The Kinetics of Dissolution of Bornite in Acidified Ferric

Sulfate Solutions
J. E. D U T R I Z A C , R. J. C. MACDONALD, AND T. R. INGRAHAM

S i n t e r e d d i s k s of s y n t h e t i c b o r n i t e w e r e d i s s o l v e d in a c i d i f i e d f e r r i c sulfate s o l u t i o n s at t e m p e r a t u r e s r a n g i n g f r o m 5~ to 94~
The d i s s o l u t i o n o c c u r s in two s t a g e s ; in the f i r s t a nons t o i c h i o m e t r i c b o r n i t e with up to 25 pct d e f i c i e n c y of c o p p e r i s f o r m e d . In the s e c o n d , the nons t o i c h i o m e t r i c b o r n i t e is c o n v e r t e d to c h a l c o p y r i t e and e l e m e n t a l s u l f u r , which a c c u m u l a t e s
on the disk s u r f a c e . At t e m p e r a t u r e s b el o w 35~ the r e a c t i o n f o l l o w s p a r a b o l i c k i n e t i c s and
stops at the n o n s t o i c h i o m e t r i c b o r n i t e s t a g e . At higher t e m p e r a t u r e s it co n t i n u es through to
c h a l c o p y r i t e and f o ll o w s l i n e a r k i n e t i c s . Both the p a r a b o l i c and l i n e a r p r o c e s s e s have a c t i v a tion e n e r g i e s of 5 to 6 kcal p e r m o l e . At h i g h e r t e m p e r a t u r e s the s e n s i t i v i t y of the r e a c t i o n
r a t e to c h a n g e s in s t i r r i n g v e l o c i t y i n d i c a t e s c o n t r o l by diffusion through the liquid boundary
l a y e r . N a t u r a l and s y n t h e t i c b o r n i t e d i s s o l v e by the s a m e p r o c e s s and at e s s e n t i a l l y the s a m e
rate.

DURING

the mining of sulfide c o p p e r o r e s , l a r g e

t o n n a g e s , a p p r o x i m a t e l y 250,000 tons p e r day, ~ of
l o w - g r a d e waste r o c k a r e p r o d u c e d in the o p e r a t i o n s .
R e c e n t l y , t h e r e has been g r o w i n g i n t e r e s t ''z in r e c o v e r i n g s o m e of the c o p p e r c o n t a i n e d in this waste
r o c k by h e a p - l e a c h i n g . In a c o m m e r c i a l o p e r a t i o n ,
a c i d is s p r a y e d on the s u r f a c e of the w a s te r o c k and
it t r i c k l e s through the p il e , r e a c t i n g s l o w l y with the
v a r i o u s m i n e r a l s . Oxidic c o p p e r m i n e r a l s a r e d i s s o l v e d rapidly by the a c i d a l o n e , but c o p p e r sulfide
m i n e r a l s r e q u i r e the p r e s e n c e of an oxidizing agent
to p r o m o t e t h e i r d i s s o l u t i o n . In h e a p - l e a c h i n g p r a c t i c e , the oxidizing agent is g e n e r a l l y the f e r r i c s u l fate f o r m e d by the action of a i r and a c i d on v a r i o u s
i r o n m i n e r a l s which a r e i n e v i t a b l y p r e s e n t in the heap.
The a c i d - f e r r i c sulfate solution o x i d i z e s and d i s s o l v e s
the copper s u l f i d e s . The c o p p e r - b e a r i n g s o l u t i o n s a r e
c o l l e c t e d at the bottom of the heap for c o n v e n t i o n a l
p r o c e s s i n g to r e c o v e r the c o p p e r .
Although c o p p e r h e a p - l e a c h i n g has b e e n p r a c t i c e d
for many y e a r s , much s t i l l r e m a i n s unknown c o n c e r n ing the c h e m i s t r y of d i s s o l u t i o n of the v a r i o u s sulfide
m i n e r a l s , p a r t i c u l a r l y the C u - F e s u l f i d e s that a r e of
great commercial importance. A recent paper from
this l a b o r a t o r y 3 s u g g e s t e d a m e c h a n i s m f o r c h a l c o p y r i t e (CuFeS2) d i s s o l u t i o n in a c i d i f i e d f e r r i c sulfate
solutions. The m i n e r a l b o r n i t e (CusFeS4) is f r e q u e n t l y
a s s o c i a t e d with c h a l c o p y r i t e o r e d e p o s i t s , and is a l s o
an i m p o r t a n t copper m i n e r a l in its own right. 4 F o r
t h e s e r e a s o n s the c h e m i s t r y of b o r n i t e d i s s o l u t i o n in
a c i d i f i e d f e r r i c sulfate s o l u t i o n s i s i m p o r t a n t f o r the
u n d e r s t a n d i n g and o p t i m i z a t i o n of the r e a c t i o n s which
o c c u r during the h e a p - l e a c h i n g of c o p p e r sulfide o r e s .
P r e v i o u s w o r k on the l e a c h i n g of b o r n i t e has c e n t e r e d a l m o s t e x c l u s i v e l y on n a t u r a l o r e s . Sullivan s
and Uchida et al.6 studied the l e a c h i n g of c r u s h e d
o r e s and Kopylov and O r l o v 7 i n v e s t i g a t e d the d i s s o lution of p o l i s h e d o r e s p e c i m e n s . Studies of this type
J. E. DUTRIZAC, R. J. C. MACDONALD,and T. R. INGRAHAM,
are Research Scientist, Technical Officer, and Head, respectively, Extraction Metallurgy Research Section, Mines Branch, Department of
Energy, Mines, and Resources, Ottawa, Canada.
Manuscript submitted July 9, 1969.
METALLURGICALTRANSACTIONS

a r e n e c e s s a r y if one is c o n c e r n e d with l e a c h i n g a
p a r t i c u l a r o r e , but the u s e of s p e c i f i c o r e s is not
the m o s t e f f e c t i v e m e t h o d f o r d e t e r m i n i n g the m e c h a n i s m s which a r e o p e r a t i v e during l e a c h i n g . T h e r e
a r e two p r i n c i p a l r e a s o n s for this. F i r s t l y , the a r e a
of b o r n i t e b e i n g l e a c h e d i s not known; t h i s is c e r t a i n l y
t r u e f o r c r u s h e d o r e s , and the p r o b l e m a l s o e x i s t s
(to a l e s s e r extent) f o r p o l i s h e d o r e s p e c i m e n s . Secondly, the p r e s e n c e of o t h er m i n e r a l s in the or e a l ways i n t r o d u c e s the p o s s i b i l i t y that i m p u r i t i e s might
s t r o n g l y influence the d i s s o l u t i o n p r o c e s s . In this
work, pure b o r n i t e was s y n t h e s i z e d and then l e a c h e d
under c o n t r o l l e d conditions to e l u c i d a t e the p r i m a r y
v a r i a b l e s that g o v e r n b o r n i t e d i s s o l u t i o n .

EXPERIMENTAL
The bornite was prepared by reaction-sintering
pellets of CuS, FeS, and Cu2S (CusFeS4 = CuS EeS
2Cu2S) in vacuum-sealed
Pyrex ampoules.
The synthesis of CuS and FeS was described elsewhere.S The
Cu2S was formed by reacting stoichiometric amounts
of hydrogen-reduced
electrolytic copper sheet (99.90
pct Cu) with purified sulfur 8,9 in a vacuum-sealed
tube.
The heating was done in a twin furnace: one end was
heated to 800~
while the other was maintained at
450~
When all the sulfur was consumed, the reaction product was transferred to a silica ampoule,
sealed under vacuum, and then homogenized
for 1
week at 800~
X - r a y d i f f r a c t i o n a n a l y s i s showed the
m a t e r i a l to be Cu2S.
The t h r e e s i m p l e s u l f i d e s w e r e ground to m i n u s
150 m e s h , weighed, m i x e d thoroughly, and then p r e s s e d
into p e l l e t s at 80,000 psi. The p e l l e t s w e r e v a c u u m s e a l e d in P y r e x a m p o u l e s , and s i n t e r e d for 3 days at
550~ a f t e r an i n i t i al h eat i n g at 450~ f o r a few h o u r s .
The p e l l e t s w e r e c r u s h e d to m i n u s 150 m e s h and then
r e p e l l e t i z e d at 80,000 psi. T h e s e p e l l e t s w e r e then
s i n t e r e d in v a c u u m - s e a l e d tubes at 825~ for 1 hr and
c o o l e d to r o o m t e m p e r a t u r e . It was n e c e s s a r y to s i n t e r the p e l l e t s on ground s i l i c a f l at s to p r e v e n t w a r p ing at high t e m p e r a t u r e s . The cooled p e l l e t s w e r e
VOLUME 1, JANUARY 1970-225

p o l i s h e d through 3/0 e m e r y p a p e r , r i n s e d in a c e t o n e ,
and then s t o r e d for future use.
The final d i s k s w e r e about 2 m m thick and 26 m m in
diam; the p o l i s h e d s u r f a c e a r e a was 5.2 cm z. The
p e l l e t s w e r e about 90 pct of the t h e o r e t i c a l b o r n i t e
d e n s i t y ; l o n g e r s i n t e r i n g t i m e s r e s u l t e d in e x c e s s i v e
c r y s t a l growth and this a c t u a l l y d e c r e a s e d the app a r e n t d e n s i t y of the pellet. On a f r e s h f r a c t u r e , the
p e l l e t s had the c h a r a c t e r i s t i c r e d d i s h c o l o r a s s o c i a t e d with b o r n i t e ; the s u r f a c e g r a d u a l l y t u r n e d blue on
standing in a i r . X - r a y d i f f r a c t i o n a n a l y s i s c o n f i r m e d
that the m a t e r i a l was t e t r a g o n a l b o r n i t e . M i c r o s c o p i c
e x a m i n a t i o n of p o l i s h e d s e c t i o n s of b o r n i t e i n d i c a t e d
a b l u e - g r e y m a t r i x containing s m a l l white oolites.
The white phase c o n s t i t u t e d l e s s than 1 pct of the v o l ume of the sulfide. E l e c t r o n m i c r o p r o b e a n a l y s i s indicated that both the m a t r i x and the o o l i t e s w e r e of a
s i m i l a r c o m p o s i t i o n that c o r r e s p o n d e d to b o r n i t e . App a r e n t l y the white phase is a r e t a i n e d h i g h - t e m p e r a t u r e p o l y m o r p h of b o r n i t e ~~ which is m e t a s t a b l e at
low t e m p e r a t u r e s . It was felt that the p r e s e n c e of
the p o l y m o r p h would not s e r i o u s l y i n t e r f e r e with the
dissolution reactions.
The p o l i s h e d b o r n i t e d i s k s w e r e c e m e n t e d to lucite
rods in such a way that only the p o l i s h e d face was e x posed to the l e a c h i n g solution, and the disks w e r e
then l e a c h e d by an e s t a b l i s h e d method. ~b~2 T h i s m e t h o d
c o n s i s t s of r o t a t i n g the disk at a given s p e e d in an
a c i d i f i e d f e r r i c sulfate solution and p e r i o d i c a l l y
s a m p l i n g and a n a l y z i n g for the amount of d i s s o l v e d
c o p p e r with a T e c h n i c o n Auto A n a l y z e r . Any solution
r e m o v e d f r o m the v e s s e l by s a m p l i n g or by e v a p o r a tion was r e p l a c e d by a r e t u r n f e e d of b a r r e n solution
or distilled water respectively.
RESULTS AND DISCUSSION
The c h e m i c a l r e a c t i o n s by which b o r n i t e d i s s o l v e s
have not been fully r e s o l v e d . Sullivan 5 s u g g e s t e d that
b o r n i t e d i s s o l v e d a c c o r d i n g to the r e a c t i o n :
CusFeS4 + 6Fe2(SO4)3 ~-5CuSO4 + 13FeSO4 + 4S

[1]

I
PERCENT
COPPER

~ll#

64

~.~,;~:~:
:

.-,.

,,, ,~-'~
. ,,:,,,,~,,r

....

48
44

BORNITE [NON S T O I C H I O M E T R I C
BORNITE

I"

,.7

"I

UNLEACHED
LEACHED
SURFACE
SURFACE
Fig. 1--Photomicrograph showing the copper analysis across
a pellet that was partly leached at 20~ in 0.1 M Fe +3 and
o.1 M H2SO4.
226-VOLUME 1, JANUARY 1970

Kopylov and O r l o v 7 found, h o w e v e r , that c h a l c o p y r i t e

was f o r m e d as an i n t e r m e d i a t e :
CusFeS4 + 4Fe2(SO4)3 ~- CuFeS2 + 4CUSO4
+ 8FeSO4 + 2S
CuFeS2 + 2Fe2(SO4)3 ~-CuSO4 + 5FeSO4 + 2S

[2]
[3]

In v i e w of t h i s u n c e r t a i n t y , the f i r s t step in this study

was to identify the d i s s o l u t i o n r e a c t i o n s . They w e r e
found to be m o r e c o m p l e x than e i t h e r of the p r e v i o u s
a u t h o r s had indicated.
When a p e l l e t of b o r n i t e was p a r t i a l l y l e a c h e d at
t e m p e r a t u r e s above 40~ and then b r o k e n in half,
t h e r e w e r e t h r e e d i s t i n c t v i s i b l e l a y e r s . A d j a c e n t to
the r e s i d u a l u n r e a c t e d b o r n i t e , t h e r e w e r e bands of
blue and y e l l o w s u b s t a n c e s . X - r a y d i f f r a c t i o n showed
the y e l l o w l a y e r ( r e m o t e f r o m the b o r n i t e but a d j a c e n t
to the solution) to be a m i x t u r e of c h a l c o p y r i t e and
sulfur. The blue m a t e r i a l gave an X - r a y p a t t e r n s i m i l a r to that of b o r n i t e but with s l i g h t l y d i f f e r e n t c e l l
s p a c i n g s . T h i s m a t e r i a l was d e s i g n a t e d a s " n o n s t o i c h i o m e t r i c b o r n i t e " . It was found that the unit
c e l l size of the n o n s t o i c h i o m e t r i c b o r n i t e g r a d u a l l y
d e c r e a s e d with i n c r e a s i n g d i s t a n c e f r o m the n o r m a l
b o r n i t e t o w a r d the c h a l c o p y r i t e l a y e r . T h i s s u g g e s t s
a g r a d u a l withdrawal of m a t e r i a l f r o m the b o r n i t e
with a r e s u l t i n g slight c o n t r a c t i o n of the unit c e l l .
When the p e l l e t s w e r e l e a c h e d for l o n g e r p e r i o d s , e.g.,
19 hr at 70~ the c h a l c o p y r i t e - p l u s - s u l f u r l a y e r
was c o v e r e d by an additional l a y e r of s u l f u r that
a r o s e f r o m the d e c o m p o s i t i o n of the CuFeS2. The nons t o i c h i o m e t r i c b o r n i t e was s t i l l p r e s e n t b e t w e e n the
c h a l c o p y r i t e and b o r n i t e when the s u l f u r l a y e r f o r m e d .
At t e m p e r a t u r e s below 40~ it was p o s s i b l e to c o n v e r t the e n t i r e p e l l e t to n o n s t o i c h i o m e t r i c b o r n i t e
without the a p p e a r a n c e of any additional p h a s e s . Once
the p e l l e t had been c o n v e r t e d to n o n s t o i c h i o m e t r i c
b o r n i t e , the d i s s o l u t i o n of c o p p e r v i r t u a l l y stopped;
one p e l l e t was l e a c h e d for an additional 15 days at
15~ without the d i s s o l u t i o n of any additional c o p p e r .
E l e c t r o n m i c r o p r o b e a n a l y s e s for c o p p e r , i r o n , and
s u l f u r have b e e n m a d e a c r o s s p e l l e t s l e a c h e d at both
70 ~ and 20~
In both i n s t a n c e s the r e s u l t s i n d i c a t e d
that the S / F e r a t i o r e m a i n e d fixed at 4.0 + 0.2 a c r o s s
both the b o r n i t e and the n o n s t o i c h i o m e t r i c b o r n i t e r e gions. The r e s u l t s a l s o i n d i c a t e d that the c o p p e r c o n c e n t r a t i o n , and a l s o the C u / S and C u / F e r a t i o s ,
d r o p p e d s t e a d i l y a c r o s s both the b o r n i t e and the nons t o i c h i o m e t r i c b o r n i t e l a y e r s . T h i s is shown in Fig.
1 for a s a m p l e d i s s o l v e d for 24 hr at 20~ in 0.1 M
Fe +3. T h e s e r e s u l t s i n d i c a t e that l a r g e a m o u n t s of
c o p p e r can be d i s s o l v e d f r o m both b o r n i t e and nons t o i c h i o m e t r i c b o r n i t e without e f f e c t i n g m a r k e d s t r u c t u r a l changes. The r e g i o n on the left side of the phot o m i c r o g r a p h was shown by X - r a y a n a l y s i s to be
b o r n i t e , but this m a t e r i a l contained a p p r o x i m a t e l y 4
pct l e s s c o p p e r than the m i n e r a l f o r m u l a would indicate. The c o m p o s i t i o n of the o r i g i n a l b o r n i t e was
c o n f i r m e d by m i c r o p r o b e a n a l y s i s . The t r a n s i t i o n
f r o m b o r n i t e to n o n s t o i c h i o m e t r i c b o r n i t e is c o n t i n uous as shown by the a n a l y s i s in Fig. 1, but the dividing line is v i s i b l y s h a r p . The t r a n s i t i o n is m a r k e d
by a s e p a r a t i o n of the p h a s e s , the roughly v e r t i c a l
line in the p e l l e t , and by a d i f f e r e n c e in c o l o r , b o r n i t e
is r e d d i s h and the n o n s t o i c h i o m e t r i c b o r n i t e is d a r k
METALLURGICALTRANSACTIONS

b l u e . T h i s t r a n s i t i o n o c c u r s at about 58 pct Cu,

Cu4.sFeS4.
The r e s u l t s suggest that at t e m p e r a t u r e s above
40~ the sequence of r e a c t i o n s is:

c r e a s e d ; this p r o b a b l y c o r r e s p o n d s to complete b l o c k ing of the pellet s u r f a c e with the s u l f u r - c h a l c o p y r i t e

r e a c t i o n product, which i s known to d i s s o l v e slowly, a
160

CusFeS4 + xFe2(SO4)3 ~-Cus_xFeS4 + xCuSO4

+ 2xFeSO4

200 RPM
[4]

Cus_xFeS4 + (4 - x)Fe2(SO4)a ~-CuFeS2 + (4 - x)CuSO4

0'1M

140

+ (8 - 2x)FeSO4 + 2S

[5]
The c h a l c o p y r i t e has been shown 3 to decompose
slowly a c c o r d i n g to the following r e a c t i o n :
CuFeS2 + 2Fe2(SO4)a ~-~CuSO4 + 5FeSO4 + 2S

[6]

R e a c t i o n s [4] and [5] a r e v e r y much f a s t e r than [6]

and hence the l a y e r of s u l f u r was o b s e r v e d only in
t e s t s made for r e l a t i v e l y long p e r i o d s . The value of
x in Eq. [4] may be a s large as 1.2. At t e m p e r a t u r e s
below 25~ the only r e a c t i o n o b s e r v e d was:

94~

120

H2SO4

Fe

90~

80~

70~

I00
DISSOLVED CU
(MG/CM 2)
80

m"
60

Cu~FeS4 + xFe2(SO4)3 ~-Cus_xFeS~ + xCuSO4

+ 2xFeSO4

[7]

In the t e s t s at low t e m p e r a t u r e s , at which the e n t i r e pellet was c o n v e r t e d to n o n s t o i c h i o m e t r i c b o r n i t e ,

it was possible (from the a m o u n t of copper dissolved)
to e s t i m a t e the value of x in Eq. [7]. Values of x a s
l a r g e a s 1.2 were obtained by this method, in a g r e e m e n t with the v a l u e s of x found by the m i c r o p r o b e
a n a l y s i s . This m e a n s that the compound which f o r m s
m a y lose about 25 pct of the copper p r e s e n t without
d r a s t i c a l l y changing its s t r u c t u r e . Negligible a m o u n t s
of i r o n and s u l f u r were attacked d u r i n g the f o r m a t i o n
of the n o n s t o i c h i o m e t r i c b o r n i t e .
Reactions [4] and [7] p r e c l u d e s u l f u r f o r m a t i o n d u r ing these r e a c t i o n p e r i o d s . At 15~ where Reaction
[7] o c c u r s a h n o s t e x c l u s i v e l y , only 4 m g of s u l f u r was
f o r m e d d u r i n g the leaching of 330 mg of copper in 20
hr; only 17 mg of sulfur was f o r m e d when 674 m g of
copper was dissolved. T h e s e r e a c t i o n s a l s o r e q u i r e a
Fe
r a t i o of 2.0. At t e m p e r a t u r e s below 25~
where Reaction [7] p r e d o m i n a t e s , the o b s e r v e d
Fe e / C u ration was 2.04 0.07. T h e s e o b s e r v a t i o n s
s u g g e s t that Reactions [4] and [7] account for the d i s solution of b o r n i t e to form n o n s t o i c h i o m e t r i c b o r n i t e .
At higher t e m p e r a t u r e s the n o n s t o i c h i o m e t r i c b o r n i t e
is attacked a c c o r d i n g to Reaction [5]. T h i s r e a c t i o n
r e q u i r e s that s u l f u r be produced in g r e a t e r q u a n t i t i e s ,
and this was the c a s e , although the a m o u n t s of s u l f u r
did not c o r r e s p o n d to those p r e d i c t e d by Eq. [5]. This
d i s c r e p a n c y i s c a u s e d by both the f o r m a t i o n of s u l f u r rich c h a l c o p y r i t e and the oxidation of some s u l f u r to
sulfate, which was not detected a g a i n s t the high b a c k ground of sulfate ion. Reaction [5] p r e d i c t s a Fe+2/Cu
ratio of 2.0, but o u r v a l u e s were g e n e r a l l y h i g h e r ,
u s u a l l y about 2.2. If some of the c h a l c o p y r i t e d i s s o l v e d ,
Eq. [6] i n d i c a t e s that the o v e r - a l l r a t i o would be
g r e a t e r than 2.0.
Fig. 2 shows the type of c u r v e that was obtained
when synthetic b o r n i t e was leached at t e m p e r a t u r e s
above 40~
The d i s s o l u t i o n k i n e t i c s a r e l i n e a r ; the
l i n e a r rate c o n s t a n t for each c u r v e was d e t e r m i n e d
by l i n e a r r e g r e s s i o n . When m o r e than 50 pct of the
copper had b e e n d i s s o l v e d , the rate of d i s s o l u t i o n deMETALLURGICALTRANSACTIONS

4O

2O

I0

12

TIME (HOURS)
Fig. 2--The dissolution of copper from synthetic bornite at
various temperatures.
1.8

LOG k = 4 . 4 4 9 - 1 , 1 6 4 / T
AH 1' -- 5'3 +- 0.8 KCAL/MOLE

1.6

1.4

i-o
LO(

8
k

( MG/CM 2. HR)
0.8

"

0"6

0.4

I
2.7

i
2.8

i
2.9

103/T

z
3.0

j
3-1

3.2

(K")

Fig. 3--Arrhenius plot for the dissolution of copper from synthetic bornite at temperatures above 40~
VOLUME l, JANUARY 1970-227

To obtain an e s t i m a t e of the a c t i v a t i o n enthalpy f o r

the r a t e - c o n t r o l l i n g p r o c e s s , the l i n e a r r a t e c o n s t a n t s
obtained f r o m r e a c t i o n c u r v e s such as those in Fig.
2, w e r e d i s p l a y e d on an A r r h e n i u s plot a s shown in
Fig. 3. Al l of the data u s e d in this plot w e r e obtained
in the t e m p e r a t u r e r a n g e 40 ~ to 94~ in which l i n e a r
k i n e t i c s w e r e o b s e r v e d . The l e a s t - s q u a r e s fit of the
data y i e l d e d the equation:
log h ( m g / c m 2 . h r ) = 4.449 - 1164/T

[8]

T h i s equation gave an a c t i v a t i o n enthalpy of 5.3 + 0.8

kcal p e r m o l e . T h i s v a l u e is in a g r e e m e n t with the
a v e r a g e a c t i v a t i o n e n e r g y of 5.2 + 1.4 kcal p e r m o l e
obtained by Kopylov and O r l o v 7 f o r n a t u r a l o r e s
l e a c h e d under s i m i l a r conditions in the t e m p e r a t u r e
r a n g e 40 ~ to 70~
The o b s e r v e d l i n e a r k i n e t i c s and low a c t i v a t i o n en thalpy s u g g es t that the d i s s o l u t i o n r a t e is c o n t r o l l e d
by diffusion through the liquid boundary l a y e r ; a conc l u s i o n r e a c h e d by Kopylov and O r l o v 7 f o r n a t u r a l
o r e s . If the rate w e r e c o n t r o l l e d by m a s s t r a n s f e r ,
then it would depend on the t h i c k n e s s of the liquid
b o u n d a r y l a y e r a d j a c e n t to the disk. L e v i c h ~3 showed
that the t h i c k n e s s of t h i s l a y e r v a r i e s i n v e r s e l y as the
s q u a r e root of the r o t a t i o n speed; h e n c e , the r a t e of a
p r o c e s s c o n t r o l l e d by liquid b o u n d a r y diffusion should
v a r y d i r e c t l y with the s q u a r e r o o t of the r o t a t i o n speed.
F i g . 4 shows the e f f e c t of the s q u a r e root of the r o t a tion s p e e d on the l i n e a r r a t e c o n s t a n t f o r synthetic
b o r n i t e d i s k s , l e a c h e d at 70~
It i n d i c a t e s a r a t e inc r e a s e with i n c r e a s i n g disk r o t a t i o n s p e e d that sugg e s t s that the r a t e of b o r n i t e l e a c h i n g is c o n t r o l l e d by
diffusion through the liquid b o u n d a r y l a y e r . In an
i d e a l i z e d solution the r a t e should be z e r o when the
disk is s t a t i o n a r y , but in p r a c t i c e this d o e s not o cc ur b e c a u s e of n a t u r a l c o n v e c t i o n . In our s y s t e m ,
t h e r m a l c o n v e c t i o n is p r o n o u n c e d b e c a u s e the s o l u tion tends to be h e a t e d at the bottom and c o o l e d at
the top.
The o b s e r v e d l i n e a r k i n e t i c s , low a c t i v a t i o n e n thalpy and r o t a t i o n a l s p e e d dependence a ll indicate
that the r a t e - c o n t r o l l i n g step in b o r n i t e d i s s o l u t i o n
at t e m p e r a t u r e s above 40~ is m a s s t r a n s f e r a c r o s s
the stagnant b o u n d a r y l a y e r a d j a c e n t to the disk. In
an e f f o r t to d i s c o v e r which diffusing s p e c i e s c o n t r o l s
the r e a c t i o n r a t e , the r a t e was m e a s u r e d in a s e r i e s

of e x p e r i m e n t s done with v a r i o u s f e r r i c ion c o n c e n t r a t i o n s . The r e s u l t s a r e shown in F i g . 5. T h i s figure shows that the r a t e depends d i r e c t l y on the f e r r i c
ion c o n c e n t r a t i o n for f e r r i c ion s t r e n g t h s l e s s than
about 0.06 M, but that it is i n s e n s i t i v e to h i g h e r f e r r i c c o n c e n t r a t i o n s . The d i s s o l u t i o n c u r v e s at all
f e r r i c c o n c e n t r a t i o n s w e r e l i n e a r . If we a s s u m e that
the c o n c e n t r a t i o n of f e r r i c sulfate which e x i s t s at the
b o r n i t e / s o l u t i o n i n t e r f a c e is e s s e n t i a l l y z e r o , i.e.,
the s u r f a c e r e a c t i o n is r a p i d , then the f e r r i c sulfate
diffusion g r a d i e n t a c r o s s the liquid b o u n d a r y l a y e r is
n u m e r i c a l l y equal to the bulk c o n c e n t r a t i o n of f e r r i c
sulfate. If the diffusion of t h i s m a t e r i a l c o n t r o l s the
r e a c t i o n , then the r a t e would v a r y d i r e c t l y with the
f e r r i c c o n c e n t r a t i o n . This type of d e p e n d e n c e is obs e r v e d at f e r r i c s t r e n g t h s b e l o w 0.06 M. T h i s sugg e s t s that the diffusion of f e r r i c su l f at e through the
liquid boundary l a y e r c o n t r o l s the r e a c t i o n at low
f e r r i c s t r e n g t h s , w h e r e a s the o u t w a r d diffusion of
one of the r e a c t i o n p r o d u c t s c o n t r o l s the r a t e at h i g h e r
ferric strengths.
In the r e g i o n s w h e r e f e r r i c sulfate diffusion is not
r a t e - c o n t r o l l i n g , the o u t w ar d diffusion of e i t h e r
c u p r i c or f e r r o u s s u l f a t e s through the b o u n d a r y l a y e r
m u s t c o n t r o l the r e a c t i o n . If the r a t e w e r e c o n t r o l l e d
by the outward diffusion of FeSO4, then:
Rate = k [ ( a F e s o 4 )sulfide/solution interface
- (afeso,)bulk solution]

[9]

When it is a s s u m e d that the c o n c e n t r a t i o n of FeSOa at

the s u l f i d e / s o l u t i o n s u r f a c e a p p r o a c h e s that of a
s a t u r a t e d solution, Eq. [9] b e c o m e s :
Rate = k [ (aFesO 4 )saturated -- (a FeSO4 )bulk]

[ 10]

F o r the d i f f e r e n c e in a c t i v i t i e s in Eq. [10] to v a r y

s i g n i f i c a n t l y , the bulk c o n c e n t r a t i o n of FeSO4 m u s t
v a r y o v e r wide l i m i t s . B e c a u s e c o n c e n t r a t e d FeSO4
so l u t i o n s could not be run in the A u t o A n a l y z e r , pipette
s a m p l e s w e r e taken a t r e g u l a r i n t e r v a l s and the c o p p e r c o n c e n t r a t i o n was d e t e r m i n e d by a t o m i c a b s o r p tion. The r e s u l t s f r o m t h e s e t e s t s at 70~ and 200
r p m rotation s p e e d a r e shown in F i g . 6. The s ol i d
points show the effect of i n i t i a l FeSOa c o n c e n t r a t i o n on
30

28

TEMR = 700C

lO

0.1M Fe"5,0-1M H2SO4

2O

RATE CONSTANT

"

(MGICMZ'HR)

RATE CONSTANT
(MG/CM2 HR)

9/"
o f

3
o

12

TEMP.= 70~
200 RPM
0.1 M H2SO4

/ ~

8
4

0.~

I0

12

14

16

18

20

22

.%/ROTATION SPEED (RPM)

Fig. 4--Effect of stirring on the rate of synthetic bornite dissolution.

228-VOLUME 1,JANUARY 1970

0"001

0.01

0"1

I'O

MOLAR CONCENTRATION OF Fe.3

Fig. 5--Effect of ferric ion concentration on the rate of synthetic bornite dissolution.
METALLURGICALTRANSACTIONS

the r a t e of c o p p e r d is s o lu ti o n at a low f e r r i c s t r e n g t h
(0.005 M Fe +3) wh e r e f e r r i c sulfate diffusion is thought
to be r a t e - c o n t r o l l i n g . As e x p e c t e d , the addition of
FeSO4 has v e r y little e f f e c t on the d i s s o l u t i o n r a t e ;
t h i s is c o n s i s t e n t with r a t e c o n t r o l by f e r r i c sulfate
diffusion at the low f e r r i c s t r e n g t h s , s e e above. The
slight e f f e c t of FeSO4 on the d i s s o l u t i o n c a n be t r a c e d
e i t h e r to an i n d i r e c t effect on the a c t i v i t y of f e r r i c
sulfate or to changes in c e r t a i n solution p a r a m e t e r s
such as v i s c o s i t y or diffusivity. T h e s e p a r a m e t e r s
a f f e c t the t h i c k n e s s of the liquid boundary l a y e r which
a f f e c t s the r a t e .
The open points c o r r e s p o n d to the data at 0.1 M Fe+3;
i.e., in a r e g i o n w h e r e f e r r i c sulfate diffusion is not
r a t e - c o n t r o l l i n g . T h i s c u r v e shows that the b o r n i t e
d i s s o l u t i o n r a t e is a function of the d i f f e r e n c e in f e r r o u s sulfate a c t i v i t y a c r o s s the liquid b o u n d a r y l a y e r .
T h i s dependence s u g g e s t s that the r a t e - c o n t r o l l i n g step
at f e r r i c c o n c e n t r a t i o n s g r e a t e r than about 0.06 M inv o l v e s the outward diffusion of f e r r o u s sulfate through
the stagnant boundary l a y e r , Eq. [10]. The d e p a r t u r e
f r o m l i n e a r i t y in Fig. 6 can be a t t r i b u t e d to d e v i a t i o n s
f r o m i d e a l i t y of the a c t i v i t y of f e r r o u s sulfate so l u t i o n s
at t h e s e high c o n c e n t r a t i o n l e v e l s .
The p r o p o s e d l e a c h i n g r e a c t i o n s do not involve a c i d
d i r e c t l y ; the d i s s o l u t i o n r a t e should be r e l a t i v e l y ins e n s i t i v e to a c i d c o n c e n t r a t i o n . Fig. 7 shows the e f f e c t
of s u l f u r i c acid c o n c e n t r a t i o n on the r a t e of b o r n i t e
d i s s o l u t i o n . The r e s u l t s indicate that a thousandfold
i n c r e a s e in the a c i d c o n c e n t r a t i o n i n c r e a s e d the d i s solution r a t e by only 40 pct. The rate i n c r e a s e could
be c a u s e d by ch an g e s in the liquid b o u n d a r y l a y e r a s

4,

IO0

TEMR= 70~
200 RPM

0-1M Fe

____z------OI0
RATE CONSTANT
(MG/CM2.HR)

0"001

0-01

0"I

I'0

MOLAR CONCENTRATION OF H2SO4

Fig. 7--Effect of H2SO4 concentration on the bornite dissolution rate.

TEMP = 7 0 ~
12

a r e s u l t of c h a n g e s in solution v i s c o s i t y or d e n s i t y . It
was d e t e r m i n e d , in s e p a r a t e t e s t s at a v a r i e t y of t e m p e r a t u r e s , that a c i d alone (0.1 M H2SO4) did not a t t a c k
sy n t h et i c b o r n i t e ; this o b s e r v a t i o n i s not in a c c o r d
with the work of Sullivan 5 on n a t u r a l b o r n i t e .
The data in Fig. 7 s u g g e s t that a c i d s t r e n g t h is not
an i m p o r t a n t v a r i a b l e in h e a p - l e a c h i n g p r a c t i c e . It
should be r e m e m b e r e d , h o w e v e r , that c o m m e r c i a l
l e a c h i n g r e l i e s on the a i r - a c i d a t t a c k of v a r i o u s i r o n
m i n e r a l s for the g e n e r a t i o n of f e r r i c sulfate. F o r
this r e a s o n it may be n e c e s s a r y to add f a i r l y s t r o n g
a c i d to the heap to produce enough f e r r i c sulfate f o r
o p t i m i z e d l each i n g . If the l e a c h i n g solution c o n t a i n s
adequate i r o n , then only enough a c i d m u s t be added to
keep the i r o n s a l t s in solution.
As the l e a c h i n g t e m p e r a t u r e was d e c r e a s e d b e l o w

O.IM

Fe

0.005

M Fe" 3

70

I0

200 RPM
0-1M Fe
H2SO4

60

50

40
DISSOLVED CU

o
RATE

o
CONSTANT

(MGZ/CM 4) x 10 -2

30

35~ /
o
//

oO/

///
//

//30~
/

o///"

-/

20~.
/

( M G / C M 2. HR)

,oy

9"

20

40

60

80

FeSO 4

4-

12

16

20

24

SATURATION

Fig. 6--Effect of initial ferrous sulfate concentration on the

leaching rate of synthetic bornite in 0.1 M Fe +3 and 0.1 M
H2SO4 solutions.
METALLURGICALTRANSACTIONS

5.c

I00
0

PERCENTAGE

TIME (HOURS)

Fig. 8--The parabolic dissolution kinetics for bornite at

temperatures below 40~
VOLUME 1, JANUARY t970-229

40~ the d i s s o l u t i o n c u r v e s b e c a m e p r o g r e s s i v e l y
m o r e p a r a b o l i c as shown in Fig. 8. A s t r a i g h t - l i n e
r e l a t i o n s h i p on these axes i n d i c a t e s p a r a b o l i c k i n e t i c s . When the t e m p e r a t u r e is d e c r e a s e d to 20~ the
c u r v e s i n d i c a t e p a r a b o l i c k i n e t i c s for long p e r i o d s .
Even at the lower t e m p e r a t u r e s , however, the c u r v e s
tend to deviate slightly f r o m the p a r a b o l i c rate. As
the t e m p e r a t u r e was l o w e r e d , the time period for
p a r a b o l i c control i n c r e a s e d .
The t r a n s i t i o n from l i n e a r to p a r a b o l i c k i n e t i c s i n d i c a t e s a change in the r a t e - c o n t r o l l i n g r e a c t i o n m e c h a n i s m . P a r a b o l i c k i n e t i c s like those shown in Fig. 8
i n d i c a t e rate c o n t r o l by diffusion through a c o n s t a n t l y
thickening l a y e r which i m p e d e s the diffusion of some
s p e c i e s . F r o m Eq. [7] it can be seen that copper is
s e l e c t i v e l y r e m o v e d from the b o r n i t e , an action which
f o r m s a " s c a l e " of n o n s t o i c h i o m e t r i c b o r n i t e on the
s u r f a c e , Fig. 1. The rate could be c o n t r o l l e d by diffusion of the " s o l u t i o n " through the c o n s t a n t l y t h i c k e n ing l a y e r of n o n s t o i c h i o m e t r i c b o r n i t e (via p o r e s or
c r a c k s ) or by the diffusion of copper ions outward
through the n o n s t o i c h i o m e t r i c b o r n i t e . E x a m i n a t i o n of
Fig. 1 shows that the n o n s t o i c h i o m e t r i c b o r n i t e l a y e r
is porous and b a d l y c r a c k e d ; it a l s o i n d i c a t e s a f a i r l y
s h a r p r e a c t i o n front b e t w e e n the n o n s t o i c h i o m e t r i c
b o r n i t e and the b o r n i t e . T h e s e o b s e r v a t i o n s s u g g e s t
that the diffusion of " s o l u t i o n " is r a t e - c o n t r o l l i n g .
To obtain additional i n f o r m a t i o n about this r e a c t i o n ,
the p a r a b o l i c rate c o n s t a n t s were d e t e r m i n e d from
the p a r t s of the c u r v e s , Fig. 8, that obeyed p a r a b o l i c
k i n e t i c s . T h e s e a r e shown on an A r r h e n i u s plot in
Fig. 9, for data obtained between 5~ and 35~
The
b e s t fit to the data y i e l d e d the equation:
log k(mg2/cm 4 . h r ) = 6 . 8 0 7 - 1354/T

[11]

+ 1.3 kcal per mole. T h i s value is v e r y s i m i l a r to

that obtained at higher t e m p e r a t u r e s and s u p p o r t s the
c o n c l u s i o n that the rate is c o n t r o l l e d by diffusion in
the liquid. The liquid path length i n c r e a s e s c o n s t a n t l y
as the t h i c k n e s s of the n o n s t o i c h i o m e t r i c b o r n i t e i n c r e a s e s , and this p r o d u c e s the p a r a b o l i c k i n e t i c s .
To d e t e r m i n e whether the diffusion of f e r r i c sulfate
or the diffusion of the r e a c t i o n p r o d u c t s c o n t r o l l e d
the r e a c t i o n rate at low t e m p e r a t u r e s , t e s t s were done
at different f e r r o u s sulfate c o n c e n t r a t i o n s but at 0.1 M
Fe .3 and 15~
It was found that the i n i t i a l f e r r o u s
sulfate c o n c e n t r a t i o n has little effect on the d i s s o l u tion rate. T h i s s u g g e s t s that the r a t e i s c o n t r o l l e d by
f e r r i c sulfate diffusion through the c o n s t a n t l y l e n g t h e n ing solution path in the porous n o n s t o i c h i o m e t r i c b o r n i t e .
IMPLICATIONS TO HEAP LEACHING
T h e r e i s no a s s u r a n c e that m i n e r a l b o r n i t e would
leach in the s a m e m a n n e r a s the synthetic m a t e r i a l s
used in this work. To r e l a t e our t e s t s to the n a t u r a l
sulfide, a h i g h - g r a d e b o r n i t e ore f r o m Butte, Mont.
was selected, cored, and sawn into " p e l l e t s " . Despite
the fact that this m a s s i v e b o r n i t e was " s p e c i m e n
g r a d e " , it s t i l l contained only about 70 pct b o r n i t e on
the polished face ( d e t e r m i n e d by p o i n t - c o u n t i n g
methods). The m a j o r i m p u r i t y was p y r i t e , with m i n o r
a m o u n t of Cu2S, CuFeS2, and CaCO3. T h e s e polished
d i s k s were leached at both 70 ~ and 15~ u n d e r c o n d i tions s i m i l a r to those used for synthetic b o r n i t e .
Duplicate r u n s were made at both t e m p e r a t u r e s , and
both s e t s of data were e s s e n t i a l l y i d e n t i c a l . The r e s u l t s for the n a t u r a l b o r n i t e were c o r r e c t e d to " u n i t
160

The a c t i v a t i o n enthalpy d e r i v e d from this was 6.2

3.0

140

NATURAL BORNITE

o SYNTHETIC BORNITE
70oc

120

LOG k = 6 . 8 0 7 - 1,354/T
AH ~'= 6.2 + 1'3 KCAL/MOLE

2.8

I00
DISSOLVED CU
(MG/CM z)

2.6

80
60

2"2

LOG4.kHR)
(MG2/CM
2.0

~ 1 7 6 ~
40
15~
20

1.8

1.6

3.1

3.2

3.3

3.4

3.5

3.6

3.7

I03/T (K-I)
Fig. 9--Arrhenius plot of the parabolic rate constant for the
dissolution of bornite at temperatures below 40~
230-VOLUME 1, JANUARY 1970

I0

12

TIME(HOURS)
Fig. 10--Comparison of the leaching rates of natural and
synthetic bornite.
METALLURGICALTRANSACTIONS

s u r f a c e a r e a " by m u l t i p l y i n g the pellet a r e a by 0.7,

and they are shown in Fig. 10, c l o s e d c i r c l e s , together
with the r e s u l t s for the synthetic sulfide, open c i r c l e s .
It is a p p a r e n t from Fig. 10 that the n a t u r a l b o r n i t e
d i s s o l v e s like the synthetic m a t e r i a l : at 70~ the d i s solution c u r v e for the m i n e r a l is l i n e a r , but at 15~
the k i n e t i c s a r e p a r a b o l i c . T h e r e i s also fair a g r e e m e n t in the absolute v a l u e s of the d i s s o l u t i o n r a t e s for
both n a t u r a l and synthetic sulfides. X - r a y diffraction
of the leached n a t u r a l b o r n i t e r e v e a l e d that the r e a c tion p r o d u c t s were i d e n t i c a l to those obtained on s y n thetic m a t e r i a l , i . e . , at 70~ n o n s t o i c h i o m e t r i c
b o r n i t e , c h a l c o p y r i t e , and s u l f u r ; while at 15~ only
nonstoichiometric bornite.
The a g r e e m e n t shown in Fig. 10 s u g g e s t s that the
r e s u l t s obtained for synthetic b o r n i t e in this study
could be applied to the h e a p - l e a c h i n g of n a t u r a l b o r n i t e
o r e s with c o n s i d e r a b l e confidence. The following obs e r v a t i o n s would then apply to the h e a p - l e a c h i n g of
bornite.
The type of f e r r i c ion c o n c e n t r a t i o n dependence
shown in Fig. 5 i m p o s e s a r e s t r a i n t on h e a p - l e a c h i n g
p r a c t i c e . The leaching rate could be i n c r e a s e d by i n c r e a s i n g the f e r r i c s t r e n g t h to only 0.06 M Fe +3. Because the c r i t i c a l f e r r i c c o n c e n t r a t i o n i s n e a r that
n o r m a l l y e n c o u n t e r e d in c o m m e r c i a l p r a c t i c e , 1 s m a l l
g a i n s in l e a c h i n g efficiency might be effected by inc r e a s i n g the f e r r i c c o n c e n t r a t i o n in the solution b e i n g
s p r a y e d on the heap.
The data in Fig. 7 suggest that acid s t r e n g t h is not
an i m p o r t a n t v a r i a b l e in h e a p - l e a c h i n g p r a c t i c e . It
should be r e m e m b e r e d , however, that c o m m e r c i a l
l e a c h i n g r e l i e s on the a i r - a c i d attack of v a r i o u s iron
m i n e r a l s for the g e n e r a t i o n of f e r r i c sulfate. F o r this
r e a s o n it m a y be n e c e s s a r y to add f a i r l y s t r o n g acid
to the heap to produce enough f e r r i c sulfate for optim i z e d leaching. If the leaching s o l u t i o n c o n t a i n s adequte i r o n , then only enough acid m u s t be added to keep
the i r o n s a l t s in solution.
The leaching rate e x p e r i m e n t s at low t e m p e r a t u r e s
r e v e a l e d s e v e r a l facts that m a y be i m p o r t a n t in c o m m e r c i a l h e a p - l e a c h i n g The k i n e t i c s a r e p a r a b o l i c ,
i . e . , the rate of copper d i s s o l u t i o n d e c r e a s e s steadily
with t i m e . Also, copper d i s s o l u t i o n v i r t u a l l y c e a s e s
when the b o r n i t e has been e n t i r e l y c o n v e r t e d to n o n s t o i c h i o m e t r i c b o r n i t e . F o r these r e a s o n s it is i m p o r t a n t that the h e a p - l e a c h i n g be done at t e m p e r a t u r e s
above 30~ and p r e f e r a b l y above 40~
T h i s advantageous p r a c t i c e could be a c h i e v e d by the use of
l a r g e heaps to r e t a i n the heat of r e a c t i o n .
CONCLUSIONS
1) The d i s s o l u t i o n of synthetic b o r n i t e (CusFeS4) in
acidified f e r r i c sulfate s o l u t i o n s in the t e m p e r a t u r e
range 40 ~ to 94~ obeys a l i n e a r rate law. This was
i n t e r p r e t e d as i n d i c a t i n g rate c o n t r o l by m a s s t r a n s -

METALLURGICALTRANSACTIONS

f e r through the liquid b o u n d a r y l a y e r a d j a c e n t to the

sulfide.
2) Over the t e m p e r a t u r e range 40 ~ to 94~ the l i n e a r
rate c o n s t a n t i s given by the equation: log k ( m g / c m 2. hr)
= 4.449 - 1164/T. This equation yields an a p p a r e n t a c t i v a t i o n enthalpy of 5.3 0.8 kcal per mole.
3) At 70~ the rate i s c o n t r o l l e d by the diffusion of
f e r r i c sulfate r e a c t a n t through the liquid boundary
l a y e r a s long a s the f e r r i c ion c o n c e n t r a t i o n is l e s s
than 0.06 M. At h i g h e r f e r r i c ion c o n c e n t r a t i o n s , the
outward diffusion of f e r r o u s sulfate c o n t r o l s the r e action.
4) In the t e m p e r a t u r e range 5~ to 35~ synthetic
b o r n i t e d i s s o l v e s , at l e a s t i n i t i a l l y , a c c o r d i n g to a
p a r a b o l i c law. This b e h a v i o r i s i n d i c a t i v e of a r e a c tion c o n t r o l l e d by diffusion of solute s p e c i e s through
the c o n s t a n t l y thickening l a y e r of solution t r a p p e d in
c r a c k s and p o r e s of the n o n s t o i c h i o m e t r i c b o r n i t e
l a y e r f o r m e d on the b o r n i t e .
5) O v e r the range 5~ to 35~ the p a r a b o l i c rate
c o n s t a n t is e x p r e s s e d by: log k(mg2/cm 4. hr) = 6.807
- 1354/T. T h i s equation yields an a p p a r e n t a c t i v a t i o n
enthalpy of 6.2 1.3 kcal p e r mole.
6) Acid alone does not attack b o r n i t e , n o r does the
acid take an active part in the d i s s o l u t i o n r e a c t i o n .
The p r e s e n c e of acid p r e v e n t s h y d r o l y s i s of the i r o n
salts.
7) At all t e m p e r a t u r e s , n a t u r a l b o r n i t e d i s s o l v e s in
a s i m i l a r m a n n e r and at a p p r o x i m a t e l y the s a m e rate
a s the synthetic b o r n i t e .
ACKNOWLEDGMENTS
The X - r a y diffraction a n a l y s e s for this p r o g r a m
were done by S. K a i m a n and P. B e l a n g e r . The e l e c t r o n
m i c r o p r o b e i n v e s t i g a t i o n s were made by P. E.
P o r t e o u s and D. C. H a r r i s .

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VOLUME 1, JANUARY 1970-231