Hydrometallurgy, 26 ( 1 9 9 1 ) 3 2 7 - 3 4 6

327

Elsevier Science Publishers B.V., A m s t e r d a m

The precipitation of lead jarosite from chloride

media
J.E. Dutrizac
Mineral Sciences Laboratories, CANMET, Energy, Mines and Resources Canada, 555 Booth Street,
Ottawa, Ontario K1A OG1, Canada
(Received August 12, 1990; accepted September 29, 1990)

ABSTRACT
Dutrizac, J.E., 1991. The precipitation of lead jarosite from chloride media. Hydrometallurgy, 26:
327-346.
Lead jarosite, Pbo.~Fe3 (SO4)2 (OH)6, was precipitated from concentrated FeCI3-LiCI-PbC12 media containing Li2SO4 as the independent sulphate source, and the parameters affecting the amount
and composition of the precipitate were determined. Lead jarosite is precipitated over the pH range
0.0-0.8 and at temperatures from 80 to 150 C; higher temperatures result in Fe203 formation. High
total chloride concentrations are required to prevent the co-precipitation of PbSO4. The amount of
product increases with increasing concentrations of PbC12, FeC13 and Li2SO4, but the product composition is significantly affected only at LieSO4 concentrations < 0.15 M. The kinetics of lead jarosite
precipitation from chloride media at 98C are relatively slow, and approximately 24 h are needed to
achieve steady state conditions. Efforts to incorporate silver in the structure of the lead jarosite were
not successful; the silver content never exceeded 70 ppm Ag. Likewise, it was not possible to precipitate end-member silver jarosite, and this behaviour is attributed to the strong complexation of silver
in concentrated chloride media.

INTRODUCTION

A variety of ferric chloride leaching processes are being developed for the
treatment of pyritic Z n - P b - C u - A g bulk concentrates made from complex
sulphide ores [ 1,2,3 ]. The ferric chloride route results in high extractions of
the sought-after metals, including Pb and Ag, but only a minor attack on the
pyrite impurity. A further advantage of ferric chloride leaching is that most
of the oxidized sulphide ion reports as elemental sulphur which can be recovered from the leach residue if desired. Although elemental sulphur is the
major sulphidic reaction product, some sulphate is also generated. In fact,
sulphate concentrations > 20 g/1 have been reported in chloride leach solutions [4]. The sulphate originates either as an impurity (e.g., gypsum or
PbSO4) in the bulk concentrate or as a minor reaction product of the oxidation of the sulphide minerals by FeC13 [ 5 ]. The presence of dissolved lead
0304-386X/91/$03.50

1991 - - Elsevier Science Publishers B.V.

328

J.E. DUTRIZAC

and silver in a ferric chloride solution containing modest concentrations of

sulphate creates the general environment for the precipitation of a variety of
jarosite-type compounds (MFe3(SO4)2(OH)6 where M is K, Na, NH4, Ag,
Pb, etc. ). The formation of Pb- or Ag-bearingjarosites is clearly undesirable
as the jarosites are normally discarded with the leach residue. For example,
losses of Pb and Ag occur in the jarosites made in the commercial O2-H2S04
pressure leach process for zinc concentrates, and are an undesirable feature
of that technology [ 6 ].
Although the factors affecting the precipitation of lead jarosite [ 7,8 ] and
silver jarosite [9,10] in sulphate solutions are well defined, relatively little is
known about the precipitation of these compounds in chloride media. Fairchild [ 11 ] demonstrated that lead jarosite could be precipitated from chloride media provided that an independent source of sulphate was available,
but did not investigate any of the parameters affecting the precipitation reaction. A preliminary study [12] on the formation of jarosite-type compounds in chloride media showed that the precipitation reaction was strongly
dependent on the precipitation temperature and the acid and sulphate concentrations. It was also demonstrated that Na was preferentially incorporated
in the jarosite structure relative to Pb. For example, the products made from
3 M NaC1 media containing 20 g/1 PbC12 assayed approximately 4% Na but
less than 1% Pb. In a subsequent study [ 13 ], it was shown that the jarosite
made in 4 M NH4C1 media containing 20 g/1 PbCI: assayed approximately
3.7% NH4 but less than 0.2% Pb. No systematic studies of the precipitation
of silver jarosite in chloride media have been reported, but it is known that
Ag is not extensively incorporated in the potassium jarosite product made at
150C from concentrated KCI media in Duval's CLEAR process [14] nor in
the jarosite-FeO-OH turbo-aeration product formed from concentrated iron
chloride solutions in the Great Central Mines process [ 15 ].
Although the formation of lead and silver jarosites during the ferric chloride leaching of pyritic Z n - P b - C u - A g bulk concentrates is of considerable
hydrometallurgical interest, relatively little is known about the precipitation
reactions. Accordingly, systematic studies were carried out to define the parameters affecting the formation of lead jarosite in concentrated chloride media and to ascertain the level of Ag incorporation in the jarosites made from
such solutions. The results of the studies are presented in this report.
EXPERIMENTAL

Reagent grade chemicals were used for all the experiments. Although most
of the experiments were carried out at 98C in glass reaction vessels fitted
with titanium baffles, some tests were also carried out at elevated temperatures using a Parr 2 1 titanium autoclave fitted with a glass liner and titanium
internals. In all the experiments, 1 1 of solution containing appropriate con-

PRECIPITATION OF LEAD JAROSITE

329

centrations of FeCI3, LiC1, PbC12, Ag C1 and Li2SO4 was heated at the selected
temperature for 24 h with good agitation. The pH of the solution was adjusted
with HC1 or Li2CO3 using a three-point calibration procedure with buffer solutions at pH 4, 2 and 1. Lithium sulphate was added as the independent
sulphate source, and Li2SO4, LiC1 and Li2CO3 were used because lithium does
not form an end-member jarosite-type c o m p o u n d [16]. At the end of the
experiments, the jarosite slurries were filtered hot and the precipitates were
washed with large volumes of hot water to remove any entrained solution.
When AgC1 was present in the solution, the residue was washed with a small
volume of 4 M NaC1 prior to water washing to prevent the precipitation of
AgCI. All the precipitates were dried at 110 C prior to analysis. Because the
synthesis solutions contained dissolved PbC12 and Li2SO4, the possibility of
PbSO4 contamination of the precipitate exists. Accordingly, all the products
were checked for possible PbSO4 contamination with a Guinier focussing Xray camera and cobalt radiation. Previous studies [ 7,8] have shown that approximately 0.25% PbSO4 is readily detected as a "trace" constituent by this
technique.
RESULTS AND DISCUSSION

Effect of pH and temperature

Figure 1 shows the effect of the initial solution pH on the amount and composition of the products made at 98C from 0.5 M FeC13-4.0 M LiCI-0.3 M
Li2SO4-20 g/1 PbC12 media. Only approximately 0.7 g of product is made at
pI-I 0.0, but the product yield increases systematically as the pH increases.
When the initial pH exceeds 0.8, iron hydrolysis and precipitation occur at
room temperature and the products are difficult to filter. This indicates that
ferric hydroxide (or a similar amorphous species) is formed at the high pH
values, and the presence of ferric hydroxide is indicated by the orange colour
of the precipitates:
Fe 3+ + 3 H 2 0 ~ F e (OH)3 + 3 H +

( 1)

All the products made at pH values between 0.0 and 0.8 had the yellow colour
characteristic ofjarosite precipitates:
Pb2+ + 3 F e 3+ + 2 S O 2- + 6H20~Pb0.sFe3 (SO4)2(OH)6 + 6H +
K e q uilibrium - -

[ pb 2+

] 0.5

[U+] 6
[ Fe 3+ ] 3 [ SO 2- ] 2

(2)
(3 )

The j arosite precipitation reaction generates large amounts of acid, and the
reaction proceeds only until the acid concentration approaches the equilibrium level (eq. (3) ). The higher the initial acid concentration, the less jaros-

330

J.E. DUTRIZAC

45

45

0 . 5 M FeCI3,4.0 M L i C I , O . 3 M LizSO4

2 0 g / L PbCI2,98aC ,24 h

40

40--

35 - - J

-.8

30--

IJ__l__O__O

c,

% SO4

o~c~___ % Fe
3O

e_
.

g
w

25

35

o
IRON
25
HYDROLYSIS--

--

20 m

20--

L5

% Pb

--I

O _ _ 0.......__0__ 0 --

I0--

5 -- / ~ / , x

,/ / E

IO

PRODUCTYIELD
--5

o.o

o.z

0.4

o.6

a8

i.o

0
1.2

pH

Fig. 1. Effect of the initial pH of the synthesis solution on the amount and composition of the
Pb-jarosite product.

ite is made before the equilibrium acid concentration is approached. For initial pH values < 0.0, the acidity is so high that no jarosite precipitation occurs.
Previous studies carried out in the presence of various initial free acid concentrations [ 12 ] showed that no product was made for free HC1 concentrations > 0.12 M. As a free acid concentration of 0.1 M HC1 yields a pH of
approximately 0 in concentrated chloride media, the results of the two studies
are in general agreement.
Although the amount of product is strongly dependent on the initial pH of
the solution, the product composition is relatively insensitive to the acidity.
Over the pH range 0.1 to 0.8, the products contain approximately 13% Pb,
31% Fe and 35% SO4; end-member lead jarosite, Pb0.sFe3 (SO4) 2 (OH) 6, contains 18.32% Pb, 29.63% Fe, 33.98% SO4 and 18.04% OH. The composition
of the precipitates is, therefore, consistent with a lead jarosite having a significant level of hydronium ( H 3 0 + ) substitution for lead [ 17]; that is, the actual formula is Pbo.s_x/2 ( H 3 0 ) xFe3 ( S O 4 ) 2 ( O H ) ~. Guinier X-ray diffraction
analysis of the products made over the pH range 0.0 to 0.8 showed only lead
jarosite; PbSO4 and PbCI2 were not detected.
Figure 2 shows the effect of synthesis temperature, in the 60-98 C range,
on the amount and composition of the products made from 0.5 M FeC13-4.0

331

PRECIPITATION OF LEAD JAROSITE

55
50

55

0.5M FeCl3,4MLiCl,O.3MLi2SO4
20g/L PbCle,pH=O.I, 7'4h

50

45

f40

40

% SO4

:55
o

s--|

taSO

% Fe
25 m

~_ 25

zo

zo

~ql,.,"~

15
I0--

%Pb

--.a"
70

5-O
60

-0
o

--

15

PRODUCTYIELD

--I0

fl

--5

I
I

80

90

I00

TEMPERATURE( *C )

I I0

Fig. 2. Variation of the amount and composition of the products with synthesis temperatures
from 60 to 98C.
M LiCI-0.3 M Li2SO4-20 g/1 PbCIz solutions at pH 0.1. No product is made
during the 24 h synthesis period at temperatures < 70 C, and this is a reflection of the slow precipitation kinetics at the lower temperatures. Although
jarosite precipitation is known to occur at room temperature, the rate is exceedingly slow. Some precipitation occurs at 70 C, and the amount of product increases systematically with increasing temperatures above this value. At
the higher temperatures, products containing approximately 14% Pb, 30.5%
Fe and 34.5% SO4 are made. Guinier X-ray diffraction analysis showed the
products made in the 80-97C temperature range to consist only of lead jarosite. The products made at 70C contained major amounts of both lead
jarosite and PbSO4, and the overall composition reflects this mixture. Only a
trace a m o u n t of product is formed at 70 C, and that product is contaminated
with PbSO4. Thus, an elevated synthesis temperature is required to produce
a pure lead jarosite product.
Although elevated temperatures enhance the kinetics of lead jarosite precipitation, it is known that a temperature is eventually reached beyond which
jarosite-type compounds are converted to FezO3 [ 18 ]:
2Pbo.5 Fe3 ( S O

4 ) 2 (OH)

6~

3Fe2 0

3 "~- PbSO4

-t- 3H20 + 3He S O 4

(4)

T o d e f i n e t h e u p p e r s t a b i l i t y l i m i t o f l e a d j a r o s i t e in c h l o r i d e m e d i a , a series

332

J.E. D U T R I Z A C

of experiments was carried out over the 80-190 C temperature range using a
titanium autoclave. The amount of product and the product composition realized at the various temperatures are presented in Fig. 3. For the 0.5 MFeCI34.0 M LiC1-0.3 M Li2SO4-20 g/1 PbC12 solutions at pH 0.6, the amount of
product increased systematically with increasing temperature to 150C. There
is an abrupt decline in the product yield at about 155 C, but relatively constant amounts of precipitate are formed at temperatures > 160 oC. Previous
studies carried out in 0.75 M FeCI3-4.0 MLiC1 media at pH 0.25 also indicated a progressive increase in the amount of product formed over the 80155 C temperature range [ 12 ].
The product composition remains relatively constant over the 8 0 - 1 5 0 C
temperature range although the Pb content rises from about 10 to about 12%
Pb as the temperature increases. At temperatures > 150C, however, the
product composition undergoes a dramatic change. The SO4 and Pb contents
drop rapidly and level offat approximately 4% SO4 and 1% Pb. The Fe content, by contrast, rises rapidly and levels off at approximately 60% Fe. The
products made over the temperature range 80-150 oC consist of lead jarosite
together with occasional traces of PbSO4 and Fe203. Because of the operational constraints associated with cooling and opening the autoclave, these
80
70

c~

O,5M FeCI3,4.0M LiCI,O.3 M Li~SO 4

2 0 g / L PbCl 2 , p H = 0 . 6 ' 1 0 0 rain-I

60--

co
50--

##
/o so4

~: 4 0 - ILl

LI.I
o. 3 0 - w

--e

20
I0

qP 8--'6
%Fe

% Pb

~-

8--tJ I

_ _~.~,

.... I-II~" "\~q

/oSO~

0--

~ ~uJ 2
I0 I
0
6O

I
80

I00
120
140
160
TEMPERATURE ( C )

I
180

I
200

Fig. 3. Variation of the amount and composition of the products with synthesis temperatures
transformation of Pb-jarosite to Fe203 at approximately 155C is

from 80 to 190C. The

apparent.

PRECIPITATION

333

OF LEAD JAROSITE

products were generally filtered at a relatively low temperature (i.e., < 60 C).
It is believed that the trace PbSO4 contamination originated during this cooling. The products made at temperatures > 150C consisted of hematite
(Fe203) and minor PbSO4, eq. (4). Although some of the, around 4%, SO4
content of the hematite is due to the presence of trace amounts of PbSO4, the
remainder is intimately associated with the Fe203 itself [ 18 ]. The precipitation of lead jarosite from chloride media is feasible at temperatures as high as
150C. The use of an autoclave to achieve temperatures above the normal
solution boiling point may result in trace contamination of the jarosite with
precipitated PbSO4, but this contamination can probably be removed by selective leaching with brine or ammonium acetate [ 7 ].

E[fect of the concentrations of PbCl2 and FeCl3

The effect of the PbCl2 concentration on the amount and composition of
the products made from 0.5 M FeC13-4.0 M LiC1-0.3 M Li2SO4 solutions at
98 C and pH 0.1 was investigated, and the results are summarized in Fig. 4.
The amount of product increases with increasing PbC12 concentrations to 20
g/l, but is relatively insensitive to higher PbC12 concentrations. The Pb con45

45

O.5M FeCI3,4.0M LiCl ,0.3M LizSO4

9BC, pH=O.I , 2 4 h

4.0

35 - - _ _ l
_~

{~

40

%S04

~30

35

/oFe_

3O
o

25

--

.-I

%Pb

I0

--15

--

~
A
.R___.~---~---Z--

_
,,~
0

2 0 rm
o

--

~ z0
~

Z5~

~L.--'

IO

--5

PRODUCT YIELD

I0

20
[PbOl,] ( g / L }

30

40

Fig. 4. Influence o f the PbCI2 c o n c e n t r a t i o n on the a m o u n t and c o m p o s i t i o n o f the Pb-jarosite

m a d e at 98C.

334

J.E. DUTRIZAC

tent of the product increases from approximately 11% Pb in the precipitates

made from 5 g/l PbC12 solutions to around 14% Pb in the precipitates made
from 30 g/l PbC12 solutions. The increase in the Pb content reflects a reduction in the relative amount ofhydronium ion in the structure of the Pb-H30jarosite. The Fe and SO4 contents of the precipitates are relatively constant
regardless of the PbCI2 concentration of the synthesis solution.
Guinier X-ray diffraction analysis of the products made from solutions
containing 0-20 g/l PbC12 indicated only lead jarosite. Several of the products made from solutions containing 25 or 30 g/l PbCI2 contained traces of
PbSO4 that presumably crystallized from the solution during filtration. Furthermore, if the solutions containing 25 or 30 g/l PbCI2 were allowed to cool
somewhat prior to filtration, PbCI2 crystals formed. For these reasons, most
of the experimental program was carried out using a 20 g/1 PbC12
concentration.
Figure 5 illustrates the effect of the FeCI3 concentration on the amount and
composition of the products made at 98 C from solutions containing 4.0 M
LiCI-0.3 M Li2SO4-20 g/1 PbC12 at pH 0.2. The amount of product increases
with increasing FeCI3 concentration to approximately 0.4 M FeCI3, but thereafter becomes nearly independent of the FeC13 concentration. The product
45

45

I
I
I
4.0M LiCI,2Og/L PbClI,O.3M LizSO. e.
98C,pH=O.2,24h

40--

-;--s--s--t--s--I

35 -

*/*

--40

SO4
- - 35
I

3O

%Fe

.Q

~5 g

o. Z5

-<

u.I

zo ~

20
w
o..
--

~ 15

I I II~
I

"A Pb

- -

l--I

IO --

- - I _ _

PRODUCT

YIELD

I_

15

_ Io

--

O /"

0.2

0.4

0.6

[ Feel:3] ( m o l / L

0.8

Fig. 5. Variation in the product yield and product composition with the FeCI3 concentration o f
the synthesis solution.

PRECIPITATION OF LEAD JAROSITE

33 5

yield versus FeCI3 concentration curve seems to extrapolate through the origin, and the implication is that there is no minimum ferric ion concentration
for the precipitation of lead jarosite in chloride media. A similar conclusion
was reached recently for the precipitation of ammonium jarosite from ammonium chloride media [ 13 ]. Although the Fe and SO4 contents of the products are relatively independent of the FeCI3 concentration, the Pb content
seems to decline slightly as the FeC13 concentration increases. The highest Pb
contents are noted in the products made from solutions which have the highest PbC12/FeC13 ratio, and the most hydronium-rich jarosites are made from
solutions having the lowest PbC12/FeC13 ratio. Despite the slight variation in
the Pb content, and hence the pb2+/H3 O+ ratio of the Pb2_x/2
( H30 ) xFe3 ( 804 ) 2(OH) 6 product, Guinier X-ray diffraction analysis showed
all the products to consist only of lead jarosite.
The role of the total chloride ion concentration
Lead sulphate and PbCI2 were sometimes detected in the products made
from solutions containing high concentrations of PbC12 or in the syntheses
effected at low temperatures. The PbSO4 and PbCI2 contaminants arise because of solubility limitations, and high chloride ion concentrations are needed
to prevent this contamination. To investigate the effect of the chloride ion
concentration on the amount and composition of the products made at 98 C,
a series of experiments was carried out using solutions containing 0.5 M FEC130.3 M Li2SO4-20 g/1 PbC12 and various concentrations of LiC1. The pH of all
the solutions was adjusted to 0.2, and of course, LiC1 was chosen as the chloride source because lithium does not form an end-member which is a jarositetype compound [ 16]. The results of these experiments are summarized in
Fig. 6. Although there is some scatter of the data, the amount of product seems
to be relatively independent of the LiC1 concentration. By contrast, the composition of the product is strongly affected by the total chloride ion concentration. In the absence of LiC1, a Pb-rich product with reduced Fe and SO4
contents is formed. Guinier X-ray diffraction analysis showed this material
to consist of a mixture of Pb-jarosite and PbSO4. The presence of major
amounts of PbSO4 is responsible for the elevated Pb content and reduced
levels of Fe and SO4. As the LiC1 concentration increases, the Pb content of
the product falls sharply and the Fe and SO4 contents rise. This trend continues to approximately 2.0 MLiC1, and further increases in the LiC1 concentration have only a minor effect on the product composition. X-ray diffraction
analysis of the products made from solutions containing 0.5, 1.0 and 1.5 M
LiCI indicated Pb-jarosite together with traces of PbSO4 and/or PbC12. The
products made from solutions containing > 1.5 M LiCI consisted of Pb-jarosite only, and the Pb, Fe and SO4 contents reflect this fact. Clearly, a high total

336

J.E. D U T R I Z A C

55

pH=0.2,98C,24

50

55

0.5M FeCI3,0.3M LizSO4,2Og/L

PbCl z

45

50

-- 4 5

.40
o

-40

% SO 4

35

e:

-~

~o ~

r~

% Pb

'

25

20

15

l,o
5~x'-

PRODUCT YIELD

ol

2
3
[ LiCl] (tool/L)

I
4

Fig. 6. Effect o f LiCI concentration on the amount and composition o f the products made at
98C.

chloride ion concentration is necessary to prevent the contamination of the

Pb-jarosite product by PbSO4 or PbCI>
If the total chloride ion concentration is increased by the addition of a salt
containing a jarosite-forming cation (e.g., K +, Na , NH~-, etc. ), then different results are obtained. In this regard, Fig. 7 illustrates the effect of the NH4C1
concentration on the amount and composition of the products made at 98 C
from 0.5 M FeCI3-0.3 M Li2SO4-20 g/l PbC12 media at pH 0.8. In the absence of NHaCI, a relatively large amount of product rich in Pb but lacking in
NH4 is precipitated. Guinier X-ray diffraction analysis showed these products to be a mixture of Pb-jarosite and PbSO4. As the NH4C1 concentration
increases to around 1 M, the amount of product declines sharply. The Pb
content of the product decreases sharply as the NH4CI concentration increases from 0.0 to 1.0 MNH4. By contrast, the NH4, Fe and SO4 contents all
increase systematically over this concentration range. Guinier X-ray diffraction analysis of these products indicated NH4-jarosite together with progressively decreasing amounts of PbSO4. The presence of > 2 M NH4C1 in the
synthesis solution results in the formation of a relatively constant amount of
ammonium j arosite (NH4Fe3 (SO4)2 (OH)6 ) containing < 0.2% Pb. The addition of even 0.25 M NH4C1 to the synthesis solution suppresses Pb-jarosite

337

PRECIPITATION OF LEAD JAROSITE

55 - -

55

0 . 5 M FeCI3,0.3 M L i 2 S 0 4 , 2 0 g / L PbC I z
50 - 45

pH= 0 . 8 , 9 8 C , 2 4

50
45

0
~40

z
p

% SO4

40

/oFe

8-

o
30~

7-

,,,,,

~O

o"

30] ?

"

25 ~

mg
~

5
O
o

~ ~"~4.

PRODUCT Y I E L D

5
,.o

2.o
3.o
[ , , . c , ] ( mo,,L

,.o

5.0

Fig. 7. Effect of NH4 concentration on the amount and composition of the precipitates. Note
that ammonium jarosite is precipitated from concentrated NH4CI solutions despite the presence of 20 g/1 PbC12.

formation and results in the precipitation of Pb-bearing a m m o n i u m jarosite.

Thus, the precipitation of end-member Pb-jarosite must be effected in concentrated chloride media free from jarosite-forming cations such as K +, Na +
or NH~-.

Effect of the concentrations of sulphate and phosphate

Jarosite formation in chloride media is possible only if an independent
source of sulphate is available. In the current experiments, the sulphate was
added as Li2SO4. Figure 8 shows the effect of the sulphate concentration on
the amount and composition of the products made at 98 C from 0.5 M FEC134.0 MLiC1-20 g/1 PbC12 solutions at pH 0.1. Only traces of a reddish product
were made in solutions containing < 0.1 M Li2SO4, and these products were
Fe-rich but deficient in Pb and SO4. Although Pb-jarosite was detected by Xray diffraction analysis of one of the products made at 0.05 M SO4, the other
precipitates were poorly crystallized. These observations seem to confirm that
a minimum sulphate concentration is required for jarosite precipitation from
chloride media [12,13], and that the critical SO4 concentration is 0.05-0.1
M. As the SO4 concentration increases above 0.1 M Li2SO4, the amount of

338

E. DUTRIZAC

45

40

--

0 . 5 M FeCl 3, 4 . 0 M L i C I , 2 0 g / L
\
98C, pH : 0 . 1 , 2 4 h

45

PbCI z
--40

% so.
35

~35

~o

~o

L_t

E
g

Fe

30

25 o

~. 25

.<

2op
7,i

~:

15 __

%Pb

./,

--

IO

--IO

(~
0

~j-E ~
/

15

~- / " E
0.1

PRODUCT YIELD

I
0.2
[ Li,S04 ]

Fig. 8. Effect of the L i 2 S O 4

in 0.5 M FeC13 media.

I
0.3
( mol/L )

I
0.4

o
0.5

concentration on the amount and composition of the products made

product also increases and in a nearly linear manner. As the sulphate concentration increases, the Pb and SO4 contents of the precipitates increase, but the
Fe content decreases. These trends continue to approximately 0.2 M Li2SO4,
and further increases in the Li2SO4 concentration have no significant effect
on the product composition. The precipitates made from the sulphate-rich
solutions contain approximately 14% Pb, 31% Fe and 34% SO4. These compositions are indicative of Pb-jarosite which was the only phase detected by
Guinier X-ray diffraction analysis. A moderately high sulphate concentration
(0.3 M SO4 ) is desirable for lead jarosite formation in chloride media.
Phosphate is a common impurity in metallurgical feeds, and the effect of
the PO4 concentration on the precipitation of Pb-jarosite from chloride media was examined. Figure 9 shows the effect of the PO4 concentration (added
as H 3 P O 4) on the composition of the products made from solutions containing 0.5 M FeC13-4.0 MLiC1-0.25 MLi2SO4-20 g/1 PbC12 at pH 0.1 and 98 C.
Although not shown on the graph, the amount of product increased in a linear
manner from 3.6 g in the solution containing 0.0 M PO4 to 17.2 g in the
medium containing 0.075 M PO4. In the absence of added phosphate, Pbjarosite containing 13% Pb, 30% Fe and 34% SO4 is precipitated. As the PO4
concentration increases, the Pb and SO4 contents decline and the PO4 content

339

PR ECI P I T A T I O N O F LEAD J A R O S I T E

I
I
I
I
[
0.5 M FeCl3,4.0 M LiCI,O.25 M Li~SO4,ZOg/L PbCI 2
pH= 0 . 1 , 9 8 C, 24 h

50
4~

3~i

z~

30,~

~:

Po i403o

35

/',

%Fe

25 ..<

15

oZ
0

% SO4

~ 15

% Pb
0.02

0.04

0.~

0.C~3

O.iO

[ P04] ( t o o l / L )

Fig. 9. Variation of the composition of the products made from solutions containing 0.25 M
ki2SO4but various concentrations of PO4.
rises sharply; by contrast, the Fe content remains relatively constant at approximately 30% Fe. Guinier X-ray diffraction analysis showed that the products made from solutions containing 0.00 or 0.01 M PO4 consisted of only
Pb-jarosite. The product made from the 0.01 M PO4 solution contains 6.2%
Pb and 3.99% PO4, and the implication is that up to 4% PO4 can substitute in
the Pb-H30-jarosite structure. This conclusion is also supported by the 33.5%
SO4 content that is indicative of "jarosite". The low Pb content, however,
could equally indicate that the product is contaminated with an amorphous
Fe-SO4-PO4 phase. X-ray diffraction analysis of the products made from solutions containing 0.02 to 0.05 M PO4 indicated Pb-jarosite with progressively increasing amounts of the ferric analogue of the ferrous-ferric phosphate, giniite [19]. Giniite has the formula FeZ+Fe 3+ (POa)4(OH)2"2H20
and the ferric analogue is Fe3.~ ( PO4 ) 4 (OH) 2" 3H20. The product made from
the solution containing 0.075 M PO4 consisted of giniite only. The compositional data, when coupled with the X-ray diffraction results, indicate that Pb
is not significantly incorporated in the giniite structure. By contrast, it seems
that up to 12.5% SO4 substitution is possible. Overall, the data suggest that
only minor amounts of P04 can be incorporated in the structure of the Pbjarosite made from chloride media. It is remarkable, however, that a rela-

340

J.E. D U T R I Z A C

tively low P O 4 concentration (0.075 M P O 4 ) can entirely suppress the precipitation of Pb-jarosite from a relatively concentrated FeC13 solution.

Effect of retention time

The effect of the retention time on the amount and composition of the
products made from 0.5 M FeC13-4.0 M LiC1-0.3 M Li2SO4-20 g/1 PbC12
solutions at pH 0.2 and 98C is illustrated in Fig. 10. Less than 0.2 g of product is made during the first 2 h of heating at 98C, but the amount of precipitate increases for longer retention times. Steady state conditions seem to be
realized after 24-30 h of heating, and the product yield stabilizes under these
conditions. It is interesting to note that this behaviour is in marked contrast
to the rate of precipitation of ammonium jarosite from ammonium chloride
media [13] where steady state conditions are realized within 8 h. The Pb
content of the product increases significantly as the retention time increases
from 3 to 24 h, and eventually levels off at around 16% Pb. The SO4 content
remains relatively constant in all the precipitates, but the Fe content seems to
decrease slightly as the retention time is increased. Guinier X-ray diffraction
analysis of the various products indicated only Pb-jarosite. The combination
of the compositional and X-ray data, however, suggest that a Pb-H30-jaros55--

50

0.SM FeCl3,4.0 M LiCI,O.3M Li~SO 4

2 0 g / L PbCl~, pH= 0 . 2 , 9 8 " C

55

50

45

45

-40

4O

% so4

o3

#_ 35 "%" "

"J--l--.

"-.

-35

oo

F- 30

oO

-30
%Fe

.<

25

-25

(.9
,~ 20
% Pb

/ | ~ ;

*o

-15

I0

I0
~

~ee

PRODUCTYIELD
_ -A------A---

ol0

~20 ~

15

c~g'l

10

20

3(3
4(3
TIME(h)

50

I o

60

Fig. 10. Influence of retention time at 98C on the amount and composition of the lead jarosite
products.

341

P R E C I P I T A T I O N O F LEAD J A R O S I T E

ite is made during the initial stages of reaction, but that this phase is gradually
transformed into a Pb-rich jarosite containing approximately 16% Pb. The
precipitation of Pb-jarosite from concentrated chloride media seems to be a
relatively slow process and approximately 24 h are required to achieve steadystate conditions.

The behaviour of silver during jarosite precipitation

Silver chloride is slightly soluble in concentrated chloride media [ 20 ], and
the effect of the AgC1 concentration on the amount and composition of the
products made from 0.5 M FeCI3-4.0 M LiC1-0.3 M LiSO4-20 g/1 PbC12 solutions at pH 0.6 is illustrated in Fig. 11. It is clear that increasing the AgC1
concentration to 1.2 g/1 has no significant effect on either the amount or composition of the products. In all instances, Pb-jarosite was the only phase detected by Guinier X-ray diffraction analysis, and the product composition is
consistent with this compound. The Ag content of the precipitates is very low
and varies from 40-70 ppm Ag; the Ag content does not increase systematically as the AgCI concentration of the solution increases.
Figure 12 presents the results of similar experiments carried out to ascerI

5C

55

0.5 M FeCls,4.0 M LiC1,0.3 M Li t S O 4

20 g / L PbClz ,98C, pH =0.6,24h

--50

4~

--

(:~ 4C
o3

SO4

45

-- 40

--

55
"o

3o

--30 ~

/oFe

--25 N

2C
--15
% Pb
IC

__~__~._

--I0

PRODUCTYIELD

,,

--5
. ~ % Ag

i
0.2

i
0~'4

i
0.-6

z
078

I
1.0

iv1.2

I
1.4

0
1.6

[~c,] (g~L~
Fig. 11. Effect of the AgCI concentration on the amount and composition of the Pb-jarosites
made in the presence of 20 g/l PbC12. The Ag contents range from 40 to 70 ppm.

342

J.E. DUTRIZAC

I 0 . 5 M Fe
LCI3,4.0M
pH:O.8,

50

I
I M L inz S O 4 I
NI"~.CI,O.3
98C, 24 h

45
%

L.

IJ

55

50

-- 45

SO4

-40

--35
o

%Fe

3(;

--30
-<

zsi

-25

2O

-20

15

,d

PRODUCT YIELD
- - - i ~ - - - -A-

--

-&--- _4

g
~"

-15

"ZI'- - -

-10

(~

J.

o.,

% NH4
o

_a~'*/#g

0.6
.8
,.o
[ . g c , ] I g , L,

,,

-- 5

,6

Fig. 12. Effect of the AgC1 concentration on the amount and composition of the ammonium
jarosites made in the presence of 4.0 M NH4CI. The Ag contents are < 50 ppm.

tain the extent of Ag incorporation in a m m o n i u m jarosite. Increasing AgC1

concentrations to 1.2 g/1 have no significant effect on either the amount or
composition of the products made from 0.5 M FeC13-4.0 M NH4C1-0.3 M
Li2SO4 solutions at pH 0.8 and 98C. Guinier X-ray diffraction analysis of
the various products indicated only NH4-jarosite and the product composition is consistent with this compound. The Ag contents of the various precipitates are consistently < 50 p p m Ag, and there is no systematic variation of
the Ag content with the AgC1 concentration. The implication is that much of
the Ag content is due to mechanical entrainment or surface adsorption.
Experiments were also carried out to determine if end-member Ag-jarosite,
AgFe3 (SO4) z (OH) 6, could be precipitated from chloride media. Figure 13
shows the effect of AgC1 concentrations as high as 2.0 g/1 on the amount and
composition of the products made from 0.5 M FeC13-4.0 M LiC1-0.3 M
Li2SO4 solutions at pH 0.6. A relatively small, and essentially constant, amount
of product is made at all the AgC1 concentrations studied. Although there is
considerable scatter of the analytical data, there does not seem to be a consistent variation in either the Fe or SO4 contents with increasing AgC1 concentration. Notable is the fact that the Fe content is greater than that of SO4, and
this suggests that the jarosite is contaminated with another phase. The Ag
contents of the precipitates range from 18 to 151 p p m Ag whereas end-mem-

PRECIPITATION OF LEADJAROSITE
5~
5C

343
i

55

O. SM FeCl3t4.O M LiCl,O.3 M Li=SO 4

O o / L PbClz,980Ci pH =0,6~ 2 4 h

4.=
%Fe

40
m

50

45

40

35 I

35

8
3o ~

% so,,

z5 P

w 25
~ 20
15

15

Io-

0
PRODUCT YIELD
._A_ _ . . A _ _ _ __.~_ _

____ZX_ . . . .

C:
o

0.5

1.0

-5

, 1 ~ "J'/* Ag,L
1.5

2.0

2.5

[AoCI ] ( 0 / L )

Fig. 13. Effect o f the AgCI concentration on the a m o u n t and composition o f the products made
in the absence o f PbC12 and jarosite-forming "alkali" chlorides. The Ag contents vary from 18
to 151 ppm.

ber Ag-jarosite contains 18.9% Ag. Guinier X-ray diffraction analysis of the
various products indicated hydronium jarosite and a poorly crystallized phase;
presumably the poorly crystallized phase is an iron-hydroxy-sulphate species
which is responsible for the high, and somewhat erratic, iron content of the
precipitates. There was no indication of Ag-jarosite in any of the precipitates,
and this observation is consistent with the very low Ag contents detected.
Figures 1 1 and 12 indicate that Ag is not significantly incorporated in the
structures of either Pb-jarosite or NH4-jarosite made from chloride media.
Furthermore, Fig. 13 shows that end-member Ag-jarosite cannot be precipitated from concentrated chloride solutions. These observations are in marked
contrast to the behaviour of Ag in sulphate media where end-member Agjarosite is readily formed and where Ag-rich jarosites are precipitated in the
presence of PbSO4 or (NH4)2SO4 [ 9,10 ]. Presumably, these differences are
attributable to the strong complexation of silver ions in concentrated chloride
media [ 21 ]:
Ag + + C1- ~ AgC1o

log K] = 3.5

(4)

AgCI+C1--,AgC1z

logK2 = 1.9

(5)

344

J.E. DUTRIZAC

AgC12- + C 1 - - , A g C I 2-

logK3 =0.3

(6)

pb2+ +C1- ~PbC1 +

logKl = 1.5

(7)

The silver-chloro complexes are two orders of magnitude more stable than
those of lead, and the high stability, coupled with the relatively low silver
solubility [20], results in very low concentrations o f " f r e e " Ag + ions in concentrated chloride media. Because uncomplexed Ag or Pb 2+ ions are probably required to form jarosite-type compounds, silver remains in solution and
does not precipitate as a jarosite-type compound.
CONCLUSIONS

Lead jarosite, Pbo.sFe3 (SO4)2 (OH)6, is readily precipitated from concentrated FeC13-LiC1-PbC12 media provided that an independent sulphate source
is available. The amount ofjarosite is strongly dependent on the solution pH;
initial pH values <0.0 result in no product whereas pH values >0.8 cause
the co-precipitation of amorphous iron compounds. The Pb-jarosite composition, however, is not significantly affected by pH variations in the 0.0-0.8
range. The amount of product increases systematically with increasing temperatures in the 70-150C range. Above 150C, however, Pb-jarosite is
unstable, and Fe203 is precipitated. Although the Pb content of the product
increases slightly as the temperature is increased, the Fe and SO4 contents of
the Pb-jarosite are relatively constant. Increasing the PbC12 concentration of
the solution causes a progressive increase in the amount of product, and a
modest increase in the Pb content of the jarosite. By contrast, the Fe and SO4
contents of the precipitate are essentially independent of the PbC12 concentration. In the presence of excess sulphate, increasing FeC13 concentrations
result in a systematic increase in the amount of Pb-jarosite precipitated. The
product composition is relatively independent of the FeC13 concentration although the Pb content decreases slightly as the ferric ion concentration increases. A m i n i m u m sulphate concentration of approximately 0.1 M is required before Pb-jarosite precipitation occurs. The amount of product,
however, increases linearly with sulphate concentrations in excess of 0.1 M.
The Pb and SO4 contents of the product increase rapidly as the SO4 concentration increases to approximately 0.2 M, but are insensitive to higher sulphate concentrations. A high total chloride ion concentration is required to
prevent the co-precipitation of PbSO4, and the presence of at least 2 M LiCI
was necessary in the current experiments. When the solution contained > 2
M LiCl, the product composition was essentially independent of the total
chloride ion concentration. Increasing the total chloride ion concentration
with NH4C1 resulted in the precipitation of a m m o n i u m jarosite containing
< 0.2% Pb. it was shown that the precipitation of Pb-jarosite from chloride
media is a relatively slow process and that approximately 24 h are required to

PRECIPITATION OF LEAD JAROSITE

345

attain steady-state conditions at 98 C. It is also notable that the Pb content

of the jarosite phase increases as the retention time is extended from 2 to 24
h. The addition of phosphate ion to the solution resulted in the progressive
precipitation of the iron phosphate, giniite, Fe4.5 (PO4) 4 ( O H ) 2" 3 H 2 0 . The
presence of only 0.075 M P O 4 in the 0.5 M FeC13 solution completely suppressed Pb-jarosite precipitation: only giniite was formed. Efforts to incorporate silver in the structures of Pb-jarosite and NH4-jarosite made from
chloride media were not successful; the silver contents never exceeded 70 ppm
Ag. Also, it was not possible to precipitate end-member Ag-jarosite, and this
behaviour is attributed to the strong complexation of silver in concentrated
chloride media.
ACKNOWLEDGEMENTS

The assistance of D.J. Hardy with the experimental program and J.L. Jambor and P. Carriere with the X-ray diffraction studies is gratefully
acknowledged.

REFERENCES
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chloride leach (FCL) process for the treatment of complex base metal sulphide ores. In:
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5 Dutrizac, J.E., Elemental sulphur formation during the ferric chloride leaching ofchalcopyrite. Hydrometallurgy, 23 ( 1990): 153-176.
6 Au-Yeung, S.C.F. and Bolton, G.L., Iron control in processes developed at Sherritt Gordon
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Ellis Horwood, Chichester, UK ( 1986 ), pp. 131-151.
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9 Dutrizac, J.E. and Jambor, J.L., Behaviour of silver during jarosite precipitation. Trans.
Inst. Min. Metall., 96 ( 1987): C206-218.

346

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10 Dutrizac, J.E. and Jambor, J.L., Formation and characterization of argentojarosite and
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