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UBC Theses and Dissertations

Research on new frothing agents Gwyn, Gerald Hamond 1938

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R E S E A R C H O N NEW FROTHING AGENTS b y GERALD HAMOND GWYN A Thesis submitted f o r the Degree of MASTER OF APPLIED SCIENCE In the Department o f METALLURGY The University of B r i t i s h Columbia A p r i l 1938* T A B L E , O F CONTENTS PABT I ^ - ' P a g e INTRODUCTION 1 HISTORY OF F L O T A T I O N 2 THEORY OF F L O T A T I O N AS' SHOWN BY A STUDY OF THE REAGENTS USED F r o t h e r s ( a ) D e f i n i t i o n and c h a r a c t e r o f F r o t h e r s . 4 ( b ) R e l a t i o n b e t w e e n F r o t h e r s and S u r f a c e t e n s i o n . 5 ( c ) R e l a t i o n b e t w e e n s t r u c t u r e and e f f i c i e n c y o f f r o t h e r s . 7 ( d ) Summary o f r e q u i r e m e n t s f o r F r o t h e r s . , 8 C o l l e c t o r s ( a ) D e f i n i t i o n . a n d c h a r a c t e r o f c o l l e c t o r s 10 (b) R e a c t i o n b e t w e e n c o l l e c t o r a n d m i n e r a l 10 ( p a r t i c l e s ( c ) Gas — s o l i d a t t a c h m e n t . 11 ( d ) P r e f e r e n t i a l C o l l e c t o r s . 14 ( e ) T y p e s o f C o l l e c t o r s . 15 A c t i v a t o r s 16 D e a c t i v a t o r s 16 D e p r e s s o r s 17 P H R e g u l a t o r s 19 M i s c e l l a n e o u s R e a g e n t s 20 PART I I .CHARACTER OF THE ORE ' 21 DESCRIPTION -OF THE MACHINES 22 DESCRIPTION AND L I S T OF REAGENTS 22 T E S T ROUTINE DISCUSSION OF THE T E S T S ( a ) I n d i v i d u a l r e a g e n t s (b) G e n e r a l D i s c u s s i o n SUMMARY CONCLUSIONS BIBLIOGRAPHY T he w r i t e r wishes t o thank P r o f e s s o r G.A. G i l l i e s f o r h i s h e l p i n p e r f o r m i n g t h i s work, a l s o W. B i s h o p and F .A. Forward f o r t h e i r a s s i s t a n c e and s u g g e s t i o n s r e g a r d i n g the a s s a y i n g . INTRODUCTION During recent years there has been extensive investigation on both the theoreti c a l and p r a c t i o a l aspects of f l o t a t i o n . In the t h e o r e t i c a l investigations, the aim has been to increase the knowledge of the chemistry of the reaotions involved i n the f l o t a t i o n processes, and thereby to aid i n the control of these processes, while i n the p r a c t i c a l investigations the aim has been to improve, and reduce the costs of, e x i s t i n g operations and to extend the process to hitherto unamenable ores* Most of the p r a c t i c a l i n v e s t i g a t i o n so far has dealt with the action of co l l e c t o r s i n an attempt to increase the knowledge of p r e f e r e n t i a l f l o t a t i o n . As a r e s u l t , many new c o l l e c t i n g agents have been discovered, some of which are not e n t i r e l y s a t i s f a c t o r y with the ex i s t i n g frothing agents. As an example, when X anthates are used as collec t o r s f o r sulphides, pine o i l i s an excellent f r o t h e r . But when soap i s used as a c o l l e c t o r f o r non-sulphides, a delicate balance must be set between the amount of soap and p i n e - o i l present, or the pine o i l interferes with the action of the soap. The investigations recorded i n this paper are a continuation of work started the previous year*-, and deal with new reagents which have been suggested as F r o t h e r s * 2 Bianco> B.B#, and Pothins, J v l . "New Frothing Agents for F l o t a t i o n " JB*A.So« Thesis, University of B.C. A p r i l , 1937. Dean, R.S., and Hersberger, A.D. "New Fl o t a t i o n Reagents" A.I.M.M.E. Tech. Pub. N O . 6 0 5 , 1 9 3 5 . - 2 -The tests were made under conditions comparable with those encountered i n actual m i l l operation. Machine, pulp density and amount of reagent used are t y p i c a l of those i n common practise, and to give a basis of comparison, quantative analysis of the concentrates were made. In the f i r s t part of the paper, an outline of the hi s t o r y of f l o t a t i o n , and a b r i e f discussion on the theory of the process as shown by a consideration of the reagents used therein, i s given. In the second part the tests are outlined, and the results discussed, and recorded HISTORY OF FLOTATION - ............. ,., rz The e a r l i e s t recorded attempts to concentrate ores by f l o t a t i o n were i n 1860 when a patent was i . , 3 issued to Haynes. His process consisted i n mixing the ore with one f i f t h to one ninth as much f a t t y or o i l y agent, a g i t a t i n g the mass with water and so segregating the o i l e d sulphides from the earthy material. This process was known as the b u l k - o i l process* Opposed to that process was the sKIn*flotation method, which made use of the d i f f e r e n t w e t t a b i l i t i e s of sulphide and non-sulphide p a r t i c l e s . Separation was effected by having a free water surface approach the dry, or drying minerals * The period from 1901 to 1905 marked the introduc-3 Gaudin, A.M. 'Flotation* Chap. I. McGraw-Hill, New York, 1932. tion of gas as the buoyant medium. Delpratt and Potter produced gas by the e f f e c t of acid on carbonates: other investigators used e l e c t r o l y s i s , vacuum generator, or d i r e c t •introduction of gas. In the l a t t e r case, the gas was usually a i r , introduced either by .agitation-* or by d i r e c t application of compressed a i r through nozzles. ,One of the main results of the use of a gas was a very large reduction i n the amounts of o i l necessary f o r sulphide f l o t a t i o n . With the b u l k - o i l method, o i l consumption was between 250 and 400 lbs/ton of orewhioh was reduced to between .3 and 2.0 lbs/ton with the introduction of gaa. The next step forward was the discovery by Perkins i n 1921, of the c o l l e c t i n g properties of various organic compounds which contained nitrogen i n the t r i v a l e n t state or sulphur i n the divalent state.- This was followed by the introduction of X anthates i n 1924, and the change from an acid to an alkaline c i r c u i t . These developments marked the beginning of 'chemical f l o t a t i o n ' , as opposed to the ' o i l - * f l o t a t i o n * , which proceeded i t . THEORY OF FLOTATION AS SHOWN BY A STUDY OF THE REAGENTS INVOLVED. The chemical reagents used i n modern f l o t a t i o n practise may be grouped under four general headings: 1; Frothers. Z» Collectors or promoters. 3. Activators, deactivators, and depressors. 4. -P.-H regulators and Miscellaneous Reagents* Each of these w i l l be dealt with i n order. °Frothers (a) D e f i n i t i o n and character of frothers. The purpose of frothers i s to make the bubbles i n the f l o t a t i o n pulp more e l a s t i c and persistant than those obtained with a pure l i q u i d . They are organic substances characterized by a heteropolar structure i n t h e i r molecule, 1.6* one part of the molecule i s polar, or water avid, and the others part i s non polar or water repellant. These parts w i l l be denoted by (x) and (R) respectively, i t is this dual character of the molecules that the frothers owe their power. Both a f f i n i t i e s can be s a t i s f i e d when the molecules are oriented at a gas-water interface, and so bubbles i n a l i q u i d containing a frother are p a r t i a l l y l i n e d with a layer of frother molecules, the polar part being absorbed i n the water, and the non polar part s t i c k i n g out into the a i r i n the bubble* When the bubble f i l m s t a r t s to stretch, more l i q u i d must come from the bulk of the solution and so the solution at the interface i s di l u t e d . Accordingly, the surface tension i s raised, and the tendency to stretch i s counteracted. This gives the bubble the needed e l a s t i c i t y and persistance. The orientation of the frother molecules at a gas-water interface i s well i l l u s t r a t e d i n the following sketch* 4 G i l l i e s , G.A., "The Story of the Buffile". Annual Meeting, G.I.M.M. Vancouver, B.C. Nov. 1937. .R Ga.seous Phase. F i g . I. In suoh a l i n e d bubble, the (X) portion absorbed i n the water w i l l lower the surface tension of the water and so give the bubble the desired e l a s t i c i t y , while the (R)part, s t i c k i n g out into the a i r presents an inactive surface to adjacent bubbles and so tends to prevent coalescence of the bubbles. Thus the above combination of (R) and (X) gives the s t a b i l i t y to a f r o t h which i s required i n the f l o t a t i o n process* (b) Relation between Frothers and Surface Tension. The r e l a t i o n between surface tension and d i l u t i o n i s shown by G-ibbs adsorption equation* a ~ - c . dr RT dc where a » amount of material adsorbed at the interface, c 5 concentration i n the bulk of the l i q u i d . B s a constant dr rate of change of surface tension with <3ic" concentration. i t i s seen that i f *a* i s large, dr i s correspondingly large, do '• : ^  and i f *a» i s small, dr w i l l he small. Organic compounds are dc strongly adsorbed, dr Is large and so a small change i n dc concentration causes considerable drop i n surface tension. On the other hand, inorganic compounds are only s l i g h t l y adsorbed and so large concentrations are required to give much change in surface tension. Therefore organic substances are favored as frothers^ Another conclusion from the above equation i s that i f a solution has a lower surface tension than the water, there w i l l be an excess of solute present i n the surface layer, over that i n the bulk of the solution. Conversely when the concentration of the surface layer is decreased by d i l u t i o n , the surface tension w i l l be raised. The change of surface tension with respect to concentration of a soluble organic substance i s shown i n the following sketch* fl. 7p\ ti 65| j ft •*>]. j S i 45, ft ^ »Si 00 * ft: ^ H 6^ V 6 0^ *M v n "> 0' ^ oa S « "0 N •: Oi 3> Oleic flcid mg.*.io : ' F i g > 2> The l e v e l portion of the curve, from A to B, corresponds to a small concentration of the solute, and the molecules are arranged haphazardly on the surface of the solvent with the soluble polar part (X) dissolved i n the water, and the insoluble, non polar (R) part l y i n g on the surface. At point B, there is a s u f f i c i e n t concentration of the solute molecules to cause them to arrange themselves i n an orderly manner at the interface* as shown i n Figure 3. Further increases i n the amount of solute, crowd them closer together, u n t i l at the point C, a closely packed monomoleoular layer of,the solute i s formed at the interface. The af f e c t o f ' greater concentrations of the solute i s not so marked, since the excess molecules can only be p i l e d up on the surface layer* and t h e i r polar parts do not have an opportunity to exert t h e i r f u l l e f f e c t i n lowering the surface tension by increasing the concentration of (X) i n the i n t e r f a c i a l layer of water. Gaseous /'/lose Licju'icL Phase F i g . .5. (c) Relation between Structure and e f f i c i e n c y of frothers. According to Traubes rule there i s a d e f i n i t e relationship between the length of the hydrocarbon chain, the s o l u b i l i t y of the compound and the lowering of the surface t e n s i o n o f t h e s o l u t i o n . F o r e a c h (GHg) a d d e d , t h e s o l u b i l i t y -i s c u t a p p r o x i m a t e l y 1/3 a n d t h e s u r f a c e t e n s i o n i s incre^s.ed by .3_, f o r e q u i m o l a r amounts o f t h e s o l u t e a d d e d . A c c o r d i n g l y when t h e h i g h e r h o m o l o g u e s o f a s e r i e s a r e u s e d , t h e s o l u t e w i l l be n e a r l y a l l a t t h e s u r f a c e , a n d when two b u b b l e s c o e l e s c e , t h e d e c r e a s e i n t h e a r e a o f t h e i n t e r f a c e w i l l c a u s e l o c a l s u p e r s a t u r a t i o n a n d d i s a p p e a r a n c e o f t h e f r o t h . T h i s w o u l d i n d i o a t e t h a t t h e i n t e r m e d i a t e h o m o l o g u e s s h o u l d be more f a v o r a b l e f o r f r o t h e r s . Dean a n d H e r s b e r g e r 5 b e l i e v e t h a t t h e a b o v e c o n s i d e r a t i o n , r e l e n g t h o f h y d r o c a r b o n c h a i n a n d i n s o l u b i l i t y , a p p l i e s o n l y i f t h e p o l a r p a r t i s r e s t r i c t e d t o a s i m p l e h y d r o x y l o r c a r b o x y l g r o u p , a n d t h a t i f s u i t & l e p o l a r g r o u p s a r e c h o s e n t o g i v e t h e p r o p e r b a l a n c e b e t w e e n t h e p o l a r a n d n o n - p o l a r p a r t s , h y d r o c a r b o n c h a i n s o f much g r e a t e r l e n g t h c a n be u s e d . I t i s a l o n g t h e l i n e s s u g g e s t e d by t h e m , t h a t t h e compounds u n d e r c o n s i d e r a t i o n i n t h i s p a p e r were f o r m e d . (d) Summary o f r e q u i r e m e n t s f o r F r o t h e r s . T h e r e q u i r e m e n t s o f a f r o t h e r h a v e b e e n s u m m a r i z e d b y G*A. G i l l i e s , a s f o l l o w s : 1.' I t m u s t be a n ' o r g a n i c s u b s t a n c e . 2 . I t s m o l e c u l e s must be h e t e r o p o l a r a n d c o n s i s t o f one ^ D e a n , R . S . , a n d H e r s b e r g e r , A . D . "New F l o t a t i o n R e a g e n t s ? A i T i M i M i E ; T e c h * P u b . N o . 6 0 5 , . 1 9 3 5 . G i l l i e s ^ G;A* ^ " T h e S t o r y o f t h e B u b b l e " A n n u a l M e e t i n g , C . I . M . M . V a n c o u v e r , B . C ; N o v . 1 9 3 7 . o r more h y d r o c a r b o n r a d i c a l s a t t a c h e d t o a p o l a r g r o u p * 3 . T h e r e s h o u l d be o n l y o n e p o l a r g r o u p , a n d i t s h o u l d p r e f e r a b l y c o n t a i n o x y g e n i n t h e (OH) (CGOH) o r (CO) f o r m , o r n i t r o g e n i n .the ( N H 2 ) o r (ON) f o r m * 4* I t m u s t n o t i o n i z e m a t e r i a l l y * 5 . I t s s o l u b i l i t y m u s t be n e i t h e r l a r g e n o r v e r y s m a l l , w i t h a r a n g e o f f r o m 0 . 2 t o 5 . 0 gms p e r l i t r e . 6* I t m u s t be r e a s o n a b l e i n c o s t a n d e a s i l y o b t a i n e d * T h e a b o v e h a s b e e n s u p p l e m e n t e d b y D e a n a n d 7 H e r s b e r g e r w i t h t h e f o l l o w i n g : " T h e p r o p e r t i e s o f a n i d e a l f r o t h e r may be s e t down as f o l l o w s : 1* I t m u s t f o r m i n l o w c o n c e n t r a t i o n s c o p i o u s b u t n o t t o o p e r s i s t e n t f r o t h * . . 2 . I t m u s t be i n s e n s i t i v e t o h y d r o g e n - i o n c o n c e n t r a t i o n o f t h e p u l p : t h a t i s i t m u s t f r o t h e q u a l l y w e l l i n a n a c i d o r a l k a l i n e medium* 3 . I t m u s t be i n s e n s i t i v e t o s a l t s , e v e n i n h i g h c o n c e n t r a t i o n s . 4 . I t m u s t be a b s o l u t e l y n o n c o l l e c t i n g t o b o t h s u l p h i d e s a n d n o n s u l p h i d e s * 5 . I t s f r o t h i n g p r o p e r t i e s m u s t n o t be a f f e c t e d by c o l l e c t i n g a g e n t s , . i n c l u d i n g s o a p , t h e m o s t g e n e r a l l y u s e d n o n - * s u l p h i d e c o l l e c t o r . . • 6 . I t m u s t r e a d i l y e m u l s i f y a n d d i s p e r s e a n y i n s o l u b l e 7 D e a n , R . S . a n d H e r s b e r g e r , A . D . "New F l o t a t i o n R e a g e n t s " : l . I * M . M * E * Tech- .Pub* N o . 6Q5, 1 9 3 5 . c o l l e c t i n g a g e n t t h a t i s l i k e l y t o be u s e d * " The r e a g e n t s t e s t e d i n t h i s work were o n e s o u t -l i n e d by D e a n a n d H e r s b e r g e r a s f u l f i l l i n g m o s t o f t h e s e r e q u i r e m e n t s * C o l l e c t o r s ( a ) D e f i n i t i o n a n d c h a r a c t e r o f c o l l e c t o r s * T h e b a s i c p r i n c i p l e o f m i n e r a l f l o t a t i o n i s t h a t i f a m i n e r a l p a r t i c l e i s i n s o l u b l e i n w a t e r , i t i s w a t e r -r e p e l l a n t a n d a i r - a v i d . T h e more i n s o l u b l e t h e m i n e r a l i s , t h e g r e a t e r t h e e a s e w i t h w h i c h i t c a n be f l o a t e d , a n d t h e m o r e s o l u b l e i t i s , t h e more d i f f i o u l t i t " i s t o f l o a t , o r t h e e a s i e r i t i s t o d e p r e s s . T h e p u r p o s e o f c o l l e c t o r s i s t o render t h e m i n e r a l p a r t i c l e s i n s o l u b l e i n t h e s o l u t i o n ; h e n c e t h e y w i l l be a t t r a c t e d t o t h e a i r b u b b l e s a n d f l o a t e d t o t h e s u r f a c e . T h e y a r e h e t e r o p a l a r compounds. , b u t u n l i k e f r o t h e r s , t h e p o l a r p a r t m u s t be a c t i v e a n d i o n i z e a p p r e c i a b l y . T h e p o l a r p a r t i s a t t a c h e d t o t h e m i n e r a l p a r t i c l e , l e a v i n g t h e n o n p o l a r p a r t s t i c k i n g o u t f r o m t h e s u r f a c e . T h i s g i v e s a h y d r o p h o b e c o a t i n g t o t h e m i n e r a l s u r f a c e a n d r e n d e r s i t a i r - a v i d . (b) R e a c t i o n b e t w e e n c o l l e c t o r s a n d m i n e r a l p a r t i c l e s . T h e e x a c t n a t u r e o f t h e c h e m i c a l r e a c t i o n w h e r e b y t h e c o l l e c t o r i s a t t a c h e d t o t h e m i n e r a l s u r f a c e i s s t i l l a m a t t e r o f d i s c u s s i o n . I n some c a s e s , s u c h a s t h e f l o t a t i o n o f c o p p e r c a r b o n a t e b y a m y l X a n t h a t e , t h e r e i s d e f i n i t e e v i d e n c e t o show t h a t c o p p e r X a n t h a t e i s f o r m e d b y m e t a t h e s i s o r d o u b l e £ e o o m p o s i t i o n . H o w e v e r t h e r e i s j u s t as much e v i d e n c e t h a t • - 11 -• ' p y r i t e d o e s n o t . f o r m i r o n X a n t h a t e , b u t t h a t t h e c o l l e c t o r i s a t t a c h e d t o t h e p y r i t e p a r t i c l e s b y a d s o r p t i o n , w h i c h i s r e a c t i o n b e t w e e n t h e p o l a r p a r t o f t h e c o l l e c t o r m o l e c u l e s , and t h e r e s i d u a l s u r f a c e v a l e n c e o f t h e p a r t i c l e s . C h r i s t m a n 3 s u g g e s t s t h a t c e r t a i n s u l p h i d e s , when s u b j e c t e i t h e r t o o x i d a t i o n o r a d s o r p t i o n o f i o n s , f o r m m a c r o i o n s j a s s e e n t h e f o l l o w i n g e x a m p l e o f g a l e n a * H H ii II " n = pb = 5 = Pb= II II " _ - 5 = Pb + Rir fV7acromo/ect//e /vjacro'/ori L T h e s e c h a r g e d p a r t i c l e s t e n d t o r e p e l e a c h o t h e r by r e a s o n o f t h e l i k e c h a r g e s t h e y c a r r y a n d so a r e d i s p e r s e d t h r o u g h o u t t h e p u l p . When t h e c o l l e c t o r i s a d d e d , i t c o m b i n e s w i t h t h e c h a r g e d m a c r o i n a n d f o r m s a h y d r o p h o b e o r g a n i c c o a t i n g o n t h e p a r t i c l e . 7^5]Pb**+ ff-r2F?5~ +2'A/a. \p~h~5\Pb[5R)z -f-2No. + R'= T h e c o l l e c t o r shown a b o v e i s o f t h e m e r o a p t a n t y p e ( c ) G a s - S o l i d a t t a c h m e n t . . . • T h e r e i s a d i f f e r e n c e o f o p i n i o n among i n v e s t i a g a -t o r s a s t o t h e e x a c t n a t u r e o f t h e p r o c e s s w h e r e b y m i n e r a l p a r t i c l e s , c o a t e d w i t h c o l l e c t o r s , a r e feound t o t h e b u b b l e s C h r i s t m a n . " C h e m i s t r y a n d t h e F l o t a t i o n P r o c e s s " A m e r i c a n C y a n a m i d C o . T e c h . P a p e r , N o . 1 7 , N o v . 1 9 3 0 . • ~ 1 2 -i n t h e p u l p a n d f r o t h * A c c o r d i n g t o G a u d i n 9 i t i s t h e p o l a r i t y o f t h e s u r f a c e o f t h e m i n e r a l w h i c h d e t e r m i n e s w h e t h e r a p a r t i c l e w i l l r e m a i n a t t a c h e d t o a b u b b l e a f t e r an e n c o u n t e r b e t w e e n t h e t w o . A s t u d y o f t h e c o n t a o t a n g l e shows t h a t i f t h e s u r f a c e o f t h e p a r t i c l e i s n o n - p o l a r , t h e r e i s a t e n d e n c y f o r t h e gas t o d i s p l a c e t h e w a t e r a t t h e s u r f a c e o f t h e s o l i d , ( F i g . 4 ( a ) . ) b u t i f t h e s u r f a c e o f t h e p a r t i c l e i s p o l a r , t h e w a t e r w i l l t e n d t o d i s p l a c e t h e g a s , a n d t h e p a r t i c l e w i l l be r e t u r n e d t o t h e l i q u i d p h a s e . ( F i g . 4 ( b ) . ) (a) ( h ) F i g . , 4 . C h r i s t m a n 1 0 s u g g e s t s t h a t t h e (R) o f t h e c o l l e c t o r i s a b s o r b e d b y t h e (R) o f t h e f r o t h e r , a n d s o f a s t e n e d t o t h e b u b b l e * I n t h e o p i n i o n o f t h e w r i t e r t h e r e a r e two f a c t o r s o p p o s i n g t h e l a t t e r v i e w p o i n t * F i r s t l y t h e (R) p o r t i o n o f t h e f r o t h e r a n d c o l l e c t o r m o l e c u l e s i s a h y d r o c a r b o n c h a i n , a v e r y i n a c t i v e s u b s t a n c e , a n d i t i s p r a c t i c a l l y i m p o s s i b l e f o r t h e r e t o be a n y r e a c t i o n o r a d s o r p t i o n b e t w e e n two s u c h 9 G a u d i n , ' A . M . " F l o t a t i o n " P . 9 8 . McGraw H i l l , New Y o r k . 1932* 1 0 A m e r i c a n C y n a m i d O o . T e c h * P a p e r N o . 17 N o v . 1 9 3 0 . c h a i n s . S e c o n d l y t h e (R) o f t h e f r o t h e r i s n o t p r e s e n t e d t o a p a r t i c l e as t h a t p a r t i o l e a p p r o a c h e s a b u b b l e * When a b u b b l e i s . i n t h e p u l p j t h e c o n d i t i o n s a r e as i n F i g * 5 . a n d t h e n o n p o l a r p a r t (R) i s i n t h e a i r . H e n c e ' w h e n t h e p a r t i c l e a p p r o a c h e s i t h e b u b b l e , t h e (R) o f t h e c o l l e c t o r .would h a v e t o r e a c t w i t h t h e (X) o f t h e f r o t h e r , o r a s i s p r o b a b l y t h e t r u e c a s e , t h e (R) o f t h e c o l l e c t o r , b e i n g w a t e r r e p e l l a n t i s a t t r a c t e d t o t h e a i r i n t h e b u b b l e a n d t h u s f a s t e n s t h e p a r t i c l e t o t h e b u b b l e . ' T h e p o l a r p a r t (X) o f t h e f r o t h e r i s i n t h e w a t e r T h a t s u c h a s t a t e , a s shown by F i g . 5 , e x i s t s a l s o i n t h e f r o t h , i s shown b y G-audins p i c t u r e o f p o l y g o n a l b u b b l e s i n h i s d i s c u s s i o n o f p u l p d r a i n a g e f r o m f r o t h s . 1 1 ( F i g . 7) G a u d i n , A . M . ' F l o t a t i o n * . P . 1 0 9 . MoGraw H i l l . N e w Y o r k 1 9 3 2 . - 14 -When t h e b u b b l e i s i n t h e p u l p o r t h e f r o t h ( e x c e p t i n g t h e s u r f a c e l a y e r o f t h e f r o t h ) v i t h e r e i s o n l y one s k i n o r w a l l t o e a c h b u b b l e , a n d h e n c e t h e r e i s o n l y one l a y e r o f f r o t h e r m o l e c u l e s p r e s e n t * as o p p o s e d t o two i n F i g . 1 . T h e m i n e r a l p a r t i c l e s a r e o o n t a i n e d i n t h e w a t e r f i l m b e t w e e n t h e b u b b l e s ^ a n d f a s t e n e d t o t h e b u b b l e s a s e x p l a i n e d a b o v e . F i g . 1 . i s t r u e f o r t h e s u r f a c e l a y e r o f b u b b l e s o f a f r o t h e r ; s u c h a b u b b l e m u s t . h a v e two s k i n s o r i n t e r f a c e s s i n c e i t i s c o m p o s e d o f a f i l m o f w a t e r , w i t h a i r o n b o t h s i d e s o f i t . (d ) P r e f e r e n t i a l C o l l e c t o r s * P r e f e r e n t i a l f l o t a t i o n d e p e n d s u p o n t h e c o l l e c t o r a c t i n g p r e f e r e n t i a l l y w i t h t h e d e s i r e d s u l p h i d e , o r e l s e f o r m i n g t h e m o s t i n s o l u b l e c o a t i n g w i t h t h e d e s i r e d s u l p h i d e . T h e f o l l o w i n g a r e t y p i c a l e x a m p l e s : X a n t h a t e s c o l l e c t P b m i n e r a l s i n p r e f e r e n c e t o Cu o r H g m i n e r a l s : L o w e r X a n t h a t e s c o l l e c t C u , F e o r Pb m i n e r a l s i n p r e f e r e n c e t o Zn o r Co m i n e r a l s : s u b s t i t u t e d d i t h i p h o s p h a t e s c o l l e c t t h e Cu m i n e r a l s , s o a p s c o l l e c t m i n e r a l s o f d i v a l e n t a n d t r i v a l e n t m e t a l s * a n d f a t t y a c i d s , s u c h as o l e i c , c o l l e c t t h e c a r b o n a t e s a n d o x i d e s o f t h e m e t a l l i c m i n e r a l s . The u s e o f f a t t y a c i d s g i v e s a p r e f e r e n t i a l s e p a r -a t i o n b e t w e e n t h e n o n - s u l p h i d e s a n d s u l p h i d e s , b u t among t h e n o n - s u l p h i d e s , s u c h a s c a r b o n a t e s a n d o x i d e s , i t i s p r a c t i c a l l y a u n i v e r s a l c o l l e c t o r . To m o d i f y t h i s a c t i o n s p e c i a l r e a g e n t s . - 15 -m u s t be u s e d . - By t h e u s e o f h y d r a t e d p h o s p h a t e s t s u c h a s s o d i u m m e t a p h o s p h a t e , a n d s o l u b l e m e t a l l i c s a l t s , o h r o m i t e was s e p a r a t e d f r o m l i m e s t o n e , a n d f l u o r s p a r . ( c a l c i u m f l u o r i d e ) f r o m l i m e s t o n e ( c a l c i u m c a r b o n a t e ) . I n t h e f i r s t c a s e , t h e s o l u b l e s a l t s u s e d w e r e l e a d n i t r a t e a n d f e r r o u s s u l p h a t e , w h i c h r e s u l t e d i n c o a t i n g t h e l i m e s t o n e w i t h i r o n c a r b o n a t e a n d t h e c h r o m i t e w i t h l e a d c h r o m i t e . T h e f o r m e r i s d e p r e s s e d b y t h e metaph.ospha.te w h i l e t h e l a t t e r i s n o t , a n d s o t h e s e p a r a t i o n was e f f e c t e d . I n t h e f l u o r s p a r , l i m e s t o n e s e p a r a -t i o n , f e r r o u s s u l p h a t e was a g a i n u s e d . A s b e f o r e i t c o a t e d t h e l i m e s t o n e , b u t d i d n o t a f f e c t t h e f l u o r s p a r , s i n c e c a l c i u m f l u o r i d e i s l e s s s o l u b l e t h a n e i t h e r f e r r o u s f l u o r i d e o r c a l c i u m s u l p h a t e . When t h e m e t a p h o s p h a t e was a d d e d i t h e l i m e s t o n e , w i t h i t s c o a t i n g o f f e r r o u s c a r b o n a t e was d e p r e s s e d , w h i l e t h e f l u o r s p a r was n o t , a n d s o c o u l d be f l o a t e d o f f as t h e c o n c e n t r a t e . ( e ) T y p e s o f C o l l e c t o r s . T h e t y p e s o f c o l l e c t o r s i n g e n e r a l u s e a r e 1* X a n t h a t e s R = A l i p h a t i c g r o u p . 2 . D i t h i o p h o s p h a t e s ( A e r o f l o a t ) R= A l i p h a -t i c o r a r o m a t i c g r o u p . S i M e r c a p t a n s R - S - H 4 . F a t t y a n d A r o m a t i c c a r b o x y l i c a c i d s s S 5 . X a n t h a t e d e r i v a t i v e s - d i x a n t h o g e n _ _ / ? - o - e - s - s - C - O - R m o n o x a n t h o g e n R-O-&-S-G-O-R. • . . • . <s <s . 12 R o s e E . H . a n d M a c D o n a l d , W . T . U . S . P a t e n t N o . 2 , 0 4 0 , 1 8 7 . - 16 -• A c t i v a t o r s A c t i v a t i n g a g e n t s a r e compounds w h i c h r e a c t w i t h a. non f l o a t a b l e s u b s t a n c e a n d s o a l t e r i t s s u r f a c e a s t o r e n d e r i t f l o a t a b l e . T h i s i s a c h i e v e d b y f o r m i n g s u c h a c o a t i n g o n t h e p a r t i c l e t h a t r e a c t i o n b e t w e e n t h i s c o a t i n g a n d t h e c o l l e c t o r w i l l r e s u l t i n t h e f o r m a t i o n o f a l e s s s o l u b l e c o m -p o u n d t h a n t h a t f o r m e d b e t w e e n t h e c o l l e c t o r and t h e m i n e r a l . A s an e x a m p l e , s p h a l e r i t e w i l l n o t f l o a t when t r e a t e d w i t h e t h y l x a n t h a t e b e c a u s e z i n c e t h y l x a n t h a t e i s r e l a t i v e l y s o l u b l e . H o w e v e r , when c o p p e r s u l p h a t e i s a d d e d , i t r e a c t s w i t h t h e s p h a l e r i t e f o r m i n g a c o a t i n g o f c o p p e r s a l t on t h e p a r t i c l e s , a n d t h i s , w i t h e t h y l x a n t h a t e f o r m s i n s o l u b l e c o p p e r e t h y l x a n t h a t e , w h i c h i s r e a d i l y f l o a t a b l e . T h e m o s t e f f e c t i v e a c t i v a t i n g a g e n t s a r e c o p p e r , l e a d o r m e r c u r y s i n c e t h e i r o r g a n i c s a l t s a r e t h e l e a s t s o l u b l e * D e a c t i v a t o r s The p u r p o s e o f d e a c t i v a t o r s i s t o u n d o a n y a c c i d e n t a l a c t i v a t i o n w h i c h h a s o c c u r r e d i n the m i l l c i r c u i t , a n d s o prevent t h e f l o t a t i o n o f some u n d e s i r e d s u l p h i d e s . I n c o m p l e x c o p p e r z i n c o r e s , t h e s p h a l e r i t e becomes a c t i v a t e d b y t h e c o p p e r w h i c h i s d i s s o l v e d i n t h e m i l l s o l u t i o n s , a n d w o u l d f l o a t w i t h t h e c h a l c o p y r i t e u n l e s s i t i s d e a c t i v a t e d * T h e d e a c t i v a t o r u s e d i s c y a n i d e , w h i c h d i s s o l v e s t h e c o a t i n g o f c o p p e r p r e v i o u s l y f o r m e d o n t h e s p h a l e r i t e , a n d h e n c e r e n d e r s i t u n f l o a t a b l e * - 17 -D e p r e s s o r s * The a c t i o n o f d e p r e s s o r s i s t o p r e v e n t t h e f l o t a t i o n o f c e r t a i n u n d e s i r e d m i n e r a l s . T h i s i s a c h i e v e d b y f o r m i n g a ' c o a t i n g o n t h e p a r t i c l e s w h i c h i s n o n s o l u b l e i n t h e o o l l e o t o r m o l e c u l e s , A S a n e x a m p l e , t h e a c t i o n o f p o t a s s i u m c h r o m a t e o n l e a d c a r b o n a t e i s t o f o r m a l a y e r o f l e a d c h r o m a t e a t t h e s u r f a c e o n t h e p a r t i c l e s w h i c h i s l e s s s o l u b l e i n t h e c o l l e c t o r t h a n t h e o r i g i n a l l e a d c a r b o n a t e . Wark a n d C o x 1 3 s t u d i e d t h e a c t i o n o f a l k a l i a n d c y a n i d e on p y r i t e a n d c o n c l u d e d t h a t t h e i r d e p r e s s i n g a c t i o n was due t o p r e v e n t i o n o f a b s o r p t i o n o f x a n t h a t e b y t h e p y r i t e , r a t h e r t h a n t o a n y c o a t i n g f o r m e d b y t h e a l k a l i o r c y a n i d e on t h e p y r i t e * W i t h o u t t h e a l k a l i a n d c y a n i d e i n t h e s o l u t i o n , t h e x a n t h a t e a b s o r b e d r e a d i l y o n the p y r i t e p a r t i c l e s a n d c o l l e c t e d them i n t h e f r o t h . T h e e f f e c t o f t e m p e r a t u r e o n t h e d e p r e s s i n g a c t i o n o f c y a n i d e o n c e r t a i n s u l p h i d e s i s shown i n F i g s . 8 a n d 9*4. I t i s s e e n t h a t a t t h e h i g h e r t e m p e r a t u r e t h e r e i s a l a r g e i n c r e a s e i n t h e amount o f c y a n i d e n e c e s s a r y t o d e p r e s s t h e p y r i t e , b u t o n l y a v e r y s m a l l i n c r e a s e i n t h e amount n e c e s s a r y t o d e p r e s s t h e s p h a l e r i t e a n d o h a l c o p y r i t e . • * Wark , I*W* a n d C o x , A * B . P r i n c i p l e s o f F l o t a t i o n I I I . A . I . M . E . " M i l l i n g M e t h o d s . " 1 9 3 4 . 14. ' W a r k , I i W . a n d G o x , A . B * P r i n c i p l e s o f F l o t a t i o n V I - •: M i n i n g T e c h n o l o g y . J a n . 1 9 3 8 . £ 7 8 9 ro II /z 13 C u S 0 4 5 H 2 0 = 150 mg / l i t r e K E t X = 25 mg / l i t r e T e m p . - i o ° c F i g . 9 . C u S 0 4 5 H 2 0 - 150 m g / l i t r e K E t I 5 25 m g / l i t r e Temp. ~ 35OQ ( I n f i g . 8 , 9 , a n d 10 t h e c u r v e s i n d i c a t e t h e t e r m i n a t i o n o f t h e a i r - m i n e r a l c o n t a c t , i . e . t h e p o i n t a t w h i c h f l o t a t i o n o f t h e m i n e r a l w i l l c e a s e . T h u s t h e a r e a b e l o w t h e c u r v e i s where f l o t a t i o n is . p o s s i b l e , a n d t h e a r e a a b o v e * where i t i s n o t ) P . H R e g u l a t o r s . T h e s e r e a g e n t s a r e a d d e d t o c o n t r o l t h e P H o f t h e f l o t a t i o n p u l p s . S i n c e t h e a d v e n t o f . • c h e m i c a l f l o t a t i o n * , a l l p u l p s , e x c e p t f o r a few s p e c i a l p r o c e s s e s , h a v e b e e n a l k a l i n e , maarly b e c a u s e t h e a l k a l i n e r e a g e n t s r e m o v e c e r t a i n s o l u b l e s a l t s i n t h e o r e s w h i c h w o u l d o t h e r w i s e p r e c i p i t a t e t h e o r g a n i c j c o l l e c t i n g a g e n t s . L i m e i s t h e commonest r e a g e n t f o r P H c o n t r o l . B y t h e u s e o f S o d i u m c a r b o n a t e o r s o d i u m s u l p h i d e , t h e p H may be h u f f e r e d b e t w e e n 8 - 9 . 5 a n d a n d 8 . 5 - 1 0 r e s p e c t i v e l y * T h e i m p o r t a n c e o f p H c o n t r o l o n c e r t a i n s e p a r a t i o n s h a s b e e n shown b y Wark a n d G o x . * I n t h e f o l l o w i n g g r a p h the c r i t i c a l p H*s f o r p y r i t e a n d s p h a l e r i t e w i t h v a r y i n g a m o u n t s o f l i m e a n d s o d i u m c y a n i d e * h a v e b e e n p l o t t e d . I t i s s e e n that t h e m o s t f a v o r a b l e c o n d i t i o n s f o r s e p a r a t i o n w o u l d be w i t h a p H o f b e t w e e n 6 a n d 8 , w h i l e i t w o u l d be v e r y d i f f i c u l t t o o b t a i n a s e p a r a t i o n a t a p H o f 11. e>u. W a r k , I . w . ..and G o x , A . B . M i n i n g T e c h n o l o g y , J a n . 1 9 3 8 . - 20 -F i g * 1 0 . C u S 0 4 5 H 2 0 150 m g / l i t r e 5 m g / l i t r e I Et X Temp 35°G M i s c e l l a n e o u s r e a g e n t s I n t h i s c l a s s a r e c e r t a i n r e a g e n t s w h i c h a r e only-u s e d when c e r t a i n p e c u l i a r i t i e s i n t h e o r e r e q u i r e m o d i f i c a t i o n A s a n e x a m p l e , when t h e r e i s much c h l o r i t i c m a t e r i a l p r e s e n t i n an o r e , i t i s u s u a l l y g r o u n d t o c o l l o i d a l s i z e , a n d comes up i n t o t h e f r o t h i n t h e f l o t a t i o n c e l l s * c a u s i n g a t o u g h f r o t h , a n d a l o w e r g r a d e r e c o v e r y . To o v e r c o m e t h i s , a d i s -p e r s i n g a g e n t , s u c h a s s o d i u m s i l i c a t e i s u s e d . T h i s coagu lates t h e c o l l o i d a l p a r t i c l e s , a n d t h e y r e m a i n w i t h t h e o t h e r gaugue m i n e r a l s . - 21 -PART I I T h e t e s t s were c a r r i e d o u t i n t h e Ore D r e s s i n g l a b o r a t o r y a t t h e U n i v e r s i t y o f B r i t i s h C o l u m b i a , b y P r o f e s s o r G"*A* G i l l i e s a n d G . H . Gwyn* CHARACTER OF . THE ORE" The o r e u s e d f o r t h e t e s t s was a n i o k e l - c o p p e r o r e s u p p l i e d b y t h e B . C . N i c k e l M i n e , C h o a t e , B . C . T h e o r e b e a r i n g r o c k i s a h o r n b l e n d e - p y r o x e n i t e w i t h v a r y i n g a m o u n t s o f h y p e r s t h e n e . T h e m i n e r a l s a r e p e n t l a n d i t e , c h a l c o p y r i t e , p y r r h o t i t e , c h r o m i t e , a n d s e v e r a l o t h e r s i n m i n o r ' a m o u n t s . T h e h i g h g r a d e o r e c a r r i e s u p t o 50$ s u l p h i d e s . -The s u l p h i d e s o c c u r : 1 . a s g r a i n s v a r y i n g i n s i z e f r o m 1 4 t o -* 200 m e s h 2. a s v e i n s i n f r a c t u r e s o f t h e h o r n b l e n d i t e , a n d f i l l i n g o f i n t e r c r y s t a l l i n e s p a c e s . 3 . a s m a s s i v e s u l p h i d e s , up t o !§• i n c h e s i n d i a m e t e r . T h e o h a l c o p y r i t e a n d p e n t l a n d i t e a r e i n t i m a t e l y m i x e d . A s m a l l amount o f t h e p e n t l a n d i t e , i n m i n u t e g r a i n s , i s l o c k e d i n t h e p y r r h o t i t e , o r l i e s i n b a y s a l o n g t h e b o r d e r s o f t h e l a t t e r . I n two p l a c e s was o b s e r v e d what was a p p a r e n t l y a e u t e c t i c a l l o y * A p a r t i a l c h e m i c a l a n a l y s i s o f t h e o r e g a v e t h e f o l l o w i n g r e s u l t s * N i 1 ; 5 9 Cu . 2 9 - 22 -F e 7° 1 1 * 7 5 s 7 . 6 5 Mgo 1 7 . 1 5 ALG 1 2 . 2 5 CaO 1 . 2 4 SIO 3 9 . 0 0 Two d i f f e r e n t s a m p l e s o f t h e o r e , b o t h h o w e v e r f r o m t h e same s e c t i o n o f t h e m i n e , were u s e d i n t h e s e t e s t s * T h e f i r s t s a m p l e , u s e d f o r t e s t s 22 t p 36 i n c l u s i v e a s s a y e d 1 . 1 2 $ N i a n d . 3 5 $ G u , w h i l e t h e s e c o n d s a m p l e * u s e d i n t e s t s 37 t o 54 i n c l u s i v e a s s a y e d . ,92$ N i a n d . 2 6 $ Gu* D E S C R I P T I O N OF THE' MACHINES A l a b o r a t o r y r o d m i l l (10« d i a m b y 11-|-" l o n g ) con?-t a i n i n g 24 s t e e l r o d s d i a m b y 11^ l o n g ) was u s e d t o g r i n d t h e o r e * I t was d r i v e n a t 44 R . P . M i •The f l o t a t i o n c e l l was. a R u t h l a b o r a t o r y m a c h i n e , o f 1000 gm s i z e . I t i s a n a g i t a t i o n t y p e m a c h i n e , d r i v e n b y a n e l e c t r i c m o t o r a t t h e t o p o f t h e s p i n d l e . F o r m e a s u r i n g t h e p H o f t h e s o l u t i o n s , a L e e d s a n d N o r t h r u p g l a s s e l e c t r o d e m a c h i n e was u s e d * .DESCRIPTION AND L I S T OF THE REAGENTS T h e r e a g e n t s t e s t e d w e r e o f t h e f o r m s u g g e s t e d b y D e a n a n d H e r s b e r g e r " 1 - " a s b e i n g s u i t a b l e f o r f r o t h i n g a g e n t s , a n d w e r e s y n t h e s i z e d i n t h e c h e m i c a l L a b o r a t o r y a t t h e Dean.j R*S.\, a n d H e r s b e r g e r , A.D*. "New F l o t a t i o n R e a g e n t s " A . I . M . M . E V T e c h * P u b . Nov 6 0 5 , 1935* - 23 -U n i v e r s i t y o f B r i t i s h C o l u m b i a * T h e y a r e o r g a n i c c o m p o u n d s : t h e number o f c a r b o n a toms i n t h e h y d r o c a r b o n c h a i n s v a r y i n g f r o m 8 t o 27* a n d t h e p o l a r g r o u p s a r e s u l p h a t e , p h o s p h a t e , p y r i d i n i u m , o r q u i n a l d i n i u m d e r i v a t i v e s * M o s t o f t h e m a r e d i f f i c u l t l y s o l u b l e i n w a t e r , s o s o l u t i o n s w i t h p u r e e t h y l a l c o h o l were made , a n d s t a n d a r d amounts o f t h e s e s o l u t i o n s a d d e d t o t h e p u l p * The s t r e n g t h o f t h e s o l u t i o n I s r e c o r d e d a s a p e r c e n t a g e : w e i g h t o f r e a g e n t ^qq = ^ S o l n t o t a l w e i g h t o f s o l v e n t a n d '° r e a g e n t T h e d r o p s o f e a c h s o l u t i o n were c a l i b r a t e d * a n d t h e w e i g h t o f t h e r e a g e n t a d d e d t o t h e p u l p was c a l c u l a t e d . I t i s t h i s , s o l u t i o n o f t h e r e a g e n t s t o w h i c h r e f e r e n c e i s made i n t h i s p a p e r , a n d w h i c h t h e c o n c l u s i o n s a r e drawn f r o m * To g i v e a b a s i s o f c o m p a r i s o n , t e s t s were r u n u s i n g t e r p i n e a l a n d :pine o i l a s t h e f r o t h i n g a g e n t s . T h e s e a r e t h e c l o s e s t a p p r o a c h t o i d e a l f r o t h e r s o f a n y t h a t a r e i n c o m m e r c i a l u s e t o d a y . No c o l l e c t i n g a g e n t s were a d d e d . F o l l o w i n g i s a l i s t o f t h e o r g a n i c r e a g e n t s , w i t h . t h e i r c h e m i c a l f o r m u l a , t h e w e i g h t o f a d r o p o f t h e s o l u t i o n , a n d t h e s t r e n g t h o f t h e s o l u t i o n . REAGENT A - P o t a s s i u m s a l t o f M o n o c e t y l p h o s p h a t e C 1 6 . % 3 - 0 " ^ 10*7 $ s o l n 1 d r o p .« . 0 6 1 7 gms* P y l e , J . J . " T h e S y n t h e s i s o f New F l o t a t i o n A g e n t s " M*A. T h e s i s U n i v e r s i t y o f B . C . A p r i l 1 9 3 7 . - 24 -REAGENT E - C a r b o o o t o x y m e t h y l p y r i d i n i u m c h l o r i d e o ° 8 H 1 7 0 - G ~ C H 2 - N - « U > 1 1 . 3 $ s o I n 1 d r o p = . 0 1 8 gms. G - G a r b o l a u r y l o x y m e t h y l p y r i d i n i u m c h l o r i d e o G 1 2 H 2 5 " 0 * 6 " C H 3 " 7 a 1 1 . 2 $ s o l n 1 d r o p s 4 0169 gms. I - G a r b o c h l o r e s t e r o x y m e t h y l q u i n a l d i n i u m bromide 0 ° 2 7 H 4 5 " 0 - C - G H 2 - N - Q 7 . 8 $ s o l n 1 d r o p = . 0 1 8 7 gms. J - C a r b o c h l o r e s t e r o x y m e t h y l p y r i d i n i u m c h l o r i d e o C 2 7 H 4 5 " G - G - C H 3 - N - <S> ci 5 . 9 7 $ s o l n 1 d r o p s . 0 1 7 2 gms* P - o< s t e a r i n d i h y d r o g e n p h o s p h a t e ° 1 7 H 3 5 ~ ?6 ~ G G H 2 - CHOHCHg - 0 - P ; o H 4 . 0 6 $ s o l n 1 d r o p " . 0 1 6 5 gms. Z - M y r i s t y l Ammonium s u l p h a t e 0 i A 9 - 0 " f - 0 N H * 4 . 0 6 $ s o l n 1 d r o p s . 0 1 9 2 gms. R - M y r i s t y l P o t a s s i u m S u l p h a t e ° 1 4 H 2 9 " ° - f ° K 4 . 0 6 $ s o l n 1 d r o p s . 0 1 9 6 gms* S - M y r i s t y l S o d i u m S u l p h a t e ?\ G , n - 0 - s - o N a 14 29 <; 4 . 0 6 $ s o l n 1 d r o p 2 *0192 gms. REAGENT Q, - s t e a r i n ammonium s u l p h a t e o G 1 7 H 3 5 - G - OCRg - GHOH - G H 2 - SOg - N H 4 4 . 0 6 $ s o l n . 1 d r o p = . 0 1 6 5 g m s . - 25 -T E S T ROUTINE 1000 gms o f o r e a n d 1000 gms o f w a t e r were p l a c e d i n t h e r o d m i l l , a n d g r o u n d f o r 15 m i n u t e s a t 4 4 R.P .M . T h e p*ulp was t h e n t r a n s f e r r e d t o t h e f l o t a t i o n c e l l , a n d t h e p u l p d i l u t i o n i n c r e a s e d t o 4 : 1 . S i x d r o p s o f t h e s o l u t i o n b e i n g t e s t e d , were a d d e d , t h e p u l p m i x e d f o r o n e m i n u t e , a n d a g i t a t e d a n d sK immed f o r 10 m i n u t e s j t h i s g a v e t h e f i r s t c o n c e n t r a t e . T h e n s u f f i c i e n t w a t e r was a d d e d t o b r i n g t h e p u l p d e p t h b a c k t o t h e o r i g i n a l l e v e l o f 4 : 1 d i l u t i o n , a n o t h e r 6 d r o p s o f t h e s o l u t i o n were, a d d e d , t h e p u l p m i x e d f o r 1 m i n u t e a n d a g i t a t e d a n d sKimmed f o r l O n m i n u t e s ; t h i s g a v e t h e s e c o n d c o n c e n t r a t e . F i v e s u c h c o n c e n t r a t e s w e r e t a k e n o f f i n e a c h t e s t . I n t h e c a s e w h e r e t h e c i r c u i t was t o be a c i d o r a l k a l i n e , t h e r e q u i r e d amount o f a c i d o r a l k a l i was a d d e d and m i x e d f o r 3 m i n u t e s ; p r e v i o u s t o t h e a d d i t i o n o f t h e f i r s t s i x f r o p s o f t h e f r o t h i n g a g e n t . T h e p H._of e a c h c o n c e n t r a t e a n d t h e t a i l i n g s was t a k e n . A f t e r b e i n g d r i e d i n an e l e c t r i c o v e n , t h e c o n c e n t r a t e s and t a i l i n g s were w e i g h e d , a n d s a c k e d , a n d s a m p l e s t a k e n f o r a s s a y i n g . T h e n i c k e l was a s s a y e d b y t h e d i m e t h y l -g l y o x i m e p r e c i p i t a t i o n m e t h o d , t h e c o n c e n t r a t e c o p p e r s b y L o r d a n d D e m o r e s t s f l u o r i d e - i o d i d e m e t h o d , a n d t h e t a i l i n g c o p p e r s b y e l e c t r o l y t i c a n a l y s i s . E a c h r e a g e n t was t e s t e d i n a n a t u r a l , a c i d ^ a n d a l k a l i n e p u l p * 1 :2 H g S 0 4 was u s e d t o o b t a i n a n a c i d c i r c u i t , a n d N a 0 H p e l l e t s t o o b t a i n a n a l k a l i n e c i r c u i t . ; DISCUSSION ON THS T E S T S ( a ) ' I n d i v i d u a l R e a g e n t s * T e s t s N o . 22 a n d 25 R e a g e n t - T e r p i n e o l . S t a n d a r d T e s t C o n d i t i o n s . T h e s e two t e s t s were r u n t o o b t a i n a c o m p a r i s o n . o f p e r f o r m a n c e b e t w e e n the new ' . R u t h . F l o t a t i o n M a c h i n e ( T e s t N o . 2 3 ] , a n d t h e R u t h F l o t a t i o n M a c h i n e i n w h i c h p r e v i o u s • 20 t e s t s h a d b e e n m a d e . T h e f © o t h was a l i t t l e d e e p e r i n t e s t 2 3 , a n d s l i g h t l y t o u g h e r , s h o w i n g t h a t t h e r e was more a g i t a t i o n i n t h e D e n v e r m a c h i n e . . S i x d r o p s o f t h e r e a g e n t were a d d e d f o r e a c h c o n c e n t r a t e , a n d t h i s a p p e a r e d t o b e more t h a n was n e o e s s a r y * A c c o r d i n g l y t h e amount was r e d u c e d t o one d r o p p e r c o n c e n t r a t e i n t h e n e x t s e t o f t e s t s . T e s t s N o . 2 4 , 25 and 26* R e a g e n t - T e r p i n e o l S t a n d a r d , T e s t C o n d i t i o n s ^ '•'.. :- ' '"'' : " ' • . . ' . ' ' . . • ' : •- • I n t h e s e t e s t s , o n e d r o p o f r e a g e n t p e r c o n c e n t r a t e was a d d e d , a n d a f t e r t h e s e c o n d a d d i t i o n t h e r e was j u s t e n o u g h f r o t h t o f i l l t h e m a c h i n e - 2|- - 3 " deep* I n t e s t 2 5 , i n t h e a c i d c i r c u i t * t h e f r o t h ?of t h e f i r s t c o n c e n t r a t e was v e r y d a r k , d u e , p r o b a b l y , t o t h e a c t i o n o f t h e a c i d s o n t h e s u l p h i d e s . 2 0 . BiS-n-qo Mb P o t k i n s n N e w F r o t h i n g A g e n t s f o r F l o t a t i o n . " B . A . S Q . ^ T h e s i s U n i v e r s i t y o f B . C . A p r i l 1 9 3 7 . ~ 27 -The s u b s e q u e n t f r o t h s were p r o g r e s s i v e l y l i g h t e r i n c o l o r . W i t h t h i s r e a g e n t , t h e r e c o v e r y o f c o p p e r was h i g h e r i n t h e n a t u r a l p u l p c i r c u i t t h a n i n e i t h e r t h e a c i d o r a l k a l i n e c i r c u i t s , b u t t h e r e c o v e r y o f n i c k e l w a s . l o w e r i n t h e n a t u r a l p u l p c i r c u i t t h a n i n t h e o t h e r tsso. T e s t s N o . 2 7 , 2 8 a n d 2 9 . R e a g e n t - #5 P i n e o i l . G- .N .S . S t a n d a r d T e s t C o n d i t i o n s I n e a c h o f t h e s e t e s t s , t h e f i r s t c o n c e n t r a t e d i d n o t h a v e as. s a t i s f a c t o r y a f r o t h a s t h e f o l l o w i n g o n e s , s h o w i n g t h a t a s u f f i c i e n t amount o f t h e r e a g e n t h a d n o t y e t b e e n a d d e d . T h e f r o t h p r o d u c e d by t h i s r e a g e n t was v e r y s i m i l a r t o t h a t o f t h e t e r p i n e o l , b o t h i n q u a n t i t y a n d p e r s i s t a n c y . H o w e v e r , w i t h i t , b o t h a c i d a n d a l k a l i n e c i r c u i t s g a v e a h i g h e r r e c o v e r y o f s u l p h i d e s t h a n d i d t h e n a t u r a l p u l p c i r c u i t ; t h e a s s a y s f o r Cu a n d N i f o r t h e n o . l . c o n c e n t r a t e i n b o t h c a s e s were 80 - 100% h i g h e r t h a n i n t h e n a t u r a l * p u l p . A c o m p a r i s o n o f t e s t s N o . 24 and 2 7 , shows t h a t p i n e o i l e x h i b i t s l e s s c o l l e c t i n g p r o p e r t i e s , i n t h e n a t u r a l p u l p c i r c u i t , t h a n d o e s t e r p i n e o l * - 23 -' T e s t s N o . 3 0 , 31 Sc. 32 R e a g e n t A - P o t a s s i u m s a l t o f M o n o c e t y l p h o s p h a t e o 16 3 3 ^-OK 1 0 . 7 $ S o l u t i o n S t a n d a r d T e s t C o n d i t i o n s T h i s s o l u t i o n d i d n o t g i v e a s s a t i s f a c t o r y a f r o t h a s t h e s t a n d a r d o i l s ( p i n e o i l a n d t e r p i n e o l ) — t h e maximum d e p t h b e i n g i n t h e n a t u r a l p u l p w h e r e i t r e a c h e d •!•§• i n c h e s . I n e a c h t e s t , t h e r e was a d e c r e a s e i n t h e d e p t h o f f r o t h i n t h e 4 t h a n d 5 t h c o n c e n t r a t e * i n d i c a t i n g t h a t t o o much f r o t h e r h a d be en a d d e d . I n a number o f t h e - r u n s , i t was n o t e d t h a t t h e f r o t h i n c r e a s e d s l i g h t l y t o w a r d s t h e e n d o f t h e s K i m m i n g p e r i o d , s h o w i n g t h a t a l o n g e r c o n d i t i o n i n g p e r i o d w o u l d be b e n e f i c i a l * T h e r e was a d e c i d e d c o l l e c t i n g a c t i o n i n t h e a c i d a n d a l k a l i n e c i r c u i t s , a s shown by g r a p h N o . 4 . I n a l l c a s e s , t h e - f i r s t two c o n c e n t r a t e s c o n t a i n e d p r a c t i c a l l y a l l t h e s u l p h i d e s b r o u g h t u p ; T h e p H o f t h e c i r c u i t h a s a d e c i d e d e f f e c t o n t h e c o l l e c t i n g p r o p e r t i e s o f t h i s s o l u t i o n . ' T h e r e c o v e r y was l e s s i n t h e n a t u r a l p u l p c i r c u i t , t h a n f o r t h e s tandard o i l s , b u t was c o n s i d e r a b l y h i g h e r i n t h e a c i d a n d a l k a l i n e c i r c u i t s . N o t e s h o u l d be t a k e n t h a t i n t h e a c i d c i r c u i t a c u m u l a t i v e r e c o v e r y o f 9 5 * 3 $ N i was o b t a i n e d , w i t h a c o n c e n t r a t i o n r a t i o o f 1 : 3 . 2 T e s t N o . 3 3 , 34 a n d 35 R e a g e n t F - C a r b o o c t o x y m e t h y l p y r i d i n i u m c h l o r i d e o G 8 H 1 7 ~ 0 ~ ^ C H 2 " N ~ < Q > CI ' 1 1 . 3 $ s o l u t i o n S t a n d a r d T e s t C o n d i t i o n s . T h i s s o l u t i o n g a v e a v e r y g o o d t y p e o f f r o t h : o f s a t i s f a c t o r y d e p t h a n d c o n s i s t a n c y . I n t h e 4 t h c o n c e n t r a t e t h e d e p t h o f f r o t h s u d d e n l y d e c r e a s e d , s h o w i n g t h a t t o o much r e a g e n t h a d b e e n a d d e d * I n t h e n a t u r a l c i r c u i t , t h e r e was l e s s c o l l e c t i n g o f b o t h o o p p e r a n d n i c k e l , t h a n i n t h e t e s t s o f t e r p i n e o l o r p i n e o i l , w h i l e t h e f r o t h was j u s t a s s a t i s f a c t o r y . H o w e v e r , t h e a f f e c t o f a c i d a n d a l k a l i o n t h e c o l l e c t i n g a c t i o n o f t h e s o l u t i o n was q u i t e s t a r t l i n g ; e s p e c i a l l y t h a t o f t h e f o r m e r . -In t h i s t e s t * a n o v e r a l l r e c o v e r y o f 9 9 . 3 6 $ N i c k e l a n d 9 3 . 1 $ c o p p e r was o b t a i n e d . None o f t h e c o n c e n t r a t e a s s a y s w e r e v e r y h i g h , b e c a u s e a l a r g e b u l k was f l o a t e d . T h i s f r o t h e r m i g h t be s a t i s f a c t o r y i n b o t h a c i d a n d a l k a l i n e c i r c u i t s w i t h i n a s m a l l r a n g e o f t h e n e u t r a l p o i n t * s i n c e t h e c o n c e n t r a t i o n o f a c i d a n d a l k a l i e m p l o y e d i n t h e t e s t s was q u i t e h i g h . v i z . PvH. o f N o . 1 c o n e . T e s t N o . 35 ~ 1 . 6 P.H. o f N o . 1 » T e s t N o . 34 = 1 1 . 0 T e s t s N o . 36," 37 a n a 38 R e a g e n t G - C a r b o L a u r y l o x y M e t h y l P y r i d i n i u m c h l o r i d e o 12 25 2 • ^ 1 1 . 2 $ S o l u t i o n S t a n d a r d T e s t C o n d i t i o n s T h i s r e a g e n t g a v e a v e r y s a t i s f a c t o r y f r o t h i n b o t h q u a n t i t y a n d c o n s i s t a n c y . I n t e s t No.. 3 7 , w i t h a n a l k a l i n e c i r c u i t , t h e r e was a s u d d e n d e c r e a s e i n t h e f r o t h a f t e r t h e s e c o n d c o n c e n t r a t e . T h e r e m u s t h a v e b e e n some r e a c t i o n b e t w e e n t h e r e a g e n t a n d t h e a l k a l i , b e c a u s e i n b o t h t h e o t h e r t e s t s i t wasn't u n t i l t h e f i f t h , c o n c e n t r a t e was t a k e n t h a t a s l i g h t d e c r e a s e i n t h e f r o t h i n d i c a t e d t h a t a n e x c e s s o f t h e f r o t h e r h a d b e e n a d d e d * T h i s r e a g e n t g a v e a n u n u s u a l l y h i g h r e c o v e r y o f c o p p e r i n t h e n a t u r a l p u l p c i r c u i t , b u t t h e c h a n g e i n t h e p H o f t h e c i r c u i t a f f e c t e d t h e c o p p e r r e c o v e r y o n l y s l i g h t l y * T e s t s N o . 3 9 , 40 a n d 41 R e a g e n t I - G a r b o c h o l e s t e r o x y M e t h y l Q u i n a l d i n i u m B r o m i d e * . 37 45 S i. > — \ 7 ; 8% S o l u t i o n C ' H S t a n d a r d T e s t C o n d i t i o n s T h i s r e a g e n t g a v e a v e r y p o o r f r o t h i n t h e n a t u r a l p u l p c i r c u i t ; o n l y v e r y l i t t l e was f o r m e d a n d i t was c o a r s e and b r i t t l e . However* i t g a v e a s a t i s f a c t o r y f r o t h i n t h e a c i d a n d a l k a l i n e c i r c u i t s . T h e a f f e o t o f p H o f t h e p u l p o n t h i s r e a g e n t i s v e r y m a r k e d * B o t h a c i d a n d a l k a l i n e c i r c u i t s g a v e much h i g h e r r e c o v e r y t h a n t h e n a t u r a l p u l p c i r c u i t * T h e s o l u b i l i t y o f t h i s r e a g e n t i s v e r y l o w , a n d i t was d i f f i c u l t t o f o r m t h e s o l u t i o n w i t h t h e e t h y l a l c o h o l * - s s -T e s t N o . 4 2 , 4 3 , a n d 44 R e a g e n t J - Ca-rbo c h l o r e s t e r o x y M e t h y l P y r i d i n i u m C h l o r i d e C - J E ^ - 0 - C 0 H o - N - € 3 27 45 2 I 5 . 9 7 $ S o l u t i o n C I S t a n d a r d T e s t C o n d i t i o n s T h i s r e a g e n t d i d n o t g i v e a s a t i s f a c t o r y f r o t h i n a n y o f t h e c i r o u i t s . I n t h e n a t u r a l a n d a l k a l i n e c i r c u i t s I t was c o a r s e , b r i t t l e a n d i n s m a l l q u a n t i t i e s , a n d a l t h o u g h t h e r e was c o n s i d e r a b l y more f r o t h i n t h e a c i d c i r c u i t , i t was s t i l l v e r y b r i t t l e . I n t h e n a t u r a l p u l p , t h i s r e a g e n t e x h i b i t e d l e s s c o l l e c t i n g a c t i o n t h a n t h e s t a n d a r d o i l s , b u t , a p p r e c i a b l y m o r e i n t h e a c i d a n d a l k a l i n e c i r c u i t s , i n d i c a t i n g s e n s i t i v i t y o f <• t h e r e a g e n t t o t h e p H o f t h e p u l p . I n t h e a c i d c i r c u i t , a v e r y h i g h n i c k e l a s s a y was o b t a i n e d ( 7 „ 0 3 $ ) . T h i s w o u l d i n d i c a t e a d e c i d e d p r e f -e r e n c e f o r p e n t l a n d i t e u n d e r the- t e s t c o n d i t i o n s , s i n c e t h e c o p p e r a s s a y - ( 3 . 1 5 $ ) was n o t a s h i g h a s t h a t o b t a i n e d i n o t h e r t e s t s . . T h i s r e a g e n t was t h e l o n g e s t c h a i n compound o f t h e h o m o l o g o u s s e r i e s , F . G . a n d J , a n d t h e l e a s t s a t i s f a c t o r y , a s r e g a r d s c o n d i t i o n o f f r o t h . T e s t Noi,- 48* 49 a n d 50 R e a g e n t P - s t e a r i n d i h y d r o g e n p h o s p h a t e ° 1 ^ 8 S " ° ' 0 C H S 0 H 0 H G H S " ° " . 4;06% s o l u t i o n S t a n d a r d T e s t ' C o n d i t i o n s I n t h e a c i d and a l k a l i n e c i r c u i t s t h i s s o l u t i o n g a v e a s a t i s f a c t o r y f r o t h , b u t i n t h e n a t u r a l c i r c u i t , t h e f r o t h was v e r y c o a r s e a n d b r i t t l e a n d o n l y o f medium q u a n t i t y . I n t h e n a t u r a l c i r c u i t , t h i s , s o l u t i o n showed c o l l e c t i n g p o w e r s o f a b o u t t h e same o r d e r a s t h e s t a n d a r d o i l s , b u t i n t h e o t h e r s c o l l e c t i o n was g r e a t l y i n c r e a s e d , e s p e c i a l l y s o i n t h e a c i d c i r c u i t . I t was n o t e d i n t h e s e t e s t s t h a t t h e maximum f r o t h was n o t p r o d u c e d u n t i l a b o u t h a l f t h e s K i m m i n g t i m e was o v e r , i n d i c a t i n g t h a t a l o n g e r c o n d i t i o n i n g t i m e w o u l d be b e n e f i c i a l . . - 34 -T e s t No 5 1 . R e a g e n t Q, - <=c s t e a r i n ammonium s u l p h a t e 0 H - 0 - 0 G H 9 C H 0 H - CBL - SO,, - N H A 17 35 s 2 i 3 4 NH^ 4 * 0 6 $ S o l u t i o n S t a n d a r d C h a r g e a n d d i l u t i o n T h i s s o l u t i o n g a v e q u i t e a n a b u n d a n t f r o t h b u t i t was v e r y u n s t a b l e a n d b r i t t l e . T h e f r o t h d i d n o t i n d i c a t e a n y c o l l e c t i n g a c t i o n ; t h e b u b b l e s were n o t m i n e r a l i z e d * S u b s e q u e n t a n a l y s i s s h o w e d q u i t e l o w c o l l e c t i n g a c t i o n . T h i s s o l u t i o n c o m p a r e s c l o s e l y w i t h s o l u t i o n P . t e s t , - 4 8 , i n b o t h f r o t h i n g c h a r a c t e r i s t i c s a n d c o l l e c t i n g a c t i o n . B o t h r e a g e n t s h a v e t h e same h y d r o c a r b o n c h a i n b u t d i f f e r i n t h e p o l a r p a r t o f t h e m o l e c u l e i T h i s s o l u t i o n was t e s t e d o n l y i n t h e n a t u r a l p u l p c i r c u i t . - 35 -T e s t N o . 52 R e a g e n t R. M y r i s t y l P o t a s s i u m S u l p h a t e G 1 4 H 2 9 - 0 ' | - ° K - o 4:,QQfo S o l u t i o n S t a n d a r d T e s t C o n d i t i o n s I t was n o t u n t i l t h e f o u r t h a d d i t i o n o f r e a g e n t t h a t t h e maximum d e p t h o f f r o t h was r e a c h e d . A t t h i s p o i n t t h e f r o t h c o m p a r e d f a v o r a b l y w i t h t h a t o f t h e s t a n d a r d o i l s , b o t h i n q u a n t i t y a n d p e r s i s t a n c y . T h e c o l l e c t i n g p r o p e r t i e s o f t h i s s o l u t i o n a l s o c o m p a r e d f a v o r a b l y w i t h t h o s e o f t h e s t a n d a r d o i l s . The r e c o v e r y o f copper was l o w e r t h a n t h a t o b t a i n e d i n t h e n a t u r a l p u l p t e s t w i t h t e r p l n e o l , a n d j u s t s l i g h t l y h i g h e r t h a n w i t h p i n e o i l . - 36 -T e s t No 5 3 . R e a g e n t S - M y r i s t y l S o d i u m S u l p h a t e o 0 . H - 0 - s - O N a . 14 29 £ 4 . 0 6 $ ' S o l u t i o n S t a n d a r d T e s t C o n d i t i o n s T h i s s o l u t i o n d i d n o t g i v e a s a t i s f a c t o r y f r o t h , e i t h e r i n q u a n t i t y o r p e r s i s t a n c y . The b u b b l e s a p p e a r e d t o be q u i t e w e l l m i n e r a l i z e d , i n d i c a t i n g t h a t t h e s o l u t i o n h a d d e c i d e d c o l l e c t i n g p o w e r s . . T h i s was b o r n e o u t b y s u b s e q u e n t a n a l y s i s . T e s t N o . 5 4 . R e a g e n t Z - M y r i s t y l ammonium S u l p h a t e ° 1 4 H 2 9 " ° " f - ° N H * 0 4^06% S o l u t i o n S t a n d a r d T e s t C o n d i t i o n s T h i s s o l u t i o n g a v e a v e r y p o o r ffloth; t h e r e was o n l y a s m a l l q u a n t i t y a n d t h e b u b b l e s w e r e l a r g e a n d b r i t t l e . T h e c o l l e c t i n g p r o p e r t i e s o f t h i s s o l u t i o n were o f t h e same o r d e r a s t h o s e o f t h e s t a n d a r d o i l s . (b) G e n e r a l D i s c u s s i o n I t w i l l be n o t e d t h a t i n t h e a c i d a n d a l k a l i n e c i r c u i t s * t h e r e was a g r a d u a l c h a n g e i n p H t o w a r d s t h e n e u t r a l p o i n t , i n c o n s e c u t i v e c o n t s . • T h e amount o f a c i d o r a l k a l i r e m o v e d by e a c h c o n c e n t r a t e , a n d t h e amount o f w a t e r a d d e d t o b r i n g t h e p u l p d e p t h b a c k t o t h e same p o i n t , w o u l d b r i n g t h e p H c l o s e r t o n e u t r a l i t y * When t h e a c i d was a d d e d t o t h e p u l p t o g i v e a n a c i d c i r c u i t * HgS g a s was g i v e n o f f . T h i s w o u l d i n d i c a t e t h a t t h e r e was a c e r t a i n amount o f r e a c t i o n b e t w e e n t h e a c i d a n d t h e s u l p h i d e s i n t h e o r e . T h e h i g h e r r e c o v e r i e s o f t h e m e t a l s o b t a i n e d i n t h e a c i d o i r c u i t s were p r o b a b l y due i n p a r t t o t h i s c h a n g e i n t h e c h a r a c t e r o f t h e o r e . R e a g e n t s w i t h t h e l o n g h y d r o c a r b o n c h a i n s , n o t e a b l y r e a g e n t s I a n d J , g a v e a v e r y b r i t t l e f r o t h . T h i s was p r o b a b l y due t o t h e i r s l i g h t s o l u b i l i t y , a n d c o r r e s p o n d -i n g l y s l i g h t l o w e r i n g o f t h e s u r f a c e t e n s i o n . The p o l a r g r o u p s o n t h e s e r e a g e n t s w e r e n o t s u f f i c i e n t l y s o l u b l e t o b a l a n c e t h e i n s o l u b i l i t y o f t h e l o n g h y d r o c a r b o n c h a i n s . R e a g e n t s Q,, S , R a n d Z were t e s t e d o n l y i n t h e n a t u r a l p u l p c i r c u i t , a n d so c a n o n l y c o m p a r e w i t h t h e o t h e r r e a g e n t s on t h a t b a s i s , • S i n c e t h e r e w a s n ' t a n y c o l l e c t i n g a g e n t a d d e d , a n y c o n c e n t r a t i o n w h i c h i s e f f e c t e d w i l l be due t o the c o l l e c t i n g a c t i o n o f t h e f r o t h e r * T h i s i s a s s u m i n g t h a t t h e r e i s no ' n a t i v e f l o t a b i l i t y ' o f t h e s u l p h i d e s , w h i c h i s a l l o w a b l e , . - 58 -b e c a u s e t h e t h e o r y o f ' n a t i v e f l o t a b i l i t y ' h a s l o s t f a v o r d u r i n g r e c e n t y e a r s . I f t h e f r o t h e r s u s e d were ' i d e a l f r o t h e r s ' , t h e a s s a y s o f t h e c o n c e n t r a t e s t a k e n o f f s h o u l d be t h e same a s t h e o r i g i n a l h a d a s s a y * I t , i s s e e n t h a t none o f t h e s o l u t i o n s t h a t were t e s t e d f u l f i l l e d t h i s i d e a l o o n d i t i o n , b u t t h e c o l l e c t i n g p r o p e r t i e s o f s e v e r a l o f them c o m p a r e d f a v o r a b l y w i t h t h o s e o f the. S t a n d a r d o i l s , p i n e o i l , a n d t e r p i n e o l . T e s t s Ho. . 45 a n d 46 a n d 47 were r u n u s i n g r e a g e n t I , a n d s o d u p l i c a t e d t e s t s N o . 3 9 , 40 a n d 4 1 . A c c o r d i n g l y t h e y a r e o m i t t e d f r o m t h e r e c o r d s a n d d i s c u s s i o n s . SUMMARY A s t u d y h a s b e e n made o f t h e f r o t h i n g p o w e r s o f c e r t a i n o r g a n i c c o m p o u n d s , i n n a t u r a l , a c i d a n d a l k a l i n e p u l p . T h e number o f c a r b o n atoms i n t h e h y d r o c a r b o n c h a i n o f t h e v a r i o u s compounds r a n g e f r o m 8 t o 2 7 . T h e p o l a r g r o u p s a r e p h o s p h a t e s , s u l p h a t e s , p y r i d i n i u m a n d q u i n a l d i n i u m d e r i v a t i v e s , 1* T h e m o s t s a t i s f a c t o r y f r o t h s were o b t a i n w i t h r e a g e n t s F a n d G-. T h e s e a r e members o f a h o m o l o g e o u s s e r i e s , w i t h 8 a n d 12 c a r b o n a t o m s , r e s p e c t i v e l y , i n t h e i r h y d r o c a r b o n o h a i n . R e a g e n t I b e l o n g s , t o t h e same s e r i e s ] b u t i t gave a v e r y b r i t t l e f r o t h , d u e , d o u b t l e s s l y , t o i t s l o w e r s o l u b i l i t y . 2. I n t h e n a t u r a l p u l p c i r c u i t , r e a g e n t R g a v e a s a t i s f a c t o r y f r o t h , b u t r e a g e n t s S a n d z , compounds w i t h t h e same n o n - p o l a r p a r t , b u t d i f f e r e n t p o l a r p a r t s , d i d n o t do s o . 5 . A c o m p a r i s o n o f t e s t s 5 2 , 53 a n d 54 showed t h a t r e a g e n t S p o s s e s s e d t h e g r e a t e s t c o l l e c t i n g p o w e r s o f a n y o f t h e a n a l o g o u s r e a g e n t s , S* R a n d z . 4 , I n a n a c i d c i r c u i t , r e a g e n t F e x h i b i t e d v e r y m a r k e d c o l l e c t i n g p o w e r s f o r t h e s u l p h i d e s . 5 . W i t h a l l t h e s o l u t i o n s t e s t e d , h i g h e r r e c o v e r i e s were o b t a i n e d i n t h e a c i d a n d a l k a l i n e c i r c u i t s , t h a n i n t h e n a t u r a l p u l p c i r c u i t . T h i s i n d i c a t e s s e n s i t i v i t y o f t h e s o l u t i o n t o t h e P H o f t h e p u l p . •CONCLUSIONS 1 . R e a g e n t s c o m p o s e d o f p y r i d i n i u m c h l o r i d e , a n d a h y d r o -c a r b o n c h a i n , w i t h c a r b o n atoms up t o 12 i n c n u m b e r a p p e a r t o be t h e m o s t p r o m i s i n g f r o t h i n g r e a g e n t s * 2* T h e p a r a l l e l ^ a c t i o n o f q u i n a l d i n i u m a n d p y r i d i n i u m c o m p o u n d s , i n r e a g e n t s I a n d J , i n d i c a t e s t h a t t h e l o w e r h o m o l o g u e s o f t h e q u i n a l d i n i u m s e r i e s s h o u l d g i v e s a t i s f a c t o r y f r o t h i n g a c t i o n * 3* Compounds w i t h m o r e t h a n 16 c a r b o n a toms i n t h e h y d r o o a r b o n c h a i n , do n o t a p p e a r t o be. s a t i s f a c t o r y f r o t h i n g a g e n t s . 4 . P o l a r g r o u p s * o f p y r i d i n i u m o r q u i n a l d i n i u m d e r i v a t i v e s do n o t a p p e a r t o be s u f f i c i e n t l y s o l u b l e t o c o u n t e r a c t t h e i n s o l u b i l i t y o f h y d r o c a r b o n c h a i n s w i t h 27 c a r b o n a t o m s . BIBLIOGRAPHY 1 . B i a n c o , R * H . a n d P o t K i n s , J . E . "New F r o t h i n g A g e n t s f o r F l o t a t i o n . " B . A . S c * T h e s i s U n i v e r s i t y o f B . C . A p r i l 1 9 3 7 . 2 . C h r i s t m a n . " C h e m i s t r y a n d t h e F l o t a t i o n P r o c e s s " A m e r i c a n . C y a n a m i d C o . T e c h . P a p e r N o . 1 7 . Nov* 1 9 3 0 . 3 . D e a n , R . S . a n d H e r s b e r g e r , A . B * "New F l o t a t i o n R e a g e n t s " A * I * M . M * E * Teoh' j Pub* N o . 6 0 5 . 1 9 3 5 . 4* ' G a u d i n , A .M.- " F l o t a t i o n " MoGaw H i l l . New Y o r k . 1 9 3 2 . 5* G i l l i e s , G . A . " T h e S t o r y o f t h e B u b b l e " A n n u a l M e e t i n g C . I . M . . M . V a n c o u v e r , B . C . N o v . 1 9 3 7 . 6 . P y l e , J . J . " T h e S y n t h e s i s o f New F l o t a t i o n A g e n t s . " M . A . T h e s i s . U n i v e r s i t y o f B . C . A p r i l 1 9 3 7 . 7 . Rose , E . H . a n d M a c D o n a l d , W . T . U . S . P a t e n t N o . 2 , 0 4 0 , 1 8 7 * 8* W a r k , " i . w . a n d G o x , A . B . " P r i n c i p l e s o f F l o t a t i o n I I I " A . I . M . E . M i l l i n g M e t h o d s * 1934 . 9 . W a r k j I.W* a n d G o x , A . B . " P r i n c i p l e s o f F l o t a t i o n . V I " M i n i n g T e c h n o l o g y * J a n * 1938* - 41 -T e s t N o . 22 Gone* N o . W t . o f G o n e . , W t ; A s s a y G u $ N i $ W e i g h t Gu .gms* N i . gms P e r c e n t Rec Gxifo Mi% 1 2 4 . 3 2 . 4 3 . 8 7 5 . 1 6 . 9 4 1*25 2 7 . 1 1 0 . 5 2 2 5 ; 0 2 . 5 2 . 0 8 2*60 «52 . 6 5 1 5 . 0 5 . 5 3 5 1 . 7 5 . 2 1*17 3 . 1 2 *60 1 . 6 1 1 7 . 4 1 3 . 6 4 34*4 3 © . 5 5 2 . 1 6 . 1 9 *74 5 . 4 6 . 2 5 30*8 3 . 1 *95 2 . 2 4 . 2 9 . 6 9 8 . 5 5*8 T a i l s 8 3 5 . 1 3 3 . 5 . 1 1 . 8 3 . 9 2 6 . 9 3 2 6 . 5 5 8 . 4 l~aOTY3 3 . 4 6 11*87 T e s t N o . 23 1 3 1 . 8 3*0 3 . 3 4 2 . 3 8 1 . 0 6 . 7 6 3 0 . 0 6 . 6 2 8 7 * 3 8 . 3 -L * 25 3 . 5 4 i ; o 9 3 . 0 7 30*9 2 6 . 7 3 3 6 . 4 3»5 *57 2*37 . 2 1 . 8 6 5 . 7 7 . 5 4 2 5 . 0 S a 5 . 4 6 1*84 . 1 1 . 4 6 3 . 3 4 . 0 5 4 0 . 8 3 . 9 . 3 8 2 . 0 0 . 1 5 . 8 2 4 . 3 7 . 1 T a i l s 8 2 6 . 5 7 9 . 0 . 1 1 . 6 7 . 9 1 5 . 5 3 2 5 . 7 4 8 . 1 1 0 4 7 . 8 3 . 5 3 11*50 T e s t N o . 24 1 3 2 . 0 3 . 2 3 . 9 1 2 . 2 0 1 . 2 5 . 7 0 3 3 . 8 5 . 4 2 26*2 2*6 1 . 8 6 2 . 0 4 . 4 9 . 5 3 12 • 2 4 . 0 3 20*1 2 . 0 1 . 4 3 1 . 4 5 . 2 9 . 2 9 7 . 8 2 . 2 4 . 11*2 1 . 1 1 . 2 8 1 . 3 7 . 1 4 . 1 5 3 . 8 1 . 2 5 1 0 . 0 1*0 1*58 1*12 . 1 6 . 1 1 4 . 3 . 8 T a i l s 9 1 2 . 0 90*1 *15 1 . 2 4 1 . 3 7 1 1 . 3 0 3 7 . 1 8 6 . 4 1 0 1 1 . 6 3 . 7 0 1 3 . 0 8 - 42 -T e s t N o . 25 G o n e . W t , o f f, A s s a y •No. Gone* Wt* Gu$ m% 1 2 3 . 3 s » s 2*85 2 . 9 8 2 38*1 3 . 7 2*60 3 . 3 4 3 29*1 2 . 8 1 . 0 6 1.9.5 4 1 7 . 3 1 . 7 . 5 9 1 . 3 8 5 15*3 1 . 5 . 3 5 1 .01 : T a i l s 9 1 2 . 8 1035*9 8 8 . 0 5 . 1 8 *85 T e s t N o . 2 6 1 1 . 9 1 . 1 6 1*88 2 3 5 . 4 3 . 5 1 . 9 7 1 . 7 2 3 2 1 . 7 2 . 1 1 . 7 9 .1 • 52 4 9*8 1 . 0 *95 1 . 4 1 5 8*5 • 8 . 7 1 1 . 3 2 T a i l s " • t • ' 9 3 2 . 8 1 0 1 7 . 1 9 1 . 7 i 2 5 Tes;t, : No ; * 1*01 27 1 3 5 . 4 3 . 5 1 . 7 3 1 . 8 1 2 1 2 . 3 1 . 2 3*18 . 1 . 8 3 3 1 9 . 0 1 . 9 1 . 6 1 1 . 5 6 4 9*4 *9 *87 1 . 4 1 5 1 6 . 8 1*6 *84 1 . 3 6 T a i l s 9 2 4 . 7 1 0 T 7 . 6 9 1 . 1 . 1 9 1 . 1 4 W e i g h t P e r c e n t R e c . G t u g m s . N i * g m s . Gnfo N i $ . . 6 6 . 6 9 1 7 . 6 6 . 6 . 9 9 1 . 2 7 2 6 . 4 12.1 . 3 1 - ' . 5 7 8 . 3 5.4, . 1 0 . 2 4 2 . 7 2*5 *05 . 1 5 1 . 3 1 . 4 1 . 6 4 3 . 7 5 7 . 5 8 1 0 . 5 0 4 3 . 7 7 2 . 2 . 2 2 *36 5 . 8 3 « 3 . 7 0 . 6 1 1 3 . 5 5 . 6 . 3 9 . 3 3 1 0 . 5 3 . 0 . 0 9 . 1 4 2 . 4 1 . 3 . 0 6 . 1 1 1 . 6 1 .0 2 . 3 5 5 . 7 9 9*43 1 0 . 9 8 6 1 . .5 3 6 , 0 . 6 1 . 6 4 1 9 . 1 5 . 3 *59 12*2 1 . 8 * 5 l *50 9 . 8 2 . 5 . 0 3 *13 2 . 5 1 . 1 . 0 2 . 23 , 6 1 . 9 1 . 7 6 5*17 1 0 . 5 5 12*07 55*5 8 7 . 2 - 43 -T e s t N o . 3 8 . C o n e ; W t . o f fo A s s a y W e i g h t P e r c e n t Rec* N o . G o n e . W t . Gu% N i $ C u . g m s . N i . g r n s * Gixfo m$ 1 3 6 . 8 3 . 5 3 . 5 1 3 . 2 2 1 . 3 0 1*20 3 9 . 7 9 . 6 3 4 7 , 4 4*5 1 . 3 9 2 . 0 2 e 66 1*43 2 0 . 1 1 1 . 4 3 4 1 0 . 9 liO . 3 6 1 . 2 1 . 0 4 *13 1 . 2 . 1 5 2 0 . 0 1 . 9 . 2 8 . 8 3 . 0 6 . 1 7 1 . 8 . 1 T a i l s 9 4 0 . 8 1 0 5 5 . 9 89*2 . 1 3 T e s t No, 1 . 0 2 , 2 9 . 1*22 3 . 2 8 9*59 X2 c.52 3 7 . 2 7 6 . 6 1 3 7 . 2 3*6 3 . 1 6 3 . 4 4 1 . 1 7 X o 2 3 3 4 , 5 1 0 . 1 3 3 1 . 5 3*1 1*56 3 . 8 8 . 4 9 1*22 1 4 . 4 9*6 3 5 4 . 3 5»3 *62 2 . 6 4 . . . 34 1 . 4 3 10*0 1 1 . 3 4 13 « 9 1 . 3 . 3 9 1 . 1 8 . 0 5 *16 1 . 5 1 . 3 5 1 0 . 8 1 . 0 . 4 6 1*15 . 0 5 *12 X A 5 . 9 T a i l s 86.1.7 1 0 2 9 . 4 8 3 . 8 . 1 5 T e s t . N o . *97 3 0 . X ft 29 3 . 3 9 8 . 4 5 1 2 . 6 6 3 8 . 0 6 6 . 7 1 2 8 . 3 2 . 8 0 1 . 8 7 1 . 9 5 . 5 3 . 5 5 1 4 . 8 4 . 6 3 2 5 . 4 2*5 2*07 1 . 9 7 . 5 3 ; 5 0 1 4 . 8 4 . 2 3 1 1 . 8 X • 2 . 9 9 1 . 3 4 *12 «X6 3 . 3 X 0 3 4 7*9 *8 . 9 0 1 . 3 1 *07 *10 2 . 0 . 8 5 . 9*7 *9 . 8 7 1 . 2 9 . 0 8 o 12 2 . 2 1 . 0 T a i l s 9 3 6 . 5 1 0 1 9 . 6 91*9 *24 1*15 2 . 2 5 3 . 5 8 1 0 . 4 8 11*91 6 2 . 8 8 7 . 9 G o n e . N o . . W t . o f G o n e . W t . T e s t No* A s s a y Gu.% KH 31 W e i g h t C u . g m s . N i . g m s P e r c e n t R e c * C u $ N M ' 1 9 2 . 0 9*2 2 . 4 0 4 . 7 7 2*21 4 * 3 8 70*5 4 0 . 0 2 ; 1 1 . 9 1*2 . 7 1 1 . 6 5 . 0 8 . 2 0 2*5 1*8 3 1 8 . 9 1*9 "*43 1 , 2 5 *08 *24 2 . 5 2 . 2 4 1 4 . 4 " 1 . 4 *38 *96 . 0 5 . 1 4 1 . 6 1 . 3 5 7 . 2 . 7 . 4 6 . 9 9 . 0 3 . 0 7 1 . 0 . 6 T a i l s 8 5 9 . 1 8 5 . 9 *08 . 7 3 *69 5 . 9 2 2 1 . 9 5 4 . 1 1 0 0 3 . 5 3 . 1 4 1 0 . 9 5 T e s t N o . 3 2 . 1 1 2 0 ; 2 1 1 . 3 1 . 6 7 3 . 6 5 2 . 0 1 4*39 4 9 . 4 5 0 . 5 2 1 7 6 . 4 1 6 . 6 . 6 8 1*88 1 . 2 0 3*32 2 9 . 5 3 8 . 2 3 3 9 . 5 3 . 7 . 3 2 . 9 3 # 1 3 . 3 7 3 . 2 4 . 3 4 2 7 . 3 2 . 5 . 3 7 . 5 6 *10 .15 2*5 1*7 \j 6 1 0 . 6 1*0 . 3 2 . 4 7 . 0 3 *05 *7 . 6 T a i l s 68-3.5 . 64*7 . 0 9 . 0 6 *60 *42 «7 . 6 1 0 6 2 . 5 4 . 0 7 8 . 7 0 T e s t 3 3 1 2 6 . 0 2*5 3 * 28 1*92 . 8 5 . 5 0 2 3 . 2 4*0 2 2 1 . 6 2 . 1 1 . 4 1 1 . 7 7 . 3 0 *38 8*3 3*0 3 1 2 . 8 1 ; 3 *93 1 . 5 1 « 3.2 *19 3 . 3 1 . 5 4 8*7 . 8 "'•99 1*30 *09 • 13. 2 . 5 *9 5 6 . 5 . 6 1 . 8 2 . 8 9 . 1 2 *Q6 3 . 3 *5 T a i l s 9 5 0 . 0 9 3 . 0 9 24: 1 . 1 9 2 . 1 3 11*30 5 9 . 6 90*1 1 0 2 5 . 6 3 . 6 6 1 2 . 5 4 T e s t . N o , 34 Gone •KP* ! . W t . o f G o n e , fa - wt..... A s s a y Cu#. N i $ W e i g h t G u . g m s . N i . g P e r c e n t Rec ana.-. Gu$ . N i$„ 1 134*5 1 3 . 0 1 . 7 7 2 . 6 8 2 . 3 8 3 . 6 3 6 1 . 8 3 7 . 6 2 : 2 3 . 0 2*2 1 , 5 1 2 . 6 7 . 3 5 . 6 1 9 . 1 6 . 3 3 1 4 . 2 1 . 4 *78 1 . 2 7 . 1 1 . 1 3 2 . 8 1 .9 4 1 4 . 0 1 . 4 . 3 3 . 9 3 . 1 2 . 1 3 3 . 1 1 . 3 5 8 . 0 . 8 *68 . 8 7 *05 *07 1 . 3 . 7 T a i l s 8 3 9 * 3 1 0 3 3 . 0 3 1 . 2 . 1 0 . 60 . . 8 4 3 . 8 5 5 . 0 4 9 . 6 6 21*8 5 2 . 4 T e s t N o . 35 1 2 3 0 . 6 27*2 1 . 0 3 3 . 6 8 2*88 1 0 . 3 2 8 2 . 3 9 3 . 0 2 7 9 . 5 7 . 7 . 2 4 *67 . 1 9 . 5 3 5 . 4 4 . 8 3 4 8 . 9 4*7 . 2 6 . 2 8 . 1 3 . 1 4 3 . 7 1 . 3 4 I S . 2 1 . 5 . 2 9 e X2 . 0 4 . 0 2 1 . 1 . 2 5 5 . 5 . 5 . 4 1 o IL 2 . 0 2 . 0 1 . 6 . 1 T a i l s 6 0 0 . 3 5 8 . 2 . 0 4 . 0 1 6 ..24 . 1 0 6 . 9 . 8 1 0 3 0 . 3*50 1 1 . 1 2 T e s t N o . 36 1 6 5 . 9 6 . 5 • 2 . 6 0 2 . 6 7 1*71 1*76 5 3 . 7 1 4 . 7 2 4 3 . 3 4L«2 1 . 1 0 2 . 6 1 . 4 8 1 . 1 4 1L*D *> «L 9 . 5 3 2 1 . 4 2 . 1 . 5 9 1 . 3 5 *40 4 . 7 3 ® 3 4 1 1 . 0 1 . 1 . 7 8 1 . 3 2 . 0 9 »15 2 • 8 1 . 3 5 1 1 . 9 1*1 . 6 4 1 . 3 8 , 0 8 . 1 6 2 • 5 1 . 3 T a i l s 8 7 9 . 8 . 1 0 3 3 . 3 8 5 . 1 , 0 8 . 9 5 , 7 0 3 . 1 9 8 . 3 5 1 1 . 9 6 2 1 . 9 6 9 . 8 - 46 -T e s t N o . 37 G o n e . N o . Wt . O f G o n e . - 1o A s s a y Gufo Mi W e i g h t G u . g m s . N i . g m s P e r c e n t Rec . Gufo mi . 1 2 1 1 . 1 2 1 . 1 1 . 0 1 3 . 7 5 2 . 1 3 7 . 9 1 6 6 . 2 8 2 . 6 2 6 9 . 3 6 . 9 . 4 9 . 8 5 . 3 4 . 5 9 1 1 . 1 6 . 2 3 1 2 . 5 1 . 3 . 4 5 . 1 6 . 0 6 . 0 2 X & 9 .»2 4 1 2 . 3 1 . 2 . 2 2 . 0 8 . 0 3 . 0 1 . 9 e l 5 8 . 0 .;. . 8 . 5 0 . 0 9 . 0 4 . 0 1 1 . 2 . 1 T a i l s 6 9 4 . 6 6 9 . 4 . 0 9 . 1 5 . 6 2 3» 22 1 . 0 4 . 9 . 5 8 1 9 . 3 1 0 . 9 T e s t N o . 38 1 1 0 5 . 3 9 . 9 1 . 2 1 5 . 3 7 1 . 2 7 5 . 6 5 5 5 . 2 5 6 . 5 l a 4 6 . 3 4*3 . 4 5 2 . 4 7 . 2 1 1 ft 1 3 9 . 1 1 1 . 5 2 66*6 6 . 2 . 4 0 1 . 4 0 . 2 7 . 9 5 1 1 . 7 9 . 3 3 2 0 . 6 1.-9 . 3 0 . 6 7 . 0 6 . 1 4 2 . 6 1 . 4 4 2 2 . 4 2 . 1 . 4 0 . 6 2 . 0 9 . 1 4 3 . 9 1 . 4 5 1 4 . 3 1 . 3 . 5 7 . 2 4 . 0 8 . 0 3 3 . 5 . 3 T a i l s 7 9 1 . 3 1 0 6 7 . 8 7 2 . 3 . 0 4 T e s t . 2 5 ; -No.: 39 . 3 2 2 . 3 0 1 . 9 7 9 . 9 9 1 3 . 9 1 9 . 7 1 1 1 . 4 1 . 1 . 4 5 1 . 0 5 . 0 5 . 1 2 2 . 4 1 © 3 2 7 . 3 . 7 2 . 5 1 1 . 0 8 . 1 8 . 0 8 8 . 6 . 3 3 12 » 4r 1 . 2 2 . 5 2 1 . 3 2 . 3 1 . 1 6 1 4 . 7 1 , 7 4 8 . 2 . 8 1 . 4 9 1 . 1 0 . 1 2 . 0 9 5 . 7 . 9 5 4 . 1 4 . 0 2 . 2 7 1 . 1 2 . 0 9 f 0 5 4*5 . 5 T a i l s : 9 6 9 . 2 1 0 1 2 . 6 9 6 . 0 . 1 4 . 9 2 1 . 3 6 2 . 1 1 8 . 9 2 9 . 4 2 6 4 . 8 9 4 . 6 % .Wt. T e s t i.''"No..-v1 40 G o n o . •MQ*. wt; o f G o n e . A s s a y Gnfo mfo Wei; Cu *gins. §ht -"''JT.iwi P e r c e n t Rec J I B S . GWfo N i $ 1 86. '6 8 . 4 1 . 9 2 4 . 6 5 1 . 6 6 4 . 0 3 6 3 . 5 4 8 . 7 2 3 8 . 3 3 . 7 . 4 5 4 . 2 3 . 1 6 1 . 6 2 6 . 1 1 9 . 6 5 2 4 . 7 2 . 4 *32 2 . 5 0 • . 0 8 . 6 2 5 . 1 7 . 5 4 9 . 8 1 . 0 . 4 9 . 7 7 *05 . 0 8 1 . 9 . 9 5 7 . 7 . 7 . 5 9 . 4 6 . 0 5 . 0 4 1 . 9 . 4 T a i l s 8 5 9 . 3 8 3 . 7 . 0 7 . 2 2 . 6 2 1 . 8 9 2 5 . 7 2 2 . 8 1 0 2 6 . 4 T e s t > ::No*,: 41 2*62 8 . 2 8 1 1 1 4 . 1 1 1 . 0 1 . 4 3 6 . 0 3 1 . 6 5 6 . 3 8 6 1 . 1 6 9 . 6 l a 9 3 . 0 8 . 9 . 5 2 2 . 2 1 *48 2 . 0 5 18*0 20*7 2 34*7 3 . 3 . 3 4 1 . 0 1 *12 *35 4*5 5 . 5 3 1 6 . 0 1 . 5 . 2 6 . 5 4 . 0 4 . 0 9 1 . 5 ; .'-9' 4 32 . 7 3 . 1 » 2 2 »22 . 0 7 ..07 2*6 .7 5 1 3 . 3 1 . 3 *88 . 1 8 . 0 4 . 0 2 1 . 5 . 2 T a i l s 7 3 7 . 1 1 0 4 0 . 9 70*8 . 0 4 T e s t *06 i N o . 42 *29 2 . 5 7 . 4 3 9 . 8 9 1 0 . 9 4 . 3 1 1 4 . 3 1 . 4 2 . 5 5 1 . 9 9 *54 *28 1 2 . 8 2 . 9 2 1 8 . 0 1*8 1 . 9 2 1 . 6 2 *35 *29 1 5 . 2 3 . 1 3 1 0 . 0 1 . 0 1 . 4 2 1 . 6 1 . 1 4 . 1 6 5 . 5 1*7 4 5 i 5 5*3 . 3 3 1 . 1 8 . 0 2 *06 . 3 *6 5 1 0 . 7 1*0 *57 . 9 7 . 0 6 . 1 0 2»3 1 . 1 T a i l s 9 7 0 . 1 1 0 2 8 . 6 9 4 . 3 . 1 3 . 8 9 1 . 7 4 2 . 6 5 8 . 6 2 9 . 5 1 6 5 . 7 ' 9 0 . 6 i T e s t N o . 45 G o n e . s W t . o f % A s s a y W e i g h t P e r c e n t R e c . N o . G o n e . . W t . . Cu.% m% C u . g m s . N i . g m s . C.u$ N i $ 1 5 G . 2 3 . 0 4 . 1 8 5 . 2 2 1 . 2 6 . 9 7 4 5 . 7 1 1 . 6 2 2 6 . 3 2 . 6 . 7 8 3 . 9 7 6 2X 1 . 0 4 7*6 12*4 3 9 . 0 . 9 . 7 9 ' 2 . 6 4 . 0 7 . 2 4 2«5 2 . 8 4 1 1 . 0 1 . 1 . 4 3 *90 . 0 5 i l O 1*8 1 . 2 5 1 4 . 3 1 . 4 . 4 6 . 6 5 . 0 7 . 0 9 2 . 5 X o X T a i l s 9 1 4 . 4 . 1 0 0 5 . 2 9 1 . 4 . 1 2 T e s t . 6 5 ; No . . 44 l . i o 2 . 7 6 5*93 8*37 5 9 . 9 7 0 . 9 1 3 1 . 3 2 . 9 3 . 1 5 7 . 0 3 . 9 9 2 . 2 0 5 2 . 4 2 2 . 8 2 4 9 . 8 4 . 7 1 . 7 9 4 . 0 8 . 8 9 2 . 0 3 2 9 . 1 2 1 . 1 3 4 3 . 4 4 . 1 1 . 5 1 1 . 6 7 . 5 7 . 7 2 1 3 . 6 7 . 5 4 1 3 . 8 1*3 . 5 4 . 6 4 *07 . 0 9 2*3 *9 5 1 4 . 5 1 . 4 . 62 . 3 5 *09 . 0 5 2 ; 9 . 5 T a i l s . 9 1 0 . 1 1 0 6 2 . 9 8 5 . 5 . *05 T e s t *50 N o . 48 . 4 5 3.06. 4 . 5 5 9 . 5 4 1 4 , 6 4 7 . 2 1 2 9 . 3 2 . 9 . 7 6 1 . 2 4 «22 . 5 6 8 . 4 3 . 8 2 4 1 . 9 4 . 2 1 . 8 2 1 . 8 3 *76 . 7 7 29*1 8 . 1 ,3 2 9 . 2 2 . 9 . 6 8 . 9 3 . 2 0 . 2 7 7 . 7 2 . 9 4 3 4 . 0 3*4 *46 . 9 7 . 1 6 . 5 5 6 . 1 3 . 5 5 2 4 . 0 2 . 4 . 5 1 . 8 1 *07 . 1 9 2*7 2 .0 T a i l s 8 5 6 . 7 1 0 1 5 . 1 8 4 * 3 . 1 4 *S8 1 . 2 0 2 . 6T 7 . 5 4 9 . 4 6 46*0 7 9 . 7 Test No. 49 Cone W t . ; o f No. Cone Wt. Assay cu% mi Weight Gu.gms. Ni.gms P e r c e n t Rec . <zu°/o m<i 1 84.4 8.4. .2.17 5.45 1.83, 4.60 71.0 49.0 2 53.3 2.74 .17 1.46 6.6 15.5 3 .27.5 2.7 X«t^-<3 .07 .36 -i<l •> 3.8 4 11.7 1 .47 .04 .05 1.6 • «-> 5 21«1 .30 O .06' .07 .7 T a i l s 8 1 8 . 9 1016.9 80.7 .05 .35 .41 2.58 2.86 9.40 30.4 Te s t No. 50 1 : 198.1 .1-3 ® _L 1 . 1 3 4.69 'fit « £_p"d: 9.30 8 5 . 3 93.8 .25.8 • p P, ..24 .55 .06 .14 1.4 •7. 23.0 .13 .18 . 0 3 .04. 1 . 1 «4 4 2.2 » IB © IS .04 . 03 1.5 .3 5 21.8 .12 .04 .03 1.5 I a i l s 7 4 6 . 5 71.8 .03 .05 .37 8.4 1038.0 2.63 9.91 Tes t No. 51 ' 1 29.9 3.0 1.61 X«uu .48 .40 17.1 4.9 2 35.9 1.57 1 O 'Z .56 -.44 20.0 5.5 5 31.4 * 1 « .94 .16 ..29 5.7 O • 4 18.3 1.8 -.29 .91 .05 .17 1. 8 5 .20.8 *o«1 ..28 .89 .06 .19 2.1 T a i i s 8 7 5 . 1 1011,4 86.6 .17 .77 1.49 .2.80 6.74 8 • si<D 53.2 81.9 Test No. 52 Cone. Mo. Wt. of Cone. % Wt. Assay Cu% • m% "Wei| Cu.gms. 5 l i t N i . g ms P e r c e n t Rec . Cu# B±% 1 21.8 <3«1 • p q 2.02 . 52 .44 22.1 4.9 2 15.6 ^.70 1.91 .42 » ti1 0 " 17.9 3 , 11.4 1.1 1.51 1.7.2 .17 .20 7.2 .2.2 4 1 « 3 1 • w .65 1.17 .08 . 14 3.4 X o 5 5. 1 ^  » D 1.-2 . 15 . 86 .0:2 .11 »8 1.2 T a i l s 949.7 92.6 • I S .83 1.14 55-. 87 48.6 86.8 1023.3 .2.35 9.06 Test No. 53 1 14.4 1.4 £)« S*D 3.20 .77 .46 32-. 0 5.1 2 -20.4 ,2.0 .2.69 4.49 .22.8 10.: • -21.4 . 58 . 12 .54 5.0 6.0 • 4 15 .4 1 K '.63 1.99 .10 8>^ .X 4.1 3.4 '5 10.2 1.0 1.03 ,04 .11 1.7 1 « ri^t T a i l s 9.20.8 *3 S « X .09 ..83 6.68 34.4 74.1 1002.6 9.02 T e s t No. 54 i 25.0 3.36 ;2.58 .84 '.65 33.0 7.4 2 . 19.4 1.9 1.48 .fe»X0 . 29 .41 11.4 4.6 ,3 oO. 8 <5 • 1 .39 X # •  ^  (C/ .12 . 38 4.7 4. ; 4 • - 321.6 fi/ * -L- e <J . 1 .07 ..20 •' .2.8 5 18.5 1.8 a 27 .78 .05 .14 ^ • 0 1.6 T a i l s 898.3 88.6 .13 .79 1.17 7.09 46.1 79.9 1013.6 © Pi A 8.87 - 51 -« • - Test Mo. 22 Cone. C u m u l a t i v e Recovery Cum. wt. F r o t h p.H. HoSO/NaOH Mo. Wt.fe Cu% Nl% Reagent C o n d i t i o n 'A ' 1 .2.4 .27.1 10.5 gms. 4e 6.5 ,2 4.9 42.1 16.0 .34 4c 7.66 5 ' 10.1 59.5 .29.6 . 51 4bc 7.8 4 13.5 64.9 35,8 .68 4be 7.12 5 1 6 . 6 73.4 41.6 Test .85 No. 23 4b 7.69 1 3.0 30.0 6.6 .17 66 7.7 tr-. J_ 1»o 60,9 .34 6c 7.0 3 - 14.8 66„6 40.8 . 51 6c 7.5 4 17.3 69.9 44.8 .68 6bc 7.5 5 21.2 51.8 T e s t . 85 Mo. 24 6bc 7.6 1 3 ..2' 53.8 5.4 . 028 6b 7.08 2 5.8 47.0 8.4' .056 7bc 7.0 3 7 . 8 - 54.8 1 1 . 6 .084 7bc . 7.0 4 . 8.9 58.6 12.8. .112 7bc 7.3 5 . 9 6.2.9 13.6 Te s t .140 No. 25 7b 7.75 I 2.2 1 $ . 6 6.6 .0.28 5bc 5.64 :2 ' 5. 44.0 18.7 .056 7be 5.30 3 8.7 24.1 .084 7b 5 9 ^ 4 . 10.4 55.0 .26.4 .112 7e 4.65 5 1 1 . 9 56.3 27.8 .140 4c 4.65 T e s t Mo. .86 Cone. Cumulative Recovery Cum. Wt. F r o t h p.H. H P S 0 4 NaOH Wo. m% Cu% m% Reagent C o n d i t i o n gms. 67 1 1.9 5.8 gms. .028 5b 7.96 2 5.4 .24»3 8.9 .056 7b 7.94 3 7.5 34.6 .084 7bc 7.6 4 8.5 37.0 .112 7bc 7.45 5 9.3 38.6 14.2 .140 7bc 7.43 Tes t Wo. .27 1 3.5 19.1 5.3 .028 7b 7.26 4,7 7.1 .056 7ab . 7.37 3 - 6.6 41.1 9.6 .084 7b 7.46 4 7.5 43.6 10.7 .112 7b 7.40 9.1 44.2 12.6 .140 7b 7.44 Tes t Mo. 28 1 3.5 38.7 . 9.6 .028 5b 5.59 50 2 8.0 59.8 31.0 .056 6b 4.41 6 '' : , • 4 9.0 61.0 22.0 .112 6b 4.34 5 10.9 .. 6.2.8 23.0 .140 6bc 4.34 Test No. 29 1 3,6 •34.5-. XO 9 X • 028 6ab 9.92 p 6,7 48.9 19.7 .056 7b 3 1 2 . 0 58.9 31.0 .084 7b 9.10 4 6 0 . 4 3:2.3 . 112 7b 8.5 5 14.4 61.9 33.2 .140 7b 8.41 1.11 Test Mo. 50 Conc. Cu m u l a t i v e Recovery Cum. Wt. F r o t h p f l . B0SO4. NaOH No. \Mt% Cu% Ml% Reagent C o n d i t i o n ^ gms gms. 1 2.8 14.8 .4.6 .03 5bc 7.56 & .29.6 8.8 .078 5ab 7.20 6.5 32.9 10.1 »117 4b 7.30 4 7.3 .34.9 10.9 .156 Sab 7.27 5 8.-2 57.1 11.9 •j 19 5 2ab 7.44 Test No. 31 1 70.5 40.0 .039 5ab 10.59? 2 10.4 73.0 4.1.8 .078 5ab 40 5 lib««6 75.5 44.0 .117 5 a 4 13.7 77.1 45.3 .1.56 4ab 8.75 5 14.4 78.1 45.9. ' o 19 «D 4ab 8.58 Test No. 52 1 11«t^ > 49.4 50.5 '.039J l a 1.76 50 27.9 78.9^3 88.7 .078 4b 1.99 5 31.6 82.1 93.0 .117 2b 2.20 4' 34.1 8.4.6 94,7 .156 l b • ,2..20 6 35.1 85.3 95.3 .196 4b •2.09. 25 T e s t No. 1 .23.2 4.0 .012 7c 7.09 2 4.6 o l . 5 7.0 . 0.24 7c 7. }£B 3 5.8 34.8 8.5 .036 7c 7.40 4 6.7 37.3 .9.4 .048 6c 7.53 5 7.3 40.6 9^9 .060 6c 7.5 - 54 -Test .No. 34 Cone. Cumulative Recovery Cum. Wt. F r o t h p . H . H0SO4 NaOH No. \ltfo Cu$ N i % Reagent C o n d i t i o n 1 face. gms. gms. 1 Xo«0 61.8 37.6 .012 7b XX * 0 0 15.2 70.9 43.9 . 024 6b 9,84 3 16.6 73.7 45,8 .036 6b 8.20 4 18.0 76.8 47.1 .048 6b 8.75 5 18.8 78.1 47.8 .060 5"b 8.79r; Test No. 35 1 '-7 9 82.3 93,0 . 012 7ab 1.6 & 34.9 87.7 97.8 .024 7bc 3 39.6 91.4 9 9 • -L .036 7bc 2.7 4 4.1.1 9 ^ «5 99.3 .048 7c - • 3.65 5 41.6 93.1 99,4 .060 6c 4.15 T e s t N o . 36 1 6.5 53,7 14.7 . 0115 7du • 7.30 2 10.7 68.1 24.2 . 0230 7du •7.35 3 XS«8 72.3 27.5 . 0345 7cu cf.53 4 13.9 75,6 .28.8 .0460 7bcu 7.52 5 15,0 78 0 X 30.1 .0575 7au 7,69 Tes t No . 37 1 S l . l 82.6 .0115 4b4 12.27 .2 :28.0 77.3 88.8 .0230 7cu 12.37 3 29.3 7 9.,2 89,0 .0345 3bu X0«53 4 30.5 80,1 89.1 .0460 3bu 9d 85 5 3X«3 81.3 8 9-"<i *£J .0575 2a bu 9.54 - 55 -Tes t No. 28 Cone. C u m u l a t i v e Recovery-No . Wt% Cv$ N i % Cuin.. Wt, Reag ent F r o t h p.H. H Q S 0 4 M i l C o n d i t i o n ' gms. — . KL.1T, ,fc/„ C.Cft — 1 ' l a 4 20.4 22. 3 24: . 4 25.7 55.2 64.3 76.0 78.6 82.5 86.0 56.5 67.8 77.1 78.5 79. 9^ ; 80.2 Test .0115 .0230 . 0345 .0460 .0575 No. 39 Test Mo. 40 6cu 6eu 6ab 7ab 7bc 3 . 6 9 i 4.46 4.50 4.70 4.72 4.70 1 X«X i 2.4 1.3 .009 2bx 6.85 2 X © 8 11.0 O '1 iO © X .013 2bx 7.8 3 3.0 25.7 3.8 .027 3bx 7.92 4 : u>. 8 31.4 4.8 .036 2bx 8.18 5 7.8 35.7 5.3 .045 2bx 7.86 1 8.4 a% '7. 48.7 .0.09 5abx 1 9 "Z. 2 XiO 9 X 6 9^ s> 4 68.3 .018 7bu 11.2 3 X4«5 72.5 75.8 .027 6bx 10.5 4 15.5 74.4 76.7 .036 6cu 9 e 9X 5- 16.2 76.-3 77.1. .045 6bcu « 5 (~y T e s t No.- 41 1 11.0 61.1 69.6 .009 6cu !EH 19.9 7 9«X 90.3 «6 4 2 iCj3 © S 83.6 93.8 .018 6eu 3.0 3 24.7 85.1 94.7 .027 6cu 3 .65 4 27.8- 87.7 9 *3 © 4 .036 7cu 4.32 5 •S9 e X 89.2 95.6 .045 6cu 4 ® 313 50 50 «2 o J§ £i - 56 -Test Mo. 42 Cone. C u m u l a t i v e Recovery Cum. Wt. F r o t h D . H . BoSO.MaOH •No. Wt% Cu.% Ni% Reagent C o n d i t i o n ^ gins. gas. 1:2 cc. .1 .1.4 12.8 .2. .006 3ax 7.4.2 2 3.2 26.0 6.0 . 012 5ax 7.5 3 4..2 31.3 7.7 .018 3ax 7.5 4 • 4.7 32.1 8.3 .024 3ax 7.33 5 5.7 34.3 9.4 .030 4ax 7.32 Te s t N o . 43 1 <5 e 0 45.7. 11.6 ,006 5ax 10.67 -2 5.6 53.3 •<j4 © 0 9 0 JL S . 4ax 10.17 3 6.5 55.8 26.8 .018 4ax 9.7 4 • 7.6 57.6 28.0 .024 4ax 9 •« 4 5 9.0 60.1 9 ^  1. .030 4ax 9.35 Rest No, 44 1 32.4 22.8 .006 7bx g 7.6 61. 5 43.9 .012 6bx 11.7 80.1 •3 -L.«4 .018 6bx 4 1*6 * 0 82.4 • 52.3 , 024 6bx 5 14.4 85.3 52.8 .030 6bx Test N o . 48 1 ;i2«9 8.4 3.8 .004 oa 7. 25 2 7.1 37.5 H « 9 .008 4ax 7. 26 3 10.0 45.2 14.8 .012 4ax 7. 26 4 13.4 S I e 3 18.3 .016 5abx 7.35 5 15.8 54.0 20.3 .020 5abx 7. 80 - 57 -Te s t .No. 49 Cone. Cumulative Recovery Cum. Wt. F r o t h p . H . E^SQ, NaOH No. m% Cu/o 111% Reagent C o n d i t i o n d gms. gms. 1 8.4 71.0 4 9 . 0 .004 5ax 9.85 13.7 77.6 64.5 .008 6b 9.63 3 1 6 . 4 80.5 68.3 .012 6b 9.43 4 17.6 81.9 68.8 .016 6b 9.17 5 19«7 84.2 69.5 „ 020 6b 9.05 Te s t No. 50 1 19.1 85.5 95.8 .004 7du o © 16 2 .21.6 87.6 9 E) © -2 .008 6dx 5.18 5 :23.8 8 8 . 7 95.6 . 012 6du 3«'</2 4 •26.0 90.2 95.9 .016 6dx O • Ay / 5 28 • 1 91.7- 96 e K J .0.20 6dx 3 ® -S7 Test No. 51 1 5.0 17 © 1 4.9 .004 4ax 6.31 s 6.5 37»1 10.2 .008 5 ax 7.01 8 9.6 42.8 15.7 .012 5ax 7.08 4 11.4' 44.6 1 5 . 8 .016 5ax 7.27 5 15.5 46.7 18.1 .020 5 ax 7.36 Test No. 52 1 « 1 fvS e 1 4.9 .005 3abx 8.65 2 •Z £ c> * O 40.0 8.2 .010 Sax 8.60 5 4.7 47.2 10.5 .015 5au 8.54 4 5.9 50.6 1 1 . 8 .020 7au 8.40 5 7 . 1 51 • 4 13.0 . .025 7bu 8.36 50 - 58 -• i ' Test No, 55 Cone. C u m u l a t i v e Recovery Cum. W t . F r o t h p.H. % S 0 4 NaOH No. \U°/o Cu% N i ^ Reagent C o n d i t i o n gms. gms... .' : 1 1.4 3.2,0 5.1 . .005 2bx 8.67 :2-''. 3.4 54.8 15.3 .010 2bx ,8.67 3 • 5»5 59.8 21.3 .015 3abx •8.38 4 7 . 0 . 63.9 24.7 .020 4ax 8.25 5 8.0 65.6. . 025 tScix 7 . 8 7 T e s t -No. 54 1 y . 5 33,0 7.4 •' .005. Sax 7.85 2; : .4.4 44.4 I f C ^ e 0 .010 3ax 7.85 3. * 7.5 49.1 16.3 ,015. 2ax '7.95 4^. . 9.6 51,9 18.6 .020 3 ax 7 . 9 7 5 ' , 11.4 53.9 20..2 .02b' 4bx . 7.97 C o n d i t i o n o f F r o t h Depth ^ o f - F r e t h . ' S i z e , o f Bubble #1 -, f f % y .bubbles near l i p § 2 - -layer. O - 4 - 2 A _ A'' _ 3flt "81 a - 5/8 : n or over b - 3/8 - 1/8 »• c - 1/8 - 1/16*' d - v e r y f i n e 5 - f . - I t K l a y e r 6. - l i - 2|» " .7... - 2|IT' - . . o v e r f l o w i n g . S t e n g t h and l a s t i n g power o f bu b b l e . T - Tough - l a s t s t i l l pah I s put i n oven, U - L a s t s t i l l a l l f r o t h r eaches pan X - B r i t t l e - b u r s t s w h i l e o v e r f l o w i n g . V*/£=/<$// r; <?/ AST T/S5T Afs 2& /?//<0LJHE\ I I GRAPH A/'?4 —/oo i . k si 76" SO ~2S-O • 07& . •07& . AS-< l / l / ^ / C T - / / F l o / f?e/?G£A/Tfynvs) /OC\ -7S — 8 - -SO -25 '07& >s^i , \ • • j ; Thsr/V93o /V/?TUR(?L\ 1 , 7~ttT A/s32 /9c/j?. \ \GRRPH /VfS 7 - 1 « .023 yV'^/&//T-\orc /?jF/?<S^/vr ferns). .OZ3 .o#<£> 7r>£r/?&£rA/r T£?z>T /V*37 flLXffl/A'e. Tks-r tf&38 fic/j?. .02-3 0'^-(a \ .O/S - : 03& : j \f(:'£-/c7G£-/VT~. 1 ' J ' .1. 7^57" A/333 A/f?TU/?fii TeZT A/ 9-4p ffLKffL/N& W T o-f f?£-/?&&/V7- ferns). x/r'/Erp&^A/r-, i vfiiL i. • o o f .0/6, iA/e/<s// T\of a^A/ r (<?'?**J k -v& 3D | I - i f 1 2S\ o • Oo3 .o/<£> <3' 1 (D SC\ 008 .o/&> /oo\ 1 — " N -8 i 7S\ SO-25\ {4//?/<S/<'77 ° / f?^/9 4 7~(govs)] -foor I' ,51 I ~/ocj\-,o/,o 54-• 020 WEIGHT of ReaG^NT(4^s). - - ^ 1 - 7 ^ -V I -si s> -^5 ' .OI'O • ' 020 • \A/E/<SHT o / REF?(3 f/VT(gms). WEIGHT d •/' £?£RQENT@ms) REHOE^IT Z ' A/flTudftL SHEET /s/s / /OOagrns ore faao c.c- HjO 77&c?c?£'/?t - £>rfro/z}& f<?/- Clo/yc^ layer1 CON Dill CN of rRC71! »/_ fewt>uirb/es/iear//f. "3 „ 2'-%: I oyer "S — li payer, "6 -• l¥+2i'-Layer *'j - 22" and oJert/owinQ ayer S/ze p-f Bu bbles a. ~ £ or over .6 - .f-f d. - Very-fine, ^ trengthdt •hst}ng..pawer_of bubbles T~ £00^/7- lasis t/ffpori /spat m o/ev?. .. U~ L<3j?i3 11//-cd.fi froth•-.reachespa/?* X - 3r/fTfe -- bursis'.wh/feoverffo^vmff. 

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