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A study on copper (II) extraction from sulphate medium via cloud-

point extraction with N-salicylideneaniline ligand in presence of


non-ionic surfactant

Mohamed Hadj Youcef*, Tayeb Benabdallah and Hocine Ilikti

Laboratory of the Chemistry and Electrochemistry of the Organometallic Complexes, Department of Chemistry,
Faculty of Sciences, University of the Sciences and Technology of Oran (U.S.T.O.MB), BP-1505 Oran El-M’naouer,
Algeria.
Received: April 5, 2006 Accepted (in revised form): July 31, 2006

Abstract Résumé

In the present work, cloud point extraction process Dans le présent travail, nous utilisons le processus
is used with bidentate Schiff base chelating ligand, N- d’extraction par point de trouble en employant le ligand
salicylideneaniline (SA or HL), to extract and separate chélatant bidenté base de Schiff, N-salicylidèneaniline
copper (II) from sulphate medium in the presence of a (SA ou HL), pour extraire et séparer le cuivre (II) à
non-ionic surfactant, Lutensol A7N. The process used is partir du milieu sulfate, en présence du surfactant non
based on the formation of copper (II) organic complex ionique, Lutensol A7N. Le processus utilisé est basé sur
that is soluble in a micellar phase of non-ionic surfactant, la formation d’un complexe organique du cuivre (II) qui
Lutensol A7N. The copper (II) complex is then extracted est soluble dans la phase micellaire du surfactant non
into the surfactant rich-phase at a temperature above ionique, Lutensol A7N. Ensuite, le complexe du cuivre
the cloud point temperature. The extraction behaviour (II) formé est extrait dans la phase riche en surfactant
of copper(II) with N-salicylideneaniline was studied by à une température au-dessus de la température du point
varying the experimental parameters, such as pH, non- de trouble. L’étude du comportement extractif de la N-
ionic surfactant concentration, ligand concentration, salicylidèneaniline a été effectuée en faisant varier les
and temperature. The results showed that the pH of paramètres expérimentaux, tels le pH, la concentration
aqueous medium had a great effect on the efficiency du ligand, la concentration du surfactant non ionique et
of the extraction process and on the percentage of la température. Les résultas obtenus ont montré que le
extraction. The extraction process was observed in the pH du milieu aqueux a un effet important sur l’efficacité
pH range of 2 - 6. The stoichiometry of the extracted du processus et sur le pourcentage d’extraction. Par
species of copper(II) was determined on the basis of ailleurs, le processus d’extraction a été observé dans
the slope analysis method. The extraction reaction la gamme de pH 2 à 6. La stoechiométrie des espèces
proceeds via the cation exchange mechanism and the extraites du cuivre (II) a été déterminée sur la base
extracted species have a composition of 1:2 (Cu:HL). de l’analyse de la méthode des pentes. La réaction
The optimum conditions of the extraction of this selected d’extraction se fait via un mécanisme d’échange de
metal have been established as the following: 2 × 10-3 cations et les espèces extraites ont une composition 1:2
M extractant; (2) 5% (m/m) surfactant; (3) pH of 5.9; (Cu:HL). Les conditions optimales de l’extraction du
and (4) temperature of 45 °C. métal ciblé ont pu être établies comme suit : (1) 2 × 10-2
M d’extractant ; (2) 5 % (m/m) de surfactant; (3) un pH
Keywords: cloud point extraction process, copper(II), N- de 5.9; et (4) une température de 45 °C.
salicylideneaniline, biodegradable non-ionic surfactant,
Lutensol A7N, Schiff base ligand. Introduction
*
Author to whom correspondence should be addressed:
e-mail: hadjyoucef_med@yahoo.com Copper is an important and valuable metallic element

Canadian Journal of Analytical Sciences and Spectroscopy


268 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti
from both industrial and environmental points of view. gands such as 1-(2-thiazolylazo)-2-naphthol (TAN) (18,
The hazardous effects of heavy metals like copper in the 19,38,39), 2-(5-bromo-2-pyridylazo)-5-diethylamino-
environment are well known. Chronic exposure to cop- phenol (Br-PADAP) (22, 40, 41), 1-(2-pyridylazo)-2-
per causes dizziness, vomiting, diarrhea, transpiration naphthol (PAN) (22, 42) and lately, dithizone(HDz)
and depending on its concentration, death from bleeding (8, 43, 44) have been used for cloud point extraction in
(1). Furthermore, copper is invariably present in various several procedures.
industrial effluent and contaminated areas. Thus, there is The Schiff base chelating ligands constitute another
an economic interest in their extraction and recovery for attractive family of extractants. Indeed, they have a high
recycling. There are many processes for the extraction sensitivity for various metal cations and structural rigid-
of metals in effluents and hydrometallurgical steams. ity (45-50). Moreover, they are well known as ligands
Among these processes, solvent extraction (2-5) is one that can be readily prepared from inexpensive starting
of the most useful because of its inherent simplicity. materials. Nevertheless, they have been rarely used in
However, this process is usually time-consuming and cloud point extraction. Therefore, the present study is
labour extensive and require relatively a large volume of aimed to investigate the cloud-point extraction process
high purity solvents. This generates concern regarding of copper(II) from sulphate medium in batch mode,
disposal of the solvent after use, which creates a severe using N-salicylideneaniline (SA) as bidentate Schiff
environmental problem (6-10). base extracting ligand and Lutensol A7N as a-non ionic
Recently, cloud point extraction (CPE), which is surfactant (Scheme 1).
based on the clouding phenomena of surfactant, has The proposed process for the extraction of copper (II)
been an attractive subject as an alternative to traditional from water consists of four steps :
solvent extraction (SX) (11-25). Upon heating a micellar 1. The bidentate extracting ligand, N-salicylidene-
solution of a non-ionic and zwitterionic surfactant, the aniline, was added to the solution to form a relatively
surfactant will change from water-soluble to oil-soluble. hydrophobic complex with copper (II).
Above a certain temperature, called the cloud point, it 2. The hydrophobic complex formed was subse-
will lose its water solubility almost completely and, quently entrapped in the non-ionic surfactant micelles,
hence, the surfactant molecules will separate out from the Lutensol A7N. Above cloud point temperature, the sur-
aqueous phase. As a result, the clear solution becomes factant became sufficiently hydrophobic so that it formed
turbid and phase separation occurs. At the cloud point, a suspension of a second liquid phase. This suspension
the homogenous surfactant-rich phase contains much was then collected into a second liquid layer.
of the surfactant while the other phase, called the water 3. Because the surfactant layer and copper (II) com-
(or aqueous) phase, contains mostly water and surfactant plex were both relatively hydrophobic, the surfactant
monomers at a concentration near its critical micelle layer extracted most of the complex out of the aqueous
concentration (CMC). Some hydrophobic compounds or layer.
organometallic complexes initially present in the solution 4. The surfactant layer containing the extracted
and bound to the micelles can be favourably extracted copper (II) complex was decanted for recovery of the
and concentrated in a small volume of surfactant-rich copper (II).
phase. The fatty alcohol ethoxylate Lutensol A7N was
The cloud point of non-ionic surfactant can be influ- chosen as non-ionic surfactant because of its low cloud
enced by many factors, such as its own concentration point temperature (about 37°C at a concentration of
(26-27) and the number of ethylene oxide units in its 1% (m/m) by the addition of 0.33 mol L-1 of Na2SO4),
molecules (28) as well as additives such as electrolytes and its high capacity to solubilize Schiff base ligands.
(26, 27, 29-31). There is another advantage to selecting this surfactant
As a new extraction process, the CPE has many as well. It contains no aromatic ring in its molecule, in
advantages over classical solvent extraction such as contrast to the commonly used surfactants such as the
reducing the consumption of and exposures to solvents, Triton series, PONPE series and Igepal series in CPE
disposal cost, and extraction time (32-34). (51-52). Thus, it is friendlier to the environment due
The first attempt involving the cloud-point extraction to its quick biodegradability. In addition, to the best of
of ionic species concerned with the separation of Ni(II) our knowledge, the use of either N-salicylideneaniline
and Zn(II) with 1-(2-pyridylazo)-2-naphthol (PAN) in ligand nor Lutensol A7N non-ionic surfactant in CPE
PONPE-7.5 micellar solutions (35-37). Extracting li- has been reported.

Volume 51, No. 5, 2006


Copper(II) extraction via cloud point extraction with N-salicylideneaniline ligand 269

Scheme 1.

Experimental Analytical procedures


Cloud point measurements
Apparatus The cloud point of aqueous surfactant solution was
A Schimadzu 1202 model UV-Visible spectropho- measured by heating 25 mL of such micellar solution in
tometer with 10 mm-optical path cells were used for a thermostated vessel. The rate of temperature increase
the determination of the concentration of metal in aque- in the water bath was st at 1°C/min or less, if necessary.
ous solution. The pH values were measured using a The cloud point was determined by visual observation
Schott-Gerate model CG820 pH-meter, equipped with a of the temperature at which the clear solution suddenly
glass-combination electrode. A thermostated water-bath turned turbid. All the cloud points reported in this work
maintained at the desired temperatures was employed for were the average of at least triplicate measurements.
the cloud-point temperature experiments. The measurement of the cloud point temperature is
reproducible within 0.2 °C.
Reagents
All chemicals used were of A.R grade. The commer- Cloud-point extraction
cial non-ionic surfactant, Lutensol A7N, supplied by the The extraction step was achieved by using Lutensol
chemical Company BASF (Germany), is a fatty alcohol A7N as the non-ionic surfactant and N-salicylideneanil-
ethoxylate with a linear hydrocarbon chain having 12-14 ine as the extractant. In a typical extraction experiment,
carbon atoms and an ethylene oxide number of 7. aliquots of 10 mL of the sample solution containing the
The bidentate Schiff base ligand, N-salicylideneani- analyte (100 ppm of Cu), N-salicylideneaniline (2 ×
line, SA, was synthesized according to the general con- 10-3 M) and lutensol A7N (5% m/m) were adjusted to
densation procedure (53). The product was recrystallized the appropriate pH value (pH = 5.9) with NaOH. Sub-
from ethanol to give a yellow powder with a yield of sequently, the samples were shaken for 5 min and left to
80% and m.p of 49-50°C (lit 51°C) (54). The purity was stand in a thermostated bath for 10 h at 45°C. The copper
checked by elemental analysis, IR, and 1H-NMR. Anal. concentration was determined spectrophometrically in
Calc. for C13H11NO: C 79.19, H 5.58, N 7.10. Found : the water phase. The overall process can be visualized
C 79.25, H 5.55, N 7.18. IR (KBr) υ 3440, 1613, 1480, as in Figure 1.
1395, 1277, 1031, 977, 894, 750 cm-1. 1H-NMR (400
MHz, CDCl3) δ 13.55 (s, 1H, OH), 8.65 (s, 1H, C(H)=N), Results and Discussion
6.8-7.5 (m, 11H, ArH).
The initial concentration of copper (II), [Cu+2]= 1.6 Calculations
× 10-3 mol L-1 (100 ppm) was prepared by dissolving The distribution coefficient parameter used to des-
CuSO4•5H2O (Fluka) in distilled water. The solution cribe the degree of metal partitioning from the aqueous
was titrimetrically standardized by the EDTA method. to the surfactant-rich phase is given by:
Na2SO4 (Prolabo) was used to maintain the ionic strength
constant ([Na2SO4] = 0.33 mol L-1 ) and H2SO4( Merck)
and NaOH (Prolabo) to adjust the pH. Distilled water (1)
was obtained from our laboratory supply.
where [M]s and [M]w are the final metal concentrations
Canadian Journal of Analytical Sciences and Spectroscopy
270 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti

Figure 1. Schematic representation of typical CPE process.

in the surfactant-rich phase and in the aqueous phase,


respectively. [M]s can be calculated from the mass bal-
ance: (5)

(2)

where [M]0 refers to the metal concentration in the origi- (6)


nal aqueous solution prior to the extraction step, and V0
is the volume of this aqueous solution. Vw and Vs are the
volumes of aqueous solution and surfactant-rich phase Phase behavior of Lutensol A7N-water
obtained after the extraction step, respectively. Figure 1 displays a phase diagram of Lutensol A7N.
The percentage of extraction of metal (yield), R%, and Below the curves, they are micellar solutions (L1), while
the efficiency of process, E%, can be expressed as: the two phase regions exist above the curves (L1+W).
The cloud-point of the Lutensol A7N micellar solution
with concentrations ranging from 0.1 to 15 % increases
monotonically with increasing surfactant concentration
(3) (Figure 2A and 2B ). In micellar solutions comprising
non-ionic surfactants of primary ethoxylated alcohols
such as C12E6 and C12E7, it has been observed that the
cloud-point temperature decreases rapidly with increas-
ing surfactant concentration from the CMC to about 1%
(m/m) and increases again monotonically until reaching
(4) the phase boundary with a further increase in surfactant
concentration (55-56). Since Lutensol A7N is a mixture
of fatty alcohol ethoxylates, similar phase behaviour
Finally, the concentration factor and the volume frac- would be expected.
tion of surfactant-rich phase are given by: The effect of the added Na2SO4 (0.33 mol L-1) on the
cloud-point temperature of the Lutensol A7N micell-
ar solutions were also examined at various surfactant
Volume 51, No. 5, 2006
Copper(II) extraction via cloud point extraction with N-salicylideneaniline ligand 271
concentrations. Figure 2B clearly demonstrates that the phase, presumably the lamellar liquid crystalline phase
addition of sodium sulphate lowers the cloud-point curve, Lα (59). This made it more difficult to separate the sur-
making it possible for the phase separation of the micel- factant-rich phase from the aqueous phase.
lar solutions to take place at lower temperatures, that is,
the cloud-point extraction process could be facilitated at Effect of experimental conditions on CPE process
lower temperatures by simply adding Na2SO4. parameters and optimization of process
It has been known that the addition of certain salts The effect of several experimental parameters (pH,
such as SO4-2 to the non-ionic surfactant solution can extractant concentration, surfactant concentration and
decrease the cloud-point temperature by decreasing the extraction temperature) on the extraction process param-
availability of non-associated water molecules to hydrate eters and micelle formation were investigated in order
the ether oxygens of the poly(ethylene oxide) chains (57). to find optimal operation conditions.
Nonetheless, Miyagishi et al. (58) suggested that the
aforementioned effect arises not only from salting-out of Effect of pH
the ethylene oxide chains but also from the salting-out of The pH was the first parameter evaluated on the ex-
the hydrocarbon chains. It must be mentioned that it is traction of copper. For this study, cloud-point extraction
not always favorable to add too much Na2SO4. Addition of copper(II) was performed in different pH solutions.
of excessive Na2SO4 to the micellar solution will lead to The separation of metal ion by cloud-point process
a very low cloud-point temperature, thus rendering the involves prior formation of a complex with sufficient
formation of unwanted and very viscous surfactant-rich hydrophobicity to be extracted into a small volume of

Figure 2. Phase diagram of Lutensol


A7N-water systems: (A) without addi-
tives; (B) in 0.33 mol L-1 Na2SO4. L1,
micellar solution; W, diluted surfactant
solution; (C) experimental temperature
.

Canadian Journal of Analytical Sciences and Spectroscopy


272 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti
surfactant-rich phase, thus obtaining the desired precon- changes. The concentration of the extractant (SA) that
centration. Extraction yield (R%) and efficiency (E%) provides the highest extraction and efficiency (100%)
depend on the pH at which complex formation is carried with a small amount of extractant and complete extrac-
out. Table 1 shows the effect of pH on the percentage tion is about 2 × 10-3 mol L-1. Thus, this concentration
extraction (yield) of copper (II) and the efficiency of was used in subsequent experiments.
process.
It was found that copper extraction increases with Effect of surfactant concentration
increasing pH of the aqueous medium in the range of A successful cloud-point extraction process would
2-5.9. At pH values above 5.9, the extraction efficiency be one which maximizes the extraction yield and ef-
starts to decrease because the complexation reaction ficiency by minimizing the phase volume fraction, thus
is more favorable in weakly acid conditions. Hence, a maximizing its concentration ability. The variation in
pH of 5.9 was chosen for a quantitative and efficient the extraction within the Lutensol A7N range of 1-7%
extraction. was examined. Quantitative extraction was observed
when the Lutensol A7N concentration was between 3-
Effect of extractant concentration 5%. Table 3 highlights the differences observed in the
Optimization of the concentration of the extractant is yields and efficiencies at different surfactant concentra-
necessary to design the optimum extraction process and tions. Increasing Lutensol A7N concentration above 5%
quick recovery of the metal. To achieve this aim, a series caused the yields and the efficiencies to decrease due to
of experiments was performed in which 10 mL of micel- the increment in the volumes and viscosity of the sur-
lar solution containing 1.6 × 10-3 mol L-1 (100 ppm) Cu factant-rich phase. Lower concentrations have also the
in 5 % (m/m) Lutensol A7N and various concentrations same effect because of the inadequacy in the assemblies
of extractant, N-salicylideneaniline, over the range of to entrap the hydrophobic complex quantitatively.
2 × 10-4 to 4 × 10-3 mol L-1 were subjected to the cloud- An amount of 5% Lutensol A7N was selected in
point extraction process under the optimum pH of 5.9 order to achieve the greatest extraction yield and high-
and constant temperature of 45°C. The results are shown est extraction process efficiency by using a single-stage
in Table 2. It is shown that the percent extraction (R%) extraction without requiring an extra cloud-point extrac-
and efficiency of process (E%) of copper increase with tion stage.
increasing concentration of the extractant. At an extract-
ant concentration higher than 1.83 × 10-3 mol L-1, the Effect of extraction temperature
percentage extraction and efficiency showed insignificant The influence of the extraction temperature on the

Table 1. Effect of pH on the percentage extraction of Cu (II), R%, and the efficiency of process, E%. [HL]* = 2 × 10-3 mol L-1. [Na2SO4] =
0.33 mol L-1. [S]** = 5% (m/m). T= 45°C.
pH R% E%
2.14 23.81 37.83
3.14 23.81 37.83
4.31 38.10 49.60
4.43 42.86 53.31
4.75 52.38 61.19
4.97 57.14 65.06
5.44 76.20 80.60
5.60 80.95 84.47
5.80 90.47 92.26
5.90 100.00 100.00
6.08 95.24 96.13
6.59 95.24 96.13
*[HL]: concentration of the extractant N-salicylideneaniline.
** [S]: concentration of the surfactant Lutensol A7N.

Volume 51, No. 5, 2006


Copper(II) extraction via cloud point extraction with N-salicylideneaniline ligand 273
Table 2. Effect of concentration of the extractant on the percentage of extraction of Cu (II), R%, and the efficiency of process, E%. pH = 5.9.
[Na2SO4] = 0.33 mol L-1. T = 45°C.
[HL] × 103 (mol L-1) R% E%
0.20 38.10 53.57
0.40 52.38 63.33
0.61 76.19 81.19
0.81 84.30 88.75
1.00 97.62 98.12
1.83 100.00 100.00
2.00 100.00 100.00
3.00 100.00 100.00
4.00 100.00 100.00

Table 3. Effect of the surfactant on the percentage extraction of Cu (II), R%, and the efficiency of process, E%. [HL] = 2 × 10-3 mol L-1.
[Na2SO4] = 0.33 mol L-1. pH = 5.9. T = 45°C.
[S] (% m/m) R% E%
1 50.95 52.89
2 64.30 67.68
3 67.62 71.69
4 73.81 78.21
5 100.00 100.00
6 50.95 66.70
7 50.95 64.44

cloud-point extraction process of copper was also investi- age and efficiency (100%) with lower solute solubility
gated. In this study, experiments were carried out from 40 and an acceptable energy consumption, the extraction
to 70°C using 5 % (m/m) Lutensol A7N and 2 × 10-3 mol temperature of 45 °C is adequate for the copper recovery
L-1 of N-salicylideneaniline. The copper concentration scheme.
was 1.6 × 10-3 mol L-1 (100 ppm). The pH of the solu-
tion was adjusted to 5.9. The results of the dependence Concentration factor, CF, and phase volume fraction,
of the percentage extraction of copper and the efficiency φs
of process on the extraction temperature are presented The performance of a cloud-point extraction process
in Table 4. It was found that the percentage of extrac- can be also assessed by its surfactant-rich phase volume
tion of copper and the efficiency initially increase up to fraction, φs, and concentration factor, CF. These two
45°C, and then decrease as the extraction temperature parameters are defined in the “calculations” section.
increased. A similar pattern of the effect of temperature Table 5 and 6 illustrate the effect of variation of the ex-
has been reported for the extraction of copper and lead traction temperature and the surfactant concentration on
with pyrogallol and Triton X-114, and the extraction the CF and φs of the SA/Lutensol A7N/copper/Na2SO4
of phenols with nonaethoxylated methyl dodecanoate cloud-point extraction process. In order to increase the
(C12E9CH3) (60-61). This behavior is ascribed to poor concentration factor (CF) of copper, we search to obtain
phase separation and to the increase of the solubility of a minimal volume fraction of surfactant–rich phase
extracted solute (metallic or organic species) where there (φs). However, logically, the obtained results indicate
is too small or too large a temperature difference between that φs increases with the surfactant concentration and
the cloud-point and extraction temperature (62). From decreases when temperature increases. These findings
Table 4, it is observed that an extraction temperature in are in general agreement with the previous reports in
the range of 40 to 45°C provides a higher percentage which the influence of the extraction temperature and
extraction of copper. Therefore, for the highest percent- the surfactant concentration upon the cloud-point extrac-

Canadian Journal of Analytical Sciences and Spectroscopy


274 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti
Table 4. Effect of the temperature on the percentage extraction of Cu (II), R%, and the efficiency of process, E%. [HL] = 2 × 10-3 mol L-1.
[Na2SO4] = 0.33 mol L-1. [S] = 5% (m/m). pH = 5.9.
T (°C) R% E%
40 70.00 79.00
45 100.00 100.00
50 58.10 64.40
55 46.67 53.56
60 64.29 67.70
65 52.40 56.64
70 40.47 45.83

Table 5. Effect of the extraction temperature on the concentration factor (CF) and surfactant-rich phase volume fraction (φs) of the CPE process
performance: [HL] = 2 × 10-3 mol L-1. [Na2SO4] = 0.33 mol L-1. [S] = 5% (m/m). pH = 5.9.
T (°C) CF φs
40 2.63 0.3
45 5.4 0.185
50 4.3 0.15
55 4.12 0.13
60 7.13 0.095
65 6.29 0.09
70 5.09 0.09

Table 6. Effect of the surfactant concentration on the concentration factor (CF) and surfactant-rich phase volume fraction (φs) of the CPE
process performance: [HL] = 2 × 10-3 mol L-1. [Na2SO4] = 0.33 mol L-1. T = 45°C, pH = 5.9.
[S] (% m/m) CF φS
1 13.22 0.04
2 7.52 0.09
3 5.74 0.125
4 4.60 0.170
5 5.56 0.18
6 2.78 0.240
7 2.34 0.275

tion of phenol and benzyl alcohol, and aluminum were


examined (34, 63) .

Stoichiometry of the extracted species and extraction


mechanism
In a liquid-liquid extraction, the system can be re-
presented by the following reactions:

where Mn+(w) and HL(w) are the metallic solute and


extracting ligand, respectively, in the aqueous phase,
MLn(HL)m(w) is the complex in the aqueous phase and
MLn(HL)m(s) is the complex in the surfactant-rich phase.
The distribution constants, KD and KM, the total forma-

Volume 51, No. 5, 2006


Copper(II) extraction via cloud point extraction with N-salicylideneaniline ligand 275
tion constant, ßn, for the extracted species and the acid
dissociation constant of HL, Ka, in the aqueous phase,
are given by:
(8)

(1)
and the distribution ratio, DM, becomes:

(9)
(2)
or

(10)
Equation (10) expresses DM as a function of the extract-
ing ligand (i.e extractant) concentration [HL], and pH
(3) of the aqueous phase.
To determine the composition and the stoichiometry
of the extracted species, the slope analysis method was
carried out by plotting log DM = f(pH) and log DM = f(log
[HL]s) by using the developed equation (10).
For both curves in Figures 3 and 4, the slope is 1
(4) and 2, respectively ( i.e. n = 1 and m = 1), suggesting
that the copper(II) should be extracted as the complex
of 1:2 (metal:extractant) with the stoichiometry of
Combining equs. 2-4 and rearraging gives:
[CuL(HL)]+.
From the results obtained above the mechanism
(5) extraction process can be described by the following
reaction:

Since the distribution ratio, DM , is given by:

Conclusions

The extractability of copper(II) from a sulfate medium


with the extracting ligand, N-salicylideneaniline, in the
(6)
presence of non-ionic surfactant, Lutensol A7N, was
studied using the cloud-point extraction process in batch
mode. Based on the results, the following conclusions
assuming that [M+n ]w >> [MLn(HL)m]w, and combining can be drawn:
eqns. 1, 5 and 6 results in: 1. The cloud point extraction is an easy, practical and
a very promising process for the extraction and separa-
tion of metal ions like copper (II). It offers an expensive
alternative to other separation extraction processes.
(7)
2. The N-salicylideneaniline (SA) proved to be an
efficient chelating extractant for cloud-point extraction
the extraction constant, Kex , can be defined by: of copper (II). The simple synthesis, the structural rigid-

Canadian Journal of Analytical Sciences and Spectroscopy


276 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti

Figure 4 . Dependency of the distribution ratio DM of copper (II) on


the concentration of extractant (SA), pH = 5.9. [Na2SO4] = 0.33 mol
Figure 3. Dependency of the distribution ratio DM of copper (II) on L-1. [S] = 5% (m/m). T = 45°C.
the pH medium. [HL] = 2 × 10-3 mol L-1. [Na2SO4] = 0.33 mol L-1,
[S] = 5% (m/m), T= 45°C.

ity, the formation of stable complexes and consistency because the “green chemistry” concept can be employed
with CPE processes are the major advantages of the use here.
of N-salicylideneaniline in cloud-point extractions of Although the suggested CPE system offers good
copper. Furthermore, with this extractant, it is possible extraction ability for copper (II), much more work is
to quantitatively extract copper (II) from dilute sulfuric obviously needed to fully understand the CPE process.
acid media (i.e in the pH range of 5-6) which may be These include the following: i) Elucidation of the nature
present in practical situations. of the interaction and binding between the extracted
3. The non-ionic surfactant, Lutensol A7N, is eco- species with this kind of extractant and the non-ionic
nomical and its toxicity is similar to the Triton and surfactant micelles; ii) separation of copper ions from
PONEP series of non-ionic surfactants and provides good copper complex-entrapped surfactant and, hence, the
surfactant-rich extractant phase for the solubilisation of regeneration of the extractant by the application of the
copper-complex and hence the recovery of copper ion. pH-switching process (64).
4. The extent of extraction is markedly influenced by Finally, engineering cost studies together with the
the pH of medium, the concentrations of extractant and development of an industrial process for the proposed
the surfactant, and the extraction temperature. procedure need to have pilot plant trials and would con-
5. The optimized experimental parameters for quan- stitute part of future researches.
titative extraction (R% = 100%, E = 100%) are: (1) 2 ×
10-3 mol L-1 of extractant; (2) 5% (m/m) surfactant; (3)
pH of 5.9 and (4) temperature of 45°C.
6. The environmental pollution is limited to a small
amount of surfactant. This fact is particularly attractive
Volume 51, No. 5, 2006
Copper(II) extraction via cloud point extraction with N-salicylideneaniline ligand 277
References 22. C. C. Nascentes, M. A. Z. Arruda, Talanta, 61,
759 (2003).
1. L. Parmeggiani, Encyclopaedia of Occupational 23. M. Garrido, M. S. Di Nezio, A. G. Lista, M.
Health and Safety, 3rd; International Labor Or- Palomeque, B. S. Fernandez Band, Anal. Chim.
ganisation: Geneva, 1983, Vol. 1. Acta., 502, 173 (2004).
2. A. K. De, S. M. Khopkar, and R. A. Chalmers, 24. S. A. Kulichenko, V. A. Doroshchuk, J. Anal.
Solvent Extraction of Metals, Van Nostrand Rein- Chem., 56, 524 (2003).
hold, London, 1970, pp. 241-242. 25. F. Shimirani, S. D. Abkenar, R. R. Kozani, M.
3. S. Nakamura, S. Takei, and K. Akiba, Anal. Sci., S. Niasari and A. A. Mioroshandel, Can. J. Anal.
18, 319 (2002). Sci. Spectrosc., 49, 31 (2004).
4. T. Hirato,W. Zhi-chu, Y. Yamada, and H. Majima, 26. L. Koshy, A. H. Saiyad, A. K. Rakshit, Colloid
Hydrometallurgy, 28, 81 (1992). Polym. Sci., 274, 582 (1996).
5. B. Anderson, Patent 2, Germany, 1973, 305-694. 27. H. Schott, J. Colloid Interface Sci., 189, 217
6. D. Sicilia, S. Rubio, D. Perez-Bendito, N. Ma- (1997).
niasso and E. A. G. Zagatto, Anal. Chim. Acta, 28. H. Schott, J. Pharm. Sci., 58, 1443 (1969).
392, 29 (1999). 29. T. Iwanaga, M. Suzuki, H. Kunieda, Langmuir,
7. S. Tagashira, Y. Murakami, S. Otobe and Y. Sa- 14, 5775 (1998).
saki, Anal. Sci., 14, 849 (1998). 30. K. G. Satish, J. Colloid Interface Sci., 212, 604
8. J. L. Manzoori and G. Karim-Nezhad, Anal. (1999).
Chim. Acta, 484, 155 (2003). 31. H. Schott, Colloids Surf. A, 186, 129 (2001).
9. M. Shibukawa, N. Nakayama, T. Hayashi, D. 32. A. Safavi, H. Abdollahi, M. R. H. Nezhad and
Shibuya, Y. Endo and S. Kawamura, Anal. Chim. R. Kamali, Spectrochim. Acta, Part A, 60, 2897
Acta, 427, 293 (2001). (2004).
10. R. Kroneld, Bull. Environ. Contam. Toxicol., 36, 33. C. C. Nascentes, M. A. Z. Arruda and N. Mani-
477 (1986). asso, Quim. Nova, 25, 483 (2002).
11. H. Ishii, J. Miura, and H. Watanabe, Bunseki 34. A. Ohashi, A. Tsuguchi, H. Imura and K. Ohashi,
Kagaku, 26, 252 (1977). Anal. Sci., 20, 1091 (2004).
12. C. D. Stalikas, Trends Anal. Chem., 21, 343 35. H. Watanabe, H. Tanaka, Talanta, 25, 585 (1978).
(2002). 36. H. Watanabe, N. Yamaguchi, H. Tanaka, Bunseki
13. R. Carabias-Martinez, E. Rodoriguez-Gonzalo, Kagaku, 28, 366 (1979).
B. Moreno-Cordero, J. l. Pérez-Pavon, C. Garcia- 37. W. B. Qi, Kao Teng Hsueh Hsiao Hua Hsueh
Pinto, and E. F. Laespada, J. Chromatogr. A, 902, Pao., 2, 385 (1981).
251 (2000). 38. J. Chen, K. C. Teo, Anal. Chim. Acta, 434, 325
14. T. Okada, Anal. Chem., 64, 2138 (1992). (2001).
15. M. A. Mesquita da Silva, V. L. A. Frescura, F. J. 39. T. Saitoh, Y. Kimura, T. Kamidata, H. Watanabe,
N. Aguilera and A. J. Curtius, J. Anal. At. Spec- K. Haragichi, Anal. Sci., 5, 577 (1989).
trom., 13, 1369 (1998). 40. M. A. Bezerra, A. L. B. Conceiçao, S. L. C. Fer-
16. E. K. Paleologos, C. D. Stalikas, S. M. Tzouwara- reira, Anal. Bioanal. Chem., 378, 798 (2004).
Karayanni, G. A. Pilidis and M. I. Karayannis, J. 41. G. M. Wuilloud, J. C. A. Wuilloud, R. G. Wuil-
Anal. At. Spectrom., 15, 287 (2000). loud, M. F. Silva, R. A. Olsina, and L. D. Marti-
17. M. C. C. Oliveros, O. Jiminez de Blas, J. L. nez, Talanta, 58, 619 (2002).
Pavon, B. M. Cordero, J. Anal. At. Spectrom., 13, 42. V. O. Doroschuck, S. O. Lelyushok, V. B.
547 (1998). Ishchenko, S. A. Kulichenko, Talanta, 64, 853
18. K. C. Teo, and J. Chen, Analyst, 126, 534 (2001). (2004).
19. J. Chen and K. C. Teo, Anal. Chim. Acta, 450, 43. J. L. Manzoori, G. Karim-Nezhad, Anal. Chim.
215 (2001). Acta, 521, 173 (2004).
20. J. L. Manzoori and G. Karim-Nezhad, Anal. Sci., 44. M. Garrido, M. S. Di-Nezio, A. G. Lista, M.
19, 579 (2003). Palomeque, B. S. Fernandez-Band, Anal. Chim.
21. E. K. Paleologos, C. D. Stalikas and M. I. Karay- Acta, 502, 173 (2004).
annis, Analyst, 126, 389 (2001). 45. C. Spinu, A. Kriza, Acta Chim. Slov., 47, 179

Canadian Journal of Analytical Sciences and Spectroscopy


278 Mohamed Hadj Youcef, Tayeb Benabdallah and Hocine Ilikti
(2000). 56. R. Strey, R. Shomacker, D. Roux, F. Nallet,
46. T. Benabdallah, A. H. Al-Taiar, H. Reffas, S. Afr. U. Ollson, J. Chem. Soc. Farad. T. I, 86, 2253
J. Chem., 57, 33 (2004). (1990).
47. S. A. Sadeeek, M. S. Refat, S. M. Teleb, Bull. 57. M. J. Rosen, Surfactants and Interfacial Phenom-
Chem. Soc. Ethiop., 18, 149 (2004). ena, Wiley, New York, 1989.
48. Y. Ohashi, Bull. Chem. Soc. Jpn, 70, 1319 (1997). 58. S. Miyagashi, K. Okada, T. Asakawa, J. Colloid
49. Z. Cimmeman, N. Galic, B. Bosner, Anal. Chim. Interface Sci., 238, 91 (2001).
Acta, 343, 145 (1997). 59. D. S. Bai, J. L. Li, S. B. Chen, B.-H. Chen, Envi-
50. C. R. Panda, V. Chakravortty, C. K. Dash, J. Ra- ron. Sci. Technol., 35, 3936 (2001).
dioanal. Nucl. Chem., 108, 65 (1987). 60. F. Schemirani, S. D. Abkenar, A. Khatouni, Bull.
51. R. Ferrer, J. L. Beltron, J. Guiteras, Anal. Chim. Korean Chem. Soc., 25, 1133 (2004).
Acta, 330, 199 (1996). 61. K. Materna, J. Milosz, I. Miesiac, G. Cote, J.
52. R. L. Revea, G. A. Makhadze, Talanta, 48, 409 Szymanowski, Environ. Sci. Technol., 35, 2341
(1999). (2001).
53. A. K. Agarwal, R. Kumar, N. Singh, B. D. Kan- 62. S. Akita, M. Rovira, A. M. Sastra, H. Takeuchi,
sal, J. Chinese. Chem. Soc., 27, 31 (1980). Sep. Sci. Technol., 33, 2159 (1998).
54. S. R. Salman, S. H. Shawkat, F. S. Kamounah, 63. B. Haddou,J. P. Canselier, and C. Gourdon,
Can. J. Applied. Spectrosc., 37, 46 (1992). Trans. Inst. Chem. Eng. Part A, 81, 1 (2003).
55. D. J. Mitchell, G. J. T. Tiddy, L. Waring, T. Bos- 64. K. Wongwailikhit, P. Tasakorn, P. Prasassarakish,
tock, M. P. McDonald, J. Chem. Soc. Farad. T. I, M. Aratono, Sep. Sci. Tech., 38, 3591 (2003).
79, 975 (1983).

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