Kinetic studies of acetophenone derivative oximes and investigation of thermal decomposition mechanism

Abstract

In this study, two acetophenone derivatives, isonitrosomethyl-p-tolyl ketone (L1) and isonitroso-p-chloroacetophenone (L2), were resynthesized, and their thermal decompositions were investigated kinetically and thermodynamically. Nitrogen gas (5, 10, 15 min flow rate) was used as an inert medium in the thermal decompositions of both ligands. Kinetic analyses were first performed independently of the model using Flynn Wall Ozawa (FWO) and Kissinger Akahira Sunose (KAS) methods, and the effective model in the progression of the reaction was examined by combining the FWO and KAS equations with the model equations together with the graphs of the variation of activation energies with the event fraction. The thermal breakdown processes of L1 and L2 occurred within 25 to 600°C. The effect of heating rate on the TG and DTG curves was studied. As the heating rate went up, so did the temperature needed for the synthetic chemical compounds to break down. The activation energies of the L1molecule, as determined by the KAS and FWO techniques, were 75.96 kJ∙mol-1 and 79.49 kJ∙mol-1, respectively. The computed values for the L2 molecule were 43.80 and 49.37 kJ∙mol-1, respectively.

Keywords

• Chemical Kinetic
• Acetophenone
• Thermogravimetry
• KAS
• FWO

Asetofenon türevi oksimlerin kinetik çalışmaları ve termal bozunma mekanizmasının incelenmesi

Öz

Bu çalışmada, iki adet asetofenon türevi olan izonitrosometil-p-tolil keton (L1) ve izonitroso-p-kloroasetofenon (L2) ligandları yeniden sentezlenerek kinetik ve termodinamik olarak termal bozunmaları incelenmiştir. Her iki ligandın termal bozunmalarında inert ortam olarak azot gazı (5, 10, 15 dak akış hızı) kullanılmıştır. Kinetik analizler ilk olarak modelden bağımsız olarak Flynn Wall Ozawa (FWO) ve Kissinger Akahira Sunose (KAS) yöntemleri kullanılarak, aktivasyon enerjilerinin olay kesriyle değişiminin grafikleri ile birlikte FWO ve KAS denklemlernini model denklemleriyle birleştirilmiş haliyle reaksiyonun ilerlemesinde etkin model incelenmiştir. İzonitrosometil-p-tolil keton (L1) ve izonitroso-p-kloroasetofenon (L2)’un termal bozunma basamakları 25 ila 600°C arasında gerçekleşti. Isıtma hızının TG ve DTG eğrileri üzerindeki etkisi incelendi. Isıtma hızı arttıkça, sentezlenen kimyasal bileşiklerin parçalanması için gereken sıcaklık da arttı. L1 molekülünün KAS ve FWO teknikleriyle belirlenen aktivasyon enerjileri sırasıyla 75,96 kJ∙mol-1 ve 79,49 kJ∙mol-1 idi. L2 molekülü için hesaplanan değerler sırasıyla 43,80 ve 49,37 kJ∙mol-1 dür.

Anahtar Kelimeler

• Kimyasal Kinetik
• Asetofenon
• Termogravimetri
• KAS
• FWO

Kaynakça

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