Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment
This study examined the thermal breakdown of Podocarpus falcatus oil (PFO) and its derived biodiesel (BPFO) under dynamic heating conditions. PFO and BPFO were characterized by spectroscopic, computational, and thermo-gravimetric analysis coupled with differential thermo-gravimetric analysis (TGA/DT...
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Elsevier
2025-06-01
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| Series: | Chemical Thermodynamics and Thermal Analysis |
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| Online Access: | http://www.sciencedirect.com/science/article/pii/S2667312625000124 |
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| author | Serges Bruno Lemoupi Ngomade Cyrille Donlifack Atemkeng Aymard Didier Tamafo Fouegue Cyrille Ghislain Fotsop Hilaire Tendongmo Théophile Kamgaing Solomon Gabche Anagho Neeraj Atray |
| author_facet | Serges Bruno Lemoupi Ngomade Cyrille Donlifack Atemkeng Aymard Didier Tamafo Fouegue Cyrille Ghislain Fotsop Hilaire Tendongmo Théophile Kamgaing Solomon Gabche Anagho Neeraj Atray |
| author_sort | Serges Bruno Lemoupi Ngomade |
| collection | DOAJ |
| description | This study examined the thermal breakdown of Podocarpus falcatus oil (PFO) and its derived biodiesel (BPFO) under dynamic heating conditions. PFO and BPFO were characterized by spectroscopic, computational, and thermo-gravimetric analysis coupled with differential thermo-gravimetric analysis (TGA/DTA). PFO and BPFO's kinetic and thermodynamic properties were examined using Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Starink isoconversional kinetic models. The conversion limit was restricted from 0.1 to 0.9 at different heating rates of 5, 7 and 10 °C.min−1. The FWO isoconversional model was properly fitted by the TGA/DTA analytical data, with the highest R2 values of 0.941. Average activation energies were 224.50 kJ.mol−1 for PFO and 108.60 kJ.mol−1 for BPFO. Nonspontaneous and endothermic thermal breakdown was confirmed by positive standard enthalpy (∆H) and standard Gibbs free energy(∆G) values. In contrast, the negative standard entropy (ΔS) indicated a more ordered process. Using density functional theory (DFT) in conjunction with the M05–2X hybrid functional, the computing study was conducted on the two most abundant FAMEs (Fatty acid methyl ester) to achieve the optimum geometry, topology analysis, and electronic properties. There was a good correlation between the computation and experimental results. This study showed that biodiesel's thermal and oxidation stability with regard to time could be accurately predicted using the TGA/DTA approach. |
| format | Article |
| id | doaj-art-027d86eeaf2d4762b5889c9fb5ce5bb4 |
| institution | DOAJ |
| issn | 2667-3126 |
| language | English |
| publishDate | 2025-06-01 |
| publisher | Elsevier |
| record_format | Article |
| series | Chemical Thermodynamics and Thermal Analysis |
| spelling | doaj-art-027d86eeaf2d4762b5889c9fb5ce5bb42025-08-20T03:10:39ZengElsevierChemical Thermodynamics and Thermal Analysis2667-31262025-06-011810017210.1016/j.ctta.2025.100172Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessmentSerges Bruno Lemoupi Ngomade0Cyrille Donlifack Atemkeng1Aymard Didier Tamafo Fouegue2Cyrille Ghislain Fotsop3Hilaire Tendongmo4Théophile Kamgaing5Solomon Gabche Anagho6Neeraj Atray7Research Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, Cameroon; Biofuel Division, CSIR-Indian Institute of Petroleum, Dehradun-248005, India; Corresponding authors.Research Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, Cameroon; Corresponding authors.Department of Chemistry, Higher Teacher Training College, The University of Bertoua, P. O. Box 652, Bertoua, CameroonResearch Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, Cameroon; Institute of Chemistry, Faculty of Process and Systems Engineering, Universitat ¨ Platz 2, Magdeburg 39106, GermanyResearch Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, CameroonResearch Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, CameroonResearch Unit of Noxious Chemistry and Environmental Engineering, Department of Chemistry, Faculty of Science, University of Dschang, Dschang, CameroonBiofuel Division, CSIR-Indian Institute of Petroleum, Dehradun-248005, India; Academy of Scientific and Innovative Research (AcSIR), Ghaziabad- 201002, India; Corresponding authors.This study examined the thermal breakdown of Podocarpus falcatus oil (PFO) and its derived biodiesel (BPFO) under dynamic heating conditions. PFO and BPFO were characterized by spectroscopic, computational, and thermo-gravimetric analysis coupled with differential thermo-gravimetric analysis (TGA/DTA). PFO and BPFO's kinetic and thermodynamic properties were examined using Kissinger-Akahira-Sunose (KAS), Flynn-Wall-Ozawa (FWO), and Starink isoconversional kinetic models. The conversion limit was restricted from 0.1 to 0.9 at different heating rates of 5, 7 and 10 °C.min−1. The FWO isoconversional model was properly fitted by the TGA/DTA analytical data, with the highest R2 values of 0.941. Average activation energies were 224.50 kJ.mol−1 for PFO and 108.60 kJ.mol−1 for BPFO. Nonspontaneous and endothermic thermal breakdown was confirmed by positive standard enthalpy (∆H) and standard Gibbs free energy(∆G) values. In contrast, the negative standard entropy (ΔS) indicated a more ordered process. Using density functional theory (DFT) in conjunction with the M05–2X hybrid functional, the computing study was conducted on the two most abundant FAMEs (Fatty acid methyl ester) to achieve the optimum geometry, topology analysis, and electronic properties. There was a good correlation between the computation and experimental results. This study showed that biodiesel's thermal and oxidation stability with regard to time could be accurately predicted using the TGA/DTA approach.http://www.sciencedirect.com/science/article/pii/S2667312625000124BiodieselDFTKineticsPodocarpous falcatus oilThermal decomposition |
| spellingShingle | Serges Bruno Lemoupi Ngomade Cyrille Donlifack Atemkeng Aymard Didier Tamafo Fouegue Cyrille Ghislain Fotsop Hilaire Tendongmo Théophile Kamgaing Solomon Gabche Anagho Neeraj Atray Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment Chemical Thermodynamics and Thermal Analysis Biodiesel DFT Kinetics Podocarpous falcatus oil Thermal decomposition |
| title | Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment |
| title_full | Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment |
| title_fullStr | Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment |
| title_full_unstemmed | Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment |
| title_short | Advanced characterization of biodiesel from Podocarpous falcatus oil via spectroscopy and DFT-based approaches: Thermal degradation kinetics and stability assessment |
| title_sort | advanced characterization of biodiesel from podocarpous falcatus oil via spectroscopy and dft based approaches thermal degradation kinetics and stability assessment |
| topic | Biodiesel DFT Kinetics Podocarpous falcatus oil Thermal decomposition |
| url | http://www.sciencedirect.com/science/article/pii/S2667312625000124 |
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