• No results found

Analytical applications of some commercial chelating extractants

N/A
N/A
Protected

Academic year: 2022

Share "Analytical applications of some commercial chelating extractants"

Copied!
11
0
0

Loading.... (view fulltext now)

Full text

(1)

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

(2)

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

(3)

DEDICATED

TO

MY PARENTS

(4)

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 .

(5)

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 .

(6)

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

(7)

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.

(8)

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

(9)

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

(10)

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

(11)

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

\

References

Related documents

Submitted to the Indian Institute of Technology, Delhi for the award of the degree of Doctor of Philosophy..

Thesis submitted to Indian Institute of Technology, Delhi for partial fulfilment of the Degree of.. Doctor of Philosophy

Ashish Sharma to the Kusuma School of Biological Sciences, Indian Institute of Technology Delhi, New Delhi for the award of the degree of “Doctor of Philosophy” is

the Indian institute o/ Jechnolog y, flew .,Delhi, /or the award o/ the Theree o/ ` Doctor of Philosophy' is a record o/ the bona/ide reeearch work carried out ty her, hae

Submitted in Fulfilment of the requirement o f the Degree of. DOCTOR OF

&#34; Some Aspects of the Chemistry oftranyl Selenites&#34;, being submitted by Mr.V.P.Verma to the Indian: Institute of Technology, Delhi, for the award of the degree of.. Doctor

Prashant Pradhan to the Kusuma School of Biological Sciences, Indian Institute of Technology Delhi, New Delhi for the award of the degree of ‘ Doctor of Philosophy ’ is a record

Dinesh Chandra Gupta,to the Indian Institute of Technology, Delhi, for the award of the degree of Doctor of Philosophy in the Department of Textile Technology, is a record