IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Separation and Extraction Micro Amount of Cadmium (II) and Mercury (II) with Liquid Anion Exchange Method S. K. Jawad , S. M. Hameed Departme nt of Chemistry , College of Education for Girls ,Kufa Unive rsity Received in :13 December 2010 Accepte d in : 12 April 2011 Abstract For extraction chloro anion comp lexes of Cd 2+ and Hg 2+ used many or ganic agents as extractant accordin g to liquid ion exchan ge method such as α-Nap hthy l amine (α-NA), 4-Amino benzoic acid (4-ABA), 2-[(4-Carboxy methy l p henyl) azo]-4,5-dip heny l imidazole (4- CM ePADPI) and Cryptand (C222). This st udy includes defin ition hy drochloric acid concentration in aqueous p hase and shaking with organic p hase necessary for extraction as well as shaking time, or ganic solv ent effect, interferences and alkaline salt effect. Thermody namic showed the ion exchan ge reaction was exothermic for α-NA, C222 and endothermic for 4-ABA, 4-CM ePADPI for extraction CdCl4 = , but for extraction HgCl4 = was exothermic with 4-ABA, 4- CM ePADPI and C222 but endothermic with α-NA. In addition st oichiometry showed the ion pair comp lex extracted was 1:1:1 Cation: Li gand: Anion. Key word: Liquid ion exchange, Cad mium, M ercury , Solvent extraction. Introduction Zn 2+ was extracted from chloride ion media with (TPP) and the definition of all p arameters effect on extraction method[1], Au 3+ was extracted from hy drochloric acid media with amine alamine304 [R3N + H,Cl - ] in Xy lene, and calculate distribution ratio for comp lex R3N + H,AuCl4 - [2]. Different new liqu id ion exchan ge [Ethy lene bis (triocty l p hosp honium)](EBTOP) used for extraction of Pb 2+ , Cu 2+ , Cd 2+ , Zn 2+ as well as Fe 3+ and In 3+ [3]. Hg 2+ was sep arated from 0.5M acetic acid by Aliquat 336S as liquid ion exchan ge, and extracted sp ecies was [2R4N + ; Hg(OAC)4 = ], this method suitable for separation from Zn, Cd, Ni, Co, Cu, Bi, M n [4]. Zn, Cd and Hg were extracted from chloride and sulp hate media by solvation and liquid ion exchan ge methods and st udied the extracted sp ecies [5]. H g 2+ extracted as chloro comp lexes anion by different high molecular weight amines and tetra ammonium salts with distribution the effective p arameters and extracted sp ecies[6], Cd 2+ extracted from sulp hate media by di(2-ethy l hexy l)phosp horic acid (D2EHPA) dissolved in Toluene, at p H=5-6 and 0.1M of reagent in Toluene [7]. IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 The present study was undertaken to invest igate the effect of various extraction p arameters on the extraction of Cd(II) and H g(II) as chloro comp lex fro m hy drochloric acid media by (α- NA),(4-ABA), (4-CM ePADPI) and (C222) p arameters studied include the effect of hy drochloric acid concentration, metal concentration, foreign ion and temp erature of extraction, organic solvent. Experime ntal Apparatus For absorbance measurements shimadzu UV-1700 sp ectrop hotometer is used with 1cm quartz cells (Jap an), p H- measurements were carried out usin g WTW, listed 8F93(Germany), for shaking used H Y-4 vibrator with AD just about sp eed multiple(Italy ). Reagents A st andard stock solutions 1mg/mL for Cd 2+ and H g 2+ was p repared by dissolving drier (0.1631 gm) of CdCl2 and (0.1354 gm) of HgCl2 [Fluk a] in 100mL d istilled water contain 1mL HCl concentration in volumetric f lask, other working solutions p repared by approp riate dilution of the st ock solution with distilled water. Stock solution of dithiazone (1×10 -2 M ) was p repared by dissolving (0.0256 gm) in 10mL carbontetrachlor ide in vo lumetric f lask, workin g solution (1×10 -4 M ) was p repared instantaneously by dilution with CCl4. Standard solutions of different ligand prepared by dissolving weighed quantities of each one in chloroform. General extraction procedure Shakin g fixed volume of ligand solution with HCl solution at op timum concentration in order to conversion ligand to liquid anion exchanger, as well aqueous p hase contains suitable concentration of HCl to form ation chloro an ion co mplex for metal ion, after that shakin g or ganic p hase with aqueous p hase to exchan ge sm all anion Cl - in liqu id anion exchan ger with chloro comp lex in aqueous p hase as in the equilibria b elow:- nLorg. + H + aq. + Cl - aq. H + LnCl - org. H + LnCl - org. +X - aq. H + LnX - org. + Cl - aq. L= -NA, 4-ABA, 4-CMePADPI, C222 X - = CdCl4 = , HCdCl4 - ,HgCl4 = , HgCl3 - ,HHgCl4 - ... ........ ....(1) .. ........ .....(2) Aft erwards determined reminder quantity of metal ion in aqueous solution and transferred quantity to organic solution at later calculate distribution ratio (D), according to dithiazone method [8]. Re sults and Discussion Effect of HCl Concentration in Aque ous S oluti ons The concentration of HCl in aqueous solutions at range (0.1-3.0M ), the concentration of HCl shaked with ligand solution was 1M to forming liquid anion exchanger, the obtained results, reported in figure (3). IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Effect of HCl Concentration on liquid ion pair formation At op timum concentration of HCl for each ion in aqueous p hase and organic p hase of each ligand shaking with HCl solution in different concentrations (0.1-3.0M ), the obtained results in figure (4). Effect of Metal ion Concentration Organic p hase of ligand shaking with HCl op timum concentration, this or ganic p hase shakin g once again with aqueous solutions contain Cd 2+ (5-100μg) and Hg 2+ (5-150μg) at optimum HCl concentration, the results as in table (2) and figure (5). Study about shaking time n ecessary for extraction, taken differ ent times for shaking (2- 20min), the obtained results, reported in table (3). The st oichiometry of the p robable extracted sp ecies was determin ed on the basis of slop e analysis method by p lotting logD versus log[L] gr aph and givin g st rait line r elation with slop e value d emonst rate the st oichiometry of ion p air comp lex extracted was 1:1:1 [HL + ]HCdCl4 - , [HL + ]HHgCl4 - , [HL + ]HgCl3 - , the results as in table (4). Organic solvent effect on extraction method illustrates there is not any linear relation between dielectric constant (ε) of organic solvents and dist ribution ratio (D), obt ain table (5). Effect of electrolyte salt on distribution ratio investigated by use KCl and NaCl salts at different concentrations, the results show there is optimum concentration of electroly te salt solution givin g h igher dist ribution ratio (D) as in Figur e (7,8). Extraction of CdCl4 = and HgCl4 = accordin g to liquid anion exchan ge by C222 and 4- CM ePADPI in foundation of cations app ear interferences with hy drogen ions, these study and results shown the cations Na + , K + , M g 2+ and Ca 2+ restrict the chloro comp lex anion CdCl4 = and HgCl4 = and decline dist ribution ratio by using C222 and transition metal cations Cu 2+ , Ni 2+ could not give st able coordination comp lex cation with 4-CM ePADPI in acidic media because the p rotonation of 4-CM ePADPI in acidic media decrease the chance of binding with Cu 2+ , Ni 2+ ions. The study about temp erature effect shows the reaction of an ion exchange was endothermic for CdCl4 = with 4-ABA and 4-CM ePADPI but exothermic with α-NA and C222, and the extraction of HgCl4 = was endothermic with α-NA but exothermic with 4-ABA, 4-CM ePADPI, C222. Obt ained results in table (6) and figure (8).And thermody namic data for extraction demonstrate in table (7). K ex = D [HMCl4 - ]aq. [L]org. ......... .......(3) Slope= -Hex 2.303 R ........ .......(4) ΔGex = -RT ln Kex …………….. (5) ΔGex = ΔHex – T ΔSex …………… (6) IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Re ferences 11-- Ababa, A. and Adekola, F.A., (2008) Extraction of Zinc (II) by Trip heny l p hosp hate hy drochloric acid: kinetics and M echanism, International Journa l of p hy sical sciences, 3 (4): 104-111. 22-- Alguacil ,F.J. (2003) Solvent extraction of Au (III) by the chloride salt of the amine alamine 304 and its app lication to a solid supp orted liquid membrane sy st em, Solvent Extraction and ion exchange, 21, Issue.6: 841-852. 33-- Akira, O.; Kunihiko, D.and M akoto T. (2009) Novel liquid anion-exchan ge extractant, ethy lene bis (Tri octy l p hosp honium) salt, Bearing two cation centers adjacently in a molecu le", Journal of the p harmaceutical Society of Jap an, 25(4): 181-187. 44-- Shivad e M .R., Shinde V.M ., (1981) Liquid anion exchange st udies and sep aration of mercury", Analytical Letters, 14, Issue.(3): 155-161. 55-- Rice, N.M .and Smith, M .R. (2007) Recovery of Zinc, Cadmium and M ercury (II) from chloride and sulf ate med ia by solvent extraction , Journa l of Ap p lied Chemist ry and Biotechnolo gy ,.25Issue (5): 379-402. 66-- Singh, O.V. and Tandon, S,N. (2003) Extraction of M ercury (II) as chloride by high molecu lar weight amines and quaternary ammoniu m salts, Journal of Inor ganic and Nuclear Chemistry , 36 Issue(2): 439-443. 77-- Asrafi, F.; Fey zbakhsh, A.and entezari, N. H. (2009) Solvent extraction of C admium (II) from sulfate medium by Bis (2-ethy l hexy l) p hosp horic acid in toluen e, International Journal of Chem. Tech. Rese arch, 1(3): 420-425. 88-- M arczenko Z., (1976) Sep aration and Sp ectrop hotometric determination of elements, Ellis - Horwood- Limited John Wiley and Sons, 2 nd ed, PP:178-179,352-353. Table (1): S andyl Sensiti vity Cd Hg Lig and α-NA 4-ABA 4-CMePADPI C222 α-NA 4-ABA 4- CMePADPI C222 S µg/mL 0.065 0.18 0.2 0.81 0.055 0.043 0.15 0.21 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table(2):Effect of Metal ion concentration on distribution ratio (D) μμgg ((CCdd 22++ ,,HHgg 22++ )) DD CCdd DD HHgg αα--NNAA 44-- AABBAA 44-- CCMMeePPAA DDPPII CC222222 αα--NNAA 44--AABBAA 44-- CCMMeePPAA DDPPII CC222222 5 No.Ex. 0.78 0.56 2.12 No.Ex. No.Ex. No.Ex. No.Ex. 10 0.42 2.12 1.27 4.55 No.Ex. No.Ex. No.Ex. 0.47 20 1.17 3.76 2.56 9.52 0.29 0.06 0.53 1.85 30 1.77 5.81 4 14 0.82 0.54 1.34 2.94 40 2.57 7.69 4.71 18 .04 1.22 1.02 2.12 4.31 50 4.55 11 .5 7.92 49 1.45 1.47 3.23 6.14 60 3.83 9.34 5.26 25 .08 1.97 1.88 3.61 6.87 70 2.5 4.38 4.88 21 .74 2.3 2.27 4.3 7.25 80 1.7 3.12 4.37 19 .05 2.47 2.66 4.88 8.3 90 1.36 1.5 4.06 16 .29 2.54 3.16 5.92 8.58 10 0 1.22 1.22 3.84 14 .12 3.03 2.62 6.63 9.99 11 0 - - - - 3.1 - 7.2 12 .41 12 0 - - - - 3.51 - 7.69 12 .95 13 0 - - - - 3.85 - 8.92 10 .76 14 0 - - - - 4.26 - 8.58 9.42 15 0 - - - - 4.1 - 8.37 7.39 Table (3):Effect of shaking ti me on distribution ratio (D) DD HHgg DD CC dd Time (min.) CC 22 22 22 44 -- CC MMee PPAADD PPII 44 -- AABB AA αα -- NN AA CC 22 22 22 44 -- CC MMee PPAADD PPII 44 -- AABB AA αα -- NN AA 11.76 8.02 3.01 3.82 10.36 4.55 4.81 0.82 2 14.78 8.55 3.12 4.07 20.01 5.09 5.94 1.52 5 12.95 8.92 3.16 4.26 49 7.92 11.5 4.55 10 11.5 8.28 3.78 4 26.77 5.57 2.78 2.67 15 10.76 7.9 3.63 3.72 9.41 3.71 1.68 1.74 20 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table (4): Effect of li gand concentration on distribution ratio (D) Table (5): Effect of organi c solvents on distributi on ratio (D) OOrrggaanniicc SSoollvveennttss εε DD CCdd DD HHgg αα--NNAA 44--AABB AA 44--CCMMeePPAADDPPII CC222222 αα--NNAA 44--AABB AA 44--CCMMeePPAADDPPII CC222222 Nitr obenzene 35. 74 2.33 3.54 7.92 11. 5 5.66 2.78 9.48 15. 21 1,2-Dichloroet hane 10. 65 5.94 2.37 9 26. 77 5.08 4.35 8.7 16. 64 Dichloromethane 9.08 2.47 1.97 5.09 24 5.25 4.05 9.83 15. 9 Chlorobenzene 5.708 2.42 8.61 6.81 21. 72 5.08 3.83 8.15 16. 14 Chlorofor m 4.806 4.55 11. 5 7.92 49 4.26 3.78 8.92 14. 78 B enzene 2.804 1.65 1.68 4.68 22. 8 5.48 3.16 7.66 15. 66 Toluene 2.438 3.46 1.84 8.61 19. 83 4.93 3.45 8.42 14. 58 Car bonte tr achloride 2.38 1.68 2.52 9.41 12. 15 5.14 5 8.28 11 DD HHgg DD CCdd CCoonncc.. OOff [[LL]] CC222222 44-- CCMMeePPAADDPPII 44--AABB AA αα--NNAA CC222222 44-- CCMMeePPAADDPPII 44--AABB AA αα--NNAA SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD SSlloopp ee DD 0 .0 6 5 20. 0 3 0 .0 9 7 13. 9 3 0 .0 5 7 5.08 0 .0 8 5 6.21 0 .6 0 2 832. 3 0 .3 31. 6 3 0 .3 49. 1 6 0 .0 6 2 6.14 1x10 -2 19. 0 9 12. 6 6 4.84 5.79 682. 4 22. 5 9 37. 8 2 5.94 5x10 -3 17. 2 1 10. 8 1 4.35 5.14 251. 4 15. 5 2 24. 6 8 5.41 1x10 -3 16. 1 3 10. 2 4.17 4.78 154. 6 11. 5 3 17. 5 3 5.09 5x10 -4 14. 7 8 8.92 3.78 4.26 49 7.92 11. 5 4.55 1x10 -4 13. 9 3 8.54 3.68 3.96 30. 8 5 6.56 9.14 4.43 5x10 -5 12. 7 9 7.27 3.36 3.45 11. 8 4.36 5.99 3.8 1x10 -5 12. 3 8 6.82 3.2 3.21 7.57 3.1 5.25 3.62 5x10 -6 10. 9 7 5.7 2.98 2.84 3.31 2.03 3.08 3.46 1x10 -6 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Table (6): Effect of Temperature on distributi on ratio (D) TT°°CC CCdd HHgg αα--NNAA 44--AABBAA 44--CCMMeePPAADDPPII CC222222 αα--NNAA 44--AABBAA 44--CCMMeePPAADDPPII CC222222 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 DD KKeexx ××1100 99 5 6.57 0.74 8.77 0.99 5.94 0.67 124 14. 09 3.24 2.31 4.69 0.52 12. 26 9.5 16. 61 13. 84 10 5.94 0.67 9.41 1.07 6.35 0.72 99 11. 25 3.4 2.43 4.48 0.5 11. 74 9.1 16 13. 33 15 5.41 0.61 10 1.13 6.93 0.78 82. 33 9.35 3.6 2.57 4.17 0.46 10. 6 8.22 15. 54 12. 95 20 4.95 0.56 10. 4 1.18 7.33 0.83 61. 5 6.98 3.92 2.8 4 0.44 9.65 7.48 15. 29 12. 74 25 4.55 0.51 11. 5 1.3 7.92 0.9 49 5.56 4.26 3.04 3.78 0.42 8.92 6.91 14. 78 12. 32 30 4.31 0.49 12. 2 1.38 8.25 0.93 40. 66 4.62 4.46 3.19 3.63 0.4 8.42 6.52 14. 45 12. 04 40 3.71 0.42 13. 7 1.55 9.41 1.07 30. 25 3.43 4.98 3.55 3.41 0.38 7.55 5.85 13. 88 11. 57 50 3.31 0.37 14. 6 1.66 10. 36 1.17 19. 83 2.25 5.42 3.87 3.12 0.35 6.83 5.29 13. 28 11. 07 60 3.03 0.34 15. 7 1.78 11. 5 1.3 15. 66 1.78 6 4.28 2.98 0.33 6.47 5.01 12. 55 10. 46 Table (7): Thermodynami c data Ligand Cd Hg ΔHex (KJ.mole -1 ) ΔGex (KJ.mole -1 ) ΔSex (J.mole -1 .K - 1 ) ΔHex (KJ.mole -1 ) ΔGex (KJ.mole -1 ) ΔSex (J.mole -1 .K -1 ) α-NA -0.0107 -46 .15 16 5.96 0.008 5 -53 .80 16 1.58 4-ABA 0.008 3 -57 .66 17 3.17 -0.0063 -45 .38 16 3.21 4-CMePADPI 0.009 1 -56 .81 17 0.62 -0.0085 -46 .72 16 8.02 C222 -0.0028 -52 .81 19 0.06 -0.0041 -47 .57 17 1.12 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Fig. (1):Calibration curve of Cd(II) Fig. (2):Calibration curve of Hg(II) Fig.(3): Effect of HCl concentration in aque ous solutions on distributi on ratio (D) - [Cd 2+ ]aq., [Hg 2+ ]aq.=50μg/5m L, [ Ligand]=1x10 - 4 M in CHCl3 Fig. (4): Effect of HCl concentration on liquid ion exchanger formation-[Cd 2+ ]aq., [Hg 2+ ]aq.=50μg/5mL, [ Ligand]=1x10 -4 M in CHCl 3 IBN AL- HAITHAM J. FOR PURE & APPL. S CI. VOL. 24 (2) 2011 Fig. (5): Effect of Cd(II), Hg( II) ions concentration Fig. (6): Effect of KCl concentration on extraction of Cd(II), Hg(II). Fig. (7): Effect of NaCl concentration on extraction of Fig.(8): Te mperature effect on the extraction method of Cd(II), Hg(II). 2011) 1( 24المجلد والتطبیقیة الصرفة للعلوم الهیثم ابن مجلة (II)الزئبق و (II)فصل واستخالص الكمیات المایكرویة من الكادمیوم طة طریقة التبادل االیوني السائلابوس صفا مجید حمید، شوكت كاظم جواد جامعة الكوفة ،كلیة التربیة للبنات ،قسم الكیمیاء 2010كانون األول 13: استلم البحث في 2011 نیسان 12: في البحث قبل الخالصة كلورو السالبة للكادمیوم ق، (II)الستخالص معقدات ال مواد مستخلصة بوصفھا عضویة ات كواشفلمعاست(II) و الزئب α-Naphthyمثل ،وفق تقنیة التبادل االیوني السائلعلى l amine (α-NA) ، 4و-Amino benzoic acid (4-ABA)، و 2-[(4-Carboxy methy l phenyl) azo]-4,5-dipheny l imidazole (4-CM ePADPI) ،و Cryptand )C222 .( م ھذه الدراسة شملت تحدید تركیز حامض الھیدروكلوریك في الوسط المائي والتركیز المناسب للرج مع الطور العضوي والالز الجانب الثرمودینامیكي . تأثیر األمالح القلویة والتداخالت،وتأثیر المذیب العضوي، وزمن الرج، فضال عن ص لعملیة االستخال ل التبادل االیوني كان باعث رارة اوضح إن تفاع رة اوماص C222و α-NAلكل من exothermicللح endothermic للحرا CM-4و ، ABA-4لكل من ePADPI عند استخالصCdCl4 = HgCl4أما عند استخالص = للحرارة افكان التفاعل باعث exothermic 4مع كل من-ABA 4و-CM ePADPI وC222 للحرارة اوماص endothermic معα-NA . فضال عن .Cation: Ligand: Anion 1:1:1دراسة تركیب معقد الترابط االیوني المستخلص أثبتت انھ .االیوني السائل، الكادمیوم، الزئبق، االستخالص بالمذیبالتبادل : الكلمات المفتاحیة