高等学校化学学报 ›› 1987, Vol. 8 ›› Issue (12): 1091.
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杨第伦, 赵文轶, 刘有成
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Yang Dilun, Zhao Wenyi, Liu Youcheng
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摘要: 用膨胀计方法测定了2,3-二氰基-2,3-二苯基丁二酸二乙酯的内消旋体(1)和外消旋体(2),于不同反应温度,分别在泰乙烯中的分解动力学和活化参数。结果表明,2比1更为稳定。用动力学链长综合常数k′来解释了1和2在较低温度时的单体极限转化率X∞大于较高温度时的X∞实验结果。
Abstract: The kinetics of the thermal decomposition of rneso-(1) and dl-dieihyl-2,3-dicyano-2,3-diphenylsuccinatc(2) in styrene at different temperatures were studied by means of dilatometry. The activation parameters were found to be. Ed=93.2 + 3kJ·mol-1, △S≠=-12.7+1 eu for 1; Ed=120.8±3kJ·mol-1, △S≠= 1.8 ±1eu for 2. The conclusion is that the dl-isomer is more stable than the meso-isomer on the basis of the rate constant for the decompositions and the half life of the two isomers.An explanation is offered for the fact that the final conversion X∞ of 1 and 2 at lower temperature is larger than that of 1 and 2 at higher temperature in terms of the comprehensive constant k' of the kinetic chain length.
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杨第伦, 赵文轶, 刘有成. 内消旋和外消旋2,3-二氰基-2,3-二苯基丁二酸二乙酯在苯乙烯中的分解动力学. 高等学校化学学报, 1987, 8(12): 1091.
Yang Dilun, Zhao Wenyi, Liu Youcheng . A Kinetic Study on The Thermal Decomposition of meso-and di-Dietnyl 2,3-Dicyano-2,3-diphenylsuccinate in Styrene. Chem. J. Chinese Universities, 1987, 8(12): 1091.
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http://www.cjcu.jlu.edu.cn/CN/Y1987/V8/I12/1091