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ISSN: 0973-4945; CODEN ECJHAO

E-Journal of Chemistry
2010, 7(1), 239-245

Copper(II) Extraction from Nitric Acid Solution with

1-Phenyl-3-methyl-4-benzoyl-5-pyrazolone as a Cation
Carrier by Liquid Membrane Emulsion
BAHARUDDIN HAMZAH*, NOOR JALALUDDIN,
ABDUL WAHID WAHAB and AMBO UPE
*

Faculty of Teacher Training and Education,

Universitas Tadulako Palu, Kampus Bumi Tadulako Tondo, 94223 Palu, Indonesia.
Faculty of Mathematics and Natural Science,
Universitas Hasanuddin Makassar,Kampus Tamalanrea, 90245 Makassar, Indonesia.
hamzahhb@yahoo.com
Received 19 March 2009; Accepted 15 May 2009
Abstract: Copper(II) extraction from nitric acid solution with 1-phenyl-3methyl-4-benzoil-5-pyrazolone (HPMBP) as a cation carrier by liquid membrane
emulsion (LME) was investigated. The HPMBP initially was synthesized and the
synthesis yield is a yellow crystal with melting point of 87-89 oC. The synthesis
efficiency is 72.04% and generally the spectra of IR, 1H NMR and 13C NMR
agree with HPMBP structure. The optimum condition for copper(II) extraction
were found as follows: concentration of mixed surfactant (span 80+span 20) was
3%, volume ratio of membrane and internal phase was 1, concentration of
HPMBP was 0.020 M, concentration of HCl was 1 M, volume ratio of emulsion
and external phase was 0.143. By using these optimum conditions, 30 mL of
LME can extract 1000 ppm of copper(II) within 210 mL of nitric acid solution
with extraction percentage of 97.97%.
Keywords: Copper(II), Extraction, Liquid membrane emulsion, HPMBP.

Introduction
Although in low concentration, the metals in wastewater cause a serious health and
environmental problem. The presence of metals in several industrial wastewater like
industry of electroplating, battery, ceramic and tannery is a complex example of pollution.
Every year, the using of metal increase and their availability decrease, therefore their
recovery from wastewater treatment is clearly important thing that must be care.
Conventional treatment techniques for metal recovery as precipitation and filtration
always generate solid wastes that need a continue treatment process. The main problems of this
method are redissolution of many precipitates, the addition of a great volume of chemical

240

B. HAMZAH et al.

reagent and the generation of an enormous amount of sludge that is not easy to dispose.
Solvent extraction for metal recovery is another alternative method, but this method is less
efficient and uneconomical because it uses several times extraction and back extraction and it
need much more solvent. Separation technique that are still developed until now is liquid
membrane emulsion technique. This technique offer high scope and potential due to its
characteristics such as easy operation, lesser energy requirement, and high selectivity. Liquid
membrane emulsion process has the ability to remove and to selectively concentrate the low
metal contents in solution, in a continue and fast process, using a thin liquid membrane that
present a great interface area, needing only a very small volume of organic solvent.
LME for metal extraction are made by forming water in oil (W/O) emulsion, stabilized
by surfactant, contains carrier in the oil phase and the stripping acid in the internal aqueous
receiving phase. This emulsion is then dispersed by mild agitation into a feed phase
(external phase) containing the metal to be extracted. After extraction, the loaded emulsion
is separated from the feed stream, demulsification yields an oil phase that can be recycled.
Electrolysis could subsequently recover the metal concentrated in the receiving phase.
Liquid membrane emulsion technique has been used for separation of phenol1,
substituted phenol2, nitro phenol compound3 and toluene/n-heptane4 from industrial effluent,
extraction of metals5-13 and amino acid14,15. In medical field, this technique has utilized for
separation of toxic compound in blood16, and extraction of cephalexin17.
A cation carrier was needed in metal extraction process by LME. The cation carriers
that usually used are salicylaldoxim18, benzoylacetone19, diisostearylphosphoric acid20,
p-tert-butylcalixaren21, trioctylmethyl ammonium chloride22, tri-n-octylamin or TOA23, di-2ethylhexyl phosphoric acid or HDEHP24-26, N-alkylcaprolactam27, tertieramine28, ketoconazol29,
dinonylnaphthalensulphonate acid30, etc. Although these carrier were deeply used in metal
extraction by LME technique, however they were used in high concentration up to 20%31.
Therefore its less efficient and uneconomical.
The alternative compound that recognized well as an effective carrier is HPMBP. Several
researches that used HPMBP as an extractant, for example, extraction behavior of rare earth
metal (except promethium and ytrium) with HPMBP was studied32. Synthesis of HPMBP and its
applied in extraction of copper, zinc, nickel, manganese and iron were investigated33. Extraction
of Pu(IV) and Th(IV) with HPMBP were done34. Extraction of lanthanum (III), europium (III)
and lutetium (III) into chloroform with fluorinated HPMBP has also been reported35.
In this paper, we present a study of copper (II) extraction from acidic nitric solution
using HPMBP as a carrier by liquid membrane emulsion technique. We use combining
surfactant (span 80+span 20) for emulsion stability, kerosene as the solvent and hydrochloric
acid solution as the internal aqueous receiving phase.

Experimental
1-Phenyl-3-methyl-5-pyrazolone was supplied by P.T. Intraco, benzoyl chloride, copper(II) sulphate,
nitric acid, hydrochloric acid, sodium hydroxide, calcium hydroxide, the surfactant (span 80+span
20), and solvents (kerosene, 1,4-dioxane) were obtained from Merck and used directly as received.

Synthesis of HPMBP
1-Phenyl-3-methyl-5-pyrazolone (15 g) was dissolved in 160 mL of 1.4-dioxane by heating.
Calcium hydroxide (24 g) was added following by benzoyl chloride (10 mL) drop wise
within 2 minutes. The temperature increased during the first few minutes. The reaction
mixture was refluxed for 30 minutes. Calcium complex of the desired compound formed in

Copper(II) Extraction from Nitric Acid Solution

241

the flask was decomposed by pouring the mixture into dilute hydrochloric acid (200 mL). A
yellowish orange precipitate was formed slowly. It was filtered under suction, washed with a
little water and 1.4-dioxane and recrystallised.

Emulsion preparation and copper(II) extraction

Water in oil emulsions were prepared by initially blending the HPMBP and mixed surfactant
(span 80+span 20) with kerosene to get the membrane phase. The internal aqueous stripping phase
(HCl) was added slowly to the membrane phase with agitation of contents at 2,000 rpm in 10 min.
Certainty volume of emulsion was added into certainty volume of copper(II) solution
(500 ppm) and stirred at 300 rpm in 15 minutes. The aqueous external phase was separated
and the copper(II) concentration was measured by AAS with wavelength of 324.7 nm.

Determination of experimental optimum condition

Several important factors which affect the percentage extraction of copper(II) with liquid
membrane emulsion are surfactant concentration, HPMBP concentration, volume ratio of the
membrane phase to the internal stripping aqueous phase, volume ratio of the emulsion to the
external phase, concentration of HCl in internal stripping aqueous phase and feed
concentration. The investigated parameters with their range as follows:
Parameter
Variation range
Surfactant concentration, % v/v
1-5
HPMBP concentration, M
0.005-0.025
Volume ratio of membrane phase to internal phase
0.5-2.0
Volume ratio of emulsion to external phase
0.1-0.2
HCl concentration, M
0.5-2.0
Feed concentration, ppm
400-1800

Results and Discussion

Synthesis of HPMBP
The synthesis yield is a yellow crystal with melting point of 87-89 oC and synthesis
efficiency is 72.04%. From the IR spectra, several band appeared at 3101, 3059, 1641, 1568 cm-1
assigned to OH stretching, aromatic C-H stretching, aromatic/non aromatic C=O, C=N
stretching, respectively. In 1H NMR spectra, several peaks appeared at chemical shift of 2.00,
7.30, 7.46, 7.50, 7.58, 7.64, 7.89 and 13.00 ppm, with total proton abundance of 14.
Whereas, the 13C NMR spectra showed some peaks in chemical shift of 15.9, 103.4, 126.7,
137.3, 120.8, 127.9, 131.9, 137.6, 128.4, 129.2, 148.0, 161.6 and 191.9, with total carbon
abundance of 17. The IR, 1H NMR and 13C NMR spectra agree with the HPMBP structure.

Effect of surfactant concentration

In emulsion liquid membrane system, a surfactant is added as an emulsifier in the liquid
membrane phase affects not only the stability of the liquid membrane but also the swelling of the
emulsion and the rate of metal extraction. Figure 1 shows the effect of surfactant concentration to
the extraction percentage of copper(II). It was observed that, when the surfactant concentration
was 1%, there was severe membrane rupture. Although the emulsion was expected to be
stabilized with increasing surfactant concentration, the degree of stability becomes relatively
constant due to the saturation of surfactants at the oil-water interface and it makes the extraction
percentage of Cu(II) is also relatively constant. It is known that the increase of surfactant
concentration does not favor extraction kinetics. Because of that, the amount of surfactant in the
membrane must be minimal, but it must be enough to stabilize the emulsion. The optimum
surfactant concentration (span 80+ span 20) was taken as 3% (v/v).

B. HAMZAH et al.

% Extraction of cu

242

Surfactant concentration, %

Figure 1. Effect of surfactant concentration to extraction percentage of Cu(II).

Effect of HPMBP concentration

% Extraction of cu

Increasing the amount of carrier (HPMBP) has two effects. First, the viscosity of membrane
phase, which limits the extraction rate, decreases on increasing the carrier concentration.
Second, hence the carrier acts as a thinner for the membrane phase and enhances the rate of
solute transport through membrane for extraction. At the same time, increasing the carrier
concentration over a certain limit decreases the stability of the emulsion. A very high
concentration of carrier in the membrane does not result in a benefit due to the increase in
viscosity, which leads to larger globules. On the other hand, the increase in the concentration of
the carrier also promotes the permeation swelling, which dilutes the internal phase and decreases
the extraction percentage of copper(II). The optimum extraction percentage of copper(II) is found
at a carrier concentration of 0.02 M based on emulsion phase as shown in Figure 2.

HPMBP concentration, M

Figure 2. Effect of HPMBP concentration to extraction percentage of Cu(II).

Effect of the volume ratio of membrane phase/internal phase

The volume ratio of the membrane phase to the internal phase were varied between 0.5- 2. It
is evident that the increase of volume ratio of the membrane phase to the internal phase leads
to an increase in the stability of the emulsion. The results may be explained on the basis that
increasing the internal phase volume makes the emulsion unstable and leads to a leakage of
the internal phase into the external phase.
From Figure 3, it is observed that the extraction percentage of copper(II) increases
slightly with the increasing of the Vm/Vi ratio from 0.5 to 1, because the ejection of the
internal phase is easier when its proportion in the emulsion is higher. It is also observed that
the extraction percentage of copper(II) decreases with the increasing of the Vm/Vi of 2.0.
This result can be explained that the decreasing of internal phase volume makes the
decreasing of the capability of the internal phase in receiving the copper(II). Therefore, it
seems that the optimum volume ratio of membrane phase to the internal phase is 1.

243

% Extraction of cu

Copper(II) Extraction from Nitric Acid Solution

Vm: Vi

Figure 3. Effect of volume ratio Vm:Vi to extraction percentage of Cu(II).

Effect of the volume ratio of the emulsion/external phase

% Extraction of cu

The volume ratio of the emulsion to external phase varied between 0.111 and 2.00. Figure 4
shows the effect of variation of this ratio on extraction percentage of copper(II). It is evident
that the increase of volume ratio of the emulsion to the external phase leads to an increase in
the rate constant of metal extraction. The increase of volume ratio of the emulsion to the
external phase from 0.143 leads to an increase of the emulsion coagulation. Indeed, with
increasing the volume ratio, the swelling phenomenon becomes remarkable, fast and
accompanied by a more significant coalescence of the internal droplets that grow. Therefore,
it seems that the optimum volume ratio of the emulsion to the external phase is 0.143.

Ve: Vex

Figure 4. Effect of volume ratio Ve:Vex to extraction percentage of Cu(II).

Effect of HCl concentration in internal phase

The extraction reaction of copper(II) occurs at the external/membrane interface with the
HPMBP, the complex being formed according to the following equation.
2HPMBP(org)+Cu 2+(aq)
Cu(PMBP)2(org)+2H+ (aq)
(1)
Cu(PMBP)2 species are highly soluble in the membrane (organic) phase and diffuse towards
the internal/membrane interface. At this interface, the Cu(PMBP)2 complex is contacted with
strongly acidic hydrochloric solution, which regenerates the HPMBP to its acid form and releases
the Cu(II) in the internal phase, according to the following back extraction reaction.
Cu(PMBP)2(org)+ 2 H+ (aq)
2HPMBP(org) + Cu 2+(aq)
(2)
Figure 5 presents the effect of hydrochloric acid concentration on the extraction
percentage of copper(II). It was observed that the extraction percentage of copper(II) is
increased by increasing the acidity in the stripping phase (internal phase). The differences
hydrogen ion chemical potentials between the two aqueous phases (external phase and

244

B. HAMZAH et al.

% Extraction of cu

internal phase) are the main driving force in the emulsion liquid membrane process. Thus,
the extraction percentage of copper(II) increases gradually with increasing the concentration
of hydrochloric acid from 0.5 to 1 M, this owing to the increase of the capacity of receiving
phase (internal phase). However, for a concentration of hydrochloric acid greater than 1 M,
the emulsion swells up due to osmosis, which leads to the dilution of the internal phase,
causing a less effective stripping. Another reason, it may be due to the reaction of the acid
with the surfactant which results in a partial loss of its surfactant properties that causing
unstable emulsion. Therefore, it is concluded that the optimum HCl concentration is 1 M.

HCl concentration, M

Figure 5. Effect of HCl concentration to extraction percentage of Cu(II).

Effect of feed concentration of copper(II) in external phase

% Extraction of cu

The effect of feed concentration on extraction percentage of copper(II) at optimum conditions

is shown in Figure 6. By using 30 mL emulsion, it is observed that the increase in feed
concentration from 400 to 1800 ppm, the extraction percentage of copper(II) is relatively
constant. However, the increase of feed concentration higher than 1000 ppm, the extraction
percentage is decrease. We concluded that the capacity of receiving phase is limited.

Cu concentration, ppm

Figure 6. Effect of feed concentration of Cu((II) to extraction percentage of Cu(II).

Conclusions
The synthesis yield is a yellow crystal with melting point of 86-87 oC and synthesis efficiency
is 72.04%. Generally the spectra of IR, H-NMR and C-NMR agree with HPMBP structure.
The optimum condition for copper(II) extraction were found as follows:
concentration of mixed surfactant (span 80 +span 20) was 3%, volume ratio of
membrane phase and internal phase was 1, concentration of HPMBP was 0.020 M,
concentration of HCl was 1 M, volume ratio of emulsion phase and external phase was
0.143. By using these optimum conditions, 30 mL of liquid membrane emulsion can
extract 1000 ppm of copper(II) within 210 mL of nitric acid solution with extraction
percentage of 97.97%.

Copper(II) Extraction from Nitric Acid Solution

245

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