The Determination, Correlation And Prediction Of The Excess Enthalpies For The Binary System Of Alcohols + Ketones

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.