Volume 10, Issue 4, April – 2025 International Journal of Innovative Science and Research Technology

ISSN No:-2456-2165 https://doi.org/10.38124/ijisrt/25apr1425

Extraction of Cu(II) Ions Using Chloroform

Solution of 4,4 ́-(1E,1E ́)-1,1 ́-(Ethane-1,2-
Diylbis(Azan-1-YL- 1ylidene))BIS(5-Methyl-2-
Phenyl-2,3-Dihydro-1H-Pyrazol-3-OL) (H2BuEtP)
Under the Influence of Acids, Anions and
Complexing Agents
Oguarabau Benson1*; Jackson Godwin2;
Shalom Udochukwu Okanezi3; Juliana Consul4
1, 2, 3
Department of Chemical Sciences, Niger Delta University, Wilberforce Island, Bayelsa State, Nigeria
4
Department of Mathematics, Niger Delta University, Wilberforce Island, Bayelsa State, Nigeria
*Corresponding Author Oguarabau Benson1

Publication Date: 2025/04/30

Abstract: The influence of selected acids, anions, and complexing agents on the removal of Cu(II) ions from aqueous solutions
was studied using chloroform solutions of H₂BuEtP both alone and in combination with HBuP. Chloroform solutions of the
single Schiff base alone or in the presence of the synergist were added to the Cu (II) solutions containing known concentrations
of the studied acids, anions, or complexing agents buffered at pH 6.0 and pH 8.75 and allowed to separate after an
equilibration time of one hour. The absorbances of the aqueous raffinates were measured using AAS at 324.8 nm and
compared with a standard Cu(II) absorbance to determine the percentage extraction (%E), distribution ratios (D), and the
number of extraction batches (n), required for 99.9% Cu(II) removal. For the single ligand system for instance at pH 6.0,
0.005 mol/L H2SO4 among the acids exhibited the highest releasing effect, with a distribution ratio of 35.59 and an extraction
efficiency of 97.28%, requiring two batches only to attain 99.9% Cu(II) extraction. Those exhibiting the highest releasing at
the same pH, are 0.01 mol/L Cl- among the anions (D = 83.74, %E = 98.82%) and 0.05 mol/L SCN⁻ among the complexing
agents (D = 88.44, %E = 98.88%) also requiring only two batches for 99.9% Cu(II) ions extraction. The binary ligand system
(H2BuEtP/HBuP) showed slightly improved extraction efficiency compared to H2BuEtP alone, in all studied systems requiring
≤ 2 batches only for 99.9% Cu(II) recovery, except for 0.1 mol/L tartrate at pH 8.75, 0.01 mol/L Cl⁻ at pH 6.0, 0.05 mol/L
HNO₃, and 0.001 mol/L CH₃COOH at pH 8.75, which required three batches. Statistical analysis of their distribution ratios
showed significant differences (P ≤ 0.05) between single H₂BuEtP and the mixed ligand systems in most cases, except for
CH₃COOH at pH 6.0 (P > 0.05). When compared to previous studies on Pb(II), U(VI), Fe(II), Ni(II), Cd(II) and Zn(II), the
results indicated strong extraction potential for both single and multi-metal systems, with selective releasing effects supporting
potential multi-metal separations. These findings highlight the efficiency of H 2BuEtP and the synergistic effect of HBuP in
Cu(II) extraction and provide insights for optimizing metal recovery from aqueous solutions.

Keywords: Acids, Anions, Complexing, Extraction Efficiency and Copper.

How to Cite: Oguarabau Benson; Jackson Godwin; Shalom Udochukwu Okanezi; Juliana Consul (2025) Extraction of Cu(II) Ions
Using Chloroform Solution of 4,4 -́ (1E,1E ́)-1,1 ́-(Ethane-1,2-Diylbis(Azan-1-YL- 1ylidene))BIS(5-Methyl-2-Phenyl-2,3-Dihydro-
1H-Pyrazol-3-OL) (H2BuEtP) Under the Influence of Acids, Anions and Complexing Agents. International Journal of Innovative
Science and Research Technology, 10(4), 2279-2288. https://doi.org/10.38124/ijisrt/25apr1425

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Volume 10, Issue 4, April – 2025 International Journal of Innovative Science and Research Technology
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I. INTRODUCTION Uzoukwu, 2012). For Ni(II) extraction, all acids showed

masking effect in all acids for the mixed ligand system
Environmental contamination by heavy metals arises (H2BuEtP/HBuP) with <10% efficiency. Most anions gave
from both natural routes and human activities (Herawati et al., enhanced extraction, but sulphate, nitrate, and iodide caused
2000). As our reliance on metals like copper increases, the reductions (<70%, <90%, and <100%, respectively). Fluoride
issue becomes even more pressing. A major contributor to this exhibited a high releasing effect (~90%) (Godwin et al.,
problem is industrial discharge, where metal-laden effluents 2012). For Fe(II) extraction, all acids caused a strong masking
are often released into freshwater systems without adequate effect (<10% efficiency), though a slight increase occurred
treatment, further exacerbating pollution (Salomons et al., between 0.01M and 0.1M, except for H3PO4. PO4²⁻ and
1995). The extraction of metals using solvent-solvent CH3COO⁻ increased extraction (>80% and >100%), while
techniques has attracted considerable attention in the field of halogen anions, except Br⁻ (<70% to <100%), showed strong
heavy metal remediation (Černá, 1995; Lee et al., 2005; Li et masking effects. Only tartrate did not show masking effect
al., 2017). Many studies have focused on evaluating the (Godwin et al., 2014). For Cd(II) extraction, upon addition of
impact of common anions, acids, and supporting complexing the synergist (HBuP) high releasing effects (>50% efficiency)
agents on their roles in either facilitating the release or occurred for all acids, anions and complexing agents. Minor
masking metal ions during extractions involving ligands, decreases occurred between 0.1M and 0.5M, except for
chelates, and Schiff bases (Nwadire et al., 2020; Qasem et al., H3PO4. CH3COO⁻ and SO4²⁻ that remained stable, while other
2021). It has been established that the nature and strength of anions showed unstable, high-releasing effects (>50%).
interactions between anions and metal ions at varying Halogen anions stayed > 60%, with Br⁻ being most unstable.
concentrations play a critical role in determining whether they Complexing agents had high-releasing effects (>50%),
act as releasing or masking agents (Al Zoubi et al., 2016; fluctuating between 0.005M and 0.05M (Godwin et al., 2019).
Narbutt, 2020). Additionally, alterations in the dielectric Out of necessity, this study aimed to evaluate the role of
constant and polarizability of solvents due to changes in acid selected anions, acids, and supplementary complexing agents
and anion concentrations have also been linked to their in the removal of copper(II) ions from buffered aqueous
influence on the distribution of metals between the organic solutions at pH 6.0 or 8.75 using chloroform solutions of the
and aqueous phases (Al Zoubi et al., 2016; Singh et al., 2014). Schiff base 4,4´-(1E,1E´)-1,1´-(ethane-1,2-diylbis(azan-1-yl-
These interactions can be exploited in multi-metal extraction 1ylidene)bis(5-methyl-2-phenyl-2,3-dihydro-1H-pyrazol-3-ol)
processes, where a particular acid or anion at a specific (H2BuEtP) only and in combination with a different Schiff
concentration may serve as a releasing agent for multiple base, 1-(3-hydroxy-5-methyl-2-phenyl-2,3-dihydro-1H-
metals (Smolinski et al., 2017). Moreover, acids and anions pyrazol-4-yl) butan-1-one (HBuP) as a synergist. This was to
can be utilized for the selective separation of metal ions. If an be achieved by investigating their releasing effects at different
acid or anion demonstrates a masking effect on one metal concentrations, calculating the theoretical number of batches
while significantly enhancing the extraction of another within required at these concentrations to achieve 99.9% extraction of
the same aqueous solution—resulting in a separation factor Cu(II) ions. and statistically comparing the results for the two
(Βxy) of at least 10⁴—then this condition could be leveraged to organic phases.
effectively separate the metal ions (Rodrigues et al., 2022;
Godwin et al., 2022). Furthermore, acids and anions have been II. EXPERIMENTAL
examined for their role in metal preconcentration and recovery
from organic solutions. At certain concentrations, they form All chemicals used for this study were of analytical grade
strong and stable bonds with metals, enabling their removal and supplied by Sigma Aldrich and used as obtained without
from the organic phase following extraction (Kara & Alkan, further purification. The compounds 4,4´-(1E,1E´)-1,1´-
2002; Ye et al., 2019). (ethane-1,2-diylbis(azan-1-yl1ylidene))bis(5-methyl-2-phenyl-
2,3-dihydro-1H-pyrazol-3-ol) (H2BuEtP) and 1-(3-hydroxy-5-
Since their synthesis by Uzoukwu et al. (1998), the methyl-2-phenyl-2,3-dihydro-1H-pyrazol-4-yl)butan-1-one
mixed Schiff base N,N-ethylenebis(4-butanoyl-2,4-dihydro-5- (HBuP) were made and characterized using procedures clearly
methyl-2-phenyl-3H-pyrazol-3-onimine) (H2BuEtP) and 1-(3- stated in literature [Uzoukwu et at., 1998]. 100 mL of a 2000
hydroxy-5-methyl-2-phenyl-2,3-dihydro-1H-pyrazol-4- mgL-1 stock solution of copper (II) sulphate pentahydrate was
yl)butan-1-one (HBuP) have been studied for extracting prepared by dissolving an appropriate amount of copper (II)
Cd(II), Fe(II), Pb(II), and Ni(II) from aqueous to organic sulphate pentahydrate salt in distilled water, followed by the
phases (Godwin & Uzoukwu, 2012a; Godwin et al., 2012, addition of 0.2 mL HNO3 to inhibit hydrolysis of copper. The
2014, 2019). For Pb(II) extraction, all acids showed a masking working concentration of 200 mg/L Cu(II) ions was obtained
effect except H2SO4 (>80% efficiency), though extraction by diluting the stock solution.
fluctuated between 0.1M and 1M. Anions reduced efficiency
from >90% to <20% with increasing concentration, except
acetate and nitrate (>90% stable). Complexing agents
decreased extraction from 0.05M to 0.5M (Godwin &

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Volume 10, Issue 4, April – 2025 International Journal of Innovative Science and Research Technology
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The amounts of mineral acids, anions and complexing between them (Sprinthall, 2011). Equation 3 was used to
agents were in the range 0.001 mol/L – 0.1 mol/L obtained estimate the number of batches needed theoretically to achieve
from dilutions of their respective stock solutions of the 99.9% extraction of Cu(II) ions where n is the number of
selected acids and sodium/ammonium salts of these anions batches needed, Caq is the concentration of metal ions
and complexing agents and buffered at 6.0 for one set and originally present in the aqueous phase and C is the
buffered at 8.75 for the other set. To each of 2 sets of 170 concentration of metal ions remaining in the aqueous phase
clearly-labelled 5 mL extraction bottles containing 0.2 mL of after extractions.
the 200 mg/L Cu(II) solution was added 0.8 mL of the
buffered solutions and 1.0 mL of the mineral acids, anions and 𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒−𝑅𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒
D=
complexing agents in their various concentrations at pH 6.0 or 𝑅𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒
8.75. Afterwards, 2 mL of chloroform solution of 0.05 mol/L ---------1
H2BuEtP was added to each bottle of one set containing the
buffered aqueous solutions and to the other set of one hundred 𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒−𝑅𝑎𝑓𝑓𝑖𝑛𝑎𝑡𝑒 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒
% E = ×
and seventy bottles were added 2 mL of chloroform solution 𝑆𝑡𝑎𝑛𝑑𝑎𝑟𝑑 𝐴𝑏𝑠𝑜𝑟𝑏𝑎𝑛𝑐𝑒
of 0.05 mol/L H2BuEtP and 0.05 mol/L HBuP in 9:1 volume 100
ratio. The three hundred and forty bottles containing the two ---------2
immiscible phases were agitated with a mechanical shaker for
60 minutes. The two phases were allowed to separate out and C/Caq = [1/(D + 1)]n
1 mL of aqueous raffinates were then taken with a
micropipette, made up to the 4 ml with distilled water and
---------3
analysed for copper by difference, using Atomic Absorption
Spectrophotometry (AAS) at wavelength of 324.8 nm
(Porento et al., 2011). Absorbance results were used to
calculate extraction parameters, distribution ratios (D) and
III. RESULTS & DISCUSSION
percentage extraction (%E) using equations 1 and 2.
The extraction parameters due to the considered mineral
The R software package was used to statistically analyze
acids, anions and complexing agents on the extraction of 200
for significant differences between distribution ratios of the
mg/L of Cu(II) ions from their buffered solutions at pH 6.0
two sets of data (single ligand and mixed ligand solutions)
and 8.75 into 0.05 mol/L H2BuEtP alone chloroform solution
using p value 0.05. If the value of the test statistics is > the
and a 9:1 volume ratio choroform solution of 0.05 mol/L
significant level of 0.05, the null hypothesis is accepted
H2BuEtP and 0.05 mol/L HBuP mixture as shown in Tables 1
indicating no significant difference between the groups of
to 6 and Figures 1 to 3 do not indicate any particular trend
interest and the null hypothesis is rejected if the test statistics
with increasing concentrations for both systems.
value is < 0.05, implying there is significant difference

Table 1: Effect of mineral acids on Cu(II) ions extraction using H2BuEtP alone
Distribution Ratio, D Number of extractions, n
Acid
Concentration HCl HNO3 H2SO4 H3PO4 CH3COOH HCl HNO3 H2SO4 H3PO4 CH3COOH
(mol/L)
pH 6.0 pH 6.0
0.001 35.59 31.20 37.33 26.75 18.87 2 2 2 2 2
0.005 33.25 26.28 35.59 27.75 21.36 2 2 2 2 2
0.01 34.77 27.24 6.89 18.87 19.37 2 2 3 2 2
0.05 29.96 30.56 9.12 17.29 19.64 2 2 3 2 2
0.1 29.37 23.76 24.96 20.46 19.37 2 2 2 2 2
pH 8.75 pH 8.75
0.001 29.37 31.85 32.54 15.77 19.12 2 2 2 3 2
0.005 30.56 31.20 30.56 16.88 19.86 2 2 2 3 2
0.01 27.24 30.56 32.54 18.63 16.69 2 2 2 2 2
0.05 30.56 29.96 6.70 18.87 18.63 2 2 3 2 2

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0.1 26.28 21.05 17.50 19.37 17.94 2 2 2 2 2

*10 mg/L Cu(II) Standard Absorbance = 0.1610; H2BuEtP system alone

Fig 1: Percent extraction of 200 mg/L of Cu(II) from solutions of mineral acids at pH 6.0 and 8.75 into (A) 0.05 M H 2BuEtP
solution, and (B) 9:1 volume ratio solution of 0.05 M H2BuEtP and 0.05 M HBuP

Table 2: Effect of mineral acids on Cu(II) ions extraction using mixed H2BuEtP/HBuP solution
Distribution Ratio, D Number of extractions, n
Acid
Concentration HCl HNO3 H2SO4 H3PO4 CH3COOH HCl HNO3 H2SO4 H3PO4 CH3COOH
(mol/L) pH 6.0 pH 6.0
0.001 140.62 243.18 359.17 191.09 24.01 1 1 1 1 2
0.005 359.17 359.17 359.17 72.50 359.17 1 1 1 2 1
0.01 334.04 29.784 359.17 227.68 159.07 1 2 1 1 1
0.05 359.17 55.277 143.07 224.10 243.18 1 2 1 1 1
0.1 104.93 359.17 359.17 359.17 23.84 1 1 1 1 2
pH 8.75 pH 8.75
0.001 98.35 359.17 435.57 359.17 359.17 2 1 1 1 3
0.005 359.17 359.17 359.17 235.18 235.18 1 1 1 1 2

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0.01 243.18 653.86 312.19 532.59 532.59 1 1 1 1 1

0.05 14.65 13.582 359.17 256.26 256.26 2 3 1 1 1
0.1 359.17 359.17 359.17 359.17 359.17 1 1 1 1 1

*10 mg/L Cu(II) Standard Absorbance = 1.4407; H2BuEtP/HBuP mixed system

Figure 2: Percent extraction of 200 mg/L of Cu(II) from solutions of anions at pH 6.0 and 8.75 into (A) 0.05 M H2BuEtP
solution, and (B) 9:1 volume ratio solution of 0.05 M H2BuEtP and 0.05 M HBuP

Table 3: Effect of anions on Cu(II) ions extraction using H2BuEtP alone

Distribution Ratio, D Number of extractions, n
Anion
Cl- I- NO3- SO42- PO43- CH3COO- Cl- I- NO3- SO42- PO43- CH3COO-
Concentration
pH 6.0 pH 6.0
(mol/L)
0.001 83.74 19.12 13.12 13.63 13.63 54.51 2 2 3 3 3 2
0.005 75.67 17.29 12.87 14.04 14.04 60.92 2 2 3 3 3 2
0.01 83.74 19.64 13.24 13.24 13.24 50.93 2 2 3 3 3 2
0.05 66.08 17.29 12.87 14.18 14.18 69.00 2 2 3 3 3 2
0.1 63.40 18.16 12.52 13.90 13.90 58.63 2 2 3 3 3 2
pH 8.75 pH 8.75
0.001 66.08 18.63 12.41 14.04 14.63 63.40 2 2 3 3 3 2
0.005 63.40 17.72 12.64 13.37 13.90 60.92 2 2 3 3 3 2
0.01 60.92 17.94 12.87 12.76 14.48 63.40 2 2 3 3 3 2

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0.05 66.08 17.94 12.64 13.12 14.18 56.50 2 2 3 3 3 2

0.1 69.00 18.16 12.08 13.24 13.37 75.66 2 2 3 3 3 2

*10 mg/L Cu(II) Standard Absorbance = 0.1610; H2BuEtP system alone

Fig 3: Percent extraction of 200 mg/L of Cu(II) from solutions of auxiliary complexing agents at pH 6.0 and 8.75 into (A) 0.05
M H2BuEtP solution, and (B) 9:1 volume ratio solution of 0.05 M H2BuEtP and 0.05 M HBuP

Table 4: Effect of anions on Cu(II) ions extraction using mixed H2BuEtP/HBuP solution
Distribution Ratio, D Number of extractions, n
Anion Cl- I- NO3- SO42- PO43- CH3COO- Cl- I- NO3- SO42- PO43- CH3COO-
Concentration
pH 6.0 pH 6.0
(mol/L)
0.001 359.17 495.79 359.17 140.24 140.24 281.49 1 1 1 1 2 1
0.005 359.17 359.17 359.17 599.29 599.29 112.44 1 1 1 1 2 1
0.01 6.64 359.17 359.17 83.74 83.74 227.68 3 1 1 2 2 1
0.05 359.17 359.17 359.17 14.76 14.76 157.31 1 1 1 2 2 1
0.1 359.17 359.17 359.17 359.17 359.17 239.11 1 1 1 1 2 1
pH 8.75 pH 8.75
0.001 359.17 359.17 359.17 89.04 359.17 176.86 1 1 1 2 1 1
0.005 513.53 359.17 359.17 60.56 359.17 157.31 1 1 1 2 1 1
0.01 422.73 359.17 359.17 168.49 359.17 155.59 1 1 1 1 1 1
0.05 350.39 359.17 359.17 359.17 359.17 199.09 1 1 1 1 1 1
0.1 359.17 399.19 359.17 359.17 359.17 359.17 1 1 1 1 1 1

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*10 mg/L Cu(II) Standard Absorbance = 1.4407; H2BuEtP/HBuP mixed system

Table 5: Effect of complexing agents on Cu(II) ions extraction using H2BuEtP alone
Distribution Ratio, D Number of extractions, n
Anion F¯ Br¯ C2O4²¯ C4H4O6²¯ EDTA⁴¯ SCN- F¯ Br¯ C2O4²¯ C4H4O6²¯ EDTA⁴¯ SCN-
Concentration pH 6.0 pH 6.0
(mol/L)
0.001 54.52 46.35 17.29 12.08 11.48 11.38 2 2 2 3 3 3
0.005 46.35 46.50 19.12 11.77 11.38 66.08 2 2 2 3 3 2
0.01 50.94 42.51 19.38 12.76 11.57 58.63 2 2 2 3 3 2
0.05 49.31 56.50 19.12 11.98 11.38 88.44 2 2 2 3 3 2
0.1 47.79 49.31 17.72 11.88 11.57 83.73 2 2 2 3 3 2
pH 8.75 pH 8.75
0.001 43.72 46.35 17.09 11.67 11.77 66.08 2 2 2 3 3 2
0.005 50.94 47.79 17.09 11.98 11.67 54.51 2 2 2 3 3 2
0.01 42.51 45.00 13.90 12.08 11.10 56.50 2 2 3 3 3 2
0.05 47.79 49.31 13.37 11.48 11.48 56.50 2 2 3 3 3 2
0.1 47.79 45.00 11.77 11.01 11.01 54.51 2 2 3 3 3 2
*10 mg/L Cu(II) Standard Absorbance = 0.1610; H2BuEtP system alone

Table 6: Effect of complexing agents on Cu(II) ions extraction using mixed H2BuEtP/HBuP solution
Distribution Ratio, D Number of extractions, n
Anion F¯ Br¯ C2O4²¯ C4H4O6²¯ EDTA⁴¯ SCN- F¯ Br¯ C2O4²¯ C4H4O6²¯ EDTA⁴¯ SCN-
Concentration pH 6.0 pH 6.0
(mol/L)
0.001 359.17 495.79 359.17 48.67 359.17 359.17 1 1 1 2 1 1
0.005 176.86 359.17 359.17 48.67 479.23 48.67 1 1 1 2 1 2
0.01 305.53 359.17 359.17 54.41 359.18 82.27 1 1 1 2 1 2
0.05 463.74 359.17 359.17 359.17 281.49 220.64 1 1 1 1 1 1
0.1 239.11 359.17 359.17 359.17 553.12 359.17 1 1 1 1 1 1
pH 8.75 pH 8.75
0.001 170.51 359.17 359.17 359.18 91.35 74.82 1 1 1 1 2 2
0.005 181.36 359.17 359.17 359.17 281.49 305.53 1 1 1 1 1 1
0.01 176.86 359.17 359.17 359.17 359.17 172.57 1 1 1 1 1 1
0.05 146.01 359.17 359.17 359.17 359.17 359.17 1 1 1 1 1 1
0.1 75.22 719.35 359.17 9.21 719.35 359.17 2 1 1 3 1 1
*10 mg/L Cu(II) Standard Absorbance = = 1.4407; H2BuEtP/HBuP mixed system

For the acids, % extraction for Cu(II) ions exceeding 8.75, which required three batches with H2BuEtP alone. At pH
90% (Figure 1A) was observed for all concentrations at both 6.0, 0.005 mol/L mol/L H2SO4 exhibited the highest releasing
pH levels when using H2BuEtP alone and in combination with effect, with a distribution ratio of 35.59 and an extraction
HBuP. However, H2SO4 exhibited a slight decline at 0.05 efficiency of 97.28%, also requiring two batches only to attain
mol/L concentration for both pH values and HNO3 at 0.01 99.9% Cu(II) extraction. These results differ from previous
mol/L at only pH 6.0 while maintaining good extraction studies on Pb(II) (Godwin & Uzoukwu, 2012a), U(VI)
efficiency (> 80%). This confirms that all mineral acids (Godwin et al., 2013), and Ni(II) (Godwin et al., 2012) using
demonstrated strong releasing effects (>80%) at both pH H2BuEtP, where masking occurred at all tested concentrations,
levels. The calculated n values shown in Table 1 suggest that except for Pb(II) with H2SO4 and U(VI) with H3PO4.
two extraction batches using all mineral acids can theoretically
achieve 99.9% Cu(II) recovery, except for 0.05 mol/L H2SO4
at both pH levels and 0.001 mol/L – 0.005 mol/L H3PO4 at pH

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When mixed with the synergist HBuP (Figure 1B, Table extractions as opposed to the study by Nwadire (2017) with
2), extraction significantly improved for all concentrations, lower Cl⁻ extraction (> 40%) for Ni(II) using H2PrEtP.
exceeding 99% at both pH levels. However, at pH 8.75, a
slight decline was observed between 0.01 mol/L and 0.05 All concentrations (0.001 mol/L to 0.1 mol/L) of the
mol/L HCl and HNO3, likely due to the formation of a less complexing agents had high percent (> 90%) extraction at
hydrophobic Cu(II) complex favouring the aqueous phase over both pH levels for H2BuEtP alone as shown in Figure 3A, with
the organic phase. The calculated n values indicate that all the values at pH 8.75 much lower at those at pH 6.0,
extractions required ≤ 2 batches for 99.9% Cu(II) recovery, especially for oxalate, tartrate and EDTA ions at lower
except for 0.05 mol/L HNO3 and 0.001 mol/L CH3COOH at concentrations. Remarkably, SCN⁻ caused a slight increase in
pH 8.75, which required three batches upon synergist addition. extraction between 0.001 mol/L and 0.005 mol/L at pH 6.0.
Notably, mineral acids at pH (8.75) exhibited high releasing The calculated n values (Table 5) show that only two
effects, achieving 99.8% extraction efficiency (Figure 1B) extraction batches using all complexing agents can
with H2SO4, H3PO4, and HNO3, requiring just one batch for theoretically achieve 99.9% Cu(II) ion recovery, except for
99.9% Cu(II) extraction. Statistical analysis revealed 0.01 mol/L – 0.1 mol/L oxalate at pH 8.75 and all
significant differences (P ≤ 0.05) in the distribution ratios concentrations of tartrate and EDTA at both pH levels, which
between single and mixed-ligand systems at both pH levels, required three batches with H2BuEtP alone. At pH 6.0, 0.05
except for CH3COOH at pH 6.0 (P > 0.05). The results for mol/L SCN⁻ exhibited the highest releasing effect, with a
H2SO4 with H2BuEtP alone align with previous findings for distribution ratio of 88.44 and extraction efficiency of 98.88%,
Fe(II) (Godwin et al., 2014) and Cd(II) (Godwin et al., 2019), also requiring only two batches for 99.9% Cu(II) ions
where extraction efficiency only decreased at higher extraction.
concentrations.
In combination with HBuP as presented in Figure 3B,
All concentrations (0.001 mol/L to 0.1 mol/L) of the six extraction remained high (> 90%) across the 0.001 mol/L –
anions investigated at both pH values, had high percent (> 0.1 mol/L range. A slight % extraction decrease from 99.7% to
90%) extraction for H2BuEtP alone as shown in Figure 2A, 90.2% was observed at 0.05 mol/L – 0.1 mol/L tartrate at pH
with the values for chloride and acetate far exceeding 98% 8.75 which can be attributed to stable Cu(II) complex
extraction. The calculated n values (as shown in Table 3) formation. The calculated n values (Table 6), show that, all
suggest that only two extraction batches are required to extractions required ≤ 2 batches for 99.9% Cu(II) recovery,
recover 99.9% of Cu(II) ions theoretically, using all except for 0.1 mol/L tartrate alone at pH 8.75, which required
concentrations of I-, CH3COO- and Cl- at both pH levels. three batches upon synergist addition. The results confirm that
Conversely, PO43-, SO42- and NO3- at both pH levels required the complexing agents enhanced Cu (II) ions extraction
three batches at all concentrations with H2BuEtP alone. At pH effectively at the studied concentration range and pH values,
6.0, 0.01 mol/L Cl- exhibited the highest releasing effect, with especially in the mixed ligand systems where very large
a distribution ratio of 83.74 and an extraction efficiency of distribution ratios were observed with only one batch of
98.82%, also requiring only two batches to attain 99.9% extraction required to theoretically attain 99.9% extraction of
Cu(II) extraction. the Cu(II) ions in solution. Statistical analysis showed
significant differences in distribution ratios (D) of the
In the presence of HBuP (Figure 2B, Table 4), all anions complexing agents for the H₂BuEtP alone solution and for
showed similar but higher extractions across all when mixed with H₂BuP for all (P ≤ 0.05) at both pH 6.0 and
concentrations. However, a slight decrease from 99.7% to 8.75 except for SCN⁻ (P = 0.053) and tartrate (P = 0.065) at
86.9% at 0.005 mol/L – 0.01 mol/L Cl⁻ at pH 6.0 was pH 6.0. Previous studies on Zn(II), Pb(II), U(VI), Ni(II), Fe(II)
observed possibly due to stable Cu(II) complex formation, and & Cd(II) showed varying masking effects (Godwin &
consequent reduction in hydrophobicity. The calculated n Uzoukwu, 2012a, 2012b; Godwin et al., 2012, 2014, 2019,
values (as shown in Figure 4) indicate that all extractions 2023) unlike this study. This study confirms H₂BuEtP
required ≤ 2 batches for 99.9% Cu(II) recovery, except for provides superior extraction efficiency in the presence of the
0.01 mol/L Cl⁻ at pH 6.0, which required three batches upon studied auxiliary complexing agents unlike the lower
synergist addition. Notably, all anions at higher pH (8.75) extraction values (>50%) reported for Ni(II) using H₂PrEtP
exhibited high releasing effects, achieving ≥ 98% extraction (Nwadire, 2017).
efficiency and requiring just one batch for 99.9% Cu(II)
extraction. Statistical analysis showed significant differences IV. CONCLUSION
(P ≤ 0.05) for all anions except SO₄²⁻ and PO₄³⁻ which showed
no difference (p = 1) at both pH values. Comparisons with All the acids, anions and auxiliary complexing agents
previous studies revealed different masking behaviours for showed potentials in the extraction of Cu(II) from an aqueous
Pb(II), U(VI), Ni(II), Fe(II), Zn(II), and Cd(II) (Godwin & solutions buffered to pH 6.0 or 8.75 using chloroform
Uzoukwu, 2012a, 2012b; Godwin et al., 2012, 2014, 2019). solutions of the Schiff base 4,4´-(1E,1E´)-1,1´-(ethane-1,2-
These findings suggest the anions' potential for multi-metal diylbis(azan-1-yl-1ylidene)bis(5-methyl-2-phenyl-2,3-

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Volume 10, Issue 4, April – 2025 International Journal of Innovative Science and Research Technology
ISSN No:-2456-2165 https://doi.org/10.38124/ijisrt/25apr1425

dihydro-1H-pyrazol-3-ol) (H2BuEtP) both alone and in [5]. Godwin, J., Abasi, C. Y., and Ebelegi, A. N. (2022).
combination with HBuP, as > 98% extraction of Cu(II) was Evaluating the potentials of complexing agents in multi-
achieved in most cases. Statistical analysis confirmed metal extractions using 4,4´-(1e,1e´)-1,1´-(Ethane-1,2-
significant differences (P ≤ 0.05) between the distribution Diylbis(Azan-1-Yl-1ylidene))Bis(5-Methyl-2-Phenyl-
ratios of single and mixed ligand systems across most 2,3-Dihydro-1h-Pyrazol-3-ol) (H2BuEtP). African
conditions, except for CH₃COOH at pH 6.0, which showed no Journal of Pure and Applied Chemistry, 16(1), 8-21.
significant variation. The binary H2BuEtP and HBuP [6]. Godwin, J., Benson, O., & Consul, J. (2023). The Effects
chloroform solution was slightly a better extractant for Cu(II) of Acids and Anions In Zinc(II) Extractions Using the
in most cases, in the presence of all the acids, anions and Schiff Base 4,4´-(1E,1E´)-1,1´-(Ethane-1,2-
complexing agents. This is indicated in the calculated n values Diylbis(Azan-1-yl-1ylidene)Bis(5-Methyl-2-Phenyl-2,3-
showing that all extractions required ≤ 2 batches for 99.9% Dihydro-1H-Pyrazol-3-Ol) (H2BuEtP). Submitted to the
Cu(II) recovery, except for 0.1 mol/L tartrate at pH 8.75, 0.01 Faculty of Sci. Conf., NDU.
mol/L Cl⁻ at pH 6.0, 0.05 mol/L HNO3 and 0.001 mol/L [7]. Godwin, J., Benson, O., & Polokeduo, N. R. (2024).
CH3COOH at pH 8.75, which required three batches at both Distribution of Zinc (II) Between Buffered Aqueous
pH levels. Comparing these results to similar reported studies Phases and Organic Phase of 4,4´-(1E,1E´)-1,1´-(Ethane-
indicated all tested acids, anions, and complexing agents 1,2-Diylbis (Azan-1-Yl-1ylidene) Bis(5-Methyl-2-
demonstrated strong extraction potential in both single and Phenyl-2,3-Dihydro-1h-Pyrazol-3-Ol) (H2BuEtP) in
multi-metal systems. These findings highlight the Chloroform. European Journal of Applied Sciences,
effectiveness of H₂BuEtP, both independently and in synergy 12(2): 205-214.
with HBuP, for Cu(II) ion extraction. [8]. Godwin, J., Chukwu, U.J and Gad, T. D. (2013); Solvent
Extraction Studies of Uranium (VI) from Aqueous Media
RECOMMENDATIONS into Chloroform Solution of N,N´-ethylenebis(4-
propionyl-2,4-dihydro-5-methyl-2-phenyl-3H-pyrazol-3-
Future studies should optimize extraction conditions, oneimine). American Chemical Science Journal, 3(4):
explore multi-metal applications, investigate alternative 479-488.
ligands and solvents, and assess kinetic and thermodynamic [9]. Godwin, J., Inengite, A. K., & Chukwu, U. J. (2014).
parameters for improved selectivity and sustainability. Effect of Common Acids and Anions on the Extraction
of Iron (II) from Aqueous Solutions into Chloroform
ACKNOWLEDGEMENT Solution of 4,4´-(1E,1E´)-1,1´-(Ethane-1,2-
Diylbis(Azan-1-yl-1ylidene))Bis(5-Methyl-2-Phenyl-2,3-
The authors are grate to the Niger Delta University for Dihydro-1H-Pyrazol-3-ol). International Journal of
the providing the laboratory work space. Chemical and Process Engineering Research (Online),
1(6), 59–72.
Conflict of Interest [10]. Godwin, J., Nwadire, F. C., and Uzoukwu, B. A. (2012).
The authors do not have any conflicting interest. Extraction of Ni (II) Ions into CHCl3 Solution of 4,4´-
(1e,1e´)-1,1´-(ethane-1,2-diylbis(azan-1-yl-
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