【作者】 夏力；

【导师】 项曙光；

【作者基本信息】 青岛科技大学 ， 化学工程， 2006， 硕士

【摘要】 在化学工业中，沸点是重要的物性数据，但人们经常在需要的时候找不到它。随着化合物种类和数量的不断增多，如对其全部进行测量也非常困难，于是人们提出了估算的想法。早期有机物沸点估算大多采用基团加和的简单基团贡献法，这些方法简便易用，但准确性较差。为了克服上述缺点，出现了复合基团贡献法。 本文总结归纳了文献中的正常沸点估算方法，筛选出现阶段应用比较广泛且估算精度较高的基团贡献法—Joback法、Joback修正方法、C-G法、M-P法和许文法。利用4068种有机物的沸点实验数据，对这5种方法进行了比较评价。结果表明，CG2使用简便，能区分部分同分异构体，估算精度高，是最好的估算方法，用于估算烷烃、氯衍生物、溴衍生物、脂环烃、芳烃、含氮化合物的正常沸点时精度最高；MP2用于估算碘衍生物；MP4用于估算氟衍生物、含氧化合物、含硫化合物；许文法用于估算烯烃和炔烃的正常沸点时精度最高；Joback修正方法对Joback法修正效果不明显，有待改进。 根据分子结构理论，本文首次提出了一种基于元素和化学键贡献的用于估算有机物正常沸点的新方法—元素和化学键贡献法，即以单个的元素和化学键取代传统的基团贡献法中的基团，来考察元素和化学键对正常沸点的贡献。在可靠的4060种实验实测沸点数掘的基础上，回归得到了7个正常沸点估算关联式，并与Joback法、Joback修正方法、C-G法、M-P法和许文法进行了比较。结果表明，该法使用简便，估算精度较高，具有很强的外推功能。但是缺乏对同种类的同分异构体辨别能力以及对烷烃、烯烃、氟衍生物、含氧化合物和含氮化合物的估算精度不高。 借鉴了现有沸点估算方法区分同分异构体的方法，从相邻化学键之间相互作用的角度，对元素和化学键贡献法进行了修正，首次提出了能很好的区分同分异构体的沸点估算方法—复合元：素和化学键贡献法。该方法以9种元素、29种化学键和32种相邻化学键之间相互作用作为基本贡献单位，用4060种有机物的正常沸点实验数据回归了6个关联式，与元素和化学键贡献法、Joback法、Joback修正方法、C-G法、M-P法和许文法比较，结果表明，此法优于相比较的其它基团贡献法，克服了元素和化学键贡献法不能区分同种类同分异构体的缺点。更多还原

【Abstract】 Data concerning the normal boiling point of organic compounds are very important in chemical dustries, but are not available when they need. It is difficult to measure all of them as the need arise. So the idea of estimation is proposed.To obtain the properties of pure compounds, simple group contribution methods, which can provide the important advantage of quick estimation are widely used at early stage. However, many of these methods are of questionable accuracy.To overcome this limitation, complex group contribution methods have been introduced into the relevant research.In this paper, the methods to estimate the normal boiling point in the literature were summarized. Then the widely used methods with high estimation accuracy were slected, which include the Joback method, modified Joback method, C-G method, M-P method and Xuwen method. On the basis of 4,068 kinds of credible experimental data, comparison and evaluation of these five methods was presented. The results show that CG2 method is convenient to use and can differentiate some isomers. It is the best method with high estimation accuracy. Especially for alkane, chloride derivative, bromide derivative, alicyclic hydrocarbon, aromatic hydrocarbon and nitrogen- containing compounds, the estimation accuracy of CG2 is the highest. For iodine derivative, the estimation accuracy of MP2 is the highest. For fluoride derivative, oxygenated hydrocarbon and sulfur- containing compounds, the estimation accuracy of MP4 is the highest. For alkene and alkyne, the estimation accuracy of XuWen is the highest. The modified Joback method does not exert obvious effects on the Joback method and needs further improvements.According to molecular structure theory, a new method based on elements and更多还原