Hydrometallurgy 160 (2016) 98–105

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Hydrometallurgy

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Silver leaching with the nitrite–copper novel system: A kinetic study

G. Alvarado-Macías a, J.C. Fuentes-Aceituno a,⁎, F. Nava-Alonso a,b, Jae-chun Lee c
a
Centro de Investigación y de Estudios Avanzados del IPN, Unidad Saltillo, Av. Industria Metalúrgica # 1062, Parque Industrial Ramos Arizpe, Ramos Arizpe, Coahuila, 25900, México
b
On sabbatical leave at Department of Mining, Metallurgical and Materials Engineering, Laval University, Quebec, QC, Canada G1K 7P4
c
Mineral Resources Research Division, Korea Institute of Geoscience and Mineral Resources (KIGAM), Daejeon 305-350, Korea

a r t i c l e i n f o a b s t r a c t

Article history: This work presents a novel leaching system involving NO2–Cu to oxidize and complex silver without the use of
Received 3 September 2015 cyanide, ammonia or thiosulfate. It is possible to oxidize metallic silver through the reduction reaction of the ni-
Received in revised form 18 December 2015 trite ions, the cupric-nitrite complexes seem to be responsible for increasing the silver leaching kinetics; the ni-
Accepted 22 December 2015
trite ions act as a complexing agent for the silver ions in the solution. The effect of cupric ions concentration
Available online 23 December 2015
(0.05 M, 0.1 M and 0.2 M) and nitrite ions concentration (1.0 M, 1.35 M and 1.5 M) on the dissolution kinetics
Keywords:
of silver was evaluated. Based on the results the best leaching conditions were worked out as: 1.5 M nitrite
Sodium nitrite ions and 0.2 M copper ions at a natural pH of 5.0. This leaching solution dissolves 80% of silver within 6 h. The
Silver nitrite effect of temperature on the dissolution kinetics of silver was studied at the room temperature till 30, 45, 50
Copper nitrite complex and 55 °C, showing a progressive increase in silver recovery from 7.69% to 10.38%, 28.62%, 44.7% and 53.93%, re-
Silver leaching spectively in 30 min. The kinetic analysis revealed that silver leaching depends on the temperature and rate con-
trolling step corresponds to the silver dissolution through the chemical reaction. The apparent activation energy of
the reaction is found to be 50.92 kJ/mol, along with the enthalpy and entropy of activation values of 48.34 kJ/mol
and −139.05 J/mol K, respectively. The kinetic model corresponding to the silver leaching can be represented by
the expression: 1 − (1 − x)1/3 = k0 exp. (−50.92/RT) t. The analysis of solid residue obtained after leaching at
pH 5 by XRD and SEM with elemental mapping showed the formation of a copper-hydroxysulfate species,
brochantite, formed in the bulk solution and not on the silver particle surface. The leaching results of silver by
the NO2–Cu system were also ratified by the species distribution diagrams.
© 2015 Elsevier B.V. All rights reserved.

1. Introduction researchers using alternative leaching systems in the presence of thio-

Cyanidation is the process traditionally employed worldwide for the
extraction of silver and gold from different sources. Metallic silver can
be found in different wastes. For example in the so-called urban ores,
it is of environmental and economic importance to leach metallic silver
from printed circuit boards (PCB's), electronics, spent catalysts and
fabrics containing silver nanoparticles (Ficeriová et al., 2008; Manju
Gurung et al., 2013; Jadhav and Hocheng, 2012; Pasricha et al., 2012).
Presently the mining and recycling industry has been involved in solv-
ing new technological and environmental challenges (Aylmore and
Muir, 2001; Ahern et al., 2006). Some of the main alternatives to replace
the cyanide from the leaching systems includes the use of thiourea
(Jing-ying et al., 2012) and thiosulfate as the lixiviant (Abbruzzese
et al., 1995; Tanriverdi et al., 2000; Aylmore and Muir, 2001; Breuer
and Jeffrey, 2000, 2002; Wan and LeVier, 2003; Zhang and Nicol,
2003; Grosse et al., 2003; Ji et al., 2003; Senanayake, 2005; Gudkov
et al., 2010a, 2010b, 2010c; Puente-Siller et al., 2014; Alvarado-Macías
et al., 2015). The leaching of metallic silver has been studied by different
⁎ Corresponding author.
E-mail address: juan.fuentes@cinvestav.edu.mx (J.C. Fuentes-Aceituno).
sulfate or ozone (Puente-Siller et al., 2013, 2014; Alvarado-Macías
et al., 2015; Rivera et al., 2015; Viñals et al., 2005). The thiosulfate sys-
tem seems to be the most promising for the extraction of precious
metals, because of its capability to increase the metal dissolution rate
from 18 to 20 times (Aylmore and Muir, 2001). However, one of the
main disadvantages of the thiosulfate system relates to its oxidative
degradation to tetrathionates (Aylmore and Muir, 2001). Therefore,
in order to reduce such degradation, researches are being carried
out using different additives such as citrate, EDTA and amino acids
(Puente-Siller et al., 2013, 2014; Feng and Van Denventer, 2010,
2011). These investigations have shown the possibility of decreasing
the oxidative degradation of the thiosulfate ions by lowering the
redox potential of the system. However, the drawback is yet to be
overcome.
Recently, Alvarado-Macías et al. (2015) examined an alternate pro-
cess for silver leaching involving S2O3-NO2-Cu which avoids the use of
cyanide or ammonia in the thiosulfate process and minimizes the envi-
ronmental impact. However, the formation of a Cu-S coating on the
surface of silver particles (Alvarado-Macías et al., 2015) due to the deg-
radation of thiosulfate has retarded the leaching (Aylmore and Muir,
2001) due to the hindered contact between the lixiviant and unreacted

http://dx.doi.org/10.1016/j.hydromet.2015.12.014
0304-386X/© 2015 Elsevier B.V. All rights reserved.
 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105 99

silver. In addition, the Cu-S catalyzes the oxidative decomposition of
thiosulfate in solution by air resulting in low silver extraction (Chanda
and Rempel, 1985; Puente-Siller et al., 2014).
In view of the above, the current researches have aptly focused on
exploring a new system to dissolve the precious metals from different
resources without the use of cyanide, thiosulfate or thiourea. Mention
may be made of a recent study in which Oraby and Eksteen (2015)
used glycine-peroxide for the gold and silver leaching. The gold leaching
rate of 0.322 μmol/m2.s was achieved using a solution of 0.5 M glycine
and 1% peroxide at pH 11 in 48 h. In fact, this result was better as com-
pared to the gold leaching rate obtained after six days with thiosulfate–
EDTA or thiosulfate–oxalate systems in the presence of thiourea. Other
systems that do not use cyanide for the leaching of silver/precious
metals are based on the nitric acid (Holloway et al., 2004; Pan-Pan
et al., 2014), the nitrogen species catalyzed (NSC) (Anderson, 1995;
Anderson and Nordwick, 1996; Anderson et al., 1996a; Anderson
et al., 1996b; Anderson, 2003a, 2003b), and the bisulfide (Hunter
et al., 1998) in the conventional leaching operations. However, the use
of nitrite ions as oxidant and complexing agent for silver has not been
investigated systematically until the present work.
In this work, use of a novel leaching system involving NO2–Cu2+ so-
lution has been investigated to understand the dissolution behavior of
silver and establish the most suitable conditions to accelerate the
leaching kinetics, with the aim of using it in future, this information
would be valuable to dissolve metallic silver contained in different
wastes (mining industry or urban mines). The research is based on the
premise that nitrite ions can oxidize the metallic silver. In fact, nitrite
reduction can produce ammonia and ammonium ions as previously
reported by Alvarado-Macías et al. (2015) according to the reactions
(1 and 2) depending on the pH of the solution. The formation of ammo-
nia and ammonium ions may cause oxidative dissolution of the precious
metals as a result of the redox process.
Thus at pH N9 ammonia is predominantly generated as Eq. (1):
NO− −
2 þ 5H2 O þ 6e →NH3 þ 7OH
−
Whereas, at pH b 9 ammonium ions are predominantly formed (2):
8Hþ þ 6e− þ NO− þ be oxidized at the anodic potential N 0.49 VSHE in the pH range 5.0–6.5.
2 →NH4 þ 2H2 O
2. Materials and methods
The leaching solutions were prepared with analytical grade reagents
and deionized water. The reagents used were: metallic silver (99.999%,
1–3 μm, spherical, Alfa Aesar), sodium nitrite (97.2%, Analytyka) and cu-
pric sulfate pentahydrate (99%, Merck).
the silver precipitation caused by light. Once the experiments were
concluded, the residues were filtered, rinsed with deionized water
and air dried.
2.2. Chemical and morphological characterization of the solid residues
The solid residues formed at 6 h were microstructurally character-
ized in order to elucidate their morphology and local chemical compo-
sition by scanning electron microscopy (SEM) (Phillips, XL30ESEM),
X-ray mapping and energy-dispersive X-ray spectroscopy (EDS)
(EDAX, Genesis). Some of the solid residues were also analyzed by
X-ray diffraction (XRD) (Phillips, X'PERT PW3040) in order to iden-
tify the predominant and other minor phases.
3. Results and discussion
Silver leaching tests at different temperatures and kinetic aspects
could be complemented with the thermodynamic analysis of the ni-
trite–copper system and characterization of the solid residue.
3.1. Thermodynamic study
In order to elucidate the predominant species (solid and liquid
phase) formed in the nitrite-copper-silver system, Pourbaix and species
distribution diagrams were constructed at different pH and room tem-
perature representing the potential leaching conditions with the help
of Medusa Software using the equilibrium data contained in the Hydra
database (Puigdomenech, 2004). As reported previously (Alvarado-
Macías et al., 2015), silver can be leached in S2O3-NO2-Cu-SO3 system
through the formation of [Ag(S2O3)x]1−2x complexes, where x = 1, 2
or 3. It is also possible to produce silver–nitrite complexes using the
nitrite ions as a co-leaching agent without using the thiosulfate ions.
ð1Þ The species distribution diagram for the NO2-Ag-H2O system construct-
ed and presented in Fig. 1 reflects the formation of nitrite-silver com-
plexes in a range of pH and redox conditions. Thus metallic silver can
ð2Þ
The stabilization of silver with nitrite ions producing predominantly
the Ag(NO2)− 2 complex can proceed according to the oxidation reaction
(3):
−
Ag þ 2NO−
2 →AgðNO2 Þ2 þ e
−
ð3Þ
This anodic reaction must occur simultaneously with a reduction re-
action, which is likely at the acidic pH [Eq. (2)] through the reduction of
nitrite ions to NH+4 ions (Alvarado-Macías et al., 2015).

2.1. Leaching tests

All silver leaching experiments were performed in an agitated batch

reactor (250 mL glass beaker) which was provided with a pH meter
(pH 538 WTW), a pH electrode (SENSOREX), a redox potential electrode
with Ag/AgCl reference (Cole-Parmer) and a magnetic stirring plate. The
general procedure for the leaching experiments was as follows: 200 mL
of the leaching solution with sodium nitrite, cupric sulfate and 0.1266 g
of metallic silver were placed in the reactor at room temperature. The
effect of cupric sulfate concentration (0.05 M, 0.1 M and 0.2 M), sodium
nitrite concentration (1.0 M, 1.35 M and 1.5 M) and temperature (19,
30, 45, 50 and 55 °C) on the silver leaching kinetics was tested during
6 h of experiments. The pH and redox potential were measured before
the silver addition and during the leaching experiments at an interval
of 60 min. Samples of the leaching solution were withdrawn at each
5 min or 30 min, during the leaching test of 6 h. Silver in the aliquot
was analyzed by atomic absorption spectrophotometry (Varian Fig. 1. Silver species distribution diagram for the Ag-NO2-H2O system with 6×10−3 M Ag
SpectrAA 220FS). All samples were stored in dark vessels to prevent and 1.5 M NO− 2 at 0.49 V vs SHE.
100 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105
Furthermore, cupric ions can be complexed with nitrite ions (cop-
per-nitrite complexes), therefore, it is possible that cupric ions can
work as a nitrite carrier which could catalyze the silver leaching kinetics.
Fig. 2 illustrates the copper species distribution diagram constructed for
the NO2-Cu-SO4-H2O system at 0.49 VSHE.
A look at Fig. 2 shows the formation of cupric–nitrite complexes such
as CuNO+ 2 and Cu(NO2)2 in the pH range 4.5–6.5, and predominance of
the latter over the former [CuNO+ 2 species]. Further, the formation of
brochantite (Cu4SO4(OH)6) can be observed in two pH ranges i.e. from
4 to 5 and from 5.5–7. It is therefore, possible to propose that nitrite
contained in the cupric-nitrite complexes Cu(NO2)2−x x (where, x = 1
or 2) can also be reduced to ammonium ions releasing the cupric ions
(Eq. (4)). This reaction can occur simultaneously with the oxidation of
silver (Eq. (3)). It is important to mention that cupric ions do not suffer
modification of its oxidation state (see Eq. (4)), which suggests that a
portion of the released cupric ions can be complexed with free nitrite
ions regenerating the Cu(NO2)2−x x species. This behavior is very similar
to a catalytic process, in which the Cu(NO2)2−x x complexes could cata-
lyze the silver dissolution kinetics.
CuðNO2 Þ2−x
x þ 8xHþ þ 6xe− →Cu2þ þ xNHþ
4 þ 2xH2 O
Eq. (4) also shows that protons are consumed and free cupric ions
are produced. Furthermore, nitrite reduction also consumes protons
(Eq. (2)) during silver oxidation. Therefore, it is possible that the local
pH (near the silver surface) would be increased, promoting the reaction
of the free cupric ions so formed with sulfate ions and water to precip-
itate brochantite (Eq. (5)).
4Cu2þ þ SO2− þ XRD, respectively. The SEM analysis (Fig. 4B) indicates the presence of
4 þ 6H2 O→Cu4 SO4 ðOHÞ6 þ 6H
3.2. Leaching of silver with the primitive nitrite–copper system
In order to demonstrate the viability of the process, experiments
were carried out for the leaching of silver at pH 6 using the nitrite
(1.5 M) and cupric ions (0.05 M) concentrations previously used
(Alvarado-Macías et al., 2015) in the thiosulfate-nitrite-copper system
and results are shown in Fig. 3. The recovery of 32% Ag in 360 min
(Fig. 3), demonstrates the potential of emerging novel leaching system
(NO2–Cu). It may also be noted that the addition of thiosulfate as a
complexing agent for silver is no more required.
However, the low recovery of silver (Fig. 3) may be caused by the
consumption of nitrite ions in several reactions that also proceed. For
example, nitrite ions are consumed as an oxidant for silver (Eq. (2))
Fig. 2. Copper Species distribution diagram for the NO2-Cu-SO4-H2O system with 0.05 M
Cu2+, 1.5 M NO− 2 and 0.05 M SO4
2−
at 0.49 VSHE.
Fig. 3. Silver recovery percentage vs time at room temperature and pH 6. Leaching
solution: 1.5 M NO−2 , 0.05 M Cu
2+
and 0.1266 g Ag.
and as weak complexing agent for Cu 2 + to produce Cu(NO 2 )2x − x
complexes (Eq. (4)), although these complexes could catalyze the
ð4Þ silver oxidation, while stabilizing it (silver ions) in the presence of
nitrite ions to form a Ag(NO2)− 2 complex (Eq. (3)). Therefore, the ni-
trite and cupric ions concentrations used in this system (1.5 M NO− 2
and 0.05 M Cu2 +) are insufficient to promote the oxidation of metal-
lic silver and complexation simultaneously, resulting in low silver re-
covery (Fig. 3).
The solid residues were characterized to determine the surface mor-
phology and phase identification by scanning electron microscopy and
ð5Þ
two types of particles: bright and dark. The corresponding EDS
(Fig. 4C) reveal that the bright particles mainly consist of silver. On
the other hand, the dark particles (Fig. 4A) consist of Cu, O and S,
which can be related to the presence of brocanthite (Cu4SO4(OH)6) as
per species distribution diagram (Fig. 2). The dark and bright particles
have very distinct morphologies clearly separated from each other. It
is therefore, plausible to state that the silver particles remain un-
coated which permits the oxidation of silver without any physical
barrier. This was further confirmed by the elemental mapping present-
ed in Figs. 4D–F. Apparently Ag mapping corresponds to the bright par-
ticles (Fig. 4D) whereas mapping of O and Cu (Figs. 4E and F) represents
the features for dark particles.
3.3. Effect of cupric and nitrite ions on the leaching kinetics of silver
Leaching experiments were carried out to optimize the recovery of
silver while varying the concentrations of cupric and nitrite ions and
results are presented in Figs. 5 and 7, respectively. Fig. 5 reflects the in-
crease of the silver recovery when cupric ions concentration was raised.
For instance, silver recoveries of 32% (solution A), 57% (solution B) and
80% (solution C) were obtained in 6 h at the cupric ions concentration of
0.05 M, 0.1 M and 0.2 M, respectively. The increase in the silver recovery
and kinetics of leaching can possibly be correlated with the formation of
the Cu(NO2)2x −x complexes (where x = 1 or 2), which is apparently
promoted by the enhanced concentration of the cupric ions. Besides
Eq. (2); it appears that the nitrite linked to the copper–nitrite complex
can be reduced (Eq. (4)) to promote the oxidation of silver (Eq. (3)).
In order to determine the rate controlling step during the silver
leaching in the present system the shrinking particle model (SPM)
was employed to fit the leaching data given in Fig. 5, and results are
shown in Fig. 6. Eq. (6) represents the SPM (Levenspiel, 1972) con-
trolled by a chemical reaction:
1−ð1−XÞ1=3 ¼ ðbkC=ρrÞ t ¼ ksa t ð6Þ
Where, X = fraction of silver reacted after time t(s), b = stoichio-
metric factor for surface reaction A(s) + bB(aq) = products, k =
 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105
Fig. 4. Morphology, local chemical composition and X-ray mapping of the solid residue formed from the silver leaching of Fig. 3. A) Elemental composition of the dark particles,
B) Morphology of the leach (solid) residue, C) Elemental composition of the bright particle. X-ray mapping of D) silver, E) oxygen and F) copper.
intrinsic rate constant of surface reaction (ms−1), C = concentration of
reagent (mol m− 3), r = particle radius assuming spherical particles
(m), ρ = molar density of silver (mol m−3), ksa = apparent rate con-
stant for shrinking particle model (s−1). One of the requirements of
this model is that the concentration of reagents (C) responsible for the
surface reaction must remain constant (Senanayake, 2007).
Data in Fig. 6 show that the leaching kinetics is controlled by the
chemical reaction on the surface of the silver particles, which means
that the silver dissolution (Eq. (3)) is the rate determining step during
the leaching. Furthermore an increase in the cupric ions concentration
accelerates the silver dissolution kinetics, i.e., an apparent rate constant
of 0.0004, 0.0007 and 0.0012 min−1 was obtained with the Cu2+ con-
centrations of 0.05 M, 0.1 M and 0.2 M, respectively. From these results,
it can be stated that the reaction rate is very close to the first order
(0.79) with respect to the copper concentration.
This is an interesting result as compared to the other alternatives
e.g., in thiosulfate–EDTA and citrate (Puente-Siller et al., 2013, 2014)
and thiosulfate–nitrite systems (Alvarado-Macías et al., 2015), the rate
determining step corresponds to the diffusion of fluid species through
a Cu–S porous layer formed on the unreacted silver surface. On the
other hand, leaching of silver in the new process (nitrite–Cu) follows
the chemical control mechanism. This further suggests that the surface
of the silver particles is free of coating by any barrier (secondary solid
product) permitting the uninterrupted oxidation of silver.
Fig. 5. Silver recovery percentage vs time with 1.5 M NO−
2 . A) 0.05 M Cu
2+
at pH 6,
B) 0.1 M Cu2+ at pH 5 and C) 0.2 M Cu2+ at pH 5.
101
The effect of nitrite ions on the silver recovery was also examined
and data are presented in Fig. 7. It is evident that the increase in the ni-
trite ions concentration has increased the rate of silver dissolution and
recovery as well. Thus the silver recovery of 30%, 55% and 80% was
attained in 360 min with 1.0 M, 1.35 M and 1.5 M NO− 2 , respectively.
This is in good agreement with the reactions shown in Eqs. (2)–(4),
wherein twin roles of nitrite ions are clearly reflected, one as the
complexing agent (Eq. (3)) and another as oxidizing agent for silver
(Eq. (2)). Furthermore, the dependency of the reaction rate with respect
to the nitrite concentration is stronger than that associated with the
cupric ions concentration. This behavior can possibly be related to the
concentration of Cu(NO2)2−x x complexes (where x = 1 or 2), which is
different in the leaching tests (Fig. 7), e.g., the concentration of the
Cu(NO2)2− x
x
complexes is lower at 1.0 M NO− −
2 than at 1.5 M NO2 . It
may thus be suggested that these cupric-nitrite complexes have a syn-
ergistic effect on the leaching rate.
Fig. 8 illustrates the leaching data of 360 min (shown in Fig. 7) fitted
to the shrinking particle model. It may be noted that the leaching kinet-
ics is controlled by the silver dissolution reaction in the nitrite concen-
tration range of 1–1.5 M. This is evident from the increase in ‘apparent
rate constant’ values (0.0003, 0.0007 and 0.0012 min−1) corresponding
to the nitrite concentration of 1.0 M, 1.35 M and 1.5 M NO− 2 . From these
results, it is possible to say that the reaction rate depends on the nitrite
ions concentration with an apparent reaction order of 3.2.
Fig. 6. Plot of shrinking sphere kinetic model for silver leaching at room temperature with
1.5 M NO− 2 , 0.1266 g Ag and different copper concentrations.
102 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105
Fig. 7. Nitrite effect on the silver recovery kinetics with 0.2 M Cu2+ and A) 1.0 M NO−2 ,
B) 1.35 M NO− −
2 and C) 1.5 M NO2 . The three experiments were carried out at pH of 5.
The kinetic analysis presented in Figs. 6 and 8 which exhibit depen-
dence on the concentrations of cupric and nitrite ions, suggests that the
metal dissolution is controlled by the surface chemical reaction of the
lixiviant on the silver particles. The reaction thus proceeds unhindered
in absence of any layer or coating on the surface of the silver particles.
The solid residue obtained from the leaching solution C with 0.2 M
Cu2+ and 1.5 M NO− 2 (Fig. 5) was characterized by SEM and elemental
mapping (Fig. 9). These results are similar to that reported in Fig. 4 for
the leaching with 0.05 M Cu2+ and 1.5 M NO− 2 . Presence of two type
of morphology (bright and dark) can be seen in Fig. 9B; EDS of the bright
particles exhibits mainly the silver (Fig. 9A) and that of the dark parti-
cles (Fig. 9C) consist of Cu, O and S. Similarly the elemental mapping
in Fig. 9 (D to G) for Cu, Ag, O and S, represents the morphological
features associated with the copper hydroxysulfate species and Ag
(Fig. 9E), besides the presence of silver particles without any coating
with the copper precipitate (Fig. 9E). This result is in good agreement
with the kinetic analysis shown in Figs. 6 and 8.
In order to validate the formation of copper hydroxysulfate species
in the solid residue during the silver leaching with 0.2 M Cu2 + and
1.5 M NO− 2 (Solution C, Fig. 5), a copper species distribution diagram
for NO2-Cu-SO4-Ag-H2O system (Fig. 11) was constructed at a potential
of 0.619 VSHE, which corresponds to the redox potential measured at 6 h
(at end of the experiment), according to Fig. 10.
The presence of the Cu4SO4(OH)6 (brochantite) phase formed pre-
dominantly at pH 5 (recorded at 360 min of leaching) can be observed
in Fig. 11. As mentioned before brochantite can be precipitated accord-
ing to Eq. (5). Furthermore, it is also possible that nitrite ions are
decomposed to nitrate species at 0.619 VSHE, according to the Pourbaix
diagram reported by Alvarado-Macías et al. (2015) for the NO2–H2O
system. Hence a decrease in the nitrite ions concentration could pro-
mote the precipitation of free cupric ions to brochantite.
Fig. 8. Plot of shrinking sphere kinetic model for silver leaching at room temperature with
0.2 M Cu2+, 0.1266 g Ag and different nitrite concentrations.
The solid residue obtained with the leaching solution C (Fig. 5) in
360 min was analyzed for XRD phase identification (Fig. 12). The XRD
pattern shows the presence of brochantite (Cu4(OH)6SO4) as the
major phase with a small amount of metallic silver, which remained un-
dissolved in the process.
3.4. Effect of temperature
The effect of temperature on the leaching kinetics was studied using
the best leaching conditions optimized in the previous section (1.5 M
NO− 2 , 0.2 M Cu
2+
for 0.1266 g Ag). Fig. 13 illustrates the increase in
leaching of silver in 30 min with temperature (19–55 °C). The silver
recovery was recorded to be 7%, 10%, 29%, 45% and 53% during the
first 30 min at 19, 30, 45, 50 and 55 °C, respectively. According to
Dreisinger and Abed (2002), for chemically controlled processes small
increments in temperature usually lead to tremendous enhancement
of reaction kinetics. As mentioned above the silver surface remained un-
coated when the solid residue obtained with this solution (1.5 M NO− 2 ,
0.2 M Cu2+) at room temperature (Fig. 9) was microscopically analyzed.
Thus, it is reasonable to assume that the process kinetics was still con-
trolled by the silver dissolution reaction at temperatures higher than
that of room temperature.
The silver recovery results shown in Fig. 13 were fitted to the chem-
ical control model (Fig. 14). It is evident that the chemical control model
adequately describes the rate controlling step in the silver leaching pro-
cess [NO2-Cu-Ag system]. With these plots the apparent rate constants
can be obtained at each tested temperature (Table 1). As expected,
when silver leaching was carried out at higher temperatures than
19 °C, the apparent rate constant increased; e.g., the corresponding
values of ksa were found to be 0.0009, 0.0013, 0.0037, 0.0063 and
0.0081 min−1 at 19, 30, 45, 50 and 55 °C.
The leaching of silver at room temperature was compared with that
of 55 °C for entire duration of 6 h (Fig. 15). Results show the recovery of
almost 80% and 92% Ag at room temperature and 55 °C, respectively,
which affirms that the temperature is an important variable to catalyze
the silver dissolution in this system. Interestingly in the experiments
carried out at 50 °C and 55 °C especially (Figs. 13 and 15, respectively),
the kinetics seems to slow down after 20 min during the leaching. This
clearly indicates that the nitrite is being consumed by reactions other
than the oxidation of silver. As mentioned before, there is a possibility
that nitrite ions can be decomposed to nitrate ions, and this decomposi-
tion can possibly be happening due to the dissolved oxygen present in
the leach solution, according to Eq. (7).
2NO− −
2 þ O2 →2NO3 ð7Þ
3.5. Kinetic analysis
Temperature dependence was used to estimate the apparent activa-
tion energy. The activation energy value N 40 kJ/mol is characterized for
the process controlled by the chemical reaction (Levenspiel, 1972). The
apparent activation energy of the system can be obtained from the Ar-
rhenius expression (Eq. (8)):
k ¼ k0 exp:ð−Ea=RTÞ ð8Þ
Where k0 is the pre-exponential factor, Ea is the apparent activation
energy and R is the universal gas constant. The apparent activation en-
ergy and the pre-exponential (frequency) factor (k0) can be estimated
based on the logarithmic form of the Arrhenius law (9):
lnk ¼ lnk0 –Ea=ðRTÞ ð9Þ
To calculate the apparent activation energy, Arrhenius plot (lnk vs
T− 1) was constructed (Fig. 16A) using Eq. (9) and the apparent rate
 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105 103

Fig. 9. Morphology, local chemical composition and X-ray mapping of the solid residue formed from the silver leaching shown in curve B of Fig. 5. A) Elemental composition of the bright
particle, B) Morphology of the solid residue, C) Elemental composition of the dark particle, and X-ray mapping for D) copper, E) silver, F) oxygen and G) sulfur.

constants obtained in Fig. 14, while the enthalpy and entropy of activa-
tion were calculated from the analysis of an Arrhenius plot in the form
of ln (k/T) vs T−1 (Fig. 16B) using the transition state theory (Eq. (10)):
kðTÞ ¼ ðkB T=hÞexp:ð−ΔGǂ =RTÞ
where kB is the Boltzman constant, h the Planck constant, T the abso-
lute temperature in °K, Δ Gǂ the free energy of activation and R the
universal gas constant (Barsa et al., 2012). A summary of the leaching
rate constants for each temperature, apparent activation energy, en-
thalpy of activation and entropy of activation values, is shown in
Table 1.
The apparent activation energy calculated for the leaching system is
50.92 kJ/mol (Table 1) which is well within the range for surface chem-
ical reaction controlled process (Levenspiel, 1972). A positive enthalpy
value of 48.34 kJ/mol (Table 1) indicates the endothermic nature of
the reaction and therefore heat has to be supplied to facilitate the reac-
tions; thus an increase in the temperature would increase the rate con-
stant, accelerating the silver recovery (Fig. 13). Similarly the entropy of
ð10Þ activation can give information about the molecularity of the rate deter-
mining step in a reaction which was calculated to be −139.05 J/mol.K.
The negative value indicates that entropy decreases upon achieving
the transition state, often related to an associative mechanism e.g. coor-
dination complexes or metallic complexes. The formation of the silver–
nitrite complex during the leaching is also reflected by the value of en-
tropy of activation.

Fig. 11. Copper species distribution diagram for the NO2-Cu-SO4-Ag-H2O system with
0.2 M Cu2+, 1.5 M NO− 2 , 0.2 M SO4
2−
and 0.006 M Ag at 0.619 V vs SHE and pH 5
Fig. 10. Redox potential vs time for silver leaching under the conditions of Curve C of Fig. 5. (measured redox potential at 6 h leaching with solution C in Fig. 5).
104 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105

Fig. 12. X-ray diffraction pattern of the solid residue obtained in the leaching with 1.5 M
NO−2 , 0.2 M Cu
2+
(Curve C, Fig. 5). Fig. 15. Comparison of the silver extraction (%) vs time for the NO2-Cu-Ag system at room
temperature and 55 °C (1.5 M NO− 2 , 0.2 M Cu
2+
and 0.1266 g Ag).

4. Conclusions

In this work a novel leaching system involving NO2–Cu species is

presented, which is able to oxidize and complex the silver metal with-
out the presence of thiosulfate or cyanide. The nitrite ions oxidize the
metallic silver, while the remaining nitrite ions act as the complexing
agent for silver. The nitrite and cupric ions concentrations play a critical
role on the leaching kinetics and recovery of the metal. The cupric-
nitrite complexes are proposed to be responsible for the synergistic
effect found on the silver leaching kinetics. When the nitrite ions con-
centration is increased from 1.0 M to 1.35 M along with 0.2 M cupric
ions, the silver recovery increased from 30% to 55%; while increase in
the cupric ions concentration from 0.05 M to 0.1 M with 1.5 M nitrite
ions promoted the silver dissolution from 32% to 57%. The best leaching
solution consists of 1.5 M nitrite and 0.2 M cupric ions at a pH of 5 which
Fig. 13. Effect of temperature on the silver leaching kinetics with 1.5 M NO−
2 , 0.2 M Cu
2+
can dissolve almost 80% of silver at room temperature in a processing
and 0.1266 g Ag at 30 min and pH 5.
time of 6 h.

Fig. 14. Plot of chemical reaction model fitting to conversion vs time at various
temperatures (1.5 M NO−
2 , 0.2 M Cu
+2
).

Table 1
Temperature dependence of reaction kinetics and related thermodynamic values.

Temperature (°C) Leaching rate constant k Activation energy

(min−1) (kJ/mol)

19 0.0009 50.92
30 0.0013 Enthalpy of activation (kJ/mol)
45 0.0037 48.34
50 0.0063 Entropy of activation (J/mol*K)
Fig. 16. Arrhenius plots of reaction rates vs inverse of temperature A) lnk and B) ln (k/T)
55 0.0081 −139.05
for the NO2-Cu-Ag system (1.5 M NO− 2 , 0.2 M Cu
2+
and 0.1266 g Ag).
 G. Alvarado-Macías et al. / Hydrometallurgy 160 (2016) 98–105
The leaching of silver at different temperatures and the calculated
enthalpy of activation (48.34 kJ/mol), show that the process is endo-
thermic and supply of heat will accelerate the silver dissolution. In
fact, it is possible to dissolve almost 92% of silver at 55 °C in 6 h using
the best leaching conditions mentioned above. The kinetic data show
best fit to the shrinking particle model controlled by the surface chem-
ical reaction of the lixiviant on the silver particles with the apparent ac-
tivation energy of 50.92 kJ/mol. The characterization of the leach
residue by SEM-EDS studies reveals the absence of any inhibiting layer
on the silver particles which is consistent with the kinetic and thermo-
dynamic (species distribution diagram: Cu-Ag-NO2 system) analysis.
This is further corroborated by the XRD phase analysis showing the
discrete presence of brochantite formed in the bulk solution and not
on the silver particles. These results suggest the needs of further re-
search to be carried out in order to prevent the copper precipitation
and consequently increasing the concentration of the cupric-nitrite
complexes which could catalyze the silver leaching kinetics.
Acknowledgements
Gabriela Alvarado Macías and Fabiola Nava-Alonso are grateful to
CONACyT (México) for the postgraduate scholarship and to the sabbat-
ical support received, respectively. Also, the collaboration of Ana Elena
Muñiz, Felipe Márquez, Sergio Rodríguez Arias and Socorro García in
this investigation is duly recognized.
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