o The S tu d y Of F l o t a t i o n on T a c o n ite s By K a l y a n j i U k a b h ai P a t e l A THESIS S u b m itte d to t h e S c h o o l o f G ra d u a te S t u d i e s o f M ic h ig a n S t a t e C o lle g e o f A g r i c u l t u r e and A p p lie d S c ie n c e i n p a r t i a l f u l f i l l m e n t o f t h e r e q u ir e m e n ts f o r th e d e g r e e o f DOCTOR OF PHILOSOPHY D e p artm en t o f C h e m ic a l E n g i n e e r in g 1954 ProQuest Number: 10008402 All rights reserved INFORM ATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a com plete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10008402 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346 A ck n o w led g em en t The a u t h o r w is h e s t o e x p r e s s h i s s i n c e r e a p p r e c i a t i o n t o P r o f e s s o r C. C. D e W itt f o r h i s g u id a n c e a n d e n c o u ra g e m e n t i n th e p u rs u a n c e o f t h i s r e s e a r c h o b je c tiv e # H is u s e o f new an d u n c o n v e n t i o n a l m e th o d s o f a p p ro a c h t o r e s e a r c h p ro b le m s h a s b een a c o n tin u in g i n s p ir a tio n # Dr# H a ro ld A# P r i c e g av e t h e v a l u a b l e s u g g e s t i o n s f o r th e s y n t h e s i s o f t h e o r g a n i c com pounds# D r. a n d M rs. E# A. B ra n d h a v e k i n d l y r e v ie w e d t h e s e v e r a l d r a f t s o f t h i s d i s s e r t a t i o n . CONTENTS I In tro d u c tio n II P u r p o s e and s c o p e III T h e o ry 1. C o n d itio n in g a g e n ts A. B. C. D* E. F ro th e r C o lle c to r D e p re sso rs A c tiv a to rs Ph r e g u l a t o r s IV P r e v i ou s w ork V D e sig n o f c o l l e c t o r s VI F l o t a t i o n m a ch in e V II S y n th e tic o re p r e p a r a tio n V III A d d itio n o f t h e r e a g e n t s IX Q u a n tita tiv e d e te rm in a tio n X A, B. D e c o m p o s itio n o f o r e s V o lu m e tr ic a n a l y s i s XI D is c u s s i o n o f t h e r e s u l t s X II C o n c lu s io n s X III A p p en d ix IVX B ib lio g ra p h y List of Tables T a b le Page 1* D i s s o c i a t i o n c o n s t a n t s o f some o r g a n ic com pounds 2. E q u ilib riu m c o n s ta n ts o r th e s t a b i l i t y 15 c o n s ta n ts o f th e c o m p le x com pounds 3- P re lim in a ry r e s u l t s o f th e f l o t a t i o n c o lle c to rs 16 ru n s o f v a rio u s ty p e s o f IB 4. F lo ta tio n o f t a c o n i t e by d e c a n o y l s a l i c y l i c a c i d 21 5. F lo ta tio n o f t a c o n i t e by d o d ecan o y l s a l i c y l i c a c id 22 6. F lo ta tio n o f ta c o n ite by te tra d e c a n o y l s a l i c y l i c 23 7. F lo ta tio n o f t a c o n i t e by d e c a n o y l B - r e s o r c y lic a c id 24 8. F lo ta tio n o f t a c o n i t e b y 4 - o c to x y B - r e s o r c y l i c a c i d 26 9. F lo ta tio n o f t a c o n i t e by d o d e c a n o y l s a l i c y l i c a c id a c id and tr i m e th y l a m in e a s d e p r e s s o r 10. F lo ta tio n o f r ic h e r ta c o n ite s y n th e tic 27 o re by t e t r a d e c a n o y l s a li c y li c a c id 11. F lo ta tio n o f r ic h e r ta c o n ite s y n th e tic 28 o re s. 29 List of Figures P age 1« F l o t a t i o n c e l l (P h o to g r a p h ) 19a 2. F l o t a t i o n c e l l (D ra w in g ) 20A P e r c e n t R e c o v e ry an d E n ric h m e n t a s f u n c t i o n s o f pH: 3. C o lle c to r 0 .2 # /to n fe e d 30 4. C o lle c to r 0 .1 # /to n fe e d 31 5. C o lle c to r 0 .0 5 # /to n fe e d 32 P e r c e n t R e c o v e ry a n d E n ric h m e n t a s F u n c tio n s o f C o l l e c t o r u s e d . 6* T e tr a d e c a n o y l S a l i c y l i c a c i d (S -1 4 ) 33 7. D odecanoyl S a l i c y l i c a c id (S -1 2 ) 34 8. D ecanoyl S a l i c y l i c a c id 35 9* D e c a n o y l B - r e s o r c y l i c a c i d (R -1 0 ) 36 10• 4 - o c to x y -B -r e s o rc y lic a c id 37 (S -1 0 ) (R E-8 ) P o u n d s o f I r o n R e c o v e re d p e r pound o f c o l l e c t o r u s e d and Im provem ent f a c t o r a s a F u n c ti o n o f pH: 11. C o lle c to r 0 .2 # /to n fe e d 38 12, C o lle c to r 0 .1 # /to n fe e d 39 13. C o lle c to r 0 .0 5 # /to n fe e d 40 P o u n d s o f I r o n R e c o v e re d p e r Pound o f C o l l e c t o r u s e d and Im provem ent F a c t o r a s a F u n c tio n o f C o l l e c t o r u s e d . 14, T e tr a d e c a n o y l S a l i c y l i c a c i d ( S -1 4 ) 41 15* D o d e c a n o y l S a l i c y l i c a c i d ( S -1 2 ) 42 16. D e c a n o y l S a l i c y l i c a c i d (S -1 0 ) 43 17- D ecanoyl B - r e s o r c y lic a c id (R -1 0 ) 44 18. 4 - o c t o x y - B - r e s o r c y l i c a c i d (R E -8 ) 45 Page E f f e c t o f t r i m e t h y l am ine a s d e p r e s s o r , 19. R e c o v e ry an d E n ric h m e n t a s a F u n c tio n o f pH 20. P o u n d s o f I r o n R e c o v e re d p e r Pound o f C o l l e c t o r u s e d and Im provem ent F a c t o r a s a F u n c tio n o f pH 46 47 The S tu d y o f R i c h e r T a c o n ite S y n t h e t i c O re : R e c o v e ry and E n ric h m e n t a s a F u n c tio n o f pH: 21. C o l l e c t o r 0 * 2 # /to n fe e d 46 22. C o lle c to r 0 .1 # /to n feed 49 P o u n d s o f I r o n R e c o v e re d p e r Pound o f C o l l e c t o r u s e d an d Im p ro v em en t F a c t o r a s a F u n c tio n o f pH. 23. C o lle c to r 0 .2 ///to n fe e d 50 24. C o lle c to r 0 .2 ///to n fe e d 51 The S tu d y o f C o n c e n tr a tio n o f t a c o n i t e o r e a s F u n c tio n o f pH. 25. R e c o v e ry a n d E n ric h m e n t f o r 0 .2 # c o l l e c t o r / t o n f e e d 26. Im p ro v em en t F a c t o r and P o u n d s o f I r o n R e c o v e re d p e r Pound o f C o lle c to r u s e d . T h re e d im e n s io n a l G ra p h s; P e r c e n t R e c o v e ry , E n r ic h m e n t, P o u n d s o f I r o n R e c o v e re d p e r P o u n d s o f C o l l e c t o r u s e d a n d Im p ro v em en t F a c t o r , v a r y i n g w ith pH and C o l l e c t o r u s e d . 27. A lk a n o y l S a l i c y l i c a c i d 28. A lk a n o y l S a l i c y l i c a c i d 29. A l k y l a t e d B- R e s o r c y l i c a c i d 30. A lk y la te d B - R e s o r c y lic a c i d 31. R i c h e r T a c o n ite o r e s w ith d o d e c a n o y l s a l i c y l i c a c i d a s c o l l e c t o r 32. R ic h e r T a c o n ite o r e s w ith d o d e c a n o y l s a l i c y l i c a c i d a s c o l l e c t o r 52 1 INTRODUCTION The p r o c e s s o f s e l e c t i v e f l o t a t i o n o r i g i n a t e d by W illia m H ay n es a s a r e s u lt o f h is re c o g n itio n o f th e d if f e r e n c e in w e t t a b i l i t y o f m in e ra ls by w a te r. H is p a t e n t , g r a n t e d i n I 8 6 0 , d e s c r i b e d t h i s new f l o t a t i o n t e c h n i q u e . In t h e s u c c e e d in g f i f t y y e a r s f l o t a t i o n p r a c t i c e s p a s s e d th r o u g h v a r i o u s p h a s e s o f d e v e lo p m e n t: such a s s k in f l o t a t i o n , b u lk o i l f l o t a t i o n , f r o t h f l o t a t i o n , an d m ore r e c e n t l y g r o s s f l o ­ ta tio n . The d e v e lo p m e n t o f t h e s e u n iq u e f l o t a t i o n t e c h n i q u e s h a s b e e n n o u r is h e d by t h e d e p l e t i o n o f t h e r i c h o r e s . F lo ta tio n , a s a p p lie d to th e s e le c tiv e s e p a ra tio n o f m ix tu r e s o f r e l a t i v e l y f i n e l y d iv id e d s o l i d s susp en d ed in th e l i q u i d s ( g e n e r a l l y i n w a t e r ) , i s a s u r f a c e phenom ena. T h e re e x i s t s in th e f l o t a t i o n l i t e r a t u r e a h e a lth y d if f e r e n c e o f o p in io n a s t o th e e x a c t n a tu r e o f t h i s s u r f a c e phenom ena. T h is c o n t r o v e r s y i s c o n c e rn e d m a in ly w ith th e r e l a t i v e im p o r­ t a n c e o f f l o t a t i o n r e a g e n t compound f o r m a tio n a t t h e s u r f a c e o f t h e eco n o m ic s o l i d s , o r a d s o r p t i o n o f t h e r e a g e n t a t t h e s o lid su rfa c e . E x a m in a tio n o f th e s t r u c t u r a l c h a r a c t e r i s t i c s o f known f l o t a t i o n r e a g e n t s i n d i c a t e s t h a t w h e th e r compound f o r m a ti o n a t t h e s u r f a c e , o r a d s o r p t i o n o c c u r s , t h e s e com­ p o u n d s h ave i n t h e i r m o le c u le s , a n e le m e n t o f g ro u p s Vb and V Ib o f th e p e rio d ic ta b le . Such a to m s in t h e i r lo w e r v a le n c e s t a t e s h a v e e x t r a e l e c t r o n s t o s h a r e w ith t h e s u r f a c e m e t a l l i c ato m s o f t h e s o l i d s . The a p p l i c a t i o n o f t h e s e f u n d a m e n ta l 2 p h y s ic o - c h e m ic a l p r i n c i p l e s s h o u ld c o n t r i b u t e much t o a b e t t e r u n d e r s t a n d i n g o f t h e e x a c t n a t u r e o f t h e s u r f a c e phenom ena a c ti v e in f l o t a t i o n p r a c tic e r e l a t e d t o th e c o n c e n tr a tio n o f e co n o m ic v a l u e s in lo w g r a d e o r e s . PURPOSE AND SCOPE C o a l a n d s t e e l a r e t h e b a ck b o n e o f o u r i n d u s t r i a l c i v i ­ liz a tio n . As t h e h ig h g ra d e an d i n t e r m e d i a t e i r o n o r e s becom e m ore a n d m ore d i f f i c u l t t o o b t a i n , t h e lo w g r a d e t a c o n i t e s c o n s t i t u t e a n a t i o n a l l y m a jo r s o u r c e o f i r o n f o r t h e f u t u r e . U n t i l now , t h e t a c o n i t e s w ere r e g a r d e d a u s e l e s s n u i s a n c e i n t h e b e n e f i c i a t i o n o f t h e eco n o m ic i r o n o r e s . T a c o n ite s a re m o st a b u n d a n t i n i r o n r a n g e a r e a s and h a v e b e e n e x c e e d in g ly d i f f ic u l t to c o n c e n tra te . The f l o t a t i o n o f t a c o n i t e s i s v e r y t y p i c a l o f t h e f e r r o u s and n o n f e r r o u s m i n e r a l s . (q u a rtz , p y r ite , r u t i l e M i n e r a l s , su ch a s k y a n i t e o re m i x t u r e ) , c e r a m ic g ra d e f e l d s p a r , m i c a s , g a r n e t s , t o u r m a l i n e , h o r n b le n d e , g l a s s s a n d s , a lu m in a , h a v e b e e n s u c c e s s f u l l y c o n c e n t r a t e d by t h e same t y p e s o f r e a g e n t s . The c h e m ic a l n a t u r e o f i r o n o x id e s an d s i l i c a t e m i n e r a l s , i s q u i t e s i m i l a r t o t h a t o f o t h e r com pounds c o n t a i n i n g o f n i c k e l , c o b a l t , u r a n iu m , t h o r i u m , v a n a d iu m , a lu m in iu m , c e r iu m , a n d , c o p p er. T h e se m i n e r a l com pounds c a n b e c o n c e n t r a t e d w ith s i m i l a r a n io n ic ty p e f l o t a t i o n c o l l e c t o r s . T h is i n v e s t i g a t i o n w as c o n c e rn e d w ith t h e u s e o f t h e f o r e ­ g o in g p h y s ic o - c h e m ic a l p r i n c i p l e s i n t h e d e s ig n o f a f l o t a t i o n 3 r e a g e n t s f o r t h e s e p a r a t i o n o f t h e o x i d e s , c a r b o n a t e s and s i l i c a t e s o f th e iro n m in e ra ls . P o la r c h e la tin g g ro u p s o f * t h e s a l i c y l i c a c i d t y p e p ro v e d n o t e f f i c i e n t . A lk y la te d s a l i c y l i c a c i d ,B - r e s o r c y l i c a c i d and m o n o -a lk y l e t h e r o f t h e l a t t e r w ere s t u d i e d i n d e t a i l . The w ork w as a l s o e x te n d e d t o s tu d y t h e e f f e c t o f t h e c h a in l e n g t h , o re c o n c e n t r a t i o n , p u lp d e n s i t y , pH e f f e c t and t h e v a r i a t i o n o f c o l l e c t o r c o n c e n t r a t i o n . THEORY I n t h e f r o t h f l o t a t i o n , m i n e r a l p a r t i c l e s s h o u ld become a tta c h e d a t th e in te r f a c e o f a i r - l i q u i d 1 0 9 ). 4 0 A, 4 0 , 4 8 , 1 0 3 , and Cn H2 n -4 ° 2 "><1 cn H2 n - 6 ° 2 “h e r e n= 14 - 2 5 ) , X - OR, NRH, 0Y o r a h e lo g e n ; Y - S a lt fo rm in g g ro u p o r e le m e n t an d a t l e a s t , R i n m o le c u le i s a f u n c t i o n i n g h y d ro c a rb o n g ro u p , DESIGN OF A COLLECTOR: S in c e f l o t a t i o n i s a su rfa c e i s t o be c o n s id e re d f i r s t . p h en o m en a, s u r f a c e e n e r g y S c r a t c h i n g , b r e a k in g o r g r i n d i n g o f s o l i d s r e q u i r e s an e x p e n d i t u r e o f e n e r g y . o f t h i s e n e r g y i s t r a n s f o r m e d t o h e a t an d t o so u n d . The m a jo r p o r t i o n some e x t e n t t o O n ly a m in u te f r a c t i o n re m a in s a s s u r f a c e e n e r g y . The i n c r e a s e i n s u r f a c e e n e r g y i s p r o p o r t i o n a l r o u g h ly t o t h e i n c r e a s e i n t h e s u r f a c e a r e a . (3 5 ) g rin d in g r e q u ir e s l e s s e n e r g y , a f a c t w hich w as o b s e r v e d a lo n g tim e ag o ( 5 5 *1 0 0 ) # The p r o p o r t i o n a l i t y o f t h e i n c r e a s e i n s u r f a c e a r e a ( s u r f a c e e n e r g y ) a n d e n e r g y consum ed i s e x p r e s s e d i n " R i t t i n g e r 1 s la w " , w h ich i s d i s c u s s e d i n d e t a i l i n D a l l a V a l l e 's b ook ( 3 5 ) # The r e l a t i v e w e t t a b i l i t y o f t h e v a r i o u s s o l i d s h a s b e e n s t u d i e d s y s t e m a t i c a l l y b y m e a s u rin g t h e c o n t a c t a n g l e s (3 3 * 9 0 )^ I t w as o b s e r v e d t h a t t h e g r e a t e r t h e c o n t a c t a n g l e , t h e g r e a t ­ e r w i l l be t h e d r i v i n g f o r c e and th e g r e a t e r w i l l b e t h e p r o b a b ility f o r th e f l o t a t i o n . But t h e r e a r e v a r i o u s l i m i ­ t a t i o n s t o t h i s w h ich a r e due t o v a r i a t i o n s i n t h e and r o u g h n e s s o f t h e p a r t i c l e s . s iz e , sh ap e The l a t t e r c a u s e s v a r i a t i o n s i n t h e s u r f a c e a r e a and c o n t a c t a n g l e s . A lso t h e c o n t a c t a n g le d e p e n d s on v a r i o u s o t h e r f a c t o r s such a s t h i c k n e s s o f t h e f i l m , 11 im p u ritie s o f s u rfa c e s . T h is m akes t h e i n t e r p r e t a t i o n o f t h e c o n t a c t a n g le m e a s u re m e n ts and p r e d i c t i o n o f t h e b e h a v i o r o f v a rio u s c o lle c to r s v e ry d i f f i c u l t . The w o rk s o f v a r i o u s i n v e s t i g a t o r s , V iv an ( 1 0 8 ) # D eW itt (A0 , 4 1 , 4 2 ) ^ HoljBan ( 6 3 )^ P e t e r s o n ( 8 9 ) , o t c . re v e a l t h e i r a tte m p ts to ( 9 2 ,1 0 3 ,1 0 9 ) i n t e r p r e t th e r e s u l t s o f t h e i r e x ­ p e r im e n ts w ith v a r i o u s c o l l e c t o r s f o r t h e s p e c i f i c m i n e r a l s . They i n d i r e c t l y s u g g e s te d t h a t t h e c o l l e c t o r s may form t h e c h e l a t e o r co m p le x com pounds w ith t h e m e t a l l i c i o n s . A cco rd ­ i n g t o t h i s v ie w v a r i o u s a n a l y t i c a l r e a g e n t s an d d y e s m ig h t be used a s c o l l e c t o r s . H ow ever, p r a c t i c a l eco n o m ic c o n s i d e r ­ a t i o n s and d e s i r e d s e l e c t i v i t y o f t e n p r e c lu d e su ch u s a g e . S u t h e r l a n d ( ^ ) a n d D eW itt w ith v a r i o u s c o w o rk e rs ( 4 1 ,8 6 ,8 7 ) c o n s i d e r e d t h i s p o i n t o f v ie w an d t h e c r y s t a l l a t t i c e c o n t i n ­ u a t i o n i n c o n j u n c t i o n w ith t h e c a l c u l a t i o n o f t h e d im e n s io n a l s i z e o f p o l a r and n o n - p o l a r g ro u p s o f c o l l e c t o r s . A c c o rd in g t o G ro u t ( 5 4 ) t a c o n i t e s w ere fo rm ed b y l e a c h i n g , o x id a tio n , p r e c ip ita tio n an d c o n g lo m e r a tio n th r o u g h t h e a g e s , t a c o n i t e s a r e m i x t u r e s o f c a r b o n a t e s and o x i d e s o f i r o n an d s ilic e o u s gangue. When t h e f r e s h l y fo rm ed p a r t i c l e s o f m i n e r a l s i n c l u d i n g t a c o n i t e s come i n c o n t a c t w ith w a t e r , t h e a c t i v e i r o n a to m s may form seme h y d r a t e s on t h e s u r f a c e . a r e w e a k ly b a s i c i n c h e m ic a l n a t u r e . H y d ra te d i r o n o x i d e s 12 C o n s id e r i n g t h i s a n d t h e v ie w s o f S u th e r l a n d D e W itt, (41>& 6,& 7) (9 2 )^ a s u r v e y o f t h e l i t e r a t u r e on co m p lex com pounds o f i r o n , 5 * 6 ,1 1 * 2 2 ,3 2 ,3 4 ,4 6 ,5 7 ,6 5 * 6 8 ,7 0 ,9 7 * 9 9 ,1 1 0 ,1 1 1 ) many p o l a r g ro u p s a r e fo u n d t o b e p r o s p e c t i v e l y a v a i l a b l e f o r th e f lo ta tio n o f iro n . Among t h e s e a r e h y d r o x y l, c a r b o x y l , s u l ­ f o n i c , s u l f a t e o r o r th o - h y d r o x y a r o m a tic a ld e h y d e , th io c o m p o u n d s . n i t r o , n itr o s o , k e to , H ow ever, none o f t h e s e r e f e r e n c e s g iv e a n y i n d i c a t i o n a s t o w hich o f t h e s e p o l a r g ro u p s w i l l b e t h e m o st e f f e c t i v e f o r t h e f l o t a t i o n o f i r o n b e a r i n g m i n e r a l s . The t h e o r y o f c l a s s i c a l quantum m e c h a n ic s i s t h e mo3t l o g i c a l one t o b e c o n s i d e r e d f o r s e l e c t i n g t h e c o l l e c t o r s . H ow ever t h e c o m p u ta tio n s becom e q u i t e c o m p lic a te d w hich n e c e s s i t a t e t h e c o n s i d e r a t i o n o f t h e f o ll o w i n g s i m p l i f i e d v ie w s b a s e d on t h e p h y s ic o - c h e m ic a l p r i n c i p l e s , (1 ) The m a in d r i v i n g f o r c e i n an y phenom ena i s t h e e l e c t r o ­ s t a t i c an d m a g n e tic f o r c e . The e l e c t r o s t a t i c fo rce i s t h e p re d o m in a n t o n e , (2 ) D ip o le moment i s an i n d i r e c t m e asu re o f t h e r e s i d u a l e l e c t r o ­ s ta tic (3 ) f o r c e s o f t h e m o le c u le s , The e l e c t r o n s h a r i n g p r i n c i p a l o f th e e le m e n ts o f G roups Vband V lb o f t h e P e r i o d i c s ta tic p rin c ip le . o rg a n ic c o l l e c t o r . a t th e s v. h a r e d^ . T ab le i 3 r e l a t e d t o t h e e l e c t r o ­ The s h a r e d e l e c t r o n i s a p a r t o f t h e W h eth e r o r n o t a compound i s f o m e d s u r f a c e o r c h e m i s o r p t io n o c c u r s , e l e c t r o n s a r e 13 (4 ) S u r f a c e t e n s i o n , a d s o r p t i o n , c h e m ic a l r e a c t i o n s an d many o t h e r p h y s i c a l and c h e m ic a l phenom ena d e p e n d on t h i s r e s i d u a l e l e c t r o s t a t i c f o r c e s o f t h e m o le c u le s and io n s * (5 ) C o n s i d e r a t i o n o f c l a s s i c a l th e rm o d y n a m ic la w s , g i v e s a re la tio n s h ip ^ ^ = ^ -A E ”r T ”"” x J b e tw e e n e q u i l i b r i u m c o n s t a n t s an d f r e e e n e r g y ; f r e e e n e r g y i s d e f in ite ly re la te d to e le c tr o s ta tic (6 ) fo rc e s. The d i s s o c i a t i o n c o n s t a n t s o f t h e c o l l e c t o r s and s t a b i l i t y c o n s t a n t s o r t h e co m p lex f o r m a t i o n c o n s t a n t s a r e th e t r u e i n d i r e c t y a r d s t i c k s f o r t h e m e a s u re m e n ts o f th e e l e c t r o ­ s ta tic (7 ) (o r d riv in g ) fo rc e s . The p r o b a b i l i t y o f c h e l a t e f o r m a tio n s h o u ld b e c o n s i d e r e d . F iv e o r m o re m em bered c h e l a t e r i n g s a r e t h e m o st s t a b l e . (8) D im e n s io n a l s i z e s o f t h e v a r i o u s p o l a r an d n o n - p o l a r g ro u p s w i l l p r e d i c t t h e (9 ) s t e r i c h in d e ra n c e i f an y . A d s o r p tio n w i l l b e m ore p ro n o u n c e d , i f t h e r e i s a n y d e ­ fin ite c h e m ic a l r e a c t i o n o r co m p lex c h e l a t e compound f o r m a ti o n p o s s i b i l i t y w ith t h e c o l l e c t o r a n d / o r some com pounds o f t h e m i n e r a l e le m e n t u n d e r c o n s i d e r a t i o n . (1 0 ) The e l e c t r o - m a g n e t i c p r o t o n r e s o n a n c e s tu d y w i l l b e t h e m o st u s e f u l s i n c e i t m ak es p o s s i b l e th e c a l c u l a t i o n o f t h e re s id u a l e le c tr o - s ta tic The l i t e r a t u r e f o r c e s o f t h e v a r i o u s com pounds. s u rv e y ( 4 , 5 , 6 , 1 1 , 2 2 , 3 2 , 3 4 , 4 6 , 5 7 , 6 5 , 6 8 , 7 0 , 9 7 , 9 9 , 1 1 0 , 1 1 1 ) ^ and c o n s i d e r a t i o n o f ab o v e v ie w p o i n t s g av e t h e fo llo w in g p o s s i b i l i t i e s f o r th e c o l l e c t o r . 14 H R ( 3) / H <) |L OH /\A H V R R (4 ) (5) R ( 6) The c o n s t a n t s a s g iv e n i n t a b l e 1 , p a g e 15 s u g g e s t m o st d e s i r a b l e t h e p o l a r g r o u p in g o f s a l i c y l i c a c id * i n t e r e s t i n g t o c o n s id e r th e s t a b i l i t y c o n s t a n t s o f t h e c o m p le x f o r m a ti o n . f o r m a ti o n i n th e l i t e r a t u r e t a b l e No. 2 ) . I t i s a l s o very- c o n s ta n ts o r e q u ilib riu m T h e re i s v e r y l i t t l e on t h e s t a b i l i t y c o n s t a n t s . in ­ (S e e T h ese s t a b i l i t y c o n s t a n t s c a n be s t u d i e d b y t h e c o l o r i m e t r i c , p o t e n t i o m e t r i e , c o n d u c to m e tr ic , p h o to m e tr ic o r s p e c t r o m e t r i c m e th o d . oh 15 TABLE NO. I D i s s o c i a t i o n c o n s t a n t s o f some o r g a n i c com pounds (45 ) p . 633 Phenol 1 . 0x 1 0 “ 10 b e n z o ic a c i d 6 .e x io -5 o -c re so l 4 . 2x l 0- a o - to l u ic a c id 1 . 3x 1 0 - ^ p -c re so l l . l x l O ”8 p - t o l u i c a c id 4 .5 x lO - 5 o—c h r o lo p h e n o l 7 . 7x l 0 - 10 S a l i c y l i c A cid 1 .0 x 1 0 - 3 o - n i t ro p h e n o l 6 .2 x 1 0 - 3 o -c h lo ro -b e n z o ic a c id 1 .3 x 1 0 - 3 p - n i t ro p h e n o l 7 x lO -3 o -B ro m o b e n z o ic a c i d 1 . 5x l 0 - 3 2 , 4- d i n i t r o p h e n o l 1x 10 “ ^ o - n itro b e n z o ic a c id 6 .2 x 1 0 - 3 C a te c h o l 4x 10” 10 3 , 5- d i n i t r o b e n z o i c a c i d G u a ic o l lx l O - 7 A n is ic a c i d 3 .2 x 1 0 * 5 re s o rc in o l 4 x l 0” 10 A n th ra n ilic a c id 1 .0 x 1 0 - 5 H y d ro q u in o n e 1x 1 0 - 10 P h th a lic a c id k , - 1 .0 x 1 0 - 3 P y ro g a llo l 1x 1 0 “ 7 P h e n y la c e tic a c id 6 .0 x 1 0 -5 P h lo r o g lu c i n o l lx lO " ? x -n a p h th o ic a c id 2x 1 0 - ^ o -a m in o p h e n o l 2x l 0 “ 10 S u lf in ic a c id 6 . 2x 10- ^ x -n a p h th o l 1x 10“ ^ F o rm ic a c i d 2 . 1x 1 0 " ^ o x a lic a c id ^ 5x lO - 2 P ro p io n ic a c id 1 . 32x 10“ " M a lo n ic a c i d 1 . 6x lO - 3 n - v a le r ic a c id 1 .5 x 1 0 -5 S u c c in ic a c i d 6 . 8xlO ~ 5 C a p r o ic a c i d 1 . 4 0x10“ 5 G l u t a r i c a c id 4 .7 x lO - 5 n - h e p ty lic a c id 1 .3 0 x 1 0 “ ** A d ip ic a c id 3 . 7x lO - 5 C a p ry lic a c id 1 .4 1 x 1 0 “ ** S u b e r ic a c i d 3 . 0x lO - 5 P e la rg o n ic a c id l .l x l O "5 A z e la ic a c i d 2 . 9x lO ~ 5 1 . 6x 1 0 ' 16 TABLE NO. 2 E q u i l i b r i u m c o n s t a n t s o r t h e s t a b i l i t y c o n s t a n t s o f t h e co m p lex co m p o u n d s. (1 ) I r o n : < U , 2 , 3 2 ,7 0 ) S a ly c ilic a c id ................................................................K=10-f P -H y d ro x y b e n z o ic a c i d .......................................................... 1 6 .3 5 10 U 5 . 2 0 -1 1 .7 L a c t i c a c i d ............... ..................................... io 4 6 - 9 G ly c o lic a c id .................................... 1 0 + 4 *7 0 -H y d ro x y a c e to p h e n o n e .......... .. ..................................... 10 0 - N i t r o p h e n o l ............. .................................... 104 P h e n o l.................................. S a l i c y l a l d e h y d e ............. 5 - 14 C o p p e r: S a l ic y la ld e h y d e io 6 - 5 3 -n - p ro p y l-2 -(0 H )- " 2 , 1- n a p h th o ld e h y d e 1 0 7 *0 5 -m e th y l-2 -(O H ) " 1 0 6 *7 2 , 3- 4 , 6-d im e t h y l - rt l 0 7 -2 A c e ty l A c . . . . 108 *7 3-e th o x y - M 1 0 7 *1 T r i - f l o u r o Ac____ 1 0 6 *1 3-m e th o x y - " 1 0 6 *6 P u r o y l Ac................. 108 ,4 4 -m e th o x y - r' 1 0 6 *9 B e n z o y l Ac............... 1 0 9 *^ 3- n i t r o - " i o 4 *1 A c e to a c e tic a c id . 10 4- n i t r o - M 10^*6 5- n i t r o - " 104 *4 3- f l u o r o - " 1 0 3 *7 3- c h l o r o - 11 1 0 5 *3 5- c h l o r o - " 1 0 5#7 w 1 0 3 *8 7 1 17 (3 ) 0 - Amino p h e n o l^ 1 1 ^ Pb - 0-A m ino B e n z o th io l C u............................................ 4 .3 8 8 x lc A Zn - 0 - " •' !* 6 7 & a O /f 1 .6 7 8 x lc A Z n..............................................9 . 9 x 103 N i.............................................. 9 . 16x 103 C o.............................................. 9 . l 6 x l 0 3 P b .................... ..........................9 .1 6 x 103 (4 ) 0 - N i t ro p h e n o l. N i.............................................. 4 . 1 x l 0 3 C u . . ......................................... 7 .1 x l 0 3 Mn.............................................. 4 .2 x 1 0 C r. .................................. 1 • 5 - 2 . 2 x l0 3 A1.............................................. 1.5X 103 Zn.............................................. 3 . 3 x l 0 3 Th...............................................4 x l0 2 C o..............................................lx lO 3 A p p ro . C e.............................................. 9 x l0 2 From a c o n s i d e r a t i o n o f t h e f o r e g o i n g t a b l e s an d p h y s ic o ­ c h e m ic a l c o n s i d e r a t i o n s p r e v i o u s l y s e t f o r t h , t h e com pounds o f t h e n a t u r e 4 *1 >6 , and a c o m b in a tio n o f 1 and 6 seem ed a l o g i c a l s e le c tio n . The r e s u l t s o f t h i s a r e g iv e n i n t a b l e No. 3 . s t u d y , s e l e c t i o n and e x p e r im e n ts From t h e s e r e s u l t s , a lk y la te d s a li c y lic a c i d and & - r e s o r c y l i c a c i d w ere s e l e c t e d f o r f u r t h e r i n v e s t i g a t i o n . T a b le No. 3 F r o th c o l l e c t e d 1 0 .3 1 3 4 5.011 6 .8 10 21 6 .3 1 3 5 .3 c 10 H21 1 4 .3 5 3 1 1 .2 CH H23 7 .0 1 2 3 .5 6 .5 1 5 3 10.02 6.U 1 1 .5 9 5 1 3 .2 12 25 ml 0 co*^xi^ 23 HO 1 1 23 HO 1 3 .4 0 1 2 .0 8 .0 0 3 .4 4 .6 1 7 18 HO H0< NHCH2 CQN4, i NKMN04 19 FLOTATION MACHINE: The f l o t a t i o n m a ch in e u s e d i n t h i s i n v e s t i g a t i o n was a l a b o r a t o r y s i z e , s u b - a e r a t i o n ty p e c e l l made o f l u c i t e . u n i t d e t a i l s a r e shown in f i g u r e s 1 an d 2• d r i v e n b y an e l e c t r i c m o to r . The a g i t a t o r was The c e l l p r o v id e d f o r v a r i a t i o n i n th e a g i t a t o r speed by u s in g v a r io u s s iz e p u lle y s . u n d er th e The s t i r r e r b y a lo w p r e s s u r e b lo w e r . A ir w as b lo w n The s t i r r e r a c t i o n b ro k e up t h e a i r s tr e a m i n t o a p p r o p r i a t e l y s i z e d b u b b l e s . The o v e r f lo w e d f r o t h was c o l l e c t e d on a n e i g h t c e n t i m e t e r B uchner f u n n e l; th e f i l t r a t e to a s u c tio n b o t t l e . fro m t h e B u c h n e r f u n n e l w as c o n d u c te d The s u c t i o n b o t t l e was p l a c e d a t a h e i g h t so t h a t on c u t t i n g o f f th e vacuum , t h e f i l t r a t e was f e d i n t o t h e c e l l so a s t o m a i n t a i n t h e c o n s t a n t p u lp l e v e l . The c o l l e c t o r was a d d ed t o t h e c e l l from a b u r e t t e , h a v in g a l o n g c u rv e d t i p , w hich made i t p o s s i b l e t o i n t r o d u c e t h e c o l l e c t o r i n s m a ll p o r t i o n s , a t a p o i n t w e l l be?_ow t h e p u lp s u r f a c e , w here i t d i s p e r s e d r e a d i l y i n t o t h e p u lp b o d y . SYNTHETIC ORE PREPARATION: The o r e an d t h e sa n d w ere d r y g ro u n d i n a b a l l m i l l . w ere u s e d a s t h e g r i n d i n g m e d ia . P e b b le s O re s and s a n d s w ere g ro u n d s e p a r a t e l y w ith o u t an y ty p e o f r e a g e n t a d d i t i o n t o a v o id c o n t a m i n a t i o n . G round m a t e r i a l s w ere s c r e e n e d b y T a y lo r S ta n d a rd S ie v e s o f - 1 2 0 t o -*-200 m esh s i z e s . T h is m esh s i z e was u s e d , b e c a u s e t h e work o f ( 51) G a u d in , G r o th , and H e n d e rso n w s ta te d th a t th e u s u a l p a r t i c l e s i z e f o r f l o t a t i o n o f a n y m i n e r a l v a r i e s b e tw e e n 50 an d 100 m ic r o n s , w h ic h c o r r e s p o n d s t o a b o u t 150 t o 3 0 0 m esh . The f i n e r 19A . FLOTATION FIG. 1. CELL. ZO Pi C o m p ressed L U C l't S 1 c e ll vacuum 1.00 GRAMM - FLOTATION FIGUBE CELL< NOo. 2* 20 t h e p a r t i c l e s t h e g r e a t e r w i l l b e t h e a c t i v a t i o n an d t h e lo w e r w ill be th e e f f ic ie n c y o f s e p a ra tio n . G au d in (5 0 ) th a t * when t h e p a r t i c l e s i z e i s re d u c e d b elo w f i v e m ic r o n s , a s lim e i s fo rm e d , w h ich d o e s n o t r e s p o n d t o l a c k s c o m p le te c o n f o r m a tio n (5 0 )^ f lo ta tio n a c tio n . T h is t h e o r y G e n e r a lly re m o v a l o f t h e s lim e p a r t i c l e s i s a good f l o t a t i o n p r a c t i c e . The f l o t a t i o n c e l l was made re a d y by p u t t i n g i n w a te r an d s t a r t i n g t h e 3t i r r e r . The g ro u n d o r e s and san d w ere w e ig h ed and t o t a l o f 100 gram s was a d d e d . The l i q u i d l e v e l was a d j u s t e d b y a d d in g w a te r so t h a t t h e f r o t h c o u ld b e skimmed o f f e a s i l y . s tirre d The s u s p e n s i o n c o n t a i n i n g a b o u t 25% s o l i d s . ADDITION OF REAGENTS: The r e a g e n t s u s e d w e re m a in ly f r o t h e r s , pH r e g u l a t o r s and c o lle c to rs . a A s m a ll d ro p o f steam d i s t i l l e d p in e o i l was u s e d a s f r o t h e r ; t h i s am ount c o r r e s p o n d e d t o not more th a n 0 . 2 p o u n d s p e r to n . A f t e r t h r e e m in u te s s t i r r i n g th e s u s p e n s io n . th e a i r was b u b b le d th r o u g h Two m in u te s l a t e r one m i l l i l i t e r s o f t h e c o l l e c t ­ o r s o l u t i o n w as a d d ed and s t i r r i n g was c o n tin u e d f o r one m in u te m o re . Dean and A m brose c e rta in C3 6 ) showed t h a t , a c o n d itio n in g p e rio d f o r c a t i o n i c r e a g e n t s may s e r i o u s l y d e c r e a s e th e e x t e n t o f flo ta tio n . In t h i s i n v e s t i g a t i o n t h e c o n d i t i o n i n g p e r i o d was s i x m in u te s f o r e a c h r u n . f o r f i v e m in u te s . Then t h e c o l l e c t i o n o f t h e f r o t h f o llo w e d The a d d i t i o n o f t h e c o l l e c t o r was d i s t r i b u t e d 21 d u r i n g t h e c o l l e c t i o n p e r i o d i n such a way t h a t t h e d e s i r e d q u a n t i t y c o u ld b e a d d e d . The c o l l e c t o r s o l u t i o n c o n t a i n s 0 .0 0 1 gram o f t h e r e a g e n t i n a b s o l u t e a l c o h o l . Ten m i l l i l i t e r s o f th e c o l l e c t o r s o lu tio n a d d itio n c o rre sp o n d s t o 0 .2 pounds o f c o l l e c t o r p e r t o n o f d r y o re f e e d . pH r e g u l a t o r s w ere a d d e d b e f o r e t h e a d d i t i o n o f an y r e a g e n t s t o a d j u s t t h e d e s i r e d pH. pH r e g u l a t o r s w ere t h e C. P . h y d ro ­ c h l o r i c a c i d and C. P . p o ta s s iu m h y d r o x id e i n 5% s o l u t i o n . A l l t h e pH m e a s u re m e n ts w ere c a r r i e d o u t u s i n g pH H y d rio n n a rro w ra n g e t e s t p a p e r s . At l e a s t tw o c h e c k s w ere made on e a c h pH fig u re . F r o th was c o l l e c t e d i n a B u c h n e r f u n n e l . f r o t h was f i l t e r e d and t h e f i l t r a t e re g u la rly . The c o l l e c t e d was fe d b a ck i n t o t h e c e l l Then t h e c o n c e n t r a t e was d r i e d w ith t h e f i l t e r p a p e r , w eig h ed and l a b e l e d . QUANTITATIVE DETERMINATION: A) D e c o m p o s itio n o f t a c o n i t e o r e s a m p le s : V a rio u s m e th o d s f o r t h e d e c a n p o s i t i o n o f t h e i r o n b e a r i n g o r e s w ere t r i e d . be: The b e s t and t h e m o st s u i t a b l e one was fo u n d t o 0 . 5 gram s o f th e o r e sam ple w e i^ ie d a c c u r a t e l y and m ixed w ith t h r e e t o f o u r g ram s o f sodiu m p e r o x i d e . The m ix tu r e was f u s e d i n a p o r c e l a i n c r u c i b l e b y h e a t i n g on a s m a ll fla m e w h ic h was g r a d u a l l y i n c r e a s e d u n t i l t h e sam ple f u s e d . b e done c a r e f u l l y , c ib le . T h is o p e r a t i o n s h o u ld s i n c e lo n g h e a t i n g d i s s o l v e s p a r t o f t h e c r u ­ The f u s i o n p e r i o d w as a b o u t 5 m i n u t e s . The f u s e d l i q u i d m a ss was s p r e a d on t h e s i d e o f t h e c r u c i b l e . A f t e r c o o l i n g t h e f u s e d m ass was d i s s o l v e d in t h e b e a k e r w ith w a te r . 22 TABLE NO, 4 F l o t a t i o n o f t a c o n i t e b y d e c a n o y l s a l i c y l i c a c i d (S -1 0 2 ) ( F i g u r e s : 3- 5 ) 8 * 1 1 -1 3 ; 1 6 ; ) S y n th e tic o r e : 4gram s t a c o n i t e + 96 g ram s s a n d . Iro n in s y n th e tic o re : O re s i z e : f 120 1 ,5 $ * - 200 m e sh . C o lle c to r # /T o n . C o n c e n tra te s . G ram s. ^F e 3. 0 ,0 .2 6 .1 6 0 4 9 .4 5 6. 0 .2 5 .2 9 6 2 2 4 .3 2 1 .0 8 5 .5 128. 1795 S. 0 .2 7 .0 0 1 3 17. a 1 4 .2 8 2 .9 125. 1176 3. 0 .1 4 .8 8 4 9 1 3 .5 1 0 .2 4 4 3 .8 132. 449. 6. 0 .1 6 .0 3 2 5 1 7 .2 1 3 .7 6 9 .3 208 950. 3. 0 .1 5 .3 2 4 7 1 6 .4 1 2 .8 6 5 8 .1 1 7 4 .6 746 3. C.C5 4 .6 7 3 7 .1 4 5 .0 5 2 2 .2 1 3 3 .5 112 6. C.C5 3 .4 1 8 1 4 .4 1 1 .0 4 3 3 .1 200. 365 a. 0 .0 5 2 .6 1 S 2 1 .7 1 8 .2 3 7 .5 227. 682 pH. ^ E n ric h m e n t 6 .8 5 ^ R e c o v e ry D e riv e d D a ta $ F e /# c o ll.I m p r o v e m e n t _________ fa c to r. 3 8 .6 7 5 8 .2 265 23 TABLE NO. 5 F l o t a t i o n o f t a c o n i t e b y d o d e c a n o y l s a l i c y l i c a c id (S -1 2 ). ( F i g u r e s : 3_ 5 ; 7 ; 1 1 - 1 3 ; 1 5 ; 2 5 ; 2 6 ) S y n th e tic o r e : 4 gram s t a c o n i t e Iro n in s y n th e tic o re s : O re s i z e : C o lle c to r pH . # / t o n __________ C.2 +120 ^ 96 grains sand • 1 .5 $ * - 2 0 0 . m esh c o n c e n tra te s g ra m s , $Fe E n ric h m e n t $ R e c o v e rs D e riv e d D a ta # F e / # c o l l . Im p ro v « n en t F a c to r, 8 .6 5 2 1 8 .3 8 6 .0 4 8 .3 7 2 .5 290 6. 7 .7 6 2 8 1 8 .4 1 4 .8 9 5 .1 143. 141 S. 9 .0 4 8 5 1 4 .8 1 1 .4 8 9 .1 134 1016 8 .4 7 1 1 3 .1 1 0 .0 6 7 3 .6 222 740 6. 5 .5 1 2 2 2 4 .0 2 0 .8 8 8 .0 265 1830 S. 5 .3 1 6 1 2 3 .2 5 2 0 .0 8 2 .5 248 1650 5 .0 4 4 7 9 .8 8 6 .4 3 2 .7 198 209 6. 5 .5 3 0 4 1 8 .5 2 1 4 .9 6 8 .2 410 1019 8. 5 .0 6 1 0 1 0 .6 4 6 .8 281 496 3. 3. 3. 0 .1 0 .0 5 1 3 .9 24 TABLE NO. 6 F l o t a t io n o f t a c o n i t e by te tr a d e c a n o y l s a l i c y l i c a c id (S -1 4 ). (F ig u re s : S y n th e tic o r e s : pH C o lle c to r # /to n C .2 ) 4 gram s t a c o n i t e —— 96 g ram s o f s a n d . Ir o n in th e s y n th e tic o re : O re s i z e : 3 - 5 , 6 , 1 1 -1 4 1.5/5* + 120 -2 0 0 m esh . c o n c e n tra te s , gram s • $ F e . E n ric h m e n t • ^ R e c o v e ry 6 .2 5 4 .3 8 56 6. 1 1 .4 7 5 5 1 2 .4 4 9 .3 2 S. 1 0 .0 8 4 1 4 .8 5 .2 9 6 3. 3. 0 .1 1 3 .4 9 4 D e riv e d d a t a //F e /V /c o ll. Improve fa c to r, 84 247 9 5 .2 142 88 7 1 1 .4 9 9 .2 149 1130 1 7 .5 1 3 .8 6 1 .9 185 855 6. 8 .0 6 8 1 7 .5 7 1 4 .0 9 4 .0 283 1316 8. 7 .5 0 3 1 5 .7 1 2 .2 3 7 8 .4 235 958 6 .0 4 6 1 1 .5 8 .5 4 46*2 277 394 6. 7 .2 3 3 1 8 .4 1 4 .8 2 9 4 .0 533 1392 8. 5 .4 4 2 1 8 .4 1 4 .8 2 7 0 .6 322 1047 3. 0 .0 5 25 TABLE NO. 7 F lo ta tio n o f t a c o n i t e by d e c a n o y l ( F ig u r e s r S y n th e tic o re : O re s i z e : + 3 - 5 ; 9 , 1 1 -1 3 4 g ram s t a c o n i t e I r o n in t h e s y n t h e t i c o r e : 120 B - R e s o r c y lic a c i d . ) ^ 96 g ram s s a n d . 1 .5 $ - 2 0 0 m e sh . C o lle c to r C o n c e n tra te s E n r ic h m e n t.^ R e c o v e r y D e r i v e d D a t a pH # / t o n gram s ,% Fe. # F e / # c o i l • im provem ent ___________ f a c t o r . _____ 3. 0 .2 5 .5 9 0 3 4 .8 3 .3 1 7 .8 4 27 59 1 0 .3 9 7 .6 6 0 .2 91 457 4 9 .5 74 32 6 6. 8 .7 3 3 8. 7 .7 6 5 7 9 .5 5 6 .6 3 .3 2 6 9 3 .3 5 2 .2 7 7 .5 22 16 6. 5 .3 1 1 2 1 0 .4 3 7 .6 3 3 6 .9 111 758 8. 5 .7 6 7 2 9 .2 6 6 .7 3 4 .9 4 .1 3 5 3 2 .9 2 .9 8 8 .0 4 8 .C 24 6. 4 .6 8 5 4 5 .1 3 .5 1 5 .8 9 5 .1 55 8. 2 .4 8 6 0 9 .6 6 .9 8 1 5 .9 9 5 .5 111 3. 3. 0 .1 .0 5 107 234 26 TABLE NO. 8 F l o t a t i o n o f t a c o n i t e b y 4 - o c to x y p - r e s o r c y l i c a c i d . (F ig u re s : S y n th e tic o re : 4 gram s t a c o n i t e Iro n in s y n th e tic o re : o re s iz e : 3 - 5 , 1 0 , 1 1 -1 3 ; 18 + 120 -f 96 g ram s s a n d . 1 .5 ^ -2 0 0 m e sh . C o l l e c t o r C o n c e n t r a t e s E n ric h m e n t ^ R e co v e ry pH # / t o n g ra m s . ^ F e . _____________________________________________ 0 .2 ) D e riv e d D a ta # F e /^ c o ll.I m p r o v e m e n t f a c t o r . _____ 5 .9 1 1 6 1 2 .5 6 9 .5 3 4 9 .4 74 524 6. 1 0 .8 3 8 2 1 2 .1 8 9 .1 9 8 .0 132 890 8. 1 1 .8 4 2 3 9 .8 9 7 .2 7 8 .0 117 560 5 .6 2 0 8 8 .7 2 6 .4 3 2 .7 9 8 .5 209 3. 3. 0 .1 6. 5 .5 3 3 5 1 1 .0 8 .1 4 0 .5 1 2 1 .5 328 8. 4 .9 7 2 8 1 2 .1 8 9 .1 4 0 .3 1 2 1 .0 366 3 .4 8 1 2 .0 7 1 .6 41 9 .9 2 3 1 .9 192 316 3 .5 7 2 2 .4 134 80 3. 0 .0 5 3 .5 7 4 6. 3 .5 8 6 8, 6 .5 2 1 5 .0 2 1 3 .4 5 .1 5 27 TABLE NO. 9 F l o t a t i o n o f t a c o n i t e o r e by d o d e c a n s y l s a l i c y l i c a c id (F ig u re s : S y n th e tic o re : 19; 20; 20 gram s t a c o n i t e Iro n in th e o re s : 7*&k% O re s i z e : - 200 m e sh . f 120 (S -1 2 ) ) 30 gram s s a n d . C o l l e c t o r C o n c e n t r a t e s E n ric h m e n t ^ R e c o v e ry D e riv e d D a ta pH # / t o n g ra m s . %Fem # F e / # c o l l . Im provem ent ___________________ _ _ __________ _________________________ f a c t o r 2 0 .2 3 S 1 5 .1 7 2 .1 3 9 .2 307 7 2 7 .5 5 5 2 0 .2 2 .9 8 7 1 .0 550 212 10 3 7 .6 1 3 1 3 .3 5 1 .9 6 4 .2 502 122 1 2 .5 5 6 2 3 .4 3 .6 3 7 .4 586 1 3 4 .5 7 S . 771 2 5 .2 3 .9 7 2 8 .0 441 112 10 8 .4 6 3 2 7 .0 4 .3 5 2 9 .2 456 127 4 4 0 .2 0 .1 8 2 .4 T r im e th y l am ine a s d e p r e s s o r u s e d : 2 5 .3 2 8 2 4 .3 3 .7 8 7 8 .5 615 297 6 1 8 .2 0 5 2 8 .5 4 .7 6 9 .8 519 328 10 4 3 .3 0 1 0 .4 1 .3 6 5 7 .5 450 1 4 .4 1 4 2 3 .1 3 .5 3 4 2 .5 664 7 7 .5 4 6 2 5 .8 4 .1 2 4 .8 390 10 8 .6 3 9 2 4 .0 3 .7 2 2 6 .4 5 414 4 4 0 .2 0 .1 7 8 .5 150 102 98. 28 TABLE NO. 10 (F ig u re s : 2 1 - 2 4 ; 2 5 ,2 6 ) F lo ta tio n o f ta c o n i te by te tra d e c a n o y l s a l i c y l i c a c id . S y n th e tic o re : 20 gram s t a c o n i t e Iro n in s y n th e tic o re : O re s i z e : pH f 120 f 80 gram s o f s a n d . 7 .8 4 $ - 2 0 0 mesh* C o l l e c t o r C o n c e n t r a t e s E n ric h m e n t .^ R e c o v e ry D e riv e d D a ta # /to n g ra m s . #Fe ^ F e / # c o l l • Im provem ent ___________ f a c t o r ____ _ 0*2 1 3 •288 2 3 .5 3 .6 2 3 9 .3 312 144 7 2 3 .7 5 7 3 1 .1 5 .3 2 9 4 .0 733 500 10 2 1 .6 5 6 2 7 .6 4 .4 3 7 6 .4 593 342 1 5 .0 1 2 2 4 .3 3 .7 3 4 6 .5 728 176 7 I S . 631 3 3 .3 6 .0 2 5 6 .5 1258 340 10 2 6 .7 1 6 1 2 0 .3 3 .0 6 9 .4 1084 208 2 .0 7 1 4 .7 4 462 31 4 4 4 0*1 0 .0 5 7 .7 2 7 5 1495 7 9 .4 3 2 2 2 .9 3 .1 7 2 7 .6 863 87 10 6 .8 4 2 2 4 .7 3 .3 7 2 1 .6 675 83 C o lle c to r: decan o y l s a l i c y l i c a c id . 2 0 .2 7 0 2 7 .3 4 .5 3 7 2 .0 564 336 9 .2 5 6 2 9 .6 4 .9 6 3 4 .9 274 173 2 1 .7 5 2 2 2 .0 3 .3 3 6 1 .0 478 203 1 7 .1 5 4 1 1 .1 1 .4 6 2 4 .3 379 35 7 9 .9 0 0 1 7 .1 5 2 .4 4 2 1 .6 339 53 10 2 6 .3 4 3 2 4 .1 3 .7 5 8 1 .0 634 303 4 0 .2 7 10 4 0 .1 29 TABLE NO. 11 ( F i g u r e s : 2 1 - 2 4 ;2 5 - 2 6 ) grams. gram * o re 50 50 1 9 .9 50 50 10 90 3 .9 3 g ra m s . %Fe # /to n S -1 2 S -10 .2 .2 4 3 5 .3 3 5 3 8 .4 7 0 .3 2 .5 5 7 2 0 .4 3 3 3 8 .7 2 5 .9 2 .5 9 10 3 0 .8 3 4 3 5 .2 2 7 .7 4 1 0 .2 2 0 2 6 .4 6 9 .0 8 .7 7 9 .9 9 8 2 5 .8 6 5 .6 8 .4 5 7 .9 6 5 .5 2 .0 7 4 8 .1 1 3 2 4 .7 1 2 .8 1 .7 3 7 3 7 .1 1 6 3 5 .5 8 4 .3 2 .9 1 10 3 8 .0 3 9 3 4 .6 8 4 .0 2 .8 4 7 .6 7 9 2 3 .8 1 1 .7 1 .6 5 7 2 0 .1 6 0 42*6 5 4 .8 3 .9 3 10 2 5 .4 9 8 3 8 .8 6 1 .9 3 .3 5 4 2 0 .2 3 8 1 5 .1 7 3 9 .2 2 .1 0 7 2 7 .5 5 5 2 0 .2 7 1 .0 2 .9 8 10 3 7 .6 1 8 1 3 .3 4 6 4 .3 1 .9 0 10 40 40 1 9 .9 S -1 2 .2 .1 20 80 7 .3 4 S -1 2 .2 3 1 .3 4 8 1N3WHDIHN3 CM (D iO Ul X 111 o C L ^ — ro CO to A U 3A 003U f t c '1N3HH0IUN3 00 CM ro 10 CD a> in *1 — « ao UJ u. o uj ro in cn in CD CM CD A H 3A 003H ‘1N3WH0IHN3 I AH3A003H tj«/. 1N3NH0IUN3 (D CM CM 09 CM to GO to ti. IO a: o lAi to o (A 10 10 001 00 CM •AH3A003!d o OtJ 1N3W H0IHN3 CM CM in ro UJ u. in oc o o a: co in CM AU3A003H 37 J.N 3 W H 0 IH N 3 CSJ 00 OJ CM to UJ UJ U- z UJ o 00 00 ro1 to tn in GO CM X Q iii UJ Dm o UJ o u. • fl 500 ro ro CM a o io a n o o ^ 40 d 'l a — X Q. ti­ o LjJ uj or o l— o ro — uj -i -J O o & 10 o X ro * d O ± 0 3 ~ l “IOD e> U. — HI *d *I CM IO 00 d UJ UJ X o oc o O o ttCM i CO IO ro, 00, 500 to _______ ro_____ d Q io a n o o CM — = 42 *31 O O op <0 CM /O CD in o Lti Ld la. u in o :X o CM id in o

e> o o o co o <0 o «• AH3A003U o OJ 47 400 • J ‘l ro nr a, ® CSI o Mi or CM CM o CM c/> o 1000 1 1 1 1 1 1 500 OU IO cvl o / 51 ro CM Q_ o UI 111 z o UJ O P CM 1000 CL CM 2 52 200 -LKJ3UIMD1UN3 GO K □ F IG .2 5 . cvj OJ GO AU3A003H 1000 r I 1 1 FIG. i 26. 1 1 ! 2000 53 \d*l aoioa-noo#^ ^ 54 H y d ro x id e s o f t h e i r o n w ith o t h e r m em bers o f t h e same g ro u p w ere p r e c i p i t a t e d fro m t h e w a te r . M ost o f t h e s i l i c a a n d o t h e r com pounds o f t h e a l k a l i n e m e ta l s re m a in e d i n s o l u t i o n . The m ix tu r e was f i l t e r e d , and p r e c i p i t a t e s w e re w ashed w ith w a te r and ta k e n up i n b e a k e r , an d d i s s o l v e d w ith d i l u t e h y d ro ­ c h lo r ic a c id . B) VOLUMETRIC ANALYSIS: The i r o n was d e te r m in e d v o lu m e tr ic a l l y by p e rm a g n a te m e th o d . (7 4 ) The r e d u c t i o n w as c a r r i e d o u t w i th s ta n d a r d s ta n n o u s c h l o r i d e s o l u t i o n a c c o r d in g t o t h e m o d if ie d Z in m e m a n -R e in h a rd t m e th o d . The r e s u l t s a r e t a b u l a t e d i n t a b l e s 4 -1 1 • DISCUSSION OF THE RESULTS: T a b le No. 3* show s f a i r l y good a g re e m e n t w ith t h e v ie w p o i n t s d i s c u s s e d on p a g e No. 11 f o r t h e d e s ig n o f t h e c o l l e c t o r . D o d e cy l p h e n o l h a s a v e r y s m a ll d i s s o c i a t i o n c o n s t a n t . T h e re i s no p o s s i b i l i t y f o r t h e c h e l a t e f o i m a t i o n , e x c e p t t h e c o m p le x f o r m a ti o n w ith t h e a c t i v e c e n t e r s on t h e s u r f a c e o f t h e new s u r f a c e a r e a o f t h e g ro u n d p a r t i c l e s . The r e s u l t showed v e r y p o o r c o l l e c t i n g pow er f o r t a c o n i t e a s e x p e c te d . D o d e c y l o r t h o —n i t r o p h e n o l shows t h e p o s s i b i l i t y o f t h e s i x m em bered c h e l a t e co m p lex compound f o r m a t i o n . I t s d is s o ­ c i a t i o n c o n s ta n t w i l l n ot be n o tic e a b ly l a r g e r th a n d o d e cy l p h e n o l. The r e s u l t d o d e c y l p h e n o l. showed l i t t l e b e t t e r c o l l e c t i n g p o w er t h a n F o r o t h e r ty p e s o f o x id e s and s i l i c a t e m i n e r a l s i t may be a gpod c o l l e c t o r . The s t u f f i n g o f th e s t a b i l i t y 55 c o n s t a n t s o f v a r i o u s c o m p le x e s w ith t h e v a r i o u s e le m e n ts i s n e c e ssa ry . O r t h o - s u l f o n i c 4 - d e c y l p h e n o l w i l l h av e s l i g h t l y l a r g e r d is s o c ia tio n c o n s ta n t. I t h a s a p o s s i b i l i t y o f fo rm in g s i x m em bered c h e l a t e d c o m p le x . At t h e same t i m e , th e co m p lex compound f o r m a ti o n w ith t h e c a lc iu m p a r t i c l e s ( n a t u r a l l y a s s o ­ c ia te d in ta c o n i te s ) , w ill d e crea se th e e ffic ie n c y o f th e c o lle c to r. T hus t h e e f f i c i e n c y o f t h e d o d e c y 1 - 0 - s u l f o n i c p h e n o l a s a c o l l e c t o r , w i l l v a r y a c c o r d in g t o t h e t y p e s o f t h e o r e s . S u lfo n a te d o i l s , f a t s , s o a p s and t h e p e tr o le u m p r o d u c t s a r e p a t e n t e d a s c o l l e c t o r s f o r t h e f l o t a t i o n o f o x id iz e d i r o n o r e s and some t a c o n i t e s a f t e r d e s lim in g and o t h e r p r e t r e a t m e n t s . O r t h o - n i t r o - 6 - s u l f o n i c - 4 - d e c y l p h e n o l show s t h e p o s s i b i l i t y o f fo rm in g a s i x m em bered c h e l a t e i n tw o w a y s, b u t t h e same r e a s o n i n g a p p l i e s t o s u l f o n i c g ro u p a s t c o - s u l f o n i c - 4 - d e c y l p h e n o l. T h u s , t h e e f f i c i e n c y o f t h e s e com pounds w i l l d ep en d on th e ty p e o f t a c o n i t e s . T h e r e f o r e , th e r e s u l t s o f t h e s e com pounds w ill not be in d ic a tiv e . D o d e c a n o y l h y d ro q u in o n e and m o n o -m eth y l e t h e r o f t h e same h a v e t h e p o s s i b i l i t y o f t h e f o r m a tio n o f s i x m em bered c h e l a t e . T h e i r d i s s o c i a t i o n c o n s t a n t s w i l l b e a b o u t t h e same a s p h e n o l ( s e e t a b l e N o. 1 ) . M o re o v er t h e a l k y l g ro u p a s l o c a t e d , w i l l h a v e a s t e r i c h in d e r a n c e e f f e c t . As a r e s u l t o f t h i s , t h e m o l e c u l a r d e n s i t y o f t h e c o l l e c t o r p e r a c t i v e ato m s o f t h e i r o n on t h e s u r f a c e w i l l b e much s m a l l e r . Thus i t i s a p p a r e n t , t h a t th e s e w i l l be poor c o l l e c t o r s f o r th e t a c o n i t e s . T h is a g r e e s 56 w ith t h e a u t h o r 1s e x p e r i m e n t a l r e s u l t s . The same r e a s o n i n g a p p e a r s t o h o ld f o r t h e a l k y l a t e d p o ly h y d r o x y a r o m a tic com pounds; b u t i n t h e s e c a s e s , t h e r e i s a p o s s i b l i t y o f tw o t y p e s o f co m p lex compound f o r m a ti o n . One i s w ith o r t h o - c a r b o x y l g ro u p an d h y d r o x y l g r o u p - ( a s i x mem bered c h e l a t e f o r m a t i o n ) and t h e o t h e r w i l l b e w ith h y d ro x y l g r o u p s . The d i s s o c i a t i o n c o n s t a n t s w i l l b e s l i g h t l y l a r g e r th a n t h e p h e n o ls a n d h y d r o q u in o n e s . Thus a l k y l a t e d p o ly h y d ro x y a r o m a tic d e r i v a t i v e s s h o u ld show good p o s s i b i l i t i e s a s c o l l e c t o r s f o r iro n o re s . T h is a g r e e s w ith t h e r e s u l t s shown i n t h e t a b l e No, 3* P r o p a n o y l c a t e c h o l h a s a p o s s i b i l i t y o f co m p lex compound fo rm a tio n . The co m p lex compound w i l l n o t be o f th e s i x o r m ore m em bered c h e l a t e ty p e . (n o n -p o la r g ro u p ). I t h a s a v e ry s m a ll a l i p h a t i c c h a in M o re o v er t h e s o u rc e o f i t was n o t known. T h u s, th e r e s u l t o f i t i s n o t r e l i a b l e . Sodium N - ( d o d e c y l p h e n y l) g l y c e n a t e h a s a p o s s i b i l i t y o f fo rm in g f i v e m em bered c h e l a t e , w h ich w i l l b e l e s s s t a b l e t h a n th e s i x o r m ore m em bered c h e l a t e , b u t i t w i l l b e m ore s t a b l e t h a n t h e u n c h e l a t e d com plex com pounds. w as n o t r e p o r t e d i n t h e l i t e r a t u r e . I t s d is s o c ia tio n c o n s ta n t I t g av e v e r y p r e f e r e n t i a l c o lle c tio n o f th e iro n o re s . The much s m a l l e r am ount o f t h e f r o t h was o b t a i n e d . g av e a lo w e r p e r c e n ta g e o f r e c o v e r y . T hus, i t I t may b e im p ro v e d by d e s l i m in g and p r e t r e a t m e n t o f t h e o r e s . T e t r a d e c a n o y l s a l i c y l i c a c i d shows s i x membered c h e l a t e c o m p le x com pound t o b e t h e m ost s t a b l e . a i) . . . . B e s id e s , d i s s o c i a t i o n c o n s t a n t o f s a l i c y l i c a c id i s c o n s i d e r a b l y l a r g e r ( s e e t a b l e l ) . A lso a c c o r d in g t o t h e l a t t i c e ta c o n ite p a r tic le s s tr u c tu r e , c o n tin u a tio n o f th e ( c a r b o n a t e and o x i d e s m i x t u r e s o f i r o n ) s h o u ld be lo g i c a l l y th e b e s t c o lle c to r f o r th e ta c o n ite s * P re lim in a ry s u r v e y o f t h e r e s u l t s o f t a b l e No, 3 showed t h e same tr e n d * E x a m in a tio n o f t a b l e s 4—1 1 , an d f i g u r e s 3 - 2 6 , i n d i c a t e s t h a t e v e r y s e r i e s o f t e s t s show good r e c o v e r y and e n ric h m e n t o f t h e i r o n o r e s fro m t h e s y n t h e t i c m i x t u r e s o f t a c o n i t e s . T h is e n r ic h m e n t an d r e c o v e r y a r e d u e t o t h e p r e s e n c e o f t h e c o l l e c t o r , s i n c e w ith o u t t h e u s e o f a c o l l e c t o r no e n ric h m e n t o r r e c o v e r y w as o b t a i n e d . On t h e c o n t r a r y s i l i c e o u s gangue p a r t i c l e s w ere f l o a t e d due t o t h e a c t i v a t i o n o f s i l i c a by t h e p r e s e n c e o f e le m e n ts s u c h a s f e r r o u s , c a lc iu m , a lu m in iu m , e t c . ,, , *u * w e ll d is c u s s e d in th e l i t e r a t u r e T h is phenom ena i s (2 8 ,3 3 ,4 9 ,5 0 ,7 9 ,9 1 ,9 5 ,9 6 ) To f a c i l i t a t e t h e d i s c u s s i o n , t h e f o llo w in g d e s i g n a t i o n s a r e em p lo y ed f o r t h e d i f f e r e n t c o l l e c t o r s : (1 ) 4 -D e c a n o y l s a l i c y l i c a c i d .................................... A A A ....................S -1 0 ( 2 ) 4 -D o d e c a n o y l s a l i c y l i c a c i d ............................... X X X X ...............S -12 ( 3 ) 4 - T e t r a d e c a n o y l s a l i c y l i c a c i d . . . . ...............O O O ............... . .S - 1 4 ( 4 ) 4-D e c a n o y l p - r e s o r c y l i c a c i d ............................. D D Q ................. .R- 1 0 ( 5 ) 3 - o c to x y p - r e s o r c y l i c a c i d ..................................4 1 4 1 # ....................RE-8 4 -ALKANOYL SALICYLIC ACID: (T a b le s 4 - 6 ; F i g . 3 - 5 ) S e v e ra l g e n e ra l tre n d s a re in d ic a te d as fo llo w s : Maximum r e c o v e r i e s a r e o b t a i n e d a t n e u t r a l pH 7 , f o r th e c o l l e c t o r c o n c e n t r a t i o n o f C .2 0 p o u n d s p e r t o n o f t h e d r y f e e d . The lo w e r t h e am ount o f c o l l e c t o r , t h e lo w e r th e d e g r e e o f 53 e n r ic h m e n t an d re c o v e ry * I n p r a c t i c a l l y a l l c a s e s ( i n each s e r i e s ) , e n ric h m e n t d e c r e a s e s c o n s i d e r a b l y b y i n c r e a s i n g pH ab o v e 7* T h is i s due t o t h e i n c r e a s e d am ount o f f r o t h . At h i g h e r pH, t h e a l k a l i n i t y c o n d i t i o n a c t i v a t e s e v e r y t h i n g in c lu d in g s ilic e o u s gangue. T h is t e n d s t o f l o a t and c a r r y o v e r ( e n tr a p s ) a l l m in e ra l p a r t i c l e s . At pH b e lo w 7 , ( i n t h e a c i d i c c o n d i t i o n o f th e p u l p ) r e c o v e r y i s d e c r e a s e d t o some e x t e n t and e n ric h m e n t i n c r e a s e d s l i g h t l y . T h is may b e due t o t h e s lim e e f f e c t , w hich c a n b e re d u c e d b y d e s lim in g and p r e ­ tre a tm e n t o f th e o r e s . The im p rev em en t f a c t o r i s b e t t e r a t pH 7 - 9 ; when 0 .1 p o und o f c o l l e c t o r p e r to n o f t a c o n i t e i s u s e d . d r o p s a t t h e sam e t i m e . The e n ric h m e n t As t h e am ount o f p o u n d s o f i r o n c o l l e c t e d i n f r o t h p e r pound o f c o l l e c t o r u s e d i n c r e a s e s , t h e e n ric h m e n t an d r e c o v e r y d r o p s . The h i g h e r t h e a l k y l c h a i n o f t h e a l k y l a t e d s a l i c y l i c a c i d , t h e b e t t e r a r e t h e r e s u l t s o f r e c o v e r y , e n r ic h m e n t , im provem ent f a c t o r and p o u n d s o f i r o n i n f r o t h c o l l e c t e d p e r p o u n d s o f c o lle c to r used. T a b le 4 - 1 1 and f i g u r e s 3 - 2 6 ; r e v e a l t h a t h i g h e r co n ce n ­ t r a t i o n o f th e s y n t h e t i c o r e r e d u c e s t h e r e c o v e r y , e n r ic h m e n t, im p ro v em e n t f a c t o r and p o u n d s o f i r o n in f r o t h p e r p ound c o lle c to r used. o f th e of T h is may b e due t o t h e i n c r e a s e d a c t i v a t i o n s i l i c e o u s gangue by h i g h e r c o n c e n t r a t i o n o f th e f e r r o u s an d n o n - f e r r o u s e le m e n ts . T h is s h o u ld b e im p ro v ed by u s in g a 59 d e p r e s s a n t f o r t h e s i l i c e o u s gangue* C a t i o n i c ty p e o f r e a g e n t s , p a r t i c u l a r l y t r i m e t h y l am ine an d d i —n—b u t y l am ine w ere t r i e d * i n few ru n s * T h ese show ed t h e d e s i r e d e f f e c t , b u t n o t en o u g h so t o c o m p e n s a te f o r t h e i n c r e a s e d c o s t o f t h e r e a g e n t s . The e f f e c t o f r e d u c in g t h e p u lp d e n s i t y was t r i e d i n s e v e r a l r u n s f o r h i g h e r c o n c e n t r a t i o n o f th e s y n t h e t i c o r e s . Some im provem ent w as n o te d b u t t h e c o n su m p tio n o f t h e c o l l e c t o r was in c re a s e d . F u r t h e r i n v e s t i g a t i o n a lo n g t h i s l i n e i s n e c e s s a r y b e f o r e a n y d e f i n i t e c o n c l u s i o n s can b e d ra w n . G a u d in , D eW itt w ith c o -w o rk e rs , and v a r i o u s o t h e r i n v e s t i g a t o r s ^ 6 ) pro v ecj t h a t u s in g f i n e r p a r t i c l e s m esh o r f i n e r ) d e c r e a s e d t h e f l o t a t i o n e f f i c i e n c y . (-2 0 0 The same e f f e c t was fo u n d i n t h e v a r i o u s r u n s , w hich a r e n o t in c lu d e d in th e r e s u l t s . p-RESORCYLIC ACID DERIVATIVES: ( T a b le s 7 -B ; f i g . 3 - 5 ) . G e n e ra l t r e n d s f o r t h e v a r i o u s f a c t o r s su ch a s pH, am ount o f c o l l e c t o r s w ith r e s p e c t t o r e c o v e r y , e n r ic h m e n t, im provem ent f a c t o r and p o u n d s o f i r o n c o l l e c t e d i n f r o t h p e r pound o f c o l l e c t o r u s e d , a r e m ore o r l e s s s i m i l a r t o t h o s e o f a l k y l a t e d s a l i c y l i c a c id d e r iv a tiv e s . The r e s u l t s o f p - r e s o r c y l i c a c i d d e r i v a t i v e s show ed a s l i g h t l y lo w e r p e r c e n t a g e s . 60 CONCLUSIONS The f o l l o w i n g c o n c l u s i o n s a r e draw n from t h e d a t a p r e s e n te d * * (1 ) The d e s ig n an d p r e d i c t i o n o f t h e b e h a v io u r o f c o l l e c t o r s can b e a c c u r a t e l y made by c o n s i d e r i n g th e f o ll o w i n g f a c t o r s : (a ) R e l a t i o n s h i p o f c h e m ic a l a f f i n i t y , d ip o le m om ent, r e s i d u a l e l e c t r o s t a t i c f o r c e s o f t h e m o le c u le s . (b ) C h e la te compound f o r m a ti o n and c h e m ic a l r e a c t i o n s . (c ) D i s s o c i a t i o n c o n s t a n t s o f c o l l e c t o r s and s t a b i l i t y c o n s t a n t s o r c o m p le x f o r m a tio n c o n s t a n t s o f t h e c o m p le x com pounds. R e l a t i o n s h i p o f f r e e e n e r g y an d e q u ilib riu m c o n s ta n ts . (d ) E l e c t r o n s h a r i n g p a i r s and e l e c t r o n d e n s i t y o f t h e p o l a r g r o u p s , i o n s o r m o le c u le s o f t h e c o l l e c t o r re a g e n ts . The p o s i t i o n o f t h e p o l a r g ro u p e l e c t r o n s h a r i n g e le m e n ts i n t h e P e r i o d i c T a b le . (e ) S i z e , d im e n s io n s and s t e r i c h i n d e r a n c e o f p o l a r and n o n - p o l a r g ro u p s and d im e n s io n a l p r o p e r t i e s o f c r y s ­ ta llin e la ttic e . (f) P h y s i c a l an d c h e m ic a l p r o p e r t i e s o f t h e o r e s an d c o lle c to rs . (2 ) A lk y la te d s a l i c y l i c a c i d i s one o f t h e b e s t c o l l e c t o r s f o r i r o n p a r t i c l e s from th e s i l i c e o u s g a n g u e . I t w as p o s s i b l e t o o b t a i n 9 0 -9 8 $ r e c o v e r y o f i r o n and a b o u t 15 e n ric h m e n t fo r th e s y n th e tic ta c o n ite s . F or th e h ig h e r c o n c e n tra tio n o f t h e s y n t h e t i c o r e s t h e r e c o v e r y and e n ric h m e n t d r o p . A lk y la te d ^ - r e s o r c y l i c a c i d and 3 -m o n o e th e r o f p - r e s o r c y lic a c id o re s. showed gpod c o l l e c t i n g powers* f o r t h e s y n t h e t i c The r e c o v e r y and e n r ic h m e n ts a r e s l i g h t l y lo w e r th a n a lk y la te d s a l i c y l i c a c id . C a t i o n i c t y p e s o f d e p r e s s o r s f o r s i l i c a , p u lp d e n s i t y and h i g h e r c o n c e n t r a t i o n o f t h e s y n t h e t i c o r e s w ere s t u d i e d , b u t f u r t h e r d e t a i l s tu d y i s r e q u i r e d t o draw an y c o n c l u s i o n s . V a r io u s p r o s p e c t i v e c o l l e c t o r s s t u d i e d a s shown i n t a b l e No, 3 , f a i l e d in t h e r o u ^ i f l o t a t i o n o f t a c o n i t e s , b u t t h e i r flo ta tio n e f f i c i e n c y may b e im p ro v ed b y d e s li m in g an d o th e r p re tre a tm e n ts o f th e o r e s . S a l i c y l i c a c i d t y p e s c o l l e c t o r s show / t h e p o s s i b i l i t y o f t h e f l o t a t i o n f o r v a r i o u s m in e r a ls o f t h e o x i d e s , c a r b o n ­ a t e s and s i l i c a t e m ix tu r e s o f i r o n , n i c k e l , c o b a l t , a lu m in iu m , c e r iu m , u ra n iu m , th o r i u m e t c . , b u t f u r t h e r s tu d y i s r e q u i r e d . S tu d y o f t h e d i s s o c i a t i o n c o n s t a n t s , s t a b i l i t y c o n s t a n t s a n d / o r co m p le x f o r m a ti o n c o n s t a n t s show ed good p r o s p e c t s f o r th e f l o t a t i o n s tu d y . 62 THE SYNTHESIS OF COLLECTORS (1 ) D o d e c y l p h e n o l. I n t h i s r e s e a r c h w o rk , c o m m e rcial g ra d e d o d e c y l p h e n o l w as u s e d . I t was o b t a i n e d fro m S h a r p ie *s c o r p o r a t i o n . The a l k y l b r a n c h was t h e co m p act t e r t i a r y t y p e . (2 ) 0 —n i t r o —p—d o d e c y l p h e n o ls A n is o le w as a l k y l a t e d b y t h e F r i e d e l - C r a f t s m ethod and r e d u c t i o n w as s u b j e c t e d a c c o r d i n g t o t h e W olf£-K p£ishner m e th o d . Then a l k y l a t e d p h e n o l w as n i t r a t e d b y a p r o c e d u r e s i m i l a r t o t h a t r e p o r t e d by C e c y l M. G allo w ay The d e t a i l s o f t h i s c a n b e fo u n d i n t h e a u t h o r 's p r e v i o u s w ork (3 ) ( SV) . O - s u l f o n i c - p - d e c y l p h e n o l: O - s u l f o n i c - p - d e c y l p h e n o l was p r e p a r e d b y t h e p ro c e d u re s i m i l a r t o t h a t r e p o r t e d b y S u t e r and M u f f e tt (1 ^ 2 ) ^ F ifty g ram s o f p - d e c y l p h e n o l w ere ta k e n in a t h r e e n e c k e d f l a s k e q u ip p e d w ith s t i r r e r and 3 0 c c s . o f c o n c e n t r a t e d s u l f u r i c a c i d w ere a d d e d . The m ix tu r e was s t i r r e d a t 100°C f o r one h o u r and t h e n a llo w e d t o c o o l . a s a tu ra te d A f t e r c o o l i n g t h e m ix tu r e was p o u re d i n t o s o l u t i o n o f sodium c h l o r i d e . The p r e c i p i t a t e o f sod iu m s a l t was r e c r y s t a l l i z e d t w ic e from h o t w a t e r . (4 ) 2—n i t r o - 4 - d e c y l - 6 - s u l f o n i c p h e n o l: The p r o c e d u r e f o llo w e d f o r t h e p r e p a r a t i o n o f 2 - n i t r o - 4 —d e c y l —6—s u lp h o n ic p h e n o l was s i m i l a r t o th e p r e p a r a t i o n o f o —s u l f o n i c —p—d e c y l p h e n o l , w hich w as m o d if ie d from t h e p r e ­ p a r a tio n o f th e p i c r i c a c id . In th is c a s e t h e s t a r t i n g com­ pound w as o - n i t r o - p - d e s y l p h e n o l i n s t e a d o f p - d e c y l p h e n o l. 63 (5 ) 2 - h y d r o x y -5 -m e th o x y u n d e c y l p h e n o l: A c c o rd in g t o Z y u n ity H ase CS o } t h e r e p o r t p u b lis h e d by M i tiz o Asano and * > t h e m eth o d o f H asan and Stedm an (C .A . 2j> 5 6 6 9 ) f o r t h e s y n t h e s i s o f a l k y l d ih y d ro x y q u in o n e s d o e s n o t w ork s m o o th ly . A sano an d Y am aguty o b t a i n e d t h e same o b j e c t i v e by a d i f f e r e n t m e th o d . (C >A. 5 0 6 9 7 ). The p r o c e d u r e f o llo w e d i s s i m i l a r t o t h a t r e p o r t e d by M itiz o A sano and z y u n i t i . One h u n d re d and t e n gram s o f d im e th o x y h y d ro q u in o n e w ere d i s s o l v e d i n a f o u r h u n d re d c u b ic c e n t i m e t e r s o f c a rb o n d i s u l f i d e s o l v e n t i n a t h r e e n e c k e d f l a s k e q u ip p e d w ith s t i r r e r and a r e f l u x c o n d e n s o r w ith d r y i n g t u b e c o n t a i n i n g c a lc iu m c h l o r i d e . Then 140 gram s (1 m o le ) o f a n h y d ro u s ATOl^ w ere added w h ile s tirrin g . Then 208 gram s o f d e c y l b ro m id e w e re a d d ed d ro p w is e w h ile s t i r r i n g c o n t i n u o u s l y . (5 h o u r s ) . H y d r o c h lo r ic a c i d fu m es w e re g iv e n o f f . The f i n a l r e a c t i o n m ix tu r e was k e p t o v e r n i g h t . v e r y v i s c o u s and o ra n g e brow n in c o l o r . was p o u re d i n a c i d i f i e d c o ld w a te r . I t was N ext d a y , t h e m ix tu r e I n i t i a l l y a y e llo w su b ­ s t a n c e a p p e a r e d b u t f u r t h e r s t i r r i n g g av e tw o l a y e r s a f t e r s e ttin g . The b o tto m l a y e r was e x t r a c t e d w ith e t h e r and m ixed w ith t h e u p p e r o i l y l a y e r . w as d i s t i l l e d o f f . c ry s ta lliz a tio n . C arbon d i s u l f i d e s o lv e n t and e t h e r The r e s i d u e was p u r i f i e d from a l c o h o l b y The c r y s t a l s w ere p a le y e llo w n e e d l e s and g av e a b o u t 78$ y i e l d * (6 ) 2 - 5 - d ih y d r o x y u n d e c y l p h e n o n e : 2 - h y d ro x y -5 -m e th o x y u n d e c y l ph en o n e was d e m e th y la te d b y 64 4 8 $ HBr s o l u t i o n i n a t h r e e n e c k e d f l a s k e q u ip p e d w ith r e f l u x co n d en so r• Then t h e m ix tu r e was w ashed w ith w a t e r and c r y s ­ t a l l i z e d fro m a l c o h o l w h ich g av e v e r y b r i g h t y e llo w n e e d l e s . The y i e l d was a lm o s t q u a n t i t a t i v e . (7 ) 4 -D o d e c a n o y l p y r o g a l l o l : V a r io u s m e th o d s h a v e b e e n r e p o r t e d a l k y l a t i o n o f p o ly h y d ro x y p h e n o n e s . re a c tio n ^ u s e ^o r F r i e ' s r e a c t i o n , N e n c k i's ( m o d i f i c a t i o n o f F r i e ' s r e a c t i o n ) , and H oesch sy n ­ t h e s i s a r e t h e m o st conmon i n u s e . Y ie ld s o f t h e a l k y l a t i o n p r o d u c t o r t h e r e a c t i o n p r o d u c t w i l l depend on th e p r o c e d u r e used. H a rt and W o o d ru ff r e p o r te d t h a t t h e y o b t a i n e d 3 0 -5 0 $ y i e l d o f t h e a l k y l a t i o n o f p y r o g a l l o l b y N e n c k i's r e a c t i o n . 68 g ram s ( 0 .5 m ole o f a n h y d ro u s ZnC l^w ere d i s s o l v e d i n 2 20 gram s ( 1 .0 5 m o le ) o f d o d e c y l a c i d w ith t h e a i d o f h e a t , w h ereu p o n 63 gram s ( 0 .5 m o le ) o f p y r o g a l l o l w ere a d d e d . The m ix tu r e w as h e a t e d a t 1 3 0 -1 4 0 ° f o r one an d o n e - h a l f h o u r s . U n r e a c te d a c i d was d i s t i l l e d o f f u n d e r vacuum . The r e s i d u a l h e a v y o i l was w ashed w ith w a te r s e v e r a l t i m e s and r e c r y s t a l i z e d from a m ix tu r e o f t o l u e n e and p e tr o le u m e t h e r . I t g av e w h ite n e e d le s h a p e d c r y s t a l s . (8 ) 4 -d o d e c a n o y l p h lo r o g lu c in o l. A 7 0 -8 5 $ y i e l d f o r t h e a l k y l a t i o n o f p h l o r o g l u c i n o l b y H o e s h 's s y n t h e s i s was r e p o r t e d . g a v e a b o u t 6 0 $ .y i e l d . F r i e 1s r e a c t i o n r e p o r t e d l y 65 H o e s c h 's r e a c t i o n : E q u im o la r q u a n t i t y o f d o d e c y l n i t r i l e an d p h l o r o g l u c i n o l i n d r y e t h e r s o lv e n t was t a k e n i n a t h r e e n e c k e d f l a s k e q u ip p e d w ith c o n d e n ^ o r w ith d r y i n g t u b e c o n t a i n i n g h y d r o c h l o r i c a c i d g a s was p a s s e d th r o u g h u s in g Z n C ^ (a n h y d r o u s ) a s t h e c a t a l y s t s t i l l s a t u r a t i o n a t 0 °C . The r e s u l t i n g m ix tu r e was h y d r o ly s e d and i n s o l u b l e k e tim in e hy­ d r o c h l o r i d e p r e c i p i t a t e s w ere f i l t e r e d and w ashed w ith d r y e th e r. The k e tim in e h y d r o c h l o r i d e p r e c i p i t a t e s w ere b o i l e d w ith w a te r f o r t h r e e h o u r s . The f i n a l m ix tu r e was c o o le d and t h e r e s u l t i n g c r y s t a l s o f k e to n e w ere b o i l e d w ith a l c o h o l and n o r i t e f o r a few m in u te s t o d e c o l o r i z e . The d e t a i l s o f t h i s w ork a r e r e p o r t e d i n p r e v io u s w o r k . ^ ^ (9 ) 4 - D o d e c a n o y lr e s o r c in o l . The y i e l d o f t h e a l k y l a t i o n o f r e s o r c i n o l b y F r i e ' s r e a c t i o n was r e p o r t e d t o be b e t t e r th a n H o e sc h ’ s r e a c t i o n . (91A) ' The p r o c e d u r e f o llo w e d was s i m i l a r t o t h a t r e p o r t e d by Masao e t a l . (73).One and one h a l f m o le s o f d o d e c y l a c i d an d 0 . 8 m ole o f a n ­ h y d r o u s Z n C ^ w ere h e a t e d i n a f l a s k a t 12 5 ° f o r h a l f h o u r . Then 0 . 5 m ole o f d r y r e s o r c i n o l was a d d ed i n p o r t i o n s and t h e m ix tu r e was h e a t e d a t 130 o f o r tw o h o u r s . The r e s u l t e d p r o d u c t was k e p t o v e r n i g h t and d eco m p o sed w ith a c i d i f i e d ic e c o ld w a te r. (2> H c l) The a q u a o u s l a y e r was e x t r a c t e d w ith b e n z e n e . The b e n z e n e l a y e r and o i l y l a y e r w ere m ixed and th e b e n z e n e w as re m o v e d . The u n r e a c t e d f a t t y a c id was rem oved b y vacuum d is tilla tio n . The r e s i d u e was t r e a t e d w ith p e tr o le u m e t h e r 66 and p u r i f i e d fro m i t b y c r y s t a l l i z a t i o n . I t gave l e a f l e t c ry s ta ls * (1 0 ) 3 > 4 - d ih y d r o x y d o d e c y l p h e n o n e . F r i e 1s r e a c t i o n an d N e n c k i* s r e a c t i o n s w ere t r i e d , b u t w ith o u t much s u c c e s s . The r e s u l t a n t p r o d u c t was a b l a c k g u n k , ( i t may b e due t o t h e a i r o x i d a t i o n i n t h e p r e s e n c e o f t r a c e s o f th e c a ta ly s t u s e d ). I n t h e s to c k 3 f 4 - d ih y d r o x y p r o p y l p h en o n e was fo u n d b u t t h e s o u r c e was unknow n. (1 1 ) Sodium n - ( 4 ~ d o d e c y l p h e n y l) g l y c i n a t e . T h is compound was p r e p a r e d by h e a t i n g n - d o d e c y l a n i l i n e w ith c h l o r o a c e t i c a c id in a m ix tu r e o f w a te r and a l c o h o l a t &0°C i n a t h r e e n e c k e d f l a s k f o r e i g h t t o t e n h o u r s . The r e s u l t i n g m ix tu r e was n e u t r a l i z e d w ith sodium h y d ro x id e and u n re a c te d c h lo ro a c e tic a c i d was d i s t i l l e d o f f . was p u r i f i e d fro m a l c o h o l by c r y s t a l l i z a t i o n . The r e s i d u e T h is p r o c e s s was m o d if ie d from t h e p r o c e s s f o r p h e n y le n e g ly c in e r e p o r t e d by A l f r e d , (1 2 ) 4 -te tra d e c a n o y l s a li c y lic a c id . V a r io u s m e th o d s w ere t r i e d b u t t h e b e s t one was fo u n d t o b e s i m i l a r t o t h a t r e p o r t e d by F e l i x S e i d e l and O tto E n g e l f r i e d . (4 4 ). I n a t h r e e n e c k e d f l a s k e q u ip p e d w ith r e f l u x c o n d e n s o r , 3 1 0 gram s o f n i t r o b e n z e n e , 32 gram s o f s a l i c y l i c a c i d and 63 gram s o f t e t r a d e c y l c h l o r i d e w ere p l a c e d . The s t i r r e r was 67 jstarsT s t a r t e d and 60 gram s o f a n h y d ro u s AIC1 w ere ad d ed s lo w ly 3 T h is m ix tu r e was k e p t o v e r ­ a t room t e m p e r a t u r e (45 m i n u t e s ) . n ig h t , The n e x t d a y , i t w as h e a t e d on a w a te r —b a th f o r tw o h o u r s , and th e n c o o le d and decom posed i n a c i d i f i e d c o ld w a t e r . (HcL) i c e The o i l y l a y e r was s e p a r a t e d , w ashed w ith w a te r an d t h e n i t r o b e n z e n e was d i s t i l l e d o f f . The r e s i d u a l m ass w as p u r i f i e d by c r y s t a l l i z a t i o n f i r s t fro m g l a c i a l a c e t i c a c i d and th e n from a l c o h o l . The c r y s t a l s w e re d u l l w h ite i n c o l o r . S i m i l a r l y d e c a n o y l and d o d e c a n o y l s a l i c y l i c a c id w ere p re p a re d . (1 4 ) A lk y l a t i o n o f ^ - R e s o r c y l i c a c i d . A l k y l a t i o n was c a r r i e d o u t by a m o d if ie d p ro c e d u re s i m i l a r to th e a lk y la tio n o f s a l i c y l i c a c id , V a rio u s i n v e s t i g a t o r s o f m e th y l - ^ - r e s o r c y l a t e . ( 3 7 3 & 70 ^ f( ' h av e r e p o r t e d t h e a c y l a t i o n They c a r r i e d o u t t h e c o n d e n s a tio n o f a n h y d ro u s a l i p h a t i c o r a r o m a tic m ono- o r d i c a r b o x y l i c a c id w ith a n h y d ro u s a lu m in iu m c h l o r i d e . The p r e v i o u s w o rk s o f D e sa i w ith c o w o rk e rs (3 7 * 3 8 ) s t a i n e d t h e s u b s t i t u t i o n i n p o s i t i o n fiv e . R e c e n t w o rk s o f T r i v e d i an d S e th n a ( ^ 7 ) o b ta i n e d t h e v a r i o u s s u b s t i t u t i o n p r o d u c t s - 5 - a c y l , 3 - a c y l and a l s o d is u b ­ s t i t u t i o n b y u s i n g v a r i o u s m o le r a t i o o f m e th y l — re s o rc y lic a c i d , a n h y d ro u s a l i p h a t i c o r a r o m a tic a c i d and A lC l^ . C o m p a riso n o f t h e s e p r o c e d u r e s i n d i c a t e s t h a t t h e su b ­ s titu tio n i s m ore l i k e l y t o b e i n 5—p o s i t i o n f o r t h e p ro c e d u re u sed in th e la b o r a to r y . 68 (1 4 ) 4 - 0 c to x y - 2 - h y d r o x y b e n z o ic a c i d , E th e rific a tio n o f r e s o r c y l i c a c i d was c a r r i e d o u t a c c o r d in g t o t h e p r o c e s s d e s c r i b e d by G o o tje s e t a l . ( 53) M e th y l B - r e s o r c y l a t e wa3 r e f l u x e d f o r e i g h te e n h o u r s i n a s o l u t i o n o f sod iu m i n a b s o l u t e a l c o h o l , a f t e r d ro p w is e a d d i t i o n o f o c t y l b ro m id e . Then t h e a l c o h o l was rem oved and t h e m ass was s a p o n i f i e d w ith 2N so d iu m h y d ro x id e s o l u t i o n . s o l u t i o n was sh ak e n w ith a c e t o n e . Then th e From t h e e x t r a c t e d s o l u t i o n a c e to n e was rem oved and t h e r e s u l t e d m ass was w ashed w ith a c i d i f i e d w a te r. I t was p u r i f i e d f u r t h e r b y c r y s t a l l i z a t i o n fro m a c e t i c a c i d and f i n a l l y from a l c o h o l . 69 BIBLIOGRAPHY 1* A lf r e d T h e o p h ilu s de M o u lp ie d ; J . C. S. 8 J 435 (1 9 0 5 ) 2. A n d erso n 0 . E . ; E ng. M in in g J . 1 ^ 3. A ndre G in o c c h io ; Rev. I n d . M in e r a ls £5 1 2 7 -3 3 (1 9 5 4 ) ;C . A.Z^8 8709b 4. 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W illia m H a n e s; B r i t i s h P a te n t 488 ( i 8 6 0 ) . 80 100 100 80 80 60 60 40 40 UJ !-> O o yj 20 20 15 05 05 05 20 o UJ .15 TON FEED. FEED. COS QQL L E C T q r t on " 14 •) - FIG. 2 7 . FEED {S SIZE- 12.) -1 2 0 -F200 ( S - 10.) MESH. feed. 400 6001 300 30 kV 40d 20Q £0 c o »o 3 200 _j 100 o o .'5 15 .05 •05 1600 1200 1600 1200 1200 800 800 400 4 00 a: o 800 h~ O < Z Ul 400 z Ul > o £C Q_ z PH 05 S - 14 S - 12. FIG- 28. - 1 2 0 -f 2 0 0 MESH S - 10. SIZE. 80 40 ui 2 0 3 ^05 -^C O L L E C T O R ^/^ 3 '0 5 R - 10. FIG. 29- TACONITES. 800 u_ l- 400 400 20 0 150 100 <-» 10 0 3 05 ^COLLECTOR^^ ^C O LLEC TO R / I t /T O N . 3-05 R E - 8 R -IO . FIG. 3 0 T A CO N IT E S. EN RICH M EN T. 80 60 a 40 o 20 -S T S - ^ collector/ t o n . 14. S — 10. FIG. 31. TACONITES - 2 0 G RA M S. 1200 a: 150 oc H o 8 0 0 '/ L uj -J .j o 400 & :o 5 4 600 *05 600 oc O h O Ul lii -J -J O 200 4 S - 05 14. S -12. FIG. 3 2 . TA CO N ITES - 2 0 GRAMS.