http://chineseinput.net/에서 pinyin(병음)방식으로 중국어를 변환할 수 있습니다.
변환된 중국어를 복사하여 사용하시면 됩니다.
헬륨기상에서 디알킬과산화물류의 열분해 반응에 대한 열역학적 특성값의 추산
이서용,신영조 ( Se Yong Lee,Young Jo Shin ) 한국화학공학회 1996 Korean Chemical Engineering Research(HWAHAK KONGHA Vol.34 No.5
The kinetics of the pyrolysis reaction over three kinds of dialkylperoxides were investigated at temperatures 353.15-453.15 K and at pressure 1013.3 hPa 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 7.482×10^(-3)s^(-1) for di-methyl peroxide(DMP), 7.980×10^(-3)s^(-1) for di-ethyl peroxide(DEP) and 3.l55×10^(-3)s^(-1) for di-tert-butyl peroxide(DTBP) at 453.15K. In addition, the pyrolysis reaction rate of dialkylperoxides were found to be apparently lst order over 3s3.1s K and its activation energies was determined by Arrhenius plot. From this results, the Arrhenius equations are as follows: k_(d. obsd) =3.079×10^(15) exp( -152.832kJ/8.314T) (DMP) k_(d. obsd) =7.938×10^(15) exp( -156.109kJ/8.314T)(DEP) k_(d. obsd) =7.568×10^(15) exp( -159.419kJ/8.314T)(DTBP) It has been also shown that the free energies of activation were 191.991 kJ㏖^(-1) for DMP, 198.836 kJ㏖^(-1) for DEP and 201.965 kJ㏖^(-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.