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Novel validation on pressure as a determination of onset point for exothermic decomposition of DTBP

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Abstract

Exothermic decomposition of di-tert-butyl peroxide (DTBP) was measured and assessed for determination of onset or threshold point which is essential for hazard evaluation or early detection of runaway reaction. Thermal decomposition of DTBP was conducted by differential scanning calorimeter and thermal scanning unit. Criteria of onset points are determined by and compared by the deflection curve of exothermic behavior (or heat flow), selected pressure, self-heat rate, or pressure-rising rate, respectively. Exothermic onset temperature of DTBP can be determined as low as 73.5 °C by pressure selected at 1.5 bar. Onset point determined by selected pressure is more sensitive and superior to the onset temperature traditionally measured by thermal analysis, adiabatic calorimetry using heat-wait-search methodology or theoretical approaches.

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Abbreviations

a :

Constant

b :

Constant

C :

Constant

C p :

Liquid specific heat at constant volume (kJ kg−1 °C−1)

ΔH rea :

Heat of reaction under reacting stage (kJ mol−1)

ΔH :

Overall heat of reaction (kJ mol−1)

k :

Rate constant (M1−n sec−1)

M g :

Molecular mass of gas (kg mol−1)

m g :

Mass of gas (kg)

n :

Order of reaction

Δn c :

Increase of moles of gases after and before decomposition by considering the corrected volume (mol)

dP/dt :

Pressure derivative with respect to time (bar min−1)

P g :

Gas pressure (bar)

P set :

Set pressure (bar)

P tot :

Total pressure (bar)

P V :

Vapor pressure (bar)

P max :

Maximum pressure measured in test bomb (bar)

ΔP :

Increase of pressure after and before decomposition (bar)

ΔP tot :

Pressure difference between final and initial state of reactant (bar)

\( \dot{Q} \) :

Heat flux (W g−1)

R :

Gas constant (8.314 J mol−1 K−1)

T :

Absolute temperature of system (K or °C)

T o :

Temperature of onset point (K or °C) (Traditional definition in thermal analysis, the temperature found by extrapolating the baseline and the leading side of the peak to their intersection)

T a :

Temperature of onset point (K or °C) (The temperature at which a deflection from the established baseline is first observed, with a signal-to-noise ratio at about 5 or heat flow larger than the sensitivity of the calorimeter)

T Mf :

Final measured temperature (K or °C)

T M0 :

Initial measured temperature (K or °C)

dT/dt :

Self-heat rate with respect to temperature or time (°C min−1)

(dT/dt)onset :

Self-heat rate at onset point (°C min−1)

V :

Volume of peroxide (m3)

V o :

Volume of test bomb (m3)

α:

Conversion

dα/dt :

Rate of conversion

Φ :

Thermal inertia

g:

Gas phase

max:

Maximum

v:

Vapor phase

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Author information

Authors and Affiliations

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

    Yih-Shing Duh, Wen-Fang Wang & Chen-Shan Kao

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

    Yih-Shing Duh

Authors
  1. Yih-Shing Duh
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  2. Wen-Fang Wang
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  3. Chen-Shan Kao
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Corresponding author

Correspondence to Chen-Shan Kao.

Appendix Chemical equations for the decomposition of DTBP

Appendix Chemical equations for the decomposition of DTBP

DTBP (stoichiometric decomposition)

$$ ({\text{CH}}_{3} )_{3} {\text{COOC}}({\text{CH}}_{3} )_{{3({\text{l}})}} \mathop{\longrightarrow}\limits^{\varDelta }2{\text{CH}}_{3} {\text{COCH}}_{{3({\text{l}})}} + {\text{C}}_{2} {\text{H}}_{{6({\text{g}})}} $$

DTBP (by GC/Mass) [12] (non- stoichiometric decomposition)

$$ 4{\text{DTBP}}\mathop{\longrightarrow}\limits^{\Delta }4\;{\text{acetone}} + 2\;{\text{isobutyleneoxide}} + {\text{methylethyl}}\;{\text{ketone}} + 2\;{\text{CH}}_{4} + {\text{C}}_{2} {\text{H}}_{6} $$

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Duh, YS., Wang, WF. & Kao, CS. Novel validation on pressure as a determination of onset point for exothermic decomposition of DTBP. J Therm Anal Calorim 116, 1233–1239 (2014). https://doi.org/10.1007/s10973-014-3690-x

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  • DOI: https://doi.org/10.1007/s10973-014-3690-x

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