Research Journal of Chemical Sciences ______________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.Sci. International Science Congress Association 30 Studies on the Extraction of Copper (II) by Pyrazoloquinazolinone Derivatives from Aqueous SolutionsKhawassek Y.M., Cheira M.F. * and Mahmoud G.M. Nuclear Materials Authority, P.O. Box 530, El-Maadi, Cairo, EGYPT Available online at: www.isca.in (Received 9th March 2012, revised 17th March 2012, accepted 23rd March 2012)Abstract Pyrazoloquinazolinone type extractants are effective reagents for extraction of Cu (II) ions from aqueous solutions. In this respect, extraction of copper (II) ions with 2-amino-3-(4- (X) phenyl azo)-8,9-dihydro-8,8-dimethyl-7H-pyrazolo [1,5-a] quinazolin-6- one (XPQ), (X= Br, Cl, OCH3 or CH) were studied. The optimum studied extractants concentrations were found at 0.04% BrPQ, 0.045% ClPQ, 0.05% OCHPQ and 0.055% CHPQ in carbon tetrachloride as a diluent. Highly extraction efficiency were found at pH 2, 1/1 O/A ratio and 5 min. shaking time at room temperature. BrPQ was selected as an appropriate structure of reagents to extract Cu (II) species. The proposed method was used in extraction of copper (II) ions in some standard reference geologic samples. Keywords: Copper (II) ions, solvent extraction, separation, determinationIntroduction Copper is the 25th most abundant element in the earth crust. It is found in earth mainly in the form of chalcopyrite (CuFeS) associated with other sulphides, such as pyrite (FeS). Copper was used as thermal conductors, electrical conductors, building material and an important constituent of various metal alloys. In view of that it was necessary to monitoring the copper in different field areas, also used in the manufacture of water pipes. Moreover, its alloys were used in jewellery and for coinsIn view of lack of mineral resources , efforts are increasingly being made to explore alternate resources. It can be extracted as a byproduct from various sources. In recent years, extraction, separation and recovery of Cu (II) ions by solvent extractions had been carried out. Two different series of N-donor pyrazole ligands had used in liquid-liquid extraction of Cu (II) ions from aqueous solution using methylene chloride as a diluent. Pyrazole derivatives were currently the subjects of several studies in extraction of copper (II) ions3-7. Various reagents were used for extraction of copper ions in environmental and geologic samples such as LIX 860, LIX 841, LIX 5410, N,N-bis (2-hydroxy-5-bromobenzyl)-1,2-diamine propane11, iso nitroso actophenone-2-amino benzoyl hydrazone12. Copper (II) ions were also extracted from nitric acid solution with 1-phenyl-3-methyl-4-benzoyl-5-pyrazolone (HPMBP) as a cation carrier by liquid membrane emulsion (LME)13 Equilibrium, structure and hydrolytic activity for complexes of copper (II), zinc(II) and nickel (II) with imidazole containing reagent and inositol derivatives were used 1-octylimidazole and 1-octyl-2-methylimidazole for extraction of Zn (II), Ni (II) in different organic solvents14. A new imidazole reagent, benzo[15-crown-5]-1H-imidazole [4,5f] [1,10] phenanthroline was synthesized as well as prepared complexes Co (II), Ni (II), Cu (II) and the complex structure found to be (2:1)15. The present work aimed to study of Cu (II) ions extraction efficiency from aqueous solution using new synthesized pyrazoloquinazolinone derivatives. The factors controlling the extraction process were determined and then applied upon geologic samples. Material and Methods Instruments: Spectrophotometer (Metertech Inc. SP-8001) was used for copper control analysis. The concentration of Cu (II) ions in the aqueous or stripping solutions was spectrophotometrically analyzed using carprizone and ammonium citrate16. The synthesized heterocyclic compounds (extractants), the organometallic complex after extraction, as well as the extractant after stripping were analyzed using a Shimadzu FTIR8101 PC infrared spectrophotometer.All the chemicals were of analytical grade and the double distilled water was used in all experiments. Synthesis of Extractants: Four multidentate compounds namely 2-amino-3-(4- (X) phenyl azo)-8,9-dihydro-8,8-dimethyl-7H-pyrazolo [1,5-a] quinazolin-6- one (XPQ), (X= Br, Cl, OCH3 or CH) were prepared. For this purpose, one ß-diketone namely; 2- ((dimethyl amino) methylene)-5,5-dimethyl cyclohexane-1,3-dione (enamindione) was selected as starting materials. The formation of the four compounds was assumed to take place via an initial Michael addition of the exocyclic amino group in the 4-aryl azo-3,5 diaminopyrazole derivatives to the -unsaturated in the enamindione. It yielded the corresponding acyclic non-isolable intermediates which undergo Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 31 cyclization and aromatization to form the four products BrPQ, ClPQ, OCHPQ and CHPQ17. Extraction Procedure: The prepared standard solution of Cu (II) ions was subjected to several solvent extraction experiments by shaking with the synthesized extractants in carbon tetrachloride. The loaded organic solvents were then contacted with different acidic and alkaline stripping solutions to back extract the copper species from the solvents under the relevant conditions. Factors affecting the extraction and stripping efficiencies of Cu (II) ions with the prepared extractants were investigated. It involved diluents type, aqueous solution pH, solvent concentration, contact time, temperature. Results and Discussion Effect of Diluents Type: Different organic diluents such as toluene, carbon tetrachloride, benzene, chloroform, methylene chloride, cyclohexane, n-hexane and xylene were employed for the extraction of Cu (II) ions. The other factors were kept constant at 0.05% extractants concentrations, (1/1) O/A ratio and 5 min. shaking time. The highest extraction efficiency of Cu (II) ions was obtained using carbon tetrachloride and methylene chloride diluents due to their polarities of bonds (table 1). In this study, carbon tetrachloride was chosen as a diluent because of a better phase separation. The four bonds of carbon tetrachloride (CCl) are polarity, but the molecule is non-polar because the bond polarity is canceled by the symmetric tetrahedral shape. When other atoms substituted some of the Cl atoms, the symmetry is broken and the molecule becomes polar as methylene chloride (CHCl18. Effect of pH: The effect of pH was studied in the range of 1 – 13 while the other experimental factors were fixed at 0.05% extractants concentrations/CCl, (1/1) O/A ratio and 5 min. shaking time. The results shown in figure 1 indicate that maximum extraction efficiency of Cu (II) ions from its aqueous solutions attained at pH 2 to all of the workable extractants. Effect of Extractant Concentration: Extraction of 5 g/ml Cu (II) ions was also investigated with varying the concentration of the synthesizedBrPQ, ClPQ, OCHPQ and CHPQ/CCl within the range of 0.005 to 0.2%. The other parameters pH 2, (1/1) O/A ratio for 5 min. shaking time were kept constant. The obtained results illustrated in figure (2) reveal that, maximum extraction efficiencies of Cu (II) ions occurred with BrPQ and ClPQ extractants whereas the percentage extraction efficiency reached 99.0 and 96.5% at 0.04 and 0.045% concentrations, respectively. On the contrary, 90.4 and 85.6% Cu extraction efficiencies occurred at 0.05 and 0.055% concentrations of OCHPQ and CHPQ extractants, respectively. Effect of Organic/Aqueous Ratio: This factor was studied in the range from O/A = 4/1 to 1/4 (figure 3). Contacting equal volumes of the organic and aqueous phases for 5 min. were led to 99.2, 96.5, 90.3 and 85.5% Cu extractions efficiencies for the workable extractants BrPQ, ClPQ, OCHPQ and CHPQ respectively. The ratio of 1:1 was applied for an efficient extraction of Cu (II) ions from their solutions. Effect of Contact Time: To study this effect, equal volumes from copper solution and the studied extractants were shaken from 1 to 30 min. It was found that loading of Cu (II) ions occurred within few minutes. As can be seen in figure 4 the extraction efficiencies of Cu (II) ions gradually increased by increasing the contact time till 5 min., which reached constant values of 98.9, 96.2, 90.15 and 85.4% for BrPQ, ClPQ, OCHPQ and CHPQ reagents respectively. As a result, the optimum shaking time for maximum extraction efficiencies of Cu (II) ions was 5 minutes. Effect of Temperature: The extraction of Cu (II) ions was studied at different temperatures ranged from 30 to 60 ºC upon the studied extractants at pH 2, (1/1) O/A ratio for 5 min. shaking time. It was observed that increasing the temperature up to 60 ºC did not affect the extraction efficiency of Cu (II) ions (table 2). This behavior may probably attributed to strong metal-extractant complexes which remain stable even at high temperature. Hence all extractions procedures carried out at room temperature. The ability of BrPQ to extract Cu (II) ions was found to be markedly higher than the other compounds ClPQ, OCHPQ and CHPQ because the atomic radius of Br ion is larger than of the other groups. Loading Capacity of Extractants: The maximum loading capacity of organic phase containing extractants was determined by contacting the four extractants with fresh aqueous 100 g/ml copper (II) ions at pH 2, (1/1) O/A ratio, 5 min. shaking time at room temperature. When both phases were separated, Cu (II) ions concentration was determined and the same organic phase reused for subsequent extraction with the same fresh aqueous solution. After successive contacts between organic and aqueous phases, the organic phase was become saturated with copper (II) ions. The obtained results showed that a maximum concentration of 370, 310, 274 and 230 g/ml of Cu (II) ions using 0.04% BrPQ, 0.045% ClPQ, 0.05% OCHPQ and 0.055% CHPQ/CCl could be loaded after four stages (figure 5). Effect of Foreign Ions on Cu Extraction: The effect of associated ions that may present in matrix solution and may cause interfering effect during the extraction of Cu (II) ions was studied (table 3). It was obvious that, more than 10 g/ml of foreign ions, Cu (II) ions can be extracted in the presence of the studied ions by using the four extractants. Above this concentration, some cations such as Fe3+, Ti4+, Ni2+, Co2+, V6+, Th4+and U6+ impart little interfering effect. Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 32 Stripping Experiments: Series of experiments were carried out to back extract Cu species into the aqueous phase from the loaded organic phases. Some relevant factors were studied to find out the stripping characteristics on the extracted copper (II) ions. Determination of Proper Stripping Agent: Different concentration of sulphuric acid and alkalis were shaken with the loaded organic solvents at an (O/A) ratio 1/1 for 5 minutes to obtain the more concentrated strip solutions (table 4). The results reveal that, potassium hydroxide exhibited the highest stripping efficiency of copper (II) ions from the four loaded extractants. Effect of Potassium Hydroxide Concentration: Different concentration of potassium hydroxide ranged from 5.0 to 15.0% was contacted with equal volumes of the working loaded solvents BrPQ, ClPQ, OCHPQ and CHPQ for 5 minutes. Stripping efficiency of copper (II) ions gradually increased until attaining maximum values of 99.4, 92.9, 88.5 and 83.7% for BrPQ, ClPQ, OCHPQ and CHPQ extractants, respectively, using 10% KOH stripping agent concentration (table 5). Effect of Contact Time: Potassium hydroxide (10%) was used to strip Cu (II) ions from the working loaded solvents by shaking equal volumes of both phases for different intervals time ranging 1 to 20 minutes. Maximum stripping efficiency was obtained at 3 minutes contact time (table 6). Effect of O/A Ratio: Tostudy this factor, the O/A ratio was varied from 4/1 to 1/4 while the other factors of 10 % potassium hydroxide and 3 min. shaking time were kept constants. The following stripping efficiencies (99.8, 94.0, 90 and 87.5%) were attained at O/A ratio 1/1 for BrPQ, ClPQ, OCHPQ and CHPQ extractants, respectively. The results showed that, the best stripping efficiency of Cu (II) ions was at O/A ratios 1/1 (table 7). IR Analysis: The free ligands BrPQ, ClPQ, OCHPQ and CHPQ/CCl, besides the loaded and the back-washed extractants were analyzed using infrared spectroscopy to compare the differences in their peaks positions and intensities (table 8). The sharp N=N peaks present in BrPQ, ClPQ, OCHPQ and CHPQ disappeared after extraction but reappeared after stripping, which may be due to the formation of the metal complex via azo group. IR analysis revealed that the ketone groups present in BrPQ, ClPQ, OCHPQ and CHPQ almost kept its positions after extraction and stripping which indicates that it was not involved in the complex formation. Extraction and determination of Cu (II) in some standard reference samples: The proposed methods using BrPQ, ClPQ, OCHPQ and CHPQ were used for the separation and determination of Cu (II) ions in some standard reference geologic (JB-2 and JB-3) samples19. The results given in table (9) reveal that, the concentration of copper (II) ions was approximately equals its reference value, (RSD = 0.64 and 0.79%). The results indicate that the proposed method can be reliably used for the extraction of Cu (II) ions efficiently. The relative standard deviation is widely used in analytical chemistry to express the precision and repeatability of an assay.Table-1 Effect of diluents on the extraction of Cu(II) ionsDiluents type z BrPQ ClPQ OCH 3 PQ CH 3 PQ Toluene Carbon tetrachloride Benzene Chloroform Methylene chloride Cyclohexane n-Hexane Xylene40.21 96.34 30.26 23.52 95.34 29.34 27.42 29.12 38.54 94.32 26.43 20.49 93.76 26.54 22.26 26.93 32.25 90.45 20.12 16.56 86.94 21.03 17.98 20.33 23.39 85.21 15.81 10.45 83.23 18.67 11.56 14.67 Results are mean of triplicate value, Cu (II) = 5 g/ml and phase ratio (A/O)=1/1,shaking time= 5 min. Table-2 Effect of temperature on extraction efficiency of Cu(II) Temp. ºC Extraction efficiency % BrPQ ClPQ OCH 3 PQ CH 3 PQ 30 40 50 60 99.00 98.81 98.62 98.75 96.49 96.41 96.25 96.34 90.35 90.01 90.00 90.31 85.67 85.43 85.68 85.54 Results are mean of triplicate value, Cu (II) = 5 g/ml and phase ratio (A/O)=1/1, shaking time = 5 min. Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 33 Table-3 Effect of interfering ions on the extraction efficiency of 5 g/ml Cu (II) ions Ions g/ml) Extraction efficiency, % BrPQ ClPQ OCH 3 PQ CH 3 PQ 10 g/ml 50 g/ml 100 g/ml 10 g/ml 50 g/ml 100 g/ml 10 g/ml 50 g/ml 100 g/ml 10 g/ml 50 g/ml 100 g/ml Si 4+ Ca2+Mg2+Na5+Mn2+NH+ Al3+Fe3+Ti4+Ba2+Cr3+Ni2+Co2+5+Th4+6+Mo6+Sc3+99.0 99.1 99.1 99.2 99.8 99.7 99.7 99.6 99.3 99.6 99.9 99.0 99.2 99.0 99.2 99.2 99.2 99.1 99.5 99.3 99.0 99.0 98.0 99.0 98.9 99.3 99.1 99.3 98.8 93.2 94.3 98.3 99.1 96.3 95.5 96.2 97.1 96. 6 99.2 99.0 99.0 99.0 98.0 99.0 98.0 99.0 99.0 99.0 98.1 83.6 87.4 98.0 99.0 90.2 89.4 90.6 90.3 90.1 98.7 98.8 99.0 99.0 99.1 99.1 99.7 99.2 99.3 99.2 99.1 99.7 99.2 99.2 99.2 99.1 99.2 99.2 99.3 99.5 99.3 99.4 99.0 99.0 98.3 98.6 99.2 99.0 98.9 99.0 98.7 91.1 95.4 99.0 99.0 96.2 96.3 96.3 96.5 96.4 99.0 99.0 99.0 99.0 98.0 98.1 99.0 98.1 98.1 98.5 98.4 81.4 88.4 98.3 98.5 90.4 90.4 90.3 90.7 90.6 99.0 99.13 99.1 99.0 99.1 99.2 99.1 99.4 99.1 99.2 99.1 99.6 99.9 99.2 99.4 99.0 99.1 99.4 99.3 99.4 99.1 99.4 99.0 99.0 98.2 98.3 98.2 99.0 98.5 99.0 98.9 90.6 95.8 98.8 99.2 96.1 96.7 97.2 96.7 96.8 98.1 99.3 99.0 99.0 98.0 99.1 98.0 98.3 98.1 98.3 98.5 80.3 88.3 98.4 99.0 90.3 90.2 90.1 90.3 90.1 98.3 99.1 99.0 99.0 99.1 99.7 99.5 99.2 99.3 99.7 99.1 99.4 99.9 99.6 99.5 99.1 99.1 99.5 99.7 99.4 99.1 99.2 99.0 99.0 98.2 99.1 99.0 99.0 98.8 99.0 98.9 90.2 95.2 99.0 99.2 96.2 95.7 97.1 96.7 96.4 99.0 99.0 99.0 99.0 98.0 99.0 98.1 98.2 98.3 98.4 98.3 80.1 88.4 98.4 99.0 90.8 90.5 91.1 90.6 90.1 98.6 98.3 Table-4 Effect of stripping agent type on the stripping efficiency of Cu (II) ions Stripping agent Stripping Efficiency, % BrPQ ClPQ OCH 3 PQ CH 3 PQ SO (0.5, 1, 2 mole/L) SO (5 mole/L) NHOH (33%) NaOH (5%) KOH (5%) nil 50.5 69.5 85.2 90.8 nil 46.3 65.3 80.9 87.7 nil 40.1 61.7 76.6 83.5 nil 30.2 56.9 72.8 79.3 Table-5 Effect of KOH concentration on the stripping efficiency of Cu (II) ions KOH Conc.%Stripping Efficiency, % BrPQ ClPQ OCH 3 PQ CH 3 PQ 5.0 7.5 10.0 15.0 90.7 95.3 99.4 99.4 87.7 90.6 92.9 92.9 83.6 86.2 88.5 88.5 79.3 81.6 83.7 83.7 Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 34 Table-6 Effect of contact time on the stripping efficiency of Cu (II) ions Contact Time, min Stripping Efficiency, % BrPQ ClPQOCH 3 PQ CH 3 PQ 1 3 5 10 15 20 90.2 99.8 99.8 99.8 99.8 99.8 85.5 94.0 94.0 94.0 94.0 94.0 80.8 90.3 90.3 90.3 90.3 90.3 76.6 87.5 87.5 87.5 87.5 87.5 Table-7 Effect of O/A ratio on the stripping efficiency of Cu (II) ions O/A ratio Stripping Efficiency, % BrPQ ClPQ OCH 3 PQ CH 3 PQ 4/1 3/1 2/1 1/1 1/2 1/3 1/4 67.2 78.5 86.3 99.8 99.8 99.8 99.8 63.0 74.4 85.6 94.0 94.0 94.0 94.0 60.1 70.8 81.9 90.3 90.3 90.3 90.3 55.2 65.6 76.4 87.5 87.5 87.5 87.5 Table-8 Infrared Data for the used synthesized extractants before, after extraction and stripping Synthetic Complex Condition Major Group (Aliphatic) C – H C=O C=N C=N N=N NH BrPQ Before extraction, cm - 1 (vs) 2945.5 1700.5 1628.6 1618.9 1928.7 3276.6 After extraction, cm-1(m) 2945.5 1687.5 1600.3 1608.4 - 3271.8 After stripping, cm - 1 (m) 2950.0 1687.5 1600.3 1608.4 1928.7 3271.8 ClPQ Before extraction, cm - 1 (vs) 2933.6 1668.7 1630.0 1555.6 1922.6 3267.8 After extraction, cm - 1 (m) 2934.8 1660.5 1620.6 1550.4 - 3260.7 After stripping, cm - 1 (m) 2940.5 1660.5 1620.6 1550.4 1922.6 3260.7 OCHPQ Before extraction, cm - 1 (vs) 2938.5 1665.4 1618.8 1554.8 1923.4 3267.5 After extraction, cm - 1 (m) 2936.6 1663.9 1618.8 1552.9 - 3263.7 After stripping, cm - 1 (m) 2936.0 1663.9 1618.8 1553.9 1924.5 3263.7 CHPQ Before extraction, cm - 1 (vs) 2930.0 1684.8 1620.7 1600.8 1925.7 3267.9 After extraction, cm - 1 (m) 2928.7 1683.5 1616.5 1600.8 - 3266.8 After stripping, cm - 1 (m) 2928.7 1683.5 1616.5 1600.8 1925.7 3266.8 Table-9 Determination of Cu (II) ions in standard reference samples using spectrophotometric technique Relative standard deviation=100S/ x (n=3), S= standard deviation and x = average Samples Certified value (19) g/ml) Determined value g/ml) Standard deviation, S RSD, % JB-2 JB-3225 194222.9 192 1.43 1.53 0.64 % 0.79 % Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 35 Figure-1 The effect of pH on the extraction efficiency of Cu (II) ions Figure-2 Effect of BrPQ, ClPQ, OCHPQ and CHPQ concentrations on the extraction efficiency of Cu (II) ions Figure-3 Effect of O/A ratio on the extraction efficiency of copper ions 40455055606570758085909510001234567891011121314Extraction, %pH (BrPQ) (ClPQ) (OCH3PQ) (CH3PQ) 40506070809010000.020.040.060.080.10.120.140.160.180.20.22Extraction, %Extractants Conc., % (BrPQ) (ClPQ) (OCH3PQ) (CH3PQ) 5060708090100(4/1)(3/1)(2/1)(1/1)(1/2)(1/3)(1/4)Extraction, %(O/A) Phase Ratio (BrPQ) (ClPQ) (OCH3PQ) (CH3PQ) Research Journal of Chemical Sciences __________________________________________________________ ISSN 2231-606X Vol. 2(6), 30-37, June (2012) Res.J.Chem.SciInternational Science Congress Association 36 Figure-4 Effect of contact time on the extraction efficiency of Cu (II) ions Figure-5 The effect of loading number on the copper (II) ions concentration of the organic phases of BrPQ, ClPQ, OCHPQ and CHPQ in carbon tetrachloride Conclusion The synthesized multidentate compounds can be fairly used for extracting Cu species from geologic matrices. The optimum conditions were found at pH 2, the optimum solvent concentrations of BrPQ, ClPQ, OCHPQ and CHPQ are 0.04, 0.045, 0.05 and 0.055%, respectively, O/A ratio is 1/1 and shaking time is 5 min. at room temperature. The maximum loading capacity showed that, the organic solvent was fully loaded with the copper (II) after four contacts between the aqueous and the organic phases. By using the optimum conditions, extraction and determination of copper (II) ions in standard reference geologic (JB-2 and JB-3) samples were carried out. 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