Ammonium jarosite formation in ferric
chloride leaching processes
J. E. Dutrizac
CANMET, Ottawa, Canada
SYNOPSIS
Ammonium jarosite is readily formed
from FeC1 3-NH4Cl leaching solutions
containing an independent source of
sulphate. The principal factors
affecting NH4-jarosite formation are pH,
temperature and the concentrations of
sulphate and FeC1 3. At 98C in 4 M
NH4Cl media, no precipitate forms when
the pH is <0.4; pH values >1.8 result in
difficult-to-filter products. Only
traces of jarosite are precipitated at
50C, but the amount of product
increases systematically with increasing
temperatures above this value. A
minimum sulphate concentration is
required for NH -jarosite precipitation,
and the critica1 sulphate concentration
is a function of the ferric ion
concentration. When excess sulphate is
present, the amount of jarosite
increases directly with the FeC1 3
concentration. The addition of jarosite
seed accelerates the precipitation
reaction. The jarosite precipitation
reaction is relatively independent of
the concentrations of NH4Cl (2.0-5.0 M)
and the FeC1 2 reaction product (0.0-
1.0 M FeCl~). Regardless of the PbC1 2
concentrat10n of the solution, the
jarosite products precipitated from 4 M
NH 4Cl solutions have Pb contents <0.2%.
The pb content of the ammonium jarosite
exceeds 1% only when the NH 4Cl
concentration is <2 M. Regardless of
the AgCl concentration of the solution,
the silver content of the ammonium
jarosite is always <0.01% Ag. The low
levels of Pb and Ag incorporation in the
ammonium jarosite are attributed to the
strong anionic complexation of these
elements in concentrated chloride media.
INTRODUCTION
Jarosite precipitation
(MFe3(SO~)2(OH)6where M is K+, Na+, NH/,
Ag+, %Pb+, etc.) is widely used in the
zinc industry to remove iron from acidic
zinc sulphate processing solutions
(1,2). The jarosite process is commonly
65
J. Vereecken, EMC '91: Non-Ferrous Metallurgy-Present and Future
Institution of Mining and Metallurgy 1991
carried out at about 95C in the
presence of jarosite seed to yield a
precipitate which can be readily
filtered and washed. Ammonium jarosite
and sodium jarosite are the species most
commonly precipitated although lead-
silver jarosite is formed unavoidably at
the higher temperatures (-155C)
associated. with the 02-H2S04 zinc
pressure leaching process (3). Although
most of the developmental work on
jarosite precipitation has focussed on
sulphate media, it is known that
jarosites can be readily precipitated
from chloride solutions provided that an
independent source of sulphate is
available (4). In fact, the Duval CLEAR
process (5) used potassium jarosite
precipitation at 150C in the second
stage of a two-stage CuC1 2-FeC1 3-KC1-
NaCl leach to control sulphate as well
as excess iron. The process ran for
several years on a demonstration plant
scale, and few problems were encountered
with the jarosite precipitation part of
the circuit. Furthermore, turboaeration
is often used to maintain the iron
balance in FeC1 3 leaching processes (6),
and the iron precipitate made in the
turboaerator consists principally of
jarosite and FeO.OH. The presence of
jarosite in the turboaerator product
helps to control the sulphate build-up
in the chloride leaching solution
although complementary methods of
sulphate control may be necessary to
maintain a low sulphate concentration
(7)
Because they produce elemental
sulphur rather than S02 gas, FeC1 3
and/or CuC1 2 leaching technologies
continue to be developed for a variety
of sulphide ores and concentrates. The
technique is especially suited for
pyrite-rich feeds because the pyrite is
not significantly attacked. In this
regard, CENIM (Centro Nacional de
Investigaciones Metalurgicas, Madrid,
Spain) and LNETI (Laboratorio Nacional
de Engenharia e Tecnologia Industrial,
Lisbon, Portugal) have recently
developed a two-stage ammonium chloride
 66
leach process for the treatment of
pyritic Zn-Pb-Cu-Ag bulk concentrates
that solubilizes the required metals
while leaving the pyrite in the leach
residue (8). The two-stage leaching
process is carried out at 105C in
concentrated NH 4Cl media and under 1 atm
02 pressure. The use of concentrated
ammonium chloride solutions offers
advantages with respect to pH control,
the rate the leaching, and the
subsequent recovery of Zn and Cu by
solvent extraction methods. These
advantages could lead to the commercial
acceptance of the CENIM-LNETI process as
well as the development of other NH4Cl-
based leaching technologies. The
presence of ferric chloride and sulphate
ion in the moderately acidic NH 4Cl
solutions likely to be employed in an
ammonium chloride leaching process could
result in the precipitation of ammonium
jarosite, NH 4Fe 3 (S04)2(OH)/i' Although
some jarosite preclpitatlon is desirable
for the control of sulphate and
impurities, the formation of excessive
amounts of jarosite would result in the
unacceptable loss of both ammonium ion
and the ferric chloride lixiviant.
Furthermore, the processing solutions
will probably contain dissolved PbCl~
and AgCl, and the incorporation of Pb or
Ag in the structure of the ammonium
jarosite, which is discarded in the
leach residue, is an undesirable
possibility.
The above discussion indicates the
importance of understanding the jarosite
precipitation reaction in concentrated
ammonium chloride media and of defining
the level of impurity incorporation in
the ammonium jarosite precipitate. To
this end, a systematic study of the
parameters affecting the formation of
ammonium jarosite in concentrated
ammonium chloride media was carried out.
The extent of Pb and Ag incorporation in
the ammonium jarosite precipitate was
also determined, and the results of
these investigations are summarized in
this report.
EXPERIMENTAL
Reagent-grade chemicals were used
for all the experiments. Most of the
experiments were carried out at 98C in
glass reaction vessels fitted with
titanium baffles. In all experiments,
appropriate concentrations of NHCl,
FeCl~, PbC1 2, AgCl, etc. were heated for
a sUltable period in a stirred solution,
the pH of which was adjusted with HCl or
Li 2C0 3 A three-point calibration
procedure, with buffer solutions at
pH = 4, 2 and 1, was used to calibrate
the pH meter. Lithium sulphate was
added as the independent sulphate
source, and in general, lithium
compounds were chosen because lithium
does not form an end-member jarosite-
type compound (9). One litre of
solution was used for each test, and the
concentrations employed bracketted those
likely to be employed in an ammonium
chloride leaching process. At the end
of the experiments, the jarosites were
filtered and washed with copious amounts
of water to remove any entrained
solution. The pH was not controlled
during either the precipitation or
washing operations. Finally, the
jarosites were dried at 110C prior to
analysis. Because the synthesis
solutions often contained dissolved
PbCl~, the possibility of PbS0 4
preclpitation exists. Accordingly, the
products were checked for possible PbS0 4
contamination by the use of a Guinier
deWolff focussing X-ray camera and
cobalt radiation. Previous studies have
shown that about 0.25% PbSO~ is readily
detected as a "trace" constltuent by
this technique.
RESULTS AND DISCUSSION
Effect of solution pH
Figure 1 illustrates the effect of
the initial pH of a 0.5 M FeC1 3 - 4.0 M
NH Cl - 0.3 M Li 2S0 4 - 20 giL poC1 2
solution on the amount and composition
of the products formed at 98C after
24 h of reaction. Negligible amounts of
product are made at pH values <0.4, and
this situation prevails even for NH4Cl
concentrations as high as 6.0 M or as
low as 0.5 M NH4Cl. Previous studies on
the precipitation of Na-jarosite from
3 M NaCl media (4) showed that no
product was precipitated for free acid
concentrations >0.1 M HCl, and this
observation is in general agreement with
the current results. The amount of
product increases in a nearly linear
manner with increasing pH values above
0.4. When the initial solution pH is
>1.8, however, iron hydrolysis and
precipitation occur at or near room
temperature, and the precipitates are
difficult to filter. The natural pH of
a O. 5 M FeC1 3 - 4. 0 M NH 4Cl - O. 3 M
Li 2S04 solution is 0.8-0.9, and as a
result, most of the subsequent
experiments were done using an initial
pH of 0.8.
Jarosite formation generates large
amounts of acid, and as a consequence,
high initial acidities reverse the
precipitation reaction and result in
reduced product yields.
NH4+ + 3Fe3+ + 2S042- + 6H20 -
In the current experiments, initial pH
values <0.4 are sufficient to prevent
the precipitation of any product. If
 67
the pH is raised too high, however, The Influence of Precipitation
other hydrolysis reactions occur, and Temperature
poorly filterable ferric hydroxide is
formed. Figure 2 shows the effect of the
synthesis temperature on the amount and
Fe 3+ + 3H 20 - Fe ( OH) 3 + 3W [ 2] composition of the products made by
heating a 0.5 M FeCl 3 - 4.0 M NH 4CI -
Although the amount of product 0.3 M Li 2S04 - 20 giL PbCl 2 solution at
increases significantly as the pH pH = O.S for 24 h.
increases, the product composition is
essentially independent of pH. Over tl 55 I I I 5
I I
pH range 0.4 to 1.S, the products 0.5 M FeCI3;4.0 M NH4 CI,O.3 M UzS~
contained 3.7% NH/, 34.5% Fe and 40.0% 50 r- pH-a.8, 24h, 20g/L PbClz -50
sot; these values correspond
approximately to those of 45 I- - 45
(NH 4)Fe 3 (S04z)2(OH)6: NH/ 3.75%, Fe %SO~-
34.93%, S04 - 40.05%. Although all the
synthesis solutions contained 20 giL 0 40 v 0 Q ~ -40
PbCI 2, the products consistently
(/)
0 g 0 ~

contained <0.2% pb. Guinier X-ray ~35 -

.Q %Fe -35
diffraction analysis of the products IL
; e - e - ,_ _e-t-'-I- "t
::t
made over the pH range 0.4 to 1.S z 30 -
:I:
-30
c
c:
confirmed that only ammonium jarosite I-
C
r
was precipitated. Lead sulphate was no z
detected in any of the products, and
~
u 25 - 6 20 gIL PbCl z
-25 ~
analysis of the solutions at the
a::
~
IL o giL PbCl z r
c:
completion of the experiments showed I-
:I:
20 ~ -20 ~
that virtually all of the lead remained S?
dissolved in the concentrated chloride ~
3: 15i- PRODUCT YIELD -15
media.
10-
.-- -~ - 10

- -
~ ...... ..- A
6
55 55 51- .- .- 6 6 %NHt - 5
0.5 M FeCI, ,4.0M NH4CI,O.3 M Li z S0 4 ~l-e-'--e--.-I-.-
50 20 gIL PbCl z ,98C,24 h 50 0""- I e.L 1 .l~%Pbl
0
60 70 80 90 100 110
45 45 TEMPERATURE 1C I

%SO~- Fig. 2 - Variation of the amount and

~
(/)40 --0
~ 8
Os a e 8 40 composition of the products

i with synthesis temperature in
e e the absence of jarosite seed.
f,35 e_e_._e_e_e_e_ 35"0
; e e ::0
e e %Fe 0
:I:
Z30 /
c Although only a small quantity of
/ 30~ material is formed at 60C, higher
I- //6 --t
Z -< temperatures result in the precipitation
~

~ 25 /
/
25 r m of significant amounts of jarosite. It
~ ...
/6
~
IL
IJ/ 6
C
is interesting to note that in the
~2O PRODUCT 6/6 IRON
HYDROL'I'SIS 20- corresponding ferric sulphate-alkali
.. sulphate systems (11), no product is
<!I /
YIELD
W
3:
15 15
formed in 24 h at temperatures <SOoC.
6/
6~
The implication is that jarosite
/
/ formation in chloride media is in many
10 /
/-9
10 respects "easier" than in the
6
/ corresponding sulphate system despite
5 y. "IoNHt
5 the fact that pH control is more
--o-,,~
/
So 6 e 61 0 critical in chloride solutions. The
%Pb
0 0
products prepared over the temperature
0 0.4 0.8 1.2 1.6 2.0 range 60-100C have relatively constant
pH ammonium, iron and sulphate contents
which are indicative of ammonium
jarosite. Although the pb contents of
the products made at temperatures >SOC
Fig. 1 - Effect of the initial pH of are always <0.2% Pb, the products formed
the synthesis solution on the at SO or 75C contained greater amounts
product yield and product of lead. Guinier X-ray diffraction
composition. analysis of these two samples showed the
presence of trace amounts of PbS0 4 and
PbCl 2 which presumably crystallized from
the concentrated chloride solutions at
the lower temperatures employed.
Because of the PbS04/PbCl 2
 68
contamination, the lower temperature
tests were repeated (solid triangles) ~r----r----r----r----r----r----rl55

us ing O. 5 M FeCI - 4. 0 M NH4CI - 0.5 MFeCls.4.0 M NH 4CI.20g/L PbCI 2

0.3 M Li 2S04 sOlulions containing no 50 pH-0.8.98OC.24h
pbCI. The results of these tests are
consistent with those obtained in the 45
45
presence of 20 giL PbCI 2 , except for the
minor contamination caused by PbS04 or % so!"
PbCI 2 The data of Figure 2 clearly g40 o
40
show that high temperatures promote i
jarosite precipitation. Unfortunately,
high temperatures are also required for J:
.
~35
e e
%Fe
e
35 'tl

~
the effective leaching of refractory Z
30~
c
sulphide minerals such as chalcopyrite .... 30 ..,
or tetrahedrite. Consequently, some ~ -<
u
ammonium jarosite precipitation is ~ 25 / 25 iTi
r
likely to occur in any FeCI 3-NH4CI
/
/1:. c
....
leaching process. i; PRODUCT YIELD ,,/
iii
20
;:r
/
~
Effect of Sulphate and Ferric Ion 15 /
/
15
Concentrations If'
/
/
The effect of the initial sulphate 10 /
/ 10
/1:.
concentration of the FeCl 3 - 4.0 M NH4CI t:."
- 20 giL PbCl 2 solution on the amount 5 // % NH! 5
and composition of the products made at -e-t-e-e---e----e ---- e -
%Pb
9SoC and pH = O.S was determined. "iY
0'~~1:.~4-~-4----~---4----4---~~0
Figure 3 presents the results obtained o 0.1 0.2 0.3 0.4 0.5 0.6
when the solutions contained 0.5 M
FeCI 3 , and Figure 4 shows the
corresponding data generated from 0.2 M - Effect of the Li 2S04
FeCl 3 media. In both systems,' .there is Fig. 3
a minimum sulphate concentration concentration on the amount
required before any jarosite is and composition of the
precipi tated. In 0.5 M FeCI solutions products made in 0.5 M FeCl 3
the critical sulphate concen~ration is media.
approximately 0.05 M whereas in 0.2 M
FeCI~ media the critical sulphate level ~r-----'------'------'------' ~
is about 0.075 M. Thus, the critical 0.2 M FeCl s 4.0 M NH 4 CI. 20 gIL PbCl z
sulphate concentration seems to increase 50 pH=0.8.98C.24h 50
as the FeCl 3 concentration decreases.
For sulphate concentrations less than 45
the critical value, only trace amounts 45 %SO~"
of an amorphous reddish phase are 0
produced. Above the critical sulphate c!40 --0 0
0
0 40
concentration, progressively greater en
amounts of yellow ammonium jarosite are If
-35 "!oFe 35
formed. In fact, the amount of product if e e
.
e
e e 'tI
increases linearly with increasing 308
:0

sulphate concentration for solutions ~30 c:

containing either 0.5 M FeCl 3 (Figure 3) ....z (')
-l
or 0.2 M FeCl 3 (Figure 4). As would be ~ 25 25~
expected, the slope of the product yield 0:: ITI
r
versus sulphate concentration curve is ~ 20_
c
.... 20
greater at the higher FeCI~ J:
I!)
oe
concentration, but the rat10 of the iii 15
slopes (-1.3) is less than the ratio of ~ 15
the initial FeCl 3 concentrations (2.5). 10
The products made from 4.0 M NH 4CI -
20 giL PbCl 2 solutions containing either
0.2 or 0.5 M FeCl 3 have virtually the 5
same composition. Furthermore, the
product compositions are essentially 0
independent of the Li 2S04 concentration; Q.4
the lead contents are conSistently <0.2%
Pb. All the compositions reflect
ammonium jarosite which was the only
phase detected by Guinier X-ray Fig. 4 - Effect of the Li 2S0 4
diffraction analysis. concentration on the amount
and composition of the
products made in 0.2 M FeCl 3
media.
 69
Previous studies on the synthesis solutions containing 20 giL PbCI 2 , the
of sodium jarosite from 0.5 M FeCI, - resulting precipitate contained -0.8% Pb
0.1 M FeCl 2 - 3 M NaCI solutions a~so (4)
indicated a critical sulphate 55 55
concentration below which no jarosite
precipitation occurred (4). In those 4.0 M NH4CI,O.3 M Li2 So..,20g/L PbCI 2
studies, the critical sulphate 50 pH=0.8,98C,24h 50
concentration was found to be -0.05 M,
in general agreement with the results of 45 45
the current investigation. A minimum %SO~-
sulphate concentration for jarosite 0
0
40
formation in chloride media seems to be r:J 40 0
0 a 0 0 0 0
<II
a general phenomenon, and the 0

implication is that jarosite ~35 35 ~

f 0
precipitation will not reduce the
sulphate concentration of a chloride
~
Z
30
-e-._e-e--e
e
e
%Fe
e-
30~
o
c:

leaching solution to low levels. The I-

practically attainable sulphate
concentration is likely to be about
0.1 M or -10 giL sot (7).
Figure 5 shows the effect of the
initial FeCl 3 concentration on the
amount and composition of the products
made at 98C from 4.0 M NH4CI - 0.3 M
Li zS04 - 20 giL PbCl 2 media at pH = 0.8.
The amount of product increases in a
linear manner with increasing FeCI
concentration, and the product yield
curve extrapolates through the origin.
That is, there does not seem to be a
critical ferric ion concentration for
jarosite formation provided adequate
sulphate is available in solution.
Although the amount of precipitate
increases with increasing FeCl 3
concentration, the composition of the
product is relatively constant at -3.2%
NH/, -32.5% Fe and -39.5% sot. It is
significant that there is no pronounced
change in the iron content of the
precipitate as the iron concentration of
the solution increases from 0.1 to 0.7 M
FeCI 3 The Pb contents of the products
made from solutions containing >0.2 M
FeCl 3 were consistently <0.1% pb. By
contrast, the Pb contents of the three
products made at 0.2 M FeCl 3 were 0.13,
0.16 and 0.43% Pb; the corresponding
analyses for the products made in 0.1 M
FeCl 3 media were 0.27 and 1.30% pb.
Although Guinier X-ray diffraction
analysis showed all the products to
consist only of ammonium jarosite, the
lead-rich products had slightly
different unit-cells indicative of an
enhanced level of ~Pbz+ substitution for
NH/ in the ammonium jarosite structure.
It seems that low ferric ion
concentrations, and their concomitant
low product yields, favour an enhanced
level of pb incorporation in the
ammonium jarosite although the extent of
pb incorporation is always relatively
small. The amount of lead incorporation
depends on the jarosite species formed
as well as on the concentrations of the
solution species. For example, when
sodium jarosite was precipitated from
0.5 M FeCl 3 - 3 M NaCI - 0.3 M Li 2S04
Z ~
I'll
W
0
II: 25 25b
~ ~
I-
20
~ 20
III
W
~
15 PRODUCT YIELD , ",fl 15
" "6
10 , " AS' 10
.......
.......'6
,6 , " 6 %NH: 5
5
_~._e_e _ _ e _ _ e _ _e-
" !'IoPb
0
0 0.1
0
0.8
Fig. 5 - Variation of the product yield
and product composition with
the FeCl 3 concentration of the
solution in the presence of
excess Li 2S04
Effect of Retention Time and Seeding
The jarosite precipitation
experiments were done in a batch mode.
The solutions were prepared at room
temperature and were then heated to the
98C reaction temperature. About 1 h
was required to heat the charge, and
some reaction inevitably occurred during
the heating-up period. This point is
reflected in Figure 6 which shows the
amount and composition of the products
as a function of the retention time at
9aoc. A modest amount of precipitate is
noted at "zero" time, and this reflects
the material precipitated during the 1 h
heating-up period. Prolonging the
reaction at 98C for 6-8 h results in
the progressive formation of more
jarosite. Thereafter, there is only a
slight increase in the product yield for
retention times as long as 48 h.
Previous work on the precipitation of
alkali jarosites in ferric sulphate
media (11) showed that -15 h was
necessary to achieve nearly steady state
conditions at 97C in the sulphate
system. A significantly shorter time is
required to achieve steady state
conditions in chloride media although
the final amount of precipitate is less
than that in the sulphate system.
 70

the one-hour heating-up period. The

0.5 M FeC1 3 ,4.0 M NH 4 CI,O.3 M Li ZS04
amount of product increases with
50 20g/L PbCl z ,9S o C, pH=O.S
prolonged retention time for about 2 h,
but thereafter the product yield
increases only gradually. Comparison
45 45 with the analogous experiments done
%S~-
c! o without seed additions (solid triangles
III -B- 40 and Figure 6) shows that steady state
i.D conditions are achieved more rapidly in
11:.35
I
z
..-
I- 30
z
.-...-:-.-----. .- -.-
%Fe 35

30
"C
::t
C

the presence of seed, but that the
product yield is ultimately the same
whether seeding is employed or not.
UJ ...,
C">
55
(,)
a: I J J . I J J I 55
-<
n. 25 iT'
UJ
25 O.5M FeC~,4.0M NH 4CI,O.3M LizS~
l- r 50'- 20g/L PbClz,9s o C,pH=0.S
I c -50
(!)
20 15 gIL NH 4 - Jarosite Seed
W 20~
~ 45- -45
15 PRODUCT YIELD 15 0
10 ~-;; __ --_-~---.A "tr- 040
III 0 -40
IO i % 50:-

.--
I ";35 I-
/),. -35

....,-.-----.---'.-
n.
5 I 5 ;
-
%Pb
-1- I
Z 30 - %Fe - 30
~
:0
0
0
O~~. .-+~--~--. .__~__~\
0 !z ~
o 52
UJ
-
-I
- 25
(,)
a: 25 ~
UJ
n. rT1
r
l- e
Fig. 6 - Influence of retention time at I
(!)
20f- - 20 ~
98C on the amount and w
composition of the products ~

~~ __i:=-__ :~:~~C~~~~~ __
-15
made in the absence of 15f-
jarosite seed.
10- /' fr ~~ . - - - -10
" ,- ,,~NoSeed
The composition of the products
made in 0.5 M FeCl 3 - 4.0 M NHFI -
0.3 M Li S04 - 20 giL PbCI media is
57

0
--.--.-.--.--.--.-
.I. .!. ..1. 1 .I.
%NH:

!y%lb
-5

0
essentiaily independent of the retention 0 2 3 4 5 6 7 S
time for periods at least as long as TIME (h)
48 h. All the precipitates contain
"3.5% NH +, 33% Fe and "40% sot; the Fig. 7 - Influence of retention time at
lead contents are consistently <0.2% Pb. 98C on the amount and
All the precipitates were shown by composition of the products
Guinier X-ray diffraction analysis to made in the presence of
consist only of ammonium jarosite. 15 giL jarosite seed.

It is known that jarosite

precipitation in sulphate media is X-ray diffraction analysis of the
accelerated by the presence of jarosite products made in the presence of seed
seed; a minimum 100% seed addition is indicated only ammonium jarosite
commonly employed to maximize the regardless of the retention time. The
precipitation kinetics (12). The effect analytical data presented in Figure 7
of seeding in the current experiments indicate that the composition of the
was studied using a 15 giL addition of ammonium jarosite is independent of the
ammonium jarosite seed. The reaction retention time, and is virtually
in the FeCI3-NH4CI-Li2S04-PbCI2 system identical to that determined in the
usually generates about 12 g of ammonium absence of seed, Figure 6.
jarosite, and hence, the 15 giL of added
jarosite seed corresponds to a 125% seed Figure 8 illustrates the effect of
addition. Figure 7 shows the effect of the synthesis temperature on the amount
retention time on the amount and and composition of the ammonium jarosite
composition of the products made at 98C precipitated in the presence of 15 giL
in the presence of 15 giL ammonium of ammonium jarosite seed. In the
jarosite seed. The product yield is the presence of seed, a significant amount
weight of the final precipitate less the of precipitation occurs at 60C; in
weight of the seed initially added to fact, a trace amount ("0.4 g) of product
the reactor. Over 50% of the reaction was formed even at 40C. Comparison
occurred at "zero" time; i.e., during with the similar experiments carried out
in the absence of seed, Figure 2, shows
that the presence of seed partly
 71
overcomes the slow jarosite presence of 20 giL PbCI 2 Only ammonium
precipitation kinetics at the lower jarosite was detected by Guinier X-ray
temperatures. At the higher diffraction analysis of the products
temperatures, 90-l00C, the amount of made from the lead-free solutions.
product made in the presence of seed is Although there is some scatter in the
approximately the same as that made in analytical data for sulphate, the
the absence of an initial seed addition. overall trend suggests that the product
This is a reflection of the fact that composition is independent of the
steady state conditions are achieved synthesis temperature. The compositions
within 8 h at the higher temperatures are virtually identical to those
whether or not seeding is used, realized in the absence of seed,
Figure 7. Seeding is most beneficial Figure 2, and indicate ammonium
under those conditions where the amount jarosite.
of precipitate is under kinetic control,
and those regions include short Effect of the Concentrations of NH~
retention times and low temperatures. and FeCl2
When the precipitation system is at
steady state, near equilibrium A high ammonium chloride
conditions, the amount of product is the concentration is required in any FeCl 3-
same in the presence or absence of seed. NH{Cl leaching process to retain PbCl 2
and AgCl in solution, to provide a
source of "ammonia" in the subsequent
55
55 metal recovery operations and to
0.5 M FeCI,,4.0M NH4 CI,O.3 M Liz 504 increase the boiling point of the
50 pH"0.8,24h,20g/L PbClz 50 lixiviant. The effect of the NH 4CI
15g/L NH 4 -Jorosite5eed concentration on the amount and
45 45 composition of the products made at 98C
0 %50~- from 0.5 M FeCl 3 - 0.3 M Li~S04 - 20 giL
t5 8 0 PbCI~ media at pH = 0.8 is 1llustrated
"!.4O 40
0 0
8 in Flgure 9. In the absence of NH4CI, a
If 0
relatively large amount of product rich
:'35 35 in lead but deficient in NH/ is
;
l:
,-1-, e e ,_e_ "U
::u precipi tated. AS the NH Cl
z30 %Fe 30 concentration increases to Nl M, the
I- amount of product declines sharply; the
Z
\U ~ amount of product decreases more
~ 25 A 20g/L PbCl z 25
\U
A 0 gIL PbCl z
~
fTI gradually for further increases in the
Q.
I-
r
0 NH 4CI concentration. The lead content
i3 20 20 .0
- of the product decreases abruptly as the
bi NH4Cl concentration increases from 0.0
~ PRODUCT YIELD .- 15 to 1.0 M, but thereafter decreases
15
J!---ir gradually. The Pb content of the
~_--6-';- 10 precipitates made from solutions

-- .... -
10 A_~
.,Q--- containing >2.0 M NH 4Cl was <0.2% Pb .
The NH/, Fe and sot contents of the
%NH: 5
5 products increased as the NH 4Cl
concentration of the solution increased
from 0 M to Nl M, but remained
relatively constant at the higher
ammonium chloride concentrations.

Fig. 8 - Variation of the amount and Guinier X-ray diffraction analysis

composition of the products of the products made from solutions
with synthesis temperature in containing <0.5 M NH4Cl indicated major
the presence of 15 giL amounts of both lead jarosite and PbS0 4 ;
jarosite seed. the elevated lead contents reflect these
compounds. The products made from
solutions containing 0.5 to 2.0 M NH4Cl
The products made in the presence consisted of ammonium jarosite with
of seed at temperatures above 70C were minor, and progressively decreasing,
shown by Guinier X-ray diffraction amounts of PbS0 4 The precipitates made
analysis to consist only of ammonium from solutions containing >2.0 M NH4Cl
jarosite. At the lower temperatures, consisted only of ammonium jarosite, and
traces of PbSO andlor pbCl were this observation is consistent with the
detected, and this is a reflection of analytical data.
the reduced solubility of these species.
Accordingly, the lower temperature
experiments were repeated without any
pbCI in the synthesis solution. These
expe~iments are indicated by the solid
triangles which follow the general trend
established by the products made in the
 72
55r---~----~-----'-----.-----r-'~ content drops. This trend continues to
0.5M FeCI.,O.3M Li,SO.,20a/L PbCl, ~0.3 M NH 4Cl, at which concentration a
pH a O.8.98"C,24h 50 product containing ~3.1% NH/ and 0.4%
pb is produced. Further increases in
the NH 4Cl concentration result in only
o modest changes in the ammonium and lead
o contents. The iron and sulphate
o 40 contents of the precipitates increase
slightly as the NH 4Cl concentration
rises from 0.0 to 0.3 M. Lead sulphate
::J:
~--.--.--.--.- 35 ~ was not detected in any of the
precipitates by Guinier X-ray
...
Z
"10Ft 30
..,
Z
()
~ diffraction analysis. Figure 9 and
Figure 10 indicate that only a modest
ffi25 NH1Cl concentration in the processing
...
CL
so ution is required to form ammonium
S 20 jarosite in preference to lead jarosite.
i 15
PRODUCT YIELD
15
55 55
0.5 M FeCI 3 ,O. 3 M Li 2 S04 ,20 gIL PbCI 2
10 "IoPb
50 [LiCI] + [ NH.tCI ] - 4.0 M 50
9s o C,24h, pH-O.S

5 5 45 %SO~- 45
0 0 0 0 0
0 0 0
0 0
O'~O~-~~~~---&~--~~~~O 0 0
1.0 2.0 3.0
[NI\Ci) i
(mol/LI
35
Fig. 9 Effect of the NH 4Cl '"
ll.

%Fe
"C
::u
J:
o
concentration on the amount Z 30 g
and composition of the I-
()
~
precipitates made under Z
lj 25 25 ~
conditions where the total a: IT1
r
chloride concentration varied w o
ll.
with the NH 4Cl concentration. ... 20
J:
20 ;;
C)
PRODUCT YIELD
W
~ 15 15
The presence of PbSO in the
precipitates made from solutions having
NHCl concentrations <2 M is a 10
reflection of the low total chloride
concentration of those solutions that 5
reduces the solubility of PbS0 4 To
investigate the influence of the NH 4Cl
concentration on the jarosite
precipitation reaction under conditions
of constant total chloride
concentration, a series of experiments Fig. 10 - Effect of the NH4Cl
was carried out in solutions containing concentration on the amount
different concentrations of NH 4Cl, but and composition of the
always having [NH 4Cl] + [LiCl] = 4.0 M. precipitates made from
The results of these experiments are solutions having a constant
summarized in Figure 10. The amount of total chloride concentration.
product increases slightly as the NH 4Cl
concentration increases, and this
behaviour is in marked contrast to the In any iron chloride leaching
abrupt reduction in product yield process, the FeC1 3 lixiviant is reduced,
observed in the corresponding tests done at least in part, to FeC1 2 by reaction
at variable total chloride with the sulphide minerals.
concentration, Figure 9. In the absence
of NHC1, that is in a solution 2FeC1 3 + PbS ~ 2FeC1 2 + PbC1 2 + SO [ 3]
containing 4.0 M LiCl, a product
containing ~11% pb and 0.0% NH+ is 4FeC1 3 + CUFeS 2 ~ 5FeC1 2 + CUC1 2 + 2So [4]
formed. X-ray diffraction analysis
indicated only Pb-jarosite, and this Hence, the effect of ferrous chloride on
observation is consistent with synthesis the jarosite precipitation reaction in
studies recently carried out on the concentrated chloride media is relevant.
formation of Pb-jarosite in chloride In this regard, Figure 11 illustrates
media (13). As the concentration of the effect of the FeCl~ concentration on
NHFl increases, the NH/ content of the the amount and composition of the
precipitate increases, and the Pb products made at 9SoC from solutions
 73

containing 0.5 M FeCl 3 - 4.0 M NH 4Cl - Incorporation of Lead and Silver in the
0.3 M Li 2S04 and 20 giL PbCl 2 at Jarosite Precipitate
pH = O.S. The amount of product
increases steadily with increasing FeCl 2 It is known that complete solid
concentration, but there is considerable solution series exist among the alkali
scatter in the product yields. Both jarosites and lead jarosite (14) and
phenomena are due to the uncontrolled among the alkali jarosites and silver
oxidation of some of the FeCl 2 to FeCl 3 jarosite (15,16). Because both PbCl 2
during the 24 h precipitation and AgCl are moderately soluble in
experiments; increasing FeCl 3 concentrated chloride media, the
concentrations precipitate more structural incorporation of Pb and/or Ag
jarosite, Figure 5. Although the amount in the ammonium jarosite is a
of product varies somewhat with the possibility. The effect of the PbCl
ferrous chloride concentration, the concentration on the extent of pb 2
composition of the products is virtually incorporation in the ammonium jarosite
independent of FeCl 2 concentrations in made at 9SoC from 0.5 M FeCl - 4.0 M
the 0-1 M FeCl~ range. FUrthermore, the NH 4Cl - 0.3 M Li 2S0 4 solution~ at
product composltion is that of ammonium pH = O.S was investigated, and the
jarosite with <0.2% pb substitution for results are summarized in Figure 12.
the ammonium ion. Guinier X-ray 55,----,-...,.--.-.--.--..-------,,....----.55
diffraction analysis of the various 0.5M FeCI,,4.0M NH.CI,O.3M LizSo.
precipitates indicated only ammonium 50 pH=0.S,9soC,24h 50
jarosite.
45 5
ffir--.~-.--.-.--.--r-~-~~ %S~-
0.5M FeCl s,O.3M Li 2 S04 ,4.0M NH4 CI o 0
20g/L PbCI 2 ,9soC,pH=0.S,24h o 40st--O-----<).---El----C'----8~--..Q- 40
5O~ -50 If) 0 0
i.
it. 35 35
____:._.......;;.:__ ____.::- Fe
"ll
451- -45 :u
o
o
Z 30 30~
.40>- -40 I- -I
g ~-o--~u-~o--v~~UT--%S~- Z
llJ -<
i. 35- -35
u
Q: 25 25p
.J:J
llJ
a. o
'; - - . - - - - . - . -......<--% Fe "ll I-
:Il J: 20 20~
~ 301- - 30 8 (!)

I- c llJ
()
~

-25:
Z
llJ 15 PRODUCT YIELD 15
~ 25-
llJ 1'1
a. r 10 10

--
I- 20-
J: PRODUCT YI ELD - 20::
(!)
llJ _-
5 5
~ 151- /),. _ - - - /),. - 15
P---------
1-- /),. 0 __~~-4~__-~--~~~-L-~0
IQ't- - 10 o 5 10 15 20 25 30 35 40
[ PbCl z] (gl Ll
51- %NHt -5
Fig. 12 - Influence of the pbCl
1 1 1 .I.
yO/otb I
concentration on the ~mount
0
0 0.2 0.4 0.6 O.S 1.0 1.2 1.4
0
1.6 and composition of the
[FeCl z ] (moI/L)
ammonium jarosite; the lead
analyses are given in Table 1.

Fig. 11 - Variation of the product yield

and product composition with Clearly, there is no significant
the FeCl 2 concentration of the variation in the amount of product as
solution, The tests were done the PbC1 2 concentration of the solution
in air, and partial oxidation increases from 0 to 30 giL pbCl. The
of the FeC1 2 likely occurred. composition is essentially that 2 0f
ammonium jarosite which was the only
p~ase de~ected by Guinier X-ray
The presence of ferrous chloride in dlffractl0n analysis. Although the
a FeCl 3-NH4Cl leaching solution will ammonium, iron and sulphate contents are
have no direct effect on the essentially independent of the PbCl
precipitation of ammonium jarosite. concentration, Table 1 shows that the Pb
~ontent of the ammonium jarosite
Some of the FeC1 2 may oxidize to FeCI,
however, and the ferric ion will 3 lncreases systematically as the Pbcl
generate additional amounts of jarosite. concentration of the solution increa~es.
The Pb content, however, reaches a value
of only 0.22% pb even in a solution
nearly saturated in PbC1 2 ; i.e., in a
 74
30 giL PbC1 2 solution. The implication
is that only modest losses of lead will 0.5M eCI.. 4.0MNKtCI,O.3M LitSo..
pH-0.8,98C,24h
occur in the ammonium jarosite 50
precipitated from concentrated NH 4CI
media. 5
"Iosof
Table 1. Effect of the pbCI o
Concentration of the Solution
on the Pb Content of the
g 40

Ammonium Jarosite i.;; 35 e

C( -t---"--e-e---=-e--e--
; "Io~
~ 30
PbCl 2 Concentration Average pb Content ~
u 25
(g/L) (% ) a:
III
IL
~ 20
0 0.01 CI
W
~ 15 15
5 0.03 PRODUCT YIELD
6.
10 -4-A-7S-~-----tr-
10 0.07 10

15 O.OS 5 5

20 0.10 OO----~-~--~--~--~--~~O
0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
25 0.13 [A4CI] (g' L)

30 0.22 Fig. 13 - Effect of the AgCl

concentration on the amount
and composition of the
products made in the absence
of dissolved PbCI 2 The Ag
Silver chloride is moderately contents are <40 ppm.
soluble in concentrated chloride media, 55
and as a consequence, silver dissolves 0.5M FeCI,,4.0M NH4 CI,O.3M Lie So..
in most chloride leaching processes. pH=0.8,98C,24h,20g/L PbCI 2
- 50
Figure 13 shows the effect of dissolved 50 -
AgCl on the amount and composition of
the products made at 9SoC from 0.5 M 45 f-
"I. SO~-
- 45
FeCI - 4.0 M NH4CI - O. 3 M Li 2SO n
solu~ions at pH = O.S. None of the 040 f-
v v v " - 40
solutions contained dissolved PbCI 2 !II
The data show that neither the amount of oj
~ 35 e e e_e_e_ -35
precipitate nor its composition are IL e "Io~
affected by AgCl concentrations as high ;
as 1.2 giL, a value near the saturation ~3O - -30
limit of AgCI in the solutions employed. ~
The product composition is essentially tla: 25f- -25

.-.,
that of ammonium jarosite which was the Ie
only phase detected by Guinier X-ray ~ 2Of- -20
diffraction analysis. The Ag contents CI
of the ammonium jarosite varied from 10 W
PRODUCT YIELD -15
~ I 5r-
to 40 ppm Ag. Clearly, silver is not
significantly concentrated in the 6 6
ammonium jarosite product. or-
~
-10

Figure 14 presents the analogous 5- "IoNH: -5

results obtained when jarosite was v v v

precipitated at 9SoC from 0.5 M FeCl 3 - o

--:-"IoPb
0
4.0 M NH4Cl - 0.3 M Li 2S04 - 20 giL pOC1 2 o 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
solutions at pH = O.S that also [AgCI) (g I L )
contained 0.0 to 1.2 giL AgCI.
Increasing the AgCI concentration of the Fig. 14 - Effect of the AgCI
solution from 0.0 to 1.2 giL AgCl has no concentration on the amount
significant effect on either the amount and composition of the
or composition of the precipitate. The products made in the presence
analytical data suggest ammonium of 20 giL PbC1 2 The Pb and
jarosite, which was the only phase Ag contents are given in
detected by Guinier X-ray diffraction Table 2.
analysis.

Table 2 lists the pb and Ag
contents of the various precipitates,
and it is clear that neither pb nor Ag
are significantly concentrated in the
ammonium jarosite. The lead contents
vary from 0.05 to 0.12% Pb, and the Ag
contents never exceed 40 ppm Ag.
Table 2. Effect of the AgCI
Concentration of the solution
on the Ag and Pb Contents of
the Ammonium Jarosite
AgCI Ag Content Pb Content
Concentration
(g/L) (ppm)
0 <10
0.2 10
0.4 30
0.6 20
0.8 40
1.0 30
1.2 30
It is well established that both
silver and lead form stable jarosite-
type compounds (2). In chloride media,
however, both Ag and Pb are strongly
complexed as a variety of chloro-species
(17) .
Ag+ + CI- .... AgCIO Log K, 3.5
Pb2+ + CI- .... PbCI + Log K, 1.5
The high level of complexation of Ag and
pb in concentrated chloride media,
coupled with the relatively low
solubilities of AgCI and PbCI 2 , results
in ver~ low concentrations of "free" Ag+
and Pb+ ions which seem to be required
to form jarosite. The consequence is
~hat lead, and especially silver, remain
1n solution and do not extensively
precipitate as jarosite-type compounds.
By contrast, free ammonium or alkali
ions are abundant and result in the
precipitation of ammonium or alkali
jarosites.
CONCLUSIONS
Ammonium j aros ite, NH 4Fe3 (S04) (OH) 6'
is readily precipitated from
concentrated FeCI 3-NH4CI media
containing Li 2S04 as the independent
sulphate source. The precipitation
reaction is strongly dependent on the
initial pH of the solution. At 98C, no
75
precipitate forms when the pH is <0.4.
The amount of j arosi te increases
linearly with increasing pH above this
value, but difficult to filter products
are formed when the pH is >1.8.
Although the amount of product strongly
depends on the pH, the composition of
the ammonium jarosite is essentially pH
independent. The amount of jarosite
decreases steadily as the temperature is
reduced, and only traces of product are
made at temperatures <60C. The product
composition, however, remains
essentially independent of temperature
over the 60-100C temperature range. An
independent source of sulphate is
required to form ammonium jarosite, and
(%) there is a critical sulphate
concentration below which no jarosite
forms. The critical sulphate
0.06 concentration is -0.05 M when the FeCI
concentration is 0.5 M, but rises to 3
0.05 0.075 M when the FeCl 3 concentration is
:educed to 0.2 M. When excess sulphate
0.11 1S present, the amount of jarosite
increases linearly with increasing FeCI
0.12 concentration; also, the composition of3
the jarosite is relatively constant for
0.11 FeCl 3 concentrations >0.1 M. The
ammonium jarosite precipitation reaction
0.12 proceeds rapidly in chloride media, and
steady state conditions are realized
0.11 within 6-8 h at 98C. The presence of
jarosite seed considerably reduces the
time needed to achieve steady state
conditions, and also allows jarosite
precipitation to occur at temperatures
as low as 40C. If the processing
solution contains dissolved PbCI 2 , high
total chloride concentrations (>2 M
NH4CI) are required to prevent the
contamination of the jarosite with PbSO
and/or PbCI 2 At high total chloride 4
[5]
concentrations, the extent of pb
incorporation in the ammonium jarosite
[6 ]
is <0.2% pb regardless of the pbCI
concentration. Silver is not 2
significantly incorporated (Ag <40 ppm)
in any of the jarosites made from
concentrated chloride media, and the
presence of PbCl 2 in the solution does
not increase the level of Ag
incorporation. The low Ag and pb
contents of the ammonium jarosite are
attributed to the strong complexation of
these metals by chloride ion that
results in the retention of both pb and
Ag in the processing solution.
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.
 76
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Improved metal recovery with the
1 - V. Arregui, A.R. Gordon and low-contaminant jarosite process.
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T.S. Mackey and T.J. O'Keefe, eds.,
TMS, Warrendale, pp. 97-123, 1979. 13 - J.E. Dutrizac, The precipitation of
lead jarosite from chloride media.
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chemistry of iron precipitation in
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and T.J. O'Keefe, eds., TMS, Akad. Nauk, Prace Geol. 22, pp.
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3 - J.E. Dutrizac and T.T. Chen, A 15 - J.E. Dutrizac and J.L. Jambor,
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7 - J.E. Dutrizac, Sulphate control in
chloride leaching processes.
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8 - J.L. Limpo Gil, A.L. Martin, A.H.
Fernandez and J.A. Priego,
Hydrometallurgical recovery of
metals from complex sulphides.
Span. Patent ES 545,698, 16 January
1986.
9 - J.E. Dutrizac and J.L. Jambor,
Behaviour of cesium and lithium
during the precipitation of
jarosite-type compounds.
Hydrometallurgy 17, pp. 251-265,
1987.
10 - J.A. Ripmeester, C.I. Ratcliffe,
J.E. Dutrizac and J.L. Jambor,
Hydronium ion in the alunite-
jarosite group. Can. Mineralogist
21, pp. 435-448, 1986.
11 - J.E. Dutrizac, Factors affecting
alkali jarosite formation. Metal.
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