Characterization on thermal decompositions of tert-butyl hydroperoxide (TBHP) by confinement test

• Published in: Journal of thermal analysis and calorimetry 2017, Vol.127 (1), p.1047-1059
• Main Authors: Duh, Yih-Shing, Kuo, Hsiang-Yu, Kao, Chen-Shan
• Format: Article
• Language: English
• Subjects: Acetone; Adiabatic flow; Analysis; Analytical Chemistry; Butanol; Butyl hydroperoxide; Calorimetry; Chemistry; Chemistry and Materials Science; Exothermic reactions; Hydrogen peroxide; Hydroxyl radicals; Inorganic Chemistry; Measurement Science and Instrumentation; Nonanes; Physical Chemistry; Polymer Sciences; Pyrolysis; Solvent effect; Solvents; Thermal decomposition; Thermal properties; Thermal stability; Thermodynamic properties; Toluene
• ISSN: 1388-6150; 1588-2926; 1572-8943
• DOI: 10.1007/s10973-016-5898-4

Thermal decomposition of 20 mass% aqueous tert-butyl hydroperoxide (TBHP) is performed by confined apparatus as a model reaction. Inductive effects are verified by of hydroxyl and tert-butoxy radicals produced by the thermolysis of H 2 O 2 and di-tert-butyl peroxide (DTBP), respectively. Solvent effects are performed by 20 mass% TBHP in acetone, n-butyl alcohol, decane, nonane, Nujol, toluene and H 2 O. Thermodynamic and kinetic features, such as exothermic onset temperature, adiabatic temperature rise, maximum self-heat rate, maximum pressure and maximum temperature, are thus measured and utilized to characterize these mentioned influences. Hydroxyl radical is firstly discovered to possess the highest inductive effect on decomposition of TBHP. Exothermic onset temperature of 20 mass% aqueous TBHP is lowered from 146.0 ± 1.0 to 138.0 ± 2.0, 133.0 ± 0.0, 97 ± 8.8 and 89 °C by adding 10 mass% DTBP, 20 mass% DTBP, 10 mass% H 2 O 2 and 20 mass% H 2 O 2 relative to the mass of TBHP, respectively. The ranking of solvent effects on the thermal stability of solvated TBHP identified by exothermic onset temperature is arranged from high to low in the following: TBHP in toluene (178.5 ± 1.5 °C) > TBHP in decane (151.0 ± 2.0 °C) > TBHP in H 2 O (146.0 ± 1.0 °C) > TBHP in nonane (143.5 ± 2.5 °C) > TBHP in Nujol (138.5 ± 0.5 °C) > TBHP in acetone (128.0 ± 2.0 °C) > TBHP in n-BuOH (122.5 ± 3.5 °C).