Thermal decomposition of 3,6-diphenyl-1,2,4,5-tetroxane in nitromethane solution
The thermal decomposition reaction of benzaldehyde diperoxide (DFT; 0.001 mol L-1) in nitromethane solution studied in the temperature range of 130.0-166.0 °C, follows a first-order kinetic law up to at least 60% DFT conversion. The organic products observed were benzaldheyde and benzoic acid. A stepwise mechanism of decomposition was proposed where the first step is the homolytic unimolecular rupture of the O-O bond. The activation enthalpy and activation entropy for DFT in nitromethane were calculated (DH# = 106.3 ± 1.0 kJ mol-1 and DS# = -58.6 ± 1.1 J mol-1K-1) and compared with those obtained in other solvents to evaluate the solvent effect.
Noller DC, Bolton DJ. Safe Handling and Storage of Organic Peroxides in the Laboratory. Anal. Chem. 35: 887-893 (1963)
Cerna JR, Morales G, Eyler GN, Cañizo AI. Bulk Polymerization of Styrene Catalyzed by Bi- and Trifunctional Cyclic Initiators. J. Appl. Polym. Sci. 83: 1-11 (2002).
Bordón AG, Pila AN, Jorge MJ, Jorge LC, Profeta MI, Romero JM, Jorge NL. Kinetic of the Thermal Decomposition of Disubstituted Tetroxanes. International Journal of Current Research 8(10): 39788-39791 (2016).
Profeta MI, Romero JM, Jorge NL. Thermal Decomposition of Benzaldehyde Diperoxide on Isopropyl Alcohol, Effect of Solvent Polarity. Asian Journal of Science and Technology 6(10): 1928-1932 (2016).
Cusati RC. Síntese e fitotoxicidade de 1,2,4,5-tetraoxanos e análise estrutural de 1,2,4-trioxolanos. Doctoral thesis (2015)+
Bach RD, Ayala PY, Schlegel HB. A Reassessment of the Bond Dissociation Energies of Peroxides. An ab Initio Study. J. Am. Chem. Soc. 118: 12758-12765 (1996).
Reguera MB, Frette S, Profeta MI, Romero JM, Jorge NL, Castro EA. Thermolysis Reaction in Diperoxide and the Effect of Functional Groups. International Journal of Chemical Modeling, 5(4): 1-4 (2013)
Profeta MI, Romero JM, Leiva LCA, Jorge NL, Gómez Vara ME and Castro EA. Solvent effect of oxygen in the thermolisys decomposition of the acetone diperoxide. Meth. Appl. Chemoinf. Chem. Eng. 96(1–2): 110–122 (2011).
Jorge NL, Romero JM, Grand A, Hernández-Laguna A Gas phase thermolysis reaction of formaldehyde diperoxide. Kinetic study and theoretical mechanisms. Chem Phys 39:37–45 (2012)
Profeta MI, Romero JM, Jorge NL, Grand AA, Hernández-Laguna A Theoretical study of the gas-phase thermolysis of 3-methyl-1,2,4,5-tetroxane. International Journal of Chemical Modeling 20:2224-2226 (2014)
Copyright (c) 2018 JOURNAL OF ADVANCES IN CHEMISTRY
This work is licensed under a Creative Commons Attribution 4.0 International License.
Authors retain the copyright of their manuscripts, and all Open Access articles are distributed under the terms of the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided that the original work is properly cited.