2014-08-012024-05-17https://scholars.lib.ntu.edu.tw/handle/123456789/682684摘要：酸在化工程序中是非常常見的化學品，常用在高分子聚合、酯化反應，酸鹼中和反應等。許多的藥物以及生物分子也是酸性強度不一的化合物。由於氫鍵作用以及解離現象的存在，讓模擬含酸性物質的系統甚具挑戰。瞭解這類系統的平衡組成，是設計、開發與最適化相關程序所必要的知識。因此在本計畫中，我們將開發精確的預測模型，用來計算各種含弱酸混合物的熱力學性質以及相行為。 在此類計算中，解離平衡常數(pKa)是決定酸性物質平衡濃度最重要的性質。本計畫的第一個目標，即是開發必要的理論模型，利用現有的解離平衡常數資料，進行含弱酸系統的向平衡計算。雖然文獻中可以找到許多不同酸在水中的解離平衡常數，然而在其他溶劑中的解離平衡常數卻相當少見。因此，本計畫的第二個目標，即是開發新的方法，透過水中的解離平衡常數，預測非水溶液中的解離平衡常數。據此，我們即可對含酸的非水混合物進行相平衡預測。本工作將有助於未來了解更複雜的生物系統，提供預測此類系統相行為重要的理論基礎。 <br> Abstract: Acids are common reagent in chemical processes, such as polymerization, esterification, and neutralisation. Many drug and biological species are also acids with varying degree of strength of deprotonation. The modeling of processes involving acids are complicated by the presence of hydrogen bonds and the dissociation of acids to its conjugate base and proton. The understanding of the equilibrium composition of mixtures containing acids is important for the design, development, and optimization of related processes. In this project, we propose to develop an accurate predictive method for the determination of thermodynamic properties and phase equilibria of mixture containing weak acids. The dissociation constant, pKa, is the key variable for the successful determination of phase equilibria of acid-containing mixture. The first objective of this work is to establish the theory and computer program that determines the phase equilibria with consideration of dissociation of acids. While abundant data of pKa are available for acids in water, only limited amount of data has been measured for nonaqueous systems. The second objective is to develop predict methods for pKa in nonaqueous solutions based on the pKa in water. With such information, the phase behavior of nonaqueous mixtures can be made. This work represents as a significant step toward the ultimate goal of predicting the phase behavior of biological systems.相平衡弱酸解離常數第一性原理計算溶劑化Phase equilibriaweak acidsdissociation constantfirst-principle predictionsolvation