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Solvent Extraction and Ion Exchange

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Solvent Extraction of Copper (II) with

Di2Methylnonylphosphoric Acid in Some Organic
Diluents
a

Wang Tao & Yukio Nagaosa

Faculty of Engineering , Fukui University , Bunkyo, Fukui, 9108507, Japan

Published online: 15 Feb 2007.

To cite this article: Wang Tao & Yukio Nagaosa (2003) Solvent Extraction of Copper (II) with Di2Methylnonylphosphoric
Acid in Some Organic Diluents, Solvent Extraction and Ion Exchange, 21:2, 273-290, DOI: 10.1081/SEI-120018950
To link to this article: http://dx.doi.org/10.1081/SEI-120018950

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SOLVENT EXTRACTION AND ION EXCHANGE

Vol. 21, No. 2, pp. 273290, 2003

Solvent Extraction of Copper (II) with

Di-2-Methylnonylphosphoric Acid
in Some Organic Diluents
Wang Tao and Yukio Nagaosa*
Faculty of Engineering, Fukui University, Bunkyo, Fukui, Japan

ABSTRACT
The extraction of copper (II) with di-2-methylnonylphosphoric acid
(DMNPA) (HA) has been investigated in n-dodecane, toluene, and
1-octanol as organic diluents at 28
0.2 C. The extracted copper (II)
species were found to be CuA2  2HA in n-dodecane, CuA2  3HA in
toluene, and CuA2 in 1-octanol. The stoichiometry of the extracted metal
species was compared with that of di-2-ethylhexylphosphoric acid
(DEHPA) under the same experimental conditions. UV-Vis and FT-IR
spectroscopic data on the extractants and their complexes indicated that
the binding mode of the metal complexes varied with the polarity of
diluents.
Key Words: Extraction; Equilibrium; Di-2-methylnonylphosphoric acid;
Copper; Stoichiometry.

*Correspondence: Yukio Nagaosa, Faculty of Engineering, Fukui University, Bunkyo,

Fukui 910-8507, Japan; E-mail: nagaosa@acbio.fukui-u.ac.jp.
273
DOI: 10.1081=SEI-120018950
Copyright # 2003 by Marcel Dekker, Inc.

0736-6299 (Print); 1532-2262 (Online)

www.dekker.com

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Tao and Nagaosa

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INTRODUCTION
Highly effective, acidic organophosphorus extractants have been extensively studied for the extraction of many heavy metal ions.[19] In a series of
such investigations, dialkylphosphoric acids have been recognized to be very
useful for mutual separation of transition or rare earth metal ions from aqueous
media. Among the dialkylphosphoric compounds as extractants, di-2-ethylhexylphosphoric acid (DEHPA) is one of the most frequently used reagent for
the purpose of metal separations. Our interest is in dialkylphosphoric acids
having longer and more hydrophobic chains as alkylgroups, because they are
expected to give greater extractability of metal ions into organic diluents. In
particular, di-2-methylnonylphosphoric acid (DMNPA) has not received much
attention for metal extraction and separation.
In the present paper, we have investigated the extraction behavior of
copper (II) with DMNPA as an extractant using n-dodecane, toluene, and
1-octanol as diluents, and also with DEHPA for comparison. Having a
comparatively long chain, DMNPA is sparingly soluble in water and acts
as a surfactant. We expected that DMNPA would show enhanced extractability of copper (II) relative to DEHPA. The stoichiometry of the
extracted metal species is discussed by using slope analysis. FT-IR and
UV-Vis spectroscopy have also been used for the investigation of the
extracted species.

EXPERIMENTAL
Reagents and Apparatus
Di-2-ethylhexylphosphoric acid, purchased from Tokyo Kasei Chemical
Industry Co Ltd., was used without further purification before use (above
95% in purity). Di-2-methylnonphosphoric acid was kindly supplied by
Daihachi Chemical Industry Co Ltd. (above 96% in purity). n-Dodecane,
toluene, and 1-octanol of reagent grade (Wako Pure Chemical Industry Co
Ltd.) were used as organic diluents. Cu(ClO4)2 and NaClO4 of reagent grade
were used without further purification. Other reagents were of analytical
reagent grade.
An Iwaki Model 2366 KM Shaker was used to equilibrate the aqueous
and organic phases. The pH of the aqueous phase was measured using a TOADKK Model IM-55G pH-meter fitted with a Model GST-5721C glass
electrode (TOA-DKK Electronics Co Ltd., Tokyo, Japan). A JASCO FT-IR
Model 620 (4000 cm1400 cm1) was used for recording the infrared spectra
of extractants investigated and the copper (II) complexes extracted into

Solvent Extraction of Cu(II)

275

diluents. A Hitachi UV Model 4000 (200 nm2000 nm) was used for recording the ultraviolet-visible spectra of the organic phases in the presence and
absence of extracted metals.

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Procedure
An equal volume of aqueous and organic phases was placed in a 50-mL
separatory funnel, and the two phases were then shaken for 1 hour and 30 min
until equilibrium was reached. The initial concentration of copper (II) was
5  103 M, and the ionic strength of the aqueous phase was kept at 0.1 with
(Na, H)ClO4. After the two phases were separated completely, the pH value
was measured. The total concentration of copper (II) in the aqueous phase
was determined by titration with 5  103 M EDTA using PAN as an
indicator.
The samples for FT-IR spectroscopy were prepared by extraction:[10] An
equal volume of the aqueous phase containing 0.350.60 M Cu(ClO4)2
solution was equilibrated with an organic phase containing 1.0 M DMNPA
or DEHPA, under which conditions there was no free extractant in the organic
phases. The pH values of the aqueous phase were adjusted to above 4.04.5 by
adding appropriate amounts of 10.0 M NaOH followed by extraction. It was
assured beforehand that the Cu(II) extraction was quantitative over the pH
regions. The organic phase was subjected to FT-IR spectroscopic
measurements.
The UV-Vis spectrophotometer was also used to obtain the absorption
spectra for extracted species in each diluent. The equal volume of the aqueous
phase containing 0.0300.060 M Cu(ClO4)2 solution with the organic phase
containing 0.1 M dialkylphosphoric acid as extractant was equilibrated, and
the acidity of the aqueous phase was adjusted to above pH 4.14.4 with
10.0 M NaOH after extraction. The organic phase after extraction was allowed
to stand for at least 1 hour, and then was subjected to UV-Vis spectral
measurements.

RESULTS AND DISCUSSION

General Treatment of Extraction Equilibrium
Figure 1 shows the extraction curves of copper (II) with DEHPA and
DMNPA into different diluents. The metal extraction curves with DMNPA
shifted to lower pH regions compared to those with DEHPA for all diluents
used. This means that DMNPA was superior to DEHPA with respect to
extractability of copper (II). As expected from a lower pKa value, DMNPA

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276

Tao and Nagaosa

Figure 1. Effect of pH on the extraction of copper (II) into different diluents. The
total DEHPA and DMNPA concentration in organic diluents were CDMNPA 0.70 M
and CDEHPA 0.73 M; the total concentration of copper (II) was CCu 5  103 M.

was a stronger complexant than DEHPA. The order of decreasing extractability for organic diluent was n-dodecane > 1-octanol > toluene.
It is well known that alkylphosphoric acids exist primarily as the dimer in
non-polar diluents such as alkane, benzene, and as the monomer in polar
diluents such as ketone, alcohol and ester. If a j-merized copper (II) species
CujA2j(HA)a is extracted into the organic phase of non-polar diluents, the
extraction equilibrium can be written as follows:
Kexja
2j a
HA2;o Cuj A2j HAa;o 2jH
2
Cuj A2j HAa;o H 2j
Kexja
Cu2  j HA2;o 2ja=2

jCu2

with
1

where (HA)2,o denotes the dimeric extractant in non-polar diluents such as

n-dodecane and toluene. The subscript o refers to the organic phase. If an

Solvent Extraction of Cu(II)

277

i-merized copper (II) species CuiA2i(HA)a is extracted into 1-octanol as a polar

diluent, the extraction equilibrium can be expressed as:
Kexia0

iCu2 2i a0 HAo Cui A2i HAa0 ;o 2iH

with

2i

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Kexia0

Cui A2i HAa0 ;o H 

Cu2 i HAo 2ia0

where (HA)o denotes the monomeric extractant in 1-octanol. Equations (1) and
(2) are then transformed into the following Eqs. (3) and (4), respectively. With
respect to the concentration of copper (II) in the organic phase,
CCu;o

XX
j

CCu;o

XX
i

jKexja Cu2  j HA2;o 2ja=2 H 2j

0

jKexi;a0 Cu2  i HAo 2ia H 2i

a0

Analysis of the Extraction Equilibrium

in n-Dodecane and Toluene
Assuming that MjA2j(HA)a is the only copper (II) species extracted into
n-dodecane or toluene, the following expression can be obtained from Eq. (3):
log CCu;o jlogCu2   2 logH 
log Kex j;a

2j a
logHA2;o log j
2
5

Obviously, the polymerization degree of the extracted species, ( j), can be

determined from the slope of the plots of log CCu,o against (log[Cu2] 
2 log[H]) at a constant [HA]2,o. The concentration of copper (II) in the
aqueous phase (CCu,w) can be written as [Cu2] CCu,w=aCu (aCu: the reaction
coefficient of copper (II) with DMNPA anion in aqueous phase). It is generally
accepted that aCu is unity (e.g., [Cu2] CCu,w) when the metal ion was
extracted with ligands having bulky substituents from more acidic media.[11,12]
Under the present experimental conditions, the side complexation of copper
(II) was not appreciable in the aqueous phase. The total concentration of
copper (II) in the aqueous phase, CCu,o may be regarded as [Cu2],

278

Tao and Nagaosa

i.e., aCu 1. With the total acid concentration (CHA), the values of [(HA)2]o
can be calculated from the following equation:

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2KD;HA



Ka
K2;HA HA KD;HA 1 HA  CHA 0
H 
2

where KD,HA ( [HA]o=[HA]), K2,HA ( [(HA)2]o=[HA]o2) and Ka

( ([H][A])=[HA]) denote the constant for partition of the monomer
extractant between the organic and aqueous phase, the dimerization constant
in the organic phase, and the dissociation constant for the dialkylphosphoric
acid, respectively. Table 1 shows the equilibrium constants of DEHPA and
DMNPA from the literatures.[1315]
Figures 2 and 3 show the results obtained with various concentrations of
DEHPA and DMNPA in n-dodecane and toluene, respectively. All slopes of
the straight lines obtained can be approximated by unity, which means that
both metal complexes are extracted only as monomers in the organic phases.
In the region where the monomer prevails, Eq. (3) is simplified to:
log CCu;o log CCu;w  2 logH  log

Kex1a HA2 o 2a=2

According to Eq. (7), the number of alkylphosphoric acid molecules involved

in the monomeric species can be determined from the slope of the plots of
(log CCu,o  log CCu,w 2 log[H]) against log[(HA)2]o. The values of
[(HA)2]o were calculated by using Eq. (6), assuming [(HA)2]o 0.5(CHA 
[HA]o  [HA]  [A])  0.5CHA for much higher concentrations of DMNPA.
Figure 4 shows the results for the copper (II) extraction with DEHPA in

Table 1.
Acid
DEHPA

Some equilibrium constants of DEHPA and DMNPA.[1315]

pKa
(water)

Diluent

2.75

n-Dodecane
Toluene
1-Octanol

DMNPA

2.71

n-Dodecane
Toluene
1-Octanol

Aqueous
phase

log KD,HA

log K2,HA

Water
0.1 M NaClO4
Water
0.1 M NaClO4
Water

2.33
1.94
3.01
4.79
4.40

4.33
4.43
4.36
5.10

Water
Water
Water

3.24
4.70
4.27

4.70
3.24

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Solvent Extraction of Cu(II)

279

Figure 2. Determination of the polymerization degree of the copper (II) species

extracted with DEHPA and DMNPA in n-dodecane. The total DEHPA and DMNPA
concentration were: CDEHPA: s, 0.30 M; n, 0.37 M; u, 0.44 M; ,, 0.58 M; e, 0.73 M;
q, 0.88 M; , 1.02 M. CDMNPA: , 0.23 M; m, 0.30 M; j, 0.35 M; ., 0.47 M; r, 0.58 M;
w, 0.70 M; , 0.82 M.

n-dodecane and toluene. Straight lines with a slope of ca. 2.0 were obtained for
n-dodecane and toluene. This suggests that the extracted species in the organic
phase should be CuA2  2HA for the two extraction systems. This agreed with
the published results for the extraction of copper (II) with DEHPA into ndodecane and toluene from nitrate medium.[1517] The extraction equilibrium
constants were determined to be log Kex(1,2) 2.70
0.01 for n-dedecane
and log Kex(1,2) 3.82
0.02 for toluene, respectively.
Figure 5 shows the results for the copper (II) extraction with DMNPA in
n-dodecane and toluene. Similarly for DEHPA, [(HA)2]o  0.5CHA was
acceptable for the DMNPA extraction. The slopes of the plots of
(log CCu,o  log CCu,w 2 log[H]) against log[(HA)2]o were 1.96
0.01
and 2.48
0.01 for n-dodecane and toluene, respectively. This implies
that the extracted species should be CuA2  2HA and CuA2  3HA, and the
extraction equilibrium constants were log Kex(1,2) 2.04
0.02 and
log Kex(1,3) 2.74
0.02, respectively.

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280

Tao and Nagaosa

Figure 3. Determination of the polymerization degree of the copper (II) species

extracted with DEHPA and DMNPA in toluene. The total DEHPA and DMNPA
concentration were: CDEHPA: s, 0.30 M; n, 0.37 M; u, 0.44 M; ,, 0.58 M; e, 0.73 M;
q, 0.88 M; , 1.02 M. CDMNPA: , 0.23 M; m, 0.30 M; j, 0.35 M; ., 0.47 M; r, 0.58 M;
w, 0.70 M; , 0.82 M.

Analysis of the Extraction Equilibrium in 1-Octanol

Assuming that MiA2i(HA)a0 is the only copper (II) species extracted into
1-octanol, the following expression can be obtained from Eq. (4):
log CCu;o ilog CCu;w  2 logH 
2i a0 logHAo log i log Kexi;a0

The degree of polymerization for the extracted species, (i), can be obtained
from the slope of log CCu,o against (log CCu,w  2 log[H]) at a constant
[HA]o. The values of [HA]o were calculated by assuming [HA]o
(CHA  [HA]  [A])  CHA in the present extraction system. It can be seen
from Fig. 6 that the straight lines with a slope of unity were obtained for both

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Solvent Extraction of Cu(II)

281

Figure 4. Determination of the number of DEHPA molecule involved in the

monomeric copper (II) complexes in n-dodecane and toluene.

Figure 5. Determination of the number of DMNPA molecule involved in the

monomeric complexes in n-dodecane and toluene.

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282

Tao and Nagaosa

Figure 6. Determination of the polymerization degree of the copper (II) extracted

species with DEHPA and DMNPA in 1-octanol. The total DEHPA and DMNPA
concentration were: CDEHPA: s, 0.15 M; n, 0.22 M; u, 0.30 M; ,, 0.44 M; e, 0.58 M;
q, 0.73 M; , 0.88 M. CDMNPA: , 0.12 M; m, 0.18 M; j, 0.23 M; ., 0.35 M; r, 0.47 M;
w, 0.58 M; , 0.70 M.

DEHPA and DMNPA, indicating that only monomers were extracted for both
alkylphosphoric acids. The Eq. (8), therefore, can be written as:
log CCu;o log CCu;w  2 logH  log

Kexi;a0 HAo 2a

a0

The number of alkylphosphoric acid molecules involved in the monomeric

copper (II) complexes can be determined from the slope of the plots of
(log CCu,o  log CCu,w 2 log[H]) against log[HA]o. The straight lines with a
slope of ca. 2.0, as shown in Fig. 7, indicate that the extracted species can be
expressed as CuA2 for the two dialkylphosphoric acids. The extraction
equilibrium constants were determined to be log Kex(1,0) 3.78
0.02 for
DEHPA and log Kex(1,0) 3.41
0.03 for DMNPA.

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Solvent Extraction of Cu(II)

283

Figure 7. Determination of the number of DEHPA and DMNPA molecules involved

in monomeric complexes in 1-octanol.

The stoichiometry of the extracted copper (II) species with DEHPA and
DMNPA in different diluents and their extraction constants are summarized in
Table 2.
Results of FT-IR and UV-Vis Spectroscopy
The organic phase containing extracted complexes and the phosphoric
acids was examined by using FT-IR and UV-Vis spectroscopy. The characteristic frequency (nPO) of the P
O bond in the infrared spectra of organophosphorus compounds reflects the charge density of the phosphoryl oxygen
atom, and can be regarded as a measure of its coordinative activity.[10,18,19]
Table 3 lists the values of nPO for the extractants studied, together with the
shift (DnPO) after their complexation with copper (II). From Table 3 it is
apparent that a shift in nPO occurs for each of the extractants upon
complexation with copper (II) in different diluents, indicating that the metal

284

Tao and Nagaosa

Table 2. Stoichiometries and stability constants of alkylphosphoric acids in different

diluents.
Extractant

Diluents

Extraction equilibrium

log Kex1a

Kex1;2

DEHPA

n-Dodecane

Cu2 2HA2;o CuA2  2HA 2H

2.70
0.01

Kex1;2

Toluene
1-Octanol

Cu2 2HA2;o CuA2  2HA 2H

2

Cu

Kex1;0

2HAo CuA2 2H

3.82
0.02
3.78
0.02

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Kex1;2

DMNPA

n-Dodecane

Cu2 2HA2;o CuA2  2HA 2H

2.04
0.02

Kex1;3

Toluene

Cu2 5=2HA2;o CuA2  3HA 2H 2.74
0.02

Kex1;0

1-Octanol

Cu2 2HAo CuA2 2H

3.41
0.03

complexes are formed by coordination bonds between the phosphoryl oxygen

atom and Cu(II), besides the ionic bonding between the hydroxyl oxygen and
Cu(II).
Figures 8 and 9 show FT-IR spectra of the extracted copper (II)
complexes with DMNPA(a) and DEHPA(b) in n-dodecane and toluene. No
obvious difference was found between the metal complexes with DMNPA
and DEHPA at the two diluents. Figure 10 shows FT-IR spectra of the metal
complexes with DMNPA(a) and DEHPA(b) in 1-octanol. For the 1-octanol
extraction system, interestingly, the absorption band at 30003500 cm1
became broader, and new peaks appeared at ca. 1645 cm1. The two
absorption peaks remained unchanged even when the 1-octanol phase after
extraction was again shaken with 3 M HClO4. This may be because the water
molecule was coextracted into the organic phase through hydrogen bonding
with 1-octanol.[19]

Table 3. nPO for extractants and its shift, DnPO, after

complexation (cm1).
Diluent

nPO

DnPOCu

DEHPA

n-Dodecane
Toluene
1-Octanol

1230
1229
1232

17
16
44

DMNPA

n-Dodecane
Toluene
1-Octanol

1231
1230
1233

21
17
43

Extractant

285

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Solvent Extraction of Cu(II)

Figure 8. FT-IR spectra of extractants and their extracted complexes in n-dodecane.

(a) DMNPA (1.0 M)=n-dodecane=Cu(ClO4)2 (0.35 M, pH 4.4); (b) DEHPA
(1.0 M)=n-dodecane=Cu(ClO4)2 (0.35 M, pH 4.4).

Tao and Nagaosa

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286

Figure 9. FT-IR spectra of extractants and their extracted complexes in toluene.

(a) DMNPA (1.0 M)=toluene=Cu(ClO4)2 (0.30 M, pH 4.3); (b) DEHPA
(1.0 M)=toluene=Cu(ClO4)2 (0.35 M, pH 4.3).

287

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Solvent Extraction of Cu(II)

Figure 10. FT-IR spectra of extractants, the extracted complexes, and the extractants
after back extraction in 1-octanol. (a) DMNPA (1.0 M)=1-octanol=Cu(ClO4)2 (0.60 M,
pH 4.1); (b) DEHPA (1.0 M)=1-octanol=Cu(ClO4)2 (0.60 M, pH 4.1).

288

Tao and Nagaosa

Table 4. Maximum wavelengths of extracted copper (II)
complexes in different diluents.

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Wavelength (nm)
Extractant

n-Dodecane

Toluene

1-Octanol

DEHPA
DMNPA

866
860

860
849

830
836

No absorption peak was found in the visible region for the solutions of
each extractant in different diluents, but an absorption peak in the ultraviolet
region was observed for DEHPA and DMNPA due to n ! p* electron
transition in P
O group of the dialkylphosphoric acid molecules. The Vis
spectra of each complex show a broad peak at ca. 800 nm in the region from
400 to 1200 nm. Table 4 lists the maximum absorption wavelengths of the
metal complexes in different diluents.
It has been reported that the coordination geometry of copper (II) complex
with DEHPA takes a square-planar bonding mode in non-polar diluents.[1820]
Here the bonding modes of the extracted metal species with DMNPA and
DEHPA in the non-polar and polar diluents are suggested, as shown in Fig. 11.
The m and n values are binding ratios of copper (II) relative to alkylphosphorus compound (ligand) in the diluents, and correspond to (2 a)=2 and
(2 a0), respectively.

CONCLUSION
By using the method of slope analysis, the extracted copper (II) species
with DMNPA were found to be CuA2  2HA in n-dodecane, CuA2  3HA in

Figure 11. Proposed binding modes of the extracted species in different diluents. The
values of m and n are binding ratios of the alkylphosphorus compounds relative to
copper (II). m (2 a)=2; n 2 a0.

Solvent Extraction of Cu(II)

289

toluene, and CuA2 in 1-octanol. DMNPA was proved to be superior to DEHPA

with respect to the metal extractability. The stoichiometry of the extracted
species varied with diluents used. The UV-Vis and FT-IR spectroscopy for
both extractants and their copper (II) complexes indicated that the binding
mode of the extracted metal species depended on the property of diluents.

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Received August 13, 2002