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Chemical kinetics on thermal decompositions of di-tert-butyl peroxide studied by calorimetry

An overview

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Abstract

An overview in the field of chemical kinetics on the thermal decomposition of di-tert-butyl peroxide (DTBP) has been performed in this study. Nowadays, DTBP has been a model compound for studying thermokinetics of organic peroxide and standardization of the DSC or adiabatic calorimeter. Thermal decompositions of DTBP in neat state or solution are conducted by heat flow or adiabatic calorimeters. Chemical kinetics on the thermal decomposition of DTBP obeyed n-th-order reaction and the type of Arrhenius equation. Order of reaction is first without any exception. DTBP in alkyl or aromatic hydrocarbon solvent behaves with excellent precision in activation energy with an averaged value of 157.0 (±4.1) and 159.7(±3.9) kJ mol−1 determined by DSC and adiabatic calorimeters, respectively. Frequency factors A (in s−1) in the form of logA are determined to be 15.8 (±1.1) and 16.3(±0.5) by DSC and adiabatic calorimeters, respectively. In the neat state of DTBP, activation energy and frequency factor in logA both possess the lower value of 128.4 (±6.2) kJ mol−1 and 12.2 (±0.8) determined by DSC. In ARC, these respective parameters are determined to be 142.0 (±17.7) kJ mol−1 and 15.5 (±1.3). Arrhenius parameters acquired from published literature with regard to the kinetics and mechanism on thermal decomposition of DTBP are summarized and discussed.

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Abbreviations

A :

Frequency factor [s−1 M1−n]

a,b,c :

Constant [dimensionless]

C p :

Heat capacity at constant pressure [kJ kg−1 K−1]

C pb :

Heat capacity of test bomb at constant pressure [kJ kg−1 K−1]

C ps :

Heat capacity of reactant at constant pressure [kJ kg−1 K−1]

D :

Bond dissociation energy [kJ mol−1]

E a :

Activation energy [kJ mol−1]

E 0 :

Activation energy in transition state theory [kJ mol−1]

ΔE a :

Activation energy difference between Hydrogen abstraction and β C–C scission [kJ mol−1]

e :

Natural exponential [dimensionless]

g(α):

A constant from the integral of kinetic model [dimensionless]

ΔH :

Heat of reaction [kJ kg−1]

ΔH 0≠ :

Enthalpy of activation

h :

Planck constant [6.6262 × 10−34 J s]

k :

Rate constant [s−1 M1−n]

k 2 :

Rate constant of recombination [s−1 M1−n]

k B :

Boltzmann constant [1.38 × 10−23 J K−1]

k D :

Rate constant of hydrogen abstraction from DTBP [s−1 M1−n]

k e :

Rate constant of ethane formation [s−1 M1−n]

k H :

Rate constant of hydrogen abstraction from solvent [s−1 M1−n]

k β :

Rate constant of β scission [s−1]

m b :

Mass of test bomb used in adiabatic calorimeter [kg]

m s :

Mass of reactant [kg]

n :

Order of reaction [dimensionless]

R :

Ideal gas constant [8.314 J g−1 K−1]

ΔS 0≠ :

Entropy of activation

T 0 :

Onset temperature of exothermic reaction [K]

T max :

Maximum temperature of exothermic reaction [K]

T p :

Temperature of maximum reaction rate [K]

T α :

Temperature at a specified degree of conversion [K]

ΔT AD :

Adiabatic temperature rise with the φ value of 1 [°C or K]

ΔT ad :

Adiabatic temperature rise with the φ value >1 [°C or K]

X i, Y i, Z i :

Constant of linear regression [dimensionless]

dH dt −1 :

Heat-releasing power [Ws−1]

dT dt −1 :

Self-heat rate [°C min−1]

α :

Degree of conversion [dimensionless]

β :

Heating rate of calorimeter [°C min−1]

ϕ :

Thermal inertia [dimensionless]

dαdt −1 :

Rate of conversion [dimensionless]

β :

β C–C scission

H:

Hydrogen abstraction

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Authors and Affiliations

  1. Department of Occupation Safety and Health, Jen-Teh Junior College of Medicine, Nursing, and Management, Miaoli, 35664, Taiwan

    Yih-Shing Duh

  2. Department of Safety, Health and Environmental Engineering, National United University, No. 1 Lien-Da, Miaoli, Taiwan

    Yih-Shing Duh & Chen-San Kao

  3. Department of Occupational Safety and Health, Chung-Shan Medical University, Taichung, Taiwan

    Wen-Lian William Lee

  4. Department of Occupational Medicine, Chung-Shan Medical University Hospital, Taichung, 40201, Taiwan

    Wen-Lian William Lee

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  1. Yih-Shing Duh
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Correspondence to Wen-Lian William Lee.

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Duh, YS., Kao, CS. & Lee, WL.W. Chemical kinetics on thermal decompositions of di-tert-butyl peroxide studied by calorimetry. J Therm Anal Calorim 127, 1071–1087 (2017). https://doi.org/10.1007/s10973-016-5859-y

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