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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
Article

Abstract

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.

Keywords

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

Nomenclature

Ei

Activation energy of the i stage, J mol−1

Eki

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

koi

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

kk0i

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

ni

Reaction order of i stage, dimensionless

nij

Reaction order of i stage for the species j, dimensionless

nki

Reaction order of i stage for model k, dimensionless

nkij

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

Q

Heat production, kJ/kg, kJ mol−1

dQ/dt

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

R

Gas constant (8.314), J mol−1 K−1

ri

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

rki

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

TMRiso

Time to maximum rate under isothermal conditions, h

T

Temperature, °C, K

t

Time, min, h

[X]

Concentration of a species X, k mol m−3

Greek letters

α

Degree of conversion (range 0–1)

dα/dt

Rate of degree of conversion, 1 s−1

Notes

Acknowledgments

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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