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The first step of biodiesel autoxidation by differential scanning calorimetry and DFT calculations

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Abstract

The radical abstraction reaction of (bis)-allylic hydrogen in biodiesel fatty acid chains is the first step of autoxidation, being the rate-determining one. Some intrinsic features of the intermediary radicals can determine the oxidative stability (OS) under thermodynamic control. In the present study, some common fatty acid methyl esters present in biodiesel (stearate, oleate, ricinoleate, and linoleate) were oxidized in non-isothermal conditions, using differential scanning calorimetry, and the results were compared with quantum chemical calculations at the density functional theory level. The OS order (saturated > monounsaturated > polyunsaturated) was observed in both approaches (experimental and theoretical). A slight deviation observed between oleate and ricinoleate OS’s was explained based on their allylic radicals resonance and the influence of vicinal hydroxyl group. A linear relationship was found between oxidation temperature by pressurized differential scanning calorimetry and the calculated bond dissociation energy (C–H) for the first step of autoxidation.

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Acknowledgements

The authors would like to thank CAPES, CNPq, and FINEP for financial support. We also thank Professor Gerd Bruno Rocha for his valuable help on all calculations as well as discussions about theoretical results and Professor José Geraldo de Paiva Espíndola for evaluation of the final manuscript.

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Authors and Affiliations

  1. Departamento de Química, CCEN, UFPB, João Pessoa, PB, 58.059-970, Brazil

    Anderson dos Reis Albuquerque, Jefferson Maul, José Rodrigues Carvalho Filho, Iêda Maria Garcia dos Santos & Antônio Gouveia de Souza

  2. Departamento de Química e Biologia, CECEN, Universidade Estadual do Maranhão, São Luís, MA, Brazil

    Antônio Francisco Fernandes Vasconcelos

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  1. Anderson dos Reis Albuquerque
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  2. Jefferson Maul
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  3. Antônio Francisco Fernandes Vasconcelos
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  4. José Rodrigues Carvalho Filho
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  5. Iêda Maria Garcia dos Santos
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  6. Antônio Gouveia de Souza
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Correspondence to Anderson dos Reis Albuquerque.

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dos Reis Albuquerque, A., Maul, J., Vasconcelos, A.F.F. et al. The first step of biodiesel autoxidation by differential scanning calorimetry and DFT calculations. J Therm Anal Calorim 117, 799–806 (2014). https://doi.org/10.1007/s10973-014-3835-y

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  • DOI: https://doi.org/10.1007/s10973-014-3835-y

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