Canadian Metallurgical Quarterly, Vol. 29, No.3, pp. 201-211, 1990 0008-4433/90 $3.00 + .

00
Printed in Great Britain Canadian Institute of Mining and Metallurgy
Pergamon Press pIc

A CRITICAL REVIEW OF THE FERRIC CHLORIDE

LEACHING OF GALENA
M. KOBAYASHI
Chemical Processing Division, National Research Institute for Metals, 2-3-12 Nakameguro, Meguro-ku,
Tokyo 153, Japan

J. E. DUTRIZAC
CANMET, Energy, Mines and Resources Canada, 555 Booth Street, Ottawa, Ontario, KIA OG1, Canada

and
J. M. TOGURI
Department of Metallurgy and Materials Science, University of Toronto,
Toronto, Ontario, M5S 1A4, Canada

(Received 10 August 1989; in revised form 11 January 1990)

Abstract-Ferric chloride leaching is a potentially attractive method of processing lead concentrates, and
many studies have been carried out on the kinetics of dissolution of galena (PbS). In this paper, the
extensive literature on galena dissolution is critically reviewed and the various results are compared on a
consistent basis. There is a consensus that the leaching reaction is rapid and that elemental sulphur is the
dominant reaction product. Although quantitative agreement among the various studies is lacking because
of differences in galena purity, experimental procedures and methods, and data interpretation, the overall
trends indicate a shallow temperature dependence, a direct total chloride concentration effect and a modest
influence of solution agitation. Furthermore, there is an abrupt change in the reaction mechanism at FeCI)
concentrations less than ,...,0.1 M. The experimental observations are consistent with rate control either by
the outward diffusion of the PbCl2 reaction product through the elemental sulfur layer or by the surface
chemical reaction. Further experiments at various total chloride concentrations will be necesssary to define
the rate controlling reaction more precisely.

NOMENCLATURE of lead from such sulfide concentrates by traditional pyro-

metallurgical routes invariably leads to the emission of sulfur
A,B constants
d particle diameter oxides as well as particulate matter. Concern about the environ-
do initial particle diameter ment has resulted in a number of innovative metallurgical pro-
Fe (ex) function of the surface reaction rate cesses to address the emission problems associated with tra-
Fd(ex) function of the diffusion rate ditionallead smelting. For example, there has been a great deal
Ke thermodynamic equilibrium constant
kb
of interest in hydro metallurgical processes since the sulfur in
overall rate constant
ke "linear" shrinking core rate constant the concentrates can be recovered as elemental sulfur rather
kd shrinking core rate constant for diffusion control than sulfur dioxide gas. In this regard, many studies have been
kr logarithmic rate constant published on the hydrometallurgical treatment of lead sulfide
ko initial rate constant concentrates in chloride media [1-22]. Chloride solvents gen-
kp parabolic rate constant
activation energy erally have been selected because of their low cost and because
Q
R gas constant lead chloride is moderately soluble in concentrated chloride
r particle radius media. These studies involve both thermodynamic measure-
ro initial particle radius ments dealing with the equilibria among the various chloro-
S surface area
T
complex ion species [4-6] and the leaching kinetics of lead
temperature (K)
t time sulfide [7-22].
W lead leached The thermodynamics of the chloride leaching system can be
fraction reacted discussed in terms of the Eh-pH diagram for the Pb-S-H20
p density of galena system, and the diagram obtained at 25°C and 1.0 M total
chloride ion concentration is illustrated in Fig. 1 [23,24]. The
arrows shown in Fig. 1 represent possible methods for extract-
INTRODUCTION ing lead from galena, and correspond to the leaching reactions
expressed by eqns (1) to (3), respectively.
Galena (PbS) is the principal lead ore mineral, and many lead
concentrates consist predominantly of galena. The production (1)
201
202 M. KOBAYASHI et at.: REVIEW OF FERRIC CHLORIDE LEACHING OF GALENA

standing can be gained of the kinetics and mechanism of the

oxidative leaching process.
0.4

COMPARISON OF THE RATE CONSTANTS

0.2

Many investigations have been carried out on the oxidative

(3)
leaching of galena in chloride media [9-22]. Since most experi-
:;- Pb2• ments have been performed in ferric chloride solutions and only
i[ 0.0 (PbCIJ
a few in cupric chloride or other media [22], the present study
--+---- (2) PbS will be confined to the data obtained from ferric chloride leach-
ing although the mechanism in CuCl2 media seems to be similar
-0.2 to that in FeCl3 solutions. The overall reaction can be rep-
(1)
resented by eqn (4).
PbS+2Fe3+ --+ Pb2+ +S+2Fe2+. (4)
Pb
-0.4
The reviewed literature is summarized in Table 1. The papers
-3 -2 -1' 0 2 4
have been restricted to those published within the last decade
pH on the ferric chloride leaching of galena as the few earlier studies
on this subject already have been reviewed [15]. The first step
Fig. 1. Schematic Eh-pH diagram for the Pb-S-H20 system at 25°C of the comparison involved the identification of the various rate
and 1.0 M total chloride; the Pb2+ region coexists with solid PbCl2 [23].
Arrows are explained in the text. equations used to analyze the data along with the experimental
conditions (range and standard values) and the dependency of
the rate constant on the various parameters. This comparison
is also shown in Table 1. Furthermore, short remarks on both
PbS+2H+ --+ Pb2+ +H2S (2) the samples used and the kinetics deduced in each paper are also
2 included. Since the rate equations used by Sohn and Baek [11]
PbS --+ Pb + + S + 2e. (3)
and Morin et ale [17] are basically identical, only the following
The direct reduction process is represented by eqn (1). six rate equations were used to analyze the data of Table 1.
Although this process is conceptually very simple, con-
1-2/3':1.- (1-ex)213 = kdt (5)
tamination of the lead product with various impurity elements
(As, Bi, Cu, Ag, etc.) present in the concentrate is inevitable, 1- (1-0:) 1/3 = ket (6)
and consequently, only a few studies [3] have been reported on
d'Y./dtlr= 0 = ko (7)
this option. Equation (2) shows the condition for non-oxidative
leaching which dissolves lead with the concomitant evolution (~:V/ S) 2 = kpt (8)
of hydrogen sulfide gas. The consensus [7,8] is that the rate
controlling step for non-oxidative leaching is the outward
Fd ('Y.)/[l-exp (- kbt)] = AFc('Y.)j[1 -exp ( -kbt)] + Bt (9)

diffusion of dissolved hydrogen sulfide through the liquid
boundary layer. The third arrow in Fig. 1 represents the process
of oxidative leaching, whereby sulfur is oxidized to the elemen-
tal form and lead reports as divalent lead ions. Thermo-
dynamically, sulfur in the PbS will be oxidized to sulfate or
bisulfate under moderately oxidizing conditions even at low pH
values. In practice, however, elemental sulfur forms during the
atmospheric leaching of galena in acidic media, and the sulfur
product does not oxidize significantly under these conditions
[23]. Despite the observed formation of small quantities of
oxidized sulfur species during galena leaching [15, 18], the region
of sulfur metastability expands to the right-hand side of Fig. 1
as suggested by the broken line [24]. The extent of the sulphur
metastability zone is not well defined, and depends on the
anions present, pH, temperature, etc. In any event, the leaching
reaction under a broad range of Eh-pH conditions can be
expressed by eqn (3).
Many kinetic studies have been performed on the oxidative
leaching reaction [9-22]. In spite of the number of studies,
however, the reported investigations do not agree consistently
on the reaction rates, the parametric dependencies or the mech-
anism of oxidative leaching. In the present study, the available
kinetic data are reviewed critically so that a better under-
-In (1-0:) = krt. (10)
The next step in the analysis involved the determination of
the relationship among the different rate constants in order that
an analysis could be made under comparable conditions. Sohn
and Baek [11] recently reanalyzed the data reported by Kim et
ale [14] and Fuerstenau et ale [16]. The resulting data from
this re-evaluation have been omitted, and only the conclusions
reached by the original authors are considered.
Relationship between kd and kc
The rate equations (5) and (6) have been applied to many
solid-liquid reactions. Both are derived from the shrinking core
model based on the uniform dissolution of monosized spherical
particles. When diffusion through a product layer, which is
formed around the particle, limits the dissolution rate, eqn (5)
can be applied. This mechanism can be tested by plotting the
data in the form 1-2/3':1.- (1-0:)213 versus t. If diffusion
through the constantly thickening product layer is rate limiting.
a straight line passing through the origin results. The slope of
this line is kd• On the other hand, if the surface reaction is
rate limiting, then eqn (6) applies and plotting the data as
1- (1-0:) 1/3 versus t results in a straight line with slope kc +
 203
Table 1. Summary of reported data

Sohn and Baek (l1J

Rate equation t = td + te
td = {l-2/30:-(1-0:)2/3}/kd
te = {1-(1-0:)1/3}/ke

They introduced a rate equation based on a mixed model which assumed both
diffusion of PbC12 through the product sulfur layer and a surface reaction in the
shrinking core model. Data obtained by Kim et al. [14] and Fuerstenau et al. [16]
were used to check the rate equation. The predicted curves fit the experimental data,
except for one test conducted at 90°C.

Rath et al. (12]

Sample Sized galena containing 86.3% Pb
Rate equation 1- (1- 0:) 1/3 = ket

Experimental Standard
conditions conditions Dependence

Particle size Jim 29-125 125 ke = 0.52/do

Temperature °C 14-80 30 Q = 43 ±4 kl/mol
Fe3+ conc M 0.05-0.2 0.1 keo: [FeH]o.76
NaCI conc M o and 5 0.5

The leaching tests were carried out at pH 1.45, and about 7% Pb dissolved according
to a non-oxidative mechanism. The dissolution reaction was electrochemical in
nature; the anodic and cathodic processes were described in terms of the Butler-
Volmer equation.

Warren et al. (13]; Kim et al. (14J

Sample Sized galena concentrate containing 78.9-80.9% Pb
Rate equation 1- (1- 0:) 1/3 = ket
(do:/dt)lt=o = ko (for low Fe3+ conc)

Experimental Standard
conditions conditions Dependence

Particle size pm 58-98 69 ke0:1/do

Temperature °C 27-57 45 Q = 72 kl/mol
Fe3+ cone M 0.008-0.8 0.2 keo: [Fe3+]O.21
NaCl cone M 1-5 4 keo: [NaCl]
HCl conc M 0.1 0.1

Non-oxidative dissolution is negligible when the activity ratio ofH+ to FeH is low,
and Cl- plays an important role in the dissolution kinetics [14]. Warren et ai. [13]
concluded that PbC12 formed by a direct electrochemical reaction and that the addition
of NaCl increased the dissolution rate of the PbC12• The overall reaction occurred in
three stages. The first stage was controlled by the surface reaction. As solid PbC12 was
produced, the diffusion of Cl- ion was equal in importance to the surface reaction.
Ultimately, the rate controlling step moved to product layer diffusion.

Dutrizac (15J
Sample Natural galena crystals", 1 cm on edge and sized galena containing
86.03% Pb
Rate equation (wt Pb leached/area) 2 = kpt (for galena cubes)
1-2/30:-(1-0:)2/3 = kdt (for sized galena)
Experimental Standard
conditions conditions Dependence

Particle size pm 32-177, cubes cubes kdo:(1/do)2

Temperature °C 28-95 80 Q = 44±2 kllmol
Fe3+ conc M 0.01-2 0.3 <0.1 M kpO:[Fe3+] 1.9
>0.1 M kpO:[FeH]-O.27
Fe2+ conc M 0-3.3 0 kp = const.
NaCl cone M 0--4 0 < 1 M kp = const.
> 1 M kpO:[NaCI] 1.27
HCl conc M 0.1-6 0.3 <3 M kp = const.
> 3 M kpO:[HCl]4.s5
PbCl2 conc M O-saturation 0 kp = -A [PbC12]+B

Parabolic kinetics were applicable to all the experimental data. The rate controlling
step was the outward diffusion of the PbC12 reaction product through the elemental
sulfur layer. The apparent activation energy of 44 kJ /mol was reduced to 16 kJ /mol
when the effect of temperature on the solubility of PbC12 was taken into account.
204 Table 1- Colltinued

Fuerstenau et al. (16]

Sample Sized galena containing 85.6% Pb
Rate equation 1-2/3(X- (I-afl3 = kdl

Experimental Standard
conditions conditions Dependence

Particle size JIm 250-550 550 kd(X(lldo) I. 77 at 50::C

kdll.(lldo) 1.21 at 90::C
Temperature °C 30-90 50,90 Q = 34 kllmol
Fe3+ cone M 0-0.8 0.1 <0.1 ~1 kd(X [Fe3+Fo25
>0.1 M kd = const.
NaCI cone M 0-3 3 kd(X [NaCI]0.48 at 50::C
kd = const. at 90::C
HCl cone M

The experimental data agreed with a product layer diffusion model. The rate
controlling step was mass transport of ferric chi oro-complexes through the product
layer in 3 M NaCI solutions at 50o-90::C. By contrast, in the absence ofNaCI at 50::C,
the rate was controlled by the outward diffusion of the PbCl2 reaction product.

Morin et al. (17]

Sample Sized galena containing 75.6% Pb
Rate equation Fd(o:)/[I-exp (-kb/)] = AFc(a)/[I-exp (-kb/)] +BI

Experimental Standard
conditions conditions Dependence

Particle size JIm 37-78 78

Temperature °C 60-95 75
Fe3+ cone M 0.00654-0.0262 0.0131
Fe2+ cone M 0.00349-0.0262 0.0131
NaCI cone M 2-4 4

Experiments were conducted at a constant Fe3+ concentration or with a constant

Fe3+ /Fe2+ ratio. A rate equation similar to that introduced by Sohn and Baek [11]
was used. The reaction was represented by this equation for up to 95% galena
dissolution.

Kametani (18, 19]

Sample Twelve concentrates containing 47.3-72.6% Pb
Rate equation -In (I-a) = krl 0: = A +B log I

Experimental Standard
conditions conditions Dependence

Particle size Jim 1.55-12.5 1110.50: lido

Temperature °C 70
Total Fe cone M 0.068
NaCI cone M 3
Potential V(SCE) 0.25-0.45 0.35 E = A +B log (1110.5)

The samples were finely ground and contained high levels of impurities. The
leaching was carried out at constant potential by adding KMn04 solution as required.
The reaction rate was represented by first order kinetics below 0.35 V. The mechanism
was related to the semiconducting properties of the galena samples. Above 0.35 V the
reaction followed a = A + B log I.

Kim et al. (20]

Sample Sized galena concentrate containing 81.6% Pb
Rate equation 1-2/3(X-(l-cx)2/3 = kdl

Experimental Standard
conditions conditions Dependence

Particle size JIm 48-180 48 kdal/do

Temperature °C 25-100 50 Q = 53 kllmol (0 M NaCI)
Q = 34 kllmol (2 M NaCI)
Fe3+ cone M 0.026-0.2 0.1 kda [Fe3+] U (0 ~1 NaCl)
kda [Fe3+f2 (3 M NaCl)
NaC] cone M 1--4 0,3 kda [NaCl]U
CaC]2 cone M 0--4 0

The reaction rate fitted the diffusion model; however, the rate constant was inversely
PLo.portional to the particle size.
 M. KOBAYASHI et ai.: REVIEW OF FERRIC CHLORIDE LEACHING OF GALENA 205

Table I-Continued

Arai et al. (21)

Sample Sized galena from the Kamioka mine (86.3% Pb) and the Galena
mine (86.4% Pb)
Rate equation 1-(1-0:) 1{3 = kct

Experimental Standard
conditions conditions Dependence

Particle size pm 65-180 60 kco:(1/do) (Kamioka)

kco:(1/do)o.64 (Galena)
Temperature °C 25-50 40 Q = 41 kllmol (Kamioka)
Q = 44 kllmol (Galena)
Fe3+ conc M 0.025-0.075 0.037 kcO: [Fe3+]o.89(Kamioka)
kcO: [Fe3+] (Galena)
HCI conc M 0.05-0.51 0.25 kc = const.

Samples were kept in an Ar atmosphere at 150-350°C, and the effect of the thermal
treatment on the leaching rate was correlated to the change of the electronic ~roperties
of the galena. The rate controlling step was the reduction of Fe3+ to Fe + on the
surface of the PbS. The Fe" t concentration was low relative to that employed by
other workers.

In most kinetic studies, however, careful analysis of the exper- Fe3+ cone (mol/I)
imental data shows that the rate rarely follows either theoretical
0.01 0.05 0.1 0.5 1.0
curve exactly over the entire reaction regime. As a result, the
evaluation of the rate constants, kd and kc' invariably involves
-2.0 I

an approximation procedure. In general, if two different kinetic I

models are applied to the same dissolution data, two different ~, l 60

\\~~v
rate constants corresponding to each model result. Although
there is no theoretical relationship between these two rate con- -2.5 \.. ,
i
I
stants, an empirical relationship can be developed to permit a
+'
c 40
oS
comparison of the available experimental data. l/)
c
The ratio kd to kc can be expressed by:
o
o \
,
~ I +
.!

•....•....• ....
-3.0
,
,
I
I 20 J:
kd/kc = {1-2/3a- (1-a)2/3}/{I- (I-a) (11) ctl .2
1/3}. cc 'E
.5 cc
Equation (11) shows that the relationship between kd and kc is -
a function of the fractional conversion, a. Substituting a = 0.3, o
0.5 and 0.7 leads to the following ratios of kd/kc: 0.104, 0.178 -5 -4 -3 -2 -1 0
and 0.258, respectively. The value of a = 0.5 for the fractional
In Fe3+ cone (mol/I)
conversion was arbitrarily selected for comparing the rate con-
stan ts ; hence: o Initial kinetics
~ Surface reaction model
(12) • Ratio of H" to Fe3+activity

It was assumed that the a = 0.5 value would be representative

Fig. 2. Ferric ion concentration dependence of ko, kc' and the ratio of
of the intrinsic reaction rate by minimizing the errors associated H+ activity to Fe3+ activity. Figure is taken from Kim et ai. [14].
with both the initial and final stages of the reaction. Hence,
eqn (12) becomes a suitable, if approximate, correlation for
comparing kd and kc'
FeCl3 concentrations likely is surface controlled; hence, the
Relationship between kc and ko initial stage of the reaction will follow eqn (6). Differentiation
of eqn (6) gives:
The initial rate constant, ko, is the slope of the reaction curve
as t ~ 0; this rate constant is often used to represent the reaction da/dtlt= ° = 3k c• (13)
rate when the leaching kinetics are unknown or do not obey
From eqns (7) and (13), the following relationship is obtained:
the conventional rate laws. For example, Kim et al. [14] found
that eqn (5) did not apply to the leaching experiments at ferric ion (14)
concentrations in the range 0.008 to 0.1 M FeCI3• Consequently,
they used the initial rate constants at low ferric ion concen- Relationship between kd and kp
trations. They explained that the change in the ratio of H+ Dutrizac [15] showed that the rate of dissolution of galena
activity to Fe3+ activity was responsible for the abrupt change cubes mounted in resin followed eqn (8) ; i.e. parabolic kinetics
in the kinetics shown in Fig. 2. The initial fast reaction at low are observed as shown in Fig. 3. Assuming that the parabolic
206 M. KOBAYASHI et al.: REVIE\V OF FERRIC CHLORIDE LEACHING OF GALENA

kinetics are equally applicable to the dissolution of monosized sulfur layers formed on the sized galena grains were usually
spherical particles, d Wand S are given by eqns (15) and (16) < 50 Ilm thick. The differences in the coefficients of eqns (21)
where 0.866 is the weight ratio of lead in galena. and (22) could be due to differences in the thickness of the
sulfur product layers.
d W = 0.866p x 4n1'2 d1' (15)
2
Although the reasons for the differences between the coefficients
S = 4m· • (16)
of eqns (21) and (22) are not wholly clear. eqn (20) was never-
Differentiation of eqn (8) yields: theless used to convert kp to kd•

d TV = (S/2)(kp/t) 1/2 dt. (17) Rate constant Jar the mixed control model with se(f-blockage of
Combination of eqns (15) to (17) gives: pores
The rate equation proposed by I\10rin et al. [17] combined
0.866p d1' = (1/2) (kp/t) 1/2 dt. (18)
the shrinking core n10del with the self-blockage of pores. This
Integration of eqn (18) yields the following rate equation. rate equation involves three terms which correspond to rate
cons+ants. The use of three rate constants to fit the experimental
[1- (I-C!.) 1/3]2 = kpt/(0.866p1'o)2 == k~t. (19)
data, of course, results in better fits although the constants
To relate kd to kp an empirical relationship derived at C!.= 0.5 derived are without physical significance. More useful is the
was used that leads to eqn (20). approach of Sohn and Baek [11] as their two rate constants
can be related to surface and diffusion phenomena. Since no
(20)
methods are available for comparing the three rate constants
Dutrizac obtained the following relationship between kd and of Morin et al. with those of the other investigators. the data
1'0 from a series of experiments using sized galena samples. \vere omitted from the discussion.

(21) Relationship betlreen kd alld kr

2 4
A value of kp = 2400 (mg /cm h - 1) was calculated from the
leaching of galena cubes under the same experimental con-
ditions as those used for the sized samples, as shown in Fig. 3.
Substituting kp = 2400 and p = 7500 (mg/cm3) into eqn (20)
yields:
(22)
A difference of about 10 times exists between the coefficients of
eqns (21) and (22). The following explanations can be given to
account for this difference.
(i) The empirical relationship is strictly valid only at 'Y. = 0.5.
As the experimental data were derived at various degrees of
reaction, an error is automatically introduced.
(ii) Each leaching experiment using galena cubes was per-
formed for more than 30 h whereas the leaching of sized
galena powders was completed within one hour. As Fig. 3
indicates, the thickness of the sulfur layer formed on the
galena cubes was 400 fim after 30 h of leaching whereas the
Equation (10) represents the rate equation for first order
kinetics; this equation is usually applied to homogeneous reac-
tions. Kametani [18] reported that the dissolution rate of galena
followed first order kinetics. He used l/to.5• the reciprocal of
the time for the fraction reaction to reach 0.5. as a representative
value of the reaction rate. The samples used were extremely fine
grained; therefore. the suspension of galena was regarded as a
homogeneous system and the rate of dissolution of galena was
treated according to first order kinetics. This assumption. how-
ever, almost certainly is not correct.
As demonstrated by Kametani. the following two relation-
ships exist between kr and l/to.5, and between kr and kc:
l/to.5 = 1.443kr (23)
kc = 0.33kr for 'l. < 0.4. (24)
It was shown that eqn (24) can be applied over a wider fractional
conversion range, and without significant error. by changing
the coefficient, 0.33 in eqn (24), to 0.4 as given by eqn (25).

kc = OAkr for 'Y. < 0.8. (25)

From eqns (12), (23), and (25), it is deduced that:

~ 100 E
N
0
.•.... a- kd = 0.0493/tO.5• (26)
0
.s
01
80 "-
CD
>-
400 ~
N
:aco 60 "-
.2
~ EFFECT OF THE VARIOUS EXPERII\,lENT AL

-
'S
(f)
'C
C1> 40 300 PARAl\IIETERS ON GALENA DISSOLUTION
> 0
(5 (f)
(f)
(f)
(f) 20 200
CD
t: All the rate constants for the ferric chloride leaching of
8 .::t:.
0 galena, except the ones introduced by I\10rin et al. [17]. were
(")
0 100 :c
....
,..
0
0 10 20 30 40 converted to kd and rewritten in the following form

kd = A(r~ [FeCI3V [NaCIY exp ( - Q/ RT). (27)

Time (h)

Fig. 3. Parabolic kinetics and the relationship between Pb leached

These equations are listed in Table 2. Other parameters such as
and the thickness of the sulfur product layer. Data are taken from ferrous ion and lead ion concentrations were omitted because
Du trizac [15]. these potentially important variables have been studied by only
 M. KOBAYASHI et al.: REVIEW OF FERRIC CHLORIDE LEACHING OF GALENA 207

Table 2. Dependencies of the rate constants converted to kd

Rath et al. [12]

5 M NaCI kd = 1360do 1 [FeCI3] 0.76exp (-42700RT)
OM NaCI kd = 3520do I [FeCI3] 0.76exp (-50600jRT)
Warren et al. [13] and Kim et al. [14]
0.08-0.1 M FeCI3 kd = 1.31 x 108do I [FeCI3]0.523 exp -72100jRT)
0.15-0.5 M FeCI3 kd = 7.65x 107do I [FeCI3]0.21 exp (-72100jRT)
0.5-0.8 M FeCI) kd = 5.20 X 107do I exp ( - 72100jRT)
Dutrizac [15]
0.01-0 ..1 M FeCI] kd = 217do2 [FeCI3] 1.84exp (-43100jRT)
0.1-2 M FeCI] kd = 1.73do2 [FeCI3]-0.27 exp (-43100jRT)
1-4 M NaCI kd = 2.28do2 [FeCI3]-0.27 [NaCI] 1.27exp (-45200jRT)
Fuerstenau et al. [16]
502C, 0.05-0.1 M FeCI] kd = 47.7do 1.77[FeCI]f25 [NaCI] 0.48exp (-33900jRT)
502C, 0.1-0.8 M FeCI) kd = 0.315do 1.77[NaCI] 0.48exp (-33900jRT)
Kametani [18, 19]
0.35 V(SCE) kd = 0.0026-0.037
Kim et al. [20]
OM NaCI kd = 5.25 X 104do I [FeCI]] 1.2exp ( - 53200jRT)
3 M NaCI kd = 977do I [FeC13f2 [NaCI] 1.2exp ( - 34300jRT)
Arai et at. [21]
Kamioka mine kd = 600da I [FeCI3]0.886 exp (-40500jRT)
Galena mine kd = 30150doo.635 [FeCI3] exp (-44200jRT)

a few workers. Fortunately for the sake of the comparison, 10-1,...--------------..,

however, the initial FeCl2 and PbCl2 concentrations were usu-

ally negligible in all the experiments listed in Table 2. A com-
I
C ~
g (7)
parison of the dependencies of the parameters given in eqn (27) ~
was carried out under the following standard conditions: (a)
particle size, 100 /lm; (b) FeCl3 concentration, 0.2 M; (c) NaCI
-~
c
l/)
~ (6,<)

c
concentration, 0 or 3 M ; (d) temperature, 50°C. These are o rS'7) 1'"6-
o '7)

approximately the average values listed in Table 1. Kametani

[18] reported only the effect of the suspension potential, and
~
a:
10-3 "\
did not investigate the other dependencies. His data are omitted
since no methods are available to compare his suspension 102 103

potentials with the other parameters. Kim et al. [14] and Rath
et al. [12] leached galena in ferric chloride solutions containing
a constant NaCI concentration of 4 M and 5 M, respectively.
Therefore the dependencies of their data are reported in 4 M
and 5 M NaCI solutions and not in 0 or 3 M NaCI solutions.
Although the HCI concentrations cited in the literature range
from 0 to 2 M HCI, the effect of HCI concentration is reported
by Dutrizac [15] to be negligible below 3 M HCI. Accordingly
the effect of the HCI concentration on galena dissolution was
not considered as low HCI concentrations likely would be
employed in a commercial leaching process.
Effect of particle size and stirring speed
Figure 4 shows the variation of kd with particle size. The rate
constants can be classified into three groups. Only the rate
constants reported by Arai et al. [21] for samples from the
Galena mine belong to the first group. These data show a 0.6th
order dependency on the reciprocal of the particle size. Most
of the rate constants are inversely proportional to the particle
size (i.e., the rate is directly proportional to the surface area),
and form the second group. Dutrizac [15] and Fuerstenau et
al. [16] reported a second order dependency on the reciprocal
of the particle size. Because of their use of parabolic kinetics,
however, this dependency also indicates that the rate increases
directly with the surface area. Their data constitute the third
group. Many of the particle size dependencies were evaluated
Particle size (J..Irn)
Fig. 4. Relationship between the rate constant and initial particle size.
(1) Ref. [12]; (2) Ref. [13]; (3) Ref. [15]; (4) Ref. [16]; (5-1) Ref. [20]
(NaCIO M); (5-2) Ref. [20] (NaCI3 M); (6-1) Ref. [21] for Kamioka
mine samples; and (6-2) Ref. [21] for Galena mine samples.
using samples with only three or four different particle sizes. It
is difficult to determine the precise dependency of the rate on
the particle size from such limited data.
Fuerstenau et al. [16] performed their experiments at an
agitation speed of 100 r.p.m. From Fig. 5, it is observed that
an increase in the agitation speed to 400 r.p.m. results in
an increase of approximately 1.8 times in the rate constant.
Dutrizac's [15] leaching experiments were done at 250 r.p.m.
The other investigators carried out their experiments under
conditions of rapid agitation where the stirring speed had no
effect on the leaching rate.
Effect of FeCI3 concentration
Figure 6 shows the relationship between kd and the FeCl3
concentration. Increasing FeCl3 concentrations result in a sharp
increase in the rate constant up to about 0.1 M FeCI3• Above
this value, the rate constant becomes relatively independent of
the FeCl3 concentration. This observation suggests that ferric
ions play an important role in limiting the reaction rate only at
208 M. KOBAYASHI et al.: REVIEW OF FERRIC CHLORIDE LEACHING OF GALENA

10-1
4 x 10-2
I
c:
.......................... ~
g
(5 0(2)
.•.• 10-2
c: §(6-2) 5 x 10-3
oS (4)
0(1
(J) (6-1)
c:
0 \!'"
0 0(3) (3)
CD
ro
c:
10-3
0(1)

0 10-1 10° 101

NaCI cone (M)

120 180

Time (min) Fig. 7. Relationship between the rate constant and the NaCI con-
centration. (1) Ref. [12]; (2) Ref. [13], (3) Ref. [15]; (4) Ref. [16]:
Fig. 5. Effect of agitation speed on the leaching rate of galena. Figure (5-1) Ref. [20] (NaCI 0 M); (5-2) Ref. [20] (NaCI 3 Nl): (6-1)
is taken from Fuerstenau et al. [16]. Ref. [21] for Kamioka mine samples; and (6-2) Ref. [21] for Galena
mine samples.

on the leaching rate. It is clear, however, that the addition of

> 0.5 M NaCI increases the rate constant, as shown in
Fig. 7. By contrast, 0-0.5 M NaCI appears to have little
effect on the leaching rate [15,16]. Several investigators [11,13,
1:
.s 10-3
15, 16] have attributed the increase in the leaching rate to the
en
c increased solubility of PbCl2 in the leaching medium. They
o
o
C1> observed crystallized PbCl2 in the pores of the sulfur product
~ 10-4 layer and at the galena surface, and considered that the
addition of NaCI influenced the reaction rate through the
enhanced solubility of PbCI2•
FeCJ3 cone (M)
Effect of temperature
Fig. 6. Relationship between the rate constant and the ferric ion con- Figure 8 is an Arrhenius plot of the rate constants obtained
centration. (1) Ref. [12], (2) Ref. [13]; (3) Ref. [15]; (4) Ref. [16];
(5-1) Ref. [20] (NaCI 0 M); (5-2) Ref. [20] (NaCI 3 M); (6--1)
by the various investigators for the FeCl3 leaching of galena.
Ref. [21] for Kamioka mine samples; and (6--2) Ref. [21] for Galena Except for the data reported by Kim et al. [14], which lead to
mine samples. an apparent activation energy of 72 kJ/mot the values of all
other investigators fall in the relatively narrow range from
34 to 53 kJ Imol. Although these moderately high activation
the lower ferric ion concentrations «0.1 M FeCI3). In the energies seem to indicate that the surface reaction controls the
more concentrated solutions of commercial interest, the rate is galena dissolution rate, Dutrizac [15] showed that these values
essentially independent of the FeCl3 concentration. The effect were not in conflict with an aqueous diffusion control model if
of the FeCl3 concentration on the form of the leaching curve corrections are made for the change of the saturation solubility
often has not been taken into consideration in the reported of PbCl2 with temperature. The "raw" value of 44 kJ Imol
kinetic studies.
Arai et al. [21] observed that the rate constant was pro- Temperature te)
portional to the ferric ion concentration, and proposed the
100 80 60 40 20
following reaction as the rate limiting step.

(28) I
C
g
Where Is,Pb represents the interface between the galena and the
.•.•c: or?
leaching solution. Rath et al. [12] showed that if the Butler-
Volmer charge transfer theory is applicable to the dissolution
oS
en
c:
10-2
/2)
of galena, the rate constant will be proportional to the square 0

root of the ferric ion concentration. At ferric ion concentrations

0
CD 10-3 r~,,",,1)
roc: (<1) (6.:. )
1
> 0.1 M FeCI3, ferric ion concentration is no longer an impor-
tant factor, and hence, it is unlikely that charge transfer is rate
2.8 3.0 3.2 3.4
controlling under these conditions.
Temperature, 1000/T (K-1)
Effect of NaCI concentration
Fig. 8. Arrhenius plot of the rate constants. (1) Ref. [12]; (2) Ref. [13]:
Only a few investigations [13-16] have been reported on the (3) Ref. [15]; (4) Ref. [16]; (5) Ref. [20]; (6-1) Ref. [21] for Kamioka
effect of the concentration of alkali chlorides, such as NaCI, mine samples; and (6--2) Ref. [21] for Galena mine samples.
 M. KOBAYASHI et at.: REVIEW OF FERRIC CHLORIDE
obtained in his experiments was reduced to 16 kJ Imol when the
solubility considerations were taken into account.
Absolute values of the rate constants
The absolute values of the reported rate constants agree with
each other to within one order of magnitude under the same
general experimental conditions, as shown in Figs 4, 6, 7 and
8. For example, the values of the rate constants noted in Fig. 7
fall in the range of 5.0 x 10-3-4.3 X 10-2 min-I under the same
conditions of 0.2 M FeCI3, 3-5 M NaCI, 90°C, and 100 ,urn
galena particle size. The agreement is relatively good when
the diversity of experimental techniques, differences in galena
purity and methods of assessing the rate constants are taken
into account.
DISSOLUTION MODELS
The effects of particle size, FeCl3 concentration, NaCI con-
centration, and temperature on the ferric ion leaching of galena
have been discussed above. Some inconsistencies are observed
in the experimentally determined rate dependencies, and only
a few investigators have considered all the relevant parameters.
Given these uncertainties, it is not possible to present an
unequivocal galena dissolution model which is consistent with
all the reported experimental data. However, modeling of the
dissolution of galena is worth discussing as it will clarify and
I (c)
I formation of chloro-complex species such as PbCI~- that in
(Fe3+)o (Fe3+)b
I
I
(Fe2')D
I
(Fe2+)b
I square of the particle size if diffusion occurs through the con-
(PbC')D (Pb2')b
I stantly thickening sulfur product layer, most of the reported
Fig. 9. Schematic distributions of ferric, ferrous and lead ions around
a galena particle being leached in FeCl3 media. The rate controlling
step is (a) the inward diffusionof ferricion; (b) the outward diffusion
of PbC12; and (c) the surface reaction.
LEACHING OF GALENA 209
identify the kind of experimental data which should be gener-
ated to define the reaction mechanism.
Diffusion model
Figure 9 is a schematic illustration of the concentration dis-
tributions of ferric, ferrous and lead ions around a galena
particle which has been leached to form a significant sulfur
layer. Although the concentrations in the bulk solution are
shown to be constant, these must have slight slopes if diffusion
is to occur. The thermodynamic equilibrium constant, Ke, for
the ferric chloride dissolution of galena is given by:
(29)
Although Ke is written in terms of the simple ions, it is under-
stood that all the species, and especially Pb2+ and Fe3+, occur
as a variety of chioro-complexes. When the diffusion of an ionic
species limits the reaction, the concentration of that species
at the surface of the galena (Co) is not equal to the bulk
concentration (Cb). For example, if the diffusion of ferric ions
is the rate controlling step, then the variations of the con-
centrations are given by Fig. 9(a). The concentrations of ferrous
and lead ions at the surface equal those in the bulk solution;
i.e. (Pb2+h = (Pb2+) 0 and (Fe2+h = (Fe2+) 0, and the value of
(Fe3+) 0 is given by:
(Fe3+)0 = (Fe2+h[(Pb2+hIKe] 1/2. (30)
14
The values of Ke are 3.12 x 1013at 25°C and 1.30 x 10 at
100°C; these terms are so large that the value of (Fe3+)0 is
approximately zero. Thus the diffusion rate and the rate con-
stant are essentially proportional to (Fe3+h.
If the diffusion of the ferrous ion reaction product limits the
rate, the value of (Fe2+) 0 is expressed by:
(Fe2+)0 = (Fe3+h[Ke/(Pb2+h] 1/2. (31)
Where (Pb +)b is equal to (Pb +) 0, and (Fe3+h is equal to
2 2
(Fe3+)0. It is considered that the diffusion of ferrous ions cannot
be rate controlling because the estimated value of (Fe2+)0 is
very large when the value of Ke is taken into account.
A somewhat similar situation prevails when the outward
diffusion of lead ions limits the reaction. However, the lead
concentration is restricted by its low solubility which, in hydro-
chloric acid solutions at room temperature, is less than one-
tenth of that of ferrous ion. If the diffusion of PbCl2 is slow
compared to the generation of lead ions at the galena surface,
lead chloride eventually will be precipitated at the reaction
surface or in the sulfur product layer. Under these circum-
stances, diffusion of lead ions from the galena surface through
the constantly thickening elemental sulfur layer to the bulk
solution limits the overall dissolution, Fig. 9(b), and parabolic
kinetics result. Chloride ions affect the diffusion rate by increas-
ing the soluble lead concentration at the galena surface by the
turn increase the PbCl2 diffusion gradient. Although the "para-
bolic" rate constant must be inversely proportional to the
rate constants are inversely proportional to the particle size. The
apparent discrepancy concerning the particle size dependence of
the rate constant can, however, be mostly attributed to the
treatment of the data according to a linear rather than a para-
210 M. KOBAYASHI ct al.: REVIE\V OF FERRIC
bolic model; i.e., by eqn (5) rather than eqn (6). Although
the observed values of the apparent activation energy seem to
support a surface chemical control model, the activation ener-
gies are reduced to significantly lower values consistent with
aqueous diffusion control when the change of the solubility of
PbCl2 with increasing temperature is taken into account.
Sll1face reactionl11odel
For surface reaction control, the concentrations of all the
ionic species at the galena surface are essentially equal to those
in the bulk solution, Fig. 9(c). The surface reaction is itself
complex, and consists of several steps such as adsorption of
ferric ions, chemical and/or electrochemical reactions between
surface PbS molecules and adsorbed ferric ions, and the desorp-
tion of lead and ferrous ions. The reaction mechanism is com-
plicated still further by the possibility of direct HCI attack of
the PbS to form Pb2+ ions and soluble HS species, but this
mechanism has not been included in the present discussion. If
the dissolution cannot be described by a classical chemical
reaction, several alternatives are possible. For example, the
Butler-Volmer relationship can be applied to the system when
the rate constant is proportional to the square root of the ferric
ion concentration. The mixed model proposed by Sohn and
Baek [11] and Morin et al. [17] also is attractive because it
embraces features of both the surface reaction and the diffusion
process. Such mixed models could be especially useful in the
transitional zone from linear (chemical control) to parabolic
(diffusion control) kinetics that occurs at "'-'0.1 M FeCl3 con-
centration.
Modeling considerations
One important observation is the change in the dissolution
mechanism at a critical FeCl3 concentration of ",-,0.1 M FeCI3.
Although many studies have been reported on the FeCl3 con-
centration dependency of the rate constant, none of these inves-
tigations determined the variation of the critical FeCl3 con-
centration when the temperature is changed, when the NaCI
concentration is varied, or when the other experimental par-
ameters are altered. Such experiments should be done to help
clarify the reaction mechanism. It would also be useful to verify
that the reaction kinetics change from linear to parabolic when
the critical FeCl3 concentration is surpassed. From an industrial
point of view, the modeling of the dissolution of galena above
the critical FeCl3 concentration is of greater interest, as a com-
mercialleaching process would use concentrated FeCl3 media.
Sodium chloride concentrations> 1 M enhance the reaction
rate whereas the leaching rate is relatively independent of lower
NaCI concentrations. Although the effect ofNaCI on the leach-
ing reaction has been investigated, more experiments are necess-
ary to ascertain the concentration effects of other alkali or
alkaline earth chlorides on both the leaching rate and the PbCl2
solubility. Studies on the effect ofHCI concentration at various
NaCllevels would be useful and could help to clarify the relative
importance of the direct and indirect leaching mechanisms. The
chloride concentration effect has not been investigated to the
same degree as temperature or particle size, and it would be
desirable to obtain "new" data on a variety of chloride salts.
Measurement of the solubility ofPbCl2 in FeCl3-alkali chloride
leaching media, and confirmation of the effect of the initial
CHLORIDE LEACHING OF GALENA
concentration of PbCl2 on the leaching rate, also will be necess-
ary to verify the model.
Most leaching experiments have been carried out with sized
samples; only a few studies have been performed with massive
samples mounted in resin. Both types of experiment yield comp-
lementary information. Although the former always contains
the uncertainties about the irregularity in shape and size of the
particles, agglomeration by sulfur. and the effects of crushing
and sieving, it produces information useful to the practical
process. The latter technique generates valuable information
on the kinetic aspects, but care must be exercised when the data
are applied to particulate samples. Conclusions reached with
particulate systems should be verified with massive samples. and
vice versa.
CONCLUSIONS
Recent studies on the oxidative leaching of galena have been
critically reviewed by comparing the rate constants used to
analyze the various leaching data on a consistent basis and
under standardized experimental conditions. The absolute
values of the reported rate constants agree within an order of
magnitude, and some trends are emerging with regard to the
dependence of the leaching rate on particle size, FeCl3 con-
centration, NaCI concentration and temperature. The leaching
mechanism in dilute ( < 0.1 M FeCI3) ferric chloride solutions
is clearly different from that in more concentrated FeCl3 media.
Models involving the outward diffusion of the PbCl2 reaction
product through the constantly thickening elemental sulfur
product layer or the surface chemical reaction have been
advanced to explain the dissolution of galena. Further experi-
ments on the effects of FeCl3 concentration and alkali halide
concentration will be necessary, however, to unequivocally
,define the dissolution mechanism.
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