【作者】 高慧；

【导师】 阎卫东；

【作者基本信息】 浙江大学 ， 化学， 2011， 博士

【摘要】 过量焓HE即混合热,是非常重要的溶液热力学性质,反映了液体混合物偏离理想溶液的程度,是衡量溶液非理想性的主要标志之一溶液过量焓的测定数据在化工设计和生产中应用十分广泛。在实际应用过程中,由于气相组成很难测定准确,导致汽液平衡数据非常不准确,尤其是当其中一个组分易挥发或两者的沸点相差很大的时候更是如此。这时,溶液过量焓数据的测定就显得尤为重要和必要。通过过量焓数据就可以推算活度系数、计算汽液平衡、液液平衡的数据；还可以检验等压汽液平衡的热力学一致性,从而大大减少工作量。本论文的主要内容如下：论文的第一章为绪论部分,简要介绍了相关的基本理论,对国内外的研究现状进行了概述；介绍了相关的理论模型和理论计算方法；阐述了本文研究的主要内容和方法。第二章是过量焓实验数据的测定。通过CSC4400型流动混合微热量热仪测量了一系列的酯醇混合体系不同温度下的过量焓数据,经过理论模型处理数据后,可以推断出过量焓随摩尔分数、温度、碳链长短变化的变化关系。第三章和第四章是理论研究部分。为了更好地解释过量焓所反映出的实验现象,用量化计算常用软件进行了更深入的量子化学计算研究。尝试从分子间的相互作用和电荷分布这两个不同的层面来解释不同体系混合溶液产生热量的不同,并在此基础上进行预测计算。希望能探索出更适合工业需要的预测方法。在最后一章,总结了全部的实验和理论工作得到的经验和不足,为后续的研究工作提供思路和参考。更多还原

【Abstract】 Excess heat enthalpy (HE), namely mixed heat, is a very important thermodynamic property of solution. It can reflect the deviation of the liquid mixture from the ideal solution. Furthermore, it is a primary symbol of non-ideality of solution.The application of excess enthalpy is very extensive in the design and production of chemical engineering. Because it is very difficult to accurately measure gas phase composition in the actual application process, vapor-liquid equilibrium (VLE) data for some systems are not very accurate, especially for the systems whose components are very different from each other in their boiling point or who has a component with easy volatility. At this time, the measurement of excessive enthalpy data of solution is important and necessary.Then we can use excess enthalpy data to estimate activity coefficients, predict liquid-liquid equilibrium and vapor-liquid equilibrium (VLE) data and test the thermodynamic consistency of the isobaric VLE data, and thus largely decrease experimental work.The main contents in this dissertation are as follows:In the first chapter, we introduce the correlative basic theories about our research. The current research contents inland and abroad were summarized and the relevant theoretical models, calculation methods and the research contents of this thesis were described.In the second chapter, we introduce the experimental contents. The excess enthalpies of esters and alcohols at different temperatures were measured by CSC4400 flow mixing micro-calorimeter. We can investigate the effects of mole fractions, temperature and the carbon numbers on excess enthalpies based on the management by theoretical models.The third chapter and the fourth chapter are the theoretical study section. In order to better explain the experimental phenomenon about excess molar enthalpies, we calculated the interaction energies and the charge distribution of the binary systems by quantum chemistry calculation. We tried to explain the reasons for the different heat produced by different systems from two aspects:molecular interactions and charge distribution and do prediction and calculation, hoping to find more suitable prediction methods for industrial processes.In the last chapter, we summarized all of the experiment and theoretical work, put forward the deficiency in this work and proposed ideas for the latter research.更多还原