International Journal of Mining Science and Technology 24 (2014) 689694

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International Journal of Mining Science and Technology

journal homepage: www.elsevier.com/locate/ijmst

Leaching kinetics in cyanide media of Ag contained in the industrial

mining-metallurgical wastes in the state of Hidalgo, Mexico
Juan Hernandez , Francisco Patino, Isauro Rivera, Ivn Alejandro Reyes, Misrael Uriel Flores,
Julio Cesar Juarez, Martn Reyes
Research Centre in Materials and Metallurgy, Autonomous University of Hidalgo, Pachuca 42184, Mexico

a r t i c l e

i n f o

Article history:
Received 11 November 2013
Received in revised form 15 February 2014
Accepted 17 April 2014
Available online 22 August 2014
Keywords:
Silver
Waste tailings
Cyanidation
Leaching

a b s t r a c t
The leaching kinetics in cyanide media of the silver contained in the Dos Carlos waste tailings at the City
of Pachuca de Soto, Hidalgo State, Mexico were carried out. The used material contained the following
chemical composition: 56  10-6 of Ag, 0.6  106 of Au and 70.43% (by weight) of SiO2; 7.032% (by
weight) of Al2O3; 2.69% (by weight) of Fe; 0.46% (by weight) of Mn; 3.98% (by weight) of K2O; 3.34%
(by weight) of CaO; 2.50% (by weight) of Na2O; 0.04% (by weight) of Zn; 0.026% (by weight) of Pb. The
mineralogical phases present were the following: Silica, albite, argentite, berlinite, orthoclase, potassium
jarosite, and natrojarosite. In the leaching kinetics in cyanide media, and under the studied conditions,
the effect of the CN concentration on the reaction rate has no effect on the whole process of alkaline
cyanidation, of which the reaction order is n  0. Temperature has an effect on the cyanidation rate of
the reaction, with an activation energy of 47.9 KJ/mol. At the same time, when the particle size decreases
there is an increase in the reaction rate, which is inversely proportional to the particle diameter; when
increasing the NaOH concentration there is an increase in the reaction rate Kexp, with a reaction order
(n) of 0.215 under the studied ranges.
2014 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

1. Introduction
In the State of Hidalgo, the processing of ores containing silver
and gold has included technologies ranging from the patio process
(grinding-amalgamation) and the Pachuca tanks, to the circuits
with current technologies like grinding, otation and cyanidation.
All of these have generated a considerable volume of waste tailings
of 112 million tons that take up 2000 hectares, resulting in four
deposits of this material, which is very important in the State of
Hidalgo for its Ag and Au contents of 30  106130  106 Ag
and 0.3  1061.0  106 Au [15]. This is due to the metal mining activity that has been carried out in the region for more than
454 years [4]. The oldest wastes are evidently found in the
deposits bottom, and are the ones that present higher Ag and Au
contents. Because of the ton, the metallic laws and these metals
prices on the market, especially silver, these deposits are very
attractive from an economic point of view. Among the problems
found with these tailings, we can cite the existence of pyritic and
quartziferous ores, where the gold and silver values are encapsulated in the quartz particles, of which the predominant size in
Corresponding author. Tel.: +52 017717172000.
E-mail address: herjuan@uaeh.edu.mx (J. Hernandez).

percentage terms is 75 lm (60%65%), making this kind of

metals extraction difcult [6]. Besides, the presence of some cyanide-consuming elements and species (cyanicides), such as pyritic
ores, in many cases helped us from achieving a proper extraction of
the metallic values of Ag and Au. It has also been observed that the
silver contained in jarosite-type compounds poses a metallurgical
problem, causing erratic recoveries of this precious metal [7,8].
For these reasons, it is necessary to carry out an alkaline cyanidation study of the waste tailings in order to determine the optimal
conditions and the highest recoveries of this metal.
2. Experimental procedure
The Dos Carlos waste pile, located in the urban zone of the City
of Pachuca, Hidalgo, Mexico was chosen for this study. Four
representative samples of 50 kg were taken, and a thorough characterization was performed by X-ray uorescence (FRX) using a
vaccum-operated SIEMENS spectrometer. The sample was irradiated with an Rh anticathode using the following crystals: LiF200,
Ge111 and T1AP; the equipment calibration was performed with
different mineral oxides of known composition. The X-ray
diffraction (XRD) was carried out by using a Phillips X-pert Gateway 2000 XRD. Atomic Absorption Spectrometry (AAS) was used

http://dx.doi.org/10.1016/j.ijmst.2014.07.003
2095-2686/ 2014 Published by Elsevier B.V. on behalf of China University of Mining & Technology.

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J. Hernandez et al. / International Journal of Mining Science and Technology 24 (2014) 689694

Table 1
Waste piles chemical analysis by XRF.
Element

Weight percent (%)

Element

Weight percent (%)

SiO2
TiO2
Al2O3
Fe2O3
MnO
MgO
CaO
Na2O

70.43
0.53
7.32
2.80
0.73
0.54
0.69
0.08

P2O5
K2O
SO3
ZnO
PbO
Ag
Au

0.120
0.080
0.940
0.045
0.031
55
0.58

to determine the Zn, Cu, Pb, Fe and Si concentration in a Perkin

Elmer 2380 spectrometer. Inductively Coupled Plasma (ICP) was
used for assessing the S, Ag and Au concentration-the equipment
was a Perkin Elmer Optima 3000 XL. SEM was performed for the
morphology study of the tailings particles and Energy dispersive
X-ray spectroscopy (EDS) was carried out to determine the nature
of the studied material. An EDS-equipped Jeol JSM 5900LV SEM
was used for this matter.
The mineral used for the leaching kinetic study was previously
ground. We found that the optimal grinding time is 8 min, because
at this grinding time 52% of the Ag is found in the predominant
sizes of 88 + 74 lm. The samples for the study were obtained
from this material [1]. The leaching experiment was performed
in a PYREX at-bottom glass reactor, 1000 mL capacity. It was

mounted on a heating plaque and magnetic stirring was applied

with supernova equipment, tolerance limit of 0.2 C and stirring
rate of 1200 r/min. The reactor had a cover with a refrigerant for
avoiding liquid loss by evaporation. The solids were kept in suspension during the whole experiment by magnetic stirring; pH
was measured with a Cornig pH/ion analyzer 455 pH-meter,
equipped with an ATC 0627 temperature meter and a pH electrode
suitable for operating under extreme acidity and alkalinity conditions (014 pH range). An OHAUS Analytical Plus AP210S digital
analytical scale with precision of 0.0001 mg was used to determine
each samples weight. The leaching kinetics in cyanide media were
carried out under the following experimental conditions: CNbetween 5  102 and 5.1  103 mol/dm3; the temperature effect
was studied in a range going from 288 K to 338 K; the mineral

SiO2

Intensity (a.u.)

3000

Name quartz reference code 46-1045

Name natrojarosite reference code 11-0302
Name berlinite reference code 86-1560
Name albite reference code 78-2315

2500
1600
SiO2

900
O

400
100

SiO2
O SiO2
J OJ
B
B A
J
A
O J

20

40

60
80
2 ()

100

120

140

(a) X-ray diffractogram of the tailings, of which the main mineral species are quartz (SiO2), orthoclase (O), albite (A), berlinite (B) and
jarosite (J)

Intensity (a.u.)

100

Name natrojarosite reference

code 11-0302

64
36
16
4
0

20

40

60

80

100

2 ()
(b) Diffractogram showing the presence of sodium jarosite (NaFe3(SO4)2(OH)6)

Intensity (a.u.)

100

Name jarosite reference code

10-0443

64
36
16
4
0

20

40

Content (g/ton)

60

80

100

2 ()
(c) Diffractogram showing the presence of potassium jarosite KFe3(SO4)2(OH)6 in the tailings
Fig. 1. Presence of quartz, argentite, albite, berlinite, orthoclase, potassium jarosite and natrojarosite.

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J. Hernandez et al. / International Journal of Mining Science and Technology 24 (2014) 689694

Si

50
40

Counts

Al

Fe

30
S K

20
10 O

Ca

Mg
Fe

Ag

Mn

Fe

(a) General view, 75 m, 300X, SEM

MEB-EDS
(%, by
weight) Element
Ca
10.58
Fe
19.81
Mn
0.46
Cu
9.28
Zn
16.92
Ag
11.11
Pb
5.30

Element
C
O
Mg
Al
Si
S
K
Zn
Cu

Pb

(%, by
weight)
0.46
0.99
21.99
2.92
2.13
0.00559
4.45

Pb

10
Energy (keV)

15

(b) Result of the general SEM-EDS microanalysis

Fig. 2. Microphotographies of the tailings.

Table 2
Average chemical composition of the Dos Carlos waste tailings.
Element

Weight percent
(%, by weight)

Used
technique

Element

Weight percent
(%, by weight)

Used
technique

Element

Weight percent
(%, by weight)

Used
technique

Te
Cr
Cu
Bi
Ni
Mn
Fe
Sn
Hg
Cd
Se

0.0051
0.0370
0.0110
0.0002
0.0050
0.0460
2.6900
0.0002
0.0003
0.0170
0.0065

AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS

SiO2
CaO
K2O
Na2O
Al2O3
TiO2
P2 O5
Mg
Ba
Sc
Co

70.0400
0.2000
2.2800
0.2000
7.0320
0.2780
0.1100
0.0050
0.3300
0.0004
0.0080

ICP
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS

Zn
Pb
As
Sr
Be
W
Sb
Hg
Ag
Au
S

0.0400
0.0260
0.0430
0.4632
0.0001
0.0053
0.0007
0.0003

AAS
AAS
AAS
AAS
AAS
AAS
AAS
AAS
ICP
ICP
ICP

1.0

X (Ag)

0.8
0.6
0.4
0.2
0

5 10 20 30 60 100 160
Time (min)

Fig. 3. Silver extraction in function of time.

weight was 40 g/L; NaOH between 5  102 and 1.1  103 mol/
dm3; solution volume 500 mL, stirring rate 750 r/min; particle size
between 180 and 38 lm. The progress of solubilized Ag at different
reaction times ranging from 0 to 240 min was analyzed by Atomic
Absorption Spectroscopy with a Perkin Elmer 2380 Spectrometer.
3. Results and discussion
Table 1 shows the results obtained by X-ray Fluorescence. From
Table 1, we can notice the predominant elements and species, such
as silica, alumina, hematite, and potassium oxide, as well as the

11.4500

Content
(g/ton)

56.0000
0.60000

less prevalent elements, such as silver, gold, sulphur, magnesium,

titanium and calcium. The trace elements are lead, zinc, copper
and sodium.
Fig. 1 presents the diffractograms. We can notice the presence
of quartz, argentite, albite, berlinite, orthoclase, potassium jarosite
and natrojarosite.
Fig. 2 is a general image of the tailings which are analyzed by
SEM-EDS. We can notice the presence of the predominant elements (including silicon, sulphur, aluminum, potassium and iron),
and the presence of the less prevalent elements (including silver,
magnesium, manganese, copper, zinc and lead).
Table 2 shows the results obtained by ICP and AAS of the mineralogical elements and species of metallurgical interest.
According to these results, the Dos Carlos waste tailings present
Ag content 56.00 g/ton and Au content of 0.6 g/ton, which are
found in a quartziferous matrix. Part of the silver is encapsulated
in the quartz particles and another part is incorporated in the
potassium jarosite and natrojarosite structure according to the
results obtained by XRD [4,6]. Another important part is found as
argentite, which could not be leached [2,6]. For these reasons, a
grinding study was carried out in order to liberate the silver values
encapsulated in the quartz particle.
In the stoichiometry of the studied system (Ag-CN), the leaching stages of silver in its three present forms are represented:

Table 3
Experimental conditions, CN effect.
[NaCN]
(mol/dm3)

[NaOH]
(mol/dm3)

Temperature
(K)

Stirring rate
(r/min)

Leaching time
(min)

Solution
volume (mL)

Mineral weight
(g/L)

Particle size

5  102
3.06  102
2.04  102
5.01  102

1  102

298

750

300

500

40

8 min grinding

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1.2

1.2
510 -2 mol/dm 3 NaCN
3.0610 -6 mol/dm 3 NaCN
2.0410 -2 mol/dm 3 NaCN
5.110 -3 mol/dm 3 NaCN

1.0

0.8

0.6

X (Ag)

X (Ag)

0.8

1.0

0.4

0.6

288
298
303
308
313
318
323
328
333

K
K
K
K
K
K
K
K
K

0.4

0.2

0.2

0
0

50

100
Time (min)

150

200

ln K exp (min -1)

log K exp

-2.0

-2.5

-2.0

-1.5

-1.0

-5.0
-5.2
-5.4
-5.6
-5.8
-6.0
-6.2
-6.4
-6.6
-6.8
-7.0
3.0

3.1

Fig. 5. Dependence of the Kexp in function of [CN1](Reaction order n  0).

4Ags 8CN O2 H2 O ! 4AgCN2 4OH

3.4

3.5

3.6

NaFe3 SO4 2 OH6S 3HOaq ! FeOH3s 2SO2

4 aq
Naaq Slow

AgOHs 2CNaq ! AgCN2 aq OHaq Quick

2

Ag2 S ! 2Ag S
Ag2 S 4CN !

3.3

Sodium Jarosite

In the case of silver sulphide [10]

2AgCN2

3.2

Fig. 7. Dependence of Kexp vs temperature (activation energy Ea = 47.9 KJ/mol).

metallic silver, silver sulde, argentian potassium and sodium jarosite respectively.
In the case of metallic silver [9]

250

1/T10 -3 (k -1)

log [ NaCN ]

200

100
150
Time (min)

Fig. 6. Ag extraction in function of time, temperature effect.

Fig. 4. Ag extraction in function of time, CN1 effect.

-3.0
-2.5

50

2

Based on the obtained results, the cyanidation in NaOH media does

not present an induction period. However, we observed a very quick
cyanidation of the metallic Ag that was in the tailings, as well as of
the part that was liberated from the quartz particles and the Ag contained in the argentite. This happened eventually with the Ag contained mostly in the potassium jarosites and in the sodium jarosites
(Fig. 3). According to this, the process occurs in two stages, and the
rst stage is the quick cyanidation of the argentite and the second
stage consists of two serial reactions. The rst one is the decomposition of the argentian sodium and potassium jarosites respectively,
resulting in silver hydroxide. The following one is the instant cyanidation of the jarosites decomposition products according to the
previously cited reactions.
Kinetic study of cyanidation in alkaline media

2S2 2H2 O O2 ! 4OH 2S #

The sulphide ion oxidizes to free sulphur, thus the silver sulphide
completely dissolves [11,12].
Potassium Jarosite

KFe3 SO4 2 OH6S 3HOaq ! 3FeOH3

2SO2
4 aq

Kaq Slow

AgOHs 2CNaq ! AgCN2 aq OHaq Quick

Table 4
Operating conditions for the temperature effect measurement.
Temperature (K)
288
298
303
308
313
318
323
328
333

[NaCN]
(mol/dm3)

[NaOH]
(mol/dm3)

Stirring rate
(r/min)

Leaching time
(min)

Mineral weight
(g/L)

Particle
size

Solution volume
(mL)

2.4  102

1  102

750

240

40

8 min grinding

500

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J. Hernandez et al. / International Journal of Mining Science and Technology 24 (2014) 689694
Table 5
Operating conditions for the particle size effect measurement.

180
150
105
75
53
38

1.2

[NaCN]
(mol/dm3)

[NaOH]
(mol/dm3)

Stirring rate
(r/min)

Mineral weight
(g/L)

Leaching time
(min)

Solution volume
(mL)

298

2.4  102

1  102

750

40

240

500

Malla
Malla
Malla
Malla
Malla
Malla

1.0
0.8
X (Ag)

Temperature (K)

0.6

1.2

80
100
140
200
270
400

0.8
0.6

0.4

0.4

0.2

0.2

0
0

50

100
Time (min)

150

200

50

100
Time (min)

150

200

Fig. 10. Silver extraction in function of time (OH- effect).

Fig. 8. Ag extraction in function of time, particle size effect.

form, Kexp against CN1, where the reaction order is n  0 under

the studied ranges. This conrms that the CN1 has no effect on
the rate of the global process.

0.007
0.006
K exp (min -1)

510 -2 [ NaOH ]
310 -2
110 -2
3.310 -3
1.110 -3

1.0

X (Ag)

Particle size lm
(8 min grinding)

0.005
0.004

3.1. Temperature effect

0.003
0.002

In order to measure the effect of temperature on the reaction

rate, temperature was varied, while the other operating parameters were kept constant, as shown in Table 4.
Fig. 6 shows the obtained values of the fraction of leached Ag in
function of time for all the studied temperatures. Notice the
increase in the reaction rate along with the temperature increase,
where recoveries up to 94% were obtained for 333 K. The activation
energy was 47.9 KJ/mol, which indicates that the process is controlled by the chemical reaction (Fig. 7).

0.001
0

1/do (m)
Fig. 9. Dependence of Kexp in function of the particle size.

In order to know the reaction rate in cyanide media of the Ag

found in the tailings, a series of experiments was performed studying the effects of cyanide concentration, temperature, particle size
and NaOH concentration.
Cyanide concentration effect
Table 3 shows the experimental conditions for the evaluation of
this effect. CN- was various, while the other parameters were kept
constant.
Fig. 4 shows the leaching time against the fraction of leached
Ag. It can be seen that the traces are parallel among themselves;
thus the rate Kexp is similar. Therefore, the cyanide concentration
has no effect on the global process. Fig. 5 presents, in logarithmic

3.2. Particle size effect

Table 5 presents the experimental conditions for measuring this
effect. The particle size was varied and the other parameters were
kept constant.
Fig. 8 shows the obtained values of the fraction of Ag extraction
in function of time for all the studied particle sizes. Notice that
when the particle size decreases, there is an increase in the reaction rate Kexp, which is inversely proportional to the diameter of
the particle, as seen on Fig. 9.

Table 6
Experimental conditions (pH effect).
[NaOH]
(mol/dm3)
5  102
3  102
1  102
3.3  102
1.1  102

Particle size

Temperature
(K)

[NaCN]
(mol/dm3)

Stirring rate
(r/min)

Leaching time
(min)

Mineral weight
(g/L)

Solution volume
(mL)

8 mi grinding

298

2.4  102

750

240

40

500

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J. Hernandez et al. / International Journal of Mining Science and Technology 24 (2014) 689694

When increasing the NaOH concentration there is an increase in

the reaction rate Kexp, establishing a reaction order of n = 0.215.
The silver contained in the tailings leaches in three stages: as
metallic silver, as silver sulphide and as jarosite.

-1.0

log K exp

-1.5

-2.0

Acknowledgments

-2.5
-3.0
-4

-3

-2

-1

log [OH -]
Fig. 11. Dependence of the Kexp in function of the [OH] (Reaction order n = 0.215).

3.3. OH- concentration effect

For the study of [OH] the concentration of sodium hydroxide
was varied, while the other parameters were kept constant
(Table 6).
Fig. 10 shows time against X[Ag]. Notice the increment in the
reaction rate Kexp when the concentration is increased. Fig. 11
shows the dependence of Kexp vs. the log [OH], establishing a reaction order of n = 0.215 under the studied ranges. Therefore, we can
conclude that hydroxide concentration has an effect on the process global rate.
4. Conclusions
The used cyanide concentration does not present any effect on
the reactions global process under the studied conditions, presenting a reaction order of n  0.
Temperature has an effect on the reactions global rate, presenting an activation energy of 47.9 KJ/mol; therefore the process is
controlled by the chemical reaction.
When decreasing the particle size, there is an increase in the
reaction rate (Kexp), which is inversely proportional to the particle
diameter.

The authors would like to thank the Autonomous University of

Hidalgo State, Mexico for the nancial support. We would also like
to thank the National Institute for Nuclear Research, Mexico for
their technical services when we carried out this project.
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