苯酚及其硝基衍生物的酸性递变规律

• 作 者: 肖鹤鸣 邓娅 曲绍清 朱乃红
• 机 构: 华东工程学院,华东工程学院,上海环境化学所,镇江船舶学院
• 出 处: 南京理工大学学报(自然科学版)
• 发表日期: 1983年04期
• 关键词: 苯酚 硝基 电荷密度 键序 氢原子 量子化 极化率 π电子 线性关系 π轨道

运用量子化学中HMO和CNDO/2方法,研究苯酚及其硝基衍生物的液相酸性,发现其pk_a和分子中羟基氧上的电荷密度(尤其是π电子密度、π轨道可极化率),以及氧、氢原子间的Wiberg和Mulliken键序之间,存在着良好的线性关系。这有助于从分子的电子微观层次深刻认识本系列炸药及其相关物的酸性递变规律,并可通过简单计算预示一些难以实测分子的离解常数。

Using the methods of HMO and CNDO / 2 in quantum chemistry to study the liquid phase acidity of phenol and its nitro derivatives, we found that the charge density (especially π electron density and π orbit polarizability) of pk_a and hydroxyl oxygen in the molecule, , And there is a good linear relationship between Wiberg and Mulliken bond order between oxygen and hydrogen atoms. This helps to deeply understand the law of acid evolution of this series of explosives and their related substances from the electronic micro-level of the molecule and can predict the dissociation constants of some difficult-to-measure molecules through simple calculations.