THE S U R F A C E CHEMISTRY AND FLOTATION OF

SPODUMENE, LEPIDOLITE AND ASSOCIATED SILICATES

IN T H E P R E S E N C E OF D O D E C Y L A M I N E

A thesis submitted in f u l f i l l m e n t of t h e r e q u i r e m e n t s of
t h e d e g r e e of D o c t o r of P h i l o s o p h y of t h e U n i v e r s i t y of London

by

Wi Ifred Ch i sha Lombe

D e p a r t m e n t of Mineral R e s o u r c e s Engi n e e r i n g
Royal School of M i n e s
Imperi a I Col lege
U n i v e r s i t y of London February 1983
 2.

Abstract

A s t u d y has been m a d e of t h e s u r f a c e c h e m i s t r y and

f l o t a t i o n c h a r a c t e r i s t i c s of s p o d u m e n e , lepidolite, beryl,

m i c r o c l i n e and m u s c o v i t e in the p r e s e n c e of a q u e o u s solutions

of dodecyI a m i n e . The investigation included m e a s u r e m e n t s of

t h e s o l u b i l i t y , c a t i o n e x c h a n g e and e I e c t r o k i n e t ? c properties

of t h e s i l i c a t e s . Several m e t h o d s o f m o d i f y i n g t h e surface

c h e m i s t r y of t h e m i n e r a l s w e r e s t u d i e d and t h e s e included

washing the silicates in H C I , N a O H a n d N a F , t h e a d d i t i o n of

p o l y v a l e n t metal s p e c i e s and t h e a d d i t i o n of s t a r c h polymers.

T h e m e c h a n i s m s of action of t h e s e a d d i t i v e s h a v e been elucidated

and t h e r e s u l t s c r i t i c a l l y c o m p a r e d w i t h t h o s e r e p o r t e d in

the literature.

In t h e a b s e n c e of m o d i f y i n g a g e n t s , the e l e c t r o p h o r e t i c

m o b i l i t i e s of t h e s i l i c a t e s w e r e very s i m i l a r . Hallimond tube

t e s t s i n d i c a t e d t h a t s e l e c t i v e s e p a r a t i o n of t h e minerals,

u n d e r t h e s e c o n d i t i o n s and in t h e p r e s e n c e of a m i n e , w a s n o t

possible. Washing the silicates in H C I , NaOH and N a F produced

e l e c t r o p h o r e t i c m o b i l i t i e s t h a t d e p e n d e d on t h e s t r u c t u r e and

c o m p o s i t i o n of t h e m i n e r a l s . H a l l i m o n d t u b e t e s t s in the

p r e s e n c e of p o t a t o and m a i z e s t a r c h e s indicated t h a t t h e amine

f l o t a t i o n of s p o d u m e n e 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 at high pH.

D o d e c y l a m i n e a d s o r b e d on t h e s i l i c a t e s by coulombic

a t t r a c t i o n and t h e formation of h y d r o p h o b i c a s s o c i a t i o n s , b u t

a t low c o n c e n t r a t i o n s , the c a t i o n e x c h a n g e p r o p e r t i e s of t h e

silicates determined the adsorption b e h a v i o u r . Starch adsorbed

 3.

on t h e m i n e r a l s by t h e f o r m a t i o n of h y d r o g e n b o n d s between

its a l c o h o l i c g r o u p s a n d s i l a n o l - t y p e s i t e s a t t h e silicate/

water interface.

Starch and d o d e c y l a m i n e did n o t e n h a n c e t h e a d s o r p t i o n of

each o t h e r a t t h e si I i c a t e / w a t e r interface. They interacted in

s o l u t i o n , by c o u l o m b i c a t t r a c t i o n and h y d r o p h o b i c association,

to form a c o m p l e x which had a h y d r o p h i l i c s u r f a c e . CompIexation,

r a t h e r than a d s o r p t i o n a t t h e s i l i c a t e / w a t e r i n t e r f a c e , is

b e l i e v e d t o be t h e main m e c h a n i s m of s t a r c h and a m i n e removal

from solution.
 4.

AcknowIedgements

I would like to e x p r e s s my g r a t i t u d e to D r H L S h e r g o l d

for g i v i n g me i n v a l u a b l e g u i d a n c e and e n c o u r a g e m e n t d u r i n g the

last t h r e e years.

My t h a n k s a r e a l s o due to my c o l l e a g u e s in t h e M i n e r a l

R e s o u r c e s E n g i n e e r i n g D e p a r t m e n t for n u m e r o u s d i s c u s s i o n s , t o

t h e m e m b e r s of staff of t h e D e p a r t m e n t for a s s i s t i n g m e a t

v a r i o u s s t a g e s of the w o r k , and to H e a t h e r f o r m a k i n g the

scribbles readable.

I a m indebted to the U n i v e r s i t y of Z a m b i a for financial

s u p p o r t d u r i n g the c o u r s e of the project.

F i n a l l y my t h a n k s a r e e s p e c i a l l y due to my w i f e , C h r i s t i n e ,

for h e r p a t i e n c e and u n d e r s t a n d i n g , and t o o u r children,

C h i s h a and M u c h i n d u who a r e t o o y o u n g to u n d e r s t a n d t h e long

h o u r s s p e n t a w a y from them.
 5

CONTENTS

Page

Abstract 2

Acknowledgements 4

List of C o n t e n t s 5

Li s t o f Fi g u r e s 9

Li s t of T a b Ies I4

1 INTRODUCTION 15

1.1 Sources and uses of lithium 16

1.2 S t r u c t u r e of s i l i c a t e m i n e r a l s 17
1.3 Flotation of lithium silicates 20
1.4 Selectivity in s i l i c a t e f l o t a t i o n 22
1.5 Surface modification in s i l i c a t e flotation 24
1.5.1 Modification by p o l y v a l e n t m e t a l cations 24
1.5.2 Modification by f l u o r i d e , HCI a n d N a O H 25
1.5.3 Modification by s t a r c h a n d d e x t r i n s 26
1.6 A i m s of t h e p r o j e c t 28

2 SOLUTION EQUILIBRIA AND SURFACE CHEMISTRY 30

2.1 S t a b i l i t y of m i n e r a l s in a q u e o u s s o l u t i o n s 31

2.1.1 S t a b i l i t y o f a Iuminosi I i c a t e s 32
2.1.2 T h e s o l u b i l i t y of s i l i c a 34
2.1.3 The solubility of alumina 38
2.2 Electrical double layer e f f e c t s 44
2.3 Adsorption of s u r f a c t a n t s and polymers a t the mineral/
water interface 53
2.3.1 A d s o r p t i o n of s u r f a c t a n t s 53
2.3.2 Polymer adsorption 55
2.3.2.1 General considerations 55
2.3.2.2 Polymer adsorption isotherms 57
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Page

2.3.2.3 Polymer adsorption mechanisms 58

2.4 A q u e o u s c h e m i s t r y of n - d o d e c y I a m i n e 62
2.5 T h e s t r u c t u r e and c h e m i s t r y of s t a r c h 66
2.5.1 T h e s t r u c t u r e of starch 66
2.5.2 Dextrins 67

3 MATERIALS AND EXPERIMENTAL METHODS 71

3.1 Materi a Is 72
3.1.1 Mi n e r a I s 72
3.1.2 Reagents 74
3.2 Experimental methods and techniques 75
3.2.1 Elemental analysis 75
3.2.2 Dissolution studies 75
3.2.3 Cation exchange measurements 76
3.2.4 Electrokinetic measurements 77
3.2.5 M e t h o d s of p r e p a r i n g d o d e c y l a m i n e and starch
solutions 79
3.2.6 Hallimond tube flotation tests 82
3.2.7 Adsorption measurements 82
3.2.8 Viscosity measurements 84
3.2.9 Surface tension measurements 86
3.3 Analytical methods 87
3.3.1 Infrared s p e c t r o s c o p y 87
3.3.2 D e t e r m i n a t i o n of a m m o n i a 88
3.3.3 D e t e r m i n a t i o n of d o d e c y l a m i n e 89
3.3.4 D e t e r m i n a t i o n of s t a r c h , d e x t r i n s and
British gum 90
3.3.5 A n a l y s i s by a t o m i c a b s o r p t i o m e t r y 91

4 DISSOLUTION AND CATION EXCHANGE STUDIES 94

4.1 Dissolution studies 95

4.2 Cation exchange studies 103

5 ELECTROKINETIC STUDIES 108

5.1 General considerations 109

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5.2 E f f e c t o f pH on t h e e l e c t r o p h o r e t i c mobi lity

of t h e s i l i c a t e m i n e r a l s ||0
5.3 E f f e c t of a c i d and a l k a l i n e w a s h i n g on t h e
e l e c t r o p h o r e t i c m o b i l i t y of t h e s i l i c a t e
m i ne ra I s I 16
5.4 E f f e c t of a g i n g on the e l e c t r o p h o r e t i c mobility
of t h e si Iicates 125
5.5 E f f e c t of f l u o r i d e on t h e electrophoretic
m o b i l i t y of t h e s i l i c a t e s |31
5.6 E f f e c t of a l u m i n i u m c h l o r i d e on t h e e l e c t r o -
p h o r e t i c m o b i l i t y of t h e s i l i c a t e s 139

6 T H E A D S O R P T I O N OF A M I N E A T T H E SI L I C A T E / W A T E R
INTERFACE A N D ITS E F F E C T ON T H E H A L L I M O N D T U B E
F L O T A T I O N OF T H E S I L I C A T E S 150

6.1 Adsorption studies 151

6.1.1 E f f e c t of a m i n e c o n c e n t r a t i o n 151
6.1.2 E f f e c t of pH on t h e a d s o r p t i o n of a m i n e
by t h e si Iicates 162
6.2 Hallimond tube studies in t h e p r e s e n c e of a m i n e |64

7 A D S O R P T I O N OF S T A R C H A T T H E S I L I C A T E M I N E R A L /
W A T E R INTERFACE A N D ITS E F F E C T ON THE H A L L I M O N D
T U B E F L O T A T I O N OF T H E S I L I C A T E S W I T H
DODECYLAMINE 167

7.1 A d s o r p t i o n of s t a r c h p o l y m e r s 168
7.1.1 E f f e c t of e q u i l i b r i u m starch c o n c e n t r a t i o n
on t h e starch a d s o r p t i o n d e n s i t y 168
7.1.2 Adsorption mechanism of starch 171
7.1.2.1 E l e c t r o k i n e t i c p r o p e r t i e s of s t a r c h
granules 171
7.1.2.2 E f f e c t of pH on the a d s o r p t i o n of s t a r c h
by s p o d u m e n e 174
7.1.2.3 E f f e c t of m e t h y l a t i o n on t h e adsorption
d e n s i t y of s t a r c h 177
+
7.1.2.4 A d s o r p t i o n of H a n d OH ions by t h e
si Ii c a t e mi n e r a I s 180
7.2 Viscosity studies 188
7.3 H a l l i m o n d t u b e f l o t a t i o n t e s t s in t h e p r e s e n c e of
starches 188
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7.3.1 H a l l i m o n d t u b e f l o t a t i o n t e s t s in t h e
p r e s e n c e of p o t a t o s t a r c h 188
7.3.2 H a l l i m o n d t u b e f l o t a t i o n s t u d i e s in t h e
p r e s e n c e of m a i z e s t a r c h , d e x t r i n s and
British gum 194
7.3.3 E f f e c t of s t a r c h p r e p a r a t i o n m e t h o d on
flotation recovery 197

8 INTERACTION OF S T A R C H A N D D O D E C Y L A M I N E W I T H EACH
O T H E R A N D THE M I N E R A L S U R F A C E 209

8.1 C o a d s o r p t i o n of s t a r c h and d o d e c y l a m i n e on
spodumene 201
8.2 C o m p l e x f o r m a t i o n b e t w e e n s t a r c h and d o d e c y l a m i n e 208
8.2.1 E f f e c t of c o n c e n t r a t i o n of a m i n e a n d
s t a r c h on c o m p l e x f o r m a t i o n 209
8.2.2 Binding i s o t h e r m s of d o d e c y l a m i n e to
starch 215
8.2.3 Influence of h y d r o p h o b i c i n t e r a c t i o n s on
complex formation 219
8.2.4 S t u d y of t h e s t a r c h - d o d e c y I a m i n e c o m p l e x by
infrared s p e c t r o s c o p y 224
8.3 A p o s s i b l e m e c h a n i s m of d e p r e s s i o n of t h e minerals
by s t a r c h 232

Conclusions 239

References 246
FIGURES
Page

I.I S t r u c t u r e of t h e s i l i c a t e minerals

2.1 A q u e o u s s i l i c a t e s p e c i e s in equiIibriurn with

a solution saturated with respect to amorphous
si Iica a t 25°C 37
2.2 A q u e o u s a Iumi ni urn s p e c i e s in equi Iibri urn wi th
a s o l u t i o n s a t u r a t e d with respect to gibbsite
( a - A I ( 0 H ) 3 ( s ) ) a t 25°C 41
2.3 T h e S t e r n - G r a h a m model of the e l e c t r i c a l d o u b l e
layer in the p r e s e n c e of n o n - s p e c i f i c and R n
specific adsorption --,u
2.4 Solubi lity of n - d o d e c y I a m i n e as a f u n c t i o n of p H 64
-4
2.5 L o g a r i t h m i c - c o n c e n t r a t i o n d i a g r a m for I x 10 M
total dodecylamine 64
2.6 S i m p l i f i e d s t r u c t u r e of s t a r c h p o l y m e r s 68
2.7 Possible dextrinisation reactions 70

3.1 E f f e c t of pH on the e f f e c t i v e c e l l ' l e n g t h in

I 0 " 3 M NaCl 79
3.2 Calibration c u r v e for t h e d e t e r m i n a t i o n of
ammon i a 89
3.3 C a l i b r a t i o n c u r v e for t h e d e t e r m i n a t i o n of
dodecylamine 91
3.4 C a l i b r a t i o n c u r v e s for t h e d e t e r m i n a t i o n of
p o t a t o s t a r c h , d e x t r i n s , B r i t i s h g u m and m a i z e
starch

4.1 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH on

t h e c o n c e n t r a t i o n of Li in t h e leach s o l u t i o n 96
4.2 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH on
t h e c o n c e n t r a t i o n of Al in the leach s o l u t i o n 97
4.3 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH on
t h e Si c o n c e n t r a t i o n in t h e leach s o l u t i o n 98
4.4 E f f e c t of pH on t h e a l u m i n i u m c o n c e n t r a t i o n in t h e
leach s o l u t i o n 99
4.5 E f f e c t of pH on the Si c o n c e n t r a t i o n in t h e leach
solution 101
4.6 E f f e c t of pH on the Al/Si m o l e r a t i o in the leach
solution 101
5.1 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y
of m u s c o v i t e and lepidolite in I O ~ 3 M NaCI
5.2 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y
of s p o d u m e n e , beryl and m i c r o c l i n e in I O ~ 3 M NaCI
5.3 E f f e c t of NaCI c o n c e n t r a t i o n on t h e e l e c t r o -
p h o r e t i c m o b i l i t y of s p o d u m e n e a t pH 9
5.4 E f f e c t of Li CI on the e I e c t r o p h o r e t i c mobility
of lepi do Iite
5.5 E f f e c t of LiCI on t h e e I e c t r o p h o r e t i c mobility
of s p o d u m e n e
5.6 T h e e f f e c t of a c i d and a l k a l i n e w a s h i n g on t h e
e l e c t r o p h o r e t i c m o b i l i t y of m u s c o v i t e in I O ~ 3 M
NaCI
5.7 T h e e f f e c t of acid and a l k a l i n e w a s h i n g on t h e
e I e c t r o p h o r e t i c m o b i l i t y of lepidolite in I O ~ 3 M
NaCI
5.8 T h e e f f e c t of a c i d and a l k a l i n e w a s h i n g on the
e l e c t r o p h o r e t i c m o b i l i t y of s p o d u m e n e in I 0 ~ 3 M
NaCI
5.9 The e f f e c t of acid and a l k a l i n e w a s h i n g on t h e
e l e c t r o p h o r e t i c m o b i l i t y of beryl in I 0 ~ 3 M NaCI
5 . 1 0 The e f f e c t of acid and a l k a l i n e w a s h i n g on t h e
e I e c t r o p h o r e t i c m o b i l i t y of m i c r o c l i n e in I 0 ~ 3 M
NaCI
5.11 G r o u p i n g of e l e m e n t s a c c o r d i n g t o t h e i r ionic
potenti a Is
5 . 1 2 E f f e c t of a g i n g on the e l e c t r o p h o r e t i c mobility
of lepi do Iite in I 0 " 3 M NaCI
5 . 1 3 E f f e c t of a g i n g on t h e e l e c t r o p h o r e t i c mobility
of s p o d u m e n e in I0~^M NaCI
5 . 1 4 E f f e c t of a g i n g on t h e e l e c t r o p h o r e t i c mobility
of beryl in 10"3m NaCI
5.15 H y p o t h e t i c a l s o l u b i l i t y of k a o l i n i t e at c o n g r u e n t
d i s s o l u t i o n as a f u n c t i o n of p H
5 . 1 6 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of
m u s c o v i t e in t h e p r e s e n c e of 5 x I 0 ~ 4 M N a F
5 . 1 7 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of
lepidolite in t h e p r e s e n c e of 5 x I 0 ~ 4 M N a F
5 . 1 8 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of
s p o d u m e n e in the p r e s e n c e of 5 x I0~^M N a F
5 . 1 9 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of
beryl in t h e p r e s e n c e of 5 x I 0 ~ 4 M NaF
5 . 2 0 E f f e c t of pH on t h e e l e c t r o p h o r e t i c m o b i l i t y of
m i c r o c l i n e in t h e p r e s e n c e of 5 x I 0 ~ 4 M N a F
 Page

5.21 L o g a r i t h m i c - c o n c e n t r a t i o n d i a g r a m for f l u o r i d e
species at 5 x IO~4M fluoride concentration 135
5 . 2 2 E f f e c t of A I C I ^ on the e I e c t r o p h o r e t i c mobility
of m u s c o v i t e as a f u n c t i o n of pH 140
5 . 2 3 E f f e c t o f A I C I ^ on the e l e c t r o p h o r e t i c mobi Iity
of l e p i d o l i t e as a f u n c t i o n of pH 140
5 . 2 4 E f f e c t of A 1 C 1 3 on the e I e c t r o p h o r e t i c mobility
of s p o d u m e n e as a f u n c t i o n of pH 141
5.25 E f f e c t of AICI 3 on the e l e c t r o p h o r e t i c mobility
of beryl as a function of pH 141
5 . 2 6 E f f e c t of AICI 3 on t h e e I e c t r o p h o r e t i c mobility
of mi c r o c line a s a f u n c t i o n of pH 142
-4
5.27 Logarithmic-concentration d i a g r a m for I x 10 M
AICI -z 144

6.1 Adsorption i s o t h e r m s of d o d e c y l a m i n e on the silicates

a t pH 9 152
6.2 C o m p a r i s o n of t h e a d s o r p t i o n d e n s i t y and e l e c t r o -
p h o r e t i c m o b i l i t y data a t pH 9 153
6.3 T h e s u r f a c e t e n s i o n of d o d e c y l a m i n e solutions
a t pH 9 161
6.4 E f f e c t of pH on the a d s o r p t i o n d e n s i t y of
d o d e c y l a m i n e at several s u r f a c t a n t c o n c e n t r a t i o n s 163
6.5 E f f e c t of pH on the f l o t a t i o n r e c o v e r y of t h e
s i l i c a t e s in 3 x dodecylamine solutions 165

7.1 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on spodumene
and beryl a s a f u n c t i o n of e q u i l i b r i u m concentration
a t pH 10 169
7.2 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on m i c r o c l i n e ,
lepidolite and m u s c o v i t e as a f u n c t i o n of
e q u i l i b r i u m c o n c e n t r a t i o n at pH 10 169
7.3 A d s o r p t i o n d e n s i t y of m a i z e s t a r c h and B r i t i s h gum
on s p o d u m e n e as a f u n c t i o n of e q u i l i b r i u m
c o n c e n t r a t i o n at pH 10 170
7.4 A d s o r p t i o n d e n s i t i e s of t h e d e x t r i n s on s p o d u m e n e
as a f u n c t i o n of e q u i l i b r i u m c o n c e n t r a t i o n a t
pH 10 172
7.5 E l e c t r o k i n e t i c p r o p e r t i e s of s t a r c h g r a n u l e s in t h e
a b s e n c e and p r e s e n c e of s a l t a s a function of pH 172
7.6 E f f e c t of pH on the a d s o r p t i o n d e n s i t y of potato
starch on s p o d u m e n e 175
 12

Page

7.7 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on
m e t h y l a t e d s p o d u m e n e a t pH 9 178
+
7.8 ' A d s o r p t i o n ' of H and OH on s p o d u m e n e , beryl
a n d m i c r o c l i n e as a f u n c t i o n of pH 182
+
7.9 E f f e c t of pH on the c o n c e n t r a t i o n of L i in
solution for spodumene 182
7.10 Intrinsic v i s c o s i t i e s of s t a r c h p o l y m e r s 186
7.11 E f f e c t of 4 0 ppm p o t a t o s t a r c h on t h e f l o t a t i o n
recovery of s p o d u m e n e , beryl, microcline and
lepidolite in 3 x I0~^M a m i n e 190
7.12 E f f e c t of HCI w a s h i n g on the f l o t a t i o n r e c o v e r y
of m i c r o c l i n e in t h e p r e s e n c e of 4 0 ppm p o t a t o
s t a r c h and 3 x I 0 " 5 M a m i n e 192
7 . 1 3 E f f e c t of HCI w a s h i n g on the f l o t a t i o n r e c o v e r y
of l e p i d o l i t e in t h e p r e s e n c e of 4 0 p p m p o t a t o
s t a r c h and 3 x I 0 ~ 5 M a m i n e 192
7.14 E f f e c t of HCI w a s h i n g on t h e r e c o v e r y of beryl
in t h e p r e s e n c e of 4 0 p p m p o t a t o s t a r c h a n d
3 x I0"5M amine 193
7.15 E f f e c t of 40 ppm m a i z e s t a r c h on the f l o t a t i o n
r e c o v e r y o f s p o d u m e n e and l e p i d o l i t e in
3 x I0"5M amine 195
7 . 1 6 E f f e c t of 4 0 p p m m a i z e s t a r c h on t h e r e c o v e r y
of m i c r o c l i n e and beryl in 3 x I0~^M a m i n e 195
7 . 1 7 E f f e c t of B r i t i s h g u m , w h i t e a n d y e l l o w d e x t r i n s
on t h e f l o t a t i o n r e c o v e r y in 3 x I0~^M a m i n e 196
7 . 1 8 E f f e c t of s t a r c h c o n c e n t r a t i o n on the f l o t a t i o n
r e c o v e r y of s p o d u m e n e a t pH 11.3 a n d 3 x I0~^M
amine 198
7.19 E f f e c t of d i f f e r e n t m e t h o d s o f s t a r c h p r e p a r a t i o n
on t h e f l o t a t i o n r e c o v e r y of s p o d u m e n e in 4 0 p p m
s o l u t i o n s a n d 3 x I0~^M a m i n e 198

8.1 E f f e c t of e q u i l i b r i u m a m i n e c o n c e n t r a t i o n on t h e
a d s o r p t i o n d e n s i t y of a m i n e on s p o d u m e n e in the
p r e s e n c e of p o t a t o s t a r c h a t pH 9 202
8.2 E f f e c t of p o t a t o s t a r c h c o n c e n t r a t i o n on t h e
a d s o r p t i o n d e n s i t y of a m i n e from fixed s u r f a c t a n t
c o n c e n t r a t i o n s a t pH 9 204
8.3 T h e s u r f a c e t e n s i o n of d o d e c y l a m i n e in t h e presence
of 4 0 p p m p o t a t o s t a r c h at pH 9 207

8.4 E f f e c t of a m i n e c o n c e n t r a t i o n on the a b s t r a c t i o n
of a m i n e from 4 0 p p m p o t a t o starch s o l u t i o n s a t
several pH v a l u e s 210
8.5 E f f e c t of a m i n e c o n c e n t r a t i o n on t h e a b s t r a c t i o n
of p o t a t o s t a r c h from 4 0 p p m s o l u t i o n s a t
several pH v a l u e s
8.6 E f f e c t of a m i n e c o n c e n t r a t i o n on t h e a b s t r a c t i o n
of s t a r c h from d i f f e r e n t s t a r c h c o n c e n t r a t i o n s
a t pH 9
8.7 E f f e c t of t h e a m o u n t of a m i n e a b s t r a c t e d on t h e
a m o u n t of s t a r c h a b s t r a c t e d a t several pH v a l u e s
from 40 ppm potato starch solutions
8.8 E f f e c t of t h e a m o u n t of a m i n e a b s t r a c t e d on t h e
a m o u n t of p o t a t o s t a r c h a b s t r a c t e d from d i f f e r e n t
s t a r c h c o n c e n t r a t i o n s a t pH 9
8.9 S c a t c h a r d p l o t f o r t h e b i n d i n g of a m i n e t o p o t a t o
s t a r c h a t several s t a r c h c o n c e n t r a t i o n s and
di f f e r e n t pH v a I u e s
8 . 1 0 S c a t c h a r d p l o t for t h e b i n d i n g of a m i n e t o potato
s t a r c h a t pH 10
8.11 S u r f a c e t e n s i o n of d o d e c y l a m i n e at pH 10
8 . 1 2 T u r b i d i t y of d o d e c y l a m i n e s o l u t i o n s containing
4 0 ppm p o t a t o s t a r c h at pH 7
8 . 1 3 E f f e c t of n - d o d e c a n o l c o n c e n t r a t i o n on p o t a t o
s t a r c h u p t a k e from 4 0 p p m s o l u t i o n s a t pH 9
8 . 1 4 C o m p a r i s o n b e t w e e n t h e a m o u n t of a m i n e
a b s t r a c t e d by c o m p l e x f o r m a t i o n with t h e ^
d i s t r i b u t i o n of a m i n e s p e c i e s a t I x 10 M a m i n e
8.15 Infrared s p e c t r u m of Nujol oil
8.16 Infrared s p e c t r u m of dodecylamine
8.17 Infrared s p e c t r u m of s t a r c h
8.18 Infrared s p e c t r a of p o t a t o s t a r c h - D A precipitate
and p o t a t o s t a r c h - D A m i x t u r e
8.19 W a v e n u m b e r r e g i o n s in w h i c h t h e indicated g r o u p s
g a v e rise t o a b s o r p t i o n b a n d s in t h e infrared
spectra
8 . 2 0 E f f e c t of e q u i l i b r i u m p o t a t o s t a r c h c o n c e n t r a t i o n
t h e a b s t r a c t i o n of s t a r c h by c o m p l e x f o r m a t i o n at
pH 9
8.21 E f f e c t of e q u i l i b r i u m p o t a t o starch c o n c e n t r a t i o n
t h e a b s t r a c t i o n of s t a r c h at pH 9 a n d in t h e
p r e s e n c e of s p o d u m e n e
 14

TABLES

Page

3.1 S o u r c e s of m i n e r a l s used 72
3.2 X R F a n a l y s i s of the m i n e r a l s 73
3.3 A n a l y s i s of t h e c a t i o n s in the m i n e r a l s s t u d i e d 73
3.4 S u r f a c e a r e a s of t h e f r a c t i o n s used in t h e
cation e x c h a n g e t e s t s 76
3.5 S u r f a c e a r e a s of t h e mineral f r a c t i o n s used in
adsorption experiments 83

4.1 M o l e r a t i o of s o l u b l e a l u m i n i u m and s i l i c o n in
e q u i I i b r i urn with t h e si Ii c a t e mi n e r a I s I 02
4.2 C a t i o n e x c h a n g e c a p a c i t i e s of m u s c o v i t e and
lepidolite 103
4.3 C a t i o n e x c h a n g e c a p a c i t i e s of s p o d u m e n e a n d
mi c r o c line 104

5.1 E f f e c t of w a s h i n g t h e s i l i c a t e m i n e r a l s in IM
HCI and IM N a O H on t h e m o l a r r a t i o , A l / S i , in
solution I 16
5.2 E f f e c t of acid and a l k a l i n e w a s h i n g on t h e
fraction (of total s a m p l e c o n t e n t ) of Fe and
Mn d i s s o l v e d 124
5.3 E f f e c t of a c i d and a l k a l i n e w a s h i n g on t h e m o l a r
r a t i o , A l / S i , in t h e s o l i d r e s i d u e 124

6.I E f f e c t of c a t i o n e x c h a n g e p r o p e r t i e s on t h e
a d s o r p t i o n d e n s i t y of DA from I x I 0 ~ 4 M DA
solutions 156

7.1 R e l a t i v e v i s c o s i t i e s of d e x t r i n s o l u t i o n s a s a
function of c o n c e n t r a t i o n a t 25°C 187
 15.

C H A P T E R ONE

INTRODUCTION
 16.

I.I S o u r c e s and uses of lithium

L i t h i u m is found m o s t l y in igneous rocks such as t h e

g r a n i t i c p e g m a t i t e s of N . C a r o l i n a and S . D a k o t a . T h e main

lithium m i n e r a l in t h e s e d e p o s i t s is the s i l i c a t e spodumene,

although the other lithium s i l i c a t e s IepI do lite a n d petalite,

and t h e p h o s p h a t e a m b l y g o n i t e , are s o m e t i m e s p r e s e n t . The

most common 'gangue' minerals are beryl, quartz, microcline

and m u s c o v i t e (I), w h i c h are s o m e t i m e s a l s o r e c o v e r e d as

commercial products. Commercial p r o d u c t i o n of Iithiurn m i n e r a I s

took place as early as 1898 from s p o d u m e n e d e p o s i t s in S . D a k o t a

b u t it w a s n o t until 1953, w i t h t h e a p p l i c a t i o n of t h e froth

f l o t a t i o n p r o c e s s a t Kings m o u n t a i n , N . C a r o l i n a , t h a t spodumene

b e c a m e a m a j o r s o u r c e of lithium (2). Some lithium is, h o w e v e r ,

obtained from b r i n e s like t h o s e of S e a r l e s lake a t T r o n a ,

C a l i f o r n i a , a s c r u d e di lithium - s o d i u m p h o s p h a t e (2) b u t

f l o t a t i o n c o n c e n t r a t e s of t h e lithium m i n e r a l s remain t h e m a i n

commercial s o u r c e of t h e m e t a l .

L i t h i u m h a s a high s p e c i f i c h e a t , e l e c t r o c h e m i c a l potential

and a f f i n i t y for o x y g e n . T h e s e p r o p e r t i e s m a k e It s u i t a b l e

for use in h e a t t r a n s f e r a p p l i c a t i o n s , a s a n o d e m a t e r i a l In

t h e m a n u f a c t u r e of b a t t e r i e s and as a d e o x l d i s e r In t h e

m a n u f a c t u r e of c o p p e r a l l o y s and s t a i n l e s s steel (2, 3 , 4 ) .

O t h e r I m p o r t a n t uses a r e in t h e c h e m i c a l engineering industry

w h e r e it is e m p l o y e d a s a c a t a l y s t in t h e p r o d u c t i o n of

s y n t h e t i c r u b b e r s and a s a b a s e for t h e m a n u f a c t u r e of a s e r i e s

of m e t a l l i c g r e a s e s of e x c e p t i o n a l viscosity stability over a

w i d e range of t e m p e r a t u r e s (2, 4 ) . L i t h i u m is a l s o finding

increasing application in t h e a e r o s p a c e industry a s an alloying

a g e n t w i t h Mg b e c a u s e of its light w e i g h t , its d e n s i t y being

o n l y half t h a t of w a t e r , a n d as n u c l e a r fuel (2, 3 ) .

I.2 S t r u c t u r e of s i l i c a t e minerals

Si licates a r e t h e m o s t a b u n d a n t m i n e r a l s in t h e e a r t h ' s

crust. Although they are sometimes i m p o r t a n t as c o m m e r c i a l

minerals, they also constitute the waste minerals in m a n y

ores. All t h e s i l i c a t e m i n e r a l s p o s s e s s o n e general similarity;

-4

t h e y c o n s i s t of (SiO^) tetrahedra in w h i c h a s i l i c o n atom

is s h a r e d by f o u r o x y g e n a t o m s . For e a c h S i - 0 bond in t h e t e t r a

hedron t h e total bonding potential of t h e o x y g e n a t o m m a y not

-4

be u t i l i s e d . The (SiO^) t e t r a h e d r a a r e t h e r e f o r e a b l e to

p o l y m e r i s e , by o x y g e n s h a r i n g , t o g i v e a d i v e r s i t y o f structural

modifications. The different structures generally determine

t h e chemical and physical p r o p e r t i e s of t h i s c l a s s of minerals.

T h e s t r u c t u r e s h a v e been s u m m a r i s e d in Fig I.I.

Both s p o d u m e n e ( L i A I S i ^ ) and beryl (Be^A 1 2 (S i6 0 f Q ) ) belon

to the m e t a s i l i c a t e g r o u p in w h i c h t h e S i - O ^ t e t r a h e d r a share

two oxygen atoms. In s p o d u m e n e t h e t e t r a h e d r a polymerise into

two-dimensional c h a i n s t h a t run parallel to the c a x i s . The

octahedral c h a i n s , w h i c h a r e a l s o parallel to the c a x i s ,

c o n t a i n t w o c a t i o n s i t e s Ml a n d M 2 (5). Ml is a regular

octahedron accommodating the c a t i o n s in 6 - f o l d coordination

w h i l e the M2 s i t e is a r e l a t i v e l y d i s t o r t e d o c t a h e d r o n and is

o c c u p i e d by L i + c a t i o n s a l s o in 6 - f o l d coordination.
 Number of Structural unit Structural Silicate class
oxygen atoms formula
shared

0 (SiO, Orthosilicate

(Si207)6" Pyrosilicates

Metasilicate
chains
pyroxene

Metasilicate
(Sio3) 2 n "
n
rings

Metasilicate
2 h Y (Si^O^) chains
^ — (amphibole)

(Si^)2 Layer silicates

4 Three dimensional (SiC^)0 Framework

network silicates

Fig I.I S t r u c t u r e of t h e s i l i c a t e minerals

 19.

T h e m a i n f e a t u r e of t h e beryl s t r u c t u r e is t h a t t h e

silica t e t r a h e d r a c l o s e to form m e t a s i l i c a t e r i n g s . These

3+ 2+

r i n g s a r e s t a c k e d a b o v e o n e a n o t h e r w i t h t h e AI and Be

cations linking s u c c e s s i v e r i n g s . The aluminium is

octahedrally coordinated while each beryllium cation occupies

a distorted tetrahedron. In both s p o d u m e n e and beryl there

is a p p a r e n t l y n o s u b s t i t u t i o n of A l 3 + in t h e tetrahedral

p o s i t i o n s (I, 5 , 6 ) .
L e rp i d o l i t e (KLi A I ( O H , F ) _ A I SiO.J and muscovite
2 3 '0'

(KAfa S'^0|o(oh^) b e long t o t h e mica g r o u p of s i l i c a t e s . In t h i s

g r o u p t h e silica t e t r a h e d r a share three oxygen atoms resulting

in t w o - d i m e n s i o n a l sheet structures. T h e s h e e t s formed by

hexagonal rings of t e t r a h e d r a a r e s t a c k e d a l o n g t h e c a x i s w i t h

all the t e t r a h e d r a in o n e s h e e t p o i n t i n g in t h e s a m e direction.

However, the tetrahedra in s u c c e s s i v e s h e e t s all p o i n t inward

2+ 3+
and a r e linked by e i t h e r M g o r Al h y d r o x i d e s to form a

composite tetrahedraI-octahedraI-tetrahedraI (t-o-t) sheet. If

3+ 4+

there is no i s o m o r p h i c s u b s t i t u t i o n of Al for Si in t h e

tetrahedral positions the t - o - t sheets are uncharged. In b o t h

lepidolite and m u s c o v i t e , h o w e v e r , i s o m o r p h i c s u b s t i t u t i o n in

t h e t e t r a h e d r a l p o s i t i o n t a k e s p l a c e so t h a t t h e c o m p o s i t e
t - o - t s h e e t s h a v e a n e t n e g a t i v e c h a r g e w h i c h is b a l a n c e d by
+ +

Li and K i n t e r l a y e r c a t i o n s in 12-fold coordination.

T h e s h a r i n g of all four o x y g e n a t o m s g i v e s rise t o a

3-dimensionaI n e t w o r k of t e t r a h e d r a s u c h as in q u a r t z (SiC^) or

microcline (KAISfaOg). T h e s t r u c t u r e of q u a r t z is e l e c t r i c a l l y
4+ 3+
neutral b u t in m i c r o c l i n e s u b s t i t u t i o n o f Si by Al in t h e
te+rahedral position takes place so t h a t K atoms are required

to balance the resultant negative c h a r g e . Distinctions between

several t y p e s of p o t a s s i u m - f e l d s p a r s are u s u a l l y m a d e (7)

corresponding to different structural m o d i f i c a t i o n s . The

mi c r o c line used in t h i s s t u d y w a s i d e n t i f i e d by X R D a s a

m i x t u r e of m a x i m u m a n d intermediate microclines, the maximum

form being the major component.

I.3 F l o t a t i o n of lithium silicates

Spodumene: In t h e flotation of s p o d u m e n e from pegmatite

o r e s both c a t i o n i c and a n i o n i c col lectors a r e o f t e n used a t

v a r i o u s s t a g e s of t h e p r o c e s s f o l l o w i n g a w i d e v a r i e t y of

conditioning procedures. Baarson e t al (8) s u m m a r i s e d t h e main

p r o c e s s d e t a i l s as

(a) f l o t a t i o n of t h e o t h e r s i l i c a t e s from spodumene;

(b) f l o t a t i o n of s p o d u m e n e from t h e o t h e r silicates;

(c) s t a g e f l o t a t i o n by c o m b i n i n g (a) and (b).

(a) F l o t a t i o n of t h e o t h e r s i l i c a t e s from spodumene

Q u a r t z , f e l d s p a r and m i c a m i n e r a l s h a v e been bulk-floated

from s p o d u m e n e w i t h an a m i n e c o l l e c t o r and s p o d u m e n e depressants

of s t a r c h and d e x t r i n (9, 10). T h e iron m i n e r a l s , w h i c h are

a l s o d e p r e s s e d by s t a r c h and dextrin if p r e s e n t , w e r e next

removed (10) by f l o t a t i o n a t low pH w i t h s o d i u m r e s i n a t e and

h y d r o f l u o r i c acid as a s p o d u m e n e depressant.

(b) Spodumene flotation from t h e o t h e r silicates

S p o d u m e n e has been floated a w a y from t h e o t h e r pegmatite

silicates with oleic acid in t h e pH range 7 to 9 . Concentrations

 21.

2 + 2 +

of i n o r g a n i c s a l t s p a r t i c u l a r l y t h o s e of Ca and M g must,

however, be low (II, 12, 13, 14). A s In (a) p r i o r conditioning

in HF and o t h e r a c i d s , and N a O H , is r e p o r t e d t o aid selectivity,

(c) Stage flotation

The initial s t a g e is u s u a l l y t h e f l o t a t i o n o f micaceous

m i n e r a l s w i t h an a m i n e c o l l e c t o r a t a c i d pH v a l u e s . This is

t h e n f o l l o w e d by t h e f l o t a t i o n of s p o d u m e n e from q u a r t z and

feldspar at low pH v a l u e s w i t h a p e t r o l e u m s u l p h o n a t e collector

(15) o r in neutral p u l p s w i t h o l e i c acid (16). The above

m e t h o d s , h o w e v e r , do n o t r e c o v e r lepidolite w h i c h if p r e s e n t

r e p o r t s with t h e micas.

Lepidolite: Lepidolite is n o t as w i d e l y d i s t r i b u t e d in

p e g m a t i t e s a s s p o d u m e n e and its c o m p o s i t i o n a p p a r e n t l y varies

considerably (17). In l a b o r a t o r y f l o t a t i o n t e s t s (18) t h e

mineral has been s e p a r a t e d from q u a r t z and f e l d s p a r w i t h amine

a t a pH of 3 . 4 . T h e South A f r i c a n Institute of M e t a l s (19) a l s o

reported successful small s c a l e f l o t a t i o n t e s t s in w h i c h

lepidolite w a s f l o a t e d from m u s c o v i t e , q u a r t z and f e l d s p a r with

a m i x e d a m i n e / p e t r o l e u m s u l p h o n a t e c o l l e c t o r a t pH 9 . Other

tests (17) i n d i c a t e t h a t the m i n e r a l may be s e p a r a t e d from

m u s c o v i t e by f l o a t i n g t h e m u s c o v i t e w i t h o l e i c acid a t pH 8

following conditioning with HF.

Beryl and m i c r o c l i n e : It is of i n t e r e s t t o c o m p a r e t h e

a b o v e f l o t a t i o n m e t h o d s with t h o s e reported for t h e o t h e r

pegmatite silicates. B e r y l , for e x a m p l e , h a s been (20)

s e l e c t i v e l y f l o a t e d from the o t h e r s i l i c a t e s with o l e i c acid a t

neutral pH f o l l o w i n g c o n d i t i o n i n g in f l u o r i d e s o l u t i o n s . Feldspars,
on t h e o t h e r h a n d , h a v e largely been r e c o v e r e d (21, 2 2 ) w i t h

amine collectors at low pH a l s o f o l l o w i n g HF t r e a t m e n t t o

depress quartz.

I.4 Selectivity in s i l i c a t e flotation

T h e main o b s e r v a t i o n t h a t can be m a d e a b o u t t h e reported

c o n d i t i o n s for s e l e c t i v e s i l i c a t e f l o t a t i o n is t h a t t h e s a m e

c o l l e c t o r s h a v e been w i d e l y used t o f l o a t d i f f e r e n t minerals

w i t h i n s i m i l a r pH r a n g e s . F o r e x a m p l e o l e i c a c i d has been used

t o f l o a t s p o d u m e n e , beryl and m u s c o v i t e u n d e r s l i g h t l y alkaline

c o n d i t i o n s w h i l e a m i n e s have been used t o f l o a t m i c r o c l i n e ,

q u a r t z and t h e m i c a s a t low pH v a l u e s . It is t h e r e f o r e apparent

t h a t each of t h e c o n s t i t u e n t m i n e r a l s will float to some degree

w i t h both a n i o n i c and c a t i o n i c c o l l e c t o r s . This is p e r h a p s not

s u r p r i s i n g for t w o reasons:

(a) Similarity in s u r f a c e c h e m i s t r y : On t h e b a s i s of t h e

structural properties outlined in s e c t i o n 1.2 it is c l e a r t h a t

d u r i n g b r e a k a g e of s p o d u m e n e , beryl and m i c r o c l i n e an increasing

n u m b e r of S I - 0 b o n d s wi I I be r u p t u r e d w i t h t h e r e s u l t t h a t t h e

p o i n t s of z e r o c h a r g e , p z c , of t h e s e m i n e r a l s will be low and

c l o s e t o e a c h o t h e r (23, 2 4 ) . It is t h e r e f o r e r e a s o n a b l e t o

expect a close similarity in t h e s u r f a c e c h e m i s t r y of spodumene,

beryl a n d m i c r o c l i n e , and p e r h a p s b e t w e e n l e p i d o l i t e and muscovite.

(b) N o n - s e l e c t i v i t y of c o l l e c t o r s : T h e col lectors t h a t are used

to float these silicate minerals (alkyl s u l p h a t e s and sulphonates,

amines and oleic acid) are not particularly s e l e c t i v e . The

a d s o r p t i o n m e c h a n i s m of such c o l l e c t o r s a t t h e si I i c a t e / w a t e r
 23.

i n t e r f a c e is m a i n l y by c o u l o m b i c a t t r a c t i o n b e t w e e n t h e collector

ion a n d t h e mineral s u r f a c e b e a r i n g an o p p o s i t e l y c h a r g e d double

layer, f o l l o w e d by t h e f o r m a t i o n of h y d r o p h o b i c associations

a t s u f f i c i e n t l y high a d s o r p t i o n densities. Several authors

(23, 2 4 , 2 5 , 2 6 ) h a v e s u m m a r i s e d t h e r e s u l t s of a s e r i e s of

investigations in w h i c h it h a s been e s t a b l i s h e d t h a t for a

large n u m b e r of s i l i c a t e s ( a d s o r p t i o n ) f l o t a t i o n b e h a v i o u r , in

t h e p r e s e n c e of a Iky I s u l p h a t e s , s u l p h o n a t e s and a m i n e s is

c o n t r o l l e d by e l e c t r o s t a t i c c o n s i d e r a t i o n s a n d t h a t (adsorption)

flotation ceases if t h e mineral p a r t i c l e s and t h e c o l l e c t o r ion

c a r r y t h e same c h a r g e . K n o w l e d g e of t h e pzc of the silicates

is t h e r e f o r e c r i t i c a l and s i m i l a r pzc v a l u e s a r e n o t likely to

lead to s e l e c t i v i t y of flotation.

A l t h o u g h o l e i c acid is c a p a b l e of c h e m i s o r p t i o n , its

m e c h a n i s m of a d s o r p t i o n on s i l i c a t e m i n e r a l s h a s n e v e r been

unambiguously defined. It is b e l i e v e d (24, 2 7 , 2 8 , 2 9 ) t h a t

fatty a c i d s in general i n t e r a c t with p o l y v a l e n t metal s i t e s in

the m i n e r a l surface resulting in t h e f o r m a t i o n of an insoluble

p h a s e of metal soap a t t h e m i n e r a I / w a t e r interface. This

mechanism is, h o w e v e r , c o m p l i c a t e d by t h e f a c t t h a t fatty acids

are weak a c i d s , the undissociated form h a v i n g a low solubility.

U n d e r s o m e c o n d i t i o n s of p H , t h e r e f o r e , it is n o t p o s s i b l e to

d e t e r m i n e w h i c h f o r m of t h e c o l l e c t o r is t h e a d s o r b i n g species.

Further the carboxylate ion can a l s o function as a c o u n t e r ion

and t h e f o r m a t i o n of h y d r o p h o b i c a s s o c i a t e s a t t h e mineraI/water

interface is p o s s i b l e . Even when c h e m i s o r p t i o n t a k e s p l a c e t h e

a m o u n t of fatty a c i d a b s t r a c t e d is o f t e n e q u i v a l e n t t o s e v e r a l

layers so t h a t it is d i f f i c u l t t o a s c e r t a i n w h e t h e r chemisorption
is f o l l o w e d by a physical adsorption p r o c e s s o r o n l y metal soap

is p r e s e n t ( 2 4 ) , e x c e p t in a few c a s e s (29) w h e r e quantitative

i n f o r m a t i o n on t h e metal soap in e q u i l i b r i u m with f a t t y a c i d

has been d e t e r m i n e d . F u e r s t e n a u and R a g h a v a n (23) s u g g e s t e d

t h a t a t pH 8 , c h e m i s o r p t i o n of o l e a t e w a s related t o o l e a t e -

aluminium i n t e r a c t i o n s on s p o d u m e n e . S i n c e all a Iuminosi Iicates

contain aluminium such a mechanism is n o t likely t o lead t o

selective flotation u n l e s s t h e s u r f a c e s of t h e s i l i c a t e s are

s e l e c t i v e l y c h a n g e d p r i o r t o t h e a d d i t i o n of t h e oleate.

I.5 Surface modification in s i l i c a t e flotation

1.5.1 Modification by p o l y v a l e n t metal cations

T h e p z c of m o s t s i l i c a t e m i n e r a l s is a t acid pH values.

A n i o n i c c o l l e c t o r s a r e t h e r e f o r e o n l y used in t h e f l o t a t i o n of

silicates in t h e p r e s e n c e of m u l t i v a l e n t metal c a t i o n s o r o t h e r

activating species. The multivalent cations specifically adsorb

in t h e pH range w h e r e h y d r o l y s i s t o low c h a r g e d h y d r o x y complexes

is p o s s i b l e , r e s u l t i n g in a s u r p l u s of p o s i t i v e c h a r g e at t h e

mineraI/water interface. T h e main s u g g e s t e d m e c h a n i s m s of cation

a d s o r p t i o n are ( 2 7 , 3 0 , 31):

(a) w a t e r f o r m a t i o n between t h e h y d r o x y I of t h e hydrolysed

c o m p l e x e s and H + ions from t h e interface;

(b) H - b o n d i n g of t h e c o m p l e x t o t h e mineral s u r f a c e ; and

(c) f o r m a t i o n a n d a d s o r p t i o n of t h e metal h y d r o x i d e at t h e

mineraI/water interface.
 25.

E x a m p l e s of t h e s e m e c h a n i s m s a r e given in s e c t i o n 5 . 6 . The

m e c h a n i s m s h e l p e x p l a i n how s u p e r e q u i v a l e n t a d s o r p t i o n of metal

cations occurs at the mineraI/water interface although it is

n o t known w h i c h m e c h a n i s m is o p e r a t i v e . U n f o r t u n a t e l y m o s t of

t h e w o r k on a c t i v a t i o n with p o l y v a l e n t metal c a t i o n s h a s been

c o n d u c t e d on q u a r t z . It is r e a s o n a b l e t o e x p e c t , h o w e v e r , t h a t

s i m i l a r c o n s i d e r a t i o n s can be a p p l i e d t o a Iuminosi Iicate

m i n e r a l s , a n d t h a t p o l y v a l e n t metal ions will a d s o r b on silicate

m i n e r a l s u n d e r s i m i l a r c o n d i t i o n s t o t h o s e o b s e r v e d with quartz.

U s e of p o l y v a l e n t metal ions is t h e r e f o r e u n l i k e l y t o lead t o

improved s e l e c t i v i t y b e t w e e n different silicates.

1.5.2 Modification by f l u o r i d e , HCI and N a O H

Fluoride in its v a r i o u s f o r m s ( N a F , H F , and N a g S i F ^ ) is

o n e of the m o s t w i d e l y used m o d i f y i n g a g e n t s in s i l i c a t e flotation.

Perhaps its b e s t known use is in t h e a c t i v a t i o n o f t h e cationic

f l o t a t i o n of f e l d s p a r from q u a r t z a t pH 2 to 3 (cf s e c t i o n 1.3)

(17, 2 3 , 3 2 , 3 3 ) . In t h e a b s e n c e of f l u o r i d e , q u a r t z and

f e l d s p a r show p r a c t i c a l l y identical flotation responses in t h e

p r e s e n c e of a m i n e . Several m e c h a n i s m s of a c t i o n of fluoride

h a v e been s u g g e s t e d . These mechanisms include the formation and

a d s o r p t i o n of a l u m i n i u m f l u o r i d e (32, 3 3 ) and fIuorosi Iicate

(34) c o m p l e x e s a t t h e a Iuminosi I i c a t e / w a t e r interface. It is

also generally believed (33) t h a t t h e main e f f e c t of fluoride

on the s i l i c a t e s is t o p r o d u c e an increase in t h e n e g a t i v e zeta

p o t e n t i a l s of t h e s i l i c a t e s . T h e f o r m a t i o n and a d s o r p t i o n of

n e g a t i v e l y c h a r g e d a l u m i n i u m f l u o r i d e and f l u o s i l i c a t e complexes

(cf s e c t i o n 5 . 5 ) help to e x p l a i n how an increase in the negative

zeta p o t e n t i a l of s i l i c a t e s is p o s s i b l e in t h e p r e s e n c e of

fluoride. A t low f l u o r i d e c o n c e n t r a t i o n s , h o w e v e r , t h e

f o r m a t i o n of such c o m p l e x e s is n o t p o s s i b l e . Under these

c o n d i t i o n s t h e m e c h a n i s m of a c t i o n of f l u o r i d e is n o t k n o w n .

Relatively less c o n t r o v e r s y is a s s o c i a t e d with t h e e f f e c t s

other acids like HCI on t h e s u r f a c e c h e m i s t r y of

a Iuminosi I i c a t e s . It has g e n e r a l l y been found t h a t t h e main

e f f e c t of a c i d w a s h i n g , a s in t h e c a s e of f l u o r i d e , is t o

increase t h e n e g a t i v e zeta p o t e n t i a l of t h e s i l i c a t e s . This has

been a t t r i b u t e d (17, 3 5 , 3 6 ) t o t h e s e l e c t i v e d i s s o l u t i o n of

aluminium to leave a s i l i c a - r i c h s u r f a c e . N a O H w a s h i n g , on

the o t h e r h a n d , does n o t a p p e a r t o s i g n i f i c a n t l y a f f e c t t h e

s u r f a c e p r o p e r t i e s of s i l i c a t e s b e c a u s e of near-stoichiometric

d i s s o l u t i o n of t h e c o m p o n e n t o x i d e s (36). It is n o t k n o w n ,

however, whether these observations are generally applicable to

the m a j o r i t y of s i l i c a t e minerals.

1.5.3 M o d i f i c a t i o n by s t a r c h and dextrins

O r g a n i c m o d i f y i n g a g e n t s such as starch and dextrin have

been w i d e l y used to improve s e l e c t i v i t y in t h e f l o t a t i o n of

mineral particles. Indeed t h e r e a r e few f l o t a t i o n m e t h o d s in

w h i c h s t a r c h , in o n e form o r a n o t h e r , has n o t been t r i e d (37).

O t h e r than t h e a b o v e a p p l i c a t i o n in t h e d e p r e s s i o n of spodumene,

starch has a l s o been used in t h e a m i n e f l o t a t i o n of siliceous

g a n g u e from iron o r e s in w h i c h the m a c r o m o l e c u l e is a d d e d to

d e p r e s s t h e iron o x i d e s (37, 38, 39). Why s e l e c t i v e depression

is o b t a i n e d in t h i s s y s t e m is n o t c l e a r l y u n d e r s t o o d . A number
of w o r k e r s ( 3 7 , 4 0 ) h a v e shown t h a t d e p r e s s i o n is a s s o c i a t e d

w i t h t h e t y p e of s t a r c h , t h e w a y it is s o l u b i l i s e d and solution

c o n d i t i o n s such as pH and t h e p r e s e n c e of i n o r g a n i c c a t i o n s . It

h a s a l s o been d e m o n s t r a t e d (37, 4 0 ) t h a t h e m a t i t e a d s o r b s more

s t a r c h than q u a r t z a t pH 7 . B a l a j e e and Iwasaki (40) s u g g e s t e d

t h a t d e p r e s s i o n w a s r e l a t e d t o the f o r m a t i o n and a d s o r p t i o n o f a

b i n a r y s t a r c h - a m i n e c o m p l e x a t the m i n e r a I / w a t e r interface. They

did n o t , h o w e v e r , p r e s e n t a n y m e a n i n g f u l experimental evidence

t o s u p p o r t the h y p o t h e s i s . F u r t h e r , t h e y did n o t c o n s i d e r w h y

t h e b i n a r y c o m p l e x w a s h y d r o p h i l i c on o n e m i n e r a l but hydrophobic

on a n o t h e r (24).

Starch h a s a l s o been s h o w n (41) t o d e p r e s s t h e fatty acid

f l o t a t i o n of c a l c i t e and b a r i t e in p r e f e r e n c e t o fluorite

a l t h o u g h the g r e a t e s t s t a r c h a d s o r p t i o n in t h i s s y s t e m occurred

on f l u o r i t e . T h e reason for t h i s is n o t known t h o u g h it a p p e a r s

t h a t t h e high a d s o r p t i o n of s t a r c h on f l u o r i t e could be related

to enhanced f o r m a t i o n of h y d r o g e n b o n d s with t h i s mineral

c o m p a r e d t o c a l c i t e and b a r i t e . T h e f o r m a t i o n of h y d r o g e n bonds

and c o u l o m b i c a t t r a c t i o n h a v e a l s o been p o s t u l a t e d a s a d s o r p t i o n

m e c h a n i s m s of s t a r c h on q u a r t z and h e m a t i t e (42). In c o n t r a s t

Somasundaran (43) c o n c l u d e d t h a t h y d r o g e n b o n d f o r m a t i o n d i d not

s i g n i f i c a n t l y a f f e c t t h e a d s o r p t i o n of starch on c a l c i t e but

t h a t c o m p l e x f o r m a t i o n b e t w e e n starch and s u r f a c e c a l c i u m species

took place. If s t a r c h h a s an a f f i n i t y for C a 2 + s p e c i e s it w o u l d

be of i n t e r e s t t o know w h y t h e a d s o r p t i o n and flotation

b e h a v i o u r of c a l c i t e and f l u o r i t e a r e w i d e l y d i f f e r e n t in t h e

p r e s e n c e of t h e macromolecule.
 T h e p r e s e n c e of s t a r c h has been found (43) t o increase

t h e a d s o r p t i o n of o l e i c acid on c a l c i t e p a r t i c l e s and vice

versa. S i m i l a r l y , dodecyIammoniurn c h l o r i d e h a s been observed

(40) t o e n h a n c e t h e adsorpti on of B r i t i s h gum on q u a r t z . It

w o u l d a p p e a r t h a t a l t h o u g h the m i n e r a l particles adsorb more

s u r f a c t a n t , t h e y still remain h y d r o p h i l i c . Somasundaran (43)

h a s a t t r i b u t e d t h i s b e h a v i o u r t o t h e f o r m a t i o n of a helical

s t a r c h / o l e a t e c l a t h r a t e on the mineral surface. Unfortunately he

did n o t g i v e a n y e x p e r i m e n t a l e v i d e n c e for t h e e x i s t e n c e of such

a c o m p l e x in h i s s y s t e m . It is n o t p o s s i b l e , t h e r e f o r e , from

current knowledge, to state whether starch simply inhibits the

a d s o r p t i o n of c o l l e c t o r a t the m i n e r a I / w a t e r interface or t h a t

there is c o m p l e x f o r m a t i o n b e t w e e n starch and t h e c o l l e c t o r , and

that this produces depression. Recently, Kitchener (44)

a p p r o p r i a t e l y d e s c r i b e d t h e p r e s e n t s t a t e of k n o w l e d g e about

t h e role of s t a r c h in t h e d e p r e s s i o n of m i n e r a l s a s 'inadequate'.

C l e a r l y m o r e w o r k h a s t o be done b e f o r e it is p o s s i b l e t o predict

w h e t h e r s t a r c h can be used to s e p a r a t e a n y p a r t i c u l a r g r o u p of

mi n e r a I s .

I.6 A i m s of t h e project

The main a i m of t h e p r o j e c t w a s t o s t u d y t h e a q u e o u s surface

c h e m i s t r y of s p o d u m e n e , lepidolite, beryl, microcline and

m u s c o v i t e with a view to p r e d i c t i n g t h e c o n d i t i o n s u n d e r w h i c h

t h e s e l e c t i v e a m i n e f l o t a t i o n of t h e lithium m i n e r a l s m i g h t be

obtained. In p a r t i c u l a r t h e main a s p e c t s of the w o r k w e r e :

 29.

(a) D e t e r m i n a t i o n of w h e t h e r o r n o t t h e m i n e r a l s possessed

sufficient differences in t h e i r s u r f a c e p r o p e r t i e s t o a c t

as a b a s i s for t h e s e l e c t i v e f l o t a t i o n of t h e lithium

m i n e r a l s with d o d e c y l a m i n e as t h e collector.

(b) D e t e r m i n a t i o n of w h e t h e r o r n o t t h e s u r f a c e p r o p e r t i e s of

the lithium m i n e r a l s can be m o d i f i e d so t h a t s e l e c t i v e

f l o t a t i o n can be o b t a i n e d . T h e e f f e c t s of t h e following

surface modification procedures were studied:

(i) acid/alkaline washing;

(ii) fIuoride/hydrofIuoric acid treatment;

(iii) t h e p r e s e n c e of m u l t i v a l e n t c a t i o n s ; and

(iv) t h e p r e s e n c e of o r g a n i c m o d i f i e r s such as s t a r c h

and dextrin.

(c) E l u c i d a t i o n of the m e c h a n i s m s of action of t h e procedures

used in (b).

The studies involved in the p r o j e c t included t h e determin-

a t i o n of t h e d i s s o l u t i o n , cation e x c h a n g e and electrokinetic

p r o p e r t i e s of t h e m i n e r a l s . M e a s u r e m e n t s w e r e m a d e of t h e

a d s o r p t i o n of s t a r c h a n d a m i n e at t h e m i n e r a I / w a t e r interface

and the e f f e c t t h a t such a d s o r p t i o n had on t h e f l o t a t i o n of

the m i n e r a l s . T h e interaction b e t w e e n a m i n e and starch in

a q u e o u s s o l u t i o n w a s also studied.
 CHAPTER TWO

SOLUTION EQUILIBRIA AND SURFACE CHEMISTRY

 31.

2. I ' Stab? I ? ty of mi riera IS i ri a q u e o u s so I u t i o n s

G e n e r a l l y , m i n e r a l s h a v e p o l a r s u r f a c e s b e c a u s e they

c o n t a i n a t o m s which a r e n o t fully c o o r d i n a t e d . In a q u e o u s

solutions, the unsaturated atoms become hydrated.as a result of

interaction with w a t e r dipoles. T h e e x t e n t of h y d r a t i o n will

be d e t e r m i n e d by t h e d i f f e r e n c e b e t w e e n t h e e n e r g y of hydration

of t h e ion and t h e s p e c i f i c a b s o r p t i o n e n e r g y of t h e ion for

the mineral substrate ( 4 5 ) . If t h e ion - w a t e r bond is s t r o n g e r

than t h e ion - mineral bond t h e ion will p a s s into s o l u t i o n . This

dissolution process eventually leads t o an e q u i l i b r i u m of t h e

form:

A B , . — mA l ? + . + nB ~ m , (2.1)
m n (s) — (aq) (aq)

A s s u m i n g a c h e m i c a l l y p u r e and c o m p o s i t i o n a I Iy i n v a r i a n t s o l i d

p h a s e t h e e q u i l i b r i u m can be d e f i n e d by t h e s o l u b i l i t y product

k
so • K ; q ) ) m K ; q > r

w h e r e t h e b r a c k e t s a r e a s s u m e d t o d e n o t e a c t i v i t i e s of t h e

e n c l o s e d s p e c i e s , w h i c h can be c o n v e r t e d t o c o n c e n t r a t i o n s by

use of a c t i v i t y c o e f f i c i e n t s . If t h e ions do n o t undergo

f u r t h e r r e a c t i o n s t h e s o l u b i l i t y of t h e mineral may be calculated

from t h e s o l u b i l i t y p r o d u c t . In m a n y s y s t e m s , h o w e v e r , t h e ions

u n d e r g o h y d r o l y s i s and c o m p l e x f o r m a t i o n s o t h a t k n o w l e d g e of

the solubility product alone is n o t a d e q u a t e f o r s o l u b i l i t y

computati o n s .
 32.

2.1.1 S t a b TIity of a f umiiibsif\cafes

T h e r e is little i n f o r m a t i o n in t h e l i t e r a t u r e on the

s o l u b i l i t y o f a Iuminosi Iicates in w a t e r . T h i s is due t o t h e

slow reaction k i n e t i c s of t h e d i s s o l u t i o n r e a c t i o n s (46) the

experimental difficulties in m a k i n g c a l o r i m e t r i c measurements

(47)and t h e f a c t t h a t in m a n y c a s e s t h e e x a c t n a t u r e of t h e

c o m p l e x r e a c t i o n s is n o t k n o w n . In c o n t r a s t , t h e r e f o r e , t o

t h e d i s s o l u t i o n of f o r e x a m p l e s a l t - t y p e m i n e r a l s , t h e r m o d y n a m i c

data on the free e n e r g y of f o r m a t i o n of a Iuminosi Iicates is

insufficient. Several a p p r o a c h e s ( 4 7 , 4 8 , 4 9 ) h a v e been m a d e t o

circumvent the problem. V

In o n e such a p p r o a c h (47) t h e s t a n d a r d G i b b s f r e e e n e r g y

of f o r m a t i o n , AG°^, o f t h e s i l i c a t e s of i n t e r e s t w e r e estimated

from t h e s t a n d a r d G i b b s free e n e r g i e s of f o r m a t i o n of t h e

e l e m e n t s , A G ° ., w i t h t h e a i d of an e q u a t i o n of t h e form:
f,'

(2.3)

where

a, b = constants

c = t h e e x t r a p o l a t e d v a l u e for t h e AG°^. of t h e m i n e r a l

of interest

x = t h e i n d e p e n d e n t v a r i a b l e d e s c r i b i n g t h e rank of a

particular £AG° 'n w ^ n i o c o r i o c o-f yap.°

values arranged in d e s c e n d i n g o r d e r of magnitude.

T h e b a s i s of t h e e q u a t i o n is t h a t a l t h o u g h a s e t of o x i d e s
o
a n d / o r s i l i c a t e s can be used t o c a l c u l a t e AG for t h e
formation r e a c t i o n of the si licate of i n t e r e s t , t h e s e t is n o t

unique. A s e r i e s of E A G ° . v a l u e s can thus be o b t a i n e d for

d i f f e r e n t c o m b i n a t i o n s of o x i d e s a n d / o r s i l i c a t e s . These

EAG°, . v a l u e s will e x h i b i t an e x p o n e n t i a l t r e n d c o n s i s t e n t with

• T'

equation (2.3).

A f u r t h e r a p p r o a c h a l s o u t i l i s e s t h e p r i n c i p l e of c o n -

s e r v a t i o n of free e n e r g y to c o m p u t e EAG°^. . for t h e formation

reaction. T h u s , in t h o s e c a s e s w h e r e t h e s t a n d a r d e n t h a l p y of

f o r m a t i o n , H ° ., and t h e s t a n d a r d e n t r o p y , S ? , of t h e constituents
T , I I
are k n o w n , use h a s been m a d e ( 4 8 , 4 9 ) o f t h e relation

SAG0, . = EAH°, . - T E S ? (2.4)

f,i f,i i

W h e r e data is o n l y a v a i l a b l e a t t e m p e r a t u r e s h i g h e r than

298.I5°K, t h e v a n ' t H o f f equation

dink = AH°

has been used ( 4 8 , 4 9 ) f o r e x t r a p o l a t i o n t o room temperature.

Although in p r i n c i p l e , it is t h e r e f o r e p o s s i b l e to

e s t i m a t e t h e s o l u b i l i t y p r o d u c t s of a ! u m i n o s i I i c a t e s , rarely

are t h e e x a c t c o m p o s i t i o n s of t h e i r s o l i d p h a s e s k n o w n . In

m a n y m i n e r a l s c a t i o n s may r e p l a c e e a c h o t h e r t o v a r y i n g degrees

with the e f f e c t t h a t t h e s o l i d p h a s e is n o t i n d e p e n d e n t of t h e

s o l u t i o n c o m p o s i t i o n ( 5 0 ) . T h e free e n e r g y and s o l u b i l i t y of

a mineral has a l s o been found t o v a r y with its crystaI Iinity

(50) with t h e d i f f e r e n t s t r u c t u r a l modifications expected to

g i v e d i f f e r e n t s o l u b i Iities ( 5 3 ) . M o r e i m p o r t a n t has been the

 34.

o b s e r v a t i o n t h a t a Iuminosi Iicates show incongruent dissolution*

(48,50,51) because solid phases like g i b b s i t e and kaolinite

have relatively lower s t a b i l i t y c o n s t a n t s . For this reason

t h e p a r e n t a Iuminosi Iicate is u n l i k e l y t o be t h e s o l i d phase

g o v e r n i n g e q u i l i b r i u m solution c o m p o s i t i o n . A l s o a t low pH

t h e f o r m a t i o n of a si lica s o l i d p h a s e m a y have t o be

considered (48). These considerations introduce the possibility

t h a t m a n y a Iuminosi Iicates a r e m e t a s t a b l e in a q u e o u s solutions

( 5 0 ) . S i n c e t h e k i n e t i c s of d i s s o l u t i o n are u s u a l l y n o t known

it is n o t e a s y t o p r e d i c t w h i c h s o l i d phases g o v e r n solution

composition. These difficulties make the detailed calculation

of t h e r m o d y n a m i c s o l u b i l i t y f o r a Iuminosi Iicates less certain.

For qualitative purposes it is o f t e n useful t o c o n s i d e r t h a t

t h e s o l u b i l i t y c h a r a c t e r i s t i c s of a Iuminosi Iicates are

d e p e n d e n t on t h e s o l u b i l i t y of its t w o c o m p o n e n t o x i d e s , n a m e l y

S i 0 2 and A^Og.

2.1.2 T h e so Iub i Ii ty of s i Ii ca

A l t h o u g h a c o n s i d e r a b l e a m o u n t of w o r k h a s been done on

t h e s o l u b i l i t y of s i l i c a , t h e r e is lack of g e n e r a l unanimity

in t h e v a l u e s t h a t h a v e been reported. Indeed, prior t o 1960

t h e r e w a s s p e c u l a t i o n t h a t q u a r t z m i g h t e x h i b i t no t r u e

equilibrium solubility in w a t e r a t o r d i n a r y t e m p e r a t u r e s ( 5 2 ) .

T h e r e a s o n s for t h e d i s c r e p a n c i e s a r e p a r t l y d u e to t h e

followi ng:

(i) Equilibrium is e s t a b l i s h e d o n l y very s l o w l y (50);

* T h e t e r m i n c o n g r u e n t is g e n e r a l l y used if a m i n e r a l during
d i s s o l u t i o n reacts t o form a new s o l i d .
(ii) T h e g r o u n d s u r f a c e of s i l i c a p o s s e s s e s a h i g h l y disordered

s t r u c t u r e of several h u n d r e d A ° t h i c k , w h i c h can lead to

a b n o r m a l l y high s o l u b i l i t i e s (53, 5 4 ) , and

(iii) D i f f e r e n t s i l i c a m o d i f i c a t i o n s h a v e w i d e l y different

solubi Iities (53).

It a p p e a r s (52),however, that certain f o r m s of silica like

c r y s t a l l i n e q u a r t z and a m o r p h o u s s i l i c a , in w h i c h t h e s u r f a c e

layer h a s been r e m o v e d by e t c h i n g in N a O H , e x h i b i t a s o l u b i l i t y

definable in t h e s e n s e of a d y n a m i c e q u i l i b r i u m b e t w e e n silica

in s o l u t i o n and in t h e s o l i d p h a s e . The equilibrium reaction

has been r e p o r t e d as (29, 5 2 , 5 4 )

S i 0 2 H S i ( 0 H , + S i 0 ( 2
2x(s) * 2°= 4(aq> 2x-I(s) "6)

T h e r e a c t i o n has been reported (53)to be r e t a r d e d by t h e

a d s o r p t i o n of s i l i c i c acid on t h e solid p h a s e , t h u s obscuring

true equilibrium. F u r t h e r , t h e s o l u b i l i t y h a s been found to be

c a t a l y s e d by the p r e s e n c e of (OH ) ions (52,55). The catalytic

e f f e c t has g e n e r a l l y been a s s u m e d t o d e r i v e f r o m t h e w e a k e n i n g

of t h e o x y g e n b o n d s , due t o a r e s u l t a n t i n c r e a s e in t h e

c o o r d i n a t i o n n u m b e r of t h e s i l i c o n a t o m to m o r e than f o u r . The

increase in a p p a r e n t s o l u b i l i t y a t pH 9 h a s t h u s been explained

on t h e b a s i s of t h e equi librium

Si(OH)^ + OH ^ SiO(OH)3 + H 2 0 (2.7)

b e t w e e n m o n o s i l i c i c a c i d and t h e m o n o s i l i c a t e ion. Although

it is known t h a t f u r t h e r i n c r e a s e in t h e pH r e s u l t s in the
f o r m a t i o n of p o l y m e r i c s i l i c a t e s p e c i e s , t h e a m o u n t of s i l i c a

w h i c h can e x i s t in s o l u t i o n u n d e r t h e s e c o n d i t i o n s has n o t y e t

been d e f i n i t e l y e s t a b l i s h e d (29).

T h e g e n e r a l l y a c c e p t e d view is t h a t t h e d i s s o l u t i o n of

silica in w a t e r is, in e f f e c t , a d e p o l y m e r i s a t i o n reaction

through hydrolysis. The 'solubility1 is t h e n t h e concentration

of m o n o s i l i c i c acid r e a c h e d as a s t e a d y s t a t e in t h e polymerisation-

depolymerisation equilibrium.

The term polymerisation is g e n e r a l l y used t o d e s c r i b e t h e

r e a c t i o n s of s i l i c i c acid t h a t r e s u l t in an i n c r e a s e in the

m o l e c u l a r w e i g h t of t h e s i l i c a , due t o t h e c o n d e n s a t i o n of

si Ianol g r o u p s (52):

- Si OH + HOSi — - S i O S i - +HgO (2.8)

T h i s h a p p e n s when t h e m o n o m e r , S i ( O H ) ^ , is p r e s e n t a t

c o n c e n t r a t i o n s g r e a t e r than t h e s o l u b i l i t y of a m o r p h o u s silica,

and in t h e a b s e n c e of a s o l i d p h a s e on w h i c h t h e s i l i c a might

d e p o s i t (52). In acid m e d i a o r in t h e p r e s e n c e of s a l t s , t h e

colloidal p a r t i c l e s a g g r e g a t e t o form 3 - d i m e n s i o n a I gels

whereas in b a s i c s o l u t i o n s t h e y remain as sols due t o mutual

electrical repulsion.

If it is a s s u m e d ( 5 0 , 5 4 ) t h a t t h e c o n c e n t r a t i o n of m o n o -

si I icic a c i d is c o n s t a n t in a s a t u r a t e d s o l u t i o n of silica,

it is p o s s i b l e t o c o n s t r u c t t h e s o l u b i l i t y d i a g r a m shown in

Fig 2.1 u s i n g t h e f o l l o w i n g equilibria:

Si0o, , . + 2Ho0 — Si(0H)4 log k = - 2 . 7 (2.9)

2(s, amorphous) 2
A q u e o u s s i l i c a t e s p e c i e s in e q u i l i b r i u m with a s o l u t i o n s a t u r a t e d with r e s p e c t to
a m o r p h o u s si I ica a t 25°C (Data from ref 5 0 )
 38.

Si(0H)4— Si0(0H)~ + H + log k = - 9 . 4 6 (2.10)

Si02(0H)2" +
Si0(0H)~ H+ log k = - 1 2 . 5 6 (2.11)

4Si (OH) .^zf: Si/10.(0H)2" + 2 H + + 4Ho0 loga k = - 1 2 . 5 7 (2.12)

4 4 6 6 2

T h e s o l u b i l i t y of m o n o s i l i c i c a c i d / a m o r p h o u s silica is used t o

represent the upper limit of d i s s o l v e d silica b e c a u s e the

t r a n s f o r m a t i o n of a m o r p h o u s s i l i c a t o q u a r t z o n l y o c c u r s in

geological time. Although further multinuclear species other

2-

than S i ^ O g t O H ) ^ a r e p o s s i b l e , t h e r e is some uncertainty

concerning their exact nature.

2.1.3 T h e s o l u b i l i t y of a l u m i n a

T h e A l 2 0 ^ - H 2 0 s y s t e m is u s u a l l y c o n s i d e r e d w i t h gibbsite

(a - AI(OH)-., ) as t h e s o l i d rp h a s e b e c a u s e t h i s is t h e s t a b l e
3(s)
form of a l u m i n i u m h y d r o x i d e a t o r d i n a r y t e m p e r a t u r e s . The

d i s s o l u t i o n of g i b b s i t e is c o m p l i c a t e d by the e x t e n s i v e
3 +

h y d r o l y s i s of t h e Al cation, particularly in a c i d i c m e d i a .

Although this hydrolysis is p e r h a p s o n e of t h e m o s t studied,

t h e r e has been m a r k e d d i s a g r e e m e n t on the f o r m u l a e o f t h e

species that are formed. C o n t r o v e r s y has a r i s e n b e c a u s e of t h e

s e v e r e d e m a n d s p l a c e d on t h e a c c u r a c y of t h e data so t h a t

d i s t i n c t i o n s can be m a d e b e t w e e n t h e v a r i o u s p o s s i b l e species

p r e s e n t (56, 5 8 ) .

In e a r l i e r e x p e r i m e n t s , like t h o s e of S c h o f i e l d and T a y l o r

( 5 7 ) , t h e k i n e t i c s of d i s s o l u t i o n w e r e n o t f o l l o w e d . It is

now r e c o g n i s e d t h a t a l t h o u g h t h e f o r m a t i o n of t h e initial
h y d r o l y s i s p r o d u c t s a t low ligand n u m b e r * , n , is rapid (58),

t h e f o r m a t i o n of large p o l y m e r s a t h i g h e r n v a l u e s , and t h e

precipitation of t h e h y d r o x i d e a r e k i n e t i c a l l y slow processes

(56, 57). It is l i k e l y , t h e r e f o r e , t h a t in t h o s e experiments

in w h i c h a low a l u m i n i u m c o n c e n t r a t i o n w a s o b t a i n e d by dilution

from m o r e c o n c e n t r a t e d s o l u t i o n s , a m e t a s t a b l e s t a t e with

regard t o t h e p r e c i p i t a t i o n of g i b b s i t e p r o b a b l y e x i s t e d . Frink

and Peech (59) h a v e p u b l i s h e d data on t h e f i r s t h y d r o l y s i s

c o n s t a n t w h i c h d e c r e a s e d on d i l u t i o n , due to t h i s effect.

F u r t h e r , t h e e x t e n t of h y d r o l y s i s will vary w i t h t h e concen-

t r a t i o n of a l u m i n i u m , so t h a t at t h e s e d i l u t i o n s , t h e hydrolysis

p r o d u c t may n o t be u n i q u e l y d e f i n e d (58).

In view of t h e n u m e r o u s , a n d s o m e t i m e s d i s c o n c o r d a n t data

t h a t h a v e been r e p o r t e d , t h e f o l l o w i n g general basis was used

to establish the solubility diagram presented in Fig 2 . 2 .

2+ +
(i) The mononuclear species, A I ( O H ) and A I ( 0 H ) 2 are

significant at relatively low metal concentrations where they

are soon f o l l o w e d by p r e c i p i t a t i o n of t h e h y d r o x i d e (58). In

* For a c i d i c and b a s i c a q u e o u s s o l u t i o n s , t h e ligand n u m b e r , n ,

is d e f i n e d as (58)

n = [h+] - rri|_| and n = . . M Q H - [oH^j respectively,

w h e r e m ^ , itIQ^ = a n a l y t i c a l c o n c e n t r a t i o n s of acid and b a s e

+
[H ] , = measured (equilibrium) acidity or basicity
mm = concentration of t h e p o l y v a l e n t metal s p e c i e s , m

A t neutra H, the c o m p l e t e e x p r e s s i o n for n is

-
n = - [OH ] - MH
a s i g n i f i c a n t c o n t r i b u t i o n , N a z a r e n k o and N e v s k a y a (60) p r o v e d
-5
t h a t at 5 x 10 M total a l u m i n i u m c o n c e n t r a t i o n o n l y t h e
2+
AI(0H) , A I ( O H ) * and A I ( 0 H ) 3 s p e c i e s w e r e p r e s e n t . Of t h e s e
2+

AI(OH) h a s been r e p o r t e d by a n u m b e r of a u t h o r s w i t h the

data b e i n g r e a s o n a b l y c o n s i s t e n t . On t h e a s s u m p t i o n t h a t for

all n v a l u e s , a t low metal c o n c e n t r a t i o n s o n l y monomeric

s p e c i e s a r e p r e s e n t , Stol e t al (61) h a v e s y n t h e s i s e d a

t i t r a t i o n c u r v e t h a t a g r e e s r e a s o n a b l y well with experimental

data.

(ii) With i n c r e a s i n g a l u m i n i u m c o n c e n t r a t i o n s , t h e b u l k of
the evidence i n d i c a t e s t h e p r e d o m i n a n c e of t h e d i m e r i c species
4+
A^tOH^ over monomers (56, 58, 6 i , 62). There is r e l a t i v e l y
5+

less a g r e e m e n t for t h e s p e c i e s A I ^ ( 0 H ) ^ although statistical

factors (58) h a v e s h o w n t h a t it p r o b a b l y e x i s t s . There is,

a l s o , general unanimity ( 5 6 , 5 8 , 6 1 ) t h a t at high aluminium

c o n c e n t r a t i o n s , n a p p r o a c h e s v a l u e s of a b o u t 2 . 5 . This has

resulted in limiting t h e n u m b e r of p o s s i b l e s p e c i e s w i t h this

ratio to one containing 14 + I AI a t o m s (58). The species

AI|^(OH)^ been c o n s i d e r e d m o r e likely on t h e e v i d e n c e of

its e x i s t e n c e in b a s i c a l u m i n i u m s a l t s (58) and X - r a y data

(56). T h e i n t e r m e d i a t e p o l y m e r i c s p e c i e s are n o t w i d e l y

s u p p o r t e d , p a r t l y b e c a u s e of t h e i r a b s e n c e in s i m i l a r h y d r o l y s

schemes (56, 58).

(iii) T h e p r e s e n c e of A I ( O H ) ^ in b a s i c m e d i a h a s n o t been

di s p u t e d .

T h e data (50)used t o c o n s t r u c t t h e s o l u b i l i t y d i a g r a m in

Fig 2 . 2 are p r e s e n t e d below:

>I »
X
TO

cn
o

Fig 2.2 Aqueous aluminium species in e q u i l i b r i u m with a s o l u t i o n s a t u r a t e d w i t h r e s p e c t t o

g i b b s i t e (a - A I ( 0 H ) 3 ( s ) ) ( C o n s t a n t s from ref 5 0 )
 log k a t 25°C

Al3+ + HgO ^ AI(OH)2+ + H+ k, = -4.97 (2.13)

A|3+ + 2HgO Al (0H>2 +

2H+ $ 2 = -9.30 (2.14)

A|3+ + 3Ho0 ^ r AI(OH),, , + 3H+ 6 , = -15.00 (2.15)

2 3(aq) 5

A|3+ + 4HgO — AI(0H)4 + 4H+ 6 4 = -23.00 (2.16)

2A13+ + 2HgO AI^(0H)g+ + 2H+ B

2 2 =
" 7 , 7
° (2.17)

3AI3+ + 4H20 ^ AI3(0H)4+ + 4H+ B

4 3 =
~13-94 (2.18)

I3AI3+ + 32H20 Al|3(0H)72 + 32H+ B32 | 3 = -98.73 (2.19)

AI (OH).., , + 3 H + ^ T A | 3 + + 3Ho0 k = 8.50 (2.20)

3(s) 2 so

The figure s h o w s t h a t the c o n c e n t r a t i o n s of t h e large

p o l y m e r i c s p e c i e s a r e s i g n i f i c a n t o n l y a t low pH v a l u e s . In

g e n e r a l , the c o n c e n t r a t i o n of a I I t h e s p e c i e s , e x c e p t AI(0H)4,

d e c r e a s e s with an increase in p H . T h e region w h e r e precipitation

-4

of g i b b s i t e is t h e r m o d y n a m i c a I l y p o s s i b l e in a I x 10 M AICI3

(used in the e x p e r i m e n t s ) is b o u n d e d by t h e vertical dashed

lines on t h e d i a g r a m . A t high pH v a l u e s t h e a l u m i n a t e ion,

A I ( 0 H ) 4 , p r e d o m i n a t e s and a c c o u n t s for t h e i n c r e a s e in s o l u b i l i t y

w i t h pH a t pH v a l u e s a b o v e a b o u t 8 .

T h e s t a b i l i t y d i a g r a m s shown in Figs 2.1 and 2 . 2 can be used

to m a k e q u a l i t a t i v e p r e d i c t i o n s of t h e b e h a v i o u r of a Iuminosi Iicates
in a q u e o u s s o l u t i o n . F o r e x a m p l e , a t high pH it is reasonable

t o e x p e c t t h e s o l u b i l i t y of a Iuminosi Iicates t o i n c r e a s e as

both o x i d e c o m p o n e n t s a r e r e l a t i v e l y u n s t a b l e u n d e r t h e s e

conditions. A f u r t h e r use is t h a t t h e y indicate t h e limiting

s o l i d p h a s e s w h i c h m i g h t be p r e s e n t in a s a t u r a t e d solution.

T h u s t h e c o n c e n t r a t i o n s of a l u m i n i u m o r silica in s o l u t i o n

w o u l d n o t be e x p e c t e d t o e x c e e d t h e s o l u b i l i t y limits of gibbsite

or amorphous s i l i c a , respectively, without the precipitation of

t h e s e soli d p h a s e s .

It is k n o w n , h o w e v e r , t h a t t h e p r e s e n c e of a l u m i n i u m ions

in s o l u t i o n lowers t h e s o l u b i l i t y of s i l i c a (63). It has been

p o s t u l a t e d t h a t t h i s is due t o t h e formation of a i u m i n o s i Iicate

s i t e s on t h e s u r f a c e of si lica w h i c h inhibit further dissolution.

T h e p r e s e n c e of s o l u b l e s i l i c a has a l s o been r e p o r t e d (63) to

lower t h e s o l u b i l i t y of a l u m i n a , due t o a simi Iar e f f e c t . At

low s i l i c a c o n c e n t r a t i o n s , h o w e v e r , t h i s does n o t a p p e a r t o be

the case.

B r a c e and M a t j e v i c (64) s t u d i e d t h e c o p r e c i p i t a t i o n of

silica with aluminium hydroxide. Their results showed that

t h e p r e c i p i t a t i o n b o u n d a r i e s of a l u m i n i u m s o l u t i o n s in t h e
-4 -3

p r e s e n c e of low s i l i c a c o n c e n t r a t i o n s ( < 5 x 1 0 - 2 x 1 0 M)

were typical of t h o s e e s t a b l i s h e d for g i b b s i t e .

At higher silica concentrations (> 2 x I 0 ~ 3 M ) , h o w e v e r , t h e

precipitation pH range w a s w i d e r due t o t h e c o p r e c i p i t a t i o n of

s i l i c a and a l u m i n a in t h e pH range 2 - 1 0 . They related this

b e h a v i o u r t o t h e e a s e of p o l y m e r i s a t i o n of s i l i c i c a c i d in t h i s

pH r a n g e . H i n g s t o n and R a u p a c h (65) a l s o c o n c l u d e d , from a

s t u d y of t h e k i n e t i c s of a d s o r p t i o n of s i l i c i c a c i d on
aluminium hydroxide, that the adsorbed layers c o u l d form by

p o l y m e r i s a t i o n of si I icic a c i d on t h e h y d r o x i d e surface.

T h e s e and o t h e r s t u d i e s leave little d o u b t t h a t dissolved

si Ii ca is a d s o r b e d on a Iumi na (and a Iumi ni urn on si Ii c a )

particles, particularly in w e a k l y a l k a l i n e s o l u t i o n s , forming

an a Iuminosi Iicate s u r f a c e . T h e i n t e r a c t i o n has been postulated

t o be of t h e form (24, 64, 65

Al(OH), + HOSi(OH) Al(0H)20Si(0H)3 + H20 (2.21)

surf surf

If g i b b s i t e , t h e r e f o r e , p r e c i p i t a t e s from a s a t u r a t e d

a Iuminosi Iicate s o l u t i o n , t h e s u r f a c e of t h e c o l l o i d a l particles

is likely t o be c o v e r e d w i t h an a Iuminosi Iicate layer, whereas

if the s i l i c a c o n c e n t r a t i o n is high c o p r e c i p i t a t e d a Iuminosi Iicates

are feasible.

2.2 Electrical double layer e f f e c t s

When a mineral is a d d e d t o w a t e r its s u r f a c e a c q u i r e s an

electrical c h a r g e due t o t h e ionisation of s u r f a c e s i t e s o r

the preferential a d s o r p t i o n of i o n s . S i n c e t h e s y s t e m as a

w h o l e m u s t remain e l e c t r i c a l l y neutral a layer of o p p o s i t e l y

charged ions ( c o u n t e r i o n s ) f o r m s in t h e s o l u t i o n a d j a c e n t t o

the mineral surface. T h e c o m b i n e d e f f e c t of t h e r m a l agitation

and e l e c t r i c a l f o r c e s p r e v e n t s t h e c o u n t e r ions f o r m i n g a

compact layer a t t h e s o l i d s u r f a c e and p r o d u c e s a d i f f u s e

layer in w h i c h t h e c o n c e n t r a t i o n of e x c e s s c o u n t e r ions decreases

in an e x p o n e n t i a l m a n n e r w i t h d i s t a n c e from t h e s o l i d surface.
 F o r e a c h c l a s s of m i n e r a l s t h e ions w h i c h g i v e rise t o

the surface potential r e f e r r e d t o as potential

determining ions (PD1) a r e u n i q u e . For salt-type minerals

2+
t h e y a r e t h e ions w h i c h m a k e up t h e ionic l a t t i c e , e . g . Ba
2-

and S O ^ are potential d e t e r m i n i n g for B a S O ^ . For oxides they

are c o n s i d e r e d t o be H + and OH . A d d i t i o n of a f r e s h l y crushed

o x i d e s u r f a c e t o w a t e r can be c o n s i d e r e d t o r e s u l t in t h e

f o r m a t i o n of a s u r f a c e acid w h o s e d i s s o c i a t i o n characteristics

wi I I b e d e p e n d e n t on t h e p H , t h u s ,

MOH , — MO (2.22)
surf surf

MOH MOH (2.23)

surf 2 surf

w h e r e M d e n o t e s a s u r f a c e metal s i t e . At a p a r t i c u l a r pH t h e

n e t c h a r g e on t h e s u r f a c e will be z e r o . T h i s pH v a l u e is

k n o w n as t h e p o i n t of z e r o c h a r g e (pzc). A distinction is

o f t e n m a d e b e t w e e n t h e p z c and t h e pH a t w h i c h t h e z e t a potential

is z e r o . The latter c o n d i t i o n is known as t h e iso-electric

p o i n t (IEP) and it e q u a l s t h e p z c in t h e a b s e n c e of specific

adsorption.

Parks (66) h a s p o s t u l a t e d a d i f f e r e n t m e c h a n i s m f o r t h e

c h a r g i n g of o x i d e s u r f a c e s w h i c h i n v o l v e s partial dissolution

of t h e o x i d e and t h e f o r m a t i o n of h y d r o x y l a t e d metal species

in s o l u t i o n , f o l l o w e d by a d s o r p t i o n of t h e s e c o m p l e x e s . For

e x a m p l e , f o r t h e metal o x i d e M O :
 2M(0H) (2.24)
3(aq)

M(OH) (2.25)
(aq)

3-m
M(OH) (2.26)
m ( a q )

Distinguishing between these two mechanisms is n o t p o s s i b l e

b e c a u s e both will i n v o l v e t h e s a m e c h a n g e in p H , and in t h e

latter c a s e , t h e s o l u b l e metal s p e c i e s will be b e l o w t h e limits

of detection in t h e pH range of interest.

T h e d e p e n d e n c e of on t h e c o n c e n t r a t i o n of t h e potential

determining ions is given by t h e N e r n s t i a n expression:

a/
t = kT In a,o (2.27)
o —
ze

where

k = Boltzmann's constant

T = absolute temperature

z = v a l e n c e of potential determining ion

e = electronic charge

a = a c t i v i t y of PDI

aQ = a c t i v i t y of PDI a t t h e pzc.

The classical statisticaI-mechanicaI t h e o r y of t h e electrical

double layer w a s i n d e p e n d e n t l y p r o p o s e d by G o u y a n d C h a p m a n . The

basic assumptions made were that:

1 the solid surface is f l a t

2 t h e c o u n t e r ions are p o i n t c h a r g e s

3 t h e s o l v e n t d i e l e c t r i c c o n s t a n t a p p l i e s up t o t h e particle

surface, and

4 in m o v i n g a c h a r g e from s o l u t i o n t o t h e s u r f a c e only

coulombic work is involved.

The Boltzmann distribution law w a s a s s u m e d valid:

n.(x) = n Q exp(-z.et(x)/kT) (2.28)

where n. = concentration of s p e c i e s at a p o i n t (x) in

solution where t = ^(x)

n = c o n c e n t r a t i o n of ions in the b u l k solution,

o

F r o m ( 2 . 2 8 ) and the P o i s s o n e q u a t i o n , t h e c h a r g e density

a t t h e i n t e r f a c e is given by t h e G o u y - C h a p m a n e q u a t i o n as:

a
f 2 n e k T
s o *) s i n h ( f ^ o ) (2.29)
^ 7T ' 2kT

where a = surface charge

e = d i e l e c t r i c c o n s t a n t of t h e solvent.

A t low p o t e n t i a l s , i . e . z e t Q << 2 k T o r t Q << 2 5 m V the

potential at a point x from t h e s u r f a c e is given by:

ip = ijj exp(-icx) (2.30)

Equation (2.30) shows that the potential decreases exponentially

with d i s t a n c e from t h e s u r f a c e , '/K is r e f e r r e d t o as t h e

' t h i c k n e s s ' of t h e d o u b l e layer and is given by t h e e q u a t i o n

/ 2
(2.31)

T h e total ionic c o n c e n t r a t i o n , I, is g i v e n by

2
(2.32)

2
Setting n z = 21 in e q u a t i o n (2.31) g i v e s

2
/k (2.33)

H e n c e t h e t h i c k n e s s of t h e d o u b l e layer is i n v e r s e l y related

t o t h e ionic s t r e n g t h . As t h e ionic s t r e n g t h is increased,

drops more rapidly.

T h e G o u y - C h a p m a n t h e o r y of t h e d i f f u s e d o u b l e layer

s u f f e r e d from a n u m b e r of d e f e c t s , t h e m o s t n o t a b l e being

its i n a b i l i t y t o r e c o g n i s e e f f e c t s d e r i v e d f r o m t h e

' d i s c r e t e n e s s of c h a r g e ' and s p e c i f i c a d s o r p t i o n . The

q u a n t i t y z.eifKx) in t h e B o l t z m a n n e q u a t i o n (2.28) interpreted

as t h e w o r k d o n e in b r i n g i n g t h e ion from infinity t o a p o i n t

x in t h e d i f f u s e layer is n o t u n a m b i g u o u s . When t h e ion is

inserted at p o i n t x , t h e s u r r o u n d i n g c h a r g e s will rearrange

so as t o m a i n t a i n a ' s e l f - a t m o s p h e r e ' (67, 68). The

contribution due t o t h i s d i s c r e t e n e s s - o f - c h a r g e e f f e c t t o
t h e mean p o t e n t i a l a s d e f i n e d in e q u a t i o n (2.28) is n o t o f t e n

i ncluded.

S e c o n d l y , an ion in a q u e o u s m e d i a is s o l v a t e d , c a r r y i n g

a strongly bound inner h y d r a t i o n shell and an o u t e r s p h e r e in

w h i c h t h e w a t e r d i p o l e s will be o r i e n t e d . F u r t h e r , the solid

surface itself will c a r r y a t least o n e layer of o r i e n t e d

water molecules. C l e a r l y such an ion can o n l y a p p r o a c h the

s u r f a c e to w i t h i n a f i n i t e distance.

T o o v e r c o m e t h e s e d e f e c t s , Stern (69) p r o p o s e d a model

for the inner p a r t of t h e d o u b l e layer in which s o m e ions

m i g h t be a s s u m e d to be a n c h o r e d t o t h e s u r f a c e through

close-range forces. T h e model w a s later r e f i n e d by G r a h a m

(70) w h o d i s t i n g u i s h e d b e t w e e n t h e locus of c l o s e s t approach

of h y d r a t e d ions (the Stern p l a n e ) and t h a t of specifically

adsorbed i o n s , which are e x p e c t e d t o be p a r t i a l l y dehydrated

a t least in t h e d i r e c t i o n of t h e s u r f a c e . Graham called the

two planes the outer and inner H e l m h o l t z p l a n e s , O H P and IHP,

respectively. Specificity in t h i s s e n s e m e a n s a d s o r p t i o n which

d e p e n d s on t h e n a t u r e r a t h e r than m e r e l y t h e c h a r g e on t h e

s u r f a c e o r ion (67). F u r t h e r , it can represent adsorption

e i t h e r in d e f i c i t o r e x c e s s of the a m o u n t w h i c h w o u l d be

e x p e c t e d a t t h e s u r f a c e from s i m p l e c o u l o m b i c considerations.

T h u s for f i n i t e a d s o r p t i o n , a | H p < a Q , and for s u p e r -

equivalent adsorption a^p > cM^I) (see Fig 2 . 3 for

notation). Specific adsorption d e p e n d s on s e v e r a l parameters;

t h e m o s t i m p o r t a n t is g e n e r a l l y c o n s i d e r e d t o a r i s e from

s o l v a t i o n e f f e c t s with t h o s e ions t h a t a r e b e r e f t of

primary hydration shells showing greater specificity.

 50

Stern Gouy
layer layer
b I HP OHP
I

©
A© % o

©
9 n ©
9 © co-ions

uc o u n t e r
i©
i C l ) i © ©

©i specifically adsorbed
ions
ions

<r <r t r
. o imp ohp
r ~ L I

( a ) (b)

Fig 2 . 3 The S t e r n - G r a h a m model of t h e e l e c t r i c a l d o u b l e layer

in t h e p r e s e n c e of (a) n o n - s p e c i f i c a n d (b) s p e c i f i c
adsorption
 51

To a c c o u n t for t h e above c o n s i d e r a t i o n s the B o l t z m a n n distri-

bution law may be m o d i f i e d , so t h a t :

n . (x) = n o e x p ( - ( z . e i M x ) - <$>)/kT) (2.34)

1
w h e r e (J) = t e r m a l l o w i n g for s p e c i f i c ' c h e m i c a l forces.

A l t h o u g h t h e successful a p p l i c a t i o n of t h e Stern-Graham

electrical double layer of Fig 2 . 3 t o q u a n t i t a t i v e interpretation

of experimental data is w i d e l y reported (see a l s o section 2.3.1),

it m u s t be noted t h a t t h e r e probably e x i s t s no unique

description of chemical and e l e c t r o s t a t i c e n e r g i e s of a d s o r p t i o n

a t t h e o x i d e s u r f a c e , with d i f f e r e n t m o d e l s being c a p a b l e of

fitting the same experimental data (72).

In the case of s i l i c a t e m i n e r a l s , t h e formation of an

electrical double layer a t the s o l i d / l i q u i d interface is

c o n s i d e r e d t o be c o n t r o l l e d by the broken bonds of both

S i - 0 and M - 0 o x i d e s , w h e r e M is Al for a Iuminosi Iicates such

as those used in this s t u d y . T h u s when immersed in w a t e r t h e

s u r f a c e of t h e s e m i n e r a l s may tend t o behave as t h a t of a

composite oxide with H + and OH being potential determining

(23,24):

S
|
i - 0 H — - S i - 0 + H + ( 2 - 3 5 )

surf surf

+ H+ , -H+

M —OH ^ —M OH ^ — M 0 (2.36)

surf surf surf

Although equations (2.35) and (2.36) are a n a l o g o u s t o t h e

c h a r g i n g m e c h a n i s m for s i m p l e o x i d e s given b e f o r e , it is

doubtful that the Nernst equation is v a l i d f o r t h e s e complex

o x i d e s w h i c h m a y show p r o g r e s s i v e d e g r a d a t i o n in s o l u t i o n ,

r a t h e r than a r e v e r s i b l e - e l e c t r o d e t y p e of equilibrium.

B e c a u s e t h e s u r f a c e p r o p e r t i e s of s i l i c a t e s a r e a function

of t h e n u m b e r and t y p e of b o n d s broken a t t h e s u r f a c e , a

n u m b e r of s t u d i e s h a v e a t t e m p t e d t o r a t i o n a l i s e t h e s e properties

on t h e b a s i s of c r y s t a l - c h e m i c a I considerations. Lai (73) and

D e j u and B h a p p u (74) p o s t u l a t e d t h a t t h e IEP of s i l i c a t e s is

a function of t h e i r O/Si r a t i o a n d t h a t as t h e r a t i o increased

m o r e o x y g e n w a s a v a i l a b l e for b o n d i n g t o c a t i o n s o t h e r t h a n

S i , therefore the IEP i n c r e a s e d . On t h e o t h e r h a n d , S m o l i k ,

H a r m a n and F u e r s t e n a u (36) c o n s i d e r e d t h e IEP t o be r e l a t e d t o

t h e Al/Si r a t i o in t h e c l e a v a g e p l a n e , and used t h i s relation-

ship t o e x p l a i n t h e i r s t r e a m i n g p o t e n t i a l r e s u l t s on sillimanite,

k y a n i t e and a n d a l u s i t e . A t t h e f i n e r p a r t i c l e s i z e s used in

electrophoresis experiments, they argued that the fractional

Al/Si bond d e n s i t y in t h e b u l k i n f l u e n c e d t h e IEP m o r e than at

c o a r s e s i z e s b e c a u s e t h e p a r t i c l e s had a m o r e r a n d o m s u r f a c e

a r r a n g e m e n t of a t o m s due t o e x t e n d e d grinding.

T h e r e s u l t s of t h e s e and m a n y o t h e r s t u d i e s (66) s u g g e s t

that the approximate IEP of a limited n u m b e r of a Iuminosi Iicates

can be e m p i r i c a l l y p r e d i c t e d , as long as e x t e n s i v e isomorphous

r e p l a c e m e n t has n o t o c c u r r e d . T h u s in t h e c a s e of t h e n o n -

s h e e t s i l i c a t e s used in t h e p r e s e n t s t u d y , m i c r o c l i n e may be

e x p e c t e d to h a v e a low IEP (about pH 2 ) , r e f l e c t i n g an increased

tendency to rupture the Si-0 bonds during grinding (23). For

 53

s p o d u m e n e and beryl t h e p r e d i c t e d IEP a r e also low but s o m e w h a t

h i g h e r than t h o s e of t h e framework s i l i c a t e s (23,24). For the

s h e e t s i l i c a t e s , h o w e v e r , i s o m o r p h i c r e p l a c e m e n t is likely t o

be e x t e n s i v e so t h a t s i m i l a r p r e d i c t i o n s c a n n o t be m a d e (66).

2.3 A d s o r p t i o n of •' s u r f a c t a n t s and po I ymers at the m i n e r a I /

water i riterface

In t h e flotation of t h e lithium s i l i c a t e m i n e r a l s a m i n e s

are often used as col lectors and starch or dextrin is added t o

improve t h e s e l e c t i v i t y . It is t h e r e f o r e useful t o b r i e f l y

c o n s i d e r how s u r f a c t a n t s and m a c r o m o l e c u l e s are adsorbed at

the m i n e r a I / w a t e r interface.

2.3.1 A d s o r p t i o n of Surfactants

The adsorption of long chain ionic s u r f a c t a n t s in the

Stern layer can be r e p r e s e n t e d by a Langmurian t y p e of e q u a t i o n

of the form:

0 +
| = C exp ((zet 0 4>)/kT) (2.37)

w h e r e 0 = the fractional s u r f a c e coverage,

c = surfactant concentration in bulk s o l u t i o n ,

(f> = the s p e c i f i c adsorption potential,

if s p e c i f i c chemical interactions a r e n o t d o m i n a n t then

a d s o r p t i o n will be d e t e r m i n e d largely by t h e m a g n i t u d e of t h e

surface charge. A d s o r p t i o n at the p z c w h e r e i|> zero

g e n e r a l l y indicates t h a t the adsorption e n e r g y is d e p e n d e n t on

some s p e c i f i c interaction t e r m , <J>.

 A n o t h e r w a y of r e p r e s e n t i n g e q u a t i o n (2.37) is in t h e

form:

r = 2 r C e x pr ( - A G ° , /RT) (2.38)
ads

where T = the adsorption density,

r = t h e radius of t h e a d s o r b e d c o u n t e r ion,

A = s
^ads ^ a n < ^ a r c ' free e n e r g y of adsorption.

F u e r s t e n a u and his a s s o c i a t e s (75-77) h a v e used t h i s Stern-Graham

t y p e e q u a t i o n t o e x p l a i n t h e a d s o r p t i o n of long chain amines,

a Iky I s u l p h a t e s and a Iky I s u l p h o n a t e s a t the oxide/water

interface. In t h e s e c a s e s a d s o r p t i o n o c c u r s predominantly

u n d e r t h e pH c o n d i t i o n s w h e r e t h e s u r f a c t a n t ions can function

as c o u n t e r i o n s . At low s u r f a c t a n t c o n c e n t r a t i o n s t h e ions

a d s o r b by ion e x c h a n g e w i t h o t h e r c o u n t e r ions in t h e diffuse

layer. U n d e r t h e s e c o n d i t i o n s t h e Stern potential (zeta potential)

is a s s u m e d to remain c o n s t a n t . As t h e b u l k c o n c e n t r a t i o n is

increased, the adsorbed ions begin t o form hydrophobic

a s s o c i a t i o n s w h i c h then p r o v i d e an a d d i t i o n a l adsorption

mechanism. T h e o n s e t of h y d r o p h o b i c i n t e r a c t i o n s p r o d u c e s a

m a r k e d i n c r e a s e in t h e a d s o r p t i o n and results in a r e d u c t i o n in

t h e m a g n i t u d e of t h e Stern p o t e n t i a l and c h a r g e r e v e r s a l . Patches

of a s s o c i a t e d s u r f a c t a n t ions h a v e been t e r m e d h e m i m i c e lies by

G a u d i n and F u e r s t e n a u (78) and t h e c o n c e n t r a t i o n a t w h i c h they

f o r m t h e critical h e m i m i c e lie c o n c e n t r a t i o n , C H M C , by analogy

with t h e C M C in b u l k solution.

In t h i s t y p e of a d s o r p t i o n p r o c e s s , A G ^ ^ can be s u b d i v i d e d

( 7 5 , 7 9 ) as follows:
 AG° = AG°. , + * (2.39)
ads elect

where = t h e e l e c t r o s t a t i c contribution t o a d s o r p t i o n ,

± zeif/ .
s
Although 4 ' m a d e up of a n u m b e r of c o n t r i b u t o r y t e r m s (see

for e x a m p l e ref. 75), it a p p e a r s t h a t the main contribution

arises from van der W a a i ' s - t y p e interactions between the

hydrocarbon chains, AG° . V a l u e s of a p p r o x i m a t e l y - k T have

'HM'
been o b t a i n e d (76,77) for A G j ^ . T h i s is of t h e same o r d e r of

m a g n i t u d e as t h a t o b t a i n e d from miceI Iization s t u d i e s in bulk

solution.

An a l t e r n a t i v e theory of ionic s u r f a c t a n t a d s o r p t i o n is

t h a t p r o p o s e d by Cases e t a I ( 2 5 , 8 0 ) . Adsorption of the

s u r f a c t a n t is a s s u m e d t o o c c u r by 2 - d i m e n s i o n a I p h a s e changes,

initially on high e n e r g y lattice s i t e s , and later on the

deposited first layer. The a d s o r p t i o n isotherm is based on

t h e F o w l e r a d s o r p t i o n m o d e l , and p r e d i c t s t h a t a t the o n s e t of

c o n d e n s a t i o n , an infinite slope is o b s e r v e d b u t as the second

layer c o n d e n s e s o n t o the f i r s t , t h e s l o p e will tend t o z e r o .

An interesting model which i n c o r p o r a t e s both t h e Fuerstenau

and Cases a p p r o a c h has recently been proposed by S c a m e h o r n et

al (81).

2.3.2 PoIymer adsorption

2.3.2.1 Generai considerations

The factors g e n e r a l l y c o n s i d e r e d to be i m p o r t a n t in p o l y m e r

adsorption are s u m m a r i s e d below (82,83):

 56

(i) Equilibrium is e s t a b l i s h e d s l o w l y . This is b e c a u s e a

large n u m b e r o f c o n f i g u r a t i o n s a t t h e s o l i d s o l u t i o n interface

are p o s s i b l e , e a c h p o l y m e r m o l e c u l e p o s s e s s i n g large n u m b e r s of

p o t e n t i a l l y a d s o r b i n g g r o u p s w i t h a high d e g r e e of mutual

independence. T h e p r o b a b i l i t y of s i m u l t a n e o u s a d s o r p t i o n or

d e s o r p t i o n of t h e g r o u p s is t h e r e f o r e low.

(ii) P o l y m e r s a r e a d s o r b e d m o r e s t r o n g l y from p o o r solvents

than from g o o d s o l v e n t s . F u r t h e r , polymers with polar groups

a r e r e a d i l y a d s o r b e d by p o l a r a d s o r b e n t s . Examples include the

a d s o r p t i o n of p o l y t h e n e o x i d e on s i l i c a (84), s t a r c h on some

salt-type minerals (41) and h y d r o l y s e d polyacryI a m i d e s (85) on

q u a r t z , a l u m i n a and o t h e r minerals.

(iii) T h e e x t e n t of a d s o r p t i o n of p o l y m e r s is g e n e r a l l y a function

of m o l e c u l a r w e i g h t , if a d s o r p t i o n o c c u r s on a n o n - p o r o u s

s u r f a c e , t h e m a x i m u m a m o u n t of a d s o r b e d p o l y m e r , A , is
' max'
related t o t h e m o l e c u l a r w e i g h t , M , by

A = kMa (2.40)
max

w h e r e k and a are c o n s t a n t s . A p a r t from the n a t u r e o f t h e

a d s o r b e n t , t h e m o l e c u l a r w e i g h t e f f e c t d e p e n d s t o a large degree

on t h e c r i t i c a l m i s c i b i l i t y t e m p e r a t u r e (82,86). In t h e region

of t h e t h e t a t e m p e r a t u r e (or in t h e t a s o l v e n t s ) h i g h e r molecular

weight fractions are only sparingly soluble whereas above the

theta temperature (or in good s o l v e n t s ) t h e e f f e c t is diminished.

(iv) T h e a d s o r b e d phase is r e g a r d e d as a fully e x t e n d e d linear

chain lying on t h e p a r t i c l e s u r f a c e . Although several 'monolayers'

a r e c o m m o n , t h e c o n c e p t of m o n o l a y e r c a n n o t be s t r i c t l y applied

t o t h e a d s o r p t i o n of p o l y m e r s . F o r e x a m p l e , in good solvents

m a n y p o l y m e r s wi II e x i s t as e x p a n d e d r a n d o m c o i l s w i t h a m u c h

larger r a d i u s of g y r a t i o n than t h a t of s m a l l e r c o i l s in p o o r

solvents. If a d s o r p t i o n o c c u r s from good solvents, relatively

fewer anchor segments are utilised; the adsorbed layer is a l s o

of c o n s i d e r a b l e t h i c k n e s s , w i t h m a n y loops a n d c h a i n s fanning

o u t into t h e s o l u t i o n p h a s e . F o r t h i s reason s o m e authors

c o n s i d e r zeta potential measurements in t h e p r e s e n c e of polymer

s o l u t i o n s t o be of limited v a l u e , due t o t h e u n c e r t a i n effect

of t h e loops on t h e p o s i t i o n of t h e s l i p p i n g p l a n e (87).

2.3.2.2 Polymer adsorption'isotherms

T h e m o s t c o m m o n l y used isothern in p o l y m e r a d s o r p t i o n is

the Langmuir equation or modifications of it. For example

F u e r s t e n a u and W i e (88) a s s u m e d t h e L a n g m u i r i s o t h e r m in

o r d e r t o e s t i m a t e t h e s t a n d a r d free e n e r g y of interaction

b e t w e e n m o l y b d e n i t e and d e x t r i n . Frequently, however, modifications

of the form

= KC (2.41)
v(l- )V

h a v e been i n t r o d u c e d to a c c o u n t for t h e f a c t t h a t the polymer

is a t t a c h e d by v s e g m e n t s t o t h e s u r f a c e . C is t h e b u l k

solution polymer concentration and K is a c o n s t a n t .

Next various statistical a s s u m p t i o n s may be introduced

into e q u a t i o n (2.41). O n e such r e s u l t a n t model is t h a t due t o

S i m h a , Frisch and Eirich (89):

 2k, 0
0 e /v
I^CC)
(I - 0) (2.42)

where k j , k^ = constants.

T h e main a s s u m p t i o n s a r e t h a t

Ci) the polymer forms localised m o n o l a y e r s on t h e surface

w i t h each a c t i v e c e n t r e b i n d i n g o n l y o n e segment,

(ii) the polymer solution is i n f i n i t e l y d i l u t e , a n d

Ciii) t h e r e is a G a u s s i a n d i s t r i b u t i o n of e n d t o e n d distances;

t h e p o l y m e r m o l e c u l e b e i n g c o n s i d e r e d t o be a f l e x i b l e

random coiI.

T h e v a l u e s p r e d i c t e d by e q u a t i o n (2.42) a r e g e n e r a l l y lower

than t h o s e d e r i v e d from the L a n g m u i r e q u a t i o n .

Further theoretical t r e a t m e n t s h a v e been p r o p o s e d , n o t a b l y

t h a t d u e t o S i l b e r b e r g , in w h i c h it has been r e c o g n i s e d that

t h e a s s u m p t i o n t h a t v is i n d e p e n d e n t of 0 is u n l i k e l y to be

valid. L i p a t o v e t al (82) h a v e s u m m a r i s e d s o m e of t h e approaches.

T h e c o m p l e x i t y of t h e e q u a t i o n s m a k e s t h e i r utilisation

d i f f i c u l t and t h e i r inclusion in t h i s w o r k h a s t h e r e f o r e been

considered unnecessary. In view of t h e c o m p l i c a t e d theoretical

treatments it is s o m e w h a t e m b a r r a s s i n g t h a t p o l y m e r a d s o r p t i o n

data a p p e a r t o fit t h e s i m p l e L a n g m u i r e q u a t i o n as well as a n y

other.

2.3.2.3 Polymer adsorption mechanisms

It is well e s t a b l i s h e d in f l o c c u l a t i o n studies that

a g g r e g a t i o n of finely d i v i d e d s u s p e n s i o n s o c c u r s predominantly

t h r o u g h an i n t e r p a r t i c l e b r i d g i n g e f f e c t by t h e a d s o r b e d polymer

chains. In c o n t r a s t , t h e p o l y m e r a d s o r p t i o n m e c h a n i s m s that
 59

m a k e p o s s i b l e t h e b r i d g i n g e f f e c t a r e d i v e r s e in c h a r a c t e r . This

is p r o b a b l y due t o t h e f a c t t h a t a d s o r p t i o n in p o l y m e r systems

is i n f l u e n c e d by m a n y f a c t o r s w h i c h i n c l u d e , for e x a m p l e , t h e

p r e s e n c e and t y p e of functional groups in the s t r u c t u r e , a n d

the molecular configuration which the polymer molecules adopt

in a p a r t i c u l a r s o l u t i o n e n v i r o n m e n t . F o r e x a m p l e , it is known

t h a t t h e a d s o r p t i o n c h a r a c t e r i s t i c s of a n o n - i o n i c p o l y m e r can

be s i g n i f i c a n t l y i m p r o v e d by i n c o r p o r a t i n g a small proportion

of ionic g r o u p s in t h e p o l y m e r c h a i n , w h i c h s e r v e t o increase

t h e m e a n e x t e n s i o n of t h e c h a i n , w h e r e a s t h e ionic s t a t e of a

p o l y e l e c t r o l y t e can i n h i b i t its a d s o r p t i o n at t h e solid/liquid

interface (90,91).

The term polyelectrolyte is c o m m o n l y used f o r p o l y m e r i c

f l o c c u l a n t s t o d i s t i n g u i s h t h e m from i n o r g a n i c c o a g u l a n t s like

alum. A l t h o u g h m a n y p o l y m e r s , both s y n t h e t i c and natural

p r o d u c t s , are p o l y e l e c t r o l y t e s , t h e r e are many e x a m p l e s of o t h e r s

which have no electrolyte character like p o l y e t h y l e n e oxide

(PEO) and u n m o d i f i e d starch (87). In t h e case of s t a r c h , it

a p p e a r s t h a t u n d e r s o m e c o n d i t i o n s of p H , ionisation of t h e

h y d r o x y Is p r e s e n t in t h e s t r u c t u r e can lead t o s u b s t a n t i a l

electrolyte character.

A l t h o u g h n u m e r o u s p o l y m e r a d s o r p t i o n m e c h a n i s m s h a v e been

proposed in t h e last few d e c a d e s , t h e i m p o r t a n t considerations

relevant to the mechanisms are relatively few and a r e summarised

below (85,87,91,92).

(a) General electrostatic forces

A s a general r u l e , an ionised p o l y m e r is a l w a y s strongly

a d s o r b e d on a s u r f a c e of o p p o s i t e c h a r g e and also t e n d s t o be
 60

r e p e l l e d from o n e of t h e s a m e c h a r g e . S c h u l z and C o o k e ( 3 7 ) , for

e x a m p l e , o b s e r v e d t h a t s u b s t i t u t i o n of a m i n o e t h y l g r o u p s in

starch markedly increased its a d s o r p t i o n on q u a r t z . A similar

e f f e c t w a s r e p o r t e d by B a l a j e e and iwasaki (42) a l t h o u g h t h e y did

n o t s p e c i f y t h e functional group(s) involved. Numerous other

e x a m p l e s of t h i s m e c h a n i s m h a v e been reported particularly with

hydrolysed polyacrylamides (PAM).

E l e c t r o s t a t i c a t t r a c t i o n can a l s o o c c u r on s u r f a c e s bearing

a c h a r g e of t h e s a m e sign as t h e p o l y m e r p r o v i d e d t h a t c h a r g e

reversal is f i r s t o b t a i n e d a t t h e m i n e r a I / w a t e r i n t e r f a c e by t h e

s p e c i f i c a d s o r p t i o n of an o p p o s i t e l y c h a r g e d s p e c i e s . Since

h e a v y metal c a t i o n s can p r o d u c e c h a r g e reversal on q u a r t z and

s i l i c a t e s , t h e y f a c i l i t a t e t h e a d s o r p t i o n of a n i o n i c p o l y m e r s

on t h e s e m i n e r a l s . Unfortunately it is often n o t p o s s i b l e , in

such c a s e s , t o d e t e r m i n e w h e t h e r t h e c a t i o n i c s p e c i e s forms a

chemical bond with t h e p o l y m e r o r m e r e l y a c t s by r e v e r s i n g t h e

Stern potential,

(b) ' Cherhica I bond formation

In p r i n c i p l e it is f e a s i b l e f o r p o l y m e r s t o a d s o r b by a

chelating or coordination reaction d e p e n d i n g on t h e t y p e of

functional g r o u p s t h e y c a r r y , e . g . p o I y e t h y l e n i m i n e on copper

carbonate minerals (87). In p r a c t i c e , h o w e v e r , t h e r e a r e few

high p o l y m e r s known t o a d s o r b by t h i s m e c h a n i s m (91).

Somasundaran (43) s u g g e s t e d t h a t s t a r c h a d s o r b s on c a l c i t e by

c o m p l e x f o r m a t i o n b e t w e e n t h e p o l y m e r and s u r f a c e calcium

species. it is r e p o r t e d (93) t h a t h y d r o x i d e s of multivalent

c a t i o n s can interact with carbohydrates through hydroxylic

p r o t o n a b s t r a c t i o n , t o form c a t i o n - c o n t a i n i n g c h e l a t e s or
 61

alcohola+es. F o r e x a m p l e F e ^ + h a s been r e p o r t e d t o form s t a b l e

c h e l a t e s with s u g a r s In m i l d l y a l k a l i n e s o l u t i o n s (93). This

m i g h t e x p l a i n w h y starch Is a b s t r a c t e d in g r e a t e r q u a n t i t y on

h e m a t i t e t h a n on q u a r t z a t a l k a l i n e pH v a l u e s (42), a l t h o u g h it

Is a l s o p o s s i b l e t h a t t h i s Is due t o d i f f e r e n c e s In s u r f a c e

p o t e n t i a l s of t h e m i n e r a l s , and h e n c e d i f f e r e n t d e g r e e s of

mutual repulsion.

Cc) Hydrogen bonding

This mechanism is c o m m o n w i t h p o l y m e r s in w h i c h non-ionised

functional g r o u p s such as - O H and - C 0 N H 2 form H - b o n d s w i t h

s u r f a c e si lanols o r o t h e r o x i d e / h y d r o x i d e s i t e s on t h e mineral

surfaces. It h a s been s u g g e s t e d , f o r e x a m p l e , t h a t P E O (84),

P A M (94) a n d p o l y v i n y l a l c o h o l (PVA) (95) a d s o r b on isolated

silanol s i t e s on s i l i c a by H - b o n d i n g , and t h a t a d s o r p t i o n is

i n h i b i t e d by e x t e n s i v e h y d r o x y I a t i o n such as t h a t p r e s e n t on

aged s i l i c a . It has a l s o been found (84) t h a t a d s o r p t i o n Is

s t r o n g l y d e p e n d e n t on t h e e x t e n t of t h e I o n i s a t l o n of t h e silanols,

decreasing with i n c r e a s e of p H . This suggests that the bridging

proton Is d o n a t e d by t h e si lanol sites.

In t h e c a s e of starch p o l y m e r s , a h y d r o g e n bonding

m e c h a n i s m has been p o s t u l a t e d f o r t h e a d s o r p t i o n of starch on

salt-type minerals (41) and q u a r t z ( 4 2 ) . Somasundaran (43),

h o w e v e r , s u g g e s t e d t h a t t h e h y d r o g e n b o n d i n g of s t a r c h on calcite

is p r o b a b l y negligible,

(d) Hydrophobic bonding

T h i s o c c u r s in t h o s e c a s e s w h e r e s o m e o r all of t h e functional

groups have sufficient amphipathic character to lead t o Interaction

with a hydrophobic particle s u r f a c e . R u b i o and K i t c h e n e r (84)

and T a d r o s (95) p o s t u l a t e d t h a t t h e a d s o r p t i o n of P E O and PVA,

r e s p e c t i v e l y , on s i l i c a w a s a i d e d by h y d r o p h o b i c associations

b e t w e e n e t h y l e n e g r o u p s and si loxane b o n d s on t h e s u r f a c e . It

h a s a l s o been s u g g e s t e d t h a t d e x t r i n s a d s o r b by hydrophobic

i n t e r a c t i o n s on m o l y b d e n i t e (88) and coal (96). In t h e s e systems

a d s o r p t i o n c a p a c i t y a p p e a r s t o be little i n f l u e n c e d by p H .

(e) Dipolar'interactions

In t h e i r s t u d i e s on t h e a d s o r p t i o n of P A M on fluorite,

S l a t e r a n d K i t c h e n e r (92) p o s t u l a t e d t h a t a d s o r p t i o n m a y o c c u r

by t h e i n t e r a c t i o n of d i p o l e s of t h e a m i d e g r o u p w i t h the

e l e c t r o s t a t i c field on t h e mineral surface. In a later p a p e r ,

however, these authors suggested that further experimental

v e r i f i c a t i o n of t h e m e c h a n i s m m i g h t be required.

Although the above adsorption mechanisms may individually

a p p l y in s o m e s y s t e m s , in m a n y o t h e r s t h e y c o m p l i m e n t o n e o r

the other. F o r e x a m p l e , T a d r o s , and R u b i o and K i t c h e n e r provided

e v i d e n c e t h a t P V A a n d P E O a d s o r b e d on si Iica by both H-bonding

and h y d r o p h o b i c interactions. B a l a j e e and Iwasaki a l s o suggested

t h a t s t a r c h a d s o r b e d on n e g a t i v e l y c h a r g e d q u a r t z by a c o m b i n a t i o n

of h y d r o g e n b o n d i n g and e l e c t r o s t a t i c f o r c e s , if c a t i o n i c

functional g r o u p s w e r e p r e s e n t in t h e s t a r c h . Finally,

Somasundaran p r o p o s e d t h a t t h e a d s o r p t i o n of starch on calcite

involved both e l e c t r o s t a t i c a t t r a c t i o n and a c o m p l e x a t i o n

reaction.

2.4 A q u e o u s c h e m i s t r y O f n - d o d e c y I am? ne

T h e e f f e c t i v e n e s s of a l k y l a m i n e s as c o l l e c t o r s in flotation

s y s t e m s is d e p e n d e n t on t h e s o l u t i o n c h e m i s t r y of t h e a m i n e
g r o u p as well as t h e s i z e of t h e h y d r o c a r b o n g r o u p . With the

e x c e p t i o n of q u a r t e r n a r y c o m p o u n d s , a m i n e s a r e w e a k b a s e s s o t h a t

d e p e n d i n g on t h e pH both c a t i o n i c and neutral s p e c i e s will be

p r e s e n t in s o l u t i o n . Smith (97) h a s shown t h a t t h e coadsorption

of both a m i n e s p e c i e s p r o d u c e s t h e m o s t h y d r o p h o b i c surfaces.

Dodecylamine (DA) is a 12-carbon p r i m a r y a m i n e w h o s e

formuI a may be w r i t t e n as C H g . C H 2 ( C H 2 ) Q . C H 2 . C H 2 N H 2 . The diameter

of t h e c h a r g e d head is r e p o r t e d t o be a b o u t 3.7°A ( 2 6 ) . The

dissolution and h y d r o l y s i s of a p r i m a r y a m i n e can be represented

as (26):

RNH,+ RN1-L, . + H + K = 2.5 x I 0 " H (2.43)

5 2(aq) a
RNHor . + hLO — RNH* + Off K. = 4 . 3 x I 0 ~ 4 (2.44)
2Caq) 2 3 b
+
RNhL, . + H o 0 ^ R N H , + 0H~ K = 8.6 x I0"9 (2.45)
2(s) 2 3 so
5
RNH2CS) - RNH2(aq) K s | =2xl0" (2.46)

A m a s s b a l a n c e on a m i n e in a s a t u r a t e d s o l u t i o n gives

S
"[RNH2(aq)] + ( 2
b V ] "47)

w h e r e S is t h e s o l u b i l i t y . Combining equations (2.43), (2.46)

and (2.47) g i v e s

S = K (I + [H + ] ) (2.48)
S
| K
a

This equation is e x p r e s s e d g r a p h i c a l l y in Fig 2 . 4 . With the

c o m b i n e d use of t h e a b o v e e q u a t i o n s , t h e logarithmic/concentration

d i a g r a m of Fig 2 . 5 can a l s o be c o n s t r u c t e d . A t pH v a l u e s below

 64

1 1 1 r

Solubi Iity Ii ne

c
O

(D
+-

C
0
o
£Z
o
o
CD
O

pH

Fig 2 . 4 S o l u b i l i t y of d o d e c y l a m i n e as a function of pH

CD
o

pH

Fig 2.5 Logarithmic concentration diagram for I x I O ~ 4 M total

dodecylamine
 -4 +
1 0 . 6 , in a I x 10 M s o l u t i o n , t h e c a t i o n i c a m i n e ion (DA )

p r e d o m i n a t e s and a t pH v a l u e s below 10 p r e c i p i t a t e d a m i n e will

be a b s e n t . The concentration of s o l u b l e u n i o n i s e d amine

decreases l o g a r i t h m i c a l l y w i t h a d e c r e a s e in pH f r o m pH 10.

R e c e n t l y , it h a s been a r g u e d (98,99) t h a t pre-micellor

a s s o c i a t i o n s and i o n - m o l e c u l a r c o m p l e x e s e n h a n c e surface

a c t i v i t y and h e n c e s i g n i f i c a n t l y c o n t r i b u t e t o t h e flotability

of m i n e r a l s . A n u m b e r of p r o p e r t i e s of s u r f a c t a n t solutions,

such as e l e c t r i c a l c o n d u c t i v i t y , h a v e been r e p o r t e d (98,100)

t o d e v i a t e from t h e i r e x p e c t e d b e h a v i o u r in sub-mi c e l l a r

concentrations, particularly for h i g h e r h o m o l o g u e s . These

d e v i a t i o n s h a v e been r e p o r t e d (100) t o be a c c o u n t e d for by

dimerisation. H o w e v e r , s t a b i l i t y data f o r d i m e r s is g e n e r a l l y

lacking a n d n o t s e l f - c o n s i s t e n t . T h i s is p r o b a b l y due t o t h e

general p r o b l e m of q u a n t i t a t i v e l y s t u d y i n g t h e self-association

of long chain m o l e c u l e s a t t h e low c o n c e n t r a t i o n s characterised

by t h e C M C . Additional c o m p l i c a t i o n s a r i s i n g from inter-ionic

i n t e r a c t i o n s h a v e n e v e r been p r o p e r l y d e f i n e d . F u r t h e r , it has

n o t been fully e x p l a i n e d w h y t h e f o r m a t i o n of m u l t i m e r s appears

t o b e r e l a t i v e l y u n i m p o r t a n t , in view of t h e well known

s t a b i l i t y of much larger a g g r e g a t e s , n a m e l y micelles.

With regard to i o n m o l e c u l a r c o m p l e x e s , S o m a s u n d a r a n and

Ananthapadmanabhan (98) c l a i m t h a t formation of t h e DA c o m p l e x

(RNH^RNH^)* in s o l u t i o n c o i n c i d e s with m a x i m u m s u r f a c e activity

as o b s e r v e d by s u r f a c e t e n s i o n and flotation response. From

t h e i r r e s u l t s , h o w e v e r , it is n o t p o s s i b l e t o distinguish
+

b e t w e e n t h e m o r e e s t a b l i s h e d t h e o r y of c o a d s o r p t i o n of DA ion

and m o l e c u l e , a n d the a d s o r p t i o n of t h e p r o p o s e d c o m p l e x a t t h e
air/water or solid/liquid interface. F u r t h e r , in t h e i r

d e r i v a t i o n of the stabi lity c o n s t a n t of t h e c o m p l e x , t h e s e

a u t h o r s used the d i e l e c t r i c c o n s t a n t for w a t e r , i.e. 7 8 .

It is well known t h a t in t h e i m m e d i a t e v i c i n i t y of an ion,

w a t e r d i p o l e s are s t r o n g l y o r i e n t e d and t h a t c o m p l e t e dielectric

s a t u r a t i o n may be o b s e r v e d . H e n c e for t h e p r i m a r y hydration

s h e l l , t h e d i e l e c t r i c c o n s t a n t is reduced from its bulk t o a

v a l u e w h i c h may be as low as 6 ( 3 1 , 1 0 1 ) . T h i s c o n s i d e r a t i o n makes

the v a l u e of t h e i r derived c o n s t a n t to be in c o n s i d e r a b l e doubt.

In s u m m a r y , a l t h o u g h t h e e x i s t e n c e of d i m e r s and ionmolecular

c o m p l e x e s is r e c o g n i s e d , t h e i r inclusion in s o l u t i o n equilibria

is n o t p o s s i b l e w i t h o u t m o r e r e l i a b l e s t a b i l i t y data.

2.5 T h e S t r u c t u r e a n d c h e m i s t r y of starch

2.5.I T h e s t r u c t u r e of starch

Starch is a g l u c o s e p o l y m e r in w h i c h t h e g l u c o s e units

are b o n d e d m a i n l y t h r o u g h a - D - ( l — > 4 ) linkages with a-D-(l-*-6)

branch p o i n t s . C a r b o n , h y d r o g e n and m o l e c u l a r w e i g h t determinations

h a v e c o n f i r m e d t h a t it may be r e p r e s e n t e d by t h e formula

(C-H.-CL) ( 1 0 2 ) . S t a r c h e s usually1 c o n t a i n small a m o u n t s of

6 10 5 n

i m p u r i t i e s such as fatty a c i d s (up t o 0 . 6 $ ) and phosphorus

(up t o 0 . 2 $ ) , t h e latter b e i n g m o r e c o m m o n in t u b e r s t a r c h e s than

in cereal starches ( 1 0 3 ) . Two principal t y p e s of carbohydrate

p o l y m e r s a r e p r e s e n t in s t a r c h e s : amylose and amylopectin.

A m y lose is e s s e n t i a l l y a linear-chain p o l y m e r c o n t a i n i n g

mostly the a-D-(l—>4) glucosidic bonds. Its a v e r a g e molecular

4 5

weight lies in t h e range 4 x 10 - 3 x 10 , d e p e n d i n g on t h e t y p e

of the p a r e n t s t a r c h . T h e c o n t e n t of a m y l o s e also v a r i e s with

the botanical source; most starches contain 14-30$ of t h e linear

p o l y m e r ( 1 0 4 ) . It Is c h a r a c t e r ! s e d c h i e f l y by its high iodine

b i n d i n g c a p a c i t y (105) and Its r e l a t i v e t e n d e n c y t o retrograde

from a q u e o u s s o l u t i o n s c o m p a r e d t o a m y l o p e c t i n (|06).

Amylopectin is c o n s i d e r a b l y b r a n c h e d and c o n t a i n s b o t h the

a - D - C I — * 4 ) and a-D-(l—»-6) b o n d s ( 1 0 4 ) . It h a s a much higher

6 6

m o l e c u l a r w e i g h t (I x 10 - 5 x 10 ) than a m y l o s e and retrogrades

o n l y s l o w l y from a q u e o u s s o l u t i o n s , p r o b a b l y due t o s t e r i c

hinderanee ( 1 0 4 ) . S i m p l i f i e d s t r u c t u r e s of t h e s t a r c h components

are presented In F i g 2 . 6 .

The term retrogradation Is used t o d e s c r i b e t h e a b i l i t y of

starch to a s s o c i a t e , particularly In p o o r s o l v e n t s , p r o b a b l y

by I n t e r m o l e c u I a r h y d r o g e n b o n d s (104). The aggregates that

are formed lead t o a partial c r y s t a l l i s a t i o n of t h e starch

m o l e c u l e s o u t of s o l u t i o n . Among the many factors that

Influence retrogradation are t h e m o l e c u l a r w e i g h t of t h e polymer

and its c o n c e n t r a t i o n , t y p e of s o l v e n t , t e m p e r a t u r e and pH of

the solutlon.

2.5.2 Dextrins

T h e t e r m d e x t r i n s h a s been loosely a p p l i e d to e x t e n s i v e l y

d e g r a d e d starch p r o d u c t s In w h i c h c l e a v a g e of t h e molecular

c h a i n s r e s u l t s in p r o d u c t s t h a t a r e i n t e r m e d i a t e b e t w e e n the

p a r e n t starch and o I i g a s a c c h a r i d e s . Several t y p e s of dextrins

a r e o b t a i n e d d e p e n d i n g on t h e t y p e of t r e a t m e n t and t h e amount

of r e a r r a n g e m e n t and r e p o l y m e r i s a t i o n allowed.

White dextrins are produced when starch is h e a t e d a t low

temperatures (79-l20°C), low a c i d i t i e s and for s h o r t t i m e s . The

(a) S e g m e n t of amy lose

(b) S e g m e n t of amylopectin

Fig 2.6 S i m p l i f i e d s t r u c t u r e of s t a r c h polymers

p o l y m e r is a r e s u l t of m a i n l y h y d r o l y t i c a c t i o n (107). Yellow

d e x t r i n s are p r o d u c e d a t h i g h e r t e m p e r a t u r e s (I50-220°C) w i t h

h i g h e r a m o u n t s of a c i d c a t a l y s t . The depolymerisation reaction

is f o l l o w e d by t r a n s g l y c o s i d a t i o n and r e p o l y m e r i s a t i o n as shown

in Fig 2 . 7 . This results in e x t e n s i v e b r a n c h i n g of t h e molecules

and a r e d u c e d t e n d e n c y t o r e t r o g r a d e ( 1 0 6 , 107). B r i t i s h g u m s are

p r o d u c e d by h e a t i n g starch with little o r no acid a t high

temperatures (I30-220°C) for r e l a t i v e l y long p e r i o d s . The

p r o d u c t s of d e x t r i n i s a t i o n are shown in Fig 2 . 7 . Although several

o p t i o n s a t C 2 , C ^ o r fa a r e a v a i l a b l e for t h e recombination

r e a c t i o n , it h a s been reported ( 1 0 8 ) t h a t t h e a-D-(I—>6)

linkage is e x p e c t e d t o form m o r e e a s i l y due t o s t e r e o c h e m i c a l

CH OH CH OH

Fig 2 . 7 Possible dextrinisation reactions: (a) h y d r o l y t i c

s c i s s i o n ; (b) t r a n s g l y c o s i d a t i o n ; (c) r e c o m b i n a t i o n (107)
 71

CHAPTER THREE

MATERIALS AND EXPERIMENTAL METHODS

3.1' Materials •

3 . 1 . 1 ' Mi rierals' •

High p u r i t y s a m p l e s o f t h e s i l i c a t e m i n e r a l s w e r e obtained

from W a r d ' s N a t u r a l S c i e n c e E s t a b l i s h m e n t , R o c h e s t e r , New York.

T h e i r s o u r c e s w e r e as follows:

T a b l e 3.1 Sources of minerals used.

Mineral Source

Lepidolite Keyston, South Dakota

Spodumene K e y s t o n , South Dakota
Beryl New England
Microcline K e y s o n , South Dakota
Muscovite Stoneham, Maine

Several h a n d - p i c k e d p i e c e s of e a c h m i n e r a l , m e a s u r i n g

about 5 x 3 c m , w e r e w a s h e d free of s u r f a c e i m p u r i t i e s by

leaching f o r several hours in 5 0 $ HCI a f t e r w h i c h t h e y were

repeatedly rinsed w i t h d i s t i l l e d w a t e r and a l l o w e d t o a i r dry.

T h e s a m p l e s w e r e then w r a p p e d in p a p e r t o m i n i m i s e contamination

d u r i n g hand c r u s h i n g with a h a m m e r , f o l l o w e d by s t a g e grinding

to different sizes in a laboratory 'Tema' agate mill. The

ground fractions were stored in t i g h t l y c o v e r e d g l a s s containers

and k e p t u n d e r r e d u c e d p r e s s u r e until required.

T h e p u r i t i e s of t h e m i n e r a l s w e r e c h e c k e d by X R F a n d

elemental analysis. R e s u l t s of t h e X R F s c a n s are given in

Table 3.2.
 73

Table 3.2 X R F a n a l y s i s of t h e minerals

Mineral Major Intermediate Minor Trace

> 5% 0.5-5% 0.05-0.5% < 0.05%

Lepidolite SI K , R b , AI C s , Mn Fe, Pb, Sr,

S , S n , Ca

Spodumene S I , AI Fe, Pb, Sn,

R b , Ca

Beryl S I , Al Fe Pb, Zn, Cs,

Ca, S, Br

Ml c r o c IIne S I , Al K , Rb Fe, Ca, Cs,

Gr

Muscovlte S I , Al K , R b , Fe Z n , P b , Ni

Elemental analysis results are given In T a b l e 3.3.

Table 3.3 A n a l y s i s of the cations in t h e m i n e r a l s studied

Element • <% j f j e m e n t p r e s e n t in jf e fn'inera I

Muscovite Lep? do Iite S p o d u m e n e BeryI Mi c r o c 11ne

SI 21.00 29.00 29.67 30.33 28.33

Al 17.67 9.43 14. 17 9.27 9.5

Li 0.093 1.20 3.47 < 167 p p m n.d.

Fe 3.07 0.07 0.07 0.58 0.05
Na 0.30 0.06 0.26 290 ppm 440 ppm
Ni < 333 ppm < 333 ppm < 333 ppm < 333 ppm < 333 ppm

Mg 400 ppm < 27 ppm 43 ppm 43 ppm < 27 ppm

Pb < 0 . 10 < 0 . 10 < 0 . 10 < 0 . 10 < 0 . 10

Zn 0.07 277 ppm 267 ppm 0.06 133 p p m

Mn 0.07 0 . 1 1 333 ppm 133 p p m n.d.
Sr < 500 ppm < 500 ppm < 500 ppm < 500 ppm < 500 ppm
Be n.d. n.d. n.d. 2.51 n.d.
K 9.77 9.87 n.d. n.d. 14

n.d. = not detected

R e a s o n a b l e a g r e e m e n t w a s o b t a i n e d b e t w e e n the v a l u e s in T a b l e 3 . 3

a n d t h e o r e t i c a l l y e x p e c t e d v a l u e s a s s u m i n g the m i n e r a l s were

'ideal'. Further indication that the samples w e r e reasonably

p u r e w a s o b t a i n e d by X R D a n a l y s i s . Several w e a k p e a k s w e r e

i d e n t i f i e d as q u a r t z , a I b i t e and t o p a z , in a s s o c i a t i o n with the

major minerals. These associations suggest that the minerals

w e r e from t y p i c a l pegmatite deposits (I).

3.1.2 Reagents

P u r e n - d o d e c y I a m i n e w a s o b t a i n e d from Koch-light

Laboratories L t d , a n d w a s used w i t h o u t f u r t h e r purification.

P o t a t o and m a i z e s t a r c h e s , t o g e t h e r with y e l l o w d e x t r i n , w e r e

of t e c h n i c a l grade. No information concerning their purity was

s u p p l i e d by t h e m a n u f a c t u r e r s (BDH). The white dextrin, also

s u p p l i e d by B D H , w a s alcohol p r e c i p i t a t e d and c o n t a i n e d less

than 4$ reducing sugars. B r i t i s h g u m w a s s u p p l i e d by Tunnel

Avebe Starches Ltd, Gillingham, Kent. All the o t h e r reagents

used w e r e of ' A n a l a r ' g r a d e .

H i g h p u r i t y c o n d u c t i v i t y w a t e r w a s p r e p a r e d by p a s s i n g

d i s t i l l e d w a t e r t h r o u g h a m i x t u r e of anion and c a t i o n exchangers

( A m b e r l i t e , B D H ) , and f i n a l l y t h r o u g h a column of a c t i v a t e d

charcoal before redistillation. T h e w a t e r t h u s p r e p a r e d had a

6
c o n d u c t i v i t y of I x 10 m h o and c o n t a i n e d n o surfactant

material as i n d i c a t e d by b u b b l e p e r s i s t e n c e tests.

T h e pH w a s m e a s u r e d with a P Y E Unicorn pH m e t e r , model 292.

B u f f e r s o l u t i o n s w e r e p r e p a r e d as s o l u t i o n s of potassium

hydrogen phthalate ( 0 . 0 5 M ) , equal a m o u n t s of p o t a s s i u m a n d

sodium dihydrogen phosphates (0.025M e a c h ) and b o r a x (0.0IM).

T h e r e s p e c t i v e pH v a l u e s w e r e 4 . 0 1 , 6 . 8 6 and 9 . 1 8 . Solutions

of N a O H o r HCI of a p p r o p r i a t e s t r e n g t h w e r e used for pH

adjustment.

3 . 2 ' Experimental'methods and techniques

T h e e x p e r i m e n t s w e r e e i t h e r c a r r i e d o u t a t a room

t e m p e r a t u r e of 20°C ± 2°C o r a t t h e t e m p e r a t u r e s p e c i f i e d In

the relevant experimental procedure. Glassware was cleaned by

c h r o m i c - s u l p h u r i c acid f o l l o w e d by r e p e a t e d w a s h i n g with

distilled water. In s o m e c a s e s w h e r e t h e g l a s s w a r e had been in

c o n t a c t with s u r f a c t a n t o r o r g a n i c s o l u t i o n s , it w a s s o a k e d in

a s o l u t i o n of c o n c e n t r a t e d N a O H and alcohol prior to washing

with w a t e r and c h r o m i c - s u I p h u r l c acid t r e a t m e n t . This procedure

produced completely hydrophilic glass surfaces.

3.2.1 Elemental analysis

0 . 3 0 0 g o f the - 4 5 y m fraction of e a c h m i n e r a l powder was

fused w i t h an e x c e s s of s o d i u m p e r o x i d e (2.5g). The fusion

mixture was dissolved in a c i d i f i e d d i s t i l l e d w a t e r and m a d e up

V
to I l i t r e , such t h a t t h e s o l u t i o n c o n t a i n e d 5 $ /v HCI.

A further 0.300 g was digested in HCI o v e r n i g h t , filtered

and m a d e up t o I litre. T h e fusion so Iutions w e r e used for

Identification of a I I t h e e l e m e n t s s h o w n in T a b l e 3 . 3 e x c e p t for

s o d i u m , for which the acid-digested sample solutions were used.

3.2.2 P I S s o l u t i on studies

I g s a m p l e s of t h e - 4 5 y m f r a c t i o n s of t h e m i n e r a l s were

weighed into 100 ml conical flasks. Distilled water (50 m l )

with t h e r e q u i r e d p H v a l u e w a s a d d e d t o each of t h e f l a s k s and

t h e s u s p e n s i o n s e q u i l i b r a t e d on a m e c h a n i c a l shaker for the

required time. Both t h e initial and final pH v a l u e s w e r e

recorded. The suspension was then centrifuged prior to

d e t e r m i n a t i o n of t h e lattice c a t i o n s in t h e supernatant.

3.2.3''Cat? on'exchange'measurements

T h e - 5 3 , + 4 5 y m f r a c t i o n s w e r e used in t h e determination.

T h e s u r f a c e a r e a s of t h e r e s p e c t i v e m i n e r a l f r a c t i o n s , as

d e t e r m i n e d by t h e s i n g l e p o i n t m e t h o d using a 'Monosorb'

apparatus (Quantachrom Inc.) a r e given in T a b l e 3 . 4 . Three

i n d e p e n d e n t m e a s u r e m e n t s w e r e m a d e f o r each determination.

Table 3.4 S u r f a c e a r e a s of t h e f r a c t i o n s used in t h e cation

exchange tests

2 -I
Mi nera I S, m g

Muscovite 14.4
Lepi do Ii te 1.9
Spodumene 0.5
Microcline 0.4
Beryl 0.2

A preliminary investigation revealed that the particles

-4

c o u l d n o t be s u s p e n d e d d i r e c t l y in I x 10 M salt solutions

b e c a u s e of t h e r e l e a s e of t h e cation of i n t e r e s t by t h e m i n e r a l

s a m p l e s , in s o m e c a s e s . Subsequently, accurately weighed I g

s a m p l e s of each m i n e r a l w e r e s u s p e n d e d in IM NlfaCI for I h (109)

in s t o p p e r e d c e n t r i f u g e t u b e s and r o t a t e d on an end-over-end

agitator. T h e s u s p e n s i o n w a s then c e n t r i f u g e d and decanted.

T h i s p r o c e d u r e w a s r e p e a t e d four t i m e s a f t e r which t h e m i n e r a l

p o w d e r w a s w a s h e d several t i m e s with methanol to r e m o v e occluded

N H ^ C I , dried a n d r e w e i g h e d . The exchange capacities were then

-4
d e t e r m i n e d a s t h e a b i l i t y of I x 10 M c h l o r i d e s a l t s to d e s o r b
+
NH^ ions from t h e s a t u r a t e d mineral p o w d e r s . Parallel

e x p e r i m e n t s , in w h i c h n o c a t i o n s w e r e p r e s e n t , w e r e a l s o
+
conducted. In both c a s e s t h e N H ^ -saturated powders were

repeatedly resuspended in s a l t s o l u t i o n s (distilled w a t e r in

+
the latter c a s e ) until little or no N H ^ ions p a s s e d into
+

solution. T h e a m o u n t of N H ^ in e a c h w a s h i n g w a s determined

and t h e e x c h a n g e c a p a c i t y d e d u c e d as t h e total N H ^ * exchanged

in s a l t s o l u t i o n less t h a t e x c h a n g e d in d i s t i l l e d w a t e r . The

e x c h a n g e e x p e r i m e n t s w e r e c o n d u c t e d a t pH 7 , u s i n g hydroxide

s o l u t i o n s of t h e p a r t i c u l a r c a t i o n to a d j u s t t h e p H . Earlier

dissolution s t u d i e s , a n d t h e s t a b i l i t y data p r e s e n t e d in C h a p t e r

2, indicated t h a t t h e r e w a s m i n i m u m d i s s o l u t i o n of t h e

s i l i c a t e s a t t h i s pH value.

3.2.4 Electrokinetic measurements

The electrophoretic mobility measurements were made with

a Rank Brothers' MK II m i c r o e l e c t r o p h o r e s i s a p p a r a t u s using a

flat quartz cell. A s u s p e n s i o n of 0 . 0 0 5 g ml ' was made up

w i t h d i s t i l l e d w a t e r and a d j u s t e d to t h e r e q u i r e d pH p r i o r t o

equilibration for t h r e e d a y s on a m e c h a n i c a l shaker. The final

pH w a s n o t e d i m m e d i a t e l y b e f o r e each m e a s u r e m e n t . At least

2 0 p a r t i c l e s w e r e t i m e d a t both s t a t i o n a r y levels and the

mobi lity v a l u e c o m p u t e d from a m e a n of t h e r e a d i n g s . In m o s t of

t h e e x p e r i m e n t s an ionic a t m o s p h e r e of 10 5 M NaCl w a s maintained.

P r e l i m i n a r y t e s t s s h o w e d t h a t n e i t h e r N a + nor CI had significant

s p e c i f i c a d s o r p t i o n e f f e c t s on any of t h e m i n e r a l s studied.

T h e e I e c t r o p h o r e t i c m o b i l i t y w a s c a l c u l a t e d from t h e e q u a t i o n

U = vj_ (3. I)
V

where v = particle velocity

V = applied potential

L = effective interelectrode distance

The effective interelectrode d i s t a n c e w a s o b t a i n e d from t h e

formuI a

L = RKA (3.2)

where R = r e s i s t a n c e a c r o s s t h e cell

K = s p e c i f i c c o n d u c t i v i t y of t h e suspension

A = cross-sectional area of t h e cell.

R w a s m e a s u r e d w i t h a Marconi I n s t r u m e n t s Universal A.C. bridge

model T . F . 2 7 0 0 . A Portland Electronics conductivity meter

(model P 3 1 0 ) , with a cell c o n s t a n t of 0 . 5 3 w a s used t o m e a s u r e

K. V a l u e s of L t h u s o b t a i n e d w e r e p l o t t e d a g a i n s t p H , for

the p a r t i c u l a r ionic s t r e n g t h u s e d , as s h o w n in Fig 3 . 1 . Below

a pH of 4 and a b o v e a pH o f 10, L w a s n o t found t o be constant.

This contradicts recent reports (29, I 10) in w h i c h L h a s been

a s s u m e d t o be c o n s t a n t below and a b o v e t h e s e pH v a l u e s . Fig 3.

w a s used t o o b t a i n v a l u e s of L w i t h i n t h e pH range s t u d i e d .
 PH

8
Fig 3.1 E f f e c t of pH on t h e e f f e c t i v e cell length in 10 M NaCI

3.2.5 M e t h o d s of p r e p a r i n g dodecy1 a m i n e arid s t a r c h solutions

D o d e C y I ami ne S o l u t i o n s . DodecyI a m i n e s o l u t i o n s w e r e p r e p a r e d by

dissolving a weighed quantity in a s l i g h t s t o i c h i o m e t r i c e x c e s s o f

8
HCI (10 M HCI). G e n t l e w a r m i n g w a s used t o i n c r e a s e t h e rate of

dissolution.

S t a r c h so I u t i o n s . T h e e f f e c t i v e n e s s of s t a r c h a n d r e l a t e d polymers

a s froth f l o t a t i o n d e p r e s s a n t s is s t r o n g l y d e p e n d e n t on t h e

solubi Iisation p r o c e d u r e u s e d . Several m e t h o d s of p r e p a r a t i o n have

been reported in t h e literature. C h a n g e t al ( 3 9 ) prepared starch

s o l u t i o n s by d i g e s t i n g t h e s t a r c h in an a u t o c l a v e a t I20°C f o r I h .

More recently, Afenya (III) p r e p a r e d s t a r c h s o l u t i o n s by boiling

t h e p o l y m e r a t I00°C for 2 0 m i n s . B a l a j e e and Iwasaki (42 )

preferred causticising their starches in 0 . 5 N N a O H . It is likely

t h a t all of t h e s e t e c h n i q u e s w o u l d p r o d u c e s o l u t i o n s of different

p r o p e r t i e s from t h e s a m e raw m a t e r i a l s .

F o r solubi IisatI on of a p o l y m e r , t h e s o l v e n t e n v l r o n m e n t m u s t

be f a v o u r a b l e in t h e r m o d y n a m i c t e r m s ; t h e p o l y m e r m u s t prefer

polymer-solvent interactions compared to polymer-polymer associations.

F o r m o s t s t a r c h e s , w a t e r Is a p o o r s o l v e n t . It a p p e a r s t h a t t h i s

is a s s o c i a t e d w i t h t h e u n i f o r m i t y of t h e linkages and t h e linearity

of t h e m o l e c u l e s . A s a general rule p o l y s a c c h a r i d e s in w h i c h the

s u g a r u n i t s a r e w h o l l y o r primari ly linked by t h e a-D-(l—>4)

g l y c o s i d i c b o n d s are I n s o l u b l e in w a t e r due t o t h e i r p r e f e r e n c e for

partial c r y s t a l l i s a t i o n (retrogradation). C o n t r a r i ly, p o l y s a c c h a r i d e s

in w h i c h a - D - ( l — b o n d s are p r e s e n t a r e s o l u b l e t o v a r y i n g extents.

It h a s been s u g g e s t e d ( I 12) t h a t t h e g r e a t e r s o l u b i l i t y results

from t h e extra d e g r e e s of f r e e d o m p r o v i d e d by t h e e q u a t o r i a l bond

b e t w e e n t h e C ^ and C ^ carbon a t o m s . T h i s r e s u l t s in h i g h e r s o l u t i o n

e n t r o p i e s for such p o l y m e r s and h e n c e lower free e n e r g i e s of solution.

T h e main c o n s i d e r a t i o n , t h e r e f o r e , Is t h a t f o r m o s t s t a r c h e s

c o l d - w a t e r solubi Iisation Is d e t e r m i n e d by t h e a m y l o s e : amypectin

ratio and not merely the solvent characteristics. T h e use of h o t

w a t e r o n l y p r o d u c e s s w e l l i n g of o t h e r w i s e intact starch granules

w h i c h a t s u f f i c i e n t l y high t e m p e r a t u r e s will b u r s t t o form g e l s

(103). Upon c o o l i n g t h e g e l s a r e e x p e c t e d t o remain In t h e

associated state (104). T h e d e p r e s s i v e p r o p e r t i e s of such starch

s o l u t i o n s m u s t t h e r e f o r e be c o n s i d e r e d d o u b t f u l . Indeed, this is

s u p p o r t e d by t h e r e s u l t s p r e s e n t e d in later s e c t i o n s .
 81

P e r h a p s t h e b e s t m e t h o d for s o l u b i l i s i n g s t a r c h e s is by

d i s p e r s i n g t h e m in dimethyl sulphoxide (103,113). However, the

use o f such a r e a g e n t is i n h i b i t i v e for industrial applications.

It is a l s o p r o b a b l e t h a t t h e r e a g e n t Is n o t s u f f i c i e n t I y p o o r t o

a l l o w for r e a s o n a b l e a m o u n t s of a d s o r p t i o n of t h e p o l y m e r at t h e

sol i d / l i q u i d interface (||4).

G o o d solubi Iisation c h a r a c t e r i s t i c s of s t a r c h e s can be

o b t a i n e d by d i s p e r s i n g t h e s t a r c h g r a n u l e s in urea o r s o d i u m

h y d r o x i d e , e v e n a t room t e m p e r a t u r e ( 4 2 , 103). It a p p e a r s t h a t t h e

main reason for t h i s is t h e u n l i k e l y e x i s t e n c e of t h e i n t e r m o l e c u Iar

h y d r o g e n b o n d s , t h a t are r e s p o n s i b l e for a s s o c i a t i v e e f f e c t s , in

these solvents (86). F u r t h e r , s u b s e q u e n t i o n i s a t i o n of t h e hydroxyls

c o n t r i b u t e t o t h e s t a b i l i t y of t h e s o l u t i o n s (112). H o w e v e r , it

a p p e a r s t h a t t h e use of high c o n c e n t r a t i o n s of s o d i u m h y d r o x i d e can

lead t o d e g r a d a t i v e e f f e c t s a n d t h e f o r m a t i o n of c a r b o x y l i c groups

C 1 0 3 ) , a p a r t from t h e d i s a d v a n t a g e of w o r k i n g w i t h a high salt

concentration upon n e u t r a l i s a t i o n t o t h e normal w o r k i n g pH v a l u e s .

F o r t h e a b o v e r e a s o n s , starch s o l u t i o n s w e r e p r e p a r e d , in t h e

p r e s e n t w o r k , by c a u s t i c i s i n g a t low N a O H c o n c e n t r a t i o n s (0.025M),

using low s t i r r e r s p e e d s (300 rpm for 3 0 m i n ) . As the effects

discussed above are concentration-dependent (e.g. retrogradation)

r e l a t i v e l y d i l u t e s o l u t i o n s a t 0 . 0 1 $ w / v (dry b a s i s ) w e r e prepared.

Such s t a r c h s o l u t i o n s w e r e o b s e r v e d t o be o p t i c a l l y c l e a r and

remained indefinitely stable. Fresh s t a r c h s o l u t i o n s w e r e , h o w e v e r ,

p r e p a r e d daily t o m i n i m i s e b i o l o g i c a l degradation effects. To

avoid retrogradation, the solutions were not neutralised until

Immediately before use.

 82

3.2.6 Ha II imorid t u b e ' f Iotation ' t e s t s

Microflotatlon t e s t s w e r e c a r r i e d o u t in a m o d i f i e d Hallimond

t u b e e q u i p p e d w i t h an e x t e n d e d s t e m t o m i n i m i s e m e c h a n i c a l carryover.

A Ig s a m p l e of - 2 1 2 + 106 ym mineral w a s c o n d i t i o n e d with 2 0 0 ml

of a m i n e s o l u t i o n a t t h e r e q u i r e d pH in a 2 5 0 ml b e a k e r f o r 2 0

mins. For tests in t h e p r e s e n c e of s t a r c h , the s t a r c h w a s added

and c o n d i t i o n e d w i t h t h e mineral b e f o r e t h e a d d i t i o n of amine.

A f t e r conditioning the suspension was transferred to the

m a g n e t i c a l l y s t i r r e d H a l l i m o n d t u b e by use of an e x t e n d e d stem

funnel. F l o t a t i o n w a s c a r r i e d o u t for I min using C O ^ - f r e e nitrogen

a t a flow rate of 2 5 - 3 0 ml min Both t h e s i n k s and f l o a t s w e r e

c o l l e c t e d , d r i e d and w e i g h e d . T h i s p r o c e d u r e e n a b l e d an o v e r a l l

p a r t i c l e r e c o v e r y t o be c a l c u l a t e d ; t h i s w a s a l w a y s g r e a t e r t h a n

96$. T h e p H of t h e s u s p e n s i o n w a s m e a s u r e d both b e f o r e and after

flotation. Generally there was little or no d i f f e r e n c e between

these two values.

3.2.7 Adsorption measurements

Adsorption d e n s i t i e s w e r e d e t e r m i n e d from t h e d i f f e r e n c e in

c o n c e n t r a t i o n b e f o r e and a f t e r c o n t a c t i n g t h e m i n e r a l particles with

the reagents. T h e - 4 5 y m fraction of e a c h mineral w a s used in t h e s e

tests. T h e c o r r e s p o n d i n g s u r f a c e a r e a s , m e a s u r e d as a m e a n of

t h r e e i n d e p e n d e n t d e t e r m i n a t i o n s , a r e given in T a b l e 3.5.
T a b l e 3.5 S u r f a c e a r e a s of t h e m i n e r a l f r a c t i o n s used in a d s o r p t i o n
experi m e n t s

c 2 -I
Mi nera I S, m g

M u s c o v i te 14.5
Le p i do Ii te 3.4
Spodumene I .3
Mi c r o c Ii ne I .2
Bery I 0.8

T h e a d s o r p t i o n t e s t s w e r e c a r r i e d o u t in 100 ml Erlenmeyer

flasks. M i n i m u m r a t e s of a g i t a t i o n w e r e used s o t h a t t h e

mineral p a r t i c l e s w e r e k e p t in s u s p e n s i o n , w i t h o u t u n d u e mechanical

b r e a k d o w n and a s u b s e q u e n t i n c r e a s e of s u r f a c e a r e a of t h e powder.

tn t h e a m i n e a d s o r p t i o n t e s t s 0 . 5 g of mineral w a s conditioned

w i t h 5 0 ml of a m i n e s o l u t i o n for Ih. A similar procedure was

used t o d e t e r m i n e t h e a d s o r p t i o n of s t a r c h and d e x t r i n s except

t h a t Ig s a m p l e s w e r e u s e d . Preliminary tests established that

e q u i l i b r i u m w a s o b t a i n e d w i t h the a m i n e and s t a r c h / d e x t r i n within

10 min of c o n d i t i o n i n g . R e v e r s i b i l i t y of t h e a d s o r p t i o n was

i n v e s t i g a t e d by u s i n g d i f f e r e n t s a m p l e weights.

In t e s t s w h e r e both the a d s o r p t i o n of s t a r c h and a m i n e w a s

d e t e r m i n e d , 0 . 5 g of s o l i d in 5 0 ml of s o l u t i o n w a s u s e d . The

mineral powder was conditioned i n i t i a l l y with 40 ml of starch

solution for 2 0 min and then 10 ml of d o d e c y l a m i n e s o l u t i o n was

a d d e d a n d c o n d i t i o n i n g c o n t i n u e d for a f u r t h e r 4 0 m i n . Equilibrium

concentrations were determined after centrifuging the solids at

relatively low s p e e d .
 U n d e r c e r t a i n a m i n e and s t a r c h c o n c e n t r a t i o n s , a reaction

o c c u r r e d b e t w e e n t h e t w o r e a g e n t s and a p r e c i p i t a t e w a s formed.

Tests were conducted to determine the starch and amine concentrations

in e q u i l i b r i u m w i t h t h i s s o l i d p h a s e . To prevent centrifugation

of t h e u n r e a c t e d s t a r c h , a s p e e d of o n l y 1000 - 1200 rpm w a s

used for a t i m e of h. A t the e n d o f this p e r i o d t h e supernatant

solution was clear.

Some a d s o r p t i o n t e s t s w e r e d o n e on m e t h y l a t e d silicate

p o w d e r s t o d e t e r m i n e t h e i n f l u e n c e of h y d r o p h o b i c i t y of t h e

mineral s u r f a c e on the a d s o r p t i o n of s t a r c h . The mineral particles

w e r e m e t h y l a t e d w i t h t r i m e t h y I c h l o r o s i lane, using t h e m e t h o d of

Laskowski and Kitchener CI 15). A 0 . 0 5 M s o l u t i o n of t h e reagent

w a s m a d e up in p u r e dry b e n z e n e and t h e p a r t i c l e s c o a t e d by

m i x i n g 2 0 g of t h e mineral p o w d e r with 100 ml of s o l u t i o n for

30 min. T h e s u s p e n s i o n w a s t h e n f i l t e r e d , w a s h e d w i t h b e n z e n e and

dried u n d e r r e d u c e d p r e s s u r e in t h e p r e s e n c e of a c t i v a t e d silica

gel and p h o s p h o r u s p e n t o x i d e . Powders treated in such a m a n n e r

w e r e found t o be p e r f e c t l y h y d r o p h o b i c when s u s p e n d e d in w a t e r

and s h o w e d n o t e n d e n c y t o d i s p e r s e . However, the aggregates

d i s p e r s e d w h e n t r e a t e d with an u l t r a s o n i c probe.

3.2.8 V?ScoSity measurements

T h e v i s c o m e t r i c q u a n t i t i e s of i m p o r t a n c e f o r a d i l u t e

p o l y m e r s o l u t i o n of c o n c e n t r a t i o n , c a r e (116):

Cal T h e r e l a t i v e v i s c o s i t y , T\
" re I

n
re I = n / n C 3
o -3)
where n , n are t h e v i s c o s i t i e s of t h e s o l u t i o n and solvent
' o

respectively;

(b) the s p e c i f i c v i s c o s i t y , n S p 5

n = (n - nl i/n
l (3/4)
sp o o

Cc) t h e v i s c o s i t y n u m b e r o b t a i n e d as n s p / c , a n d

Cd) the limiting v i s c o s i t y n u m b e r , [ n j , (the intrinsic

v i s c o s i t y ) o b t a i n e d by e x t r a p o l a t i o n of h S p / c Infinite dilution,

i .e.

[n] = lim C n s / c ) (3.5)

c-» 0

A l t h o u g h t h e i n t r i n s i c v i s c o s i t y can be r e l a t e d t o t h e

v i s c o s i t y a v e r a g e m o l e c u l a r w e i g h t * , M v , by t h e Mark-Houwink

expression as

[n] = K(Mv)a (3.6)

w h e r e K and a a r e e m p i r i c a l c o n s t a n t s for a given polymer-

s o l v e n t s y s t e m , a b s o l u t e v a l u e s of M v are rarely o b t a i n e d due t o

the t e d i o u s n a t u r e of d e t e r m i n i n g K and a , p a r t i c u l a r l y for

highly polydisperse systems (116). Viscosity measurements by

t h e m s e l v e s p r o v i d e t h e m o s t c o n v e n i e n t m e t h o d of determining

relative molecular sizes.

* T h e r e a r e s e v e r a l w a y s of d e f i n i n g t h e m o l e c u l a r w e i g h t of a
p o l y d i s p e r s e s y s t e m . See for e x a m p l e ref. 117.
 The measurements reported in t h i s w o r k w e r e c a r r i e d out

in a m o d i f i e d U b b e I h o d e - t y p e v i s c o m e t e r , with a nominal constant

of 0.01 cS s '. T h e v i s c o m e t e r had a w a t e r e f f l u x t i m e of 8 3 s

a n d w a s t h e r m o s t a t t e d at 2 5 ± 0.5°C. Kinetic energy corrections

w e r e c a l c u l a t e d t o be n e g l i g i b l e by c o m p a r i s o n of d e t e r m i n e d to

known v i s c o s i t i e s for several analytically pure reagents (116).

F o r s t a r c h e s , c o n c e n t r a t i o n s of up t o 2 g litre ' in 0.05 M

NaOH were investigated. T h i s c o n c e n t r a t i o n w a s f o u n d t o be t o o

low f o r t h e d e x t r i n s for w h i c h a m a x i m u m c o n c e n t r a t i o n of 5 g

litre ' was used.

In a l l , a total of 3 e f f l u x t i m e s w e r e m e a s u r e d t o ± 0.01 s

a n d t h e m e a n of t h e m e a s u r e m e n t s taken t o be i n d i c a t i v e of t h e

flow t i m e for t h a t s o l u t i o n . The intrinsic viscosity, [ h ] , was

d e t e r m i n e d as t h e i n t e r c e p t f r o m a p l o t of C l n n r e | / c ) a g a i n s t t h e

starch concentration (c) in g ml a l t h o u g h s i m i l a r v a l u e s of

n ] c o u l d be o b t a i n e d by p l o t t i n g h S p / c a g a i n s t t h e concentration.

3.2.9 Surface tension measurements

T h e s u r f a c e t e n s i o n of t h e a q u e o u s a m i n e / s t a r c h solutions

w e r e m e a s u r e d by t h e drop v o l u m e m e t h o d ( 1 1 8 ) , u s i n g an 'AglaT

m i c r o m e t e r s y r i n g e a t t a c h e d t o a g l a s s c a p i l l a r y of o u t e r radius

0 . 3 7 6 ± 0.001 c m , as m e a s u r e d by a t r a v e l l i n g m i c r o s c o p e . The

c a p i l l a r y w a s held p e r p e n d i c u l a r l y a n d t h e drop f o r m e d on t h e

c a p i l l a r y tip c o u l d be h e l d o r r e l e a s e d as d e s i r e d by manipulating

the micrometer. T w o d r o p s of s o l u t i o n w e r e i n i t i a l l y released

and the difference in m i c r o m e t e r r e a d i n g s n o t e d . A third drop

w a s f o r m e d a t 9 0 $ of t h i s d i f f e r e n c e and held on t h e t i p of t h e

capillary f o r 2 min f o r equi Iibriurn to be e s t a b I i s h e d . Longer

 87

a g i n g t i m e s did n o t p r o d u c e any s i g n i f i c a n t d i f f e r e n c e in s u r f a c e

tension. T h e drop w a s t h e n s l o w l y d i s c h a r g e d a l l o w i n g i t , as

n e a r as p o s s i b l e , t o detach itself. T h e v o l u m e of t h e drop was

then d e d u c e d from t h e d i f f e r e n c e in t h e m i c r o m e t e r r e a d i n g s . in

all 5 such m e a s u r e m e n t s w e r e t a k e n and t h e v o l u m e c o m p u t e d as a

mean of t h e measurements.

T h e s u r f a c e t e n s i o n , y , w a s c a l c u l a t e d from t h e Harkins-Brown

equation CI 18):

y = Cmg/r)F (3.7)

where

m = w e i g h t of t h e drop ( i . e . d e n s i t y x v o l u m e )

g = gravitational acceleration

F = correction f a c t o r , d e f i n e d by v3/p

v = v o l u m e of d r o p

r = radius of capi Ilary t i p .

T h e o u t e r radius of t h e c a p i l l a r y m e a s u r e d as a b o v e a g r e e d w i t h

t h a t d e t e r m i n e d by m e a s u r i n g t h e s u r f a c e t e n s i o n s of s e v e r a l

a n a l y t i c a l l y p u r e r e a g e n t s of known y.

3.3 Analytical methods

3.3.I 'infrared-spectrometry

Infrared s p e c t r a of d o d e c y l a m i n e , p o t a t o s t a r c h , p o t a t o starch-

d o d e c y l a m i n e m i x t u r e s and p o t a t o s t a r c h - d o d e c y I a m i n e precipitates

w e r e o b t a i n e d w i t h a P e r k i n E l m e r , model 599B, double beam

spectrometer. T h e s p e c t r u m of d o d e c y l a m i n e w a s o b t a i n e d by
smearing liquid a m i n e b e t w e e n t w o NaCl discs and u s i n g a NaCl

d i s c as a r e f e r e n c e . S a m p l e s of s t a r c h and s t a r c h - a m i n e mixtures

and p r e c i p i t a t e s w e r e p r e s e n t e d t o the s p e c t r o m e t e r as Nujol

mulls. B e f o r e m a k i n g e a c h mull t h e s o l i d s w e r e d r i e d over

p h o s p h o r u s p e n t o x l d e and then g e n t l y g r o u n d In an a g a t e pestle

and m o r t a r . Nujol oil w a s then a d d e d and the g r i n d i n g continued

until t h e s o l i d s w e r e c o m p l e t e l y s u s p e n d e d In t h e o i l . The

t r a n s l u c e n t p a s t e w a s then s q u e e z e d b e t w e e n t w o NaCl windows.

T h e K B r d i s c m e t h o d of p r e p a r i n g s a m p l e s for infrared

a n a l y s i s w a s n o t used b e c a u s e it w a s found t h a t t h e a m i n e extruded

o u t of t h e d i s c s d u r i n g t h e p r e s s i n g stage.

3 . 3 . 2 ' D e t e r m i n a t i o n of ammoni a

T h e m e t h o d o u t l i n e d by Vogel (119) using N e s s l e r ' s reagent

Can a l k a l i n e s o l u t i o n of p o t a s s i u m t e t r a l o d o m e r c u r a t e ( I I)) w a s used.

When t h e r e a g e n t is a d d e d t o a d i l u t e a m m o n i u m s a l t solution,

the liberated a m m o n i a reacts t o form an o r a n g e - b r o w n product

w h i c h can be used f o r c o l o r i m e t r i c d e t e r m i n a t i o n s . A Perkin Elmer

200 double beam spectrophotometer was used.

Reagents: N e s s l e r ' s r e a g e n t , NH^CI stock solution.

A s t o c k a m m o n i u m c h l o r i d e s o l u t i o n w a s p r e p a r e d by dissolving

3.141 g of N H ^ C I , d r i e d at I00°C, In a m m o n i a - f r e e distilled water,

and d i l u t i n g t o I litre. Standard solutions were obtained by

d i l u t i n g s u i t a b l e a l i q u o t s of t h e s t o c k solution.

' Procedure: 5 ml of t h e s a m p l e s o l u t i o n w a s p i p e t t e d Into

a 5 0 ml v o l u m e t r i c flask and d i l u t e d t o n e a r - c a p a c i t y with

distilled water. I ml of N e s s l e r ' s r e a g e n t w a s a d d e d and t h e

flasks b r o u g h t t o the m a r k by a d d i t i o n of m o r e d i s t i l l e d water.

 4 8 12 16 20 24

5
NH^ concentration, M x 10

Fig 3 . 2 Calibration curve for the determination of ammonia

T h e flasks w e r e left t o s t a n d f o r a t least 15 min. b e f o r e determination

o f t h e a b s o r b a n c e at a w a v e l e n g t h of 4 2 0 n m , u s i n g a r e a g e n t b l a n k

m a d e with d i s t i l l e d w a t e r . The calibration curve obtained for the

NH^CI s t a n d a r d s o l u t i o n s is s h o w n in Fig 3 . 2 .

3.3.3 Determ? h a t i on of dodecyI ami ne

T h e c o n c e n t r a t i o n of d o d e c y l a m i n e in s o l u t i o n w a s determined

by a c o l o r i m e t r i c m e t h o d i n v o l v i n g a s u I p h o n a p h t h a l e n e indicator

and e x t r a c t i o n into c h l o r o f o r m (120).

 Reagents: Chloroform, bromocresol green and c o n c . h ^ S O ^ .

T h e i n d i c a t o r s o l u t i o n w a s p r e p a r e d by d i s s o l v i n g 0 . I g of solid

bromocresol green in 6 0 ml of a I c o h o l , a c i d i f y i n g w i t h 0.5 ml

of c o n c e n t r a t e d F ^ S O ^ and d i l u t i n g t o 100 ml with distilled

water.

' Procedure: I ml of t h e i n d i c a t o r s o l u t i o n w a s a d d e d to

5 ml of t h e s a m p l e s o l u t i o n and t h e w h o l e d i l u t e d t o 10 m l .

5 ml of c h l o r o f o r m w a s t h e n a d d e d and t h e m i x t u r e inverted

rapidly about 100 t i m e s , c a r e b e i n g t a k e n n o t t o form an e m u l s i o n .

A f t e r s e p a r a t i o n of t h e p h a s e s , t h e a b s o r b a n c e of t h e organic

layer w a s d e t e r m i n e d a t 416 n m . A calibration curve (Fig 3 . 3 )

w a s o b t a i n e d by d e t e r m i n i n g t h e a b s o r b a n c e of a m i n e solutions

of k n o w n concentrations.

3.3.4 Deterriii nation of S t a r c h , ' dextr? ns'arid'Brit? s h ' g u m

T h e m e t h o d o u t l i n e d by D u b o i s e t al (121) w a s used for t h e

a n a l y s i s of s t a r c h and r e l a t e d compounds.

Reagents: 5% w / v p h e n o l , c o n c . h ^ S O ^ .

5 g phenol w a s d i s s o l v e d in 100 ml d i s t i l l e d water.

Procedure: 2 ml of s t a r c h s o l u t i o n w a s p i p e t t e d into 2

identical 2 0 ml c a p a c i t y g l a s s v i a l s and I ml of 5% phenol added.

5 ml of c o n c e n t r a t e d F ^ S O ^ w a s then a d d e d , d i r e c t i n g t h e s t r e a m

a t t h e c e n t r e of t h e vial for a d e q u a t e m i x i n g . The vials were

a l l o w e d t o cool in a i r for 15 m i n , a f t e r w h i c h t h e y w e r e shaken

and immersed in a w a t e r bath a t room t e m p e r a t u r e f o r a further

20 min. T h e a b s o r b a n c e of t h e s o l u t i o n s w a s d e t e r m i n e d at

486 n m . C a l i b r a t i o n c u r v e s f o r p o t a t o and m a i z e s t a r c h e s , B r i t i s h

gum and t h e d e x t r i n s are s h o w n in Fig 3 . 4 . Slight differences in

 91

0.8

0.6

CD
o
c 0.4
<u
-Q
L_
o
-Q
<

0.2

1 2 3 4 5
5

Amine concentration, M x 10

Fig 3 . 3 C a l i b r a t i o n c u r v e for t h e d e t e r m i n a t i o n of dodecylamine

absorbance were observed in t h e c u r v e s . These differences

m a y h a v e been due t o small variations In t h e m o i s t u r e c o n t e n t of

the compounds.

3.3.5 ' Ana I ys i s b y atorhi c ' absbrpt? orhetry

T h e c o n c e n t r a t i o n s of t h e c a t i o n s (cf T a b l e 3 . 3 ) in s o l u t i o n

w e r e d e t e r m i n e d by a t o m i c a b s o r p t i o m e t r y using a B a i r d A l p h a I

spectrometer. S t a n d a r d s o l u t i o n s w e r e o b t a i n e d from BDH and

diluted to the recommended working range s e t o u t in t h e

instrument manual. For t h e m a j o r i t y of t h e e l e m e n t s , t h e

 0.8

0.7

0.6

0.5

(D _ .
u 0.4
c
CD
J21
L
O
U)
<
JO

0.3

0.2

0 . I

10 20 30 40 50 60

C o n c e n t r a t i o n , mg litre '

Fig 3 . 4 C a l i b r a t i o n c u r v e s for t h e d e t e r m i n a t i o n of p o t a t o
s t a r c h , d e x t r i n s , B r i t i s h g u m and m a i z e s t a r c h .

instrument was operated in t h e a b s o r p t i o n m o d e w h i l e

c o n c e n t r a t i o n s of t h e a l k a l i n e e a r t h c a t i o n s w e r e determined
by f l a m e e m i s s i o n p h o t o m e t r y . In t h e cases w h e r e ionisation

p r o b l e m s w e r e e n c o u n t e r e d , an e x c e s s of lanthanum (1000 p p m ) ,

as t h e c h l o r i d e , w a s a d d e d t o both s t a n d a r d s and t h e s a m p l e

solutions. W h e r e high c o n c e n t r a t i o n s of Si w e r e t o be

determined the standards were prepared in d i l u t e N a O H t o a v o i d

p r e c i p i t a t i o n of silica.
 CHAPTER FOUR

DISSOLUTION AND CATION EXCHANGE STUDIES

4 . I ' Dissoiutiori studies

T h e o b j e c t i v e of t h e d i s s o l u t i o n e x p e r i m e n t s w a s twofold;

t o a s s e s s t h e t i m e required f o r e q u i l i b r i u m t o be e s t a b l i s h e d

and t o d e t e r m i n e w h e t h e r o r n o t p r e f e r e n t i a l dissolution of

any of t h e lattice c a t i o n s o c c u r r e d . The latter w a s achieved

by c o m p a r i n g r a t i o s of t h e e l e m e n t a l concentrations in t h e leach

s o l u t i o n s w i t h t h o s e in t h e b u l k (35, 3 6 , 122).

The results presented in Figs 4.1 t o 4 . 3 f o r s p o d u m e n e are

typical of those obtained. F r o m t h e f i g u r e s it a p p e a r s t h a t an

' e q u i l i b r i u m ' is e s t a b l i s h e d in t h e l i t h i u m , a l u m i n i u m and silicon,

d i s s o l u t i o n a f t e r a b o u t 5 0 h of agitation.

The aluminium concentration in e q u i l i b r i u m with t h e different

s i l i c a t e s w a s at a m i n i m u m a t a pH of a p p r o x i m a t e l y 7 , and t h i s

is d e m o n s t r a t e d for l e p i d o l i t e , s p o d u m e n e , beryl and microcline

in Fig 4 . 4 . T h e s e results a r e c o n s i s t e n t with t h e e f f e c t of pH

on t h e t h e r m o d y n a m i c s o l u b i l i t y of g i b b s i t e p r e s e n t e d in s e c t i o n

2.1.3. At low pH v a l u e s , t h e p r e s e n c e of A | 3 + , m o n o and polynuclea

h y d r o l y s i s p r o d u c t s e n h a n c e s t h e s o l u b i l i t y and a t high p H , t h e

solubility i n c r e a s e s again due t o t h e f o r m a t i o n of aluminate

i ons.

It is h i g h l y u n l i k e l y , h o w e v e r , t h a t t r u e e q u i l i b r i u m was

established. C o m p a r i s o n of Fig 2 . 2 t o 4 . 4 i n d i c a t e s t h a t t h e s e

s o l u t i o n s c o n t a i n e d a t least ca 6 0 t i m e s t h e total soluble

aluminium in a s a t u r a t e d s o l u t i o n of g i b b s i t e . T h u s if g i b b s i t e

w a s a s s u m e d t o be t h e s o l i d p h a s e c o n t r o l l i n g t h e solution

c o m p o s i t i o n , t h e s e s o l u t i o n s w o u l d be s u p e r s a t u r a t e d with respect
 96

20 40 60 80 100

Dissolution time, h

Fig 4.1 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH

on t h e c o n c e n t r a t i o n of L i + in the leach s o l u t i o n
 Dissolution time, h

Fig 4 . 2 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH on

t h e c o n c e n t r a t i o n of Al in t h e leach s o l u t i o n
 Dissolution time, h

Fig 4 . 3 Spodumene: E f f e c t of d i s s o l u t i o n t i m e and pH on

t h e Si c o n c e n t r a t i o n in t h e leach s o l u t i o n
Fig 4 . 4 E f f e c t of pH on t h e a l u m i n i u m c o n c e n t r a t i o n In t h e
leach s o l u t i o n
to gibbsite. H o w e v e r , t h e v a l i d i t y of such an a s s u m p t i o n is

doubtful in t h e light of t h e c o n s i d e r a t i o n s o u t l i n e d In s e c t i o n

2.1.3. Along similar l i n e s , it is later shown (aging experiments)

t h a t the approach to true equilibrium in s u s p e n s i o n s containing

a Iuminosi 11cates n e c e s s i t a t e s t h e p r e s e n c e of a s i l i c a t e solid

p h a s e , rather than gibbsite. Hence 11ttIe q u a n t i t a t i v e significance

can be a t t a c h e d t o t h e a b o v e comparison.

It m i g h t be n o t e d , h o w e v e r , t h a t m o s t a IuminosI 11cates are

metastable states (49) in c o m p a r i s o n t o t h e i r w e a t h e r i n g residues

like g i b b s i t e o r k a o l i n i t e . In a q u e o u s s o l u t i o n s , t h e r e f o r e ,

thei r r e l a t i v e l y h i g h e r solubi lities wi I I p r o b a b l y lead t o a

saturated state with respect to gibbsite before precipitation of

the latter is i n i t i a t e d . It is a l s o p o s s i b l e t h a t t h e presence

of a d i s t u r b e d layer on t h e m i n e r a l s ' s u r f a c e c o n t r i b u t e d to

t h e high s o l u b i l i t y . Such e f f e c t s h a v e been w i d e l y reported

( 53, 54, 66).

An a l t e r n a t i v e e x p l a n a t i o n is t h a t t h e p r e s e n c e of soluble

a I u m i n o s i I i c a t e s p e c i e s In s o l u t i o n c o n t r i b u t e d t o t h e high

s o l u b i l i t y of a l u m i n i u m . Although these condensation-type reactions

a r e f e a s i b l e in p r e c i p i t a t e s , it is n o t known w h e t h e r t h e y o c c u r

in s o l u t i o n and If t h e y do w h a t form t h e y t a k e . If s o l u b l e

a Iuminosi Iicates w e r e r e s p o n s i b l e for t h e high s o l u b i l i t y of

aluminium in s o l u t i o n , it w o u l d be r e a s o n a b l e t o e x p e c t s i l i c a

t o show s i m i l a r s o l u b i l i t i e s . This explanation is t h e r e f o r e

di ffi c u 1 1 t o Justi f y .

With the exception of m u s c o v i t e , t h e s i l i c o n concentration

In e q u i l i b r i u m w i t h t h e m i n e r a l s w a s found t o be i n d e p e n d e n t of

p H a t pH v a l u e s b e l o w 9 (Fig 4 . 5 ) and w a s lower than the solubility

 PH

Fig 4.5 E f f e c t of pH on t h e Si c o n c e n t r a t i o n in t h e leach

solution

1 1 1 1 1 i 1 i 1
1 1 i

o Lepi doli te
V Spodumene

\ A Ml c r o c 1 1 n e -

\ O Muscovite

• Bery 1

I M i i i . • . i

10 12

PH

Fig 4.6 E f f e c t o f pH on t h e Al/Si m o l e ratio in t h e leach

so Iution
 102

of a m o r p h o u s s i l i c a r e p o r t e d in Fig 2 . 1 . A t high pH v a l u e s , t h e

a m o u n t of s i l i c a p a s s i n g into s o l u t i o n increased m a r k e d l y . This

w a s a t t r i b u t e d t o t h e f o r m a t i o n of t h e v a r i o u s ionic s i l i c a t e

species outlined in s e c t i o n 2.1.2.

Stober C 5 3 ) argued that even for N a O H - t r e a t e d silica,

a reversible solubility equilibrium is n e v e r a t t a i n e d due t o t h e

s l o w r e a d s o r p t i o n of s i l i c i c acid on t h e m i n e r a l . It is p o s s i b l e

that a similar effect was operative in t h e p r e s e n t w o r k . Another

reasonable explanation for the observed undersaturation is t h a t

consistent with the comments in s e c t i o n 2 . 1 . 3 , t h a t t h e solubility

limit of s i l i c a is lowered in t h e p r e s e n c e of a l u m i n i u m ions.

T h e r e s u l t s shown in Figs 4 . 4 and 4 . 5 , and s u m m a r i s e d in

T a b l e 4.1 and Fig 4 . 6 , show t h a t a l t h o u g h a l u m i n i u m and s i l i c o n

pass into s o l u t i o n , t h e y do n o t g i v e t h e s a m e m o l a r r a t i o in

s o l u t i o n as in t h e m i n e r a l .

T a b ie 4.I: Mo Ie rati o of so IubIe a Iumi n i urn and si Iicon in

equi Iibri urn with t h e si Ii c a t e m i n e r a l s

Experimental Al/Si m o l e r a t i o in
Mineral Approximate chem formula Al/Si m o l e leach s o l u t i o n
(I) r a t i o (Table pH 2 pH 5 pH 9 pH 12
3 ^ 3 )

Lepi d o l i t e KLi ( A l ( 0 H , F ) 2 AlCSi03)3) 0 . 34 1.29 0.22 0 . 23 0 . 41

Spodumene Li A1 (Si 0 3 > 2 0 . 50 1.28 0.31 0 . 36 0 . 58

Be ry 1 0 . 32 1.29 0 . 12 0 . 13 0 . 35
3 2 3 6
Muscovi te K AI3(Si04)3 0 . 87 1.33 0.73 0 . 80 1. 19

Mi c r o c 1i ne K AlSfaOg 0 . 35 1.81 0.34 0 . 33 0 . 44

It a p p e a r s t h a t p r e f e r e n t i a l di s s o l u t i on of Al o c c u r s a t low

pH. A t high pH t h e ratio in s o l u t i o n is cl o s e t o t h a t i n t h e

b u l k m i n e r a l s , a l t h o u g h m a r g i n a l l y h i g h e r d i s s o l u t i o n of Al
still t a k e s p l a c e . A t i n t e r m e d i a t e pH v a l u e s , m o r e Si t e n d s t o

dissolve although dissolution is a g a i n n e a r l y stoichiometric.

S i m i l a r o b s e r v a t i o n s h a v e been m a d e by o t h e r w o r k e r s (35, 36,

122). T h e s e r e s u l t s s u g g e s t the p o s s i b l e e f f e c t s of acid and

a l k a l i n e s c r u b b i n g of t h e s e m i n e r a l s p r i o r t o flotation.

Qualitatively, a silica-rich surface or a near-stoichiometric

s u r f a c e will be o b t a i n e d , d e p e n d i n g on t h e t y p e of scrubbing

used.

4.2 Cation exchange Studies

The cation exchange capacity (CEC) of a m i n e r a l m a y be

d e f i n e d as t h e total a m o u n t of c a t i o n s held e x c h a n g e a b l y by a

u n i t w e i g h t of the mineral (123). A l t h o u g h t h e total a m o u n t of

c a t i o n s p a s s i n g into s o l u t i o n w a s m e a s u r e d , t h e r e s u l t s obtained

did not n e c e s s a r i l y r e p r e s e n t total cation exchange capacities,

owing to difficulties associated with defining the CEC (123).

F u r t h e r , it h a s been a s s u m e d t h a t t h e e x c h a n g e p r o c e s s was

equivalent. T h i s may be r e g a r d e d as a c o n s e q u e n c e of t h e condition

of e l e c t r i c a l neutrality for t h e d o u b l e layer. The results that

were obtained are presented in T a b l e s 4.2 and 4.3.

Tab Ie '4.2: Cation e x c h a n g e c a p a c i t i e s of m u s c o v i t e and lepidolite

Muscovite Lep? doli te

2+ 2+ 2+ + 2+ 2+ „ 2 + . +
Ba Mg Ca Na Ba Mg Ca Na
+
Total yeq N H 4 6 J Q 7 6 Q > 6 g 5 6 J Q 5 - 3 6 |2.50 11.22 11.48
exchanged

yeq N H 4 + / g 55.52 47.24 39.45 32.83 2.62 11.02 8.49 8.37

Table 4.3: C a t i o n e x c h a n g e c a p a c i t i e s of s p o d u m e n e and microcline

Spodumene Microcline
2 + 2 + 2 + + 2 + 2 + 2 + +
Ba Mg Ca Na Ba Mg Ca Na

Total yeq N H 4 2 6 Q 3 Q 6 3 Q 6 4 Q 8 2 5 5 2 Q ] 2 5 5 3 5 ?

exchanged

yeq N H 4 + / g 3.18 3.51 3.18 4.14 3.12 3.19 2.69 3.67

In t h e t a b l e s t h e r e s u l t s h a v e been r e p o r t e d on t h e b a s i s of unit

m a s s r a t h e r than u n i t a r e a . The main reasons for t h i s are:

(i) t r a d i t i o n a l l y all e x c h a n g e p r o p e r t i e s a r e q u o t e d on t h e

b a s i s of u n i t w e i g h t ( 1 0 9 , 123, 124^* s o t h a t comparisons

of t h e r e s u l t s t o t h o s e o b t a i n e d with s i m i l a r minerals

can be m a d e ;

(ii) t h e p o r o s i t y of the m i n e r a l s used in t h e s t u d y w a s unknown;

t h e e f f e c t of t h i s on t h e e x c h a n g e p r o p e r t i e s c o u l d not

t h e r e f o r e be assessed;

Ciii) in t h e layer s i l i c a t e s , a l t h o u g h a small a m o u n t of e x c h a n g e

can t a k e p l a c e on t h e s h e e t s t h e m s e l v e s , it is recognised

( 1 2 4 , 1 2 5 ) t h a t the b u l k e x c h a n g e p r o c e s s t a k e s p l a c e at

t h e w e d g e - s h a p e d c r a c k s t h a t d e v e l o p on t h e e d g e s of t h e

s h e e t s , at i n t e r l a y e r p o s i t i o n s . Thus the effective

e x c h a n g e area is o n l y a small p r o p o r t i o n of t h e total

s u r f a c e area f o r t h e s e minerals.

T h e r e s u l t s o b t a i n e d f o r m u s c o v i t e and lepidolite showed

s t r o n g and m o d e r a t e cation e x c h a n g e p r o p e r t i e s , respectively.

S p o d u m e n e and m i c r o c l i n e s h o w e d o n l y w e a k e x c h a n g e b e h a v i o u r w h i l e
beryl had n o m e a s u r e a b l e e x c h a n g e properties.

T o e x p l a i n w h y t h e m i n e r a l s of T a b l e 4 . 2 s h o w e d g o o d cation

e x c h a n g e c h a r a c t e r i s t i c s , it is n e c e s s a r y t o r e m e m b e r t h a t in

s h e e t si Iicates n o n s t o i c h i o m e t r i c isomorphous substitution

of Al f o r Si in t h e t e t r a h e d r a I s i t e s o r Mg f o r Al in o c t a h e d r a l

sites produces a non-specific intrinsic space charge on t h e

s u r f a c e s of t h e s h e e t s w h i c h is n e u t r a l i s e d by i n t e r l a y e r cations

( 6 6 , 124 ). T h e i n t e r l a y e r c a t i o n s are n o t t h e m s e l v e s p a r t of

t h e s t r u c t u r e , and will c o n s e q u e n t l y h y d r a t e and be e x c h a n g e d

for o t h e r c a t i o n s as t h e y are o n l y loosely h e l d . That muscovite

showed s t r o n g e r exchange ability than lepidolite can p e r h a p s be

e x p l a i n e d f r o m t h e a l u m i n i u m c o n t e n t of t h e t w o m i n e r a l s given in

Table 3.3. F o r e a c h a l u m i n i u m a t o m in a t e t r a h e d r a I site one

negative charge results. As c a t i o n e x c h a n g e b e h a v i o u r will be

p a r t l y d e p e n d e n t on interlayer change density ( 1 2 3 ) , it is n o t ,

therefore, surprising that cation exchange activity increases with

i n c r e a s i n g AI c o n c e n t r a t i o n (126, 127).

T h e s e l e c t i v i t y of an e x c h a n g e r is a m e a s u r e of its relative

affinity for ions. For t h e c a t i o n s u s e d , m u s c o v i t e s h o w e d the

affinity sequence B a 2+ > M g 2 + > Ca2+ > Na+. Barshad (109)

reported a s i m i l a r o r d e r for m u s c o v i t e , a l t h o u g h a d i f f e r e n t o r d e r

w a s o b t a i n e d on v e r m i c u l i t e . In t h e c a s e of lepidolite the
2+ 2+ + 2+
s e l e c t i v i t y s e q u e n c e w a s Mg > Ca > Na > Ba The quantities

exchanged in t h e c a s e of m i c r o c l i n e and s p o d u m e n e w e r e considered

t o be t o o small t o be s i g n i f i c a n t . E x a m i n a t i o n of t h e sequences

for t h e s h e e t m i n e r a l s s h o w s t h a t d i v a l e n t c a t i o n s w e r e preferred

to sodium at the same molarity (124). Further, the exchange

s e q u e n c e of lepidolite f o r t h e d i v a l e n t c a t i o n s w a s t h e r e v e r s e of
 2+
that observed for m u s c o v i t e , if i+ is a s s u m e d t h a t Mg occupied

an a n o m o l o u s p o s i t i o n in t h e m u s c o v i t e sequence.

T h e b a s i s for t h e a f f i n i t i e s of v a r i o u s c a t i o n s for p a r t i c u l a r

e x c h a n g e s u b s t r a t e s h a s n o t been u n e q u i v o c a l Iy e s t a b I i s h e d . For

t h e s i m p l e o x i d e s , f o r e x a m p l e , t h e r e is a p p a r e n t l y little

consistency in t h e s e l e c t i v i t y s e q u e n c e , even for s i m i l a r materials

C|24)• Originally, selectivity was discussed in t e r m s of

crystaIlographic radii and t h e a b i l i t y of p a r t i c u l a r c a t i o n s to

fit into h o l e s p o s t u l a t e d as e x i s t i n g in t h e h e x a g o n a l oxygen

lattice ( 1 0 9 ) , |n m o r e r e c e n t w o r k , h o w e v e r , t h e significance

of c a t i o n h y d r a t i o n h a s b e e n n o t e d , a l t h o u g h n o t unambiguously.

T h u s S h a i n b e r g and K e m p e r (101) h a v e s h o w n t h a t a m o n g t h e alkaline

metal c a t i o n s , t h o s e t h a t a r e least h y d r a t e d , and w i t h probably

+ +

incomplete primary hydration shells ( e . g . Cs and Rb ) will tend

t o be m o r e s p e c i f i c a l l y a d s o r b e d . Several other workers ( |24,

127, 128) h a v e c o n s i d e r e d t h e a s s u m p t i o n t h a t e x c h a n g e equilibria

are d o m i n a t e d by (a) c o u l o m b i c i n t e r a c t i o n s b e t w e e n t h e counter

ions (in v a r i o u s s t a t e s of h y d r a t i o n ) and t h e s u b s t r a t e exchange

g r o u p s , and (b) t h e i o n - d i p o l e and ion induced d i p o l e interactions

b e t w e e n t h e c o u n t e r ions and w a t e r m o l e c u l e s (ionic hydration).

Thus the 'normal' affinity sequence ( H o f m e i s t e r s e r i e s ) of

+ + + + 2 + 2 + 2 + 2 +
Cs > K > Na > Li o r Ba > Sr > Ca > Mg for a l k a l i n e

e a r t h c a t i o n s , has been e x p l a i n e d by a s s u m i n g t h a t t h e cations

a d s o r b p r i m a r i l y by c o u l o m b i c i n t e r a c t i o n , r e t a i n i n g t h e i r primary

hydration sheath. T h e ion with t h e s m a l l e s t h y d r a t e d radius will

t h e r e f o r e be held m o s t s t r o n g l y ( 1 0 1 , 124, 127). Other hypotheses

h a v e been p r o p o s e d in o r d e r to e x p l a i n t h e r e v e r s e s e q u e n c e . One

plausible interpretation has been t h a t t h e o r d e r e d w a t e r m o l e c u l e s

 107

c l o s e t o t h e s u r f a c e f a v o u r a d s o r p t i o n of ions t h a t can maintain

this order CI24). These constitute ions t h a t are relatively

m o r e h y d r a t e d , and show g r e a t e r s p e c i f i c a d s o r p t i o n . The reverse

sequence is t h u s a s s o c i a t e d w i t h s t r u c t u r e - p r o m o t i n g surfaces,

w h i l e t h e normal s e q u e n c e is s h o w n by structure-breaking

surfaces C|24). T h e a b i l i t y of a s u r f a c e t o o r d e r interfacial

water molecules is o b v i o u s l y r e l a t e d t o t h e p o l a r i t y and field

strength of the solid (Fig 5 . 1 1 ) . S i n c e t h e field s t r e n g t h decreases

w i t h t h e i n c r e a s e of Al c o n t e n t ( 1 2 7 ) , lepidolite m i g h t be e x p e c t e d

to show t h e r e v e r s e s e q u e n c e t o m u s c o v i t e as w a s f o u n d . The
2+

a n o m o l o u s p o s i t i o n of Mg in t h e m u s c o v i t e s e q u e n c e m i g h t be

r e l a t e d t o its p r e s e n c e as an i n t e r layer cation in t h i s

mineral (see T a b l e 3.3).

A l t h o u g h t h e s e c o n s i d e r a t i o n s are n o t u n r e a s o n a b l e , t h e y do

n o t e x p l a i n w h y beryl s h o w e d n o c a t i o n e x c h a n g e activity.

M e a s u r e m e n t of t h e c a t i o n s p a s s i n g into s o l u t i o n indicated that

t h e p r o c e s s o c c u r r e d p r e d o m i n a n t l y t h r o u g h t h e r e l e a s e of m o n o -

valent cations. This might s u g g e s t that the poor cation

adsorption r e s p o n s e f o r beryl w a s " r e l a t e d t o the a b s e n c e of t h e

generally weakly held monovalent cations. in a q u e o u s solutions

t h e s e c a t i o n s h a v e been w i d e l y r e p o r t e d to be e a s i l y exchangeable

( 2 3 , 66 , 74 ). T h e b e r y l l i u m c a t i o n , on t h e o t h e r h a n d , w o u l d

be m o r e t i g h t l y held b e c a u s e of its high p o l a r i s i n g p o w e r . This

conclusion is c o l l a b o r a t e d by t h e r e s u l t s r e p o r t e d in later

s e c t i o n s on t h e a d s o r p t i o n of a m i n e a t low c o n c e n t r a t i o n s and

acid/base titrations.
 C H A P T E R F I V E

E L E C T R O K I N E T I C S T U D I E S
5.1 General considerations

When an e l e c t r i c p o t e n t i a l is a p p l i e d t o an a q u e o u s

mineral s u s p e n s i o n , the p a r t i c l e s m i g r a t e t o t h e o p p o s i t e l y

c h a r g e d e l e c t r o d e , t a k i n g with t h e m p a r t of t h e d o u b l e layer

e n c l o s e d b e t w e e n t h e s o l i d s u r f a c e and a zone of s h e a r situated

j u s t o u t s i d e t h e Stern p l a n e . T h e potential at this shear plane,

known as t h e zeta p o t e n t i a l ( ? ) , Is t h e only p o t e n t i a l t h a t can

be m e a s u r e d by e I e c t r o k l n e t i c m e t h o d s . The v a l u e of t h e zeta

potential can be o b t a i n e d from e I e c t r o p h o r e t l c m o b i l i t y (EM)

m e a s u r e m e n t s by a p p l i c a t i o n of t h e He I m h o l t z - S m o l u c h o w s k i

equati o n :

v = EM = (5.1)
E 4nn

w h e r e v Is t h e v e l o c i t y of t h e p a r t i c l e u n d e r t h e i n f l u e n c e of

an e l e c t r i c field E , in a s o l u t i o n of p e r m i t i v i t y e a n d viscosity

n. For a q u e o u s s o l u t i o n s a t 25°C, t h e form

C(rnv) = 12.83 x EM ( y m / s e c / v / c m ) (5.2)

Is o f t e n used ( 6 7 , 110 ) .

In m o s t c a s e s , e q u a t i o n (5.1) m u s t be m o d i f i e d t o a l l o w for

r e t a r d a t i o n , r e l a x a t i o n and v i s c o e l e c t r l c e f f e c t s . It h a s a l s o

been s h o w n ( 6 7 ) t h a t t h e He I m h o I t z - S m o l u c h o w s k i equation Is o n e

of t w o limiting forms of t h e H e n r y ' s equation

v =-Ee£ (I + X f (i<a)) (5.3)

6irn
w h e r e X = t e r m t o a l l o w for e l e c t r i c a l c o n d u c t i v i t y of particles,

a = r a d i u s of c u r v a t u r e of particle.

F o r large < a , e q u a t i o n (5.1) is a p p l i c a b l e , w h e r e a s f o r small

ica t h e Huckel e q u a t i o n m a y be used (67 )

_v = eg (5.4)
E 6 7TT1

Although Henry's equation i n c l u d e s a r e t a r d a t i o n e f f e c t it

does n o t i n c l u d e a r e l a x a t i o n e f f e c t ( 6 7 , 129 ). A large n u m b e r

of w o r k e r s ( 1 3 0 , 131) h a v e p r o p o s e d m o d i f i c a t i o n s t o e q u a t i o n

(5.3) in w h i c h t h e s e e f f e c t s a r e c o n s i d e r e d . A further possibility

t h a t e and n , w h i c h are a s s u m e d c o n s t a n t in m o s t d e r i v a t i o n s , may

be i n f l u e n c e d by locally high e l e c t r i c f i e l d s h a s been assessed

(132, 133). H u n t e r (133) c o n c l u d e d t h a t u n d e r m o s t conditions

t h e c o m b i n e d e f f e c t s of e and n are s m a l l . However, exact

c o r r e c t i o n s a r e n o t p o s s i b l e until t h e e x a c t m a n n e r in w h i c h

n and e d e p e n d on E is k n o w n .

F u r t h e r d i f f i c u l t i e s a r i s e from t h e u n c e r t a i n n a t u r e of

the location of t h e s l i p p i n g p l a n e (and how m u c h s o l v e n t is

entrapped within it) and d i s c r e t e n e s s of c h a r g e e f f e c t s (132).

In view of t h e s e d i f f i c u l t i e s , t h e c o n v e r s i o n of E M v a l u e s t o

g potentials was not considered necessary in t h e p r e s e n t w o r k .

5.2 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of the s i l i c a t e

mi n e r a I s

Due t o t h e i m p o r t a n c e of pH in t h e c h a r g e generation

m e c h a n i s m for s i l i c a t e s , e l e c t r o k i n e t i c p r o p e r t i e s w e r e measured

as a f u n c t i o n of pH.
 The e f f e c t of pH on the E M o f the m i n e r a l s is s u m m a r i s e d

in F i g s 5.1 and 5 . 2 . The IEP (zero e l e c t r o p h o r e t i c m o b i l i t y ) of

m u s c o v i t e , s p o d u m e n e and beryl o c c u r r e d a t pH v a l u e s of 5.7,

2 . 8 and 3 r e s p e c t i v e l y . M i c r o c l i n e and lepidolite w e r e still

n e g a t i v e l y c h a r g e d a t a pH of 2 . 7 . The mobiI ity-pH c u r v e s for

l e p i d o l i t e , s p o d u m e n e , beryl and m i c r o c l i n e w e r e v e r y similar

to one another. This p r o b a b l y h e l p s to e x p l a i n t h e p r o b l e m s o f

selectivity that are encountered in t h e f l o t a t i o n of t h e s e

minerals. Further, the mobilities showed a marked dependence

on p H , e x c e p t p e r h a p s a t high pH v a l u e s . These results are

si mi lar t o t h o s e o b t a i n e d for q u a r t z and o t h e r si Iicates (134,

I 3 5 ) and s u g g e s t t h a t H + and OH ions a r e p o t e n t i a l determining.

Fig 5 . 3 s h o w s t h e e f f e c t of NaCI c o n c e n t r a t i o n on t h e mobi lity

of s p o d u m e n e a t pH 9 . Si mi lar c u r v e s t o t h i s w e r e o b t a i n e d for

t h e o t h e r si licate m i n e r a l s . It is a p p a r e n t t h a t NaCI a c t s as

an i n d i f f e r e n t e l e c t r o l y t e for s p o d u m e n e and t h e o t h e r silicates.

T h u s t h e reduction in E M a t high ionic strengths is d u e t o

c o m p r e s s i o n of t h e d o u b l e layer. Li+ , although p r e s e n t as a

lattice cation in s p o d u m e n e and lepidolite, gave similar results

+

t o t h o s e o b t a i n e d with Na . This indicated t h a t it did n o t h a v e

a potential determining role on t h e m i n e r a l s . This is illustrated

in F i g s 5 . 4 and 5.5.

The IEP v a l u e s of s p o d u m e n e and beryl c o m p a r e favourably

w i t h t h o s e found by o t h e r w o r k e r s ( 73 , 74 ). Reported IEP

v a l u e s for m i c r o c l i n e a r e a t v e r y acid pH v a l u e s (approximately

1.7) ( 7 3 ) , and this is c o n s i s t e n t with t h e n e g a t i v e mobilities

obtained in t h e pH range 2 . 7 t o 11.4 in the p r e s e n t w o r k . In t h e

 i 1 1 1 1 r

• Muscovite
+4
O Lepidolite

+2

1 1 1 r

Fig 5.1 E f f e c t of pH on t h e e l e c t r o p h o r e t i c m o b i l i t y of
m u s c o v i t e , lepidolite and a m b l y g o n i t e in 10 M NaCl

+4 h
O Spodumene
o • Be ry I
>
[j Mi c r o c I i ne
\
M
+2
p-
+-

I 0
o
0
pH

LU i = f i -

-4

j L

Fig 5.2 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of spodumene,

beryl and m i c r o c l i n e in lO^-^M NaCl
 I 13

Fig 5 . 3 E f f e c t of NaCl c o n c e n t r a t i o n on t h e eIectrophoretic

m o b i l i t y of s p o d u m e n e a t pH 9

c a s e of t h e s h e e t s i l i c a t e s , m u s c o v i t e and l e p i d o l i t e , such

c o m p a r i s o n s a r e often not m e a n i n g f u l b e c a u s e of t h e pronounced

isomorphic substitutions in both the t e t r a h e d r a l and octahedral

positions. It h a s been shown in C h a p t e r 4 t h a t t h e main effect

of t h i s is to p r o d u c e a c a t i o n e x c h a n g e a f f i n i t y . For these

minerals the IEP will t h e r e f o r e be d e p e n d e n t on t h e t y p e of

inter layer c a t i o n s p r e s e n t and t h e c a t i o n e x c h a n g e capacity

(66 ). These considerations probably also apply to the non-sheet

a Iuminosi Iicate s t r u c t u r e s t o a lesser degree.

T h e i n t e r p r e t a t i o n of IEP v a l u e s for a Iuminosi Iicates is

f u r t h e r c o m p l i c a t e d by p r o b l e m s of n o n - s t o i c h i o m e t r i c dissolution

a n d e f f e c t of c l e a v a g e (66 ). A p a r t from d e t e r m i n i n g t h e e x t e n t

of cation e x c h a n g e a c t i v i t y , t h e t y p e of s u b s t i t u t i n g cation

a l s o d e t e r m i n e s t h e d e g r e e of a c i d i t y o r b a s i c i t y of t h e lattice

site ( 6 8 ) and its s u b s e q u e n t d e g r e e of ionisation in a g i v e n

 I 14

1 1 1 1
1 1
1

+4
0 in 10 NaCI
e
O
> • in I0"3 LiCI

^ +2
e

-h
0
E
-Q
1 1 1 | i i -
o 10 pH
"cfl 4 6 8
e
O

-
£ -2
O
_c
CL
o
o
® -4
LU

. 1 1 1 1 — •

Fig 5.4 E f f e c t of LiCI on t h e e lectrophoreti c m o b i l i t y of

lepi do Iite

Fig 5.5 E f f e c t of LiCI on the e l e c t r o p h o r e t i c m o b i l i t y of

spodumene
 I 13

aqueous environment (cf s e c t i o n 5 . 3 ) ( 1 2 4 ) . On t h e o t h e r hand,

the location of t h e c a t i o n r e l a t e s t o c l e a v a g e and t h e degree

of e x p o s u r e of t h e c a t i o n t o t h e s o l u t i o n e n v i r o n m e n t . Although

t h e t e n d e n c y of c l e a v a g e t o c o n t r o l cation exposure is p r o b a b l y

n o t lost d u r i n g t h e g r i n d i n g of m i n e r a l s , t h e s u r f a c e of t h e

p r o d u c t s will u n f o r t u n a t e l y be u n l i k e l y t o a s s u m e a s i m i l a r

cation d i s t r i b u t i o n b e c a u s e of t h e d i s o r d e r e d n a t u r e of such a

surface ( 66). T h e e f f e c t of c l e a v a g e and t h e c o m p o s i t e nature

of t h e s i l i c a t e m i n e r a l s in w h i c h both a c i d i c and b a s i c o x i d e s

a r e p r e s e n t , will lead t o n o n - s t o i c h i o m e t r i c d i s s o l u t i o n and

t h e p o s s i b i l i t y of r e a d s o r p t i o n o f t h e h y d r o l y s i s p r o d u c t s on

t h e mineral surfaces.

It is a little s u r p r i s i n g t h a t t h e EM of t h e s h e e t m i n e r a l s

w a s s t r o n g l y d e p e n d e n t on p H . It is g e n e r a l l y a s s u m e d ( 2 3 , 66 )

that the cleavage planes in t h e s e m i n e r a l s are of constant

c h a r g e and t h e s e s u r f a c e s p r e d o m i n a t e . In t h e c a s e of muscovite

it m i g h t be a r g u e d (cf T a b l e 3 . 3 ) t h a t some r e a d s o r p t i o n of iron

hydrolysis species took place under slightly acidic conditions.

Such a m e c h a n i s m c a n n o t be a p p l i e d to lepidolite b e c a u s e it

c o n t a i n e d much f e w e r p o l y v a l e n t c a t i o n s . It w o u l d t h e r e f o r e appear

t h a t e i t h e r t h e s u r f a c e of t h e lepidolite sheets contained a

c o n s i d e r a b l e n u m b e r of i o n i s a b l e g r o u p s o r t h a t t h e small

p r o p o r t i o n of e d g e s i t e s e x e r t e d a s i g n i f i c a n t l y large influence

on t h e total a m o u n t of s u r f a c e c h a r g e . A pH-dependent surface

c h a r g e h a s been o b s e r v e d on t a l c ( 2 3 ) and s t r o n g l y hydrophobic

si Iica (115).
 I 16

5.3 E f f e c t of aci d arid a I ka I i ne w a s h i n g on t h e e 1 e c t r o p h o r e t i c

mobi I it Fes of the si i icate miriera I s

T a b l e 4.1 s h o w e d t h a t a t pH 2 n o n - s t o i c h i o m e t r i c dissolution

of l e p i d o l i t e , s p o d u m e n e , b e r y l , m u s c o v i t e and microcline

p r o d u c e d AI/Si ratios in t h e leach s o l u t i o n t h a t w e r e higher

than in t h e s o l i d s . A t pH 12, t h e r e w a s a t e n d e n c y for t h e

s o l u b l e Al/Si r a t i o t o a p p r o x i m a t e t o t h a t in t h e s o l i d s e x c e p t

for p e r h a p s m u s c o v i t e . To determine whether or not the dissolution

of t h e s i l i c a t e lattice a f f e c t e d t h e e l e c t r i c a l double layer a t

t h e si I i c a t e / w a t e r i n t e r f a c e , e l e c t r o p h o r e t i c m o b i l i t y measurements

w e r e c o n d u c t e d on s a m p l e s w h i c h had been w a s h e d in IM HCI and IM

N a O H for 16 h . A n a l y s i s of t h e w a s h liquors p r o d u c e d t h e results

summarised in T a b l e 5 . 1 . T h e m o b i l i t y c u r v e s of t h e HCI and NaOH

w a s h e d m i n e r a l s are shown in F i g s 5.6 t o 5 . 1 0 , inclusively.

T a b l e 5.1 E f f e c t of w a s h i n g t h e s i l i c a t e m i n e r a l s in IM HCI
a n d IM N a O H on the m o l a r r a t i o , A l / S i , in s o l u t i o n

M o l e r a t i o , A l / S i , in s o l u t i o n Mole ratio, Al/Si,

Mineral ft . , n . , " n mineral
Acidic wash Basic wash

Muscovite 4.25 I.01 0.87

Lepidolite 1.51 0.66 0.34

Spodumene 1.97 0.63 0.60

Beryl 1.22 0.36 0.32

Microcline 1.66 0.40 0.35

Fig 5.6 T h e e f f e c t of a c i d and a l k a l i n e w a s h i n g on t h e
e l e c t r o p h o r e t i c m o b i l i t y of m u s c o v i t e In ICF M N a C l .
(The d a s h e d lines a r e redrawn from Fig 5.1 a n d Fig 5 . 2 )

Fig 5 . 7 T h e e f f e c t of a c i d and a l k a l i n e w a s h i n g on the

e l e c t r o p h o r e t i c m o b i l i t y of lepidolite in 1 0 " % NaCl
Fig 5 . 8 E f f e c t of acid and a l k a l i n e w a s h i n g on t h e electrophoretic
m o b i l i t y of s p o d u m e n e in 10 M NaCl

Fig 5.9 T h e e f f e c t of acid and a l k a l i n e w a s h i n g on t h e electrophoreti

m o b i l i t y of beryl in I 0 " 3 M NaCl
 I 16

Fig 5 . 1 0 E f f e c t of a c i d and a l k a l i n e w a s h i n g on the electrophoretic

m o b i l i t y of m i c r o c l i n e in 10 M NaCI

C o m p a r i s o n of T a b l e s 4.1 and 5.1 s h o w s t h a t a l t h o u g h the

s a m e AI/Si ratios w e r e n o t o b t a i n e d in t h e t w o c a s e s because

of t h e d i f f e r e n t c o n d i t i o n s u s e d , t h e c o n c l u s i o n s a r e similar.

W a s h i n g m u s c o v i t e , l e p i d o l i t e and m i c r o c l i n e with a c i d (Figs

5 . 6 , 5 . 7 and 5 . 1 0 r e s p e c t i v e l y ) p r o d u c e d a s h i f t in t h e

e l e c t r o p h o r e t i c m o b i l i t y V s pH c u r v e t o m o r e n e g a t i v e mobility

values. The shift was l a r g e s t for m u s c o v i t e , w h i c h also

exhibited the greatest dissolution e f f e c t . T h e EM of spodumene

and beryl (Figs 5 . 8 and 5 . 9 ) w a s u n a f f e c t e d by w a s h i n g the

minerals in a c i d s o l u t i o n s . T h i s is s u r p r i s i n g in view of t h e

s u r p l u s of a l u m i n i u m leached into s o l u t i o n . W o r k by o t h e r

authors ( 1 7 , 35 , 3 6 , 122 ) h a s s h o w n t h a t AI is preferentially

leached from s i l i c a t e m i n e r a l s in a c i d i c s o l u t i o n s . It a p p e a r s

h o w e v e r , that acidic scrubbing does not necessarily produce a

silica-rich surface. In view of t h e high Al c o n c e n t r a t i o n in

the leach s o l u t i o n , it w o u l d s e e m t h a t t h e d i s t u r b e d silicate

s u r f a c e m u s t c o n t a i n a s o m e w h a t h i g h e r AI c o n c e n t r a t i o n than

t h e b u I k mi n e r a I .

T a b l e 5.1 f u r t h e r s h o w s t h a t w a s h i n g t h e s i l i c a t e minerals

in alkali p r o d u c e d n e a r l y s t o i c h i o m e t r i c s o l u b l e Al/Si ratios

e x c e p t for m u s c o v i t e and l e p i d o l i t e , w h e r e a s l i g h t e x c e s s of

Al d i s s o l u t i o n t o o k p l a c e . In line with t h i s , t h e s h i f t t o

negative mobilities in t h e EM-pH c u r v e s of N a O H w a s h e d

muscovite, lepidolite and m i c r o c l i n e w a s much less than that

obtained for the acid w a s h e d s a m p l e s of t h e s e m i n e r a l s . In the

c a s e of s p o d u m e n e a n d b e r y l , h o w e v e r , r e l a t i v e l y m o r e positive

m o b i l i t i e s , than t h o s e of t h e u n l e a c h e d s a m p l e s , w e r e obtained

after NaOH s c r u b b i n g . It a p p e a r s t h e r e f o r e t h a t N a O H scrubbing

did n o t n e c e s s a r i l y p r o d u c e a s u r f a c e with a c o m p o s i t i o n simila

t o t h a t of t h e b u I k .

It can be c o n c l u d e d from t h e d i s c u s s i o n of t h e r e s u l t s in

t h i s and p r e c e d i n g c h a p t e r s t h a t a s y s t e m a t i c m e t h o d of

i n t e r p r e t i n g t h e b e h a v i o u r of a l u m i n o s i Iicates in a q u e o u s

s o l u t i o n d o e s n o t e x i s t due t o t h e i r c o m p l e x n a t u r e . A helpful

g u i d e m i g h t be s o m e p r o p e r t y , c l o s e l y r e l a t e d t o t h e e l e c t r o -

n e g a t i v i t y of t h e lattice ions (and t h e r e f o r e lattice s i t e

b e h a v i o u r ) , such as t h e ionic p o t e n t i a l , IP ( 1 3 6 ) . The IP m a y

be d e f i n e d n u m e r i c a l l y a s t h e ratio of t h e c h a r g e (z) t o t h e

i o n i c radius (r). Fig 5.11 s h o w s a g r o u p i n g of s o m e e l e m e n t s

 2.0-
(Q)
"(b) aquo cations
^ -Cs(66)
\
3
X ' R b ( 8 M
T V
K(S4) •Ba /
/

o<
.Sr (79)
pronounced
,0" "-Ca (79) h y d r o Iysi s
•Na(# v
in
zj
.Fe(72)^ "n • Zr( 67)
"O
(D •Mg(74) V . F e ( 5 1 ) -Ti
•Li(79) X
7lr ^
° 0.5
-Al( 63)
- ""'Si( 4 0 )
• B^ (50J — — """ X X 'p
- —" ^
/
sol ub le a n i o n s 'C X
j i « i i i i

I 2 3 4 5
Ionic c h a r g e

Fig 5.I I G r o u p i n g of e l e m e n t s a c c o r d i n g to t h e i r ionic

p o t e n t i a l s . F i g u r e s in b r a c k e t s are % i o n i c
bond, (a) and (b) d e n o t e d i r e c t i o n of i n c r e a s e
of a c i d i t y and i o n i c i t y , r e s p e c t i v e l y .

a c c o r d i n g t o t h e i r ionic p o t e n t i a l s . The information contained

in t h e f i g u r e can be used t o q u a l i t a t i v e l y e x p l a i n s o m e of the

e f f e c t s t h a t h a v e been o b s e r v e d in t h e p r e s e n t a n d o t h e r authors'

work. Such i n f o r m a t i o n h a s , for e x a m p l e , been used t o e x p l a i n

t h e b e h a v i o u r of s i l i c a t e m i n e r a l s in w e a t h e r i n g experiments

(137). T h e ions h a v e been a r r a n g e d into t h r e e g r o u p s : (a) t h o s e

with low IP (Z/r < 3 . 0 ) , such as N a + , K + , C a 2 + and M g 2 + , which

a r e w e a k l y held by p r e d o m i n a n t l y ionic b o n d i n g and a r e usually

o b s e r v e d t o r e a d i l y p a s s into s o l u t i o n (23 , 44 , 6 6 (b) t h o s e

with intermediate IP (3.0 < Z / r < 9 . 5 ) such as A l 3 + , F e 3 + and

 +
Be w i t h a high t e n d e n c y t o h y d r o l y s e and p r e c i p i t a t e due t o

their low s o l u b i l i t i e s and (c) t h o s e with high IP (Z/r > 9 . 5 ) s u c h

4+

as Si , w h i c h form a n i o n i c r a d i c a l s in s o l u t i o n .

On t h i s b a s i s , for e x a m p l e , t h e p o o r cation exchange

r e s p o n s e of beryl is c o n s i s t e n t w i t h t h e a b s e n c e of t h e m o b i l e

c a t i o n s of g r o u p (a) in t h e m i n e r a l , as e a r l i e r e x p l a i n e d . As

a c o r o l l a r y , t h o s e a Iuminsi Iicates in which such c a t i o n s are

p r e s e n t can be e x p e c t e d to show a finite e x c h a n g e a f f i n i t y . It

can a l s o be inferred from t h e d i r e c t i o n of t h e d e c r e a s e of

ionicity t h a t t h e S i - 0 bond is t h e s t r o n g e s t in a Iuminosi Iicates

(73 f 74 , 1 3 8 ) . T h i s is r e f l e c t e d in the f a c t t h a t cleavage

planes in s i l i c a t e m i n e r a l s run parallel to t h e S i - 0 groupings.

Q u a r t z , with no t e t r a h e d r a l s u b s t i t u t i o n by A l , has n o p r o n o u n c e d

cleavage (I ). M i c r o c l i n e , a n o t h e r f r a m e w o r k m i n e r a l , has g o o d

c l e a v a g e due t o t h e f a c t t h a t AI g o e s o n l y into c e r t a i n tetrahedral

positions to avoid 'overbonding' the oxygens ( 7 ). As t h e

substitution of AI for Si i n c r e a s e s the t e t r a h e d r a l bond

distance, T - 0 , increases (138) and the bond s t r e n g t h decreases.

In the p o l y m e r i s e d t e t r a h e d r a l s t r u c t u r e s of a Iuminosi I i c a t e s ,

t h e Al-O-Si bond therefore forms the weakest linkage. In

s p o d u m e n e and b e r y l , t h e r e is no such s u b s t i t u t i o n so that the

polymerised tetrahedra are relatively stable towards degradative

acidic l e a c h i n g , t h e Si-O-Si bond probably limiting accessibility

t o w e a k e r ionic b o n d s , p a r t i c u l a r l y in m i n e r a l s with p o o r c l e a v a g e

like b e r y l . For the minerals in w h i c h Al-O-Si bonds were present

(i.e. m u s c o v i t e , l e p i d o l i t e and m i c r o c l i n e ) d e g r a d a t i v e leaching

p r o b a b l y c o n t r i b u t e d t o the n e g a t i v e s h i f t in t h e E M - p H curve

during a c i d i c w a s h i n g . Loughnan (137) r e p o r t e d a s i m i l a r

 123

observation in t h e w e a t h e r i n g of f e l d s p a r m i n e r a l s . From the

r e l a t i v e s t r e n g t h s of the A I - 0 and S i - 0 b o n d s , it m i g h t be

s p e c u l a t e d t h a t It Is p o s s i b l e to c r e a t e a s o m e w h a t higher

c o n c e n t r a t i o n of AI on t h e s u r f a c e of t h e m i n e r a l during grinding.

T h e d i r e c t i o n of i n c r e a s e of t h e a c i d i t y of t h e c a t i o n s is

a l s o shown in Fig 5 . 1 1 . T h e p r e s e n c e of d i f f e r e n t c a t i o n s imparts

d i f f e r e n t d e g r e e s of s u r f a c e a c i d i t y / b a s i c i t y to the minerals.

Acidic lattice s i t e s will be u n s t a b l e in b a s i c m e d i a w h i l e b a s i c

s i t e s will be leached in a c i d i c m e d i a , a s long as t h e r e is no

structural h i n d e r a n c e of a c c e s s i b i l i t y t o t h e s i t e s .

T a b l e s 5.2 and 5 . 3 show a m o r e d e t a i l e d a n a l y s i s of t h e w a s h

solutions and of the leached r e s i d u e . It is c l e a r . f r o m these

r e s u l t s t h a t for t h e alkali w a s h , t h e b a s i c c a t i o n s , n o t a b l y Fe,

t e n d e d to be c o n s e r v e d In t h e m i n e r a l , b u t w e r e substantially

lost d u r i n g acid w a s h i n g . For t h e m i n e r a l s with a reasonable

c o n c e n t r a t i o n of t h e s e c a t i o n s , t h e e I e c t r o p h o r e t i c mobilities

were relatively positive following scrubbing in N a O H , b u t n o t for

lepidolite and m i c r o c l i n e w h i c h both c o n t a i n e d s i g n i f i c a n t l y less

basic c a t i o n s .

T h e e f f e c t of c l e a v a g e Is a l s o a p p a r e n t from t h e tables.

B e r y l , with imperfect cleavage lost t h e lowest a m o u n t of available

Fe d u r i n g a c i d i c w a s h i n g , c o m p a r e d t o say m u s c o v i t e . Under the

same conditions, muscovite and l e p i d o l i t e had g r e a t l y similar

electrophoretic mobilities (Figs 5 . 6 and 5 . 7 ) c o n f i r m i n g the

observation (|39) t h a t t h e t w o m i n e r a l s d i f f e r e d m a i n l y in t h e

s t r u c t u r e and c o m p o s i t i o n of t h e o c t a h e d r a l layer.
Table 5.2 E f f e c t of a c i d a n d a l k a l i n e w a s h i n g on t h e f r a c t i o n
(of total s a m p l e c o n t e n t ) of Fe and Mn d i s s o l v e d

% c a t i o n in leach s o l u t i o n on
b a s i s of m i n e r a l c o m p o s i t i o n
(see T a b l e 3 . 3 )
A c i d i c wash Basic wash
Mi nera1 Fe Mn Fe Mn

M u s c o v i te 2 3 . 12 21 .71 0.19 0.46

Lepido 1ite 8. 1 1 10. 18 1 .54 0.29
Spodumene 7.07 - 1 .33 -

Beryl 3.09 - 0.73 -

Mi crocli ne 7.6 -
2.16 -

Table 5.3 E f f e c t of a c i d and a l k a l i n e w a s h i n g on t h e m o l a r ratio,

A I / S i , in the s o l i d r e s i d u e

M o l a r r a t i o , A l / S i , in solid residue
MlneraI A c i d i c wash Basic wash In mineral

Muscovi te 0.75 0.85 0.87

Lepi do Iite 0.33 0.33 0.34
Spodumene 0.47 0.54 0.50
Beryl 0.34 0.33 0.32
Mi crocli ne 0.37 0.36 0.35
 In s u m m a r y , it m a y be c o n c l u d e d t h a t for a Iuminosi I i c a t e s ,

if t h e p o l y m e r i s e d t e t r a h e d r a do n o t c o n t a i n AI a t o m s , t h e

m i n e r a l s will be r e l a t i v e l y s t a b l e t o a c i d i c e x p o s u r e ; m o r e so

if t h e m i n e r a l has p o o r c l e a v a g e . If Al s u b s t i t u t e s for Si,

the mineral will p r o b a b l y d e g r a d a t i v e I y leach, p a r t i c u l a r l y if it

has good c l e a v a g e . A t high p H , t h e t e t r a h e d r a t h e m s e l v e s , a n d

consequently the mineral s t r u c t u r e , will be unstable.

T h e s h o r t c o m i n g s of t h e a b o v e t r e a t m e n t a r e i l l u s t r a t e d by

the limited n a t u r e of t h e i n f o r m a t i o n t h a t can be o b t a i n e d from

t h e u s e of s o l u t i o n c o m p o s i t i o n to s t u d y the s u r f a c e atomic

rearrangement which takes place during grinding. Perhaps

increased use of t e c h n i q u e s like E S C A (140) will s u p p l y more

relevant information. T h e e f f e c t of c l e a v a g e on t h e surface

composition is a l s o inadequately defined. It is n o t e a s y t o

c a l c u l a t e the d i s t r i b u t i o n of a t o m s on c l e a v a g e p l a n e s (|4|).

Even if t h i s c o u l d be d o n e , t h e c o m p o s i t i o n of t h e actual disturbed

layer w o u l d still have t o be r e l a t e d t o t h a t of t h e undisturbed

cleavage plane. T h e s e c o n s i d e r a t i o n s a r e b e y o n d t h e s c o p e of t h i s

thes i s .

5.4 E f f e c t of a g i n g on t h e e l e c t r o p h o r e t i c m o b i l i t y of t h e
si Iicates

It is known (134) t h a t t h e a g i n g of silica suspensions

results in a d r i f t in zeta p o t e n t i a l s t o less n e g a t i v e values.

E l e c t r o p h o r e t i c m e a s u r e m e n t s w e r e t h e r e f o r e m a d e on silicate

m i n e r a l s w h i c h had been aged in 10 NaCl for d i f f e r e n t times.

T h e r e s u l t s o b t a i n e d for l e p i d o l i t e , s p o d u m e n e and beryl are

summarised in F i g s 5 . 1 2 to 5 . 1 4 inclusive.
Fig 5 . 1 2 E f f e c t of a g i n g on the e I e c t r o p h o r e t i c m o b i l i t y of
lepi do Iite in I O " 3 M NaCl

n r
•
A g e d for 2 w e e k s
+ 4| O A g e d for I m o n t h
A A g e d for I w e e k on a m e c h a n i c a l
shaker

+ 2 P

-2

-4 r

Fig 5 . 1 3 E f f e c t of a g i n g on t h e e I e c t r o p h o r e t i c m o b i l i t y of
s p o d u m e n e in I O ~ 3 M NaCl
 +4 .
O A g e d for I month
O A g e d for 2 w e e k s

+2 -

-2 .

-4i -

Fig 5 . 1 4 E f f e c t of a g i n g on t h e e l e c t r o p h o r e t i c m o b i l i t y of
beryl in I 0 _ 3 M NaCI

In g e n e r a l , t h e EM of t h e m i n e r a l s b e c a m e less n e g a t i v e with

an increase in a g i n g t i m e . These observations are therefore

s i m i l a r t o t h o s e reported for s i l i c a (134) and s i l i c a t e minerals

(142). However, after long a g i n g t i m e s (I m o n t h ) t h e EM-pH

curves displayed a 'hump 1 in t h e pH range 4 - 8 . In s i m p l e r m i n e r a l s

like q u a r t z , t h e d e c r e a s e of t h e n e g a t i v e EM may be r e l a t e d t o t h e

i n c r e a s e in crystal Iinity w i t h a g i n g t i m e . In a Iuminosi Iicate

s y s t e m s , h o w e v e r , it is u n l i k e l y t h a t the d e c r e a s e in EM is due

to this e f f e c t .
 It w a s s u g g e s t e d In s e c t i o n 2 . 1 . 3 t h a t due t o the presence

of s o l u b l e s i l i c a in s a t u r a t e d a Iuminosi Iicate s o l u t i o n s , a n y

g i b b s i t e p a r t i c l e s t h a t p r e c i p i t a t e will be c o v e r e d with a

surface layer of an a I u m i n o s i I i c a t e p h a s e . It Is d i f f i c u l t t o

a s s e s s t h e p h y s i c a l s i g n i f i c a n c e of t h i s layer in t h e a b s e n c e of

t h e r e l e v a n t s t a b i l i t y data for the a Iuminosi 11cate s o l i d . Further,

b e c a u s e t h e k i n e t i c s of d i s s o l u t i o n are n o t k n o w n , t h e actual

a Iuminosi Iicate p h a s e t h a t m a y be formed u n d e r t h e e x p e r i m e n t a l

conditions is a l s o n o t k n o w n . F o r I l l u s t r a t i v e p u r p o s e s It w a s

t h e r e f o r e a s s u m e d t h a t t h e p o s s i b l e a I u m i n o s i 1 1 c a t e m i g h t be

similar to kaolinite (64 ). This assumption is r e a s o n a b l e because

in soil s c i e n c e s t u d i e s , It is w i d e l y r e p o r t e d ( 1 3 7 , 143) t h a t

this mineral c o m m o n l y f o r m s t h e w e a t h e r i n g r e s i d u e for t h e

a Iuminosi Iicates s t u d i e d In the p r e s e n t w o r k . This is o b v i o u s l y

related t o t h e low s o l u b i l i t y of k a o l i n i t e (49 , 1 4 3 ) .

A solubility diagram similar to that calculated for gibbsite

(Fig 2 . 2 ) w a s d e t e r m i n e d for k a o l i n i t e using t h e a s s u m p t i o n that

the mineral d i s s o l v e s c o n g r u e n t l y a c c o r d i n g t o t h e reaction 5.5

(143):

AloSio0c-(0H). + 6 H + ^ r 2AI3+ + 2 H . S i O . + H „ 0 log k = 7 . 6 3 (5

2 2 5 4/ \ 4 4 2
(s)

F u r t h e r r e a c t i o n s w e r e d e r i v e d by c o m b i n i n g e q u a t i o n (5.5) w i t h

reactions ( 2 . 1 3 ) t o (2.16) t o y i e l d t h e e q u a t i o n s :
 129

Al Si (OH) + 4H + H90^2AI(0H) + 2H.SiO log k . = -2.31

Z 2 ( s ) Z 4 4 1
(5.6)

AI2Si2(0H)4 + 2H + 3H20 — 2AI(0H)2 + 2H4Si04 log fa = - 1 0 . 9 7

(5.7)

2 A I ( 0 H ) + 2H
4S'°4 l o k
AI2Si2(0H)4 + 5 H 2 0 = 3 ( a q ) 9 3 = "22.37

(5.8)

AI2Si2(0H)4(s) + 7 H 2 0 z ^ r 2AI(0H)~ + 2 H 4 S i 0 4 + 2H log fa = - 3 8 . 3 7

(5.9)

T h e a b o v e e q u i l i b r i a w e r e s o l v e d for t h e s p e c i e s X J using

the observation that

K < 0 < * ] " [H 4 SI0 4 ] (5.10)

T h e r e s u l t i n g s o l u b i l i t y d i a g r a m is shown in Fig 5.15.

C o m p a r i s o n of t h e d i a g r a m with Fig 2 . 2 i n d i c a t e s , as e x p e c t e d , t h a t

gibbsite is m o r e s t a b l e than k a o l i n i t e o v e r a w i d e pH r a n g e . From

t h e c o n c e n t r a t i o n s of s o l u b l e a l u m i n i u m o b t a i n e d in t h e dissolution

s t u d i e s , it w o u l d t h e r e f o r e a p p e a r t h a t g i b b s i t e p r o b a b l y does

form, especially in t h e neutral pH range w h e r e it is o n l y sparingly

soluble. A I u m i n o s i Iicates in general cannot, therefore, dissolve

c o n g r u e n t l y w i t h o u t t h e p r e c i p i t a t i o n of gibbsite.

However, as dissolution p r o c e e d s t h e c o n c e n t r a t i o n of silicic

acid in s o l u t i o n increases. On the basis of e q u a t i o n (2.21),

increased c o n v e r s i o n of t h e g i b b s i t e s u r f a c e t o an a I u m i n o s i I i c a t e

p h a s e will t h e r e f o r e t a k e p l a c e . In t h e g i b b s i t e / k a o l i n i t e model
 I
X
ho

CO
o

10

PH

Fig 5.15 Hypothetical s o l u b i l i t y of k a o l i n i t e a t c o n g r u e n t d i s s o l u t i o n as a f u n c t i o n of pH

OJ
o
 131

s y s t e m , it may be shown ( 1 4 3 ) , using e q u a t i o n s (5.5) and (2.20),

t h a t t h e t r a n s i t i o n b e t w e e n g i b b s i t e and k a o l i n i t e is d e f i n e d by
-5

a silicic acid concentration of G - ^ S i O ^ ) = 2 x 10 M , i.e. above

t h i s c o n c e n t r a t i o n t h e p r e s e n c e of k a o l i n i t e , o v e r t h a t of gibbsite,

is t h e r m o d y n a m i c a I Iy f a v o u r e d . C o m p a r i s o n of t h e t h e o r e t i c a l

s o l u b i l i t y of a m o r p h o u s s i l i c a t o t h e a b o v e v a l u e a l s o s h o w s t h a t

a s o l i d a Iuminosi Iicate like k a o l i n i t e is m o r e likely t o

p r e c i p i t a t e , f r o m a s a t u r a t e d a Iuminosi Iicate s o l u t i o n , than

silica. In t h e p r e s e n t e x p e r i m e n t s t h e r e f o r e w h e r e t h e solubility

of silica w a s n o t e v e r e x c e e d e d s i l i c a w a s n o t a s t a b l e solid

phase.

In t h e a g i n g e x p e r i m e n t s t h e d r i f t t o w a r d s less n e g a t i v e

EM v a l u e s m i g h t t h e r e f o r e be a s s o c i a t e d with t h e p r e s e n c e of a

c o m p o s i t e g i b b s i t e / a I u m i n o s i Iicate s u r f a c e on t h e m i n e r a l

particles. P r e s u m a b l y , t h e g i b b s i t e fraction will be h i g h e r in

t h e neutral pH range than a t a c i d i c pH v a l u e s , w h e r e t h e solubility

of g i b b s i t e increases. T h u s t h e d r i f t in the E M - p H c u r v e upon

aging is m o r e p r o n o u n c e d in t h e n e u t r a l pH range than a t low p H .

T h e s e c o n c l u s i o n s a r e c o n s i s t e n t with a n u m b e r of results

obtained in w e a t h e r i n g s t u d i e s and t h e partial e q u i l i b r i a that

e x i s t s b e t w e e n t h e s o l i d p h a s e s p r e s e n t in a s a t u r a t e d a Iuminosi Iicate

suspension (51, 1 3 7 , 143).

5.5 E f f e c t of f f u o r i d e on the e l e c t r o p h o r e t i c m o b ! I i t y of t h e
ST Iicates

T h e w i d e u s e of f l u o r i d e as a m o d i f y i n g a g e n t in silicate

flotation was noted in C h a p t e r I. Its e f f e c t on c e r t a i n types

of s i l i c a t e s h a s been f u r t h e r s u m m a r i s e d by Read and M a n s e r (122).

 132

In view of t h e w i d e l y r e p o r t e d s u c c e s s f u l a p p l i c a t i o n of t h i s

modifier in s i l i c a t e f l o t a t i o n , its e f f e c t on t h e s i l i c a t e s used

in t h i s s t u d y w a s d e t e r m i n e d . The electrophoretic mobilities

of t h e u n t r e a t e d , acid and alkali w a s h e d s i l i c a t e s a m p l e s were

-4

measured in t h e p r e s e n c e of 5 x 10 M N a F as a f u n c t i o n of pH.

The results obtained with m u s c o v i t e , lepidolite, spodumene,

beryl and m i c r o c l i n e are s u m m a r i s e d In Figs 5 . 1 6 t o 5 . 2 0 . The

a d d i t i o n of N a F had n o s i g n i f i c a n t e f f e c t on t h e m o b i l i t i e s of

t h e s i l i c a t e m i n e r a l s at a l k a l i n e pH v a l u e s , i r r e s p e c t i v e of

w h e t h e r t h e s a m p l e s had been acid o r alkali w a s h e d . A t acid pH

v a l u e s , h o w e v e r , the m o b i l i t i e s w e r e m o r e n e g a t i v e than those

obtained in t h e a b s e n c e of f l u o r i d e for all t h e samples

investigated. In t h e c a s e of l e p i d o l i t e and s p o d u m e n e prior

acid o r a l k a l i n e w a s h i n g did n o t p r o d u c e s i g n i f i c a n t l y different

EM v a l u e s c o m p a r e d t o the u n t r e a t e d s a m p l e s (cf F i g s 5 . 1 7 and

5.18). With m u s c o v i t e and m i c r o c l i n e (Figs 5 . 1 6 and 5 . 2 0 respectively),

h o w e v e r , p r i o r w a s h i n g of t h e s a m p l e s e n h a n c e d t h e e f f e c t of

fluoride so that more negative potentials were obtained. The

r e s u l t s o b t a i n e d with beryl (Fig 5 . 1 9 ) w e r e s o m e w h a t contradictory

with f l u o r i d e p r o d u c i n g a m o r e n e g a t i v e s u r f a c e on acid w a s h e d

material a n d a less n e g a t i v e o n e on t h e alkali w a s h e d s a m p l e . It

w o u l d a p p e a r , h o w e v e r , t h a t in g e n e r a l , t h e e f f e c t of fluoride

on t h e e l e c t r o p h o r e t i c m o b i l i t y is g r e a t e r than t h a t of acid o r

alkali washing.

Fig 5.21 s h o w s a d i s t r i b u t i o n d i a g r a m of t h e different

-4

f l u o r i d e s p e c i e s for a total f l u o r i d e c o n c e n t r a t i o n of 5 x 10 .

T h e s t a b i l i t y c o n s t a n t s of t h e s p e c i e s c o n s i d e r e d a r e (122):
 133

1 1 1 1 1 1 ' 1
+4

o Untreated sample
• HCI w a s h e d sample
+2 A NaOH washed sample
E

\
XI \
\ i i i
O
e 8 10
\s v
\ \ pH-
\ \
0
L_
o - 2
x
Q.
o
+-
u
0
L±J -4
1 1 i i . i i l . i

Fig 5 . 1 6 E f f e c t of pH on t h e e l e c t r o p h o r e t i c m o b i l i t y of muscovite
in t h e p r e s e n c e of 5 x 1 0 " % N a F

+4 t 1 r

O Untreated sample
e
U • HCI w a s h e d sample
N> +2
\ A
(/) NaOH washed sample
e

1 1 1 1 r
4 6 8 10
XI pH-
O

o
- 2
0
o
X
cl
o
o -4
_0
LU

Fig 5 . 1 7 E f f e c t of pH on t h e e I e c t r o p h o r e t l c m o b i l i t y of
IepI do lite in t h e p r e s e n c e of 5 x I 0 ~ 4 M N a F
 n ' 1 i 1 1 r

O Untreated sample
• HCI w a s h e d sample
A NaOH washed sample

1 1 1 1 i 1 r
\ 4 6 8 10

j i | i | i i l

5.18 E f f e c t of pH on t h e e l e c t r o p h o r e t i c mobi Iity of spodumene

in t h e p r e s e n c e of 5 x 10 4 M N a F

5.19 E f f e c t of pH on the e l e c t r o p h o r e t i c m o b i l i t y of beryl

in t h e p r e s e n c e of 5 x I 0 ~ 4 M N a F
 135

T 1 1 1 ' 1 1 1 I

O Untreated sample
• HCI w a s h e d sample
A NaOH washed sample

1 1 1 1 1 1 1 1

4 6 8 10
pH -

j i • » »

Fig 5 . 2 0 E f f e c t of pH on t h e e l e c t r o p h o r e t i c m o b i l i t y of
m i c r o c l i n e in t h e p r e s e n c e of 5 x I0~^M N a F

3 4 5 6 7
pH

Fig 5.21 L o g a r i t h m i c - c o n c e n t r a t i o n d i a g r a m for f l u o r i d e species

a t 5 x I0~4m f l u o r i d e c o n c e n t r a t i o n
 H + F — HF log k = 3 . 1 8 (5.11)

H+ + 2 F " — HF~ log k = 3 . 7 6 (5.12)

It w a s f u r t h e r a s s u m e d t h a t o n l y [F ] and [HF] w e r e significant

w i t h i n t h e p H range c o n s i d e r e d ( i . e . pH 2 to 7 ) . The maximum

error involved in m a k i n g such an a s s u m p t i o n w a s c a l c u l a t e d t o be

less than \% f o r t h e given pH range.

T h e f i g u r e s h o w s t h a t t h e c o n c e n t r a t i o n of m o l e c u l a r HF

i n c r e a s e s c o n t i n u o u s l y with a d e c r e a s e of p H . A t a pH of 3.1

t h e s o l u t i o n c o n t a i n s equal a m o u n t s of F and H F . A t pH 2 . 2 t h e

c o n c e n t r a t i o n of H F is ten t i m e s t h a t of F and v i c e v e r s a at a

pH of 4 . 1 . T h e f a c t t h a t f l u o r i d e c o n d i t i o n i n g had no e f f e c t on

t h e EM of t h e s i l i c a t e s in t h e pH range w h e r e F is t h e predominant

species and that there was a progressive increase towards more

n e g a t i v e z e t a p o t e n t i a l s b e l o w pH 7 , w h e r e t h e c o n c e n t r a t i o n of

HF i n c r e a s e d , s u g g e s t s t h a t H F , r a t h e r t h a n F , is t h e active

species. S i m i l a r c o r r e l a t i o n s h a v e been o b s e r v e d for beryl and

m i c r o c l i n e by o t h e r a u t h o r s (33 , 44 ).

However, although it is g e n e r a l l y a c c e p t e d t h a t HF Is t h e

a c t i v e s p e c i e s a n d t h a t t h e main e f f e c t of f l u o r i d e is t o increase

the n e g a t i v e zeta potential of t h e m i n e r a l s t h e reason why s u c h

an Increase t a k e s p l a c e is n o t known (24). Several explanations

h a v e been proposed.

(I) B u c k e n h a m and R o g e r s ( 3 2 ) considered fIuoride adsorption

by a Iuminosi Iicates t o p r o c e e d by t h e f o r m a t i o n of a l u m i n i u m

f l u o r i d e c o m p l e x e s on t h e m i n e r a l surface:
 AI-OH , + H+ + 2F"— (>I-F: ) H + + OH (5.13)
surf / 7. _ ,
surf

(2) Joy e t a 1 ( 3 5 ) p r o p o s e d t h e e x c h a n g e of OH for F on

s u r f a c e si lanols:

,Si-OH , + F Y i - F + OH (5.14)
surf / s u r f

(3) S m i t h and his a s s o c i a t e s (34, 144, 145 ) c o n s i d e r e d t h a t t h e

a d s o r p t i o n of fIuorosi Iicate i o n s , d e r i v e d from t h e dissolution

of t h e m i n e r a l l a t t i c e , on a l u m i n i u m s i t e s occurred:

A I
"0Hsurf + S i F S i F + 0 H ( 5
6~ = > - 6 " "l5)
surf

(4) W a r r e n and K i t c h e n e r ( 3 3 ) s u g g e s t e d s p e c i f i c adsorption

of f l u o r i d e t o form s u r f a c e complexes:

^ ' " ^ s u r f + F = > - F s u r f + 0 H ( 5 J 6 )

:AI
"Fsurf + F A I
"F2 ( 5
= / t "l7)
surf

A|
-°Hsurf + F A ( 5
— " < f - -l8)
surf

T h e s e m o d e l s are c o n s i s t e n t with t h e i n c r e a s e of pH t h a t

is o b s e r v e d in t h e p r e s e n c e of f l u o r i d e . However, Shergold (24)

+ +
has p o i n t e d o u t t h a t e x c h a n g e of K , Na and o t h e r s i m i l a r cations
+

on t h e m i n e r a l s u r f a c e , for H in s o l u t i o n , will lead t o a s i m i l a r

increase in s o l u t i o n pH. T h e r e s u l t s shown in s e c t i o n 4.2

d e m o n s t r a t e t h a t s u c h an e x c h a n g e d o e s in f a c t o c c u r with the

silicates studied in t h i s p r o j e c t . A rise in pH c a n n o t therefore

be used as an i n d i c a t i o n of w h i c h m e c h a n i s m is a p p l i c a b l e .

M e c h a n i s m 2 is n o t c o n s i s t e n t w i t h t h e i n c r e a s e of n e g a t i v e EM

found in t h i s w o r k and e l s e w h e r e ( 33 ). Read and M a n s e r (122)

h a v e d e d u c e d t h e p r o b a b l e f l u o r i d e s p e c i e s for a w i d e range of

concentrations in s i l i c a t e s y s t e m s . The predominant species

-3 2+

b e l o w a total f l u o r i d e c o n c e n t r a t i o n of I x 10 M are AlF ,

A I F * , and A I F ^ . The A I F ^ species is p r e s e n t o n l y a t a c o n c e n t r a t i o n

g r e a t e r than ca 2 x 10 3 M. T h i s m a k e s t h e e x i s t e n c e of negatively

c h a r g e d a l u m i n i u m f l u o r i d e c o m p l e x e s on t h e m i n e r a l , a s suggested

by m e c h a n i s m s I and 4 , d o u b t f u l , a t t h e c o n c e n t r a t i o n of fluoride

used. However, at higher concentrations specific adsorption to

3
form such s u r f a c e c o m p l e x e s a p p e a r s f e a s i b l e . In the I x 10 to
-2
I x 10 M c o n c e n t r a t i o n range W a r r e n and K i t c h e n e r ( 3 3 ) r e p o r t e d
e n h a n c e d a d s o r p t i o n on c o r u n d u m and m i c r o c l i n e b u t n o t on q u a r t z ,

a t pH 7 and b e l o w . T h e y f u r t h e r found t h a t a f l u o r i d e concentration

-2

of 10 M w a s r e q u i r e d to r e v e r s e t h e zeta potential on corundum,

at a pH of 5 .

The above comments are also relevant t o mechanism 3. It

h a s been shown ( 33 , 122 ) t h a t the c o n c e n t r a t i o n of f I uorosi I i c a t e

s p e c i e s will be i n s i g n i f i c a n t a t t h e c o n c e n t r a t i o n of fluoride

used in t h e p r e s e n t w o r k . Further, aluminium and ferric fluoride

c o m p l e x e s a r e much m o r e s t a b l e than t h e f I u o r o s i I i c a t e ion so t h a t

the latter will n o t form a p p r e c i a b l y u n l e s s all t h e a l u m i n i u m and

iron a r e c o m p l e x e d f i r s t (24, 32 ).
 T h e s e c o n s i d e r a t i o n s s u g g e s t t h a t a l t h o u g h t h e e f f e c t of

f l u o r i d e has been s o m e t i m e s a s c r i b e d t o t h e f o r m a t i o n of surface

f l u o r i d e c o m p l e x e s , it m i g h t be related t o e n h a n c e d leaching of

aluminium ( 4 4 ), p a r t i c u l a r l y at low f l u o r i d e concentrations.

5.6 E f f e c t of a i urn?hi urn c h l o r ? d e on t h e e I e c t r o p h o r e t i c mobiIity

of t h e sf f i c a t e itinera I s

P o l y v a l e n t metal ions a r e known t o a d s o r b at t h e q u a r t z /

water i n t e r f a c e and t o p r o d u c e c h a r g e reversal in a pH range

which is c h a r a c t e r i s t i c of t h e metal cation ( 3 0 , 146 ). It is

r e a s o n a b l e t o a s s u m e t h a t a si mi lar e f f e c t wi I I o c c u r on the

s u r f a c e of s i l i c a t e m i n e r a l s . To determine whether this is t h e

c a s e , e I e c t r o p h o r e t i c m o b i l i t y m e a s u r e m e n t s w e r e m a d e in t h e

p r e s e n c e of a l u m i n i u m c h l o r i d e . T h i s metal was c h o s e n b e c a u s e it

is known to form a s e r i e s of h y d r o l y s i s p r o d u c t s a l t h o u g h the

p o l y m e r i c s p e c i e s a r e not well c h a r a c t e r i s e d . Furthermore, soluble

aluminium is p r e s e n t in s o l u t i o n b e c a u s e of t h e d i s s o l u t i o n of t h e

silicate minerals. T h e r e s u l t s o b t a i n e d with m u s c o v i t e , lepidolite,

-5
s p o d u m e n e , beryl and m i c r o c l i n e , in t h e p r e s e n c e of I x 10 M and
-4

I x 10 M AICI^ are summarised in F i g s 5 . 2 2 t o 5 . 2 6 inclusive.

T h e general s h a p e of t h e E M / p H c u r v e s for each of t h e silicate

m i n e r a l s , in t h e p r e s e n c e of A I C I ^ , is s i m i l a r a n d in a g r e e m e n t

with that reported for quartz ( 30 , 31, 146 ). A t pH v a l u e s

b e l o w 3 , A I C I 3 had n o e f f e c t on t h e EM of t h e si l i c a t e s . A s t h e pH

w a s i n c r e a s e d , h o w e v e r , t h e EM d e v i a t e d from t h a t o b t a i n e d in t h e

a b s e n c e of A I C I ^ and b e c a m e less n e g a t i v e o r p o s i t i v e . Maximum

deviation occurred in t h e pH range 4 - 6 . With a f u r t h e r increase

 140

+4 O I x IO" 5 M A I C I
•
I x IO" 4 M A I C I

+2

-2

-4

J i L

Fig 5.22 E f f e c t of A I C I ^ on t h e e l e c t r o p h o r e t i c m o b i l i t y of
m u s c o v i t e as a f u n c t i o n of pH

Fig 5 . 2 3 E f f e c t o f A I C I 3 on t h e e l e c t r o p h o r e t i c m o b i l i t y of
l e p i d o l i t e as a f u n c t i o n of pH
 141

Fig 5 . 2 4 E f f e c t of AlCI on the e l e c t r o p h o r e t i c m o b i l i t y of

s p o d u m e n e as a function of pH

Fig 5 . 2 5 E f f e c t of AICI on t h e e l e c t r o p h o r e t i c m o b i l i t y of
beryl as a function of pH
 142

+4 -
o
>

e
>- +2

O
e
O

0
o
-£=
CL
O - 2 -
+-
o
0
UJ

-4 -

Fig 5.26 E f f e c t of A I C I ^ on t h e e l e c t r o p h o r e t i c m o b i l i t y of
m i c r o c l i n e as a function of pH

in p H , t h e m o b i l i t y r e t u r n e d t o t h a t o b t a i n e d in t h e a b s e n c e of

AlCly W i t h an increase in A I C I ^ c o n c e n t r a t i o n , t h e E M b e c a m e

m o r e p o s i t i v e and t h e pH range o v e r which c h a r g e reversal was

obtained increased. A t high p H , h o w e v e r , the c h a r g e reversal was

invariably located a t pH 9 . 1 , e x c e p t f o r m u s c o v i t e .

The IEP of m u s c o v i t e w a s e a r l i e r n o t e d to o c c u r a t a pH of

5.7. Fig 5 . 2 2 s h o w s t h a t b e l o w t h i s pH v a l u e , t h e p r e s e n c e of

A I C I ^ i n c r e a s e d t h e m a g n i t u d e of t h e p o s i t i v e c h a r g e on t h e

mineral. T h i s , together with the above o b s e r v a t i o n s , suggested

t h a t AI s p e c i e s w e r e n o t o n l y a d s o r b i n g s p e c i f i c a l l y on all the

silicate m i n e r a l s , but were potential determining.

 A l t h o u g h t h e e f f e c t s of h y d r o l y s a b l e metal c a t i o n s on

o x i d e s and s i l i c a t e m i n e r a l s a r e r e a s o n a b l y well k n o w n , t h e

m e c h a n i s m s by w h i c h t h e s e e f f e c t s o c c u r h a v e n o t been unambiguously

defined. G e n e r a l l y , t h e pH range in w h i c h t h e reversal of t h e EM

t o p o s i t i v e v a l u e s t a k e s p l a c e is c o i n c i d e n t with t h a t in w h i c h

h y d r o l y s e d metal species are present (27, 3 0 ) . Similar

o b s e r v a t i o n s h a v e been m a d e in a n u m b e r of r e l a t e d experiments

such as coagulation ( 1 4 7 , 148) and H a l l i m o n d t u b e flotation

studies (149). This has led t o t h e c o n c l u s i o n t h a t t h e observed

e f f e c t s a r e p r o d u c e d by h y d r o l y s e d metal s p e c i e s of t h e f o r m

M(0H)(n"l)+ (30, 149) and M ( 0 H ) 2 n " 2 ) + (146) r a t h e r than the

u n h y d r o l y s e d metal cation.

-4

Fig 5 . 2 7 s h o w s a p H - l o g c o n c e n t r a t i o n d i a g r a m for a Ix10 M

AICI3 solution. T h e p r e s e n c e of p o l y m e r i c Al c o m p l e x e s has been

ignored. It is seen from t h e f i g u r e t h a t t h e c o n c e n t r a t i o n s of

A I ( 0 H > 2 and A l ( 0 H ) 2 + a r e at a m a x i m u m in t h e pH range 4 - 6 . As

this is t h e pH range in w h i c h t h e m a x i m u m p o s i t i v e EM w a s

o b s e r v e d , it is t e m p t i n g t o c o n c l u d e t h a t t h e form of t h e EM

c u r v e s r e f l e c t the c o n c e n t r a t i o n s of t h e s e s p e c i e s . Indeed,

on t h e b a s i s of s i m i l a r c o r r e l a t i o n s , F u e r s t e n a u and co-workers

( 2 7 , 3 0 , 149), M a c k e n z i e (146) and H e a l y e t a I (150) s u g g e s t e d

m e c h a n i s m s by w h i c h t h e M ( 0 H ) ^ n o r MCOH)^ 1 " 1 species adsorb

on t h e q u a r t z s u r f a c e . In t h e s e m e c h a n i s m s t h e a d s o r p t i o n was

a s s u m e d t o involve a c o m b i n a t i o n of c o u l o m b i c f o r c e s b e t w e e n the

p o s i t i v e l y c h a r g e d c o m p l e x and t h e n e g a t i v e m i n e r a l s u r f a c e , and

hydrogen bonds between (OH) g r o u p s of the c o m p l e x ions and those

on t h e mineraI.

T h e s u g g e s t e d m e c h a n i s m s can be r e p r e s e n t e d in t h e

folIowing way:
 144

x I 0 " 4 M AICI
Fig 5.27 Logarithmic-concentration diagram for

V /OH OH
\ \
M
/ I .
Al (5.19)
M + Al(0H)?
/ \ 0 H
/ ^OH ~7—OH
f surf
surf

2+
/OH OH-AI
\ / 0H + M (5.20)
M Al(OH)
/ \
'OH
surf
/ \ Q H
surf

0 Al - OH
\ / 0H \M /
/ V
+ HgO (5.21)
M + Al(0H)9
/ N o "
surf surf
 0 Al - OH
\ /u \ /

/ V'
M + Al (OH). M OH (5.22)
/ \ n "
surf
surf

0 Al2 - OH
2+ \M /
/ V
M + Al(OH) (5.23)
/ \ n "
surf surf

M-OH — M-OH
I
0 + Al (OH) 2* — I OH
I +
(5.24)
M-OH 0 Al
I , I
surf 1 OH
— M-OH
I
surf

w h e r e M d e n o t e s SI o r A l . T h e h y d r o g e n b o n d i n g r e a c t i o n s in

( 5 . 1 9 ) , (5.20) and (5.24) are a n a l o g o u s t o t h o s e p r o p o s e d for

t h e b o n d i n g of m o l e c u l a r w a t e r on si Iica (151, 152, 153).

Mechanisms (5.19) and (5.24) are a l s o s i m i l a r e x c e p t t h a t in

( 5 . 1 9 ) t h e b r i d g i n g reaction is on t w o d a n g l i n g b o n d s t h a t

o c c u r on t h e s a m e s u r f a c e s i t e w h e r e a s in ( 5 . 2 4 ) t h e c a t i o n is

a s s o c i a t e d with o n l y o n e d a n g l i n g b o n d . Further reactions

i n v o l v i n g cation e x c h a n g e b e t w e e n h y d r o x y l a t e d Al s p e c i e s and

t h e s u r f a c e h a v e been s u g g e s t e d ( 148):

v /OH /0 Al ( 0 H ) ( H 2 0 ) 4
M + AI(0H)(H20)^ ^ M + H30 (5.25)
/ \0H , ^ surf
surf

How e a s i l y p o l y m e r i c h y d r o l y s i s p r o d u c t s can e x c h a n g e w i t h

p r o t o n s of t h e s u r f a c e h y d r o x i d e and w h e t h e r t h e e x c h a n g e is
 146

e q u i v a l e n t Is n o t k n o w n .

All t h e r e a c t i o n s (5.19) t o ( 5 . 2 5 ) , e x c e p t ( 5 . 2 2 ) , will

produce superequivalent adsorption within the IHP and subsequent

c h a r g e reversal as o b s e r v e d In t h e p r e s e n t r e s u l t s . Reaction

( 5 . 2 2 ) , h o w e v e r , can n o t p r o d u c e c h a r g e r e v e r s a l . This has led

some workers (147, 154) + o c o n s i d e r t h a t c h a r g e reversal in t h e

pH range 4 t o 7 Is due t o t h e a d s o r p t i o n of p o l y m e r i c species

4+

(possibly A l g ( O H ) 2 0 ) . H o w e v e r , c a l c u l a t i o n s of t h e concentrations

of such s p e c i e s w i t h i n t h i s pH range s h o w s t h a t t h e s e are

e x t r e m e l y small and c a n n o t p r o d u c e s u p e r e q u i v a l e n t adsorption.

F r o m t h e e q u i l i b r i u m c o n s t a n t s r e p o r t e d In C h a p t e r 2 , t h e
5+ 7+
c o n c e n t r a t i o n s of t h e s p e c i e s A I ^ ( O H ) ^ and AI ^ ^ ( O H ) w e r e
-14 -24

c a l c u l a t e d to be 3 . 6 3 x 10 M and 5 . 8 9 x 10 M respectively.

T h u s t h e p r e s e n c e of p o l y m e r i c s p e c i e s Is u n l i k e l y t o be

r e s p o n s i b l e for t h e o b s e r v e d e l e c t r o k i n e t i c behaviour.

T h e a b o v e m e c h a n i s m s do n o t e x p l a i n w h y t h e unhydrolysed

Al3+ c a t i o n d e e s n o t r e v e r s e t h e s u r f a c e c h a r g e o r indeed w h y
+ 2+

A l ( 0 H ) 2 or Al(OH) a p p e a r t o do s o . As outlined In C h a p t e r 4,

t h e r e Is e v i d e n c e t o s u g g e s t t h a t a d s o r b e d p o l y v a l e n t cations

retain a t least o n e layer of t h e i r h y d r a t i o n w a t e r (101, 124).

Ionic h y d r a t i o n m a y t h e r e f o r e p r e v e n t t h e c l o s e a p p r o a c h of

highly charged (highly h y d r a t e d ) c a t i o n s t o t h e s u r f a c e . The

lowering of I o n i c p o t e n t i a l s by h y d r o l y s i s d e c r e a s e s Ion-solvent

interactions. T h i s r e s u l t s in a s m a l l e r h y d r a t i o n s p h e r e f o r t h e

ion and p e r m i t s c l o s e r a p p r o a c h to t h e s u r f a c e so t h a t g r e a t e r

c o u l o m b i c a n d s h o r t range i n t e r a c t i o n s a r e p o s s i b l e . On t h i s
3+
b a s i s , t h e h i g h l y h y d r a t e d AI cation is e x p e c t e d t o reside
outside the IHP and t h e r e f o r e show n o s p e c i f i c a d s o r p t i o n or

c h a r g e reversal effect.

S i m i l a r c o n s i d e r a t i o n s h a v e been s u m m a r i s e d by J a m e s and

Healy ( 31 ) w h o c o n s i d e r e d t h e c h a n g e in free e n e r g y upon

a d s o r p t i o n of t h e s p e c i e s K^G0^., be a c o m b i n a t i o n of t h e

changes in c o u l o m b i c e n e r g y , secondary solvation,

AG • , and c h e m i c a l a f f i n i t y7 , AG ,
s o I v,i ' chem,i

AG°. . A G ° .. + AG° . . + AG°, . (5.26)

ads,i coul,i solv.i chem,i

As AG„ , is of orprp o s i t e siqn

a
t o both AG . a n d AG , , a
solv coul chem

r e d u c t i o n of c h a r g e on t h e c a t i o n by h y d r o x y Iation favours

s p e c i f i c a d s o r p t i o n by r e d u c i n g AG° q | v .

T h e s i g n i f i c a n c e of h y d r o l y s i s p h e n o m e n a in e x p l a i n i n g the

EM r e s u l t s , t h e r e f o r e , a p p e a r s t o be r e l a t e d t o t h e presence

of w e a k l y h y d r a t e d A l ( l l l ) s p e c i e s f o r w h i c h t h e r e e x i s t s a

p o s s i b i l i t y of c o o p e r a t i v e h y d r o g e n and c o u l o m b i c bonding.

Other evidence, however, suggests that the relationship

b e t w e e n a d s o r p t i o n of metal c a t i o n s and h y d r o l y s i s is n o t a

simple one. J a m e s and H e a l y ( 31 ) o b s e r v e d t h a t a t high pH w h e r e

t h e c o n c e n t r a t i o n of C o O H + w a s e x t r e m e l y low, t h e r e w a s n o

decrease in the a d s o r p t i o n of C o ( I I I ) s p e c i e s on q u a r t z . Figs

5 . 2 2 t o 5.26 show t h a t in t h e pH range 6 t o 9 , a t I x I 0 " 4 M AICI3,

t h e si licate p a r t i c l e s w e r e p o s i t i v e l y c h a r g e d . A t a pH of 7,

t h e c a l c u l a t e d c o n c e n t r a t i o n s of A l ( O H ) * and A l ( 0 H ) 2 + a r e 1.58 x 10

and 3 . 3 9 x 10 ''m r e s p e c t i v e l y . These low c o n c e n t r a t i o n s are

u n l i k e l y t o p r o d u c e t h e high p o s i t i v e m o b i l i t i e s o b s e r v e d a t t h i s pH
J a m e s and H e a l y ( 31 ) a r g u e d t h a t t h e a b r u p t n e s s of t h e first

c h a r g e reversal ( - t o + ) in t h e pH r a n g e 3 to 5 is typical

of a s y s t e m in w h i c h a critical c h a n g e in t h e s o l u t i o n properties

is t a k i n g p l a c e . They therefore related this charge reversal

t o t h e p r e s e n c e of a s u r f a c e - n u c l e a t e d metal hydroxide

precipitate. According to these workers, above the precipitation

p H , t h e q u a r t z p a r t i c l e s r e f l e c t e d t h e p r o p e r t i e s of t h e metal

h y d r o x i d e , d e p e n d e n t on t h e d e g r e e of s u r f a c e c o v e r a g e . This

t h e o r y e x p l a i n s a n u m b e r of t h e o b s e r v a t i o n s m a d e in t h e

present investigations. F o r e x a m p l e , a pH of 9 c o r r e s p o n d s

approximately to the IEP of A I ( O H ) , ( 155). A t h i g h e r pH

( s )

t h e r e f o r e both t h e m i n e r a l p a r t i c l e s and p r e c i p i t a t e h a v e charges

of t h e same sign so t h a t c o u l o m b i c a d s o r p t i o n o f t h e precipitate

is n o t p o s s i b l e . A reduction in t h e metal cation concentrations

w o u l d reduce t h e a m o u n t of metal h y d r o x i d e o b t a i n e d and h e n c e t h e

surface coverage. A s h i f t in t h e p o i n t of z e r o EM t o lower pH

v a l u e s for t h e c o m p o s i t e mineral s u r f a c e would t h e r e f o r e be

expected. F o r beryl the s h i f t w a s r e l a t i v e l y small (low surface

c o v e r a g e ) and for lepidolite (high s u r f a c e c o v e r a g e ) n o p o s i t i v e

m o b i l i t y w a s o b s e r v e d a t low a l u m i n i u m concentrations.

H o w e v e r , a l t h o u g h t h e r e s u l t s o b t a i n e d a r e c o n s i s t e n t with

t h e p r e s e n c e of an a l u m i n i u m h y d r o x i d e layer, it is n o t p o s s i b l e

to unambiguously separate the effects of hydrolysed aluminium

s p e c i e s and an a l u m i n i u m h y d r o x i d e p r e c i p i t a t e , as both the

p r o d u c t s a r e p r e s e n t w i t h i n t h e pH r a n g e in w h i c h c h a r g e reversal

was obtained. T h i s is c l e a r l y d e m o n s t r a t e d in Fig 5 . 2 7 . If it

is a s s u m e d , a s h a s been s u g g e s t e d (27 , 3 0 ) t h a t c h a r g e reversal

( - t o + ) in t h e pH range 3 - 5 is due to h y d r o l y s e d s p e c i e s , s o m e

c h a n g e in t h e E M c u r v e m i g h t be e x p e c t e d as t h e t r a n s i t i o n is

m a d e t o w a r d s t h e p r e s e n c e of metal h y d r o x i d e p r e c i p i t a t e on t h e

s u r f a c e of t h e m i n e r a l , a t h i g h e r pH v a l u e s . Such a c h a n g e w a s

n o t o b s e r v e d , n e i t h e r has it been n o t i c e d in the adsorption

s t u d i e s by o t h e r w o r k e r s ( 3 1 ). F u r t h e r , if t h e a b o v e assumption

is t r u e , c o u l o m b i c a d s o r p t i o n of AI(OH)^. , which is p o s i t i v e

b e l o w pH 9 , on t h e p o s i t i v e m i n e r a l s u r f a c e , p r o d u c e d by t h e

initial a d s o r p t i o n of h y d r o l y s e d s p e c i e s , is u n l i k e l y . Along

similar l i n e s , t h e p r e s e n c e of A I ( O H ) , in s o l u t i o n does n o t
^ ( s )

readily e x p l a i n how p o s i t i v e metal h y d r o x i d e s p e c i e s increased

t h e p o s i t i v e m o b i l i t y on m u s c o v i t e (Fig 5 . 2 2 ) .

From the results obtained in t h i s w o r k , it is n o t possible

to determine the mechanism of i n t e r a c t i o n of a l u m i n i u m a t t h e

si I i c a t e / w a t e r interface. The results do, however, suggest t h a t

a si m i l a r m e c h a n i s m is i n v o l v e d w i t h all the si Iicate m i n e r a l s

s t u d i e d and t h a t a f t e r t h e a d d i t i o n of A I C I ^ s i m i l a r eIectrophoreti

mobilities are obtained.

 CHAPTER S I X

THE ADSORPTION OF AMINE AT THE SI LICATE/WATER INTERFACE"

AND ITS EFFECT ON THE HALLIMOND TUBE FLOTATION OF THE SILICATES

 151

6.I Adsorption studies

T h e a d s o r p t i o n of d o d e c y l a m i n e a t t h e s i l i c a t e mineral/

w a t e r i n t e r f a c e w a s m e a s u r e d a s a function of a m i n e concentration

and pH and t h e results o b t a i n e d c o m p a r e d to e I e c t r o k i n e t i c

measurements under similar conditions.

6.1.1 E f f e c t of DA cohceritration

The adsorption i s o t h e r m s of DA on lepidolite, spodumene,

m i c r o c l i n e and b e r y l , a t pH 9 . 0 , a r e shown In Fig 6 . 1 . The

isotherms are consistent with the generally accepted theory

for t h e a d s o r p t i o n of long chain e l e c t r o l y t e s by o x i d e s and

silicates outlined in C h a p t e r 2 . All t h e isotherms were

sigimoidal and of a s i m i l a r s h a p e to t h o s e d e s i g n a t e d as S2

in G i l e s e t al c l a s s i f i c a t i o n system (156). This suggests that

although the adsorbing species were monofunctionaI, they had

m o d e r a t e van d e r W a a l s i n t e r a c t i o n s a t t h e mineraI/water

interface (156). T h e s h a p e of the i s o t h e r m s a l s o indicates

that there was strong competition for t h e n e g a t i v e substrate

s i t e s from i n o r g a n i c c a t i o n s p r e s e n t in b u l k s o l u t i o n . All the

isotherms were i n d e p e n d e n t of t h e so I i d s / 1 i q u i d ratio in

s o l u t i o n , indicating that adsorption was reversible. This is

s h o w n for s p o d u m e n e in Fig 6 . 1 .

F i g 6 . 2 c o m p a r e s t h e EM of s p o d u m e n e and t h e a m i n e adsorption

d e n s i t y as a function of t h e e q u i l i b r i u m c o n c e n t r a t i o n of

d o d e c y l a m i n e a t pH 9 . 0 . The similarity in s h a p e of t h e t w o

c u r v e s s u g g e s t s t h a t both t h e e l e c t r o k i n e t i c and adsorption

data w e r e c o n c e r n e d with t h e s a m e s u r f a c e p h e n o m e n o n (135).

 152

1 1 1 1 1 — i — i — i — » 1 t r
O Lep i do Ii te
a Spodumene
3 Mi c r o c line
D
Beryl
* D e s o r p t i o n on s p o d u m e n e
Vertically oriented monolayer assuming cross •
s e c t i o n a l a r e a of 20°A for h y d r o c a r b o n c h a i n ^

IxlO 5x10 1x10 -4

5x10
E q u i l i b r i u m c o n c e n t r a t i o n of a m i n e , M

Fig 6.1 Adsorption i s o t h e r m s of DA on t h e s i l i c a t e s a t p H 9

 1 1 1 r i i it 1 r 1
12
O E l e c t r o p h o r e t i c mobi I ity
OJ
i Adsorpti on

- / + 4
~ 1 0

Region 3 /
vo /
o
/
/
x /
/ o +2
4-
(/) Region 2 j q ^
A
0
-a
c 0
O
4-
a
$_.
o
0
XJ
to -2
0
c

Region 1

-4
• i i * i • i i 1 1 1
2xlO"5 5xlO-5 IxI0"4 5xTO"4

Equilibrium amine concentration, M

Fig 6 . 2 C o m p a r i s o n of the a d s o r p t i o n density and electrophoretic

mobi Ii ty data a t pH 9

It is c o n v e n i e n t to discuss the isotherms by d i v i d i n g

t h e m into t h r e e d i f f e r e n t regions as d e m o n s t r a t e d in Fig 6 . 2 .

Region I: In t h i s r e g i o n , t h e r e w a s a slow increase in t h e

adsorption d e n s i t y with the l o g a r i t h m i c DA c o n c e n t r a t i o n . The

s l o p e of t h e EM c u r v e in the region w a s , h o w e v e r , n o t zero as

has been r e p o r t e d in m a n y s i m i l a r s t u d i e s ( 7 7 , 110, 135). Furthe

different adsorption levels w e r e o b s e r v e d for the different

silicates; lepidolite a p p a r e n t l y a d s o r b e d the m o s t and beryl the

least a m o u n t of a m i n e .

R e g i o n 2: T h e region w a s c h a r a c t e r i s e d by a m a r k e d increase in

the a d s o r p t i o n d e n s i t y of DA and a c o r r e s p o n d i n g d e c r e a s e in t h e
EM to less n e g a t i v e v a l u e s . The mobility subsequently reversed
-5

sign a t a DA c o n c e n t r a t i o n of 8 x 10 M. A l t h o u g h the m i n e r a l s

had d i f f e r e n t a d s o r p t i o n densities in region I, t h e e q u i l i b r i u m

c o n c e n t r a t i o n a t w h i c h the m a r k e d a d s o r p t i o n increase took place

(CHMC) w a s a p p r o x i m a t e l y t h e s a m e for all t h e minerals.

R e g i o n 3: In t h i s r e g i o n , t h e i n c r e a s e in a d s o r p t i o n density

with amine concentration b e c a m e s m a l l e r than t h a t in region 2.

A t high DA c o n c e n t r a t i o n , t h e i s o t h e r m s w e r e c h a r a c t e r i s e d by a

n e a r - z e r o s l o p e , a n d c o n v e r g e n c e t o t h e same a d s o r p t i o n density.

Region 1: T h e p a r t of the a d s o r p t i o n isotherms in t h i s region

r e v e a l e d several interesting characteristics when compared to

those reported in the literature. Firstly, the observed adsorption

d e n s i t i e s w e r e m u c h h i g h e r than t h o s e r e p o r t e d for a IkyIammoniurn

ions on q u a r t z a n d a l u m i n a ( 1 3 5 , 157, 1 5 8 ) . A t a p H of 9 a n d a
-5
dodecyIammoniurn c h l o r i d e (DAC) c o n c e n t r a t i o n of 5 x 10 M , Li
-12

and De Bruyn f o u n d an a d s o r p t i o n d e n s i t y of ca 2 x 10 moles

- 2

cm on q u a r t z . T h i s is t w o o r d e r s of m a g n i t u d e less than the

a d s o r p t i o n d e n s i t i e s shown in Fig 6.1 a t s i m i l a r concentrations.

S e c o n d l y , a t pH 9 , t h e EM v a l u e s of lepidolite, spodumene,

beryl a n d m i c r o c l i n e w e r e (Figs 5.1 a n d 5 . 2 ) 3 , 3 . 3 , 3.5 and 3.5

ym s e c '/volt c m ' respectively. The corresponding estimates of

t h e zeta p o t e n t i a l s using e q u a t i o n 5 . 2 are 3 8 . 5 , 4 2 . 3 , 4 4 . 9 and

44.9 m V , r e s p e c t i v e l y . The similarities in t h e zeta potential

values suggest that the coulombic contribution to the adsorption

of a m i n e in t h e Stern layer s h o u l d be a l m o s t t h e s a m e for t h e

silicates studied. However, different adsorption densities were

obtained. T h u s , in the case of beryl and m i c r o c l i n e , similar

 155

EM v a l u e s w e r e o b t a i n e d a t pH 9 b u t t h e a d s o r p t i o n d e n s i t y of
-5

DA on m i c r o c l i n e a t a c o n c e n t r a t i o n of 5 x 10 M , was nearly

t w i c e t h a t on beryl.

The different levels of DA a b s t r a c t i o n o b t a i n e d therefore

suggest t h a t some additional m e c h a n i s m , other than simple ion

exchange in t h e d i f f u s e layer, was o p e r a t i v e . Reference to the

cation exchange results shown in section 4.2 s u g g e s t s t h a t t h i s

additional mechanism is r e l a t e d t o t h e cation e x c h a n g e properties

of t h e m i n e r a l s . T h i s is b e c a u s e t h e o r d e r in w h i c h t h e adsorption

d e n s i t i e s d e c r e a s e , i.e. l e p i d o l i t e > s p o d u m e n e microcline >

beryl c o r r e s p o n d s t o t h e d e c r e a s e in t h e c a t i o n e x c h a n g e ability

of the si I i c a t e s .

T o t e s t t h e v a l i d i t y of t h i s h y p o t h e s i s , t h e concentrations

of m o n o v a l e n t lattice c a t i o n s (Li+ and/or K + ) in e q u i l i b r i u m with

t h e m i n e r a l s , in t h e p r e s e n c e and a b s e n c e of D A , w e r e determined.

The results, summarised in T a b l e 6 . 1 , w e r e c o m p a r e d t o t h e

a d s o r p t i o n d e n s i t y of a m i n e at t h e m i n e r a I / w a t e r interface. To

f a c i l i t a t e c o m p a r i s o n s t h e c o n c e n t r a t i o n s of t h e lattice c a t i o n s

in e q u i l i b r i u m with the m i n e r a l s w e r e e x p r e s s e d in m o l e s per

u n i t area of e a c h mineral.

It is c l e a r from t h e s e r e s u l t s t h a t the p r e s e n c e of a m i n e in

solution increased the concentration of t h e lattice c a t i o n s in

equilibrium with l e p i d o l i t e , s p o d u m e n e and m i c r o c l i n e . Although

+ + .

beryl contained little o r n o Li and K (cf T a b l e 3 . 3 ) , it is

included in T a b l e 6.1 t o f a c i l i t a t e c o m p a r i s o n of its a d s o r p t i o n

density with the other s i l i c a t e s . If the e x c h a n g e d c a t i o n s a r e

ignored in c o m p u t i n g t h e a d s o r p t i o n densities (i.e. column 2

s u b t r a c t column 5 ) , t h e a d s o r p t i o n density (column 6 ) o b t a i n e d

 4
T a b l e 6.1 E f f e c t of c a t i o n e x c h a n g e p r o p e r t i e s on t h e a d s o r p t i o n d e n s i t y of DA from I x 10 M
DA s o l u t i o n s

Mi neraI Total a m i n e 2 Total c a t i o n s in C a t i o n s in so In Total c a t i o n Ads density excluding

a d s (moles/m ) s o In (moles/m ) in a b s e n c e of exchanged cations exchanged
DA ( m o l e s / m ) (moles/m ) (moles/m2)
(Li + K) (Li + K)

- 6 -6 -6 -6 -6
Mi c r o c Ii ne 4.03 x 10 4.78 x 10 3.25 x 10 I.53 x 10 2.5 x 10

Spodumene
-6 -5 -5 - 6 -6
4.75 x 10 I.74 x 10 I .53 x 10 2 . 1 0 x 10 2.65 x 10
-6 -6 - 6 - 6 , - 7
Lep i do Iite 2 . 6 8 x 10 8.87 x 10 6.58 x 10 2.29 x 10 3.9 x 10
-6 -6
Bery I 3.18 x 10 3.18 x 10
for s p o d u m e n e and m i c r o c l i n e (weak e x c h a n g e r s ) a r e s i m i l a r to

t h a t of beryl (non-exchanger). It is p r o b a b l e t h e r e f o r e that

a t low DA c o n c e n t r a t i o n s , t h e p r e d o m i n a n t m e c h a n i s m of

adsorption is by c a t i o n e x c h a n g e ; t h i s is p a r t i c u l a r l y t r u e for

t h e m i n e r a l s with good c a t i o n e x c h a n g e c a p a c i t i e s . In t h e c a s e

of l e p i d o l i t e , for e x a m p l e , p r a c t i c a l l y all t h e DA w a s abstracted

-4

t h r o u g h cation e x c h a n g e (cf c o l u m n s 5 and 6 ) a t I x 10 M DA.

H o w e v e r , t h i s d o e s n o t mean t h a t c o u l o m b i c forces are unimportant;

t h e y p r o v i d e t h e d r i v i n g f o r c e for t h e e x c h a n g e w h i l e t h e presence

and a m o u n t of w e a k l y held c a t i o n s d e t e r m i n e t h e d e g r e e of e x c h a n g e

activity. These results are therefore in a g r e e m e n t w i t h the

observations made in C h a p t e r 4 t h a t m o n o v a l e n t c a t i o n s , w h i c h

a r e held p r e d o m i n a n t l y by w e a k ionic f o r c e s , a r e r e a d i l y exchanged.

T h e c o n c e n t r a t i o n s of AI and Si in s o l u t i o n w e r e n o t i n c l u d e d in

T a b l e 6.1 b e c a u s e t h e y did n o t c h a n g e s i g n i f i c a n t l y in t h e

p r e s e n c e of DA.

A f u r t h e r p o i n t of i n t e r e s t is w h e t h e r t h e D A + ions s h o u l d

be c o n s i d e r e d to be s p e c i f i c a l l y a d s o r b e d o r m e r e l y concentrated

in t h e d i f f u s e d o u b l e layer, as r e p o r t e d by a large n u m b e r of

authors (26 , 2 7 , 77 , 135, 157). According to double layer

t h e o r y , an ion located in t h e d i f f u s e layer is n o t a s s o c i a t e d

w i t h any d i s c r e t e e x c h a n g e s i t e on t h e s u r f a c e of t h e m i n e r a l

(101). It is u n l i k e l y , t h e r e f o r e , t h a t n o n - s p e c i f i c a I Iy a d s o r b e d

DA+ ions w o u l d lead t o an i n c r e a s e of i n o r g a n i c c a t i o n s in s o l u t i o n

as d e m o n s t r a t e d by t h e r e s u l t s in T a b l e 6 . 1 .

S h a i n b e r g and K e m p e r (101) h a v e a s s e s s e d t h e role of ionic

hydration in e l e c t r i c a l double layers. They estimated that the

fraction of Li , Na a n d Ka which have a completely oriented

f i r s t m o l e c u l a r shell of w a t e r Is 0 . 9 7 , 0 . 8 0 and 0.46,

respectively. If t h e i r model is a p p l i e d t o dodecyIammoniurn

and trimethyIammoniurn i o n s , t h e fraction of t h e ions w i t h a

c o m p l e t e p r i m a r y h y d r a t i o n shell is a b o u t 0 . 2 3 and 0.07,

respectively. Leja (159) is of s i m i l a r o p i n i o n , t h a t for

+

monovalent cations larger than K , t h e e f f e c t i v e n u m b e r of b o u n d

water molecules is n e a r l y z e r o due to t h e i r low I o n i c potentials.

It a p p e a r s , t h e r e f o r e , t h a t L I + a n d N a + a r e completely

hydrated In a q u e o u s s o l u t i o n s . This would explain why Li+ did

n o t show a n y p o t e n t i a l d e t e r m i n i n g e f f e c t on lepidolite and

s p o d u m e n e , a n d w h y N a + a c t e d as an indifferent electrolyte for

t h e m i n e r a l s as h a s a l s o been o b s e r v e d for q u a r t z ( 7 8 ). It does

n o t e x p l a i n , h o w e v e r , why i n c o m p l e t e l y h y d r a t e d alkylamonium

ions a d s o r b n o n - s p e c i f i c a I l y on q u a r t z , a t low a m i n e concentrations

( 78 ). It m a y be t h a t b e c a u s e q u a r t z is a n o n - e x c h a n g e r , t h e low

adsorption d e n s i t i e s do n o t lead t o s i g n i f i c a n t c h a n g e s in the

Stern p o t e n t i a l s . T h u s the s l o p e of t h e zeta p o t e n t i a l - amine

concentration c u r v e r e m a i n s z e r o a t low s u r f a c t a n t concentrations.

In the c a s e of a IuminosiI i c a t e s , h o w e v e r , a m i n e adsorption

densities, at low c o n c e n t r a t i o n , are h i g h e r due t o f i n i t e exchange

capacities. The changes in Stern p o t e n t i a l s in r e s p o n s e to

specific adsorption are t h e r e f o r e s i g n i f i c a n t . It Is t h u s possible

t h a t t h e I n c r e a s e of s l o p e o b s e r v e d in the EM c u r v e of Fig 6 . 2 in
+
region I w a s r e l a t e d t o s p e c i f i c a l l y a d s o r b e d DA ions.

A practical e x a m p l e of t h e a b o v e c o n s i d e r a t i o n s Is the
+ + + +
f l o t a t i o n of s a l t s . For t h e alkali h a l i d e s of Li , Na , K , Rb ,
Cs and N H ^ , F u e r s t e n a u and F u e r s t e n a u (160) o b t a i n e d flotation

with d o d e c y I a m m o n i u m c h l o r i d e o n l y w h e r e t h e lattice cation was

+ 2 + 2 +
larger t h a n K . For t h e a l k a l i n e e a r t h c h l o r i d e s of Mg , Ca ,
0 2+ 2+

Sr and Ba , only B a C I 2 f l o a t e d with t h e s a m e c o l l e c t o r . These

authors considered that ionic sizes controlled flotation and

that D A + ions c o u l d f i t into t h e lattice s i t e s o f t h e floatable

saIts.

It has been a r g u e d (161), however, that this theory is

u n l i k e l y b e c a u s e a Iky I s u l p h a t e s a l s o f l o a t KCI b u t n o t N a C I ,

a l t h o u g h both lattices contain the chloride ion. A more likely

explanation (161) is t h e r e f o r e t h a t s a l t s of NaCI a n d LiCI are

s t r o n g l y h y d r a t e d c o m p a r e d t o t h o s e of KCI o r of larger s i z e d

cations (162). DodecyIammonium ions, that are themselves only

w e a k l y h y d r a t e d , a r e t h e r e f o r e c a p a b l e of a d s o r b i n g specifically

on t h e f l o a t a b l e salts.

Region 2: A c c o r d i n g t o t h e g e n e r a l l y a c c e p t e d t h e o r y of long

chain s u r f a c t a n t a d s o r p t i o n on o x i d e s , t h e a b r u p t i n c r e a s e in

adsorption density in region 2 is b e c a u s e of t h e f o r m a t i o n of

hydrophobic associates (hemi-miceIles) between the surfactant

hydrocarbon chains. T h e f o r m a t i o n of h e m i - m i c e I Ies a t t h e

mineral s u r f a c e t h u s p r o v i d e s an a d d i t i o n a l adsorption mechanism

which is b e l i e v e d (NO, 158, 163) to be driven by entropic

c h a n g e s a r i s i n g from h y d r o g e n b o n d s b e t w e e n w a t e r molecules.

T h e h e m i - m i c e I l e s w e r e c o n c e i v e d , by G a u d i n and Fuerstenau

(78 ), as a r i s i n g from a p a r t i c u l a r level of s u r f a c t a n t adsorption

at the mineraI/water interface. If, t h e r e f o r e , t w o m i n e r a l s have

d i f f e r e n t zeta p o t e n t i a l s , d i f f e r e n t C H M C v a l u e s are e x p e c t e d in
region I. T h e s i l i c a t e s used in t h i s s t u d y had d i f f e r e n t a m i n e

adsorption d e n s i t i e s a t t h e C H M C , a l t h o u g h t h e i r zeta potentials

w e r e s i m i l a r a t pH 9 . If t h e f o r m a t i o n of h y d r o p h o b i c associations

is s o l e l y i n i t i a t e d by a p a r t i c u l a r a m i n e a d s o r p t i o n density,

t h e C H M C v a l u e s of t h e s i l i c a t e s s h o u l d h a v e been d i f f e r e n t . The

s i m i l a r i t y of t h e a m i n e c o n c e n t r a t i o n a t the C H M C therefore

suggests that the adsorption density was not the only critical

factor that determined the location of t h e C H M C .

Smith ( 2 6 ) h a s s u g g e s t e d t h a t in t h e dodecyI a m i n e / o x i d e

s y s t e m , t h e C H M C d e p e n d s on t h e r a t i o of c h a r g e d to neutral

s p e c i e s both in the d o u b l e layer and t h e bulk a q u e o u s phase.

T h u s in t h i s s y s t e m t h e C H M C w o u l d a p p e a r to be a b u l k solution

p r o p e r t y , so t h a t van d e r W a a l ' s a s s o c i a t i o n s a r e n o t o n l y

i n i t i a t e d by a p a r t i c u l a r D A + a d s o r p t i o n density a t the silicate-

solution i n t e r f a c e , b u t by t h e p r e s e n c e of a p a r t i c u l a r concentration

of neutral m o l e c u l e s in b u l k s o l u t i o n . This conclusion agrees with

a n u m b e r of s t u d i e s i n v o l v i n g a l k y I a m m o n i urn col lectors ( 32 , 9 7 ,

135 , 164) in w h i c h t h e g r e a t e s t s u r f a c e a c t i v i t y of t h e surfactant

is o b s e r v e d in t h e p r e s e n c e of u n i o n i s e d a m i n e species.

R e g i o n 3: The decrease in s l o p e in t h e a d s o r p t i o n isotherms at

t h e s t a r t of region 3 h a s been a t t r i b u t e d ( 77 ) t o t h e formation

of a s u r f a c e w h i c h r e t a r d s f u r t h e r a d s o r p t i o n of c a t i o n i c amine.

An a l t e r n a t i v e v i e w p o i n t ( 2 5 , 80 , 81 ) is t h a t condensation

t a k e s p l a c e on increasingly less e n e r g e t i c s i t e s a s saturation

of t h e mineral surface is a p p r o a c h e d .

Fig 6 . 3 s h o w s t h e s u r f a c e t e n s i o n of DA a s a f u n c t i o n of

c o n c e n t r a t i o n a t a pH of 9 . It is c l e a r t h a t t h e C M C of DA a t
-4
t h i s pH o c c u r r e d a t a c o n c e n t r a t i o n o f 3.2 x 10 M. Comparison
 —r —I t n

80 1 - 1 x I 0 " 2 NaCI

60 -

40 •
H-xO—Q—Ol_o— o

20

• _J 1 1

5xlO"5 4
IxlO 5x10~4 IxlO"3 5xl0"3

Amine concentration, M

Fig 6 . 3 T h e s u r f a c e t e n s i o n of d o d e c y l a m i n e s o l u t i o n s a t pH 9

with Fig 6.1 s h o w s t h a t s a t u r a t i o n adsorption levels o c c u r r e d

at amine concentrations at or slightly above the C M C . Similar

o b s e r v a t i o n s h a v e been m a d e by a n u m b e r of o t h e r a u t h o r s ( 81 ,

I 10 , 158).

The adsorption d e n s i t y m a r k e d as a m o n o l a y e r in Fig 6.1 was

o b t a i n e d by a s s u m i n g t h a t t h e c r o s s s e c t i o n a l area of t h e

h y d r o c a r b o n c h a i n w a s 20°A 2 (134, 161, 165) and t h a t t h i s area

was larger t h a n t h a t o c c u p i e d by t h e p o l a r h e a d . Using this

value a close packed, vertically oriented monolayer would be

—6 — 2
f o r m e d a t an a d s o r p t i o n d e n s i t y of 8 . 3 x 10 moles m . For the
i s o t h e r m s in Fig 6 . 1 , s a t u r a t i o n a d s o r p t i o n t h e r e f o r e occurred

at 1.3 m o n o l a y e r s . Similar saturation adsorption densities have

been o b t a i n e d by o t h e r w o r k e r s ( 81 , 1 1 0 ) w h e r e t h e y h a v e been

e x p l a i n e d by t h e f o r m a t i o n of a bi layer s u r f a c e , in w h i c h a

second layer of s u r f a c t a n t m o l e c u l e s a r e o r i e n t e d w i t h their

hydrophilic polar heads towards bulk solution. Such a m e c h a n i s m

w o u l d e x p l a i n t h e c o n v e r g e n c e of t h e a d s o r p t i o n isotherms at

high DA c o n c e n t r a t i o n s . A c c o r d i n g t o t h e p s e u d o - p h a s e model for

surfactants ( 1 6 6 ) , b e y o n d t h e C M C t h e c o n c e n t r a t i o n of micelles

increases linearly with increase in s u r f a c t a n t concentration.

T h e i n v a r i a n t s l o p e of t h e i s o t h e r m s t h e r e f o r e s h o w s t h a t m i c e l l e s

do n o t a d s o r b t o a n y s i g n i f i c a n t e x t e n t on a s u r f a c e consisting

of a bi l a y e r . An a l t e r n a t i v e e x p l a n a t i o n is t h a t s u g g e s t e d by

S c a m e h o r n e t a I ( 81 ) t h a t o n l y m o n o m e r a d s o r b s . S i n c e the

c o n c e n t r a t i o n of m o n o m e r is c o n s t a n t b e y o n d t h e C M C saturation

adsorption is o b s e r v e d under these conditions.

6.1.2 E f f e c t of pH on t h e a d s o r p t i o n of a m i n e by t h e Sit i c a t e s

Fig 6 . 4 s h o w s t h e e f f e c t of pH on t h e a d s o r p t i o n density

of DA on s p o d u m e n e a t t h r e e d i f f e r e n t c o n c e n t r a t i o n s of t h e

surfactant. In general the a d s o r p t i o n density increased with pH

and t h i s is t o be e x p e c t e d b e c a u s e of t h e i n c r e a s e d coulombic

a t t r a c t i o n b e t w e e n t h e mineral and t h e c a t i o n i c a m i n e i o n . Similar

s h a p e d c u r v e s h a v e been r e p o r t e d by De Bruyn (157) f o r t h e

a d s o r p t i o n of a m i n e on q u a r t z . I n t e r e s t i n g l y , t h e c u r v e s did not

d i s p l a y a gradual increase in a d s o r p t i o n d e n s i t y w i t h pH; rather

the adsorption density i n c r e a s e d m o r e m a r k e d l y a t high pH v a l u e s .

 O |.5 x I0"4M
A
I.0 x I0"4M
0 -
• 6 x I0"*5M

Monolayer coverage

8 -

6_

4-

2.

6 7 8 9 10 II 12

pH

Fig 6 . 4 E f f e c t of pH on t h e a d s o r p t i o n d e n s i t y of dodecylamine
a t several s u r f a c t a n t c o n c e n t r a t i o n s

C o n s i d e r a t i o n of t h e s o l u t i o n e q u i l i b r i a of d o d e c y l a m i n e shows

t h a t a t a l k a l i n e pH v a l u e s t h e c o n c e n t r a t i o n of neutral molecules

i n c r e a s e s a t t h e e x p e n s e of a d e c r e a s e in t h e c o n c e n t r a t i o n of

cationic species. The m a r k e d increase in a d s o r p t i o n density at

a l k a l i n e pH v a l u e s c a n , t h e r e f o r e , be a t t r i b u t e d to the formation

of h y d r o p h o b i c a s s o c i a t e s in w h i c h t h e neutral amine molecules

a c t as b r i d g e s . This theory is c o n s i s t e n t w i t h t h e considerations

o u t Ii ned a b o v e and has been w e I I expI a i ned by Smi th ( 2 6 , 9 7 , 164 ).

 T h e h i g h e s t c o n c e n t r a t i o n of DA i n v e s t i g a t e d w a s determined
-4

by p H - s o l u b i Iity c o n s i d e r a t i o n s . At 1.5 x 10 M DA t h e r e is a

clear tendency towards saturation adsorption in t h e isotherm at

1.3 m o n o l a y e r s . In t h i s c a s e it is p r o b a b I y v a I i d to consider

t h a t t h i s c o r r e s p o n d s t o t h e f o r m a t i o n of a bi layer as e x p l a i n e d
-4

above. At I x 10 M amine there was a tendency to saturation

adsorption although the packing density was less than a m o n o l a y e r .

H o w e v e r , t h e data a t high pH is i n s u f f i c i e n t t o unequivocally

confirm this observation. In a s t u d y of t h e e f f e c t of pH on t h e

a d s o r p t i o n d e n s i t y of d o d e c y I t r i m e t h y I a m m o n i u r n c h l o r i d e on

alumina, Doss (158) found t h a t s a t u r a t i o n a d s o r p t i o n w a s dependent

on pH and t h a t p l a t e a u a d s o r p t i o n c o u l d be o b t a i n e d a t s u r f a c e

c o v e r a g e s of m u c h less than a m o n o l a y e r . It a p p e a r s , t h e r e f o r e ,

t h a t u n d e r some c o n d i t i o n s of pH a n d s u r f a c t a n t concentration

c l o s e p a c k e d m o n o l a y e r s and b i l a y e r s a r e n o t formed although

p l a t e a u a d s o r p t i o n m a y be o b t a i n e d . Under such conditions

s a t u r a t i o n a d s o r p t i o n a p p e a r s to be r e l a t e d t o t h e c o n s t a n t supply

of m o n o m e r b e y o n d t h e C M C ( 81 ) r a t h e r than t h e p r e s e n c e of

bi layers on t h e mineral surface.

6.2 Ha I Iimond t u b e s t u d i e s in t h e p r e s e n c e o f amine

F i g 6 . 5 s h o w s t h e r e s u l t s of Hal Iimond t u b e f l o t a t i o n tests

on s p o d u m e n e , b e r y l , m i c r o c l i n e , l e p i d o l i t e and m u s c o v i t e , in t h e
-5

p r e s e n c e of 3 x 10 M DA. T h e s e r e s u l t s are c o n s i s t e n t w i t h the

adsorption r e s u l t s a n d s h o w t h a t good flotation was obtained in t h e

pH r a n g e c o r r e s p o n d i n g t o good a m i n e a d s o r p t i o n . A s the pH

decreased towards the IEP v a l u e s of t h e s i l i c a t e s t h e r e w a s a

 pH

Fig 6 . 5 E f f e c t of pH on t h e f l o t a t i o n r e c o v e r y of t h e silicates
in 3 x I d o d e c y l a m i n e s o l u t i o n s

d e c r e a s e in r e c o v e r y . M u s c o v i t e , h o w e v e r , s h o w e d an i n c r e a s e in

r e c o v e r y below the IEP. T h i s w a s p r o b a b l y due t o an i n c r e a s e in

t h e c a t i o n e x c h a n g e a c t i v i t y a s t h e pH d e c r e a s e d (cf a c i d / b a s e

titrations, Chapter 7).

T h e good e x c h a n g e r s , m u s c o v i t e a n d lepidolite, showed a

m o r e gradual increase in r e c o v e r y w i t h p H . The poor exchangers,

on t h e o t h e r h a n d , s h o w e d a m o r e d e f i n e d c r i t i c a l pH of flotation

at w h i c h t h e r e w a s a m a r k e d i n c r e a s e in recovery.

A t pH v a l u e s a b o v e 12, t h e r e was a s h a r p drop in f l o t a t i o n

recovery. T h i s can be a t t r i b u t e d t o t h e p r e c i p i t a t i o n of t h e

a m i n e from s o l u t i o n and the low levels of c a t i o n i c a m i n e present

in s o l u t i o n . U n f o r t u n a t e l y d i r e c t c o m p a r i s o n of t h e Hallimond

t u b e and a d s o r p t i o n data is n o t p o s s i b l e b e c a u s e of t h e differences

in the c o n c e n t r a t i o n of a m i n e used in t h e i n v e s t i g a t i o n s . At the

lowest initial D A c o n c e n t r a t i o n used in t h e a d s o r p t i o n tests

-5
(5x10 M ) a s u r f a c e c o v e r a g e of a b o u t 2 5 $ w a s i n d i c a t e d on
-5
s p o d u m e n e a t an e q u i l i b r i u m c o n c e n t r a t i o n of 1.4 x 10 M (Fig 6 . 1 ) .
-5

H e n c e a t an initial c o n c e n t r a t i o n of 3 x 10 M , which is t h a t used

in t h e f l o t a t i o n t e s t s , a lower s u r f a c e c o v e r a g e is indicated.

T h i s is in line with t h e o b s e r v a t i o n t h a t o n l y a small surface

c o v e r a g e is r e q u i r e d for c o m p l e t e f l o t a t i o n ( 1 5 7 , 165) to o c c u r .
 CHAPTER SEVEN

ADSORPTION OF STARCH AT THE S I L I C A T E MINERAL/WATER

INTERFACE AND ITS EFFECT ON THE HALLIMOND TUBE

FLOTATION OF THE SILICATES WITH DODECYLAMINE

 168

7.I A d s o r p t i o n of s t a r c h polymers

T h e a d s o r p t i o n d e n s i t i e s of s e v e r a l d i f f e r e n t s t a r c h e s on

t h e d i f f e r e n t s i l i c a t e m i n e r a l s w e r e m e a s u r e d as a function of

e q u i l i b r i u m c o n c e n t r a t i o n and p H . The different polysaccharides

used in t h i s s t u d y w e r e p o t a t o a n d m a i z e s t a r c h e s , B r i t i s h gum

and both w h i t e and y e l l o w dextrins.

7.1.1 E f f e c t of e q u i I i b r i u m S t a r c h ' c o n c e n t r a t i o n on the starch

adsorption density

T h e a d s o r p t i o n d e n s i t i e s of p o t a t o s t a r c h on s p o d u m e n e and

beryl (Fig 7 . 1 ) , m i c r o c l i n e , lepidolite and muscovite (Fig 7 . 2 )

a r e shown in F i g s 7.1 and 7.2 as a function of equilibrium

concentration a t pH 10. The isotherms are similar to those

reported by S h u l z and C o o k e ( 3 7 ) f o r t h e a d s o r p t i o n of potato

starch on q u a r t z , and a r e b e s t d e s c r i b e d as of t h e Freundlich

type. With i n c r e a s e of s t a r c h c o n c e n t r a t i o n , t h e adsorption

d e n s i t y did n o t e x h i b i t s a t u r a t i o n . Such i s o t h e r m s have a l s o

been r e p o r t e d ( 8 2 ) t o a p p l y t o t h e a d s o r p t i o n of polysaccharides

on a c t i v a t e d c o a l . All t h e i s o t h e r m s w e r e r e v e r s i b l e ; t h i s w a s

d e t e r m i n e d by u s i n g d i f f e r e n t s o l i d t o liquid r a t i o s in suspension.

T h i s s u g g e s t e d t h a t t h e a d s o r b i n g f o r c e s w e r e w e a k such as t h o s e

operative in a physical a d s o r p t i o n p r o c e s s . Reversible adsorption

i s o t h e r m s h a v e a l s o been r e p o r t e d f o r the a d s o r p t i o n of P E O on

silica ( 8 4 ) although it is g e n e r a l l y a g r e e d t h a t m o s t polymer

adsorption i s o t h e r m s a r e i r r e v e r s i b l e b e c a u s e of t h e difficulty

of s i m u l t a n e o u s a d s o r p t i o n and desorption.

The adsorption i s o t h e r m s of m a i z e s t a r c h and B r i t i s h g u m on

s p o d u m e n e , a t pH 10 (Fig 7 . 3 ) w e r e s i m i l a r in s h a p e t o t h o s e
 169

1
Equilibrium starch c o n c e n t r a t i o n , mg I

Fig 7.1 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on s p o d u m e n e a n d
beryl a s a f u n c t i o n of e q u i l i b r i u m c o n c e n t r a t i o n a t pH 10

E q u i l i b r i u m s t a r c h c o n c e n t r a t i o n , mg I '

Fig 7.2 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on mi c r o c Ii n e ,
lepidolite and m u s c o v i t e as a f u n c t i o n of equi I i bri urn
c o n c e n t r a t i o n a t pH 10
 E q u i l i b r i u m c o n c e n t r a t i o n , mg I '

Fig 7 . 3 A d s o r p t i o n d e n s i t y of m a i z e s t a r c h and B r i t i s h g u m on s p o d u m e n e a s a f u n c t i o n of
e q u i l i b r i u m c o n c e n t r a t i o n a t pH 10
 171

o b t a i n e d with p o t a t o s t a r c h . T h o s e of t h e d e x t r i n s (Fig 7 . 4 ) ,

h o w e v e r , w e r e m o r e L a n g m u i r i a n and s i m i l a r in s h a p e t o t h e L2

curves in G i l e s e t al (156) s y s t e m of c l a s s i f i c a t i o n , w i t h the

a d s o r p t i o n d e n s i t i e s b e i n g an o r d e r of m a g n i t u d e less t h a n those

of s t a r c h . P u b l i s h e d data (82 , 88 , 156) i n d i c a t e t h a t a d s o r p t i o n

i s o t h e r m s of low m o l e c u l a r w e i g h t p o l y m e r s are b e s t d e s c r i b e d by

the Langmuir isotherm. T h e reason f o r t h i s is, h o w e v e r , n o t

known a l t h o u g h it a p p e a r s t h a t it m a y be r e l a t e d t o t h e observation

that low m o l e c u l a r w e i g h t p o l y m e r s a p p e a r t o lie c l o s e r t o t h e

s u r f a c e than t h o s e of g r e a t e r c h a i n length (114). As explained in

C h a p t e r 2 , it is p o s s i b l e t o f i t a v a r i e t y of t h e o r e t i c a l isotherms

to the same experimental polymer adsorption data. For this reason

n o a t t e m p t w a s m a d e t o c a l c u l a t e t h e p a r a m e t e r s of t h e suggested

theoretical isotherms. It w a s n o t e d , h o w e v e r , t h a t t h e adsorption

d e n s i t y of the b i o p o l y m e r s on s p o d u m e n e d e c r e a s e d in t h e o r d e r

p o t a t o s t a r c h > m a i z e starch ^ B r i t i s h gum > dextrins. It is

later shown ( v i s c o s i t y s t u d i e s ) t h a t t h i s w a s due t o differences

in t h e m o l e c u l a r w e i g h t s of t h e p o l y m e r s . Other studies (37 )

a l s o indicate t h a t d e x t r i n s do n o t a d s o r b on q u a r t z t o t h e same

e x t e n t as w h o l e starches.

7.I.2 A d s o r p t i o n m e c h a n i s m of starch

7.I.2.I E i e c t r o k i n e t i c p r o p e r t i e s of s t a r c h granules

T h e s t a r c h s o l u t i o n s used in t h e a d s o r p t i o n e x p e r i m e n t s were

o p t i c a l l y c l e a r and c o u l d n o t t h e r e f o r e be used d i r e c t l y in t h e

d e t e r m i n a t i o n of t h e sign of c h a r g e of t h e b i o p o l y m e r s in a q u e o u s

solutions. T h e r e p o r t e d EM r e s u l t s w e r e o b t a i n e d for p o t a t o
 0.05-

0.04

CM
i
0.03-
CD

0.02 -
X
0
t3 • Yellow dextrin
"o
0 O White dextrin
x
t_
o
0 0.01 ~
tj
<

20 40 60 80 100

Equilibrium dextrin concentration, mg I '

Fig 7.4 A d s o r p t i o n d e n s i t i e s of t h e d e x t r i n s on s p o d u m e n e a s
a f u n c t i o n of e q u i l i b r i u m c o n c e n t r a t i o n a t pH 10

o • In 2 . 5 x I 0 " 2 M NaCl
> +2 -
\ O In a b s e n c e of NaCl
0
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0
10 i i
x PH
o
o
- 2 -
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o
x
-o-
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-4 .

LU
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Fig 7.5 E l e c t r o k i n e t i c p r o p e r t i e s of starch g r a n u l e s in t h e

a b s e n c e and p r e s e n c e of NaCl as a f u n c t i o n of pH
starch granules suspended In w a t e r a t t h e d e s i r e d pH and t o w h i c h

w a s a d d e d , In s o m e c a s e s , NaCI e q u i v a l e n t to t h a t w h i c h w o u l d be

p r e s e n t as a r e s u l t of n e u t r a l i s i n g t h e c a u s t i c i s e d s t a r c h solutions

t o s i m i l a r pH vaIues.

T h e EM r e s u l t s o b t a i n e d a t d i f f e r e n t pH v a l u e s a r e summarised

in Fig 7 . 5 . It Is e v i d e n t t h a t starch Is p r e d o m i n a n t l y negatively

c h a r g e d a t a I I a l k a l i n e pH v a l u e s , the m a g n i t u d e of t h e E M b e i n g

greater In t h e a b s e n c e of a d d e d s a l t . Similar results were

r e p o r t e d by B a l a j e e and Iwasaki ( 4 2 ) and S t e r l i n g (167). Apparently

t h e n e g a t i v e c h a r g e a r i s e s from t h e d i s s o c i a t i o n of alcoholic

h y d r o x y I g r o u p s p r e s e n t in t h e s t a r c h s t r u c t u r e (cf s e c t i o n 2.5).

T h e m a g n i t u d e of t h e n e g a t i v e c h a r g e , h o w e v e r , s u g g e s t s that

t h e a l c o h o l i c h y d r o x y Is in s t a r c h a r e c o m p a r a t i v e l y m o r e acidic

than t h o s e of m o n o h y d r i c , a l i p h a t i c a l c o h o l s . For e x a m p l e , t h e

dissociation c o n s t a n t In a q u e o u s s o l u t i o n at 25°C of m e t h a n o l
i fo
and o t h e r s i m p l e a l c o h o l s is ca I x 10 (93). In c o n t r a s t , t h e

d i s s o c i a t i o n c o n s t a n t s for c a r b o h y d r a t e s are r e p o r t e d t o lie In

-12 -14

the range 10 - 10 ( 9 3 ) and in p a r t i c u l a r the p k of s t a r c h

is a p p r o x i m a t e l y 12 ( 1 6 8 ) . Q u a l i t a t i v e l y , the h i g h e r a c i d i t y of

h y d r o x y I g r o u p s in c a r b o h y d r a t e s has been a t t r i b u t e d t o t h e

g r e a t e r n u m b e r of such g r o u p s In the p o l y m e r i c s t r u c t u r e (93 ,169 )

and t h e h i g h e r lability of t h e proton of t h e h e m i a c e t a l hydroxyl

In t h e a n o m e r i c p o s i t i o n . The latter c o n d i t i o n a p p a r e n t l y stems

from t h e e l e c t r o n - w i t h d r a w i n g e f f e c t e x e r t e d on t h e g r o u p by t h e

neighbouring ring o x y g e n ( 9 3 ). T h e m o n o h y d r i c a l c o h o l s h a v i n g no

strong electron-withdrawing s u b s t i t u e n t s are r e l a t i v e l y weaker

aci d s .
 174

By a n a l o g y with t h e s e r e s u l t s , it can be a s s u m e d t h a t t h e

causticised starch polymers were negatively charged under the

c o n d i t i o n s used in the a d s o r p t i o n e x p e r i m e n t s . It is h i g h l y

unI ike Iy, t h e r e f o r e , t h a t e l e c t r o s t a t i c a t t r a c t i o n s w e r e

r e s p o n s i b l e for a d s o r p t i o n of t h e p o l y m e r s on t h e silicate

m i n e r a l s a t t h e high pH v a l u e u s e d , p a r t i c u l a r l y as multivalent

cations were absent. T h e s e c a t i o n s can lead t o neutralisation

and reversal of t h e n e g a t i v e c h a r g e a t t h e m i n e r a I / w a t e r interface,

t h e r e b y a i d i n g t h e a d s o r p t i o n of starch.

7.I.2.2 E f f e c t of pH on t h e a d s o r p t i o n of s t a r c h by s p o d u m e n e

Fig 7.6 s h o w s t h e a d s o r p t i o n d e n s i t y of p o t a t o starch on

s p o d u m e n e as a f u n c t i o n of pH a t t h r e e d i f f e r e n t initial starch

concentrations. With a d e c r e a s e of pH below pH 12, t h e a d s o r p t i o n

density increased l i n e a r l y , and the s a m e s l o p e w a s o b t a i n e d for

the different starch concentrations. Similar results have been

o b t a i n e d for t h e a d s o r p t i o n of starch on q u a r t z ( 3 7 , 4 2 ) and

calcite (43). B e y o n d a pH of 12 t h e a d s o r p t i o n d e n s i t y decreased

markedly.

T h e d e c r e a s e of a d s o r p t i o n w i t h i n c r e a s e of pH s u g g e s t s that

a d s o r p t i o n of s t a r c h t o o k p l a c e via s i t e s w h o s e form strongly

d e p e n d e d on p H . T h e s i t e s on the m i n e r a l surface most likely to

be i n v o l v e d in t h e a d s o r p t i o n p r o c e s s a r e t h e si lanol s i t e s . The

d e g r e e of d i s s o c i a t i o n of t h e s e s i t e s w o u l d increase with p H . In

t h e c a s e of s t a r c h t h e a p p r o p r i a t e s i t e s w o u l d be t h e alcoholic

hydroxy I groups w h i c h , as discussed above, become more anionic

w i t h an increase in p H . It w o u l d a p p e a r f e a s i b l e , t h e r e f o r e , t h a t

the starch adsorption i n c r e a s e d with a d e c r e a s e of pH b e c a u s e of

 75

0.81—

0.6h

0.4 h

0.2 L

PH

Fig 7.6 E f f e c t of pH on t h e a d s o r p t i o n d e n s i t y of p o t a t o
s t a r c h on s p o d u m e n e a t s e v e r a l starch c o n c e n t r a t i o n s
 176

t h e f o r m a t i o n of h y d r o g e n b o n d s b e t w e e n s u r f a c e s i l a n o l s and other

M - O H g r o u p s , and t h e s t a r c h h y d r o x y I g r o u p s . A t high pH v a l u e s ,

t h e p r o g r e s s i v e d i s s o c i a t i o n of both s e t s of h y d r o x y l sites made

h y d r o g e n bond f o r m a t i o n unlikely. T h e i n c r e a s e of mutual repulsion

w o u l d a l s o be e x p e c t e d t o d e c r e a s e t h e a d s o r p t i o n d e n s i t y as t h e

pH i n c r e a s e d . A n o t h e r c o n t r i b u t o r y f a c t o r c o u l d be t h a t w i t h an

increase in p H , t h e s o l u t i o n e n v i r o n m e n t b e c a m e a ' b e t t e r ' s o l v e n t

for starch resulting in d e c r e a s e d a d s o r p t i o n o f t h e polymer.

It w a s m e n t i o n e d in C h a p t e r 2 t h a t in t h e a d s o r p t i o n of P E O

on silica by h y d r o g e n b o n d i n g , t h e b r i d g i n g p r o t o n a p p e a r s t o be

d o n a t e d by t h e si lanol s i t e . B r e m e n k o and S e r g i e n k o (170) further

c o n c l u d e d t h a t a d s o r p t i o n of P E O on s i l i c a o c c u r r e d on strongly

a c i d i c s i l a n o l s w h i c h had a m a x i m u m c a p a c i t y f o r h y d r o g e n bonding

due t o a high p r o t o n lability. In t h e P E O - s i l i c a system the

d e c r e a s e of a d s o r p t i o n density with increase o f pH c a n , t h e r e f o r e ,

be a s s o c i a t e d o n l y w i t h a d e c r e a s e of u n d i s s o c i a t e d si lanol sites

with i n c r e a s e of pH.

In t h e p r e s e n t s y s t e m , h o w e v e r , both the s u r f a c e hydroxide

and t h e a l c o h o l i c h y d r o x y l s p o s s e s s both d o n o r and acceptor

properties. It is r e a s o n a b l e t o e x p e c t , t h e r e f o r e , t h a t in

weakly alkaline solution multiple hydrogen bonding reactions are

p o s s i b l e b e t w e e n , for e x a m p l e , S i - O H a n d R - O H , S i - 0 and R-OH,

and S i - O H and R - 0 s i t e s , w h e r e R - O H is t h e a l c o h o l i c hydroxyl

a n d R - 0 " its a l c o h o l ate a n i o n . A t pH v a l u e s g r e a t e r than 9 , it

is likely t h a t o n l y S i - 0 t y p e s i t e s a r e p r e s e n t on t h e surface,

as found for e x a m p l e on s i l i c a (153). In t h i s c a s e adsorption

can o n l y t a k e p l a c e b e t w e e n S i - 0 and R - O H s i t e s . In t h e

n e i g h b o u r h o o d of t h e p k v a l u e of s t a r c h , a d s o r p t i o n is d r a s t i c a l l y
reduced b e c a u s e all s i t e s a r e now p r e s e n t o n l y In t h e dissociated

form. It is well e s t a b l i s h e d in c a r b o h y d r a t e c h e m i s t r y t h a t t h e

a c i d i t y of t h e a l c o h o l i c h y d r o x y Is d e c r e a s e In t h e o r d e r C 2 ~ 0 H >

C6-OH > C -OH > C 4 - 0 H (93). These differences in p r o t o n lability

w o u l d be c o n s i s t e n t with t h e p r o g r e s s i v e d e c r e a s e of s t a r c h

adsorption with i n c r e a s e of pH o b s e r v e d up t o pH 12.

7.1.2.3 E f f e c t of m e t h y l a t i o n on t h e a d s o r p t i o n d e n s i t y of starch

A d s o r p t i o n of p o t a t o s t a r c h on m e t h y l a t e d s p o d u m e n e was

c a r r i e d o u t t o c o n f i r m t h a t a d s o r p t i o n o c c u r r e d by a h y d r o g e n

bonding reaction. T h e reaction b e t w e e n t r i m e t h y I c h l o r o s i lane

and si lanol g r o u p s Is r e p o r t e d as ( 1 1 5 , 153):

—;SI - O H , + (CH,),SICI — ^ S i -O-Si ( C H , ) ^ + HCI (7.1)

/ surf 3 3 / 3 3 ,
surf

It was t h e r e f o r e a r g u e d t h a t if a d s o r p t i o n of s t a r c h t o o k place

on s u r f a c e s i l a n o l s , a d e c r e a s e In a d s o r p t i o n density should

r e s u l t upon r e p l a c e m e n t of t h e s e g r o u p s with t r i m e t h y I si lyI

groups.

Fig 7 . 7 s h o w s t h e r e s u l t s o b t a i n e d . Clearly there was a

decrease in t h e a d s o r p t i o n d e n s i t y of starch upon s i l y l a t i o n of

t h e mineral surface a l t h o u g h s o m e a d s o r p t i o n w a s still taking

place. T h i s w a s a t t r i b u t e d t o t h e f a c t t h a t c o n v e r s i o n of t h e

s u r f a c e h y d r o x y Is w a s p r o b a b l y n o t q u a n t i t a t i v e b e c a u s e t h e

t r i m e t h y I s i lyI g r o u p Is a p p a r e n t l y t o o large and b l o c k s a c c e s s to

adjacent sites (153). E s t i m a t e s from s i m i l a r s t u d i e s on silica

s u g g e s t t h a t o n l y 4 0 - 5 0 $ of si lanol g r o u p s form t r i m e t h y l s i loxane

bonds (115, 153). It is a l s o p o s s i b l e t h a t s o m e r e h y d r a t i o n of

 178

I .4

.2 _

0.8 -

0.4 -

10 20 30 40 50
E q u i l i b r i u m s t a r c h c o n c e n t r a t i o n , mg I

O Untreated spodumene
• Methylated spodumene
U n t r e a t e d s p o d u m e n e a t pH 10

Fig 7 . 7 A d s o r p t i o n d e n s i t y of p o t a t o s t a r c h on methylated
s p o d u m e n e a s a function of e q u i l i b r i u m concentration
a t pH 9
the hydrophobic surface took place (||5) a t t h e a Ika)ine pH used,

and t h a t this resulted in t h e a b s t r a c t i o n of a small a m o u n t of

hydrogen bonded polymer. T h e r e s u l t s of Fig 7 . 7 a r e , h o w e v e r , in

q u a l i t a t i v e a g r e e m e n t w i t h t h e r e s u l t s of a large n u m b e r o f

studies i n v o l v i n g p o l y m e r s which a d s o r b by a h y d r o g e n bonding

m e c h a n i s m and in w h i c h a d e c r e a s e in a d s o r p t i o n w a s o b t a i n e d by

e i t h e r a m e t h y l a t i o n t e c h n i q u e o r d e h y d r o x i lation by h e a t

treatment ( 84 , 95 , 1 1 4 , 170 ).

T h e f o r m a t i o n of a l c o h o l a t e s m i g h t be of r e l e v a n c e t o t h e

adsorption mechanism, particularly since there was a significant

a m o u n t of NaCI in s o l u t i o n . A reduction in t h e n e g a t i v e charge

of s t a r c h could h a v e , for e x a m p l e , t a k e n p l a c e t h r o u g h t h e formation

of c a t i o n - c o n t a i n i n g c h e l a t e s of t h e form s u g g e s t e d by Rendleman

(93):

C C

H — 0 0

Na

T h i s a u t h o r r e p o r t s a l s o t h a t c h e l a t e s of m u l t i v a l e n t c a t i o n s are

m o r e s t a b l e than t h o s e of m o n o v a l e n t a n a l o g u e s . It m i g h t be

a r g u e d , h o w e v e r , t h a t if f o r m a t i o n o f such s p e c i e s is s i g n i f i c a n t ,

beryl w i t h m o r e Fe on t h e s u r f a c e t h a n s p o d u m e n e w o u l d have

a b s t r a c t e d m o r e s t a r c h than t h e latter. The contrary w a s , however,

o b s e r v e d t o be t r u e , s u g g e s t i n g t h a t if f o r m a t i o n of t h e s e species

took place, they were not significant contributors to the

adsorption mechanism.
 180

7.1.2.4 A d s o r p t i o n of H + arid OH ions by the si I icate mirieraI s

Although the preceeding considerations indicate that

a d s o r p t i o n of s t a r c h o c c u r s by h y d r o g e n b o n d i n g , t h i s d o e s n o t

r e a d i l y e x p l a i n t h e o b s e r v e d o r d e r of a d s o r p t i o n on t h e silicates

which decreased in t h e s e q u e n c e s p o d u m e n e > m i c r o c l i n e > beryl >

lepidolite > m u s c o v i t e . It has been a d e q u a t e l y shown ( 84 , 94 ,

95, 170 ) t h a t t h e a d s o r p t i o n of s o m e s y n t h e t i c p o l y m e r s on

s i l i c a , by h y d r o g e n b o n d i n g , is d e p e n d e n t on t h e s u r f a c e silanol

density. By a n a l o g y , it w o u l d be e x p e c t e d t h a t t h e observed

o r d e r of p o t a t o s t a r c h a d s o r p t i o n on t h e s i l i c a t e s w o u l d be

i n f l u e n c e d by s i m i l a r c o n s i d e r a t i o n s . Acid/base titrations were

therefore conducted to obtain more i n f o r m a t i o n on t h e d e n s i t y of

a c i d i c s i t e s on t h e s i l i c a t e m i n e r a l s . S i m i l a r s t u d i e s h a v e been

used s u c c e s s f u l l y in t h e c h a r a c t e r i s a t i o n of s i l a n o l g r o u p s on

different silica modifications (153).

The experimental technique (171) c o n s i s t e d of t h e potentio-

m e t r i c t i t r a t i o n of t h e mineral suspensions in a q u e o u s electrolyte

( I 0 ~ 3 M N a C l ) s o l u t i o n s with H + o r 0 H ~ ions a t 25°C. A blank

e l e c t r o l y t e s o l u t i o n of the same v o l u m e w a s t h e n t i t r a t e d with

a c i d o r alkali in t h e s a m e m a n n e r . The difference between the

a m o u n t s of OH or H + ions r e q u i r e d t o p r o d u c e t h e s a m e pH in the

s i l i c a t e s u s p e n s i o n and t h e b l a n k s a m p l e of e l e c t r o l y t e , g i v e s

t h e a m o u n t of OH or H + ions a d s o r b e d a t t h e silicate/water

interface. A gas-tight titration vessel w a s used and purified

nitrogen was passed through to avoid contamination from atmospheric

C02. A f t e r e a c h a d d i t i o n of acid o r a l k a l i , . t h e s u s p e n s i o n was

equilibrated f o r 3 0 m i n s b e f o r e pH m e a s u r e m e n t . Preliminary tests

 181

s h o w e d t h a t a reasonably s t e a d y pH value was o b t a i n e d within

this time limit.- The pH of the suspension was k e p t lower than

pH 9 to avoid bulk d i s s o l u t i o n of t h e s i l i c a t e minerals.

The results o b t a i n e d for s p o d u m e n e , beryl and m i c r o c l i n e are

shown in Fig 7 . 8 . M u s c o v i t e and lepidolite w e r e not included in

t h e s e e x p e r i m e n t s due to t h e i r good cation e x c h a n g e properties.

The a d s o r p t i o n d e n s i t y , r ( H - O H ) , on s p o d u m e n e w a s o b s e r v e d to

decrease m a r k e d l y upon m e t h y l a t i o n of the mineral a s w o u l d be

e x p e c t e d from the above c o n s i d e r a t i o n s . With a d e c r e a s e of pH

below pH 8 , t h e r e w a s a general increase in t h e r(H-0H ) v a l u e s .

The o r d e r of a b s t r a c t i o n on the m i n e r a l s was s p o d u m e n e £ m i c r o c l i n e

> beryl. As t h i s o r d e r is s i m i l a r to t h a t o b s e r v e d for the

adsorption of starch on the m i n e r a l s , it is t e m p t i n g t o c o n c l u d e

t h a t a d s o r p t i o n of starch is related to p a r t i c u l a r s u r f a c e h y d r o x y I

d e n s i t i e s on the respective silicates.

H o w e v e r , this o r d e r is a l s o s i m i l a r t o t h a t e s t a b l i s h e d in

the cation e x c h a n g e s t u d i e s . F u r t h e r , comparison of t h e a b o v e

data t o s i m i l a r results on q u a r t z (I "71) and a l u m i n a (1*72) shows

t h a t a d s o r p t i o n d e n s i t i e s in t h e p r e s e n t w o r k are much higher

than t h o s e o b t a i n e d in many s i m i l a r s t u d i e s , it is t h e r e f o r e likely

t h a t t h e r e w a s an e x c h a n g e of H + and N a + ions with monovalent

cations p r e s e n t on the mineral s u r f a c e , as was e a r l i e r indicated

in the s t u d y on t h e adsorption of DA a t low c o n c e n t r a t i o n s . If

this is the c a s e , which s e e m s likely, the results of Fig 7.8 do

not represent true adsorption.

The c o n c e n t r a t i o n of m o n o v a l e n t c a t i o n s in s o l u t i o n , a f t e r

addition of e a c h t i t r a n t ' d o s e ' and e q u i l i b r a t i o n , w a s determined.

Fig 7.9 s h o w s the results o b t a i n e d for a suspension of s p o d u m e n e .

 1 1
1 — — 1 l i — i ' i > i

o Spodumene

a Mi crocli ne
\ • Beryl

o v \ 3 Methylated spodumene

1 i i .
4 5 6 7 8 9

PH

Fig 7 . 8 ' A d s o r p t i o n ' of H + and OH on s p o d u m e n e , beryl and

m i c r o c l i n e as a function of pH

csl
i

P 2.5

o
X

Fig 7.9 E f f e c t of pH on t h e c o n c e n t r a t i o n of in s o l u t i o n
for spodumene
1+ is c l e a r t h a t t h e c o n c e n t r a t i o n of Li+ . i n s o l u t i o n increased

with a d e c r e a s e of p H b e l o w pH 8 due t o an i n c r e a s e in c a t i o n

exchange activity. F u r t h e r m o r e , from t h e form of t h e c u r v e and

the concentration level of L i + p a s s i n g into s o l u t i o n , it is

possible that the titration r e s u l t s in F i g 7 . 8 w e r e significantly

i n f l u e n c e d by t h e c a t i o n e x c h a n g e b e h a v i o u r o f t h e m i n e r a l s . Thus,

although it is p o s s i b l e t h a t t h e r e l a t i v e (H+-0H ) abstraction

observed r e f l e c t e d d i f f e r e n t d e g r e e s of s u r f a c e a c i d i t y or

h y d r o x i d e c o n c e n t r a t i o n , it is n o t p o s s i b l e t o unambiguously

s e p a r a t e t h i s from e f f e c t s d e r i v e d from t h e c a t i o n exchange

p r o p e r t i e s of t h e s i l i c a t e s using a c i d / b a s e t i t r a t i o n s . Similar

c o n s i d e r a t i o n s a p p l y t o a n y o t h e r m e t h o d of e s t i m a t i n g surface

acidity of these minerals in w h i c h i o n g e n i c s p e c i e s are utilised,

i r r e s p e c t i v e of w h e t h e r t h e s p e c i e s are i n o r g a n i c o r o r g a n i c

ions. It is t h e r e f o r e n o t p o s s i b l e t o s t a t e w i t h c e r t a i n t y that

the d i f f e r e n t s t a r c h a d s o r p t i o n s o b t a i n e d on t h e different

silicate minerals is r e l a t e d t o t h e d e n s i t y of t h e silanol sites.

7.2 Viscosity studies

It is known ( 37 , 42 ) t h a t t h e a d s o r p t i o n characteristics

of s t a r c h a r e s t r o n g l y i n f l u e n c e d by t h e m e t h o d in w h i c h it is

prepared. T h e v i s c o s i t y s t u d i e s t h e r e f o r e had t w o a i m s : to

c o m p a r e t h e e f f e c t s o f s e v e r a l m e t h o d s of s o l u b i l i s i n g potato

starch on t h e m o l e c u l a r w e i g h t and t o o b t a i n i n f o r m a t i o n on t h e

relative molecular w e i g h t s of the different starch polymers used

in t h e a d s o r p t i o n and H a l l i m o n d t u b e f l o t a t i o n s t u d i e s . The

u t i l i t y of v i s c o s i t y m e a s u r e m e n t s in t h e d e t e r m i n a t i o n of relative
 184

m o l e c u l a r s i z e s in p o l y m e r s o l u t i o n s h a s a l r e a d y been n o t e d in

Chapter 3.

T h e s e v e r a l m e t h o d s of p r e p a r a t i o n of starch solutions

investigated were:

Method A: T h i s m e t h o d c o r r e s p o n d e d t o t h e general solubi Iisation

procedure outlined in s e c t i o n 3 . 2 . 5 , e x c e p t t h a t larger q u a n t i t i e s

of r e a g e n t s a s s e t o u t in s e c t i o n 3 . 2 . 8 w e r e u s e d . The method

w a s a l s o used in t h e i n v e s t i g a t i o n of r e l a t i v e m o l e c u l a r weights

as it is later s h o w n t h a t t h e p r o c e d u r e r e s u l t e d in t h e least

a m o u n t of s t r u c t u r a l b r e a k d o w n of t h e p o l y m e r chains.

M e t h o d B: About 100 ml of b o i l i n g w a t e r , c o n t a i n i n g the

requisite amount of N a O H , was added to a beaker containing a

w e i g h e d q u a n t i t y of s t a r c h d i s p e r s e d in several c m 5 of w a t e r . The

s t a r c h w a s then s w e l l e d g e n t l y for several m i n u t e s b e f o r e cooling

and v o l u m e t r i c dilution.

M e t h o d C: T h e s t a r c h w a s c a u s t i c i s e d as in M e t h o d A b u t w i t h

s i m u l t a n e o u s h e a t i n g to a b o u t 85°C for 3 0 m i n .

M e t h o d D: The s t a r c h w a s c a u s t i c i s e d a t room t e m p e r a t u r e as in

A e x c e p t t h a t t h e b e a k e r w a s fitted with s t a i n l e s s steel buffles

to p e r m i t t h e f o r m a t i o n of high s h e a r rates in t h e s o l u t i o n . The

stirring speed was increased to 1000 rpm and t h e solubi Iisation

time extended to I h.

M e t h o d E: Si mi lar t o M e t h o d C e x c e p t t h a t n o N a O H w a s a d d e d

d u r i n g solubi I i s a t i o n . T h e starch s o l u t i o n s p r e p a r e d by t h i s

m e t h o d w e r e e x t r e m e l y v i s c o u s a n d it w a s a p p a r e n t t h a t e x t e n s i v e

gel f o r m a t i o n had occurred.

 T h e s t a r c h s o l u t i o n s p r e p a r e d by t h e s e m e t h o d s w e r e all

o b s e r v e d t o be v i s i b l y c l e a r , s u g g e s t i n g t h a t t h e p o l y m e r s w e r e

reasonably dispersed.

T h e r e s u l t s of t h e v i s c o s i t y t e s t s a r e s h o w n in Fig 7.10.

AI I t h e c u r v e s w e r e c o n s t r u c t e d by t h e least s q u a r e s m e t h o d . The

extrapolated intrinsic viscosities, [ n ] , for the different

m e t h o d s of p r e p a r a t i o n w e r e 2 9 5 , 2 8 6 , 2 7 8 and 2 5 8 litres mg

for m e t h o d s A , B , C and D r e s p e c t i v e l y . Assuming the applicability

of t h e M a r k - H o u w i n k e q u a t i o n , t h e d i f f e r e n c e s in t h e v a l u e s of

[njindicate that the different agitation and thermal treatments

used did n o t s i g n i f i c a n t l y a f f e c t t h e m o l e c u l a r w e i g h t s of t h e

dissolved polymers. T h e s t a r c h s o l u t i o n s p r e p a r e d by m e t h o d E

showed non-Newtonian flow p r o p e r t i e s in t h e v i s c o m e t e r employed.

T h i s w a s o b v i o u s l y d u e t o t h e high d e g r e e of a s s o c i a t i o n obtained

in t h i s case.

Fig 7 . 1 0 a l s o s h o w s v i s c o s i t y p l o t s f o r B r i t i s h g u m and

maize starch prepared u n d e r s i m i l a r c o n d i t i o n s to t h o s e used for

t h e p o t a t o starch (method A ) . The extrapolated intrinsic

v i s c o s i t i e s w e r e 2 5 . 2 and 162 litres m g ' for t h e t w o polymers

respectively. S i m i l a r p l o t s c o u l d n o t be c o n s t r u c t e d for t h e

d e x t r i n s b e c a u s e t h e d i f f e r e n c e s b e t w e e n t h e e f f l u x t i m e of t h e

s o l v e n t and s o l u t i o n w e r e s m a l l . This is for e x a m p l e demonstrated

in t h e v a l u e s of t h e r e l a t i v e v i s c o s i t i e s shown in T a b l e 7.1.

Although in p r i n c i p l e h i g h e r p o l y m e r c o n c e n t r a t i o n s t h a n those

in T a b l e 7.1 c o u l d h a v e been u s e d , v i s c o s i t y e q u a t i o n s assume

( 1 1 6 , 117) t h a t t h e d e n s i t y of t h e s o l u t i o n a p p r o x i m a t e s to t h a t

of t h e s o l v e n t . A t high c o n c e n t r a t i o n this assumption would no

longer be v a l i d a n d t h e v i s c o s i t y e q u a t i o n s b e c o m e m o r e complex.
 C o n c e n t r a t i o n of B r i t i s h g u m , mg I

Starch concentration, mg I

Fig 7 . 1 0 Intrinsic v i s c o s i t i e s of s t a r c h p o l y m e r s ; t h e
letters r e f e r t o t h e m e t h o d s of s o l u b i I i s a t i o n
(see t e x t )
T a b l e 7.1 R e l a t i v e v i s c o s i t i e s o f d e x t r i n s o l u t i o n s as a
function of c o n c e n t r a t i o n a t 25°C

Relati vi s c o s i t y
Dextrin concen-
White dextrin Ye I Iow dextri n
t r a t i o n , mg litre '

1000 1.013 I .009

2000 I .02! 1.019

3000 I .029 1.028

4000 1.041 I .037

5000 I .050 I .045

F r o m t h e r e s u l t s , it can be c o n c l u d e d t h a t t h e m o l e c u l a r weights

of the p o l y m e r s used d e c r e a s e d in t h e o r d e r p o t a t o s t a r c h > m a i z e

starch British gum > dextrins. T h i s o r d e r is r e f l e c t e d in

the adsorption d e n s i t i e s o f t h e s e c o m p o u n d s on spodumene.

In t h e a b o v e c o n s i d e r a t i o n s it h a s been a s s u m e d t h a t polymer-

solvent interactions r e m a i n e d a p p r o x i m a t e l y t h e s a m e for t h e

different starch compounds used. It can be a r g u e d t h a t t h i s

assumption is n o t u n r e a s o n a b l e b e c a u s e t h e c u r v e s in Fig 7 . 1 0

are of a s i m i l a r form t o t h e H u g g i n s e q u a t i o n ( 1 1 7 , 174, 175):

+ s
vel/c =
M H2c (7 2)
-

A l t h o u g h t h e H u g g i n s s l o p e c o n s t a n t , 3 , m a y be i n f l u e n c e d by a

n u m b e r of f a c t o r s ( e . g . p o l y d i s p e r s i t y , d e g r e e of b r a n c h i n g , e t c )

it is t h o u g h t (117) t h a t for h o m o l o g o u s f r a c t i o n s of t h e s a m e

p o l y m e r , t h e v a l u e of 3 d o e s n o t c h a n g e much as long as t h e

s o l v e n t is t h e s a m e . T h e s i m i l a r i t y of s l o p e s in t h e r e s u l t s of

Fig 7 . 1 0 m i g h t t h e r e f o r e p r o v i d e s o m e j u s t i f i c a t i o n f o r the above

assumption.

7.3 H a [ I I m o n d t u b e f 1 o t a t i o n t e s t s in t h e p r e s e n c e of s t a r c h e s

7.3.I Hai f imorid t u b e f l o t a t i o n t e s t s in t h e p r e s e n c e of potato

starch

T h e r e s u l t s of Hal Iimond t u b e f l o t a t i o n t e s t s in t h e presence

-5

of p o t a t o s t a r c h a n d 3 x 10 M DA a r e s h o w n in Fig 7 . 1 1 . At a

starch concentration of 40 p p m , s p o d u m e n e w a s m o r e o r less

completely depressed while lepidolite was about 50$ depressed at

 189

PH

^ MicrocIine
• Beryl

• Lepi do Iite

O Spodumene

Fig 7.11 E f f e c t of 4 0 ppm p o t a t o s t a r c h on t h e f l o t a t i o n

r e c o v e r y of m i c r o c l m e , b e r y l , l e p i d o l i t e a n d
s p o d u m e n e in 3 x 10 5 M DA
pH II. In c o n t r a s t , beryl and m i c r o c l i n e s h o w e d complete

f l o t a t i o n a l t h o u g h t h e pH r a n g e for f l o t a t i o n w a s considerably

reduced from t h a t o b t a i n e d in t h e a b s e n c e . o f s t a r c h (cf Fig 6 . 5 ) ,

indicating that some depression did t a k e p l a c e e v e n for t h e s e

minerals. T h e i n a b i l i t y of p o t a t o s t a r c h to d e p r e s s microcline

t o a c o m p a r a b l e e x t e n t t o t h a t o b t a i n e d for s p o d u m e n e is

s u r p r i s i n g s i n c e it had been e s t a b l i s h e d in t h e a d s o r p t i o n tests

t h a t m i c r o c l i n e a b s t r a c t e d a s i m i l a r a m o u n t of p o t a t o s t a r c h at

pH 10. T h i s s u g g e s t s , t h e r e f o r e , t h a t t h e a b i l i t y of s t a r c h to

a c t as a d e p r e s s a n t is n o t m e r e l y d e p e n d e n t on a d s o r p t i o n density

b u t is i n f l u e n c e d by additional f a c t o r s , such as t h e configuration

of t h e a d s o r b e d p o l y m e r . A g r e a t deal of e v i d e n c e h a s been

accumulated that starch molecules exist in t h e h e l i c a l conformation

in t h e p r e s e n c e of o r g a n i c r e a g e n t s . Some of t h i s e v i d e n c e is

considered in g r e a t e r detail later.

Another reasonable explanation for the above observation is

t h a t the d e g r e e of d e p r e s s i o n o b t a i n e d d e p e n d e d p a r t l y on t h e zeta

p o t e n t i a l s of t h e s i l i c a t e s . T h i s view is s t r o n g l y s u p p o r t e d by

flocculation results obtained in t h e p r e s e n c e of a e r y I a m i d e

polymers (85 , 176, 177) in w h i c h t h e zeta p o t e n t i a l s on t h e

m i n e r a l s r e m a i n e d n e g a t i v e a f t e r a d s o r p t i o n of t h e p o l y m e r s . In

such c a s e s a d s o r p t i o n of c a t i o n i c c o l l e c t o r ions by a c o u l o m b i c

mechanism is t h e r e f o r e still p o s s i b l e , a l t h o u g h it m i g h t be

i n f l u e n c e d by t h e d e g r e e of s t e r i c h i n d e r a n c e d u e t o t h e a d s o r b e d

polymer chains. T h e EM r e s u l t s p r e s e n t e d in Fig 5 . 2 s h o w e d that

in t h e pH r a n g e II t o 12 w h e r e c o m p l e t e f l o t a t i o n of microcline

w a s o b t a i n e d , t h e n e g a t i v e EM w a s g r e a t e s t on t h i s m i n e r a l . It is
 191

reasonable to c o n c l u d e , t h e r e f o r e , t h a t although microcline

adsorbed relatively large a m o u n t s of s t a r c h , its lack of

depression is r e l a t e d t o its r e l a t i v e l y larger zeta potential

and h e n c e g r e a t e r a m i n e a d s o r p t i o n ability.

This conclusion is e x p e r i m e n t a l l y e a s y t o d e m o n s t r a t e because

it w a s e s t a b l i s h e d in s e c t i o n 5.3 t h a t t h e n e g a t i v e electrophoretic

m o b i l i t i e s of m i c r o c l i n e and lepidolite were enhanced following

a c i d i c s c r u b b i n g w h i l e t h a t of beryl remained unchanged. Hallimond

t u b e t e s t s w e r e t h e r e f o r e c o n d u c t e d u s i n g acid w a s h e d specimens

of the three m i n e r a l s . Figs 7 . 1 2 , 7 . 1 3 and 7 . 1 4 s h o w t h e results

of t h e s e t e s t s . It can be seen t h a t for both m i c r o c l i n e and

lepidolite t h e i n c r e a s e in t h e n e g a t i v e zeta p o t e n t i a l resulted

in an e x t e n d e d pH range of f l o t a t i o n and t h a t lepidolite was no

longer d e p r e s s e d in 4 0 ppm p o t a t o s t a r c h . In t h e c a s e of beryl,

however, there was no change in t h e f l o t a t i o n recovery of the

mineral following acidic washing.

It m i g h t , t h e r e f o r e , be c o n c l u d e d from t h i s and t h e preceeding

c o n s i d e r a t i o n s t h a t the d e p r e s s a n t a b i l i t y of s t a r c h probably

d e p e n d s on a n u m b e r o f f a c t o r s such as t h e t y p e and n u m b e r of

surface hydroxide sites (i.e. surface acidity/basicity), the

c o n f o r m a t i o n of t h e s t a r c h m o l e c u l e s in s o l u t i o n and in t h e

a d s o r b e d s t a t e , and t h e Stern p o t e n t i a l on t h e s i l i c a t e minerals.

A s t h e s e f a c t o r s a r e all s t r o n g l y i n f l u e n c e d by p H , it is likely

t h a t they are highly interrelated. For example, the adsorption

density is d e t e r m i n e d by t h e n u m b e r of u n d i s s o c i a t e d h y d r o x y Is

on both t h e mineral and s t a r c h , t h e p o l y m e r c o n f i g u r a t i o n in

s o l u t i o n and t h e mutual e l e c t r o s t a t i c r e p u l s i o n b e t w e e n polymer

and m i n e r a l particle. In t u r n t h e a d s o r p t i o n density determines

 192

100

80

60

q
>
o
o 40
0
c
o

° 20

j i i i i l
8 m 10 12 14
pH

Fig 7 . 1 2 E f f e c t of HCI w a s h i n g on t h e f l o t a t i o n r e c o v e r y of
m i c r o c l i n e in t h e p r e s e n c e of 40 ppm p o t a t o s t a r c h
and 3 x 1 0 ~ 5 DA
-i 1 1 r
100

80

60
0
>
o
o
0
40

+-
0
o
Ll_
20

j i i l
6 8 u 10 12
pH
Fig 7 . 1 3 E f f e c t of HCI w a s h i n g on t h e f l o t a t i o n r e c o v e r y of
lepidolite in t h e p r e s e n c e of 4 0 ppm p o t a t o s t a r c h
and 3 x I 0 " 5 M DA
 193

-i r
100
/
I
i

9
80

60

0 i
>-
1 i
i o
0
> 40
o
o
0)
c
o
CD
20 O I
4— /
O /
ll_

j i i l.
8 u 10 12
ph
Untreated mineral in 4 0 ppm s t a r c h

-5,
U n t r e a t e d mineral In 3 x 10 M DA only

HCI w a s h e d mineral in 4 0 ppm starch

Fig 7 . 1 4 E f f e c t of HCI w a s h i n g on t h e f l o t a t i o n r e c o v e r y of
beryl in t h e p r e s e n c e of 4 0 ppm s t a r c h and 3 x I 0 ~ 5 M
DA
the d e g r e e of p r o t e c t i v e c o l l o i d a c t i o n a n d , t h e r e f o r e , t h e

a c c e s s i b i I i t y of c o l l e c t o r ions t o t h e ionised s i t e s a t t h e

s iIi c a t e / w a t e r i n t e r f a c e .

It m i g h t a l s o be b r i e f l y n o t e d t h a t a l t h o u g h lepidolite

did n o t show a p a r t i c u l a r l y high s t a r c h a d s o r p t i o n d e n s i t y , it

w a s r e l a t i v e l y m o r e d e p r e s s e d than both beryl and microcline.

T h i s s u g g e s t s t h a t t h e a c c e s s i b l e area on t h i s mineral to t h e

s t a r c h m o l e c u l e s m i g h t h a v e been c o n s i d e r a b l y less t h a n that

available for N 2 adsorption.

7.3.2 Hal Iimond t u b e f l o t a t i o n s t u d i e s in t h e p r e s e n c e of m a i z e

s t a r c h , d e x t r i n s and B r i t i s h gum

F i g s 7 . 1 5 and 7.16 show t h e f l o t a t i o n r e c o v e r y of spodumene

and l e p i d o l i t e , m i c r o c l i n e and beryl in t h e p r e s e n c e of m a i z e

s t a r c h a s a f u n c t i o n of p H . For c o m p a r a t i v e p u r p o s e s t h e results

o b t a i n e d with p o t a t o s t a r c h are a l s o s h o w n . It is c l e a r t h a t m a i z e

starch is a less e f f e c t i v e d e p r e s s a n t than p o t a t o s t a r c h for all

the m i n e r a l s s t u d i e d . A l t h o u g h c o m p l e t e d e p r e s s i o n of microcline

and beryl had n o t been o b t a i n e d with p o t a t o s t a r c h , t h e flotation

pH range of t h e t w o m i n e r a l s w a s r e l a t i v e l y w i d e r in t h e presence

of m a i z e s t a r c h . No change in t h e f l o t a t i o n r e c o v e r y of t h e

minerals was obtained in t h e p r e s e n c e of B r i t i s h g u m , w h i t e

d e x t r i n and y e l l o w d e x t r i n , a l t h o u g h relatively larger concentrations

(100 p p m ) w e r e used.

T h i s is t y p i f i e d by t h e r e s u l t s shown in Fig 7 . 1 7 . This

s u g g e s t s t h a t t h e a b i l i t y of t h e s t a r c h p o l y m e r s t o f u n c t i o n as

depressants is s t r o n g l y related t o their respective molecular

weights. T h e r e f o r e , for t h e c o n c e n t r a t i o n r a n g e of B r i t i s h gum

 i 1 1 « 1 1 r
5235
O Spodumene
a Lepi do Iite
S p o d u m e n e in 4 0 ppm p o t a t o starch
80
Lepidolite in 4 0 ppm potato starch

60

40

20

10 12
pH
Fig 7.15 E f f e c t of 4 0 ppm m a i z e starch on t h e flotation
recovery of s p o d u m e n e and Iepido Iite in 3 x 10 M
DA

Fig 7.16 E f f e c t of 4 0 ppm m a i z e starch on t h e recovery of

mi c r o c line and beryl in 3 x 1 D A
 196

1 R 1 t 1 » i

%
100 -

9 /a
80 - 6* 1
D
P
/ A

/ 1
' 1
•as. 60 -

•t 4I \
1
i
0)
> / i
o
o
CD 40 - 9L i
c 1 i
o A / i
'+-
(u
-h
1 1
o 20 _
Ll_ / i
/ i
o/ 8i
J* i . I .
pH
-5
In 3 x 10 M dodecylamine only

• In 5 0 ppm B r i t i s h gum

o In 100 ppm B r i t i s h gum

In 100 ppm w h i t e dextrin
O
In 100 ppm y e l l o w dextrin
A

Fig 7 . 1 7 E f f e c t of B r i t i s h g u m , w h i t e and y e l l o w d e x t r i n s
on t h e f l o t a t i o n r e c o v e r y in 3 x DA
and t h e d e x t r i n s used in t h e t e s t s , n o d e p r e s s i o n w a s o b t a i n e d

due t o t h e r e l a t i v e l y low m o l e c u l a r w e i g h t s of t h e s e compounds

(cf a d s o r p t i o n studies). F u r t h e r , e v e n for t h e high molecular

weight polymers like p o t a t o and m a i z e s t a r c h e s , d e p r e s s i o n

d e p e n d s on t h e c o n c e n t r a t i o n of p o l y m e r in s o l u t i o n . Fig 7 . 1 8

s h o w s t h a t as t h e c o n c e n t r a t i o n of p o l y m e r in s o l u t i o n increased

t h e r e w a s o n l y a small decrease in f l o t a t i o n r e c o v e r y until a

critical concentration of s t a r c h w a s r e a c h e d , d e p e n d i n g on t h e

m o l e c u l a r w e i g h t of t h e s t a r c h , a t w h i c h p o i n t a m a r k e d decrease

in r e c o v e r y t o o k place.

7.3.3 E f f e c t of s t a r c h p r e p a r a t i o n m e t h o d of f l o t a t i o n recovery

A limited n u m b e r o f H a l l i m o n d t u b e t e s t s w a s c a r r i e d o u t t o

d e m o n s t r a t e t h e e f f e c t of t h e d i f f e r e n t m e t h o d s of p r e p a r i n g the

s t a r c h s o l u t i o n s on t h e f l o t a t i o n recovery. Fig 7.19 s h o w s the

r e s u l t s o b t a i n e d for p o t a t o s t a r c h p r e p a r e d by the several methods

described earlier. It is a p p a r e n t t h a t t h e d e p r e s s a n t a b i l i t y of

s t a r c h d e p e n d e d on t h e m a n n e r in w h i c h t h e s t a r c h w a s solubilised

and d e c r e a s e d in t h e o r d e r m e t h o d A > B > C > D . T h u s , as t h e

level of s h e a r a p p l i e d in p r e p a r i n g t h e s t a r c h increased, there

was a slight decrease in d e p r e s s a n t a b i l i t y of t h e s t a r c h . The

a b o v e o r d e r is, t h e r e f o r e , c o n s i s t e n t with the d e c r e a s e of

m o l e c u l a r w e i g h t f o r t h e d i f f e r e n t solubi Iisation p r o c e d u r e s , as

h a s a l r e a d y been e l u c i d a t e d . This illustrates the need to

maintain low s h e a r f o r c e s in s o l u t i o n during the preparation of

starch solutions.
g 7.18 E f f e c t of s t a r c h c o n c e n t r a t i o n on t h e f l o t a t i o n
r e c o v e r y of s p o d u m e n e a t pH II.3 a n d 3 x I O ~ 5 M DA

pH
g 7.19 E f f e c t of m e t h o d s of starch p r e p a r a t i o n on t h e
f l o t a t i o n r e c o v e r y of s p o d u m e n e In 4 0 ppm starch
and 3 x I 0 ~ 5 m DA
 P o t a t o s t a r c h s o l u t i o n s p r e p a r e d by b o i l i n g in w a t e r in

t h e a b s e n c e of N a O H w e r e found t o h a v e Iittle and irreguIar

depressant ability. This was attributed to a decrease in the

n u m b e r of s i t e s w i t h a latent a d s o r p t i v e a f f i n i t y for t h e

m i n e r a l p a r t i c l e s and the i r r e g u l a r rheological p r o p e r t i e s of

gel s y s t e m s . These considerations highlight the significance

of chain e x t e n s i o n t h a t t a k e s p l a c e f o r starch c o m p o u n d s in

t h e p r e s e n c e of N a O H .
 CHAPTER EIGHT

INTERACTION OF S T A R C H A N D D O D E C Y L A M I N E WITH E A C H OTHER

AND THE MINERAL SURFACE

 In t h e p r e c e e d i n g c h a p t e r s t h e a d s o r p t i o n m e c h a n i s m s of

starch and D A h a v e been d i s c u s s e d . T h e initial aim of t h e

work described in t h i s c h a p t e r w a s t o e s t a b l i s h t h e coadsorption

b e h a v i o u r of s t a r c h and DA on t h e s i l i c a t e m i n e r a l s . However,

t h e i n v e s t i g a t i o n s w e r e e x t e n d e d t o include a s t u d y of t h e

interaction b e t w e e n starch and DA in t h e a b s e n c e of m i n e r a l

particles. T h i s w a s b e c a u s e t h e m i x i n g of s t a r c h and amine

solutions in c e r t a i n p r o p o r t i o n s p r o d u c e d a p r e c i p i t a t e .

8.I C o a d s o r p t i o n of s t a r c h and d o d e c y l a m i n e on spodumene

Fig 8.1 s h o w s t h e a d s o r p t i o n d e n s i t y of DA on spodumene

in t h e p r e s e n c e of t w o d i f f e r e n t s t a r c h c o n c e n t r a t i o n s a t pH 9 .

For comparative reasons the adsorption i s o t h e r m of DA in t h e

a b s e n c e of s t a r c h a n d a t t h e s a m e pH v a l u e h a s been included.
-4

With an i n c r e a s e in DA c o n c e n t r a t i o n beyond a b o u t I x 10 M

there was a marked increase in t h e a d s o r p t i o n d e n s i t y of a m i n e

in t h e p r e s e n c e of s t a r c h . The increase in t h e a d s o r p t i o n did

n o t , h o w e v e r , show a t e n d e n c y t o w a r d s s a t u r a t i o n , a s w a s found

f o r t h e a d s o r p t i o n of DA on s p o d u m e n e in the a b s e n c e of starch.

It w o u l d a p p e a r t h a t in t h e p r e s e n c e of 4 0 p p m s t a r c h , a p l a t e a u

m i g h t h a v e b e e n o b t a i n e d had h i g h e r c o n c e n t r a t i o n s of a m i n e

been u s e d . In t h e p r e s e n c e of 8 0 ppm s t a r c h , h o w e v e r , t h e r e w a s

n o i n d i c a t i o n of a p l a t e a u a t t h e h i g h e s t DA c o n c e n t r a t i o n used

which w a s d e t e r m i n e d by a m i n e so Iubi Iity-pH considerations

(cf Fig 2 . 4 ) . F u r t h e r m o r e , t h e r e w a s not m u c h d i f f e r e n c e in

the adsorption d e n s i t i e s of DA o b t a i n e d at t h e two s t a r c h

 Equilibrium concentration of a m i n e , M
• In 80 ppm s t a r c h
O In 4 0 ppm starch
^ No starch added
M o n o l a y e r c o v e r a g e a s s u m i n g c r o s s s e c t i o n a l a r e a of
20°a2 f o r h y d r o c a r b o n chain

Fig 8.1 E f f e c t of e q u i l i b r i u m a m i n e c o n c e n t r a t i o n on t h e
a d s o r p t i o n d e n s i t y of a m i n e on s p o d u m e n e in t h e
p r e s e n c e of p o t a t o s t a r c h a t pH 9
 203

concentrations used.

F u r t h e r c o m p a r i s o n of t h e i s o t h e r m s reveal t w o a d d i t i o n a l
-4

features. A t a m i n e c o n c e n t r a t i o n s below a b o u t 2 . 4 x 10 M , the

adsorption d e n s i t y of DA in t h e p r e s e n c e of s t a r c h w a s consistently

lower t h a n t h a t o b t a i n e d in the a b s e n c e of t h e m a c r o m o I e c u l e ,

but at higher concentrations the opposite was true. It w o u l d

therefore appear that at low a m i n e c o n c e n t r a t i o n s , the presence

of starch i n h i b i t e d t h e a d s o r p t i o n of DA on s p o d u m e n e w h i l e a t

r e l a t i v e l y high c o n c e n t r a t i o n s , a d s o r p t i o n of t h e c o l l e c t o r w a s

enhanced. Further experiments were therefore conducted to

explain this contrasting behaviour.

The adsorption d e n s i t y of a m i n e w a s m e a s u r e d a s a f u n c t i o n

of s t a r c h c o n c e n t r a t i o n a t pH 9 and in t h e p r e s e n c e of two

fixed c o n c e n t r a t i o n s of a m i n e . The two amine concentrations

-4 -4

were I x 10 M and 5 x 1 0 M , and t h e s e w e r e c h o s e n such that

the corresponding equilibrium concentrations would lie in t h e

' d e p r e s s e d ' and 'enhanced' amine adsorption regions (Fig 8.1),

-4

respectively. T h e C M C of DA a t pH 9 o c c u r r e d a t 3.2 x 10 M,

the lower a m i n e c o n c e n t r a t i o n used w a s t h e r e f o r e below t h e C M C

while the higher concentration was above this value.

The results obtained are summarised in Fig 8 . 2 . It is

c l e a r t h a t an i n c r e a s e in t h e s t a r c h c o n c e n t r a t i o n resulted in a

progressive decrease in t h e a d s o r p t i o n d e n s i t y of DA on
-4 -4

s p o d u m e n e from I x 10 M DA s o l u t i o n s w h e r e a s in 5 x 10 M

a m i n e , a d s o r p t i o n of t h e s u r f a c t a n t i n c r e a s e d w i t h an increase

in p o l y m e r c o n c e n t r a t i o n . T h e s e r e s u l t s a r e t h e r e f o r e in

a g r e e m e n t with t h e o b s e r v a t i o n s m a d e in Fig 8 . 1 . The decreased

-4"
o
cxi

Initial p o t a t o s t a r c h c o n c e n t r a t i o n , mg I '

Fig 8.2 E f f e c t of p o t a t o s t a r c h c o n c e n t r a t i o n on t h e a d s o r p t i o n d e n s i t y of a m i n e from fixed

s u r f a c t a n t c o n c e n t r a t i o n s a t pH 9
 205

a d s o r p t i o n o f a m i n e a t low c o n c e n t r a t i o n s m i g h t be r e l a t e d to

t h e a d s o r p t i o n of s t a r c h m o l e c u l e s on a d j a c e n t s i t e s , s h i e l d i n g

p o s s i b l e DA a d s o r p t i o n (or c a t i o n e x c h a n g e ) s i t e s . In c o n t r a s t ,

it is n o t r e a d i l y a p p a r e n t w h y t h e p r e s e n c e of s t a r c h should

e n h a n c e t h e a d s o r p t i o n of DA on s p o d u m e n e a t high amine

concentrations.

It h a s been reported ( 1 7 8 , 179) t h a t the p r e s e n c e of s t a r c h

e n h a n c e s t h e a d s o r p t i o n of s u r f a c t a n t s on m i n e r a l particles and

t h a t t h e a d s o r p t i o n of starch itself is e n h a n c e d by t h e presence

of s u r f a c t a n t . T h e reasons for t h i s a r e n o t r e a l l y understood.

E n h a n c e m e n t in t h e a d s o r p t i o n o f B r i t i s h gum 9 0 8 4 on q u a r t z , in

t h e p r e s e n c e of dodecyIammoniurn c h l o r i d e (DAC) has been

attributed to a reduction in the e l e c t r o s t a t i c repulsion between

t h e s t a r c h and q u a r t z (40). Although a decrease in t h e

e l e c t r o s t a t i c r e p u l s i o n b e t w e e n starch and t h e s i l i c a t e s probably

takes place in t h e p r e s e n c e of a m i n e (cf Fig 6 . 2 ) , t h i s is

u n l i k e l y t o r e s u l t in e n h a n c e d a d s o r p t i o n of s t a r c h . This is

b e c a u s e t h e a d s o r p t i o n of a m i n e a t t h e s i l i c a t e / w a t e r interface

usurps the hydrophilic Si-0 sites resulting in a hydrophobic

mineral surface. S i n c e s t a r c h a d s o r b s on the s i l i c a t e s by

interaction with the hydrophilic Si-0 and S i - O H sites,

h y d r o p h o b i c i s a t i o n of the mineral s u r f a c e should r e s u l t in

d e c r e a s e d a d s o r p t i o n of the m a c r o m o I e c u Ie a t t h e mineraI/water

i n t e r f a c e a s , f o r e x a m p l e , o b s e r v e d on m e t h y l a t e d q u a r t z samples.

The amine adsorption isotherm in t h e p r e s e n c e of starch

(Fig 8 . 1 ) e x t e n d s t o a d s o r p t i o n d e n s i t i e s in e x c e s s of a m o n o l a y e r

o r a bi layer and c o n t i n u e s t o i n c r e a s e a b o v e the C M C o f

 206

dodecyI a m i n e . T h i s s u g g e s t s t h a t t h e m e c h a n i s m of a m i n e

abstraction differs appreciably from t h a t in t h e a b s e n c e of

starch. F u r t h e r m o r e , t h e a b s e n c e of an i n f i n i t e s l o p e in t h e

amine adsorption isotherm indicates t h a t the amine is n o t

a d s o r b i n g by a c o n d e n s a t i o n - t y p e p r o c e s s a t t h e si I i c a t e / w a t e r

interface. It w o u l d t h e r e f o r e a p p e a r t h a t t h e a m i n e abstraction

mechanism is n o t o n e of c o a d s o r p t i o n . An i n t e r a c t i o n between

amine and starch in b u l k s o l u t i o n to form a s o l u b l e o r an

i n s o l u b l e c o m p l e x w o u l d be c o n s i s t e n t with t h e s e results.

T o d e t e r m i n e w h e t h e r o r n o t t h e a m i n e and s t a r c h were

i n t e r a c t i n g w i t h e a c h o t h e r in b u l k s o l u t i o n , t h e e f f e c t o f

s t a r c h on t h e C M C of DA a t pH 9 w a s s t u d i e d by s u r f a c e tension

measurements. Fig 8 . 3 s h o w s t h e e f f e c t of 4 0 p p m p o t a t o starch

on t h e s u r f a c e t e n s i o n (y) of DA as a f u n c t i o n of t h e surfactant

concentration (C). In c o m p a r i s o n t o the s u r f a c e t e n s i o n results

obtained in t h e a b s e n c e o f s t a r c h , t w o t r a n s i t i o n p o i n t s , Tj and

T ^ , were clearly identified a t DA c o n c e n t r a t i o n s of about

-4 -3

2 . 4 x 10 and I x 10 M, respectively. Below T| and a b o v e T2

t h e s t a r c h had little e f f e c t on t h e s u r f a c e t e n s i o n of a m i n e

solutions. A t T j , h o w e v e r , t h e rate of d e c r e a s e of t h e surface

t e n s i o n with i n c r e a s e of a m i n e c o n c e n t r a t i o n b e c a m e zero and

r e m a i n e d s o until t h e c o n c e n t r a t i o n a p p r o a c h e d T 2 , w h e r e u p o n it

increased. A b o v e T ^ t h e rate d e c r e a s e d to z e r o a g a i n . Arai et

al (180) o b t a i n e d s i m i l a r r e s u l t s in t h e i r s t u d y of t h e interaction

b e t w e e n p o l y v i n y l p y r r o l i d o n e and s o d i u m alkyl s u l p h a t e by t h e

surface tension method.

From the Gibbs adsorption i s o t h e r m the s u r f a c e e x c e s s , T,

is p r o p o r t i o n a l to dy/dlnC, I.e. the s]6pe in t h e y vs log C c u r v e .

 207

Fig 8 . 3 T h e s u r f a c e t e n s i o n of d o d e c y l a m i n e in t h e presence
of 4 0 ppm p o t a t o starch a t pH 9

The fact that dy/dlnC (and h e n c e D d e c r e a s e d a t Tj d u e to

the p r e s e n c e of s t a r c h , t h e r e f o r e , implies t h a t t h e a d d e d
-4
s u r f a c t a n t b e y o n d 2 . 4 x 10 M DA w a s c o n s u m e d e i t h e r by

a d s o r p t i o n o n t o o r by c o m p l e x f o r m a t i o n with s t a r c h in b u l k

solution. C o n s i s t e n t w i t h t h i s is t h e f a c t t h a t a p r e c i p i t a t e

was observed in s o l u t i o n s a t a m i n e c o n c e n t r a t i o n corresponding

to T | . T h e p o i n t Tj m a y t h e r e f o r e be i n t e r p r e t e d a s t h e c o n -

c e n t r a t i o n of DA a t w h i c h c o m p l e x f o r m a t i o n b e t w e e n s t a r c h and

DA is i n i t i a t e d and T 2 as t h a t a t w h i c h it c e a s e s (180, 181).

The latter c o n s i d e r a t i o n is s u p p o r t e d by the coincidence

b e t w e e n t h e two s u r f a c e t e n s i o n c u r v e s b e y o n d T ^ w h i c h implies

t h a t d o d e c y f a m i n e m i c e l l e s formed u n d e r t h e s e c o n d i t i o n s (180, 181).

An i n t e r e s t i n g d e d u c t i o n m a y a l s o be m a d e from t h e similarity

of t h e s u r f a c e t e n s i o n v a l u e s b e y o n d T ^ in t h e a b s e n c e and

p r e s e n c e of s t a r c h . Since dy/dlnC provides a quantitative

m e a s u r e of s u r f a c t a n t m o n o m e r a d s o r p t i o n a t t h e gas/liquid

i n t e r f a c e , b e y o n d T ^ the n u m b e r of m o l e c u l e s of a m i n e adsorbed

at the i n t e r f a c e p e r u n i t area w a s n o t a f f e c t e d by t h e presence

of s t a r c h . T h u s t h e r e w a s n e g l i g i b l e a d s o r p t i o n of t h e s t a r c h -

ami ne c o m p l e x a t t h e I n t e r f a c e so t h a t t h e c o m p l e x had no

s u r f a c t a n t p r o p e r t i e s , I . e . It was p r e d o m i n a n t l y hydrophilic.

C o m p a r i s o n of t h e a d s o r p t i o n b e h a v i o u r of DA on spodumene

in t h e p r e s e n c e of starch (Fig 8 . 1 ) with t h e s u r f a c e tension

r e s u l t s shows t h a t t h e a m i n e c o n c e n t r a t i o n beyond which

a d s o r p t i o n of a m i n e i n c r e a s e d m a r k e d l y c o r r e s p o n d s t o t h a t a t

which the starch-DA precipitate Is f o r m e d in s o l u t i o n . It can

t h e r e f o r e be c o n c l u d e d t h a t a t DA c o n c e n t r a t i o n s h i g h e r t h a n
-4

2 . 4 x 10 M , n o t all of t h e a d d e d s u r f a c t a n t a d s o r b e d on

s p o d u m e n e , s o m e of it w a s c o n s u m e d by p r e c i p i t a t e formation with

the s t a r c h . These preliminary considerations are reassessed in

g r e a t e r detail in t h e n e x t t w o sections.

8.2 C o m p l e x f o r m a t i o n b e t w e e n s t a r c h and dodecylamine

T h e i n t e r a c t i o n b e t w e e n s t a r c h and DA in t h e a b s e n c e of

mineral particles was further studied under different conditions

of pH and r e a g e n t c o n c e n t r a t i o n s t o e l u c i d a t e t h e mechanism

of association between the two c o m p o u n d s . M e t h o d s used In t h e

study included a b s t r a c t i o n m e a s u r e m e n t s (by c e n t r i f u g a t i o n ) and

infrared spectroscopy.
8.2.1 E f f e c t of c o n c e n t r a t i o n of a m i n e and s t a r c h on complex
formation

Figs 8.4 and 8 . 5 show t h e a m o u n t of s t a r c h and amine

removed from s o l u t i o n a s a f u n c t i o n of s u r f a c t a n t concentration

a t several pH v a l u e s . The arrows in t h e f i g u r e s indicate the

p o i n t s a t w h i c h a p r e c i p i t a t e was o b s e r v e d in s o l u t i o n . All the

data p o i n t s t o t h e r i g h t of t h e a r r o w s had a p r e c i p i t a t e present,

b u t n o t t h o s e to t h e left. T h e t e r m p r e c i p i t a t e w a s used t o

denote a distinct condensed phase which was observed but

excluded slight clouding which was noticeable at incipient

precipitation. N o p r e c i p i t a t e f o r m a t i o n was o b s e r v e d a t pH 4

a n d 7 a t the a m i n e c o n c e n t r a t i o n investigated.

T h e r e s u l t s in Figs 8.4 and 8.5 show t h a t t h e a m o u n t of

DA o r starch a b s t r a c t e d increased slowly initially with

i n c r e a s e of DA c o n c e n t r a t i o n . Beyond a critical amine

concentration there was a marked i n c r e a s e in t h e a b s t r a c t i o n of

both s t a r c h and DA a t pH v a l u e s 9 and 10. F u r t h e r m o r e , with

i n c r e a s e of pH from 9 t o 10, t h e c o n c e n t r a t i o n of a m i n e required

t o form t h e p r e c i p i t a t e d e c r e a s e d . A t pH 4 and 7 , h o w e v e r , t h e r e

w a s n o sudden increase in t h e a b s t r a c t i o n of both DA and starch.

It is p o s s i b l e t h a t a t pH 10 t h e m a r k e d increase in a b s t r a c t i o n

w a s c a u s e d by both p r e c i p i t a t i o n of t h e c o m p l e x and a m i n e . At

pH 9 , h o w e v e r , t h e a m i n e c o n c e n t r a t i o n s w e r e well below the

theoretical s o l u b i l i t y of d o d e c y l a m i n e so t h a t the u p s w i n g in

DA a b s t r a c t i o n can be a t t r i b u t e d to p r e c i p i t a t i o n of t h e complex.

C o m p a r i s o n of Figs 8 . 4 and 8.1 s h o w s t h a t t h e a m o u n t of DA

 lo

"o
0
+-
u
0
+-
If)
j2l
0
0
tz
TD
0

U)
j2>
0
0
c
'i
0 jz)
0
E
zj
c

o
i-

5x10 1x10 5x10

Equilibrium concentration, M

Fig 8 . 4 E f f e c t of DA c o n c e n t r a t i o n on t h e a b s t r a c t i o n of DA from 4 0 ppm p o t a t o s t a r c h solutions

a t several pH v a l u e s

isj
o
 CD
40
-o
0
CD
E

TD 0
0 30 X
-4- 0
u
0
-f-
0
x
0
20

+-
c
Z3
o
E
0

o
i—

j i i i i l _l l j l
-5 -4 -4 -3
5x10 " Ix10 ' 5x10 I x 10

Equilibrium amine concentration, M

Fig 8.5 E f f e c t of DA c o n c e n t r a t i o n on the a b s t r a c t i o n of p o t a t o s t a r c h from 4 0 p p m solutions

a t several pH v a l u e s (legend as in Fig 8 . 4 )
 212

abstracted in t h e a b s e n c e of s p o d u m e n e c o r r e s p o n d e d to t h a t

abstracted when spodumene was a d d e d . Thus at amine concentrations

-4

above 2 x 1 0 t h e main m e c h a n i s m of a m i n e removal is by complex

formation r a t h e r t h a n by adsorption.

F i g s 8.4 and 8.5 a l s o show t h a t b e y o n d t h e precipitation

p o i n t v i r t u a l l y all the s t a r c h w a s r e m o v e d from solution;

n e v e r t h e l e s s t h i s did n o t s t o p f u r t h e r a b s t r a c t i o n of DA a t

high s u r f a c t a n t c o n c e n t r a t i o n s . T h i s is p r o b a b l y e x p l a i n e d by

t h e f a c t t h a t the i n t e r a c t i o n b e t w e e n s t a r c h and DA does not

c e a s e until t h e c o n c e n t r a t i o n o f a m i n e in s o l u t i o n corresponds

t o T , as w a s e a r l i e r s u g g e s t e d in t h e s u r f a c e t e n s i o n studies

a t pH 9 .

T h e e f f e c t of d i f f e r e n t s t a r c h c o n c e n t r a t i o n s on t h e

a b s t r a c t i o n of s t a r c h by c o m p l e x f o r m a t i o n w a s s t u d i e d . Fig

8.6 s h o w s t h e a m o u n t of s t a r c h a b s t r a c t e d by c o m p l e x a t i o n at

t h r e e d i f f e r e n t c o n c e n t r a t i o n s of t h e p o l y m e r and as a f u n c t i o n

of e q u i l i b r i u m a m i n e c o n c e n t r a t i o n . The results were similar

t o t h o s e of Fig 8 . 5 , with m o r e o r less all of t h e starch In

s o l u t i o n b e i n g c o n s u m e d by p r e c i p i t a t e f o r m a t i o n a t all starch

c o n c e n t r a t i o n s and a t high a m i n e c o n c e n t r a t i o n s . Notably,

however, the amine concentration at which marked abstraction

of the polymer took place was approximately constant regardless

of t h e s t a r c h c o n c e n t r a t i o n . This observation Is s i m i l a r to

r e p o r t e d r e s u l t s of s u r f a c e t e n s i o n studies ( 1 8 0 , 182) in w h i c h

the surfactant concentration at which complex formation Is

Initiated is i n d e p e n d e n t of p o l y m e r c o n c e n t r a t i o n . It w o u l d

a p p e a r t h a t w h a t e v e r the e f f e c t Is r e s p o n s i b l e for precipitation

of t h e s t a r c h - D A c o m p l e x , It is s t r o n g l y d e p e n d e n t on a c r i t i c a l
 O 80 ppm starch
A 6 0 ppm starch
• 4 0 ppm starch

o — -

j i i « • • -i i i l.
-5 -4 -4
5x10 ' I x 10 ' 5x10

Equilibrium amine concentration, M

Fig 8.6 E f f e c t of DA c o n c e n t r a t i o n on t h e a b s t r a c t i o n of s t a r c h
from d i f f e r e n t s t a r c h c o n c e n t r a t i o n s a t pH 9

surfactant concentration r a t h e r than t h a t of starch.

F i g s 8.7 and 8 . 8 p r e s e n t t h e data from F i g s 8.5 and 8.6

r e s p e c t i v e l y , as t h e a m o u n t of s t a r c h a b s t r a c t e d plotted

a g a i n s t the level of DA a b s t r a c t i o n . Below t h e precipitation

p o i n t , i . e . b e f o r e all t h e s t a r c h was r e m o v e d from solution,

t h e r e l a t i v e a m o u n t s of s t a r c h and DA c o n s u m e d by complexation

w e r e a p p r o x i m a t e l y c o n s t a n t i r r e s p e c t i v e of pH and reagent

concentration. Thus below the precipitation point the starch-DA

c o m p l e x was of c o n s t a n t composition.
 214

40 •o"
o)
E

"o
0)
+• A pH 10
O
(d O pH 9
L.
4-
l/)
xi V pH 7
(d
x • pH 4
o
i
+-
tj
U)

0
c
3
o
E
<

I 2 3 4 5
A m o u n t of DA a b s t r a c t e d , x 10 M
F i g 8.7 E f f e c t of t h e a m o u n t of DA a b s t r a c t e d on t h e a m o u n t of
s t a r c h a b s t r a c t e d a t several pH v a l u e s from 4 0 p p m p o t a t o
starch solutions

A m o u n t of DA a b s t r a c t e d , x I04M

Fig 8 . 8 E f f e c t of t h e a m o u n t of DA a b s t r a c t e d on t h e a m o u n t of
p o t a t o s t a r c h a b s t r a c t e d from d i f f e r e n t s t a r c h
c o n c e n t r a t i o n s a t pH 9
8.2.2 Binding i s o t h e r m s of d o d e c y l a m i n e to s t a r c h

An a l t e r n a t i v e w a y of p r e s e n t i n g t h e data of F i g s 8.4-8.6

is by use of q u a n t i t a t i v e r e l a t i o n s h i p s d e r i v e d for describing

the interaction between organic ligands and p r o t e i n s (163, 183).

In t h e r e l a t i o n s h i p s it is a s s u m e d t h a t t h e r e a r e n b i n d i n g sites

p e r protein m o l e c u l e and t h a t t h e s i t e s are identical (i.e.

h a v e equal c h a n c e of i n t e r a c t i n g w i t h a ligand m o l e c u l e ) . The

a v e r a g e n u m b e r of bound ligand m o l e c u l e s p e r p r o t e i n molecule,

v , is then r e l a t e d t o t h e e q u i l i b r i u m c o n c e n t r a t i o n of free

organic ligand by the e q u a t i o n (163)

v
/(n - V) = k X f (8.1)

where

k = an e q u i l i b r i u m o r i n t r i n s i c a s s o c i a t i o n c o n s t a n t for

t h e b i n d i n g reaction a t e a c h site;

= m o l e fraction of ligand a t equilibrium;

f = activity coefficient.

In d i l u t e ligand c o n c e n t r a t i o n s X is a p p r o x i m a t e d by C , t h e
e e
e q u i l i b r i u m c o n c e n t r a t i o n of o r g a n i c ligand so t h a t

V
/(n - v) - kC (8.2)
e

P l o t s of v a g a i n s t fa a t c o n s t a n t pH and t e m p e r a t u r e h a v e been

termed binding isotherms (163). Alternatively, equation (8.2)

m a y be p u t into t h e form
 v
/c = k(n - v ) (8.3)

V
and /Ce plotted against v . Such p l o t s have been r e f e r r e d to

as t h e S c a t c h a r d p l o t s ( 1 8 3 , 184, 185). The intrinsic association

c o n s t a n t , k , is t h e n o b t a i n e d as t h e s l o p e of t h e resulting

Ii n e a r curve.

S c a t c h a r d p l o t s w e r e o b t a i n e d for t h e data of F i g s 8.4 t o

8.6 and a r e s h o w n in F i g s 8.9 and 8 . 1 0 . As t h e m o l e c u l a r weight

of p o t a t o s t a r c h w a s not known v w a s d e f i n e d a s t h e average

n u m b e r of m o l e s of bound DA p e r g of s t a r c h . A t pH 9 and 10

the S c a t c h a r d p l o t s c o n s i s t e d of two linear s e g m e n t s w i t h a

transition at the point where precipitation of t h e c o m p l e x w a s

V
o b s e r v e d , as shown by t h e a r r o w s . Below t h i s p o i n t /Ce increased

s l o w l y w i t h v , b u t a b o v e the p o i n t t h e i n c r e a s e w a s m a r k e d . At

pH 4 and 7 , h o w e v e r , the S c a t c h a r d p l o t w a s a s s o c i a t e d w i t h only

one curve. Furthermore, at low v , t h e slope of t h e line w a s

a p p r o x i m a t e l y c o n s t a n t (about 5 0 0 litre m o l e ') i r r e s p e c t i v e

of starch c o n c e n t r a t i o n and p H . A t high v t h e s l o p e s of t h e

lines w e r e d i f f e r e n t ; t h a t a t pH 10 (6030 litre m o l e ') b e i n g

g r e a t e r than t h e c o r r e s p o n d i n g v a l u e a t pH 9 ( 1 5 3 0 litre m o l e ').

It h a s been s u g g e s t e d (184, 185) t h a t in t h e c a s e w h e r e t w o

linear s e g m e n t s a r e p r e s e n t , it is n e c e s s a r y t o a s s u m e t h a t t h e r e

a r e two t y p e s of b i n d i n g r e a c t i o n s at t w o s e t s of s i t e s on t h e

p o l y m e r , with a s s o c i a t i o n c o n s t a n t s k| and k ^ . It w o u l d appear,

t h e n , t h a t t h e i n t e r a c t i o n b e t w e e n p o t a t o s t a r c h and DA a t pH 9

and 10 involved two s e p a r a t e b i n d i n g m e c h a n i s m s with a t r a n s i t i o n

between the two mechanisms a t the precipitation point. The slope

 -- i i * 1

/
A t pH 9 :
16
O 4 0 ppm s t a r c h
• 6 0 ppm s t a r c h
-

V 80 p p m s t a r c h
12 ® 4 0 p p m s t a r c h a t pH 4
A 4 0 ppm s t a r c h a t pH 7
° /a®
o 6
8 - v D

• /

O
-
4 O O•
V A
3 A
a 3
• • i .i
4
Ixl0 5xlO~4 IX10~3 5x1 C f 3 IxI c f 2
v

Fig 8.9 S c a + c h a r d p l o t for t h e b i n d i n g of DA t o p o t a t o s t a r c h a t

several p o t a t o s t a r c h c o n c e n t r a t i o n s and d i f f e r e n t pH
v a l u e s (lines f i t t e d by least s q u a r e s )

Fig 8 . 1 0 S c a t c h a r d p l o t for t h e b i n d i n g of DA t o p o t a t o
starch a t pH 10 ( l i n e s fitted by least s q u a r e s )
c o n s t a n t , k , is a m e a s u r e of t h e a f f i n i t y of t h e b i n d i n g of

the o r g a n i c ligand t o t h e m a c r o m o I e c u l e (163). The large

v a l u e s of k a t a l k a l i n e pH v a l u e s and high D A concentrations

(high v ) t h e r e f o r e s u g g e s t s t h a t u n d e r t h e s e c o n d i t i o n s , t h e

b i n d i n g of DA t o p o t a t o s t a r c h is largely a c o o p e r a t i v e

p r o c e s s in w h i c h a large n u m b e r of a m i n e m o l e c u l e s are

incorporated in t h e c o m p l e x w i t h i n a n a r r o w c o n c e n t r a t i o n range

of s u r f a c t a n t ( 1 6 3 ) . F u r t h e r , w i t h i n c r e a s e of pH from 9 t o 10,

the a f f i n i t y o r c o o p e r a t i v e n a t u r e of t h e b i n d i n g reaction

i ncreases.

A t pH 7 o r low v , t h e low v a l u e of k i n d i c a t e s t h a t t h e

r e l e v a n t m e c h a n i s m of i n t e r a c t i o n is r e l a t i v e l y less c o o p e r a t i v e

and of r e d u c e d a f f i n i t y . F u r t h e r , t h e i n d e p e n d e n c e of k of pH

and s t a r c h c o n c e n t r a t i o n indicates t h a t u n d e r t h e s e conditions

t h e a f f i n i t y of DA m o l e c u l e s f o r p o t a t o s t a r c h is a p p r o x i m a t e l y

the same. This would appear to explain why the composition of

the c o m p l e x below t h e p r e c i p i t a t i o n p o i n t is a p p a r e n t l y constant.

A possible low a f f i n i t y m e c h a n i s m at low a m i n e concentrations

is e l e c t r o s t a t i c a t t r a c t i o n b e t w e e n aminiurn and inorganic

cations in t h e b u l k s o l u t i o n and R - 0 s i t e s on t h e s t a r c h . At

high DA c o n c e n t r a t i o n s and pH v a l u e s t h e c o o p e r a t i v e n a t u r e of

t h e i n t e r a c t i o n and t h e p r e v i o u s l y o b s e r v e d e f f e c t of pH on t h e

concentration of DA r e q u i r e d f o r p r e c i p i t a t i n g the complex,

a r e a n a l o g o u s t o t h e e f f e c t of pH and c o n c e n t r a t i o n of amine

on t h e C M C of D A . Under these conditions the driving force for

the interaction b e t w e e n s t a r c h and DA a p p e a r s t o h a v e been van

der W a a l ' s forces of a s s o c i a t i o n between the hydrophobic C-H

 219

g r o u p s on t h e s t a r c h and t h e a m i n e c o l l e c t o r . Alternatively,

t h e a m i n e m o l e c u l e s c o u l d c o a d s o r b with t h e c a t i o n i c a m i n e ions

h e l d by c o u l o m b i c a t t r a c t i o n t o t h e R - 0 sites.

8.2.3 Inf I uetice of h y d r o p h o b i c I n t e r a c t i o n s on c o m p lex f o r m a t i o n

F u r t h e r s t u d i e s of t h e m e c h a n i s m of I n t e r a c t i o n between

s t a r c h and DA w e r e m a d e . These involved s u r f a c e t e n s i o n and

turbidity measurements.

Fig 8.11 s h o w s the s u r f a c e t e n s i o n of DA a s a f u n c t i o n of

amine concentration in t h e a b s e n c e of s t a r c h , a t pH 10. In

-4

t h i s c a s e , t h e C M C o f DA o c c u r r e d a t a b o u t 1.7 x 10 M. Comparison

of t h i s v a l u e w i t h t h a t r e q u i r e d t o p r e c i p i t a t e t h e starch-amine

c o m p l e x at pH 10 (Figs 8.4 and 8 . 5 ) s h o w s t h a t , like a t pH 9 , t h e

p r e c i p i t a t e forms o n l y a t s u b m i c e l l a r c o n c e n t r a t i o n s , i.e.

r e l a t i v e t o t h e C M C of a m i n e in s t a r c h - f r e e s o l u t i o n s . This

observation Is s i m i l a r t o t h a t r e p o r t e d for c o m p l e x formation

b e t w e e n a n u m b e r of p o l y m e r s a n d s u r f a c t a n t s (180, 181, 182).

It has f u r t h e r been s h o w n In t h e s e s t u d i e s t h a t t h e free e n e r g y

c h a n g e for t r a n s f e r r i n g a m e t h y l e n e g r o u p f r o m b u l k solution

t o the c o m p l e x is of t h e s a m e m a g n i t u d e (i.e. I.I k T p e r C H ^

g r o u p ) as t h a t required for t h e f o r m a t i o n of m i c e l l e s in

polymer-free surfactant solutions. The c o n s i s t e n t proximity

t o the C M C , a t both pH 9 and 10, of t h e c o n c e n t r a t i o n of DA a t

w h i c h p r e c i p i t a t i o n of t h e c o m p l e x t o o k p l a c e is t h e r e f o r e strong

evidence that precipitation is Induced by van d e r W a a l ' s forces.

It w o u l d a p p e a r t h a t at pH 7 p r e c i p i t a t i o n of t h e c o m p l e x w a s

n o t o b s e r v e d b e c a u s e of t h e r e l a t i v e l y low DA c o n c e n t r a t i o n range
 220

t 1—i—r~r t—i—r

80 "

E
O
0
g 60
>*
tj
D
o
0 .-
c 40
o

£ 20

' « i i i i—l J I I L
-5 -4 -4
5x10 " 1x10 5x10

Amine concentration, M

Fig 8.11 S u r f a c e t e n s i o n of d o d e c y l a m i n e a t pH 10

i n v e s t i g a t e d c o m p a r e d t o the C M C v a l u e w h i c h h a s been reported

(26 ) t o be a t 1.4 x I 0 ~ 2 M DA a t t h i s p H . It can be argued,

t h e r e f o r e , t h a t at c o n c e n t r a t i o n s of DA c l o s e t o t h e C M C , a

starch-DA precipitate should form.

Fig 8 . 1 2 s h o w s t h e t u r b i d i t y of DA s o l u t i o n s in t h e presence

of 40 ppm p o t a t o s t a r c h , a s a f u n c t i o n of a m i n e concentration.

f
T h e m e a s u r e m e n t s w e r e c o n d u c t e d with an EELf (Evans

Electroseleniurn L t d , E n g l a n d ) n e p h e I o m e t e r . A 4 0 ppm potato

starch s o l u t i o n was used as a b l a n k t o cancel o u t e r r o r s arising

from light s c a t t e r e d by t h e b u l k y p o t a t o starch m o l e c u l e s (117).

With i n c r e a s e of DA c o n c e n t r a t i o n t h e r e w a s o n l y a small increase

in t u r b i d i t y b u t in t h e region of t h e C M C t h e i n c r e a s e in

t u r b i d i t y w a s m a r k e d due t o t h e f o r m a t i o n o f a precipitate.
 221

<D
O
sz
(0
x
0
01
x
<

Fig 8 . 1 2 T u r b i d i t y of d o d e c y l a m i n e s o l u t i o n s c o n t a i n i n g 4 0 p p m
p o t a t o starch at pH 7

It is t h e r e f o r e c l e a r t h a t a t all pH v a l u e s a starch-DA

precipitate is o b t a i n e d as long as t h e bulk c o n c e n t r a t i o n of

amine is c l o s e t o t h a t r e q u i r e d for miceI Iisation in starch-free

solutions. It is n o t c o m p l e t e l y c l e a r , h o w e v e r , w h e t h e r a t

low a m i n e c o n c e n t r a t i o n s t h e small increase in t u r b i d i t y is

s o l e l y due t o e l e c t r o s t a t i c interaction between D A + ions and

R-0 s i t e s , o r is i n f l u e n c e d by t h e i n c r e a s i n g p r e s e n c e of

neutral amine molecules with i n c r e a s e of DA concentration.

 222

T o f u r t h e r d e f i n e the r e s p e c t i v e roles of DA ions a n d

neutral a m i n e m o l e c u l e s , t h e s t a r c h a b s t r a c t i o n w a s m e a s u r e d

in t h e p r e s e n c e of a neutral long c h a i n a l c o h o l , n - d o d e c y l

a l c o h o l , and a s t r o n g l y ionising cationic surfactant,

cetyItrimethylammoniurn bromide (CTAB). T h e alcohol was

prepared in p u r e b e n z e n e and w a s a d d e d t o t h e s t a r c h solutions

such t h a t the a m o u n t of b e n z e n e i n t r o d u c e d in b u l k s o l u t i o n

w a s r e l a t i v e l y small and a l w a y s a p p r o x i m a t e l y c o n s t a n t . If

the alcohol-starch solution was equilibrated for short periods

(< 16 h ) no p r e c i p i t a t e w a s formed and t h e a m o u n t of starch

r e m o v e d from s o l u t i o n w a s n e g l i g i b l e . After prolonged

equilibration times (> 4 8 h ) , h o w e v e r , a p r e c i p i t a t e w a s

o b s e r v e d t o form in s o l u t i o n . The results obtained in t h i s

-4

latter c a s e a r e s h o w n in Fig 8 . 1 3 . In t h e p r e s e n c e of I x 10 M

a l c o h o l o r g r e a t e r , n e a r l y all the starch w a s p r e c i p i t a t e d out

of s o l u t i o n . In t h e c a s e of C T A B , h o w e v e r , n o precipitate

was observed i r r e s p e c t i v e of t h e e q u i l i b r a t i o n time. Furthermore,

little s t a r c h w a s a b s t r a c t e d from s o l u t i o n in the C T A B concentration

range I x I0~5M to I x I 0 ~ 3 M and pH 7 t o 10.

T h e s e results show t w o main a s p e c t s of t h e interaction

b e t w e e n p o t a t o s t a r c h and D A . In t h e s t a r c h - D A system

p r e c i p i t a t i o n of t h e c o m p l e x w a s o b s e r v e d w i t h i n a b o u t 3 0 min

of m i x i n g t h e s t a r c h and a m i n e s o l u t i o n s . The longer e q u i l i b r a t i o n

t i m e r e q u i r e d f o r t h e alcohol to p r e c i p i t a t e the s t a r c h therefore

s h o w s t h a t in t h e s t a r c h - D A s y s t e m e l e c t r o s t a t i c attractions

between amine ions and R - 0 sites probably aids the kinetics

of c o m p l e x f o r m a t i o n . T h e fact t h a t t h e r e is n e g l i g i b l e interaction
 /

i i i i i i i i i i i
IxlO-5 5x1 C f 3 IxlO-4

Initial c o n c e n t r a t i o n of n - d o d e c a n o l , M

Fig 8 . 1 3 E f f e c t of n - d o d e c a n o l c o n c e n t r a t i o n on p o t a t o starch
u p t a k e f r o m 4 0 ppm s o l u t i o n s a t pH 9

b e t w e e n C T A B and s t a r c h s u g g e s t s t h a t t h e a d s o r p t i o n of cationic

a m i n e on starch w o u l d n o t r e s u l t in s i g n i f i c a n t a b s t r a c t i o n of

t h e s u r f a c t a n t from s o l u t i o n . T h u s c o a d s o r p t i o n of a m i n e ion

and m o l e c u l e p r o b a b l y t a k e s p l a c e e v e n a t low a m i n e concentrations.

F u r t h e r m o r e , t h e f a c t t h a t a neutral long chain a l c o h o l can

p r e c i p i t a t e the s t a r c h e m p h a s i s e s t h e h y d r o p h o b i c n a t u r e of t h e

p r e c i p i t a t ion m e c h a n i s m . These considerations agree with a

large a m o u n t of e v i d e n c e w h i c h has been a c c u m u l a t e d on the

s e l e c t i v e s e p a r a t i o n of s t a r c h f r a c t i o n s by p r e c i p i t a t i o n with

hydrophobic organic ligands. Some of t h i s e v i d e n c e is r e v i e w e d

in s e c t i o n 8.3.
 224

Fig 8 . 1 4 s h o w s a l o g a r i t h m i c c o n c e n t r a t i o n diagram for

-4

I x 10 M DA In w h i c h t h e d i s t r i b u t i o n of a m i n e s p e c i e s Is

c o m p a r e d w i t h t h e a m o u n t of s t a r c h a b s t r a c t i o n as a f u n c t i o n of

pH. T h e data p o i n t s In t h e f i g u r e w e r e o b t a i n e d from Fig 8.5

-4

a t a c o n s t a n t e q u i l i b r i u m c o n c e n t r a t i o n of I x 10 M amine.

A l t h o u g h t h e data is l i m i t e d , It is c l e a r t h a t t h e level of

starch abstraction is of a s i m i l a r form t o t h e v a r i a t i o n in

a S a c a n
^^2(aq) PR- T h e r e f o r e be s u g g e s t e d

that the i n t e r a c t i o n b e t w e e n s t a r c h and DA is in m a n y respects

s i m i l a r t o the a d s o r p t i o n m e c h a n i s m of a m i n e on t h e silicate

minerals. At low a m i n e c o n c e n t r a t i o n s c o a d s o r p t i o n of aminium

ion and a m i n e m o l e c u l e t a k e s p l a c e on t h e s t a r c h m o l e c u l e but

at a particular concentration of a m i n e in s o l u t i o n , van d e r W a a l ' s

associations lead t o Increased a b s t r a c t i o n of a m i n e and precipitation

of the s t a r c h - D A c o m p l e x o c c u r s . The major difference between the

t w o m e c h a n i s m s m i g h t p e r h a p s be t h e i n h e r e n t h y d r o p h o b i c groups

on s t a r c h , w h i c h a r e c a p a b l e of e n g a g i n g in van d e r W a a l ' s

associations with surfactants even in t h e a b s e n c e of ionised

species. A t the mineraI/water Interface, however, the hydrophilic

n a t u r e of t h e s u r f a c e r e q u i r e s t h a t van d e r W a a l ' s associations

+
t a k e p l a c e on o r b e t w e e n a d s o r b e d DA ions.

8.2.4 S t u d y of t h e s t a r c h - d o d e c y l a m i n e c o m p l e x by infrared
spectroscopy

T h e I n f r a r e d s p e c t r u m of t h e p r e c i p i t a t e d c o m p l e x w a s

examined mainly to confirm that chemical interactions were

a b s e n t In t h e a s s o c i a t i o n b e t w e e n s t a r c h and D A . This was

a c h i e v e d by c o m p a r i s o n of t h e s p e c t r u m of t h e p r e c i p i t a t e with
 c
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Fig 8 . 1 4 C o m p a r i s o n b e t w e e n t h e a m o u n t of a m i n e a b s t r a c t e d by
c o m p l e x f o r m a t i o n _ ^ i t h t h e d i s t r i b u t i o n of a m i n e
s p e c i e s a t I x 10 M DA

the s p e c t r a of D A , p o t a t o s t a r c h and a p o t a t o s t a r c h - D A mixture.

The spectra obtained are shown in Figs 8.15 t o 8 . 1 8 . The method

used t o o b t a i n t h e s p e c t r a is a l s o given in t h e f i g u r e s . Fig

8.19 o u t l i n e s t h e a b s o r p t i o n b a n d s in w h i c h v i b r a t i o n s of t h e

indicated c h e m i c a l groups were observed.

T h e s p e c t r a of Nujol oil and d o d e c y l a m i n e (Figs 8.15 and

8 . 1 6 ) c o m p a r e d well with t h e r e p o r t e d spectra in t h e literature

(145, 186, 187, 188). N o s p e c t r u m of s t a r c h c o u l d be found in

the l i t e r a t u r e a l t h o u g h n u m e r o u s s p e c t r a of s u g a r s h a v e been

recorded (188, 189). It is a l s o a p p a r e n t In t h e spectrum for

starch (Fig 8 . 1 7 ) t h a t t h e r e w a s o v e r l a p in t h e C - H stretching

and b e n d i n g m o d e s with simi lar v i b r a t i o n s from t h e muI Iing oi I.

100

i
80

60

Fi Im

40

20

4000 3500 3000 2500 2000 1800 1600 1400 1200 1000 800

W a v e n u m b e r , cm

Fig 8.15 Infrared s p e c t r u m of Nujol oil

ho
ho
CD
 W a v e n u m b e r , cm

Fig 8.16 Infrared s p e c t r u m of dodecylamine

k)
n)
--j
 Nujol muI I

800 1600 400 200 000 800

Fig 8 . 1 7 Infrared s p e c t r u m o f p o t a t o starch

k)
n>
00
 W a v e n u m b e r , cm

Fig 8 . 1 8 Infrared s p e c t r a of p o t a t o s t a r c h - DA p r e c i p i t a t e and p o t a t o s t a r c h - DA m i x t u r e

m
w
vo
 Group
... r . • i

^ a s £s - CH3

V V 6s
as, s > CH2
1 1
-c-c-
V 1 1

JL -NH2

-NH*

V -C-N-
1
V
6 -OH

V I i
-c-o-c
1 1

-CH2- OH

• • •

3000 2000 1000

W a v e n u m b e r , cm '

Fig 8.19 W a v e n u m b e r r e g i o n s in w h i c h t h e indicated g r o u p s g a v e rise t o a b s o r p t i o n

b a n d s in t h e infrared s p e c t r a

k>
LU
o
 231

It w a s c o n f i r m e d , h o w e v e r , by t h e K B r - d i s c m e t h o d , t h a t t h e s e

b a n d s w e r e a l s o p r e s e n t in s t a r c h . A f u r t h e r f e a t u r e of t h e

starch s p e c t r u m w a s its d i f f u s e n a t u r e p a r t i c u l a r l y in t h e

s o - c a l l e d f i n g e r p r i n t region (i.e. 1300 - 9 0 0 cm '). It is

reported (190) t h a t band r e s o l u t i o n in t h e f i n g e r p r i n t region

is g e n e r a l l y n o t as g o o d as in the u p p e r r e g i o n s (functional

r e g i o n ) e v e n for s i m p l e s u g a r s , p r e s u m a b l y due t o interaction

between the numerous vibrations that take place within the

region (191). T h e p o s s i b l e a b s o r p t i o n b a n d s in t h i s region

probably include in-plane - OH v i b r a t i o n s , C - 0 , ( ^ - O H and C - C

stretching modes (186, 188, 190).

In t h e functional region t h e starch s p e c t r u m s h o w e d a

b r o a d a b s o r p t i o n band b e t w e e n 3 6 0 0 and 3 0 0 0 cm '. The

b r o a d n e s s of t h e band s u g g e s t s t h a t t h e r e w a s e x t e n s i v e

association of the hydroxyl g r o u p with p r o b a b l y both intra and

intermolecular molecular hydrogen bonds being present. However,

it is a l s o a p p a r e n t t h a t a l t h o u g h t h e starch w a s dried for long

p e r i o d s u n d e r reduced p r e s s u r e , s o m e h y d r a t e w a t e r persisted

in t h e s a m p l e . The p r e s e n c e of h y d r a t e w a t e r w a s strongly

s u p p o r t e d by the c h a r a c t e r i s t i c d e f o r m a t i o n band of molecular

water at 1640 cm ' (192).

T h e s p e c t r a of t h e s t a r c h - D A m i x t u r e and t h e s t a r c h - D A

precipitate are compared in Fig 8 . 1 8 . In both s p e c t r a the

p r e s e n c e of the d e f o r m a t i o n b a n d of m o l e c u l a r w a t e r at 1640

cm ' indicates that some hydrate water was p r e s e n t . The OH/NH^

s t r e t c h i n g band a t high w a v e n u m b e r s s h o w s m o r e d e f i n i t i o n in

t h e c a s e of t h e p r e c i p i t a t e than in the m i x t u r e . This may

i n d i c a t e t h a t t h e p r e c i p i t a t e had r e l a t i v e l y less h y d r o g e n
 232

bonding associations in t h i s region than t h e p a r e n t starch.

S i m i l a r l y t h e f i n g e r p r i n t region s h o w e d improved resolution

between 1200 and 1000 cm '. Theoretically, improved band

r e s o l u t i o n a r i s e s from a well d e f i n e d e n e r g y of i n t e r a c t i o n of

t h e i n f r a r e d r a d i a t i o n w i t h t h e m o l e c u l e so t h a t perturbation

e f f e c t s from t h e field of force of n e i g h b o u r i n g m o l e c u l e s are

resisted (191). Such a c a s e could h a v e a r i s e n if t h e

precipitated structure was a relatively more refined geometrical

structure (cf s e c t i o n 8 . 3 ) o r e x t r a n e o u s impurities were

excluded during precipitation.

The single most important conclusion from the spectra,

h o w e v e r , is t h a t t h e i n t e r a c t i o n b e t w e e n s t a r c h and D A did n o t

i n v o l v e t h e f o r m a t i o n of a n y new and c h e m i c a l l y different

compounds. This conclusion is in a g r e e m e n t with t h e physical

n a t u r e of t h e i n t e r a c t i o n b e t w e e n starch and D A , as h a s been

o u t Ii ned above.

8.3 A p o s s i b l e m e c h a n i s m of d e p r e s s i o n of t h e m i n e r a l s by starch

Fig 8 . 2 0 a n d 8.21 show a c o m p a r i s o n b e t w e e n t h e a m o u n t of

starch abstracted in the a b s e n c e and p r e s e n c e of spodumene,

r e s p e c t i v e l y , a n d u n d e r identical c o n d i t i o n s of p H , s t a r c h and

amine concentration. In t h e a b s e n c e of m i n e r a l (Fig 8 . 2 0 ) t h e r e

is a g e n e r a l increase in t h e a m o u n t of s t a r c h a b s t r a c t i o n with

increase in DA c o n c e n t r a t i o n . A t high a m i n e concentration

-4

( i . e . 5 x 10 M) the starch abstraction c u r v e is n e a r l y vertical,

i n d i c a t i n g t h a t p r a c t i c a l l y all t h e s t a r c h is r e m o v e d f r o m solution

by p r e c i p i t a t i o n of t h e c o m p l e x . In t h e p r e s e n c e of spodumene
 I
-4
A In 5 x 10 M DA
-4
V In 2 x 10 M DA
-4
• In 1 x 10 M DA
In 5 x I O " M DA
5

60 O

40

20

10 20 30 40 50

E q u i l i b r i u m p o t a t o s t a r c h c o n c e n t r a t i o n , mg I

Fig 8 . 2 0 E f f e c t of e q u i l i b r i u m p o t a t o s t a r c h c o n c e n t r a t i o n on
the a b s t r a c t i o n of s t a r c h by c o m p l e x f o r m a t i o n a t pH 9

E q u i l i b r i u m p o t a t o s t a r c h c o n c e n t r a t i o n , mg I '

Fig 8.21 E f f e c t of e q u i l i b r i u m p o t a t o starch c o n c e n t r a t i o n on

the a b s t r a c t i o n of s t a r c h at pH 9 and in t h e p r e s e n c e
on s p o d u m e n e
 234

(Fig 8 . 2 1 ) a s i m i l a r i n c r e a s e in t h e starch a b s t r a c t i o n with

-4

increase in DA c o n c e n t r a t i o n takes place. A t 5 x 10 M DA,

p r a c t i c a l l y all t h e s t a r c h is r e m o v e d from s o l u t i o n as w a s

observed in Fig 8 . 2 0 . For c o m p a r a t i v e reasons t h e a m o u n t of

starch adsorbed in t h e a b s e n c e of a m i n e is i n c l u d e d in Fig 8.21.

A t all a m i n e c o n c e n t r a t i o n s i n v e s t i g a t e d the a m o u n t of starch

a b s t r a c t e d w a s g r e a t e r than t h a t a d s o r b e d on s p o d u m e n e in t h e

a b s e n c e of t h e surfactant.

S i m i l a r r e s u l t s to t h o s e of Fig 8.21 and 8.1 h a v e been

erroneously i n t e r p r e t e d as i n d i c a t i n g t h a t mutual e n h a n c e m e n t of

a d s o r p t i o n of s t a r c h and s u r f a c t a n t t a k e s p l a c e in t h e presence

of e a c h o t h e r ( 4 0 , 4 3 , 1 7 8 , 179 ). It is b e l i e v e d t h a t t h e

evidence presented in t h i s t h e s i s is u n a m b i g u o u s ; in t h e

p r e s e n c e of e a c h o t h e r , starch and D A a s s o c i a t e by a p h y s i c a l

mechanism resulting in t h e p r e s e n c e in s o l u t i o n of a c o m p l e x .

T h e h y p o t h e s i s of mutual e n h a n c e m e n t of a d s o r p t i o n of surfactant

and s t a r c h on m i n e r a l particles is c l e a r l y n o t v a l i d . On t h e

contrary, the experimental evidence (cf Figs 8.1 and 8 . 2 ) s u g g e s t

t h a t the a d s o r p t i o n of a m i n e on s p o d u m e n e d e c r e a s e s in t h e

p r e s e n c e of s t a r c h and at low s u r f a c t a n t c o n c e n t r a t i o n s . In a n y
-4

c a s e , at high a m i n e c o n c e n t r a t i o n s ( e . g . 5 x 10 M a m i n e a t pH

9) there is n o free s t a r c h , as s u c h , in solution so t h a t

' e n h a n c e d ' a d s o r p t i o n of s t a r c h is impossible.

in a t t e m p t i n g t o e l u c i d a t e t h e m e c h a n i s m by w h i c h starch

a c t s as a s e l e c t i v e d e p r e s s a n t for c e r t a i n m i n e r a l s , it is

n e c e s s a r y t o a c c o u n t for the a d s o r p t i o n b e h a v i o u r of t h e starch-

a m i n e c o m p l e x w h i c h on t h e b a s i s of t h e p r e s e n t , and similar,

evidence ( 8 6 , 1 9 3 ) a p p e a r s t o be p r e s e n t a t a I I s t a r c h and D A
concentrations.

In t h e last c h a p t e r t h e main e l e m e n t s of t h e mechanism

of a c t i o n of s t a r c h as a d e p r e s s a n t w e r e identified as the

(a) s u r f a c e c o v e r a g e of t h e a d s o r b e d starch;

(b) s u r f a c e c h a r g e on t h e mineral p a r t i c l e s ; and

(c) geometrical s t r u c t u r e of t h e a d s o r b e d starch.

T h e r e l e v a n c e of (a) and (b) w a s e x p e r i m e n t a l l y demonstrated.

For e x a m p l e , the fact that a critical starch concentration,

i r r e s p e c t i v e of starch t y p e , w a s r e q u i r e d t o d e p r e s s spodumene

indicates that a particular starch adsorption density is c r i t i c a l

for d e p r e s s i o n . H o w e v e r , a l t h o u g h m i c r o c l i n e had n e a r l y the

s a m e starch a d s o r p t i o n d e n s i t y as s p o d u m e n e , it w a s relatively

less d e p r e s s e d by DA b e c a u s e of its h i g h e r s u r f a c e charge.

Condition (c) w a s not e x p e r i m e n t a l l y d e m o n s t r a t e d . Consideration

of t h e e x p e r i m e n t a l results, however, suggests that the geometrical

s t r u c t u r e o f t h e c o m p l e x is c r i t i c a l . For e x a m p l e , t h e

d e p e n d a n c e of t h e d e g r e e of d e p r e s s i o n on t h e s u r f a c e c h a r g e of

t h e m i n e r a l s s u g g e s t s t h a t t h e a d s o r p t i o n of t h e c o m p l e x a t t h e

mineraI/water i n t e r f a c e d o e s n o t c o m p l e t e l y p r e v e n t the adsorption

of a m i n e ions on S i - 0 type sites. If t h e c o m p l e x is a d s o r b e d

a s a f l a t c o i l , it is r e a s o n a b l e t o a s s u m e t h a t t h e s e s i t e s w o u l d

be o b s c u r e d from b u l k s o l u t i o n . A further difficulty is t h a t of

a c c o u n t i n g f o r t h e p o s i t i o n of t h e h y d r o p h o b i c r e g i o n s of t h e

complex following its a d s o r p t i o n . T h e p r e s e n c e of such regions

in the c o m p l e x is well s u p p o r t e d by the r e s u l t s p r e s e n t e d in

this thesis. S i n c e c o m p l e t e d e p r e s s i o n of s p o d u m e n e is o b t a i n e d

in t h e Hal Iimond t u b e t e s t s , t h e m i n e r a l ' s s u r f a c e is p r e s u m a b l y

hydrophilic. T h e h y d r o p h o b i c r e g i o n s of t h e c o m p l e x cannot

t h e r e f o r e be o r i e n t e d t o w a r d s b u l k s o l u t i o n . An alternative

assumption is t h a t they a r e o r i e n t e d t o w a r d s t h e m i n e r a l

surface. In t h i s c a s e , the c o m p l e x can o n l y a d s o r b If t h e

mineral surface itself is h y d r o p h o b i c . Such a d s o r p t i o n is n o t ,

h o w e v e r , e x p e c t e d t o be s e l e c t i v e . The latter s u g g e s t i o n does

not therefore appear likely s i n c e s e l e c t i v e d e p r e s s i o n was

obtained in t h e Hal Iimond t u b e f l o t a t i o n t e s t s of t h e silicates.

T h e r e is a large a m o u n t of e v i d e n c e in t h e field of starch

c h e m i s t r y t h a t s u g g e s t s t h a t in t h e p r e s e n c e of o r g a n i c

complexing a g e n t s , starch molecules adopt a helical conformation

Such a g e o m e t r i c a l structure in a q u e o u s is p o s s i b l e for s t a r c h

for w h i c h t h e -OH and C - H f u n c t i o n a l groups have conflicting

solvation characteristics (86). T h e m a c r o m o l e c u Ie t h e r e f o r e

s e e k s t o e x p o s e a m a x i m u m n u m b e r of t h e h y d r o p h i lie -OH g r o u p s

t o t h e s o l u t i o n e n v i r o n m e n t b u t w i t h m i n i m u m e x p o s u r e of t h e

hydrophobic C-H groups. A s s e s s m e n t of a v a i l a b l e hydrodynamic

evidence ( 86 , 193) has led t o t h e c o n c l u s i o n t h a t the helical

s t r u c t u r e of s t a r c h m o l e c u l e s in o r g a n i c a q u e o u s s o l u t i o n s is

imposed upon t h e m a c r o m o l e c u l e by t h e h y d r o p h o b i c i t y of t h e

organic Iigands.

Along similar lines a n u m b e r of w o r k e r s h a v e shown that

s t a r c h can be p r e c i p i t a t e d from s o l u t i o n by a w i d e v a r i e t y of

o r g a n i c r e a g e n t s and t h a t t h e p r e c i p i t a t e is a h e l i c a l c l a t h rate

Several m e t h o d s h a v e been used t o d e d u c e t h a t t h e organic

m o l e c u l e s a r e coaxial with and e n c l o s e d by t h e s t a r c h helix.

For e x a m p l e , optical studies (194, 195, 196) h a v e s h o w n t h a t t h e

precipitate is p l e o c h r o i c , s u g g e s t i n g t h a t s t r o n g a l i g n m e n t of
 237

the organic molecules takes place. Other evidence has included

F o u r i e r p r o j e c t i o n s of e l e c t r o n density ( 1 9 6 , 197) and

crystallographic studies (185, 194, 197,198-201). In the

XRD studies it has been a s s u m e d (159, 199, 202) g e n e r a l l y that

the cylindrical n a t u r e of t h e h e l i x is r e f l e c t e d by a

pseudohexagonaI unit cell w h o s e p a r a m e t e r s d e p e n d on t h e nature

of t h e e n c l o s e d o r g a n i c m o l e c u l e s ( i . e . chain l e n g t h , d e g r e e of

branching, etc).

In view of t h e o v e r w h e l m i n g e v i d e n c e for t h e helical

m o d e l , t h e r e is little reason t o d o u b t t h a t s t a r c h molecules

a r e p r e s e n t in the h e l i c a l conformation in a m i n e s o l u t i o n s , w i t h

t h e a l c o h o l i c h y d r o x y Is o r i e n t e d t o t h e bulk s o l u t i o n . Adsorption

of t h e c o m p l e x on t h e m i n e r a l s by h y d r o g e n b o n d f o r m a t i o n between

S i - O H and o t h e r s u r f a c e metal h y d r o x i d e s i t e s , and t h e R - O H

group is t h e r e f o r e p o s s i b l e in a s i m i l a r m a n n e r . t o the adsorption

of s t a r c h on t h e m i n e r a l s . This theory is r e a s o n a b l e because

t h e a l c o h o l i c h y d r o x y Is a r e n o t u s u r p e d by t h e a s s o c i a t i o n between

s t a r c h and a m i n e . The a d s o r p t i o n of t h e c o m p l e x on t h e silicates

c o u l d not h a v e o c c u r r e d by e l e c t r o s t a t i c a t t r a c t i o n because EM

t e s t s on t h e p r e c i p i t a t e indicated that the complex was essentially

uncharged. Little is known a b o u t t h e m e c h a n i s m of d e p r e s s i o n of

mineral f r a c t i o n s by s t a r c h . A c o m p a r i s o n of t h e a b o v e theory

to other mechanisms is t h e r e f o r e n o t p o s s i b l e . However, the

p r e s e n c e of a helical starch/amine clathrate in s o l u t i o n and its

a d s o r p t i o n a t the m i n e r a I / w a t e r i n t e r f a c e by h y d r o g e n bonding

w o u l d be c o n s i s t e n t with a n u m b e r of o b s e r v a t i o n s m a d e in t h i s

thesis. In p a r t i c u l a r t h e t h e o r y w o u l d e x p l a i n why:
 238

(a) T h e s u r f a c e of t h e c o m p l e x r e m a i n s h y d r o p h i l i c as w a s

found in t h e s u r f a c e t e n s i o n s t u d i e s , a l t h o u g h

s t a r c h a d s o r b s a large q u a n t i t y of a m i n e especially at

high pH and s u r f a c t a n t c o n c e n t r a t i o n . Furthermore, because

t h e c o m p l e x h a s a h y d r o p h i l i c e x t e r i o r , its a d s o r p t i o n at

the m i n e r a I / w a t e r interface is e x p e c t e d t o r e s u l t in a

hydrophilic mineral surface.

(b) Spodumene is r e l a t i v e l y m o r e d e p r e s s e d than t h e other

silicates. By a n a l o g y t o the a d s o r p t i o n m e c h a n i s m of

starch elucidated in s e c t i o n 7 . 1 . 2 it w o u l d a p p e a r t h a t

a d s o r p t i o n of t h e c o m p l e x is g r e a t e s t on t h i s mineral

and t h a t t h i s r e s u l t s in a r e l a t i v e l y g r e a t e r d e g r e e of

h y d r o p h i Iicity in c o m p a r i s o n t o the o t h e r silicates.

(c) The d e g r e e of d e p r e s s i o n is d e p e n d e n t on t h e surface

c h a r g e of t h e m i n e r a l s . B e c a u s e of its c y l i n d r i c a l

s h a p e the h e l i x a d s o r b s on t h e mineral surface presumably

a t r e l a t i v e l y few a n c h o r p o i n t s s o t h a t s o m e S i - 0 sites

still remain e x p o s e d . A d s o r p t i o n of c a t i o n i c a m i n e on

t h e s e s i t e s is t h e r e f o r e p o s s i b l e and i n c r e a s e s w i t h the

i n c r e a s e in t h e n e g a t i v e zeta p o t e n t i a l . Thus although

mi c r o c line a d s o r b s n e a r l y as m u c h s t a r c h as s p o d u m e n e it

is r e l a t i v e l y less d e p r e s s e d than t h e latter b e c a u s e of

its h i g h e r zeta potential.

 239

CONCLUSIONS
 A c o m p a r a t i v e s t u d y h a s been m a d e of t h e s u r f a c e chemistry

of s p o d u m e n e , l e p i d o l i t e , m u s c o v i t e , beryl and m i c r o c l i n e In

a q u e o u s s o l u t i o n s of d o d e c y l a m i n e , with a view t o Improving

the flotation selectivity between the lithium m i n e r a l s and

the other silicates. T h e t e c h n i q u e s used included measurement

of t h e s o l u b i l i t y , cation e x c h a n g e , e l e c t r o k i n e t i c , a d s o r p t i o n

and f l o t a t i o n p r o p e r t i e s of t h e m i n e r a l s . T h e e f f e c t of surface

modification p r o c e d u r e s such as a c i d / a l k a l i n e w a s h i n g , t h e

a d d i t i o n of f l u o r i d e and p o l y v a l e n t metal Ions on t h e m e a s u r e d

properties were determined.

F r o m t h e results o b t a i n e d t h e f o l l o w i n g c o n c l u s i o n s can

be m a d e :

D I s S o I u t i o n , efectrokiiietic and c a t ion e x c h a n g e properties

(a) T h e d i s s o l u t i o n b e h a v i o u r of t h e a Iuminosi Iicates In

aqueous solutions is c o n s i s t e n t w i t h t h e s t a b i l i t y of t h e

component oxides. At low pH p r e f e r e n t i a l d i s s o l u t i o n o f Al

occurs. A t high pH d i s s o l u t i o n is m o r e o r less stoichiometric.

(b) The I.EP v a l u e s of m u s c o v i t e , s p o d u m e n e and beryl o c c u r a t

pH v a l u e s of 5 . 7 , 2 . 8 and 3 r e s p e c t i v e l y . T h o s e of lepidolite

and m i c r o c l i n e a r e a t very acid pH v a l u e s (less than pH 2 . 7 ) .

(c) H + and OH a p p e a r t o be p o t e n t i a l d e t e r m i n i n g for t h e

silicates studied. Al s p e c i e s a r e s p e c i f i c a l l y a d s o r b e d at

the silicate/water Interface. L i + and N a + behave as indifferent

ions a l t h o u g h Li+ Is a lattice c a t i o n in s p o d u m e n e and lepidolite.

T h i s a p p e a r s t o be due t o t h e f a c t t h a t the two c a t i o n s are

nearly completely hydrated in a q u e o u s solutions.

(d) T h e a g i n g of s i l i c a t e s u s p e n s i o n s r e s u l t s in less n e g a t i v e

EM v a l u e s . T h i s can be e x p l a i n e d by the p r e s e n c e of a c o m p o s i t e

g i b b s i t e / a I u m i n o s i Iicate s u r f a c e on t h e m i n e r a l particles. The

actual a I u m i n o s i I i c a t e s o l i d t h a t forms is, h o w e v e r , unknown.

(e) T h e e f f e c t s of a c i d and a l k a l i n e w a s h i n g on t h e EM of t h e

a Iuminosi Iicates d e p e n d on t h e s t r u c t u r e and c o m p o s i t i o n of

t h e mi n e r a I s .

(i) W a s h i n g s p o d u m e n e a n d beryl in HCI does not

s i g n i f i c a n t l y a f f e c t t h e E M of the t w o m i n e r a l s . This appears

t o be due t o the f a c t t h a t t h e s e m i n e r a l s do n o t c o n t a i n AI

in the t e t r a h e d r a I positions. The polymerised tetrahedra are

therefore relatively stable in a c i d i c m e d i a , t h e s i l o x a n e b o n d

probably limiting a c c e s s i b i l i t y to w e a k e r ionic b o n d s , particularl

in m i n e r a l s with poor c l e a v a g e like beryl.

(ii) Washing muscovite, lepidolite and m i c r o c l i n e in HCI

i n c r e a s e s t h e n e g a t i v e EM v a l u e s of t h e m i n e r a l s . Due to the

p r e s e n c e of AI in the t e t r a h e d r a , d e g r a d a t i v e leaching probably

contributes to the loss of b a s i c c a t i o n s r e s u l t i n g in more

n e g a t i v e EM v a l u e s .

(iii) W a s h i n g t h e a Iuminosi Iicates in N a O H does n o t a l t e r

t h e i r EM v a l u e s s i g n i f i c a n t l y unless they contain reasonable

a m o u n t s of b a s i c c a t i o n s in w h i c h c a s e the n e g a t i v e EM decreases.

(f) T h e p r e s e n c e of N a F h a s n o e f f e c t on t h e EM of the a Iumino-

si I icates a t a l k a l i n e pH v a l u e s . A t acid pH v a l u e s , however,

fluoride i n c r e a s e s t h e n e g a t i v e EM for all t h e silicates

studied. C o n s i d e r a t i o n of t h e d i s t r i b u t i o n o f f l u o r i d e species

i n d i c a t e s t h a t HF is t h e a c t i v e species.
 242

(g) A d s o r p t i o n of Al s p e c i e s results in c h a r g e reversal at the

a IuminosiIicate/water interface. T h e pH range of c h a r g e reversal

is d e p e n d a n t on the c o n c e n t r a t i o n of Al in s o l u t i o n . The

r e s u l t i n g EM v a l u e s a r e , h o w e v e r , s i m i l a r for all t h e silicates

studied. T h i s i n d i c a t e s t h a t t h e m e c h a n i s m of c h a r g e reversal

is s i m i l a r for all the m i n e r a l s . It is n o t p o s s i b l e , however,

t o tell from t h e data w h e t h e r the c h a r g e reversal is due t o t h e

a d s o r p t i o n of A I ( O H ) * A I ( O H ) 2 + or colloidal Al(OH),
2 3
(s)

(h) T h e c a t i o n e x c h a n g e p r o p e r t i e s of t h e s i l i c a t e s decrease

in t h e o r d e r m u s c o v i t e > lepidolite > s p o d u m e n e ~ microcline.

Beryl has no m e a s u r a b l e cation e x c h a n g e a f f i n i t y . The cation

e x c h a n g e p r o c e s s o c c u r s p r e d o m i n a n t l y t h r o u g h t h e r e l e a s e , by

t h e a Iuminosi Iicate l a t t i c e , of t h e w e a k l y held (ionically

bonded) monovalent cations. The lack of e x c h a n g e a f f i n i t y for

beryl h a s b e e n a t t r i b u t e d to an a b s e n c e of such c a t i o n s in its

latti c e .

A d s o r p t i o n of a m i n e and S t a r c h at t h e si Ii c a t e / w a t e r interface

(a) T h e a d s o r p t i o n of DA a t t h e s i I i c a t e / w a t e r interface is

c o n s i s t e n t w i t h t h e t h e o r y of c o u l o m b i c a t t r a c t i o n and t h e

f o r m a t i o n of h y d r o p h o b i c a s s o c i a t i o n s . However,

(i) a t low DA c o n c e n t r a t i o n t h e p r e d o m i n a n t m e c h a n i s m of

adsorption is by c a t i o n e x c h a n g e p a r t i c u l a r l y if t h e alumino-

si I icate has g o o d c a t i o n e x c h a n g e properties;

(ii) t h e s l o p e of t h e E M - D A c o n c e n t r a t i o n curve at low a m i n e

concentration is n o t z e r o for a Iuminosi I i c a t e s . It is c o n s i d e r e d

t h a t t h i s a r i s e s from t h e r e l a t i v e l y high DA a d s o r p t i o n densities

due t o t h e f i n i t e cation e x c h a n g e c a p a c i t i e s of t h e a l u m i n o s i I i c a t e s .
(b) Starch a d s o r b s on t h e a Iuminosi Iicates by H - b o n d i n g

between its a l c o h o l i c h y d r o x y l s a n d s u r f a c e s i l a n o l s and other

M - O H g r o u p s on t h e m i n e r a l . Adsorption decreases with increase

in t h e ionic s t a t e of both h y d r o x y l types. M e t h y l a t i o n of t h e

hydroxyl g r o u p s on t h e mineral surface also decreases the

s t a r c h a d s o r p t i o n d e n s i t y and t h e interaction b e t w e e n H + and OH

and t h e m i n e r a l surface.

(c) The adsorption d e n s i t y of s t a r c h on t h e m i n e r a l s decreases

in t h e o r d e r s p o d u m e n e > m i c r o c l i n e > beryl > l e p i d o l i t e >

muscovite. It is p r o b a b l e t h a t t h i s o r d e r is r e l a t e d t o different

d e g r e e s of s u r f a c e a c i d i t y . Potentiometric acid/base titrations

c o u l d n o t , h o w e v e r , c o n f i r m t h i s b e c a u s e of t h e e x c h a n g e of H+

f o r o t h e r c a t i o n s on t h e mineral surfaces.

(d) The adsorption d e n s i t y on s p o d u m e n e of t h e polysaccharides

used d e c r e a s e in t h e o r d e r p o t a t o s t a r c h > m a i z e s t a r c h » British

gum > d e x t r i n . T h i s o r d e r is t h e same as t h a t of t h e molecular

w e i g h t s of t h e compounds.

H a l l i m o n d t u b e f l o t a t i o n of t h e silicates

(a) The flotation b e h a v i o u r of t h e a Iuminosi Iicates in t h e

p r e s e n c e of d o d e c y l a m i n e is c o n s i s t e n t with t h e t h e o r y of

a d s o r p t i o n of DA a t t h e s i l i c a t e / w a t e r interface. Good flotation

is o b s e r v e d a b o v e t h e IEP of the m i n e r a l s . A t pH 12 f l o t a t i o n

is d r a s t i c a l l y r e d u c e d due t o t h e p r e c i p i t a t i o n of a m i n e from

s o l u t i o n and t h e low levels of c a t i o n i c a m i n e present.

(b) Modification by p o t a t o and m a i z e s t a r c h e s results in t h e

s e l e c t i v e d e p r e s s i o n of t h e a m i n e f l o t a t i o n of s p o d u m e n e and,

to a lesser d e g r e e , l e p i d o l i t e at high p H . B r i t i s h gum and t h e

d e x t r i n s a r e i n e f f e c t i v e as d e p r e s s a n t s w i t h i n t h e concentration

range investigated.

(c) D e p r e s s i o n of the s i l i c a t e s in the p r e s e n c e of a m i n e and

starch is p a r t l y influenced by

(i) a c r i t i c a l starch c o n c e n t r a t i o n , and

(ii) the m a g n i t u d e of the s u r f a c e c h a r g e o n t h e m i n e r a l particles.

(d) Excessive mechanical and/or thermal shear during

s o Iubi Iisation of t h e s t a r c h results in r e d u c e d depressive

a b i l i t y of t h e p o l y m e r . Preparing starch in d i l u t e alkali

avoids self-association of t h e starch c h a i n s and improves the

e f f e c t i v e n e s s of starch as a depressant.

Interaction of starch and DA w i t h e a c h other

(a) Starch and DA do n o t e n h a n c e t h e a d s o r p t i o n of e a c h o t h e r a t

the silicate/water interface. The two compounds i n t e r a c t in

solution resulting in t h e f o r m a t i o n of a s t a r c h - D A c o m p l e x w h i c h

has no s u r f a c t a n t p r o p e r t i e s . Thus complex formation, rather

t h a n a d s o r p t i o n a t the si I i c a t e / w a t e r i n t e r f a c e , is t h e main

m e c h a n i s m of s t a r c h and DA a b s t r a c t i o n from s o l u t i o n particularly

-4

at amine concentrations > 2 x 1 0 M.

(b) T h e m e c h a n i s m of i n t e r a c t i o n b e t w e e n starch and DA is

p u r e l y p h y s i c a l , i n v o l v i n g c o u l o m b i c a t t r a c t i o n and hydrophobic

associations. In the C M C region of s t a r c h - f r e e a m i n e solutions

t h e s t a r c h - D A c o m p l e x p r e c i p i t a t e s o u t of s o l u t i o n . Other

hydrophobic I i g a n d s , such as n - d o d e c a n o l , can a l s o precipitate

the starch.
Selectivity considerations

(a) In t h e a b s e n c e of m o d i f y i n g a g e n t s , the a Iuminosi Iicates

have greatly similar eIectrokinetic, amine adsorption and

Hallimond tube flotation c h a r a c t e r i s t i c s . S e l e c t i v i t y of

flotation is n o t t h e r e f o r e p o s s i b l e w i t h o u t m o d i f y i n g t h e silicate

surfaces.

(b) The similarities in t h e EM v a l u e s of t h e s i l i c a t e s in t h e

p r e s e n c e of f l u o r i d e o r A I C I ^ i n d i c a t e s t h a t m o d i f i c a t i o n by

f l u o r i d e o r p o l y v a l e n t metal c a t i o n s is u n l i k e l y t o improve t h e

s e l e c t i v i t y of f l o t a t i o n of t h e a Iuminosi l i c a t e s .

(c) The commercial p r a c t i c e of u s i n g starch a s a s p o d u m e n e

depressant appears reasonable. F u r t h e r w o r k w i t h high molecular

weight polysaccharides might therefore produce improved

flotation results. A further approach to improve selectivity

m i g h t be t o e x p l o i t t h e e f f e c t of a c i d w a s h i n g on t h e alumino-

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74 D e j u , R A and B h a p p u , R B , A c h e m i c a l i n t e r p r e t a t i o n of
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76 F u e r s t e n a u , D W , H e a l y , T W and S o m a s u n d a r a n , P , T h e role
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77 F u e r s t e n a u , D W and W a k a m a t s u , T , T h e e f f e c t of h y d r o c a r b o n
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78 G a u d i n , A M and F u e r s t e n a u , D W , Q u a r t z f l o t a t i o n w i t h
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80 P r e d a l i , J J and C a s e s , J M , T h e t h e r m o d y n a m i c s of t h e
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81 S c a m e h o r n , J F, S c h e c h t e r , R S and W a d e , W H , A d s o r p t i o n of
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82 L i p a t o v , Yu S a n d S e r g e e v a , L M , A d s o r p t i o n of polymers,
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83 K i p l i n g , J J , A d s o r p t i o n from s o l u t i o n s of non-e1ectroIytes,
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84 R u b i o , J and K i t c h e n e r , J A , T h e m e c h a n i s m of a d s o r p t i o n of
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85 K u z k i n , S F , N e b e r a , W P and Z o l i n , S N , A s p e c t s of t h e
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86 B a n k s , W and G r e e n w o o d , C T , T h e c o n f o r m a t i o n of amy lose

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88 W i e , J M a n d F u e r s t e n a u , D W , T h e e f f e c t of d e x t r i n on
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89 S i m h a , R , F r i s h , H L and E i r i c h , F R , T h e a d s o r p t i o n of
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90 M i c h a e l s , A S , A g g r e g a t i o n of s u s p e n s i o n s by p o l y e l e c t r o -
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91 S l a t e r , R W , C l a r k , J P and Kitchener, J A , Chemical

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92 S l a t e r , R W and K i t c h e n e r , J A , C h a r a c t e r i s t i c s o f
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93 R e i n d l e m a n , J A , lonisation of c a r b o h y d r a t e s in t h e
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94 G r i o t , 0 and K i t c h e n e r , J A , R o l e of s u r f a c e si lanol
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95 T a d r o s , Th F , A d s o r p t i o n of p o l y v i n y l a l c o h o l on s i l i c a
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96 M i l l e r , J D and L a s k o w s k i , J , Dextrin a d s o r p t i o n on oxidised

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98 S o m a s u n d a r a n , P and A n a n t h a p a d m a n a b h a n , K P , S o l u t i o n
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99 K u l k a n i , R D , S o m a s u n d a r a n , P and A n a n t h a p a d m a n a b h a n , K P ,
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100 M u k e r j e e , P , T h e n a t u r e of a s s o c i a t i o n e q u i l i b r i a and
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101 S h a i n b e r g , I and K e m p e r , W D , H y d r a t i o n s t a t u s of a d s o r b e d
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102 P i g m a n , W W and G o e p p , R M J r , C h e m i s t r y of t h e carbohydrates,

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103 G r e e n w o o d , C T , Starch and g l y c o g e n iri T h e c a r b o h y d r a t e s ,

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