Anda di halaman 1dari 179

FLOTATION CHARACTERISTICS OF ARSENOPYRITE

by

M o r r i s John A l o y s i u s Vreugde

B.A.Sc. The U n i v e r s i t y of B r i t i s h Columbia, 1971


M.A.Sc. The U n i v e r s i t y of B r i t i s h Columbia, 1973

A THESIS SUBMITTED IN PARTIAL FULFILMENT OF


THE REQUIREMENTS FOR THE DEGREE OF
DOCTOR OF PHILOSOPHY
in

THE FACULTY OF GRADUATE STUDIES

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

© M o r r i s John A l o y s i u s Vreugde, 1 982


In p r e s e n t i n g t h i s t h e s i s i n p a r t i a l f u l f i l m e n t of the
requirements f o r an advanced degree a t the University
o f B r i t i s h Columbia, I agree t h a t the L i b r a r y s h a l l make
it f r e e l y a v a i l a b l e f o r reference and study. I further
agree t h a t p e r m i s s i o n f o r e x t e n s i v e copying o f t h i s t h e s i s
f o r s c h o l a r l y purposes may be granted by the head o f my
department or by h i s o r her representatives. It i s
understood t h a t copying or p u b l i c a t i o n of t h i s t h e s i s
f o r f i n a n c i a l gain s h a l l not be allowed without my written
permission.

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.

ESCA s t u d i e s confirmed the formation of oxidized iron


layers at the surface of arsenopyrite and revealed that
e s s e n t i a l l y a l l the a r s e n a t e which was formed was incorporated
in these l a y e r s . Sulphur became o x i d i z e d a t the pH s t u d i e d and
t o a l a r g e e x t e n t went i n t o s o l u t i o n .

F l o t a t i o n s t u d i e s demonstrated the use of oxidation for


arsenopyrite depression. In the presence of oxidation,
i n c r e a s i n g pH above pH = 7 r e s u l t e d in increased arsenopyrite
depression w h i l e i n c r e a s i n g temperature had l i t t l e e f f e c t u n t i l
a temperature of 40°C was exceeded. Previously activated
arsenopyrite could be depressed through the use of o x i d i z i n g
agents. Arsenopyrite c o u l d be s e l e c t i v e l y d e p r e s s e d from a bulk
pyrite-arsenopyrite concentrate through the use of o x i d i z i n g
agents.
ACKNOWLEDGEMENT

The a u t h o r wishes t o e x p r e s s s i n c e r e thanks t o Dr. G.W.


Poling f o r h i s support and guidance d u r i n g t h e c o u r s e of t h i s
work.

P a r t i c u l a r a p p r e c i a t i o n i s expressed t o D r . W.G. Bacon


without whose help t h i s p r o j e c t c o u l d not have been initiated
and who ensured t h e c o n t i n u e d support of Bacon, Donaldson and
Associates Ltd.

The i n c e n t i v e t o i n i t i a t e t h i s p r o j e c t and t h e endurance t o


carry i t through t o c o m p l e t i o n r e s u l t s from an unending desire
t o c a r r y my e d u c a t i o n t o t h e h i g h e s t a t t a i n a b l e l e v e l . My most
h e a r t f e l t a p p r e c i a t i o n i s e x p r e s s e d t o my p a r e n t s f o r i n s t i l l i n g
in me the desire t o l e a r n and t o my w i f e , K a t e , whose t o t a l
support and o f t e n e s s e n t i a l encouragement enabled me t o fulfill
my d e s i r e .

Appreciation i s also expressed t o Morny w i t h o u t whose


u n s e l f i s h e f f o r t s t h i s manuscript c o u l d not have been completed.
Mr. Stephen P i c k e t t of t h e Department of Chemistry is
a p p r e c i a t e d f o r h i s time i n p e r f o r m i n g t h e ESCA a n a l y s e s .

Financial a s s i s t a n c e i n t h e form of a B.C. S c i e n c e C o u n c i l


Grant i s g r a t e f u l l y acknowledged.
iv

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

2.2 Nature Of Adsorbed Xanthate S p e c i e s 10

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

2.5 A r s e n o p y r i t e C o m p o s i t i o n And Phase R e l a t i o n s 16


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 A r s e n o p y r i t e 19
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 20
3 OBJECTIVES OF THE PRESENT INVESTIGATION 23
4 ELECTROCHEMICAL STUDIES 25
4.1 E l e c t r o d e P o t e n t i a l Measurements 25
4.1.1 E x p e r i m e n t a l 25
4.1.2 O x i d i z i n g Agents 28
4.2 R e s u l t s And D i s c u s s i o n 32
4.3 C y c l i c Voltammetry 40
4.3.1 E x p e r i m e n t a l 42
4.3.2 R e s u l t s And D i s c u s s i o n 45
A. S i n g l e Sweep Voltammograms 45
B. M u l t i p l e Sweep ( C y c l i c ) Voltammetry 57
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 Formation 70
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 73
E. E f f e c t Of Sweep Rate 76

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

H. Other M i n e r a l s In The Fe - As - S System 95

( i ) Experimental 95

( i i ) Results 97

I . Ring D i s c Study 101

J. Influence Of Hydroxide Formation On Xanthate

Oxidation 105

4.4 Discussion 109

5 ESCA STUDIES 113

5.1 Experimental 114

5.2 R e s u l t s And D i s c u s s i o n 115

6 FLOTATION STUDIES 122

6.0.1 Rougher F l o t a t i o n 122

6.0.1.1 E x p e r i m e n t a l 122

6.0.2 R e s u l t s And Discussion 124

6.0.3 Depression 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 ..126

6.0.3.1 E x p e r i m e n t a l .....126

6.0.3.2 R e s u l t s And Discussion 128

6.0.4 Selective 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 ..130

6.0.4.1 E x p e r i m e n t a l And Results 130

( i ) Equity Concentrate 130

( i i ) Giant Y e l l o w k n i f e Concentrate 131

6.0.4.2 D i s c u s s i o n 134

7 CONCLUSIONS 138

8 RECOMMENDATIONS FOR FUTURE WORK 141

Appendix I - P o t e n t i a l / p H Diagrams For The Iron - Arsenic -

S u l p h u r - Water System 142


Appendix I I - E q u a t i o n s Used For The C o n s t r u c t i o n Of The

Diagrams 150

Appendix I I I - F o l d o u t Of Important Diagrams 156

References 157
vi i

T a b l e of F i g u r e s

1 M i n e r a l s i n the Fe-As-S system 4

2 A r s e n o p y r i t e from Hedley, B.C. (3600x) 5


3 G i a n t Y e l l o w k n i f e Mines Flowsheet 6

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

21 M u l t i p l e sweep voltammograms f o r s t a t i o n a r y and r o t a t i n g


e l e c t r o d e s a t pH = 11.7 61
vi ii

22 M u l t i p l e sweep voltammograms a t pH = 5.8 69

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

41 T r a n s p o r t p a t t e r n of soluble species at a ring - disc


electrode 104

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

43 I n f l u e n c e of arsenopyrite oxidation at pH = 11.8 on


xanthate o x i d a t i o n 108

44 Comparison of a r s e n o p y r i t e rest potential and oxidation


peak p o t e n t i a l w i t h o p e r a t i n g p l a n t c o n d i t i o n s (70) 111

45 XPS peaks associated with the i r o n 2p e l e c t r o n s of the


various minerals 117

46 XPS peaks a s s o c i a t e d w i t h the a r s e n i c 3d e l e c t r o n s of the


various minerals 118

47 XPS peaks a s s o c i a t e d w i t h the s u l p h u r 2d e l e c t r o n s of the


various minerals 119
48 F l o a t a b i l i t y of arsenopyrite at increasing pH in the
presence and absence of o x i d a t i o n 125
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 f l o a t a b i l i t y 127
50 I n f l u e n c e of oxidation on pyrite and arsenopyrite
f l o a t a b i l i t y a t i n c r e a s i n g pH 133
51 D e p r e s s i o n of arsenopyrite from bulk concentrate with
i n c r e a s i n g xanthate a d d i t i o n 135
52 D e p r e s s i o n of arsenopyrite from bulk concentrate with
i n c r e a s i n g permanganate a d d i t i o n 136
53 A r s e n o p y r i t e stability diagram at 10" 6
M activity of
dissolved species 144
54 A r s e n o p y r i t e stability diagram at 10" 3
M activity of
dissolved species 145
55 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
species 146

56 L o e l l i n g i t e stability diagram at 10~ 3


M activity of
dissolved species 147
X

57 A r s e n o p y r i t e stability diagram considering FeS,FeS 2 and

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

7 XPS Intensity Ratios 120


8 F l o t a t i o n Conditions 128
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 Oxidant ....129
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 Oxidant .130
11 F l o t a t i o n Test R e s u l t s With E q u i t y C o n c e n t r a t e 13.1
12 Thermodynamic Data At 25°C 143
1

Chapter 1

INTRODUCTION

A r s e n i c o c c u r s i n n a t u r e w i t h numerous other elements. A


number of p r i m a r y and secondary arsenic minerals are l i s t e d i n
Table 1. Those a r s e n i c m i n e r a l s which l i e i n t h e Fe-As-S system
are shown i n F i g u r e 1. A r s e n o p y r i t e i s t h e most common m i n e r a l
c o n t a i n i n g a r s e n i c . I t i s found w i t h silver and copper ores,
g a l e n a , s p a l e r i t e and p y r i t e .

In certain ores arsenopyrite has c o n s i d e r a b l e economic


s i g n i f i c a n c e s i n c e i t c a r r i e s t h e major p o r t i o n of g o l d i n the
ore. Such g o l d may occur as d i s c r e t e g r a i n s between i n d i v i d u a l
c r y s t a l s of a r s e n o p y r i t e and as such be recoverable from an
a r s e n o p y r i t e c o n c e n t r a t e by d i r e c t c y a n i d a t i o n ( 1 ) .

Gold may also occur in solid solution or as minute


inclusions i n arsenopyrite (2) and may require more exotic
recovery procedures ( 3 ) . An example of such an o c c u r r e n c e from
the Hedley a r e a of B r i t i s h Columbia i s shown i n F i g u r e 2. The
most s u c c e s s f u l treatment of o r e s of t h i s type t o date has been
a c h i e v e d by f l o t a t i o n of an arsenopyrite bearing concentrate
which i s subsequently r o a s t e d and then c y a n i d e d . Such a p r o c e s s
is i n operation at Giant Yellowknife Mines Ltd. ( 4 , 5 ) . A
f l o w s h e e t f o r t h i s o p e r a t i o n i s shown i n F i g u r e 3 .

While this process f o r the recovery of gold from


a r s e n o p y r i t e i s very s u c c e s s f u l from a metallurgical point of
view, there are serious p o l l u t i o n consequences ( 6 ) . The data
2
Table 1
Arsenic Minerals

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

Pearcite (Ag,Cu), As S,! 6 2

Tennantite (Cu,Fe,Zn,Ag), As S, 2 fl 3

Sperrylite PtAs 2

Allemontite AsSb
Geocronite Pb (Sb,As) S
5 2 8

Scorodite FeAsO «2H 0 a 2

Pitticite Fe (As0 )(SO„)OH»2H 0


2 2 2

Pharmacosiderite 6FeAsO„«2Fe(OH) «12H 0 3 2

Symplesite Fe As 0 «8H 0
3 2 3 2

Erythrite C0 (AsO«) «8H 0


3 2 2

Annabergite Ni (AsO„) «8H 0


3 2 2

shown i n T a b l e 2 i n d i c a t e t h a t 47.5% of arsenic emissions in


Canada result from t h e 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 o r e s .
The predominant source of aqueous c o n t a m i n a t i o n by arsenic i s
also i n d u s t r i a l smelting operations (6).
As a commodity, a r s e n o p y r i t e i s of minor consequence. While
in the 1920's the m i n e r a l was viewed as a v a l u a b l e p o t e n t i a l
source of a r s e n i c f o r t h e c o n t r o l of pests such as the boll
w e a v i l ( 7 ) , a t p r e s e n t i t i s viewed as a troublesome impurity i n
base metal concentrates (8,59). While t h e a r s e n i c p r e s e n t i n
such c o n c e n t r a t e s i s r e c o v e r e d t o some e x t e n t , t h e t o t a l yearly
demand for arsenic i n t h e U.S. i s o n l y 15,000 tons (13,600
tonnes) (9) and t h e r e c o v e r y of a r s e n i c from waste streams is
c o s t l y . Smelters at present p r e f e r t o receive concentrates which
are e s s e n t i a l l y f r e e of a r s e n i c .
3

The presence of a r s e n o p y r i t e i n s u l p h i d e c o n c e n t r a t e can

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

s m e l t e r gases w i t h a r s e n i c . The presence of a r s e n o p y r i t e i n such

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

gold precipitation in cyanide circuits (10) or

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 ) .

The association of arsenopyrite with pyrite is of

particular interest. This association i s wide spread and can

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

Arsenopyrite f r o m H e d l e y , B.C. (3600x)


PRIMARY
CRUSHING
Underground

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 -

TAILINGS<HSAND PLANT P [CONCENTRATE


STORAGE
Thickening
. >| CYCLONE I lit CALCINE
WASH
S
BACKFILL

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

acid by arsenic ( 1 1 ) . In gold ores t h e g o l d v a l u e s may be


e n t i r e l y associated with either mineral.

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.

S i n c e fundamental i n v e s t i g a t i o n s of the aqueous surface


chemistry of a r s e n o p y r i t e have p r e v i o u s l y not been u n d e r t a k e n , a
comprehensive literature survey relating t o t h i s m i n e r a l was
c a r r i e d o u t . W h i l e c e r t a i n a s p e c t s of t h i s review may not have
apparent s i g n i f i c a n c e t o t h e f l o t a t i o n response of a r s e n o p y r i t e
they a r e b e l i e v e d t o c o n t r i b u t e t o t h e o v e r a l l u n d e r s t a n d i n g of
i t s occurence and b e h a v i o u r .
8

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 .

Sutherland and Wark ( 1 2 ) showed the c r i t i c a l pH (above


which flotation d i d not o c c u r ) f o r f l o t a t i o n of a r s e n o p y r i t e
9

w i t h 25 mg. p e r l i t r e of e t h y l x a n t h a t e t o be pH=8.4 compared t o


a v a l u e of pH=l0.5 f o r p y r i t e .

Mitrofanov (13) i n d i c a t e d the maximum recovery of


a r s e n o p y r i t e t o be a c h i e v e d i n t h e range of pH from 4 t o 6.

Plaksin (14) and l a t e r G l e m b o t s k i e t a l (15) d i s c u s s e d t h e


i n f l u e n c e of c r y s t a l s t r u c t u r e on t h e o x i d a t i o n of p y r i t e and
arsenopyrite. The position of s u l p h u r atoms i n t h e p y r i t e was
considered t o be such t h a t they c o u l d i n t e r a c t w i t h oxygen and
produce soluble species which l e f t the s u r f a c e as new p y r i t e ,
s t i l l able t o react with reagents. The more complex s t r u c t u r e of
a r s e n o p y r i t e was b e l i e v e d t o r e s u l t i n slower oxidation rates
than f o r p y r i t e . P r o l o n g e d o x i d a t i o n was b e l i e v e d t o r e s u l t i n
d e c o m p o s i t i o n of t h e a r s e n o p y r i t e l a t t i c e w i t h both s u l p h u r and
a r s e n i c being o x i d i z e d . The a r s e n i c o x i d e groups were p o s t u l a t e d
t o remain a t t h e m i n e r a l ' s surface.
The different susceptibility of t h e two minerals to
o x i d a t i o n has been e x p l o i t e d by Nekrasov (16) and Machovic (17)
to achieve a separation. A bulk pyrite - arsenopyrite
concentrate was produced and conditioned with an oxidizing
agent. Nekrasov used an a d d i t i o n of Mn0 2 f o l l o w e d by a two hour
conditioning period with aeration t o depress arsenopyrite.
Machovic used a d d i t i o n s of KMnO„ t o depress a r s e n o p y r i t e while
floating pyrite. Similar use of permanganate to depress
a r s e n o p y r i t e and p y r r h o t i t e s e l e c t i v e l y from p y r i t e has been t h e
s u b j e c t of p a t e n t s (18).

Glembotski et a l . (15) related the greater oxygen


concentration required for arsenopyrite flotation compared to
that required for pyrite flotation to their different
10

s u s c e p t i b i l i t y t o o x i d a t i o n . Rand (19) p r o v i d e d an explanation


for t h e d i f f e r e n t oxygen r e q u i r e m e n t s which i s more i n keeping
with current f l o t a t i o n theory. He showed that pyrite has a
greater oxygen r e d u c t i o n a c t i v i t y than has a r s e n o p y r i t e . P y r i t e
t h e r e f o r e r e q u i r e s lower oxygen concentration in solution to
provide the cathodic oxygen reduction reaction required to
balance t h e anodic o x i d a t i o n of x a n t h a t e . Similar results and
i n t e r p r e t a t i o n s were p r e s e n t e d by B i e g l e r e t a l . ( 2 0 ) .

The use of magnesia mixture as a depressant for


a r s e n o p y r i t e has been proposed ( 2 1 ) . The depressant mixture was
prepared from magnesium c h l o r i d e , ammonium c h l o r i d e and ammonium
hydroxide w i t h d i s t i l l e d w a t e r . The m i x t u r e was found t o g i v e a
h i g h degree of a r s e n o p y r i t e d e p r e s s i o n a t pH v a l u e s g r e a t e r than
8. C h a l c o p y r i t e was a l s o found t o be d e p r e s s e d by this mixture
i f t h e m i n e r a l was f i r s t c o n d i t i o n e d w i t h A s l . P y r i t e was found
3

to be unaffected by the mixture. I t was concluded that


depression r e s u l t e d from t h e f o r m a t i o n of a s t r o n g l y h y d r o p h i l i c
compound, MgNH AsO(,6H 0fl 2 on the surface of arsenopyrite. No
d i r e c t e v i d e n c e t o support t h i s c o n c l u s i o n was p r e s e n t e d .

2.2 Nature of Adsorbed X a n t h a t e Species

Very l i m i t e d work has been r e p o r t e d i n t h e l i t e r a t u r e w i t h

regard to t h e nature of adsorbed xanthate species on

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

reaction product. The l i m i t s of d e t e c t i o n were i n d i c a t e d t o be

such t h a t up t o 5 p e r c e n t of t h e minor product (i.e. ferric

x a n t h a t e ) c o u l d be p r e s e n t .

Although additional i n v e s t i g a t i o n s i n t o t h e nature of t h e


11

r e a c t i o n p r o d u c t s of a r s e n o p y r i t e w i t h x a n t h a t e have not been


reported, i t i s of interest to note the s i m i l a r i t i e s w i t h
p y r i t e . Both m i n e r a l s were r e p o r t e d t o have d i x a n t h o g e n as t h e
predominant collector product and both have f e r r i c x a n t h a t e as
the a l t e r n a t i v e c o l l e c t o r p r o d u c t (22,24). I n t h e presence of
oxygen, both minerals also have mixed p o t e n t i a l s which a r e
g r e a t e r than t h e e q u i l i b r i u m p o t e n t i a l f o r x a n t h a t e o x i d a t i o n t o
dixanthogen.

In s p i t e of t h e seeming consistency of these findings,


controversy has continued as to t h e n a t u r e of the p r o d u c t s
formed by t h e i n t e r a c t i o n of p y r i t e w i t h x a n t h a t e in solution.
Various investigators (23,24,25,26) have s t u d i e d t h e n a t u r e of
the c o l l e c t o r s p e c i e s on pyrite. Each of these studies has
c o n c l u d e d t h e predominant s u r f a c e product t o be d i x a n t h o g e n . The
continued controversy appears t o r e s u l t from t h e d e t e r m i n a t i o n
of some i n v e s t i g a t o r s t o e s t a b l i s h a s i n g l e adsorbed p r o d u c t and
to n e g l e c t t h e r o l e p l a y e d by minor c o n c e n t r a t i o n s of other
adsorbed s p e c i e s (27,28).

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 electrochemical oxidation of adsorbed xanthate to


d i x a n t h o g e n can be r e p r e s e n t e d by:

X 2 + 2e" == 2X" (1)

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 ) .

1/2 0 2 + H 0 + 2e" == 20H'


2 (2)

0 2 + 4H +
+ 4e" == 2H 0 2 (3)

The above r e a c t i o n s o c c u r i n g v i a p e r o x i d e intermediate (23).


In the iron system, o x i d a n t s o t h e r than oxygen a r e a l s o
possible (24).

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)

Although the preceding review was based on work with


pyrite, i t appears consistent t o assume that t h e same
c o n c l u s i o n s can be made f o r the a r s e n o p y r i t e - xanthate - oxygen
system.

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 arsenopyrite has been investigated by

Buerger (33,34) and Morimoto and C l a r k ( 3 6 ) . Buerger d e t e r m i n e d

the s t r u c t u r e t o be monoclinic, closely related to that of

marcasite and l o e l l i n g i t e (34,35). Each i r o n atom i s surrounded

by a d i s t o r t e d o c t a h e d r o n of which one face is a triangle of

three arsenic atoms and t h e o t h e r a t r i a n g l e of t h r e e sulphur

atoms. The a r s e n o p y r i t e s t r u c t u r e i s complex and i s further


13

complicated by t h e f a c t t h a t the m i n e r a l almost always o c c u r s as


twins. The e f f e c t of t w i n n i n g i s t o g i v e the m i n e r a l a pseudo-
o r t h o r h o m b i c symmetry.

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.

It can be seen t h a t the s t r u c t u r e i s a body c e n t e r e d cubic


s t r u c t u r e w i t h r e g a r d t o i r o n . Sulphur and a r s e n i c occur as As-S
groups a l o n g c e l l edges.
B u e r g e r ( 3 3 ) e x p l a i n e d observed variations in interatomic
s p a c i n g on the b a s i s t h a t i r o n i n p y r i t e i s i n t h e f e r r o u s s t a t e
while iron i n marcasite, l o e l l i n g i t e and a r s e n o p y r i t e i s i n t h e
ferric state.
Although Glembotski (15) and Plaksin (14) based their
arguments for oxidation of pyrite and arsenopyrite on the
r e l a t i v e a c c e s s i b i l i t y of the s u l p h u r atoms t o i n t e r a c t i o n with
oxygen, it appears that significantly more complex
considerations are controlling in this regard. While both
marcasite and arsenopyrite are known t o o x i d i z e more r e a d i l y
than pyrite the results presented by those investigators
indicate that arsenopyrite i s passivated during oxidation while
marcasite i s not ( 3 7 ) . The v a r i a t i o n i n b e h a v i o u r of the v a r i o u s
minerals under o x i d i z i n g conditions therefore appears to be
controlled by the nature of both s u l p h u r and i r o n o x i d a t i o n
products.

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

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 of a r s e n o p y r i t e has received

l i m i t e d s t u d y . K o s t i n a and Chernyak (29,30,31) p r e s e n t e d results


IRON

ARSENIC

SULPHUR

Figure 4

Crystal 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 (33))


15

for oxidation experiments carried out with both p y r i t e and


a r s e n o p y r i t e . The o b j e c t i v e of t h e i r work was to f i n d conditions
under which a r s e n o p y r i t e would be r a p i d l y o x i d i z e d and thereby
r e l e a s e any entrapped g o l d . They demonstrated t h a t the oxidation
of both m i n e r a l s occurred at lower p o t e n t i a l s as c o n d i t i o n s were
changed from acid t o a l k a l i n e pH. Arsenopyrite demonstrated a
d i s t i n c t o x i d a t i o n peak i n a l k a l i n e (sodium h y d r o x i d e ) s o l u t i o n .
Increasing temperature was found to increase the rate of
o x i d a t i o n at a g i v e n p o t e n t i a l .

Pyrite was found to oxidize at a lower r a t e at a given


p o t e n t i a l than d i d a r s e n o p y r i t e . I t was a l s o observed that the
difference in oxidation rates increased with increasing
potential (30). This contradicts the assumptions made by
G l e m b o t s k i (15) as p r e v i o u s l y d i s c u s s e d in section 2.1.
Analysis of solutions following prolonged oxidation in
caustic solutions showed that under moderate oxidation
conditions, a r s e n i c and sulphur were leached from arsenopyrite.
Almost e q u a l amounts of t r i - v a l e n t and p e n t a - v a l e n t a r s e n i c were
formed. Sulphur o x i d a t i o n r e s u l t e d i n v a r y i n g r a t i o s of sulphate
to t h i o s u l p h a t e with varying o x i d a t i o n p o t e n t i a l (30).
Vakhontova and Grudnev (32) measured a r s e n o p y r i t e electrode
p o t e n t i a l as a f u n c t i o n of pH. Observed v a r i a t i o n s i n the Eh-pH
relationship were related to changes in the nature of
decomposition products. Under a c i d c o n d i t i o n s i r o n was concluded
t o go i n t o s o l u t i o n as f e r r o u s w h i l e under n e u t r a l and alkaline
conditions it went into s o l u t i o n as f e r r i c . In the supergene
zone of ore d e p o s i t s the alteration product of arsenopyrite
under acidic conditions were found t o be s y m p l e s i t e (ferrous
16

a r s e n a t e ) w h i l e under n e u t r a l or a l k a l i n e conditions scorodite


( f e r r i c a r s e n a t e ) was formed.

2.5 Arsenopyrite C o m p o s i t i o n and Phase R e l a t i o n s

The compositional v a r i a t i o n s of both s y n t h e t i c and natural


a r s e n o p y r i t e s have been considered in several investigations
(38,36,39).
Clark (38) in studying phase relations i n the Fe-As-S
system observed that arsenopyrite synthesized under varying
c o n d i t i o n s of temperature and bulk c o m p o s i t i o n d e v i a t e d from the
ideal FeAsS formula. X-ray diffraction data were used to
determine the d 1 3 1 spacing of arsenopyrite synthesized in
various u n i v a r i a n t assemblages as a f u n c t i o n of t e m p e r a t u r e . I t
was observed t h a t w h i l e at any g i v e n temperature the variation
in arsenopyrite composition i s s m a l l , throughout the range of
temperatures investigated, the variation in composition is
significant. Only a qualitative relation was established
however, s i n c e i n s u f f i c i e n t c o m p o s i t i o n a l data were a v a i l a b l e t o
quantify the dependence of d 1 3 1 on the S/As ratio in
arsenopyrite.
In addition to compositional v a r i a t i o n s of a r s e n o p y r i t e ,
Clark presented data which show the l i m i t s of s t a b i l i t y of the
various mineral assemblages. The maximum temperature of
formation of a r s e n o p y r i t e was shown t o be 702° ± 3°C. If native
arsenic coexists with a r s e n o p y r i t e the d e p o s i t i o n temperature
was below 688° ± 3°C. The maximum temperature of pyrite
arsenopyrite coexistence i s 491° ± 12°C.

Morimoto and Clark (36) presented chemical analyses for


17

sixteen n a t u r a l l y occuring arsenopyrites. From those analyses

which were considered to be consistent w i t h the associated

m i n e r a l assemblages they d e t e r m i n e d the c o m p o s i t i o n of n a t u r a l l y

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,.

The majority of analyses were shown t o be on the sulfur-rich

s i d e of the i d e a l FeAsS c o m p o s i t i o n which was considered to be

consistent with the predominance of sulphide - type over

arsenide - type m i n e r a l deposits.

Kretschmar and Scott (39) made a further contribution to

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

to a review of published s t u d i e s on a r s e n o p y r i t e composition

they p r e s e n t e d detailed analyses for 31 synthesized and 54

naturally occurring arsenopyrites.

Analyses were c a r r i e d out by means of e l e c t r o n m i c r o p r o b e

determinations.

The r e l a t i o n between atomic % a r s e n i c and the d, 3 1 X-ray

peak p o s i t i o n was determined to be:

As = 866.67d, , - 1381.12
3

w i t h an e s t i m a t e d standard d e v i a t i o n of ±0.45% As.

A temperature - c o m p o s i t i o n section for arsenopyrite which

was p r e p a r e d (39) is shown in Figure 5. The data used to

c o n s t r u c t the diagram were o b t a i n e d by s y n t h e s i z i n g arsenopyrite

a t v a r y i n g t e m p e r a t u r e s and e q u i l i b r i u m assemblages. The diagram

i l l u s t r a t e s the range of c o m p o s i t i o n s for arsenopyrite depending

on the conditions of f o r m a t i o n . The diagram i s a l s o u s e f u l i n

the c o n v e r s e sense i n t h a t if an arsenopyrite is accurately

analyzed and i t s e q u i l i b r i u m assemblage i s d e t e r m i n e d then the

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 %.

The limits of arsenopyrite composition presented by


Kretschmar and Scott are FeAso.gS,,, to FeAs 1 < 5 S .8 5
0

corresponding t o an approximate range i n atomic % As of 30% to


38%.

Clark (38) and Kretschmar and S c o t t (39) observed t h a t


a r s e n o p y r i t e formed w i t h a g i v e n c o m p o s i t i o n does not readily
re-equilibrate if subjected to a new set of conditions.
Arsenopyrite present in highly metamorphosed deposits will
therefore be characteristic of the initial conditions of
formation of the deposit.
Natural arsenopyrites are almost always compositionally
zoned ( 3 9 ) . In S - r i c h assemblages the c e n t r e of c r y s t a l s are S-
r i c h r e l a t i v e t o the rims while in As-rich assemblages the
c e n t r e s are A s - r i c h r e l a t i v e t o the rims.

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

Arsenopyrite i s a s e m i c o n d u c t i n g m i n e r a l w i t h a band gap of

about 0.2 eV ( 4 5 ) . Shuey summarized the m i n e r a l as having a low

c a r r i e r m o b i l i t y and c o n s i s t e n t l y high carrier concentration.

Resistivity values reported by several investigators are

presented i n Table 3.

Arsenopyrite near stoichiometric composition is an

intrinsic semiconductor at room temperature. A r s e n i c d e f i c i e n c y

or the presence of i m p u r i t i e s make most a r s e n o p y r i t e n-type, but

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.

42 2.0 X 10" - 3.0 X 10"


3 2

43 1.10 X 10" - 6.0 X 10-


2 2

44 7.5 X 10" - 4.5 X 10"


2 1

45 3.0 X TO" 2

46 1.5 X 10- - 7.0 X 10-


3 1

Krasnikov (40) d e t e r m i n e d t h a t a r s e n o p y r i t e i n a gold ore


deposit varied from p-type i n h i g h t e m p e r a t u r e , lower horizons
t o n-type i n lower t e m p e r a t u r e , upper horizons. Favorov (41)
discussed the results of a s t a t i s t i c a l treatment of s p e c t r a l
a n a l y s i s and thermo-emf measurements f o r 2000 samples of pyrite
and a r s e n o p y r i t e . A r s e n o p y r i t e was found t o v a r y from p-type f o r
high temperature, low s u l p h u r p a r t i a l p r e s s u r e a s s o c i a t i o n s t o
n-type f o r d e c r e a s i n g temperature and i n c r e a s i n g s u l p h u r partial
pressure a s s o c i a t i o n s .

The p o s s i b l e i n f l u e n c e of semiconductor p r o p e r t i e s on the


f l o t a t i o n behaviour of a r s e n o p y r i t e must be c o n s i d e r e d .

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

Sulphide minerals are generally semiconductors. These

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

r e s i s t i v i t y , band gap, c a r r i e r c o n c e n t r a t i o n and conductor-type

( 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

to influence the adsorption or e l e c t r o o x i d a t i o n of c o l l e c t o r

molecules a t the mineral surfaces.

P l a k s i n and Shafeev (46) were t h e f i r s t t o study the n a t u r e

of charge c a r r i e r s i n s u l p h i d e m i n e r a l s (in particular galena)


21

and the effect of charge c a r r i e r type on x a n t h a t e adsorption


They c o n s i d e r e d t h a t the presence of free electrons in the
surface l a y e r of s u l p h i d e s p r e v e n t s the f o r m a t i o n of adsorption
bonds w i t h x a n t h a t e . The a c t i o n of oxygen on g a l e n a was believed
t o r e s u l t from an i n v e r s i o n of the s u r f a c e l a y e r from n-type to
p-type.

Subsequent investigators i n t h i s f i e l d proposed a l t e r n a t e


r o l e s f o r oxygen and concluded that semiconductor properties
were not controlling with regard to xanthate - mineral
interaction (47,48,49).

Recently, B i e g l e r (50) c o n c l u d e d t h a t t h e r e was no obvious


correlation between k i n e t i c parameters f o r oxygen r e d u c t i o n on
p y r i t e and the nature of s e m i c o n d u c t i o n . He further concluded
that i f i m p u r i t i e s were the p r i m a r y i n f l u e n c e on d i f f e r e n c e s i n
electrochemical behaviour their influence was not exerted
t h r o u g h t h e i r e f f e c t s on the s e m i c o n d u c t i n g p r o p e r t i e s .
It appears therefore that while sulphide minerals are
semiconductors and display a l l the electrical properties
a s s o c i a t e d w i t h t h i s c l a s s of c o n d u c t o r s , the f l o t a t i o n response
of these s u l p h i d e m i n e r a l s i s not c o n t r o l l e d p r i m a r i l y by these
e l e c t r i c a l p r o p e r t i e s . A l t h o u g h the i n f l u e n c e of semiconducting
properties on the e l e c t r o c h e m i c a l behaviour of a r s e n o p y r i t e has
not been r e p o r t e d i n the l i t e r a t u r e , a r e a s o n a b l e deduction can
be made. The b e h a v i o u r of a r s e n o p y r i t e as an e l e c t r o c a t a l y s t f o r
oxygen reduction has been shown (20) t o be s i m i l a r t o t h a t of
o t h e r s u l p h i d e s such as p y r i t e and g a l e n a . It is therefore a
reasonable assumption that the semiconducting p r o p e r t i e s of
arsenopyrite will not be a principal influence on
22

electrochemical behaviour throughout the potential range


r e l e v a n t t o f l o t a t i o n of the m i n e r a l .
23

Chapter 3

OBJECTIVES OF THE PRESENT INVESTIGATION

The o b j e c t i v e of the p r e s e n t r e s e a r c h program was to study


the surface chemistry of a r s e n o p y r i t e so t h a t i t s f l o t a t i o n or
d e p r e s s i o n c o u l d be more e f f e c t i v e l y c o n t r o l l e d than has been
p o s s i b l e to date.

A review of the literature r e v e a l e d t h a t the flotation


response of arsenopyrite had received only limited study.
Fundamental i n v e s t i g a t i o n s of the nature of s u r f a c e r e a c t i o n 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 had not been c a r r i e d out
previously.
Information obtained from the l i t e r a t u r e and p r e l i m i n a r y
i n v e s t i g a t i o n s f o r the p r e s e n t r e s e a r c h program indicated that
surface o x i d a t i o n r e a c t i o n s c o u l d be s i g n i f i c a n t i n c o n t r o l l i n g
a r s e n o p y r i t e f l o t a t i o n . In a d d i t i o n , the a d s o r p t i o n of xanthate
at the arsenopyrite surface involves electron transfer
r e a c t i o n s . E l e c t r o c h e m i c a l i n v e s t i g a t i o n s have t h e r e f o r e been a
principal research method for this program. In p a r t i c u l a r ,
cyclic voltammetry of stationary and rotating arsenopyrite
e l e c t r o d e s has been used t o study s u r f a c e o x i d a t i o n r e a c t i o n s .
E l e c t r o n spectroscopy (ESCA) has been used t o augment these
surface oxidation studies. This technique enables surface
o x i d a t i o n f i l m s t o be a n a l y z e d . In addition to verifying the
formation of surface iron hydroxide, f i l m s , the behaviour of
a r s e n i c and s u l p h u r d u r i n g the formation of these films was
determined. The behaviour of a r s e n i c and s u l p h u r c o u l d not be
24

r e s o l v e d through the use of voltammetry a l o n e .

S i n c e a r s e n o p y r i t e i s most commonly r e c o v e r e d in flotation


systems employing xanthate as the c o l l e c t o r , the i n f l u e n c e of
the s u r f a c e 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 interaction with
xanthate was a l s o considered.

Flotation experiments to evaluate the e f f e c t i v e n e s s of


v a r i o u s o x i d a t i o n p r o c e d u r e s on a r s e n o p y r i t e have been carried
out. Arsenopyrite which had not been f l o a t e d p r e v i o u s l y w i t h
xanthate as well as some which had been floated was
investigated.

Compositional variations of arsenopyrite used for


electrochemical or flotation experiments have not been
considered s i n c e these a r e not e x p e c t e d t o c o n t r o l the o x i d a t i o n
of the m i n e r a l or i t s i n t e r a c t i o n w i t h x a n t h a t e , provided large
amounts of i m p u r i t i e s a r e not p r e s e n t .
25

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

The p o t e n t i a l a c h i e v e d i n t h e absence of oxidizing agents


g i v e s an i n d i c a t i o n of the tendency of the m i n e r a l t o o x i d i z e i n
the presence of aeration (51). Potentials achieved i n the
presence of o x i d i z i n g agents can be c o r r e l a t e d w i t h results of
electrochemical investigations to predict relative oxidation
r a t e s as w e l l as t h e n a t u r e of o x i d a t i o n products.

Mixed p o t e n t i a l measurements were c a r r i e d out i n order to


determine the p o t e n t i a l a c h i e v e d by the m i n e r a l i n t h e absence
of any w e l l d e f i n e d redox c o u p l e and then t o observe t h e e f f e c t s
of v a r i o u s o x i d i z i n g agents on e l e c t r o d e potential.
Measurements were c a r r i e d out a c r o s s t h e range of pH v a l u e s
commonly encountered i n s u l p h i d e f l o t a t i o n c i r c u i t s (pH = 4 to
pH = 12).

4.1.1 Experimental

Electrode potential measurements were carried out i n a

spherical glass c e l l containing 1.25 l i t r e s of s o l u t i o n a t room

temperature (25-28°C). Test s o l u t i o n s were p r e p a r e d from s i n g l e

distilled water w i t h a s t a n d a r d a d d i t i o n of 0.1 molar KC1. The

desired pH v a l u e f o r each t e s t was a c h i e v e d through the use of


26

sodium tetraborate (0.05 M) w i t h sodium h y d r o x i d e or sulphuric


a c i d to r a i s e or lower the pH respectively.

Solutions were deoxygenated by b u b b l i n g argon through them.


B u b b l i n g was c o n t i n u e d throughout the test and was the only
source of solution stirring. Traces of oxygen (3 to 5 ppm),
p r e s e n t i n the argon were removed by p a s s i n g the gas through a
pyrogallol solution.

Potential measurements were carried out relative to a


s a t u r a t e d c a l o m e l e l e c t r o d e and c o n v e r t e d to the hydrogen scale
by taking the p o t e n t i a l of the SCE to be -0.243 v o l t s r e l a t i v e
t o a hydrogen e l e c t r o d e a t 25°C.
P o t e n t i a l s were measured w i t h a Beckman E l e c t r o s c a n 30. A
potential having a drift of l e s s than 2 mV over a ten minute
period was generally achieved within 5 minutes. The potential
was recorded after 20 minutes t o ensure s t a b l e c o n d i t i o n s had
been a c h i e v e d i n each case. Potentials could be determined
within ±5 mV. The r e p r o d u c i b i l i t y of p o t e n t i a l s at a g i v e n pH
v a l u e was found to be ±20 mV.
In t e s t s i n v o l v i n g o x i d i z i n g agents the e l e c t r o d e was first
p l a c e d i n d i s t i l l e d water and was a l l o w e d a 20 minute p e r i o d to
achieve a stable potential. After t h i s period the oxidizing
agent was added to the s o l u t i o n and a g a i n a 20 minute p e r i o d was
a l l o w e d b e f o r e the p o t e n t i a l was recorded.
E l e c t r o d e s were constructed using arsenopyrite crystals
from two sources.

One sample was obtained from Ward's S c i e n t i f i c and was

indicated t o come from Parral, Chihuahua. This material was

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.

The e l e c t r o d e prepared from t h i s sample had an exposed a r e a


of a p p r o x i m a t e l y 0.7 cm . 2

The second sample of a r s e n o p y r i t e was s u p p l i e d by Mr. Joe


Nagel of t h e UBC Department of G e o l o g i c a l S c i e n c e s and came from
R i o n d e l , B.C. There was insufficient sample to carry out a
c h e m i c a l a n a l y s i s of t h i s m a t e r i a l but a c o m p a r a t i v e analysis to
the sample from Mexico was c a r r i e d out by means of a s c a n n i n g
e l e c t r o n microscope equipped w i t h an energy d i s p e r s i v e analyzer
(SEM-EDX). The a n a l y s i s gave s i m i l a r i r o n , a r s e n i c and s u l p h u r
peaks as t h e Mexican m a t e r i a l and d i d not exhibit any peaks
i n d i c a t i v e of e x c e s s i v e c o n c e n t r a t i o n s of any i m p u r i t i e s .

The electrode prepared from t h i s m a t e r i a l had an exposed


a r e a of a p p r o x i m a t e l y 0.74 cm . 2

The semiconductor type of each m a t e r i a l was determined by

means of a s i m p l e d e t e r m i n a t i o n employing t h e Seebeck e f f e c t . A

m i l l i v o l t m e t e r was used t o measure t h e p o t e n t i a l across a hot

probe and a c o l d probe i n c o n t a c t w i t h the a r s e n o p y r i t e c r y s t a l .


28

In each case the hot j u n c t i o n was found t o be p o s i t i v e r e l a t i v e


t o the c o l d j u n c t i o n i n d i c a t i n g the samples t o be n-type semi-
conductors .

A pyrite electrode was prepared using material from


Hanaoka, Japan. The polished electrode was examined
m i c r o s c o p i c a l l y and was d e t e r m i n e d t o be f r e e from i n c l u s i o n s of
other s u l p h i d e m i n e r a l s . The exposed area of t h i s e l e c t r o d e was
approximately 0.38 cm .2

The method of e l e c t r o d e c o n s t r u c t i o n i s shown i n F i g u r e 6.


A s e c t i o n of the m i n e r a l was mounted i n epoxy c o n s i s t i n g of one
p a r t d i e t h y l e n e t r i a m i n e t o 10 p a r t s Epon 828. Immediately a f t e r
p l a c i n g t h e l i q u i d epoxy on the sample i t was p l a c e d i n a vacuum
t o e l i m i n a t e a i r b u b b l e s and t o e n a b l e t h e epoxy t o s e a l cracks
in the sample. Both s i d e s of t h e mounted s e c t i o n were ground
down t o expose the m i n e r a l . One s i d e then had a thin layer of
gold vacuum deposited i n two a r e a s . A copper w i r e was fastened
t o each a r e a w i t h s i l v e r c o n d u c t i n g cement.

A second epoxy s e c t i o n was prepared with a glass tube


inserted through one side. The w i r e s from the m i n e r a l sample
were i n s e r t e d t h r o u g h t h e g l a s s tube and the two sections were
glued together using a f a s t s e t t i n g epoxy.

Prior t o each experiment t h e s e c t i o n was wet ground on 600


mesh paper and then r i n s e d w i t h distilled water before being
i n s e r t e d i n t o the t e s t solution.

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

out reactions r a n g i n g from p u l p b l e a c h i n g t o e f f l u e n t c o n t r o l .


29

WIRE

//-> EADS

GLASS
TUBE

GOLD PLATING
SILVER CEMENT

Figure 6

Method of e l e c t r o d e construction
30

Only l i m i t e d use i s made of oxidizing agents i n the mineral


processing- industry. These a r e used primarily for a l k a l i n e
c h l o r i n a t i o n of cyanide solutions and as oxidants f o r the
leaching of uranium ore ( 5 4 ) . Use has a l s o been made of
p o t a s s i u m permanganate t o i n c r e a s e the o x i d a t i o n of pyrrhotite
during g r i n d i n g and t h e r e b y d e c r e a s e i t s f l o a t a b i l i t y (52).

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.

The oxidizing agents used i n the present study were


selected on t h e b a s i s of e i t h e r a l r e a d y h a v i n g some a p p l i c a t i o n
in processing plants (NaCIO, KMn0 ) or b e i n g c o n s i d e r e d
4 t o be a
non-polluting, cost competitive reagent ( H 0 ) . W h i l e a d d i t i o n a l
2 2

oxidizing agents such as c h l o r i n e or Caro's a c i d ( H S 0 ) c o u l d 2 5

a l s o be a p p r o p r i a t e , the range of mixed p o t e n t i a l s achieved by


the present series of agents was found t o cover t h e range of
i n t e r e s t as determined by e l e c t r o c h e m i c a l experiments described
in subsequent sections. The current (1982) costs f o r the
r e a g e n t s used i n t h e study a r e shown i n T a b l e 4. Table 4 also
shows the a v a i l a b l e o x i d i z i n g u n i t s per kilogram. These u n i t s
are t h e p r o d u c t of the number of moles of o x i d a n t per kilogram
times t h e number of electrons t r a n s f e r r e d assuming a l k a l i n e
conditions.

The v a r i a t i o n i n o x i d i z i n g power of these r e a g e n t s can be

d e t e r m i n e d from a s e r i e s of o x i d a t i o n s t a t e diagrams (53). These


31
Table 4
Cost of O x i d i z i n g Agents

OXIDIZING COST OXIDIZING


AGENT $/kg. O x i d a n t units/kg

Hydrogen P e r o x i d e (50% S o l u t i o n ) 1.10 - 1.32 58.8


P o t a s s i u m Permanganate 3.75 - 4.75 25.3
Sodium h y p o c h l o r i t e (12% S o l u t i o n ) 3.48 - 5.61 26.8

diagrams graphically present the v o l t e q u i v a l e n t of a compound


or i o n as a f u n c t i o n of i t s o x i d a t i o n s t a t e . The volt equivalent
i s the product of the o x i d a t i o n s t a t e and the redox potential
relative t o the element i n i t s s t a n d a r d s t a t e and i s r e l a t e d to
the f r e e energy f o r the s p e c i e s a c c o r d i n g to AG = -nFE. The
g r a d i e n t of the l i n e j o i n i n g two p o i n t s on such a diagram i s the
redox p o t e n t i a l of the couple represented by the p o i n t s . A l a r g e
positive gradient represents a s t r o n g o x i d i z i n g c o u p l e and a
large negative gradient, a strong reducing couple.
Diagrams for the chlorine, manganese and oxygen-water
systems are shown in F i g u r e s 7,8 and 9. The diagrams i n c l u d e
both acid (a o H + = l) and alkaline (a o M . = l) conditions. The
variation of the oxidizing power with pH is an important
c o n s i d e r a t i o n s i n c e f l o t a t i o n of s u l p h i d e s i s g e n e r a l l y carried
out at pH values greater than pH=4 and more commonly i n the
range of pH=8 t o pH=11. Thus the diagram f o r manganese i n d i c a t e s
that while in acid media permanganate represents a strong
oxidizing agent capable of being reduced to Mn ++
ions, in
a l k a l i n e media a much lower g r a d i e n t i s apparent and manganese
oxides and h y d r o x i d e s are formed. The use of Mn0 2 i n a c i d media
c o u l d be expected t o r e s u l t i n reasonable oxidation while at
high pH this reagent would be i n e f f e c t i v e as an o x i d a n t . This
32

c o u l d i n p a r t e x p l a i n t h e two hour conditioning period which


Nekrasov (16) required when using Mn0 2 for arsenopyrite
oxidation.

In t h e case of the c h l o r i d e system hypochlorite is


i n d i c a t e d t o be a s t r o n g e r o x i d i z i n g agent than c h l o r a t e .

While the diagrams are useful f o r representing the


o x i d a t i o n p o t e n t i a l of v a r i o u s reagents i t must be h e l d i n mind
t h a t p a r t i c u l a r l y i n a heterogeneous system, k i n e t i c f a c t o r s may
in fact control t h e i r r e l a t i v e effectiveness.

4.2 R e s u l t s and D i s c u s s i o n

Preliminary experiments with a platinum electrode in


deoxygenated d i s t i l l e d water gave t h e r e l a t i o n
Eh = 850 - 62.3 pH ,mV
r = -1.00
Since t h i s i s i n reasonable agreement w i t h t h e r e l a t i o n s h i p
Eh = 800 - 59 pH ,mV
which has been d e v e l o p e d elsewhere (55) t h e r e c o r d i n g equipment
was c o n s i d e r e d t o be c a p a b l e of p r o v i d i n g r e l i a b l e measurements.
A variation of up t o 100 mV i n t h e i n t e r c e p t p o t e n t i a l can be
expected because while t h e pH i s buffered and therefore
accurately controlled, the potential i s to some extent
c o n t r o l l e d by k i n e t i c f a c t o r s and may therefore deviate from
thermodynamically d e r i v e d v a l u e s . The e x p e r i m e n t a l r e l a t i o n was
achieved by v a r y i n g t h e pH and then measuring the electrode
potential without r e p o l i s h i n g o r c l e a n i n g t h e e l e c t r o d e between
measurements. Slow k i n e t i c s w i t h r e g a r d t o e q u i l i b r a t i o n of t h e
system c o u l d account f o r t h e d e v i a t i o n of both t h e i n t e r c e p t and
33

- 1 0 I 2 3 4 5 6 7
Oxidation s t a t e

Figure 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


34

-4-
1 1 1 1 I I i i
0 I 2 3 4 5 6 7
Oxidation state

Figure 8

O x i d a t i o n s t a t e diagram f o r manganese system


35

Figure 9

O x i d a t i o n s t a t e diagram f o r the oxygen system


36

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.

Mixed potentials measured with arsenopyrite and p y r i t e

e l e c t r o d e s a r e shown i n F i g u r e s 10 and 11.

The p o t e n t i a l measured w i t h arsenopyrite in deoxygenated

water over t h e pH range from 3.8 t o 11.2 g i v e s t h e r e l a t i o n


Eh = 586 - 48.2 pH ,mV
r = -0.9976
At pH g r e a t e r than 11.2 t h e p o t e n t i a l s f a l l below t h i s line
with i n c r e a s i n g d e v i a t i o n as t h e pH i n c r e a s e s . At t h e same time
an e l e c t r o d e which was a l l o w e d t o reach a s t a b l e p o t e n t i a l a t pH
g r e a t e r than 11.2 was observed to develop a visible surface
oxide layer. This s u r f a c e d e p o s i t had a brown appearance when
the e l e c t r o d e was a l l o w e d t o d r y .

Another o b s e r v a t i o n was t h a t i f t h e pH of t h e s o l u t i o n was


lowered a f t e r t h e e l e c t r o d e had reached a s t a b l e p o t e n t i a l a t pH
greater than 11.2, the electrode p o t e n t i a l followed along the
same c u r v e as f o r f r e s h l y p o l i s h e d e l e c t r o d e measurements. The
points obtained in this way are shown i n Figure 10. The
d e v i a t i o n from a s t r a i g h t l i n e a t pH g r e a t e r than 11.2 i n d i c a t e s
a r s e n o p y r i t e t o be inherently unstable in this region. The
mineral decomposes, leaving a surface oxide l a y e r . Since the
e l e c t r o d e p o t e n t i a l s i n t h e presence of this visible oxide
follow the same relation as obtained for a freshly polished
e l e c t r o d e , t h e same o x i d e f i l m must be p r e s e n t with the fresh
electrode but i s too thin to be readily observed. The
composition of t h i s s u r f a c e oxide will be discussed i n the
s e c t i o n on voltammetry.

There are several differences i n the behaviour of t h e

p y r i t e e l e c t r o d e compared t o t h e arsenopyrite electrode. Over


37

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

the pH range from 7 t o 12.2 the p o t e n t i a l f o l l o w e d the relation

Eh = 643 - 49.0 pH
r = -0.993

indicating p y r i t e t o be a more noble m i n e r a l than a r s e n o p y r i t e .


Unlike arsenopyrite, pyrite shows no deviation from this
relation at high pH. The p o t e n t i a l of an e l e c t r o d e which had
reached a s t a b l e p o t e n t i a l at pH = 12.2 f o l l o w e d the same Eh-pH
r e l a t i o n down t o pH = 3.4. Only a s l i g h t t a r n i s h was v i s i b l e for
the p y r i t e e l e c t r o d e a t pH = 12.2.

Potentials measured with a c l e a n p y r i t e e l e c t r o d e at pH


l e s s than 7 fall below the line represented by the above
relation. Similar observations have been made f o r p y r i t e and
other s u l p h i d e s by other i n v e s t i g a t o r s ( 5 5 ) . The deviation from
the r e l a t i o n below pH = 7 was e x p l a i n e d on the b a s i s t h a t below
t h i s pH the p a s s i v a t i n g o x i d e l a y e r was not forming and the
electrode i s in a corrosion region.
The c o n c e n t r a t i o n of each o x i d i z i n g agent which was used i n
tests involving these additions was based on the r e s u l t s of
p r e l i m i n a r y f l o t a t i o n e x p e r i m e n t s . The f l o t a t i o n experiments had
i n d i c a t e d t h a t these c o n c e n t r a t i o n s of o x i d i z i n g agent were in
the range which c o u l d be r e q u i r e d f o r a r s e n o p y r i t e depression.
Potential measurements made w i t h an a r s e n o p y r i t e electrode
i n the presence of o x i d i z i n g agents are shown i n F i g u r e 10. In
the case of p o t a s s i u m c h l o r a t e the p o t e n t i a l s i n the r e g i o n of
pH from 7 t o 10 were found t o f a l l on the same line as those
obtained i n the absence of any o x i d i z i n g agents.

The remaining p o t e n t i a l s f o l l o w the relations:

W i t h 160 mg/1 Hydrogen P e r o x i d e


Eh = 688 - 46.9 pH
r = -0.9886.
40

With 57 mg/1 P o t a s s i u m Permanganate


Eh = 663 - 34.1 pH
r = -0.9533
With 54.3 mg/1 Sodium H y p o c h l o r i t e
Eh = 1037 - 82.9 pH
r = -0.9966
A few measurements were carried out with the pyrite
e l e c t r o d e i n the presence of hydrogen peroxide and potassium
permanganate. As in the case of a r s e n o p y r i t e the p o t e n t i a l
a c h i e v e d w i t h p y r i t e i n the presence of permanganate is higher
than with, p e r o x i d e over the pH r e g i o n of interest.

4.3 C y c l i c Voltammetry

References cited i n the l i t e r a t u r e review on arsenopyrite


f l o t a t i o n i n d i c a t e t h a t the s u r f a c e oxidation of the mineral
could play a major r o l e i n c o n t r o l l i n g i t s f l o t a t i o n response.
The r e s u l t s of e l e c t r o d e measurements p r e s e n t e d i n the previous
section indicate that surface oxide deposits are formed on
a r s e n o p y r i t e a t h i g h pH or under moderate o x i d i z i n g conditions.
It is therefore of i n t e r e s t t o determine the nature of these
s u r f a c e o x i d e d e p o s i t s so t h a t t h e i r f o r m a t i o n and t h e r e f o r e the
f l o t a t i o n response of a r s e n o p y r i t e can be b e t t e r c o n t r o l l e d than
has p r e v i o u s l y been p o s s i b l e .
C y c l i c voltammetry, i n a d d i t i o n t o e n a b l i n g the interaction
of e l e c t r o d e s with dissolved electroactive species such as
xanthate to be s t u d i e d , p r o v i d e s a means f o r s t u d y i n g surface
o x i d a t i o n r e a c t i o n s of e l e c t r o d e s . By carrying out repetitive
scans the i n f l u e n c e on s u r f a c e changes of e x c u r s i o n s t o v a r i o u s
p o t e n t i a l ranges can be o b s e r v e d .

C y c l i c voltammetry has been used t o study the o x i d a t i o n of


41

ethyl xanthate and the i n f l u e n c e of f l o t a t i o n d e p r e s s a n t s on


pyrite electrodes ( 2 3 ) . The interaction of flotation reagents
w i t h (57) and the s u r f a c e o x i d a t i o n (58) of g a l e n a has a l s o been
s t u d i e d by t h i s technique.

Electrochemical reactions i n v o l v i n g p a r t i c u l a r species in


the absence of c h e m i c a l r e a c t i o n mechanisms have been studied
using noble metal electrodes (23,49) and employing cyclic
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

c a t h o d i c peak i s o b s e r v e d . The reversible potential for the


xanthate - dixanthogen couple i s 0.15 V a t the c o n c e n t r a t i o n of
xanthate used. The anodic peak can be associated with the
o x i d a t i o n of xanthate t o d i x a n t h o g e n w h i l e the c a t h o d i c peak can
be associated with the reverse r e a c t i o n . In the presence of
xanthate, hydrogen and oxygen a d s o r p t i o n i s i n h i b i t e d and peaks
a s s o c i a t e d w i t h these s p e c i e s are t h e r e f o r e not o b s e r v e d .

The height of the xanthate peaks would be i n c r e a s e d by


stirring of the solution or by increasing the xanthate
concentration. Both of these a c t i o n s would i n c r e a s e the supply
of xanthate t o the e l e c t r o d e s u r f a c e .

Although voltammetric sweeps are sometimes c a r r i e d out at


slow scan speeds ( l e s s than 1mV/sec.) i n g e n e r a l the scan speeds
employed are greater than 1 mV/sec. At i n c r e a s i n g scan speeds
the c u r r e n t peaks due t o charge t r a n s f e r r e a c t i o n s are increased
and may be more f u l l y studied.
For a f i x e d sweeprate and current scale, increased peak
height is associated with an increased reaction rate. An
i n c r e a s e i n the a r e a under a peak i n d i c a t e s an i n c r e a s e in the
r e a c t i o n products ( i . e . a greater t o t a l current i s passed).

4.3.1 Experimental

Voltammetry was carried out with both stationary and

r o t a t i n g e l e c t r o d e s . For s t a t i o n a r y electrode experiments the

electrodes were the same ones as used f o r e l e c t r o d e p o t e n t i a l

measurements.

The r o t a t i n g e l e c t r o d e was c o n s t r u c t e d as shown in Figure

12. An arsenopyrite disc was prepared using a diamond


43

impregnated g l a s s d r i l l . The c r y s t a l used f o r t h i s e l e c t r o d e was


the same one from R i o n d e l , B.C. as was used f o r the s t a t i o n a r y
electrode. One face of t h e d i s c was g o l d c o a t e d and t h i s face
was f a s t e n e d t o t h e end of t h e b r a s s r o d which formed t h e c e n t r e
of t h e e l e c t r o d e . The space between the a r s e n o p y r i t e and t h e
surrounding teflon tube was filled i n t h r e e stages u s i n g a
hypodermic s y r i n g e f i l l e d w i t h epoxy. The e l e c t r o d e was equipped
w i t h a g o l d r i n g which was s i l v e r s o l d e r e d to a brass sleeve
leading to the electrode connections. The remaining physical
f e a t u r e s and manner of c o n n e c t i o n was as for a standard Pine
Instruments r o t a t i n g e l e c t r o d e ( 8 4 ) .

The measurement c i r c u i t employed f o r voltammetry i s shown


i n F i g u r e 13. The p o t e n t i o s t a t used was a Wenking 68 TS10.
Cyclic potential functions were controlled by means of a
Princeton Applied Research Model 175 Universal programmer.
Currents were r e c o r d e d by means of a K e i t h l e y Model 171 d i g i t a l
multimeter in series with the platinum counter electrode.
Current - potential scans were recorded with an Electro
I n s t r u m e n t s Model 520 XY recorder. Rotating experiments were
carried out by means of a P i n e I n s t r u m e n t s Model ASR 2 r o t a t o r .
All instruments were plugged i n t o a m u l t i - o u t l e t extension to
e l i m i n a t e ground - l o o p problems.
Tests were carried out i n a c o n v e n t i a l H - c e l l w i t h the
working e l e c t r o d e compartment h a v i n g a volume of 850 cc and
being separated from the counter e l e c t r o d e by a f r i t t e d glass
d i s c . A l l t e s t s were c a r r i e d out a t room temperature (22±2 °C).
A s t a n d a r d a d d i t i o n of 0.1M p o t a s s i u m c h l o r i d e was made t o each
t e s t . The pH was a d j u s t e d by means of sodium tetraborate with
BRASS

TEFLON

SILVER CEMENT

EPOXY GOLD RING


ARSENOPYRITE

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

sodium hydroxide or sulphuric acid. A l l reagents used f o r

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

By earring out voltammetry across a wide range of pH,


v a r i a t i o n s i n both anodic and c a t h o d i c peak positions can be
observed. By noting both peak positions and s h i f t s i n peak
position with pH, possible elecrochemical surface reactions
associated with these peaks can be postulated. Reversible
potentials for postulated reactions can be calculated and
c o r r e l a t e d w i t h peak p o s i t i o n s .

Voltammograms r e s u l t i n g from the a p p l i c a t i o n of t r i a n g u l a r


p o t e n t i a l c y c l e s t o a r s e n o p y r i t e a c r o s s the range of pH = 5.85
t o pH = 11.95 a r e shown i n F i g u r e s 14 and 15.
Between pH = 6.6 and 7.3 an anodic peak becomes apparent i n
the r e g i o n of 0.6 t o 0.7 v o l t s . T h i s peak becomes more prominent
and shifts to more cathodic potentials with i n c r e a s i n g pH
a c c o r d i n g t o the r e l a t i o n .
Ep = 1216 - 78.6 pH mV.
r = - 0.99
The scans shown i n f i g u r e s 14 and 15 s t a r t w e l l below the rest
potential of a r s e n o p y r i t e . A d d i t i o n a l anodic scans were c a r r i e d
out s t a r t i n g from t h e r e s t p o t e n t i a l t o ensure t h a t the anodic
peak is not associated with products r e s u l t i n g from c a t h o d i c
c u r r e n t s observed a t the s t a r t of the scans. Anodic peaks for
46

PROGRAMMER
RECORD E

POTENTIOSTAT
CONTROL*
W ••
R •• REF C WE
C
GROUND*
MULTIMETER =:RECORD I

COMMON
ROTATOR

F i g u r e 13

C o n t r o l and measurement c i r c u i t used f o r voltammetry


47

scans s t a r t i n g a t the r e s t p o t e n t i a l were found t o occur a t the


same p o t e n t i a l and t o be of the same magnitude as those for
scans s t a r t i n g a t the lower p o t e n t i a l s .

The anodic peak lies in the p o t e n t i a l r e g i o n which i s


r e l e v a n t t o f l o t a t i o n systems. The electrode potentials which
were measured in the presence of hydrogen peroxide and
permanganate are i n d i c a t e d i n F i g u r e 16 and F i g u r e 2, Appendix
II, on a voltammogram obtained at pH = 8.2. The p o t e n t i a l s
achieved w i t h these oxidizing agents should result in the
reaction associated with the anodic peak proceeding at a
significant rate.

Since a KC1 supporting electrolyte was used and good


connections to the e l e c t r o d e were made and the r e s i s i t i v i t y of
the electrode material is low ( i e . 10" 2
ohm - cm) peak
potentials are believed t o be a c c u r a t e even a t the relatively
h i g h c u r r e n t s (800 microamperes) o b s e r v e d f o r some scans.
The r e p e a t a b i l i t y of scans was found to be within 10
m i l l i v o l t s and was l i m i t e d p r i m a r i l y by the a b i l i t y t o determine
accurately the peak position on the chart recorder. Peak
c u r r e n t s were found t o be s e n s i t i v e to the condition of the
g r i n d i n g paper used t o p r e p a r e the e l e c t r o d e s u r f a c e . P r o v i d e d a
fresh area of g r i n d i n g paper was used t o f i n i s h the e l e c t r o d e
preparation, currents could be reproduced to within 20
microamperes.

A s m a l l anodic prewave becomes apparent a t approximately

-0.1 V at pH = 9.6 in Figure 14. T h i s prewave becomes more

apparent over the pH range from 9.6 t o 10.55 and then decreases

over the range of pH 11.05 t o 11.95. The peak p o s i t i o n s h i f t s t o


pH 5-85

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

Voltammogram f o r a r s e n o p y r i t e a t pH = 8.2 showing potentials


a c h i e v e d w i t h o x i d i z i n g agents
51

more cathodic potentials with increasing pH. Such prewaves


p r e v i o u s l y have been i n t e r p r e t e d as being a s s o c i a t e d with thin
o x i d a t i o n l a y e r s ( 7 9 ) . In the p r e s e n t study the peak i s b e l i e v e d
to result from the presence of i r o n h y d r o x i d e f i l m s formed
d u r i n g e l e c t r o d e p r e p a r a t i o n as w i l l s u b s e q u e n t l y be d i s c u s s e d .

The behaviour of arsenopyrite and pyrite across the


potential region of interest i s compared i n Figure 17. The
o x i d a t i o n of a r s e n o p y r i t e i s o b s e r v e d t o commence a t potentials
approximately 200 mV lower that those required for pyrite
oxidation. The main pyrite oxidation reaction becomes
significant a t p o t e n t i a l s g r e a t e r than t h a t of the a r s e n o p y r i t e
o x i d a t i o n peak. T h i s d i f f e r e n c e i n the b e h a v i o u r of these two
minerals further indicates that the a n o d i c peak observed f o r
a r s e n o p y r i t e c o u l d be s i g n i f i c a n t i n a t t e m p t i n g to control the
s e l e c t i v e f l o t a t i o n or d e p r e s s i o n of a r s e n o p y r i t e .

Possible reactions associated with the oxidation of


a r s e n o p y r i t e can be determined by considering the stability
diagram f o r a r s e n o p y r i t e shown i n F i g u r e 18. Thermodynamic data
used to construct the diagram and additional stability
considerations for arsenopyrite are presented i n Appendix I .
These diagrams were c o n s t r u c t e d as p a r t of the p r e s e n t study.
At pH = 4 t o pH = 7

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 + +
)

or i f o x i d a t i o n t o form H A s 0 3 3 and SO*,"" i s c o n s i d e r e d


52

—' " 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

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.


53

Fe + +
+ H As0 3 3 + SO -- + 11H a
+
+ 11e" = FeAsS + 7H 0 2

(7)

E = 0.283 + 0.005 l o g ( F e ) ( H A s 0 ) ( S O , " " ) -


+ +
3 3 0.0591 pH At pH
g r e a t e r than 7

Fe(OH) 2 + H As0
3 3 + SO,,"- + 13H +
+ 1 1 e" = FeAsS+9H 0 2

(8)

E = 0.346 + 0.005 l o g ( H A s 0 ) ( S 0 " " ) - 0.070 pH


3 3 4

The appearance of t h e a n o d i c peak a t 0.6 V between pH = 6.6


and 7.3 can be r e l a t e d t o the f o r m a t i o n of F e ( O H ) 2 a t pH g r e a t e r
than approximately 7. The exact pH a t which F e ( O H ) 2 becomes
stable r e l a t i v e to F e + +
depends on t h e a c t i v i t y of Fe a t the
s u r f a c e of t h e e l e c t r o d e .

The observed anodic peak or half wave potentials are


c o n s i d e r a b l y a n o d i c t o the r e v e r s i b l e p o t e n t i a l s c a l c u l a t e d from
the above e q u a t i o n s . Assuming a c t i v i t i e s of 10" M 3
for example
e q u a t i o n 8 p r e d i c t s a r e v e r s i b l e p o t e n t i a l of -0.422 v o l t s . Such
a shift i n peak p o t e n t i a l may be due t o i r r e v e r s i b i l i t y of t h e
r e a c t i o n , t o t h e f o r m a t i o n of a p a s s i v e l a y e r or t o b o t h .

At t h e o b s e r v e d peak p o t e n t i a l s the iron hydroxide which


s h o u l d be formed i s Fe(OH) 3 rather than the F e ( O H ) 2 i n d i c a t e d by
equation 8. The reversible potential f o r Fe(OH) 2 t o Fe(OH) 3

oxidation i s g i v e n by

Fe(OH) 3 + H +
+ e" = F e ( O H ) 2 + H0 2 (9)

E = 0.28 - 0.059 pH from which a value of E = -0.342 V is

o b t a i n e d a t pH = 10.55.

It can be seen i n Figure 18 t h a t a t the o b s e r v e d peak


54

Figure 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 10" M. 3
55

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 .

The formation of Fe(OH) 3 during the anodic process is


c o n s i s t e n t w i t h c e r t a i n a d d i t i o n a l f e a t u r e s of the voltammograms
shown i n F i g u r e s 14 and 15. A c a t h o d i c p o t e n t i a l sweep starting
near the rest potential i s shown a t pH = 11.95. The cathodic
peaks for the complete potential sweeps show significatly
greater currents than those for cathodic sweeps only. The
increased cathodic peak current for the complete sweeps
indicates that species formed during the anodic p a r t of the
p o t e n t i a l c y c l e are being reduced. These c a t h o d i c peaks occur at
p o t e n t i a l s c o n s i s t e n t with equation 9 and can be i n t e r p r e t e d to
represent the r e d u c t i o n of F e ( O H ) 3 formed d u r i n g the o x i d a t i o n
reaction.

The c a t h o d i c peak a t pH g r e a t e r than 11.0 in Figure 15 is


actually a double peak. This could represent a two step
r e d u c t i o n of F e ( O H ) 3 or c o u l d i n d i c a t e t h a t additional species
such as s u l p h u r are being reduced.
Voltammograms a t lower pH and p a r t i c u l a r l y a t pH = 5.85 in
F i g u r e 14 show a prominent c a t h o d i c peak a l t h o u g h no anodic peak
associated with iron hydroxide formation is evident. It is
believed that t h i s c a t h o d i c peak r e s u l t s from the f o r m a t i o n of
s u l p h u r or a s u l p h u r compound d u r i n g the anodic sweep.
The s m a l l prewave o b s e r v e d d u r i n g the anodic scan results
from the oxidation of a s m a l l amount of Fe(OH) 2 formed on the
electrode during electrode polishing and preparation as
d i s c u s s e d i n Chapter 5.

Figure 19 shows a c u r r e n t - decay curve f o r an arsenopyrite


56

electrode which was stepped.from the r e s t p o t e n t i a l t o +343 mV


at pH = 10.6. T h i s potential represents the anodic peak
potential a t t h i s pH. The c u r r e n t decays from t h e i n i t i a l value
of s e v e r a l thousand microamps t o l e s s than 100 microamps i n l e s s
than one minute. Such a c u r r e n t decay i s associated with the
build-up of o x i d a t i o n p r o d u c t s a t t h e s u r f a c e of t h e e l e c t r o d e .
The presence of these o x i d a t i o n p r o d u c t s at the surface of t h e
electrode passivates i t , making f u r t h e r r e a c t i o n i n c r e a s i n g l y
difficult. This rapid decay of current confirms that the
o x i d a t i o n of a r s e n o p y r i t e r e s u l t s i n s o l i d p r o d u c t s which remain
at the e l e c t r o d e s u r f a c e .

An estimate was made of t h e q u a n t i t y of i r o n hydroxide


formed on t h e s u r f a c e d u r i n g an anodic scan. The area under the
anodic peak a t pH = 11.55 was determined i n o r d e r t o determine
the c u r r e n t passed. From t h e s t a r t of the o x i d a t i o n peak t o t h e
inflection i n t h e curve just past t h e peak, a c u r r e n t of
approximately 11700 micro coulombs was passed. U s i n g e q u a t i o n 8,
which shows 11 e l e c t r o n s per mole of arsenopyrite oxidized,
together with equation 9, which i n d i c a t e s an e x t r a e l e c t r o n f o r
every mole of F e ( O H ) 2 o x i d i z e d t o F e ( O H ) , t h e q u a n t i t y of FeAsS
3

which i s o x i d i z e d d u r i n g t h e scan i s 0.102 X 1 0 - 7


mole. Assuming
a stochiometric composition, t h i s means t h a t t h e same amount of
iron i s o x i d i z e d t o the f e r r i c s t a t e . Using the p r o j e c t e d area
of t h e e l e c t r o d e of 28.3 s q . mm. and assuming a s o l i d product of
Fe 0 2 3 w i t h a d e n s i t y of 5 (60) an o x i d e t h i c k n e s s of 40 A° i s
determined. This i s an o r d e r of magnitude e s t i m a t e o n l y s i n c e
the s t r u c t u r e c o u l d d i f f e r from t h e assumed one and since the
real surface area can be e x p e c t e d t o be s e v e r a l times greater
57

than the p r o j e c t e d a r e a .

Taking i n t o account the r e a l s u r f a c e area c o u l d result in


an e s t i m a t e of the o x i d e t h i c k n e s s as low as 10 A . A l e s s dense 0

iron hydroxide structure than has been assumed in the


c a l c u l a t i o n on the o t h e r hand c o u l d r e s u l t i n the actual oxide
t h i c k n e s s b e i n g s e v e r a l times the c a l c u l a t e d v a l u e .

B. M u l t i p l e Sweep ( C y c l i c ) Voltammetry

By allowing the triangular potential c y c l e t o repeat a


number of t i m e s , changes w i t h time i n the s u r f a c e c o m p o s i t i o n of
the e l e c t r o d e can be d e t e c t e d . In this way the build-up of
s u r f a c e o x i d e s or o t h e r e l e c t r o a c t i v e s p e c i e s can be d e t e c t e d .
Cyclic voltammograms for stationary and rotating
a r s e n o p y r i t e e l e c t r o d e s a t pH = 10.6 a r e shown i n F i g u r e 20. The
anodic peak a t 0.35 V i s observed to decrease with continued
cycling while the i n i t i a l l y s m a l l anodic peak a t -0.025 V and
the c a t h o d i c peak a t about -0.4 V s t e a d i l y i n c r e a s e in height.
These o b s e r v a t i o n s a r e c o n s i s t e n t w i t h the f o r m a t i o n of F e ( O H ) 3

d u r i n g the anodic decomposition peak.


The o x i d a t i o n peak a t 0.35 V d e c r e a s e s w i t h each subsequent
c y c l e due t o the e l e c t r o d e becoming p a s s i v a t e d by the build-up
of surface hydroxide. At the same time the c a t h o d i c peak
increases i n height since there is an increasing amount of
hydroxide t o be reduced from F e ( O H ) 3 t o F e ( O H ) . The i n c r e a s i n g
2

amount of F e ( O H ) 2 thus formed r e s u l t s in the anodic peak at


-0.25 V i n c r e a s i n g i n h e i g h t w i t h subsequent c y c l e s .

Similar peaks and changes w i t h c y c l i n g were o b t a i n e d with


a r s e n o p y r i t e e l e c t r o d e s from the two d i f f e r e n t localities.
O io o 10 o
CVJ CVJ — — 6
VUJ / ju a J J n 3

Figure 19

Current - 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.


59

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

M u l t i p l e sweep voltammograms f o r s t a t i o n a r y and r o t a t i n g


e l e c t r o d e s a t pH = 10.6
60

The e f f e c t of r o t a t i n g the e l e c t r o d e i s t h a t the oxidation


peaks a t 0.35 i n F i g u r e 20 are i n c r e a s e d i n h e i g h t . At the same
time the a n o d i c peak at - 0.25 V becomes narrower and an
a d d i t i o n a l anodic peak a t -0.35 V becomes e v i d e n t w i t h continued
cycling. This additional anodic peak suggests that the
Fe(OH) /Fe(OH)
2 3 redox reaction results in the formation of
additional iron species than these h y d r o x i d e s . The e f f e c t of
r o t a t i o n i s d i s c u s s e d more f u l l y f o l l o w i n g the d i s c u s s i o n of a
r e a c t i o n mechanism.

Cyclic voltammograms at pH = 11.7 are shown i n F i g u r e 21


and F i g u r e 3, Appendix I I . The vertical scale in this figure
represents greater c u r r e n t s than t h a t of F i g u r e 20. As f o r the
r e s u l t s obtained at pH = 10.6 the effect of rotating the
electrode is to increase the currents associated with the
o x i d a t i o n peak a t 0.35 V, t o r e s u l t i n the a n o d i c peak at - 0.35
V becoming narrower and, the f o r m a t i o n of a d d i t i o n a l anodic and
cathodic peaks in the r e g i o n of i r o n h y d r o x i d e o x i d a t i o n and
r e d u c t i o n . These a d d i t i o n a l peaks a t pH = 11.7 are much more
apparent than those which r e s u l t from s t i r r i n g a t lower pH. The
reason why these peaks are more apparent a t h i g h pH i s explained
later in this chapter.
An a d d i t i o n a l f e a t u r e of the voltammogram f o r the rotating
electrode at pH = 11.7 is that w h i l e the o x i d a t i o n peak a t
0.35 V decreases from the first to the second cycle, it
i n c r e a s e s on subsequent c y c l e s .

For each of the tests shown i n F i g u r e s 20 and 21, the


e l e c t r o d e became covered w i t h a v i s i b l e brown o x i d e during the
multiple potential c y c l e s . T h i s o x i d e l a y e r became i r r i d e s c e n t
61

F i g u r e 21

M u l t i p l e sweep voltammograms f o r s t a t i o n a r y and r o t a t i n g


e l e c t r o d e s a t pH = 11.7
62

i n c o l o r , v a r y i n g from b l u e a t low pH t o y e l l o w - green- a t high


pH. Such c o l o r s have been shown t o r e l a t e t o i r o n o x i d e l a y e r s
i n t h e range of 200 t o 400 angstroms i n t h i c k n e s s ( 6 0 ) .

S i n c e t h e peaks have been related to redox reactions


involving iron species, a reaction sequence from Fe t o i r o n
hydroxides w i l l be c o n s i d e r e d . Such a r e a c t i o n sequence has been
proposed f o r an i r o n e l e c t r o d e ( 6 1 ) .

In the following equations brackets denote reaction


intermediates whose surface coverage i s of t h e order of a
f r a c t i o n of a monolayer and b r a c e s i n d i c a t e species eventually
related to the formation of new phases and which may undergo
ageing (61).

[Fe(OH)]ad + e = Fe + OH" (10)

[ F e ( O H ) ] a d + e = [Fe(OH)]ad
+
(11)

{Fe(OH) } = [ F e ( O H ) ] a d + OH"
2
+
(12)

HFe0 " + H 0 = {Fe(OH) } + OH"


2 2 2 (13)

F e 0 " + H 0 = HFe0 " + OH"


2
2
2 2 (14)

{FeOOH} + H 0 + e = {Fe(OH) } + OH"


2 2 (15)

{Fe 02 3 • H 0} = {FeOOH} + {FeOOH}


2 (16)
63

The above e q u a t i o n s a r e w r i t t e n w i t h FeOOH as t h e o x i d i z e d


hydroxide while the d i s c u s s i o n so f a r has c o n s i d e r e d Fe(OH) .3

The p r e c i s e form present on t h e e l e c t r o d e cannot be determined


from results of the present i n v e s t i g a t i o n . Throughout the
l i t e r a t u r e r e l a t i n g t o i r o n e l e c t r o d e s the p r e f e r r e d structure
is FeOOH. The two forms will be used interchangeably as
referring to f e r r i c hydroxide.

In c o n s i d e r i n g the r e a c t i o n sequence during a potential


cycle from the cathodic l i m i t t o t h e a n o d i c l i m i t and back t o
the s t a r t i n g p o i n t , t h e r e a c t i o n s would occur i n t h e f o l l o w i n g
order as shown i n F i g u r e 21 and i n F i g u r e 3, Appendix I I .

1. The i n i t i a l anodic p o t e n t i a l sweep r e s u l t s i n t h e o x i d a t i o n


of a r s e n o p y r i t e t o form FeOOH. The o x i d a t i o n i s a s s o c i a t e d
w i t h peak I I I . At t h e same time arsenic i s released as
arsenate ions and sulphate i s r e l e a s e d as s u l p h a t e ions.
Arsenate i s e l e c t r o i n a c t i v e and therefore does not
participate i n reactions associated with t h e remaining
peaks. T h i s w i l l be more f u l l y d i s c u s s e d i n s e c t i o n 4.3.2C.
Based on t h e r e s u l t s of ESCA experiments presented in
Chapter 5, i t i s b e l i e v e d t h a t a r s e n a t e p r e c i p i t a t e s i n the
ferric hydroxide d e p o s i t s . The c o m p o s i t i o n of t h e a r s e n i c
complex so formed i s not known. Sulphate is also
electroinactive and i s b e l i e v e d t o d i f f u s e s l o w l y through
the f e r r i c h y d r o x i d e l a y e r .
2. On the reduction cycle FeOOH i s reduced to Fe(OH) 2

according t o r e a c t i o n 15. T h i s r e a c t i o n i s a s s o c i a t e d with


peak I V .

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

12, 11 and 10 i s indicated by peak V. T h i s peak has a


somewhat g r e a t e r c u r r e n t a s s o c i a t e d w i t h i t than does peak
IV because although some F e ( O H ) 2 i s solubilized according
t o r e a c t i o n s 13 and 14, e q u a t i o n s 10 and 11 i n v o l v e a two
electron t r a n s f e r r e a c t i o n while equation 15 i n v o l v e s o n l y
one.

4. The second and successive anodic scans involve the


conjugated r e a c t i o n t o t h a t a s s o c i a t e d w i t h peak V as peak
I , namely t h e f o r m a t i o n of Fe(OH) 2 from reduced iron -
hydroxy s p e c i e s .

5. The F e ( O H ) 2 formed a t peak I i s o x i d i z e d t o FeOOH a c c o r d i n g


to reaction 15 a t peak I I . As f o r peaks IV and V, peak I I
i s again l e s s than peak I since only a one electron
transfer i s involved.
6. At high pH the hydroxide concentration i s such t h a t a
c o n s i d e r a b l e amount of F e ( O H ) 2 i s dissolved according to
reactions 13 and 14, so t h a t t h e c u r r e n t a s s o c i a t e d w i t h
peak I I I i n c r e a s e s on subsequent scans. I n the case of a
stationary e l e c t r o d e these p r o d u c t s a r e not swept away and
as a consequence t h e peak c u r r e n t becomes depressed with
c o n t i n u e d c y c l i n g due t o a g r e a t e r b u i l d - u p of h y d r o x i d e a t
the s u r f a c e .

The influence of e l e c t r o d e r o t a t i o n and i n c r e a s i n g pH can

now be c o r r e l a t e d t o t h e above r e a c t i o n sequence. Reaction 15

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.

Reaction 10 can similarly be 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 and t h e same arguments as p r e s e n t e d above explain the
appearance of peaks I and V w i t h s t i r r i n g o r i n c r e a s i n g pH.
Similar arguments have been p r e s e n t e d elsewhere (62) f o r
the f o r m a t i o n of n i c k e l h y d r o x i d e films according t o .

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)

To t h i s p o i n t a p a r t from t h e a r s e n o p y r i t e oxidation peak

(peak I I I ) no peaks have been a s s i g n e d t o a r s e n i c or s u l p h u r


66

s p e c i e s . At the peak p o t e n t i a l s observed f o r t h e main oxidation


peak for arsenopyrite ( peak I I I ) a r s e n i c o x i d a t i o n t o the
a r s e n a t e s t a t e and s u l p h u r o x i d a t i o n t o the s u l p h a t e state are
expected.

The irreversibility of sulphate formation is well


e s t a b l i s h e d and r e d u c t i o n peaks a s s o c i a t e d w i t h t h i s s p e c i e s a r e
not e x p e c t e d . In the case of p y r i t e and pyrrhotite, elemental
sulphur has been shown t o be formed even a t h i g h pH and h i g h
o v e r p o t e n t i a l ( 6 3 ) . The presence of s u l p h u r was shown t o result
in the f o r m a t i o n of FeS d u r i n g c o n t i n u e d c y c l i n g (63). Although
the f o r m a t i o n of s u l p h u r during arsenopyrite oxidation is a
reasonable expectation there i s no evidence i n the p r e s e n t
r e s u l t s t h a t t h i s i s i n f a c t o c c u r i n g i n the pH range where i r o n
hydroxide f i l m s a r e formed s i n c e no peaks associated with FeS
are observed.
In addition to the formation of FeS, the presence of
e l e m e n t a l s u l p h u r c o u l d be expected to result in increasing
t h i o s u l p h a t e f o r m a t i o n w i t h i n c r e a s i n g pH a c c o r d i n g t o

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)

E = + 0.04 - 0.007 l o g ( S 0 " ) 2 3


2
- 0.074 pH

(so, -) 2 2

The peaks associated with t h e above r e a c t i o n s would l i e

w i t h i n t h e peaks a s s i g n e d t o i r o n s p e c i e s as would any peaks

resulting from the r e d u c t i o n of t h i o s u l p h a t e t o s u l p h i d e . The


67

e f f e c t of e l e c t r o d e r o t a t i o n would be t o reduce peaks a s s o c i a t e d


w i t h t h i o s u l p h a t e r e d u c t i o n and subsequent sulphide oxidation.
No peaks whose height decreases with electrode rotation are
observed and t h e r e f o r e t h i o s u l p h a t e and s u l p h u r do not appear t o
be produced.

The f o r m a t i o n of a r s e n a t e during arsenopyrite oxidation is


also irreversible and peaks a s s o c i a t e d w i t h a r s e n a t e reduction
are not expected. T h i s w i l l be d i s c u s s e d more f u l l y i n t h e next
section.

The i r r e v e r s i b i l i t y of both s u l p h a t e and a r s e n a t e formation


in part accounts f o r the d e v i a t i o n of t h e observed peak
potential f o r arsenopyrite oxidation from the calculated
reversible value.
Since both arsenic and s u l p h u r form s o l u b l e s p e c i e s t h e
e f f e c t of s t i r r i n g or e l e c t r o d e r o t a t i o n i s e x p e c t e d t o be that
the anodic peak height increases, as i s observed. This
observation i s t h e r e f o r e c o n s i s t e n t with the o x i d a t i o n of a l l
t h r e e elements i n a r s e n o p y r i t e .
Consideration has also been given t o t h e p o s s i b l i t y of
f e r r i c arsenate p r e c i p i t a t i o n at the electrode surface according
to

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)

pH = 5.30 + log(H AsO„") 2


68

At t h e pH v a l u e s b e i n g c o n s i d e r e d i n the p r e s e n t work the


formation of f e r r i c a r s e n a t e would not be expected. The minimum
solubility of f e r r i c a r s e n a t e l i e s at about pH = 2.2 and at
greater pH i t decomposes t o g i v e F e ( O H ) 3 and H AsO " a c c o r d i n g
2 ft

to r e a c t i o n 25 ( 6 4 ) .

The o x i d a t i o n of a r s e n o p y r i t e t o form h y d r o x i d e results in


the release of H.
+
Equation 8 for instance i n d i c a t e s the
f o r m a t i o n of 13 moles of H +
f o r every mole of FeAsS which is
oxidized. At the r a p i d sweep r a t e s (20 mV/sec.) employed the pH
at the e l e c t r o d e s u r f a c e c o u l d t h e r e f o r e be s i g n i f i c a n t l y lower
than the bulk solution pH. F e r r i c a r s e n a t e c o u l d form a t the
e l e c t r o d e s u r f a c e i n t h e presence of such h i g h H +
concentration.

Voltammograms produced a t d e c r e a s i n g pH v a l u e s s h o u l d have


enhanced peaks due t o t h e f o r m a t i o n of FeAsO fl s i n c e the bulk pH
would be a p p r o a c h i n g t h e pH g e n e r a t e d a t the e l e c t r o d e surface.
Figure 22 shows a m u l t i p l e sweep voltammogram c a r r i e d out a t
pH = 5.8. The absence of t h e peaks which a r e o b s e r v e d a t higher
pH a t -0.35V i n d i c a t e s t h a t those peaks a r e not a s s o c i a t e d w i t h
FeAsO a formation.
The c a t h o d i c l i m i t of the p o t e n t i a l c y c l e s were kept w i t h i n
the s t a b i l i t y l i m i t s f o r FeAsS which a r e shown i n F i g u r e 18. It
was r e c o g n i z e d however t h a t the a c t i v i t i e s of d i s s o l v e d s p e c i e s
a t the e l e c t r o d e could be different from those assumed in
construction of the diagram. C a t h o d i c decomposition reactions
c o u l d t h e r e f o r e be o c c u r r i n g i f the limits of cycling were
a c t u a l l y beyond the s t a b i l i t y l i m i t s of the m i n e r a l .

F i g u r e 23 shows voltammograms produced w i t h c a t h o d i c limits


of -0.7 V and -0.55 V. The same peaks a r e e v i d e n t i n each case
69

» ' 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.

F i g u r e 24 shows a voltammogram produced with a cathodic


limit of -0.55 V and an a n o d i c l i m i t of +0.24 V. The anodic
peaks at -0.2 V which are e v i d e n t in Figure 23 are completely
absent in F i g u r e 24. A p o r t i o n of a scan c a r r i e d out a f t e r the
e l e c t r o d e was h e l d a t the c a t h o d i c l i m i t f o r 5 minutes is also
shown in Figure 24. Only a minor peak a s s o c i a t e d w i t h F e ( O H ) 2

o x i d a t i o n i s e v i d e n t . I t i s t h e r e f o r e reasonable t o assume that


the peaks at -0.2 V are associated with anodic oxidation
p r o d u c t s when the anodic l i m i t is 0.6V.

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

W h i l e a r s e n i c ( I I I ) can be o x i d i z e d or reduced i n solution

(65), arsenic (V) has been reported to be electroinactive


(66,67). The determination of arsenic by polarographic or

voltammetric methods r e q u i r e s the r e d u c t i o n of a r s e n i c (V) w i t h

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).

Figure 25 demonstrates the irreversibilty of arsenate

f o r m a t i o n a t pH = 9.2 and 10.7. Peak A i n t h i s f i g u r e represents

the oxidation of As to As ( I I I ) w h i l e peak B r e p r e s e n t s the

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

cathodic peak representing As(V) reduction to As (III)

corresponding to peak B. Peak C r e p r e s e n t s the d e p o s i t i o n of

a r s e n i c onto the g o l d electrode. The effect of holding the


71

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

electrode at the c a t h o d i c l i m i t f o r 5 minutes p r i o r t o c a r r y i n g


out the p o t e n t i a l sweep i s t o deposit a greater quantity of
a r s e n i c onto the e l e c t r o d e . T h i s i s made e v i d e n t by the increase
i n the h e i g h t of peak A i n t h i s c a s e . Peak B at the same time i s
unnaffected since the c o n c e n t r a t i o n of As (III) available for
o x i d a t i o n t o As (V) i s not changed.

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 .

None of the observed peaks are enhanced by i n c r e a s i n g


a r s e n i c a d d i t i o n s . The c o n c l u s i o n t h a t none of the peaks are
associated with arsenic oxidation or reduction i s therefore
F i g u r e 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
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

20 mV s-', pH=IO-6 , 1000 rpm

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.

The model which has been developed f o r the o x i d a t i o n of


arsenopyrite across the pH range of i n t e r e s t i s t h a t i r o n i n the
mineral is oxidized to form a surface deposit of ferric
hydroxide which increases i n t h i c k n e s s w i t h t i m e . At the same
time a r s e n i c and sulphur i n the m i n e r a l are o x i d i z e d to soluble
a r s e n a t e and s u l p h a t e respectively.
The formation of such an ever - thickening surface
hydroxide layer has implications to the electrochemical
behaviour of arsenopyrite. The hydroxide l a y e r w i l l tend t o
i n h i b i t activation controlled reactions and further oxidation
w i l l become d i f f u s i o n l i m i t e d .
By analyzing the i n f l u e n c e of sweep r a t e on peak current
and p o t e n t i a l , k i n e t i c parameters and the e x t e n t to which they
are a f f e c t e d by the h y d r o x i d e l a y e r may be d e t e r m i n e d . •

Under linear diffusion conditions reversible charge


t r a n s f e r p r o c e s s e s g i v e peak p o t e n t i a l s which a r e independent of
sweep r a t e .

Voltammograms were o b t a i n e d a t pH = 10.6 for sweep rates


77

from 1 mV/sec. t o 80 mV/sec. The r e s u l t s a t 2, 30 and 80 mV/sec


are shown i n F i g u r e 27 and a l l t h e r e s u l t s a r e " p l o t t e d i n F i g u r e
28. I t i s apparent t h a t t h e a n o d i c peak a s s o c i a t e d w i t h mineral
oxidation i s greatly affected by sweep r a t e i n d i c a t i n g t h i s
o x i d a t i o n p r o c e s s t o be i r r e v e r s i b l e .

The c a t h o d i c peak a s s o c i a t e d w i t h the r e d u c t i o n of Fe(OH) 3

is insensitive to sweep rate i n d i c a t i n g t h i s r e a c t i o n t o be


r e v e r s i b l e , as e x p e c t e d . At low sweep r a t e s the cathodic peak
exhibits the fact that i t represents a two stage r e a c t i o n ,
d i s p l a y i n g a double peak. T h i s i s c o n s i s t e n t w i t h the argument
presented in the section on m u l t i p l e sweep voltammetry t h a t
i m p r o v i n g the c o n d i t i o n s f o r p r o t o n or h y d r o x i d e d i f f u s i o n will
make the f e r r o u s h y d r o x i d e r e d u c t i o n r e a c t i o n more favoured.

If the anodic reaction i s considered to be a t o t a l l y


irreversible electrode process involving a single rate
determining step, the f o l l o w i n g r e l a t i o n s should apply (56,68)

Ep = E 0 + (RT//3naF) (0.78 + ln(Db) v 6


- InKs) (26)

Ep - E p 2 = 1 .857 (RT//3naF) = 0.048//Jna (27)

i p = 3 X I0 n(/3na) V 5 2
A D/ 1 2
C° (28)

where

Ks = rate constant when e l e c t r o d e i s a t E°

n = total number of electrons involved in the e l e c t r o d e

process

na=number of e l e c t r o n s i n v o l v e d i n the r a t e - determining step


pH 10-6

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

Scan rate / mV s" 1

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

<x = transfer coefficient

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

Ep 2 = h a l f peak p o t e n t i a l where i = 1/2 i p


ip = maximum c u r r e n t i n the c u r r e n t peak
0 = 1 -c*
b = /3naFv/RT
v = scan r a t e
According to equation 26, a plot of Ep vs. log v i s
expected t o be a s t r a i g h t l i n e . The p l o t shown i n F i g u r e 29 is
clearly not l i n e a r and e q u a t i o n 26 t h e r e f o r e does not a p p l y t o
the o x i d i z i n g a r s e n o p y r i t e . At the two h i g h e s t scan r a t e s shown
the peaks were very broad and a r e t h e r e f o r e r e p r e s e n t e d by bars
r a t h e r than by p o i n t s .
Additional consideration of the results indicates that
e q u a t i o n s 27 and 28 a l s o do not a p p l y . V a l u e s of na 0 d e t e r m i n e d
according t o e q u a t i o n 27 a r e shown i n Table 5. W h i l e a c o n s t a n t
v a l u e s h o u l d be o b t a i n e d f o r an a c t i v a t i o n controlled process,
the r e s u l t s a r e observed t o d e c r e a s e c o n t i n u o u s l y over the range
of sweep r a t e s c o n s i d e r e d .

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

Plot 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


e^ej U B O S 6ox s n s j S A luaaano ifeed 6oq

0£ 8^061,3
83

I t i s apparent t h a t the model used f o r t h e s e e q u a t i o n s does

not apply i n the p r e s e n t c a s e . D e v i a t i o n from the model may i n

p a r t r e s u l t from the e x i s t e n c e of more than one r a t e d e t e r m i n i n g

s t e p . A more s i g n i f i c a n t cause of deviation from the model

likely results from the proposed oxidation mechanism. The

formation of the ferric hydroxide surface deposit during


oxidation results in a p r o c e s s c o n t r o l l e d by d i f f u s i o n r a t h e r
than by a c t i v a t i o n p r o c e s s e s .

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

Since the flotation of arsenopyrite appears to be

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

of interest to determine the i n f l u e n c e of temperature on the

f o r m a t i o n of these l a y e r s . The results of this study should

indicate t h e e x t e n t t o which temperature can be used t o c o n t r o l


84

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

The same p o l a r i z a t i o n equipment and t e s t s e t - up as was


d e s c r i b e d i n the s e c t i o n on voltammetry was used f o r e x p e r i m e n t s
at different temperatures. In t h i s case the c e l l was equipped
w i t h a water j a c k e t connected t o a C o l o r a Type K t h e r m o s t a t . The
s o l u t i o n i n the c e l l c o u l d be c o n t r o l l e d t o w i t h i n ± 1°C.

( i i ) R e s u l t s and D i s c u s s i o n

A s e r i e s of voltammograms was o b t a i n e d a c r o s s the range of


temperature from 19°C t o 60.5°C. The s o l u t i o n used f o r the t e s t
sequence was pH = 10.75 a t 22°C. The voltammograms obtained at
the two temperature extremes a r e shown i n F i g u r e 31. The most
apparent d i f f e r e n c e i n the two voltammograms is the cathodic
shift and increased peak current associated with the
a r s e n o p y r i t e o x i d a t i o n peak.
The peak p o t e n t i a l , h a l f wave p o t e n t i a l and peak current
a c r o s s the temperature range a r e shown i n F i g u r e 32.
The peak p o t e n t i a l d e c r e a s e s w i t h temperature a c c o r d i n g t o
Ep = 479 - 4T
r = - 0.9957 where T = t e m p e r a t u r e , °C
W h i l e the h a l f wave p o t e n t i a l d e c r e a s e s a c c o r d i n g t o
Ep 2 = 274.2 - 2.8T
r= - 0.9756

The d i f f e r e n c e i n s l o p e s of the two r e l a t i o n s i n d i c a t e s the

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 .

The dependence of peak current on temperature shows a

complex r e l a t i o n s h i p . I f the n a t u r e of the surface hydroxide

layer was consistent across the temperature range the peak


85

pH 10-75

-0-6 -0-4 -0-2 0 0-2 0-4 0-6


Potential / V vs SHE

F i g u r e 31

Voltammograms a t 19°C and a t 60.5°C.


86

T e m p e r a tu re / °C
F i g u r e 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


87

current could be expected to be constant under diffusion


control. The present results indicate a d e v i a t i o n from t h i s
behaviour.

At temperatures below a p p r o x i m a t e l y 30°C the h y d r o x i d e film


development i s incomplete and the current therefore increases
with increasing temperature. Across the range from 30°C t o
approximately 45°C a c o n s t a n t f i l m t h i c k n e s s i s d e v e l o p e d . Above
45°C an i n c r e a s e i n c u r r e n t i s observed i n d i c a t i n g the diffusion
b a r r i e r to be d i m i n i s h e d . I t i s postulated that this increase
r e s u l t s from a change i n the morphology of the h y d r o x i d e film, a
more porous film being d e v e l o p e d . Thus w h i l e the f i l m b u i l d s
rapidly in thickness, its porous nature allows the anodic
process to c o n t i n u e .

This i s confirmed by F i g u r e 33 which shows a m u l t i p l e sweep


voltammogram obtained at 58.5°C. While t h e r e i s a d e c r e a s e i n
c u r r e n t a s s o c i a t e d w i t h the anodic peak ( I I I ) from the 1st. to
2nd. c y c l e s , on subsequent c y c l e s the c u r r e n t s t a y s e s s e n t i a l l y
constant while the peak shifts to slightly more anodic
potentials. Both these observations are consistent with the
presence of a s t e a d i l y t h i c k e n i n g but porous f i l m . The increase
in the peak h e i g h t of the peaks I and V i s c o n s i s t e n t w i t h the
presence of an increasing amount of surface hydroxide. The
electrode at the c o m p l e t i o n of t h i s experiment was observed t o
be v e r y h e a v i l y t a r n i s h e d .
The f o r m a t i o n of a porous f i l m r e s u l t s i n peaks I and V
becoming more prominent than peaks I I and IV. T h i s i s c o n s i s t e n t
with the e f f e c t s noted upon e l e c t r o d e r o t a t i o n or i n c r e a s i n g pH
(section 4.3.2 -B) and confirms improved conditions for
88

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 .

Anodic scans f o r p y r i t e and a r s e n o p y r i t e a t 60°C a r e shown

i n F i g u r e 34. The d i f f e r e n c e i n p o t e n t i a l between t h e two c u r v e s

at the h a l f peak potential f o r arsenopyrite i s 30 mV. The

difference observed at the same p o i n t a t 22°C and pH 11 was

190 mV ( F i g u r e 1 7 ) .

G. I n f l u e n c e of Cyanide

Cyanide i s used as a flotation depressant f o r gangue


sulphides such as pyrite. It i s therefore of interest to
determine t h e e x t e n t to which cyanide may be e f f e c t i v e at
depressing arsenopyrite.

The i n t e r a c t i o n of c y a n i d e w i t h p y r i t e has been s t u d i e d by


measuring t h e z e t a p o t e n t i a l and mixed p o t e n t i a l of pyrite at
v a r y i n g pH w i t h i n c r e a s i n g a d d i t i o n of c y a n i d e , f e r r o c y a n i d e and
ferricyanide ( 6 9 ) . The z e t a p o t e n t i a l was observed t o decrease
with increasing cyanide a d d i t i o n s i n d i c a t i n g that the cyanide
species adsorb chemically on pyrite. Mixed potential
measurements for pyrite i n t h e presence of cyanide were
determined to l i e i n t h e r e g i o n of s t a b i l i t y of t h e compound
Fe,[Fe(CN) ] . 6 3 The f o r m a t i o n of s u r f a c e f e r r i c f e r r o c y a n i d e was
therefore concluded to be responsible f o r t h e d e p r e s s i o n of
p y r i t e by c y a n i d e .

These i n v e s t i g a t o r s (69) a l s o determined t h a t v a r i a t i o n s i n

the degree of d e p r e s s i o n achieved w i t h equal cyanide additions

to various. pyrite samples resulted from varying pyrite

solubility. More soluble pyrite samples were found t o be


—I I I I J I
-0-6 -0-4 -0-2 0 0-2 0-4
Potential / V vs SHE

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

depressed to a l e s s e r degree by c y a n i d e than was l e s s s o l u b l e


p y r i t e . More s o l u b l e p y r i t e was p o s t u l a t e d t o r e s u l t in higher
levels of dissolved iron i n s o l u t i o n , r e s u l t i n g i n i n e f f e c t i v e
cyanide consumption. The results of electrochemical
investigations into pyrite - cyanide interaction (23) were
i n t e r p r e t e d on the b a s i s that the ferric ferrocyanide which
formed on pyrite inhibited 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 of
x a n t h a t e and thus r e s u l t e d i n d i m i n i s h e d floatability.

A s e r i e s of voltammograms was o b t a i n e d for arsenopyrite in


the presence of 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 t pH = 10.6.
The cyanide concentration was varied from 1 X 10 " -
M to
8 X lO' M 4
sodium cyanide. Across this range of cyanide
concentration the only significant change in multiple sweep
voltammograms is that the anodic peak associated w i t h the
o x i d a t i o n of ferrous hydroxide to ferric hydroxide becomes
diminished with increasing cyanide concentration.
F i g u r e 35 shows a m u l t i p l e sweep voltammogram o b t a i n e d a t a
cyanide concentration of 2.8 X 1 0 - 3
molar. At t h i s cyanide
concentration the f e r r o u s h y d r o x i d e oxidation peak disappears
completely. Comparison of F i g u r e 35 w i t h F i g u r e 20 r e v e a l s t h a t
i n t h e presence of c y a n i d e the e l e c t r o d e becomes p a s s i v a t e d t o a
much l e s s e r degree than i n the absence of cyanide. It appears
t h e r e f o r e t h a t c y a n i d e a c t s t o d i s s o l v e f e r r o u s h y d r o x i d e formed
at the surface of the e l e c t r o d e . Any i r o n - c y a n i d e complexes
which a r e formed are less effective inhibitors to further
o x i d a t i o n than i s the h y d r o x i d e .

Curve A in Figure 36 represents a p o t e n t i a l sweep on

a r s e n o p y r i t e c a r r i e d out a f t e r the e l e c t r o d e had been held at


92

+343 mV f o r 15 m i n u t e s . T h i s p o t e n t i a l i s j u s t below t h e peak


p o t e n t i a l f o r a r s e n o p y r i t e o x i d a t i o n . The e f f e c t of h o l d i n g the
electrode at this anodic potential i s to enhance the
Fe(OH) /Fe(OH)
2 3 peaks while diminishing the arsenopyrite
o x i d a t i o n peak.

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.

Curves B and C i n F i g u r e 36 r e p r e s e n t p o t e n t i a l sweeps


c a r r i e d out a f t e r holding the e l e c t r o d e at +343 mV f o r 15
minutes i n t h e presence of 2X10" 4
M and 2.8X10" 3
M cyanide.
Increasing cyanide concentration results in the ferrous
hydroxide oxidation peak becoming d i m i n i s h e d , the arsenopyrite
peak becoming enhanced and t h e f e r r i c h y d r o x i d e reduction peak
being unaffected.
Curve D represents a potential sweep c a r r i e d out a f t e r
h o l d i n g t h e e l e c t r o d e a t +343 mV f o r 15 minutes followed by
conditioning the electrode for 5 minutes i n t h e presence of
1.63X10' 3
M c y a n i d e w i t h no a p p l i e d p o t e n t i a l . Compared t o c u r v e
A t h e f e r r o u s peak i s d i m i n i s h e d while the a r s e n o p y r i t e and
f e r r i c peaks a r e enhanced.
It i s apparent t h a t t h e a c t i o n of c y a n i d e i s t o d i s s o l v e
f e r r o u s h y d r o x i d e from t h e e l e c t r o d e . T h i s d e c r e a s e s the e f f e c t
of oxidation by removing the oxidation products from the
s u r f a c e . The a r s e n o p y r i t e o x i d a t i o n c u r r e n t s a f t e r holding the
electrode at a corroding p o t e n t i a l are therefore increased i n
the presence of c y a n i d e .

The implication of this removal of surface hydroxide


93

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

2 0 mV s-», pH = !0.6 , 2 . 8 2 x | 0 " M 3


Na CN

F i g u r e 35

M u l t i p l e sweep voltammogram f o r a r s e n o p y r i t e i n t h e presence of


2.82X10' M NaCN3
94

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

d e p o s i t s from a r s e n o p y r i t e by c y a n i d e i s t h a t c y a n i d e may act as


an activating agent rather than as a depressant for
arsenopyrite.

A similar elimination of Fe(OH) /Fe(OH) 2 3 peaks in the


presence of cyanide i s observed f o r p y r i t e as shown i n F i g u r e
37. P y r i t e i n the presence of 1 . 6 3 X 1 0 " 3
M c y a n i d e does not show
any ferrous hydroxide peak. I t was determined however t h a t the
anodic current at 0 . 4 4 3 V i n the presence of cyanide was only
400MA w h i l e i n the absence of c y a n i d e i t was 640MA. The cyanide
t h e r e f o r e a c t s as an o x i d a t i o n i n h i b i t o r i n the case of pyrite.
Such a d e c r e a s e i n anodic c u r r e n t i n the presence of c y a n i d e is
not observed f o r a r s e n o p y r i t e . The c y a n i d e complexes which are
known to be formed on pyrite are a p p a r e n t l y not formed on
arsenopyrite.

H. Other M i n e r a l s i n the Fe - As - S System.

M u l t i p l e sweep voltammograms were o b t a i n e d a t pH = 1 0 . 6 f o r


s e v e r a l other minerals i n the Fe - As - S system as w e l l as for

i r o n . The purpose of t h i s s e r i e s of experiments was to determine

whether ferric hydroxide formed d u r i n g the o x i d a t i o n of these

m i n e r a l s . D i f f e r e n c e s i n f l o a t a b i l i t y of these m i n e r a l s can then

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

The pyrite electrode was the same electrode as was

previously described. The marcasite e l e c t r o d e was made from a

marcasite sample o b t a i n e d from Wards' S c i e n t i f i c . The electrode

was i r r e g u l a r i n shape w i t h an exposed s u r f a c e of approximately


96

F i g u r e 37

Voltammogram f o r p y r i t e i n the presence of 1 . 6 2 X 1 0 -3


M NaCN
97

4 square m i l l i m e t e r s .

The loellingite sample was obtained from the UBC Department


of G e o l o g i c a l S c i e n c e s and was i n d i c a t e d to come from Cobalt,
Ontario. The electrode was i r r e g u l a r i n shape w i t h an exposed
a r e a of a p p r o x i m a t e l y 59 square millimeters. The loellingite
sample was a n a l y z e d by means of an SEM - EDX a n a l y s i s . The major
constituents were found to be a r s e n i c and i r o n and the o n l y
t r a c e c o n s t i t u e n t which was d e t e c t e d was antimony.

E l e c t r o d e s were prepared as was previously described but


w i t h o n l y one w i r e connected t o them.

The iron electrode was made from a p i e c e of Armco pure


i r o n . The e l e c t r o d e was square i n shape w i t h an exposed area of
approximately 14 square m i l l i m e t e r s . T h i s e l e c t r o d e was made by
s o l d e r i n g a copper w i r e t o one f a c e of the i r o n cube and then
encasing the assembly i n epoxy. The f a c e o p p o s i t e the attached
w i r e was ground down t o 600 g r i t paper p r i o r t o use.
(ii) Results
Voltammograms f o r p y r i t e and m a r c a s i t e are shown i n Figure
38. The r e s u l t s f o r p y r i t e are s i m i l a r t o those for arsenopyrite
in that the Fe(OH) /Fe(OH)
2 3 peaks are prominent but d i f f e r in
t h a t no anodic peak due to oxidation of pyrite itself is
apparent. As previously discussed, the oxidation of p y r i t e
o c c u r s a t h i g h e r p o t e n t i a l s than does o x i d a t i o n of a r s e n o p y r i t e .
Peak A f o r p y r i t e has been a t t r i b u t e d (63) t o the formation
of s u l p h u r d u r i n g p y r i t e o x i d a t i o n . T h i s peak is observed to
become d i m i n i s h e d w i t h c o n t i n u e d cycling.

The results for marcasite show less significant


Fe(OH) /Fe(OH)
2 3 peaks but enhanced peaks a s s o c i a t e d w i t h reduced
I I I I I I —I 1
-0.8 -0.6 -0.4 -0.2 0 0,2 0.4 0.6
Potential / V vs SHE

20mV s - , pH = 10.6

F i g u r e 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


99

i r o n - hydroxy s p e c i e s . The oxidation of marcasite occurs at


more anodic p o t e n t i a l s than p y r i t e . M a r c a s i t e shows a much lower
tendency to passivate with continued scanning than does p y r i t e
or a r s e n o p y r i t e . The r e s u l t s are c o n s i s t e n t w i t h the formation
of more soluble iron species during marcasite o x i d a t i o n . This
observation i s c o n s i s t e n t w i t h the f a c t t h a t m a r c a s i t e is known
to decompose with the f o r m a t i o n of f e r r o u s s u l p h a t e (37). The
r a t e of o x i d a t i o n of m a r c a s i t e has been reported to be nine
times as f a s t as p y r i t e (37).

Figure 39 shows a voltammogram for loellingite. The


Fe(OH) /Fe(OH)
2 3 peaks are apparent as is an anodic peak
associated with with loellingite oxidation. The loellingite
o x i d a t i o n peak i s a p p r o x i m a t e l y 100 mV more anodic than the
arsenopyrite oxidation peak under s i m i l a r c o n d i t i o n s (Figure
20).
A minor r e v e r s i b l e r e a c t i o n i s apparent i n F i g u r e 39 a t 0.2
to 0.3 V. The peaks r e s u l t from a s p e c i e s which i s oxidized on
the f i r s t anodic sweep and then r e v e r s i b l y reduced and o x i d i z e d
on subsequent sweeps. A l t h o u g h antimony was d e t e c t e d as a minor
constituent in the l o e l l i n g i t e , the peak p o t e n t i a l s cannot be
r e l a t e d t o antimony r e a c t i o n s . C o n s i d e r i n g the fact that the
loellingite originated i n a s i l v e r producing area i n Canada i t
was considered possible that the peaks were due to trace
concentrations of s i l v e r which had not been d e t e c t e d d u r i n g the
sample a n a l y s i s .

A voltammogram f o r a g o l d electrode in the presence of


dissolved silver i s shown i n F i g u r e 39. The peak p o s i t i o n s show
good agreement w i t h those observed f o r l o e l l i n g i t e .
100

F i g u r e 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


101

F i g u r e 40 shows a voltammogram f o r iron. This experiment

was c a r r i e d out w i t h o u t KC1 in solution since excessive currents

and formation of s u r f a c e h y d r o x i d e s p e c i e s were encountered i n

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

the voltammogram i s more complex than those f o r m i n e r a l s . T h i s

i n c r e a s e d c o m p l e x i t y i s assumed t o result from the different

physical n a t u r e of i r o n h y d r o x i d e f i l m s formed on i r o n compared

to those formed on m i n e r a l s .

Based on t h i s s e r i e s of experiments, some possibilities

regarding the variable floatability of t h e s e m i n e r a l s can be

c o n s i d e r e d . The oxidation behaviour of loellingite is very

similar to that of a r s e n o p y r i t e and similar flotation

characteristics would be a n t i c i p a t e d . M a r c a s i t e shows behaviour

more comparable t o t h a t of p y r i t e w i t h the e x c e p t i o n t h a t more

s o l u b l e i r o n - hydroxy s p e c i e s a r e formed. It is expected that

this unstable behaviour of marcasite would make it more

difficult to float with xanthate and would make it more

d i f f i c u l t t o d e p r e s s w i t h c y a n i d e than i n the case of p y r i t e .

None of the m i n e r a l s c o n s i d e r e d show b e h a v i o u r s i m i l a r t o

t h a t of i r o n . A l t h o u g h i r o n h y d r o x i d e d e p o s i t s of some form are

developed i n each c a s e , each m i n e r a l shows a n o d i c d e c o m p o s i t i o n

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

The rotating arsenopyrite electrode was equipped with a

gold ring to detect electroactive oxidation products. The

purpose of these experiments was to determine whether any


F i g u r e 40

Voltammogram f o r i r o n e l e c t r o d e
103

o x i d a t i o n p r o d u c t s which had p r e v i o u s l y not been c o n s i d e r e d were


escaping into solution. Experiments were c a r r i e d out o n l y a t
pH = 10.6 so t h a t the p o s s i b l e f o r m a t i o n of e l e m e n t a l sulphur at
lower pH v a l u e s was not i n v e s t i g a t e d .

F i g u r e 41 shows the s o l u t i o n flow from the d i s c t o the ring


and the 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 formed a t the disc
(71). Such ring - d i s c e l e c t r o d e s have been used t o study the
a n o d i c d e c o m p o s i t i o n of galena (72) as w e l l as the c o r r o s i o n of
dental alloys (73).

The efficiency with which the ring collects species


released at the disc is dependent on electrode geometry
according to

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

The geometry of the a r s e n o p y r i t e e l e c t r o d e g i v e s a v a l u e

f o r the c o l l e c t i o n e f f i c i e n c y of 0.77. This value i s very high

due to the fact t h a t the g o l d r i n g i s very. wide. Such a wide

r i n g i s s u b j e c t t o e x c e s s i v e n o i s e p i c k - u p . An attempt was made

to determine the a c t u a l c o l l e c t i o n e f f i c i e n c y of the e l e c t r o d e .

The a r s e n o p y r i t e was found to give high background currents


104

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

however and a m e a n i n g f u l r e s u l t c o u l d not be achieved.

Two experiments were carried out w i t h t h i s e l e c t r o d e a t


pH = 10.6. One experiment i n v o l v e d h o l d i n g the a r s e n o p y r i t e d i s c
a t the a n o d i c peak p o t e n t i a l w h i l e scanning the g o l d ring. The
second experiment i n v o l v e d c a r r y i n g out a t r i a n g u l a r p o t e n t i a l
sweep of the a r s e n o p y r i t e w h i l e h o l d i n g the ring first at an
anodic and second a t a c a t h o d i c potential.

In n e i t h e r experiment were any ring currents detected. This


result is consistent with the formation of sulphate and
a r s e n a t e , both of which are e l e c t r o i n a c t i v e , at the a r s e n o p y r i t e
disc. The formation of solid oxidation products such as
elemental s u l p h u r or A s S
2 2 would be c o n s i s t e n t w i t h the results
of these experiments. The voltammetry experiments which
p r e v i o u s l y have been d i s c u s s e d show no e v i d e n c e of these species
and they are not b e l i e v e d t o be p r e s e n t . W h i l e more e l a b o r a t e
e x p e r i m e n t s c o u l d have been c a r r i e d o u t , i t seemed u n l i k e l y t h a t
these would c o n t r i b u t e s i g n i f i c a n t l y t o the present study and
t h i s a r e a t h e r e f o r e was not pursued f u r t h e r .

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 .

It is generally accepted t h a t d i x a n t h o g e n i s the a c t i v e

c o l l e c t o r species in pyrite flotation (27). The nature of

adsorbed xanthate species on arsenopyrite has not been

i n v e s t i g a t e d but i t i s e x p e c t e d t h a t dixanthogen will be the

active collector species.

Since the oxidation of arsenopyrite has been shown t o

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,

it is of i n t e r e s t t o determine the i n f l u e n c e of t h i s hydroxide


106

b u i l d - u p on the o x i d a t i o n of xanthate to dixanthogen.

(i) Experimental.

Anodic o x i d a t i o n scans were c a r r i e d out a t a scan r a t e of 5


mV per second.

X a n t h a t e used f o r these e x p e r i m e n t s consisted of Hoechst


potassium ethyl xanthate which was p u r i f i e d by d i s s o l v i n g i n
acetone and r e c r y s t a l l i z i n g by a d d i t i o n of e t h e r .

( 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

• Fresh FeAsS, 2-6 x 10" M KEtX 5

Oxidized FeAsS,2-6xiO- M KEtX 8

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

Fresh Fe AsS , 2-6X|0" M KEtX 3

—Oxidized FeAsS , 2-6x I0~ M KEtX 3

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.

A further difference i s that while at pH = 5.9 the


electrode was hardly affected by holding at an oxidizing
potential, at pH = 11.8 the electrode i s passivated to a
significant degree. The oxidation of xanthate i s greatly
i n h i b i t e d by the presence of t h i s p a s s i v a t i n g h y d r o x i d e l a y e r .

W h i l e these e x p e r i m e n t s c l e a r l y show t h a t t h e presence of


thick ferric hydroxide layers such as c o u l d be formed under
f l o t a t i o n c o n d i t i o n s ( i . e . 5 minutes conditioning with KMnO«)
will prevent the formation of dixanthogen a t t h e s u r f a c e , t h e
a d s o r p t i o n of x a n t h a t e i o n s a t the h y d r o x i d e l a y e r has not been
ruled out.

4.4 D i s c u s s i o n

The oxidation of a r s e n o p y r i t e under m o d e r a t e l y o x i d i z i n g

conditions has been shown to result in the formation of

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

time the arsenic and sulphur are oxidized t o a r s e n a t e and

sulphate r e s p e c t i v e l y . At the lower end of the pH range studied

elemental s u l p h u r can be expected t o be a product of o x i d a t i o n .

The influence of oxidation on the floatability of

arsenopyrite i s exerted through the b u i l d - u p of the hydroxide

layer on the surface of the mineral. The presence of t h i s

hydroxide layer inhibits the oxidation of xanthate to

dixanthogen. The m i n e r a l i s t h e r e f o r e not r e n d e r e d h y d r o p h o b i c .


110

At t h e same time t h e h y d r o x i d e l a y e r i t s e l f can be expected to


be strongly hydrophilic and t h e m i n e r a l i s therefore strongly
depressed.

The oxidation potentials required to bring about the


oxidation of a r s e n o p y r i t e have been shown t o be a c h i e v e d i n the
presence of s e v e r a l common o x i d i z i n g a g e n t s .

In addition, the o x i d i z i n g potentials required for


arsenopyrite depression a r e e n c o u n t e r e d i n some p l a n t s even i n
the absence of o x i d i z i n g a g e n t s . F i g u r e 44 shows v a r i o u s Eh - pH
c o n d i t i o n s which were measured i n p l a n t s (70) as well as t h e
r e s t p o t e n t i a l and o x i d a t i o n peak p o t e n t i a l f o r a r s e n o p y r i t e . I t
is apparent t h a t i n some c a s e s t h e c o n d i t i o n s r e q u i r e d f o r t h e
o x i d a t i o n and t h u s the d e p r e s s i o n of arsenopyrite are being
achieved.
Current peaks associated with arsenopyrite oxidation
increase with increasing pH. The build-up of hydroxide is
therefore expected to be greater with increasing pH and
flotation should be more difficult. Maximum flotation of
arsenopyrite w i t h x a n t h a t e i s e x p e c t e d a t pH l e s s than 7, where
f e r r i c h y d r o x i d e does not form and where the formation of
surface deposits of e l e m e n t a l s u l p h u r would f u r t h e r c o n t r i b u t e
to the hydrophobicity of t h e m i n e r a l .
The influence of temperature on the oxidation of
arsenopyrite showed a complex v a r i a t i o n . Over t h e range of 15°C
to 30°C, increasing temperature resulted in increasing
development of surface hydroxide. Over t h e temperature range
30°C t o 40°C temperature has no apparent i n f l u e n c e on hydroxide
build-up while at temperature greater than 40°C, i n c r e a s i n g
Ill

Figure 4 4

Comparison of a r s e n o p y r i t e r e s t p o t e n t i a l and o x i d a t i o n peak


p o t e n t i a l w i t h o p e r a t i n g p l a n t c o n d i t i o n s (70)
112

temperature r e s u l t s i n a rapid increase i n the q u a n t i t y of


f e r r i c hydroxide. The i n f l u e n c e of temperature on 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 by o x i d a t i o n i s t h e r e f o r e e x p e c t e d t o be m i n i m a l
u n t i l a temperature of 40°C i s exceeded. Above t h i s t e m p e r a t u r e ,
t h i c k , h y d r o p h i l i c l a y e r s of f e r r i c h y d r o x i d e a r e formed.

Differential flotation of a r s e n o p y r i t e and p y r i t e through


the use of oxidizing agents should be possible in the
temperature r e g i o n near 20°C. At t h i s t e m p e r a t u r e , a r s e n o p y r i t e
o x i d i z e s a t s i g n i f i c a n t l y lower o x i d a t i o n p o t e n t i a l s than does
pyrite. Increasing temperature can be e x p e c t e d t o d i m i n i s h t h e
e f f i c i e n c y of t h e d i f f e r e n t i a l f l o t a t i o n of t h e s e minerals. At
elevated temperature (60°C) the p o t e n t i a l s a t which t h e two
minerals o x i d i z e at a s i g n i f i c a n t rate are c l o s e r together than
at low t e m p e r a t u r e s .
The addition of cyanide to solution resulted in a
d i s s o l u t i o n of t h e h y d r o x i d e s u r f a c e d e p o s i t s p r e v i o u s l y formed
on arsenopyrite. It i s e x p e c t e d t h a t c y a n i d e a d d i t i o n s would
r e s u l t i n increased arsenopyrite f l o a t a b i l i t y by d i m i n i s h i n g t h e
e f f e c t s of o x i d a t i o n .
113

Chapter 5

ESCA STUDIES

X-ray p h o t o e l e c t r o n s p e c t r o s c o p y (XPS) or more commonly


known as ESCA, i s an e x p e r i m e n t a l t e c h n i q u e which p e r m i t s the
a n a l y s i s of a s u r f a c e l a y e r on a s o l i d sample. The thickness of
the surface layer which w i l l be a n a l y z e d may vary from a few
angstroms t o 50 angstroms.

The method c o n s i s t s of bombarding the sample t o be studied


with nearly monoenergetic photons and measuring the kinetic
energy d i s t r i b u t i o n of the e j e c t e d e l e c t r o n s ( 7 4 ) . Each element
w i l l have a c h a r a c t e r i s t i c s e t of p h o t o e l e c t r o n peaks due t o the
different electronic l e v e l s . The photon e n e r g i e s used t o e j e c t
e l e c t r o n s a r e i n the range of 1 KeV or more.
The b i n d i n g energy of e l e c t r o n s i n a g i v e n e l e c t r o n i c level
can be measured with sufficient precision to detect shifts
resulting from differences i n the c h e m i c a l s t a t e of the atom.
For i n s t a n c e , the energy f o r e l e c t r o n s i n a g i v e n energy state
for a metal will be different than for the metal oxide.
Similarly, variations in oxidation state will result in
v a r i a t i o n of the b i n d i n g energy of core e l e c t r o n s .
ESCA studies have been c a r r i e d out on p y r i t e t o determine
the n a t u r e of s u f a c e compounds formed d u r i n g f l o t a t i o n (75). It
was determined that iron hydroxide formed on p y r i t e d u r i n g
g r i n d i n g and a t h i g h pH d u r i n g f l o t a t i o n . For v a l u e s of pH less
than 7, surface hydroxide f i l m s are d i s s o l v e d l e a v i n g a clean
p y r i t e s u f a c e . Only l i m i t e d q u a n t i t i e s of e l e m e n t a l s u l p h u r were
114

d e t e c t e d even a t pH = 3.0.

T h i s o b s e r v a t i o n t h a t l i m i t e d sulphur was detected suggests


t h a t the method may be i n s e n s i t i v e t o s u r f a c e c o n c e n t r a t i o n s of
elemental sulphur since sulphur i s known t o form d u r i n g the a c i d
oxidation of pyrite ( 7 6 ) . W h i l e no e x p l a n a t i o n has p r e v i o u s l y
been o f f e r e d i n the l i t e r a t u r e i t i s proposed t h a t any elemental
sulphur present on the s u r f a c e of p a r t i c l e s is volatilized at
the h i g h vaccuum ( 1 0 " 7
t o r r ) encountered during a n a l y s i s , before
i t can be detected.

In the present study, the results of electrochemical


e x p e r i m e n t s on a r s e n o p y r i t e have been i n t e r p r e t e d as indicating
the formation of f e r r i c h y d r o x i d e with concurrent o x i d a t i o n of
a r s e n i c and sulphur to arsenate and sulphate respectively. The
r e s u l t of ESCA e x p e r i m e n t s w i l l be used to c o n f i r m the existence
of i r o n hydroxide s u r f a c e f i l m s and t o show the e x t e n t t o which
arsenate and s u l p h a t e are i n c o r p o r a t e d i n these films.

5.1 Experimental

Samples of a r s e n o p y r i t e , p y r i t e and l o e l l i n g i t e were of the

same o r i g i n as those used for electrochemical studies. Other

mineral samples were obtained from Ward's S c i e n t i f i c and were

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 .

A l l samples were p u l v e r i z e d w i t h a porcelain mortar and

pestle to minus 74 m i c r o n s and stored in sealed v i a l s p r i o r to

use.

The a r s e n o p y r i t e which i s shown i n f i g u r e s 45 t o 47 and in

Table VI to have been treated a t pH = 11.5 was prepared by

s t i r r i n g 2 grams of sample i n 100 ml. of water adjusted to


115

pH. = 11.5 with sodium hydroxide. Following 15 minutes of


c o n d i t i o n i n g the sample was f i l t e r e d and d r i e d under argon at
35°C.

Samples to be analyzed were dusted onto double sided


c e l l u l o s e tape which c o u l d be f a s t e n e d t o the sample h o l d e r for
i n s e r t i o n i n t o the spectrometer.

XPS measurements were carried out u s i n g a V a r i a n IEE-15


spectrometer equipped with a magnesium anode. Spectra were
recorded at approximately 10 " 7
torr.
From ten t o f o r t y scans were made of each m i n e r a l . The data
points were collected in d i g i t a l form and a G a u s s i a n f i t was
a p p l i e d t o the data n o r m a l i z e d t o overcome the variable number
of scans.

5.2 R e s u l t s and D i s c u s s i o n

The iron, arsenic and sulphur peaks for the various


m i n e r a l s i n c l u d e d i n the study a r e shown i n Figures 45,46 and
47. The b i n d i n g e n e r g i e s and i n t e n s i t y data a s s o c i a t e d w i t h the
peaks are summarized i n Table 6. I n t e n s i t i e s a r e based on the
counts per second at the peak. B i n d i n g e n e r g i e s r e l a t e t o the
i r o n 2p, a r s e n i c 3d and s u l p h u r 2p o r b i t a l e l e c t r o n s .
The purpose of i n c l u d i n g the v a r i o u s minerals other than
arsenopyrite in the study i s t o p r o v i d e a b a s i s f o r comparison
of peak p o s i t i o n s and r e l a t i v e i n t e n s i t y of o x i d i z e d and reduced
s p e c i e s f o r each m i n e r a l . I n t e n s i t i e s f o r the same element in
different m i n e r a l s can be expected t o vary i n d e p e n d e n t l y of the
compositional r a t i o for that element. Factors such as real
surface area and volume per u n i t c e l l , t a k i n g i n t o account the
116

number of formula u n i t s per u n i t c e l l , w i l l influence intensity

ratios between m i n e r a l s . S i n c e XPS a n a l y z e s a t h i c k n e s s of the

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.

Mineral Element B i n d i n g Energy Counts/sec.


eV

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

o r d e r of 50 angstroms the result for surface product layers

thinner than this will represent a composite of the surface

product and the s u b s t r a t e .

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

pyrite, marcasite and a r s e n o p y r i t e are summarized i n Table 7.


117

Figure 45

XPS peaks a s s o c i a t e d w i t h the i r o n 2p e l e c t r o n s of the various


minerals
118

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

XPS p e a k s a s s o c i a t e d w i t h the a r s e n i c 3d e l e c t r o n s of the


v a r i o u s m i n e r a l s
119

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

XPS peaks a s s o c i a t e d w i t h the s u l p h u r 2d e l e c t r o n s of the


various minerals
120

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

g r e a t e r o x i d a t i o n r a t e s than p y r i t e (37) and w i t h p r e v i o u s l y

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

r e s u l t s of some of the e l e c t r o c h e m i c a l e x p e r i m e n t s . The

v o l t a m m e t r y r e s u l t s i n d i c a t e d t h a t i r o n h y d r o x i d e was not formed

below a pH of a p p r o x i m a t e l y 7.0. At the same t i m e the r e s t

p o t e n t i a l s m e a s u r e d at pH l e s s than 7.0 o b e y e d the same r e l a t i o n

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

Pyrite 0..12 0..20 - 0..97


Marcasite 0..24 0..29 - 1 .33
.
Arseno. - DRY 0,.67 0..31 0..69 5.0 4..71
Arseno - p H = 11.5 0..90 0..50 0,.88 5.6 7..93

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

d u r i n g the e l e c t r o d e p r e p a r a t i o n . T h i s h y d r o x i d e controlled the


electrode potential measurements but was of insufficient
t h i c k n e s s t o a f f e c t the voltammetry experiments.

As expected, based on results of electrode potential


measurements, subjecting arsenopyrite t o pH = 11.5 r e s u l t s i n
r a p i d decomposition of the m i n e r a l lattice. For each of the
three elements Table 7 shows the r a t i o of o x i d i z e d t o reduced
atoms t o i n c r e a s e a f t e r o x i d a t i o n due to dissolved oxygen at
pH = 11.5. While the ratio of iron to sulphur increases
s i g n i f i c a n t l y a f t e r treatment, the ratio of iron to arsenic
i n c r e a s e s o n l y a s m a l l amount.

These r e s u l t s i n d i c a t e t h a t a t t h e same time as t h e s u r f a c e


layer of ferric hydroxide i s formed, much of t h e s u l p h u r goes
i n t o s o l u t i o n presumably as s u l p h a t e , w h i l e t h e a r s e n i c remains
at the surface i n a o x i d i z e d s t a t e . I t i s proposed t h a t t h i s
a r s e n i c i s adsorbed on the f e r r i c h y d r o x i d e since i t i s known
that a r s e n i c can be removed from s o l u t i o n i n t h i s way ( 7 8 ) . The
e x i s t e n c e of such a s u r f a c e o x i d a t i o n product i s also consistent
with the existence of such secondary arsenic minerals as
pitticite ( F e ( A s 0 ) ( S 0 ) OH«2H 0)
2 4 4 2 and pharmacosiderite
(6FeAsO„«2Fe(OH) '12H 0). 3 2

The results of this spectroscopic study confirm the


conclusions drawn from e l e c t r o c h e m i c a l e x p e r i m e n t s . At h i g h pH
v a l u e s , a r s e n o p y r i t e decomposes t o form i r o n hydroxide surface
deposits. Arsenic i n the form of a r s e n a t e and some sulphur i n
the form of s u l p h a t e a r e i n c o r p o r a t e d i n t h i s hydroxide layer.
Such hydroxide layers can be expected to result i n the
depression of a r s e n o p y r i t e d u r i n g f l o t a t i o n w i t h xanthate.
122

Chapter 6

FLOTATION STUDIES

F l o t a t i o n s t u d i e s were c a r r i e d out w i t h r e a l ore samples t o


v e r i f y t h e i n t e r p r e t a t i o n s made of electrochemical experiments
as they r e l a t e t o the f l o t a t i o n response of a r s e n o p y r i t e .

Three types of experiments were c a r r i e d o u t . In t h e f i r s t


type, conditions were controlled to observe the flotation
operation.

In t h e second t y p e , a rougher a r s e n o p y r i t e c o n c e n t r a t e was


prepared and i t s subsequent depression through the use of
o x i d i z i n g agents was s t u d i e d .
In t h e t h i r d t y p e , bulk p y 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 s
were prepared. The extent to which arsenopyrite could be
selectively depressed from t h i s c o n c e n t r a t e through the use of
o x i d i z i n g agents was e x p l o r e d .

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 .

Rougher f l o t a t i o n t e s t s were c a r r i e d out on selected high

grade samples from the property of G.M. Resources L t d . at

Hedley, B.C. The sample contained 51.2 percent by weight

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

the material indicated only minor p y r i t e t o be p r e s e n t . The


123

a r s e n o p y r i t e was assayed t o c o n t a i n 270 t o 340 grams per tonne


Au i n t h e form shown i n F i g u r e 2. Minor c o n c e n t r a t i o n o f o t h e r
metals a r e a l s o i n d i c a t e d i n F i g u r e 2 as determined by SEM - EDX
analysis.

For each t e s t , 1000 grams of o r e was ground i n a l a b o r a t o r y


rod m i l l t o a p p r o x i m a t e l y 92% minus 200 mesh. Vancouver tapwater
having a pH of 5.5 was used f o r a l l t e s t s .
For t e s t s c a r r i e d out a t v a r y i n g pH t h e temperature was
24±1°C. The pH was observed t o i n c r e a s e from t h e water v a l u e of
pH=5.5 t o a n a t u r a l v a l u e of pH=8.0 during grinding. Such an
increase i n pH r e s u l t s from t h e presence of s l i g h t l y alkaline
rock forming c o n s t i t u e n t s i n t h e o r e . The pH was adjusted from
the natural value of 8.0 to t h e d e s i r e d v a l u e u s i n g sodium
hydroxide o r s u l p h u r i c a c i d . F o l l o w i n g pH a d j u s t m e n t s t h e s l u r r y
was c o n d i t i o n e d f o r 15 minutes w i t h an a i r f l o w of 2.4 litres
per minute i n an A g i t a i r f l o t a t i o n c e l l a t 1000 RPM.
F o l l o w i n g t h i s c o n d i t i o n i n g p e r i o d w i t h a i r , an a d d i t i o n of
250 grams per tonne of i s o p r o p y l xanthate was made and a l l o w e d
to c o n d i t i o n f o r 2 m i n u t e s .
Rougher f l o t a t i o n was c a r r i e d out f o r 15 minutes with an
a d d i t i o n of 20 grams p e r tonne of Dowfroth 250 f r o t h e r .
Tests carried out a t varying temperature were a t the
n a t u r a l pH of 8.0. Some t e s t s were a l s o c a r r i e d out w i t h t h e pH
adjusted to 9.0 u s i n g sodium h y d r o x i d e . Temperature t e s t s were
carried out in a jacketed stainless steel cell with the
temperature c o n t r o l l e d by means of a C o l o r a Type - K thermostat.

Once t h e temperature had been s t a b i l i z e d the c e l l a i r was


t u r n e d on and c o n d i t i o n i n g was c a r r i e d out as f o r the t e s t s a t
124

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

The r e s u l t s of t e s t s c a r r i e d out a t v a r y i n g pH a r e shown i n


Figure 48. The r e c o v e r y of a r s e n o p y r i t e i s 90% o r g r e a t e r until
approximately pH=7.5 at which point i t starts to decrease
steadly u n t i l approximately pH=l0.5. Above pH=l0.5 t h e r e c o v e r y
continues t o decrease but a t a lower r a t e than below t h i s pH.

R e s u l t s a r e a l s o shown f o r two t e s t s carried out i n the


absence of o x i d a t i o n . The r e s u l t s of these t e s t s , particularly
a t pH = 10 i n d i c a t e t h a t t h e d e c r e a s e i n r e c o v e r y observed with
increasing pH i s not the r e s u l t of pH a l o n e . The o x i d a t i o n
r e s u l t i n g from a e r a t i o n during conditioning i s necessary to
b r i n g about a r s e n o p y r i t e depression.
The f l o t a t i o n t e s t r e s u l t s agree w i t h t h e r e s u l t s obtained
w i t h voltammetry. The voltammograms shown i n F i g u r e s 14 and 15
indicate t h e anodic peak a s s o c i a t e d w i t h a r s e n o p y r i t e o x i d a t i o n
to f e r r i c h y d r o x i d e t o appear i n t h e v i c i n i t y of approximately
pH = 7. The o x i d a t i o n peak h e i g h t s i n c r e a s e w i t h i n c r e a s i n g pH.
In t h e p r e s e n t flotation tests the r e s u l t of the i n c r e a s i n g
amount of f e r r i c h y d r o x i d e a s s o c i a t e d w i t h these i n c r e a s i n g peak
heights i s observed to lead to decreasing f l o a t a b i l i t y of t h e
m i n e r a l . F o r maximum r e c o v e r y of a r s e n o p y r i t e a pH of l e s s than
7.0 s h o u l d be used w h i l e f o r maximum d e p r e s s i o n a pH a p p r o a c h i n g
12.0 would be a p p r o p r i a t e . The pH used f o r d e p r e s s i o n i n most
cases would be d i c t a t e d by t h e pH dependance of t h e f l o a t a b i l i t y
of o t h e r m i n e r a l s b e i n g recovered.

The r e s u l t of t e s t s c a r r i e d out a t increasing temperature


Figure 48

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

are shown i n F i g u r e 49. The r e c o v e r y i n c r e a s e s somewhat over the


temperature range from 7°C to 40°C. Above 40°C t h e r e c o v e r y
decreases w i t h i n c r e a s i n g temperature. The r e c o v e r y a t 60°C in
the absence of oxidation was higher than at the lower
temperatures with oxidation. If arsenopyrite depression was
desired there would be no benefit d e r i v e d from h e a t i n g the
s l u r r y s i n c e p l a n t temperatures can n o r m a l l y be expected to be
i n the range of 10°C t o 20°C.

The r e s u l t s a c h i e v e d a t pH = 9.0 show s i m i l a r behaviour t o


those a c h i e v e d a t pH = 8.0 w i t h i n c r e a s i n g temperature. In each
case the c o n c e n t r a t e grade was i n s e n s i t i v e t o temperature.

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

Tests were c a r r i e d out u s i n g ore samples d e s c r i b e d i n the

p r e v i o u s s e c t i o n . Two s e r i e s of tests were carried out, one

using hydrogen peroxide as the oxidant and t h e o t h e r u s i n g

sodium h y p o c h l o r i t e .

In each case a two kilogram sample was ground in a

laboratory rod mill t o 74 p e r c e n t p a s s i n g 200 mesh. A c l e a n e d

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

c o n d i t i o n s shown i n Table 8. The rougher flotation was carried

out at the natural pH of 8.0. The c l e a n e d c o n c e n t r a t e was

f i l t e r e d and s p l i t i n t o p o r t i o n s of 120 grams f o r t h e i n d i v i d u a l

t e s t s . These t e s t s were c a r r i e d out i n a 500 gram Agitair cell

a t 800 RPM, a temperature of 20° and pH = 8.0.


- J —1 — J J 1 I

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

O x i d a t i o n was c a r r i e d out a t pH = 8.0 f o r the time shown i n


t h e r e s u l t s . F l o t a t i o n was allowed t o proceed f o r 5 minutes.

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 .

6.0.3.2 R e s u l t s and Discussion

The r e s u l t s of f l o t a t i o n t e s t s u s i n g hydrogen peroxide as


an o x i d a n t are shown i n Table 9. The a d d i t i o n of 357 m g / l i t r e of
hydrogen peroxide resulted in a significant decrease in
arsenopyrite f l o a t a b i l i t y . I n c r e a s i n g the c o n d i t i o n i n g time from
5 t o 15 minutes gave a f u r t h e r d e c r e a s e i n floatability.
Comparison of the p o t e n t i a l s a c h i e v e d by the arsenopyrite
electrode in these t e s t s w i t h the voltammogram a t pH = 8.2 in
Figure 14 reveals that the potentials lie partway up the
a r s e n o p y r i t e o x i d a t i o n peak. -

For the test shown i n T a b l e 9, an a d d i t i o n of up t o 900


grams per tonne of e t h y l x a n t h a t e gave no further increase in
recovery w i t h 357 m g / l i t r e H 0 2 2 and an i n c r e a s e of 3.1% with 214
129

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.

The results using sodium h y p o c h l o r i t e as an o x i d a n t a r e


shown i n T a b l e 10. The r e c o v e r y i n t h e absence of oxidation is
lower i n t h i s t e s t s e r i e s than i n t h e s e r i e s shown i n Table 9.
While the concentrate was produced from t h e same ore i n each
case, slight variations i n t h e rougher f l o t a t i o n procedure
caused t h e v a r i a t i o n i n f l o a t a b i l i t y . As f o r the peroxide, a
significant decrease i n arsenopyrite f l o a t a b i l i t y was a c h i e v e d
t h r o u g h t h e use of h y p o c h l o r i t e . The addition of hypochlorite
required f o r depression t o be a c h i e v e d i s much lower than t h e
required peroxide addition. The reason for this lower
hypochlorite requirement is not apparent from the
electrochemical i n v e s t i g a t i o n s which have been c a r r i e d out. I t
is b e l i e v e d t h a t the two r e a g e n t s r e s u l t e d i n d i f f e r e n t degrees
of o x i d a t i o n not r e f l e c t e d by t h e p o t e n t i a l s . The p o t e n t i a l of
the arsenopyrite electrode with hypochlorite jumped to
a p p r o x i m a t e l y +343 mV and then d e c r e a s e d d u r i n g t h e c o n d i t i o n i n g
p e r i o d . W h i l e a t 389 m g / l i t r e NaCIO the a d d i t i o n of a large
a d d i t i o n of x a n t h a t e f a i l e d t o r e s u l t i n a r s e n o p y r i t e flotation,
130

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

Test Conditions Arsenopyrite As


No. Eh,mV Recovery %

1 No o x i d a t i o n 203 t o 223 83.1


2 389 m g / l i t r e NaCIO 343 t o 283 0.0
cond. 5 min.
3 77.6 m g / l i t r e NaCIO 343 t o 283 0.0
cond. 5 min.
4 19.4 m g / l i t r e NaCIO 343 t o 193 28.7
cond. 5 min.
5 19.4 m g / l i t r e NaCIO 343 t o 203 22.5
cond. 15 min.

at t h e lower NaCIO a d d i t i o n s xanthate a d d i t i o n s r e s u l t e d i n 20

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

S e l e c t i v e f l o t a t i o n t e s t s were c a r r i e d out on bulk p y 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 s from G i a n t Y e l l o w k n i f e Mines and from
E q u i t y S i l v e r Mines L i m i t e d .

6.0.4.1 E x p e r i m e n t a l and R e s u l t s .

(i) Equity Concentrate

Tests were carried out on a bulk c o n c e n t r a t e s u p p l i e d by

E q u i t y M i n e s . The c o n c e n t r a t e had been produced a t t h e s i t e by

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 )

t a i l i n g . The c o n c e n t r a t e c o n t a i n e d a p p r o x i m a t e l y five times as

much p y r i t e a s a r s e n o p y r i t e . Some o x i d a t i o n was observed on t h e

concentrate and i t was therefore reground, filtered and

refloated with 85 grams per tonne i s o p r o p y l xanthate. This


131

r e f l o a t e d c o n c e n t r a t e was then f i l t e r e d and s p l i t into portions


for the i n d i v i d u a l tests.

The tests were carried o u t i n an A g i t a i r f l o t a t i o n cell


u s i n g 150 grams c o n c e n t r a t e i n a 500 gram (1.4 l i t r e ) c e l l . The
repulped c o n c e n t r a t e was found t o have a pH of 5.7 and t h i s was
a d j u s t e d t o pH = 9.2 u s i n g NaOH. A f t e r the pH was adjusted the
o x i d i z i n g agent was added and c o n d i t i o n e d . F l o t a t i o n was c a r r i e d
out for 3 minutes with an addition of 5 grams p e r tonne
Downfroth 250. The o x i d a n t used was H 0 .
2 2 A l l tests were at
20°C. The t e s t r e s u l t s a r e shown i n Table 11.

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

Several series of tests were carried out on a bulk

c o n c e n t r a t e produced a t t h e m i n e s i t e . T h i s c o n c e n t r a t e had been

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 .

Microscopy of t h i s m a t e r i a l r e v e a l e d numerous m i d d l i n g s and i t


was therefore reground t o .94% minus 200 mesh p r i o r t o b e i n g

used. The reground c o n c e n t r a t e was r e f l o a t e d w i t h an a d d i t i o n of

25 grams p e r tonne i s o p r o p y l x a n t h a t e and cleaned twice more

with no f u r t h e r a d d i t i o n s . The c l e a n e d c o n c e n t r a t e was f i l t e r e d


132

and split i n t o 90 gram p o r t i o n s f o r i n d i v i d u a l tests.

The pH f o r each t e s t was a d j u s t e d u s i n g H S O 2 a or NaOH as


required. The c o n d i t i o n i n g p e r i o d f o r each t e s t was 15 minutes
and t h e temperature was 20°C.

The r e s u l t s of t e s t s u s i n g both a i r and h y p o c h l o r i t e as the


o x i d a n t a r e shown i n F i g u r e 50. W h i l e w i t h a i r t h e arsenopyrite
recovery i s somewhat lower than f o r p y r i t e , w i t h h y p o c h l o r i t e
the two m i n e r a l s show e s s e n t i a l l y the same b e h a v i o u r . The r e s u l t
of these t e s t s when compared w i t h those shown i n Table 11 as
w e l l as w i t h those f o r t h e a r s e n o p y r i t e t e s t e d i n d i v i d u a l l y make
it apparent that each ore o c c u r r e n c e can be expected t o show
some v a r i a t i o n i n response to depression by oxidation. Such
factors as the r a t i o of p y r i t e t o a r s e n o p y r i t e and the p r e v i o u s
f l o t a t i o n h i s t o r y of t h e samples can be expected to influence
the results.

Additional tests were carried out on a bulk concentrate


p r e p a r e d i n the l a b o r a t o r y from G i a n t Y e l l o w k n i f e o r e .
The c o n c e n t r a t e was p r e p a r e d by g r i n d i n g 2 k i l o g r a m s of ore
in a laboratory rod m i l l t o 80% p a s s i n g 200 mesh. F l o t a t i o n was
carried out w i t h 65 grams per tonne i s o p r o p y l x a n t h a t e 25 grams
per tonne amyl x a n t h a t e and 10 grams per tonne Dowfroth 250 at
pH = 6.0. The concentrate was cleaned t w i c e without further
a d d i t i o n s and was then f i l t e r e d and s p l i t into three portions
for testing.

Two test series were carried o u t , one with constant


p o t a s s i u m permanganate a d d i t i o n and the second with increasing
permanganate addition and constant x a n t h a t e a d d i t i o n . I n each
case a f i v e minute c o n d i t i o n i n g p e r i o d was used following the
133

!00

80

>*60
0 FeAsS,77.6mg r'NaCIO
>
O
• FeS ,7 76 mg r'NaCIO
«40 2

EC D FeAsS , 2.4 Ipm air

20h 1 FeS , 2.4 Ipm air


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

permanganate a d d i t i o n . At the end of t h i s p e r i o d n e i t h e r p y r i t e


nor a r s e n o p y r i t e were found t o f l o a t . The xanthate and 12 mg.
per l i t r e Dowfroth 250 were added and f l o t a t i o n was then c a r r i e d
out. The addition of frother alone f a i l e d t o r e s u l t i n any
flotation.

6.0.4.2 D i s c u s s i o n

The result of tests on the Equity concentrate, using


hydrogen peroxide show g r e a t e r d e p r e s s i o n of a r s e n o p y r i t e than
p y r i t e . Maximum d e p r e s s i o n of a r s e n o p y r i t e i s achieved with a
high peroxide addition (357 m g . / l i t r e ) . Much lower peroxide
additions can be used but with increasing arsenopyrite
floatability resulting. P y r i t e appears to be l e s s f l o a t a b l e i n
the presence of low p e r o x i d e a d d i t i o n s than w i t h high peroxide
additions. Increasing conditioning time does not improve the
s e p a r 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 .
The r e s u l t s of t e s t s with Giant Yellowknife concentrate
show both pyrite and a r s e n o p y r i t e t o be e q u a l l y d e p r e s s e d by
hypochlorite while air oxidation results in preferential
depression of a r s e n o p y r i t e .
While the addition of p o t a s s i u m permanganate, d e p r e s s e d
both p y r i t e and a r s e n o p y r i t e , a subsequent a d d i t i o n of xanthate
resulted in preferential pyrite flotation.
The complete depression of both minerals followed by
p r e f e r r e n t i a l a c t i v a t i o n of the p y r i t e with xanthate has not
been a t t e m p t e d w i t h o x i d a n t s o t h e r than permanganate.

The selective flotation of pyrite from a bulk pyrite-

arsenopyrite concentrate appears to be feasible although


Figure 51

D e p r e s s i o n of a r s e n o p y r i t e from bulk c o n c e n t r a t e with increasing


xanthate a d d i t i o n
136

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 .

The results of the various tests in which p r e v i o u s l y


floated arsenopyrite has been depressed though the use of
o x i d i z i n g agents r e v e a l t h a t a g r e a t e r i n f l u e n c e on floatability
is e x e r t e d by the f e r r i c h y d r o x i d e s u r f a c e d e p o s i t s than by the
adsorbed c o l l e c t o r layer.
138

Chapter 7

CONCLUSIONS

1. C y c l i c v o l t a m m e t r i c s t u d i e s have r e v e a l e d the oxidation of


arsenopyrite across the pH range from 7 - 12 t o r e s u l t i n the
formation of ferric hydroxide surface deposits with the
concurrent oxidation of arsenic to the arsenate s t a t e and
s u l p h u r t o the s u l p h a t e s t a t e . A c r o s s the pH range s t u d i e d , the
hydroxide f i l m t h i c k n e s s i n c r e a s e s w i t h i n c r e a s i n g pH.

At temperatures below 30°C, i n c r e a s i n g temperature r e s u l t s


in i n c r e a s i n g hydroxide f i l m t h i c k n e s s . Across the temperature
range from 30°C to 45°C, film development appears to be
independent of t e m p e r a t u r e . At temperatures g r e a t e r than 45°C,
f i l m t h i c k n e s s increases r a p i d l y w i t h i n c r e a s i n g temperature.
Below pH = 7, f e r r i c h y d r o x i d e d e p o s i t s a r e not formed but
the f o r m a t i o n of e l e m e n t a l sulphur a t the electrode surface is
indicated.
2. ESCA s t u d i e s have r e v e a l e d t h a t most of t h e a r s e n a t e and some
of the sulphate i s incorporated i n the ferric hydroxide
deposits.
3. E l e c t r o d e p o t e n t i a l measurements i n t h e presence of several
oxidizing agents indicate that the potentials required for
f e r r i c hydroxide formation (as i n d i c a t e d by c y c l i c voltammetry)
w i l l be a c h i e v e d w i t h these agents.

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.

Temperatures greater than 40°C result in increased


depression of a r s e n o p y r i t e .
The influence of both pH and temperature on t h e
floatability of arsenopyrite correlate well with the
interpretations of e l e c t r o c h e m i c a l e x p e r i m e n t s . I t i s c o n c l u d e d
that the f l o a t a b i l i t y of arsenopyrite i s controlled by t h e
formation of f e r r i c h y d r o x i d e s u r f a c e deposits.
The depression of a r s e n o p y r i t e which has p r e v i o u s l y been
floated with xanthate and the selective depression of
arsenopyrite from bulk c o n c e n t r a t e s through t h e use of o x i d i z i n g
agents has been demonstrated. I t i s t h e r e f o r e c o n c l u d e d t h a t t h e
f l o a t a b i l i t y of t h e m i n e r a l i s i n f l u e n c e d t o a g r e a t e r degree by
the f e r r i c h y d r o x i d e d e p o s i t s formed by o x i d a t i o n of t h e m i n e r a l
than by adsorbed c o l l e c t o r l a y e r s .
6. V o l t a m m e t r i c s t u d i e s i n t h e presence of c y a n i d e i n d i c a t e t h a t
cyanide does not contribute t o t h e development of d e p r e s s a n t
f i l m s on a r s e n o p y r i t e and may i n f a c t r e s u l t i n some degree of
activation.

7. Electrochemical studies of other minerals i n t h e Fe-As-S


system r e v e a l s i g n i f i c a n t d i f f e r e n c e s i n t h e n a t u r e of surface
140

hydroxide deposits which correlate well with observed

d i f f e r e n c e s i n m i n e r a l s o l u b i l i t y and may explain variations in

their f l o a t a b i l t y with xanthate.


141

Chapter 8

RECOMMENDATIONS FOR FUTURE WORK

Additional work t o be carried out on t h e f l o t a t i o n of


arsenopyrite can be divided into fundamental and applied
categories.

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

P o t e n t i a l / p H diagrams f o r the I r o n - A r s e n i c - S u l p h u r - Water


System

Potential/pH diagrams have been p r e p a r e d f o r the i r o n -

a r s e n i c - sulphur - water system a t 25°C. The assumptions made

f o r each diagram a r e as f o l l o w s :

F i g u r e 53. A r s e n o p y r i t e s t a b i l i t y diagram assuming i r o n , a r s e n i c


and sulphur a c t i v i t i e s of 10' 6
M. A s S 2 2 and A s S 2 3 a r e shown as

s t a b l e s p e c i e s . S o l u b l e a r s e n i c s p e c i e s are not shown.

F i g u r e 54. A r s e n o p y r i t e s t a b i l i t y diagram assuming i r o n , a r s e n i c


and s u l p h u r a c t i v i t i e s of 1 0 - 3
M. A s S 2 2 and A s S 2 3 are shown as
stable species.

F i g u r e 55. A r s e n o p y r i t e s t a b i l i t y diagram assuming i r o n , a r s e n i c


and sulphur activities of 1 M. A s S 2 2 and A s S 2 3 a r e shown as
s t a b l e s p e c i e s . S o l u b l e a r s e n i c s p e c i e s a r e not shown.

F i g u r e 56. Loellingite stability diagram assuming iron and

a r s e n i c a c t i v i t i e s of 10~ 3
M.

Figure 57. A r s e n o p y r i t e s t a b i l i t y diagram c o n s i d e r i n g F e S , 2 FeS

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

are i n d i c a t e d . S o l u b l e arsenic and sulphur species are not

shown. A c t i v i t y of each d i s s o l v e d s p e c i e s = 10~ 6


M.
143

Ferric arsenate i s not shown i n F i g u r e s 53 t h r o u g h 57. At

low i r o n and a r s e n i c a c t i v i t y i t has only a narrow stability

region near the ferric ion - f e r r i c hydroxide boundary. The

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

and a r s e n i c i s shown i n F i g u r e 58.

T a b l e 12
Thermodynamic Data a t 25°C

Spec i e s State G°f 298°K


Kcol/mole

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

Arsenopyrite stability d i a g r a m at 10~ 6


M activity of dissolved
spec i e s
145

Figure 54

Arsenopyrite stability diagram at 10" 3


M activity of dissolved
species
146

Figure 55

Loellingite stability diagram at 10" 3


M activity of dissolved
spec i e s
147

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

Arsenopyrite stability diagram c o n s i d e r i n g FeS,FeS 2 and F e A s 2 as


stable products
Figure 58

Stability r e g i o n of ferric arsenate at 1 M activity


Appendix I I
E q u a t i o n s Used For The C o n s t r u c t i o n Of The Diagrams

1. FeAsS + 2H +
= Fe + +
+ H S + As.
2

-0.030 = 0.0591 l o g ( F e ) ( H S ) + 0.118 pH + +


2

2. F e 2 +
+ H As0
3 3 + HS + H 2
+
+ 3e" = FeAsS + 3H 0 2

E = 0.236 - 0.0197 l o g ( F e ) ( H A s 0 ) ( H S ) - 0.0197 pH 2 +


3 3 2

3. F e ( O H ) 2 + H3ASO3 + SO," + 13H +


+ 1 l e " = FeAsS + 9H 0 2

E = 0.396 + 0.005 l o g ( H A s 0 ) ( S O , " " ) - 0.070 pH 2 3

4. F e ( O H ) 2 + H A s 0 - + SO,'" + 14H
2 3
+
+ 11e" = FeAsS + 9H 0 2

E = 0.396 +0.005 l o g ( H A s 0 " ) ( S O , " " ) - 0.075 pH


2 3

5. F e ( O H ) 2 + HAs0 " + SO,-" + 15H


2
3
+
+ l i e ' = FeAsS + 9H 0 2

E = 0.461 + 0.005 l o g ( H A s 0 - ) ( S O , - - ) - 0.080 pH 3


2

6. F e ( O H ) 2 + HAs0 - 3
2 +
HS" + 6H +
+ 3e" = FeAsS + 5H 0 2

E = 1.025 + 0.0197 l o g ( H A s 0 " ) ( H S " ) - 0.118 pH 3


2

7. FeAsS + 5H +
+ 3e" = A s H 3 + Fe + +
+ HS 2

E = - 0.354 - 0.0197 l o g ( A s H ) ( F e ) ( H S ) - 0.0985 pH 3


+ +
2

8. FeAsS + 5H +
+ 5e~ = A s H 3 + H S + Fe 2

E = -0.376 - 0.0118 l o g ( A s H ) ( H S ) - 0.0591 pH 3 2


151

9. FeAsS + 4H +
+ 5e" = A s H 3 +HS" + Fe

E = - 0.459 - 0.0118 l o g ( A s H ) ( H S - ) - 0.0473 pH 3

10. FeAsS + H +
+ 2e" = A s H 3 + HS" + Fe

E = - 0.631 - 0.0295 log(HS") - 0.0295 pH

11. 2 H A s 0 3 3 + 3HSO - + 27H q


+
+ 24e" = A s S 2 3 + 18H 0 2

E = 0.348 + 0.0025 l o g ( H A s 0 ) ( H S 0 " ) 3 3


2
4
3
- 0.066 pH

12. 2 H A s 0
3 3 + SO„-- + 30H +
+ 24e" = A s S 2 3 + 18H 0 2

E = 0.363 + 0.0025 l o g ( H A s 0 ) ( S O " " ) 3 3


2
f t
3
- 0.074 pH

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

E = 0.352 + 0.0033 log(H As0 ) (SO«"-) 3 3


2 2
- 0.0722 pH

16. 2 H A s 0 " + 2SO "- + 24H


2 3 ft
+
+ I8e" = A s S 2 2 + 14 H 0 2

E = 0.412 + 0.0033 log(H As0 ") (SO„"') 2 3


2 2
- 0.0788 pH

17. H A s 0 - + 2HS" + 6H
2 3
+
+ 2e" = A s S 2 2 + 6H 0 2

E = 1.719 + 0.0295 l o g ( H A s 0 ) ( H S " ) 2 3


2 2
- 0.1773 pH

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'

E = - 0.193 - 0.0295 log(HS") - 0.0295 pH

20. A s S 2 2 + S 0 " - + 3H
4
+
+ 6e" = A s S 2 3 + 4H 0 2

E = 0.395 + 0.0098 l o g ( S O - " ) - 0.0788 pH a

21. 1/2 A s S 2 3 + Fe ++
+ H +
+ 3e" = FeAsS + 1/2 H S 2

E = -0.012 - 0.0295 l o g ( H S ) V * - 0.0197 pH 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 = 0.358 + 0.007 l o g ( H A s 0 " ) 2 3


2
- 0.074 pH

29. 2 H A s 0 " + Fe(OH)


3
2
2 + 12H +
+ 8e" = F e A s 2 + 8H 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

E = 0.362 + 0.0042 l o g ( F e ) (SO,, ") - 0.068 pH 2 + 2 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

E = -0.118 - 0.0295 l o g ( H S ) - 0.059 pH 2

34. F e S 2 + As + H +
+ 2e" = FeAsS + HS"

E = -0.325 - 0.0295 log(HS') - 0.0295 pH

35. F e ( O H ) 2 + 2SO "- + 18H tt


+
+ 14e" = F e S 2 + 10H 0 2

E = 0.412 + 0.0042 l o g ( S O " - ) a


2
- 0.076 pH

36. F e S 2 + H A s 0 " + 5H
2 3
+
+ 5e" = FeAsS + HS" + 3H 0 2

E = 0.115 - 0.012 l o g (HS~) - 0.059 pH


154

(H As0 ~) 2 3

37. F e S 2 + H +
+ 2e~ = FeS + HS"

E = - 0.372 - 0.0295 pH - 0.0296 l o g HS"

38. F e ( O H ) 2 + HS" + H +
= FeS + 2H 0 2

1.039 = 0.059 log(HS') - 0.059 pH

39. FeAsS + As + 2H +
+ 2e" = F e A s 2 + HS 2

E = - 0.153 - 0.0295 l o g ( H S ) - 0.059 pH 2

40. FeAsS + As + H +
+ 2e" = F e A s 2 + HS"
E = -0.359 - 0.0295 log(HS') - 0.0295 pH

41. FeS + 2 H A s 0 - + 9H2 3


+
+ 8e" = F e A s 2 + HS" + 6H 0 2

E = 0.229 - 0.007 l o g (HS") - 0.066 pH


(H As0 -) 2 3
2

42. HFe0 " + 2 H A s 0 " + 13H


2 3
2 +
+ 8e" = F e A s 2 + 8H 0
2

E = 0.677 + 0.007 l o g ( H A s 0 " ) ( H F e 0 " ) - 0.096 pH 3


2 2
2

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+

44. FeAsO« + 3H 0 = F e ( O H )2 3 + H AsO„- + H


2
+

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

E = 0.647 -0.020 l o g ( H A s 0 ) ( F e ) - 0.098 pH


3 3
2 +
156
A P P E N D I X I I I

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,

-0-6 -0-4 -0-2 0 0-2 0-4 0-6


Polentlol / V vi SHE
20mV ; p H - 8 2 , lOOOrpm

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

-0.8 -0.6 -0.4 -0.2 0.2 0.4 Ofi

Potential / V vs SHE
157

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