
1
50 63 113
C . E . for c y a n i d e o x i d a t i o n / % 13 13.2 3 12.8 3
C . E . for c o p p e r d e p o s i t i o n / % 91.8 91.9 2 92.1 1
5.3.3 Effects of thiocyanate and mole ratio of cyanide to c o p p e r
T h i o c y a n a t e is expected to be present i n the c o p p e r - c y a n i d e e l e c t r o w i n n i n g s o l u t i o n .
T h e m o l e ratio o f c y a n i d e to copper is a v e r y important parameter affecting the a n o d i c a n d
c a t h o d i c processes. Therefore experiments have been c o n d u c t e d o n s o l u t i o n s w i t h different
m o l e ratios o f c y a n i d e to copper i n the presence a n d absence o f thiocyanate. T h e results are
l i s t e d i n T a b l e 5-4.
69
T a b l e 5-4 R e s u l t s o f copper e l e c t r o w i n n i n g at 2 5 0 A m " a n d 6 0 C . E l e c t r o l y t e : 7 0 g L " C u ,

2 1
C N : C u m o l e ratio = 3-4.5, 63 g L " ' N a S 0 2 3 a n d 10 g L " N a O H i n the presence a n d absence o f

1
SCN".
CN:Cu mole Average cell Copper Energy Anodic Anode cathode
ratio voltage C. E. / % consumption C.E. for CN' surface copper
/V / kWh kg' 1
/% condition
3 1.92 93.1 0.873 11.3 a very little small
(no SCN') black dendrite
coating
3 1.72 95.6 0.759 11.6 a very little coral-like
(40 g L' SCN')
1
black deposits
coating
3.2 2.05 89.2 0.968 13.8 no black small
(no SCN') coating dendrite
3.2 1.93 93.8 0.867 14.0 no black small
(40 g L' SCN)
1
coating dendrite
3.5 2.08 77.85 1.13 17.9 no black small
3.5 1.97 89.0 0.934 18.0 no black small
(40 g L' SCN')
1
coating dendrite
4 2.15 40.9 2.22 37.0 no black almost no
4 2.08 58.8 1.49 38.8 no black very small
(40 g L' SCN)
1
coating dendrite
4.5 2.11 7.85 11.4 54.9 no black no dendrite
(no SCN') coating
4.5 2.05 8.53 10.1 54.1 no black no dendrite
(40 g L' SCN')
1
coating
F r o m F i g u r e 5-4, the cathodic current e f f i c i e n c y o f copper d e p o s i t i o n decreases w i t h
i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. A t a C N : C u m o l e ratio < about 3 . 3 , the current
e f f i c i e n c y decreases s l i g h t l y w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to c o p p e r a n d at a C N : C u
m o l e ratio > 3.3, it decreases s i g n i f i c a n t l y w i t h i n c r e a s i n g C N : C u m o l e ratio. F r o m F i g u r e 3 -
3, w i t h i n c r e a s i n g C N : C u m o l e ratio, the e q u i l i b r i u m potential for the C u ( I ) / C u c o u p l e
decreases s i g n i f i c a n t l y a n d the species o f copper c y a n i d e shifts f r o m the l o w l y c o o r d i n a t e d
complexes (Cu(CN) " 2 and Cu(CN) " 3

2
to the h i g h l y c o o r d i n a t e d complex (Cu(CN) "). 4
3
Therefore at a h i g h e r C N : C u m o l e ratio, the discharge o f copper (I) takes p l a c e at a m o r e
negative potential w h e r e m o r e h y d r o g e n w a s e v o l v e d . I n another aspect, free cyanide
suppresses the h y d r o g e n e v o l u t i o n [113]. W i t h i n c r e a s i n g C N : C u m o l e ratio, the h y d r o g e n
e v o l u t i o n s h o u l d be suppressed. Increasing m o l e ratio o f c y a n i d e to c o p p e r has m u c h m o r e
i n h i b i t i n g effect o n copper d e p o s i t i o n than o n the h y d r o g e n e v o l u t i o n . Therefore the current
e f f i c i e n c y decreases w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper.

70
T h i o c y a n a t e c a n increase the current e f f i c i e n c y o f c o p p e r d e p o s i t i o n . T h e effect o f
thiocyanate is dependent o n the C N : C u m o l e ratio. A t a C N : C u m o l e ratio = 3-3.3, the effect
is s m a l l a n d at a C N : C u m o l e ratio = 3.3 - 4.4, the effect is significant. A t a C N : C u m o l e ratio
= 4.5, the effect is v e r y s m a l l . A t a l o w C N : C u m o l e ratio (3-3.3), the current e f f i c i e n c y o f
copper d e p o s i t i o n is v e r y h i g h and w i l l not be i m p r o v e d s i g n i f i c a n t l y b y thiocyanate. A t a
C N : C u m o l e ratio - 4.5, the free c y a n i d e c o n c e n t r a t i o n is h i g h (about 0.5 M ) . F r e e c y a n i d e
also suppresses the h y d r o g e n e v o l u t i o n s i g n i f i c a n t l y [113]. T h e effect o f free c y a n i d e o n
h y d r o g e n e v o l u t i o n m a y be m u c h h i g h e r than that o f thiocyanate or the co-effect o f free
c y a n i d e a n d thiocyanate o n the h y d r o g e n e v o l u t i o n is close to that o f free c y a n i d e . T h e r e f o r e
thiocyanate does not i m p r o v e the current efficiency very m u c h . H o w e v e r , thiocyanate
accelerates the f o r m a t i o n o f dendrites o n the cathode a n d produces p o o r q u a l i t y copper. T h i s
m a y be another r e a s o n for the increase i n copper current e f f i c i e n c y i n the presence o f
thiocyanate. A t a C N : C u m o l e ratio = 3, the electrolyte b e c a m e b r o w n w h e n a d d i n g C u C N ,
NaSCN, Na S0 2 3 and N a O H into the E r l e n m e y e r flask. T h i s m a y be caused b y a n u n k n o w n
r e a c t i o n b e t w e e n thiocyanate a n d sulphite. T h e energy c o n s u m p t i o n increases s l i g h t l y w i t h
i n c r e a s i n g C N : C u m o l e ratio f r o m 3 to 3.5 a n d increases s i g n i f i c a n t l y at a C N : C u m o l e ratio
> 4 due to the s i g n i f i c a n t decrease i n the current e f f i c i e n c y . S i n c e thiocyanate increases the
current e f f i c i e n c y a n d the c o n d u c t i v i t y o f the electrolyte, the energy c o n s u m p t i o n i n the
presence o f thiocyanate is l o w e r than that i n its absence.
F i g u r e 5-5 s h o w s the a n o d i c current e f f i c i e n c y o f c y a n i d e v s . C N : C u m o l e ratio at 60
C a n d 2 5 0 A m" . T h e a n o d i c current e f f i c i e n c y o f c y a n i d e increases w i t h i n c r e a s i n g C N : C u

2
m o l e ratio. I n the C N : C u m o l e ratio range 3-3.2, the a n o d i c current e f f i c i e n c y o f c y a n i d e
increases s l i g h t l y w i t h i n c r e a s i n g C N : C u m o l e ratio. A t a C N : C u m o l e ratio > 3.5, the a n o d i c
current e f f i c i e n c y o f c y a n i d e increases r a p i d l y w i t h i n c r e a s i n g C N : C u m o l e ratio. A t a
C N : C u m o l e ratio = 3, a v e r y s m a l l amount o f b l a c k copper o x i d e w a s o b s e r v e d o n the anode
a n d at a C N : C u m o l e ratio > 3.2, no precipitate w a s o b s e r v e d o n the anode. T h i s is apparently
due to the fact that c y a n i d e stabilizes copper i n the f o r m o f copper(I) c y a n i d e c o m p l e x . T h e
presence o f thiocyanate does not decrease the c o n s u m p t i o n o f c y a n i d e .

71
3 3.5 4 4.5
Mole ratio of C y a n i d e to c o p p e r
F i g u r e 5-4 C a t h o d i c current e f f i c i e n c y o f copper d e p o s i t i o n ( C . E . ) a n d p o w e r c o n s u m p t i o n

( P . C . ) v s . the C N : C u m o l e ratio at 60 C and 2 5 0 A m" . E l e c t r o l y t e : 7 0 g L " C u , 63 g L "
2 1 1
N a S 0 , 10 g L " N a O H , and different c y a n i d e concentrations i n the presence a n d absence o f

2 3
1
40 g L " S C N " .
1 1
60% -r
0% J i 1 1
3 3.5 4 4.5
Mole ratio of cyanide to copper
F i g u r e 5-5 A n o d i c current e f f i c i e n c y for c y a n i d e o x i d a t i o n v s . the m o l e ratio o f c y a n i d e to

c o p p e r at 2 5 0 A m" a n d 60 C . E l e c t r o l y t e : 7 0 g L ' C u , 63 g L " N a S 0 , 10 g L " N a O H , a n d
2 1 1
2 3
1
different c y a n i d e concentrations i n the presence and absence o f 4 0 g L " 1

SCN" .1
T h e c e l l voltage v s . t i m e o f e l e c t r o l y s i s at different C N : C u m o l e ratios is s h o w n i n
F i g u r e 5-6. I n the C N : C u m o l e ratio range 3-4, the c e l l voltage first increases q u i c k l y to a
certain v a l u e a n d then decreases w i t h i n c r e a s i n g t i m e o f the e l e c t r o l y s i s . H o w e v e r , at a

72
C N : C u m o l e ratio = 4.5, the c e l l v o l t a g e increases s l o w l y w i t h i n c r e a s i n g t i m e o f e l e c t r o l y s i s
a n d then quite r a p i d l y w i t h t i m e a n d exceeds the values for l o w e r C N : C u m o l e ratios, a n d
f i n a l l y reaches a m a x i m u m v a l u e and decreases s l i g h t l y w i t h t i m e . G e n e r a l l y , the c e l l v o l t a g e
increases w i t h i n c r e a s i n g C N : C u m o l e ratio. These p h e n o m e n a are p r o b a b l y l a r g e l y related to
the c a t h o d i c process. A t the b e g i n n i n g o f the e l e c t r o l y s i s , the cathode w a s not c o v e r e d w i t h
c o p p e r a n d the overpotential for h y d r o g e n o n S S 316 stainless steel is m u c h l o w e r than o n
c o p p e r a n d h y d r o g e n e v o l u t i o n a c c o u n t e d for a s i g n i f i c a n t part o f the c a t h o d i c current. A f t e r
the cathode w a s c o v e r e d w i t h copper, the overpotential for h y d r o g e n e v o l u t i o n b e c a m e
larger. Therefore the c a t h o d i c potential h a d to m o v e to a m o r e negative p o t e n t i a l to m a i n t a i n
a constant current, r e s u l t i n g i n the increase i n the c e l l v o l t a g e . T h i s is consistent w i t h the
observations o f the cathode: at the b e g i n n i n g , m o r e h y d r o g e n b u b b l e s appeared o n the
cathode and after the cathode w a s c o v e r e d w i t h copper, the quantity o f b u b b l e s decreased a n d
c e l l v o l t a g e increased. A t a C N : C u m o l e ratio = 3-4, the c o p p e r w a s ready to deposit o n the
cathode a n d c o m p l e t e l y c o v e r e d the cathode i n a short t i m e .
A t a C N : C u m o l e ratio = 4.5, it w a s d i f f i c u l t to deposit c o p p e r o n the cathode a n d it
t o o k a l o n g e r t i m e (5 hours) to c o v e r the cathode w i t h c o p p e r c o m p l e t e l y . W h e n the t i m e o f
the e l e c t r o l y s i s w a s i n the range 0.5 to 4 hours, the coverage o f c o p p e r w a s l o w a n d so
h y d r o g e n o v e r p o t e n t i a l w a s l o w , the c e l l v o l t a g e w a s l o w e r than the v a l u e s w i t h l o w e r
C N : C u m o l e ratios. T h e deposit a n d its dendrites were g r o w i n g w i t h t i m e a n d the distance
b e t w e e n the cathode a n d the anode decreased a n d the real surface area b e c a m e larger,
r e s u l t i n g i n a l o w p o l a r i z a t i o n . Therefore a l o w e r c e l l voltage is needed to k e e p a constant
current.
T h e increase i n the c e l l voltage w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to c o p p e r c a n be
e x p l a i n e d b y the decrease i n the r e d o x potential for C u ( I ) / C u a n d the increase i n the
o v e r p o t e n t i a l o f h y d r o g e n e v o l u t i o n . T h e increase i n the C N : C u m o l e ratio s i g n i f i c a n t l y
shifts the p o t e n t i a l for C u ( I ) / C u to m o r e negative values a n d the d i s t r i b u t i o n o f c o p p e r
c y a n i d e shifts f r o m the electroactive species ( d i c y a n i d e or p r o b a b l y t r i c y a n i d e ) to the n o n -
electroactive species (tetracyanide), r e s u l t i n g i n a l o w exchange current. F u r t h e r m o r e , the
increase i n the C N : C u m o l e ratio also increases the free c y a n i d e c o n c e n t r a t i o n , w h i c h i n t u r n
increases the o v e r p o t e n t i a l o f h y d r o g e n e v o l u t i o n [113].Therefore the cathode has to be k e p t
at a l o w e r p o t e n t i a l to m a i n t a i n a constant current. T h e increase i n the m o l e ratio o f c y a n i d e

73
to copper c a n increase the c o n d u c t i v i t y o f the electrolyte a n d decrease the c e l l v o l t a g e , but
the decrease i n IR i n the electrolyte is s m a l l e r than the increase i n the absolute v a l u e o f
cathode p o t e n t i a l .
2.3
0 2 4 6 8 10 12
Time / Hours
F i g u r e 5-6 C e l l v o l t a g e v s . t i m e o f e l e c t r o l y s i s at 2 5 0 A m" a n d 60 C . E l e c t r o l y t e : 7 0 g L "

2 1
C u , 63 g L " N a j S C ^ , 10 g L " N a O H , and different c y a n i d e concentrations i n the absence o f

1 1
SCN' . 1
5.3.4 Effect of T e m p e r a t u r e
Temperature is expected to be a n important factor affecting b o t h the a n o d i c a n d
c a t h o d i c processes. T h r e e temperatures (40, 50 a n d 60 C ) w e r e tested a n d the results are
g i v e n i n T a b l e s 5-4 a n d 5-5. T h e c a t h o d i c current e f f i c i e n c y o f copper d e p o s i t i o n decreases
w i t h d e c r e a s i n g temperature. T h e a n o d i c current e f f i c i e n c y o f c y a n i d e o x i d a t i o n decreases
w i t h i n c r e a s i n g temperature a n d the c e l l v o l t a g e decreases w i t h i n c r e a s i n g temperature. The
increase i n the c e l l v o l t a g e w a s partly caused b y the decrease i n the c o n d u c t i v i t y o f the
electrolyte.
74
T a b l e 5-5 R e s u l t s o f copper e l e c t r o w i n n i n g at 2 5 0 A m " 2

a n d different temperatures.
E l e c t r o l y t e s : 70 g L " C u , C N : C u m o l e ratio = 3, 63 g L ' N a S 0
1 1
2 3 a n d 10 g L " N a O H i n the
1
presence and absence o f S C N " .

[SCN ] / g L"
1 1
Temp. / Average Copper Anodic Anode cathode
C cell C. E. / % C.E. for CN" / surface copper
voltage % condition
/V
0 50 2.12 85 3 21 5 a very little small dendrite
black coating
40 50 2.01 88 3 20 5 a very little coral-like
black coating deposits
0 40 2.20 82 + 3 25 5 a very little small dendrite
black coating
40 40 2.07 86 3 25 + 5 a very little coral-like
black coating deposits
5.4 Summary
Of four s a c r i f i c i a l species (sulphite, m e t h a n o l , thiocyanate and ammonia), only
sulphite c a n e f f e c t i v e l y l i m i t the o x i d a t i o n o f c y a n i d e . W h e n the c o m p o s i t i o n o f the
electrolyte w a s c o n t r o l l e d at 50-60 g L " N a 2 S 0 , 70 g L " C u , C N : C u m o l e ratio = 3-3.2, the

1
3
1
a n o d i c current e f f i c i e n c y o f c y a n i d e decreased f r o m about 100 % to 10-20 % i n the current
range 2 5 0 - 5 0 0 A m " a n d the temperature range 5 0 - 6 0 C . T h e c o p p e r d e p o s i t i o n current

2
e f f i c i e n c y w a s 90-96 % a n d the energy c o n s u m p t i o n w a s 0.76-1.0 k W h / k g C u . T h e a n o d i c
current e f f i c i e n c y o f c y a n i d e increased f r o m about 15 % to 56 % w i t h i n c r e a s i n g C N : C u
m o l e ratio f r o m 3 to 4.5 at [ C u ] = 70 g L " . W i t h i n c r e a s i n g current density, the a n o d i c current

1
e f f i c i e n c y o f c y a n i d e decreases greatly at the current > 500 A m " and s l i g h t l y at the current <
2
500 A m" . T h e a n o d i c current e f f i c i e n c y o f c y a n i d e decreases s l i g h t l y w i t h i n c r e a s i n g

2
temperature. T h e copper d e p o s i t i o n current e f f i c i e n c y decreases w i t h i n c r e a s i n g C N : C u m o l e
ratio and decreasing temperature. T h e presence o f thiocyanate increases the c o p p e r d e p o s i t i o n
current e f f i c i e n c y at C N : C u m o l e ratio > 4. 5.

75
6. THE ANODIC OXIDATION OF SULPHITE ON A GRAPHITE

ANODE IN ALKALINE SOLUTION
I n C h a p t e r 5, it w a s noted that o f the additives tested o n l y sulphite c o u l d e f f e c t i v e l y
l i m i t the o x i d a t i o n o f c y a n i d e o n a graphite anode. I n order to further the d e v e l o p m e n t , it
therefore is i m p o r t a n t to understand the k i n e t i c s o f the a n o d i c o x i d a t i o n o f sulphite o n
graphite. H o w e v e r , the a n o d i c o x i d a t i o n o f sulphite i n a l k a l i n e s o l u t i o n s has not been
i n v e s t i g a t e d t h o r o u g h l y a n d the p u b l i s h e d results are inconsistent. F o r the purpose o f u s i n g
sulphite o x i d a t i o n as a n alternative anode r e a c t i o n i n copper c y a n i d e e l e c t r o w i n n i n g , the
a v a i l a b l e i n f o r m a t i o n is inadequate and further studies o n the a n o d i c o x i d a t i o n o f sulphite i n
a l k a l i n e s o l u t i o n are needed. Therefore a study o f the a n o d i c o x i d a t i o n o f sulphite was
c o n d u c t e d o n a graphite electrode u s i n g the rotating d i s c technique a n d the p o t e n t i a l sweep
method.
6.1 Some Fundamental Aspects of Rotating Disk Electrodes
R o t a t i n g d i s k electrodes ( R D E ) have been e m p l o y e d for the study o f a great v a r i e t y o f
e l e c t r o c h e m i c a l processes due to certain advantages o v e r other types o f s o l i d electrodes. T h e
major advantage l i e s i n the d e v e l o p m e n t o f a u n i f o r m d i f f u s i o n layer, the t h i c k n e s s o f w h i c h
c a n be c a l c u l a t e d at a g i v e n rotational speed. S o , the u n i f o r m m a s s transfer t o w a r d s a n d a w a y
f r o m the electrode surface c a n be c h a n g e d b y c h a n g i n g the rotational speed i n a pre-
d e t e r m i n e d w a y . R D E theory has been d e s c r i b e d b y L e v i c h [322] w h i l e a c o m p r e h e n s i v e
presentation o n these electrodes is d i s c u s s e d i n t w o m o n o g r a p h s b y P l e s k o v a n d F i l i n o v s k i i
[323] a n d b y O p e k a r a n d B e r a n [324]. W h e n a rotating d i s k rotates i n a v i s c o u s a n d
i n c o m p r e s s i b l e l i q u i d at a n angular v e l o c i t y co, the l i q u i d l a y e r i m m e d i a t e l y adjacent to the
d i s c surface takes part i n the rotational m o t i o n . T h e layers not i m m e d i a t e l y adjacent to the
d i s c must also rotate o w i n g to the v i s c o u s forces. U s i n g c y l i n d r i c a l coordinates (r, (p, z) the
l i q u i d v e l o c i t y c a n be d i v i d e d into three c o m p o n e n t s : V r - radical direction caused by
centrifugal force, V^, - a z i m u t h a l d i r e c t i o n due to the l i q u i d v i s c o s i t y a n d V - a x i a l d i r e c t i o n

z
r e s u l t i n g f r o m the pressure drop. These v e l o c i t y c o m p o n e n t s d e s c r i b e d b y the N a v i e r - S t o k e s
e q u a t i o n are a f u n c t i o n o f rotational speed, l i q u i d v i s c o s i t y , v e r t i c a l distance f r o m the d i s k (z)

76
a n d r a d i a l distance (r). U n d e r these c o n d i t i o n s : (1) the f l o w is non-turbulent ( d V / d t = 0), (2)
the f l o w is independent o f the coordinate cp, because o f a x i a l s y m m e t r y , (3) the f l u i d is
i n c o m p r e s s i b l e a n d the b o u n d a r y is h o r i z o n t a l , (4) v a r i a t i o n s i n the pressure i n the b o u n d a r y
l a y e r are dependent o n l y o n z a n d a sufficient angular v e l o c i t y generates strong c o n v e c t i o n ,
so that c o n t r i b u t i o n s f r o m extraneous forces are e l i m i n a t e d [324]. T h e s e three c o m p o n e n t s
c a n be represented b y the f o l l o w i n g equations [323, 3 2 4 ] :
V = rcoF(Q
r V = rcoG(%)
v V__ = Jr~^H(^) (6-1)
w h e r e , = (co/v) 1/2
z - d i m e n s i o n l e s s distance f r o m the d i s k surface, v is the k i n e m a t i c
v i s c o s i t y , co the angular v e l o c i t y , r the r a d i a l distance and z the v e r t i c a l distance f r o m the
disk. F ( ^ ) , G ( ^ ) a n d H ( ^ ) are d i m e n s i o n l e s s functions w h i c h have different f o r m u l a e .
F i g u r e 6-1 R o t a t i n g d i s k coordinate s y s t e m u s e d i n c a l c u l a t i o n s o f l i q u i d f l o w near the
rotating d i s k .
T h e t h i c k n e s s o f the d i f f u s i o n layer (8) depends o n S c h m i d t n u m b e r ( S c = v / D ) [323].
W h e n S c is larger than 1000, the w e l l - k n o w n L e v i c h e q u a t i o n ( E q u a t i o n 6-2) has sufficient
a c c u r a c y to express the thickness o f the d i f f u s i o n layer. F o r aqueous s o l u t i o n s , the L e v i c h
e q u a t i o n c a n be a p p l i e d since S c = v / D 1 0 . 3
8 = 1.611(D / v ) 1 / 3
( v / co) ' = 1.61 W v V
1 2 m l 2
(6-2)
W h e n S c is b e l o w 1000, the f o l l o w i n g equations s h o u l d be used:
5= 1.611( D/v)
J
1 / 3
(v/<y)- 1 / 2
(l + 0.3539(>/v) 0 3 6
) 2 5 0 < S c < 1000 (6-3)
S- 1.611(D/ v ) 1 / 3
(Wffl)" 1 / 2
(l + 0.3539(D/ v)" 1 / 3
+ 0.14514(D/ v 2 / 3
) S c > 100 (6-4)
77
T h e a b o v e equations are based o n the l a m i n a r f l o w c o n d i t i o n . W h e n the R e y n o l d s
n u m b e r ( R e = cor /v) exceeds a c r i t i c a l v a l u e , the f l u i d f l o w changes q u a l i t a t i v e l y f r o m

2
l a m i n a r to turbulent. C o n v e r s i o n is gradual. First, the edge o f the d i s k is affected by
turbulence a n d this g r a d u a l l y extends t o w a r d the center w i t h i n c r e a s i n g v e l o c i t y o f rotation.
T h e c r i t i c a l R e v a l u e is 1.8-3.Ix 1 0 5
[324]. T o a v o i d turbulence, the m a x i m u m r o t a t i o n a l
speed for 10 m m rotating d i s k is (1.8-3.1)xl0 (60v/27cr ) = 1 7 2 0 0 - 2 9 6 0 0 r p m . W h e n the d i s k

5 2
vibrates a x i a l l y or r a d i a l l y and the surface is u n e v e n , turbulence appears at R e v a l u e s b e l o w
the c r i t i c a l v a l u e s .
A n o t h e r extreme occurs for R e 10, w h e n the thickness l a y e r b e c o m e s c o m p a r a b l e
w i t h the d i m e n s i o n s o f the d i s k and natural c o n v e c t i o n i n the s o l u t i o n b e g i n s to p l a y a r o l e .
Therefore the r o t a t i o n a l speed must be m u c h larger than 10(60v/27rr ) 1 r p m . T h e t h i c k n e s s

2
o f the b o u n d a r y l a y e r is sufficiently s m a l l e r than the radius o f the d i s k a n d R e is s u f f i c i e n t l y
large to m a k e natural c o n v e c t i o n n e g l i g i b l e . T h e rotational speed e m p l o y e d is u s u a l l y f r o m
100 to 6 0 0 0 r p m and so the L e v i c h e q u a t i o n c a n be accurately a p p l i e d . T h e ratio o f the
diameters o f the outer insulator to the electrode d i s c s h o u l d be large e n o u g h to m i n i m i z e the
edge effects.
T h e l i m i t i n g current density (i,) for the s i m p l e r e a c t i o n ( O + ne = R ) equals the
d i f f u s i o n current density ( i ) and c a n be expressed as

d
nFDC b
(6-5)
S
where n is the n u m b e r o f electrons transferred, F the F a r a d a y constant ( 9 6 4 8 7 A s m o i " ) , C 1
b
the b u l k c o n c e n t r a t i o n ( m o i dm" ) a n d D the d i f f u s i o n coefficient. It s h o u l d be n o t e d that

3
E q u a t i o n 6-5 is o n l y v a l i d w h e n the transport n u m b e r o f electroactive species i (t ) is z e r o . ;
W h e n the transport n u m b e r ( t ) is not n e g l i g i b l e but is s m a l l e r than 0.1 a n d the charge n u m b e r
o f the i o n i c species is equal to n , the l i m i t i n g current density c a n be expressed b y the
f o l l o w i n g e q u a t i o n [325]:
nFDC b 0.62nFD y- G) C
2/3 m U2
b
h = 3(1-0' (6-6)
F r o m E q u a t i o n 6-5, the d i f f u s i o n coefficients for e l e c t r o c h e m i c a l species c a n be c a l c u l a t e d
f r o m the slopes o f the straight lines for the p l o t o f i, v s . co . ,/2

78
T h e rotating d i s k is a p o w e r f u l t o o l for d e t e r m i n i n g r e a c t i o n order a n d the rate
constant. T h e r e are m a n y methods to determine the r e a c t i o n order u s i n g a rotating d i s k a n d
s o m e o f t h e m are d i s c u s s e d i n p u b l i s h e d m o n o g r a p h s [323, 3 2 4 ] . T h e d e r i v a t i o n o f a f o r m u l a
w h i c h c a n be a p p l i e d to determine the r e a c t i o n order a n d rate constant w h e n the l i m i t i n g
currents h a v e been m e a s u r e d is g i v e n b e l o w .
T h e current density for m i x e d k i n e t i c s at a rotating d i s k electrode is d e t e r m i n e d b y the
heterogeneous r e a c t i o n w i t h the d i f f u s i o n o f the reactant and the rate o f the heterogeneous
r e a c t i o n b e i n g e q u a l to the d i f f u s i o n rate under steady-state c o n d i t i o n s . Therefore w h e n the
charge transfer coefficient is independent o f the reactant c o n c e n t r a t i o n a n d the reverse
r e a c t i o n is n e g l i g i b l e , the current density for a s i m p l e r e d o x r e a c t i o n ( O + ne = R ) c a n be
expressed as:
i = nFk(C )"' s (6-7)
i = nFD() sinface = nFD^^ = - ^-) (6-8)
w h e r e i is the current density, n the r e a c t i o n order, k the r e a c t i o n rate constant, a n d C

r s the
electrode surface concentration. F r o m E q u a t i o n s 6-7 a n d 6-8, w e h a v e the following
equations:
Q = Q(1--) (6-9)
h
I
i = nFkC " (1 - )"' = i
b
r
T k 1-7- (6-10)
I, V i,J
i
log i = log i + n log(l - 7 )
k r (6-11)
h
where i = nFkC " is the k i n e t i c a l l y c o n t r o l l e d current. T h e r e a c t i o n order c a n be c a l c u l a t e d

k b
r
f r o m the p l o t o f l o g i v s . l o g ( l - i / i , ) and the k i n e t i c a l l y c o n t r o l l e d current c a n be o b t a i n e d f r o m
the intercept o n the y - a x i s . T h e r e a c t i o n order is obtained at constant i o n i c strength a n d the
effects o n the d o u b l e l a y e r a n d the a c t i v i t y coefficient are n e g l i g i b l e due to the change i n the
reactant c o n c e n t r a t i o n . Furthermore, i n this m e t h o d it is not necessary to know the
c o n c e n t r a t i o n o f the reactant. T h e exchange current a n d T a f e l slope c a n be o b t a i n e d f r o m the
plot o f i v s . o v e r p o t e n t i a l . I f n = 1 (first order), w e get the K o u t e c k y - L e v i c h e q u a t i o n f r o m

k r
E q u a t i o n 6-10:
79
I__L 1 (6-12)
/' z i, t
E q u a t i o n s 6-7, 6-8, 6-11 a n d 6-12 are also v a l i d f o r r e d o x reactions s u c h as O + X
+ne = R w h e n the r e a c t i o n order w i t h respect to X is zero or the c o n c e n t r a t i o n o f X is kept at
an elevated level so that there is n o difference between the surface a n d the bulk
concentration. I n these cases, the k i n e t i c e x p r e s s i o n c a n be r e d u c e d to E q u a t i o n 6-7.
6.2 Thermodynamics of Sulphite Oxidation
A s w a s d i s c u s s e d i n Chapter 2 , S e c t i o n 2 . 5 , sulphite exists i n the f o r m o f S 0 (aq), 2
H S O y a n d S 0 " i n aqueous s o l u t i o n . S 0
3
2
2 (aq), H S 0 " a n d S 0 " species are p r e d i c t e d to
3 3
2
predominate o v e r the p H ranges < 1.8, 1.8 - 7 a n d > 7, r e s p e c t i v e l y . A t p H > 12, the
d o m i n a n t species i n s o l u t i o n is S 0 " . T h e a n o d i c o x i d a t i o n o f sulphite i n a l k a l i n e s o l u t i o n o n

3
2
graphite c a n be expressed b y the f o l l o w i n g equations:
S0 3
2
" + 20FT = S0 4
2
" +H 2 0 + 2e (6-13)
2S0 3
2
" =S 0 2 6
2
'+2e (6-14)
T h e p r o d u c t i o n o f dithionate o n graphite ( E q u a t i o n 6-14) c a n be n e g l e c t e d a c c o r d i n g to the
literature [211].The standard e q u i l i b r i u m potentials for E q u a t i o n 6-13 are -0.936 , - 0.957, -
0 . 9 7 1 , -0.985 V v s . S H E at 2 5 , 4 0 , 50 a n d 60 C r e s p e c t i v e l y o b t a i n e d b y c a l c u l a t i o n u s i n g
r e l i a b l e t h e r m o d y n a m i c s data [295, 2 9 6 ] . T h e N e r n s t e q u a t i o n for the e q u i l i b r i u m p o t e n t i a l
for E q u a t i o n (6-13) is expressed as:
n R T
,
a
SO/- H 0
a
2
(6-15)
\ SO*- OH- J
a a 2
T h e r e are m a n y m e t h o d s f o r c a l c u l a t i n g a c t i v i t y coefficients i n strong electrolytes s u c h as the
Guggenheim, Bromley, Meissner, Chen and Pitzer's methods [326]. Pitzer's ion-ion
i n t e r a c t i o n m o d e l is g o o d for c a l c u l a t i n g the a c t i v i t y coefficient o f a s i n g l e species i n m u l t i -
component strong electrolytes [326-328] a n d it has been used i n this study. I n P i t z e r ' s
80
m e t h o d , the c o n c e n t r a t i o n is expressed i n m o l a l i t y a n d so the a c t i v i t y o f species i , is a, = m^ y . (
T h e m o l a l i t y o f species i ( m j has the f o l l o w i n g r e l a t i o n s h i p w i t h the m o l a r i t y ( Q ) [329]
m
< =
p-0.001EC,M, ( 6
' 1 6 )
w h e r e p is the density o f electrolyte. I n the presence o f 1 M N a S 0 2 4 s u p p o r t i n g electrolyte, mj
1.02 Cj (p = 1.12 [330]). F o r c o n v e n i e n c e , the m o l a r i t y replaces the m o l a l i t y as an
a p p r o x i m a t i o n for c a l c u l a t i o n . T h e interaction o f S 0 " w i t h N a a n d O H " is r o u g h l y s i m i l a r to

3
2 +
that o f S 0 " [328] a n d the a c t i v i t y coefficients o f S 0 " a n d S 0 " are c l o s e [331]. T h e r e f o r e

4
2
3
2
4
2
the a c t i v i t y coefficient o f S 0 " is a s s u m e d to equal to that o f S 0 " . T h e a c t i v i t y coefficients

3
2
4
2
o f water a n d h y d r o x i d e i o n s have been c a l c u l a t e d u s i n g P i t z e r ' s m e t h o d (see A p p e n d i x 5).
T h e c a l c u l a t e d water a c t i v i t y , a c t i v i t y coefficient o f h y d r o x i d e a n d the p o t e n t i a l for
S 0 " a n d S 0 " c o u p l e at 2 5 , 4 0 , 50 and 60 C are l i s t e d i n T a b l e 6 - 1 . T h e water a c t i v i t y i s

4
2
3
2
a l m o s t independent o f the temperature and the h y d r o x i d e a c t i v i t y c o e f f i c i e n t decreases
s l i g h t l y w i t h i n c r e a s i n g temperature.
T a b l e 6-1 T h e a c t i v i t i e s and a c t i v i t y coefficients for 0.1 M N a S 0 , 0.25 M N a O H a n d 1 M

2 3
Na S0 2 4 at 2 5 , 4 0 , 50 a n d 60 C
Temperature / C 25 40 50 60
a^ v 1.03 1.03 1.03 1.03
YOH(I) 0.486 0.470 0.459 0.448
E ( S 0 7 S 0 " ) vs S H E / V
4
2
3
2
-0.822 -0.837 -0.8.46 -0.855
6.3 Experimental Apparatus and Set-up
A n N E - 1 5 0 graphite r o d (impregnated w i t h r e s i n a n d c a r b o n i z e d at 5 0 0 C i n
v a c u u m ) f r o m N a t i o n a l E l e c t r i c C a r b o n C o . w a s used to m a k e a graphite rotating d i s k . T h e
graphite w a s m a c h i n e d to 4 m m and t i g h t l y surrounded w i t h a p l a s t i c s h i e l d . A s p r i n g w a s
u s e d to c o n d u c t the e l e c t r i c i t y f r o m the shaft to the graphite electrode. F i g u r e 6-2 s h o w s the
schematic d i a g r a m o f the rotating d i s k .

81
Shaft
Steel holder Screw
Cu for electrical contact
Plastic holder - Spring

(Outer insulator) Cu for electrical contact
Graphite electrode
F i g u r e 6-2 S c h e m a t i c d i a g r a m o f rotating d i s k
T h e electrode surface w a s first g r o u n d u s i n g 6 0 0 - g r i t sandpaper, p o l i s h e d w i t h 4 0 0 0 -
grit s i l i c o n c a r b i d e sandpaper a n d then soft tissue paper. F i n a l l y the surface w a s c h e c k e d
under a m i c r o s c o p e for surface smoothness. T o ensure r e p r o d u c i b l e results, the electrode w a s
first treated b y c y c l i c v o l t a m m e t r y b e t w e e n 0 a n d 0.75 V v s . S C E at 100 m V s" for 3 0 1
m i n u t e s a n d p o l a r i z e d at l m V s" u n t i l the electrode reached a stable c o n d i t i o n . T h e electrode

1
w a s tested i n ferrous a n d ferric c y a n i d e s o l u t i o n . T h e l i m i t i n g current density w a s the same as
o n a P t rotating d i s k f r o m E G & G C o . a n d w a s p r o p o r t i o n a l to the square root o f the
r o t a t i o n a l speed. Therefore the graphite electrode w a s c o n s i d e r e d to be u n i f o r m .
T h e graphite h a v i n g a 1 2 - m m diameter w a s f a s h i o n e d as a rotating d i s k for the
c o u l o m e t r i c measurements.
T h e rotating d i s c electrode s y s t e m w a s a n E G & G PARC M o d e l 636 Electrode
Rotator. T h e potentiostat w a s a S O L A R T R O N 1286 E l e c t r o c h e m i c a l Interface. 100 m L o f
the s o l u t i o n o f the required composition were placed i n an E G & G water-jacketed
electrolytic cell whose temperature was controlled by a water bath circulator. The
e x p e r i m e n t s w e r e c a r r i e d out under an a r g o n atmosphere to protect the sulphite from
o x i d a t i o n b y air. T h e reference electrode w a s a F I S H E R saturated c a l o m e l electrode ( S C E )
w h i c h w a s c o n n e c t e d to the c e l l electrolyte b y a n electrolyte b r i d g e . T h e c a l o m e l electrode
w a s p l a c e d i n a tube c o n t a i n i n g the same electrolyte as i n the c e l l . T h e temperature w a s k e p t
at 25 C u s i n g a water bath. T h e o h m i c drop b e t w e e n the w o r k i n g electrode a n d the reference
electrode w a s c o m p e n s a t e d b y the current i n t e r r u p t i o n technique. A s c h e m a t i c d i a g r a m o f the

82
e x p e r i m e n t a l set-up is s h o w n i n F i g u r e 6-3. E x c e p t as noted, the p o l a r i z a t i o n c u r v e s w e r e
generated u s i n g the potential s w e e p i n g m e t h o d at 1 m V s". 1
C E O
Ag-C bush S C E e i t ode
ec r
Pt counter electrode Electrolyte bridge
Cover
F i g u r e 6-3 S c h e m a t i c d i a g r a m o f the e x p e r i m e n t a l setup
A C a n n o n - F e n s k e routine v i s c o m e t e r (size 25) w a s u s e d to measure the k i n e m a t i c
v i s c o s i t y o f the solutions studied. T h e e x p e r i m e n t a l set-up a n d the m e a s u r i n g p r o c e d u r e are
s h o w n i n A p p e n d i x 6. T h e c o n c e n t r a t i o n o f sulphite w a s m e a s u r e d b y a d d i n g a n excess o f
standard i o d i n e s o l u t i o n f o l l o w e d b y b a c k titration w i t h standard thiosulphate s o l u t i o n (see
A p p e n d i x 4).
T h e l i q u i d j u n c t i o n potential, estimated b y the Henderson equation [332] (see
A p p e n d i x 7), w a s b e l o w 2 m V a n d so c a n be neglected. T h e t h e r m a l l i q u i d j u n c t i o n p o t e n t i a l
w a s m e a s u r e d u s i n g t w o c a l o m e l reference electrodes w h i c h w e r e p l a c e d o n the t w o sides o f
a n electrolyte b r i d g e .
R e a g e n t grade c h e m i c a l s were used throughout the i n v e s t i g a t i o n .
6.4 Polarization Measurements
T h e p o l a r i z a t i o n measurements were c a r r i e d out at 2 5 , 4 0 , 50 a n d 60 C i n 1 M
Na S0
2 4 s o l u t i o n s c o n t a i n i n g 0.025 to 0.5 M N a S 0
2 3 and 0.025 - 0.25 M N a O H . I f the a p p l i e d
p o t e n t i a l w a s larger than about 1.0 V v s . S C E , the surface o f the electrode w a s c o r r o d e d a n d

83
b e c a m e r o u g h , affecting the current measurements (e.g. the l i m i t i n g current b e c a m e m u c h
l o w e r a n d the current v s . potential w a s n o n - r e p r o d u c i b l e ) . Therefore the electrode surface
w a s r e p o l i s h e d for e v e r y p o l a r i z a t i o n measurement to ensure r e p r o d u c i b l e results. T y p i c a l
p o l a r i z a t i o n c u r v e s for 0.1 M N a S 0
2 3 solutions c o n t a i n i n g 0.25 M N a O H are s h o w n i n F i g u r e
6-4 a n d those for 0.05, 0.2, 0.4 a n d 0.5 M N a S 0 2 3 i n F i g u r e s A - l to A - 4 i n A p p e n d i x 8. T h e
a n o d i c o x i d a t i o n o f sulphite b e g a n at 0.16, 0.12, 0.08 a n d 0. 04 V v s . S C E for 2 5 , 4 0 , 5 0 a n d
6 0 C r e s p e c t i v e l y . D u e to the presence o f sulphite i o n s , o x y g e n e v o l u t i o n w a s suppressed
and the c o r r o s i o n o f the electrode w a s d i m i n i s h e d . T h e h i g h e r the c o n c e n t r a t i o n o f s u l p h i t e ,
the greater w e r e these effects. T h e o x y g e n e v o l u t i o n increases w i t h i n c r e a s i n g temperature.
A t [ N a S 0 ] > 0.4 M a n d 25 - 60 C , a l m o s t n o o x y g e n b u b b l e s w e r e f o r m e d a n d the graphite

2 3
w a s o n l y s l i g h t l y c o r r o d e d . W h e n the current reached a l i m i t i n g v a l u e , it b e c a m e independent
o f the p o t e n t i a l . A t [ N a S 0 ] =
2 3 0.05-0.4 M , the limiting current w a s a p p r o x i m a t e l y
p r o p o r t i o n a l to the sulphite concentration. H o w e v e r , the increase i n the l i m i t i n g current due
to the increase i n sulphite c o n c e n t r a t i o n f r o m 0.4 to 0.5 M w a s m u c h s m a l l e r t h a n e x p e c t e d .
T h e l i m i t i n g current w a s l i m i t e d p r o b a b l y b y O H " d i f f u s i o n at 0.5 M N a S O .

2 s
T h e b a c k g r o u n d current i n the absence o f sulphite is independent o f the r o t a t i o n a l
speed ( F i g u r e A - 5 i n A p p e n d i x 8). H o w e v e r , the current m e a s u r e d i n the presence o f sulphite
is sensitive to the rotational speed a n d the l i m i t i n g current is p r o p o r t i o n a l to the square root
o f the r o t a t i o n a l speed. O x y g e n e v o l u t i o n a n d the c o r r o s i o n o f graphite are greatly suppressed
i n the presence o f sulphite. A t 100 r p m ( F i g u r e 6-4), the o x y g e n e v o l u t i o n e v e n decreased the
current p o s s i b l y because the o x y g e n b u b b l e s w e r e not r e m o v e d e f f i c i e n t l y . T h e r e f o r e the
b a c k g r o u n d current i n the presence o f sulphite c o u l d be m u c h s m a l l e r t h a n that m e a s u r e d i n
the absence o f sulphite a n d c o u l d m a k e a n e g l i g i b l e c o n t r i b u t i o n to the total current. T h e
b a c k g r o u n d current i n the absence o f sulphite w a s inappropriate for c o r r e c t i n g the current for
the sulphite o x i d a t i o n due to o x y g e n e v o l u t i o n at h i g h potentials. T h e c o n d i t i o n o f the surface
o f the graphite electrode v a r i e d after the electrode surface w a s r e n e w e d e a c h t i m e . T h e r e f o r e
after the same treatment o f the electrode, the values o f current v s . p o t e n t i a l scattered to s o m e
extent ( 1 5 % ) . H o w e v e r , the l i m i t i n g currents scattered less ( 2 % ) .

84
0.2 0.4 0.6 0.8 1.0 0.40 0.60 0.80 1.00 1.20
Potential vs SCE/V Potential / V vs. SCE
(a) 25 C (b) 4 0 C
3000 3500
3000 - _ _ 4 9 0 0 rpm
CM -m- 3600 rpm
E
2500 - _ * _ 2 5 0 0 rpm
< _ * _ 1600 rpm
< 2000 - _ * _ 900 rpm
'in
c - - 4 0 0 rpm
1500 - _ , _ 100 rpm
c
1000
t_
3
500 4-
0.00 0.20 0.40 0.60 0.80 1.00 1.20 0.2 0.4 0.6 0.8 1.0
Potential / V vs. SCE Potential vs. SCE /V
(c) 50 C (d) 60 C
F i g u r e 6-4 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 50 a n d 60

C . E l e c t r o l y t e : 0.1 M N a S 0 , 0.25 M N a O H and 1 M N a S 0 .
2 3 2 4
F r o m F i g u r e 6-5, the p o l a r i z a t i o n curves for 0.1 M N a S 0 2 3 s o l u t i o n s c o n t a i n i n g 0.05
M N a O H are quite different f r o m those c o n t a i n i n g 0.25 M N a O H . T h e current first r e a c h e d a
l i m i t i n g v a l u e , a n d then increased s l i g h t l y w i t h i n c r e a s i n g p o t e n t i a l a n d f i n a l l y i n c r e a s e d w i t h
i n c r e a s i n g p o t e n t i a l a n d reached a s e c o n d l i m i t i n g v a l u e . V e r y little o x y g e n w a s e v o l v e d at
potentials > 1.4 V v s . S C E . S i m i l a r p o l a r i z a t i o n curves for 0.2 a n d 0.4 M N a S 0 2 3 are s h o w n
i n F i g u r e s A - 6 a n d 7 i n A p p e n d i x 8. T h e first l i m i t i n g current i n c r e a s e d s l i g h t l y w i t h
i n c r e a s i n g sulphite c o n c e n t r a t i o n f r o m 0.1 to 0.4 M a n d w a s m u c h s m a l l e r t h a n the v a l u e
expected for the c o r r e s p o n d i n g sulphite concentration. T h e s e c o n d l i m i t i n g current ( o b s e r v e d

85
at 100, 4 0 0 a n d 900 r p m ) w a s p r o p o r t i o n a l to the square root o f the rotational speed a n d w a s
a little h i g h e r than the l i m i t i n g v a l u e obtained i n the s o l u t i o n c o n t a i n i n g 0.25 M N a O H at the
same sulphite concentration.
A t [ N a O H ] = 0.05 M , the m o l e ratios o f sulphite to h y d r o x i d e i n the s o l u t i o n are 2, 4,
8 r e s p e c t i v e l y for 0.1, 0.2 a n d 0.4 M N a S 0 . T h e o x i d a t i o n o f one sulphite i o n needs t w o

2 3
h y d r o x i d e i o n s a c c o r d i n g to R e a c t i o n 6-13. S o the equivalent ratios o f sulphite to h y d r o x i d e
are 4, 8 a n d 16 r e s p e c t i v e l y for 0.1, 0.2 a n d 0.4 M N a S 0 . S o the m a s s transfer rates o f

2 3
h y d r o x i d e i o n s have to be 4, 8, 16 t i m e s those o f sulphite ions r e s p e c t i v e l y for 0 . 1 , 0.2 a n d
0.4 M to m a i n t a i n the a l k a l i n e c o n d i t i o n o n the electrode surface. A t i n f i n i t e d i l u t i o n , the
d i f f u s i o n coefficient o f h y d r o x i d e (5.26x10" m 9 2
s" at 25 C ) is 4.96 t i m e s that o f sulphite
1
i o n s (1.06 x l O " m s" ) [318].

9 2 1
A t [ N a S 0 ] = 0.2 a n d 0.4 M , the current b e c o m e s so h i g h that the m a s s transfer rate

2 3
o f h y d r o x i d e i o n s is not h i g h e n o u g h to m a i n t a i n the h y d r o x i d e c o n c e n t r a t i o n a b o v e a c e r t a i n
v a l u e (close to zero). Therefore the species o f sulphite shifts f r o m S 0 " to H S 0 " a n d S 0 3

2
3 2 and
the properties o f the surface o x y g e n - c a r b o n f u n c t i o n groups c a n be c h a n g e d due to the p r o t o n
e x c h a n g e [334]. T h e a n o d i c o x i d a t i o n o f H S 0 " a n d S 0 b e g i n s at h i g h e r potentials [240] a n d

3 2
the change i n the properties o f the surface f u n c t i o n g r o u p m a y result i n a p a s s i v a t i n g effect.
Therefore w h e n the first l i m i t i n g current appeared, the o x i d i z e d species o f sulphite c h a n g e d
f r o m S 0 " to H S 0 " a n d S 0
3
2
3 2 and w i t h further increase i n p o t e n t i a l , the current i n c r e a s e d due
to the o x i d a t i o n o f H S 0 " and S 0 . F i n a l l y the current reached a s e c o n d l i m i t i n g v a l u e related

3 2
to the m a x i m u m d i f f u s i o n rate o f the sulphite species.
I n the presence o f 1 M N a S 0 2 4 as s u p p o r t i n g electrolyte, the d i f f u s i o n c o e f f i c i e n t o f
h y d r o x i d e i o n s c o u l d decrease m o r e than that o f sulphite i o n s a n d so the ratio o f the d i f f u s i o n
coefficients m a y be l o w e r than 4. Therefore t w o l i m i t i n g currents for the s o l u t i o n c o n t a i n i n g
0.1 M N a S 0 2 3 a n d 0.05 M N a O H appeared. T h i s c o u l d be the same as that o b s e r v e d for the
s o l u t i o n c o n t a i n i n g 0.5 M N a S 0 2 3 a n d 0.25 M N a O H because the m o l e ratio o f sulphite to
N a O H (2) is the same.
A t [ N a O H ] = 0.05 a n d 0.25 M , the p o l a r i z a t i o n curves m e a s u r e d i n the solutions
c o n t a i n i n g 0.1 M , 0.2 a n d 0.4 M N a S 0 2 4 at 4 0 0 r p m are s h o w n i n F i g u r e 6-6. C o m p a r e d to
the p o l a r i z a t i o n curves w i t h the same sulphite concentrations, w e c a n see: (1) at a current <
about 3 8 0 A i n , the current for 0.05 M N a O H is a l m o s t the same as that for 0.25 M N a O H ,
2
86
(2) at a current density > about 380 A m" , w i t h further increase i n p o t e n t i a l , the
2
current
densities for 0.05 M N a O H are l o w e r than those for 0.25 M N a O H . T h i s p h e n o m e n o n m a y be
related to the l i m i t e d m a s s transfer o f h y d r o x i d e w h i c h s h o u l d be the same at a constant
c o n c e n t r a t i o n o f h y d r o x i d e and rotational speed.
A t a current density < about 3 8 0 A m" , w h e n the concentrations o f h y d r o x i d e at the

2
surface for a l l the solutions are above a certain v a l u e ( p r o b a b l y p H > 9). T h e sulphite o n the
surface exists o n l y i n the f o r m o f S 0 " w h i c h is d i s c h a r g e d o n the anode a n d the r e a c t i o n

3
2
order w i t h respect to O H " is zero. H e n c e , the current is dependent o n l y o n the p o t e n t i a l a n d
the c o n c e n t r a t i o n o f sulphite. A t a current density > about 3 8 0 A m" , the c o n c e n t r a t i o n o f

2
h y d r o x i d e at the surface for solutions w i t h 0.05 M N a O H b e c o m e s so l o w that H S 0 " a n d 3
S0 2 increase o n the electrode surface and S 0 " decreases, w h i c h decreases the 3

2
current
density. H o w e v e r , the c o n c e n t r a t i o n o f h y d r o x i d e at the surface for the s o l u t i o n s w i t h 0.25 M
N a O H is s t i l l h i g h a n d the c o n c e n t r a t i o n o f S 0 " does not decrease due to the shift o f the

3
2
sulphite species f r o m S 0 " to H S 0 " and S 0 .

3
2
3 2
T h e s e c o n d l i m i t i n g current for the s o l u t i o n w i t h 0.05 M N a O H is larger t h a n that for
the s o l u t i o n w i t h 0.25 M N a O H a n d the ratios o f the f o r m e r to the later are 1.08, 1.12 a n d
1.18 r e s p e c t i v e l y for 0.1, 0.2 a n d 0.4 M N a S 0 . T h e reason c o u l d be: (1) the decrease i n the
2 4
c o n c e n t r a t i o n o f h y d r o x i d e f r o m 0.25 to 0.05 M decreases the v i s c o s i t y o f the s o l u t i o n a n d
w e a k e n s the i n t e r a c t i o n o f ions, resulting i n a h i g h e r d i f f u s i o n c o e f f i c i e n t a n d a h i g h e r
d i f f u s i o n l i m i t e d current, (2) the anode r e a c t i o n c o n s u m e s h y d r o x i d e a n d e v e n generates
h y d r o g e n i o n s w h i c h diffuse to the b u l k s o l u t i o n and react w i t h S 0 " i n the d i f f u i s o n l a y e r to

3
2
f o r m H S 0 " . T h e d i f f u s i o n coefficient o f H S 0 " (1.33 x 10" m s" at i n f i n i t e d i l u t i o n [318]) is

3 3
9 2 1
larger than that o f S 0 " (1.06 x 10" m

3
2 9 2
s at i n f i n i t e d i l u t i o n [330]). T h e c o n c e n t r a t i o n
-1
gradient o f S 0 " is increased, resulting i n a larger l i m i t i n g current. T h i s effect increases w i t h

3
2
i n c r e a s i n g sulphite c o n c e n t r a t i o n because m o r e h y d r o g e n i o n s are generated at a constant
h y d r o x i d e c o n c e n t r a t i o n i n the b u l k s o l u t i o n and therefore the ratio o f the l i m i t i n g currents
increases w i t h sulphite concentration.

87
Potential vs. S C E / V Potential vs. SCE
(a) 25 C (b) 4 0 C
3500
4900 rpm 3000

-.- 3600 rpm CM
-tr- 2500 rpm E 2500 --

< 2000 --
M 1600 rpm <
'
MC 900 rpm 2000 --
Cui rrent densi
(A
1500 -- 400 rpm C
4)
- 4 - 100 rpm a 1500 --
c
1000 -- a
k_
k_ 1000 --
3
o
500 --
0 it
0.4 0.6 0.8 1 1.2 1.6 0.4 0.6 0.8 1 1.2

Potential vs. S C E / V Potential vs. S C E / V
(c) 50 C (d) 60 C
F i g u r e 6-5 P o l a r i z a t i o n c u r v e s o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 50 a n d 60

C . E l e c t r o l y t e : 0.1 M N a j S O j , 0.05 M N a O H and 1 M N a ^ .
88
2500
Potential vs. S C E / V
F i g u r e 6-6 C o m p a r i s o n o f the p o l a r i z a t i o n curves w i t h different sulphite a n d h y d r o x i d e

concentrations at 25 C and 4 0 0 r p m .
6.5 Coulometric Measurements
C o n t r o l l e d potential c o u l o m e t r y w a s used to determine the n u m b e r o f the electrons
transferred (n) for the a n o d i c o x i d a t i o n o f the sulphite i o n . T h e electrode potentials were
c o n t r o l l e d at 0.6 a n d 0.9 V v s . S C E to a v o i d o x y g e n e v o l u t i o n and c o r r o s i o n o f the graphite.
T h e results are g i v e n i n T a b l e 6-2. I n a l l cases, the n u m b e r o f the electrons transferred per
one sulphite i o n ranges f r o m 1.92 to 1.98. T h i s means that a l m o s t a l l o f the sulphite w a s
o x i d i z e d to sulphate i n t w o - e l e c t r o n reaction. H e n c e the o x i d a t i o n o f sulphite to dithionate
c a n be neglected. P o t e n t i a l and temperature h a d a l m o s t no effect o n the p r o d u c t s o f the
a n o d i c o x i d a t i o n o f sulphite. These results are i n agreement w i t h those reported b y G l a s s t o n e
a n d H i c k l i n g [211].
T a b l e 6-2 N u m b e r o f the electrons transferred for the a n o d i c o x i d a t i o n o f sulphite

Concentration o f Potential / Temperature / N u m b e r o f electrons
sulphite / m o i dm" 3
V vs. S C E C transferred (n) per sulphite
ion
0.1 0.6 25 1.94 0 . 0 3
0.1 0.9 25 1.98 0 . 0 2
0.1 0.6 60 . 1.93 0 . 0 3
0.1 0.9 60 1.97 0 . 0 3
0.4 0.6 25 1.92 0 . 0 4
89
6.6 Reaction Order
F o r the a n o d i c o x i d a t i o n o f sulphite, the concentrations o f sulphite a n d h y d r o x i d e c a n
affect the reaction rate. Therefore the kinetics were first studied by changing the
c o n c e n t r a t i o n o f one species w h i l e the potential a n d the concentrations o f the other species
w e r e m a i n t a i n e d constant. W h e n the potential and p H were m a i n t a i n e d constant, the current
i n c r e a s e d w i t h i n c r e a s i n g sulphite concentration, i n d i c a t i n g that the r a t e - c o n t r o l l i n g step
involved sulphite ions. H o w e v e r , w h e n the potential a n d sulphite c o n c e n t r a t i o n were
m a i n t a i n e d constant, the current w a s independent o f p H , suggesting that the r e a c t i o n order
w i t h respect to h y d r o x i d e is z e r o . Therefore o n l y the sulphite c o n c e n t r a t i o n affects the rate o f
the sulphite o x i d a t i o n a n d the k i n e t i c e x p r e s s i o n for the a n o d i c o x i d a t i o n o f sulphite i o n s c a n
be r e d u c e d to E q u a t i o n 6-7 o v e r the p H range studied (11.9-13). I n the m i x e d c o n t r o l r e g i o n ,
E q u a t i o n 6-11 c a n be a p p l i e d to calculate the r e a c t i o n order w i t h respect to sulphite. T h e data
(current v s . potential) scattered to some extent due to the inherent surface v a r i a b i l i t y after the
e l e c t r o c h e m i c a l c o n d i t i o n i n g . T h e data i n F i g u r e s 6-4 w e r e generated w i t h s o m e v a r i a t i o n o f
surface c o n d i t i o n a n d therefore cannot be u s e d d i r e c t l y to calculate the r e a c t i o n order. F o r the
present e x p e r i m e n t s , the stability o f the graphite surface w a s m a i n t a i n e d b y l i m i t i n g the
p o t e n t i a l range o f the experiments (0 - 0.7 V v s . S C E ) .
F i g u r e 6-7 s h o w s the p o l a r i z a t i o n curves m e a s u r e d o n the same electrode surface i n
the p o t e n t i a l range o f 0 - 0.7 V v s . S C E a n d i n a s o l u t i o n c o n t a i n i n g 0.1 M N a S 0 , 0.25 M

2 3
N a O H a n d 1 M N a S 0 . U s i n g the data s h o w n i n F i g u r e 6-7, the p l o t o f l o g i v s . l o g ( l - i / i , ) at

2 4
25 C is a straight l i n e ( F i g u r e 6-8). A c c o r d i n g to E q u a t i o n 6 - 1 1 , the slope o f the l i n e (i.e. the
r e a c t i o n order) a n d the intercepts o n the l o g i a x i s ( l o g i ) w e r e c a l c u l a t e d b y least squares

k
fitting a n d are g i v e n i n T a b l e 6-3. T h e r e a c t i o n order w i t h respect to the sulphite i o n is 1. F o r
the first order reaction, E q u a t i o n 6-12 c a n be a p p l i e d a n d the p l o t o f 1/i v s . 1/i, i s a straight
l i n e a n d the intercept o n the 1/i a x i s is l / i . F r o m F i g u r e 6-9, the plots o f 1/i v s . 1/i, are l i n e a r
k
a n d the slopes are 1. T h e intercepts o f the p l o t o f l o g i v s . l o g (1-i/ii) are the same as - l o g o f
the intercepts o f the plots o f 1/i v s . at the same p o t e n t i a l (see T a b l e 6-2). T h i s m e a n s that
the r e a c t i o n order is 1 a n d therefore the t w o methods m a t c h v e r y w e l l . T h e same results h a v e
b e e n o b t a i n e d i n solutions 0.4 M N a S 0 , 0.25 M N a O H a n d 1 M N a S 0 . T h e y are s h o w n i n

2 3 2 4
F i g u r e s 6-10 a n d 6-11 a n d T a b l e 6-4. T h e r e a c t i o n order w i t h respect to the sulphite i o n at

90
4 0 , 50 a n d 60 C w a s m e a s u r e d at potentials b e l o w 0.65 V v s . S C E a n d w a s s t i l l one. T h e
results at 4 0 , 50 a n d 60 C for 0.1 M N a ^ C ^ are s h o w n i n F i g u r e A - 8 .
900 ,
0 0.2 0.4 0.6 0.8

F i g u r e 6-7 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 25 C . E l e c t r o l y t e :

0.1 M N a S 0 , 0.25 M N a O H and 1 M N a ^ .
2 3
T a b l e 6-3 R e a c t i o n order and k i n e t i c current c a l c u l a t e d u s i n g different m e t h o d s for 0.1 M

Na S0 .
2 3
Potential vs. S C E / V 0.50 0.55 0.60 0.65 0.70

S l o p e o f the p l o t o f L o g i v s . 1.05 1.01 1.01 1.01 0.99
Log(l-i/i,)
Intercepts o f the p l o t o f L o g i v s . 2.08 2.35 2.62 2.90 3.14
L o g ( l - i / i , ) , i.e. i / A m "
k
2
S l o p e o f p l o t o f 1/i v s . 1/i, 1.04 1.01 1.00 1.01 1.00

- L o g ( i n t e r c e p t s o f p l o t o f 1/i 2.08 2.35 2.62 2.90 3.14
v s . 1/i,), i.e. i / A m "
k
2
L o g ( i / ( l - i / i , ) ) , i.e. i / A m"
k
2
2.06 2.33 2.61 2.89 3.15
T a b l e 6-4 R e a c t i o n order and k i n e t i c current c a l c u l a t e d u s i n g different m e t h o d s for 0.4 M

Na SQ .
2 3
Potential vs. S C E / V 0.50 0.55 0.60 0.65 0.70

S l o p e o f the p l o t o f L o g i v s . 1.04 1.04 1.00 1.00 1.03
Log(l-i/i,)
Intercepts o f the p l o t o f L o g i v s . 2.64 2.90 3.19 3.39 3.62
L o g ( l - i / i , ) , i.e. i / A m "
k
2
S l o p e o f p l o t o f 1/i v s . 1/i, 1.03 1.01 1.01 1.02 1.03

- L o g ( i n t e r c e p t s o f p l o t o f 1/i 2.64 2.90 3.19 3.39 3.62
v s . 1/ij), i.e. i / A m "
k
2
L o g ( i / ( l - i / i , ) ) , i.e. i / A m "
k
2
2.65 2.92 3.21 3.42 3.63
91
F i g u r e 6-8 L o g i v s . L o g ( l - i / i , ) at constant potential a n d 25 C . E l e c t r o l y t e : 0.1 M N a j S C ^ , 1

M N a j S C ^ a n d 0.25 M N a O H .
0.012
0.50 V
0.01
0.55 V
0.60 V
0.008
X 0.65 V
X 0.70 V
0.006 + L
0.004
0.002 4-
0
0.0005 0.001 0.0015 0.002 0.0025
(i, / A r r f ) -
2 1
F i g u r e 6-9 1/i v s . 1/i, at constant potential ( V v s . S C E ) 25 C . E l e c t r o l y t e : 0.1 M N a S 0 , 12 3
M N a S 0 a n d 0.25 M N a O H .
2 4
92
2.4
-0.5 -0.4 -0.3 -0.2 -0.1 0
LOG(1-l/i|)
F i g u r e 6-10 L o g i v s . L o g ( l - i / i , ) at constant potential a n d 25 C . E l e c t r o l y t e : 0.4 M N a S 0 ,

2 3
1 M N a S 0 a n d 0.25 M N a O H .
2 4
F i g u r e 6-11 1/i v s . 1/i, at constant potential ( V v s . S C E ) 25 C . E l e c t r o l y t e : 0.4 M N a 2 S 0 , 1

3
M N a S 0 a n d 0.25 M N a O H .
2 4
93
I n the l o w p o l a r i z a t i o n r e g i o n , the current is s m a l l a n d therefore the concentrations at
the electrode a n d i n the b u l k are the same. I n this case, o n l y E q u a t i o n 6-7 is n e e d e d to
a n a l y z e the k i n e t i c s . E q u a t i o n 6-8 is not r e q u i r e d because the m a s s transfer is not important.
Therefore the r e a c t i o n order w a s not c a l c u l a t e d u s i n g the slope o f the p l o t o f l o g i v s . l o g ( 1 -
i/i,), rather it w a s c a l c u l a t e d f r o m the p l o t o f l o g i as a f u n c t i o n o f the sulphite c o n c e n t r a t i o n .
T h e plots o f l o g ( i ) v s . l o g [ S 0 " ] at 0.2 and 0.4 V v s . S C E at 25 C are s h o w n i n F i g u r e 6-12.

3
2
A t 0.4 V v s . S C E , the r e a c t i o n order w a s close to 1. A t 0.2 V v s . S C E , the r e a c t i o n order w a s
below 1 and appeared to be nonlinear with i n c r e a s i n g reactant concentration. This
n o n l i n e a r i t y c o u l d be caused b y the v a r i a b l e a d s o r p t i o n o f sulphite i o n s o n the graphite
electrode surface.
2.5
-2 -1.5 -1 -0.5 0
Log ([S0 -]/moi d m )
3
2 3
F i g u r e 6-12 L o g i v s . l o g [ S 0 - ] at 25 C a n d 4 9 0 0 r p m . E l e c t r o l y t e : 1 M N a S 0
3
2
2 4 and
0.25 M N a O H . 1
I f the r e a c t i o n order is 1, the p l o t o f l o g ( i /(1-i/i,)) (corrected for the difference i n
c o n c e n t r a t i o n o f sulphite b e t w e e n the b u l k electrolyte a n d that at the electrode surface) v s .
p o t e n t i a l s h o u l d be a straight l i n e . A t l o w current, (1-i/i,) is c l o s e to 1 a n d the c o n c e n t r a t i o n
difference c a n be neglected. T h e plots o f l o g (i /(1-i/i,)) v s . p o t e n t i a l at 2 5 , 4 0 , 50 a n d 6 0 C
are s h o w n i n F i g u r e 6-13. T h e corrected current (i/( 1-i/i,)) is the same as the k i n e t i c current
(i,J c a l c u l a t e d u s i n g the a b o v e methods (see T a b l e 6-2). T h e r e are t w o T a f e l slopes. T h e first
T a f e l slope at l o w potentials w a s 0.059 -0.066 V decade" a n d the charge transfer c o e f f i c i e n t

1
94
w a s about 1. T h e s e c o n d T a f e l slope at h i g h potentials w a s 0.19-0.22 V decade" 1

w i t h the
charge transfer c o e f f i c i e n t b e i n g i n the range o f 0.29 - 0.31. T h e T a f e l slopes for the different
potentials ranges a n d temperatures are listed i n T a b l e 6-5.
T a b l e 6-5 T a f e l slopes ( V decade" ) for the different potential ranges at 2 5 , 4 0 , 5 0 a n d 6 0 C

1
Temperature 25 C 40 C 50 C 60 C
L o w p o t e n t i a l range (vs. S C E / V ) 0.16-0.25 0.11 - 0 . 2 2 0.08-0.18 0.04-0.15
T a f e l slopes for l o w potential range 0.059 0.061 0.064 0.066
H i g h p o t e n t i a l range (vs. S C E / V ) 0.4 - 0.7 0.38-0.66 0.38 - 0.64 0.36 -0.64
T a f e l slopes for h i g h potential range 0.19 0.20 0.21 0.22
T h e first T a f e l slope (0.060 V decade" ) corresponds to a n o n l i n e a r r e a c t i o n order (less

1
t h a n 1) at l o w potential (0.16 - 0 . 25 V vs. S C E ) a n d the s e c o n d T a f e l slope c o r r e s p o n d s to a
first order r e a c t i o n at h i g h potentials (0.4 - 0.7 V v s . S C E ) at 25 C . T h i s i n f o r m a t i o n
suggests that there are t w o r e a c t i o n m e c h a n i s m s .
T h e change i n T a f e l slope, hence i n the m e c h a n i s m w a s not due to the p o t e n t i a l -
dependent change i n the nature of electrode surface because after electrochemical
c o n d i t i o n i n g , the electrode surface w a s stable o v e r the potential range 0 - 0.7 V v s . S C E . F o r
e x a m p l e , at 25 C , the b a c k g r o u n d current w a s a l m o s t constant o v e r the p o t e n t i a l range 0 -
0.6 V v s . S C E , but the change i n the T a f e l slope h a p p e n e d b e t w e e n 0.3 - 0.4 V v s . S C E (see
F i g u r e 6-13). T h e T a f e l slope change c o u l d be due to the f o l l o w i n g : at l o w p o t e n t i a l , the
o x i d a t i o n o f the adsorbed sulphite w a s d o m i n a n t a n d at h i g h p o t e n t i a l , the o x i d a t i o n o f
u n a d s o r b e d sulphite w a s d o m i n a n t . T a r a s e v i c h et a l . [240, 243] reported that the first T a f e l
slope w a s 0.060 - 0.070 V decade" a n d the r e a c t i o n order o b t a i n e d b y the change o f sulphite

1
c o n c e n t r a t i o n w a s c l o s e to 1, H o w e v e r , these authors d i d not g i v e the other T a f e l s l o p e .

95
0.7
0 -I 1 1 -H \ 1 1
-1.5 -0.5 0.5 1.5 2.5 3.5 4.5
Log / A m" ] 2
F i g u r e 6-13 P o t e n t i a l v s . l o g ( ( i / ( l - i / i , ) ) at different temperatures. E l e c t r o l y t e : 0.1 M N a S 0 ,

2 3
1 M Na S0 2 4 a n d 0.25 M N a O H .
6.7 Effect of pH
T h e effect o f p H w a s studied b y c h a n g i n g the s o d i u m h y d r o x i d e c o n c e n t r a t i o n i n the
electrolyte c o n t a i n i n g 1 M N a S 0 . H o w e v e r , the electrolyte c o n t a i n e d 1 M N a 2 S 0 a n d the

2 4 4
pH measurement was not accurate because the electrolyte had a large background
c o n c e n t r a t i o n o f N a S 0 . Therefore the a c t i v i t y coefficient o f O H " w a s c a l c u l a t e d b y P i t z e r ' s

2 4
m o d e l (see A p p e n d i x 5). F i g u r e 6-14 s h o w s the p o l a r i z a t i o n curves i n 0.1 M N a S 0 2 3 solution
w i t h different concentrations o f h y d r o x i d e . T h e plots o f the current (corrected for the
difference o f c o n c e n t r a t i o n b e t w e e n the electrode surface a n d the b u l k s o l u t i o n ) v s . p H are
s h o w n i n F i g u r e 6-15. T h e current at a constant potential appears to be a l m o s t independent o f
p H . Therefore the r e a c t i o n order w i t h respect to O H " is a l m o s t z e r o . T h i s result i s consistent
w i t h those reported b y T a r a s e v i c h et a l . [240, 243] a n d m e a n s that the r a t e - c o n t r o l l i n g step
does not i n v o l v e O H " .

96
800
Potential v s . S C E / V
F i g u r e 6-14 P o l a r i z a t i o n curves at different h y d r o x i d e concentrations a n d 25 C . E l e c t r o l y t e :

0.1 M N a S 0 a n d 1 M N a S 0 .
2 3 2 4
3.5
0.7 V vs. S C E
3.0

0.6 V vs. S C E
2.5 *
* * *
2.0 0.5 V vs. S C E

-X
E X
x x
< 1.5 0.4 V vs. S C E
A
A 4
1.0 4-
o 0.5
0.3 V vs. S C E

0.0 4-
-0.5
0.2 V vs. S C E
-1.0 I
I

i i

i i ii I
11.9 12.1 12.3 12.5 12.7 l
12.9 13.1
PH
F i g u r e 6-15 E f f e c t o f p H o n sulphite o x i d a t i o n at different potentials a n d 25 C .

E l e c t r o l y t e : 0.1 M N a S 0 , 1 M N a S 0 at v a r i a b l e p H
2 3 2 4
97
6.8 Calculation of Activation Energy for the Kinetic Current
A t a constant p o t e n t i a l , the f o l l o w i n g equation c a n be w r i t t e n :
T . Ui() / -a FE
:
a
Log i t = constant + = constant + (6-17)

B k
2.303RT 2.303RT ^ ;
W h e r e U* (E) is the a c t i v a t i o n energy at potential E , U ++

the a c t i v a t i o n energy at p o t e n t i a l =
0, a a the a n o d i c charge transfer coefficient a n d R the gas constant. T h e a c t i v a t i o n energy c a n
be c a l c u l a t e d f r o m the slope o f the plot o f l o g i v s . 1/T ( F i g u r e 6-16). T h e slopes o f these

k
l i n e a r plots w e r e c a l c u l a t e d b y least squares fitting. T h e a c t i v a t i o n energy decreases q u i c k l y
w i t h i n c r e a s i n g potential at l o w potentials and f i n a l l y behaves l i n e a r l y w i t h p o t e n t i a l at
potentials > 0.4 V v s . S C E . T h i s is due to a change i n the r e a c t i o n m e c h a n i s m w h i c h results
i n a change i n the charge transfer coefficient.
4.0 -
3.5 J
^ 4 5 . 3 kJ m o r (0.6 V )
1
3.0 -
2.5 - ~ ^ 4 8 ^ 4 kJ m o r (0.5 V )
1
2.0 . * " ^ J 5 1 5 kJ m o r (0.4 V ) 1
1.5 -
~ " ~ ~ - . ^ 5 7 . 2 kJ m o r ( 0 . 3 V )
s 1
1.0 -
0.5 -
^ ~ ^ ~ - - ^ 8 5 . 2 kJ m o r (0.2 V ) 1
0.0 -
0.5 -
0.003 0.0031 0.0032 0.0033 0.0034
(T/K)- 1
F i g u r e 6-16 L o g i v s . l / T at different potentials ( V v s . S C E ) . E l e c t r o l y t e : 0.1 M N a S 0 , 1 M

k 2 3
Na S0
2 4 a n d 0.25 M N a O H .
6.9 Diffusion Coefficient Estimation
T h e plots o f d i f f u s i o n current v s . rotational speed at different temperatures are s h o w n
i n F i g u r e 6-17. These plots p e r m i t the c a l c u l a t i o n o f the d i f f u s i o n coefficients o f S 0 " u s i n g 3

2
98
the slopes o f the l i n e s a n d E q u a t i o n 6-4. T h e slopes w e r e c a l c u l a t e d u s i n g least squares
fitting. T h e k i n e m a t i c v i s c o s i t y values for 0.05 M N a 2 0 3 , 0.25 M N a O H a n d I M N a S 0 2 4
w e r e 1.345, 0.982, 0.818 and 0.695 x 10' m 6 2

s r e s p e c t i v e l y for 2 5 , 4 0 , 50 a n d 60 C . T h e
d i f f u s i o n coefficients at 2 5 , 4 0 , 50 a n d 60 C w e r e 5.6, 8.6, 9.99 a n d 12.4 x 10" 10

m 2
s"1
r e s p e c t i v e l y . T h e d i f f u s i o n coefficient obtained at 25 C (5.6 x 10" 10

m 2
s" )
1
is m u c h l o w e r
t h a n the v a l u e at infinite d i l u t i o n ( 1 . 0 6 x l 0 " m 9 2

s" ) [330]. T h i s difference c o u l d be c a u s e d b y
1
the h i g h i o n i c strength (above 3.1 M ) w h e r e the i o n - i o n interaction is s i g n i f i c a n t a n d the
k i n e m a t i c v i s c o s i t y is 35 % greater than that for water, d e c r e a s i n g the d i f f u s i o n coefficient.
T h e coefficient at 25 C is close to the values (6 - 7 x l 0 " 1 0

m 2
s"' i n 0.5 M N a S 0 ) r e p o r t e d b y
2 4
Hunger et a l . [254]. A t infinite d i l u t i o n , the diffusion coefficient has the following
temperature dependence:
L o g D = constant - ^ (6-18)
B
2.303RT v
'
w h e r e D is the d i f f u s i o n coefficient, E a the d i f f u s i o n a c t i v a t i o n energy, R the gas constant, T
the absolute temperature.
T h e d i f f u s i o n a c t i v a t i o n energy calculated f r o m the slope o f the l o g p l o t o f d i f f u s i o n
coefficient v s . 1/T ( F i g u r e 6-18) is 18 k J mole" . 1
F i g u r e 6-17 D i f f u s i o n current density v s . the square root o f rotational speed at different

temperatures. E l e c t r o l y t e : 0.05 M N a S 0 , l M N a S 0 , 0.25 M N a O H .
2 3 2 4
99
-8.9
0.003 0.0031 0.0032 0.0033 0.0034

(T/K)- 1
F i g u r e 6-18 L o g p l o t o f d i f f u s i o n coefficient v s . 1/T.
6.10 Potential Sweep Study
T h e p o t e n t i a l sweep m e t h o d w a s u s e d to study the a n o d i c o x i d a t i o n o f sulphite.
F i g u r e 6-19 s h o w s the c y c l i c v o l t a m m o g r a m s after subtraction o f the b a c k g r o u n d current f o r
different s c a n rates. T h e r e i s n o negative current c o r r e s p o n d i n g to the r e d u c t i o n o f the
o x i d i z e d products (or intermediates) a n d the o x i d a t i o n o f sulphite i s therefore i r r e v e r s i b l e .
T h e peak current density ( i ) is g i v e n b y the f o l l o w i n g e q u a t i o n for the i r r e v e r s i b l e r e a c t i o n

p
[333]:
i p = (2.99 x 1 0 > ( a ) 1 / 2
C D
b
, / 2
v 1 / 2
= Bv 1 / 2
(6-19)
w h e r e n i s the n u m b e r o f transferred electrons, a the r a t e - c o n t r o l l i n g step charge transfer
coefficient, C the b u l k reactant concentration, D the d i f f u s i o n coefficient,

b v the p o t e n t i a l
scan rate a n d B = (2.99 x 1 0 ) n ( a ) 5 1 / 2

C D
b
1 / 2
. T h e peak current i s p r o p o r t i o n a l to the square
root o f the p o t e n t i a l scan rate. T h e p l o t o f i v s . v p

1 / 2
gave a l i n e a r r e l a t i o n s h i p ( F i g u r e 6-20).
T h e slope ( B ) w a s c a l c u l a t e d b y least squares fitting. T h e f o l l o w i n g r e l a t i o n s h i p obtains:

100
1.857i?r
E
p- pn=^T-
E
(6-20)
w h e r e E i s the peak potential a n d E

p p / 2 the potential w h e n i = i / 2 .
F r o m the above equation w e o b t a i n a n apparent charge transfer coefficient o f 0.33 w h i c h i s
close to that (0.30-0.31) c a l c u l a t e d u s i n g the T a f e l slope at h i g h potentials. T h e total n u m b e r
o f the electrons transferred i s 1.98, 1.98, 2.00, 1.98 b y c o m b i n a t i o n o f B , C , oc , D at 2 5 , 4 0 ,

b a
50 a n d 6 0 C r e s p e c t i v e l y . T h i s n u m b e r corresponds to the s t o i c h i o m e t r y i n d i c a t e d b y
E q u a t i o n 6-13.
F i g u r e 6-19 V o l t a m m o g r a m s at different scan rates at 25 C . E l e c t r o l y t e : 0.1 M N a j S C ^ ,

1 M N a S 0 , 0.25 M N a O H .
2 4
101
600
500
~ 400
tfl
c
o
73 300 i -
C
0)
l_
k- 200
3
U
ro 100
Q.
0.1 0.2 0.3 0.4 0.5 0.6
(Potential scanning rate / V s" ) ' 1 1 2
F i g u r e 6-20 P e a k current v s . potential scan rate at 25 C . E l e c t r o l y t e : 0.1 M

Na S0 , 1M Na S0
2 3 2 4 a n d 0.25 M N a O H .
6.11 Possible reaction mechanism
F r o m F i g u r e 6 - 1 3 , there are t w o T a f e l regions. T h e first one i s 0.059 -0.066 V
decade" f r o m 25 to 6 0 C at l o w potentials a n d the s e c o n d i s 0.19-0.22 V decade"

1 1
at h i g h e r
potentials. T h e c o r r e s p o n d i n g charge transfer coefficients are 1 a n d 0.3 r e s p e c t i v e l y . T h e s e
v a l u e s suggest a change i n the r e a c t i o n m e c h a n i s m or i n the r a t e - c o n t r o l l i n g step. T h e
r e a c t i o n order at l o w potentials i s b e l o w 1 a n d n o n l i n e a r . It decreases s l i g h t l y w i t h i n c r e a s i n g
sulphite c o n c e n t r a t i o n i n d i c a t i n g that the adsorbed sulphite c o u l d b e g i n to be o x i d i z e d at l o w
potentials. T h e r e are n o peaks c o r r e s p o n d i n g to the a d s o r p t i o n i n the v o l t a m m o g r a m s . T h i s
m e a n s that o n l y a v e r y s m a l l amount o f sulphite adsorbs o n the electrode surface. T a r a s e v i c h
et a l . [239] studied the a d s o r p t i o n a n d e l e c t r o o x i d a t i o n o f sulphite o n p l a t i n u m u s i n g
r a d i o a c t i v e tracers. T h e y f o u n d that S 0 " w a s w e a k l y adsorbed o n the surface a n d the

3
2
a m o u n t o f a d s o r b e d S 0 " d i d not change o v e r the potential range -0.24 - 0. 2 6 V v s . S C E . It

3
2
decreased to zero w i t h i n c r e a s i n g potential f r o m 0.26 to 0.56 V v s . S C E at 2 2 C . I n the
present study, it w a s f o u n d that S 0 " begins to be o x i d i z e d o n a graphite anode at 0.16 V v s .

3
2
S C E at 2 5 C a n d the T a f e l slope w a s a constant v a l u e o f 0.060 V decade" o v e r the p o t e n t i a l

1
range 0.16 - 0.25 V v s . S C E . W i t h further increase i n potential, the T a f e l slope i n c r e a s e d w i t h

102
i n c r e a s i n g p o t e n t i a l . W h e n the potential e x c e e d e d 0.4 V v s . S C E , the T a f e l slope r e m a i n e d at
0.19 V decade" a n d w a s independent o f the potential.

1
T h e above p h e n o m e n o n c a n be e x p l a i n e d as f o l l o w s : (1) at 0.16 -0.25 V v s . S C E , the
adsorbed S 0 " i s o x i d i z e d a n d the coverage o f adsorbed S 0 " i s independent o f p o t e n t i a l a n d

3
2
3
2
therefore the T a f e l slope (0.060 V decade "') is independent o f the p o t e n t i a l a n d the r e a c t i o n
order w i t h respect to S 0 " is b e l o w 1 a n d n o n l i n e a r ; (2) at 0.25 - 0.4 V v s . S C E , the c o v e r a g e

3
2
o f a d s o r b e d S 0 " decreases w i t h i n c r e a s i n g potential. Therefore the T a f e l slope increases

3
2
w i t h i n c r e a s i n g p o t e n t i a l ; (3) at potential > 0.4 V , the amount o f a d s o r b e d S 0 " i s n e g l i g i b l e 3

2
a n d the direct o x i d a t i o n o f unadsorbed S 0 " dominates. T h u s the T a f e l slope

3
2
becomes
independent o f the potential a n d the r e a c t i o n order w i t h respect to S 0 " b e c o m e u n i t y . T h e 3

2
r e a c t i o n order w i t h respect to O H " i o n s i s a l m o s t z e r o . T h i s means that the r a t e - c o n t r o l l i n g
steps f o r the t w o T a f e l slope regions do n o t i n v o l v e O H " . T h e r e are n u m e r o u s c a r b o n o x i d e
surface groups o n graphite [243, 334] a n d sulphur c o u l d b e b o u n d to these surface groups
d u r i n g the a d s o r p t i o n . I n accordance w i t h the these p h e n o m e n a , the f o l l o w i n g r e a c t i o n
mechanism is proposed:
A t l o w potentials (< 0.25 V S C E ) , sulphite first adsorbs o n the graphite, then loses the
first electron, f i n a l l y u n d e r g o i n g o x y g e n transfer a n d l o s i n g the s e c o n d e l e c t r o n . F o r
example,
Step 1 : S0 ~ <^> 5 0 -
3
2
3
2
( a r f .)
Step 2 : SO ' ad.) S0 \ .) + e

2
( 3 ad
Step 3: S0 \ad.)
3 - > S03
Step 4: SO, + 20H~ - > SO '

1 2
+H0 + e
2
C o n s i d e r i n g the theory o f m u l t i s t e p electrode reactions [ 3 3 5 , 3 3 6 ] , i f step 1 i s rate-
c o n t r o l l i n g , the current s h o u l d be independent o f potential. I f step 2 i s r a t e - c o n t r o l l i n g , the
Tafel slope s h o u l d b e above 0.059 V decade" 1

at 25 C (because the charge transfer
coefficient < 1). I f step 4 i s the r a t e - c o n t r o l l i n g step, the T a f e l slope s h o u l d b e a r o u n d 0.040
V decade" 1
at 25 C a n d the r e a c t i o n order w i t h respect to O H " i o n s s h o u l d b e 1 o r m o r e . I f
step 3 is r a t e - c o n t r o l l i n g , the T a f e l slope i s 0.059 V decade" at 25 C . T h e r e a c t i o n order w i t h

1
respect to O H " i o n s c o u l d be z e r o . L o o k i n g at the e x p e r i m e n t a l results, Step 3 c o u l d be rate-
controlling.
103
A t h i g h potentials ( > 0.4 V v s . S C E ) , sulphite first loses one electron, subsequently
undergoes o x y g e n transfer and loses the second electron.
Step 1: SO ' 2
-> S0 '+e 3
Step 2 : S03 + 20H' SO '

2
+H 0 + e
2
T h e charge transfer coefficient is o n l y about 0.3, suggesting that the loss o f the first
e l e c t r o n is the r a t e - c o n t r o l l i n g step. T h i s is i n agreement w i t h the r e a c t i o n order w i t h respect
to sulphite i o n s . T h e r e a c t i o n order w i t h respect to h y d r o x i d e i o n s is zero, suggesting that the
r a t e - c o n t r o l l i n g step does not i n v o l v e h y d r o x i d e i o n s . Therefore step 1 c o u l d be the rate-
c o n t r o l l i n g step at h i g h potentials. It s h o u l d be noted that a s m a l l a m o u n t o f S0 ~ 3 could
c o m b i n e to f o r m dithionate and therefore the n u m b e r o f the electrons transferred is s l i g h t l y
b e l o w 2.
6.12 Summary
A t l o w potentials ( e.g. < 0.25 V v s . S C E at 25 C ) , the r e a c t i o n order for the
o x i d a t i o n o f sulphite is b e l o w 1 a n d decreases w i t h i n c r e a s i n g sulphite c o n c e n t r a t i o n . T h e
T a f e l slope is 0.059 -0.065 V decade" i n the temperature range 2 5 - 6 0 C . A t h i g h potentials

1
(> 0.4 V v s . S C E ) , the r e a c t i o n order w i t h respect to sulphite i o n s is 1 up to 0.4 M sulphite
a n d the T a f e l slope is 0.19 - 0.21 V decade" . T h e r e a c t i o n order w i t h respect to h y d r o x i d e

1
i o n s is c l o s e to zero at surface p H > about 9.
T h e a c t i v a t i o n energy for the k i n e t i c current decreases f r o m 85.2 k J m o l " at 0.2 V v s .

1
S C E to 45.3 k J m o l " 1
at 0.6 V v s . S C E . T h e d i f f u s i o n coefficients o f sulphite i o n s w e r e
o b t a i n e d a n d s h o w n to have a n a c t i v a t i o n energy o f 18 k J m o i " .

1
Sulphite oxidation i n alkaline solution appears to undergo a radical-electron
m e c h a n i s m . A t l o w potentials, the adsorbed sulphite o x i d a t i o n is d o m i n a n t a n d at h i g h
potentials, the sulphite ions are o x i d i z e d d i r e c t l y o n the electrode surface. T h e loss o f the first
e l e c t r o n f r o m sulphite i o n s appears to be the r a t e - c o n t r o l l i n g step at h i g h potentials.

104
7. ANODIC OXIDATION OF COPPER CYANIDE ON A GRAPHITE

ANODE IN ALKALINE SOLUTION
T o decrease the c o n s u m p t i o n o f c y a n i d e , it is important to understand the a n o d i c
o x i d a t i o n o f c o p p e r c y a n i d e . H o w e v e r , the i n f o r m a t i o n a v a i l a b l e is inadequate a n d further
studies are needed. Therefore a study o f the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e w a s
c o n d u c t e d u s i n g the rotating d i s k technique.
T h e graphite rotating d i s k w a s the same as d e s c r i b e d i n S e c t i o n 6.3. T o ensure
r e p r o d u c i b l e results, the electrode w a s first treated b y c y c l i c v o l t a m m e t r y b e t w e e n 0 -0.75 V
v s . S C E i n 0.25 M N a O H a n d I M N a S 0 2 4 s o l u t i o n at 100 r p m f o r 30 m i n u t e s a n d p o l a r i z e d
at 1 m V s" u n t i l the electrode reached a stable c o n d i t i o n . G r a p h i t e h a v i n g diameters o f 12

1
a n d 2 4 m m w a s f a s h i o n e d as a rotating d i s k for c o u l o m e t r i c measurements. A pyrolytic
graphite rotating d i s k h a v i n g a diameter o f 4 m m a n d a p l a t i n u m electrode h a v i n g a d i a m e t e r
o f 5 m m were m a d e b y the E G & G C o .
T h e rotating d i s k electrode s y s t e m w a s a n E G & G P A R C M o d e l 6 3 6 E l e c t r o d e
Rotator. T h e potentiostats were M o d e l S O L A R T R O N 1286 a n d P A R C 2 7 3 A e l e c t r o c h e m i c a l
Interface. A r g o n gas w a s first b u b b l e d t h r o u g h the s o l u t i o n a n d the e x p e r i m e n t s were
conducted under an argon atmosphere to a v o i d the p o s s i b l e effect o f the air. T h e
e x p e r i m e n t a l set-up w a s the same as s h o w n i n F i g u r e 6-3. T h e p o l a r i z a t i o n c u r v e s w e r e
generated u s i n g the p o t e n t i a l sweep m e t h o d at 1 m V s" as noted.1
A L E Y B O L D M A X 2 0 0 X P S instrument w a s u s e d to a n a l y z e the anode precipitate.
A S i e m e n s diffractometer D 5 0 0 0 0 w a s u s e d to o b t a i n the X - r a y d i f f r a c t i o n pattern o f the
precipitate. S a m p l e s o f the anode precipitate f o r X P S a n d X - r a y d i f f r a c t i o n w e r e p l a c e d i n a
bottle f i l l e d w i t h A r gas to protect against o x i d a t i o n b y air.
T h e s t o p p e d - f l o w technique a n d spectrometry using a S H I M A D Z U Model U V -
2 4 0 I P C U V spectrometer were e m p l o y e d to detect the c u p r i c c y a n i d e species. N a C N a n d
CuS0 4 s o l u t i o n s w e r e injected into a T -tube i n one s e c o n d a n d w e l l m i x e d , finally e n t e r i n g
the quartz c e l l f o r U V detection. T h e e x p e r i m e n t a l set-up is s h o w n i n F i g u r e 7 - 1 .

105
T - tube
Syringe
F i g u r e 7-1 S c h e m a t i c d i a g r a m for detection o f c u p r i c c y a n i d e species
T h e k i n e m a t i c v i s c o s i t y o f the s o l u t i o n w a s measured u s i n g a C a n n o n - F e n s k e routine
v i s c o m e t e r (size 2 5 ) (see A p p e n d i x 6).
T h e l i q u i d j u n c t i o n potential for a dilute copper c y a n i d e s o l u t i o n w a s c a l c u l a t e d b y
the H e n d e r s o n e q u a t i o n (see A p p e n d i x 7). T h e l i q u i d j u n c t i o n f o r concentrated copper
c y a n i d e w a s n o t c o n s i d e r e d because there are n o data f o r copper c y a n i d e species a n d the
m o b i l i t i e s o f copper c y a n i d e species are expected to be c l o s e to that o f s o d i u m i o n . T h e
t h e r m a l l i q u i d j u n c t i o n potential w a s measured u s i n g t w o c a l o m e l reference electrodes w h i c h
were p l a c e d o n the t w o sides o f a n electrolyte bridge.
T h e c y a n i d e c o n c e n t r a t i o n w a s measured u s i n g the d i s t i l l a t i o n - a b s o r p t i o n - t i t r a t i o n
procedure (see A p p e n d i x 2 ) . T h e copper c o n c e n t r a t i o n w a s m e a s u r e d b y o x i d i z i n g c o p p e r
c y a n i d e to c u p r i c nitrate u s i n g concentrated n i t r i c a c i d a n d titration w i t h E D T A (see
A p p e n d i x 3).
R e a g e n t grade c h e m i c a l s were used i n a l l the experiments.
7.2 Polarization Measurements and Identification of the Precipitate
7.2.1 A n o d i c B e h a v i o u r for Dilute C o p p e r C y a n i d e Solution
T o d e v e l o p a n understanding o f the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e , the study o f
the electrode k i n e t i c s w a s first c a r r i e d out i n dilute copper c y a n i d e s o l u t i o n i n the presence o f
a n excess o f inert s u p p o r t i n g electrolyte. A s a result, a l l the o b s e r v e d potential difference w a s

106
concentrated o n the electrode s o l u t i o n interface and a v a i l a b l e for affecting the a c t u a l rate o f
the electrode reaction.
T h e p o l a r i z a t i o n measurements were c o n d u c t e d at 2 5 , 4 0 , 50 a n d 60 C i n a l k a l i n e
s o l u t i o n w i t h different concentrations o f c y a n i d e , copper a n d s o d i u m h y d r o x i d e . A s c o p p e r
o x i d e a n d h y d r o x i d e were precipitated o n the electrode surface d u r i n g the p o l a r i z a t i o n
measurement, the electrode surface was r e p o l i s h e d after every p o l a r i z a t i o n to ensure
r e p r o d u c i b l e results. T h e p o l a r i z a t i o n curves for 0.05 M c y a n i d e a n d a C N : C u m o l e ratio o f 3
at 2 5 , 4 0 , 50 a n d 60 C are s h o w n i n F i g u r e 7-2. T h e a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e c a n
be d i v i d e d into three potential regions. I n the first r e g i o n ( a p p r o x i m a t e l y 0 - 0.4 V v s . S C E ) ,
no precipitate w a s f o r m e d o n the electrode. I n the s e c o n d r e g i o n ( a p p r o x i m a t e l y 0.4 - 0.6 V
v s . S C E ) , copper o x i d e a n d h y d r o x i d e were f o r m e d o n the electrode surface a n d the current
i n c r e a s e d sharply w i t h i n c r e a s i n g potential. I n the t h i r d r e g i o n (about > 0.6 V S C E ) , the
oxygen was evolved.
T h e b e h a v i o r o f current v s . potential w a s dependent o n the temperature a n d the
rotational speed. A t 25 C ( F i g u r e 7-2a), w h e n the rotational speed w a s 100 r p m , the current
reached a l i m i t i n g v a l u e and d i d not decrease w i t h i n c r e a s i n g potential. H o w e v e r , w h e n the
rotational speed w a s above 100 r p m , the current reached a m a x i m u m value and then
decreased w i t h i n c r e a s i n g potential. A t 4 0 C ( F i g u r e 7-2b), w h e n the rotational speed w a s
b e l o w 1600 r p m , the current d i d not decrease w i t h potential. W h e n the rotational speed w a s
a b o v e 2 5 0 0 r p m , the current reached a m a x i m u m v a l u e , then s t a b i l i z e d a n d f i n a l l y decreased
w i t h i n c r e a s i n g potential. A t 50 and 60 C ( F i g u r e 7-2c a n d d), the current d i d not decrease
w i t h i n c r e a s i n g potential. T h i s a n o d i c o x i d a t i o n b e h a v i o u r o f c o p p e r c y a n i d e is related to the
precipitation o f copper oxide.
F r o m the c y c l i c v o l t a m m e t r y ( F i g u r e 7-3), the effect o f the p r e c i p i t a t i o n o f the c o p p e r
o x i d e w a s dependent o n the a p p l i e d potential. A t 25 C a n d 100 r p m ( F i g u r e 7-3a), w h e n the
potential w a s swept f r o m 0 to 0.55 V v s . S C E and then b a c k to 0 V v s . S C E , the current for
the n e g a t i v e - g o i n g sweep w a s larger than that for the p o s i t i v e - g o i n g sweep. T h i s m e a n s that
the precipitate h a d a c a t a l y t i c effect o n the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e . W h e n the
potential w a s swept f r o m 0 to 0.60 V v s . S C E a n d then b a c k to 0 V v s . S C E , the current for
the n e g a t i v e - g o i n g sweep w a s s m a l l e r than that for the p o s i t i v e - g o i n g current. T h i s indicates

1
that the precipitate h a d a p a s s i v a t i n g effect o n the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e . T h e

107
change i n the c a t a l y t i c properties o f copper o x i d e m a y be caused b y the a d s o r p t i o n o f o x y g e n
p r o d u c e d i n the electrode reaction. T h e c y c l i c v o l t a m m e t r y at 40 C a n d 100 a n d 1600 r p m
( F i g u r e 7-3b) s h o w s a g a i n the catalytic effect o f the precipitate o f c o p p e r o x i d e .
F r o m F i g u r e A - 9 ( A p p e n d i x 8), the p r e c i p i t a t e d c o p p e r o x i d e has a m u c h m o r e
p r o n o u n c e d c a t a l y t i c effect o n the c y a n i d e o x i d a t i o n than the graphite a n d c o p p e r i o n s i n the
solution.
F r o m the X P S a n a l y s i s o f the precipitate ( F i g u r e s A - 9 a n d A - 1 0 i n A p p e n d i x 8), the
precipitate w a s f o u n d to be copper o x i d e . T h e c u r v e fitting o f the X P S s p e c t r u m ( F i g u r e s A -
11 a n d A - 1 2 i n A p p e n d i x 8) c o n f i r m e d that the precipitate w a s a c o m b i n a t i o n o f c o p p e r
o x i d e a n d copper h y d r o x i d e . T h e contents o f C u O and C u ( O H ) 2 o n the surface were
r e s p e c t i v e l y about 50 % at 25 C a n d 70 % at 60 C . S o the ratio o f C u O to C u ( O H ) 2 i n the
precipitate increased w i t h i n c r e a s i n g temperature.
T h e p r e c i p i t a t i o n o f copper o x i d e a n d h y d r o x i d e suggests that c o p p e r c y a n i d e c a n be
o x i d i z e d to copper o x i d e and cyanate. T h e onset o f the p r e c i p i t a t i o n o f c o p p e r o x i d e depends
o n the C N : C u m o l e ratio a n d potential. A t l o w rotational speeds, the onset o f the p r e c i p i t a t i o n
o f copper o x i d e appears at l o w e r potentials than at h i g h rotational speeds l e a d i n g to h i g h e r
currents. T h e reason c o u l d be that at the same potential, the C N : C u m o l e ratio at the electrode
surface for a l o w rotational speed is l o w e r than that at the h i g h r o t a t i o n a l speed, also the
l o w l y c o o r d i n a t e d c o p p e r c y a n i d e c o m p l e x e s are less stable than the h i g h l y c o o r d i n a t e d
c o m p l e x e s a n d are easier to o x i d i z e to copper o x i d e and cyanate. T h e onset o f the f o r m a t i o n
of copper o x i d e o c c u r s at h i g h e r potentials at a h i g h e r C N : C u m o l e ratio f r o m the
p o l a r i z a t i o n measurement.
In the t h i r d r e g i o n (potentials > about 0.6 V v s . S C E ) , a gas w a s e v o l v e d , w h i c h c o u l d
be o x y g e n or n i t r o g e n due to the further o x i d a t i o n o f cyanate. T h e current d i d not change
u n i f o r m l y w i t h i n c r e a s i n g rotational speed because the f i l m o f copper o x i d e o n the graphite
w a s f o r m e d i r r e g u l a r l y . E v e n part o f it d r o p p e d f r o m the electrode. T h e c o a t i n g o f C u O
s i g n i f i c a n t l y increases the o x y g e n e v o l u t i o n (see F i g u r e A - 1 4 i n A p p e n d i x 8). T h e current
decreased w i t h i n c r e a s i n g potential after it reached a m a x i m u m v a l u e because the o x i d e f i l m
b e c a m e l o o s e l y adherent o n the graphite. I n fact, s o m e o f it d r o p p e d f r o m the electrode due to
the o x y g e n e v o l u t i o n . I n the absence o f copper c y a n i d e , the p o l a r i z a t i o n c u r v e s for the
electrode w i t h p r e c i p i t a t e d copper o x i d e i n the case o f the s o l u t i o n c o n t a i n i n g 0.05 M cyanate

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w e r e a l m o s t the same as those w i t h o u t cyanate. T h i s suggests that the e v o l u t i o n o f o x y g e n
was dominant.
I n c r e a s i n g the C N : C u m o l e ratio (decreasing [Cu]) results i n a change i n the a n o d i c
b e h a v i o u r o f copper c y a n i d e ( F i g u r e s A - 1 5 to A - 1 8 i n A p p e n d i x 8). T h e p o l a r i z a t i o n c u r v e s
for the solutions w i t h C N : C u m o l e ratios o f 3.5 a n d 4 are s i m i l a r to those for the s o l u t i o n
w i t h a C N : C u m o l e ratio o f 3. T h e difference is that the onset o f the p r e c i p i t a t i o n o f c o p p e r
o x i d e b e g i n s at a h i g h e r potential. H o w e v e r , at C N : C u m o l e ratios o f 6 a n d 12, there w e r e no
w e l l d e f i n e d l i m i t i n g currents because the p r e c i p i t a t i o n o f c o p p e r o x i d e b e g a n at about 0.6 V
vs. S C E a n d o x y g e n is ready to be e v o l v e d o n the copper o x i d e , affecting the o x i d a t i o n o f
copper c y a n i d e . A t a C N : C u m o l e ratio o f 6 (25 to 50 C ) or 12, the p r e c i p i t a t e d o x i d e w a s
not t i g h t l y adherent to the graphite. Therefore the e v o l u t i o n o f o x y g e n w a s not c a t a l y z e d
s i g n i f i c a n t l y b y the copper o x i d e as o b s e r v e d at l o w e r m o l e ratios o f c y a n i d e . H o w e v e r , at a
C N : C u m o l e ratio o f 6 a n d 60 C the current increased c o n t i n u a l l y w i t h i n c r e a s i n g potential
because the copper o x i d e w a s r e l a t i v e l y w e l l deposited o n the electrode and catalyzed
s i g n i f i c a n t l y the e v o l u t i o n o f o x y g e n .
D e c r e a s i n g h y d r o x i d e concentration also leads to the change i n the a n o d i c b e h a v i o u r
o f c o p p e r c y a n i d e (see F i g u r e A - 1 9 to A - 2 4 i n A p p e n d i x 8).
A t [OH"] = 0.05 M , the p o l a r i z a t i o n curves for 0.05 C N " solutions w i t h C N : C u m o l e
ratios o f 3, 4 a n d 12 are s h o w n i n F i g u r e s A - 1 9 to A - 2 1 ( A p p e n d i x 8) r e s p e c t i v e l y . T h e
a n o d i c b e h a v i o u r o f the copper c y a n i d e s o l u t i o n c a n be d i v i d e d into the three p o t e n t i a l
r e g i o n s s i m i l a r to those w i t h 0.25 M N a O H . H o w e v e r , the f o r m a t i o n o f c o p p e r o x i d e a n d
o x y g e n e v o l u t i o n w a s suppressed.
A t [OH"] = 0.01 M , the p o l a r i z a t i o n curves for 0.05 M C N " solutions w i t h C N : C u
m o l e ratios o f 3, 4 and 12 are s h o w n i n F i g u r e s A - 2 2 to A - 2 4 r e s p e c t i v e l y . T h e f o r m a t i o n o f
c o p p e r o x i d e a n d o x y g e n e v o l u t i o n w a s s i g n i f i c a n t l y decreased. A t C N : C u m o l e ratio = 1 2 ,
a l m o s t no c o p p e r o x i d e w a s f o r m e d .
C o m p a r i n g the a n o d i c b e h a v i o u r o f copper c y a n i d e w i t h 0.25 M N a O H ( F i g u r e 7-2,
7-11 a n d 7-13), 0.05 M N a O H ( F i g u r e s A - 1 9 to A - 2 1 ) a n d 0.01 M N a O H ( F i g u r e s A - 2 2 to
A - 2 4 ) , h y d r o x i d e a n d copper concentrations affect the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e
s i g n i f i c a n t l y i n some potential regions a n d the effect o f h y d r o x i d e c o n c e n t r a t i o n is dependent

109
o n c o p p e r c o n c e n t r a t i o n because the a n o d i c b e h a v i o u r is related to the d i s t r i b u t i o n o f c o p p e r
c y a n i d e species, as d i s c u s s e d i n Sections 7-4 and 7-5.
3000 ,
4900 rpm 2 3 /
3600 rpm
2500 " . . . . 2500 rpm oxygen evolution _/
-jof copper oxide

precipitation
. -1600 rpm Si j \ \
E
< 2000 . 900 rpm
400 rpm
(0
c
1500
100 rpm
/ / , */ A
a
1000 1
3 no precipitation
o 500 of copper oxide
0 J
0.00 0.20 0.40 0.60 0.80 1.00 1.20 0.00 0.20 0.40 0.60 0.80 1.00 1.20
(a) 25 C (b) 40 C
5000 12000
-4900 rpm
4500
. 3600 rpm
10000
^ 4000 . 2500 rpm
-1600 rpm E
^ 3500
_900 rpm < 8000 4J
3000 _400 rpm
. 100 rpm to
c 2500 c 6000
0) a
a
2 2000 c
2 4000
1500
i
3
3
o 2000
O 1000
500
o 4
0.00 0.20 0.40 0.60 0.80 1.00 1.20 0.00 0.20 0.40 0.60 0.80 1.00 1.20
(c) 50 C (d) 60 C
F i g u r e 7-2 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. E l e c t r o l y t e :

0.05 M C N " , C N : C u = 3, 0.25 M N a O H and 1 M N a S 0 . 2 4
110
0 0.1 0.2 0.3 0.4 0.5 0.6

(a) 25 C a n d 100 r p m
1000 -,
(b) 40 C , 100 r p m a n d 1600 r p m
F i g u r e 7-3 C y c l i c v o l t a m m e t r y at 25 a n d 40 C . E l e c t r o l y t e : 0.05 M C N ' , C N : C u = 3, 0.25

M Na S0 2 4 and 1 M N a ^ C v
Ill
7 . 2 . 2 A n o d i c B e h a v i o r of C o n c e n t r a t e d C o p p e r C y a n i d e Solution
I n order to o b t a i n a reasonable copper d e p o s i t i o n e f f i c i e n c y , the c o p p e r cyanide
c o n c e n t r a t i o n s h o u l d be c o n t r o l l e d a r o u n d 1 M . Therefore the study o f the a n o d i c o x i d a t i o n
o f c o p p e r c y a n i d e w a s also c o n d u c t e d for a h i g h c o n c e n t r a t i o n copper c y a n i d e s o l u t i o n .
T h e a n o d i c b e h a v i o u r for 0.5 M C N " ( F i g u r e A - 2 5 i n A p p e n d i x 8) w a s quite different
f r o m that for 0.05 M C N " ( F i g u r e 7-2). T h e current also d i d not increase as e x p e c t e d f r o m the
increase i n c o p p e r c y a n i d e concentration. T h e p r e c i p i t a t i o n o f c o p p e r o x i d e resulted i n a
s i g n i f i c a n t p a s s i v a t i o n . O x y g e n e v o l u t i o n w a s suppressed s i g n i f i c a n t l y .
F r o m F i g u r e 7-4, at [CN"] = 3 M , a C N : C u m o l e ratio o f 3, [OH"] = 0.25 a n d [ N a S 0 ] 2 4
= 0.5 M , the a n o d i c o x i d a t i o n o f copper c y a n i d e c a n be d e s c r i b e d b y the three p o t e n t i a l
regions. I n the first r e g i o n , a n o d i c o x i d a t i o n p r o c e e d e d w i t h o u t the f o r m a t i o n o f c o p p e r
o x i d e . I n the s e c o n d r e g i o n , copper o x i d e w a s precipitated, r e s u l t i n g the p a s s i v a t i o n o f the
electrode. W h e n the electrode w a s coated w i t h copper o x i d e b y s w e e p i n g the p o t e n t i a l o f the
electrode to 0.48 V v s . S C E ( F i g u r e s 7-4b, c a n d d), there w a s n o d i s t i n c t p e a k a n d the
current w a s l o w e r at potentials b e l o w about 0.4 V v s . S C E . H e n c e the decrease i n the current
w a s due to the f o r m a t i o n o f copper o x i d e . I n the t h i r d r e g i o n ( > about 1.0 V v s . S C E ) ,
several b u b b l e s w e r e observed. T h e p r e c i p i t a t i o n o f copper o x i d e o n the electrode i n c r e a s e d
s i g n i f i c a n t l y the resistance b e t w e e n the graphite a n d the s o l u t i o n . T h e I R d r o p at 1.0 V v s .
S C E w a s o v e r 1.0 V , w h i c h w a s estimated f r o m the difference b e t w e e n the potentials
m e a s u r e d b y a potentiostat (using current interruption technique) a n d a m u l t i m e t e r .
A c c o r d i n g to the X - r a y d i f f r a c t i o n patterns o f the anode precipitate p r o d u c e d at 25
a n d 60 C ( F i g u r e s A - 2 6 and A - 2 7 i n A p p e n d i x 8), the precipitates w e r e d e f i n e d as a
c o m b i n a t i o n o f c o p p e r h y d r o x i d e and copper o x i d e . A t 25 C , there w a s n o d i s t i n c t p e a k
c o r r e s p o n d i n g to C u O and so most o f the precipitate w a s C u ( O H ) . A t 60 C , there w e r e o n l y

2
s m a l l peaks c o r r e s p o n d i n g to the strongest peaks o f C u O , a n d C u ( O H ) 2 was dominant.
Cu(OH) 2 is s u p p o s e d to be have less catalytic effect o n c y a n i d e o x i d a t i o n . C o m p a r e d to
F i g u r e 7-2 (0.05 M C N " , a C N : C u m o l e ratio o f 3), the current d i d not increase, a n d e v e n
decreased a l t h o u g h the c o n c e n t r a t i o n o f copper c y a n i d e increased b y 59 t i m e s . T h i s m a y be
related to the c o m p o s i t i o n o f the anode precipitate. M o r e than h a l f o f the anode precipitate
p r o d u c e d i n 0.05 M C N " s o l u t i o n w i t h a C N : C u m o l e ratio o f 3 w a s C u O , w h i c h h a d a g o o d

112
c a t a l y t i c effect o n the o x i d a t i o n o f copper c y a n i d e . H o w e v e r , f r o m the X - r a y d i f f r a c t i o n
patterns, w e c a n p r e d i c t that the a m o u n t o f C u O i n the precipitate p r o d u c e d i n 3 M C N "
s o l u t i o n w i t h a C N : C u m o l e ratio o f 3 is v e r y s m a l l a n d the precipitate e x h i b i t e d a p o o r
c a t a l y t i c effect o n the o x i d a t i o n o f c o p p e r c y a n i d e . It is also p o s s i b l e that the c o n c e n t r a t i o n o f
c o p p e r c y a n i d e is so h i g h that it p o i s o n e d the c a t a l y t i c properties o f c o p p e r o x i d e a n d
suppressed the e v o l u t i o n o f o x y g e n s i g n i f i c a n t l y p o s s i b l y due to the s i g n i f i c a n t a d s o r p t i o n o f
c o p p e r c y a n i d e species.
W h e n the c y a n i d e c o n c e n t r a t i o n w a s increased f r o m 3 to 3.5 M , the a n o d i c b e h a v o u r
o f c o p p e r c y a n i d e b e c a m e different ( F i g u r e 7-5). A t 25 C , the c o p p e r o x i d e w a s p r e c i p i t a t e d
at a l l r o t a t i o n a l speeds. H o w e v e r , at 50 a n d 60 C , there w a s a little c o p p e r o x i d e (a s p i r a l
b l a c k l i n e ) f o r m e d o n the electrode o n l y at 1600 and 4 9 0 0 r p m . T h e r e w a s n o c o p p e r o x i d e at
100 a n d 4 0 0 r p m . T h e f o r m a t i o n o f copper o x i d e resulted i n a n increase or decrease or auto-
o s c i l l a t i o n i n the current due to the change i n the c o n d i t i o n o f the electrode ( p a s s i v a t i o n a n d
a c t i v a t i o n p o s s i b l y related to the f o r m a t i o n a n d d i s s o l u t i o n o f c o p p e r o x i d e ) w i t h i n c r e a s i n g
p o t e n t i a l . A t 60 C a n d potentials > 0.45 a n d 0.54 V v s . S C E r e s p e c t i v e l y for 100 r p m a n d
4 0 0 r p m , a s i g n i f i c a n t a m o u n t o f bubbles w a s e v o l v e d . These gas b u b b l e s i m m e d i a t e l y
d i s s o l v e d w h e n the current w a s turned off. T h e gas w a s thought to be c y a n o g e n because the
graphite w a s not c o r r o d e d and o x y g e n w a s not r e a d i l y e v o l v e d . T h e current b e c a m e so h i g h
that the mass-transfer rate o f h y d r o x i d e w a s l o w e r than the rate o f c y a n o g e n generation a n d
c y a n o g e n gas w a s f o r m e d .
W h e n the c y a n i d e c o n c e n t r a t i o n w a s increased to 4 M ( F i g u r e 7-6), n o anode
precipitate w a s f o r m e d o n the electrode. A t 4 0 C (100 a n d 4 0 0 r p m ) , 50 a n d 6 0 C ( 1 0 0 -
1600 r p m ) , w h e n the p o t e n t i a l e x c e e d e d a c e r t a i n v a l u e ( s h o w n i n F i g u r e 7-6), large b u b b l e s
(1-4 m m diameter) w e r e r a p i d l y e v o l v e d , r e s u l t i n g i n a sharp increase i n the current. L a r g e
b u b b l e s f o r m e d and b r o k e d o w n r e s u l t i n g i n the irregular change i n the current with
p o t e n t i a l . T h e b u b b l e s d i s s o l v e d r a p i d l y after the current w a s turned o f f a n d the graphite w a s
not s e r i o u s l y c o r r o d e d a n d so the gas w a s b e l i e v e d to be c y a n o g e n . T h e r a p i d e v o l u t i o n o f
large b u b b l e s s i g n i f i c a n t l y c h a n g e d the mass transfer o n the rotating d i s k . T h u s the current
c h a n g e d i r r e g u l a r l y w i t h i n c r e a s i n g rotational speed. A t a h i g h r o t a t i o n a l speed, the b u b b l e s
e v o l v e d o n the electrode were r e m o v e d r a p i d l y , h a v i n g less c h a n c e to c o m b i n e a n d f o r m

113
large b u b b l e s . T h e h i g h rotational speed also increases the m a s s transfer o f h y d r o x i d e to the
electrode a n d reduces the f o r m a t i o n o f c y a n o g e n .
T h e f o r m a t i o n o f copper o x i d e is related to the p H o f the s o l u t i o n . Therefore a
decrease i n h y d r o x i d e c o n c e n t r a t i o n s h o u l d affect the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e .
F i g u r e 7-7 s h o w s the p o l a r i z a t i o n curves for the s o l u t i o n w i t h 3 M C N " , a C N : C u m o l e ratio
o f 3, 0.05 M N a O H a n d 0.5 M N a j S Q , . A t 25 C , a t h i n film o f copper oxide was
p r e c i p i t a t e d , r e s u l t i n g i n changes i n the current w i t h the potential. C o m p a r e d to the a n o d i c
b e h a v i o u r o f c o p p e r c y a n i d e i n the s o l u t i o n w i t h 0.25 M N a O H ( F i g u r e 7-4), the current w a s
m u c h s m a l l e r a n d m u c h less copper o x i d e w a s f o r m e d o n the electrode. A t 40 C , the current
v s . p o t e n t i a l for 1600 a n d 4 9 0 0 r p m w a s s t i l l s i m i l a r to that at 25 C . H o w e v e r , at 100 a n d
4 0 0 r p m , the current increased c o n t i n u o u s l y to a m a x i m u m v a l u e a n d then decreased s l i g h t l y .
A t 50 C a n d 100 r p m , some gas w a s e v o l v e d at 0.38 V v s . S C E a n d there w a s a l m o s t n o
c o p p e r o x i d e f o r m e d o n the electrode. A t 4 0 0 - 4 9 0 0 r p m , a v e r y s m a l l a m o u n t o f c o p p e r
o x i d e w a s p r e c i p i t a t e d o n the anode. A t 60 C , the gas b u b b l e s were o b s e r v e d at potentials >
0.29 a n d 0.32 V v s . S C E for 100 and 4 0 0 r p m and n o copper o x i d e w a s f o r m e d .
F i g u r e 7-8 s h o w s the p o l a r i z a t i o n curves for the s o l u t i o n w i t h 4 M C N " , 1 M C u , +
0.05 M O H " a n d 0.5 M N a S 0 . C o m p a r e d to the a n o d i c b e h a v i o u r o f c o p p e r c y a n i d e at 0.25

2 4
M O H " ( F i g u r e 7-6), the e v o l u t i o n o f c y a n o g e n b e g a n at a r e l a t i v e l y l o w e r p o t e n t i a l , l e a d i n g
to the difference i n the current. T h e potential for the r a p i d e v o l u t i o n o f large c y a n o g e n
bubbles increased with i n c r e a s i n g rotational speed because the h i g h rotational speed
i n c r e a s e d the h y d r o x i d e m a s s transfer a n d so suppressed the f o r m a t i o n o f large c y a n o g e n
b u b b l e s . A t 100 or 4 0 0 r p m , the bubbles o f c y a n o g e n were not r e m o v e d e f f i c i e n t l y , r e s u l t i n g
i n the o s c i l l a t i o n o f the current. T h e r a p i d e v o l u t i o n o f large b u b b l e s s i g n i f i c a n t l y affected
the m a s s transfer. Therefore the current for a l o w rotational speed w a s e v e n larger t h a n that
for the h i g h e r rotational speed i n some potential r e g i o n .
T h e increase i n the concentration o f h y d r o x i d e s h o u l d suppress the f o r m a t i o n o f
c y a n o g e n a n d p r o m o t e the f o r m a t i o n o f copper o x i d e . W h e n the c o n c e n t r a t i o n o f h y d r o x i d e
increased to 0.5 M a n d the concentrations o f c y a n i d e , copper a n d s o d i u m sulphate w e r e kept
at 4 M , I M a n d 0.5 M r e s p e c t i v e l y , the a n o d i c b e h a v i o u r o f c o p p e r c y a n i d e ( F i g u r e 7-9)
b e c a m e quite different f r o m that for the solutions w i t h 0.25 a n d 0.05 M N a O H ( F i g u r e s 7-6
a n d 8). A t h i n film o f c o p p e r o x i d e w a s precipitated o n the anode at the p o t e n t i a l > a c e r t a i n

114
v a l u e ( s h o w n i n F i g u r e s 7-28 a and b). T h e e v o l u t i o n o f m a s s i v e gas b u b b l e s c o n s i d e r e d to
be c y a n o g e n w a s o n l y o b s e r v e d at 100 a n d 4 0 0 r p m for 50 C , a n d 100 to 1600 r p m for 60
C.
300
4900 rpm
250 1600 rpm
E 400 rpm
< 100 rpm
4900 rpm-CuO
in
c
O) 150
73
C
a>
i 100
3
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
0.2 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.0

Potential vs. S C E / V Potential vs. SCE / V
(c) 50 C (d) 60 C
F i g u r e 7-4 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. E l e c t r o l y t e : 3

M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . K e y s : 1 - no p r e c i p i t a t i o n o f
2 4
c o p p e r o x i d e , 2 - p r e c i p i t a t i o n o f copper o x i d e a n d 3 - e v o l u t i o n o f o x y g e n .
115
5000 12000
4500 4900 rpm

1600 rpm 10000
4000
400 rpm
E
3500 . . 100 rpm
< 8000 4-
3000
Precipitation ^
2500 -of copper oxide /' \ ^ ' c 6000
/ r"\ 1- O
2000 \ \ \ / A 1
TJ
4-*
C
1500 \ \\/ / y i A V ^ 4000
"Vr-l ^
o
1
1000 [' -''/ y " 'An ~~~~

r !
'\ '
2000
500
''\ \
0 \ . V - ' ' - - ' "
D 0.2 0.4 0.6 3.8 1 1 0.4 0.6 0.8 1.0

Potential v s . S C E / V Potential v s . S C E / V
(a) 25 C (b) 40 C
30000
4900 rpm
25000 1600 rpm
400 rpm
100 rpm
20000
V) Precipitation
c 15000 of copper oxide
0)
73
10000
5000
"4 Evolution of cyanogen bubbles
0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
F i g u r e 7-5 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. E l e c t r o l y t e :

3.5 M C N " , C N : C u m o l e ratio = 3.5, 0.25 M N a O H and 0.5 M N a S 0 . 2 4
116
14000 30000
-4900 rpm 4900 rpm

12000 -- 25000
r
CN .1600 rpm ' 1600 rpm
CN
E 10000 -- . 400 rpm E 400 rpm
.100 rpm
< <

20000 - . . 100 rpm
8000
(A in 15000 .
C
u
o 6000 -- a / A/V\
Rapid evolution / / / \
3 4000

10000 - - of large bubbles
/
./// riA V ^
o 3
o
2000 5000
/' - Affected by bubbles
0
0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
30000 45000
.4900 rpm 40000
CN
25000 .1600 rpm -4900 rpm
. 400 rpm 35000 . 1600 rpm
E
. 100 rpm . 400 rpm
< 20000 30000
-100 rpm
in 25000
den
15000 --
20000 4-
Rapid evolution
of big bubbles
0) 10000 -- 15000 of large bubbles
i_
3 10000
o
5000 -' Affected by bubbes
5000
;/ Affected by bubbles
0
0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0
(c) 50 C (d) 60 C
F i g u r e 7-6 P o l a r i z a t i o n c u r v e s at different r o t a t i o n a l speeds a n d temperatures. E l e c t r o l y t e : 4

M C N " , C N : C u m o l e ratio = 4, 0.25 M N a O H a n d 0.5 M N a S 0 . 2 4
117
120 1400
-4900 rpm
1 0 0
. 1600 rpm
N
. 400 rpm
E
< 80
in
60
40
3
o 20
0.0 0.4 0.6 0.8 1.0 0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
6000 9000
4900 rpm 8000 4900 rpm
5000 1600 rpm 1600 rpm
fM 400 rpm <N 7000 400 rpm
E E
100 rpm _. _ 100 rpm
< 4000 < 6000
in Precipitation ^ 5000
c 3000 in
0) of copper oxide / V c
a
g 4000
2000
3 O 3000 i-
o O 2000
1000 1000 4-
0.0 0.4 0.6 0.8 0.0 0.4 0.6 0.8 1.i 1.2
(c) 50 C (d) 60 C
F i g u r e 7-7 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures. E l e c t r o l y t e : 3

M C N \ C N : C u m o l e ratio = 3, 0.05 M N a O H a n d 0.5 M N a S 0 2 4
118
(a) 25 C (b) 40 C
45000 60000
40000 _4900 mm 4900 rpm
__ 1600 rpm 50000 1600 rpm
N 35000 ... 400 rpm CM 400 rpm
E
..100 rpm E 100 rpm
< 30000 < 40000
& 25000 c 30000
.g 20000 Rapid evolution
of large bubbles
S 15000 20000 Rapid evolution
of large bubbles
rj 10000 3
o 10000
5000
affected by bubbles V v
Affecte'cTby bubbles
0 0J
0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8
(c) 50 C (d) 60 C
Figure 7-8 Polarization curves at different rotational speeds and temperatures. Electrolyte: 4
M CN", C N : C u mole ratio = 1, 0.05 M NaOH and 0.5 M N a S 0 2 4
119
(a) 25 C (b) 4 0 C
35000 30000
4900 rpm
30000 4900 rpm 1600 rpm
25000
1600 rpm CM
400 rpm
25000 400 rpm E _.-100 rpm
100 rpm < 20000
20000 Precipitati
Precipitatio of, c 15000 of copper oxide / ^
0)
a; 15000 jcopper oxide TJ A/
TJ
*~>
C
10000
S 10000
k- 3
3
o o 5000
Rapid evolution of
xyanogen bubbles
5000
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0 Potential v s . S C E / V Potential vs. SCE / V
(c) 50 C (d) 6 0 C
F i g u r e 7-9 P o l a r i z a t i o n c u r v e s at different rotational speeds a n d temperatures. E l e c t r o l y t e : 4

M C N " , C N : C u m o l e ratio = 1, 0.50 M N a O H a n d 0.5 M N a S 0 2 4
120
7.3 Coulometric Measurement
F r o m the literature r e v i e w , it appears that the s t o i c h i o m e t r y for the a n o d i c o x i d a t i o n
o f c o p p e r c y a n i d e has not been c a r e f u l l y studied a n d the results are i n c o m p l e t e and
conflicting. I n this study, c o n t r o l l e d potential c o u l o m e t r y w a s u s e d to determine the
s t o i c h i o m e t r y o f the a n o d i c o x i d a t i o n o f copper c y a n i d e per F a r a d a y . T h e anode p o t e n t i a l
w a s c o n t r o l l e d at values to m i n i m i z e the rates o f side reactions s u c h as o x y g e n e v o l u t i o n .
T h e w o r k i n g electrode (anode) w a s separated f r o m the counter electrode (the cathode) to
m i n i m i z e the effect o f the change i n the C N : C u m o l e ratio due to c o p p e r d e p o s i t i o n at the
cathode. T h e v o l u m e o f the catholyte w a s o n l y about 1-2 c m a n d its i n i t i a l c o n c e n t r a t i o n o f

3
NaOH was 10 t i m e s that o f the anolyte. T h e e v o l u t i o n o f h y d r o g e n c a u s e d a high
c o n c e n t r a t i o n o f h y d r o x i d e w h i c h c a n be transported to the anode c o m p a r t m e n t to m a i n t a i n
the c o n c e n t r a t i o n o f h y d r o x i d e i n the anolyte w h o s e p H w a s m o n i t o r e d . T h e results are g i v e n
i n T a b l e 7-1. Tests 1-4 s h o w the amount o f o x i d i z e d c y a n i d e a n d c o p p e r (I) per F a r a d a y at
0.05 M C N " , a C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a ^ O , .
I f the r e a c t i o n o f the a n o d i c o x i d a t i o n proceeds a c c o r d i n g to the f o l l o w i n g r e a c t i o n :
C u ( C N ) " + 8 0 H " = 3 C N O " + C u ( O H ) + 3 H 0 + 7e

3
2
2 2 (7-1)
the amounts o f c y a n i d e and C u ( I ) i o n o x i d i z e d per F a r a d a y are 0.429 a n d 0.143 mole
r e s p e c t i v e l y . T h e c o r r e s p o n d i n g values o f these tests are c l o s e to the v a l u e s i n d i c a t e d b y
R e a c t i o n 7 - 1 . Therefore the a n o d i c reaction o f copper c y a n i d e under these c o n d i t i o n s c a n be
expressed a p p r o x i m a t e l y b y R e a c t i o n 7-1. T h e current e f f i c i e n c i e s for this r e a c t i o n w e r e
f o u n d to be 99.8, 102, 103, 105 % r e s p e c t i v e l y at 2 5 , 4 0 , 50 a n d 60 C . Tests 5 - 9 s h o w the
a m o u n t o f o x i d i z e d c y a n i d e to copper per F a r a d a y at 0.05 M C N " , C N : C u m o l e ratio = 4,
0.25 M N a O H and 1 M N a S 0 . Tests 5 - 8 were c o n d u c t e d at the p o t e n t i a l w h e r e the current

2 4
reached the l i m i t i n g current at 100 r p m .
I f the r e a c t i o n for the a n o d i c o x i d a t i o n proceeds as f o l l o w s :
Cu(CN) 4
3 _
+ 10OH- = 4CNO"+Cu(OH) 2 + 4 H 0 + 9e
2 (7-2)
the amounts o f o x i d i z e d c y a n i d e a n d copper (I) i o n s per F a r a d a y e l e c t r i c i t y are 0.444 a n d
0.111 m o l e r e s p e c t i v e l y . T h e amount o f c y a n i d e o x i d i z e d per F a r a d a y is a little h i g h e r t h a n
0.444 a n d the a m o u n t o f copper (I) o x i d i z e d is a little l o w e r than 0.111 m o l e . T h e r e f o r e the
a n o d i c r e a c t i o n o f copper c y a n i d e under these c o n d i t i o n s c a n be expressed a p p r o x i m a t e l y b y

121
R e a c t i o n 7-2. T h e current efficiencies for this r e a c t i o n were f o u n d to be 9 9 . 5 , 100, 103, 105
% r e s p e c t i v e l y at 2 5 , 4 0 , 50 a n d 60 C . W h e n the p o t e n t i a l w a s c o n t r o l l e d at a v a l u e w h e r e
no c o p p e r o x i d e w a s f o r m e d (Test 9), the amount o f c y a n i d e o x i d i z e d per F a r a d a y is 0.505
m o i F " . T h e r e a c t i o n c a n be expressed as f o l l o w s :
1
C N " + 2 0 F T = C N O " + H 0 + 2e 2 (7-3)
Tests 10-13 s h o w the amount o f c y a n i d e to copper o x i d i z e d per F a r a d a y at 0.05 M
C N " , C N : C u m o l e ratio = 12, 0.25 M N a O H a n d 1 M N a S 0 . T h e a m o u n t o f c y a n i d e

2 4
o x i d i z e d w a s v e r y c l o s e 0.5 m o i F " , i.e. c y a n i d e is o x i d i z e d to cyanate.

1
When the
c o n c e n t r a t i o n o f h y d r o x i d e w a s 0. 01 M N a O H , the a m o u n t o f c y a n i d e o x i d i z e d w a s s t i l l
c l o s e to 0.5 m o i F " (Tests 1 4 - 1 7 ) .

1
T a b l e 7-1 A m o u n t o f c y a n i d e a n d copper (I) o x i d i z e d per F a r a d a y at 100 r p m a n d different

C N : C u m o l e ratios and h y d r o x i d e concentrations
No. Composition of Temperature Potential cyanide copper o x i d i z e d
solution /C vs. S C E / V oxidized / m o i F" 1
/ m o i F" 1
1 0.05 M C N " , 25 0.5 0.435 0.126

2 0.01667 M C u +
40 0.5 0.443 0.136
3 CN:Cu = 3 50 0.48 0.445 0.139
4 0.25 M N a O H 60 0.46 0.439 0.159
5 0.05 M C N " , 25 0.5 0.447 0.102
6 0.0125 M C u +
40 0.5 0.449 0.106
7 CN:Cu = 4 50 0.48 0.467 0.110
8 0.25 M N a O H 60 0.46 0.470 0.110
9 25 0.3 0.505 0
10 0.05 M C N " , 25 0.45 0.508 0
11 0.0125 M C u +
40 0.45 0.509 0
12 C N : C u = 12 50 0.45 0.510 0
13 0.25 M N a O H 60 0.45 0.512 0
14 0.05 M C N " , 25 0.6 0.510 0
15 0.0125 M O T 40 0.6 0.511 0
16 C N : C u = 12 50 0.6 0.512 0
17 0.01 M N a O H 60 0.6 0.515 0
T a b l e 7-2 lists the c o u l o m e t r i c results for the s o l u t i o n w i t h h i g h concentrations o f
copper c y a n i d e u s i n g the c o n t r o l l e d current m e t h o d (400 A m" ). F o r the s o l u t i o n w i t h 3 M

2
C N a n d 1 M C u , at [ O H " ] = 0.25 M , the a n o d i c current e f f i c i e n c y for c u p r o u s i o n s is a l m o s t

+
that e x p e c t e d f r o m R e a c t i o n 7-1 a n d the c y a n i d e current e f f i c i e n c y is s l i g h t l y l o w e r t h a n that

122
expected f r o m R e a c t i o n 7 - 1 , p o s s i b l y due to the e v o l u t i o n o f o x y g e n . A t [OH"] = 0.1 M , the
current e f f i c i e n c y for cuprous i o n s b e c a m e m u c h l o w e r a n d the current e f f i c i e n c y for c y a n i d e
i n c r e a s e d to about 100 % . F o r the s o l u t i o n w i t h 4 M C N " a n d I M C u , the c y a n i d e current

+
efficiencies w e r e a l m o s t 100 % a n d the current e f f i c i e n c i e s for c u p r o u s i o n w e r e zero.
Therefore the s t o i c h i o m e t r y o f the a n o d i c o x i d a t i o n o f copper c y a n i d e is dependent o n the
s o l u t i o n c o m p o s i t i o n , temperature and potential.
T a b l e 7-2 A m o u n t o f c y a n i d e and copper (I) o x i d i z e d per F a r a d a y at 4 0 0 A m " , 100 r p m

2
different C N : C u m o l e ratios a n d h y d r o x i d e concentrations

No. Composition of Temperature / C Cyanide oxidized Copper oxidized
solution / m o i F" 1
/ m o i F" 1
1 3 M CN", 1 M C u +
50 0.412 0.135
CN:Cu = 3
2 0.25 M N a O H 60 0.408 0.138
3 3 M CN", 1 M C u +
50 0.498 0.034
CN:Cu = 3
4 0.10 M N a O H 60 0.501 0.037
5 4 M CN", 1 M C u +
50 0.492 0
CN:Cu = 4
6 0.25 M N a O H 60 0.496 0
7 4 M CN", 1 M C u +
50 0.498 0
CN:Cu = 4
8 0.10 M N a O H 60 0.503 0
7.4 Effect of CN.Cu Mole Ratio
T h e p o l a r i z a t i o n curves for the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e w i t h different
C N : C u m o l e ratios a n d a constant c y a n i d e c o n c e n t r a t i o n (0.05 M ) are g i v e n i n F i g u r e 7-10.
T h e y s h o w that copper has a s i g n i f i c a n t catalytic effect o n c y a n i d e o x i d a t i o n . A t a C N : C u
m o l e ratio o f 3, the a n o d i c o x i d a t i o n o f copper c y a n i d e b e g a n at 0.090, 0.045, 0.016 a n d 0.00
V v s . S C E r e s p e c t i v e l y for 2 5 , 4 0 , 50 and 60 C . A t a C N : C u m o l e ratio > 4, the a n o d i c
o x i d a t i o n o f copper c y a n i d e b e g a n at 0.170, 0.145, 0.115, 0.085 r e s p e c t i v e l y for 2 5 , 4 0 , 50
a n d 60 C . T h e l o w e r the m o l e ratio o f c y a n i d e to copper, the l o w e r the p o t e n t i a l for the
onset o f the f o r m a t i o n o f copper o x i d e . W h e n the C N : C u m o l e ratio e x c e e d e d 6, n o w e l l -

123
d e f i n e d l i m i t i n g current w a s obtained because o x y g e n w a s e v o l v e d before the current
reached a l i m i t i n g v a l u e . T h e p l o t o f potential vs. l o g (current density) for 25 a n d 60 C is
s h o w n i n F i g u r e 7-11 a n d that for 4 0 and 50 C i n F i g u r e A - 2 8 ( A p p e n d i x 8). T h e c o n d i t i o n
o f the surface o f the graphite electrode v a r i e d after the e l e c t r o c h e m i c a l c o n d i t i o n i n g due to
the inherent surface v a r i a b i l i t y . T h e data for F i g u r e 7-10 were generated w i t h s o m e v a r i a t i o n
i n the surface c o n d i t i o n because every measurement w a s c o n d u c t e d o n a r e n e w e d electrode
surface. H o w e v e r , the data for F i g u r e 7-11 were generated o n the same electrode surface b y
l i m i t i n g the p o t e n t i a l w e l l b e l o w the v a l u e at w h i c h c o p p e r o x i d e b e g a n to precipitate.
Therefore the data for F i g u r e 7-11 cannot c o m p a r e d d i r e c t l y to those i n F i g u r e 7-10. T h i s
e x p l a n a t i o n w i l l also be a p p l i e d i n the next paragraphs.
A l t h o u g h there is n o c o r r e c t i o n for the c o n c e n t r a t i o n difference b e t w e e n the b u l k a n d
the surface s o l u t i o n , at l o w potentials, the current w a s m u c h l o w e r than 10 % o f the l i m i t i n g
current. T h u s the concentration difference c a n be neglected. W h e n the concentration
difference b e c a m e significant, the f o r m a t i o n o f copper o x i d e b e g a n a n d the current i n c r e a s e d
sharply. W h e n c o p p e r o x i d e w a s precipitated o n the anode, e v e n at a constant p o t e n t i a l , the
current kept i n c r e a s i n g . A t a C N : C u m o l e ratio o f 3, the T a f e l slope w a s about 0.12 V
decade" . A t a C N : C u m o l e ratio > 4, t w o T a f e l slope ranges appear w i t h the first T a f e l slope

1
b e i n g about 0.060 V decade" and the s e c o n d one about 0.17-0.20 V decade" . F r o m F i g u r e 7-

1 1
12, there is o n l y one w e l l - d e f i n e d T a f e l slope o n a p y r o l y t i c graphite electrode at a C N : C u
m o l e ratio > 4 a n d the current at a C N : C u m o l e ratio o f 3 w a s larger than those at a C N : C u
m o l e ratio > 4. Therefore the a n o d i c b e h a v i o u r o f copper c y a n i d e is dependent o n the anode
materials.
T h e increase f r o m 3 to over 4 i n the C N : C u m o l e ratio resulted i n a s i g n i f i c a n t change
i n the p o t e n t i a l v s . l o g (current) curves (Figures 7-11 and 7-12). T h i s c a n be due to a change
i n the d i s c h a r g e d species. A t a constant potential a n d c y a n i d e c o n c e n t r a t i o n , the current at a
C N : C u m o l e ratio o f 6 ( l o w e r copper concentration) is larger than that at a C N : C u m o l e ratio
o f 4 (higher c o p p e r concentration) and the current at a C N : C u m o l e ratio o f 4 is larger t h a n
that at a C N : C u m o l e ratio o f 12. T h i s p h e n o m e n o n s h o u l d be due to the change i n the
c o n c e n t r a t i o n o f the d i s c h a r g e d species as c o n f i r m e d i n S e c t i o n 7.6.
When the concentration o f copper was fixed at 0.00833 M and the cyanide
concentrations w e r e fixed at 0.025, 0.05, 0.1, 0.2 a n d 0.4 M (the c o r r e s p o n d i n g C N : C u m o l e

124
ratios were 3, 6, 12, 2 4 and 48 r e s p e c t i v e l y ) , the a n o d i c b e h a v i o u r o f c o p p e r c y a n i d e
c h a n g e d w i t h c y a n i d e c o n c e n t r a t i o n ( F i g u r e 7-13 for 25 a n d 60 C a n d F i g u r e A - 2 9
( A p p e n d i x 8 ) for 4 0 a n d 50 C ) . A t [CN"] = 0.025 M (a C N : C u m o l e ratio o f 3), the p l o t s o f
p o t e n t i a l v s . l o g (current density) are linear. A t [CN"] > 0.05 M (a C N : C u m o l e ratio > 6),
s i m i l a r to F i g u r e 7 - 1 1 , there are t w o T a f e l slopes i n the plots o f p o t e n t i a l v s . l o g (current
density).
T h e c u r v e s for potential v s . l o g (current density) are p a r a l l e l to e a c h other, but d o not
shift u n i f o r m l y w i t h i n c r e a s i n g concentration o f c y a n i d e . Therefore p r o b a b l y the d i s c h a r g e d
species is not free c y a n i d e ions, but one copper c y a n i d e species. F r o m the plots o f p o t e n t i a l
vs. l o g (current density) o n a p y r o l y t i c graphite electrode ( F i g u r e 7-14), the T a f e l slope for
0.025 M C N " (a C N : C u m o l e ratio o f 3) is a little different f r o m those for h i g h e r c y a n i d e
concentrations. H o w e v e r , at a C N : C u m o l e ratio > 6, the T a f e l slopes are the same a n d the
curves are p a r a l l e l to each other and shift non-uniformly with increasing cyanide
concentration.
F r o m F i g u r e 7-15, the increase i n c y a n i d e c o n c e n t r a t i o n f r o m 3 to 4 M results i n a
s i g n i f i c a n t increase i n the current density. A t [ C N ] = 3 (i.e. a C N : C u m o l e ratio o f 3), the
current is m u c h l o w e r than those for 3.5 a n d 4 M C N " due to the p a s s i v a t i o n effect o f the
p r e c i p i t a t i o n o f copper o x i d e at a l o w e r p o t e n t i a l (0.2 V v s . S C E ) . F r o m the p l o t s o f
p o t e n t i a l v s . l o g (current density) ( F i g u r e 7-16), at [CN"] = 3 M , there is a T a f e l slope o f 0.10
V decade" . H o w e v e r , at [CN"] = 3.5 a n d 4 M , there are t w o T a f e l slopes,- the first one b e i n g

1
0.66 V decade ( R T / F ) and the s e c o n d 0.16 V decade" . T h e s e c o n d T a f e l slope appears to

1
increase s l i g h t l y w i t h i n c r e a s i n g potential p r o b a b l y due to the c o n c e n t r a t i o n change o f
c y a n i d e o n the surface. T h e results at 2 5 , 40 and 50 C are s i m i l a r .

125
1200 2000
1800 _*_CN:Cu =3
1600 -D-CN:CU = 4
-4_CN:Cu =6
1400
< -*_CN:Cu =12
1200 __NoCu
g 1000
2 800
3
o 400
200
0
0.2 0.4 0.6 0.8 0.2 0.4 0.6
Potential vs. SCE/ V Potential vs. SCE / V
(a) 25 C (b) 40 C
3000 3500
2500 -- 3000 __CN:Cu =3

E CN
_o-CN:Cu =4
< E 2500
2000 -- < _*_CN:Cu =6
_x_CN:Cu =12
'in 2000
c in
c
-as no Cu
a> 1500 --
T3 0)
c
o
k_
TJ 1500
1_ 1000
3 a.
o 3 1000
500 -- o
500
0 -- 0
0.2 0.4 0.6 0.2 0.4 0.!
Potential vs. SCE/V Potential vs. SCE/V
(c) 50 C (d) 60 C
Figure 7-10 Effect of the mole ratio of cyanide to copper on cyanide oxidation -current vs.
potential on a graphite rotating disk at 4900 rpm and different temperatures. Electrolytes:
0.05 M CN", CN:Cu mole ratio = 3, 4, 6, 12 and no copper, 0.25 M NaOH and 1 M N a S 0 . 2 4
126
F i g u r e 7-11 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n - p o t e n t i a l

v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0 r p m (25 a n d 60 C ) . E l e c t r o l y t e s
: 0.05 M C N " , C N : C u m o l e ratio = 3, 4, 6, 12 and n o copper, 0.25 M N a O H a n d 1 M N a S 0 . 2 4
0.10 1 1 1 1 1
-1.5 -0.5 0.5 1.5
L o g ( c u r r e n t d e n s i t y / A m" ) 2
F i g u r e 7-12 E f f e c t o f the m o l e ratio o f c y a n i d e to c o p p e r o n c y a n i d e o x i d a t i o n - p o t e n t i a l

v s . l o g current density o n a p y r o l y t i c graphite rotating electrode at 4 9 0 0 r p m a n d 25 C .
E l e c t r o l y t e s : 0.05 M C N " , C N : C u m o l e ratio = 3, 4, 6, 12 a n d 0.25 M N a O H a n d 1 M
Na S0 .
2 4
127
F i g u r e 7-13 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n - p o t e n t i a l v s .

l o g (current density) o n a graphite rotating d i s k at 4 9 0 0 r p m (25 a n d 60 C ) . E l e c t r o l y t e s :
[ C u ] = 0 . 0 0 8 3 3 , [CN"] = 0.025, 0.05, 0.1, 0.2 a n d 0.4 M , 0.25 M N a O H a n d 1 M N a S 0 .
+
2 4
0.6
0.025 M C N ~
0.5 - Q _ 0.050 M C N ~
-_ 0.100 M C N ~
LU
O - e - 0.200 M C N ~
</) 0.4
oi
-- 0.400 M C N ~
>
0.3
c
o
o
" 0.2
0.1
-1 -0.!
0.5 0 0.5 1 1.5
-2vz
L o g ( c u r r e n t d e n s i t y / A m" )

l o g (current density) o n a p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s
: [ C u ] = 0.00833 M , [CN"] = 0.025, 0.05, 0.1, 0.2 a n d 0.4 M , 0.25 M N a O H a n d 1 M
+
Na S0 .
2 4
128
40000
F i g u r e 7-15 E f f e c t o f the m o l e ratio o f c y a n i d e to c o p p e r o n c y a n i d e o x i d a t i o n - current v s .

p o t e n t i a l o n a graphite rotating d i s k at 4 9 0 0 r p m and 60 C . E l e c t r o l y t e s : 1 M C u , [CN"] = +
3, 3.5 a n d 4 M , 0.25 M N a O H a n d 0.5 M N a ^ .
0.4 -,
-0.1 I | | | | I
0 1 2 3 4 5
Log (current density / A m") 2

l o g (current density) o n a graphite rotating d i s k at 4 9 0 0 r p m a n d 60 C . E l e c t r o l y t e s : 1 M
C u , [CN"] = 3, 3.5 a n d 4 M , 0.25 M N a O H and 0.5 M N a ^
+
129
7.5 Effect of pH
A t a C N : C u m o l e ratio o f 3, a n d [ C N ' ] = 0.05 M , the c o n c e n t r a t i o n o f h y d r o x i d e
s i g n i f i c a n t l y affects the a n o d i c b e h a v i o u r o f copper c y a n i d e ( F i g u r e 7-17). I n the l o w
p o l a r i z a t i o n r e g i o n , w i t h decreasing concentration o f h y d r o x i d e , the T a f e l slope decreases
f r o m 0.130 to 0.060 V decade" a n d the current decreases at a constant p o t e n t i a l ( F i g u r e 7-18

1
for 25 a n d 60 C a n d F i g u r e A - 3 0 for 40 a n d 50 C ( A p p e n d i x 8)). T h i s suggests that the
r a t e - c o n t r o l l i n g step changes or the m e c h a n i s m changes. I n the h i g h p o l a r i z a t i o n r e g i o n ,
c o p p e r c y a n i d e is o x i d i z e d to copper o x i d e and cyanate. T h e current is sensitive to the
h y d r o x i d e c o n c e n t r a t i o n and does not r e a c h a w e l l - d e f i n e d l i m i t i n g v a l u e at l o w h y d r o x i d e
c o n c e n t r a t i o n . T h i s means that h y d r o x i d e ions are i n v o l v e d i n the r a t e - c o n t r o l l i n g step. T h e
results o b t a i n e d o n p y r o g r a p h i t e ( F i g u r e 7-19) and P t rotating d i s k s ( F i g u r e A - 3 0 i n
A p p e n d i x 8) are s i m i l a r .
A t a C N : C u m o l e ratio o f 4, [CN"] = 0.05 M , the effect o f p H o n the a n o d i c o x i d a t i o n
depends o n the a p p l i e d potential ( F i g u r e 7-20, a n d F i g u r e 7-21 a n d F i g u r e A - 3 2 ( A p p e n d i x
8)). I n the l o w p o l a r i z a t i o n r e g i o n , p H has little effect o n the a n o d i c o x i d a t i o n o f c y a n i d e .
T h e T a f e l slope w a s independent o f p H a n d the current decreased s l i g h t l y w i t h d e c r e a s i n g
pH. S i m i l a r results w e r e obtained o n p y r o l y t i c graphite ( F i g u r e 7-22). T h i s m e a n s that
h y d r o x i d e is not i n v o l v e d i n the r a t e - c o n t r o l l i n g step.
In the h i g h p o l a r i z a t i o n r e g i o n (> about 0.5-0.6 V v s . S C E ) , c o p p e r c y a n i d e w a s
o x i d i z e d to c o p p e r o x i d e a n d cyanate w i t h the current d e p e n d i n g greatly o n the h y d r o x i d e
c o n c e n t r a t i o n . G e n e r a l l y , the current decreases w i t h decreasing h y d r o x i d e c o n c e n t r a t i o n . A t
25 C a n d a p o t e n t i a l > 0.65 V v s . S C E , the current for 0.25 M N a O H w a s b e l o w that for
0.05 M N a O H due to p a s s i v a t i o n ( p o s s i b l y the a d s o r p t i o n o f the o x y g e n ) . T h e o x y g e n
e v o l u t i o n a n d the f o r m a t i o n o f copper o x i d e decreased significantly with decreasing
c o n c e n t r a t i o n o f h y d r o x i d e . Therefore the current is dependent o n the c o n c e n t r a t i o n o f
h y d r o x i d e a n d h y d r o x i d e is i n v o l v e d i n the r a t e - c o n t r o l l i n g step.
F r o m F i g u r e s 7-23, 7-24 a n d F i g u r e A - 3 3 , the effect o f p H at a C N : C u m o l e ratio =
12 is s i m i l a r to that at C N : C u m o l e ratio = 4. I n the l o w p o l a r i z a t i o n r e g i o n (< about 0.5 V
S C E ) , the current w a s s l i g h t l y affected b y p H a n d the T a f e l slope w a s independent o f p H .
T h e results o b t a i n e d o n a p y r o l y t i c graphite electrode ( F i g u r e 7-25) also s h o w that p H has

130
a l m o s t n o effect o n the a n o d i c o x i d a t i o n o f copper c y a n i d e at a p o t e n t i a l < 0.6 V v s . S C E . A t
a p o t e n t i a l > about 0.5 V v s . S C E ( F i g u r e 7-23), p H affected the current. T h e difference
b e t w e e n the currents for 0.25 a n d 0.05 M O H " is r e l a t i v e l y s m a l l a n d the difference b e t w e e n
the currents for 0.25 (or 0.05 ) and 0.01 M O H " is significant. A t 25 a n d 40 C , the current
for 0.25 M O H " w a s e v e n l o w e r than that for 0.05 M O H " i n one p o t e n t i a l r e g i o n p o s s i b l y
because the e v o l u t i o n o f o x y g e n d i m i n i s h e d the o x i d a t i o n o f c o p p e r c y a n i d e .
At a CN:Cu m o l e ratio o f 3 and [CN"] = 3 M , the effect o f the hydroxide
c o n c e n t r a t i o n w a s dependent o n the temperature ( F i g u r e 7-26). A t 25 C , the current
decreased w i t h decreasing c o n c e n t r a t i o n o f h y d r o x i d e and the a n o d i c o x i d a t i o n o f c o p p e r
c y a n i d e w a s affected b y the p r e c i p i t a t i o n o f copper o x i d e o n the electrode.
A t the temperature > 40 C , i n the i n i t i a l p o t e n t i a l r e g i o n the current decreased w i t h
i n c r e a s i n g c o n c e n t r a t i o n o f h y d r o x i d e . I n the h i g h e r potential r e g i o n , the currents for 0.50 M
O H " w a s larger than that for 0.25 M O H " . H o w e v e r , i n some p o t e n t i a l r e g i o n s , the current for
0.05 M O H " w a s larger than that for 0.25 M O H " or e v e n 0.50 M O H " . T h i s p h e n o m e n o n is
p r o b a b l y related to the fact that the amount o f the precipitated c o p p e r o x i d e for 0.05 M O H
decreased s i g n i f i c a n t l y w i t h i n c r e a s i n g temperature, r e s u l t i n g i n the less p a s s i v a t i o n o f the
electrode. A t 60 C , there w a s a l m o s t no precipitate o n the electrode at 0.05 M O H " , but at
0.25 or 0.50 M O H " , a t h i c k copper o x i d e f i l m w a s f o r m e d , l e a d i n g to the difference i n the
anodic behaviour.
F r o m F i g u r e 7-27, at 0.25 and 0.50 M O H " , the T a f e l slope w a s about 0.10

1
V
decade" . A t 0.05 M O H " , there w e r e t w o T a f e l slopes, the first b e i n g about 0.66 V decade"
1 1
a n d the s e c o n d one 0.11 V decade' . T h e change i n p H c o u l d result i n a change i n the

1
d i s c h a r g e d species or the rate-determining step.
A t a C N : C u m o l e ratio o f 4 a n d [CN"] = 4 ( F i g u r e 7-28), i n the l o w e r p o l a r i z a t i o n
r e g i o n (< 0.50 V v s . S C E ) , the current was s l i g h t l y affected b y the change in the
c o n c e n t r a t i o n o f h y d r o x i d e . A t potentials > about 0.5 V v s . S C E , the c o n c e n t r a t i o n o f
h y d r o x i d e s i g n i f i c a n t l y affected the b e h a v i o u r o f the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e .
A t [OH"] = 0.5 M , w h e n the current increased to a certain v a l u e , the m o l e ratio o f
c y a n i d e to c o p p e r o n the surface became l o w , but the h y d r o x i d e c o n c e n t r a t i o n o n the surface
w a s s t i l l h i g h a n d reacted w i t h c u p r i c i o n s to f o r m copper c y a n i d e , r e s u l t i n g i n p a s s i v a t i o n o f
the a n o d i c o x i d a t i o n o f c y a n i d e . A t [OH"] = 0.05 M , w h e n the current b e c a m e so h i g h that

131
the pH on the surface was low and (CN) gas was formed. A t [OH"] = 0.25 M , the anodic
2
behaviour of copper cyanide is between those at [OH] = 0.5 and 0.05 M . From the plot of
potential vs. log (current density) (Figure 7-29) in the low polarization region, the current
decreases slightly with decreasing hydroxide concentration.
From the above discussion, we can see that the anodic behaviour of copper cyanide is
a function of the total cyanide concentration, the mole ratio of cyanide to copper, hydroxide
concentration and temperature.
700 1600
600 1400
CN
E 1200
^ 500 < - 0.25 M OH"
<
1000 -0.05 MOH"
& 400 .0.01 MOH"
'35 in
c
800
a>
O 300 a
c C 600
a> i
t 200 = 400
o3
100 200
0
0 0.1 0.2 0.3 0.4 0.5 0.1 0.2 0.3 0.4 0.5
(a) 25 C (b) 40 C
4500 T 3500
4000 --
3000
CN 3500 .0.25 M OH
E .0.25 M OH CM
.0.05 M OH"
E 2500
.0.05 MOH" .0.01 M OH"
< 3000 -- <
.0.01 MOH"
jfr 2000
nsity
2500
'35
O) c
TJ 2000 --
.g 1500
Cm rrent
1500 -- +J
c
1000 8j 1000
500 500
0.1 0.2 0.3 0.4 0.6 0.1 0.2 0.3 0.4 0.5 0.6
(c) 50 C (d) 60 C
Figure 7-17 Effect of pH on cyanide oxidation - current vs. potential on a graphite rotating
disk at 4900 rpm and different temperatures. Electrolytes : 0.05 M CN", a CN:Cu mole ratio
of 3, [OH"] = 0.25, 0.05 and 0.01M and 1 M N a S 0 . 2 4
132
L o g (current density IA m' ) 2

L o g (current density / A m" ) 2
F i g u r e 7-18 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current d e n s i t y ) o n a

graphite rotating d i s k at 4 9 0 0 r p m (25 and 60 C ) . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u m o l e
ratio o f 3, [OH"] = 0.25, 0.125, 0.05, 0.025 a n d 0 . 0 1 M and 1 M N a ^ .
0.5
O- 0.1 i -
o -! i i i i i i |
-2 -1.5 -1 -0.5 0 0.5 1 1.5

F i g u r e 7-19 E f f e c t o f o f p H o n c y a n i d e o x i d a t i o n - p o t e n t i a l v s . l o g (current d e n s i t y ) o n a
p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u
m o l e ratio o f 3, [OH"] = 0.25, 0.125, 0.05, 0.025 and 0 . 0 1 M and 1 M N a S 0 2 4
133
1400 2500
0.0 0.2 0.4 0.6 0.8 1.0 1.2

(a) 25 C (b) 4 0 C
3500 ,
3000 i-
0.00 0.20 0.40 0.60 0.80

Potential v s . S C E / V E vs. S C E / V
(b) 50 C (b) 6 0 C
F i g u r e 7-20 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - current v s . potential o n a graphite r o t a t i n g

d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : 0.05 M C N " , a C N : C u m o l e ratio
o f 4, [ O H ] = 0.25, 0.05, a n d 0 . 0 1 M a n d 1 M N a S 0 . 2 4
134
L o g (current density / A m' ) 2

(a) 25 C (b) 60 C
F i g u r e 7-21 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current density) o n a

graphite rotating d i s k 4 9 0 0 r p m (25 and 60 C ) . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u m o l e
ratio o f 4, [OH"] = 0.25, 0.05, and 0 . 0 1 M and 1 M N a ^ .
0.1 -I 1 1 1 1
- 2 - 1 0 1 2
F i g u r e 7-22 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - p o t e n t i a l v s . l o g (current d e n s i t y ) o n a
p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u
m o l e ratio o f 4, [OH"] = 0.25, 0.05, a n d 0 . 0 1 M and 1 M N a S 0 . 2 4
135
1800 2500
(a) 25 C (b) 4 0 C
3000 -. 4000 -.
(c) 5 0 C (d) 6 0 C
F i g u r e 7-23 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - current v s . potential o n a graphite rotating

d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : 0.05 M C N " , a C N : C u m o l e ratio
o f 12, [OH"] = 0.25, 0.05, and 0 . 0 1 M and 1 M NajSCv
136
F i g u r e 7-24 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - p o t e n t i a l v s . l o g (current d e n s i t y ) o n a
graphite rotating d i s k at 4 9 0 0 r p m (25 and 60 C ) . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u m o l e
ratio o f 12, [OH"] = 0.25, 0.05 and 0 . 0 I M a n d 1 M N a S 0 . 2 4

p y r o l y t i c graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : 0.05 M C N " , a C N : C u
m o l e ratio o f 12, [OH"] = 0.25, 0.125, 0.05, 0.025 a n d 0 . 0 1 M and 1 M N a S 0 . 2 4
137
400 T
1600
(a) 2 5 C (b) 4 0 C
5000 -i ! 9000
4500 l
(c) 5 0 C (d) 6 0 C
F i g u r e 7-26 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - the p l o t o f the current v s . the p o t e n t i a l o n a

graphite rotating d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : 3 M C N " , a
C N : C u m o l e ratio o f 3, 0.50, 0.25 a n d 0.05 M O H " a n d 0.5 M N a j S O ^
138
-0.1
L o g ( c u r r e n t d e n s i t y / A m" )
2

graphite rotating d i s k at 4 9 0 0 r p m and 60 C . E l e c t r o l y t e s : 3 M C N " , a C N : C u m o l e ratio o f
3, 0.50, 0.25, a n d 0.05 M O H " and 0.6 M N a S 0 . 2 4
18000 , 25000
Potential vs. SCE / V Potential vs. SCE / V
(a) 25 C (b) 4 0 C
139
35000
-0.50 M O H
30000
- 0.25 M O H "
-0.05 M O H "
25000
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 O.i

Potential vs. SCE / V Potential vs. S C E / V
(c) 50 C (d) 60 C
F i g u r e 7-28 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - current v s . p o t e n t i a l o n a graphite r o t a t i n g

d i s k at 4 9 0 0 r p m a n d different temperatures. E l e c t r o l y t e s : 4 M C N " , a C N : C u m o l e ratio o f 4,
[OH"] = 0.5 a n d 0.25 and 0.05 M a n d 0.5 M N a S 0 . 2 4
0.4
.0.50 M O H
.0.25 M O H "
> 0.3
.0.05 M O H "
111
O
co
to
> 0.2
c
CD 0.1
o
a.
-0.1
Log (current density / A m )

graphite rotating d i s k at 60 C . E l e c t r o l y t e s : 4 M C N " , a C N : C u m o l e ratio o f 3, [OH"] =
0.50, 0.25 a n d 0.05 M and 0.5 M N a S 0 . 2 4
140
7.6 Reaction Order
I n order to determine w h i c h o f the copper c y a n i d e species is d i s c h a r g e d at the
electrode surface, the r e a c t i o n order w i t h respect to copper c y a n i d e species w a s c a l c u l a t e d b y
c h a n g i n g the c o p p e r c y a n i d e c o n c e n t r a t i o n and the m o l e ratio o f c y a n i d e to c o p p e r a n d
m e a s u r i n g the current v s . concentration o f copper c y a n i d e species at a constant p o t e n t i a l .
T h e concentrations o f copper c y a n i d e species ( C u ( C N ) " , C u ( C N ) " a n d C u ( C N ) " ) w e r e

2 3
2
4
2
c a l c u l a t e d b y s o l v i n g the m a s s balance equations ( E q u a t i o n s 3-1 a n d 3-2) related to
R e a c t i o n s 2-3 to 2-6.
A t a C N : C u m o l e ratio o f 3, the p o l a r i z a t i o n curves were m e a s u r e d i n the c y a n i d e
c o n c e n t r a t i o n range 0.025 - 0.2 M a n d the temperature range 25 to 60 C . T h e current
i n c r e a s e d u n i f o r m l y w i t h i n c r e a s i n g concentration o f copper c y a n i d e a n d the T a f e l slope
r e m a i n e d at about 0.120 V decade" ( F i g u r e A - 3 4 i n A p p e n d i x 8). T h i s m e a n s that the k i n e t i c

1
parameters do not change w i t h c h a n g i n g concentration. A b o u t 97 % o f the c o p p e r exists i n
the f o r m o f C u ( C N ) " a n d its concentration is p r o p o r t i o n a l to the c o n c e n t r a t i o n o f the total

3
2
c o p p e r c y a n i d e . T h e concentrations o f C N " , C u ( C N ) " and C u ( C N ) " are v e r y l o w a n d do not

2 4
2
increase u n i f o r m l y w i t h i n c r e a s i n g concentration o f the total c o p p e r c y a n i d e . T h e plots o f
l o g (current) v s . l o g (concentrations o f t r i c y a n i d e ) at constant potentials gave straight l i n e s
h a v i n g slopes 0.97-0.99 ( F i g u r e 7-30). T h i s suggests that the r e a c t i o n order w i t h respect to
t r i c y a n i d e is one. Therefore C u ( C N ) " c o u l d be d i s c h a r g e d at the electrode f o r m i n g C u ( C N ) "

3
2
3
. T h e same results w e r e obtained o n a p y r o l y t i c graphite rotating d i s k ( F i g u r e s A - 3 5 a n d A -
36 i n A p p e n d i x 8).
From F i g u r e s 7-13 and 7-14, at [Cu] = 0.00833 M , the increase in cyanide
c o n c e n t r a t i o n f r o m 0.025 M (a C N : C u m o l e ratio o f 3) to 0.05 M (a C N : C u m o l e ratio o f 6)
resulted i n a change i n the T a f e l slope. T h i s m e a n s that the d i s c h a r g e d species or the rate-
c o n t r o l l i n g step changed. H o w e v e r , w h e n the c o n c e n t r a t i o n o f c y a n i d e i n c r e a s e d f r o m 0.05
to 0.4 M , the T a f e l slope d i d not change. T h e p o l a r i z a t i o n c u r v e s shifted a n d w e r e a l m o s t
p a r a l l e l to e a c h other. T h i s shift c o u l d be due to a change i n the c o n c e n t r a t i o n o f s o m e
copper c y a n i d e species. T h e current at a constant potential w a s a l m o s t p r o p o r t i o n a l to the
c o n c e n t r a t i o n o f C u ( C N ) " but not the other copper c y a n i d e species. A t 25 C , the plots o f

4
3
l o g current v s . l o g ( [ C u ( C N ) " ] ) at 0.2 a n d 0.4 V v s . S C E gave straight l i n e s h a v i n g slopes o f

4
3
141
0.96 a n d 1.0 r e s p e c t i v e l y ( F i g u r e 7-31). T h e slopes obtained o n a p y r o l y t i c graphite rotating
d i s k at 0.4 a n d 0.6 V v s . S C E were 1.01 a n d 0.98 ( F i g u r e 7-32). T h e results at 4 0 , 50 a n d 60
C are the same.
(a) 25 C (b) 60 C
F i g u r e 7-30 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a graphite r o t a t i n g d i s k at

3
2
4 9 0 0 r p m (25 a n d 60 C ) . E l e c t r o l y t e s : [CN"] = 0.025, 0.05, 0.1 a n d 0.20 M , a C N : C u m o l e

ratio = 3, [ O H ] = 0.25 M a n d 1 M N a S 0 . 2 4
2.5
2.0
E
<
>, 1.5
(A
C
CD
T3 1.0 o 0.2 V vs. S C E
c . 0.4 V vs. S C E
0.5
3
Oi 0.0
o
-0.5
-2.5 -2.4 -2.3 -2.2 -2.1
Log([Cu(CN) T / m o i dm" )
4
3 3

4
2
4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [ C N ' ] = 0.05, 0.1, 0.20 a n d 0.40 M , [ C u ] = 0.00833 M ,

+
[OH"] = 0.25 M a n d 1 M N a S 0 . 2 4
142
2.0 T
CM
i
E
5 1.5-
'55
c
a>
~ 1.0 -
C

I 0.5 -
TO
o
-I
0.0 -
-2.5 -2.4 -2.3 -2.2 -2.1
L o g ( [ C u ( C N ) l / moi dm" )
4
3 3
F i g u r e 7-32 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a p y r o l y t i c graphite

3
2
rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [CN"] = 0.05, 0.10, 0.20 a n d 0.40 M , [ C u ] +
= 0 . 0 8 3 3 , [ O H ' ] = 0.25 M and 1 M N a j S O , .
F i g u r e 7-33 s h o w s the plots o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) w h e n the 4

2
total c y a n i d e c o n c e n t r a t i o n w a s kept at 0.4 M a n d the c o p p e r c o n c e n t r a t i o n w a s c h a n g e d . T h e
slopes o f the curves were 0.96 a n d 0.93 r e s p e c t i v e l y for 0.2 a n d 0.4 V v s . S C E , w h i c h
c o r r e s p o n d to the t w o T a f e l slope ranges. T h e r e a c t i o n order w i t h respect to Cu(CN) ~ 4

3
obtained o n a p y r o l y t i c graphite electrode w a s 1.0. Y o s h i m u r a et a l . [144] s t u d i e d the a n o d i c
o x i d a t i o n o f copper c y a n i d e o n p l a t i n u m a n d thought that a l m o s t a l l o f the c o p p e r exists i n
the f o r m o f C u ( C N ) " . T h e y plotted l o g current v s . l o g [ C u ]

4
3
T o t a l a n d o b t a i n e d a slope o f 0.9.
H o w e v e r , f r o m o u r c a l c u l a t i o n , 32 -24 % o f the copper exists i n the f o r m o f C u ( C N ) " i n the 3

2
c o n c e n t r a t i o n range studied a n d the c o n c e n t r a t i o n o f C u ( C N ) " is not e x a c t l y p r o p o r t i o n a l to

4
3
the total c o p p e r concentration. T h e p l o t o f l o g [ C u ( C N ) " ] v s . l o g [ C u ]

4
3
T o t a l gave a slope o f
0.901. Therefore the corrected r e a c t i o n order w i t h respect to C u ( C N ) " s h o u l d be 0.99 for 4

3
R e f . 144.
F r o m F i g u r e 7-11 and 7-12, at [ C N ] t o t a l = 0.05 M , the p o l a r i z a t i o n c u r v e s for C N : C u
m o l e ratios o f 4, 6, a n d 12 are v e r y c l o s e a n d the current for a C N : C u m o l e ratio o f 6 ( [ C u ] =
0.00833 M ) at a constant potential is e v e n larger than that for a C N : C u m o l e ratio o f 4 ( [ C u ]

143
= 0.0125 M ) . T h i s is because the c o n c e n t r a t i o n o f C u ( C N ) " for a C N : C u m o l e ratio 6 is

4
3
larger than that for a C N : C u m o l e ratio o f 4.
T h e r e a c t i o n order w i t h respect to the copper c y a n i d e species w a s also c a l c u l a t e d b y
c h a n g i n g the total c o p p e r c y a n i d e c o n c e n t r a t i o n and k e e p i n g C N : C u m o l e ratio at 4 8 . A t this
m o l e ratio, m o s t o f copper exists i n the f o r m o f C u ( C N ) " . T h e current is a l m o s t p r o p o r t i o n a l

4
3
to the c o n c e n t r a t i o n o f C u ( C N ) " , but not to that o f C u ( C N ) " . T h e plots o f log(current) v s .

4
3
3
2
l o g ( [ C u ( C N ) " ] ) gave straight lines h a v i n g slopes o f 1.1 a n d 1.0 r e s p e c t i v e l y at 0.2 V a n d 0.4

4
3
V v s . S C E . T h e r e a c t i o n order m e a s u r e d o n a p y r o l y t i c graphite electrode w a s 1.0.
T h e r e a c t i o n order w i t h respect to h y d r o x i d e w a s d e t e r m i n e d by changing the
h y d r o x i d e c o n c e n t r a t i o n . F r o m F i g u r e s 7-18 a n d 7-19, at a C N : C u m o l e ratio o f 3, the T a f e l
slope changes w i t h h y d r o x i d e c o n c e n t r a t i o n a n d the r a t e - c o n t r o l l i n g step or the r e a c t i o n
m e c h a n i s m changes. F r o m F i g u r e s 7 - 2 1 , 7-22, 7-24 and 7-25, i n the l o w p o l a r i z a t i o n r e g i o n ,
at a C N : C u m o l e ratio > 4, the current changes o n l y s l i g h t l y w i t h h y d r o x i d e c o n c e n t r a t i o n
a n d the r e a c t i o n order w i t h respect to h y d r o x i d e is close to z e r o . T h u s the r a t e - c o n t r o l l i n g
step does not i n v o l v e h y d r o x i d e .
2.7 -,
-3.5 -3 -2.5 -2 -1.5

L o g ( [ C u ( C N ) l / moi dm" )
4
3 3

3
2
4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [CN"] = 0.40 M , [ C u ] = 0.0167, 0 . 0 0 8 3 3 , 0 . 0 0 4 1 7 ,

+
0 . 0 0 2 0 8 , 0.00104 M , [OH"] = 0.25 M and 1 M N a S 0 . 2 4

144
7.7 Reaction Between Cyanide and Copper(ll)
T h e r e a c t i o n b e t w e e n c y a n i d e and C u ( I I ) ions p r o d u c e s C u ( C N ) " i o n s w h i c h h a v e a

4
2
v i o l e t c o l o r a n d r a p i d l y d e c o m p o s e into c y a n o g e n and a c o p p e r c y a n i d e species [ 5 8 - 7 3 ] . T h e
c o n d i t i o n s i n the literature reports are different f r o m those i n this study a n d the results
cannot be c o m p a r e d . Therefore the experiments o n the r e a c t i o n b e t w e e n c y a n i d e a n d C u ( I I )
were c o n d u c t e d to understand the p h e n o m e n a o b s e r v e d i n this study. M i x i n g sodium
cyanide and C u S 0 4 gave a transient v i o l e t c o l o r w h i c h disappeared i n less than one s e c o n d .
U s i n g U V s p e c t r o s c o p y a n d s t o p - f l o w t e c h n o l o g y a transient species w a s detected at 535 n m
w h i c h w a s a s s u m e d to b e l o n g to C u ( C N ) " [49].
4
2
F i g u r e s 7-34 and 7-35 s h o w the absorbance v s . t i m e at 535 3 n m w h e n 2.5 c m o f 3
0.05 M c y a n i d e solutions w i t h 0.25 a n d 0.05 M O H " w e r e m i x e d w i t h 0.4 c m 3

o f 0.05 M
c o p p e r sulphate s o l u t i o n . F r o m F i g u r e 7-36, the d e c o m p o s i t i o n rate o f C u ( C N ) " 4

2
was
decreased when the concentration o f cyanide was increased to 1 M . The plot of
(1/absorbance) v s . t i m e ( F i g u r e 7-37) is a straight l i n e g i v i n g a r e a c t i o n order w i t h respect to
C u ( C N ) " o f t w o . T h e s e l e c t i o n o f the t i m e range for F i g u r e 7-37 is based o n the fact that at

4
2
the t i m e < 6.5 s, the c o n c e n t r a t i o n o f C u ( C N ) " w a s too h i g h to be p r o p o r t i o n a l to the

4
2
absorbance a n d at the t i m e > 9 s, the c o n c e n t r a t i o n o f C u ( C N ) " w a s too s m a l l a n d w a s

4
2
interfered b y the e n v i r o n m e n t .
2.5 -,
2.0 J-
1
0)
1.5 -
re
n
0.5 l
0.0
0 2 4 8 10
Time Is
F i g u r e 7-34 A b s o r b a n c e v s . t i m e w h e n 2.5 c m o f 0.05 M c y a n i d e s o l u t i o n w i t h 0.25 M O H '

3
w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r sulphate s o l u t i o n at 25 C .

3
145
2.5 ,
Time Is
F i g u r e 7-35 A b s o r b a n c e v s . t i m e w h e n 2.5 c m o f 0.05 M c y a n i d e s o l u t i o n w i t h 0.05 M O H

3
w e r e m i x e d w i t h 0.4 c m o f 0.05 M copper sulphate s o l u t i o n at 25 C .

3
Time Is
F i g u r e 7-36 A b s o r b a n c e v s . time w h e n 2.5 c m 3

o f 1 M c y a n i d e s o l u t i o n w i t h 0.25 M O H "
w e r e m i x e d w i t h 0.4 c m o f 0.05 M c o p p e r sulphate s o l u t i o n at 25 C .
3
146
0.1 M C u S 0 4 s o l u t i o n w a s also g r a d u a l l y added to 0.05 M s o d i u m c y a n i d e s o l u t i o n s
w i t h 0.25 M N a O H a n d 0.01 M N a O H . I n the case o f the s o l u t i o n c o n t a i n i n g 0.25 M N a O H
at 25 C , after C u S 0 4 w a s added to the reactor, the l o c a l s o l u t i o n b e c a m e b l u e a n d b l a c k .
T h e n the w h o l e s o l u t i o n b e c a m e p u r p l e , this c o l o u r d i s a p p e a r i n g i n less t h a n one s e c o n d .
W h e n the a m o u n t o f copper added m a d e the m o l e ratio o f c y a n i d e to c o p p e r e x c e e d about
2.85, the w h o l e s o l u t i o n b e c a m e a l i g h t b l u e , w h i c h c o l o u r g r a d u a l l y disappeared. N o p u r p l e
c o l o r w a s o b s e r v e d . A t a m o l e ratio o f c y a n i d e to c o p p e r < 2 . 7 5 , b l u e C u ( O H ) 2 b e g a n to
precipitate u p o n the further a d d i t i o n o f c u p r i c i o n s . A t 50 C , the precipitate h a d a m i x e d
c o l o r o f b l a c k , b r o w n and b l u e . A p p a r e n t l y c u p r i c i o n s reacted w i t h c y a n i d e i o n s a n d f o r m e d
c u p r i c c y a n i d e w h i c h d e c o m p o s e d into cuprous c y a n i d e a n d c y a n o g e n . C u p r i c i o n s also
reacted w i t h h y d r o x i d e to f o r m copper h y d r o x i d e or o x i d e .
W h e n o n l y a s m a l l amount o f c u p r i c i o n s w a s added, the m o l e ratio o f c y a n i d e to
c o p p e r a n d free c y a n i d e w a s h i g h and the r e a c t i o n b e t w e e n c y a n i d e a n d c u p r i c i o n s w a s
f a v o r e d . W h e n a large amount o f c u p r i c ions w a s added, the c o n c e n t r a t i o n o f free c y a n i d e
b e c a m e so l o w due to the f o r m a t i o n o f v e r y stable cuprous c o m p l e x e s that the r e a c t i o n
b e t w e e n c u p r i c i o n a n d h y d r o x i d e is favored.
W h e n the c o n c e n t r a t i o n o f s o d i u m h y d r o x i d e w a s decreased to 0.01 M , n o b l u e
precipitate w a s o b s e r v e d . A f t e r the a d d i t i o n o f c u p r i c ions, a l o c a l y e l l o w i s h c o l o r appeared

147
w h i c h b e c a m e p u r p l e a n d disappeared i n one second. W h e n the m o l e ratio o f c y a n i d e to
c o p p e r w a s b e l o w 1.6, a w h i t e precipitate appeared a n d the p H decreased to 4-4.3 due to the
c o n s u m p t i o n o f h y d r o x i d e i o n s i n the r e a c t i o n b e t w e e n c y a n i d e a n d c u p r i c i o n :
2Cu 2 +
+ C N " + 2 0 F T = 2Cu(I) + C N O " + H 0 2 (7-4)
U p o n further a d d i t i o n o f c u p r i c ions, m o r e w h i t e precipitate w a s p r o d u c e d . T h e w h i t e
precipitate w a s apparently C u C N .
I n the l i g h t o f the above observations, the p h e n o m e n o n o f the a n o d i c o x i d a t i o n o f
c o p p e r b e c o m e s easy to understand. A t a l o w potential, the current is l o w a n d the m o l e ratio
o f c y a n i d e to c o p p e r o n the surface is h i g h , p r e v e n t i n g the p r e c i p i t a t i o n o f c o p p e r o x i d e due
to the o x i d a t i o n o f copper c y a n i d e . W h e n the potential exceeds a c r i t i c a l v a l u e a n d the
current is so h i g h that the m o l e ratio o f c y a n i d e to copper is l o w , the o x i d a t i o n o f c o p p e r
c y a n i d e p r o d u c e s copper o x i d e . W h e n the copper c o n c e n t r a t i o n is l o w , the p o t e n t i a l needs to
be h i g h e r to m a k e the current r e a c h a c r i t i c a l v a l u e w h e r e the m o l e ratio o f c y a n i d e to c o p p e r
o n the surface b e c o m e s l o w e n o u g h to favour the p r e c i p i t a t i o n o f c o p p e r o x i d e . D e c r e a s i n g
the h y d r o x i d e c o n c e n t r a t i o n suppresses the f o r m a t i o n o f copper o x i d e f r o m the v i e w p o i n t o f
b o t h t h e r m o d y n a m i c s and k i n e t i c s . T h i s is i n agreement w i t h the results o n the anodic
oxidation o f copper cyanide.
7.8 Cyclic Voltammetry
U s i n g c y c l i c v o l t a m m e t r y , w e c a n evaluate the r e v e r s i b i l i t y o f the a n o d i c o x i d a t i o n o f
c o p p e r a n d k n o w the stability o f the intermediate products. D u r i n g the p o s i t i v e p o t e n t i a l
s c a n n i n g , c u p r o u s c y a n i d e species are o x i d i z e d to c u p r i c c y a n i d e species w h i c h m a y be
r e d u c e d d u r i n g the negative potential s c a n n i n g . T h e s c a n n i n g rate w a s kept a b o v e 10 V s" to 1
a v o i d the p r e c i p i t a t i o n o f copper o x i d e and the m a x i m u m p o t e n t i a l w a s b e l o w 1 V v s . S C E
to a v o i d the s i g n i f i c a n t e v o l u t i o n o f o x y g e n . F i g u r e 7-38 s h o w s the c y c l i c v o l t a m m e t r y o f
the s o l u t i o n c o n t a i n i n g 0.05 M C N , 0.01666 M C u a n d 0.25 M N a O H at 25 C after

-
subtraction o f the b a c k g r o u n d current. T h e r e w a s n o r e d u c t i o n current d u r i n g the n e g a t i v e -
g o i n g s c a n n i n g . T h e a n o d i c o x i d a t i o n o f copper c y a n i d e seems to be i r r e v e r s i b l e . T h e
c h e m i c a l r e a c t i o n o f the o x i d i z e d copper c y a n i d e species is too fast to be detected d u r i n g the

148
negative s c a n n i n g . B y i n c r e a s i n g the m o l e ratio o f c y a n i d e to c o p p e r a n d d e c r e a s i n g the p H ,
there w a s s t i l l n o r e d u c t i o n current d u r i n g the negative potential s c a n n i n g .
2000
CM .200V/S
E

1500 --
.100V/S
< 50V/S
> 1000 - . 20 V/s
Curi*ent densi
10V/S
500 --
-500
-0.4 0.1 0.6
F i g u r e 7-38 C y c l i c v o l t a m m e t r y at 25 C . E l e c t r o l y t e : 0.025 M C N " , C N : C u m o l e ratio =3,
0.25 M N a O H and 1 M N a S 0 . 2 4
7.9 Possible Reaction Mechanism
A t a C N : C u m o l e ratio = 3 a n d [OH"] = 0.25 M , o v e r 9 7 % o f the c o p p e r exists i n the
f o r m o f C u ( C N ) " a n d the current i s p r o p o r t i o n a l to the c o n c e n t r a t i o n o f C u ( C N ) " b u t n o t

3
2
3
2
the concentrations o f Cu(CN) " 2 and Cu(CN) ". 4

3
T h i s suggests that Cu(CN) "
3
2
c a n be
d i s c h a r g e d a n d o x i d i z e d to C u ( C N ) " at the electrode. C u ( C N ) " i s unstable a n d d e c o m p o s e s

3 3
to f o r m c y a n o g e n . C y a n o g e n reacts w i t h h y d r o x i d e to p r o d u c e cyanate.
W h e n the electrode potential e x c e e d e d a certain v a l u e , c o p p e r o x i d e w a s f o r m e d o n
the electrode (both o n the graphite a n d the outer insulator) a n d the current i n c r e a s e d s h a r p l y
to a l i m i t i n g v a l u e .
C o p p e r o x i d e o r h y d r o x i d e c a n be f o r m e d b y three w a y s : (1) c o p p e r cyanide
d e c o m p o s e s into free c y a n i d e a n d cuprous i o n s w h i c h are o x i d i z e d to c o p p e r o x i d e o n the
anode, (2) c o p p e r c y a n i d e i s o x i d i z e d to free c y a n i d e a n d c u p r i c i o n s w h i c h react w i t h
h y d r o x i d e to f o r m c o p p e r o x i d e a n d (3) cuprous c y a n i d e i s o x i d i z e d to c u p r i c c y a n i d e w h i c h
reacts w i t h h y d r o x i d e to f o r m copper o x i d e . T h e f o r m a t i o n o f c o p p e r o x i d e o n the outer

149
insulator means that c u p r i c species diffuse to the surface o f the outer i n s u l a t o r a n d react w i t h
O H " to f o r m c o p p e r o x i d e a n d h y d r o x i d e . T h e m o s t l i k e l y m e c h a n i s m i s : the cuprous
c o m p l e x ( C u ( C N ) " ) is o x i d i z e d to c u p r i c c o m p l e x ( C u ( C N ) " ) a n d s o m e o f the c u p r i c

3
2
3
c o m p l e x d e c o m p o s e s to f o r m c y a n o g e n . S o m e o f it reacts w i t h h y d r o x i d e to f o r m h y d r o x i d e
o n the anode a n d a s m a l l a m o u n t diffuses to the surface o f the outer i n s u l a t o r to f o r m c o p p e r
o x i d e . T h e m e c h a n i s m o f the a n o d i c o x i d a t i o n o f c y a n i d e at h i g h potentials is different f r o m
that at l o w potentials.
W i t h d e c r e a s i n g c o n c e n t r a t i o n o f h y d r o x i d e , the current a n d the T a f e l s l o p e decrease.
T h i s means that h y d r o x i d e affects the r a t e - c o n t r o l l i n g step. T h e decrease i n the T a f e l slope
f r o m 0.12 V to 0.060 V decade" 1

means the r a t e - c o n t r o l l i n g step changes or e v e n the
m e c h a n i s m changes. A t h i g h h y d r o x i d e concentration, the t h e r m o d y n a m i c s t a b i l i t y o f the
c o p p e r (I) species is r e l a t i v e l y l o w a n d the species are m o r e e a s i l y o x i d i z e d . W i t h d e c r e a s i n g
h y d r o x i d e c o n c e n t r a t i o n , the e l e c t r o c h e m i c a l stability o f C u ( C N ) " increases a n d c o p p e r

3
2
c y a n i d e b e c o m e s less e l e c t r o c h e m i c a l l y activated.
A s the C N : C u m o l e ratio increases, the current and T a f e l slope also decrease at l o w
potentials. T h e T a f e l slope decreases to about 0.060 V decade" w h e n the m o l e ratio exceeds

1
4 at [CN"] = 0.05 M . T h i s means that the r a t e - c o n t r o l l i n g step or the r e a c t i o n m e c h a n i s m
changes. W i t h further increase i n potential, the s e c o n d T a f e l slope (0.160 to 0.200 V decade"
') appeared. T h e current at a constant potential is p r o p o r t i o n a l to the c o n c e n t r a t i o n o f
C u ( C N ) " a n d but independent o f the c o n c e n t r a t i o n o f h y d r o x i d e . T h e d i s c h a r g e d species are

4
3
not sensitive to h y d r o x i d e i o n a n d therefore it is u n l i k e l y that C u ( C N ) " is d i s c h a r g e d .

3
2
C u ( C N ) " is m o s t l i k e l y to be d i s c h a r g e d at the electrode.

4
3
A t [OH"] = 0.01 M a n d a constant potential, the ratio o f the current m e a s u r e d i n 0.05
M C N " s o l u t i o n s w i t h C N : C u m o l e ratios o f 3 a n d 4 is c l o s e to the m o l e ratio o f C u ( C N ) " o f 4

3
the s o l u t i o n s . Therefore the d i s c h a r g e d species c o u l d transfer f r o m C u ( C N ) " a n d C u ( C N ) "

3
2
4
3
to C u ( C N ) " w i t h d e c r e a s i n g h y d r o x i d e concentration. A t h i g h h y d r o x i d e c o n c e n t r a t i o n ,
4
3
C u ( C N ) " is d i s c h a r g e d m u c h faster than C u ( C N ) " a n d the current c o n t r i b u t e d b y C u ( C N ) "

3
2
4
3
4
3
can be n e g l e c t e d c o m p a r e d to that o f C u ( C N ) " . W i t h d e c r e a s i n g h y d r o x i d e c o n c e n t r a t i o n ,

3
2
the discharge o f C u ( C N ) " is suppressed and the discharge o f C u ( C N ) " m a i n t a i n s

3
2
4
3
the
constant rate a n d b e c o m e s the d o m i n a n t d i s c h a r g e d species.

150
T h e amount o f copper o x i d e f o r m e d decreases w i t h i n c r e a s i n g C N : C u m o l e ratio a n d
d e c r e a s i n g h y d r o x i d e concentration. N o copper o x i d e f o r m e d at the outer i n s u l a t o r at a
C N : C u m o l e ratio >3.5 or [OH"] < 0.05 M . W h e n c o p p e r o x i d e w a s p r e c i p i t a t e d o n the
electrode, w i t h decreasing h y d r o x i d e concentration, the current decreases w i t h d e c r e a s i n g
h y d r o x i d e concentration. T h e h i g h e r the C N : C u m o l e ratio, the less the effect o f h y d r o x i d e ,
the h i g h e r the p o t e n t i a l for the p r e c i p i t a t i o n o f copper o x i d e a n d the m o r e stable the c o p p e r
(I) species.
T h e f o l l o w i n g p o s s i b l e m e c h a n i s m s are p r o p o s e d :
(1) I n the l o w p o t e n t i a l r e g i o n (< about 0.4 V v s . S C E ) :
A t a C N : C u m o l e ratio = 3 and a h i g h concentration o f h y d r o x i d e (0.25 M O H " )
Step 1 C u ( C N ) " -> C u ( C N ) - + e

3
2
3
Step 2 2 C u ( C N ) " -> 2 C u ( C N ) " +

3 2 (CN)2
Step 3 ( C N ) + 2 0 H " -> C N O " + C A T + H 0

2 2
Step 1 c o u l d be the r a t e - c o n t r o l l i n g step f r o m a T a f e l slope o f 0.12 V decade" 1

[335,
336] a n d the discharge o f C u ( C N ) " is n e g l i g i b l e c o m p a r e d to C u ( C N ) " . Step 1 is c a t a l y z e d

4
3
3
2
b y h y d r o x i d e i o n s . H y d r o x i d e ions m i g h t be w e a k l y b o u n d to C u ( C N ) " to f o r m a surface

3
2
c o m p l e x s u c h as C u ( C N ) " O H " w h i c h is m o r e r e a d i l y d i s c h a r g e d o n the

3
2
anode. With
decreasing p H , the a b o v e r e a c t i o n is suppressed p r o b a b l y due to the decrease i n the surface
c o m p l e x concentration, the current decreases, a n d the discharge o f C u ( C N ) " b e c o m e s the 4

3
dominant anodic reaction.
I n c r e a s i n g C N : C u m o l e ratio has a s i m i l a r effect because it shifts the d i s t r i b u t i o n o f
c o p p e r c y a n i d e species f r o m l o w l y c o o r d i n a t e d c o m p l e x e s to a h i g h l y c o o r d i n a t e d c o m p l e x
( C u ( C N ) " ) a n d p r o b a b l y also suppresses the f o r m a t i o n o f a surface

4
3
complex (such as
C u ( C N ) " O H " ) . T h e c r i t i c a l v a l u e for the C N : C u m o l e ratio depends o n the total c o p p e r

3
2
c y a n i d e c o n c e n t r a t i o n because the d i s t r i b u t i o n o f copper c y a n i d e species is dependent o n
c y a n i d e concentration. F o r e x a m p l e , at [CN"] = 0.05 M , w h e n a C N : C u m o l e ratio > about 4,
the discharge o f C u ( C N ) " is d o m i n a n t . H o w e v e r , at [CN"] =3.5, w h e n C N : C u m o l e ratio >

4
3
3.5, the discharge o f C u ( C N ) " b e c o m e s d o m i n a n t .

4
3
W h e n the d o m i n a n t d i s c h a r g e d species is C u ( C N ) " , the a n o d i c r e a c t i o n p r o b a b l y

4
3
consists o f the f o l l o w i n g steps a c c o r d i n g to the o b s e r v e d k i n e t i c s :

151
Step 1 C u ( C N ) - 4
3
Cu(CN) 4
2
- ( a A ) + e
Step 2 Cu(CN) 4
2
- ( f l A ) C u ( C N )4
k_ 2
Step 3 2 C u ( C N ) ' 4
2
2Cu(CN) - + (CN) 3
2
2
Step 4 ( C N ) + 2 0 F T -> C N O + C N " + H 0

2 2
T h e a d s o r p t i o n rate for the coverage o f C u ( C N ) " , (d9/dt), c a n be e x p r e s s e d b y the 4

2
f o l l o w i n g equation:
dB
= k (\- x 0)[Cu(CN) -]- 4
3
k_ 6- x k 0+ k_ (\ - 9)[Cu{CN) ~}
2 2
2
(7-5)
w h e r e 9 is the coverage o f C u ( C N ) " o n the electrode, k, the rate constant 4

2
for the
e l e c t r o c h e m i c a l adsorption, k , the rate constant for the e l e c t r o c h e m i c a l d e s o r p t i o n , k the rate 2
constant for the c h e m i c a l d e s o r p t i o n and k the rate constant for the c h e m i c a l a d s o r p t i o n . 2
A t steady state, d9/dt = 0 a n d i f 9 0 and k , k , the f o l l o w i n g e q u a t i o n c a n be o b t a i n e d

2
f r o m E q u a t i o n 7-5:
e= ^mli .
(7 6)
k_[ + k 2
I n the i n i t i a l l o w p o t e n t i a l r e g i o n , i f k , k , the f o l l o w i n g e q u a t i o n c a n be o b t a i n e d :
2
k, , k , exp(aFE IRT)
0 k ,
0 FE
6 = --4Cu(CN) -] = T , ^ , = TêxpC)
4
3
g < n (7-7)
k., A: _ exp(-(l-a)F//?7/) :_, RT 0 1
w h e r e a is the charge transfer coefficient, k , a n d kg., the rate constants r e s p e c t i v e l y for 0
o x i d a t i o n a n d r e d u c t i o n at E = 0 and k, = ko j e x p ( a F E / R T ) a n d k , = k o . , e x p ( - ( l - a ) F E / R T ) .
R e a c t i o n rate = k 9 2 (7-8)
Fk k FE
i = Fk 0 = ^ [ C ^ C N ) ,
2
3
- ]exp() (7-9)
K -l0
K 1
F r o m E q u a t i o n 7-9, the r e a c t i o n order w i t h respect to C u ( C N ) " is one a n d the T a f e l slope is 4

3
R T / F ( a b o u t 0.06 V decade" ). Therefore the 1

above a s s u m p t i o n is consistent w i t h the
e x p e r i m e n t a l results.
W h e n the p o t e n t i a l increases to a v a l u e w h e r e k , k , f r o m E q u a t i o n 7-6, the

2
coverage o f the adsorbed C u ( C N ) " c a n be expressed as: 4

2
152
k,[Cu(CN) -] 4
3
e= 1 4
(7-10)
k 2
t^zFE
i = Fk # = Fk,[Cu(CN) -] = Fk ,[Cu(CN)
2 4
3
0 4
3
-]exp(^r) (7-11)
F r o m the a b o v e equation, the r e a c t i o n order w i t h respect to C u ( C N ) " is one a n d the T a f e l 4

3
slope is R T / a F . T h i s is consistent w i t h the e x p e r i m e n t results. It s h o u l d be p o i n t e d out that
Step 3 i n v o l v e s some elementary reactions. F r o m the p l o t o f log(current density) v s . p o t e n t i a l
(or p o t e n t i a l v s . l o g (current density) a c c o r d i n g to E q u a t i o n s 7-9 a n d 7 - 1 1 , w e c a n c a l c u l a t e
F k k ^ [ C ^ C N ) / " ] / ] ^ . , a n d Fkg , [ C u ( C N ) " ] . Therefore k y k

2 0 4
3
o 2 c a n be c a l c u l a t e d f r o m the
a b o v e v a l u e s . A t [CN"] = 0.1 M , C N : C u m o l e ratio = 12 and 25 C , F k k 2 0 ,[Cu(CN) \|/k 4

3
M
a n d F k o , [ C u ( C N ) " ] are about 8.33x10" and 0.546 A m " r e s p e c t i v e l y . S o

4
3 4 2
k JkQ 2 is 7 2 6 a n d
k , / k is 726 e x p ( - ( l - o c ) F T / R T ) . A t potentials < 0.20 V v s . S C E , k , / k is a b o v e 10 a n d so the

2 2
T a f e l slopes are about 0.060 V decade" . A t a potential > 0.35 V v s . S C E , k , / k is b e l o w 1/10

1
2
a n d the T a f e l slope is about 0.171 V decade" ( a = 0.35). E q u a t i o n 7-6 c a n be rearranged as: 1
(k, / k , ) [ C u ( C N ) - ] _ ( k , / k 4
3
0 0 H )[Cu(CN) -]exp(FE / RT) 4
3
l + k /k_, 2 l+ tk./kêxp^l-cOFE/RT) (
" )
F(k k 2 0 f l / k _ )[Cu(CN) -]exp(FE / RT)

0 1 4
3
i = bk~,t) = (7-13)
1 + ( k / k _!)exp((l - a ) F E / R T )
2 0
F r o m the above equation, the r e a c t i o n order w i t h respect to C u ( C N ) " is one at any p o t e n t i a l . 4

2
F i g u r e 7-39 s h o w s the plots o f potential v s . l o g (current density) u s i n g data m e a s u r e d
a n d p r e d i c t e d u s i n g E q u a t i o n 7-13. T h e p r e d i c t e d data are consistent w i t h the data m e a s u r e d
at a p o t e n t i a l < 0.45 V v s . S C E . H o w e v e r , at potentials > 0.45 V , the m e a s u r e d data appear to
deviate f r o m the p r e d i c t e d v a l u e . T h i s is because at potentials > 0.45 V , the a s s u m p t i o n s are
not v a l i d a n d the difference i n the copper c o n c e n t r a t i o n b e t w e e n the b u l k s o l u t i o n a n d the
surface is not n e g l i g i b l e . T h e current is so h i g h that the coverage o f C u ( C N ) " cannot be 4

2
n e g l e c t e d a n d the c h e m i c a l d e s o r p t i o n determines the w h o l e r e a c t i o n rate. C u ( C N ) " i s m u c h 4

2
less a d s o r b e d o n a p y r o l y t i c graphite electrode. Therefore there appears to be o n l y one w e l l -
d e f i n e d T a f e l slope.
W i t h further increase i n potential, the current reaches a c r i t i c a l v a l u e a n d the C N : C u
m o l e ratio o n the electrode surface decreases to s u c h a l o w v a l u e that c o p p e r o x i d e or
h y d r o x i d e is p r e c i p i t a t e d o n the anode. F r o m the standpoint o f t h e r m o d y n a m i c s , d i c y a n i d e

153
a n d t r i c y a n i d e are less stable a n d m o r e r e a d i l y o x i d i z e d to copper o x i d e a n d c y a n i d e . T h e
effect o f the p r e c i p i t a t e d copper o x i d e o n the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e depends o n
the a p p l i e d potential, temperature and total c y a n i d e concentration.
A t [CN"] = 0.05 M and a temperature > 40 C , c o p p e r o x i d e c a t a l y z e s the o x i d a t i o n o f
c o p p e r c y a n i d e . A t a temperature < 4 0 C , copper o x i d e has a l i m i t e d c a t a l y t i c effect o n the
c y a n i d e o x i d a t i o n . It m a y e v e n e x h i b i t a n i n h i b i t i n g effect at a potential > 0.6 V v s . S C E . A t
[ C u ] = I M a n d [CN"] = 3 M , the f o r m a t i o n o f copper o x i d e or h y d r o x i d e s i g n i f i c a n t l y

+
i n h i b i t s the a n o d i c o x i d a t i o n o f copper c y a n i d e . T h i s m a y be related to the properties o f the
p r e c i p i t a t e d c o p p e r o x i d e and to the adsorption o f copper c y a n i d e .
T h e o x i d a t i o n o f free c y a n i d e w a s c a t a l y z e d b y c u p r i c o x i d e f o r m e d o n the electrode
because i n the absence o f copper, the a n o d i c current o f free c y a n i d e o n the c o p p e r o x i d e -
coated anode is s i g n i f i c a n t l y h i g h e r than that o n the anode w i t h o u t c o p p e r o x i d e . C u ( I I I )
species s u c h as C u 0 2 3 c a n be p r o d u c e d i n the potential range studied [ 3 4 1 - 3 4 5 ] . F o r e x a m p l e ,
C u ( I I I ) o x i d e phase w a s s t a b i l i z e d at a p p r o x i m a t e l y 0.48 V v s . S C E a n d 0 C i n a l k a l i n e
s o l u t i o n [341]. T h e o x i d a t i o n o f the C u ( I I ) species b e g a n at about 0.35 V v s . S C E a n d 24 C
i n 1 M N a O H [343] a n d the i n t r i n s i c r e d o x potential for C u ( I I I ) / C u ( I I ) i n the s o l i d o x i d e is
0.42 V v s . S C E at p H 14 a n d 20 C [344]. It is p o s s i b l e for C u ( I I I ) to f o r m o n the surface a n d
c a t a l y z e the c y a n i d e o x i d a t i o n as w a s suggested b y W e l l s a n d J o h n s o n [157]. O x y g e n
e v o l u t i o n w a s also c a t a l y z e d p o s s i b l y b y the f o r m a t i o n a n d d e c o m p o s i t i o n o f C u 0 2 3 [345].
T h e r e a c t i o n procedure c a n be expressed b y the f o l l o w i n g set o f p o s s i b l e reactions:
Step 1 C u ( C N ) - " n
( n , )
-> C u ( C N ) - " -
n
( 2 )
M , ) +e ( n = 2 , 3, 4)
Step 2 C u ( C N ) " " n

( n 2 )
( a * ) + 2 0 H ~ -> nCN~ (ads) + C u ( O H ) (or C u O + H 0 )
2 2
Step 3 C u t C N ) ^ " - ' - Cu{CN); ' 1 (n 2)

+e
Step 4 Cu(CN)- "- ( 2)

= Cu(CN) _ - "-
(n ]}
{ 2)
+ \/2(CN) 2
Step 5 C N - ( f l *) + 2 0 H - ) C N Q - + H 0 2
W i t h d e c r e a s i n g p H a n d i n c r e a s i n g m o l e ratio o f c y a n i d e to copper, Step 1 (n = 2 a n d
3), Step 2 , Step 3 (n = 3) a n d Step 5 are suppressed. T h i s results i n a decrease i n the current
a n d it is i n agreement w i t h the e x p e r i m e n t a l results. A t a h i g h C N : C u ratio a n d l o w p H , no
copper o x i d e is f o r m e d . T h e catalysis o f copper o x i d e w a s prevented w i t h i n c r e a s i n g the
p o t e n t i a l a n d the c o p p e r c y a n i d e concentration.
154
0.5
> 0.4
LU
W 0.3 -
CO
>
.5 0.2 --
c
o
t? 0.1 --
0 -I . .
- 1 0 1 2 3
L o g ( c u r r e n t d e n s i t y / A m" )2
F i g u r e 7-39 P l o t s o f p o t e n t i a l vs. l o g (current density) u s i n g data m e a s u r e d a n d p r e d i c t e d

u s i n g E q u a t i o n 7-12 at 2 5 C . E l e c t r o l y t e : 0.1 M C N " , C N : C u m o l e ratio = 12 0 2 5 M N a O H
and 1 M N a S 0 . 2 4
7.10 Diffusion Coefficient Estimation
In the presence o f a large amount o f supporting electrolyte, the l i m i t i n g current for a
s i m p l e e l e c t r o c h e m i c a l r e a c t i o n o n the rotating d i s k c a n be expressed b y E q u a t i o n 6-5. T h e
d i f f u s i o n coefficients c a n be c a l c u l a t e d f r o m the slopes o f the straight l i n e s for the p l o t s o f i ,
vs. co . I n this study, w h e n the current reaches the l i m i t i n g v a l u e , c u p r o u s c y a n i d e is

1/2
o x i d i z e d to c u p r i c c y a n i d e w h i c h undergoes t w o further r e a c t i o n paths. O n e is that c u p r i c
c y a n i d e reacted w i t h h y d r o x i d e to p r o d u c e copper o x i d e or h y d r o x i d e a n d free cyanide
w h i c h is further o x i d i z e d to cyanate. A n o t h e r is that c u p r i c c y a n i d e species diffuse f r o m the
surface a n d r a p i d l y d e c o m p o s e to f o r m c y a n o g e n a n d l o w e r c o o r d i n a t e d c o p p e r c y a n i d e . T h e
d i f f u s i o n o f c u p r i c species to the b u l k s o l u t i o n has the f o l l o w i n g effect o n the limiting
current: (1) the d e c o m p o s i t i o n i n the d i f f u s i o n l a y e r results i n the shift o f the d i s t r i b u t i o n to
the f o r m a t i o n o f the l o w l y c o o r d i n a t e d copper (I) c o m p l e x a n d affects the concentration
gradient o f c o p p e r c y a n i d e species and affects the l i m i t i n g current; (2) the u n d e c o m p o s e d
c u p r i c species d u r i n g the d i f f u s i o n b r i n g c y a n i d e to the b u l k r e s u l t i n g i n the decrease i n the
l i m i t i n g current.
155
F r o m the c o u l o m e t r i c measurement, at a C N : C u m o l e ratio = 3 a n d [OFT] = 0.25 M ,
the a n o d i c o x i d a t i o n o f copper c y a n i d e c a n be expressed as R e a c t i o n 7 - 1 , i.e. the o x i d a t i o n
o f one c o m p l e x gave 7 electrons and C u ( C N ) " is c o m p l e t e l y o x i d i z e d to cyanate a n d c o p p e r

3
2
o x i d e . S o the a m o u n t o f c u p r i c c y a n i d e r e a c h i n g the b u l k s o l u t i o n is v e r y s m a l l . O t h e r w i s e
m o r e c y a n i d e a n d less c u p r o u s i o n s are o x i d i z e d . T h e d e c o m p o s i t i o n o f c u p r i c c y a n i d e
( m a i n l y C u ( C N ) " ) produces C u ( C N ) \ w h i c h does not affect the c o n c e n t r a t i o n o f C u ( C N ) "

3 2 3
2
i n the d i f f u s i o n l a y e r a c c o r d i n g to the c a l c u l a t i o n at C N : C u < 3.
T h e plots o f the l i m i t i n g current v s . co 1/2

for 0.05 M C N " a n d a C N : C u m o l e ratio = 3
( F i g u r e 7-40) are linear. T h e slopes were c a l c u l a t e d u s i n g least-squares f i t t i n g . A t C N : C u =
3, 97 % o f copper a n d c y a n i d e exist i n the f o r m o f C u ( C N ) " a n d the c a l c u l a t e d d i f f u s i o n

3
2
coefficients c a n be a s s u m e d to be that o f C u ( C N ) " . T h e d i f f u s i o n coefficients for C u ( C N ) "

3
2
3
2
at 4 0 , 50 a n d 60 C w e r e f o u n d to be 1 . 0 5 x l 0 " , 1 . 2 9 x l 0 " a n d 1 . 5 2 x l 0 " m

9 9 9 2
s" r e s p e c t i v e l y .
1
T h e d i f f u s i o n a c t i v a t i o n energy is 16.6 k J / m o l e . F r o m the a c t i v a t i o n energy a n d E q u a t i o n 6-
18, the p r e d i c t e d d i f f u s i o n coefficient at 25 C is 0.76x10" m s " \ 9 2
F i g u r e 7-40 L i m i t i n g current v s . rotational speed at 4 0 , 50 a n d 60 C . E l e c t r o l y t e : 0.05 M

C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . 2 4
W h e n the m o l e ratio o f c y a n i d e to copper is v e r y large, C u ( C N ) " i s d o m i n a n t a n d is

4
3
o x i d i z e d to C u ( C N ) " w h i c h diffuses f r o m the surface a n d d e c o m p o s e s to f o r m C u ( C N ) "

4
2
3
2
156
a n d c y a n o g e n . C u ( C N ) " reacts w i t h free c y a n i d e to regenerate C u ( C N ) " . T h e r e f o r e

3
2
4
3
the
o b s e r v e d l i m i t i n g current is larger than that expected f r o m the L e v i c h e q u a t i o n .
7.11 Activation Energy Calculation for the Kinetic Current
A t a constant p o t e n t i a l , E q u a t i o n 6-17 c a n be a p p l i e d . T h e a c t i v a t i o n energy c a n be
c a l c u l a t e d f r o m the slope o f the p l o t o f l o g i v s . 1/T. T h e slopes o f these l i n e a r p l o t s w e r e
c a l c u l a t e d b y least-squares fitting. W h e n the m o l e ratio o f c y a n i d e to c o p p e r is 3 a n d the
c o n c e n t r a t i o n o f h y d r o x i d e is 0.25 M , the d i s c h a r g e d species is C u ( C N ) " . F r o m

3
2
the
c a l c u l a t i o n , the c o n c e n t r a t i o n o f C u ( C N ) " is a l m o s t constant i n the temperature range o f 25

3
2
to 60 C a n d the change i n the concentration o f C u ( C N ) " does not need to be c o n s i d e r e d for

3
2
the a c t i v a t i o n energy c a l c u l a t i o n . A t [CN"] =0.05 M , a C N : C u m o l e ratio = 3, [OH"] = 0.25
M , the plots o f l o g i v s . 1/T a n d the a c t i v a t i o n energies are s h o w n i n F i g u r e 7 - 4 1 .
2.0
CM
i
1.0
0.003 0.0031 0.0032 0.0033 0.0034
(T / K ),-1
7-41 A c t i v a t i o n energy c a l c u l a t i o n - p l o t o f l o g (current density) v s . 1/T at constant

potentials. E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . 2 4
157
7.12 Summary
T h e e l e c t r o c h e m i c a l k i n e t i c b e h a v i o r o f copper c y a n i d e is dependent o n C N : C u m o l e
ratio, p H a n d total c y a n i d e concentration. A t l o w potentials ( r o u g h l y 0 to 0.4 V v s . S C E ) ,
c u p r o u s c y a n i d e is o x i d i z e d to c u p r i c c y a n i d e c o m p l e x e s w h i c h p r o d u c e c y a n o g e n , w h i c h i n
t u r n reacts w i t h h y d r o x i d e to f o r m cyanate. A t a C N : C u m o l e ratio = 3 a n d [OH"] = 0.25 M ,
the T a f e l slope is about 0.12 V decade" 1

a n d the r e a c t i o n order w i t h respect to C u ( C N ) " is 3
2
one. C u ( C N ) " is d i s c h a r g e d at the electrode. T h e current a n d T a f e l slope decrease w i t h

3
2
d e c r e a s i n g h y d r o x i d e c o n c e n t r a t i o n and so h y d r o x i d e is i n v o l v e d i n the rate-determining
step. I n c r e a s i n g C N : C u m o l e ratio also results i n the change i n the a n o d i c b e h a v i o u r o f
c o p p e r c y a n i d e . W h e n the C N : C u m o l e ratio is larger than a certain v a l u e w h i c h depends o n
the total c y a n i d e concentration, e. g. about 4 at [CN"] = 0.05 M a n d 3.5 at [ C N " ] = 3.5 M , a
T a f e l slope o f about 0.06 V decade" w a s o b s e r v e d o v e r the p o t e n t i a l range 0.1 - 0.25 V v s .

1
S C E . A s e c o n d T a f e l slope o f about 0.17 -0.20 V decade" w a s n o t e d o v e r the h i g h e r p o t e n t i a l

1
range.
T h i s change is related to the change i n the d i s t r i b u t i o n o f c o p p e r c y a n i d e species
w h i c h i n t u r n depends o n the total c y a n i d e concentration. T h e current is p r o p o r t i o n a l to the
concentration of cuprous tetracyanide and almost independent o f the total cyanide
c o n c e n t r a t i o n . p H has little effect o n c y a n i d e o x i d a t i o n . C u ( C N ) " is d i s c h a r g e d at

4
3
the
electrode.
In the m i d d l e potential r e g i o n ( r o u g h l y 0.4 to 0.6 V v s . S C E ) , c o p p e r o x i d e is
p r e c i p i t a t e d o n the electrode. C o p p e r c y a n i d e is o x i d i z e d to c o p p e r o x i d e a n d cyanate. T h e
p o t e n t i a l for the p r e c i p i t a t i o n o f copper o x i d e is dependent o n C N : C u m o l e ratio and
temperature. T h e h i g h e r the m o l e ratio o f c y a n i d e to copper, the h i g h e r the p o t e n t i a l for the
precipitation o f copper oxide. H o w e v e r , w h e n cyanide concentration was h i g h and hydroxide
c o n c e n t r a t i o n w a s l o w , n o copper o x i d e w a s precipitated, but c y a n o g e n gas w a s e v o l v e d .
T h e current decreases w i t h decreasing h y d r o x i d e c o n c e n t r a t i o n a n d the rate-
c o n t r o l l i n g step i n v o l v e s h y d r o x i d e . T h e catalysis o f copper o x i d e p r e c i p i t a t e d decreases w i t h
i n c r e a s i n g c o p p e r c y a n i d e concentration.
T h e a n o d i c b e h a v i o u r o f copper c y a n i d e c o u l d be c o m p a r e d to that o f sulphite a n d the
m i x t u r e o f sulphite a n d copper c y a n i d e to understand h o w sulphite c a n l i m i t the o x i d a t i o n o f
cyanide.
158
8. ANODIC OXIDATION OF MIXED COPPER CYANIDE AND

SULPHITE IN ALKALINE SOLUTION
T h e a n o d i c b e h a v i o u r o f sulphite and copper c y a n i d e has been d i s c u s s e d i n C h a p t e r s
6 a n d 7 w h e n they are i n the s o l u t i o n separately. T h e a n o d i c b e h a v i o u r o f m i x e d sulphite a n d
copper c y a n i d e s o l u t i o n is presented i n this Chapter. T h e objective o f this study has been to
understand h o w sulphite is o x i d i z e d as a s a c r i f i c i a l species w h i l e p r o t e c t i n g the c y a n i d e f r o m
o x i d a t i o n . T h e study w a s c o n d u c t e d u s i n g the rotating d i s k technique.
T h e graphite rotating d i s k w a s the same as d e s c r i b e d i n S e c t i o n 6.3. T h e electrode
treatment w a s the same as i n C h a p t e r 7. G r a p h i t e r o d h a v i n g 12- and 2 4 - m m diameters w a s
f a s h i o n e d as rotating d i s k s for c o u l o m e t r i c measurements. T h e w o r k i n g electrode (anode)
w a s separated f r o m the counter electrode (the cathode) to m i n i m i z e the effect o f the change
i n the C N : C u m o l e ratio due to copper d e p o s i t i o n at the cathode. T h e v o l u m e o f the catholyte
w a s o n l y about 1-2 c m and the i n i t i a l concentration o f h y d r o x i d e w a s ten t i m e s that i n the

3
anolyte. T h e e v o l u t i o n o f h y d r o g e n b u i l t a h i g h c o n c e n t r a t i o n o f h y d r o x i d e w h i c h c a n be
transported to the anode c o m p a r t m e n t to m a i n t a i n the c o n c e n t r a t i o n o f h y d r o x i d e i n the
anolyte. T h e p H o f the anolyte w a s m o n i t o r e d .
T h e rotating d i s k electrode s y s t e m was a n E G & G m o d e l 6 3 6 E l e c t r o d e R o t a t o r . A
S O L A R T R O N 1286 E l e c t r o c h e m i c a l Interface w a s u s e d as the potentiostat. E x c e p t as noted,
the p o l a r i z a t i o n curves were generated at a s c a n n i n g rate o f 1 m V s" . T h e e x p e r i m e n t a l set-up

1
w a s the same as s h o w n i n F i g u r e 6-3.
T h e l i q u i d j u n c t i o n potential w a s not c o n s i d e r e d since the c o n c e n t r a t i o n o f h y d r o x i d e
is not v e r y h i g h and the m o b i l i t i e s o f the i o n s o f sulphate, sulphite a n d c o p p e r c y a n i d e
species are c l o s e to that o f the s o d i u m i o n . T h e t h e r m a l l i q u i d j u n c t i o n p o t e n t i a l was
m e a s u r e d u s i n g t w o c a l o m e l reference electrodes w h i c h were p l a c e d o n the t w o sides o f a n
electrolyte b r i d g e .
Samples were taken for cyanide analysis ( A p p e n d i x 2) and sulphite analysis
( A p p e n d i x 4). T h e c o p p e r c o n c e n t r a t i o n w a s measured b y o x i d i z i n g c o p p e r c y a n i d e to c u p r i c
159
nitrate u s i n g concentrated n i t r i c a c i d a n d titrating w i t h E D T A (see A p p e n d i x 3). T h e a n a l y s i s
o f copper i n the a n o d i c precipitate was c o n d u c t e d b y d i s s o l v i n g the precipitate i n n i t r i c a c i d
and titrating w i t h E D T A .
R e a g e n t grade c h e m i c a l s were u s e d throughout a l l the e x p e r i m e n t s .
8.2 Anodic Behaviour of Mixed Sulphite and Copper Cyanide Solution
8.2.1 A n o d i c Behaviour of Dilute C o p p e r C y a n i d e Solution with Sulphite
T h e a n o d i c o x i d a t i o n o f m i x e d sulphite a n d copper c y a n i d e has been studied as a
f u n c t i o n o f temperature, the m o l e ratio o f c y a n i d e to copper, sulphite c o n c e n t r a t i o n a n d
h y d r o x i d e c o n c e n t r a t i o n . F i g u r e 8-1 s h o w s the p o l a r i z a t i o n curves o f the s o l u t i o n w i t h 0.05
M C N " , a C N : C u m o l e ratio o f 3, 0.4 M N a ^ , 0.25 M N a O H and 1 M N a S 0 . 2 4
A t 25 a n d 40 C , the current first increased and then decreased sharply to a m i n i m u m
v a l u e w i t h the f o r m a t i o n o f copper o x i d e o n the anode. W i t h further increase i n p o t e n t i a l , the
current increased a g a i n . A t a potential > about 0.8 V v s . S C E , some gas b u b b l e s were
o b s e r v e d o n the anode. T h e y were b e l i e v e d to be due to o x y g e n e v o l u t i o n . T h e p a s s i v a t i o n is
p r o b a b l y due to the p r e c i p i t a t i o n o f copper o x i d e a n d the a d s o r p t i o n o f o x y g e n . A v e r y t h i n
l a y e r o f c o p p e r o x i d e w a s precipitated o n the graphite but not o n the outer insulator.
W h e n o n l y copper c y a n i d e was present i n the s o l u t i o n , copper o x i d e w a s p r e c i p i t a t e d
b o t h o n the graphite a n d the outer insulator w i t h the amount o f c o p p e r o x i d e b e i n g m u c h
larger. Therefore sulphite c a n reduce c u p r i c ions to cuprous i o n s a n d decrease the extent o f
copper o x i d e f o r m a t i o n .
A t 50 C , the p o l a r i z a t i o n curves ( F i g u r e 8 - l c ) became different. A t 100 r p m , the
current increased to a l i m i t i n g v a l u e , w h i c h w a s a p p r o x i m a t e l y the s u m o f c o p p e r c y a n i d e
and sulphite l i m i t i n g currents w h e n they are present separately i n the s o l u t i o n . A t 4 0 0 a n d
1600 r p m , the current first increased and then decreased to a m i n i m u m v a l u e w i t h the
p r e c i p i t a t i o n o f c o p p e r o x i d e . A t a potential > 0.64 V v s . S C E , the current rose sharply to a
l i m i t i n g v a l u e a n d the electrode surface was reactivated. A t a p o t e n t i a l > 1.0 V v s . S C E ,
b u b b l e s w e r e o b s e r v e d a n d the current decreased sharply. O x y g e n e v o l u t i o n p a s s i v a t e d the
electrode surface.
160
A t 60 C , the a n o d i c b e h a v i o u r for 100 a n d 4 0 0 r p m is s i m i l a r to that for 100 r p m at
50 . H o w e v e r , at 1600 r p m , the p o l a r i z a t i o n curve w a s s t i l l s i m i l a r to that at 50 C . T h i s
dependence o f the a n o d i c b e h a v i o u r o n the rotational speed is due to the difference i n the
c o m p o s i t i o n at the electrode surface at different rotational speeds. T h e difference i n the
c o m p o s i t i o n s o f the electrolyte c a n affect the p r e c i p i t a t i o n o f c o p p e r o x i d e a n d e v o l u t i o n o f
o x y g e n and f i n a l l y the e l e c t r o c h e m i c a l properties.
F r o m F i g u r e 8-2, it c a n been seen that the p a s s i v a t i o n decreased w i t h i n c r e a s i n g
potential scan rate. A t 5 raV/s, the current increased to a m a x i m u m a n d decreased w i t h the
p r e c i p i t a t i o n o f copper o x i d e f i n a l l y i n c r e a s i n g to a l i m i t i n g v a l u e . A t 10 a n d 20 m V / s , the
current i n c r e a s e d c o n t i n u o u s l y to a l i m i t i n g v a l u e . T h i s current w a s related to the ratio o f the
p r e c i p i t a t e d copper o x i d e to copper h y d r o x i d e .
F r o m the p o l a r i z a t i o n curves o n the electrode w i t h a n d w i t h o u t pre-coated copper
o x i d e ( C u r v e s 1 a n d 2 i n F i g u r e 8-3) i n the s o l u t i o n c o n t a i n i n g b o t h c o p p e r c y a n i d e a n d
sulphite, the c o p p e r o x i d e h a d a n i n h i b i t i n g effect o n the o x i d a t i o n o f c o p p e r c y a n i d e a n d
sulphite. H o w e v e r , i n c o m p a r i n g the p o l a r i z a t i o n curves c o n t a i n i n g o n l y sulphite ( C u r v e s 3-
5) i n F i g u r e 8-3, the copper c y a n i d e o x i d e d i d not s h o w a large i n h i b i t i n g effect o n the
o x i d a t i o n o f sulphite. Therefore the p a s s i v a t i o n m i g h t be caused b y the a d s o r p t i o n o f c o p p e r
c y a n i d e species i n the presence o f sulphite or c o n c o m i t a n t effect o f c o p p e r c y a n i d e a n d
sulphite. I n c o m p a r i n g three p o l a r i z a t i o n curves r e s p e c t i v e l y for (1) m i x e d sulphite and
c o p p e r c y a n i d e , (2) sulphite a n d (3) copper c y a n i d e ( F i g u r e 8-4), it c a n been seen that c o p p e r
c a t a l y z e d the o x i d a t i o n o f sulphite.
T h e a n o d i c b e h a v i o u r for 0.2 M a n d 0.1 M N a S 0 2 3 was shown i n A p p e n d i x 8
( F i g u r e s A - 3 7 and A - 3 8 ) is different f r o m that for 0.4 M N a S 0 . M o r e c o p p e r o x i d e w a s

2 3
f o r m e d a n d m o r e o x y g e n e v o l v e d . I n the potential range 0.6 -1.0 V v s . S C E , the current d i d
not change s i g n i f i c a n t l y w i t h decreasing sulphite c o n c e n t r a t i o n f r o m 0.4 to 0.1 M . T h e
decrease i n the sulphite concentration resulted i n an increase i n o x y g e n e v o l u t i o n .
W h e n the m o l e ratio o f c y a n i d e to copper increased f r o m 3 to 4 ( [ C u ] decreased f r o m

+
0.0167 to 0.0125 M ) at [CN"] = 0.05 M , the p o l a r i z a t i o n curves w e r e different ( F i g u r e s A - 3 9
to A - 4 0 i n A p p e n d i x 8). T h e difference is due to the change i n the d i s t r i b u t i o n o f c o p p e r
c y a n i d e species.
161
T h e p r e c i p i t a t i o n o f copper o x i d e affected the a n o d i c o x i d a t i o n o f sulphite a n d c o p p e r
c y a n i d e . T h e c o n c e n t r a t i o n o f h y d r o x i d e w a s decreased to 0.05 M f r o m 0.25 M to see its
effect o n the a n o d i c b e h a v i o u r o f sulphite and copper c y a n i d e . F i g u r e 8-5 shows the
p o l a r i z a t i o n curves for the s o l u t i o n w i t h 0.05 M C N , 0.0167 M C u - +

( C N : C u = 3), 0.4 M
Na S0
2 3 , 0.05 M N a O H and 1 M N a S 0 . T h e current first i n c r e a s e d s m o o t h l y
2 4 with
i n c r e a s i n g p o t e n t i a l . W h e n the potential w a s larger than a certain v a l u e (dependent o n the
r o t a t i o n a l speed), it rose r a p i d l y to a l i m i t i n g v a l u e and then decreased slightly with
i n c r e a s i n g potential. A t the potential > about 0.70 V vs. S C E , the current i n c r e a s e d s l i g h t l y
and became stable a r o u n d 1.0 V v s . S C E . N o v i s i b l e copper o x i d e w a s f o r m e d .
F r o m F i g u r e 8-6, at a potential < about 0.30 V v s . S C E , the sulphite o x i d a t i o n d i d not
seem to be c a t a l y z e d b y the o x i d a t i o n o f copper c y a n i d e . H o w e v e r , at a p o t e n t i a l > about 0.3
V v s . S C E , the current increased r a p i d l y a n d the sulphite o x i d a t i o n w a s c a t a l y z e d b y the
o x i d a t i o n o f c o p p e r c y a n i d e . T h e potential for the sharp increase i n the current for m i x e d
sulphite a n d c o p p e r c y a n i d e is almost the same as that for copper c y a n i d e . A t a p o t e n t i a l >
about 0.9 V v s . S C E , the current d i d not increase as expected f r o m the further o x i d a t i o n o f
sulphite species ( H S 0 " or S 0 ) p o s s i b l y because the o x i d a t i o n o f S 0 " , but not H S 0 " a n d

3 2 3
2
3
2
S 0 , w a s ready to be c a t a l y z e d b y the o x i d a t i o n o f copper c y a n i d e a n d the electrode surface

2
w a s passivated for the o x i d a t i o n o f H S 0 " a n d S 0 .

3 3
2
W h e n the sulphite concentration decreased f r o m 0.4 M to 0.2 M , c o p p e r o x i d e a n d
h y d r o x i d e w a s precipitated o n the electrode. H e n c e the a n o d i c b e h a v i o u r (see F i g u r e A - 4 2 i n
A p p e n d i x 8) b e c a m e quite different.
T h e a n o d i c b e h a v i o r for 0.05 M C N " , 0.0125 M C u ( C N : C u = 4 ) , 0.4 M N a S 0

+
2 3 and
1 M Na S0 2 4 ( F i g u r e A - 4 3 i n A p p e n d i x 8) w a s s i m i l a r to that for C N : C u = 3 ( F i g u r e 8-5).
T h e current first increased s m o o t h l y and then rose r a p i d l y to a m a x i m u m v a l u e . W h e n the
c o n c e n t r a t i o n o f sulphite w a s decreased to 0.2 M , the a n o d i c b e h a v i o u r ( F i g u r e A - 4 4 i n
A p p e n d i x 8) w a s s i m i l a r to that for 0.4 M N a S 0 2 3 ( F i g u r e A - 4 4 ) . H o w e v e r , w h e n the
c o n c e n t r a t i o n o f sulphite was decreased to 0.1 M , the a n o d i c b e h a v i o u r ( A - 4 5 i n A p p e n d i x 8)
w a s different due to the f o r m a t i o n o f copper o x i d e . F r o m F i g u r e 8-7, it appears that sulphite
o x i d a t i o n w a s c a t a l y z e d b y the o x i d a t i o n o f copper c y a n i d e at a p o t e n t i a l > about 0.35 V v s .
SCE.
162
800 2500
Evolution 1600 rpm
700 1600 rpm of oxygen
400 rpm
(M 400 rpm
. . . 100 rpm
E 600 . . . . 100 rpm
< Precipitation
500 Precipitation of copper oxide
<
'55
of copper oxide _
c 400
a>
TJ
*-
C 300

200
Cu
100
0 -I
0.0 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8
Potential vs. SCE / V Potential vs. S C E / V
(a) 25 C (b) 4 0 C
7000 9000 j
Evolution of oxygen 1600 rpm hvoiution ot oxygen
1600 rpm 8000
6000 400 rpm
. 400 rpm CM
7000 -- . . . . 100 rpm
. . . 100 rpm E
5000 4-
< 6000 -- Precipitation
4000 5000 -- of copper oxide

Precipitation in J ir \
of copper oxide c
o>
3000 a 4000 -- \ \
\ \
c 3000
2000 V
3 2000
o V
1000 4- 1000 --
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (c) (d) 60 C
F i g u r e 8-1 P o l a r i z a t i o n c u r v e s at different temperatures. E l e c t r o l y t e : 0.05 M C N " , 0 . 0 1 6 7 M

Cu +
( C N : C u m o l e ratio = 3), 0.25 M N a O H , 0.4 M N a S 0 2 3 and 1 M N a S 0 2 4
163
9000
Potential v s . S C E
F i g u r e 8-2 E f f e c t o f potential s c a n n i n g rate o n the a n o d i c b e h a v i o u r o f m i x e d sulphite a n d

c o p p e r c y a n i d e at 4 9 0 0 r p m a n d 6 0 C . E l e c t r o l y t e : 0.05 M C N " , 0.0167 M C u ( C N : C u m o l e
+
ratio = 3), 0.25 M N a O H , 0.4 M N a S 0 2 3 and 1 M N a S 0 .

2 4
4000
F i g u r e 8-3 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0167 M C u a n d 0.4 M N a S 0 , (2) the
+
2 3
same c o m p o s i t i o n as (1), the electrode coated w i t h c o p p e r o x i d e at 0.5 V v s . S C E f o r 10

m i n u t e s i n the same s o l u t i o n . (3) 0.4 M N a S 0 , (4) 0.4 M N a S 0
2 3 2 3 o n the electrode coated
w i t h c o p p e r o x i d e i n the same s o l u t i o n as (1), a n d (5) 0.4 M N a S 0 2 3 o n the electrode coated
w i t h c o p p e r o x i d e f r o m 0.05 M C N " a n d 0.0167 M C u at 4 0 0 r p m a n d 6 0 C . S u p p o r t i n g
+
electrolyte: 0.25 M N a O H a n d 1 M N a S 0 . 2 4
164
4000
0.0 0.2 0.4 0.6 0.8 1.0

F i g u r e 8-4 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0167 M C u ( C N : C u m o l e ratio = 3)

+
a n d 0.4 M N a S 0 , (2) 0.4 M N a S 0 a n d (3) 0.05 M C N " and 0.0167 M C u at 4 0 0 r p m a n d

2 3 2 3
+
60 C . S u p p o r t i n g electrolyte: 0.25 M N a O H and 1 M N a S 0 .

2 4
165
3500 4500 j
4000 -- 4900 rpm
CN . 1600 rpm
3500 -- - - - 400 rpm
E
< 3000 -- . - -100 rpm
nsity
2500
a
u 2000
| 1500
O 1000
500
0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential v s . S C E / V Potential vs. S C E / V
(a) 25 C (b) 4 0 C
5000 6000
4500 4900 rpm 4900 rpm
- 1600 rpm 5000 1600 rpm
CN 4000
. - 400 rpm CN _ 400 rpm
E 3500
. -100 rpm E - -100 rpm
< < 4000
3000
co CO
c 2500 c 3000
CD CD
D 2000 o
4

c1
a> 1500
3
o 1000
500
0
0.0 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8 1.0
(c) 50 C (d) 6 0 C
F i g u r e 8-5 P o l a r i z a t i o n c u r v e s at different temperatures. E l e c t r o l y t e : 0.05 M C N " , 0 . 0 1 6 7 M

Cu +
( C N : C u m o l e ratio = 3), 0.05 M N a O H , 0.4 M N a 2 S 0 3 and 1 M N a S 0 .
2 4
166
3500
3000 --
0.0 0.2 0.4 0.6 0.8 1.0 1.2

F i g u r e 8-6 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0167 M C u ( C N : C u m o l e ratio = 3) a n d

+
0.4 M N a S 0 , (2) 0.4 M N a S 0 and (3) 0.05 M C N " a n d 0.0167 M C u at 4 0 0 r p m a n d 60

2 3 2 3
+
C . S u p p o r t i n g electrolyte: 0.05 M N a O H and 1 M N a S 0 . 2 4
3500 -r
0.0 0.2 0.4 0.6 0.8 1.0 1.2

F i g u r e 8-7 P o l a r i z a t i o n curves for (1) 0.05 M C N " , 0.0125 M C u a n d 0.4 M N a S 0 , (2) 0.4
+
2 3
M N a S 0 , (3) 0.05 M C N " , 0.0125 M C u and 0.2 M N a S 0 , (4) 0.2 M N a S 0 a n d (5) 0.05
2 3
+
2 3 2 3
M C N " a n d 0.0125 M C u at 4 0 0 r p m and 60 C . S u p p o r t i n g electrolyte: 0.05 M N a O H a n d 1

+
M Na S0 .
2 4
167
8.2.2 A n o d i c B e h a v i o u r of C o n c e n t r a t e d C o p p e r C y a n i d e Solution with Sulphite
T h e p o l a r i z a t i o n curves for the s o l u t i o n w i t h 3 M C N " , 1 M [ C u ] a n d 0.5 M N a S 0

+
2 3
and 0.25 M N a O H are s h o w n i n F i g u r e 8-8. A t 25 C , the current first i n c r e a s e d a n d then
decreased s l i g h t l y w i t h the p r e c i p i t a t i o n o f copper o x i d e . A t a p o t e n t i a l > about 0.52 V v s .
S C E , the current increased to a peak v a l u e and decreased r a p i d l y . T h e s e c o n d p a s s i v a t i o n is
p r o b a b l y due to o x y g e n adsorption. A t 40 C , the p o l a r i z a t i o n curves at 4 0 0 a n d 1600 r p m
were s i m i l a r to those at 25 C . H o w e v e r , at 100 r p m , the current reached a l i m i t i n g v a l u e a n d
b e c a m e independent o f potential. T h e o x i d e f o r m e d i n the potential range 0.38 to 0.5 V v s .
S C E w a s d i s s o l v e d w h e n the current w a s at its l i m i t i n g v a l u e . T h i s is w h y the current d i d not
decrease w i t h potential after the current sharply increased to a l i m i t i n g v a l u e .
T h i s dependence o f the a n o d i c b e h a v i o u r o n the rotational speed is related to the
c o m p o s i t i o n o f the reactive species o n the surface o f the electrode. A t a p o t e n t i a l > about 0.5
V vs. S C E , the current increased sharply w i t h increasing potential and was almost
independent o f the rotational speed. Therefore the concentration o f hydroxide o n the
electrode surface decreased w i t h decreasing rotational speed. A t 100 r p m , the c o n c e n t r a t i o n
o f h y d r o x i d e w a s so l o w that the f o r m a t i o n o f copper o x i d e w a s not f a v o r e d . E v e n c o p p e r
oxide was more readily reduced b y sulphite ions a n d d i s s o l v e d . Therefore a second
p a s s i v a t i o n w a s not observed. A t 4 0 0 and 1600 r p m , the c o n c e n t r a t i o n o f h y d r o x i d e o n the
surface w a s s t i l l h i g h a n d the f o r m a t i o n o f copper o x i d e w a s s t i l l f a v o r e d . W i t h i n c r e a s i n g
p o t e n t i a l , the s e c o n d p a s s i v a i o n appeared p r o b a b l y due to the a d s o r p t i o n o f o x y g e n .
A t 50 C and 100 r p m , the current increased c o n t i n u o u s l y to a l i m i t i n g v a l u e a n d n o
c o p p e r o x i d e w a s f o r m e d o n the electrode. A t 4 0 0 r p m , the a n o d i c b e h a v i o u r o f current v s .
potential w a s s i m i l a r to that at 100 r p m and 40 C . A t 1600 r p m , the a n o d i c b e h a v i o u r w a s
s t i l l s i m i l a r to that at 50 C . A t 60 C a n d a rotational speed o f 100 or 4 0 0 r p m , the current
i n c r e a s e d c o n t i n u o u s l y to a l i m i t i n g v a l u e and became independent o f the p o t e n t i a l . T h e
a n o d i c b e h a v i o u r at 1600 r p m w a s s i m i l a r to that at 100 r p m a n d 40 C .
T h e a n o d i c o x i d a t i o n o f sulphite and c y a n i d e increases w i t h i n c r e a s i n g temperature
m u c h faster than the d i f f u s i o n o f the h y d r o x i d e i o n . Therefore e v e n at a h i g h e r rotating speed,
the h y d r o x i d e c o n c e n t r a t i o n o n the surface o f anode is so l o w that no c o p p e r h y d r o x i d e w a s
f o r m e d a n d the current reached a l i m i t i n g v a l u e .

168
F i g u r e 8-9 s h o w s the plots o f the current v s . t i m e at different potentials at 4 0 0 r p m .
A t 25 C a n d 0.4 V v s . S C E , the current first decreased r a p i d l y a n d then s l o w l y a n d finally
b e c a m e stable. A t h i n l a y e r o f copper o x i d e w a s precipitated o n the anode. A t 0.60 V v s .
S C E , the current increased to a certain v a l u e a n d then b e c a m e stable. N o c o p p e r o x i d e w a s
p r e c i p i t a t e d o n the electrode. A t 0.80 V v s . S C E , the current decreased to a l i m i t i n g v a l u e a n d
b e c a m e stable w i t h no copper o x i d e appearing o n the anode. It s h o u l d be noted that at 25 C
a n d 0.80 V v s . S C E , the current densities i n F i g u r e 8-9a do not m a t c h those i n F i g u r e 8-8a.
T h i s c a n be e x p l a i n e d b y : (1) the current obtained i n F i g u r e 8-9a w a s o b t a i n e d u s i n g the
c o n t r o l l e d p o t e n t i a l m e t h o d . W h e n the potential w a s a p p l i e d , the instantaneous current
reached a v a l u e where the concentration o f h y d r o x i d e o n the electrode surface w a s l o w so
that c o p p e r o x i d e w a s not f o r m e d a n d the current w a s s t a b i l i z e d at a l i m i t i n g v a l u e ; (2) the
current i n F i g u r e 8-8a w a s generated b y a potential scan at 1 m V s" a n d so the current never

1
reached a v a l u e at w h i c h copper o x i d e was r e a d i l y r e d u c e d a n d d i s s o l v e d . H e n c e it p a s s i v a t e d
the electrode surface.
A t 4 0 C ( F i g u r e 8-9b), the results are s i m i l a r to those at 25 C (8-9a). A t 50 C and
0.3 V v s . S C E , the current decreased a n d became stable. A t 0.4 V v s . S C E , the current
density increased a n d then decreased and was f i n a l l y s t a b i l i z e d . T h e current w a s m u c h h i g h e r
than those i n F i g u r e s 8-8 b . T h e reason for this b e h a v i o u r is the same as d i s c u s s e d for 25 C .
A t a p o t e n t i a l > 0.60 V v s . S C E , the current is the same as that o b t a i n e d u s i n g a p o t e n t i a l
scan rate o f 1 m V s" . A t 60 C and 0.2 or 0.3 V v s . S C E , the current decreased,

1
then
increased to a certain v a l u e and w a s s t a b i l i z e d . A t a potential > 0.4 V v s . S C E , the current
decreased or increased to a l i m i t i n g v a l u e and became stable. T h e current i n F i g u r e 8-9d is
the same as that i n F i g u r e 8-8d.
The p r e c i p i t a t i o n o f copper oxide affected the anodic behaviour. Hence the
c o n c e n t r a t i o n o f h y d r o x i d e w a s decreased to investigate the effect o f p H o n the a n o d i c
b e h a v i o u r . F i g u r e s 8-10 and 8-11 s h o w the p o l a r i z a t i o n curves for the s o l u t i o n c o n t a i n i n g 0.1
and 0.05 M N a O H . T h e p a s s i v a t i o n d i d not appear because there w a s n o precipitate o n the
anode.
F i g u r e 8-12 s h o w s the p o l a r i z a t i o n curves for m i x e d sulphite a n d c o p p e r c y a n i d e
s o l u t i o n , sulphite s o l u t i o n and copper c y a n i d e s o l u t i o n w i t h 0.25 M N a O H at 60 C . S u l p h i t e
o x i d a t i o n appears to be c a t a l y z e d b y copper c y a n i d e o x i d a t i o n . T h e o x i d a t i o n o f c o p p e r
169
c y a n i d e also seems to be affected b y sulphite. F r o m F i g u r e 8-13, w h e n the h y d r o x i d e
c o n c e n t r a t i o n decreased to 0.05 M , the o x i d a t i o n o f c o p p e r c y a n i d e a n d sulphite was
s i g n i f i c a n t l y c a t a l y z e d b y each other. T h e increase i n sulphite c o n c e n t r a t i o n f r o m 0.2 to 0.4
M resulted i n the increase i n the current. H o w e v e r , its l i m i t i n g v a l u e is m u c h s m a l l e r than
that expected f r o m the increase i n the concentration p o s s i b l y because the p H o n the electrode
w a s so l o w that the s p e c i a t i o n o f sulphite shifted f r o m S 0 " to H S 0 " a n d S 0 w h i c h w e r e

3
2
3 2
less active.
W h e n the c o n c e n t r a t i o n o f c y a n i d e increased f r o m 3 to 3.5 M and the concentrations
o f the other species w e r e m a i n t a i n e d constant, the p o l a r i z a t i o n curves ( F i g u r e 8-14) b e c a m e
different a n d no p a s s i v a t i o n w a s observed. A t 25 C , the current i n c r e a s e d w i t h i n c r e a s i n g
p o t e n t i a l a n d then reached a l i m i t i n g v a l u e a n d b e c a m e independent o f the p o t e n t i a l . A t 4 0 ,
5 0 , a n d 60 C , there w a s n o l i m i t i n g current and n o p a s s i v a t i o n . A t 50 a n d 60 C , w h e n the
p o t e n t i a l e x c e e d e d 0.4 V v s . S C E , a significant amount o f b u b b l e s w a s o b s e r v e d at 100 and
4 0 0 r p m . T h e b u b b l e s were r a p i d l y d i s s o l v e d i n t w o seconds after t u r n i n g o f f the current. T h e
graphite w a s not c o r r o d e d . A t s u c h a h i g h current, sulphite o n l y l i m i t e d a part o f the c y a n i d e
o x i d a t i o n a n d p H o n the electrode surface w a s so l o w that the rate o f the p r o d u c t i o n o f ( C N ) 2
w a s h i g h e r than the rate o f the reaction b e t w e e n ( C N ) and O H " . Therefore ( C N )

2 2 bubbles
were evolved.
F i g u r e 8-15 s h o w s the p o l a r i z a t i o n curves for m i x e d sulphite a n d copper cyanide
s o l u t i o n , c o p p e r c y a n i d e and sulphite. T h e current for m i x e d copper c y a n i d e a n d s u l p h i t e is
h i g h e r than that for copper c y a n i d e or sulphite. S o the o x i d a t i o n o f b o t h sulphite a n d c o p p e r
c y a n i d e c o n t r i b u t e d to the total a n o d i c current.
F i g u r e 8-16 s h o w s the p o l a r i z a t i o n curves for the s o l u t i o n w i t h 4 M C N " , 1 M C u , +
0.5 M N a S 0 2 3 a n d 0.25 M N a O H . T h e current increased c o n t i n u o u s l y w i t h i n c r e a s i n g
p o t e n t i a l . W h e n the current e x c e e d e d a certain v a l u e ( d e p e n d i n g o n the r o t a t i o n a l speed), a
l a y e r o f b u b b l e s w a s f o r m e d o n the graphite. W i t h i n c r e a s i n g p o t e n t i a l , the b u b b l e s b e c a m e
larger a n d h a d a s i g n i f i c a n t effect o n the m a s s transfer. T h u s the current increased
s i g n i f i c a n t l y . D u e to the f o r m a t i o n o f the b u b b l e layer, the I R drop w a s e v e n larger than 1 V .
F i g u r e 8-17 s h o w s the p o l a r i z a t i o n curves for m i x e d sulphite a n d copper cyanide
s o l u t i o n , c o p p e r c y a n i d e and sulphite. T h e current for m i x e d copper c y a n i d e a n d sulphite w a s

170
a little h i g h e r than that for copper c y a n i d e . S o the o x i d a t i o n o f sulphite d i d not contribute
v e r y m u c h to the total a n o d i c current.
900 2500
800 1600 rpm

1" 700 . 400 rpm
E . . . 100 rpm
< 600
Ic 500
* 400
S 300
O 200
100
0
0.0 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.2
(a) 25 C (b) 4 0 C
6000 18000

t 16000 4
5000 . 1600 rpm t 1600 rpm
CN 400 rpm I1I CM 14000 400 rpm
E
< 4000
. . . . 100 rpm
/J ^ 12000
. . . . 100 rpm
fl < 10000
(0 1
c 3000 i-
I
T3
2000
3
1000
0 -I
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.2 0.4 0.6 0.8 1 1.2
Potential vs. S C E / V Potential v s . S C E / V
(c) 50 C (b) 60 C
F i g u r e 8-8 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 3 M C N " , 1 M C u , 0.25 +
M N a O H , 0.5 M N a S 0 . 2 3
171
3500 6000
3000 5000
CM
E E
< 2500
< 4000
0.4 VSCE
in
2000 0.6 VSCE
Hsu
c
0.8 VSCE 3000 -0.4 V vs. SCE
"O 1500 TJ -0.6 V vs. SCE
c
P C
2000 0.8 V vs. SCE
3
o
500 1000
0
50 100 150 200 50 100 150 200
Time / s Time Is
(a) 25 C (b) 4 0 C
10000
400 rpm 9000 0.2 V vs. SCE
0.3 Vvs.SCE
^ 8000 0.4 Vvs.SCE
J 7000 0.5 V vs. SCE
0.6 V vs. SCE
^ 6000 0.8 V vs. SCE
C 5000
4000
3000
2000
1000
0
100 200 100 200 300 400
Time / s
Time Is
(c) 5 0 C (d) 6 0 C
F i g u r e 8-9 C u r r e n t density v s . t i m e at constant potential, 4 0 0 r p m a n d different temperatures.

E l e c t r o l y t e : 3 M C N " , 1 M C u , 0.25 M N a O H , 0.5 M N a S 0 .
+
2 3
172
9000 12000
8000 - 4 9 0 0 rpm
1600 rpm 10000
* 7000 - - 4 9 0 0 rpm
. 4 0 0 rpm E
E 1600 rpm
< 6 0 0 0 --
- 1 0 0 rpm < 8000
. 400 rpm
- 1 0 0 rpm
5000 --
in in
c c
TJ
4000
S 4000
3000 j
O
O 2000 2000
1000 -j-
0 0.2 0.4 0.6 O.J 0.0 0.2 0.4 0.6

0.0 Potential vs. S C E / V
(a) 25 C (a) (b) 4 0 C
25000
0.2 0.4 0.6 0.2 0.4 0.<

(c) 50 C (d) 60 C
F i g u r e 8-10 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 3 M C N ' , 1 M C u , 0.1 +
M N a O H , 0.5 M N a 2 S 0 3 .
173
8000 - 10000
9000 -4900 rpm

7000 - -4900 rpm
1600 rpm 8000 1600 rpm
<N
6000 - . 400 rpm
'E . 400 rpm
7000
< 5000 -
-100 rpm -100 rpm
6000
in 4000 - 5000
c
01
D 4000
3000 .
C
3000
3 2000 -
2000
o
1000 - 1000
0 - 0
0.4 0.6 1.0 0.2 0.4 0.6 O.t" 1.0
Potential vs. S C E / V Potential v s . S C E / V
(a) 25 C (b) 60 C
20000
18000
4900 rpm
16000 1600 rpm
14000 . . . .400 rpm

- - 1 0 0 rpm
12000
10000
8000 4-
6000
4000
2000
0
0.0 0.2 0.4 0.6 0.
Potential vs. SCE / V
(c) 50 C (d) 60 C
F i g u r e 8-11 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 3 M C N " , 1 M C u +
0.05 M N a O H , 0.5 M N a ^ .
174
7000 -,
F i g u r e 8-12 P o l a r i z a t i o n curves for (1)3 M C N " , 1 M C u ( C N : C u m o l e ratio = 3), 0.25 M

+
N a O H and 0.5 M N a S 0 , (2) 0.5 M N a S 0 , 0.25 M N a O H and 1 M N a S 0

2 3 2 3 2 4 a n d (3) 3 M
C N " , 1 M C u , 0.25 M N a O H and 0.5 M N a 2 S 0 at 4 0 0 r p m and 60 C .
+
4
F i g u r e 8-13 P o l a r i z a t i o n curves at 4 0 0 r p m a n d 25 C for (1) 3 M C N " + 1 M C u + 0.4 M +
Na S0
7 3 + 0.1 M N a S 0 2 4 (2) 3 M C N " + 1 M C u + 0.2 M N a S 0
+
2 3 + 0.3 M N a S 0 , (3) 0.4 M
2 4
Na S0
2 3 + 1 M N a S 0 , (4) 0.2 M N a S 0
2 4 2 3 + 1 M Na S0 2 4 (5) 3 M C N " + 1 M C u + 0.5 M +
Na S0
2 4 at [ N a O H ] = 0.05 M N a O H .
175
30000
-1600 rpm
25000
400 rpm 1600 rpm
. 100 rpm E 400 rpm

< 20000 . . . . 100 rpm
in
c 15000
TJ
c
10000

3
o 5000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 O.J 1.0
(a) 25 C (b) 4 0 C
30000
I '
/ /
1600 rpm / /
400 rpm / /
. . . . 100 rpm / /
< 20000 4- / /
/ >
/ /"
1
1
J
/ /
1/
/f
yt . -
0.0 0.2 0.4 0.6 0.8 0.2 0.4 0.6

(c) 50 C (d) 60 C
F i g u r e 8-14 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 3.5 M C N " , 1 M C u , +
0.25 M N a O H , 0.5 M N a ^ .
176
F i g u r e 8-15 P o l a r i z a t i o n curves for (1)3.5 M C N " , 1 M C u , 0.25 M N a O H and 0.5 M

+
N a S 0 , (2) 3 M C N " , 1 M C u , 0.25 M N a O H and 0.5 M N a S 0 a n d (3) 0.5 M N a S 0 , 0.25

2 3
+
2 4 2 3
M N a O H at 4 0 0 r p m and 60 C .
177
30000 , 30000 ,
2 5 0 0 0 4- 2 5 0 0 0 4- 1600 rpm
CN
1600 rpm <N
4 0 0 rpm
E 4 0 0 rpm E
- . . . 100 rpm
< 2 0 0 0 0 -- . . . . 100 rpm
< 20000
Pr.
i;su
i;su
15000 15000 --
TJ TJ
C
10000 -- C 10000 --
0)_
L 0)
k_
3 3
o o
5000 5000 - -
o -J
0.0 0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8
(a) 25 C (b) 4 0 C
30000 , 30000
25000 25000
- 1 6 0 0 rpm 1600 rpm
CN
E 4 0 0 rpm E 4 0 0 rpm
< - 1 0 0 rpm < 20000 . . . . 100 rpm
2 0 0 0 0 4-
ID
C 15000
i
a I 15000
TJ
<* a>
C 10000 TJ
3 g 10000
o o
5000 5000
0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8

(c) 50 C (d) 6 0 C
F i g u r e 8-16 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 4 M C N " , 1 M C u +
0.25 M N a O H , 0.5 M N a S 0 . 2 3
178
30000 -,
CM
25000 -
2
E
3
< 20000
15000 -
CD
T3
c 10000 -
O 5000 -
0
0 0.2
2 0.4 C0.6 0.8
F i g u r e 8-17 P o l a r i z a t i o n curves f o r (1) 4 M C N " + 1 M C u + 0.25 M N a O H + 0.5 M

+
N a S 0 , (2) 0.5 M N a S 0
2 3 2 3 + 0.25 M N a O H + 1 M N a S 0 2 4 a n d (3) 4 M C N " + 1 M C u + 0.25 +
M N a O H + 0.5 M N a S 0 2 4 at 4 0 0 r p m a n d 6 0 C .
8.3 Coulometric Measurements
The c o u l o m e t r i c measurements were conducted using controlled potential and
c o n t r o l l e d current methods to investigate the a n o d i c current e f f i c i e n c i e s o f c y a n i d e a n d
c o p p e r o x i d a t i o n i n the presence o f sulphite. T h e results obtained u s i n g the c o n t r o l l e d
p o t e n t i a l m e t h o d are l i s t e d i n T a b l e 8-1.
Tests 1-4 s h o w the a n o d i c current efficiencies o f c y a n i d e a n d copper for the s o l u t i o n
w i t h 0.05 M C N " , 0.0167 M ( C N : C u m o l e ratio = 3), 0.4 M N a S 0 , 0.25 M O H " a n d 1 M

2 3
N a S 0 . I n the presence o f 0.4 M N a S 0 , the current e f f i c i e n c y decreased f r o m 86 % to

2 4 2 3
about 10 % for c y a n i d e ( C N " - > C N O " ) a n d f r o m 13 % to about 3 % f o r c o p p e r ( C u - > C u O +
or C u ( O H ) ) . T h i s m e a n s that sulphite c a n effectively l i m i t the a n o d i c o x i d a t i o n o f c o p p e r

2
c y a n i d e . T h e a n o d i c current e f f i c i e n c y f o r c y a n i d e at 0.5 V v s . S C E w a s a little b i t h i g h e r
than that at 0.3 V v s . S C E because at 0.5 V S C E , the current f o r sulphite a n d c o p p e r c y a n i d e
w a s closest to a l i m i t i n g v a l u e a n d sulphite w a s less efficient i n l i m i t i n g the o x i d a t i o n o f
c o p p e r c y a n i d e . T h e a n o d i c current e f f i c i e n c y at 6 0 C is a s l i g h t l y h i g h e r than that at 5 0 C .
Tests 5-8 s h o w the a n o d i c current efficiencies o f c y a n i d e a n d c o p p e r f o r the s o l u t i o n
w i t h 0.05 M C N " , 0.0125 M ( C N : C u m o l e ratio = 4 ) , 0.4 M N a S 0 , 0.25 M O H " a n d 1 M

2 3
N a S 0 . I n the presence o f 0.4 M N a S 0 , the a n o d i c current e f f i c i e n c y decreased f r o m 9 0 %

2 4 2 3
179
to about 12 % for c y a n i d e a n d f r o m 10 % to about 2 % for c o p p e r (I). S i m i l a r to Tests 1-4,
the a n o d i c current e f f i c i e n c i e s o f c o p p e r c y a n i d e at 0.60 V v s . S C E are s l i g h t l y h i g h e r t h a n
those at 0.4 V v s . S C E . T h e a n o d i c current e f f i c i e n c y o f c y a n i d e i n Tests 5-8 is h i g h e r than
that i n Tests 1-4, the a n o d i c current e f f i c i e n c y o f c o p p e r (I) i n Tests 5-8 is l o w e r t h a n that i n
Tests 1-4 p o s s i b l y because the s p e c i a t i o n o f c o p p e r c y a n i d e shifted to C u ( C N ) " a n d m o r e 4

3
free c y a n i d e w a s present i n the s o l u t i o n .
T a b l e 8-1 C u r r e n t e f f i c i e n c i e s f r o m copper c y a n i d e u s i n g c o n t r o l l e d potential c o u l o m e t r i c

measurements ( s u p p o r t i n g electrolyte: 1 M N a S 0 ) 2 4
Test Composition Controlled Temperature Rotational Current Current

No. potential (Q speed efficiency efficiency
(V vs. SCE) (rpm) for CN (%) for Cu (%)
1 0.05 M CN", 0.3 50 100 9 2
2 CN:Cu = 3 0.3 60 100 8 2
3 0.4 M S 0 - 3
2
0.5 50 100 12 3
4 0.25 M OH- 0.5 60 100 13 3
5 0.05 M CN", 0.4 50 100 11 1
6 CN:Cu = 4 0.4 60 100 12 1
7 0.4 M S0 - 3
2
0.6 50 100 13 2
8 0.25 M OH- 0.6 60 100 14 2
T a b l e 8-2 lists the a n o d i c current e f f i c i e n c i e s o f c y a n i d e a n d c o p p e r (I) for the
solutions w i t h different c o m p o s i t i o n u s i n g the c o n t r o l l e d current m e t h o d . Tests 1-6 list the
a n o d i c current e f f i c i e n c i e s o f c y a n i d e a n d copper for the s o l u t i o n w i t h 0.05 M C N " , 0.0167 M
( C N : C u = 3), 0.4 M N a S 0 , 0.25 M O H " a n d 1 M N a S 0

2 3 2 4 at different current densities a n d
r o t a t i o n a l speeds. T h e r o t a t i o n a l speeds ( 1 0 0 - 1 6 0 0 r p m ) a n d the current densities ( 2 5 0 - 5 0 0 A
m" ) do not s i g n i f i c a n t l y affect the current e f f i c i e n c i e s o f c y a n i d e a n d c o p p e r (I). S i m i l a r

2
results for the solutions w i t h 0.05 M C N " , 0.0125 M C u , 0.4 M N a S 0 , 0.25 M N a O H a n d 1

+
2 3
M Na S0
2 4 (Tests 7-12) w e r e obtained. T h e difference is that a l m o s t no c o p p e r o x i d e w a s
f o r m e d o n the anode due to the h i g h m o l e ratio o f c y a n i d e to copper. T h e current e f f i c i e n c y
o f c y a n i d e d i d not change v e r y m u c h w h e n the c y a n i d e c o n c e n t r a t i o n w a s i n c r e a s e d f r o m
0.05 M to 0.4 M (Tests 13-16) a n d 1 M (Tests 17-20) a n d the concentrations o f the other
species w e r e kept constant.
F r o m Tests 1-8 a n d Tests 2 1 - 2 6 , at C N : C u m o l e ratio = 3, w h e n the c o n c e n t r a t i o n o f
h y d r o x i d e decreased f r o m 0.25 M to 0.05 M a n d the concentrations o f the other species w e r e
kept at constants, the a n o d i c current e f f i c i e n c y o f c y a n i d e decreased w h i l e the a n o d i c current
e f f i c i e n c y o f c o p p e r (I) decreased to a l m o s t zero. T h i s means that sulphite w a s m o r e efficient

180
i n l i m i t i n g the o x i d a t i o n o f copper c y a n i d e at l o w h y d r o x i d e concentration. H o w e v e r , at
C N : C u m o l e ratio = 4, the decrease i n the c o n c e n t r a t i o n o f h y d r o x i d e f r o m 0.25 to 0.05 M
d i d not affect the a n o d i c current e f f i c i e n c y . T h i s m a y be related to the d i s t r i b u t i o n o f c o p p e r
c y a n i d e species.
T a b l e 8-2 C u r r e n t efficiencies f r o m copper c y a n i d e u s i n g c o n t r o l l e d current c o u l o m e t r i c

measurements (supporting electrolyte: 1 M N a S 0 ) 2 4
Test Composition Controlled current Temperature Rotational Current Current

No. (A m") 2
(Q speed efficiency efficiency

(rpm) for CN (%) for Cu (%)
1 0.05 M C N \ 250 50 1600 13 3
2 CN:Cu = 3 250 60 1600 10 2
3 0.4 M S 0 - 3
2
250 50 100 14 2
4 0.25 M OH" 250 60 100 11 3
5 500 50 100 13 3
6 500 60 100 12 3
7 0.05 M C N \ 250 50 1600 14 0
8 CN:Cu = 4 250 60 1600 11 0
9 0.4 MSO3 - 2
250 50 100 13 0
10 0.25 M OH- 250 60 100 11 0
11 500 50 100 15 -
12 500 60 100 12 -
13 0.4 M CN", 500 50 100 14 0
14 CN:Cu = 3 500 60 100 9
0.4 MSO3 - 2
0.25 M OH"
15 0.4 M CN", 500 50 100 17 0
16 CN:Cu = 4 500 60 100 15
0.4 M S0 - 3
2
0.25 M OH-
17 1 M CN", CN:Cu 500 50 100 15 2
18 =3 500 60 100 10 0
0.4 MSO3 - 2
0.05 M OH"
19 1 M CN", CN:Cu 500 50 100 18
20 =4 500 60 100 14
0.4 MSCy - 2
0.25 M OH"
21 0.05 M CN", 250 50 1600 10
22 CN:Cu = 3 250 60 1600 6
23 0.4 MSO3 - 2
500 50 1600 9
24 0.05 M OH" 500 60 1600 8
25 500 50 100 8
26 500 60 100 7
27 0.05 M CN", 250 50 1600 14 0
28 CN:Cu = 4 250 60 1600 13 0
29 0.4 M S O 3 2
- 500 50 1600 14 0
30 0.05 M OH" 500 60 1600 12 0
T a b l e 8-3 lists the a n o d i c current efficiencies o f c y a n i d e and c o p p e r w h e n the c y a n i d e
c o n c e n t r a t i o n w a s increased to 3 or 4 M . F r o m Tests 1-4, i n the presence o f 0.5 M N a S 0 , at 2 3
[CN"] = 3 M a n d [ C u ] = 1 M , the a n o d i c current e f f i c i e n c y o f c y a n i d e decreased to a r o u n d

+
12 % f r o m about 82 % i n the absence o f sulphite a n d the a n o d i c current e f f i c i e n c y o f c o p p e r
(I) decreased to about 2.5 % f r o m 13.6 % i n the absence o f sulphite. T h u s sulphite c a n l i m i t
the o x i d a t i o n o f c o p p e r c y a n i d e . T h e decrease i n the c o n c e n t r a t i o n o f h y d r o x i d e f r o m 0.25 to
0.10 M (Tests 5-8) or 0.05 M (Tests 9-12) resulted i n a slight decrease i n the a n o d i c current
e f f i c i e n c y . T h e r e w a s n o p r e c i p i t a t i o n o f copper o x i d e w h e n the other c o m p o s i t i o n s w e r e the
same. S o sulphite m o r e e f f i c i e n t l y l i m i t s the o x i d a t i o n o f copper c y a n i d e at a l o w p H . F r o m
Tests 1-4 a n d Tests 13-24, the current e f f i c i e n c y o f c y a n i d e i n c r e a s e d w i t h i n c r e a s i n g
c o n c e n t r a t i o n o f c y a n i d e . F r o m Tests 9-12 and 2 5 - 2 8 , the a n o d i c current e f f i c i e n c y for
c y a n i d e increased b y about 7-8 % w i t h decreasing sulphite c o n c e n t r a t i o n f r o m 0.5 to 0.3 M .
T a b l e 8-3 C u r r e n t efficiencies f r o m copper c y a n i d e u s i n g c o n t r o l l e d current c o u l o m e t r i c

measurements at 100 r p m (0.5 M N a S 0 ) 2 4
Test Composition Controlled Temperature Current efficiency Current efficiency

No. current (A m") 2
(C) for CN (%) for Cu (%)

1 3 M CN", l M C u +
250 50 13 2.4
2 (CN:Cu = 3) 250 60 12 2.6
3 0.5 M S0 " 3
2
500 50 12 2.0
4 0.25 M OH 500 60 11 2.5
5 3 M CN", l M C u +
250 50 13 0
6 (CN:Cu = 3) 250 60 12 0
7 0.5 M S0 " 3
2
500 50 12 0
8 0.10 MOH" 500 60 11 0
9 3 M CN", l M C u +
250 50 10 0
10 (CN:Cu = 3) 250 60 9 0
11 0.5 M S0 " 3
2
500 50 12 0
12 0.05 M OH" 500 60 11 0
13 3.2 MCN", l M C u +
250 50 13 0
14 (CN:Cu = 3.2) 250 60 12 0
15 0.5 M S0 " 3
2
500 50 15 0
16 0.25 M OH" 500 60 14 0
17 3.5 MCN", l M C u +
250 50 19 0
18 (CN:Cu = 3.5) 250 60 18 0
19 0.5 M S0 " 3
2
500 50 22 0
20 0.25 M OH 500 60 21 0
21 4 MCN", l M C u +
250 50 40 0
22 (CN:Cu = 4) 250 60 39 0
23 0.5 M S0 " 3
2
500 50 45 0
24 0.25 M OH" 500 60 46 0
25 3 MCN", l M C u +
250 50 17 0
26 (CN:Cu = 3) 250 60 16 0
27 0.3 M S0 " 3
2
500 50 18 0
28 0.05 M OH" 500 60 16 0
182
I n the a b o v e tests, the a n o d i c current efficiencies o f c y a n i d e a n d c o p p e r (I) w e r e
o b t a i n e d f r o m the a n a l y s i s o f the c y a n i d e concentration a n d the a m o u n t o f the c o p p e r o x i d e
p r e c i p i t a t e d o n the anode. F r o m the a n o d i c current e f f i c i e n c i e s o f c y a n i d e a n d c o p p e r (I), w e
cannot p r e d i c t the a m o u n t o f o x i d i z e d sulphite because sulphite c a n be o x i d i z e d to sulphate
(two electrons process) a n d dithionate (one electron process) a n d there are p o s s i b l e side
reactions such as o x y g e n e v o l u t i o n . Therefore the amount o f oxidized sulphite was
determined directly.
T a b l e 8-4 lists the a n o d i c current efficiencies o f c y a n i d e , copper (I) a n d sulphite
( a s s u m i n g sulphite w a s o x i d i z e d to sulphate). F r o m T a b l e 8-4, the s u m o f the a n o d i c current
e f f i c i e n c i e s o f c y a n i d e , copper (I) and sulphite is v e r y close to 100 % a n d so sulphite w a s
o x i d i z e d to sulphate. T a b l e 8-5 lists the current e f f i c i e n c y for c y a n i d e , c o p p e r a n d sulphite
u s i n g c o n t r o l l e d p o t e n t i a l m e t h o d . A t a h i g h e r potential, the current w a s at a l i m i t i n g v a l u e
a n d the a n o d i c current e f f i c i e n c y for sulphite was l o w .
T a b l e 8-4 C u r r e n t e f f i c i e n c y for copper c y a n i d e u s i n g c o n t r o l l e d current c o u l o m e t r i c

measurements (supporting electrolyte: 1 M N a S 0 2 4 for Tests 1 and 2) at 100 r p m *
Test Composition Controlled Temperature Current Current Current
No. current (Q. efficiency efficiency efficiency
(A m") 2
for S0 " (%)
3
2
for CN (%) for Cu (%)
+
1 0.05 M CN", 500 50 86 12 1.6

2 0.0167 M C u +
500 60 89 10 1.8
0.4 M S0 - 3
2
0.25 M OH"
3 3 M CN\1M 250 50 83 14 2.2
4 Cu (CN:Cu = 3)
+
250 60 86 13 2.4
5 0.5 M SCy 500 50 84 15 2.5
6 0.25 M OH" 500 60 86 12 2.6
7 3 M CN\1M 250 25 88 15 0
8 Cu (CN:Cu = 3)
+
250 40 88 14 0
9 0.5 M S0 " 3
2
250 50 89 10 0
10 0.05 M OH" 250 60 87 09 0
* F o r Tests 3-10, the i n i t i a l concentration o f sulphite w a s 0.6 M . T h e a m o u n t o f e l e c t r i c i t y
passed decreased the concentration o f sulphite to 0.4 M a s s u m i n g 85 % for the a n o d i c current
e f f i c i e n c y o f sulphite.
183
T a b l e 8-5 C u r r e n t e f f i c i e n c y for copper c y a n i d e u s i n g c o n t r o l l e d p o t e n t i a l c o u l o m e t r i c

measurements (supporting electrolyte: 1 M N a S 0 2 4 for Tests 1 and 2) at 100 r p m *
Test Composition Controlled Temp. Current Current Current
No. potential (C) efficiency efficiency efficiency
(V vs. SCE) for CN (%) for Cu (%) for S0 " (%)
+
3
2
1 0.05 MCN", 0.0167 M C u +

0.3 60 11 2.2 87
2 0.4 M S0 " 0.25 M OH"
3
2
0.5 60 13 2.9 84
3 0.05 MCN", 0.0125 M C u +
0.4 60 10 1.3 85
4 0.4 M S0 " 0.25 M OH"
3
2
0.6 60 13 2.8 83
5 0.05 MCN", 0.0167MCu +
0.25 60 9 0 89
6 0.4 M S0 " 0.05 M OH-
3
2
0.6 60 11 0 90
9 0.05 M C N , 0.0125 M C u +
0.25 60 11 0 89
10 0.4 M SO, " 0.05 M OH" 2
0.6 60 13 0 88
11 3 M CN", 1 M Cu +
0.3 60 13 2.3 87
12 0.5 M S 0 \ 0.25 M NaOH
3
2
0.6 60 52 0 47
13 3 M CN", 1 M Cu +
0.3 60 11 0 87
14 0.5 M S0 ", 0.05 M NaOH
3
2
0.6 60 48 0 57
F o r Tests 11-14, the i n i t i a l concentration o f sulphite w a s 0.6 M . T h e amount o f e l e c t r i c i t y
passed decreased the concentration o f sulphite to 0.4 M a s s u m i n g 85 % f o r the a n o d i c current
e f f i c i e n c y o f sulphite.
8.4 Possible Anodic Reactions
T h e a n o d i c b e h a v i o u r o f m i x e d copper c y a n i d e a n d sulphite s o l u t i o n i s a f u n c t i o n o f
hydroxide, sulphite a n d c y a n i d e concentrations, the m o l e ratio o f c y a n i d e to copper,
temperature a n d rotational speed. T h e current for m i x e d c o p p e r c y a n i d e s o l u t i o n w a s not j u s t
the s u m o f the currents o f copper c y a n i d e a n d sulphite w h e n they are present separately i n the
s o l u t i o n . S u l p h i t e o x i d a t i o n w a s affected s i g n i f i c a n t l y b y the o x i d a t i o n o f c o p p e r c y a n i d e .
C o p p e r c y a n i d e o x i d a t i o n w a s also affected b y sulphite ions. C o m p a r i n g F i g u r e s 8-12, 15
a n d 17, the h i g h e r the m o l e ratios o f c y a n i d e to copper , the less the effect o n the o x i d a t i o n o f
c o p p e r c y a n i d e a n d sulphite. T h i s m a y be related to the d i s t r i b u t i o n o f c o p p e r c y a n i d e
species. P r o b a b l y the discharge o f C u ( C N ) " i s less affected b y sulphite. S o sulphite also has
4
3
a s m a l l e r effect o n the o x i d a t i o n o f c y a n i d e . T h e o x i d a t i o n o f C u ( C N ) " i s m o r e affected b y

3
2
sulphite. S o sulphite has a greater effect o n the o x i d a t i o n o f copper c y a n i d e . O n e effect o f
sulphite is to reduce the p r e c i p i t a t i o n o f copper o x i d e a n d so affect the o x i d a t i o n o f c o p p e r
cyanide. A t a concentration o f h y d r o x i d e b e l o w a certain l e v e l , sulphite completely
suppresses the p r e c i p i t a t i o n o f copper o x i d e . Therefore the p r o b a b l e anode reactions are:
Cu(CN)- - ( n
Cu(CN) " -
n
( n 2 )
+ e (n= 2 , 3, 4) (8-1)
184
S0 3
2
" + 2 0 H " -> S 0 ~ + H 0 + 2e 4
2
2 (8-2)
2Cu(CN) " " n

( n 2 )
+ 2CN~ -> 2C(C/V)~ "~ ( 1)
+ (CN) 2 (8-3)
(CN) 2 + 20H~ -> CN~ + CNOr + H 0 2 (8-4)
2Cu(CN) " - n
( n 2 )
+ S0 3
2
" + 20H -> 2 C u ( C N ) ' " n
( n 1 )
+ S0 4
2
" + H 0 2 (8-5)
Cu(CN)~ ( n _ 2 )
+ 20H" Cu(CN) " n
( n _ 1 )
+ Cu(OH) (or CuO + H 0 ) 2 2 (8-6)
R e a c t i o n 8-5 m a y undergo the f o l l o w i n g steps s i m i l a r to the r e a c t i o n between
f e r r i c y a n i d e and sulphite [337]:
Cu(CN) - - n
( n 2 )
+ S0 3
2
" -> C u ( C N ) - - S 0 " n
( n 2 )
3
2
(8-7)
C u ( C N ) " " S 0 " + Cu(CN) -'-

( n 2 )
3
2
x
2)
-> Cu(CN); "- SO; { 2)
+ Cu(CN); "- ( l)
(8-8)
Cu(CN) - n
( n - 2 )
S 0 " + 2 0 H ~ -> C u ( C N ) "
3 n
( n _ , )
+ S0 4
2
" + H 0 2 (8-9)
R e a c t i o n 8-1 is c a t a l y z e d b y sulphite ions w h e n n = 3. S 0 " m a y be b o u n d to 3

2
C u ( C N ) " a n d f o r m C u ( C N ) " S 0 ' w h i c h m a y be d i s c h a r g e d faster than C u ( C N ) \ S o the

3
2
3
2
3
2
3
2
o x i d a t i o n o f sulphite a n d copper c y a n i d e is s i g n i f i c a n t l y c a t a l y z e d . W i t h i n c r e a s i n g m o l e
ratio o f c y a n i d e to copper, the concentration o f C u ( C N ) " is decreased and so it is less 3

2
affected b y sulphite.
8.5 Summary
T h e a n o d i c b e h a v i o u r o f m i x e d sulphite and copper c y a n i d e is not j u s t the s u m o f
sulphite a n d copper c y a n i d e w h e n they are present separately i n the s o l u t i o n . S u l p h i t e
o x i d a t i o n is e n h a n c e d b y the presence o f copper c y a n i d e .
T h e effect o f sulphite o n l i m i t i n g the o x i d a t i o n o f copper c y a n i d e decreases w i t h
i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. T h i s is related to the shift i n the d i s c h a r g e d
species f r o m C u ( C N ) " to C u ( C N ) " w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to

3
2
4
3
copper.
S u l p h i t e i o n s affect the discharge o f C u ( C N ) " m o r e than that o f C u ( C N ) " . 3

2
4
3
S u l p h i t e is o x i d i z e d to sulphate. A t [ C u ] = a r o u n d 1 M , C N : C u m o l e ratio = 3 - 3 . 2 ,
[OH"] = 0.05-0.25 M , [ S 0 " ] = 0.4-0.6 M a n d the temperature = 5 0 - 6 0 C , the a n o d i c current

3
2
e f f i c i e n c y o f sulphite o x i d a t i o n reached 8 0 - 9 0 % . T h e above c o n d i t i o n s are suitable for

185
o b t a i n i n g a g o o d c o p p e r d e p o s i t i o n current e f f i c i e n c y a n d therefore w o u l d be suitable for
industrial application.
186
9. CONCLUSIONS
The following are the principal conclusions resulting from the study of the
thermodynamics o f copper cyanide, direct copper electrowinning from dilute cyanide
s o l u t i o n , c o p p e r e l e c t r o w i n n i n g f r o m concentrated copper c y a n i d e s o l u t i o n u s i n g alternative
a n o d i c reactions, the a n o d i c o x i d a t i o n o f sulphite, the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e a n d
the a n o d i c o x i d a t i o n o f m i x e d sulphite and copper c y a n i d e s o l u t i o n .
(1) T h e d i s t r i b u t i o n s and the e q u i l i b r i u m potentials o f copper c y a n i d e species, c a l c u l a t e d
u s i n g r e l i a b l e stability constants, are s h o w n to be functions o f the m o l e ratio o f c y a n i d e to
copper, total c y a n i d e concentration, p H and temperature.
W i t h i n c r e a s i n g C N : C u m o l e ratio, the d i s t r i b u t i o n o f copper c y a n i d e species shifts
more completely to the highly coordinated complex ( C u ( C N ) " ) at

4
3
a high cyanide
c o n c e n t r a t i o n than that at a l o w c y a n i d e concentration. W i t h i n c r e a s i n g C N : C u m o l e ratio,
the e q u i l i b r i u m potential for C u ( I ) / C u decreases r a p i d l y at a C N : C u m o l e ratio < about 4 a n d
m o r e s l o w l y at a C N : C u m o l e ratio > about 4. Increasing p H is s i m i l a r to i n c r e a s i n g free
c y a n i d e concentration.
I n c r e a s i n g temperature results i n decreasing the stability constants. Therefore the
d i s t r i b u t i o n o f c o p p e r c y a n i d e shifts to the l o w l y c o o r d i n a t e d c o m p l e x e s .
T h e potential measurements have c o n f i r m e d the v a l i d i t y o f the c a l c u l a t e d results.
I n the p H - potential diagrams. C u C N , Cu(CN) \ 2 C u ( C N ) - and C u ( C N ) '

3
2
4
3
can
p r e d o m i n a t e i n the different p H regions.
(2) T h e current e f f i c i e n c y o f copper d e p o s i t i o n o n a graphite felt electrode decreases w i t h
i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. D u e to the l o w c o n d u c t i v i t i e s o f the s o l u t i o n a n d
the graphite felt, the potential and current distribution o f copper throughout the 3-
d i m e n s i o n a l electrode are not u n i f o r m . T h e a c c u m u l a t i o n o f deposited c o p p e r o n the graphite
felt as the p l a t i n g proceeds s i g n i f i c a n t l y i m p r o v e s the c o n d u c t i v i t y o f the graphite felt a n d
increases the s p e c i f i c surface area benefiting copper d e p o s i t i o n .
C o p p e r c a n be e f f i c i e n t l y deposited o n the graphite felt f r o m s o l u t i o n s o f l o w
c o n c e n t r a t i o n (0.5 g -2 g L " C u ) at a h i g h m o l e ratio o f c y a n i d e to c o p p e r ( C N : C u = 3-9).

1
187
T h e energy requirement for copper d e p o s i t i o n w a s as l o w as 1-2 k w h / k g C u ( 1 0 0 0 - 2 0 0 0
k w h / t o n n e C u ) i n the current range 3 0 - 1 0 0 A m " . These v a l u e s c o m p a r e f a v o r a b l y w i t h that

2
obtained in conventional copper electrowinning from sulphuric acid-copper sulphate
solutions.
(3) O f four s a c r i f i c i a l species (sulphite, m e t h a n o l , thiocyanate a n d a m m o n i a ) , o n l y sulphite
can e f f e c t i v e l y l i m i t the o x i d a t i o n o f c y a n i d e . W h e n the c o m p o s i t i o n o f the e l e c t r o l y t e w a s
c o n t r o l l e d at 5 0 - 6 0 g L " Na2S0 , 70 g L " C u , C N : C u = 3-3.2, the a n o d i c current e f f i c i e n c y o f

1
3
1
c y a n i d e decreased f r o m about 100 % to 10-20 % i n the current range 2 5 0 - 5 0 0 A m " a n d the 2
temperature range 5 0 - 6 0 C . U n d e r the above c o n d i t i o n s , the c o p p e r d e p o s i t i o n current
e f f i c i e n c y w a s 90-96 % a n d the energy c o n s u m p t i o n w a s 0.76-1.0 k W h / k g C u . T h e a n o d i c
current e f f i c i e n c y o f c y a n i d e increased f r o m about 15 % to 56 % w i t h i n c r e a s i n g C N : C u
m o l e ratio f r o m 3 to 4.5 at [Cu] = 70 g L " . W i t h i n c r e a s i n g the current density, the a n o d i c

1
current e f f i c i e n c y o f c y a n i d e decreases greatly at a current density > 500 A m " a n d s l i g h t l y at 2
a current density < 500 A m" . T h e a n o d i c current e f f i c i e n c y o f c y a n i d e decreases s l i g h t l y

2
with i n c r e a s i n g temperature. The copper d e p o s i t i o n current e f f i c i e n c y decreases with
increasing C N : C u m o l e ratio and decreasing temperature. T h e presence of thiocyanate
increases the copper d e p o s i t i o n current e f f i c i e n c y at C N : C u m o l e ratio > 4.5.
(4) A t l o w potentials ( e.g. < 0.25 V vs. S C E at 25 C ) , the r e a c t i o n order for the o x i d a t i o n o f
sulphite is b e l o w 1 a n d decreases w i t h i n c r e a s i n g sulphite c o n c e n t r a t i o n . T h e T a f e l slope is
0.060 -0.065 V decade" . A t h i g h potentials (> 0.4 V v s . S C E ) , the r e a c t i o n order w i t h respect

1
to sulphite i o n s is 1 up to 0.4 M and the T a f e l slope is 0.19 - 0.21 V decade" . T h e r e a c t i o n 1
order w i t h respect to h y d r o x i d e ions is close to zero.
T h e a c t i v a t i o n energy for the k i n e t i c current decreases f r o m 85.2 k J m o l " at 0.2 V v s . 1
S C E to 45.3 k J m o l " at 0.6 V v s . S C E .

1
T h e d i f f u s i o n coefficients o f sulphite ions were 5.6, 8.6, 9.99 a n d 12.4 x 10" 10

m 2
s" 1
r e s p e c t i v e l y for 2 5 , 4 0 , 50 and 60 C .
Sulphite oxidation i n alkaline s o l u t i o n appears to undergo a radical-electron
m e c h a n i s m . A t l o w potentials, the adsorbed sulphite o x i d a t i o n is d o m i n a n t a n d at h i g h
potentials, the sulphite i o n s are o x i d i z e d d i r e c t l y o n the electrode surface.

188
(5) C o p p e r has a s i g n i f i c a n t catalytic effect o n c y a n i d e o x i d a t i o n . A t l o w potentials ( r o u g h l y
0 to 0.4 V v s . S C E ) , cuprous c y a n i d e is o x i d i z e d to c u p r i c c y a n i d e c o m p l e x e s w h i c h p r o d u c e
c y a n o g e n , w h i c h i n t u r n reacts w i t h h y d r o x i d e to f o r m cyanate. I n the m i d d l e p o t e n t i a l r e g i o n
( r o u g h l y 0.4 to 0.6 V v s . S C E ) , cuprous c y a n i d e is o x i d i z e d to c u p r i c o x i d e a n d cyanate. T h e
potential for the p r e c i p i t a t i o n o f copper o x i d e increases w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e
to copper. I n the h i g h potential r e g i o n (> about 0.60 V v s . S C E ) , o x y g e n is e v o l v e d at the
electrode. H o w e v e r , w h e n the c o n c e n t r a t i o n o f c y a n i d e w a s h i g h a n d the c o n c e n t r a t i o n o f
h y d r o x i d e w a s l o w , no copper o x i d e was precipitated and but c y a n o g e n gas w a s e v o l v e d .
T h e e l e c t r o c h e m i c a l k i n e t i c b e h a v i o r is dependent o n C N : C u m o l e ratio, p H a n d total
c y a n i d e c o n c e n t r a t i o n . A t C N : C u = 3 a n d [OH"] = 0.25 M , the T a f e l slope is about 0.12 V
decade" 1
a n d the r e a c t i o n order w i t h respect to C u ( C N ) " is one. C u ( C N ) " is d i s c h a r g e d o n
3
2
3
2
the electrode. T h e current and T a f e l slope decrease w i t h decreasing h y d r o x i d e c o n c e n t r a t i o n
a n d so h y d r o x i d e is i n v o l v e d i n the rate-determining step.
W i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper, the a n o d i c b e h a v i o u r o f c o p p e r
c y a n i d e changes. W h e n the m o l e ratio o f c y a n i d e to copper is larger than a certain v a l u e
w h i c h depends o n the total c y a n i d e concentration, e. g. about 4 at [ C N ] = 0.05 M a n d 3.5 at
[CN"] = 3.5 M , a T a f e l slope o f about 0.06 V decade" w a s o b s e r v e d o v e r the p o t e n t i a l range

1
0.1 - 0.25 V v s . S C E . A s e c o n d T a f e l slope o f about 0.17 -0.20 V decade" w a s n o t e d o v e r the

1
h i g h e r p o t e n t i a l range. T h i s change is related to the change i n the d i s t r i b u t i o n o f c o p p e r
c y a n i d e species. T h e current is p r o p o r t i o n a l to the c o n c e n t r a t i o n o f tetracyanide a n d a l m o s t
independent o f the total c y a n i d e concentration.
p H has little effect o n c y a n i d e o x i d a t i o n a n d the T a f e l slopes do not change w i t h p H .
In the p o t e n t i a l r e g i o n where copper o x i d e was precipitated, the current at a constant p o t e n t i a l
decreases w i t h decreasing h y d r o x i d e concentration a n d the r a t e - c o n t r o l l i n g step i n v o l v e s
hydroxide. The catalysis o f copper o x i d e is l i m i t e d with increasing copper cyanide
c o n c e n t r a t i o n and temperature.
(6) T h e a n o d i c b e h a v i o u r o f m i x e d sulphite a n d copper c y a n i d e is not j u s t the s u m o f sulphite
a n d c o p p e r c y a n i d e w h e n they are present separately i n the s o l u t i o n . S u l p h i t e o x i d a t i o n is
c a t a l y z e d b y the o x i d a t i o n o f copper c y a n i d e . It also affects the o x i d a t i o n o f c o p p e r c y a n i d e .

189
T h e effect o f sulphite o n the o x i d a t i o n o f copper c y a n i d e decreases w i t h i n c r e a s i n g m o l e ratio
o f c y a n i d e to copper. T h i s is related to the shift i n the d i s c h a r g e d species f r o m C u ( C N ) " to 3

2
C u ( C N ) " w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. S u l p h i t e i o n s affect the d i s c h a r g e

4
3
o f C u ( C N ) - m o r e than that o f C u ( C N ) \ A t [ C u ] = a r o u n d 1 M , C N : C u = 3 - 3 . 2 , [ O H ] =
3
2
4
3
0.05-0.25 M , [ S 0 " ] = 0.4-0.6 M and the temperature = 5 0 - 6 0 C , the a n o d i c

3
2
current
e f f i c i e n c y o f sulphite reached 8 0 - 9 0 % . I n r e l a t i o n to the r e c o v e r y o f c o p p e r f r o m c y a n i d e
g o l d l e a c h s o l u t i o n , it has been s h o w n that i n the e l e c t r o w i n n i n g step, it is p o s s i b l e to l i m i t
the o x i d a t i o n o f c y a n i d e b y u s i n g the o x i d a t i o n o f sulphite as a n alternative anode r e a c t i o n
w i t h a n electrolyte h a v i n g a c o m p o s i t i o n s i m i l a r to that i n d i c a t e d above. A t a current d e n s i t y
o f 2 5 0 to 5 0 0 A m " , copper c a n be e l e c t r o w o n at a current e f f i c i e n c y o f 95 % w i t h a energy

2
requirement o f about 0.8 k W h / k g C u .

190
10. RECOMMENDATIONS
M a n y i m p o r t a n t aspects have not been investigated due to the t i m e constraint.
R e g a r d i n g the fundamental aspects and the p r a c t i c a l a p p l i c a t i o n o f copper e l e c t r o w n n i n g , the
f o l l o w i n g areas need to be studied i n the future.
T h e m o r p h o l o g y a n d d i s t r i b u t i o n o f the copper deposit s h o u l d be s t u d i e d to better
understand the effect o f the copper deposit o n the copper d e p o s i t i o n current e f f i c i e n c y . T h e
B E T m e t h o d needs to be u s e d to measure the real surface area o f the graphite fibre w i t h a n d
w i t h o u t a copper deposit. T h e objective w o u l d be to understand h o w the c o p p e r deposits so
as to i m p r o v e the current e f f i c i e n c y o f copper d e p o s i t i o n . P o l a r i z a t i o n curves s h o u l d be
m e a s u r e d to better understand copper d e p o s i t i o n o n the graphite f r o m c y a n i d e s o l u t i o n . T h e
measurement s h o u l d be c a r r i e d out for current p a s s i n g i n the same a n d opposite d i r e c t i o n s to
the electrolyte f l o w . T h e effect o f temperature, C N : C u ratio, s u p p o r t i n g e l e c t r o l y t e , d e p o s i t e d
c o p p e r a n d f l o w rate s h o u l d be studied. H y d r o g e n e v o l u t i o n o n the graphite fibre w i t h a n d
w i t h o u t deposited copper c o u l d be studied u s i n g steady-state p o l a r i z a t i o n measurements.
T h e r e are some reports o n the effect o f thiocyanate [92, 9 4 - 9 6 , 98] a n d sulphite [90]
i n c o p p e r c y a n i d e p l a t i n g baths. H o w e v e r , there is a l a c k o f fundamental w o r k about h o w
thiocyanate and sulphite affect the copper d e p o s i t i o n process. T h e c o n d i t i o n s u s e d i n p l a t i n g
m a y not be the same as those e m p l o y e d i n copper e l e c t r o w i n n i n g . F o r e x a m p l e , the
d e p o s i t i o n t i m e for e l e c t r o w i n n i n g is m u c h l o n g e r than that for p l a t i n g . S o m e p h e n o m e n a
o c c u r r i n g i n e l e c t r o w i n n i n g m a y not be o b s e r v e d i n p l a t i n g . S o the effect o f thiocyanate a n d
sulphite o n the e l e c t r o w i n n i n g process needs to be studied c a r e f u l l y . Comprehensive
experiments s h o u l d be c o n d u c t e d u s i n g a s m a l l - s c a l e p i l o t c e l l operating c o n d i t i o n s to
o p t i m i z e the e l e c t r o w i n n i n g c o n d i t i o n .
H y d r o x i d e a n d sulphite catalyze the discharge o f C u ( C N ) " o n the anode. H o w e v e r , it

3
2
is not clear h o w they affect the a n o d i c o x i d a t i o n o f c o p p e r c y a n i d e . It is p o s s i b l e that
h y d r o x i d e a n d sulphite are b o u n d to C u ( C N ) " . S p e c t r o s c o p i c studies s u c h as R a m a n , U V ,

3
2
n u c l e a r m a g n e t i c resonance m i g h t be useful i n l e a d i n g to a n understanding o f the above
phenomena.
191
11. REFERENCES
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211
Appendix 1 Initial Economic Assessment
T h e e c o n o m i c assessment o f the copper e l e c t r o w i n n i n g process for g o l d e x t r a c t i o n is
based o n the process m a s s balance and process data ( s h o w n i n c a l c u l a t i o n section). T h e costs
o f c a p i t a l , maintenance a n d l a b o u r are estimated based o n s i m i l a r h y d r o m e t a l l u r g i c a l p l a n t
values. T h e c o m p o s i t i o n s a n d some properties o f treated ore are l i s t e d i n T a b l e 1. T h e v a l u e s
o f the materials i n v o l v e d are l i s t e d i n T a b l e 2 .
T a b l e 1 C o m p o s i t i o n s and properties o f ore
Au Soluble C u Compound Recovery Recovery o f Cyanide Recoverable
ofCu of A u Cu consumption cyanide
2 2 Vi C u S2 90% 90% 5.4 4.63
g/tonne k g / tonne 7 CuO

2
k g / tonne kg/tonne
T a b l e 2 V a l u e s o f the materials i n v o l v e d
Au value o f E c o n o m i c potential Value of recycled E c o n o m i c potential
cyanide without recovery o f recovered C u cyanide with recovery o f
consumed N a C N and C u value N a C N and C u
14.4 7.02 7.45 2.97 6.02 16.44
$/tonne $/tonne $/tonne $/tonne $/tonne $/tonne
F r o m T a b l e 2, i f c o m p l e x e d copper c y a n i d e a n d c y a n i d e are not r e c o v e r e d , the total
e c o n o m i c p o t e n t i a l is o n l y 7.45 $/tonne ore and the e c o n o m i c s o f the g o l d e x t r a c t i o n p r o c e s s
are p o o r due to the cost o f g o l d r e c o v e r y process. I f copper a n d c y a n i d e are r e c o v e r e d , the
total e c o n o m i c potential is about 16.44 $/tonne ore, m u c h h i g h e r than the former. T h e costs
for direct e l e c t r o w i n n i n g process are l i s t e d i n T a b l e 3. T h e total potential benefit i s 15.01
$/tonne ore i f c o p p e r a n d c y a n i d e are r e c o v e r e d u s i n g direct e l e c t r o w i n n i n g process.

212
T a b l e 3 C o s t o f direct e l e c t r o w i n n i n g process
Power Reagents Maintenance C a p i t a l cost L a b o u r cost T o t a l cost N e t benefit
0.167 0.126 0.08 0.335 0.167 0.80 15.01
$/ k g C u $/ k g C u $/ k g C u $/ k g C u $/ k g C u $/ k g C u $/ tonne ore
T h e costs for solvent extraction-electro w i n n i n g are l i s t e d i n T a b l e 4. T h e p o t e n t i a l
e c o n o m i c potential benefit is about 14.12 $/tonne
T a b l e 4 C o s t o f solvent e x t r a c t i o n - e l e c t r o w i n n i n g process
Cost o f C o s t o f solvent Cost o f A V R T o t a l cost net benefit
electrowinning extraction
0.59 0.464 0.23 1.29 14.12
$/ k g C u $/ k g C u $/ k g C u $/ k g C u $/ tonne ore
Conclusions
T h e i n i t i a l e c o n o m i c assessment o f the copper e l e c t r o w i n n i n g process for the g o l d
e x t r a c t i o n process w a s c o n d u c t e d based o n the mass balance. T h e e c o n o m i c benefit w i t h the
r e c o v e r y o f l e a c h e d copper and the r e c y c l e o f c o m p l e x e d c y a n i d e is m u c h h i g h e r t h a n that
w i t h o u t the r e c o v e r y o f copper c y a n i d e . T h e d e v e l o p e d copper e l e c t r o w i n n i n g processes
w o u l d greatly benefit the g o l d extraction process.

Calculation
The flowsheet of developed gold extraction process is shown below:
NaCN Recycled NaCN
A
barren
Leaching cyanide
Au and Cu leaching solution ki Au recovery process solution Recovery of cyanide
and copper
Cu
Au
Reagents: NaCN Au Cu NaOH Na S0

2 3 H S0
2 4 CaO
Price ($/kg) 1.3 8040 1.65 0.1 0.1 0.025 0.057
Molecular weight (g/mole): 49.01 197 63.54 39.998 126.04 98.076 56
Reagents: XI 78 Solvessi: Exxsol D-80:

Price ($/kg) 5 (per liter 1 (/liter) 1 (liter)
The prices of NaCN, NaOH, H2S04 and CaO are from Chemical Marker Reported,
The prices of Na2S03 is based on the consumption of sulphur and sodium hydroxide.
the prices of Au and Cu are from Financial Post, the prices of XI78,Solvessi annd Exssol D-80 from Henkel C
Au Cu
Contents in ore (kg/ton): 0.002 2
Half copper soluble in cyanide solution is CuO and the other is Cu S 2
Leaching reaction (Au cyanidation is neglected):
2CuO + 7 NaCN + H 0 = 2 Na Cu(CN) + NaCNO + 2 NaOH

2 2 3
C u S+ 7 NaCN + H20 + 1/20 = 2 Na Cu(CN) + NaCNS + 2 NaOH

2 2 2 3
Cyanide consumption: 1 mole Cu consumes 3.5 mole NaCN
Cyanide consumption per ton ore: 5.40 kg/ tonne ore
Value for cyanide consumption: 7.02 $/tonne ore
Recovery for Au: 0.90

Extractable Au: 0.0018 kg/tonne ore
Value of Au: 14.47 $/tonne ore
If cyanide and copper are not recovered,

Total economic potential: 7.45 $/tonne ore
If cyanide and copper are recovered,

Recovery for Cu: 90.00%
Extracted Cu: 1.80 kg/ tonne ore
Value of extracted Cu 2.97 $/tonne ore
Recycled cyanide: 4.63 kg/ tonne ore
Value of recycled cyanide: 6.02 $/tonne ore
Value for Cu and cyanide: 8.99 $/tonne ore
Total economic potential: 16.44 $/tonne ore
Cost for copper direct electrowinng process
The flowsheet of copper direct electrowinning processs is shown below:
Cu depleted solution ^ R e t u r n to gold leaching
Barren
solution* Cu electrowinning Cu Cu electrorefining Pure Cu
NaOH
Composition of barren cyanide leach solution:

Cu: 1 g/l
CN:Cu: 3
NaOH: 0.4 g/l
SCN ;
-
0.5 g/l
Power for electrowinning:
Cell reaction
(4/x)NaOH (anolyte) + 4 Na (Cu(CN) = (1/x)0 + 12 NaCN + 4 Cu + (2/x)H 0 + (4/x - 4) NaOH(catholyte)

2 3 2 2
where x = current efficiency for Cu

Current density : 60 A/nrf
Current efficiency: 50.00%
Cell voltage 3 V
Power consumption: 2.53 kwh/kg Cu
Power price: 0.06 $/kwh
Power cost: 0.15 $/kg/Cu
Power for electrorefining:

Reaction of electrorefining (in sulphate solution):
Anode: Cu = C u 2 +
+ 2e
Cathode: C u 2 +
+ 2e = Cu
Current density: 250 A/m 2
Current efficiency: 100.00%

Cell voltage: 0.3 V
Power cost: 0.015 $/kg Cu
Total power cost: 0.167 $/kg Cu

Reagent: NaOH
Consumption of NaOH : 2 mole NaOH/mole Cu

1.259 kg NaOH/kg Cu
Value of NaOH: 0.126 $NaOH/kg Cu
Capital cost for electrowinning

Cathode cost: 300 $/m 2
Anode cost: 200 $/m 2
Membrane Cost: 800 $/m 2
Miscellaneous 100 $/m 2
Total for electrowinning: 1400 $/m 2
Capital cost for electrorefining:

Cell cost: 200 $/m 2
Miscellaneous: 100 $/m 2
Total for refining: 600 $/m 2
Total for electrowinning & refini 2000 $/m 2
Assume the life of plant: 10 years

Capital cost per year: 200 $
Working days per year: 350 days/year
Cu produced per year 597.34 kg
Capital cost for Cu: 0.335 $/kg Cu
Maintenance Cost: 50 $/m year

2
Maintenance Cost for Cu: 0.08 $/kg Cu
Labour cost: 50 $/m year

2
Labour cost for Cu: 0.08 $/kg Cu
Total cost: 0.80 $/kg Cu
Benefit 15.01 $/tonne ore

C o s t for s o l v e n t extraction - e l e c t r o w i n n i n g p r o c e s s
The flowsheet of solvent extraction - electrowinning process is shown below:
1 1 1
Raffinate Na,S0 3 Ca(CN) 2
Barren Org. phase Electrolyte Bleed

solution* 3 4 HCN
T T
Org. phase ictrolyte ÛCN
H S02 4 NaOH NaOH H S0

2 4 CaO
where 1 -Loading, 2 - stripping, 3 - electrowinning, 4 - acidification - volatilization, 5 - neutralization
The process consists of solvent extraction (loading -1 and stripping - 2), electrowinning (3), and acidification
volatilization - regeneration (acidification - 4, netrualization - 5)
(1) Cost for electrowinning:

Power
Current density: 100 A/rrT
Current efficiency for Cu: 95.00%
Current efficiency for sulphite: 90.00%
Cell voltage: 1.7 volts
Power price: 0.060 $/kwh
Power cost: 0.045 $/kg Cu
Reagents: sulphite, NaOH

Reaction for electrowinning:
(y/x)Na S0 + 2Na Cu(CN) + 2NaOH + 2(1/x-1)H 0 = (y/x)Na S0 + 2Cu + (6-(1-y)/x)NaCN + (1/x-1)H

2 3 2 3 2 2 4 2
+((1-y)/x)NaCNO
where x - copper current efficiency, y - sulphite anodic current efficiency
Composition of electrolyte:
Cu: 70 g/l
NaOH: 4 g/l
CN:Cu mole ratio: 3
Na S0 :
2 3 30 g/l
SCN": 40 g/l
0.5 (after acidification-volatization-regeneration)
CN.Cu mole ratio for precipitate:
1 mole NaOH/mole Cu (for anodic reaction)
Consumption of NaOH: 0.63 kg NaOH/kg Cu
0.95 mole Na S0 /mole C (for anoidic reaction)
2 3
Consumption of N a S 0 :
1.88 Kg Na S0 /kg Cu
2 3
2 3
Bleed: 16.55 liters/kg Cu

Consumption of NaOH: 0.07 kg NaOH/kg Cu (for bleed)
217
Consumption of Na S0 : 2 3 0.50 kg Na S0 /kg Cu 2 4 (for bleed)

Value of NaOH: 0.07 $/kg Cu (for electrowinning)
Value of Na S0 : 2 3 0.24 $/kg Cu (for electrowinning)
Consumption of NaCN: 0.11 mole NaCN/mole Cu
0.081 kg NaCN/kg Cu
Value of NaCN: 0.11 $/kg Cu
Reagent cost for electrowinning: 0.41 $/kg Cu
Capital cost:
Anode cost: 200 $/m 2
Cell cost: 200 $/m 2
Miscellaneous cost: 200 $/m

2
Total capital cost: 1000 $/m

2
Assume the life of plant 10 years

Capital cost per year: 100 $/year
Working days per year: 350 days/year
Cu production rate: 1891.58 kg Cu/year
cost for Cu: 0.053 $/kg Cu
Maintenance cost: 100 $/year

Maintenance cost for Cu 0.05 $/Cu
Labour cost: 50 $/m year 2
Labour cost for Cu: 0.026 $/kg Cu
Total cost for electrowinning: 0.59 $/kg Cu
(2) Solvent-extraction:
Reagents:
Loading reaction:
Na Cu(CN) +2R NOAr (org.) + 1.5H S0 = (R N) Cu(CN) (org.) + 2HOAr(org.) + 1.5Na S0 + 2 H 0
2 3 4 2 4 4 2 3 2 4 2
where, R N - solvent extractant,

4
Stripping reaction:
(R N) Cu(CN) (org.) + 2HOAr + 2NaOH = Na Cu(CN) +2R NOAr(org.) + 2 H 0
4 2 3 2 3 4 2
Consumption of H S 0 : 2 4 1 mole H S0 / mole C (for solvent extraction)

2 4
1.54 kg H S0 /kg Cu 2 4
Value of H S 0 : 2 4 0.04 $ H S0 /kg Cu2 4
Consumption of NaOH: 2 mole NaOH/mole Cu (for stripping)

1.26 kg NaOH/kg Cu
Value of NaOH: 0.13 $ NaOH/kg Cu
Composition of barren solution: 1 g/ICu

Extraction efficiency for Cu: 99.00%
Volume of barren solution: 1010.10 liters/kg Cu
Loss of of organic phase: 0.0001 liter/liter barren solution
Loss of of organic phase for Cu: 0.10 liter/kg Cu
Composition of organic phase:
XI 78: 12%
Exxsol D-80: 70%
Solvessi: 18%
Consumption of XI 78: 0.012 liter/kg Cu

Value of XI 78 0.061 $/kg Cu
Consumption of Exxsol D-80: 0.071 liter/kg Cu
Value of Exxsol D-80: 0.071 $/kg Cu
Consumption of Solvesso: 0.018 liter/kg Cu
Value of Solvesso: 0.018 $/kg Cu
Cost of organic phase: 0.149 $/kg Cu
Total cost of reagent for SX: 0.314 $/kgCu
Capital cost: 0.050 $/kg Cu

Maintenance cost: 0.050 $/kg Cu
Labour cost: 0.050 $/kg Cu
Total cost for solvent extraction: 0.464 $/kg Cu
(3) Cost for acidfication volatilization regeneration (AVR):

Reagents: sulphuric acid, lime
Acidification reaction:
2NaCN + H S 0 = 2HCN + N a S 0
2 4 2 4
Consumption of H S 0 : 2 4 1.5 mole H S0 /mole Cu

2 4
2.32 kg H S0 /kg Cu
2 4
Value of H S 0 :
2 4 0.06 $/kg Cu
Neutralization reaction:
2HCN + CaO = Ca(CN) + H 0 2 2
Consumption of CaO: 1.5 mole CaO/mole Cu

1.32 kg CaO/kg Cu
Value of CaO: 0.075 $/kg Cu
Capital cost: 0.05 $/kg Cu

Maintenance cost: 0.05 $/kg Cu
Labour cost: 0.05 $/kg Cu
Total cost for AVR: 0.23 $/kg Cu
Total cost for SX-EW: 1.29 $/kg Cu
Benefit: 14.12 $/tonne ore

219
Appendix 2 Total Cyanide Analysis
Introduction
T h i s m e t h o d for total c y a n i d e a n a l y s i s consists o f (1) the separation o f c y a n i d e f r o m
s o l u t i o n s as H C N b y d i s t i l l a t i o n at p H 4 i n the presence o f E D T A , (2) a b s o r p t i o n o f H C N gas
i n caustic s o l u t i o n a n d (3) titration w i t h s i l v e r nitrate. E D T A s t r o n g l y c o m p l e x e s t r a n s i t i o n
m e t a l cations a n d helps facilitate d i s s o c i a t i o n o f c y a n i d e f r o m the metals. T h e m e t h o d is
l a r g e l y based u p o n a p u b l i s h e d procedure [338].
A c o m m o n l y a p p l i e d d i s t i l l a t i o n m e t h o d i n v o l v e s the use o f a s u l f u r i c a c i d - M g C l 2
s o l u t i o n . T h i o c y a n a t e i n s u c h a s y s t e m d e c o m p o s e s to f o r m C O S a n d other species. T h i s i n
t u r n h y d r o l y z e s to f o r m sulfide, w h i c h i n the basic absorber s o l u t i o n is o x i d i z e d to f o r m
e l e m e n t a l sulfur. U l t i m a t e l y , these sulfur species react w i t h c y a n i d e to r e f o r m t h i o c y a n a t e ,
w h i c h results i n a negative interference, or the sulfide m a y react w i t h s i l v e r d u r i n g the
titration to g i v e a b l a c k precipitate, o b s c u r i n g the endpoint. T h e use o f a p H 4 d i s t i l l a t i o n
s o l u t i o n m i n i m i z e s thiocyanate h y d r o l y s i s . T h i o c y a n a t e c a n also react w i t h o x i d a n t s s u c h as
nitrate to f o r m c y a n i d e a n d sulfate, a p o s i t i v e interference. T h i s c a n be o v e r c o m e with
s u l f a m i c a c i d ( N H S 0 H ) w h i c h acts as a r e d u c i n g agent. F r e e sulfide interferes b y d i s t i l l i n g

2 3
as H S . T h i s causes essentially the

2 same p r o b l e m as thiocyanate h y d r o l y s i s to C O S
m e n t i o n e d earlier. I n a d d i t i o n , sulfide i n the sample m a y be o x i d i z e d to e l e m e n t a l sulfur
w h i c h then c o n s u m e s c y a n i d e as above. C o p p e r above a t h r e s h o l d c o n c e n t r a t i o n causes
losses o f c y a n i d e also. T h i s c a n be o v e r c o m e b y u s i n g s m a l l amounts o f s a m p l e . S u l f i t e i n
the presence o f copper s i g n i f i c a n t l y l o w e r s the amount o f cyanide recovered in the
d i s t i l l a t i o n . B a r i u m c h l o r i d e c a n be u s e d to precipitate sulfite as B a S 0 . B a S 0
3 3 is r e m o v e d
f r o m the s a m p l e before d i s t i l l a t i o n b y centrifugation or f i l t r a t i o n , since B a S 0 3 is s o l u b l e i n
a c i d s o l u t i o n . T h i o s u l f a t e i f present i n sufficient amount c a n interfere b y h y d r o l y z i n g d u r i n g
d i s t i l l a t i o n to f o r m sulfur d i o x i d e and p o s s i b l y other r e d u c e d sulfur species.
S o m e m e t a l c y a n i d e c o m p l e x e s , m o s t n o t a b l y those o f C o a n d A u d o not liberate
c y a n i d e d u r i n g the d i s t i l l a t i o n i n v o l v i n g E D T A . It m a y be that s o m e o f the c y a n i d e b o u n d to

220
m e r c u r y is not liberated either. I f samples are h i g h i n m e r c u r y , a test w i t h a m e r c u r y c y a n i d e
s o l u t i o n s h o u l d be done to see what k i n d o f recoveries are a c h i e v e d .
Sample Preservation and Handling
I d e a l l y the s a m p l e s h o u l d be a n a l y z e d r i g h t after it is c o l l e c t e d . T h i s is not a l w a y s
p r a c t i c a l . I n order to preserve the s a m p l e it s h o u l d be treated w i t h N a O H s u c h that the p H is
>12. T h e s a m p l e s h o u l d then be stored i n a refrigerator i n the dark. U n d e r these c o n d i t i o n s it
c a n keep for several w e e k s . T o prevent sulfide interference the s a m p l e must be treated w i t h a
m e t a l salt s u c h as P b ( 0 C C H )
2 3 2 or P b C 0 3 or C d C 0 3 etc. to precipitate a m e t a l s u l f i d e . T h e
s a m p l e must then be filtered r i g h t a w a y to r e m o v e the s o l i d since freshly f o r m e d m e t a l
sulfides are p r o n e to air o x i d a t i o n , a g a i n f o r m i n g elemental sulfur. T h e treatment to r e m o v e
sulfide s h o u l d be done p r i o r to adjusting the b a s i c i t y o f the sample.
Apparatus and Reagents
A d i a g r a m o f the d i s t i l l a t i o n apparatus is s h o w n i n F i g u r e 1. G r o u n d glass j o i n t s are
preferred for a l l c o n n e c t i o n s , but rubber stoppers, w r a p p e d w i t h t e f l o n tape, are also suitable.
A l l c o n n e c t i o n s i n v o l v i n g g r o u n d glass j o i n t s o n l y s h o u l d be l i g h t l y greased w i t h s i l i c o n e
grease. C o n n e c t i o n s i n v o l v i n g rubber stoppers s h o u l d not be greased.

221
Figure 1 Schematic diagram o f distillation
T h e f o l l o w i n g is a list o f e q u i p m e n t for the d i s t i l l a t i o n :
- v a r i a b l e v o l t a g e transformer
-heating m a n t l e (e.g. 380 watts)
- 1 - L r o u n d b o t t o m flask w i t h g r o u n d glass standard taper 2 4 / 3 9 j o i n t or e q u i v a l e n t
- m a g n e t i c s t i r r i n g plate
-teflon coated m a g n e t i c stir bar
-glass beads (3-5 m m )
- t w o - n e c k adapter, w i t h standard taper 2 4 / 3 9 j o i n t s
-thistle tube, seated s n u g l y i n #5 rubber stopper, teflon taped
-water c o o l e d c o n d e n s o r (preferably A l l i h n type, but a straight tube c o n d e n s o r w i l l d o ) , fitted
i n s i d e #5
stopper, t e f l o n taped
-glass tube, ~ 6 m m i . d . , seated i n rubber stopper (as per d i a g r a m )
-coarse p o r o s i t y gas d i s p e r s i o n tube fitted into a t w o - h o l e #8 rubber stopper
- b u t y l o r neoprene rubber t u b i n g to connect glass tube a n d d i s p e r s i o n tube
- 3 8 X 2 0 0 m m test tube
V
222
-water aspirator (a m a n i f o l d h a v i n g at least s i x l i n e s c a n be attached to a s i n g l e aspirator)
- t u b i n g a n d s t o p c o c k or needle v a l v e connected to aspirator a n d the #8 stopper (see d i a g r a m )
-centrifuge (eg 3 0 0 0 r p m ) w i t h c a p a c i t y for 5 0 - m L sample tubes
-centrifuge tubes, p l a s t i c , 50 m L
T h e titration requires the a b i l i t y to dispense s m a l l v o l u m e s , readable to w i t h i n 0.001
m L , or less preferably 0.01 m L . T h i s is a c c o m p l i s h e d w i t h a n autotitrator. T h e f o l l o w i n g
e q u i p m e n t for the titration is used for titration:
- R a d i o m e t e r A B U 80 A u t o b u r r e t t e , e q u i p p e d w i t h a 1 0 - m L buret, or e q u i v a l e n t e q u i p m e n t
- 2 5 0 - m L E r l e n m e y e r flask
- m a g n e t i c s t i r r i n g plate
-teflon coated m a g n e t i c stir bar
T h e f o l l o w i n g a n a l y t i c a l reagent grade a n d d e i o n i z e d water are used t h r o u g h the a n a l y s i s :
- d e i o n i z e d water
-0.25 M N a O H (10 g / L )
-1 M N a O H (40 g / L )
-0.2 M B a C l 2 s o l u t i o n (49 g / L )
-sulfamic acid ( N H S 0 H ) 2 3
-Na EDTA2H 0
2 2
- m e t h y l red i n d i c a t o r (1 g / L i n ethanol, 9 5 % )
-acetate buffer (54 g N a 0 C C H 3 H 2 0 + 100 m L g l a c i a l acetic a c i d , to 1 L , p H adjusted to

2 3
4.00 w i t h
NaOH)
-0.018 M A g N 0 3 s o l u t i o n (3.06 g / L ) ; prepare w e e k l y a n d store i n a glass v e s s e l i n the dark,
- p - d i m e t h y l a m i n o b e n z a l rhodanine i n d i c a t o r (200 m g / L i n acetone)
-standard N a C l s o l u t i o n (0.04 M = 2.3377 g / L prepared e v e r y t w o w e e k s f r o m NaCl,
p o w d e r e d a n d d r i e d 2 4 hours at 120C)
-chromate i n d i c a t o r (50 g / L K C r 0 ) 2 4
Procedure
223
P r e s e r v e the s a m p l e u p o n c o l l e c t i o n as o u t l i n e d i n the a p p e n d e d material. The
presence o f sulfide c a n be ascertained b y d i p p i n g a p i e c e o f l e a d acetate test paper m o i s t e n e d
w i t h p H 4 buffer into a p o r t i o n o f the sample. I f the paper turns b r o w n or b l a c k , P b S has
f o r m e d a n d sulfide is present. I f sulfide is d e t e r m i n e d to be present, the s a m p l e s h o u l d be
treated to r e m o v e it right a w a y . O n c e this has been a c c o m p l i s h e d , adjust the a l k a l i n i t y o f the
s a m p l e , i f necessary, so that the p H is above 12. Store samples i n t i g h t l y sealed p l a s t i c bottles
i n a refrigerator a n d i n the dark.
Set up the d i s t i l l a t i o n apparatus as s h o w n i n F i g u r e 1, but do not attach the r o u n d
b o t t o m flask yet. A d d 50 m L o f 0.25 M N a O H to the absorber test tube. A t t a c h this to the
glass tube b y means o f a 2-3 c m l e n g t h o f rubber t u b i n g . M a k e sure a l l c o n n e c t i o n s are
secure. A d d a t e f l o n stir bar (2 c m ) a n d ~5 glass beads (3-5 m m ) to the flask. A d d e n o u g h
d e i o n i z e d water to the flask s u c h that the v o l u m e o f water p l u s s a m p l e i n the flask w i l l be
- 5 0 0 m L A d d e n o u g h 1 M N a O H to ensure than the p H is above 12. M i x w e l l .
M a k e a n appropriate d i l u t i o n o f the sample as r e q u i r e d s u c h that a c o n v e n i e n t v o l u m e
w i l l c o n t a i n at least 0.5 m g o f c y a n i d e (but preferably 1 m g or m o r e ) as C N , a n d not m o r e
than 5 m g o f copper. C o p p e r acts to l o w e r the a m o u n t o f c y a n i d e r e c o v e r e d , perhaps b y
o x i d a t i o n . T h e s a m p l e s h o u l d be added to a s o l u t i o n o f N a O H s u c h that the p H o f the f i n a l
s o l u t i o n w i l l be >12. I f the sample also contains sulfite, B a C l 2 must be added d u r i n g the
d i l u t i o n step. T h e a m o u n t o f B a 2 +
added s h o u l d e x c e e d the sulfite c o n c e n t r a t i o n b y a factor o f
at least f i v e . I f there is m u c h sulfate present, the B a 2 +

s h o u l d e x c e e d the sulfite p l u s sulfate b y
>5 t i m e s . I f n e e d be, a m o r e concentrated s o l u t i o n o f B a C l 2 m a y be used. A d d the B a C l 2
s o l u t i o n after the s a m p l e has been added to the N a O H s o l u t i o n . M i x w e l l a n d m a k e u p to
v o l u m e . T h e v o l u m e o c c u p i e d b y the s o l i d precipitate w i l l be n e g l i g i b l e i f the sulfite p l u s
sulfate content is not greater than the c y a n i d e content. C e n t r i f u g e the s a m p l e to settle out the
precipitate. T h e t i m e r e q u i r e d depends o n the speed o f the centrifuge. T h e supernatant l i q u i d
s h o u l d be clear. I f n e e d be the s a m p l e m a y be filtered instead. A 0.2 u m p o r e size m e m b r a n e
filter ( n y l o n or teflon) s h o u l d suffice. Pipette a p o r t i o n o f the centrifuged or filtered s a m p l e
into the r o u n d b o t t o m flask.

224
A t t a c h the flask c o n t a i n i n g the sample to the rest o f the apparatus. Start the air p u r g e
b y adjusting the v a l v e or stopcock attached to the absorber. T h e rate o f b u b b l i n g s h o u l d be
about 3-4 b u b b l e s per second. A froth s h o u l d f o r m o n the absorber s o l u t i o n that is about 0.5
c m t h i c k . G e n t l y stir the s o l u t i o n . A d d 2 g o f s u l f a m i c a c i d t h r o u g h the top o f the thistle tube.
W a s h it i n w i t h water. S t i r u n t i l d i s s o l v e d . A d d 5 g o f N a E D T A 2 H 0
2 2 a n d stir u n t i l
d i s s o l v e d . A fine w h i t e precipitate m i g h t g r a d u a l l y f o r m , p r o b a b l y the protonated E D T A .
A d d 6 drops o f m e t h y l r e d indicator. W a s h this i n . I f the s o l u t i o n turns red, it is a c i d w i t h
respect to m e t h y l red. I n this case add 1 M N a O H u n t i l the c o l o u r b e c o m e s j u s t pale orange.
I f the s o l u t i o n turns faint y e l l o w u p o n a d d i n g the indicator, it is r e l a t i v e l y basic. I f this o c c u r s
a d d 0.5 M H S 0 2 4 u n t i l the c o l o u r is a g a i n faint orange. F i n a l l y a d d 55 m L o f the acetate
buffer a n d w a s h this i n .
Stop the stirring a n d put the heating m a n t l e i n place. H e a t the s o l u t i o n to b o i l i n g . It is
better to heat the s o l u t i o n at h i g h heat (e.g. f u l l p o w e r w i t h the 380 watt heating m a n t l e s ) for
an i n i t i a l p e r i o d o f t i m e a n d then to b a c k o f f the p o w e r a f e w m i n u t e s p r i o r to b o i l i n g
c o m m e n c i n g . A t the onset o f b o i l i n g the flask f i l l s w i t h v a p o u r s a n d this c a n cause l i q u i d to
rise i n the thistle tube. T h i s s h o u l d be a v o i d e d . A d j u s t the air s u c t i o n rate i f necessary. O n c e
b o i l i n g has s t a b i l i z e d readjust the s u c t i o n rate i f need be to k e e p a froth o n the absorber
s o l u t i o n that is about 0.5 c m t h i c k . A d j u s t the heat s u c h that the r e f l u x rate is about 2-3 drops
per s e c o n d f r o m the condensor a n d the vapours do not rise m o r e than ~3/4 o f the w a y u p the
c o n d e n s o r . R e f l u x the s o l u t i o n for 2 hours. C h e c k o c c a s i o n a l l y to be sure the s y s t e m is
stable. A f t e r t w o h o u r s r e m o v e the heating m a n t l e and continue the air p u r g e for at least 15
minutes.
R e m o v e the thistle tube. T u r n o f f the aspirator s u c t i o n a n d b r e a k the connection
b e t w e e n the absorber a n d the aspirator t u b i n g , D e t a c h the absorber f r o m the glass t u b i n g .
Q u a n t i t a t i v e l y transfer the contents o f the absorber into a 2 5 0 - m L E r l e n m e y e r flask. T h e gas
d i s p e r s i o n tube s h o u l d be r i n s e d t h o r o u g h l y w i t h d e i o n i z e d water, e.g. w i t h the use o f a large
pipet b u l b to f l u s h it. R i n s e the glass c o n n e c t i n g tube w i t h a little water also a n d p o u r this
into the E r l e n m e y e r flask. M a k e up the v o l u m e o f the s o l u t i o n to about 150 m L . A d d 15
drops o f rhodanine i n d i c a t o r s o l u t i o n . Titrate the s o l u t i o n w i t h standardized 0.018 M A g N 0 3

225
s o l u t i o n u n t i l the y e l l o w c o l o u r turns into a l i g h t orange-pink. T h e endpoint is sharp a n d
clear, e v e n t h o u g h the c o l o u r s are light. It is r e c o m m e n d e d that the analyst p r a c t i c e the
p r o c e d u r e o n a n N a C N / N a O H s o l u t i o n w h i c h is a n a l y z e d b y titration w i t h a n d w i t h o u t
d i s t i l l a t i o n . T h e results s h o u l d agree w i t h i n about 9 9 % after some f a m i l i a r i z a t i o n .
A b l a n k c o r r e c t i o n is required. P o u r about 50 m L o f 0.25 M N a O H into a 2 5 0 - m L
E r l e n m e y e r flask. A d d e n o u g h water to m a k e the v o l u m e - 1 5 0 m L . A d d 15 drops o f
rhodanine i n d i c a t o r s o l u t i o n a n d titrate w i t h 0.018 M N a O H as above. W i t h a little p r a c t i c e
b l a n k values o f <0.1 m L c a n be a c h i e v e d r o u t i n e l y . T h e titration r e a c t i o n and c a l c u l a t i o n are:
Ag +
+ 2CN" = Ag(CN) " 2
[CN-] = { [ A g N 0 ] X ( V t - V b ) X 2 X D F } / V s
3
[ C N ] = c y a n i d e content ( m o l / L ; m u l t i p l y b y 26.018 for C N i n g / L )
[ A g N 0 ] = s i l v e r titrant c o n c e n t r a t i o n ( m o l / L )
3
V t = titration v o l u m e ( m L )
V b = blank correction volume ( m L )
V s = sample v o l u m e ( m L )
D F = d i l u t i o n factor
T h e s i l v e r nitrate s o l u t i o n m a y be standardized b y any c o n v e n i e n t m e t h o d . C h e c k this
d a i l y . O n e w a y is titration w i t h standardized N a C l . S o d i u m c h l o r i d e c a n be d r i e d i n a n o v e n
at 120 C for 2 4 hours and stored i n a desiccator. Pipette 4.00 m L o f 0.04 M N a C l into a
beaker. A d d 12 m L o f water. A d d 0.50 m L o f the chromate i n d i c a t o r . Titrate the s o l u t i o n
w i t h the 0.018 M A g N 0 3 u n t i l the l e m o n y e l l o w c o l o u r turns into a m o r e ochre y e l l o w . T h e
change is subtle, but distinct. A t the endpoint A g C r 0 2 4 forms, w h i c h is a d a r k r e d s o l i d .
Potentiometric endpoint detection m a y also be e m p l o y e d . A g a i n a b l a n k c o r r e c t i o n is
required. A n adequate b l a n k titration m a y be m a d e b y a d d i n g 25 m L o f water to a beaker a n d
0.25 g o f C a C 0 . T h e latter p r o v i d e s a w h i t e b a c k g r o u n d s i m i l a r to that f o r m e d b y A g C l

3
d u r i n g the standardization. A d d 0.50 m L o f chromate i n d i c a t o r . Titrate as a b o v e . Blank

226
v a l u e s o f -0.1 m L m a y be anticipated. T h e s t o i c h i o m e t r y for the standardization is one to
one:
Ag +
+ Cf = AgCl
[Ag ] = { [ C l - ] X 4 } / { V t - V b }
+
4 = v o l u m e o f c h l o r i d e standard ( m L )
[ A g + ] = s i l v e r concentration ( m o l / L )
[C1-] = standard c h l o r i d e concentration ( m o l / L )
V t = titration v o l u m e ( m L )
V b = blank correction volume ( m L )
O n c e the c y a n i d e titration is c o m p l e t e d , the apparatus s h o u l d be t h o r o u g h l y r i n s e d
w i t h d e i o n i z e d water. It is then ready for the next analysis.

227
Appendix 3 Copper Titration using EDTA
1. Method
E x c e s s E D T A is a d d e d to a copper s o l u t i o n ( a l l C u i n +2 state; no strong c o m p l e x i n g
agents present). T h e r e s i d u a l E D T A is titrated w i t h standardized Z n 2 +

u s i n g x y l e n o l orange as
the i n d i c a t o r . T h e p H must be c o n t r o l l e d at 5 - 5.5 or else the i n d i c a t o r w i l l not respond
p r o p e r l y [339].
2. Reagents
0.015 M E D T A s o l u t i o n ( N a ^ D T A 2 H 0 (over 99.7 %) is d r i e d at 80 C for several h o u r s to

2
r e m o v e r e s i d u a l traces o f water)
0.2 % x y l e n o l orange s o l u t i o n as i n d i c a t o r
1 M sodium cyanide solution
1 g / L z i n c nitrate standard s o l u t i o n
solid hexamine
3. Procedure
Standardization o f E D T A
Pipette 5 m L o f E D T A s o l u t i o n to a 2 5 0 - m L beaker w i t h a stir bar a n d m a k e up 70 m L
s o l u t i o n , a d d s o l i d h e x a m i n e ( O . l g ) to the beaker, measure the p H w i t h a c a l i b r a t e d p H p r o b e
( p H 7 a n d 4 buffers), adjust the p H o f the s o l u t i o n to 3 to 4 w i t h 1 M N a O H , a d d about 0.1 g
s o l i d h e x a m i n e ( a v o i d a d d i n g m u c h h e x a m i n e because it c o m p e t e s w i t h E D T A for m e t a l i o n s
at too h i g h concentration), adjust the p H to 5.5 w i t h 0.1 - 1 M H C 1 or 1 M N a O H as r e q u i r e d ,
a d d 3 drops o f x y l e n o l orange s o l u t i o n (the s o l u t i o n b e c o m e y e l l o w ) a n d f i n a l l y is titrated
w i t h z i n c nitrate standard s o l u t i o n f r o m a y e l l o w or y e l l o w i s h c o l o u r to p i n k . T h r o u g h o u t the
titration m a i n t a i n the p H at 5.0 - 5.5.
C o p p e r titration
228
A n excess o f E D T A s o l u t i o n is added to a n a c i d s a m p l e s o l u t i o n c o n t a i n i n g 2 - 1 0 mg
c o p p e r to 2 5 0 - m L beaker a n d m a k e up 70 m L s o l u t i o n , insert the p H probe. A d j u s t the p H 3 -
4. A d d 0.1 g s o l i d h e x a m i n e . p H is adjusted to 5.5 w i t h s o d i u m h y d r o x i d e . A d d x y l e n o l
orange i n d i c a t o r , b a c k titrated w i t h z i n c nitrate s o l u t i o n f r o m y e l l o w to p i n k .
Blank Correction
A d d 7 0 m L o f water to a 2 5 0 - m L beaker c o n t a i n i n g a stir bar. A d d 0.1 g h e x a m i n e . Insert the
p H probe. A d j u s t the p H to 5.5. A d d 2 drops o f the x y l e n o l i n d i c a t o r . Titrate to a p i n k i s h -
p u r p l e c o l o u r w i t h Z n . A v a l u e o f about 0.006 m L w a s obtained. T o get a better i d e a o f the

2 +
b l a n k i n the presence o f copper, titrate the b l a n k s o l u t i o n w i t h a c o m b i n a t i o n o f Z n 2 +

+ Cu 2 +
e a c h at 0.0075 M . T h e c o n c e n t r a t i o n need not be k n o w n w i t h h i g h p r e c i s i o n since the b l a n k
error is s m a l l .
229
Appendix 4 Determination of Sulphite Ions by the Iodimetric Method
1. M e t h o d
T h e i o d i m e t r i c d e t e r m i n a t i o n is based o n the f o l l o w i n g equations [340]:
S0 " + I + H 0 = S0
3
2
2 2 4
2
' + 2 F T + 21"
H S 0 - + I + H 0 = S 0 " + 3 H + 21"
3 2 2 4
2 +
M o l e c u l a r i o d i n e is o n l y s l i g h t l y s o l u b l e i n water (0.0013 M at 2 0 C ) , but its s o l u b i l i t y is
greatly e n h a n c e d b y c o m p l e x a t i o n w i t h i o d i d e .
I (aq) + T = I -
2 3 K = 0.007
P u r e p o t a s s i u m iodate a n d K I are used to g i v e a standard s o l u t i o n o f I \ A d d i t i o n o f excess 3
strong a c i d ( p H about 1) g i v e s a quantitative reverse d i s p r o p o r t i o n a t i o n r e a c t i o n i n w h i c h I " is 3
formed:
I C V + 81" + 6 F f = 3I - + 3 H 0 3 2
A freshly a c i d i f i e d s o l u t i o n o f iodate p l u s i o d i d e c a n be u s e d to standardize t h i o s u l p h a t e a n d
titrate sulphite. T h e reagent must be used i m m e d i a t e l y , o r else air o x i d a t i o n o f f takes p l a c e .
T h e excess o f the above s o l u t i o n is added to titrate s o d i u m sulphite. T h e excess o f i o d i n e is
t h e n titrated w i t h standard s o d i u m thiosulphate. T h e r e a c t i o n i s :
2 S 0 " + I = S 0 " + 21"

2 3
2
2 4 6
2
S t a r c h is u s e d as a n i n d i c a t o r for i o d i n e . I n a s o l u t i o n w i t h n o other c o l o r e d species, it is
p o s s i b l e to see the c o l o r o f 0.00005 M I \ W i t h a starch i n d i c a t o r , the l i m i t o f d e t e c t i o n is

3
extended b y about a factor o f ten.
2. Reagents
(1) 25 g N a S 0 . 5 H 0 + 10 M m g H g l
2 2 3 2 2 i n one liter o f freshly b o i l e d , d e i o n i z e d water ( p H
is adjusted to about 9 w i t h 0.1 - 0.2 g o f s o l i d N a ^ C ^ ) . T h i s m a k e s a 0 . 1 M t h i o s u l p h a t e
s o l u t i o n . Store i n a n amber glass bottle.
(2) 5.35g o f K I 0 3 ( 9 9 . 9 % , d r i e d at 120 C for 1 hour) i n one liter o f water.
(3) S o l i d p o t a s s i u m i o d i d e .
(4) S t a r c h i n d i c a t o r s o l u t i o n . ( M i x 2 g o f s o l u b l e starch and 2 m g o f H g l 2 w i t h 20 m L o f
water. P o u r this into 2 0 0 m l o f b o i l i n g water and continue to b o i l u n t i l clear. Prepare this
fresh every other day.)
(5) 4 M h y d r o c h l o r i c a c i d s o l u t i o n .
(6) 1 M B a C l 2 solution
3. P r o c e d u r e
1. S t a n d a r d i z a t i o n o f 0.1 M thiousulphate.
(1) Pipette 20 m l o f 0.025 M K I 0 3 into 2 5 0 - m l E r l e n m e y e r flask a n d add 1.6 g K I a n d 10 m l
o f 4 M HC1.
(2) I m m e d i a t e l y titrate w i t h the thiosulphate s o l u t i o n u n t i l the c o l o u r is straw y e l l o w .
(3) A d d e n o u g h water to m a k e the v o l u m e up to 2 0 0 m L and add 2 m L o f starch s o l u t i o n .
(4) C o n t i n u e the titration u n t i l the last trace o f blue c o l o u r disappears.
2. T i t r a t i o n o f S u l p h i t e
(1) Pipette 10 m l o f 0.025 M K I 0 3 into 2 5 0 - m l flask and a d d 1.6 g K I u n t i l the c o m p l e t e
d i s s o l u t i o n o f K I . A d d 5 m l 4 M H C 1 and m i x b r i e f l y .
(2) A d d the sulphite s o l u t i o n sample (react w i t h about 75 % o f i o d i n e ) s l o w l y w i t h g o o d
stirring, titrate the excess i o d i n e w i t h standard s o d i u m thiosulphate u s i n g starch i n d i c a t o r .
3. D e t e r m i n a t i o n o f S u l p h i t e i n C o p p e r C y a n i d e S o l u t i o n
(1) T a k e the s o l u t i o n c o n t a i n i n g about 0.001 m o l e o f sulphite to a 50 m L test tube, a d d 2 0
m L o f 1 M N a O H a n d 20 m L o f I M B a C l . 2
(2) P u t the test tube into a centrifuge to separate B a S 0 3 f r o m the s o l u t i o n , transfer the
s o l u t i o n to a v o l u m e t r i c flask for c y a n i d e analysis, add some water into a test tube a n d
p u l l out the s o l u t i o n into the v o l u m e flask a n d repeat the above w a s h i n g p r o c e d u r e 4 -5
t i m e s . W a t e r s h o u l d be gently added to a v o i d stirring B a S 0 . I f the w h i t e precipitate is

3
m i x e d w i t h the s o l u t i o n , the s o l u t i o n s h o u l d be c e n t r i f u g a l i z e d again. T h e alternative is to
use a m e m b r a n e filter to separate the s o l i d f r o m the s o l u t i o n .

231
(3) W a s h the s o l i d into a 2 5 0 - m L E r l e n m e y e r flask to m a k e up about 100 m L o f s o l u t i o n a n d
use a m a g n e t i c stir bar to disperse the s o l i d particles c o m p l e t e l y .
(4) A d d 25 m L o f 0.025 M K I 0 3 and 1.6 g o f K I into the flask
(5) A d d 50 m L o f 4 M H C 1 a n d w a i t for o v e r 1 m i n u t e to m a k e the c o m p l e t e o x i d a t i o n o f
sulphite to sulphate ( B a S 0 is o x i d i z e d to B a S 0 ) b y I . ( B a S 0 + 2 H = B a
3 4 2 3
+ 2 +
+ S0 2 +
H 0 , S 0 + I + H 0 = S 0 - + 21" + 2 H and B a
2 2 2 2 4
2 + 2 +
+ S0 4
2
' = BaS0 )4
(6) titrate the excess i o d i n e w i t h standard s o d i u m thiosulphate u s i n g starch i n d i c a t o r . T h e
a n a l y z e d result is 96 - 98 % o f the actual v a l u e f r o m the analysis tests.

232
Appendix 5 Calculation of Activity Coefficient Using Pitzer Method
T h e excess G i b b s free energy i s due to the i o n i c i n t e r a c t i o n a n d c a n be expressed b y the
f o l l o w i n g e q u a t i o n [326, 3 2 8 ] :
G ex
1 1
- = n f(i) w + E^( H 7 -rE S I/',.*"/';"*
/ w +
(!)
K 1 n
wi j n
wi j k
where:
n w - k i l o g r a m s o f solvent
n - m o l e s o f solutes i , j , k
1 = 0.5 2>,z, 2
Z j - i o n i c charge
m, = n Q / n f w ionic molality
Q - the n u m b e r o f m o l e s o f solvent i n a k i l o g r a m (55.51 for water)
f(I) - f u n c t i o n d e s c r i b i n g the long-range electrostatic effects as a f u n c t i o n o f temperature i n
the D e b y e - H i i c k e l manner.
A,y - t e r m for d e s c r i b i n g the short-range i n t e r i o n i c effects as a f u n c t i o n o f i o n i c strength to
d i s p l a y the type o f b e h a v i o u r caused b y the h a r d core effect. It is a s s u m e d to be s y m m e t r i c a l .
p i j k - t e r m f o r t r i p l e i o n interactions w h i c h ignores a n y i o n i c strength dependence. It i s
a s s u m e d to be s y m m e t r i c a l .
T h e c h e m i c a l potentials o f species i (p^) is expressed as:
H = ju- + RTlna, = + RTm(m ) M iYi (2)
w h e r e u , i s the c h e m i c a l potential i n the solute ( m o l a l i t y ) standard state, a the a c t i v i t y , m f (
the m o l a l i t y a n d y the a c t i v i t y coefficient. F o r the solvent as water, the c h e m i c a l p o t e n t i a l i s :

l
Mw = ju +RT\na
w w (3)
where p w i s the standard potential o f pure water. T h e a c t i v i t y o f water a^, i s c o m m o n l y
expressed b y the o s m o t i c coefficient
^ = -(Q/I,)lntf (4)
where Znij c o v e r s a l l solute species. T h e total G i b b s free energy o f m i x i n g f r o m the standard
is
K G = n (M - Ml) + T.n (ju - ju-) = RT(n \na + E , In a,.)

X w w i i w w (5)
233
From Equations 2, 4 and 5 and ni; = njQ/n , the following equation is obtained: w
A G = RTT,n [-0 + ki(m y )]

mb I i i (6)
The Gibbs free energy from mixing can be divided into two parts: one part independent of y {
or <j) which gives the primary dependence of the Gibbs free energy on solution composition,
and a second part for the corrective terms in (1-(|>) and Vj. The later can be called an excess
Gibbs free energy which can expressed as:
G = A G + RTT,n,(l - him,) = RTZn^l -0+\ny,)

ex
mlx (7)
The activity coefficient (Y;)is derived from the Gibb's excess free energy equation according
Equations 1 and 7:
l n / i =
ifÊ~ ~2 =Z f +
% ' -'
m z +
? 5X(y4 + 3/W (8)
where:
f - df/dl
A,' - dA-i/dl
y
After rearranging, the activity coefficients for anion A can be expressed as:
^7 A =Af 7
+T^B H2Y m z )C ]cA J a a cA + Y rn (20 +^m^ )
J a Aa Aac
(9)
c a c c
where:
f
^-A*[[i7&7+!ta<1+W7)]
A = ( l / 3 ) ( 2 ^ V J / 1 0 0 0 ) ( e / ekTf' - the Debye-Huckel constant for the osmotic
1/2 2 2
0 0 w
coefficient, 0.3915, 0.4023, 0.4103,0.4190 respectively for 25, 40, 50 and 60 C.

b = 1.2
a - subscript denoting anions

c - subscript denoting cations
By = J3 + ^ f - [ l - (1 + a,
0 V7) expC-a, V7)] + ^ 7 [1 - (1 - a2 V7) exp(-a V7)]
2
By = - T ^ [ - 1 + (1 + a, V7 + 0.5a )exp(-a, V7)] + 2

+ (1 + a V7 + 0.5a )exp(-a V7)]
2
2
2 2
in the case of Equation 9, i denotes A

234
a , = 2.0 for 1-1, 2 - 1 , 1-2,3-1, 4-1 electrolyte
a 2 = 0.0 for 1-1, 2 - 1 , 1-2,3-1, 4-1 electrolyte
Po - P i t z e r ' s parameter
Pi - P i t z e r ' s parameter
P - P i t z e r ' s parameter for 2-2 electrolyte

2
C = C*/[2(Z Z-) +
1/2
]
C * - P i t z e r ' s parameter
6 - P i t z e r ' s i n t e r a c t i o n parameter for l i k e charged i o n s
\\i - P i t z e r ' s ternary parameter
(j) c a n be c a l c u l a t e d b y the f o l l o w i n g equation and so the a c t i v i t y o f water c a n be c a l c u l a t e d :
^ - l + & )" P//'+2XI m m (Bt 1

1
c a + C> ) +
Zc Ym m.(6
c
c +16 +'Ym y/ .
u
a ) + Y Ymm (6
a d
a .+16'. + Y\m i//
c
c .)]
where:
6 is P i t z e r ' s parameter for u n - s y m m e t r i c a l m i x i n g w h i c h c a n be n e g l e c t e d for s o l u t i o n s o f
electrolytes w h i c h are s i m i l a r or not too different
Bt =fi +/?, exp(-a,V7)

0 + /3 2 exp(-ar 2 V7)
(X mz) = X OT
k I +
2 c c
z
T a b l e 1 P i t z e r ' s parameters for N a S 0 2 4 and N a O H [326, 328]
dpo/5T ( N a 5p,5/5T (Na , S 0 )

+ 2
Po ( N a , S 0 - )
+
4
2 +
, S0 ') 4
2
P, ( N a , S 0 " )
+
4
2
4
0.01958 0.00236 1.113 0.00563
Po ( N a +
, OH") 5po/5T ( N a , O H " )
+
P, ( N a +
, OH) ap^/dT ( N a , O H ) +
0.0864 0.0007 0.253 0.000134

C* ( N a , S 0 - )
+
4
2
dC*/ST (Na ,SO 0 + 2 C* ( N a +

, OH") aC*/5T ( N a , OH")
+
0.00497 -0.000486 0.0044 -0.000189

C (Na ,S0 ") +
4
2
C ( N a , OH")
+
6 ( O H \ S0 ") 4 vi; ( O H \ S 0 4
2
,Na ) +
0.00176 -0.0022 -0.013 -0.009

235
Appendix 6 Measurement of the Kinematic Viscosity
T h e k i n e m a t i c v i s c o s i t y is m e a s u r e d u s i n g C a n n o n - F e n s k e routine v i s c o m e t e r ( S i z e
2 5 ) . T h e v i s c o m e t e r constant ( C ) at 24 C is 0.001802 m m s" a n d its temperature c o e f f i c i e n t

0
2 2
( B ) is 4 6 x l 0 " C . Therefore the v i s c o m e t e r constant at temperature T is C ( 1 - B ( T - T ) . T h e

6
0 0
k i n e m a t i c v i s c o s i t y is the efflux t i m e m u l t i p l i e d b y the v i s c o m e t e r constant.
T h e e x p e r i m e n t set-up is s h o w n i n the f o l l o w i n g figure:
S c h e m a t i c d i a g r a m for the v i s c o s i t y measurement
M e a s u r i n g procedure:
1. C l e a n the v i s c o m e t e r u s i n g acetone a n d b y p a s s i n g pure N 2 gas t h r o u g h the instrument to
r e m o v e the f i n a l traces o f solvents. P e r i o d i c a l l y , traces o f o r g a n i c deposits are r e m o v e d
with chromic acid.
2. I f there is a p o s s i b i l i t y o f lint, dust, or other s o l i d m a t e r i a l i n the l i q u i d s a m p l e , filter the
s a m p l e t h r o u g h a sintered glass filter or fine m e s h screen.

236
3. T o charge the s a m p l e into the v i s c o m e t e r , invert the instrument a n d a p p l y s u c t i o n to tube
G , i m m e r s i n g tube A i n the l i q u i d sample, and d r a w l i q u i d to m a r k E . W i p e c l e a n a r m A ,
a n d t u r n the instrument to its n o r m a l v e r t i c a l p o s i t i o n .
4. P l a c e the v i s c o m e t e r into the holder, a n d insert into the constant temperature bath.
5. A l l o w about 15 minutes for the sample to c o m e to the bath temperature.
6. A p p l y s u c t i o n to tube A (or pressure to tube F ) a n d d r a w the l i q u i d s l i g h t l y a b o v e m a r k
C.
7. T o measure the efflux t i m e , a l l o w the l i q u i d s a m p l e to f l o w freely d o w n past m a r k C ,
m e a s u r i n g the t i m e for the m e n i s c u s to pass f r o m m a r k C to m a r k E .
8. A c h e c k r u n m a y be m a d e b y repeating steps 6 and 7.
9. C a l c u l a t e the v i s c o s i t y o f the sample b y m u l t i p l y i n g the efflux t i m e b y the v i s c o m e t e r
constant.
237
Appendix 7 Calculation of Liquid Junction Potential
T h e l i q u i d j u n c t i o n p o t e n t i a l arises f r o m t w o different i o n i c s o l u t i o n s ( c o n c e n t r a t i o n
difference, or different electrolytes) i n contact due to the different m o b i l i t i e s o f i o n s across
the junction. The reference electrode is often isolated from the working electrode
c o m p a r t m e n t b y a salt b r i d g e or a L u g g i n c a p i l l a r y . H e n c e a l i q u i d j u n c t i o n p o t e n t i a l exists
a n d affects the potential measurement o f the w o r k i n g electrode. T h e direct p o t e n t i o m e t r i c
measurement o f a j u n c t i o n potential is not p o s s i b l e because o f the i m p o s s i b i l i t y o f d i r e c t l y
m e a s u r i n g a s i n g l e electrode potential. H o w e v e r , it is p o s s i b l e to estimate j u n c t i o n potentials
i n d i r e c t l y or to m a k e c a l c u l a t i o n s based o n assumptions about the g e o m e t r y a n d d i s t r i b u t i o n
o f the i o n s i n the r e g i o n o f the j u n c t i o n . T h e basic equation r e l a t i n g the j u n c t i o n p o t e n t i a l (Ej)
b e t w e e n Phases p and a to the transport number, charge a n d a c t i v i t y o f the i o n s f o r m i n g the
junction is:
RT
E =Efi- * lY -d\na
E = t i (1)
FH J
J
a ^ Z;
Z.
w h e r e t is the transport n u m b e r (related to the m o b i l i t y o f the i o n ) o f the i t h i o n , Z j the

;
a l g e b r a i c v a l u e o f the charge o n the i o n , a the a c t i v i t y o f the i o n , a n d n the n u m b e r o f the

(
i o n s . It is too d i f f i c u l t to s o l v e the above equation because w e have to k n o w h o w the
c o n c e n t r a t i o n , the a c t i v i t y coefficient a n d the transport n u m b e r o f e a c h species v a r y i n the
j u n c t i o n r e g i o n . I f the a c t i v i t y coefficients are taken to be u n i t y a n d the c o n c e n t r a t i o n o f e a c h
i o n is a s s u m e d to v a r y l i n e a r l y f r o m C a to C , the l i q u i d j u n c t i o n p o t e n t i a l c a n be e x p r e s s e d
p
as [332]:
J
~ F
Skktcf-cn i k k c
' , ' (2)
RT r^[cf-cn i k Kef
F
Ekktcf-cn sk-k-cT
w h e r e X is the e q u i v a l e n t c o n d u c t i v i t y o f the species i (|Zi|UjF), C " and C , the concentrations
{
p
i n Phases a a n d p. F o r a c c u r a c y , it is better to use the m o b i l i t y or e q u i v a l e n t c o n d u c t i v i t y i n
the t w o phases. H o w e v e r , these data are l a c k i n g . A s a n a p p r o x i m a t i o n , the equivalent

238
conductivities can be used to estimate the liquid junction potential. The equivalent
c o n d u c t i v i t i e s for S 0 4
2
\ S0 3
2
\ CI", O H " , N a +
and K +
at infinite d i l u t i o n are 80, 80, 76.34,
197.6, 50.1 a n d 73.6 x l O " m m h o equiv."' [330] T a b l e 1 lists the l i q u i d j u n c t i o n potentials at

4 2
different potentials. T h e concentration o f saturated K C 1 s o l u t i o n is 4.16 M at 25 C [325].
T a b l e 1 L i q u i d j u n c t i o n potentials for different c o m p o s i t i o n s b e t w e e n the solutions i n the
c e l l a n d saturated p o t a s s i u m c h l o r i d e s o l u t i o n (Ej = E c e l l -E S C E )
Na S0 / M
2 4 Na 2 S0 " / M
3 NaOH / M Ej/mV
1 0.05 0.25 0.2
1 0.1 0.25 0.2
1 0.2 0.25 ~0
1 0.4 0.25 -0.2
1 0.5 0.25 -0.3
1 0.1 0.025 -1.8
1
0.1 0.025 -1.9
239
Appendix 8 Figures
0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0

(a) 25 C (b) 4 0 C
1600
1400 4-
4900 rpm
1200
3600 rpm
< 2500 rpm
~ 1000
-*- 1600 rpm
'55
c 800 -a- 900 rpm
CD
B 400 rpm
+J
C 600 100 rpm
->-
CD
3 400
200
0
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8
(c) 50 C (d) 60 C
F i g u r e A - l P o l a r i z a t i o n c u r v e s o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 50 a n d
60 C . E l e c t r o l y t e : 0.05 M N a S 0 , 0.25 M N a O H a n d 1 M N a S 0 .
2 3 2 4
240
3500
3000
4900 rpm
3600 rpm
2500
2500 rpm
- X - 1600 rpm
2000
-*- 900 rpm
1500 --
-- 400 rpm
-1- 100 rpm
1000
500
0
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
(a) 25 C (b) 40 C
7000
6000
-4900 rpm
_ 3600 rpm
E 5000
_ 2500 rpm
_ 1600 rpm
4000
_ 900 rpm
-400 rpm
g 3000
+^ _ 100 rpm
c
a>
fc 2000
3
o
1000
0.0 0.2 0.4 0.6 0.8 1.2 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
F i g u r e A - 2 P o l a r i z a t i o n curves o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 50 a n d

60 C . E l e c t r o l y t e : 0.2 M N a S 0 , 0.25 M N a O H a n d 1 M N a S 0 .
2 3 2 4
241
9000
8000
t 7000
^ 6000
~ 5000
e
S 4000 |
O 3000
O 2000
1000
0
0.2 0.4 0.6 0.8 1 0.2 0.4 0.6 0.8
(a) 25 C (b) 40 C
12000
-4900 rpm
_ 3600 rpm
-2500 rpm
-1600 rpm
-900 rpm
_ 400 rpm
^ 4000 1
_ 100 rpm
0.2 0.4 0.6 0.8 1 0.4 0.6 0.8

(c) 50 C (d) 60 C
Figure A-3 Polarization curves of sulphite oxidation using rotating disk at 25, 40, 50 and
60 C. Electrolyte: 0.4 M N a S 0 , 0.25 M N a O H and 1 M N a ^ O ^
2 3
242
10000 -r
(a) 25 C (b) 40 C
12000 14000
(c) 50 C (d) 60 C

60 C . E l e c t r o l y t e : 0.5 M N a S 0 , 0.25 M N a O H and 1 M N a S 0 .
2 3 2 4
243
(c) 50 C (d) 60 C
F i g u r e A - 5 B a c k g r o u n d current density v s . potential o n graphite rotating d i s k at 2 5 , 4 0 ,

50 a n d 60 C . E l e c t r o l y t e : 0.25 M N a O H and 1 M N a ^ .
244
(a) 25 C (b) 40 C
(c) 50 C (d) 60 C

60 C . E l e c t r o l y t e : 0.2 M NajSOj, 0.05 M N a O H and 1 M N^SO^
245
(a) 25 C (b) 4 0 C
14000
12000
. 4900 rpm
_ 3600 rpm
10000
- 2500 rpm
. 1600 rpm
8000
- 900 rpm
c
- 400 rpm a>
TJ 6000
. 100 rpm
C
2 4000
L_
3
o 2000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
F i g u r e A - 7 P o l a r i z a t i o n c u r v e s o f sulphite o x i d a t i o n u s i n g rotating d i s k at 2 5 , 4 0 , 50 a n d
60 C . E l e c t r o l y t e : 0.4 M N a S 0 , 0.05 M N a O H and 1 M N a S 0 .
2 3 2 4
246
3.0 0.0045
y = 0.98x + 3.09
2.9 0.0040
0.0035
2.8
y = 0.98x + 2.84
0.0030
2.7
2.6 \ 0.0025
y=0.99x + 0.00145
y = 0.97x + 2.57 < 0.0020
2.5 y = 0.99x + OÔOOSl'
0.0015
0.60 Vvs.SCE
2.4 , 0.50 V vs. S C E
.0.55 Vvs.SCE 0.0010
. 0.55 V vs. S C E
2.3 A 0.50 V vs. SCE 0.0005
A 0.60 V vs. S C E
2.2 0.0000
-0.3 -0.2 0.0005 0.001 0.0015
Log (1-i/i,)
(i, / A m" )- 2 1
(la) 40 C
(1 b) 4 0 C
0.0030
+ 3.37
3.0 0.0025
2.9 = 1.01X + 3.11 y= 1.04x +0.00138

0.0020
2.8
0.0015
2.7 <
-
1.01X + 2.85 0.0010 ,0.50 V vs. S C E
2.6
,0.60 V vs. SCE ,0.55 V vs. S C E
y= 1.02X +0.000426
2.5 4- ,0.55 V vs. SCE 0.0005 A 0.60 V vs. S C E
A 0.50 V vs. SCE
2.4 0.0000
-0.6 -0.5 -0.4 -0.3 -0.2 -0.1 0.0005 0.001
2-1
Log (1-i/i,) (i, / A nr*)- V
(2a) 50 C (2 b) 50 C
3.3 0.0025
, 0.60 vs. SCE ,0.50 V v s . S C E
y=1.04x + 3.54
3.2 . 0.55Vvs.SCE .0.55 V v s . S C E
0.0020
i 0.50 V vs. SCE 0.60 V vs. S C E
/* y=1.06x + 3.31
A
3.1
0.0015 y= 1.01 x +0.000871

3.0
X y = 1.01x + 3.06
2.9 < 0.0010
y=1.02x + O000495
2.8
0.0005 000293
2.7
2.6 0.0000
-0.7 -0.5 -0.3 -0.1 0.1 0.0002 0.0004 0.0006 0.0008 0.001 0.0012
Log (1-i/i,) (i/Arn )- 2 1
(3a) 6 0 C (3 b) 6 0 C
F i g u r e A - 8 L o g (i) v s . L o g (1-1/i,) (a) and 1/i v s . 1/i, (b) at 4 0 (1), 50 (2) a n d 6 0 (3) C
a n d the c o r r e s p o n d i n g fitted f u n c t i o n (y vs. x ) are i n the d i a g r a m . E l e c t r o y t e : 0.1 M
N a S 0 , 0.25 M N a O H and 1 M N a S 0 .
2 3 2 4
247
350
-CuOcoated Graphite (0.05 M C N ) - CuO-coated Graphite (0.05 M C N ) -
300
Graphite (0.05 M C N ) -
Graphite (0.05 M C N ) -
. Graphite (0.05 M C N a n d CN:Cu = 3)

-
250 . Graphite (0.05 M C N a n d CN:Cu = 3)

-
200
150 .
100 .
50
0
0.2 0.4 0 0.2 0.4 0.6 0.8
(a) 25 C (b) 4 0 C
600 600
.CuO-coated Graphite (0.05 M C N ) CuO-coated Graphite (0.05 M CN )
500 . Graphite(0.05 M C N ) -
500 Graphite (0.05 M C N ) -
. Graphite (0.05 M C N a n d CN:Cu = 3)

-
E Graphite (0.05 M C N a n d CN:Cu = 3)

-
400 .
< 400
in
300 . g
-a
300
200 S 200
3
100
o
100
0.2 0.4 o.e 0.8 0.2 0.4 0.6 0.8

(c) 50 C (d) 60 C
Figure A - 9 C o m p a r i s o n o f the effects o f C u O - c o a t e d graphite a n d c o p p e r i o n s i n the

s o l u t i o n at 100 r p m and different temperatures. E l e c t r o l y t e : 0 . 2 5 M N a O H a n d 1 M
Na S0 .
2 4
248
Binding energy / eV
Figure A - 1 0 X P S s p e c t r u m o f the precipitate prepared at 25 C a n d 0.5 V v s . S C E .

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 .
2 4
Binding Energy / eV

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 .
2 4
938 936 934 932 930
Binding energy / eV

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . 2 4
Cu2p
23000"
22000-
21000- / CuO \
ty / cps
20000-
19000-
C3
n 18000- r/ Cu(OH) 2 V
17000-
16000"
15000-
14000-
i 1 1 r 1 1
1 1
1 1
1 1 r-
939 938 937 936 935 934 933 932 931
Binding Energy / eV

E l e c t r o l y t e : 0.05 M N a C N , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . 2 4
250
1800 -
1600 .
1600 rpm-CuO
CN 1400 -
E 400 rpm-CuO
<

1200 -
. . . . 100 rpm-CuO
& 1000 - . -1600rpm(noCuO) I
V)
c0) 800 -
-a
c 600 .
3
400 -
o
200 -
0
0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Potential vs.SCE/V Potential vs. SCE/V
(a) 25 C (b) 4 0 C
12000 .
0.2 0.4 0.6 0.8 0.2 0.4 0.6 0.8 1.0

(c) 50 C (d) 60 C
F i g u r e A - 1 4 P o l a r i z a t i o n curves o n the graphite c o a t e d w i t h C u O a n d n o C u O i n the

absence o f c y a n i d e a n d c o p p e r at different temperatures. E l e c t r o l y t e : 0.25 M N a O H a n d 1
M Na S0 .
2 4
251
1200 3000
.4900 rpm 4900 rpm
1600 rpm 2500 3600 rpm
CM'
. 400 rpm IN 2500 rpm
'
< -100 rpm 'E 1600 rpm
800 - < 2000 900 rpm
- . 400 rpm
rrent densi
600 -- c 1500 . . . . 100 rpm

Q)
TJ
400 - O 1000
3
3
o o
200 500
0.0 0.2 0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 40 C
10000
9000 . 4900 rpm

3600 rpm
^ 8000
J 7000 -
2500 rpm
1600 rpm
3
\
f '.
900 rpm
6000
400 rpm
.' .'iv.
'35
c 5000 . . . . 100 rpm A
CD 2 1 i\ ' .' ^ .'
//\ ' ' '
"2 4000
c
CD
t 3000
3
0
2000 1
' f.
Mi y /
1000
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
Figure A-15 Polarization curves at different rotational speeds and temperatures.

Electrolyte: 0.05 M C N \ CN:Cu mole ratio = 3.5, 0.25 M NaOH and 1 M N a S 0 . Keys: 2 4
1 - no precipitation of copper oxide, 2 - precipitation of copper oxide and 3 - evolution of

oxygen.
252
1400 2500
-4900 rpm 4900 rpm
1200 3600 rpm
. 1600 rpm
CN 2000 2500 rpm
. 400 rpm
E
1000 1600 rpm
. 100 rpm
< 900 rpm
& 800 1500 400 rpm
to
10 c . . . . 100 rpm
c 0)
CD TJ
TJ 600 C 1000
c
CD 400 3
O o 500
200
0 4
0.2 0.4 0.6 0.8 0.4 0.6 0.8
(a) 25 C (b) 40 C
14000
4900 rpm
12000 3600 rpm
2500 rpm
E
10000 1600 rpm
< 900 rpm 2
3* 8000 400 rpm
to
c . . . . 100 rpm
// / / \
to
TJ 6000
c
P 4000
///' /'
3 1
o 2000 i
!; .' ^ " v
/V*''
0
0.4 0.6 0.8 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
Figure A - 1 6 P o l a r i z a t i o n curves at different rotational speeds and temperatures.

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 3.5, 0.25 M N a O H a n d 1 M N a S 0 . K e y s : 2 4
1 - n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f copper o x i d e a n d 3 - e v o l u t i o n o f
oxygen.
253
1400 T 2000
1800
1200 -- -4900 rpm
.4900 rpm
1600
_ 3600 rpm
. 3600 rpm
1000 -.
. 2500 rpm E 1400 . 2500 rpm
< .1600 rpm
< -1600 rpm
800 -- 1200
. 900 rpm
CO 900 rpm &
c
.400 rpm
'55 1000 -400 rpm
c
TJ 600 -- CD . 100 rpm
. 100 rpm a 800
c ->
CD c
k_ 400 -- 600
3
o 200 --
400
200
0 -. 0
0.2 0.4 0.6 0.8 1.2 0.4 0.6 0.8 1.2
(a) 25 C (b) 40 C
3500
3000 4900 rpm

3600 rpm
2500 2500 rpm
<
1600 rpm
2000 900 rpm
to
c
CD 400 rpm
~ 1500 . . . . 100 rpm
->
c
1000
500
0
0.2 0.4 0.6 0.8 0.0 0.4 0.6 0.8 1.0 1.2
Potential vs. SCE/V Potential vs.SCE/V
(c) 50 C (d) 60 C
Figure A-17 P o l a r i z a t i o n curves at different rotational speeds a n d temperatures.

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 6, 0.25 M N a O H a n d 1 M N a S 0 . K e y s : 1 2 4
- n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f c o p p e r o x i d e , 3 - e v o l u t i o n o f
o x y g e n a n d 2+3 - c o p p e r o x i d e and o x y g e n appeared almost at the same p o t e n t i a l .
254
2000
1800
.4900 rpm
4900 rpm
. 3600 rpm 1600
E 3600 rpm
. 2500 rpm < 1400 2500 rpm
_ 1600 rpm
1200 1600 rpm
. 900 rpm CO
900 rpm
.400 rpm c 1000
400 rpm
. 100 rpm 0)
D 100 rpm
800
600
400
200
0
0.4 0.6 0.8 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
4000 -
2 +3
3500 - 4900 rpm 2 +3 /
4900 rpm
3600 rpm
CN 3600 rpm
3000 -
E 2500 rpm
2500 rpm
< . ..1600 rpm
. . 1600 rpm 2500 -
!......
900 rpm 900 rpm
c
CO
400 rpm 2000 - 400 rpm
i:r ' / d>
100 rpm 100 rpm
ij 1 T3 1500 -
/' C ft s
//
Ii !
If / 3 1000 -
1 1
o
500 -
- -~
0 .
0.2 0.4 0.6 0.8 1.2
o.o 1.0 0.2 0.4 0.6 0.8 1.2
(c) 50 C (d) 60 C

E l e c t r o l y t e : 0.05 M C N " , C N : C u m o l e ratio = 12, 0.25 M N a O H a n d 1 M N a S 0 . K e y s : 2 4
1 - n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f c o p p e r o x i d e , 3 - e v o l u t i o n o f
o x y g e n a n d 2+3 - c o p p e r o x i d e and o x y g e n appeared almost at the same p o t e n t i a l .
255
0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.1

(a) 25 C (b) 4 0 C
1800 1800
-4900 rpm 4900 rpm
1600 _ 1600 rpm 1600 J- __1600 rpm
. 400 rpm ... 400 rpm
1400 f 1400
_ 100 rpm 2 .-100 rpm
< 1200 < 1200
f 100 1000
800 a 800
600 S 600
3
400 O 400
o
200 200
0 0 4
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.1 1.2
(c) 50 C (d) 60 C

E l e c t r o l y t e : 0.05 M C N \ C N : C u m o l e ratio = 3, 0.05 M N a O H a n d 1 M N a S 0 . K e y s : 1 2 4
- no p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f copper o x i d e a n d 3 - e v o l u t i o n o f
oxygen.
256
1400 1800
4900 rpm -4900 rpm
1600 -|
1200 3600 rpm _ 3600 rpm
2500 rpm 1400 . 2500 rpm
1000 1600 rpm -1600 rpm
900 rpm 1200 900 rpm /
800 400 rpm .400 rpm
CO
1000
. . . . 100 rpm . 100 rpm
c
CD 600 800
13
->
c 600
400
9
O 400
200
200
0
0.4 0.6 0.8 1.0 0.2 0.4 0.6 0.8 1.0
Potential vs.SCE/V Potential vs.SCE/V
(a) 25 C (b) 4 0 C
2000 3000
-4900 rpm
1800
. 3600 rpm
1600 . 2500 rpm
1400 .1600 rpm

. 900 rpm
1200
-400 rpm
1000 . 100 rpm
800
600
O 400
200 4-
0.0 0.2 0.4 0.6 0.8 1.0 0.4 0.6 0.8 1.2
(c) 50 C (d) 60 C

- n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f copper o x i d e a n d 3 - e v o l u t i o n o f
oxygen.
257
(a) 25 C (b) 4 0 C
3000 3500
4900 rpm 4900 rpm

3000
CN 2500 3600 rpm 3600 rpm
'E ....... 2500 rpm 2500 rpm
<
- 2000 1600 rpm
2500
1600 rpm
900 rpm 900 rpm
to 2000
c 400 rpm 400 rpm
a> 1500 . . . . 100 rpm
u . . . . 100 rpm
1500
c
0)
L_
k_ 1000 --
3 1000
O
500 500
0
0.0 0.2 0.4 0.6 0.8 1.0 0.0 0.2 0.4 0.6 0.8
(c) 50 (d) 60 C

1 - n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f c o p p e r o x i d e a n d 3 - e v o l u t i o n o f
oxygen.
258
0.2 0.4 0.6 0.8 1.0 0.4 0.6 0.8

(a) 25 C (b) 4 0 C
).0 0.2 0.4 0.6 0.8 1.0 1.2 0.2 0.4 0.6 0.8 1
(c) 50 C (d) 60 C

oxygen.
259
450 600
400
-4900 rpm
500
' 350 .3600 rpm
. 2500 rpm E
<
300 .1600 rpm
< 400
. 900 rpm
in 250 m
c -400 rpm c
<u 300
CD
-100 rpm a
~ 200 4-1
c
200
| 150 CD
3 3
100 100
50 o
0.4 0.6 0.8 1 1.2 0.4 0.6 0.8 1.0 1.2

(a) 25 C (b) 4 0 C
700 800
700 -4900 rpm

600 -4900 rpm
. 3600 rpm
_ 3600 rpm
600 . 2500 rpm
500 . 2500 rpm
-1600 rpm
_ 1600 rpm < . 900 rpm
> 400 . 900 rpm
in 500 -400 rpm
- 4 0 0 rpm c
c . 100 rpm
CD CD
. 100 rpm TJ
D 300 400
+J
C 300
c
CD CD
t 200 3 200
3
o o
100 4- 100 .1
0.4 0.6 0.8 1.2 0.0 0.2 0.4 0.6 .0.8 1.0 1.2
(c) 50 C (d) 60 C

oxygen.
260
900 1200
800 2
4900 rpm 4900 rpm
1000
700 3600 rpm 3600 rpm
2500 rpm
E
2500 rpm
600 < 800
1600 rpm . .-1600 rpm
900 rpm 900 rpm
500 CO
400 rpm
c 600 4- 400 rpm
/f/ f
yti: -
--
400 . . . 100 rpm CD 100 rpm
TJ
300
C
CD 400 -- 1 ^
3
200
o 200 - -
100
0 I I 1
0.2 0.4 0.6 0.8 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
1200 1400
. 4900 rpm 1200 .4900 rpm

1000
. 3600 rpm . 3600 rpm
. 2500 rpm
E
1000 . 2500 rpm
800 . 1600 rpm
<
.1600 rpm
. 900 rpm 800 900 rpm
. 400 rpm co
600 c - 400 rpm
CD
. 100 rpm 600 . 100 rpm
c
<D 400 400
200 200
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.4 0.6 0.8 1.2
(c) 50 C (d) 60 C

E l e c t r o l y t e : 0.05 M C N ' , C N : C u m o l e ratio = 12, 0.01 M N a O H a n d 1 M N a S 0 . K e y s : 2 4
1 - n o p r e c i p i t a t i o n o f copper o x i d e , 2 - p r e c i p i t a t i o n o f copper o x i d e a n d 3 - e v o l u t i o n o f
oxygen.
261
E
<
CO
c
<L>
a
c

o
0.4 0.6 0.8 0.2 0.4 0.6

Potential vs. SCE/V Potential vs.
(a) 25 C (b) 4 0 C
18000
16000 -4900 rpm

. 1600 rpm
14000
. 400 rpm
12000 . 100 rpm
10000
8000
6000
4000
2000
0
0.4 0.6 0.8 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C

E l e c t r o l y t e : 0.5 M C N " , C N : C u m o l e ratio = 3, 0.25 M N a O H a n d 1 M N a S 0 . K e y s : 1 -
2 4
no precipitation o f copper oxide, 2 - precipitation o f copper oxide and 3 - evolution o f

oxygen.
262
2000
0 10 20 30 40 50 60
2-theta
F i g u r e A - 2 6 X - r a y d i f f r a c t i o n pattern o f the a n o d i c precipitate prepared under the

c o n d i t i o n s : 3 M C N " , 1 M C u (I), 0.25 M N a O H , 0.5 M N a S 0 , 25 C , 0.5 V v s . S C E ,
2 4
a n d 100 r p m .
10000
X
9000 I o
o
8000
X
7000 o
o
6000 -|
5000
o
4000 X
o
-' CM
3000
r- 9.
^ O
2000 *~ co
1000
A J \ A
0
10 20 30 40 50 60
2-theta
F i g u r e A - 2 7 X - r a y diffraction pattern o f the a n o d i c precipitate prepared under the

c o n d i t i o n s : 3 M C N \ 1 M C u (I), 0.25 M N a O H , 0.5 M N a ^ , 6 0 C , 0.5 V v s . S C E ,
a n d 100 r p m .
263
Log (Current density / A m ) Log (Current density / A m") 2
(a) 40 C (b) 50 C
Figure A - 2 8 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n -

p o t e n t i a l v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0 r p m (40 a n d 50 C ) .
E l e c t r o l y t e s : 0.05 M C N " , C N . C u m o l e ratio = 3, 4, 6, 12 a n d no copper, 0.25 M N a O H
and 1 M N a S 0 . 2 4
0.5
0.4
O
o CO 0.3
CCOO >
> "to
'g 0.2
c 3
Si o
o
a. 0. 0.1
0 4-
-1.0 0.0 1.0 2.0 3.0 -1 0 1 2
(a) 40 C (b) 50 C
F i g u r e A - 2 9 E f f e c t o f the m o l e ratio o f c y a n i d e to copper o n c y a n i d e o x i d a t i o n -

potential v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0 r p m (40 a n d 50 C ) .
E l e c t r o l y t e s : [ C u ] = 0.00833 M , [ C N ] = 0.025, 0.05, 0.1, 0.2 a n d 0.4 M , 0.25 M N a O H
+
and 1 M N a S 0 . 2 4
264
F i g u r e A - 3 0 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current density) o n a

graphite rotating d i s k at 4 9 0 0 r p m (40 a n d 5 0 C ) . E l e c t r o l y t e s : 0.05 M " C N " , a C N : C u
m o l e ratio o f 3, [ O H ] = 0.25, 0.125, 0.05, 0.025 a n d 0 . 0 1 M and 1 M N a S 0 . 2 4
F i g u r e A - 3 1 E f f e c t o f p H o n c y a n i d e o x i d a t i o n - potential v s . l o g (current d e n s i t y ) o n a
Pt graphite rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : 0.05 M " C N " , a C N : C u
m o l e ratio o f 3, [OH"] = 0.25, 0.125, 0.05, 0.025 a n d 0 . 0 1 M a n d 1 M N a S 0 . 2 4
265

Log (current density / A m' )
2
(a) 4 0 C (b) 50 C

graphite rotating d i s k 4 9 0 0 r p m (40 and 50 C ) . E l e c t r o l y t e s : 0.05 M " C N " , a C N : C u
m o l e ratio o f 4, [OH"] = 0.25, 0.05, and 0 . 0 1 M and 1 M N a S 0 . 2 4

Log (current density / A m")2
(a) 40 C (b) 50 C

graphite rotating d i s k at 4 9 0 0 r p m (40 and 50 C ) . E l e c t r o l y t e s : 0.05 M " C N " , a C N : C u
m o l e ratio o f 12, [OH"] = 0.25, 0.05 a n d 0 . 0 1 M and 1 M N a S 0 . 2 4
266
0.4
> 0.3 -
SCE
> 0.2 --
0.200 M C N
ra .0.200 M C N
Poltent
0.100 M C N " 0.100 M C N "
A 0.050 M C N " 0.1 A 0.050 M C N "
o 0.025 M C N " o 0.025 M C N "
-1.2 -0.2 0.8 -1.5 -0.5 0.5 1.5 2.5

(a) 25 C (b) 4 0 C
0.4
0.200 M C N
> 0.3 0.100 M C N "
A 0.050 M C N "
O o 0.025 M C N "
0.2
c
B
o
a. 0.1
-1.5 -0.5 0.5 1.5 2.5

Log (current density / A m ) 2
(c) 50 C (d) 60 C
F i g u r e A - 3 4 P l o t s o f potential v s . l o g (current density) o n a graphite rotating d i s k at 4 9 0 0

r p m a n d different temperatures. E l e c t r o l y t e s : [CN"] = 0.025, 0.05, 0.1 a n d 0.20 M , a
C N : C u m o l e ratio - 3, [OH"] = 0.25 M a n d 1 M N a S 0 . 2 4
267
-1.0 0.0 1.0 2.0

Figure A - 3 5 P l o t s o f the potential vs. l o g (current density) o n a p y r o l y t i c graphite

rotating d i s k at 4 9 0 0 r p m a n d 25 C . E l e c t r o l y t e s : [CN"] = 0.025, 0.05, 0.1 a n d 0.20 M , a
C N : C u m o l e ratio = 3, [OH"] = 0.25 M and 1 M N a S 0 . 2 4
-1.0 I 1 1 | ; 1
; I
-2.2 -2.0 -1.8 -1.6 -1.4 -1.2 -1.0
Log([Cu(CN) 7 moi d m )
3
2 3
F i g u r e A - 3 6 P l o t s o f l o g (current density) v s . l o g ( [ C u ( C N ) " ] ) o n a p y r o l y t i c graphite

3
2
rotating d i s k at 4 9 0 0 r p m and 25 C . E l e c t r o l y t e s : [CN"] = 0.025, 0.05, 0.1 a n d 0.20 M , a

C N : C u m o l e ratio = 3, [ O f f ] = 0.25 M and 1 M N a ^ .
268
1200
.1600 rpm Evolution of oxygen
1600 rpm 400 rpm
.1000
400 rpm Evolution of oxygen . 100 rpm
. . . . 100 rpm
< 800 Precipitation
Precipitation , of copper oxide
of copper oxide
S 600
S 400
3
o 200
0.2 0.4 0.6 0.8 1.0 1.2 0.00 0.20 0.40 0.60 0.80 1.00 1.20
(a) 25 C (b) 40 C
10000
1600 rpm Evolution of oxygen 1600 rpm Evolution of oxygen

400 rpm 8000 400 rpm
. . . . 100 rpm 'E . . . . 100 rpm
<
, 6000
Precipitation '35 Precipitation
of copper oxide c of copper oxide
o
2 4000
c
o.o 0.2 0.4 0.6 0.8 1.0 1.2 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C
F i g u r e A - 3 7 P o l a r i z a t i o n curves at different temperatures. E l e c t r o l y t e : 0.05 M C N " ,

+
2 3 and 1 M N a S 0 . 2 4
269
4000
(a) 50 C
.1600 rpm
400 rpm
. 100 rpm
Evolution of oxygen
Precipitation
of copper oxide
0.0 0.2 0.4 0.6 0.8 1.0 1.2

(b) 60 C

+
2 3 and 1 M N a ^ .
270
3000 10000
4900 rpm 9000

4900 rpm
2500 . 1600 rpm Evolution of oxygen
CN M 8000 1600 rpm
'E . . . 400 rpm E . . . . 400 rpm
<
2000 . - - 1 0 0 rpm - - 1 0 0 rpm
< 7000
CO 6000
C 1500 Precipitation
cu '35 Precipitation
TJ of copper oxide
c 5000 of copper oxide
CD
0> 1000 4- 4000
c
3 t 3000
3
o 500
2000
1000
0.4 0.6 0.8 1.0 0.4 0.6 0.8

(a) 25 C (b) 4 0 C
14000 18000
4900 rpm 16000 4900 rpm

12000 f volution
1600 rpm 1600 rpm if oxygen
CM 14000
- - - - 400 rpm . . . . 400 rpm
^ 10000
. - 1 0 0 rpm 12000 - - 1 0 0 rpm
<
S 1
8000 10000 Precipitation
to
of copper oxide
c Precipitation 8000
D 6000 of copper oxide
4-*
C 6000
V
t 4000 4
4000
o
2000
2000
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.4 0.6 0.8 1.2
0 Potential vs. SCE/V Potential vs. SCE/V
(c) 50 C (d) 60 C

+
2 3 and 1 M N a S 0 .
2 4
271
3000 5000
Precipitation Precipitation
of copper oxide Evolution 4500 of copper oxidel Evolution
2500 of oxygen of oxygen
4000
E 4900 rpm
3500
< 2000
1600 rpm
3000
. . . . 400 rpm
co -4900 rpm
c 1500 1600 rpm
2500 - - 1 0 0 rpm
CD
a . 400 rpm
*-i 2000
c -100 rpm
1000 J.
P 1500
3
o 500
1000
500
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.4 0.6 0.8 1.0 1.2
(a) 25 C (a) (b) 4 0 C
6000 12000 ,
Precipitation Evolution of oxygen
Precipitation Evolution
of copper oxide of copper oxide of oxygen
5000 10000
'E
< 4000 < 8000 4900 rpm
-4900 rpm 1600 rpm

in 1600 rpm - - - - 400 rpm
c co
3000 e 6000
CD . 400 rpm CD . - 1 0 0 rpm
a a
. 100 rpm
CD 2000 4- S 4000
3 3
o 1000 o 2000
0 J
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.4 0.6 0.8 1.2
Potential / V vs. SCE Potential/V vs. SCE
(c) 50 C (d) 60 C

0.0125 M C u ( C N : C u m o l e ratio = 4), 0.25 M N a O H , 0.2 M N a j S O j a n d 1 M N a j S O ^
+
272
2500 2500
Precipitation Precipitation
of copper oxide of copper oxide)
CM 2000 -- 2000
' Evolution E 4900 rpm
<

-4900 rpm
of oxygen < 1600 rpm
1500 1600 rpm
1500 . . . . 400 rpm
. 400 rpm
tO 3) - - 1 0 0 rpm
C -100 rpm c
<t> cu
TJ
4-
1000 2 1000
C c
CU cu
l_ k_
I
3 3
O 500 -- O 500
0.4 0.6 0.8 1.2 0.4 0.6 0.8 1.0 1.2

(a) 25 C (b) 4 0 C
4500 12000
PrecipitationEvolution of oxyi
4000 of copper oxide Precipitation Evolution
10000 of copper oxide of oxygen
3500 4900 rpm CM
E 1600 rpm E
< 3000 < 8000 4-
. . . . 400 rpm 4900 rpm
2500 _ . _ 100 rpm 1600 rpm
to to
c c 6000 . . . . 400 rpm
cu 2000 cu
TJ TJ _ . - 1 0 0 rpm
c c
1500
CD 4000
3 3
1000
o o
500 2000
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C

+
2 3 and 1 M N a S 02 4
273
350 -, 900 -,
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
Potential vs. SCE/V Potential/V vs. SCE
(a) 25 C (b) 4 0 C
1200 1400
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C

0.0167 M C u ( C N : C u m o l e ratio = 3), 0.05 M N a O H , 0.2 M N a S 0 a n d 1 M N a S 0 .
+
2 3 2 4
274
4000 - 5000
4500 -4900 rpm

3500 - -4900 rpm
1600 rpm
1600 rpm CM 4000
CM
- 400 rpm
'E 3000 - . 400 rpm
E -100 rpm
< 2500 -
-100 rpm
<t 3500
JSU
,< 3000
2000 -
CD '35
TJ C 2500
c 1500 - at
01
2 2000
1000 -
3
c
O a>
500 -
t 1500
3
1000
0 -
0.4 0.6 0.8 1.0 1.2 500 0.0 0.2 0.4 0.6 0.8 1.0 1.2
0
(a) 25 C (b) 4 0 C
6000 7000
-4900 rpm -4900 rpm

6000 1600 rpm
5000 1600 rpm
CM
- 400 rpm . 400 rpm
E E 5000 -100 rpm
< 4000 -- -100 rpm <
4000
to 35
c 3000 -- c
01 CD
TJ TJ 3000
c 2000 --
2000
3
o 1000
1000
0
0.20 0.40 0.60 0.80 1.20 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C

+
2 3 and 1 M N a ^ .
275
1400
1200 1600 rpm

. 400 rpm
1000 . . . 100 rpm
<

800
CO
c
cu
T3 600
C
C_
kD
t_ 400
3
o 200
0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.4 0.6 0.8 1.2
(a) 25 C (b) 40 C
2500 2500
1600 rpm 1600 rpm

. 400 rpm 400 rpm
2000 <M 2000
E . . . 100 rpm - . . . 100 rpm
< <
1500 1500
co 'co
c c
CD CD
~ 1000 w 1000
c c
CD
3 3
500 4-
o 500
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 60 C

0.0125 M C u ( C N : C u m o l e ratio = 4), 0.05 M N a O H , 0.2 M N a ^ a n d 1 M N a S 0 .
+
2 4
276
1200 , 1400
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(a) 25 C (b) 4 0 C
1800 -T 1800 T
0.0 0.2 0.4 0.6 0.8 1.0 1.2 0.0 0.2 0.4 0.6 0.8 1.0 1.2
(c) 50 C (d) 6 0 C

0.0125 M C u ( C N : C u m o l e ratio = 4), 0.05 M N a O H , 0.1 M N a 2 S 0 a n d 1 M N a S 0 .
+
3 2 4

Copper Electrowinning From Cyanide Solutions by Lu Jianming PDF

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COPPER ELECTROWINNING FROM CYANIDE SOLUTIONS

A THESIS SUBMITTED IN PARTIAL F U L F I L L M E N T OF

THE REQUIREMENTS FOR T H E DEGREE OF

W e accept this thesis as c o n f o r m i n g

THE UNIVERSITY OF BRITISH C O L U M B I A

department or by his or her representatives. It is understood that copying or

The University of British Columbia

T h e objective o f this research w a s to e x p l o r e a n efficient process to r e c o v e r c y a n i d e

a n d c o p p e r f r o m barren g o l d c y a n i d e s o l u t i o n . T h e research w o r k d e s c r i b e d here c o n c e r n s a n

i n v e s t i g a t i o n into fundamental and p r a c t i c a l aspects o f t w o options for e l e c t r o w i n n i n g c o p p e r

f r o m c y a n i d e s o l u t i o n . These t w o options are: (a) the use o f a n alternative anode r e a c t i o n to

limit the e l e c t r o - o x i d a t i o n o f c y a n i d e i n concentrated c y a n i d e solutions a n d (b) the use o f a

graphite fibre cathode to e l e c t r o w i n copper f r o m dilute c y a n i d e s o l u t i o n .

(1) A c r i t i c a l literature survey w a s c o n d u c t e d to e x a m i n e the s t a b i l i t y constants o f

c o p p e r c y a n i d e species. T h e distributions and the e q u i l i b r i u m r e d o x potentials o f c o p p e r

cyanide species were c a l c u l a t e d u s i n g the most r e l i a b l e stability constants. They are

dependent o n the m o l e ratio o f c y a n i d e to copper, total c y a n i d e c o n c e n t r a t i o n , p H a n d

temperature. P o t e n t i a l measurements have c o n f i r m e d the v a l i d i t y o f the c a l c u l a t e d results.

T h e p H - p o t e n t i a l d i a g r a m w a s d r a w n u s i n g the G i b b s free energy data d e r i v e d b y s e l e c t i n g

the most r e l i a b l e stability constants.

(2) D i r e c t copper e l e c t r o w i n n i n g f r o m dilute c y a n i d e solutions w a s c o n d u c t e d i n a

m e m b r a n e c e l l . T h e a c c u m u l a t i o n o f deposited copper o n the graphite felt as the p l a t i n g

proceeds s i g n i f i c a n t l y i m p r o v e s the c o n d u c t i v i t y o f the graphite felt, increases the s p e c i f i c

surface area a n d benefits copper d e p o s i t i o n . C o p p e r c a n be deposited o n the graphite felt

f r o m l o w c o n c e n t r a t i o n solutions (1-2 g L " C u a n d C N : C u m o l e ratio = 3-4) w i t h 5 0 - 8 0 %

current e f f i c i e n c y , the r e m o v a l o f a r o u n d 4 0 % C u a n d an energy c o n s u m p t i o n o f 1 -2 k W h / k g

C u i n the s u p e r f i c i a l current density range 30 - 100 A m " at 40 C .2

(3) C o p p e r e l e c t r o w i n n i n g f r o m concentrated copper c y a n i d e s o l u t i o n (70 g L " C u ) 1

w a s c o n d u c t e d u s i n g four s a c r i f i c i a l species (sulphite, m e t h a n o l , thiocyanate a n d a m m o n i a )

at 4 0 to 60 C . O n l y sulphite c a n decrease the a n o d i c current e f f i c i e n c y o f c y a n i d e o x i d a t i o n

f r o m ~ 100 to 10-20 % o v e r the current density range o f 2 5 0 - 5 0 0 A m " . W i t h i n c r e a s i n g2

C N : C u m o l e ratio f r o m 3 to 4.5, the a n o d i c current e f f i c i e n c y o f c y a n i d e o x i d a t i o n i n c r e a s e d

a n d the c o p p e r d e p o s i t i o n current e f f i c i e n c y decreased. A s regards the r e c o v e r y o f c o p p e r

f r o m barren g o l d c y a n i d e s o l u t i o n , it has been s h o w n that u s i n g sulphite o x i d a t i o n as a n

alternative anode reaction, copper c a n be e l e c t r o w o n f r o m a c y a n i d e electrolyte c o n t a i n i n g

about 70 gL~' C u ( C N : C u = about 3) a n d 0.5 M N a S 0 2 3 at a cathode current e f f i c i e n c y o f

about 9 5 % w i t h a energy c o n s u m p t i o n o f about 0.8 k W h / k g C u at 2 5 0 A m " . 2

(4) I n a l k a l i n e solutions, sulphite is o x i d i z e d to sulphate o n the graphite anode i n a

t w o - e l e c t r o n reaction. T h e reaction order w i t h respect to sulphite i o n s is b e l o w 1 at l o w

potentials(< 0.4 V v s . S C E ) a n d 1 at h i g h potentials. T h e r e a c t i o n order for h y d r o x i d e i o n s is

c l o s e to z e r o . T w o T a f e l slopes were observed, 0.060 - 0.64 V decade"' at l o w potentials a n d

(5) T h e a n o d i c o x i d a t i o n o f copper c y a n i d e has been studied u s i n g a graphite r o t a t i n g

temperature (25-60 C ) a n d h y d r o x i d e c o n c e n t r a t i o n (0.01-0.25 M ) . C o p p e r h a d a s i g n i f i c a n t

c a t a l y t i c effect o n c y a n i d e o x i d a t i o n . I n the l o w p o l a r i z a t i o n r e g i o n (< about 0.4 V v s . S C E ) ,

c u p r o u s c y a n i d e is o x i d i z e d to c u p r i c c y a n i d e c o m p l e x e s w h i c h further react to f o r m cyanate.

A t a C N : C u ratio o f 3 a n d [OH"] = 0.25 M , the T a f e l slope w a s about 0.12 V decade"'.

C u ( C N ) " w a s d i s c h a r g e d o n the electrode surface. W i t h i n c r e a s i n g C N : C u m o l e ratio a n d

decreasing p H , the d o m i n a n t d i s c h a r g e d species shifted to C u ( C N ) " . I n the h i g h p o l a r i z a t i o n

r e g i o n (about 0.4 -0.6 V v s . S C E ) , cuprous c y a n i d e c o m p l e x e s were o x i d i z e d to c o p p e r o x i d e

and cyanate. W h e n the concentration o f c y a n i d e w a s h i g h and the p H l o w , c y a n o g e n w a s

(6) S u l p h i t e o x i d a t i o n is enhanced b y the presence o f copper c y a n i d e . T h e effect o f

sulphite o n l i m i t i n g the o x i d a t i o n o f copper c y a n i d e decreases w i t h i n c r e a s i n g m o l e ratio o f

c y a n i d e to copper. T h i s is related to the shift i n the d i s c h a r g e d species f r o m C u ( C N ) " to 3

C u ( C N ) " w i t h i n c r e a s i n g m o l e ratio o f c y a n i d e to copper. S u l p h i t e is o x i d i z e d to sulphate.

A t [ C u ] = a r o u n d 1 M , C N : C u = 3 -3.2, [OH"] = 0.05-0.25 M , [ S 0 " ] = 0.4-0.6 M a n d the 3

temperature = 50 - 60 C , the anode current e f f i c i e n c y o f sulphite o x i d a t i o n r e a c h e d 80-90%)

2.3.1 Cyanide Oxidation in Alkaline Solution 17

5.1 E x p e r i m e n t a l A p p a r a t u s and Set-up for E l e c t r o w i n n i n g 62

5.3 E f f e c t o f S o m e Parameters o n the A n o d i c and C a t h o d i c Processes i n the 67

5.3.3 Effect o f T h i o c y a n a t e and M o l e R a t i o o f C y a n i d e to C o p p e r 68

5.3.4 Effect o f Temperature 73

6.1 Some Fundamental Aspects o f Rotating D i s k Electrodes 75

6.3 E x p e r i m e n t a l A p p a r a t u s and Set-up 80