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Isothermal versus non-isothermal calorimetric technique to evaluate thermokinetic parameters and thermal hazard of tert-butyl peroxy-2-ethyl hexanoate

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Abstract

Liquid organic peroxides have been broadly employed in the process industries such as tert-butyl peroxy-2-ethyl hexanoate (TBPO). This study investigated the thermokinetic parameters of TBPO, a typical liquid organic peroxide, by isothermal kinetic algorithms and non-isothermal kinetic algorithms with thermal activity monitor III, and differential scanning calorimetry, respectively. An attempt has been made to determine the thermokinetic parameters by simulation software, such as exothermic onset temperature (T 0), maximum temperature (T max), decomposition (∆H d), activation energy (E a), self-accelerating decomposition temperature, and isothermal time to maximum rate (TMRiso). A liquid thermal explosion model was established for a reactor containing liquid organic peroxide of interest. From experimental results, liquid organic peroxides’ optimal conditions for avoiding a violent runaway reaction of storage and transportation were created.

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Abbreviations

A :

Frequency factor (s−1)

C p :

Heat capacity (J g−1 K−1)

E a :

Activation energy (kJ mol−1)

k :

Thermal conductivity (W m−1 K−1)

k 0 :

Reaction rate constant (min−1)

k i :

Reaction rate constant at isothermal temperature (min−1, i = 0, 1, 2, 3)

n i :

Reaction order of ith stage (dimensionless)

Q max :

Maximum heat flow (W g−1)

SADT:

Self-accelerating decomposition temperature (°C)

T :

Absolute temperature (K)

T 0 :

Exothermic onset temperature (°C)

T e :

Ambient temperature (°C)

T f :

Final temperature (°C)

T iso :

Isothermal temperature (°C)

T P :

Peak temperature (°C)

TMRiso :

Time to maximum rate under isothermal condition (h)

t :

Time (s)

Z :

Autocatalytic constant (dimensionless)

α i :

Degree of conversion (dimensionless)

β:

Heating rate (°C min−1)

∆H d :

Heat of decomposition (J g−1)

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Acknowledgements

The authors are indebted to Dr. J. M. Tseng for their technical assistance on this study.

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Authors and Affiliations

  1. Department of Safety Engineering, School of Chemical Engineering, Nanjing University of Science and Technology, 200, Xiao Ling Wei Street, Nanjing, 210094, China, PRC

    Lung-Chang Tsai

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

    Yun-Ting Tsai, Shang-Hao Liu & Chi-Min Shu

  3. Department of Health and Nutrition Biotechnology, College of Health Science, Asia University, 500, Lioufeng Rd., Wufeng, Taichung, 41354, Taiwan, ROC

    Chun-Ping Lin

  4. Department of Safety, Health, and Environmental Engineering, Hungkuang University, 34, Chung-Chie Rd., Shalu, Taichung, 43302, Taiwan, ROC

    Tsung-Chih Wu

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  1. Lung-Chang Tsai
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Correspondence to Chi-Min Shu.

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Tsai, LC., Tsai, YT., Lin, CP. et al. Isothermal versus non-isothermal calorimetric technique to evaluate thermokinetic parameters and thermal hazard of tert-butyl peroxy-2-ethyl hexanoate. J Therm Anal Calorim 109, 1291–1296 (2012). https://doi.org/10.1007/s10973-012-2519-8

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  • DOI: https://doi.org/10.1007/s10973-012-2519-8

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