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通过亚硝酸酯作为中间体的CO气相催化氧化偶联制草酸酯及碳酸酯的反应体系是十分复杂的。体系内热力学可行的反应多达十几个。对每个反应而言,其热力学函数在较窄的温度范围内都可表达成:△H=AT+BT~2+CT~3+D;△G=-AT1nT+A′T-BT~2+B′T~3+D。本文利用PC-1500计算机,由文献值出发,得出了草酸二甲酯及碳酸二甲酯合成体系中各可能反应的△H、△G表达式中的各项系数值(298-500k)和相应温度区间内特定温度点各反应的△H、AG和Kp值。从计算结果得出,得到主产物高选择性的途径不仅是选择有效的催化剂,还要通过降低反应温度来控制副反应的发生。
The reaction system of oxalic acid ester and carbonate by gas phase catalytic oxidation of nitrite as an intermediate is very complicated. There are as many as a dozen thermodynamic feasible reactions in the system. For each reaction, the thermodynamic function can be expressed in a narrow temperature range: ΔH = AT + BT ~ 2 + CT ~ 3 + D; ΔG = -AT1nT + A’T-BT ~ 2 + B’T ~ 3 + D. In this paper, PC-1500 computer, starting from the value of the literature, obtained the oxalic acid dimethyl carbonate and dimethyl carbonate synthesis system in the reaction △ H, △ G expression of the coefficient values (298-500k) and △ H, AG and Kp values of each reaction at specific temperature in the corresponding temperature range. Obtained from the calculation results, the main route to obtain high selectivity is not only an effective choice of catalyst, but also by reducing the reaction temperature to control the incidence of side effects.