The Kinetics of Leaching Galena with Ferric Nitrate

M . C . FUERSTENAU, C. O. NEBO, B. V. ELANGO, and K . N . HAN

The kinetics of leaching galena with ferric nitrate as oxidant has been studied. Experimental results
indicate that the rate of galena dissolution is controlled by surface chemical reaction. Rate is propor-
tional to the square root of the concentration of ferric ion. The addition of more than one mole/liter
sodium nitrate decreases reaction rate. With nitrate additions below this concentration, rate either
remains constant or is slightly enhanced. An activation energy of 47 kJ/mol was measured, and rate
is proportional to the inverse of the initial size of galena particles. These results are explained in terms
of mixed electrochemical control. The anodic reaction involves the oxidation of galena to lead ion and
elemental sulfur, and the cathodic reaction involves the reduction of ferric ion to ferrous ion.

I. INTRODUCTION II. EXPERIMENTAL

THErecovery of lead from galena v i a a hydrometallurgical
route has been studied by several investigators under various
chemical environments. 1-~7A hydrometallurgical alternative
has been sought because of the growing concern about the
adverse environmental impact of high-temperature process-
ing of galena.
Anderson e t al. ~ have observed complete dissolution of
finely-ground galena particles (325 • 400 mesh) in 1.2
hours at a reaction temperature of 150 ~ and an oxygen
pressure of 5.7 atm.
Seraphim and Samis ~ have demonstrated that galena can
be leached with oxygen at neutral pH by forming acetate
complexes and elemental sulfur at temperatures and oxygen
pressures in the vicinity of 120 ~ and 3 atm, respectively.
Awakura e t a l . H studied the kinetics of galena dissolution
in hydrochloric acid and in perchloric acid solutions. They
reported that the dissolution rates under such chemical envi-
ronments were controlled by chemical reactions on the sur-
face of galena.
Haver e t al. lo investigated the recovery of lead and sulfur
from galena using ferric sulfate as oxidant. The leach resi-
due was treated with an ammonium carbonate solution to
alter the lead to an acid soluble form and to produce am-
monium sulfate.
The leaching of galena in chloride bearing lixiviants has
been investigated by various researchers. 3'6'7'~2-J7 Ferric
chloride leaching in the presence of hydrochloric acid and
sodium chloride has proven to be a possible means of extrac-
ting lead v i a the hydrometallurgical route, since soluble
lead-bearing species and elemental sulfur are formed. Vari-
ous researchers have noted these important attributes of the
chloride-beating lixiviants containing ferric ion. Economics
appears to be a problem with this technique, however.
Lead nitrate does not exhibit the solubility problems that
contribute to the poor economics of the lead chloride sys-
tem. As such, ferric nitrate would seem to offer attractive
possibilities as an oxidant for galena. It was the objective of
this investigation to establish the kinetics of leaching galena
with this oxidant and develop a model for this system.
M.C. FUERSTENAU, Professor and Head, C.O. NEBO, Research
Assistant, B.V. ELANGO, former Research Assistant, and K.N. HAN,
Professor, are with the Department of Metallurgical Engineering, South
Dakota School of Mines and Technology, Rapid City, SD 57701.
Manuscript submitted June 2, 1986.
MATERIALS AND PROCEDURES
All of the galena samples used in this study were obtained
from the Galena Mine, Kansas. The lead and sulfur contents
were 85.6 pct and 13.0 pct, respectively. X-ray diffraction
analysis of the galena sample and leached solid product
showed that the galena d-spacings are almost identical
to those of the ASTM values and also that the solid prod-
uct after leaching is pure elemental sulfur. Only reagent-
grade materials and distilled water were used in preparation
of the lixiviants.
Galena leaching was conducted in a covered two-liter
glass reaction vessel. Openings were incorporated in the
cover for admission of a stirring rod, a thermometer, a gas
dispersion tube, and a sampling device. The sampling de-
vice contained a glass tube through which nitrogen gas was
admitted to the solution.
Dissolution experiments were initiated by placing an
evacuated capsule containing one gram of galena in the
reaction vessel. One liter of lixiviant was then added to the
vessel which was covered and placed in a constant tem-
perature bath. When the solution attained the desired tem-
perature, high purity nitrogen gas was passed through
the lixiviant for 60 minutes at the rate of 0.5 l/min to
purge dissolved oxygen and to preclude air from entering
the system.
The reaction was initiated by breaking a galena-bearing
capsule with a stirrer. A 10-ml sample of solution was with-
drawn at predetermined intervals and filtered, and the lead
concentration in the sample was established by atomic ab-
sorption spectrophotometry.
III. EXPERIMENTAL RESULTS
Rate of dissolution of galena was examined first as a
function of particle size. As shown in Figure 1, fractional
conversion of galena increases substantially with decrease in
particle size or increase in surface area. For example, after
two hours of leaching, approximately 50 pct of the 14 • 28
mesh particles are dissolved, while complete dissolution of
48 • 65 mesh particles is effected.
The dependence of rate on ferric ion concentration was
also established. In order to maintain ionic strength of the
solution constant, 2 M N a N O 3 w a s added in each experi-
ment, and the ferric ion concentration was held at low value.

METALLURGICALTRANSACTIONS B VOLUME 18B, MARCH 1987--25

 I.O 1.0
Size ( m e s h ) f / . , . . - O ~" NaNO 3 (M)
0.8 0.8
o 35,48 ~ ~ _9-"
o,o
g
0.6 "2 0.6
.=
O

0.4 ~ 0.4

0.2 0.2

0 0 I I I I I I
20 40 60 80 I00 120 140 0 20 40 60 80 I00 120 IZlO
Time (rain) Time (min)
Fig. 1- - T h e effect of particle size on fractional conversion with 0.25 M Fig. 3 - - T h e effect of NaNO, addition on fractional conversion with
Fe(NO~)3 at 50.5 ~ pH !.2 to 1.4, and 100 rpm. 0.25 M Fe(NO~)3 at 50.5 ~ pH 1.2 to 1.4, 28 x 35 mesh, and 100 rpm.

The rate data obtained are shown in Figure 2. It can be noted

that rate increases with increased Fe § concentration. 1,0

The effect of sodium nitrate on the rate of galena dis- Temperoture(*C)

solution was then studied. The results are shown in Fig- ix 18 ~ - -

ure 3. Dissolution rate was observed to decrease when more O 32.5 / "
%
than 0.5 M NaNO3 is added.
The next area of investigation involved establishing the
effect of temperature on the rate of galena dissolution. As E
shown in Figure 4, after two hours of leaching in the pres-
ence of 0.25 M Fe(NO3)3 at pH 1.2 to 1.4, about 40 pet of 0.4 ~
the galena is leached at 32.5 ~ while complete dissolution
is effected at 70 ~ tt.

0.2 A A

IV. DISCUSSION OF RESULTS

0
A shrinking core model for cubic systems has been devel- 20 40 60 80 I00 120 140
oped in an earlier investigation, 17 and three integrated rate Time (min)
equations for film diffusion, product layer diffusion, and Fig. 4 - - T h e effect of temperature on fractional conversion with 0.25 M
chemical reaction control are given as below: Fe(NO0~, pH 1.2 to 1.4, 28 • 35 mesh, and 100 rpm.
for film diffusion

t//comp = O~ I I1 where
pBL
1.0 loomp -- _ _
b km CA
Fe(N03) 3 (M) for product layer diffusion
0.8
/x 0.075
t/lcomp = I -- 3(1 -- O~)2/3 + 2(1 -- O~) [2]
g 0 0.10
'~ 0.6 where
c
o pBL 2
/comp =
~ 0.4 4bDeCa
for chemical reaction
0.2 t/tcomp = 1 -- (1 -- Or) 1/3 [31
where
0 I I I I I I
0 20 40 60 80 I00 120 140 3psL
Time (min) tcomp- bkC~
Fig. 2 - - T h e effect of ferric nitrate concentration on fractional conversion
of 28 x 35 mesh galena in the presence of 2 M NaNO3 at 50.5 0(2, pH 1.2 Integral rates were plotted for all three mechanisms given
to 1.4, and 100 rpm. in Eqs. [1], [2], and [3] using the experimental data of

26--VOLUME 18B, MARCH 1987 METALLURGICAL TRANSACTIONS B

Figures 1, 2, and 3. It was found that when 1 - (1 - ~)~/3 0.7
was plotted as a function of leaching time, straight lines
were obtained (Figures 5, 6, and 7), while plots given by 0.6 Added NaN03 (M)
Eqs. [1] and [2] exhibited curves. The data obtained in this A 0 /
study, therefore, indicate that the rate-controlling mecha-
nism for the dissolution of galena with ferric nitrate involves 0.5 I':'1 0.5 . ~
surface electrochemical phenomena. o,o
A plot of 1/tcomp VS concentration of NaNO3 is pre- Q 2.o
0.4 0
sented in Figure 8. The fact that leaching rate decreases
with increased levels of sodium nitrate is probably due
to a decrease in the activity of ferric ion with increased , 0,.3
ionic strength.
0.2

0.7

Particle Size (mesh) / 6

/ j
0.1

0.6
O 48x 65 ~ 0
[] 35x48 ~ / / P " 0 20 40 60 80 100 120 140
0.5
0 28x :35 ,~ / Time (rnin)
A 14x28 / J Fig. 7 - - P l o t s of 1 - (1 - 0/)1/3, chemical reaction control, v s leaching
~- 0.4 time for various sodium nitrate additions. Conditions: 0.25 M Fe(NO3)3,
50.5 ~ pH 1.2 to 1.4, 28 • 35 mesh, and 100 rpm.
i

' 0.3
[3 Q
4.0
0.2

0.1

O I I I I I I
0 20 40 60 80 100 120 140 3.0(
I
r-
Time (rain)
E
Fig. 5 - - P l o t s of 1 - (1 - O/) 1/3, chemical reaction control, v s leaching
time. Conditions: 0.25 M Fe(NO3)3, 50.5 ~ pH 1.2 to 1.4, and 100 rpm. _o
&
0.7
E
0

2.0 D

0.6
Fe(N03)3 Conc. (M)
A 0.075
0.5
E) 0.10
0 o.15
0.4 ra 0.25
I.O I I I I
I
0 0.5 1.0 1.5 2.0 2.5
i
0.3
[NaN03~ M
Fig. 8 - - T h e effect of NaNO3 addition on leaching rate with 0.25 M
0.2 Fe(NO3)3 at 50.5 ~ pH 1.2 to 1.4, 28 x 35 mesh, and 100 rpm.

0.1
Another test for chemical reaction control is a plot of
0
l/tcomp as an inverse function of initial particle size. If this
0 20 40 60 80 I00 120 140 relationship is a straight line passing through the origin,
Time (min) chemical reaction control is indicated. As shown in Fig-
Fig. 6 - - P l o t s of 1 - (1 - 0/)1/3, chemical reaction control, v s leaching
ure 9, this phenomenon is observed.
time for various ferric nitrate concentrations. Conditions: 2 M NaNO3, When the logarithm of 1/tcomp is plotted as a function of
50.5 ~ pH 1.2 to 1.4, 28 x 35 mesh, and 100 rpm. the logarithm of ferric nitrate concentration, if pore dif-

METALLURGICAL TRANSACTIONS B VOLUME 18B, MARCH 1987--27

 I0.0 0.7
/
0.6 Temperature (~ /

8.0 /~. 18 /
Q 32.5 [ 3 /
0.5 Q 5o,5
, Q
.__
E 6.0 tO
rO
0.4 -
_o
x i

4-.0 _, 0.3

0.2
2.0

O.I

0
0 1.0 2.0 3.0 4.0 5.0 0
0 20 40 60 80 I00 120 140
(xlO3)p.m I Time (rain)
Fig. 9 Relationship between I/t~,,,,,p and inverse initial particle size. Fig. I1 --Plots of I - (1 - o~)~/3,chemical reaction control, v s leaching
Conditions: 0.25 M Fe(NO:0~, 50.5 ~ and 100 rpm, time. Conditions: 0.25 M Fe(NO ) 50.5 ~ pH 1.2 to 1.4, 28 x 35
mesh, and 100 rpm.

fusion is controlling, then a linear relationship of unit slope

should be obtained (see Eq. 13]). As shown in Figure 10, a
linear relationship is obtained; however, the slope is 0.48 as
obtained by regression analysis. Pore diffusion is obviously
not controlling.
In an earlier investigation, t7 where ferric chloride was
used instead of ferric nitrate, a similar plot gave a straight
line with unit slope. It was observed that pore diffusion
through the product layer was indeed the rate-controlling
mechanism with ferric chloride.
An integrated rate plot was constructed for the leaching
of particles at various temperatures (Figure 4). As shown
in Figure 1 !, linear relationships are present when the quan-
tity 1 - (1 - a) "3 is plotted as a function of leaching time.
An Arrhenius plot was made by plotting the logarithm of
l/t~,,,, r as a function of reciprocal temperature (Figure 12),
and an apparent activation energy value of 47 k J / m o l
was obtained. This value is consistent with chemical reac-
tion control.
to- 2
I I I I I I

3.0

E
t'~
io -3
E
O
2 2.5 8
0

2.0 I
0.5 1.0 1.5 io - 4 I I I I I I
2.8 2.9 3;0 3. I 3.2 3.3 :3.4 3.5
-log [Fe(,II)]
I / T x l O 3 ( K-I)
Fig. 10--Relationship between the logarithm of tcomp and the negative
logarithm of ferric nitrate concentration. Conditions: 2 M NaNO3, 50.5 ~ Fig. 1 2 - - A n Arrhenius plot for the leaching of 28 • 35 mesh galena with
pH 1.2 to 1.4, 28 x 35 mesh, and 100 rpm. 0.25 M Fe(NO3)3, pH 1.2 to 1.4, and 100 rpm.

28--VOLUME 18B, MARCH 1987 METALLURGICAL TRANSACTIONS B

 It should also be noted that microscopic examination 1 1/2 1/2 1/2 1/2 1/2 1/2
of the reaction product indicated that the sulfur product rate = -~-ka kc f~' f~ yFe§ A [141
layer formed in this study was porous and, therefore,
non-protective. Equation [14] predicts that the rate will vary with the
square root of the concentration of Fe(III). This relationship
Reaction Mechanism is indeed observed as shown by the data presented in Fig-
ure 10 where rate is shown to be proportional to (Fe+3) ~
Since electron exchange occurs at the reaction interface, This agreement provides further evidence for surface
it is apparent that the chemical reaction is electrochemical in phenomena control in this system.
nature. The dissolution of galena occurs through the estab-
lishment of electrochemical couples on the surface of the
galena particles.
LIST OF SYMBOLS
Since nitrate does not complex Fe +3, the cathodic reaction
is simply the reduction of ferric ion to ferrous ion as follows, A total area of galena particles
Fe +3 + e - ---, Fe +2 [4] Aa, Ac anodic and cathodic areas, respectively
aFe+3 activity of Fe +3
The anodic reaction is given by, b stoichiometric coefficient
PbS~Pb +2 + S ~ + 2 e - [5]
CA concentration of diffusion species
De effective diffusion coefficient
The rate model for galena dissolution can be obtained by Ea,Ec anodic and cathodic potentials, respectively
using the Butler-Volmer equation 19'2~ for the anodic and EM mixed potential
cathodic half-cells in the above reactions. F Faraday constant
[Fe(III)] molar concentration of Fe +3
[ ~aZf 1
ia : 2Fka exp[--ff -EoJ [6] fa,fc
ka,k~
anodic and cathodic fractions of surface area
anodic and cathodic rate constants, respectively
k reaction rate constant
i~ = -Fkcave+~exp[.-(i R~3~)ZFE~] [7] km mass transfer coefficient
io,i~ anodic and cathodic current densities, respectively
Because galena is an electrical conductor, both the anodic L edge of cubes
and cathodic sites will have the same potential which is the n reaction order
mixed potential, Eu. Additionally, electrical charge conser- R gas constant
vation principles necessitate that
T absolute temperature
t reaction time
iaAa = -icA~ [8] tcomp time to complete the reaction
z number of electrons transferred in rate-controlling
Assuming a symmetrical energy barrier, /~a : ~c : 1//2,
step
O~ fractional conversion
2FAaka exPL2~J = FA~kcaF,+3exp -2~J [9] l~a,/3c anodic and cathodic transfer coefficients,
respectively
Equation [9] can be rearranged to obtain an expression for PB molar density of solid reactant
the mixed potential as follows: T~e+3 activity coefficient of Fe +3
2.303RT rA~k~aF~+3]
eM- T ,og[-2-a-~k.J [10]
ACKNOWLEDGMENT
The molar concentration and activity of Fe +3 are related
through activity coefficient as, The authors gratefully acknowledge the financial support
provided by the United States Bureau of Mines, Department
[Fe(IlI)] - aFe+3 [11] of the Interior.
~/Fe+3

Equation [10] can therefore be written as,

REFERENCES
2.303RT [Ackc'YFe+3[Fe(III)] "1 1. J.E. Anderson, J. Halpern, and C . S . Samis: Trans. AIME, 1953,
EM- ----U-'~ J [121 vol. 197, pp. 554-58.
2. D. E Seraphim and C . S . Samis: Trans. AIME, 1956, vol. 206,
The rate expression for the dissolution of galena can be pp. 1096-99.
obtained by substituting Eq. [12] into the rate equation for 3. M.I. Sherman and J. D. H. Strickland: Trans. AIME, 1957, vol. 209,
pp. 795-800.
the anodic reaction,
4. V.V. Vasilev and N. E. Muratova: Uchen, Zap. Leningr. Gos. Univ.,
A . A . Z h d a n o r a No. 211, Ser. K h i m N a u k . , 1957, vol. 15,
rate - iaAa
~ - kaAa exp [ 2 ~ EM] [13] pp. 129-34.
5. R . A . Agracheva, A . N . Volskii, and A . M . Egorov: Iz Akad. Nauk
USSR. Otel. Tekh. Nauk. Met. Toplivo, 1959, vol. 3, pp. 37-40.
If the relationships, Aa = faA and Ac = fcA, are used, 6. J.E. Murphy, F. P. Haver, and M. M. Wong: USBM RI 7913, 1974,
then Eq. [131 becomes, 8pp.

METALLURGICAL TRANSACTIONS B VOLUME 18B, MARCH 1987-- 29

 7. E P. Hayer, C.H. Elges, D.L. Bixby, and M.M. Wong: USBM
RI 8166, 1976, 8 pp.
8. E P. Haver, D. L. Bixby, and M.M. Wong: USBM RI 8276, 1978,
11 pp.
9. A. Vizsolyi, G. Veltman, and F.A. Forward: Unit Processes in
HydrometaUurgy, M. E. Wadsworth and F. T. Davis, eds., Gordon and
Breach Sci. Publ., New York, NY, 1963, vol. 24, pp. 326-44.
10. E P. Haver, K. Uchida, and M.M. Wong: USBM RI 7360, 1970,
13 pp.
11. Y. Awakura, S. Kamei, and H. Majima: Metall. Trans. B, 1980,
vol. liB, pp. 377-81.
12. E P. Haver and M. M. Wong: USBM RI 8105, 1976, 17 pp.
13. B.J. Scheiner, G. A. Smyres, and R. E. Lindstrom: 1975 Fall Meeting
30--VOLUME 18B, MARCH 1987
of SME-AIME, Preprint Number 75-B-314, 1974.
14. J.E. Dutrizac: ll4th Annual AIME Meeting, New York, NY, 1985.
15. D. Morin, A. Gaunand, and H. Renon: Metall. Trans. B, 1985,
vol. 16B, pp. 31-39.
16. A.Y. Lee, A. M. Wetherington, and E. R. Cole: ll5th Annual AIME
Meeting, New Orleans, LA, 1986.
17. M.C. Fuerstenau, C. C. Chen, K. N. Han, and B. R. Palmer: Metall.
Trans. B, 1986, vol. 17B, pp. 415-23.
18. J. Pande: German Patent 680578, 1939.
19. J.A.V. Butler: Trans. Faraday Soc., 1924, vol. 9, pp. 729-33.
20. T. Erday-Gruz and M. Volmer: Z. Physick. Chem. (A), 1930,
vol. 150, pp. 203-13.
METALLURGICALTRANSACTIONS B