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

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Abstract

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 H2O2 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 H2O. 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% H2O2 and 20 mass% H2O2 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 H2O (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).

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Abbreviations

A :

Frequency factor (s−1 M1−n)

E a :

Activation energy (kJ mol−1)

ΔH :

Heat of reaction (kJ mol−1)

R:

Gas constant (8.314 J mol−1 K−1)

s :

Specific heat (J g−1 K−1)

T A :

Corrected temperature of TBHP formulation under runaway reaction (K)

T A0 :

Corrected onset temperature of TBHP formulation under runaway reaction (K)

T M :

Measured temperature of TBHP formulation under runaway reaction (K)

T M0 :

Measured onset temperature of TBHP formulation under runaway reaction (K)

dT/dt :

Self-heat rate (°C min−1)

(dT/dt)A(ψ=1) :

Self-heat rate corrected to ψ = 1 (°C min−1)

(dT/dt)M(ψ>1) :

Measured self-heat rate at ψ > 1 (°C min−1)

ΔT AD(ψ=1) :

Adiabatic temperature rise corrected to ψ = 1 (K)

ψ :

Thermal inertia

A:

Adiabatic

AD:

Adiabatic

M:

Measured

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Acknowledgements

The authors wish to thank National Science Council, R.O.C., for financial support of this study under Contract No. NSC 101-2221-E-239-017-MY3.

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Authors and Affiliations

  1. Department of Occupational Safety and Health, Jen-Teh Junior College of Medicine, Nursing and Management, Miaoli, Taiwan

    Yih-Shing Duh

  2. Department of Safety Health and Environmental Engineering, National United University, Miaoli, Taiwan

    Yih-Shing Duh, Hsiang-Yu Kuo & Chen-Shan Kao

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  1. Yih-Shing Duh
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Correspondence to Chen-Shan Kao.

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Duh, YS., Kuo, HY. & Kao, CS. Characterization on thermal decompositions of tert-butyl hydroperoxide (TBHP) by confinement test. J Therm Anal Calorim 127, 1047–1059 (2017). https://doi.org/10.1007/s10973-016-5898-4

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