Journal of Thermal Analysis and Calorimetry

, Volume 96, Issue 3, pp 751–758 | Cite as

Hierarchical kinetic simulation for autocatalytic decomposition of cumene hydroperoxide at low temperatures

  • Jiann-Rong Chen
  • Shyh-Yuch Cheng
  • Min-Hao Yuan
  • Arcady A. Kossoy
  • Chi-Min ShuEmail author


A hierarchical set of kinetic models were proposed and discussed for simulation of autocatalytic decomposition of cumene hydroperoxide (CHP) in cumene at low temperatures. The hierarchy leads from a formal model of full autocatalysis, which is based on conversion degree as a state variable, through a two-stage autocatalytic concentration-based model to a meticulous multi-stage model of the reaction. By the ForK (Formal Kinetics) and DesK (Descriptive Kinetics) software, developed by ChemInform Saint Petersburg (CISP) Ltd., the related kinetic parameters and their significance have also been estimated and elucidated. Through this best-fit approach, it is possible to formulate a systematic methodology on the kinetic studies for thermal decomposition of typical organic peroxides with autocatalytic nature, specifically at low temperature ranges.


Autocatalytic decomposition Best-fit approach Cumene hydroperoxide (CHP) Kinetic parameters Meticulous multi-stage model 



Activation energy of the i stage, J mol−1


Activation energy of the i stage for model k, J mol−1


Frequency factor of the i stage, mol1−n/(Ln−1 s) = M1−n s−1


Frequency factor of the i stage for model k, mol1−n/(Ln−1 s) = M1−n s−1


Reaction order of i stage, dimensionless


Reaction order of i stage for the species j, dimensionless


Reaction order of i stage for model k, dimensionless


Reaction order of i stage for model k for the species j, dimensionless


Heat production, kJ/kg, kJ mol−1


Heat production rate, kJ min−1 kg −1

\( Q_{i}^{\infty } \)

Heat effect of i stage, kJ mol−1

\( Q_{ki}^{\infty } \)

Heat effect of i stage for model k, kJ mol−1


Gas constant (8.314), J mol−1 K−1


Reaction rate of i stage, mol (L s)−1 = M s−1


Reaction rate of i stage for model k, mol (L s)−1 = M s−1


Time to maximum rate under isothermal conditions, h


Temperature, °C, K


Time, min, h


Concentration of a species X, k mol m−3

Greek letters


Degree of conversion (range 0–1)


Rate of degree of conversion, 1 s−1



The authors are deeply grateful to Mr. A. M. Janeshek of The Dow Chemical Co., Freeport, Texas, USA for his valuable assistance and suggestions, and to Mr. V. Belokvostov of Russian Scientific Center Applied Chemistry for his immense help in evaluating kinetics.


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Copyright information

© Akadémiai Kiadó, Budapest, Hungary 2009

Authors and Affiliations

  • Jiann-Rong Chen
    • 1
    • 2
  • Shyh-Yuch Cheng
    • 3
  • Min-Hao Yuan
    • 4
  • Arcady A. Kossoy
    • 5
  • Chi-Min Shu
    • 2
    Email author
  1. 1.General EducationHsiuping Institute of TechnologyDaliTaiwan, ROC
  2. 2.Doctoral Program, Graduate School of Engineering Science and TechnologyNational Yunlin University of Science and TechnologyDouliouTaiwan, ROC
  3. 3.Department of Occupational Safety and HygieneChia-Nan University of Pharmacy and ScienceTainanTaiwan, ROC
  4. 4.Graduate Institute of Environmental EngineeringNational Taiwan UniversityTaipeiTaiwan, ROC
  5. 5.ChemInform Saint Petersburg (CISP) LtdSt. PetersburgRussia

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