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Experimental study and theoretical analysis on decomposition mechanism of benzoyl peroxide

Jiayu Lv, Wanghua Chen * , Liping Chen, Haisu Gao, Yingtao Tian, Xin Sun Dept. of Safety Eng., Nanjing University of Science and Technology, Nanjing, Jiangsu, 210094, China

Abstract

Benzoyl peroxide (BPO), a source of radical used as initiator, is an important member in the organic peroxide family. To master its thermal characters, experimental study and theoretical analysis were employed on studying its decomposition mechanism. The autocatalytic process, which was deduced from dynamic experimental data by differential scanning calorimeter (DSC), was testified by isothermal DSC tests. Thermal scanning unit (TSU) was taken to predict pressure hazard of BPO

decomposition and accelerating rate calorimeter (ARC) tests were conducted to investigate the thermal behavior of BPO in adiabatic condition. The high pressure and fast pressure release rate indicated a high possibility of accompanied pressure hazard once the runaway decomposition was trigged. Combined with experimental results, quantum chemistry method was used to locate the most possible reaction path and calculate thermodynamic energies of BPO molecule in gas phase. The calculated total released heat during the whole decomposition was in good accordance with the values tested by thermal analysis instruments. And bond dissociation enthalpy (BDE) obtained at different theory levels provided a comparable value in runaway possibility analysis. Keywords: Benzoyl peroxide; Micro-calorimeter; Autocatalysis; Thermal analysis; Quantum chemistry

1. Introduction

Benzoyl peroxide (BPO) is widely used in fine chemistry industry as initiator because of its special structure. The free radicals provided by peroxy group ( -O-O-) in BPO play a crucial role in chemical transformations. Nevertheless, like a double -edged sword, thermal instability and explosion property were also brought [1,2]. Many countries ha ve suffered accidents due to BPO’s high sensitivities to heat, shock, impact and friction [3]. BPO decomposed with strong exothermic reaction and its kinetics was sensitive to temperature: not detectable at ambient temperature, but as soon as the temperature rises, the decomposition rate can quickly become important. Thus, the follow-up of such reactions seems to be practically impossible in calorimetric reactions because of the energy released during its realization [4]. Although several studies [5-8] have been done to detect the thermal behavior of BPO, most of them were focused on the usual kinetic methods which were based on nth reaction, or presented the experimental results without further mechanism analysis. Besides, papers which applied quantum chemistry method to calculate thermal ability of organic peroxide were less common. This paper tried to work out a comprehensive thermal evaluation of BPO. Differential scanning calorimeter (DSC), thermal scanning unit (TSU) and accelerating rate calorimeter (ARC) were employed to track the temperature histories and violent pressure during BPO’s decomposition, testing under dynamic, isothermal and adiabatic condition respectively. T hermal kinetic parameters such as activation energy E a and frequency factor A were calculated.

*

Corresponding author. Tel.: 0086-025-84315526-8005 E-mail address: chenwh_nust@163.com (Prof. Chen)

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Based on quantum chemistry, the optimized structures of BPO and its corresponding radicals were obtained using density-functional method (DFT) B3LYP and B3PW91 with the 6-31G(d) basis set. After analyzing related energies of the assumptive intermediates, we pointed out the most possible reaction route and presented overall reaction path to study the reaction mechanism. Then, peroxy group ’s gas-phase bond dissociation enthalpy BDE was calculated.

2. Experimental

2.1. Dynamic and isothermal modes by DSC

BPO, with a purity of 98%, was provided by Shanghai Lingfeng Chemical reagent co., LTD. DSC (DSC1, Mettler Toledo) conducted tests both in dynamic and isothermal modes with extra pure nitrogen purging (30mLmin -1 ). Stainless steel high pressure crucibles were used for the experiment. Sample masses in this work were around 2mg. Fig. 1 illustrated the heat flow versus temperature of BPO decomposition at various heating rate β (1, 2, 4 and 8 ºCmin -1 ) at the range of 30-200ºC. A sudden temperature rise appeared just following with a sharp endothermic peak due to fusion of BPO, which meant the decomposition of BPO overlapped with its fusion in dynamic mode. Because of this, the exothermic onset temperature T 0 was unable to accurately determine. However, the maximum temperature T p could be obtained directly by DSC dynamic scanning tests [9] and the heat of decomposition ΔH was calculated by DSC analysis software STARe, showed in Fig.1. And with the increase of β, the value of ΔH added except 8ºCmin -1 , which might due to stronger endothermic reaction during BPO’s fusion at a quick forced heating.

Based on quantum chemistry, the optimized structures of BPO and its corresponding radicals were obtained using

Fig. 1 Heat flow during DSC experiments on BPO at various heating rates

To estimate kinetic parameters, Kissinger method [10], presented as the following equation, was chosen.

ln

(

  • 2 )

i
i

β T

pi

=

ln AR E − E a a
ln AR E
− E
a
a

RT

pi

(i=1,2,…,6)

(1)

Where β is the heating rate, T p is the temperature maximum, A is the frequency factor, E a is the activation energy of the reaction, and R is the gas constant. By plotting of ln(β i /T 2 pi ) vs. 1/T pi (β=1, 2, 4 ºCmin -1 were chosen), which was expected to be a straight line, E a and lnA were calculated as 637kJmol -1 and 204s -1 with a correlation coefficient value of 0.9995 (Fig. 2).

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Fig. 2 Estimated Ea for BPO by Kissinger’s method The E mentioned above wa s apparent

Fig. 2 Estimated Ea for BPO by Kissinger’s method

The E a mentioned above wa s apparent activation energy. For E a between 220 and 1000kJmol -1 , the decompositions were of autocatalytic nature [11]. These types of reactions require d our special attention and should be clearly distinguished from nth order reactions because of their high hazards. The high values of steepness of the exothermal peak in Fig. 1 also indicated the great probability that this decomposition reaction was autocatalytic. Considering isothermal measurements were the most reliable way to detect and characterize an autocatalytic decomposition [12], we showed the thermal profiles of BPO in isothermal mode DSC in Fig. 3. Temperatures were set at 96ºC, 94ºC, 92ºC, 90ºC and 88ºC.

Fig. 2 Estimated Ea for BPO by Kissinger’s method The E mentioned above wa s apparent

Fig. 3 BPO decomposition in the isothermal condition

In Fig. 3, the heat flow passe d through a maximum exothermic peak after an induction period θ and then decreased again. And the higher the isothermal temperature was, the shorter the θ was gained. The corresponding θ were 17min, 30min, 55min, 100min and 180min respectively. Fig. 3 also indicated that as the temperature increased, the exothermic peak became sharper and had a poorer symmetry. At 88 and 90ºC, the DSC curves were symmetrical and identified as bell-shaped curve s, which confirmed that BPO decomposes in autocatalytic mechanism. From 92ºC, the curve symmetry decreased gradually because heat released in exothermic reaction was covered by decalescence in the beginning of reaction. From this phenomenon, we deduced that the fusion point of BPO was approximately from 90 to 92ºC. To estimate isothermal kinetic parameters of BPO, we employed the Prout-Tompkins model [13]:

k

+ → 2 B

AB

with

r =− dC

A

A

Fig. 2 Estimated Ea for BPO by Kissinger’s method The E mentioned above wa s apparent

dt = k C

C

AB

(2)

Where r is reaction rate, k is constant of reaction rate, t is time and C is concentration. In isothermal condition, r is proportional to C of the product. So the rate equation can express as a function of conversion α:

Fig. 2 Estimated Ea for BPO by Kissinger’s method The E mentioned above wa s apparent

dα dt

=

()

kC αα

A 0

1-

After integral, function below can be get:

ln α (1-α )  = kt + c

Fig. 2 Estimated Ea for BPO by Kissinger’s method The E mentioned above wa s apparent

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(3)

(4)

Where c is constant. By inserting the k values calculated in different temperatures into Arrhenius’ equation, E a and A was revealed as 191kJmol -1 and 4.18E25s -1 (Fig. 4).

Where c is constant. By inserting the k values calculated in different temperatures into Arrhenius’ equation,

Fig. 4 Kinetic parameters calculated with P -T model

2.2. Thermal scanning by TSU

DSC tests have presented a heat release details of BPO’s decomposition and pointed out its autocatalytic property. To understand both temperature and pressure histories during decomposition, 0.4g sample was added into a 316ss test bomb (8mL) for TSU (HEL in UK) scanning, and the ramp rate was 0.5°Cmin -1 . Temperature and pressure recorded was drawn in Fig. 5.

Where c is constant. By inserting the k values calculated in different temperatures into Arrhenius’ equation,

Fig. 5 Temperature and pressure histories of BPO by TSU

After an initial delay due to “thermal lagging” effects, the sample temperature was found to follow the oven ramp at the same rate with a slight offset. To get the exact T 0 value, we used iQ software to reduce the raw data and calculate dT/dt value, presented in Fig. 6. At 90°C, dT/dt started to drift from 0. The maximum dT/dt was above 220°Cmin -1 , and high pressure presented by TSU indicated that failures during manufacture or transportation might give rise to a pressure hazard and more attention should be paid.

Where c is constant. By inserting the k values calculated in different temperatures into Arrhenius’ equation,

Fig.6 Temperature rate vs. temperature of BPO by TSU

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2.3. Adiabatic test in ARC

Considering the case of an adiabatic runaway, test was further conducted by esARC (THT. UK). T he start temperature was 70°C based on results above and temperature step was 3°C. Temperature rate sensitivity was set 0.02°C·min -1 . Sample mass was 0.32g. Relationship between temperature, pressure and time was displayed in Fig. 7. For better analyzing, the temperature and pressure history during exothermal was zoomed in into Fig. 8.

2.3. Adiabatic test in ARC Considering the case of an adiabatic runaway, test was further conducted

Fig. 7 BPO decomposition in adiabatic condition

2.3. Adiabatic test in ARC Considering the case of an adiabatic runaway, test was further conducted

Fig. 8 Temperature and pressure of BPO’s decomposition during exothermal

T 0 of this decomposition was obtained as 94.3°C, and the rises of temperature and pressure were 38°C and 7bar respectively. The maximum value of dT/dt and dT/dt tested by ARC were above 150°C·min -1 and 16bar·min -1 (Fig. 9). Released heat after thermal inertia correction was 1120J·g -1 .

2.3. Adiabatic test in ARC Considering the case of an adiabatic runaway, test was further conducted

Fig. 9 Temperature and pressure rate vs. temperature of BPO by ARC

Within the tested temperature range, BPO had only one exothermic curve. The temperature remained stable during the induction period and suddenly increased sharply, which was different from the case of nth order reactions (dash line in Fig. 8). This was due to the fact that BPO’s autocatalytic reaction initially shows no or only a small heat release (with an onset temperature rate of 0.089°C·min -1 ). As stated by Manfred A. Bohn [ 14], the steeper the slope of the self-heat rate is the greater the part of autocatalytic decomposition, decomposition process of BPO showed a high autocatalytic feature from ARC test. Whilst, the delay of temperature increase leaded a later detection of runaway reaction until the reaction rate became sufficiently fast. If a temperature alarm wa s set as a design of emergency

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measure [15], it wa s not effective because there was no time left to take measures due to the sharp temperature increase.

3. Theoretical study

  • 3.1. Computational details

Density-functional quantum mechanical method, B3LYP [16] and B3PW91 [17,18] were employed to calculate the thermal energies for hemolytic cleavage of bonds which may break during BPO’s decomposition, with a basis set 6-31G(d) [19]. After that, two more basis sets and one more quantum chemical method were designated to calculate the O-O bond dissociation energy BDE(O-O) based on the molecular structures optimized with B3LYP/6-31G(d). The calculations were performed with the Gaussian 03 program package [20].

  • 3.2. Design of reaction path

Although for most organic peroxides, the decomposition reactions were regarded as taking up from the break of peroxy bond, the existence of benzoxy radical was controversial [21,22]. In this study, the reaction mechanism of BPO decomposition in gas phase is described below:

 

(C H CO)OO(COC H )

  • 6 →

5

6

5

1

2(C H CO)O

6

5

IM1

2

  • 6 →

5

6

5

(C H CO)OOCO

6

5

⋅+ ⋅

C H

6

5

(C H CO)OO(COC H ) (C H CO)OO(COC H )

  • 6 →

5

6

5

3

6

5

IM2

(C H CO)OO

 

⋅+

C H

6

5

IM5

CO

 

IM3

IM4

  • 3.3. Results and discussion

 

Table 1 Calculated energies of the five structures (Hartree)

 
 

BPO

IM1

IM2

IM3

IM4

 

IM5

B3LYP/6-31G(d)

-840.3435

-420.1517

-608.7362

-495.2962

 

-344.9206

 

-231.5613

B3PW91/6-31G(d)

-840.0171

-419.9878

-608.4948

-495.1032

-344.7850

-231.4719

 

6

/ 9

Geometries of the parent molecules and the corresponding radical (noted as IM1, IM2, Im3, IM4 and IM5) have been optimized at the theory levels, followed by a frequency calculation. To confirm that stationary points were minimum energy structures, vibration frequency was analyzed. Table 1 showed calculated energies E of the five structures, and the lower E values obtained by B3LYP illustrated that this method level gave more stable structures, presented in Fig. 10.

Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in ° ) In Fig.dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D (3,2,4,5), D (9,1,2,4) and D (2,4,5,6) were 0.0001, 179.9994 and -179.9503 ° , which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]: ∆ E =∆ E +∆ ZPE ∆ EE =∆ +∆ E +∆ E +∆ E ∆ H =∆ E +∆ RT Where E is original energy, E is electronic energy, ZPE is zero-point energy, E is thermal energy, E is vibrational energy, E is rotational energy, E is translation energy and H is thermal enthalpy. 0 0 elec vib rot trans Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol) Path 1 2 3 4 5 6 B3LYP/6-31G(d) Δ E 91.3359 100.4438 318.3944 17.2653 -455.4087 -329.5423 Δ E 89.1357 103.1244 317.2260 17.1340 -457.2124 -333.8087 Δ H 91.6142 105.6029 319.7045 19.6125 -459.6909 -328.8518 B3PW91/6-31G(d) Δ E 94.1084 110.3261 323.8423 16.1600 -457.0287 -330.6003 Δ E 92.0422 109.2024 322.7396 25.9788 -458.7903 -334.7906 Δ H 94.5206 111.6809 325.2181 18.4573 -461.2688 -329.8337 7 / 9 " id="pdf-obj-6-2" src="pdf-obj-6-2.jpg">
Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in ° ) In Fig.dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D (3,2,4,5), D (9,1,2,4) and D (2,4,5,6) were 0.0001, 179.9994 and -179.9503 ° , which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]: ∆ E =∆ E +∆ ZPE ∆ EE =∆ +∆ E +∆ E +∆ E ∆ H =∆ E +∆ RT Where E is original energy, E is electronic energy, ZPE is zero-point energy, E is thermal energy, E is vibrational energy, E is rotational energy, E is translation energy and H is thermal enthalpy. 0 0 elec vib rot trans Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol) Path 1 2 3 4 5 6 B3LYP/6-31G(d) Δ E 91.3359 100.4438 318.3944 17.2653 -455.4087 -329.5423 Δ E 89.1357 103.1244 317.2260 17.1340 -457.2124 -333.8087 Δ H 91.6142 105.6029 319.7045 19.6125 -459.6909 -328.8518 B3PW91/6-31G(d) Δ E 94.1084 110.3261 323.8423 16.1600 -457.0287 -330.6003 Δ E 92.0422 109.2024 322.7396 25.9788 -458.7903 -334.7906 Δ H 94.5206 111.6809 325.2181 18.4573 -461.2688 -329.8337 7 / 9 " id="pdf-obj-6-4" src="pdf-obj-6-4.jpg">
Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in ° ) In Fig.dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D (3,2,4,5), D (9,1,2,4) and D (2,4,5,6) were 0.0001, 179.9994 and -179.9503 ° , which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]: ∆ E =∆ E +∆ ZPE ∆ EE =∆ +∆ E +∆ E +∆ E ∆ H =∆ E +∆ RT Where E is original energy, E is electronic energy, ZPE is zero-point energy, E is thermal energy, E is vibrational energy, E is rotational energy, E is translation energy and H is thermal enthalpy. 0 0 elec vib rot trans Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol) Path 1 2 3 4 5 6 B3LYP/6-31G(d) Δ E 91.3359 100.4438 318.3944 17.2653 -455.4087 -329.5423 Δ E 89.1357 103.1244 317.2260 17.1340 -457.2124 -333.8087 Δ H 91.6142 105.6029 319.7045 19.6125 -459.6909 -328.8518 B3PW91/6-31G(d) Δ E 94.1084 110.3261 323.8423 16.1600 -457.0287 -330.6003 Δ E 92.0422 109.2024 322.7396 25.9788 -458.7903 -334.7906 Δ H 94.5206 111.6809 325.2181 18.4573 -461.2688 -329.8337 7 / 9 " id="pdf-obj-6-6" src="pdf-obj-6-6.jpg">
Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in ° ) In Fig.dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D (3,2,4,5), D (9,1,2,4) and D (2,4,5,6) were 0.0001, 179.9994 and -179.9503 ° , which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]: ∆ E =∆ E +∆ ZPE ∆ EE =∆ +∆ E +∆ E +∆ E ∆ H =∆ E +∆ RT Where E is original energy, E is electronic energy, ZPE is zero-point energy, E is thermal energy, E is vibrational energy, E is rotational energy, E is translation energy and H is thermal enthalpy. 0 0 elec vib rot trans Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol) Path 1 2 3 4 5 6 B3LYP/6-31G(d) Δ E 91.3359 100.4438 318.3944 17.2653 -455.4087 -329.5423 Δ E 89.1357 103.1244 317.2260 17.1340 -457.2124 -333.8087 Δ H 91.6142 105.6029 319.7045 19.6125 -459.6909 -328.8518 B3PW91/6-31G(d) Δ E 94.1084 110.3261 323.8423 16.1600 -457.0287 -330.6003 Δ E 92.0422 109.2024 322.7396 25.9788 -458.7903 -334.7906 Δ H 94.5206 111.6809 325.2181 18.4573 -461.2688 -329.8337 7 / 9 " id="pdf-obj-6-8" src="pdf-obj-6-8.jpg">
Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in ° ) In Fig.dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D (3,2,4,5), D (9,1,2,4) and D (2,4,5,6) were 0.0001, 179.9994 and -179.9503 ° , which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]: ∆ E =∆ E +∆ ZPE ∆ EE =∆ +∆ E +∆ E +∆ E ∆ H =∆ E +∆ RT Where E is original energy, E is electronic energy, ZPE is zero-point energy, E is thermal energy, E is vibrational energy, E is rotational energy, E is translation energy and H is thermal enthalpy. 0 0 elec vib rot trans Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol) Path 1 2 3 4 5 6 B3LYP/6-31G(d) Δ E 91.3359 100.4438 318.3944 17.2653 -455.4087 -329.5423 Δ E 89.1357 103.1244 317.2260 17.1340 -457.2124 -333.8087 Δ H 91.6142 105.6029 319.7045 19.6125 -459.6909 -328.8518 B3PW91/6-31G(d) Δ E 94.1084 110.3261 323.8423 16.1600 -457.0287 -330.6003 Δ E 92.0422 109.2024 322.7396 25.9788 -458.7903 -334.7906 Δ H 94.5206 111.6809 325.2181 18.4573 -461.2688 -329.8337 7 / 9 " id="pdf-obj-6-10" src="pdf-obj-6-10.jpg">

Fig. 10 B3LYP/6-31G(d) optimized structures (Bond distances in Å, bond angle in °)

In Fig. 10, the bond distances R and bond angle A were partly marked. For BPO, the experimental R(4,5) and R(1,2) were 1.45Å and 1.54Å [23], which proved the creditability of our calculated results. Fig.11 showed that the R, A and symmetry of IM1 to IM4 differed with these of BPO, which had a high symmetrical characteristic. Actually, advantages brought by optimized structures to study the properties of materials were more than this. For instance, dihedral angle s D of atoms illustrated the positional relation. In BPO, the calculated value s of D(3,2,4,5), D(9,1,2,4) and D(2,4,5,6) were 0.0001, 179.9994 and -179.9503°, which meant these atoms were almost coplane. To confirm the most possible reaction mechanism of BPO, the changed thermodynamic values between resultants and reactants were listed in Table 2. Equations used were showed as follows [24]:

E =∆E +∆ZPE EE =∆ +∆E +∆E +∆E H =∆E +∆ RT Where E 0 is original energy, E elec is electronic energy, ZPE is zero-point energy, E is thermal energy, E vib is vibrational energy, E rot is rotational energy, E trans is translation energy and H is thermal enthalpy.

0

0

elec

vib

rot

trans

Table 2 Thermodynamic calculations of the three reaction paths (298K, kJ/mol)

Path

1

2

3

4

5

6

B3LYP/6-31G(d)

ΔE 0

91.3359

100.4438

318.3944

17.2653

-455.4087

-329.5423

ΔE

89.1357

103.1244

317.2260

17.1340

-457.2124

-333.8087

ΔH

91.6142

105.6029

319.7045

19.6125

-459.6909

-328.8518

B3PW91/6-31G(d)

ΔE 0

94.1084

110.3261

323.8423

16.1600

-457.0287

-330.6003

ΔE

92.0422

109.2024

322.7396

25.9788

-458.7903

-334.7906

ΔH

94.5206

111.6809

325.2181

18.4573

-461.2688

-329.8337

Table 2 displayed that the change of thermodynamics parameters were in good consistency by both methods, and values of ΔE 0 , ΔE and ΔH were sequenced as path1 < path2 < path3. Thinking of this in thermodynamic way, path1 was the easiest reaction path for BPO’s decomposition. H. Fischer [25] described the NMR diagram when BPO decomposed in cyclohexanone, and the absorption spectrum of benzene was obtained. According to this, the reaction mechanism followed with path1 could be composed as:

(C H CO)O

6

5

4

⋅ →⋅

C H

65

+CO

2

2CH

6

5

5

→

CHCH

6

56

5

Therefore, the overall reaction path of decomposition reaction of BPO was concluded below:

6

(C H CO)OO(COC H ) → C H C H +2CO

6

5

6

5

6

56

5

2

The related energies were superadded to Table 2. Negative values listed in Table 2 illustrated that reaction path5, generation of biphenyl, was heat generating reaction. And the total heat released during the decomposition was calculated to be 333.8 and 334.8 kJ·mol -1 using the two different methods, equal to 1378 and 1382J·g -1 , which provided good convenience in dealing with hazardous evaluation of dangerous substances due to its approximate heat data compared to calorimetr y tests. Table 3 were BDE(O-O) values under different methods and basis sets. It was shown that with the increase of basis set, the BDE had a tendency of diminution. Limited by the hardware, higher basis sets were abandoned. However, due to the dipole and Π-Π affection in BPO molecule, polarization should be included. If considering the same basis set, B3LYP theory level was more accurate than MP2 method.

Table 3 BDE of O-O calculated with different methods (298K, kJ/mol)

 

B3LYP/6-31G(d)

B3LYP/6-31+G(d)

B3LYP/6-311G(d,p)

MP2/6-31+G(d)

BDE

105.2826

94.5180

89.7921

119.1977

4. Conclusions

The hazards of heat release and pressure generation were predicted by three micro -calorimeters under dynamic, isothermal and adiabatic modes. In dynamic DSC measurements, an endothermic process precedes the exothermic decomposition of BPO, which hindered the T 0 capture . By analyzing kinetic parameters using Kissinger method, we found this conversion affected method was not suitable for BPO’s autocatalytic decomposition. Therefore, based on isothermal results, E a and A was revealed as 191kJmol -1 and 4.18E25s -1 by P-T model and the fusion point of BPO was deduced approximately from 90 to 92ºC. T 0 obtained by TSU and ARC was 90 and 94.3°C, meanwhile, heat release rates and pressure generation observed in these experiments showed high possibility of thermal runaway. By applying quantum chemistry method on further mechanism study, the most possible reaction path of BPO’s decomposition was O-O bond dissociated into benzoxy radical according to calculation by Gaussian 03 software package. The total released heat was in good accordance between experimental calorimetr y and theoretical results. BDE(O-O) was calculated at B3LYP theory level and MP2 level with three different basis sets, and B3LYP method had a more accurate values.

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