Separation and Purication Technology 22-23 (2001) 571 581 www.elsevier.

com/locate/seppur

Effect of thiourea on the facilitated transport of silver and copper using a crown ether as carrier
A. Gherrou a, H. Kerdjoudj a,*, R. Molinari b, E. Drioli b,c
Laboratory of Ore Valorisation, U.S.T.H.B -Institute of Chemistry, B.P 32 El Alia, 16111, Algiers, Algeria b Department of Chemical and Materials Engineering, Uni6ersity of Calabria, I -87030 Rende (CS), Italy c Research Institute on Membranes and Modeling of Chemical Reactors, CNR -IRMERC, c /o Uni6ersity of Calabria, I -87030 Rende (CS), Italy
a

Abstract Facilitated co-transport of both silver and copper ions in acidic-thiourea medium has been studied. Thiourea can form successive complexes, which are less mobile than the free metal cation. In fact, the mass-transport uxes of both silver and copper ions decrease when the concentration of thiourea in the feed phase increases. The results obtained have been conrmed by the partition of the different species in the feed aqueous phase versus the concentration of thiourea by means of a conditional calculation which showed that Ag+ and Cu2 + species predominate at very low thiourea concentration (10 5 10 4 M) and are substituted by complexes M(Tu)+ n (M = Ag, Cu with n = 1 4) with increasing Tu concentration. The fundamental parameters inuencing the transport of silver and copper ions have also been determined: Thiourea concentration in the feed phase, pH of the feed-solution, silver and copper concentration in the feed phase, crown-ether concentration in the membrane phase and the membrane support characteristics. It was possible to take advantage of the different chemical characteristics of Ag+ and Cu2 + in presence of thiourea. Working in the right conditions the selectivity of the transport (J Ag+/J Cu2 + ) increased from 1.6 to 5.5 with increasing Tu concentration from zero to 10 1 M. 2001 Elsevier Science B.V. All rights reserved.
Keywords: Facilitated transport; Thiourea; DB18C6; Copper; Silver

1. Introduction Today, membrane processes are used in a wide range of applications. It is possible to use a liquid as a membrane with the advantage of higher diffusion coefcients with respect to solid membranes. Liquid membranes are only used in some
* Corresponding author. Fax: + 213-2-247311. E -mail addresses: agherrou@yahoo.fr (A. ccic@ist.cerist.dz (H. Kerdjoudj).

Gherrou),

specic applications because of their rather low stability and in some cases, low selectivity. Selectivities are mainly based on differences in the distribution coefcients of the metal ions from the aqueous phase to the organic phase containing the extractant. The diffusivities of the metal ions of comparable size are similar so that the selectivity, which is determined by differences in solubility and diffusivity, will not be very high in this case. Then, the improvement of this selectivity can be performed by means of the complexation in

1383-5866/01/$ - see front matter 2001 Elsevier Science B.V. All rights reserved. PII: S1383-5866(00)00140-4

572

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

solution and testing some new more selective extractants. Among a wide variety of carriers used in liquid membranes, macrocyclic crown ethers and their derivatives have been demonstrated to be excellent cation carriers [1 5]. Crown ethers have stimulated much interest since their discovery was reported by Pedersen in 1967 [6 8]. However, little attention has been directed towards the transport of precious metal ions by macrocyclic ligands. Both the specity and the binding strength are determined by the conformations adopted by the macrocycles and the nature of the intramolecular interactions. These interactions are mediated by the exibility of the crown ether, which permits conformational changes that optimize the geometry of the crown cavity to suitably accommodate the guest cation. The selectivity of binding to different cationic species is thus determined by both the nature of the electronic interactions and the ability of the crown ether to adopt specic conformations that maximize these interactions. In this work, we are interested in solutions containing precious metals in complex form. In fact, silver and copper are dissolved by reagents susceptible to give rise to charged stable complexes. It was shown that thiourea (S C(NH2)2) is an excellent leaching reagent for precious metals [9,10]. Thiourea in acidic medium can form cationic species extractable by an exchanger ligand like a crown ether. Swaminathan and Irving [11], showed by means of IR spectra that in thiourea there are almost equal contributions from the following three canonical forms (Eq. (1)): (1)

thiourea solutions will be a fundamental parameter for the formation of M(Tu)+ n (M = Ag, Cu) complexes and their stabilities. The rst identication of copper thiourea complexes has been realised by Onstott and Laitinen [12]. They have characterised at rst the Cu(Tu)+ 4 complex which has a log i = 15.39 (i is the global constant of the complex). Pilipenko and Lisetskaya [13] have characterised the Cu(Tu)+ 3 complex with log i = 12.83. Hocjanowski et al. [14] have characterised the successive complexes + + Cu(Tu)+, Cu(Tu)+ 2 , Cu(Tu)3 and Cu(Tu)4 . The logarithms of their global constants were equal to 11, 12.8, 14 and 15.4, respectively. Copper thiourea complexes can be formed according to the following reaction: 1 2+ Cu2 + + (n + 1)TuUCu(Tu)+ n + fds 2 (2)

and fds2 + = where Tu = SC(NH2)2 2+ [(NH2)2CSSC(NH2)2] ; with n = 1 4 and the constant of the equilibrium can be written as: Kn =
2 + 1/2 ] [Cu(Tu)+ n ][fds 2+ n+1 [Cu ]free[Tu]free

(3)

The redox reaction which gives simultaneously copper(I) and formamidine disulde takes place at rst. It is followed by complexation reactions according to the equation: Cu+ + n TuUCu(Tu)+ n with [Cu(Tu)+ n ] in + [Cu ]free[Tu]n free (5) (4)

Hence, thiourea is potentially capable of forming coordinate bonds through both sulphur and nitrogen even though the extremely low basicity of the ligand militates against the formation of nitrogen-metal bonds. In acidic medium, thiourea is protonated and the proton will be bonded to the sulphur atom favouring the bonding of the metal ions to nitrogen atoms. And then after, the proton is released in solution. However, the pH of

These two types of reactions show that the nature and the concentration of the different species depends on several parameters. Ratajczac et al. [15], showed by means of a polarographic study that in function of the initial ratio of the concentration of Cu(II) and thiourea, complexes of variable compositions can be formed. When the ratio [Cu(I)]/[Tu] is less than 1, formamidine disulde can act as a ligand and can give rise to combined complexes [Cu(fds)n (Tu)m ]+. In the case of silver, Pawelka [16], have put in evidence a complex of Ag(Tu)+ formula. The 3 logarithm of the global constant of this complex

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

573

was calculated by Pilipenko and Lisetskaya [13] and was equal to 13.14. This value means that this complex is relatively stable but less than the same copper complex. De Marco et al. [17] have characterized two other silver thiourea complexes, Ag(Tu)+and Ag(Tu)+ 2 . The logarithms of the global constants were equal to 9.25 and 10.21, respectively. The formation of formamidine disulde in the case of silver in thiourea medium is not signaled in literature. From this fact, formation of silver thiourea complexes can be expressed by the following expression: Ag+ + n TuUAg(Tu)+ n with in [Ag(Tu) ] [Ag+]free[Tu]n free
+ n

electrodialysis of copper in a thiourea medium becomes possible when the solutions are obtained by means of elution of cuprocyanides by thiourea. In the present work, our interest goes to the extraction of two valorizable metals, silver and copper in acidic thiourea medium using a supported liquid membrane containing dibenzo-18crown-6 (DB18C6) as carrier.

2. Theory The mass balance in the case of copper allows to write: [Tu]total = [Tu]free + 2[fds2 + ] + % n [Cu(Tu)+ n ]
n=1 4

(6)

(7)

(8) [Cu]total = [Cu

2+

The global stability constants of the different silver and copper complexes in acidic-thiourea medium are recapitulated in Table 1. Few work has been performed using thiourea as a complexant in SLMs and all are related to the use of this specic complexant of transition metals as a stripping reagent. However, there is no work up to date on the use of thiourea as a ligand in the feed phase concerning the SLMs process. In a previous work [18,19] it was shown that the electrodialysis of copper thiourea solutions was constrained by the presence of formamidine bisulde which is a low mobility cation retained by the cation exchange membrane. It can provoke an increase in the electric resistance of the membrane, which prevents the current passing. In a recent work [20], it was shown that the
Table 1 Global stability constants of silver and copper complexes in acidic thiourea medium Complex Cu(Tu)+ Cu(Tu)+ 2 Cu(Tu)+ 3 Cu(Tu)+ 4 Ag(Tu)+ Ag(Tu)+ 2 Ag(Tu)+ 3 Log i 11.00 12.80 14.00 15.40 9.25 10.21 13.14 Reference [12] [12] [12] [12] [15] [15] [9]

]free + % [Cu(Tu)+ n ]
n=1

(9)

where [Tu]free and [Cu2 + ]free represent the free concentrations of thiourea and Cu2 + at the equilibrium, respectively. [fds2 + ] represents the concentration of formamidine disulde which equals half of that of Cu+. On the other hand, we can neglect [Cu+]free in solution. [fds2 + ] = 1 4 % [Cu(Tu)+ n ] 2 n=1 (10)

By introducing Cu(Tu)+ n expressed in Eq. (9) and taking in account Eqs. (3) and (8)
4 [Cu2 + ]free +1 [Tu]total=[Tu]free+ % (n+1)Kn [Tu]n free [fds2 + ]1/2 n=1 (11) +1 [Tu]total = [Tu]free + % (n + 1)Kn [Tu]n free n=1 4

[Cu ]free Kn [Cu2 + ][Tu]n + 1 2

2+

1/2

(12)

from Eq. (3), Eq. (9) Extracting Cu(Tu)+ n becomes

4 [Cu ]free +1 [Cu]total = [Cu2 + ]free + % Kn [Tu]n 1/2 free [fds2 + ] n=1
2+

(13)

574

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

[Ag+]total = [Ag+]free + % [Ag(Tu)+ n ]

n=1

(19) (20) (21) (22) (23)

[Tu]total = [Tu]free + % n [Ag(Tu)+ n ]

n=1

in =
+

[Ag(Tu)+ n ] + [Ag ]free[Tu]n free

[Ag ]total = [Ag+]free 1 + % in [Tu]n e free

n=1

Fig. 1. Mechanism of transport through the SLM.

[Ag+]free =

[Ag+]total 1 + % in [Tu]
n=1 3 n free 3

[Ag+]free % nin [Tu]n free

+1 [Cu]total = [Cu2 + ]free + % Kn [Tu]n free n=1 4

[Tu]total = [Tu]free + [Ag+]free 100 = %Ag+ = [Ag+]total

1 + % in [Tu]n free
n=1

n=1 3

(24)

[Cu ]free Kn [Cu2 + ][Tu]n + 1 2

2+

1/2

(14)

100 1 + % in [Tu]n free

n=1 3

n+1 and B = 4 Putting: A = 4 n + 1Kn [Tu]free n = 1(n + +1 1)Kn [Tu]n . free The following expression can be established:

(25)

[Cu]total =

 '  
3

2 [Tu]total [Tu]free 2 A+B

[Tu]total [Tu]free A+B

n


2

%Ag(Tu)+ n = =

[Ag(Tu)+ n ] 100 [Ag+]total in [Tu]n free 1 + % in [Tu]n free

n=1 3

100

(26)

(15)

This equation permits to calculate the concentrations of free thiourea considering the total concentrations of copper and thiourea as known. The calculation is effected by itteration using a computer programme elaborated in GW-BASIC. Thus, we can calculate the concentrations of all the species formed: [Cu [fds
2+

2.1. SLM system

A SLM usually consists of an organic solution, immobilized in the pores of a hydrophobic microporous membrane, containing a complexing agent (carrier), which binds one of the components very selectively in the feed solution. The SLM separates, by means of two interfaces, the aqueous solution containing the diffusing species (feed) and the solution into which the species will diffuse (strip). The permeation of the species is due to a chemical potential gradient (the driving force of the process) existing between the two opposite sides of the SLM. Transport of silver and copper ions in acidothiourea medium by using crown ethers, obeys to a facilitated co-transport. The transport mechanism is represented in Fig. 1. The metal thiourea

]free = ]=

2+

[Tu]total [Tu] A+B

[Cu2 + ]free A 2 2

 
2/3

A 2

1/2

(16) (17) (18)

2/3

[Cu(Tu)+ n ]=

Kn [Cu2 + ][Tu]n + 1 [fds2 + ]1/2

In the case of silver few expressions will be used because of the formation of only three forms of complexes in the aqueous phase and the absence of formamidine disulde.

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

575

complex cation is complexed at the interface feedphase/membrane and the complex formed diffuses through the membrane phase to the interface membrane/strip-phase where the decomplexation of the metal-complex is realized. The equilibrium reaction can be schematised as:
M(Tu)+ n + m L + A UM(Tu)n Lm A

(27)

with M(Tu)+ n the metal thiourea complex, L the ligand and A the co-ion (NO 3 in this work). The bars indicate that the species are in organic phase. The mass uxes J (mol cm 2 s 1) of the metal ions through the membrane from the feed side to the strip side can be determined applying its denition: J= Dn S Dt (28)

where Dn represents the variation of the number of moles of the metal ions in the solution, S the membrane surface and the reference time. The mass transfer of silver and copper across the membrane will be described by considering only diffusional parameters. The interfacial ux due to the chemical reaction will be neglected (the chemical reactions seem to take place at the interface aqueous feed solution/membrane and membrane/ stripping aqueous-solution). It can be considered as occuring instantaneously relative to the diffusion process.

3. Experimental All the reagents were analytical grade reagents. Copper nitrate, silver nitrate, nitric acid, chloroform and thiourea were products of Fluka. Dibenzo-18-crown-6(DB18C6) was a product of
Table 2 Supports physical characteristics Support Porosity (%) Pore size (mm) 0.04 0.02 0.02 0.10 Thickness (mm) 25 25 50 75110

Aldrich. The at sheet membranes used were microporous polypropylene Celgard type (supplied by Hoechst Celanese Corporation, North Carolina, USA) and Accurel (supplied by Akzo Nobel, Germany) type with different characteristics (see Table 2). The useful area of the supports in the transport cell was 8.04 cm2. The aqueous phases were prepared by dissolving the different reagents in distilled water. The organic phase was prepared by dissolving DB18C6 in chloroform. DB18C6 cavities size is 2.60 3.20 and the ionic radius of Ag(I), Cu(II) and Cu(I) are 1.26, 0.69 and 0.96, respectively. Different concentrations have been used for performing the experiments. The transport cell used consisted of two compartments, made of Teon with a maximum capacity of 45 ml, separated by the supported liquid membrane. Each compartment, the feed containing the metal thiourea solution and the strip containing distilled water, was provided with a mechanical stirrer. In the mass transfer reactions through the SLM, the support was soaked in the carrier solution for 1 h, then put between the two half cells (43 ml each). The experiments began by starting the stirring motors in the two compartments of the cell. Separation of copper and silver has been realized from an equimolar synthetic solution. A mixture of 0.02 M of silver and copper has been prepared in distilled water and a 0.2 M solution of thiourea at pH 1 is then added to the metal solution. The total mixture is then used as the feed phase in the transport cell. The strip phase was distilled water. At different intervals, aliquots of 0.5 mL each were withdrawn from the feed and strip solutions and analysed at a spectrophotometer of atomic absorption (A.A.S.) Perkin Elmer 2380. The concentration of the metal in the organic phase was determined from the mass balance. All the experiments were performed in a thermostated bath at 25 9 1C.

4. Results and discussion

Celgard 2500 Celgard 2400 Celgard 2402 Accurel

45 38 38

4.1. Partition of metal thiourea species in the aqueous phase

Fig. 2 shows the partition of the species formed

576

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

Fig. 2. Partition of copperthiourea species in the feed phase versus the concentration of thiourea. [Cu2 + ] = 0.01 M.

Fig. 3. Partition of copperthiourea species in the feed phase versus the concentration of copper. [Tu] = 0.1 M.

between copper and thiourea in feed aqueous phase calculated from Eqs. (16) (18) The results showed that in the range of 10 5 10 3 M thiourea concentration only Cu2 + species will be transported. Between 10 3 and 10 2 M, Cu(Tu)+ species will be carried quantitatively which is more stable in this range of thiourea concentration. Beyond 10 2 M, the speciesCu(Tu)+ 4 is pratically the single one to predominate and a small quantity of Cu(Tu)+ 3 is also present in the solution. Fig. 3, shows the variation of the percentage of Cu complexes formed in the aqueous phase changing the initial concentration of copper and maintaining the concentration of thiourea constant at 0.1 M. Pratically in the complete range of 10 5 10 2 M of copper, only Cu(Tu)+ is 4 formed. Beyond 10 2 M, Cu2 + and Cu(Tu)+ predominate in the solution. Fig. 4 shows the partition of the species formed between silver and thiourea in the feed aqueous phase calculated from Eqs. (25) and (26). The results show that in the range of 10 5 10 4 M of thiourea only Ag+ species predominate. Between 10 4 and 10 2 M, the species carried will be Ag(Tu)+which is more stable in this range of thiourea concentration. Beyond 10 2 M, the Ag(Tu)+ 3 species is pratically the only one present. One can see that the Ag(Tu)+ 2 species not predominate in all the concentration range. Fig. 5, shows the variation of the percentage of the species formed in the aqueous phase changing the initial concentration of silver and maintaining the concentration of thiourea constant at 0.1 M. Almost in the complete range of 10 5 10 2 M of silver, only the Ag(Tu)+ 3 complex is formed. Beyond 10 2 M, Ag+ and Ag(Tu)+ predominate in the solution. So, for develloping transport the experiments, a concentration of 10 2 M of copper and silver, for giving rise to the most stable complexes Cu(Tu)+ 4 and Ag(Tu)+ 3 , has been used.

4.2. Extraction equilibrium

Fig. 4. Partition of silverthiourea species in the feed phase versus the concentration of thiourea. [Ag+] = 0.01 M.

The extraction of silver and copper ions in

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

577

acidic thiourea medium by the organic extractant DB18C6 dissolved in chloroform has been studied and described elsewhere [21]. Complexes of 1:1 type with the carrier were found and characterized by UV-visible spectroscopy. However, the extraction equilibrium can be described by reaction (29) and extraction constant (Eq. (30)) described as:
M(Tu)+ n + L + NO3 UM(Tu)n L(NO3)

thiourea, n = 14 in the case of copper and n = 13 in the case of silver thiourea complexes that will generate the new complexes with the carrier. The values of the extraction constants Kex were 9.9 106 and 2.2 106 for silver and copper, respectively by analysing the organic phases using molar ratios method [22].

(29) (30)

4.3. Inuence of pH of source phase solution

Since thiourea has both basic and acidic groups, a dependence of the extraction efciency on the pH in the source phase is important. Solutions of thiourea of different values of pH have been prepared by adding an adequate volume of Nitric acid before mixing with silver and copper solutions. Fig. 6 shows the variation of the mass ux of silver and copper in the strip phase versus the initial pH of thiourea in the source phase. The obtained results showed that transport ux of both silver and copper reaches a maximum at pH 1. In fact, beyond this value, the protonation of thiourea gives more stable metal thiourea complexes [19]. Thus, the separation of Ag+ and Cu2 + is more selective at pH greater or equal to 1. On the other hand, the pH values of the source and strip phases do not change in the course of transport. This is in conrmity with the mechanism described by Eq. (1) according to Swaminathan and Irving [11]. The protons do not participate in the formation of M(Tu)n L(NO3) complexes as shown in Eq. (29).

K=

[M(Tu)n L(NO3)]
+ [NO 3 ][L][M(Tu)n ]

where the bar means organic phase. Depending on the initial concentration of

Fig. 5. Partition of silverthiourea species in the feed phase versus the concentration of silver. [Tu] = 0.1 M.

4.4. Inuence of thiourea concentration in the feed phase

The transport experiments have been realised as described in Section 3. The solutions of thiourea have been prepared by adjusting the pH at 1 and then mixing with a volume of silver (or copper) solution. The strip phase was distilled water. In Table 3, silver and copper transport mass uxes, calculated after 5 h of transport, versus the concentration of thiourea in the feed phase are reported. The obtained results showed that silver and copper ions were transported with higher uxes in the absence of thiourea but, selectivities

Fig. 6. Evolution of the mass ux through the SLM versus pH of the feed solution. [DB18C6] = 0.001 M; support, Celgard 2500, [Ag+] = [Cu2 + ] = 0.01 M, [Tu] = 0.1 M.

578

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

Table 3 Variation of the transport mass uxes of silver and copper versus the concentration of thiourea in the feed phase after 5 h of transporta [Tu] (M) J (silver)1010 (mol cm2 s1) 5.16 5.14 4.06 3.88 3.60 J (copper.)1010 (mol cm2 s1) 3.27 2.73 2.13 1.11 0.76 0.68

4.5. Effect of carrier concentration

The membrane support was soaked in DB18C6 solutions of different concentrations. Fig. 8 shows the variation of the uxes of silver and copper in the strip phase versus the concentration of DB18C6. As the carrier concentration is increased, the extraction efciency is increased. Above a concentration of 10 3 M, the carrier concentration has no effect on the mass ux for both silver and copper. However, DB18C6 showed a higher selectivity versus silver. This can be due, in absence of thiourea, to the Ag(I) ion size diameter (2.52) which is closer to the carrier cavities size (2.60 3.20) than the Cu(II) ion size diameter (1.38). But, when thiourea is present in the feed solution, the difference in M(Tu)+ n (M = Ag, Cu) complexes stabilities and mobilities are probably the main reasons for this selectivity.

0 105 104 103 102 101

a

SLM, DB18C6/chloroform 1 mM; support, Celgard 2500 impregnated during 1 h. [Ag+]initial = [Cu2+]initial = 0.01 M, pH 1.

(J Ag+/J Cu2 + ) increased from 1.58 to 5.25 increasing [Tu] from 0 to 10 3 M. This is due to the formation of successive complexes of silver and copper with thiourea as shown in Figs. 2 and 4. In fact, these complexes become less mobile and their coordinance increases from 1 to n (n = 1 3, n = 1 4) by increasing the concentration of thiourea. Moreover, in the case of silver, when the concentration of thiourea in the feed phase was higher than 0.01 M, a black lm (probably a sulde compound) was found on the membrane support. At this concentration no transport of silver was obtained. In the case of copper, a progressive formamidine disulde (product of thiourea oxidation) lm was deposed on the membrane support. The surface of the supports used in these two cases has been analyzed by means of a scanning electron microscope. Fig. 7a c represent the surface view of a Celgard 2500 support, respectively, before and after transport of silver and copper using a concentration of thiourea of 10 2 M at pH 1, [Ag+] = [Cu2 + ] = 0.01 M, [DB18C6] = 0.001 M. Fig. 7bc show that all the pores of the membrane supports are covered and blocked by the deposited lm. The formation of the less mobile successive complexes of copper with thiourea, when the coordinance increases from 1 4 by increasing the concentration of thiourea, can also be the cause of the mass ux decrease as mentioned before.

4.6. Effect of sil6er and copper concentration

Fig. 9 shows a plot of the initial silver and copper ion ux (J ) versus the concentration of silver and copper ranging from 10 5 to 0.01 M in the source phase solution. It is observed that at low silver and copper ion concentrations, the average initial ux is a strong function of the initial concentration in the source phase. However, in the case of copper, beyond a 10 3 M concentration, J approaches a maximum value and becomes constant. This could be due rstly, to the quantitative formation of formamidine disulde which increases the membrane resistance, and secondly, to the low effective membrane area of the SLM owing to the saturation of metal-carrier species. In the case of silver, the ux increases with the increase of the initial concentration of silver in the feed phase without reaching a constant value.

4.7. Inuence of the support characteristics

Thickness and porosity of the support are some of the fundamental parameters which act on the stability of the SLM and thus on the mass uxes and the permeabilities of the metal ions. The inuence of these parameters has been studied using three supports of different characteristics.

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

579

The obtained results, reported in Table 4, show (for the two ions) that mass uxes: (i) increase with increasing the porosity of the support; (ii) decrease with increasing the thickness of the support. The Celgard 2500 membrane, with the highest porosity and the lowest thickness, gives the highest mass uxes of silver and copper ions.

and copper in the strip phase versus the transport time. The obtained results show that silver can be separated from copper when using a concentration of 0.1 M of thiourea at pH 1. This can be due to the fact that copper thiourea complexes are more stable in the aqueous phase than silver thiourea complexes. So, in this case, thiourea plays the role of a masking agent.

4.8. Separation of sil6er and copper from their mixture

The separation temptative of silver and copper was realized as described in Section 3. Fig. 10 shows the evolution of the concentration of silver

5. Conclusion It has been shown that separation of silver and copper as thiourea complexes using a supported liquid membrane process can be done taking ad-

Fig. 7. (a) Scanning electron micrographs of Celgard 2500 support before use. (b) Scanning electron micrograph of Celgard 2500 support after transport of silver. Organic phase, DB18C6/chloroform 0.001 M; Aqueous phase, Ag(NO3) 0.01 M, thiourea 0.01 M, pH 1. (c) Scanning electron micrograph of Celgard 2500 support after transport of copper. Organic phase, DB18C6/chloroform 0.001 (M); Aqueous phase, Cu(NO3)2 0.01 M, thiourea 0.1 M, pH 1.

580

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581

Fig. 8. Evolution of the mass ux through the SLM versus the concentration of DB18C6. Support, Celgard 2500, [Ag+] = [Cu2 + ] = 0.01 M, [Tu] = 0.1 M, pH 1.

Fig. 10. Evolution of the metal concentrations in the strip phase versus transport time. [DB18C6] = 0.001 M; support, Celgard 2500, [Ag+] = [Cu2 + ] = 0.01 M, [Tu] = 0.1 M, pH 1.

Fig. 9. Evolution of the mass ux through the SLM versus the concentration of silver and copper. [DB18C6] = 0.001 M; support, Celgard 2500, [Tu] = 0.1 M, pH 1

Table 4 Inuence of the support characteristics on the mass ux of silver and coppera Support J1010 (mol cm2 s1) Silver Celgard 2500 Celgard 2400 Celgard 2402 Accurel
a

Copper 0.68 0.41 0.21 :0.00

vantage of their different chemical characteristics in presence of thiourea. In fact, at [Tu] = 0.1 M and [Cu] ] 10 3 M formation of formamidine disulde (a product of thiourea oxidation by copper) is probably the main cause of the limiting Cu2 + ux. In contrast, the Ag+ ux increased for increasing Ag+ concentration (also above to 0.01 M) but it dropped almost to zero at [Tu] \ 0.1 M. Working at right range of concentrations, the Ag+, Cu2 + separation can be carried out. The formation of the successive complexes M(Tu)+ n (M = Ag, Cu) which are less mobile than the metal cation alone (n = 1 to 4), can be a second reason for a lower decrease in ux with respect to the absence of thiourea. These results were conrmed by the curves of the partition of the different species in the feed aqueous phase versus the concentration of thiourea by means of a conditional calculation. On the other hand, DB18C6 in the membrane organic phase reacts with the M(Tu)+ n complexes and provokes a competition of Ag+ and Cu2 + complexes resulting from a different selectivity. An Ag+ ux 5.3 times higher than that of Cu2 + was obtained.

3.60 1.72 0.44 :0.00

References
[1] J.D. Lamb, R.M. Izatt, D.G. Garrick, J.S. Bradshaw, The inuence of macrocyclic ligand structure on carrierfacilitated cation transport rates and selectivities through liquid membranes, J. Membr. Sci. 9 (1981) 83.

[Tu] = 0.1 M, pH 1 SLM; DB18C6/chloroform 0.001 M; support impregnated during 1 h.

A. Gherrou et al. / Separation /Purification Technology 22-23 (2001) 571581 [2] Y. Hasegawa, M. Miyata, S. Yoshida, Synergtistic extraction of copper(II) and zinc(II) with tributyl phosphate and crown ether, Bull. Chem. Soc. Jpn. 59 (1986) 3003. [3] T.M. Flyes, On the rate limiting steps in the membrane transport of cations across liquid membranes by DB18C6 and lipophilic crown ether carboxylic acids, J. Membr. Sci. 24 (1985) 229. [4] F. Wilman, W.F. Van Straaten, F. De Jong, Macrocyclic carriers in supported liquid membranes, Recl. Trav. Chim. Pays Bas 112 (1993) 273. [5] R.M. Izatt, D.V. Dearden, P.R. Brown, J.J. Bradshaw, J.J. Christensen, Cation transport at 25C from binary Na+ Mn+,Cs+ Mn+, and Sr+ Mn+ nitrate mixtures in a H2O CHCl3 H2O liquid membrane system containing a series of macrocyclic ligand carriers, J. Am. Chem. Soc. 105 (7) (1983) 1785. [6] C.J. Pedersen, Cyclic polyethers and their complexes with metal salts, J. Am. Chem. Soc. 89 (26) (1967) 7017. [7] J. Pedersen, Crystalline salt complexes of macrocyclic complexes, J. Am. Chem. Soc. 92 (2) (1970) 386. [8] C.J. Pedersen, Crystalline complexes of macrocyclic polyethers with thiourea and related compounds, J. Org. Chem. 36 (1971) 1690. [9] T. Groenewald, The dissolution of gold in acidic solutions of thiourea, Hydrometallurgy 1 (1976) 277. [10] E. Becker, M. Knothe, J. Lo bel, Gold recovery from non-metallic secondary raw materials by leaching with thiourea and adsorption on ion exchangers, Hydrometallurgy 11 (1983) 265. [11] K. Swaminathan, H.M.N.H. Irving, Infra-red absorption spectra of complexes of thiourea, J. Inorg. Nucl. Chem. 26 (1964) 1291. [12] E.I. Onstott, H.A. Laitinen, J. Am. Chem. Soc. 72 (1950)

581

[13]

[14]

[15]

[16] [17]

[18]

[19]

[20]

[21]

[22]

4724; in: Stability constants, The Chemical Society, London, 1970. A.T. Pilipenko, T.S. Lisetskaya, Ukr. Khim. Zh. 19 (1953) 81; in: Stability constants, The Chemical Society, London, 1970. O.I. Hocjanowski, W.M. Ledovskii, W.M. Molodcova, Zh. Oshash. Khim. 44 (4) (1974) 727; in: Stability constants, The Chemical Society, London, 1970. H.M. Ratajczak, L. Pajdowski, M. Ostern, Polarographic studies on aqueous copper(II) solutions with thiourea, Electrochem. Acta 20 (1975) 427. F.G. Pawelka, Z. Electrochem. 30 (1924) 180; in: Stability constants, The Chemical Society, London, 1970. D. De Marko, A. Bellomo, A. Casale, G. Mauceri, Formation of mixed complexes of Ag(I) with three ligands in aqueous solution. Systems with thiourea, thiousulphate ion, iodide ion and thiourea, thiocyanate and thioacetamide, Ann. Chim. 74 (1984) 447. D.E. Akretche, S. Kara-Slimane, H. Kerdjoudj, Selective leaching of a polymetallic complex ore by sulphuric acid and thiourea mixed with sea water, Hydrometallurgy 38 (1995) 189. D.E. Akretche, H. Kerdjoudj, C. Gavach, Electrodialysis of copper thiourea solutions, Hydrometallurgy 34 (1993) 231. D.E. Akretche, A. Gherrou, H. Kerdjoudj, Electrodialysis of solutions obtained by elution of cyanide complexes from anionic exchange resin by means of acidic thiourea, Hydrometallurgy 46 (1997) 287. A. Gherrou, H. Kerdjoudj, R. Molinari, E. Drioli, in: Proceedings of the Fifth Congress of Algerian Chemical Society, Bejaia, Algeria, 11 13 May 1999, p. 57. J. Inczedy, Analytical Applications of Complex Equilibria, Ellis Horwood, London, 1976.