Yeni karbazit türevlerinin sentezi ve geçiş metalleri ile komplekslerinin termodinamik fonksiyonlarının incelenmesi
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Dosyalar
Tarih
1999-05-21
Yazarlar
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Dergi ISSN
Cilt Başlığı
Yayıncı
Selçuk Üniversitesi Fen Bilimleri Enstitüsü
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
Bu çalışmada l-(2,4-dinitrofenil)-4-fenil semikarbazit (DSK), l-(2,4-dinitrofenil)-4- fenil tiyosemikarbazit (DTSK), 4-fenil-l-[4-(triflorometil)fenil] semi-karbazit (FSK) ve 4- fenil-l-[4-(triflorometil)fenil] tiyosemikarbazit (FTSK) ilk defa sentezlendi ve metal kompleksleri hazırlandı. DSK'nın Cu(II), Ni(II), Co(II), Zn(II) ve Cd(II) metalleri ile, DTSK ve FTSK'nın Cu(II) hariç diğer metaller ile oluşturdukları 1 : 1 komplekslerinin termodinamik parametreleri 60:40 dioksan-su ortamında Bjerrum-Calvin pH titrasyon tekniği kullanılarak hesaplandı. Proton-ligand, logKf, ve metal-ligand, logK, kararlılık sabitleri hem Bjerrum'un hem de Irving-Rossotti'nin hesaplama metodlarına göre hesaplandı ve sonuçlar karşılaştırıldı. Her iki metodla bulunan değerlerin birbiriyle uyum içinde olduğu görüldü. Her bir sıcaklık için logK ile iyon şiddeti arasında çizilen lineer doğruların sıfır iyonik şiddete ekstrapole edilmesiyle termodinamik kararlılık sabitleri, logK°, bulundu. Her bir metal-ligand sistemi için logK° ile l/T arasında çizilen lineer doğrunun eğiminden AH° ve logK° eksenini kesim noktasından da AS0 değerleri hesaplandı. AG°=-2.3031ogK° eşitliğinden de AG° değerleri hesaplandı. Ayrıca proton-ligand sistemlerine ait termodinamik parametreler de benzer şekilde hesaplandı. Çalışmada elde edilen sonuçlara göre; semikarbazitlerin proton-ligand ve metal- ligand kararlılık sabitlerinin tiyosemikarbazitlerinkinden daha büyük olduğu tespit edildi.
In this study, firstly l-(2,4-dinitrophenyl)-4-phenyl semicarbazide (DSC), l-(2,4- dinitrophenyll)-4-phenyl thiosemicarbazide (DTSC), 4-phenyl-l-[4-(trifluoromethyl)phenyl] semicarbazide (PSC) and 4-phenyl-l-[4-(trifluoromethyl) phenyl] thiosemicarbazide (PTSC) have been synthesized and their metal complexes were prepared. The thermodynamic parameters for the 1:1 complexes of DSC with Cu(II), Ni(II), Co(II), Zn(II) and Cd(II), and 1:1 complexes of DTSC and PTSC with all those metals except Cu(II) have been calculated by the Bjerrum-Calwin pH method in the 60:40 dioxane-water medium. Proton-ligand, log K|*, and metal-ligand, logK, stability constants have been calculated by both Irving-Rossotti and Bjerrum methods and the results were compared. The results obtained from both methods are in good agreement with each other. For every temperature, thermodynamic stability constants, logK°, have been determined from the graph of logK versus ionic strength by extrapolating the lines at zero ionic strength. The graph of logK° versus 1/T was drawn, AH° values from the slope and AS0 values from the intercept have been calculated for each metal-ligand system. AG° values have been calculated from the equation, AG°=-2.303 logK0. Furthermore, thermodynamic parameters that on belong to proton-ligand system, have been calculated in the same way. According to the results obtained from this study, it has been determined that proton-ligand and metal-ligand stabilitiy constants of semicarbazides are bigger than the stability constants of thiosemicarbazides.
In this study, firstly l-(2,4-dinitrophenyl)-4-phenyl semicarbazide (DSC), l-(2,4- dinitrophenyll)-4-phenyl thiosemicarbazide (DTSC), 4-phenyl-l-[4-(trifluoromethyl)phenyl] semicarbazide (PSC) and 4-phenyl-l-[4-(trifluoromethyl) phenyl] thiosemicarbazide (PTSC) have been synthesized and their metal complexes were prepared. The thermodynamic parameters for the 1:1 complexes of DSC with Cu(II), Ni(II), Co(II), Zn(II) and Cd(II), and 1:1 complexes of DTSC and PTSC with all those metals except Cu(II) have been calculated by the Bjerrum-Calwin pH method in the 60:40 dioxane-water medium. Proton-ligand, log K|*, and metal-ligand, logK, stability constants have been calculated by both Irving-Rossotti and Bjerrum methods and the results were compared. The results obtained from both methods are in good agreement with each other. For every temperature, thermodynamic stability constants, logK°, have been determined from the graph of logK versus ionic strength by extrapolating the lines at zero ionic strength. The graph of logK° versus 1/T was drawn, AH° values from the slope and AS0 values from the intercept have been calculated for each metal-ligand system. AG° values have been calculated from the equation, AG°=-2.303 logK0. Furthermore, thermodynamic parameters that on belong to proton-ligand system, have been calculated in the same way. According to the results obtained from this study, it has been determined that proton-ligand and metal-ligand stabilitiy constants of semicarbazides are bigger than the stability constants of thiosemicarbazides.
Açıklama
Anahtar Kelimeler
Semicarbazide, Yarı karbazit, Thiosemicarbazide, Tiyosemikarbazit, Thermodynamics, Termodinamik, Potentiometric titration, Potansiyometrik titrasyon, Stability constant, Kararlılık sabiti, Transition metals, Geçiş metalleri
Kaynak
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Künye
Alpaydın, S. (1999). Yeni karbazit türevlerinin sentezi ve geçiş metalleri ile komplekslerinin termodinamik fonksiyonlarının incelenmesi. Selçuk Üniversitesi, Yayımlanmış doktora tezi, Konya.
