Sıvı-sıvı ekstraksiyonu ile yeni şelat yapıcılar kullanarak çeşitli örneklerdeki bazı ağır metallerin tayini
Determination of some heavy metals in various samples with liquid-liquid extraction by using new chelators
Yazar: ŞERİFE SAÇMACI
Danışman: PROF.DR. ŞENOL KARTAL
Erciyes Üniversitesi / Fen Bilimleri Enstitüsü / Kimya Ana Bilim Dalı
Derece: Doktora, 2006
Konu: Kimya = Chemistry

Özet:
iiiSIVI-SIVI EKSTRAKSIYONU ILE YENI SELAT YAPICILAR KULLANARAKÇESITLI ÖRNEKLERDEKI BAZI AGIR METALLERIN TAYINISerife SAÇMACIErciyes Üniversitesi, Fen Bilimleri EnstitüsüDoktora Tezi, Agustos 2006Tez Danismani: Prof. Dr. Senol KARTALÖZETBu çalismada, sivi-sivi ekstraksiyon ve geri ekstraksiyon tekniklerini esas alan organikbir çözücüyle sulu fazdan bazi eser elementlerin zenginlestirilmesi ve türlemesi içinyöntem gelistirilmesi amaçlandi. Ayirma-zenginlestirme ve krom türlemesinde organikçözücü olarak metil izo-bütil keton (MIBK) kullanildi. Bu çalisma süresince kullanilanyeni ligandlarin metallerle kompleks olusturma özellikleri incelenerek, baglanmaninhangi fonksiyonel gruplar üzerinden oldugu spektroskopik yöntemlerle aydinlatilmayaçalisildi. S ularda organik maddelerle kompleks olusturan ve askida kati maddelere bagliolan metaller ayri ayri tayin edildi. Her bir yeni ligandla metaller için dagilma oranlaribelirlendi. Gelistirilen yöntemler pH, sallama zamani, ligand miktari, örnek hacmi,çözüc ü türü ve hacmi, sicaklik etkisi vb. yönünden optimize edilerek, analitik ölçütleraçisindan degerlendirildi. Çevre örneklerindeki eser metallerin tayini alevli atomikabsorpsiyon spektrometri (FAAS) ile yapildi.Çalismanin ilk bölümünde agir metallerle 4-(4-metoksibenzoil)-5-(4-metoksifenil)-2-fenil-2,3-dihidro-1H-3-pirazolon'un olusturdugu selat komplekslerinin, MIBK/sivi-siviekstraksiyonunu esas alan yöntem optimize edildi. Analitik parametreler olarak örnekçözeltisinin pH'i, örnek hacmi, iyonik siddet, sallama zamani, sicaklik etkisi ve yabanciiyonlarin vb. etkisi incelendi. MIBK/sivi-sivi ekstraksiyon sistemi ile pH 8.5'da Ni(II),Cu(II), Co(II), Fe(III), Pb(II), Cd(II) ve Mn(II) için yeterli geri kazanma degerleri eldeedildi. Gelistirilen yöntem çme suyu, deniz suyu, sertifikali deniz suyu (CRM 403),isediment ve toprak örneklerine uygulandi. Ortalama geri kazanma degerleri % 95-100,bagil standart sapmalar % 2.0-6.6 araliginda degismektedir. Alevli AAS ile tayinlerdegözlenebilme sinirlari Cu(II), Ni(II), Co(II), Fe(III), Pb(II), Mn(II) ve Cd(II) içinivsirasiyla 0.063, 0.018, 0.104, 0.087, 0.039, 0.059 ve 0.049 Âµg L-1 olarak bulundu (3s/b,N=20).Çalismanin ikinci bölümünde, 2-(4-me toksibenzoil)-N'-benziliden-3-(4-metoksifenil)-3-okso-N-fenil-propanohidrazit ile iyon çifti kompleksi olusumunu temel alan sivi-siviekstraksiyon yöntemiyle çevre örneklerindeki eser metal tayinleri yapildi. pH 9.5'daNi(II), Cu(II), Co(II), Fe(III), Mn(II), Pb(II), Cd(II), Zn(II) ve Cr(III) için yeterli gerikazanma degerleri elde edildi. Bagil standart sapmalar % 0.5-3.2 araligindadegismektedir.MIBK/2-(4-metoksibenzoil)-N'-benziliden-3-(4-metoksifenil)-3-okso-N-fenil-propano-hidrazit/sivi-sivi ekstraksiyon yöntemi, krom türlemesinin alevli AAS ile tayini içinincelendi. Cr(III) pH 8.0'de tayin edilirken, Cr(VI) asidik ortamda NH2OH?HCl ileCr(III)'e indirgendikten sonra tayin edildi. Yöntem, çesme suyu, atik su ve tekstilfabrikasi atik su örneklerine uygulandi. Yöntemin dogrulugu analit ilavesi ile kontrolagil standart sapmasi % 2.4 iken, gözlenebilme siniri xkör + 3s kör 'eedildi. Yöntemin bgöre 0.5 Âµg L -1 olarak elde edildi.Sivi-sivi ekstraksiyonu yöntemiyle, eser elementlerin 4-asetil-5-metil-1-fenil-1H-pirazol-3-karboksilik asit ile olusturdugu selat kompleksinin zenginlestirmede yeni birligand olarak kullanilabilirligi tezin son bölümünde incelendi. pH 9.5'da Pb(II), Ni(II),Co(II), Fe(III), Cu(II), Cd(II) ve Zn(II) için dogal su ve göl suyu örneklerinde FAAS ilekantitatif geri kazanma degerleri elde edildi. Bagil standart sapmalar % 0.7-10.8araliginda degismektedir.Anahtar Sözcükler MIBK, Sivi-sivi Ekstraksiyonu, Eser Metaller, Türleme,:Pirazolon, Propanohidrazit, Pirazol 3-Karboksilik Asit, Su, Toprak, Sediment Örnegi.

Abstract:
vDETERMINATION OF SOME HEAVY METALS IN VARIOUS SAMPLESWITH LIQUID -LIQUID EXTRACTION BY USING NEW CHELATORSSerife SAÇMACIErciyes University, Graduate School of Natural and Apllied SciencesPh. D. Thesis, August 2006Thesis Supervisor: Prof. Dr. Senol KARTALABSTRACTIn this study, it was aimed to develop new methods for preconcentration and speciationof some trace elements from aquueous phase to organic solvent by liquid-liquidextraction and back extraction techniques. As organic solvent, methyl iso-buthyl ketone(MIBK) was used for seperation-preconcentration and chromium speciation. During thestudy, by examining the properties of new ligands forming complexes with metals, itwas studied explaining the binding of metals to ligands on which functional groups byspectroscopic methods. The metals that form complexes with organic matters and boundto suspended particulate matter in waters were determined separately. Distribution ratiosof the metals were determined for every new ligand. The developed methods wereoptimised for some analytical parameters such as pH, shaking time, concentration ofligand, sample volume, kind of solvent, volume, effect of temperature, etc., andevaluated in terms of analytical criteria. The determination of trace metals present inenvironmental samples was done by flame AAS.In first part of the study, the method was optimised based on the MIBK/liquid-liquidextraction of the chelate complexes of heavy metals with 4-(4-methoxybenzoyl)-5-(4-methoxyphenyl)-2-phenyl-2,3-dihydro-1H-3-pyrazolone. As analytical parameters, thepH of sample solution, sample volume, ionic strength of the medium, shaking time,volume of MIBK, number of extraction stages, temperature effect and the effect ofmatrix ions etc. were investigated. At pH 8.5, sufficient recovery values were obtainedby using the MIBK/liquid-liquid extraction system for Ni(II), Cu(II), Co(II), Fe(III),Pb(II), Cd(II) and Mn(II) ions. The developed method was applied to drinking water,sea water, certified sea water (CRM-403), sediment and soil samples. The averagerecovery values and the relative standard deviations were in the range of 95-100% andviof 1.0-5.2%, respectively. The detection limits in the determinations with FAAS forCu(II), Ni(II), Co(II), Fe(III), Pb(II), Mn(II) and Cd(II) (3s/b, N=20) were found to be0.063, 0.018, 0.104, 0.087, 0.039, 0.059 and 0.049 Âµg L -1, respectively.In the second part of the study, the determination of the trace metals in environmentalsamples were performed by the liquid-liquid extraction method based on the formationof ion-pair complexes of metals with 2-(4-methoxybenzoyl)-N'-benzylidene -3-(4-methoxyphenyl)-3-oxo-N-phenyl-proponohydrazide. The recovery values were found tobe satisfactorily for Ni(II), Cu(II), Co(II), Fe(III), Mn(II), Pb(II), Cd(II), Zn(II) andCr(III) ions at pH 9.5. The relative standard deviations changed in the range of 0.5-3.2%.MIBK/2-(4-methoxybenzoyl)-N'-benzylidene -3-(4-methoxyphenyl)-3-oxo-N-phenyl-proponohydrazide /liquid-liquid extraction method was tested for the speciation ofchromium species by flame atomic absorption spectrometry. Cr(VI) was determinedafter reducing it to Cr(III) with NH 2OHÂ·HCl in acidic medium, while Cr(III) wasdetermined at pH 8.0. The method was applied to tap water, waste water and textilewaste water samples. The accuracy of the method was checked by recovery studies byadding analyte in known amounts. While the relative standart deviation of the methodwas found to be 2.4%, the detection limit was 0.5 Âµg L-1 according to the equation ofxblank + 3 sblank .In the last part of study, the applicability of chelate complexes of heavy metals with 4-acetyl-5-methyl-1-phenyl-1H-pyrazole-3-carboxylic acid as a new ligand was examinedby using liquid-liquid extraction method to enrich some trace elements. The quantitativerecoveries were obtained from the natural water and lake water samples for Pb(II),Ni(II), Fe(III), Cu(II), Cd(II), Mn(II) and Zn(II) elements by FAAS at pH 9.5. Therelative standart deviations were found to be in the range of 0.7-10.8%.Keywords: MIBK, Liquid -liquid extraction, Trace metals, Speciation, Pyrazolone,Proponohydrazide, Pyrazole -3-carboxylic acid, Water, Soil, Sediment sample.