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Thiosubstituted Organophosphorus Acids as Selective
Extractants for Ag(I) from Acidic Thiourea Solutions
Z. Gamino Arroyo a; M. Stambouli a; D. Pareau a; A. Buch a; G. Durand a; M. Avila
Rodriguez b
a
Laboratoire de Génie des Procédés et Matériaux, Ecole Centrale Paris, Cedex,
France
b
Facultad de Química, Universidad de Guanajuato, Guanajuato, Gto., México
Online Publication Date: 01 March 2008

To cite this Article: Arroyo, Z. Gamino, Stambouli, M., Pareau, D., Buch, A.,
Durand, G. and Rodriguez, M. Avila (2008) 'Thiosubstituted Organophosphorus
Acids as Selective Extractants for Ag(I) from Acidic Thiourea Solutions', Solvent
Extraction and Ion Exchange, 26:2, 128 - 144
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Solvent Extraction and Ion Exchange, 26: 128–144, 2008

Copyright # Taylor & Francis Group, LLC
ISSN 0736-6299 print/1532-2262 online
DOI: 10.1080/07366290801904855
Thiosubstituted Organophosphorus Acids as

Selective Extractants for Ag(I) from Acidic
Thiourea Solutions
Z. Gamino Arroyo,1 M. Stambouli,1 D. Pareau,1 A. Buch,1

G. Durand,1 and M. Avila Rodriguez2
1
Ecole Centrale Paris, Laboratoire de Génie des Procédés et Matériaux,
Cedex, France
2
Facultad de Quı́mica, Universidad de Guanajuato, Guanajuato, Gto.,
México
Abstract: This paper deals with the solvent extraction of silver from thiourea leaching
Ag ore liquors as an alternative to the traditional process involving cyanide. The inves-
tigation of the extraction mechanism of silver from acidic thiourea solution had not
been clearly established to date.
The extraction behavior of silver using di(2-ethylhexyl)dithiophosphoric acid
(D2EHDTPA) and di(2,4,4-trimethylpentyl) thiophosphinic acid (CYANEX 302)
was studied. The effect of various parameters such as concentrations of metal,
mineral acid, thiourea, and extractant has been investigated. The extracted
complexes have been identified through a slope method analysis as AgX(HX)5 for
CYANEX 302 and AgX for D2EHDTPA, where HX denotes the extractant.
Moreover, complete stripping was ensured with a mixture of NH4SCN and
H2SO4. In addition we showed that a first step of extraction with D2EHPA or
CYANEX 272 results in the preferential separation of Fe(III) from the Ag(I)
leach solution.
Keywords: Silver extraction, acidic thiourea, D2EHDTPA, CYANEX 302
Received 21 March 2007, Accepted 14 November 2007

Address correspondence to Z. Gamino Arroyo, LGPM, Ecole Centrale Paris,
Grande Voie des Vignes, Chatenay-Malabry 92295, France. E-mail: gamino@lgpm.
ecp.fr
128
Solvent Extraction of Silver from Thiourea Leaching 129
INTRODUCTION
The use of thiourea (TU) for the recovery of gold and silver from ores as an
alternative to the traditional process involving cyanide has been suggested
by several authors.[1 – 5] The thiourea leaching of gold and silver presents
some advantages over the common cyanide process such as faster kinetics
and lower toxicity. But the costs due to high thiourea consumption, caused
by its fast degradation, limit its industrial application.
In the presence of a suitable oxidizing agent, such as, O2, H2O2, or Fe,
thiourea solubilizes Ag(I) according to the following reaction:
Agþ þ 3CS(NH2 Þ2 ! Ag[CS(NH2 Þ2 þ
3
Various processes were considered for gold and/or silver recovery from
thiourea or cyanide solutions: activated carbon adsorption,[6] polyurethane
foam loaded with tributyl phosphate,[7] ion exchange,[8] microorganisms,[9]
electrowinning,[10] and solvent extraction.[11 – 15]
The extraction of Ag(I) has been extensively studied with different extrac-
tants and in different acid and basic media. Tributyl thiophosphate (TBPS) and
triiso-octyl thiophosphate (TOTP) are higly selective for recovery Ag (I) in
nitric acid media by a solvating mechanism. For TOTP, the extracted
complex AgNO3TOTP was identified.[16]
The separation of silver and copper in nitric acid media with triisobutyl
phosphine sulfide (TIBPS or CYANEX 471x) has been reported with Kext ¼
(5.4 + 0.4) . 107 (mol/L)22 and the complex AgNO3(TIBPS)2[17] determined.
The extraction of Ag(I) with TIBPS from chloride solutions has been also
studied and the extracted specie is AgCl(TIBPS)2.[18] From chloride media
other silver extraction has been led with commercial sulfur-containing extrac-
tants: SFI-6R (dihexyl sulfide), MSP-8 (di(2-ethylhexyl) monothiophosphoric
acid), CYANEX 302, and CYANEX 301. Some authors reported that two
molecules are coordinated to one silver atom when the extractant is present
in a dimeric form (MSP-8, CYANEX 302) and only one in the case of
monomeric extractants (CYANEX 301).[19]
In previous works the extraction of Ag(I) with di-n-butyl phosphorothioic
acid in CCl4 from aqueous solutions of HCl or H2SO4 has been reported but
the extraction mechanisms are not clearly understood.[20] From the same
aqueous media, if the separation is carried out with CYANEX 301 then
metal can not be stripped from the organic phase.[21]
In nitrate media, the extraction of Ag(I) has been achieved with
CYANEX 272, CYANEX 301, and CYANEX 302. The extracted complex
was characterized and identified as a 1:1 complex.[22] The LIX 79 recovery
of gold and silver from alkaline cyanide leach liquors was studied. The extrac-
tion mechanism was identified as ion exchange.[23]
Some authors report the synthesis of various calix[n]arene derivatives and
crown ethers in order to perform silver extraction but their industrial
application is not economically viable.[24]
130 Z. G. Arroyo et al.
Table 1. Structures of the extractants relevant to this study and their abbreviations
Di-(2-ethylhexyl)dithiophosphoric acid (D2EHDTPA) is reported as an

extractive reagent for the separation of different metals from sulfuric and
hydrochloric acid.[25] Dialkyl phosphorodithioic acids exibit high chemical
stability at room temperature; thus, they could be quite suitable for the
selective extraction of several metals including silver and gold.[26] For
example the extraction of Ag(I) from nitrate media has been studied by the
D2EHDTPA. The complex was identified as a 1:1 complex with Ag(I).[27]
On the other hand, relatively little research on silver solvent extraction
from acidic thiourea solutions has been carried out. The recovery of silver
from thiourea solutions with solvating extractants (CYANEX 471x) has
been studied but the results were not conclusive.[28]
Some authors stated that silver was extracted in an anionic form from
thiourea solutions with nitrobenzene as solvent in presence of 2,4,6 –trinitro-
phenol (TNP) and ammonium tetranitrodiammine cobaltate (TNDC). At pH
higher than 1 and in the presence of TNP the silver is extracted as an
Ag(TU)þ .
n TNP complex, where n ¼ 2 or 1.5. From sulfuric acid media
(pH , 1), authors report a better rate of extraction.[29] In the case of a
sulfato-chloride media, the extracted complex with TBP was proven to be
AgCl(TU)(TBP)3(H2O)X.[30]
In the present paper, the extraction characteristics of silver from a
thiourea leach solution containing Fe(III) as a metal ion contaminant were
investigated. Many commercial extractants were tested: TBP, di(2-ethylhexyl)
phosphoric acid (D2EHPA), trioctyl amine (TOA), CYANEX 272, CYANEX
302, triisobutyl phosphine sulfur (CYANEX 471x), and D2EHDTPA. The
structures of these extractants are reported in Table 1.
EXPERIMENTAL
Reagents and Materials
The extractants CYANEX 272, CYANEX 301, CYANEX 302, and CYANEX
471x (Table 1) were supplied by CYTEC Canada Inc. TBP and TOA were
supplied by Across Organics and D2EHPA by Alfa-Aesar. All these extrac-

tants have been used without further purification. The D2EHDTPA has
been obtained either by stripping from a commercial zinc salt (Rhein
Chemie) or synthesized by the reaction of phosphorus pentansulfide with the
appropriate alcohol, according to published procedures.[25,31] The purity of
D2EHDTPA was determined by potentiometric titration (Titrino 716,
Metrohm) in a ethanol:water (1:3) solution with NaOH at 0.1 Mol/L. Purity
of 95% was determined.
The extractants were diluted in pure dodecane (Across organic), or even-
tually mixed with 10% (v/v) of n-octanol (Across organic). All other chemical
products were of analytical reagent grade.
The metals were analyzed with a Varian type atomic adsorption spectro-
photometer. The thiourea concentration was determined by titration with
potassium iodate using starch as indicator[8,32] and with UV-Visible spectropho-
tometry (Varian 300 Scan).[33] A Knick Digital pH meter with a combined glass
electrode was used to measure the pH of the aqueous solutions.
Experimental Procedure
Equal volumes (10 –20 mL) of the aqueous and the organic phase were stirred
for 30 min with a mechanical shaker at 20 + 18C. The pH was adjusted by
addition of a very small volume of diluted H2SO4 or NH4OH solution. The
concentration of metal ion species in the loaded organic phase was determined
after complete stripping with a mixture of NH4SCN and H2SO4. (Two contacts
with A/O ¼ 2 or 4).
The determination of the distribution ratio (D ¼ [Ag]org/[Ag]aq) and the
extraction rate (% ¼ 100[Ag]org/[Ag]aq þ [Ag]org) are obtained by measure-
ment of the equilibrium concentration in the aqueous phase ([Ag]aq) and in
the organic phase ([Ag]org) by using atomic adsorption. Mass balance was
always verified.
RESULTS AND DISCUSSION
Extraction Kinetics
Kinetic studies were performed by contact of 20 mL of aqueous solution of

Ag(I) with 20 mL of extractant solution diluted in dodecane. 1 mL of each
phase has been taken at different time and concentration of Ag(I) measured
by atomic absorption.
Figure 1 illustrates the extraction yield of Ag(I) by D2EHDTPA extrac-
tant as a function of time at constant pH and thiourea concentration. Equili-
brium is reached in nearly 2 min. No decrease of extraction efficiency was
observed during the entire duration of the experiment.
Figure 1. Effect of the extraction time on the Ag(I) recovery. Aqueous phase:
[AgI] ¼ 0.5 mmol/L, [TU] ¼ 0.1 mol/L organic phase: [D2EHDTPA] ¼ 0.5 mmol/L
phase ratio ¼ 1, pH ¼ 2, T ¼ 208C.
The same experiment has been performed with all the extractants tested.
According to our results, equilibrium has been considered as reached after
10 min for all of these extractants. In order to be certain to reach the equili-
brium shaking time has been chosen equal to 30 min.
Effect of the Nature of the Extractant
Table 2 presents the equilibrium extraction concentration of Ag(I) and Fe(III)

with various extractants at different concentrations from a similar leach
Table 2. Extraction of silver and iron with various extractants. [AgI] ¼ 0.5 mmol/L,
[FeIII] ¼ 2.7 mmol/L, [TU] ¼ 0.1 mol/L, pH ¼ 2. Phase ratio Org.:Aq. ¼ 1:1. 20 C.
T ¼ 208C
Extraction of Extraction of
Ag(I) % Fe(III) %
Concentration
of extractant % Octanol without without
Extractant (mol/L) (v/v) TU with TU TU with TU
TBP 0.1 0 3.2 1.6 4.5 1.1

D2EHPA 0.1 0 9.7 4.7 100 92.9
TOA 0.1 0 5.7 2.3 19.2 0
CYANEX 302 0.1 10 100 73.7 96.6 81
CYANEX 471x 0.1 10 100 0 4.4 0.5
CYANEX 272 0.1 10 4.5 0.9 99.2 94.7
D2EHDTPA 1.1023 0 100 99.9 41.8 32.8
solution with or without thiourea (0.1 mol/L). When a third phase is present,
octanol was added in order to prevent its formation.
Due to the formation of metal-thiourea complex, in the presence of
thiourea, the extraction of both Fe(III) and Ag(I) is less important whatever
the nature of the investigated extractants.
In the absence of thiourea, CYANEX 471x shows a good selective extrac-
tion of Ag(I) over Fe(III). However, in the proceeding studied, the silver solu-
balization is always performed by thiourea leaching, it means in the presence
of thiourea. Furthermore, a low level of concentration (4.4%) of Fe(III) is
extracted by CYANEX 471x. The presence of Fe(III) could also be a
problem for the purification processing of silver. This is why CYANEX
471x has been ruled out.
In thiourea media, the extraction is nearly complete for Fe(III) with
CYANEX 272 or D2EHPA and with CYANEX 302 or D2EHDTPA for
Ag(I). This very interesting result could be explained through Pearson’s
concept of soft/hard acids and bases (HSAB).[34,35] Soft acid and bases
tend to have high polarizability and low electronegativity. Thus soft acids pre-
ferentially bind soft bases.
The organo-phosphorous extractants are considered as soft bases with the
increasing order of softness: POOH , PS , PSOH , PSSH. As a hard acid,
Fe(III) would be preferentially complexed by phosphorus acid such as
CYANEX 272 or D2EHPA. Being a soft acid, Ag(I) would then preferentially
form complexes with the dithiophosphate molecules (i.e., CYANEX 302 or
D2EHDTPA).
Though, a new process could be proposed based on a primary selective
extraction of Fe(III) using CYANEX 272 or D2EHPA, followed by a
selective extraction of Ag(I) with D2EHDTPA.
Effect of Thiourea Concentration
The effect of thiourea concentration (0.05 –0.5 mol/L) on the extraction of

Ag(I) has been investigated using CYANEX 302 (100 mmol/L) or
D2EHDTPA (2 mmol/L). A plot of logD versus log[TU] is shown in
Fig. 2. The slopes of the straight lines are ranging from 23 to 24.
Thiourea acts then as an inhibitor of Ag(I) extraction in relation with the
predominance of the complexes Ag(TU)þ þ
3 and Ag(TU)4 in the aqueous
phase. This explanation is in accordance with the speciation diagram
shown in Fig. 3. The speciation diagram has been plotted by using the
global stability constant of the various thiourea complexes present in
solution. The material balance of each species has been performed and
the percentage of each complex formed versus the thiourea concentration
has been determined.
In addition, ultraviolet spectroscopy analysis showed that the extracted
metallic complex does not include any thiourea molecule.
Figure 2. Effect of thiourea concentration on the extraction of Ag(I). Aqueous phase:

[AgI] ¼ 1 mmol/L [TU] ¼ (0.02– 0.5 mol/L). Organic phase: [CYANEX
302] ¼ 0.1 mol/L or [D2EHDTPA] ¼ 1 mmol/L. Phase ratio ¼ 1, pH ¼ 2,
T ¼ 208C.
Extraction Equilibrium of Ag(I)
Assuming mononuclear metal ion species, the extraction of Ag(I) with

CYANEX 302 or D2EHDTPA could be represented by the following
Figure 3. Partition of silver-thiourea species in the aqueous phase versus the concen-
tration of thiourea. [Ag(I)] ¼ 1 mmol/L. Global stability constants of silver complexes
in acid thiourea medium: logb1 ¼ 7.11, logb2 ¼ 10.62, logb3 ¼ 12.73, logb4 ¼ 13.57.[39]
general equation:[36]
mþn
Agþ þ ðHXÞp ! AgXn ðHXÞm þ nHþ ð1Þ
p
where the upper lined denote species in the organic phase, HX is the mono or
dithioorganophosphorus acids, and p the degree of aggregation of the
extractant.
The equilibrium constant for the extraction is given by:
½AgXn ðHXÞm ½Hþ n

Kext ¼ ð2Þ
½Agþ ½ðHXÞp mþn=p
The distribution coefficient, D is defined as the ratio of the metal concentration

in the organic phase on the total metal concentration in the aqueous phase.

Ag AgXn ðHXÞm
D¼ ¼ ð3Þ
½Ag ½Ag
The complex formation of Ag(I) with acid thiourea solutions can be described
as follows:
Agþ þ iTU $ AgðTUÞþ

i ð4Þ
The global stability constant of this reaction is defined as:

AgðTUÞþ
i
bi ¼ þ ð5Þ
Ag ½TUi
where, i ¼ 1,2,3,4, and the complex coefficient a is the following:
½Ag X4
aAgfð½TUÞ ¼
þ ¼1þ bi½TUi ð6Þ
Ag i¼1
If we introduce expression of D and [Agþ] into Equation (2) we obtain the

following equation
½Hþ n
Kext ¼ DaAgf ð½TUÞ ð7Þ
½ðHXÞp mþn=p
Using the logarithm form with the Equation (7) gives the following
expression:
m+n
log D ¼ n pH þ log HX p log aAg f ð½TUÞ þ log Kext ð8Þ
p
Aggregation Study
For D2EHDTPA, VPO measurements (Vapor Pressure Osmometry) were

conducted using trioctyl amine as the reference material and pentane as the
solvent at 298C according to the procedure presented by Buch et al.[37,40]
VPO is based on the measurement of DT temperature difference between
two thermistors. The value for DT is estimated based on the difference in
resistance DR measured by a Wheatstone bridge. The DR is proportional to
the concentration of TOA (Standard) or D2EHDTPA in the solution present
on the thermistor. The following relation is obtained: DR ¼ kS where S is
the molality (mol . kg21 of solvent) of D2EHDTPA and k is a constant, to
be determined by a preliminary calibration. The results expressed as
functions of DR versus the total concentration of the extractant are
presented in Figs. 4 and 5 for the standard TOA and D2EHDTPA respectively.
For the standard TOA which does not aggregate, the variations of DR
versus S(mol/kg) are strictly linear (Fig. 4) and can be defined by the
expression: DR ¼ kTOA S. The values of kTOA for the temperatures of 298C
are respectively 1057.3 + 0.8. For the D2EHDTPA the variations of DR
versus S in g/kg are also strictly linear (Fig. 5) and can be defined by the
expression: DR ¼ kD2EHDTPA S. Values of kD2EHDTPA for the temperatures
of 298C are respectively 3.5 + 0.1.
From these results, the mean molar mass of D2EHPDTPA can be
obtained with the following expression:
kTOA
Mðg mol1 Þ ¼
kD2EHDTPA
The apparent average molecular weight of D2EHDTPA aggregates in pentane
is proved to be 347 g . mol21. As the molecular weight of D2EHDTPA is
354 g . mol21, thus, it seems there is no aggregation in solution. Therefore,
Figure 4. DR as a function of TOA total concentration in pentane at 298C.

Figure 5. DR as a function of D2EHDTPA total concentration in pentane at 298C.
D2EHDTPA is mainly in a monomeric form in the investigated range of con-

centration (,0.1 mol/L). The mean aggregation number for CYANEX 302 in
aliphatic non polar diluents such as dodecane is reported in the literature as
p ¼ 2.[38]
Effect of Metal Ion Concentration
The effect of Agþ concentration on the extraction of Ag(I) has been investi-
gated using organic phases containing CYANEX 302 (100 mmol/L) and
D2EHDTPA (1 mmol/L) respectively and 0.1 mol/L aqueous thiourea
solutions, the pH of which was kept constant at 2.0.
The experimental results are illustrated in Fig. 6. The plotted points show a
straight line of slope 1 for both D2EHDTPA and CYANEX 302 extraction, indi-
cating that only mononuclear species are extracted into the organic phase as we
assumed previously taking into account the low level of metal ion concentrations.
Effect of pH
Figure 7 shows the effect of the pH on the log of the extracted Ag(I) according
to the slope method. The concentration of all the other reagents is kept
constant. (i.e., thiourea concentration is 0.1 mol/L, the metal ion concen-
tration is 1 mmol/L, and the extractant concentrations of CYANEX 302
and D2EHDTPA are respectively 100 mmol/L and 1.0 mmol/L). The exper-
imental values of n is 1.2 for both CYANEX and D2EHDTPA. Thus only one
proton is exchanged through silver extraction. This result is compatible with
the electro-neutrality principle.
Figure 6. Effect of the metal ion concentration on the extraction of Ag(I). [CYANEX
302] ¼ 100 mmol/L, aqueous phase: [AgI] ¼ 0.1– 10 mmol/L, [TU] ¼ 0.1 mol/L.
[D2EHDTPA] ¼ 1 mmol/L, aqueous phase: [Ag(I)] ¼ 0.2– 0.8 mmol/L,
[TU] ¼ 0.1 mol/L. Phase ratio ¼ 1, pH ¼ 2, T ¼ 208C.
Effect of Extractant Concentration
The effect of the concentration of CYANEX 302 (20 –200 mmol/L) and
D2EHDTPA (0.2 –1 mmol/L) on the silver extraction from acidic thiourea
(0.1 mol/L) solutions has been studied. Initial concentrations of metal ions,
acid, and thiourea were kept constant. According to the slope method
analysis (Fig. 8), the experimental values of (m þ n)/p are nearly 1 and 3
for D2EHDTPA and CYANEX 302 respectively.
Figure 7. Effect of pH on the extraction of Ag(I). Aqueous phase: [AgI] ¼ 1 mmol/

L, [TU] ¼ 0.1 mol/L Organic phase: [CYANEX 302] ¼ 0.1 mol/L or
[D2EHDTPA] ¼ 1 mmol/L. Phase ratio ¼ 1, T ¼ 208C.
Figure 8. Effect of extractant concentration on the Ag(I) extraction. Aqueous phase:

[AgI] ¼ 1 mmol/L, [TU] ¼ 0.1 mol/L. Organic phase: [CYANEX 302] ¼ 20 –
200 mmol/L or [D2EHDTPA] ¼ 0.2 – 1 mmol/L. Phase ratio ¼ 1, pH ¼ 2, T ¼ 208C.
In order to confirm the results obtained with D2EHDTPA, the organic sat-
uration method was applied. Organic phases containing different concentrations
of D2EHDTPA were loaded up to saturation in constant aqueous conditions
(pH ¼ 2.0; TU ¼ 0.1 mol/L). After saturation the organic phases were
stripped and analysed. The results are illustrated in Fig. 9. The experimental
value of the ratio [Ag]org/[D2EHDTPA] equal to 1.05 confirms the previous
1:1 stoichiometry. This stoichiometry was reported by Shong et al.[27]
Complex Stoichiometry
The experimental results related to the extracted complex stoichiometry are

summarized in Table 3. The mean value of the apparent extraction constant
was determined and reported in Table 3. For the CYANEX 302
log(Kext) ¼ 11.37 + 0.10 and for the D2EHDTPA, log(Kext) ¼ 12.64 +
0.19. A comparison between the experimental results and the developed
model is illustrated in Fig. 10 for CYANEX 302 and Fig. 11 for
D2EHDTPA. A good agreement was observed.
Effect of Stripping Agents
Different stripping agents have been tested alone or coupled. Some stripping
performances are illustrated in Table 4. The mixture (NH4)SCN (1 mol/
L) þ H2SO4 (0.5 mol/L) would be preferred for the selective stripping
of Ag(I).
Figure 9. The experimental value of the ratio [Ag]org/[D2EHDTPA], Aqueous

phase: [AgI] ¼ 125 mmol/L, [TU] ¼ 0.1 mol/L. Organic phase: [D2EHDTPA] ¼
0.5– 2.2 mmol/L. Phase ratio ¼ 2, pH ¼ 2, T ¼ 208C.
Table 3. Experimental results for the extracted complex stoechiometry
Extractant (HX) p n m Extracted complex log Kext
CYANEX 302 2 1 5 AgX . (HX)5 11.37 + 0.10

D2EHDTPA 1 1 0 AgX 12.64 + 0.19
Figure 10. Theoretical and experimental distribution coefficient versus the CYANEX
302 concentration. CYANEX 302, experimental data (†), continuous lines represent
those obtained from the model. [TU] ¼ 0.1 mol/L phase ratio ¼ 1, pH ¼ 2, T ¼ 208C.
Figure 11. Theoretical and experimental distribution coefficient versus the

D2EHDTPA concentration. D2EHDTPA, experimental data: (†) [TU] ¼ 0.1 mol/L;
(B) [TU] ¼ 0.15 mol/L, (O) [TU] ¼ 0.2 mol/L continuous lines represent those
obtained from the model, phase ratio ¼ 1, pH ¼ 2, T ¼ 208C.
Table 4. Efficiency of different stripping agents for the back extraction of Ag(I).
[AgI]org ¼ 0.4 mmol/L, [CYANEX 302] ¼ 0.1 mol/L, 10% (v/v) of octanol,
[D2EHDTPA] ¼ 1 mmol/L. Phase ratio Org.:Aq. ¼ 1:3, T ¼ 208C
Stripping agent
(NH4)2S2O3 (NH4)SCN (NH4)SCN (1 mol/L) þ

Extractant (1 mol/L) (1 mol/L) H2SO4 (0.5 mol/L)
CYANEX 302 84.9% — 99.8%

D2EHDTPA 42.2% 4.5% 89.6%
CONCLUSION
This study clearly demonstrates the performances of CYANEX 302 or

D2EHDTPA for the extraction of Ag(I) from acidic thiourea solutions. For
both, exhaustive thermodynamic studies were investigated. Apparent equili-
brium constants were determined and the stoechiometry of the extracted
metal complexes identified as AgX(HX)5 and AgX for CYNANEX 302 and
D2EHDTPA respectively. Different stripping reagents were tested and the
best stripping performances were achieved with a mixture of NH4SCN and
H2SO4.
In the frame of the development of a new process of silver recovery from
a silver leach solution containing Fe(III), either D2EHPA or CYANEX 272
could suitably be used for the selective elimination of Fe(III) primarily to

Ag(I) recovery using D2EHDTPA (or at a lesser degree, CYANEX 302).
ACKNOWLEDGMENTS
We thank CONACYT (The National Council on Science and Technology of

Mexico-Consejo Nacional de Ciencia y Tecnologı́a México) for the financial
support under ECOS-SEP-CONACYT M01-P04 project and for the first
author’s scholarship grant. We also thank CYTEC Canada Inc and Rhein
Chemie (Mannheim, Germany) for supplying the working samples.
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Solvent Extraction and Ion Exchange

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Solvent Extraction and Ion Exchange, 26: 128–144, 2008

Thiosubstituted Organophosphorus Acids as

Z. Gamino Arroyo,1 M. Stambouli,1 D. Pareau,1 A. Buch,1

Keywords: Silver extraction, acidic thiourea, D2EHDTPA, CYANEX 302

Received 21 March 2007, Accepted 14 November 2007

Solvent Extraction of Silver from Thiourea Leaching 129

130 Z. G. Arroyo et al.

Di-(2-ethylhexyl)dithiophosphoric acid (D2EHDTPA) is reported as an

Reagents and Materials

Solvent Extraction of Silver from Thiourea Leaching 131

supplied by Across Organics and D2EHPA by Alfa-Aesar. All these extrac-

RESULTS AND DISCUSSION

Kinetic studies were performed by contact of 20 mL of aqueous solution of

132 Z. G. Arroyo et al.

Effect of the Nature of the Extractant

Table 2 presents the equilibrium extraction concentration of Ag(I) and Fe(III)

TBP 0.1 0 3.2 1.6 4.5 1.1

Solvent Extraction of Silver from Thiourea Leaching 133

Effect of Thiourea Concentration

The effect of thiourea concentration (0.05 –0.5 mol/L) on the extraction of

134 Z. G. Arroyo et al.

Figure 2. Effect of thiourea concentration on the extraction of Ag(I). Aqueous phase:

Extraction Equilibrium of Ag(I)

Assuming mononuclear metal ion species, the extraction of Ag(I) with

Solvent Extraction of Silver from Thiourea Leaching 135

½AgXn ðHXÞm ½Hþ n

The distribution coefficient, D is defined as the ratio of the metal concentration

Agþ þ iTU $ AgðTUÞþ

The global stability constant of this reaction is defined as:

where, i ¼ 1,2,3,4, and the complex coefficient a is the following:

If we introduce expression of D and [Agþ] into Equation (2) we obtain the

136 Z. G. Arroyo et al.

For D2EHDTPA, VPO measurements (Vapor Pressure Osmometry) were

Figure 4. DR as a function of TOA total concentration in pentane at 298C.

Solvent Extraction of Silver from Thiourea Leaching 137

Figure 5. DR as a function of D2EHDTPA total concentration in pentane at 298C.

D2EHDTPA is mainly in a monomeric form in the investigated range of con-

Effect of Metal Ion Concentration

138 Z. G. Arroyo et al.

Effect of Extractant Concentration

Figure 7. Effect of pH on the extraction of Ag(I). Aqueous phase: [AgI] ¼ 1 mmol/

Solvent Extraction of Silver from Thiourea Leaching 139

Figure 8. Effect of extractant concentration on the Ag(I) extraction. Aqueous phase:

The experimental results related to the extracted complex stoichiometry are

Effect of Stripping Agents

140 Z. G. Arroyo et al.

Figure 9. The experimental value of the ratio [Ag]org/[D2EHDTPA], Aqueous

Table 3. Experimental results for the extracted complex stoechiometry

Extractant (HX) p n m Extracted complex log Kext

CYANEX 302 2 1 5 AgX . (HX)5 11.37 + 0.10

Solvent Extraction of Silver from Thiourea Leaching 141

Figure 11. Theoretical and experimental distribution coefficient versus the

(NH4)2S2O3 (NH4)SCN (NH4)SCN (1 mol/L) þ

CYANEX 302 84.9% — 99.8%

This study clearly demonstrates the performances of CYANEX 302 or

142 Z. G. Arroyo et al.

could suitably be used for the selective elimination of Fe(III) primarily to