ANALYTICAL APPLICATIONS OF SOME COMMERCIAL CHELATING EXTRACTANTS
by
VISVANATHAN RAMESH
Th esis subm itted to
Indian Institute o f Technology, Delhi fo r the a w a rd o f the degree of
DOCTOR OF PHILOSOPHY
OflO'
Department of Chemistry
INDIAN INSTITUTE OF TECHNOLOGY, DELHI.
1986
ANALYTICAL APPLICATIONS OF SOME COMMERCIAL CHELATING EXTRACTANTS
VISVANATHAN RAMESH
T h e s i s s u b m i t t e d t o
INDIAN I N S T I T U T E OF TECHNOLOGY NEW DELHI
f o r t h e award o f t h e d e g r e e o f
DOCTOR OF PHILOSOPHY
D e p a r t m e n t o f C h e m i s t r y
INDIAN IN ST IT U TE OF TECHNOLOGY
NEW DELHI - 110 016
DEDICATED
TO
MY PARENTS
C E R T I F I C A T E
T h i s i s t o c e r t i f y t h a t t h e s i s e n t i t l e d
"ANALYTICAL APPLICATIONS OF SOME COMMERCIAL CHELATING EXTRACTANTS" b y V i s v a n a t h a n Ramesh
i s a r e c o r d o f o r i g i n a l b o n a f i d e r e s e a r c h c a r r i e d o u t u n d e r my s u p e r v i s i o n and h a s n o t b e e n s u b m i t t e d e l s e w h e r e f o r a d e g r e e .
( G . N . Rao) P r o f e s s o r
D e p a r t m e n t o f C h e m i s t r y
I n d i a n I n s t i t u t e o f T e c h n o l o g y New D e l h i - 1 1 0 0 1 6 .
I t i s my immense p l e a s u r e and d u t y t o e x p r e s s my hu m bl e g r a t i t u d e t o P r o f . G . N . Rao w i t h o u t whose h e l p t h i s t h e s i s wo ul d n o t h a v e t a k e n t h i s s h a p e . H i s m o t i v a t i o n and d r i v e t o w a r d s t h e g o a l h a s k e p t me up.
I am t h a n k f u l t o him f o r p r o v i d i n g me a s t i m u l a t i n g a n d c h a l l e n g i n g e n v i r o n m e n t i n w hich I h a v e been
w e l c o m e d , i n s p i r e d and a b u n d a n t l y a s s i s t e d .
I am g r a t e f u l t o P r o f . N . K . Jha, Ex-Head and
P r o f . B . L . K h a n d e l w a l , Head, D ep ar t m en t o f C h e m i s t r y f o r p r o v i d i n g a l l t h e n e c e s s a r y f a c i l i t i e s . '
I am e x t r e m e l y t h a n k f u l t o M r . C . R . M e r i g o l d , H e n k e l C o r p o r a t i o n , U . S . A . , f o r k i n d l y a i f t i n q a l l t h e " L I X "
J r e a a e n t s .
I am t h a n k f u l t o D r . H . C . J -r o r a , D r . C . S . R. Niurthy, D r . Roma B h a t t a c h a r y a , M u r a r i Ratnam, J y o t h i , K a n e a a r a j , B h a n d a r i , R a j e s h w a r , J a i n and a l l t h e M. Te ch , 1985 b a t c h
s t u d e n t s f o r t h e i r c o - o p e r a t i o n and a s s i s t a n c e .
Thanks a r e due t o M u r t h y ' s , P a r a s u r a m a n ' s, K r i s h n a n f o r t h e i r a f f e c t i o n end w e l l w i s h e s t h a t h a v e k e p t me up
Th e f i n a n c i a l a s s i s t a n c e g i v e n b y I . I . T . D e l h i i s g r a t e f u l l y a c k n o w l e d g e d .
A w o r d o f a p p r e c i a t i o n f o r M r . T . S . R . I y e r f o r h i s e x c e l l e n t t y p i n g .
ABSTRACT
E x t r a c t i o n - o f some s e l e c t e d m e ta ls ( C u ( I I ) , Z n ( I I ) c a ( l l ) , , : M n ( I I ) , N K I I ) , R h ( I I I ) , F e ( I I ) , F e ( I I I ) , 0 0(1 1) , P b ( I I ) , P d ( I l ) and S b ( l l l ) ) w i t h t h e f o l l o w i n g commercial e x t r a c t a n t s c o n t a in in g d i f f e r e n t f u n c t i o n a l groups?
(a ) LIX26 ( s u b s t i t u t e d 8- h y d r o x y q u in o lin e ) (b) LIX54 ( s u b s t i t u t e d p - d i k e t o n e ) (c ) LIX864 ( a m ix tu re o f
s u b s t i t u t e d a rom atic and a l i p h a t i c hydroxyoxim e) (d)LIX622 ( s u b s t i t u t e d s a l i c y l a l d o x i m e ) has been s tu d ie d . S in c e both t h e e x t r a c t a n t s and t h e i r c o rre s p o n d in g metal c h e l a t e s are s o l u b l e t o a g r e a t e r e x t e n t in v a r i o u s o r g a n ic solven ts/
t h e y can be used t o e x t r a c t some o f t h e s e m eta ls b oth in m a c r o s c a le w e l l as m icro s c a l e ; pH^ v a lu e s and l o g v a l u e s in a l l t h e systems w h erever i t i s p o s s i b l e have b e en c a l c u l a t e d . The o r d e r o f e x t r a c t i o n o f m e ta ls w ith
LIX26 e x t r a c t a n t ( l % v / v in MIBK) ;
P d ( I l ) < C u ( I I ) < S b ( I I I ) < F e ( I I ) < C o ( H ) < Z n ( I I ) < N i ( I I )
approx imatfity
^.Pb ( I I ) <,Mn ( I I ) <C.Cd(Il) a g rees w ith the o r d e r o f e x t r a c t i o n o f m e ta ls w ith 0 . 0 1 M o x i n e in c h lo r o fo r m : F e ( I I I ) ^ C u ( I l ) </ Ni ( I I ) O o ( I I ) < Z n ( I I ) ^ C d d l X ^ P b d D
<M n(I I) .
S i m i l a r t r e n d s in t h e e x t r a c t i o n o f m eta ls w ith t h e o t h e r commercial e x t r a c t a n t s and t h e i r c o rre s p o n d in g
p a r e n t analogues has been o b s e rv e d . Q u a n t it a t iv e s e p a r a t ic
o f m e t a ls which a r e f e a s i b l e u sing t h e s e e x t r a c t a n t s have b e i n d i c a t e d .
LIX26 appears t o be v e r y p ro m is in g e x t r a c t a n t f o r th e p r e c o n c e n t r a t i o n o f t r a c e m e ta ls p r e s e n t in v a r i o u s samples.
P r e c o n c e n t r a t i o n o f some s e l e c t e d m eta ls p r e s e n t in u r in e , w a t e r , s o i l s , m ilk and l u b r i c a t i n g o i l s using LIX2 6
e x t r a c t a n t f o l l o w e d b y t h e i r d e te r m in a t io n using atom ic a b s o r p t io n s p ec tro p h o to m e try havfcbeen i n v e s t i g a t e d and th e a n a l y t i c a l method i s found s a t i s f a c t o r y .
S y n e r g i s t i c enhancement o f m a n g a n es e (II) e x t r a c t i o n o f b e n z o y l t r i f l u o r o a c e t o n e (BTa) o r 4 - b e n z o y l - 3 - m e t h y l -1-
p h e n y l - 5 - p y r a z o l o n e (BMPP) w ith t h e a u x i l i a r y l i g a n d s l i k e p y r i d i n e N -o x id e (PNO), 2-methyl p y r i d i n e N -o x id e (2MPN0),
4 -m e th yl p y r i d i n e N - o x id e (4 MPNO), d ib e n z y ls u lfo x id e (D B S O ) and 8-a m in o q u in o lin e (8AC) has been o b s e rv e d . From t h e
d i s t r i b u t i o n data, e x t r a c t i o n c o n s t a n ts and adduct fo rm a tio n c o n s t a n t s have been computed. The e x t r a c t e d adduct s p e c ie s h a v e been i d e n t i f i e d .
Mass s p e c t r a o f c h e l a t e s o f t h e n o y l t r i f l u o r o a c e t o n e w i t h c o p p e r ( I I ) , l e a d ( l l ) , and cadm iu m (II) have been
s t u d i e d . Since d i f f e r e n t io n d i s s o c i a t i o n mechanisms a re l i k e l y ^ o n t h e n a tu re o f th e m eta l, p r o b a b le fr a g m e n ta t io n p a t t e r n s ha ve been i n d i c a t e d based on th e e x p e rim e n ta l data.
CONTENTS
ACKNOWLEDGEMENT (i*1)
ABSTRACT
Ov)
LIST OF FIGURES ( ? )
CHAPTER I
INTRODUCTION 1
1 . 1 . C l a s s i f i c a t i o n o f E x t r a c t io n Systems 3 1 . 1 . 1 . E x tr a c ta n ts I n v o l v i n g Compound 4
F orm ation .
1 . 1 . 2 . E x tr a c ta n ts I n v o l v i n g I o n - A s s o c i a t i o n . 17 1 . 1 . 3 . E x tr a c ta n ts I n v o l v i n g S o l v a t i o n . 22
1 . 2 . Synergism and Mixed E x tr a c ta n ts 28
1 .3 . M o n ito r in g o f T r a c e M etals 29
1 .4 . Scope o f th e P r e s e n t Work. 31
1 .5 . R e fe r e n c e s 34
CHAPTER I I
SOLVENT EXTRACTION OF METALS USING LIX26 EXTRACTANT 44 I
2 .0 . INTRODUCTION 44
2 .1 . E xperim ental P ro c e d u re 46
2 . 1 . 1 . Apparatus and Reagents 46
2 . 1 . 2 . E x t r a c t io n P ro ced u re. 47
v i i
2 .2 . R e s u lt s and D is c u s s io n . 48
£.3 M etal LIX2 6 systems* . 5 4
2.4 Q u a n t i t a t iv e s e p a ra t io n s w ith LIX26 60 e x t r a c t a n t .
2 . 3 . R e fe re n c e s . 53
CHAPTER I I I
EXTRACTION OF METALS WITH A COMMERCIAL ji-DIKETONE 55 EXTRACTANT (LIX54)
3.0 INTRODUCTION 65
3 .1 . E xperim ental P ro ced u re 67
3 .2 . R e s u lt s and D iscu ssio n 7 2
3*3 M etal LIX54 Systems 74
3.4. . M etal -LIX 5 4 - 10 p h e n a n th r o lin e qq Systems.
3 .3 . Q u a n t i t a t i v e S e p a r a tio n s using LIX54 E x tra c ta n t qo
3 ,€ , R e fe r e n c e s 85
CHAPTER IV
EXTRACTION STUDIES OF SOME METALS KITH COMMERCIAL 87
OXIME EXT RACT ANT S .
4 .0 . INTRODUCTION 87
4 . 1 . E xp erim en ta l P ro c e d u re 89
4 .2 . R e s u lt s and D iscu ssio n 92
4-3. M etal LIX622 ^nd Metal LIX8 64 systems. 94
4.6-. R e fe r e n c e s . 10 2
v i i i
CHAPTER V ‘
U T IL IT Y OP LIX26 EXTRACTANT 1M TRACE NETAL
DETERMINATION . io5
5 . 0 . INTRODUCTION 105
5 . 1 . E xp erim en ta l 110
5 . 2 . Sample P r e p a r a t io n 112
5 . 2 . 1 . D ilu t e d W ater S o lu t io n . 112
5 . 2 . 2 . S o i l Sample S o lu tio n 112
5 . 2 . 3 . M ilk sample p r e p a r a t io n 114
5 . 2 . 4 . L u b r ic a t in g O i l Sample P r e p a r a t io n 115
5 . 2 . 5 . U rin e Sample S o lu tio n . 115
5 . 2 . 6 . Blank S o lu t io n 116
5 . 3 . Standard S o lu tio n o f M eta ls f o r C a l i b r a t i o n 116 5 . 4 . G en era l P r e c o n c e n t r a t io n P ro ced u re 117
5 . 5 . R e s u lt s and D is c u s sio n 118
5 . 5 . 1 . D ilu t e d w a t e r s o l u t i o n 118
5 . 5 . 2 . U rin e samples 121
5 . 5 . 3 . L u b r i c a t i n g o i l s 127
5 . 5 . 4 . S o i l a n a l y s i s 130
5 . 5 . 5 . M ilk sample 131
5 . 6 . R e fe r e n c e s 136
i x
CHAPTER V I
STUDIES IN THE SYNERGISTIC EXTRACTION OP MANGANESE( I I ) 142
6 .0 . INTRODUCTION 142
6 .1 . Experim ental P ro c e d u re 144
6 . 2 . R e s u lt s and D is c u s sio n 145
6 . 3 . R e fe r e n c e s 162
CHAPTER V I I
MASS SPECTRA OF SOME METAL CHELATES OF TRENQYL
TRIFLUORO ACETONE 165
7 . 0 . INTRODUCTION 165
7 . 1 . E xperim ental P ro c e d u re 166
7 . 2 . R e s u lt s and D isc u s sio n
7 . 3 . R e fe r e n c e s 17 2
SUMMARY !7 4
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