方阱链流体状态方程的应用及其模型参数的理论预测

发布时间：2018-04-17 03:24

本文选题：COSMO + 状态方程　；参考：《华东理工大学》2015年硕士论文

【摘要】：流体的状态方程是计算物质热力学性质的主要工具,许多热力学性质如活度(逸度)系数、饱和蒸汽压、溶解度、密度等都可以通过状态方程计算得到。如何得到状态方程中的模型参数,特别是在不依赖实验数据的情况下预测出模型参数一直是热力学研究的重要课题之一。本文基于COSMO原理得到了各类有机化合物的变阱宽方阱链流体状态方程(SWCF-VR)的模型参数,并将模型参数应用到了纯流体有机物密度、二元有机混合物密度和相平衡计算中。最后考察了SWCF-VR方程在氨基酸水溶液的密度及氨基酸在水中的溶解度等热力学性质中的应用效果。将COSMO预测模型参数的方法(COSMO+SWCF-VR)应用到有机物模型参数的计算中,得到了烃类、卤代烃、酮、醚、酯、醇等192种有机化合物的模型参数。随后将得到的模型参数应用到纯流体有机化合物及其二元混合物密度的计算中,得到的直链烷烃、直链烯烃以及醇类密度的平均相对误差分别为0.23%、0.17%、2.05%,计算得到的烷烃与芳香烃混合密度的总平均偏差为0.47%。除此之外,将模型参数用来计算了二元有机物气液相平衡,计算时引入了一个与温度无关的二元相互作用参数kij后,得到恒压(恒温)条件下的系统中气相组成总的平均绝对偏差为3.08%。以上结果表明,COSMO方法获取的模型参数用来计算有机物的热力学性质是比较可靠的。为了考察SWCF-VR方程在缔合系统中的应用,将SWCF-VR应用到氨基酸水溶液热力学性质计算中,结合氨基酸水溶液的密度数据获得了17种氨基酸分子的模型参数。方程关联和预测氨基酸水溶液密度的总平均相对偏差分别为0.012%和0.43%,方程预测得到的四种氨基酸在水中溶解度的平均相对偏差分别为0.2%(甘氨酸)、0.30%(L-丙氨酸)、0.18%(L-精氨酸)和1.04%(L-脯氨酸)。预测结果令人满意。
[Abstract]:The state equation of fluid is the main tool to calculate the thermodynamic properties of matter. Many thermodynamic properties such as activity (fugacity) coefficient saturated vapor pressure solubility density and so on can be calculated by the equation of state.How to obtain the model parameters of the equation of state, especially the prediction of the model parameters without the dependence of experimental data, has been one of the important topics in thermodynamics research.Based on the COSMO principle, the model parameters of the fluid state equation of variable well wide square well chain (SWCF-VR) for various organic compounds are obtained, and the model parameters are applied to the calculation of the density of pure fluid organic matter, the density of binary organic mixture and the phase equilibrium.Finally, the application of SWCF-VR equation to the thermodynamic properties of amino acid aqueous solution, such as the density of amino acid solution and the solubility of amino acid in water, was investigated.COSMO SWCF-VR) was applied to the calculation of the model parameters of organic compounds, and the model parameters of hydrocarbons, halocarbons, ketones, ethers, esters, alcohols and other organic compounds were obtained.The obtained model parameters are then applied to the calculation of the density of pure fluid organic compounds and their binary mixtures.The average relative error of the density of alkenes and alcohols is 0.230.170.17 and 2.05, respectively. The total average deviation of the mixed density of alkanes and aromatic hydrocarbons is 0.47.In addition, the model parameters are used to calculate the gas-liquid equilibrium of binary organic compounds, and a temperature independent binary interaction parameter kij is introduced in the calculation.The total mean absolute deviation of gas composition in the system under constant pressure (constant temperature) is 3.08.The above results show that the model parameters obtained by the COSMO method are reliable for calculating the thermodynamic properties of organic compounds.In order to investigate the application of SWCF-VR equation in association system, SWCF-VR was applied to the calculation of thermodynamic properties of amino acid aqueous solution. The model parameters of 17 amino acid molecules were obtained by combining the density data of amino acid solution.The average relative deviations of the total mean relative deviations for the densities of amino acids in aqueous solution were 0.012% and 0.43%, respectively. The average relative deviations for the solubility of the four amino acids in water were 0.2% and 0.18% and 1.04%, respectively.The forecast results are satisfactory.
【学位授予单位】：华东理工大学
【学位级别】：硕士
【学位授予年份】：2015
【分类号】：TQ019

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