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by
M o r r i s John A l o y s i u s Vreugde
Department of M i n i n g and M i n e r a l
Process Engineering
We a c c e p t t h i s t h e s i s as c o n f o r m i n g
to the required standard
The U n i v e r s i t y of B r i t i s h Columbia
October 1982
Department o f M i n i n g and M i n e r a l P r o c e s s E n g i n e e r i n g
The U n i v e r s i t y of B r i t i s h Columbia
1956 Main Mall
Vancouver, Canada
V6T 1Y3
Date
DE-6 (3/81)
Supervisor: D r . G e o r g e W. Poling
ABSTRACT
E l e c t r o c h e m i c a l methods, s u r f a c e s p e c t r o s c o p y and f l o t a t i o n
t e s t s have been used t o study the i n f l u e n c e of the o x i d a t i o n of
a r s e n o p y r i t e on i t s f l o a t a b i l i t y w i t h xahthate.
C y c l i c voltammetric s t u d i e s i n d i c a t e d t h a t t h e o x i d a t i o n of
arsenopyrite at pH g r e a t e r than 7 r e s u l t s i n t h e f o r m a t i o n of
f e r r i c h y d r o x i d e d e p o s i t s on the s u r f a c e of the m i n e r a l . Arsenic
i s o x i d i z e d t o arsenate and sulphur i s o x i d i z e d t o s u l p h a t e . The
arsenate i s incorporated i n the f e r r i c h y d r o x i d e d e p o s i t s while
sulphate diffuses into solution. Below pH=7, soluble iron
s p e c i e s a r e formed and t h e s u r f a c e becomes i n c r e a s i n g l y covered
with elemental sulphur with decreasing pH. Increasing
temperature has no i n f l u e n c e on the q u a n t i t y of h y d r o x i d e formed
over the range 30° t o 45°C but r e s u l t s i n t h i c k , porous f i l m s a t
temperature g r e a t e r than 45°C. The o x i d a t i o n of a r s e n o p y r i t e was
demonstrated t o occur a t lower oxidation potentials than for
pyrite although this effect decreased with increasing
temperature.
Mixed potential studies indicated that the p o t e n t i a l s
required f o r arsenopyrite oxidation could be achieved with
common o x i d i z i n g a g e n t s . S e l e c t i v e o x i d a t i o n of a r s e n o p y r i t e in
a bulk pyrite-arsenopyrite concentrate was indicated t o be
possible.
The formation of i r o n h y d r o x i d e d e p o s i t s on t h e s u r f a c e of
arsenopyrite r e s u l t e d i n the i n h i b i t i o n of subsequent o x i d a t i o n
of x a n t h a t e t o d i x a n t h o g e n a t the m i n e r a l ' s surface.
Table of Contents
1 INTRODUCTION 1
2 LITERATURE REVIEW 8
2.1 S t a t e Of The A r t Of A r s e n o p y r i t e F l o t a t i o n 8
2.3 C r y s t a l S t r u c t u r e *. .1 2
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 Of A r s e n o p y r i t e 13
F. E f f e c t Of Temperature 83
( i ) Experimental 84
V
( i i ) R e s u l t s And Discussion 84
G. I n f l u e n c e Of Cyanide 89
( i ) Experimental 95
( i i ) Results 97
Oxidation 105
6.0.1.1 E x p e r i m e n t a l 122
6.0.3.1 E x p e r i m e n t a l .....126
6.0.4.2 D i s c u s s i o n 134
7 CONCLUSIONS 138
Diagrams 150
References 157
vi i
T a b l e of F i g u r e s
4 C r y s t a l S t r u c t u r e of A r s e n o p y r i t e ( a f t e r Buerger ( 3 3 ) ) 14
5 Atomic % A r s e n i c i n A r s e n o p y r i t e 18
6 Method of e l e c t r o d e c o n s t r u c t i o n 29
7 O x i d a t i o n s t a t e diagram f o r the c h l o r i n e system 33
8 O x i d a t i o n s t a t e diagram f o r manganese system 34
9 O x i d a t i o n s t a t e diagram f o r the oxygen system 35
10 Eh v e r s u s pH f o r a r s e n o p y r i t e 37
11 Eh v e r s u s pH f o r p y r i t e 38
12 C o n s t r u c t i o n of r o t a t i n g a r s e n o p y r i t e e l e c t r o d e 44
13 C o n t r o l and measurement c i r c u i t used f o r voltammetry 46
14 Voltammograms f o r a r s e n o p y r i t e a t i n c r e a s i n g pH v a l u e s 48
15 Voltammograms f o r a r s e n o p y r i t e a t h i g h pH 49
16 Voltammogram for arsenopyrite at pH = 8.2 showing
p o t e n t i a l s a c h i e v e d w i t h o x i d i z i n g agents 50
17 Voltammograms f o r p y r i t e and a r s e n o p y r i t e a t pH = 11 52
18 Eh - pH diagram f o r a r s e n o p y r i t e . A c t i v i t y f o r each species
taken t o be 1 0" 3
M 54
19 C u r r e n t - decay c u r v e f o r A r s e n o p y r i t e a t +0.0343 V 58
20 M u l t i p l e Sweep Voltammograms f o r S t a t i o n a r y and Rotating
E l e c t r o d e s a t pH = 10.6 59
23 I n f l u e n c e of c a t h o d i c l i m i t on voltammogram 71
24 I n f l u e n c e of a n o d i c l i m i t on voltammogram 72
25 Voltammogram f o r g o l d e l e c t r o d e i n a r s e n i c s o l u t i o n 74
26 E f f e c t of arsenic additions on arsenopyrite potential
sweeps 75
27 Voltammograms a t i n c r e a s i n g sweep r a t e 78
28 I n f l u e n c e of sweep r a t e on peak p o t e n t i a l 79
29 P l o t of peak p o t e n t i a l as a f u n c t i o n of l o g scan r a t e 81
30 Log peak c u r r e n t v e r s u s l o g scan r a t e 82
31 Voltammograms a t 19°C and a t 60.5°C 85
32 I n f l u e n c e of temperature on peak p o t e n t i a l and peak c u r r e n t
86
33 M u l t i p l e sweep voltammogram a t 58.5°C 88
34 Comparison of pyrite and arsenopyrite voltammograms a t
59.8°C 90
35 M u l t i p l e sweep voltammogram for arsenopyrite in the
presence of 2.82X10" 3
M NaCN 93
36 I n f l u e n c e of c y a n i d e on f o r m a t i o n of i r o n h y d r o x i d e f i l m s
on a r s e n o p y r i t e 94
37 Voltammogram f o r p y r i t e i n t h e presence of 1.62x10" 3
M NaCN
96
38 Voltammograms f o r p y r i t e and m a r c a s i t e a t pH = 10.6 98
39 M u l t i p l e sweep voltammogram f o r l o e l l i n g i t e a t pH = 10.6 ..100
40 Voltammogram f o r i r o n e l e c t r o d e 102
42 I n f l u e n c e of a r s e n o p y r i t e o x i d a t i o n a t pH = 5.9 on x a n t h a t e
oxidation 107
FeAs 2 as s t a b l e p r o d u c t s 148
58 S t a b i l i t y r e g i o n of f e r r i c a r s e n a t e at 1 M a c t i v i t y 149
L i s t of Tables
1 Arsenic Minerals 2
2 Arsenic Emissions In Canada,1972 ( 6 ) 3
3 Arsenopyrite R e s i s t i v i t y Values 20
4 Cost Of O x i d i z i n g Agents 31
5 I n f l u e n c e Of Scan Rate On K i n e t i c Parameters 83
6 E l e c t r o n B i n d i n g E n e r g i e s And Intensities For Elements In
Various Minerals. 116J
Chapter 1
INTRODUCTION
Arsenic As
Loellingite FeAs 2
Realgar AsS
Orpiment As S2 3
Arsenopyrite FeAsS
Glaucodot (Co,Fe)AsS
Cobaltite CoAsS
Gersdorffite NiAsS
Skutterudite (Co,Ni,Fe)As 3
Niccolite NiAs
Enargite Cu AsS„
3
Proustite Ag AsS
3 3
Tennantite (Cu,Fe,Zn,Ag), As S, 2 fl 3
Sperrylite PtAs 2
Allemontite AsSb
Geocronite Pb (Sb,As) S
5 2 8
Symplesite Fe As 0 «8H 0
3 2 3 2
Table 2
A r s e n i c e m i s s i o n s i n Canada,1972 (6)
SOURCE EMISSIONS
TONS PERCENT
INDUSTRY
Primary copper and n i c k e l 661 16.2
Primary l e a d p r o d u c t i o n 18 0.4
Primary z i n c p r o d u c t i o n 359 8.8
Primary i r o n and s t e e l 1041 25.6
M e t a l l u r g i c a l p r o c e s s i n g of g o l d 1934 47.5
M i s c e l l a n e o u s sources 15 0.4
Subtotal 4028 98.9
FUEL COMBUSTION/STATIONARY SOURCES
Power G e n e r a t i o n 25 0.6
I n d u s t r i a l and commercial 13 0.3
Domestic <1 <0.1
Subtotal 38 0.9
Transportation <1 <0.1
S o l i d waste i n c i n e r a t i o n 1 <0. 1
Pesticide application 6 0.2
Total 4073 100.0
l e a d t o s e r i o u s h e a l t h hazards a p a r t from t h e c o n t a m i n a t i o n of
c o n c e n t r a t e has on o c c a s i o n r e s u l t e d i n a r s i n e g e n e r a t i o n d u r i n g
h y d r o m e t a l l u r g i c a l p r o c e s s i n g and r e f i n i n g ( 1 1 ) .
r e s u l t i n s i g n i f i c a n t economic consequences. I f p y r i t e i s t o be
recovered f o r t h e p r o d u c t i o n of s u l p h u r i c a c i d t h e presence of
a r s e n o p y r i t e i s h i g h l y u n d e s i r a b l e due t o c o n t a m i n a t i o n of t h e
4
Fe
orpiment realgar
Figure 1
Minerals i n t h e F e - A s - S S y s t e m (600°C)
5
Area A - G o l d w i t h minor s i l v e r
Area B - B i s m u t h and t e l l u r i u m
Area C - G o l d and a n t i m o n y
Area D, E - B i s m u t h
Figure 2
CRUSHING PRIMARY
GRINDING CLASSIFIERS
3 Stogts
T*
^
Boll Mills
| SECONDARY
FLOTATION
ur SECONDARY
GRINDING K - i CYCLONES <jr
PRIMARY
FLOTATION
Boll MILLS
I 1
- BULK SULPHIDE CONCENTRATE -
aJZ! FLUOSOLIDS
CYCLONES |
HOT ROASTING [2nd CALCINE
C0TTRELL 2 Slogei
WASH
[CARBON PLANT]
CONDITIONING
Thickening
CRUDE CYANIDATION
A. 0
2 3
H THICKENING PREGNANT
SOLUTION
LOADED CARBON Storoge
Dried STRIPPING -(FILTRATION
Shipped
ILARIFIOATION
ARSENIC
SUPPRESSION IPRECIPITATTONI
I Llmi )
pjlTHICKENING
ARSENIC GOLD
TAILINGS <-) SUPPRESSION BULLION
(Lime)
Figure 3
G i a n t Y e l l o w k n i f e Mines flowsheet
7
The r e c o v e r y or d e p r e s s i o n of a r s e n o p y r i t e d u r i n g sulphide
f l o t a t i o n i s of apparent i n t e r e s t . I n t h e case of g o l d o r e s , t h e
maximum recovery of a r s e n o p y r i t e may be d e s i r a b l e t o maximize
the r e c o v e r y of a s s o c i a t e d g o l d v a l u e s . On t h e o t h e r hand, t h e
maximum depression of arsenopyrite i s d e s i r a b l e d u r i n g base
metal production.
Chapter 2
LITERATURE REVIEW
2.1 S t a t e of t h e A r t of A r s e n o p y r i t e Flotation
In reviewing the l i t e r a t u r e r e l a t i n g t o t h e f l o t a t i o n of
arsenopyrite i t i s apparent t h a t the s e p a r a t i o n of arsenopyrite
from pyrite i s among t h e most s i g n i f i c a n t s e p a r a t i o n s t o be
considered. Whether i t i s f o r a n a l y t i c a l purposes to determine
whether associated gold i s w i t h p y r i t e o r a r s e n o p y r i t e or f o r
the p r o d u c t i o n of a pure p y r i t e p r o d u c t , f r e e of arsenic, the
s e p a r a t i o n of t h e s e two m i n e r a l s receives frequent mention.
In discussing the c h a r a c t e r i s t i c s of a r s e n o p y r i t e under
f l o t a t i o n c o n d i t i o n s , frequent reference w i l l be made t o the
behaviour of p y r i t e under t h e same c o n d i t i o n s . T h i s comparison
w i l l be useful since the depression of arsenopyrite would
o b v i o u s l y not be of any r e a l s i g n i f i c a n c e i f most o t h e r sulphide
minerals would be depressed under the same conditions.
Consideration of t h e b e h a v i o u r of pyrite therefore gives at
l e a s t a l i m i t e d measure of whether c o n d i t i o n s f o r t h e d e p r e s s i o n
of a r s e n o p y r i t e a r e e x c e s s i v e . Another b e n e f i t of comparing t h e
response of pyrite to that of arsenopyrite i s that while
arsenopyrite has received o n l y very l i m i t e d s t u d y , p y r i t e has
been e x t e n s i v e l y i n v e s t i g a t e d .
a r s e n o p y r i t e . A l l i s o n e t a l . (22) r e p o r t e d d i x a n t h o g e n t o be t h e
x a n t h a t e ) c o u l d be p r e s e n t .
The m a j o r i t y of r e s e a r c h e r s now b e l i e v e t h a t d i x a n t h o g e n i s
the active collector species i n p y r i t e f l o t a t i o n while a t the
same time a d d i t i o n a l minor c o n t r i b u t i o n s t o h y d r o p h o b i c i t y can
be made by ferric hydroxyxanthate or by elemental sulphur
r e s u l t i n g from m i n e r a l o x i d a t i o n .
The c o r r e s p o n d i n g c a t h o d i c r e a c t i o n i s g e n e r a l l y c o n s i d e r e d
12
to be t h e r e d u c t i o n of oxygen ( 2 3 ) .
0 2 + 4H +
+ 4e" == 2H 0 2 (3)
2Fe 3 +
+ 2X" == 2 F e 2+
+ X 2 (4)
2Fe(OH) 3 + 6H +
+ 2X" == 2 F e 2 +
+ 6H 0 + X
2 2 (5)
2.3 C r y s t a l S t r u c t u r e
The s t r u c t u r e of a r s e n o p y r i t e as p r e s e n t e d by Buerger is
shown i n F i g u r e 4.
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 of A r s e n o p y r i t e
ARSENIC
SULPHUR
Figure 4
o c c u r r i n g a r s e n o p y r i t e to vary from F e A s o . S , . , t o
9 FeAs^^o.j,.
determining the c o m p o s i t i o n of n a t u r a l a r s e n o p y r i t e . In a d d i t i o n
determinations.
As = 866.67d, , - 1381.12
3
t e m p e r a t u r e of f o r m a t i o n can be e s t a b l i s h e d .
18
32 33 ' 34 35 36 37
A t o m i c % A r s e n i c in Arsenopyrite
Figure 5
Atomic % a r s e n i c i n a r s e n o p y r i t e
19
Arsenopyrite i s s l i g h t l y n o n - s t o i c h i o m e t r i c , showing an Fe
deficiency. Morimoto and Clark (36) and Kretschmar and Scott
(39) d e t e r m i n e d the Fe d e f i c i e n c y t o be l e s s than 0.7 atomic %.
2.6 E l e c t r o p h y s i c a l P r o p e r t i e s of Arsenopyrite
presented i n Table 3.
i n a r s e n i c - r i c h environments i t i s p - t y p e .
20
Table 3
Arsenopyrite R e s i s t i v i t y Values
Source R e s i s t i v i t y , ohm-cm.
45 3.0 X TO" 2
2.7 E l e c t r o p h y s i c a l E f f e c t s i n F l o t a t i o n
m i n e r a l s v a r y w i d e l y i n t h e i r e l e c t r o p h y s i c a l p r o p e r t i e s such as
( 4 5 ) . These v a r y i n g e l e c t r o p h y s i c a l p r o p e r t i e s c o u l d be e x p e c t e d
Chapter 3
Chapter 4
ELECTROCHEMICAL STUDIES
4.1 E l e c t r o d e P o t e n t i a l Measurements
4.1.1 Experimental
a n a l y z e d as follows:
27
Measured Theoretical
As = 46.0 ±0.2% 46.01
Fe = 34.0 ±1.0% 34.30
S =19.8 ±0.1% 19.69
Co = not d e t e c t e d (<0.02%)
Ni = not d e t e c t e d (<0.02%)
Sb = not d e t e c t e d (<0.04%)
Cu = not d e t e c t e d (<0.01%)
Pb = 0.27%
Zn = 0.06%
T h i s c o m p o s i t i o n shows a s l i g h t i r o n d e f i c i e n c y compared t o
stoichiometric composition, as has generally been noted f o r
a r s e n o p y r i t e ( 3 9 ) . The c o m p o s i t i o n a l s o shows a s l i g h t excess i n
the s u l p h u r t o a r s e n i c r a t i o and would be expected t o be an n-
type semiconductor.
4.1.2 O x i d i z i n g Agents
A v a r i e t y of o x i d i z i n g agents a r e used i n i n d u s t r y t o c a r r y
WIRE
//-> EADS
GLASS
TUBE
GOLD PLATING
SILVER CEMENT
Figure 6
Method of e l e c t r o d e construction
30
In o r d e r f o r an o x i d i z i n g agent t o be a c c e p t a b l e f o r use i n
controlling the f l o t a t i o n response of m i n e r a l s i t must meet
several c r i t e r i a i n addition t o being an effective oxidant.
Among these c r i t e r i a a r e t h a t i t must be c o s t c o m p e t i t i v e , must
not be e x c e e d i n g l y d i f f i c u l t or dangerous t o handle and mustnnot
r e s u l t i n p o l l u t i o n problems.
4.2 R e s u l t s and D i s c u s s i o n
- 1 0 I 2 3 4 5 6 7
Oxidation s t a t e
Figure 7
-4-
1 1 1 1 I I i i
0 I 2 3 4 5 6 7
Oxidation state
Figure 8
Figure 9
s l o p e of t h e e x p e r i m e n t a l r e l a t i o n from t h e o r e t i c a l values.
J 1 I I I L
2 4 6 8 10 12
PH
Q I n d i v i d u a l measurement
0 T i t r a t i o n point
Figure 10
Eh v e r s u s pH f o r a r s e n o p y r i t e
F i g u r e 11
Eh v e r s u s pH f o r pyrite
39
Eh = 643 - 49.0 pH
r = -0.993
4.3 C y c l i c Voltammetry
C y c l i c voltammetry i s s i m i l a r t o l i n e a r sweep p o l a r i z a t i o n
but with the added f e a t u r e t h a t the p o t e n t i a l v a r i a t i o n w i t h
time i s r e v e r s e d at some p o i n t and returned to the starting
potential. In this way both the o x i d a t i o n and r e d u c t i o n of
e l e c t r o a c t i v e s p e c i e s at the e l e c t r o d e s u r f a c e can be studied.
For example, if xanthate is oxidized to d i x a n t h o g e n at an
e l e c t r o d e d u r i n g an a n o d i c p o t e n t i a l sweep and the sweep i s then
reversed, the:reduction r e a c t i o n can be m o n i t o r e d . By measuring
both anodic and c a t h o d i c c u r r e n t s , i t can be d e t e r m i n e d t h a t the
dixanthogen formed at the e l e c t r o d e remains at the s u r f a c e and
does not d i f f u s e i n t o the b u l k s o l u t i o n .
S e v e r a l f i g u r e s which are e s s e n t i a l t o the discussion in
this thesis are i n c l u d e d on a f o l d - out page as Appendix I I .
Figure 1 i n Appendix I I i s taken from r e f e r e n c e 49 t o illustrate
the e s s e n t i a l f e a t u r e s of a voltammogram. In the presence of
xanthate an anodic potential sweep starting a t -0.4V shows
e s s e n t i a l l y no c u r r e n t b e i n g passed u n t i l a p o t e n t i a l of 0.2V is
exceeded. Beyond t h i s p o t e n t i a l t h e r e i s a rapid r i s e in current
t o a peak, f o l l o w e d by a g r a d u a l decline. Once the potential
falls below 0 V dixanthogen is reduced, at which point a
42
4.3.1 Experimental
measurements.
TEFLON
SILVER CEMENT
r, = 3-l75mm
r =3-99 mm
2
r =4-40 mm
3
F i g u r e 12
C o n s t r u c t i o n of r o t a t i n g a r s e n o p y r i t e electrode
45
p r e p a r a t i o n of s o l u t i o n s or f o r a d d i t i o n of s p e c i f i c ions were
reagent or a n a l y t i c a l grade.
4.3.2 R e s u l t s and D i s c u s s i o n
A. S i n g l e Sweep Voltammograms
PROGRAMMER
RECORD E
POTENTIOSTAT
CONTROL*
W ••
R •• REF C WE
C
GROUND*
MULTIMETER =:RECORD I
COMMON
ROTATOR
F i g u r e 13
apparent over the pH range from 9.6 t o 10.55 and then decreases
pH 6-6
pH 7-3
pH 9-2
pH 9*6
I I I
-0-8 -0-6 -0-4 -0-2 0 0-2 0-4 0-6 0-8
Potential / V vs SHE
F i g u r e 14
Voltammograms f o r a r s e n o p y r i t e a t i n c r e a s i n g pH v a l u e s
49
I 1 1 I I I I I
-0-8 -0-6 -0-4 -0-2 0 0-2 0-4 0-6
Potential / V vs SHE
F i g u r e 15
Voltammograms f o r a r s e n o p y r i t e a t h i g h pH
50
F i g u r e 16
1/2 A s S 2 3 + Fe + +
+ H +
+ 3e" = FeAsS + 1/2 H S 2 (6)
E = - 0.012 - 0.0295 l o g ( H S ) / 2
1 2
- 0.0197 pH
(Fe + +
)
—' " 1 1 1 u
0-4 -0-2 0 0-2 0-4 0-6
Potential / V vs SHE
20 mV s-' , pH= 110
F i g u r e 17
Fe + +
+ H As0 3 3 + SO -- + 11H a
+
+ 11e" = FeAsS + 7H 0 2
(7)
Fe(OH) 2 + H As0
3 3 + SO,,"- + 13H +
+ 1 1 e" = FeAsS+9H 0 2
(8)
oxidation i s g i v e n by
Fe(OH) 3 + H +
+ e" = F e ( O H ) 2 + H0 2 (9)
o b t a i n e d a t pH = 10.55.
Figure 18
p o t e n t i a l s a r s e n i c i s e x p e c t e d t o be o x i d i z e d to arsenate and
sulphur i s e x p e c t e d t o be o x i d i z e d t o s u l p h a t e .
than the p r o j e c t e d a r e a .
B. M u l t i p l e Sweep ( C y c l i c ) Voltammetry
Figure 19
1
-0.8 -0.6 -0.4 -0.2 0 0.2- 0.4 0.6
Potentiol / V vs SHE
20 mV s - ' , pH = l0.6
F i g u r e 20
F i g u r e 21
[ F e ( O H ) ] a d + e = [Fe(OH)]ad
+
(11)
{Fe(OH) } = [ F e ( O H ) ] a d + OH"
2
+
(12)
3. A f u r t h e r r e d u c t i o n of t h e F e ( O H ) 2 according to equations
64
can be r e w r i t t e n i n terms of p r o t o n t r a n s f e r as f o l l o w s .
FeOOH + H +
+ e = Fe(OH) 2 (17)
and
65
H +
+ OH" = H 0 2 (18)
The f o r m a t i o n of f e r r i c h y d r o x i d e a c c o r d i n g t o r e a c t i o n 17
then r e s u l t s i n f o r m a t i o n of H +
i n a d d i t i o n t o FeOOH. The H +
so
formed i s neutralized according to reaction 18 either by
d i f f u s i o n of H +
away from t h e r e a c t i o n s i t e due t o c o n c e n t r a t i o n
g r a d i e n t s or by d i f f u s i o n of OH" t o the s i t e . Conditions which
promote the d i f f u s i o n or transport of these s p e c i e s should
t h e r e f o r e i n c r e a s e t h e r a t e of FeOOH p r o d u c t i o n . T h i s i s i n f a c t
o b s e r v e d s i n c e t h e e f f e c t of r o t a t i o n i s t o i n c r e a s e t h e height
of peak I I I . At t h e same time i n c r e a s i n g pH i n c r e a s e s t h e peak
h e i g h t s i n c e a g r e a t e r c o n c e n t r a t i o n of OH" i s a v a i l a b l e f o r H +
neutralization.
NiOOH + H 0 + e = N i ( O H )
2 2 + OH" (19)
or
NiOOH + H +
+ e = Ni(OH) 2 (20)
and
H +
+ OH" = H 0 2 (21)
S 0
2 3
2
- + 6H +
+ 4e = 2S + 3H 0 2 (22)
E = + 0.26 + 0.015 l o g ( S 0 - ) 2 3
2
- 0.089 pH
2 S O - + 10 H
a
2 +
+ 8 e = S 0 2 3
2
- + 5 H0 2 (23)
(so, -) 2 2
FeAsO„ + 3H +
= H AsO, + F e
3
3 +
(24)
pH = 0.12 - 1/3 l o g ( H A s O ) ( F e )
3 a
3 +
or
FeAsO, + 3H 0 = F e ( O H )
2 3 + H AsO„- + H
2 (25)
to r e a c t i o n 25 ( 6 4 ) .
» ' I I I I L_
-0.6 -0.4 -Q2 0 02 0.4 0.6
Potential / V vs SHE
20 mV s-' f pH = 5.8
Figure 2 2
M u l t i p l e sweep voltammograms a t pH = 5 . 8 .
70
although the shape of the peaks and the rate at which peak
currents change differ somewhat due to a decrease i n t o t a l
c a t h o d i c c u r r e n t passed w i t h the l e s s n e g a t i v e c a t h o d i c l i m i t . A
l e s s c a t h o d i c l i m i t does not r e s u l t i n e l i m i n a t i o n of any peaks.
C. I r r e v e r s i b i l i t y of A r s e n a t e F o r m a t i o n
r e d u c i n g agents p r i o r t o d e t e r m i n a t i o n (67).
o x i d a t i o n of As ( I I I ) t o As ( V ) . I t can be seen t h a t t h e r e i s no
I 1 1 I I I |
-0-6 -0-4 -0-2 0 0-2 0-4 0-6
Potential / V vs SHE
20 mV s - ' , pH = 10.6
F i g u r e 23
I n f l u e n c e of c a t h o d i c l i m i t on voltammogram
72
after 5 min
I I L_ I I 1
-0.6 -0.4 -0.2 0 0.2 0.4
Potentiai / V vs SHE
20 mV s - ' , pH = I 0.6
F i g u r e 24
I n f l u e n c e of a n o d i c l i m i t on voltammogram
73
D. I n f l u e n c e of D i s s o l v e d A r s e n i c on Voltammetry
The o x i d a t i o n of a r s e n o p y r i t e a c c o r d i n g to equations such
as 8 shows soluble arsenic as a product. The i n f l u e n c e of
i n c r e a s i n g d i s s o l v e d a r s e n i c i n s o l u t i o n s h o u l d t h e r e f o r e be to
d e p r e s s the a n o d i c peak and t o s h i f t i t to higher p o t e n t i a l s .
At the same time by carrying out voltammetry i n the
presence of d i s s o l v e d a r s e n i c , peaks due t o a r s e n i c o x i d a t i o n or
r e d u c t i o n should be enhanced. The absence of peak enhancement
will c o n f i r m the p r e v i o u s c o n c l u s i o n t h a t a l l observed peaks a t
pH g r e a t e r than 7 are due to i r o n species.
F i g u r e 26 shows the influence of arsenic additions to
solution. As e x p e c t e d the a r s e n o p y r i t e o x i d a t i o n peak at 0.35V
i s diminished by such a d d i t i o n as w e l l as b e i n g s h i f t e d to more
anodic potentials. As a consequence of the d i m i n i s h e d anodic
r e a c t i o n , the c a t h o d i c peak associated with ferric hydroxide
r e d u c t i o n a l s o becomes d i m i n i s h e d .
Voltammogram f o r g o l d e l e c t r o d e i n a r s e n i c s o l u t i o n
75
I i I i i i u
-0-6 -0-4 -0-2 0 0-2 0-4 0-6
Potential / V vs SHE
Figure 26
E f f e c t of a r s e n i c a d d i t i o n s on a r s e n o p y r i t e p o t e n t i a l sweeps
76
supported.
Peaks due t o the o x i d a t i o n of a r s e n i c I I I t o a r s e n i c V are
not observed although considerable arsenic I I I i s present i n
s o l u t i o n . T h i s i s expected s i n c e the potentials required for
As(III) oxidation which a r e p r e s e n t e d i n the p r e v i o u s section
lie i n the r e g i o n where c u r r e n t s due t o arsenopyrite oxidation
are a l r e a d y s u b s t a n t i a l .
E. E f f e c t of Sweep Rate.
i p = 3 X I0 n(/3na) V 5 2
A D/ 1 2
C° (28)
where
process
F i g u r e 27
Voltammograms a t i n c r e a s i n g sweep r a t e
79
pH = 10-6
-L
10 20 30 40 50 60 70 80
Figure 28
I n f l u e n c e of sweep r a t e on peak p o t e n t i a l
80
of the e l e c t r o d e p r o c e s s , f o r a s i n g l e s t e p p r o c e s s n = na
C° = bulk c o n c e n t r a t i o n of the r e a c t a n t
E = E l e c t r o d e p o t e n t i a l = E° + vt
E° = standard electrode p o t e n t i a l
D = diffusion constant
A = e l e c t r o d e area
Ep = peak p o t e n t i a l c o r r e s p o n d i n g t o the o x i d a t i o n peak
Equation 28 indicates t h a t a p l o t of l o g i p v e r s u s l o g v
should give a s t r a i g h t l i n e having a slope of 0.5. Figure 30
shows a s t r a i g h t l i n e but h a v i n g a s l o p e of 0.77.
Figure 29
0£ 8^061,3
83
Table 5
I n f l u e n c e of Scan Rate on, K i n e t i c Parameters
Scan I max Ep Ep 2
Ep-Ep 2 n/3
Rate
mV/sec mA. V V
1 .055 .223 . 1 38 .085 0.56
2 .105 .243 . 1 48 .095 0.51
5 .185 .301 . 1 77 .124 0.39
10 .260 .343 .201 .142 0.34
20 .450 .408 .223 . 185 0.26
30 .630 .443 .248 .195 0.25
40 .695 .463 .250 .205 0.23
50 .880 .493 .263 .230 0.21
60 .990 .533 .278 .255 0.19
70 1 .200 (.543) .286 .267 0.18
80 1 .1 50 (.603) .310 .268 0.18
F. E f f e c t of Temperature
c o n t r o l l e d by the f o r m a t i o n of s u r f a c e o x i d a t i o n l a y e r s , i t is
the f l o t a t i o n of a r s e n o p y r i t e .
(i) Experimental
( i i ) R e s u l t s and D i s c u s s i o n
peak t o become s t e e p e r w i t h i n c r e a s i n g t e m p e r a t u r e .
pH 10-75
F i g u r e 31
T e m p e r a tu re / °C
F i g u r e 32
V
I I I I I 1 1—
-0-8 -0-6 -0-4 -0-2 0 0-2 0-4
Potential / V vs S H E
2 0 m V s-» , pH =10-75
F i g u r e 33
M u l t i p l e sweep voltammogram a t 58.5°C
89
d i f f u s i o n of s p e c i e s t o and from t h e e l e c t r o d e .
190 mV ( F i g u r e 1 7 ) .
G. I n f l u e n c e of Cyanide
Figure 34
Comparison of p y r i t e and a r s e n o p y r i t e voltammograms a t 59.8°C
91
The peak f o r t h e o x i d a t i o n of f e r r o u s h y d r o x i d e t o f e r r i c
h y d r o x i d e i s b e l i e v e d t o r e s u l t from t h e f o r m a t i o n of a small
amount of f e r r o u s h y d r o x i d e a t t h e s t a r t of t h e p o t e n t i a l sweep.
I 1 1 I I I t •
-0.8 -0.6 -0.4 -0.2 0 02 0.4 0.6
Potential / V vs SHE
F i g u r e 35
Potential / V vs SHE
Figure 36
I n f l u e n c e of c y a n i d e on f o r m a t i o n of i r o n h y d r o x i d e f i l m s on
arsenopyrite
95
be r e l a t e d t o the v a r i a t i o n i n s u r f a c e composition,
(i) Experimental
F i g u r e 37
4 square m i l l i m e t e r s .
20mV s - , pH = 10.6
F i g u r e 38
F i g u r e 39
i t s p r e s e n c e . The F e ( O H ) / F e ( O H )
2 3 peaks are apparent although
to those formed on m i n e r a l s .
c u r r e n t s i n the r e g i o n where i r o n i s p a s s i v a t e d .
I . R i n g D i s c Study
Voltammogram f o r i r o n e l e c t r o d e
103
N = ir/id = r 3
- r 3
2/3 (29)
r 3 r 2
r 1
r
3
r1
r
3
l_
where
r , = r a d i u s of d i s c
r 2 = i n n e r r a d i u s of ring
r 3 = o u t e r r a d i u s of ring
i r = ring current
id = disc current
Figure 41
T r a n s p o r t p a t t e r n of s o l u b l e s p e c i e s a t a r i n g - d i s c electrode
105
J. I n f l u e n c e of Hydroxide F o r m a t i o n on Xanthate O x i d a t i o n .
r e s u l t i n a r a p i d b u i l d - u p of f e r r i c h y d r o x i d e on the surface,
(i) Experimental.
( i i ) R e s u l t s and Discussion
F i g u r e 42 shows the r e s u l t s of experiments c a r r i e d out at
pH = 5.9. An anodic scan i s shown f o r an a r s e n o p y r i t e e l e c t r o d e
which had been f r e s h l y p o l i s h e d . A scan i s a l s o shown for the
same electrode after it had been held for 5 minutes a t a
p o t e n t i a l of + 460 mV. T h i s p o t e n t i a l i s p a r t way up the anodic
curve for arsenopyrite and represents the p o t e n t i a l region
achieved i n the presence of permanganate a t t h i s pH. The anodic
treatment i s observed t o r e s u l t i n o n l y a minor p a s s i v a t i o n .
Two scans are shown in the presence of 2.6 X 10" 3
M
p o t a s s i u m e t h y l x a n t h a t e . One scan is for a fresh electrode
while the o t h e r i s f o r an e l e c t r o d e as d e s c r i b e d above. At this
pH the o x i d a t i o n of a r s e n o p y r i t e has a n e g l i g i b l e e f f e c t on the
oxidation of xanthate to dixanthogen. This i s consistent with
the view t h a t h y d r o x i d e f i l m s are not formed by the o x i d a t i o n of
a r s e n o p y r i t e at t h i s pH.
Figure 43 shows the results for a similar set of
experiments c a r r i e d out a t pH = 11.8. At t h i s pH, visible films
of f e r r i c h y d r o x i d e are formed.
S e v e r a l d i f f e r e n c e s w i t h the r e s u l t s o b t a i n e d at pH = 5.9
are a p p a r e n t . W h i l e a t pH = 5.9 the o x i d a t i o n of xanthate occurs
107
5 mV s-'
1000 rpm
pH 5-9 Fresh
I I I I I
0 0-2 0-4 0-6
Potential / V vs SHE
F i g u r e 42
I n f l u e n c e of a r s e n o p y r i t e o x i d a t i o n a t pH = 5.9 on x a n t h a t e
oxidation
108
0-4i
5 m V s~ l
1000 rpm
pH 118
0-3
Fresh/ /
FeAsS / /
no X" /
0-2|
< oxidized
E FeAsS
~ 0-1 no X-
J_
-0-2 0 0-2 0-4
Potent i ai / V vs SHE
Figure 4 3
I n f l u e n c e of a r s e n o p y r i t e o x i d a t i o n a t pH = 11.8 on x a n t h a t e
oxidation
109
at potentials which a r e c a t h o d i c t o a r s e n o p y r i t e o x i d a t i o n , a t
pH = 11.8 these two c u r v e s a r e reversed. This indicates that
oxidation of arsenopyrite will be favored over xanthate
o x i d a t i o n a t t h i s pH.
4.4 D i s c u s s i o n
r e l a t i v e l y t h i c k s u r f a c e l a y e r s of f e r r i c h y d r o x i d e . At the same
Figure 4 4
Chapter 5
ESCA STUDIES
d e t e c t e d even a t pH = 3.0.
5.1 Experimental
v i s u a l l y judged t o be f r e e of o t h e r m i n e r a l i m p u r i t i e s .
use.
5.2 R e s u l t s and D i s c u s s i o n
Table 6
E l e c t r o n b i n d i n g e n e r g i e s and i n t e n s i t i e s f o r elements i n
various minerals.
FeOOH Fe 713.6 21 1 37
AS 2 S 3 S 163.4 7406
AS 44.1 4403
FeS 2 (pyrite) Fe 712.3 758
709.4 5758
S 169.7 1 352
163.7 5395
FeS 2 (marc.) Fe 713.7 1879
709.5 5949
S 170.9 1692
164.9 4187
FeAs 2 Fe 713.9 1707
709.5 2347
As 46.9 1546
43.8 2289
FeAsS (dry) Fe 712.9 5646
708.6 2761
As 47.2 1 1 67
44.1 525
S 170.6 549
165.0 1234
FeAsS (pH 11.5) Fe 712.8 1 1 921
708.5 1322
AS 47.1 2067
43.4 281
S 171.1 837.8
165.5 831 .4
I n t e n s i t y r a t i o s of o x i d i z e d t o t o t a l s u r f a c e species for
Figure 45
FeAs,
FeAsS-
FeAsS
A s
a 3
S
± ± JL
33-3 36-8 40-4 439 47-5 510 54-5
BINDING ENERGY / eV
F i g u r e 46
I I I I I I I
162-6 165-6 168-5 171-5 174-5 177-5
BINDING ENERGY / eV
Figure 4 7
S e v e r a l t r e n d s in t h e s e d a t a a r e c o n s i s t e n t w i t h p r e v i o u s l y
c i t e d c h a r a c t e r i s t i c s f o r m a r c a s i t e c o m p a r e d to p y r i t e and w i t h
the e l e c t r o c h e m i c a l r e s u l t s f o r a r s e n o p y r i t e w h i c h a r e p r e s e n t e d
in t h i s s t u d y .
M a r c a s i t e shows a g r e a t e r p r o p o r t i o n of o x i d i z e d s p e c i e s
than d o e s p y r i t e . T h i s i s c o n s i s t e n t w i t h m a r c a s i t e s h o w i n g
p u b l i s h e d XPS r e s u l t s f o r t h e s e m i n e r a l s (77).
A r s e n o p y r i t e shows an even g r e a t e r p r o p o r t i o n of o x i d i z e d
s u r f a c e s p e c i e s than e i t h e r p y r i t e or m a r c a s i t e . It i s a p p a r e n t
t h a t a l t h o u g h the a r s e n o p y r i t e was c r u s h e d in a d r y f o r m , a
s u r f a c e o x i d e l a y e r was f o r m e d . T h i s h e l p s to e x p l a i n the
as t h o s e at h i g h e r p H , i n d i c a t i n g a c o n s i s t e n t s u r f a c e l a y e r to
be p r e s e n t . T h e s e r e s u l t s c a n now be r e c o n c i l e d on the b a s i s
T a b l e 7
XPS I n t e n s i t y r a t i o s
M i n e r a l ox F e / F e ox S / S ox A s / A s F e / A s F e / S
t h a t in e a c h c a s e a s u r f a c e l a y e r of i r o n h y d r o x i d e was formed
121
Chapter 6
FLOTATION STUDIES
6.0.1 Rougher F l o t a t i o n
6.0.1.1 E x p e r i m e n t a l .
a r s e n o p y r i t e i n a s i l i c e o u s gangue. A m i c r o s c o p i c e x a m i n a t i o n of
v a r y i n g pH.
6.0.2 R e s u l t s and D i s c u s s i o n
F l o a t a b i l i t y of a r s e n o p y r i t e at i n c r e a s i n g pH i n the presence
and absence of o x i d a t i o n
126
6.0.3 D e p r e s s i o n of P r e v i o u s l y A c t i v a t e d A r s e n o p y r i t e
6.0.3.1 Experimental
sodium h y p o c h l o r i t e .
a r s e n o p y r i t e c o n c e n t r a t e was p r e p a r e d a c c o r d i n g t o t h e f l o t a t i o n
10 20 30 40 50 60
Temperature / °C
Figure 49
I n f l u e n c e of temperature on a r s e n o p y r i t e floatability
128
Table 8
F l o t a t i o n Conditions
Stage Isopropyl Amyl/ Dowfroth Time
Xanthate Xanthate 250 minutes
g/tonne g/tonne g/tonne
Conditioning 150 50 5 2
Rougher 37.5 10 17.5 15
1st. Cleaner 20 10 2.5 10
2nd. Cleaner 10 — 2.5 8
A f r e s h l y p o l i s h e d a r s e n o p y r i t e e l e c t r o d e was immersed i n t o
the f l o t a t i o n c e l l f o r each t e s t and the e l e c t r o d e p o t e n t i a l was
monitored r e l a t i v e to a calomel electrode.
The a r s e n o p y r i t e recovery shown f o r each t e s t i s t h a t which
was achieved w i t h no a d d i t i o n of x a n t h a t e f o l l o w i n g o x i d a t i o n .
mg/litre H 0 . 2 2
Table 9
F l o t a t i o n r e s u l t s u s i n g hydrogen p e r o x i d e as an o x i d a n t
Test Conditions Arsenopyrite As
No. Eh,mV Recovery %
1 No o x i d a t i o n 213 t o 233 97.1
2 357 m g / l i t r e H 0 2 2 363 1 1 .6
cond. 5 min.
3 357 m g / l i t r e H 0 2 2 368 3.3
cond. 15 min.
4 214 m g / l i t r e H 0 2 2 323 t o 353 6.0
cond. 15 min.
T a b l e 10
F l o t a t i o n r e s u l t s u s i n g sodium h y p o c h l o r i t e as an o x i d a n t
p e r c e n t t o 30 p e r c e n t a d d i t i o n a l a r s e n o p y r i t e r e c o v e r y .
6.0.4 S e l e c t i v e F l o t a t i o n of P y r i t e From A r s e n o p y r i t e
6.0.4.1 E x p e r i m e n t a l and R e s u l t s .
flotation of t h e s i l v e r c i r c u i t ( t e t r a h e d r i t e and c h a l c o p y r i t e )
Table 11
F l o t a t i o n Test R e s u l t s w i t h E q u i t y Concentrate
H 0 2 2 Conditioning Arsenopyrite Pyrite
mg/litre Time Recovery Recovery
minutes % %
0 - 92.3 92.4
357 5 17.5 61.4
178 5 18.5 55.2
178 0 35.1 63.2
71 5 23.6 53.2
71 15 26.3 49.2
( i i ) Giant Y e l l o w k n i f e Concentrate
produced w i t h a d d i t i o n s of copper s u l p h a t e as w e l l as x a n t h a t e .
!00
80
>*60
0 FeAsS,77.6mg r'NaCIO
>
O
• FeS ,7 76 mg r'NaCIO
«40 2
8 9 10 12
PH
F i g u r e 50
I n f l u e n c e of o x i d a t i o n on p y r i t e and a r s e n o p y r i t e floatability
a t i n c r e a s i n g pH
134
6.0.4.2 D i s c u s s i o n
IOOI ;
71 m g r« NaEtX
80-
^60-
a>
S40-
o
rr
250
KMn04 / m g I"1
F i g u r e 52
D e p r e s s i o n of a r s e n o p y r i t e from b u l k c o n c e n t r a t e w i t h i n c r e a s i n g
permanganate a d d i t i o n
137
c o n s i d e r a b l e e f f o r t would be r e q u i r e d t o o p t i m i z e the c o n d i t i o n s
f o r s e p a r a t i o n . These optimum c o n d i t i o n s can be expected t o vary
depending on the p y r i t e t o a r s e n o p y r i t e r a t i o and on the h i s t o r y
of the c o n c e n t r a t e .
Chapter 7
CONCLUSIONS
4. The p r e s e n c e of f e r r i c h y d r o x i d e d e p o s i t s on t h e s u r f a c e of
arsenopyrite inhibits t h e o x i d a t i o n of xanthate to dixanthogen.
Dixanthogen i s believed t o be the a c t i v e c o l l e c t o r s p e c i e s on
139
arsenopyrite.
5. Flotation studies show arsenopyrite to be increasingly
depressed with increasing pH when the ore s l u r r y has been
conditioned i n t h e presence of aeration prior to xanthate
a d d i t i o n . T h i s i n f l u e n c e of pH h o l d s t r u e over t h e pH range from
7 t o 12. At pH l e s s than 7, a r s e n o p y r i t e shows h i g h floatability
due to t h e absence of hydroxide films and t h e presence of
elemental sulphur.
Chapter 8
Fundamental r e s e a r c h s h o u l d be d i r e c t e d a t f u r t h e r study of
the growth and morphology of h y d r o x i d e f i l m s on a r s e n o p y r i t e .
The i n f l u e n c e of v a r i o u s d e p r e s s a n t s and activating agents on
the structure of the hydroxide layers should also be
i n v e s t i g a t e d . While additional electrochemical studies could
contribute much t o t h e u n d e r s t a n d i n g of these s u r f a c e deposits,
the use of s p e c t r o s c o p i c t e c h n i q u e s w i l l be r e q u i r e d t o g i v e a
complete a p p r e c i a t i o n of t h e i r nature.
Applied research should be directed at optimizing the
utilization of surface oxidation for the depression of
arsenopyrite from o t h e r m i n e r a l s , p a r t i c u l a r l y p y r i t e . W h i l e t o
some e x t e n t t h e optimum conditions can be expected t o be
specific f o r each m i n e r a l o c c u r r e n c e , a s i g n i f i c a n t common base
i s a n t i c i p a t e d . The i n f l u e n c e of o t h e r d i s s o l v e d s p e c i e s such as
calcium i o n or soluble silicates on arsenopyrite depression
s h o u l d a l s o be e v a l u a t e d .
142
Appendix I
f o r each diagram a r e as f o l l o w s :
a r s e n i c a c t i v i t i e s of 10~ 3
M.
and F e A s 2 as p o s s i b l e s t a b l e s p e c i e s . S t a b i l i t y domains of A s S 2 2
s t a b i l i t y r e g i o n f o r f e r r i c a r s e n a t e a t 1 molar a c t i v i t y of i r o n
T a b l e 12
Thermodynamic Data a t 25°C
HS" aq 2.88 80
s - 2
aq 20.5 80
HS0 - 4 aq -180.69 80
S0 " 4
2
aq -177.97 80
HS 2 aq -6.66 80
s s 0 80
H AsO„
3 aq -184.0 82
H AsO
2 ft
_
aq -181.0 82
HAsOa " 2
aq -171.5 82
AsO„ ' 3
aq -155.8 82
H As0
3 3 aq -154.4 82
H As0 "
2 3 aq -141.8 82
HAs0 ~ 3
2
aq -125.3 82
AsH 3 aq 23.8 82
AS s 0 82
As S 2 2 s -17.0 81
As S 2 3 s -23.0 81
FeAsS s -26.2 81
FeAs 2 s -12.5 81
FeAsOo s -185.18 83
Fe 3 +
aq -1.1 80
Fe 2 +
aq -18.85 80
HFe0 " 2
aq -90.6 80
FeS s -24 80
FeS 2 s -38.3 80
Fe(OH) 2 s -116.3 80
Fe(OH) 3 s -116.5 80
144
Figure 53
Figure 54
Figure 55
Figure 56
A r s e n o p y r i t e s t a b i l i t y diagram at 1 M a c t i v i t y of d i s s o l v e d
spec i e s
148
Figure 57
1. FeAsS + 2H +
= Fe + +
+ H S + As.
2
2. F e 2 +
+ H As0
3 3 + HS + H 2
+
+ 3e" = FeAsS + 3H 0 2
4. F e ( O H ) 2 + H A s 0 - + SO,'" + 14H
2 3
+
+ 11e" = FeAsS + 9H 0 2
6. F e ( O H ) 2 + HAs0 - 3
2 +
HS" + 6H +
+ 3e" = FeAsS + 5H 0 2
7. FeAsS + 5H +
+ 3e" = A s H 3 + Fe + +
+ HS 2
8. FeAsS + 5H +
+ 5e~ = A s H 3 + H S + Fe 2
9. FeAsS + 4H +
+ 5e" = A s H 3 +HS" + Fe
10. FeAsS + H +
+ 2e" = A s H 3 + HS" + Fe
12. 2 H A s 0
3 3 + SO„-- + 30H +
+ 24e" = A s S 2 3 + 18H 0 2
13. A s S 2 2 + 4H +
+ 4e" = 2As + 2H S 2
E = - 0.040 - 0.0148 l o g ( H S ) 2
2
- 0.0591 pH
14. A s S 2 2 + 2H +
+ 4e" = 2As + 2HS"
E = -0.0247 - 0.0148 l o g ( H S " ) 2
- 0.0295 pH
15. 2 H A s 0
3 3 + 2SO„-- + 22H +
+ I8e" = A s S 2 2 + 14H 0 2
17. H A s 0 - + 2HS" + 6H
2 3
+
+ 2e" = A s S 2 2 + 6H 0 2
18. A s S 2 3 + 2H +
+ 2e" = A s S 2 2 + HS 2
152
E = 0.0143 -0.0148 l o g ( H S ) 2
2
- 0.0591 pH
19. A s S 2 3 + H +
+ 2e" = A s S 2 2 + HS'
20. A s S 2 2 + S 0 " - + 3H
4
+
+ 6e" = A s S 2 3 + 4H 0 2
21. 1/2 A s S 2 3 + Fe ++
+ H +
+ 3e" = FeAsS + 1/2 H S 2
(Fe ) ++
22. 1/2 A s S 2 2 + Fe + +
+ 2e" = FeAsS
E = -0.025 +0.0295 l o g ( F e ) + +
23. 2 H A s 0
3 3 + Fe(OH) 2 + 8H +
+ 8e" = F e A s 2 + 8H 0 2
E = 0.220 + 0.007 l o g ( H A s 0 ) 3 3
2
- 0.059 pH
24. F e + +
+ 2As + 2e" = F e A s 2
E = -0.138 + 0.0295 l o g ( F e ) + +
25. 2 H A s 0
3 3 + Fe + +
+ 6H +
+ 8e" = FeAs + 6H 0 2 2
E = 0.135 + 0.007 l o g ( H A s 0 ) 3 3
2
( F e ) - 0.044 pH
+ +
26. FeAs2 + 6H +
+ 6e" = Fe + 2AsH 3
E = -0.434 - 0.010 l o g ( A s H ) 3
2
- 0.059 pH
27. F e A s 2 + 6H +
+ 4e" = F e + +
+ 2AsH 3
153
E = - 0.447 - 0.015 l o g ( A s H ) 3
2
( F e ) - 0.089 pH
+ +
28. 2 H A s 0 - + Fe(OH)
2 3 2 + 10H +
+ I8e" = F e A s 2 + H 0 2
E = 0.537 + 0.007 l o g ( H A s 0 - ) 3
2 2
- 0.089 pH
30. 1/2 A s S 2 3 + Fe + +
+ 2e" = FeAsS + 1/2 S
E = - 0.090 + 0.0295 l o g ( F e ) + +
31. F e 2 +
+ 2SO, - + 14e" = F e S
2
2 + 8H 0 2
32. F e S 2 + 4H +
+ 2e" = F e 2 +
+ 2H S 2
E = - 0.133 - 0.0296 l o g ( F e ) ( H S ) 2 +
2
2
- 0.118 pH
33. F e S 2 + 2H +
+ 2e" + As = FeAsS + H S 2
34. F e S 2 + As + H +
+ 2e" = FeAsS + HS"
36. F e S 2 + H A s 0 " + 5H
2 3
+
+ 5e" = FeAsS + HS" + 3H 0 2
(H As0 ~) 2 3
37. F e S 2 + H +
+ 2e~ = FeS + HS"
38. F e ( O H ) 2 + HS" + H +
= FeS + 2H 0 2
39. FeAsS + As + 2H +
+ 2e" = F e A s 2 + HS 2
40. FeAsS + As + H +
+ 2e" = F e A s 2 + HS"
E = -0.359 - 0.0295 log(HS') - 0.0295 pH
43. FeAsO« + 3H +
= H AsO„ + F e
3
3 +
pH = 0.12 - 1/3 l o g ( H A s O , , ) ( F e ) 3
3+
pH = 5.30 + l o g ( H A s O - ) 2 fl
45. FeAsO„ + 3H +
+ e- = F e 2 +
+ H AsO 3 a
E = 0.766 - 0.0.59 l o g ( F e ) (H AsO«) - 0.177 pH
2+
3
FeAsO fl + 5H +
+ 3e" = H A s 0
3 3 + Fe 2 +
+ H 0
2
100
• Figure 1.
oxidation
Voltammograms f o r p l a t i n u m
i n presence and absence of <
xanthate ( 4 9 ) . 3.
Q
I—
£ -too
a. Reduction
3
-150 j i_
-04 0 04 08
POTENTIAL/ V (vs. S H.E.)
Figure 2.
Voltammogram f o r a r s e n o p y r i t e
a t pH = 8.2 s h o w i n g p o t e n t i a l s
a c h i e v e d with o x i d i z i n g agents,
Figure 3.
M u l t i p l e sweep voltammogram
for rotating electrode at
pH = 11.7
500/1 A
20 m V s - i , H=II.7
P
Potential / V vs SHE
157
REFERENCES
( 1 963) .
p r o p e r t i e s of p y r i t e e l e c t r o d e s ", J . E l e c t r o a n a l . Chem.