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通常认为化学反应系统中目的产物的最高产率是由热力学预计的平衡产率决定的。在同一反应条件下,目的产物的实际最高产率不能超过其平衡产率。本文提出了如下的新观点:对于复杂化学反应系统,必需区分两种平衡产率,一是潜平衡产率(PMEY),二是总平衡产率(GEY)。用化学热力学方法计算所得的平衡产率不是前者而是后者,反之,最高产率的热力学限度不是后者而是前者。目的产物的实际最高产率可以超过其总平衡产率,但不能超过其潜平衡产率。本文用改进的松弛法搜索了总平衡产率,用热力学分析法求得了潜平衡产率,用动力学方法计算了目的产物的实际峰值产率。例如,乙烷裂解反应系统于1300°K 进行反应,乙烯的总平衡产率为5.6×10~(-6),潜平衡产率为0.9745,总平衡产率为0.669(摩尔分率),由此说明了作者的新观点。
It is generally accepted that the highest yield of the target product in a chemical reaction system is determined by the equilibrium yield predicted by thermodynamics. Under the same reaction conditions, the actual highest yield of the target product can not exceed its equilibrium yield. In this paper, we propose the following new viewpoints: For complex chemical reaction systems, it is necessary to distinguish between two kinds of equilibrium yields, one is the subsidence yield (PMEY) and the second is the total equilibrium yield (GEY). The equilibrium yield calculated by the method of chemical thermodynamics is not the former but the latter. On the contrary, the thermodynamic limit of the highest yield is not the latter but the former. The actual highest yield of the product of interest may exceed its total equilibrium yield but not exceed its sub-equilibrium yield. In this paper, the improved equilibrium relaxation method was used to search the total equilibrium yield, and the equilibrium yield was obtained by thermodynamic analysis. The actual peak yield of the target product was calculated by kinetic method. For example, the ethane crack reaction system reacts at 1300 ° K with a total equilibrium yield of ethylene of 5.6x10 -6, a subloc balance of 0.9745, and a total equilibrium yield of 0.669 (molar fraction) from This illustrates the author’s new point of view.