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Thermochimica Acta
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Article history: Study on chemical kinetics related to the thermal decomposition of cumene hydoperoxide (CHP) in
Received 18 February 2016 cumene is summarized in this work. It is of great importance to gather and compare the differences
Received in revised form 3 June 2016 between these kinetic parameters for further substantial applications in the chemical industry and pro-
Accepted 5 June 2016
cess safety. CHP has been veried to possess an autocatalytic behavior by using microcalorimetry (such
Available online 6 June 2016
as TAM and C-80) operated at isothermal mode in the temperature range from 70 C to 120 C. However,
it exhibits a reaction of n-th order detected by non-isothermal DSC scanning and adiabatic calorime-
Keywords:
ter. By the isothermal aging tests, activation energy and frequency factor in logA(s1 ) were averaged to
Organic peroxide
Cumene hydroperoxide
be (117.3 5.9) kJ mol1 and (11.4 0.3), respectively. Kinetic parameters acquired from data of inter-
Chemical kinetics laboratories by using heat-ow calorimetry, the averaged activation energy and frequency factor in
Thermal decomposition logA(s1 ) were (119.3 11.3) kJ mol1 and (12.0 0.2), respectively. On the analogy of results from adia-
Calorimetry batic calorimetry, the activation energy and frequency factor in logA(s1 ) were respectively averaged to
be (122.4 9.2) kJ mol1 and (11.8 0.8). Five sets of kinetic models in relation to autocatalytic reactions
are collected and discussed as well.
2016 Elsevier B.V. All rights reserved.
http://dx.doi.org/10.1016/j.tca.2016.06.003
0040-6031/ 2016 Elsevier B.V. All rights reserved.
Y.-S. Duh / Thermochimica Acta 637 (2016) 102109 103
Table 1
Kinetic parameters on thermal decompositions of CHP by isothermal methods.
Note: activation energy and frequency factor in logA are averaged to be 117.3 5.9 kJ mol1 and 11.4 0.3, respectively.
NA: Not available.
Table 2
Kinetic data for n-th order thermal decomposition of CHP by heat-ow calorimetry.
Concentration (mass%)/diluent Calorimeter/Methodology Scanning rate (K min1 ) Order (n) Eaa (kJ mol1 ) Log Ab (s1 ) Reference
Note: activation energy and frequency factor expressed in logA are averaged 119.3 11.3 kJmol1 and 12.0 0.2, respectively.
NA: Not available
a
Ea > 140.0 kJ mol and Ea < 00.0 kJ mol 1 are disregarded in averaged value.
b
logA > 14.0 and logA < 10.0 are disregarded in averaged value.
Table 3
Kinetic parameters on autocatalytic thermal decomposition of CHP determined by heat-ow calorimetry.
Concentration (mass%)/diluent LogA01 (s1 ) n1 Ea1 (kJ mol1 ) LogA02 (s1 M1n ) n2 Ea2 (kJ mol1 ) Reference
NA NA NA 120 12 NA NA NA [8]
1.85.4 M 9.25 0.1 1 108.5 0.1 8.67 0.1 1 97.2 0.0 [9]
88/cumene 6.086 0.638 48.682 19.2 n21 = 0.547, n22 = 1.295 180.176 [11]
80/cumene NA NA NA NA n21 = 0.5, n22 = 0.5 NA [12]
80/cumene 8.87 1.8 102.47 9.98 n21 = 4.02, n22 = 3.00 95.81 [13]
80/cumene 9.3 0.1 1 102.0 2.0 8.2 0.1 1 89.0 2.0 [14]
Note: the divergency in chemical kinetics of autocatalytic decompositions is too immense to be good for taking mean values.
NA: Not available.
Table 4
Rate equations proposed on autocatalytic thermal decomposition of CHP.
under the phi-factor approaching unity. Therefore, scientists con- the thermal runaway of CHP under the thermal inertia less than 1.2.
secrated to the following three approaches to solve the hindrances The thermal inertia of the reaction system has been improved to be
distorted by high thermal inertia. First, using large quantities of as low as 1.1 by a thin can made of stainless steel with a volume
diluted sample in ARC bomb was commonly adopted for lowering of 110 ml. The lower heat capacity of the cell assured the excellent
the phi value and overcoming the defect of phi-factor. The second adiabatic condition to perform the real runaway behavior within
way was to use the VSP or Phi-TECH instrument, in which a thin the test sample. Temperature, pressure and derivative data such as
cell with a maximum volume of 112 ml for holding sample about self-heat rate or adiabatic temperature rise under excellent ther-
50 ml, which cell had been capable of improving the phi-factor mal inertia can therefore be applied directly to process scale. Even
as low as 1.1. Third, some researchers established the theoretical realizing the importance of reducing the phi effect on the thermal
approaches to simulate thermal runaway for the energetic materi- decomposition of CHP, only a few exothermic decompositions of
als which could not be either diluted with solvent or used in large pure CHP were carried out by using adiabatic calorimeters.
quantity in adiabatic calorimeters [3032].
An adiabatic calorimeter with the enhanced capability of
improving thermal inertia, the Vent Sizing Package II (VSP II) man-
ufactured by Fauske and Associates Corp. [33] was used to measure
Y.-S. Duh / Thermochimica Acta 637 (2016) 102109 105
Table 5
Kinetic parameters on thermal decomposition of CHP determined by adiabatic calorimetry.
Concentration (mass%)/diluent Adiabatic calorimeter Thermal inertia Ordera (n) Ea b (kJ mol1 ) Log Ac (s1 M1n ) Reference
Note: activation energy and frequency factor in logA are averaged to be 122.4 9.2 kJ mol1 and 11.8 0.8, respectively.
NA: Not available
a
Order has been determined by the Arrhenius plot of ln k* versus 1/T using ARC theory.
b
Ea > 140.0 kJmol1 and Ea < 100.0 kJmol1 are disregarded in averaged value.
c
logA > 14.0 and logA < 10.0 are disregarded in averaged value.
d
DIB is the abbreviation of 2,2,4-trimethyl-1,3-pentaanediol diisobutyrate. Due to the different dynamics of H-abstraction and C C scission of cumyloxy radical in
addition to the induced decomposition of CHP proceeding in diverse solvents, these activation energies have not been adopted in the averaged activation energy.
2.5. Methodologies for acquiring kinetic parameters 2.6. Search for kinetic parameters on thermal decomposition of
CHP
2.5.1. Differential thermal analysis
By the dynamic scanning using DSC, the thermal curve of CHP Thermal curves identied by isothermal, non-isothermal and
decomposition appeared to be a simple curve. As a rule of thumb, adiabatic modes have been implemented in diversely interna-
this means that the thermal curve upon thermal decomposition tional laboratories. Concentrations of CHP solutions in cumene
of CHP must be a smoothly well-behaved one with nice conversion distributed from 12 mass% to about 82 mass%. Kinetic param-
versus temperature relation. Interferences of shoulders, overlapped eters searched from calorimetric studies were collected and
multiple peaks, shifts in baselines or discontinuous steps have not summarized. These kinetic results mainly determined by the com-
ever observed in thermal curves of CHP. Kinetic parameters in rela- mercial calorimeters such as DSC, TAM, ARC, RSST, C-80 and
tion to the thermal curve can be extracted by using a suitable kinetic VSP2. These laboratories had chosen methodology or software
model. Because of its simplest feature in thermal curve, method- package for analyzing the kineic parameters such as the method
ology of thermal safety software supplied by CISP (Cheminform St. of Flynn/Wall/Ozawa (ASTM E698) [34], method of Borchardt &
Petersburg Ltd., Russian) or thermal analysis methods (such as the Daniels (ASTM E2041) [24], method of model-free, Townsends the-
method of Flynn/Wall/Ozawa or the method of Borchardt & Daniels) ory (ASTM E1981) [29], Thermal safety software (TSS) [36] and
of DSC can be applied for determining the chemical kinetics on ther- Thermokinetics software (Advanced Kinetics and Technology Solu-
mal decomposition of CHP [24,3436]. These approaches provided tions, AKTS) [37]. Owing to the existed large discrepancy among
the efcacious procedures for determining activation energy, fre- kinetic parameters, a detailed inspection of these data was val-
quency factor and order of reaction by using differential thermal idated to discriminate the reasonable data from the published
analysis with excellent precision. kinetic parameters. A data judged to be acceptable or not was based
on the bias of individual parameter with an uncertainty compared
to the averaged value less than that recommended by ASTM E2041
2.5.2. Adiabatic calorimetry and townsends theory [24].
By using the adiabatic thermal curve, data analysis has based on
the assumption of the simple reaction scheme of one reactant. By 3. Results and discussion
obeying the Townsends theory in conjunction with the application
of adiabatic calorimeter, kinetic parameters on thermal decompo- 3.1. Chemical kinetics
sition of CHP can be deduced from self-heat rate (dT/dt) versus
reciprocal of the absolute temperature. Intrinsically, k is propor- 3.1.1. Isothermal methods
tional to self-heat rate (dT/dt) in rate equation. By the method of Applications of isothermal methodology for exploring the
trial and error, the plot of ln(k*) as a function of the reciprocal of exothermically autocatalytic reactions have been emphasized by
absolute temperature was used to identify the reaction order. A lin- the guidelines in ASTM E487 [3,4]. Autocatalytic decomposition of
ear tted line can thus be obtained by selecting a correct n, thereon energetic compound can be thus detected by the programmatic
Ea (kJ mol1 ) and A(s1 M1n ) will be explicitly determined by the isothermal mode within the heat-ow calorimeter. Isothermal
straight line of ln (dT/dt) vs. 1/T [28]. experiment keeping the excellent thermal equilibrium is of benet
106 Y.-S. Duh / Thermochimica Acta 637 (2016) 102109
Table 6
The proposed mechanism on thermal decomposition of CHP in cumene.
to eliminate the thermal lag effect. Thermal decomposition of CHP 3.1.2. n-th order reaction determined by heat-ow calorimetry
at temperature above 100 C behaved as a n-th order reaction. The Kinetic parameters on thermal decompositions of CHP in various
fact was judged from the thermal curve detected in the isothermal solutions studied by DSC or related methodology are depicted in
mode in DSC, i.e. the maximum peak power appeared at the ini- Table 2 [3,6,10,11,18,19]. Order of reaction equals 0.5 0.02 which
tial 0% conversion at the instant of isothermal test. Table 1 lists the has been delicately veried by means of calorimetry operated
kinetic parameters on thermal decompositions of CHP determined in isotherml and non-isothermal modes [3,4]. Activation ener-
by isothermal methods [3,4,8,10]. gies exhibit excellent agreement in the range between 120 and
126 kJ mol1 . Frequency factor expressed in logA is validated to
be about 11.7 0.5. Due to the analogous dissipating pathway of
cumyloxy radical liberated by the decomposition of CHP and DCPO,
Y.-S. Duh / Thermochimica Acta 637 (2016) 102109 107
logA should present a reasonable value in the range of 1114 [35]. Table 7
Kinetic parameters of CHP on n-th order thermal decompositions.
Recently, Reyes Valdes et al. studied the thermal decompositions
of DCPO solvated both in 2,2,4-trimethyl-1,3-pentanediol diisobu- CHP mass%/cumene Ea logA Methodology/Calorimetry
tyrate (DIB) and cumene with concentrations of 20, 30 and 40 (kJ mol1 ) (s1 M1n )
mass% by using adiabatic calorimetry [20,21]. The comparable fre- 2080 mass% 117.3 5.9 11.4 0.3 Isothermal tests
quency factors (in logA) were reported to be within the range of 35, 80 and 88 mass% 119.3 11.3 12.0 0.2 Heat-ow calorimetry
14.015.33 in addition to the activation energies were reported to 1280 mass% 122.4 9.2 11.8 0.8 Adiabatic calorimetery
chemistry on thermal decomposition of CHP in cumene is presented reactions. After excluding those less competitive elementary reac-
as follows: tions, a dominant reaction pathway was determined based on
ve elementary Reactions (1)(4) and (8). The overall reaction
C6 H5 C(CH3 )2 OOH C6 H5 C(CH3 )2 O + OH (1)
was balanced by the dominant elementary reactions as follows:
C6 H5 C(CH3 )2 O C6 H5 COCH3 + CH 3 (2) CHP + 2 cumene C6 H5 COCH3 + CH4 + H2 O + [C6 H5 C(CH3 )2 ]2 [17].
CH
The predicted reaction pathway also agreed with the available
C6 H5 C(CH3 )2 H + 3 C6 H5 C(CH3 )2 + CH4 (3) experimental results of methane and acetophenone. When the CHP
C6 H5 C(CH3 )2 H + OH
C6 H5 C(CH3 )2 + H2 O (4) concentration is lower than 40 mass%, the reaction followed the
proposed reaction pathway since cumene was sufcient in the
reaction system. Once the concentration exceeded this 40 mass%,
C6 H5 C(CH3 )2 O + C6 H5 C(CH3 )2 Reactions (3)(5) in the dominant pathway were no longer kineti-
cally competitive because of lack of cumene: Reactions (6) and (7)
H C6 H5 C(CH3 )2 OH + C6 H5 C(CH3 )2 (5) become active because radicals OH needed to be consumed [17].
Rado et al. had studied the kinetics of the induced reaction due
to the abstraction of hydroperoxy hydrogen atoms by cumyloxy
C6 H5 C(CH3 )2 O + OH CH3 COCH3 + C6 H5 OH (6a) radicals [39]. Eqs. (9) and (10) presented that the cumylperoxy
radical can be produced by the induced decomposition of CHP
C6 H5 C(CH3 )2 O CH3 COCH3 + C6 H5 (6b)
and cumyloxy radical. Two cumylperoxy radicals formed a dimeric
C6 H5 C(CH3 )2 + OH C6 H5 CH3 C = CH2 + H2 O (7) intermediate then completing the induced reaction by generating
a DCPO molecule and releasing an oxygen [46].
C6 H5 C(CH3 )2 + C6 H5 C(CH3 )2 [C6 H5 C(CH3 )2 ]2 (8a)
C6 H5 + C6 H5 [C6 H5 ]2 (8b) 3.3. Kinetic parameters on n-th order thermal decomposition of
CHP
CH3 + CH3 C2 H6 (8c)
4. Conclusions
[C6 H5 C(CH3 )2 O]2 2C6 H5 C(CH3 )2 O (11)
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Computational aspects of kinetic analysis Part A: the ICTAC kinetics