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HWAHAK KONGHAK,
Vol.34, No.5, 592-596, 1996
Vol.34, No.5, 592-596, 1996
헬륨기상에서 디알킬과산화물류의 열분해 반응에 대한 열역학적 특성값의 추산
Estimation of Thermodynamic Properties on the Pyrolysis of Dialkyl Peroxides in the Helium Gas
3종류의 디알킬과산화물에 대한 열분해 반응속도를 온도 353.15-453.15K, 1013.3hPa의 조건에서 단열봄메열량계를 사용하여 저압 열분해법(very-low-pressure pyrolysis technique : VLPP)에 의해 기체헬륨 분위기하에서 측정하였다. 453.15K에서의 속도상수는 과산화디메틸은 7.482 X 10-3 s-1, 과산화디에틸은 7.980 X 10-3s-1 그리고 과산화디제3부틸은 3.155 X 10-3s-1이었다. 아울러 온도 353.15K이상에서 디알킬과산화물류의 열분해 반응은 외관상 1차로 진행하였으며 Arrhenius plot를하여 다음과 같이 활성화에너지를 구하였다.
kd,obsd=3.079 X 1015 exp (-152.832kJ/8.314T) (과산화디메틸)
kd,obsd=7.938 X 1015 exp (-156.109kJ/8.314T) (과산화디에틸)
kd,obsd=7.568 X 1015 exp (-159.419kJ/8.314T) (과산화디제3부틸)
또한 453.15K에서의 활성화 자유에너지는 과산화디메틸은 191.991kJmol-1, 과산화디에틸은 198.836kJmol-1 그리고 과산화디제3부틸은 201.965kJmol-1이었다. 이것들로부터 디알킬과산화물류의 산소-산소 결합의 열분해 활성화 에너지와 활성화 자유에너지는 과산화디메틸<과산화디에틸<과산화디제3부틸의 순서로 증가함을 알았다. 이러한 연구결과들은 디알킬과산화물류의 효율적인 산업응용이나 합리적인 안전관리에 이용될 수 있다.
kd,obsd=3.079 X 1015 exp (-152.832kJ/8.314T) (과산화디메틸)
kd,obsd=7.938 X 1015 exp (-156.109kJ/8.314T) (과산화디에틸)
kd,obsd=7.568 X 1015 exp (-159.419kJ/8.314T) (과산화디제3부틸)
또한 453.15K에서의 활성화 자유에너지는 과산화디메틸은 191.991kJmol-1, 과산화디에틸은 198.836kJmol-1 그리고 과산화디제3부틸은 201.965kJmol-1이었다. 이것들로부터 디알킬과산화물류의 산소-산소 결합의 열분해 활성화 에너지와 활성화 자유에너지는 과산화디메틸<과산화디에틸<과산화디제3부틸의 순서로 증가함을 알았다. 이러한 연구결과들은 디알킬과산화물류의 효율적인 산업응용이나 합리적인 안전관리에 이용될 수 있다.
The kinetics of the pyrolysis reaction over three kinds of dialkylperoxides were investigated at temperatures 353.15-453.15 K and at pressure 1013.3hPa in the modified adiabatic bomb calorimeter. The pyrolysis reaction has been carried out using the very-low-pressure pyrolysis technique(VLPP) in the presence of helium gas. The pyrolysis reaction rate constants were determined to be 7.482 X 10-3s-1 for di-methyl peroxide(DMP), 7,980 X 10-3s-1 for di- ethyl peroxide(DEP) and 3.155 X 10-3s-1 for di-tert-butyl peroxide(DTBP) at 453.15K. In addition, the pyrolysis reaction rate of dialkylperoxides were found to be apparently 1st order over 353.15K and its activation energies was deter- mined by Arrhenius plot. From this results, the Arrhenius equations are as follows:
kd,obsd=3.079 X 1015 exp (-152.832kJ/8.314T) (DMP)
kd,obsd=7.938 X 1015 exp (-156.109kJ/8.314T) (DEP)
kd,obsd=7.568 X 1015 exp (-159.419kJ/8.314T) (DTBP)
It has been also shown that the free energies of activation were 191.991kJmol-1 for DMP, 198.836kJmol-1 for DEP and 201.965kJmol-1 for DTBP at 453.15K. Therefore, the activation energies and free energies of activation for the O-O bond dissociation of dialkylperoxides were found to be increased in the order of DMP<DEP<DTBP from the reaction system. This results can be used to develop an industrial application process aiming for high productivity and rational safety guard.
kd,obsd=3.079 X 1015 exp (-152.832kJ/8.314T) (DMP)
kd,obsd=7.938 X 1015 exp (-156.109kJ/8.314T) (DEP)
kd,obsd=7.568 X 1015 exp (-159.419kJ/8.314T) (DTBP)
It has been also shown that the free energies of activation were 191.991kJmol-1 for DMP, 198.836kJmol-1 for DEP and 201.965kJmol-1 for DTBP at 453.15K. Therefore, the activation energies and free energies of activation for the O-O bond dissociation of dialkylperoxides were found to be increased in the order of DMP<DEP<DTBP from the reaction system. This results can be used to develop an industrial application process aiming for high productivity and rational safety guard.
Keywords:
Pyrolysis; Dialkyl Peroxides; Very-Low-Pressure Pyrolysis Technique(VLPP); Arrhenius Equations; Thermodynamic Properties
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