氢-水同位素交换反应热力学理论研究

Thermodynamics Study on Hydrogen and Water Isotopic Exchange Reaction

摘要: 本文采用量子化学从头计算法对氢同位素分子及相应的氢同位素水分子进行了几何结构优化和振动频率计算，得到了6种氢水同位素交换体系的热力学函数和气相反应平衡常数。研究结果表明：平衡常数的理论计算值与实验结果吻合，在0.1 MPa和283.2～373.2 K的反应条件下，HD-H₂O体系平衡常数的计算值与实验值间相对偏差小于6%。

Abstract: Thermochemical quantities and equilibrium constants for six isotopic exchange reactions between hydrogen and water vapor were obtained through the geometrical optimization and vibration frequency calculations by ab initio. The results show that the calculated equilibrium constants of HD-H₂O isotopic reaction agree well with existing literature data within a reasonable relative deviation of less than 6% under the conditions of 283.2-373.2 K and 0.1 MPa.