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Thermal reactive hazards of 1,1-bis(tert-butylperoxy)cyclohexane with nitric acid contaminants by DSC

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Abstract

With two active O–O peroxide groups, 1,1-bis(tert-butylperoxy)cyclohexane (BTBPC) has a certain degree of thermal instability. It is usually used as an initiator in chemical processes, and therefore reckless operation may result in serious thermal accidents. This study focused on the runaway reactions of BTBPC alone and mixed with various concentrations of nitric acid (1, 2, 4, and 8 N). The essential thermokinetic parameters, such as exothermic onset temperature (T o), activation energy (E a), frequency factor (A), time to maximum rate under adiabatic condition (TMRad) and time to conversion limit (TCL), were evaluated by differential scanning calorimetry at the heating rate of 4 °C min−1, and a kinetics-based curve fitting method was used to assess the thermokinetic parameters. All the results indicated that BTBPC mixed with one more than 4 N nitric acid dramatically increased the degree of thermal hazard in the exothermic peak and became more dangerous. However, it was relatively safe for BTBPC mixed with less than 1 N nitric acid under 34.5 °C.

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Abbreviations

A :

Frequency factor of reaction (s−1 M1−n)

C p :

Specific heat capacity (J g−1 K−1)

E a :

Activation energy of reaction (kJ mol−1)

ΔHd :

Heat of decomposition (kJ kg−1)

k o :

Pre-exponential factor (s−1)

m :

Mass of reactant (g)

N :

Normality of nitric acid (eq mol−1)

n :

Order of reaction (dimensionless)

n i :

Reaction order of ith stage (dimensionless)

Q :

Total heat of decomposition (kJ kg−1)

r i :

Reaction rate of ith stage (g s−1)

r ij :

Reaction rate of ith stage of jth sub-stage (g s−1)

ΔTad :

Adiabatic temperature rise (°C)

TCL:

Time to conversion limit (day)

T max :

Maximum temperature at which the peak point occurs (°C)

TMRad :

Time to maximum rate under adiabatic condition (day)

T o :

Exothermic onset temperature of reaction (°C)

z :

Autocatalytic constant (variable)

α :

Degree of conversion (dimensionless, from 0 to 1)

β :

Heating rate of DSC experiment (°C min−1)

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Acknowledgements

The authors wish to express their gratitude to Dr. Arcady A. Kossoy of ChemInform Saint Petersburg (CISP), Ltd., St. Petersburg, Russia, for providing technical assistance. The authors would also like to thank Dr. Jo-Ming Tseng for valuable suggestions on experiments and the measurements of a runaway reaction.

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Authors and Affiliations

  1. Department of Safety, Health, and Environmental Engineering, Chung Hwa University of Medical Technology, 89, Wen-Hwa 1st St., Jen-Te, Tainan, 71703, Taiwan, ROC

    Kuang-Hua Hsueh

  2. Doctoral Program, Graduate School of Engineering Science and Technology, National Yunlin University of Science and Technology (NYUST), 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC

    Kuang-Hua Hsueh

  3. Department of Safety, Health, and Environmental Engineering, National Yunlin University of Science and Technology (NYUST), 123, University Rd., Sec. 3, Douliou, Yunlin, 64002, Taiwan, ROC

    Wei-Ting Chen, Yung-Chuan Chu, Lung-Chang Tsai & Chi-Min Shu

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  1. Kuang-Hua Hsueh
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  2. Wei-Ting Chen
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Correspondence to Chi-Min Shu.

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Hsueh, KH., Chen, WT., Chu, YC. et al. Thermal reactive hazards of 1,1-bis(tert-butylperoxy)cyclohexane with nitric acid contaminants by DSC. J Therm Anal Calorim 109, 1253–1260 (2012). https://doi.org/10.1007/s10973-012-2338-y

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  • DOI: https://doi.org/10.1007/s10973-012-2338-y

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