紫外-可见光谱 - 合肥工业大学化学与化工学院.doc

紫外-可见光谱技术在化学研究中的应用 何建波* 朱燕舞 （合肥工业大学 化学工程学院，合肥 230009） 摘 要： 关键词：紫外-可见光谱； 中图分类号： 文献标志码：A 文章编号： Application of in Chemical Research HE Jian-bo ZHU Yan-wu (School of Chemical Engineering, Hefei University of Technology, Hefei 230009, China) Abstract: The application of ultraviolet-visible (UV-Vis) spectroscopy has expanded from conventional identification and content determination of compounds to cover diverse aspects of the determination of chemical reaction thermodynamics and kinetics. In order to guide students to use UV-Vis spectroscopy technology flexibly in experiments and research, its application in chemical research is summarized based on the examples available in the literature and the experimental data in our lab. The discussed aspects include the equilibrium constant measurement of different types of chemical reactions such as acid-base dissociation reaction, coordination reaction and small molecule-DNA interaction, the rate constant measurement taking a polymerization reaction as an example, and in situ UV-Vis spectroelectrochemical measurement for electrode reactions. The cited examples show that UV-Vis spectroscopy technology can play an important role in chemical reaction study, based on the appropriate design of experiments. Key words: Ultraviolet-Visible (UV-Vis) spectroscopy; equilibrium constant; reaction rate constant; spectroelectrochemistry; cyclic voltabsorptometry 引言 紫外-可见(UV-Vis)光谱测试对象主要是具有共轭结构的分子，尤以药物、天然产物和生物分子为常见。UV-Vis光谱是分子内电子跃迁的结果，不同分子结构的化合物，电子跃迁的类型不同，其特征吸收峰波长和强度不同用于化合物结构鉴定依据Beer-Lambert定律定量分析于在UV-Vis无吸收的化合物通过显色反应转化为有吸收的化合物[1]。 ，数据重现性好，应用范围广，除化合物结构鉴定和含量测定外，还用于反应平衡常数和反应动力学测定等多方面。 UV-Vis光谱用于测量化学平衡常数 UV-Vis光谱广泛地用于研究溶液平衡，如测定碱离解常数配合物的组成及稳定常数、有机物平衡等，前提是所研究的酸碱配合物物质在UV-Vis光区有吸收 2.1 一元酸碱离解平衡常数 具有共轭结构的有机弱酸和弱碱，如多数酸碱指示剂、酚类和芳胺类化合物等，可利用其分子和离子两种形态的UV-Vis吸收光谱的差异，来测定其离解常数。对一元弱酸HA，其电离反应HA = H+ + A( 的离解常数Ka及其负对数pKa值表为 (1) 可见测定Ka或pKa值，就是测出HA和A(两种组分的平衡浓度。以7-羟基香豆素7-HC)为例，7-HC的UV-Vis光谱随溶液pH的变化[2]。图中324 nm和366 nm吸收峰分别是7-HC