p-toluidino-p-klorofenilglioksim ligandı ve bazı metal komplekslerinin termal davranışlarının incelenmesi ve normal koordinat analizi
Küçük Resim Yok
Tarih
1998
Yazarlar
Dergi Başlığı
Dergi ISSN
Cilt Başlığı
Yayıncı
Niğde Üniversitesi
Erişim Hakkı
info:eu-repo/semantics/openAccess
Özet
ÖZET p-TOLUİDİNO-p-KLOROFENİLGLİOKSİM LİGANDI VE BAZI METAL KOMPLEKSLERİNİN TERMAL DAVRANIŞLARININ İNCELENMESİ VE NORMAL KOORDİNAT ANALİZİ ARSLAN, Hakan Niğde Üniversitesi Fen Bilimleri Enstitüsü Kimya Ana Bilim Dalı Danışman: Prof. Dr. Necdet TARKAN Ortak Danışman: Yrd. Doç. Dr. Nilgün ÖZPOZAN Haziran- 1998, 146 sayfa p-Toluidino-p-klorofenilglioksim ligandı ve Co", Cu" ve Ni" komplekslerinin DTA/TG analizleri yapıldı. Ligand ve komplekslerin erime ile birlikte aynı anda pirolize uğradıkları; ligandın iki basamakta, komplekslerin ise üç basamakta piroliz olduğu; sonuçta ligandın gaz ürünler vererek ortamı tamamen terk ettiği; komplekslerin de metal oksitlerine (NiO, CtıO ve CoO) dönüştükleri belirlendi. DTA/TG ve GC-MS çalışmaları sonucunda ligandın farklı iki ayrı reaksiyon mekanizması üzerinden bozunduğu ve her iki mekanizmanın da iki farklı basamakta gerçekleştiği, ayrıca her iki bozunma mekanizmasında da ikinci basamakların aynı olduğu belirlendi. Karedüzlem yapıya sahip olan Ni" ve Cu11 komplekslerinin aynı mekanizma üzerinden üç basamakta bozunduğu ve sonuçta metal oksitlerinin kaldığı tespit edildi.Horowitz & Metzger ve Coats & Redfern kinetik yöntemleri kullanılarak piroliz reaksiyonlarının kinetik analizini yapabilen, QBASIC program dilinde "TERMAL Ver. 1.00" PC programı yazıldı, derlendi ve CaCO3 bileşiği ile programın doğruluğu test edildi. Program ile p-Toluidino-p-klorofenilglioksim Co11, Cu11 ve Ni11 komplekslerinin kinetik parametreleri (E*, AS*, n, A) hesaplandı. Sonuçta kompleksteki metal iyonlarının azalan yarıçaplarına bağlı olarak piroliz aktivasyon enerjisinin Co11, Ni" ve Cun sırasında artış gösterdiği tespit edildi. DTA analizlerinde görülen ürünlerin kararlılıklarından kaynaklanan ekzotermik pikleri doğrular nitelikte negatif değerli piroliz aktivasyon entropileri hesaplandı. Ligand ve kompleksler için Coats & Redfern ve Horowitz & Metzger kinetik yöntemleri yardımıyla çizilen grafiklerde, korelasyon katsayıları bire yakın değerler olarak bulundu. Reaksiyon derecelerinin, ligandta bir, şelatlarında ise her bir basamak için bire yakın değerlere sahip olduğu belirlendi. Ayrıca metal iyonlarının artan yarıçaplarına bağlı olarak bozunmanın başlangıç sıcaklığının daha düşük sıcaklıklara kaydığı tespit edildi. Ni" (453 K, rNİ:72 pm) > Cu" (383 K, rCu:70 pm) p-Toluidino-p-klorofenilglioksim bileşiği ile bu bileşiğin nikel ile yaptığı ML2 tipindeki (M: Nikel, L: p-Toluidino-p-klorofenilglioksim bileşiği) kompleksin FT İR spektrumları ölçüldü. Fluoresans nedeniyle Raman sinyalleri görülemeyen bileşiklere ait titreşim spektrumları SPSIM paket programı yardımıyla hesaplandı ve bilinmeyen bandlar simulasyon yöntemiyle aydınlatılmaya çalışıldı. Bileşiklerin geometrisi, her bir bağın uzunluğu, bağ açısı ve kuvvet sabiti gibi veriler kullanılarak frekanslar, atom yarıçapları; elektronegatiflikler kullanılarak da IR ve Raman aktiflikleri hesaplandı. Bileşiklere ait nokta grubu simetrileri üzerinden Normal Koordinat Analizleri yapıldı. Hesaplamalarda Wilson'un GF matris yöntemini temel alan programlarda, bileşiklere ait Değerlik Kuvvet Alanları (Valence Force Field), kuvvet sabit türü olarak seçildi.İncelenen bileşiklerin titreşim spektrumlarının hesaplanmasında asetonoksim, Klorobenzen, formaldoksim, trans-N-benzilidenanilin, N-metilasetamid, toluen, benzoik asit bileşiklerinden ve Ni-bis-dimetilglioksim kompleksinin kuvvet sabitlerinden faydalanıldı. Teorik olarak incelenen moleküllere ait titreşim spektrumları ile yine bu moleküllerin deneysel spektrumları karşılaştırıldı. Teorik hesaplanan spektrumlar yardımıyla, deneysel (gözlenen) titreşim spektrumlarındaki tüm bandlar yorumlandı. Kompleks oluşumuna bağlı olarak değişikliğe uğrayan bağların spektrumda gösterdiği değişiklikler özel olarak değerlendirildi. Her bir bileşiğin titreşim spektrumunu hesaplayabilen yeni değerlik kuvvet alanları (VFF) geliştirildi ve önceden yapılmış çalışmaların ışığında sonuçların geçerliliği tartışıldı. Anahtar Sözcükler: Oksim, Termal Davranışlar, Bozunma Kinetiği, DTA/TG Analizi, İR, Raman, Normal Koordinat, Normal Koordinat Analizi, Kuvvet Sabiti
VI SUMMARY INVESTIGATION OF THERMAL BEHAVIOURS AND NORMAL COORDINATE ANALYSIS OF p-TOLUTOINO-p-CHLOROPHENYLGLYOXIME AND SOME OF ITS METAL COMPLEXES ARSLAN, Hakan University of Niğde Graduate School of Natural and Applied Sciences Department of Chemistry Supervisor: Prof. Dr. Necdet TARKAN CO-Advisor: Assist. Prof. Dr. Nilgün ÖZPOZAN June- 1998, 146 pages DTA/TG analyses of p-Toluidino-p-chlorophenylglyoxime ligand and its Co, Cu and Ni complexes were performed. It was realized that the ligand pyrolysis is parallel to melting process. Ligand undergoes pyrolysis in two steps and the complexes undergo pyrolysis in three steps. At the end of the pyrolysis, ligand leaves the medium by transforming completely into gas products and the complexes were converted into their oxides (i.e. NiO, CuO, CoO). The ligand decomposes in two different ways undergoing a different reaction mechanism in each case. It was determined that both mechanisms took places in two steps and the second step was the same in each mechanism.VII Ni and Cu complexes both have squareplanar geometry and they both decomposes in three steps by the same mechanism. Their oxides were found to be the final decomposition products. A computer program was written in Quick Basic v.4.5 to perform kinetic analysis of pyrolitic reaction according to the methods of Coats-Redfern and Horowitz-Metzger. The accuracy of the program "TERMAL Ver. 1.00" was tested by using the precalculated kinetic data used for CaCC«3. The kinetic parameters (E*, AS*, n, A) of complexes of p-toluidino-p-chlorophenylglyoxime were calculated by the program. It was determined that pyrolitic activation energies of the complexes were increased in the order Co(II), Ni(II) and Cu(II) complexes inversely depending on the decreasing ionic radii of the metals. Negative activation entropies of the pyrolitic decomposition of complexes were calculated in DTA analyses supporting exothermic peaks originating from the stability of the products. The correlation coefficients of the curves of the ligand and the complexes plotted to calculate activation energy according to the methods of Coats-Redfern and Horowitz-Metzger were found nearly to be unity. The reaction order for the ligand is one and in case of complexes it was found to be closer to one in each step. Depending on the increasing ionic radii, it was found that the initial decomposition temperature for each complexes shifted to lower values. Nin (453 K, rNi:72 pm) > Cun (383 K, rCu:70 pm)) In the part of the vibrational analysis, the FT IR spectra of both p-toluidino-p- chlorophenylglyoxime ligand and its Ni complex in the form of ML2 (Where M:Ni, L:p-toluidino-p-chlorophenylglyoxime ligand) were recorded. Due to the photo luminescence, the Raman spectra excited with Ar ion LASER could not be obtained. Theoretical spectra were calculated by the program package SPSIM and a complete assignment for the vibrational spectra were made.VIII Vibrational frequencies were calculated from the geometrical parameters, atomic masses and force constants as input data. The IR and Raman activities were calculated from atomic radii, electronegativities of the atoms of the compounds. Group theory for the point group phenomena was employed for the Normal Coordinate Analysis of both compounds. The programs used in the calculations use valence force field type potential energy function based on the Wilson' GF matrix method. To calculate the vibrational spectra of the ligand and the complexes, the force constants and the geometrical parameters were transferred partly from the compounds; acetonoxime, chlorobenzene, formaldoxime, trans-N-benzilydeneaniline, N-methylacetamid, toluene, benzoic acid and Ni-bis- dimethylglyoxime. The calculated spectra were examined in relation to the observed spectra of the molecules from which the input data transferred. By the aid of calculated spectra, the vibrational bands in the experimental spectra were assigned. The discussion was focused on the bonds which undergo changes during the formation of complex. New valence force fields were developed for both compounds and the validity of them were discussed taking the previous studies into account. Key Words: Oxim, Thermal Behaviour, Kinetic, DTA/TG Analysis, IR, Raman, Valence Force Field, Normal Coordinate, Normal Coordinate Analysis, Force Constant
VI SUMMARY INVESTIGATION OF THERMAL BEHAVIOURS AND NORMAL COORDINATE ANALYSIS OF p-TOLUTOINO-p-CHLOROPHENYLGLYOXIME AND SOME OF ITS METAL COMPLEXES ARSLAN, Hakan University of Niğde Graduate School of Natural and Applied Sciences Department of Chemistry Supervisor: Prof. Dr. Necdet TARKAN CO-Advisor: Assist. Prof. Dr. Nilgün ÖZPOZAN June- 1998, 146 pages DTA/TG analyses of p-Toluidino-p-chlorophenylglyoxime ligand and its Co, Cu and Ni complexes were performed. It was realized that the ligand pyrolysis is parallel to melting process. Ligand undergoes pyrolysis in two steps and the complexes undergo pyrolysis in three steps. At the end of the pyrolysis, ligand leaves the medium by transforming completely into gas products and the complexes were converted into their oxides (i.e. NiO, CuO, CoO). The ligand decomposes in two different ways undergoing a different reaction mechanism in each case. It was determined that both mechanisms took places in two steps and the second step was the same in each mechanism.VII Ni and Cu complexes both have squareplanar geometry and they both decomposes in three steps by the same mechanism. Their oxides were found to be the final decomposition products. A computer program was written in Quick Basic v.4.5 to perform kinetic analysis of pyrolitic reaction according to the methods of Coats-Redfern and Horowitz-Metzger. The accuracy of the program "TERMAL Ver. 1.00" was tested by using the precalculated kinetic data used for CaCC«3. The kinetic parameters (E*, AS*, n, A) of complexes of p-toluidino-p-chlorophenylglyoxime were calculated by the program. It was determined that pyrolitic activation energies of the complexes were increased in the order Co(II), Ni(II) and Cu(II) complexes inversely depending on the decreasing ionic radii of the metals. Negative activation entropies of the pyrolitic decomposition of complexes were calculated in DTA analyses supporting exothermic peaks originating from the stability of the products. The correlation coefficients of the curves of the ligand and the complexes plotted to calculate activation energy according to the methods of Coats-Redfern and Horowitz-Metzger were found nearly to be unity. The reaction order for the ligand is one and in case of complexes it was found to be closer to one in each step. Depending on the increasing ionic radii, it was found that the initial decomposition temperature for each complexes shifted to lower values. Nin (453 K, rNi:72 pm) > Cun (383 K, rCu:70 pm)) In the part of the vibrational analysis, the FT IR spectra of both p-toluidino-p- chlorophenylglyoxime ligand and its Ni complex in the form of ML2 (Where M:Ni, L:p-toluidino-p-chlorophenylglyoxime ligand) were recorded. Due to the photo luminescence, the Raman spectra excited with Ar ion LASER could not be obtained. Theoretical spectra were calculated by the program package SPSIM and a complete assignment for the vibrational spectra were made.VIII Vibrational frequencies were calculated from the geometrical parameters, atomic masses and force constants as input data. The IR and Raman activities were calculated from atomic radii, electronegativities of the atoms of the compounds. Group theory for the point group phenomena was employed for the Normal Coordinate Analysis of both compounds. The programs used in the calculations use valence force field type potential energy function based on the Wilson' GF matrix method. To calculate the vibrational spectra of the ligand and the complexes, the force constants and the geometrical parameters were transferred partly from the compounds; acetonoxime, chlorobenzene, formaldoxime, trans-N-benzilydeneaniline, N-methylacetamid, toluene, benzoic acid and Ni-bis- dimethylglyoxime. The calculated spectra were examined in relation to the observed spectra of the molecules from which the input data transferred. By the aid of calculated spectra, the vibrational bands in the experimental spectra were assigned. The discussion was focused on the bonds which undergo changes during the formation of complex. New valence force fields were developed for both compounds and the validity of them were discussed taking the previous studies into account. Key Words: Oxim, Thermal Behaviour, Kinetic, DTA/TG Analysis, IR, Raman, Valence Force Field, Normal Coordinate, Normal Coordinate Analysis, Force Constant
Açıklama
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Fen Bilimleri Enstitüsü, Kimya Ana Bilim Dalı
Fen Bilimleri Enstitüsü, Kimya Ana Bilim Dalı
Anahtar Kelimeler
Kimya, Chemistry
