Chapter 9 紫外光谱课件.pptVIP

Ultraviolet Spectroscopy  紫外光谱 9.1 Basics of Ultraviolet Spectroscopy The UV involves the absorption of ultraviolet light by a molecule causing the promotion of an electron from a ground electronic state to an excited electronic state. The transitions are generally between a bonding or lone-pair orbital and an unfilled non-bonding or anti-bonding orbital. The wavelength of the absorption is then a measure of the separation of the energy levels of the orbitals concerned. 芳香族化合物的吸收（环状共轭体系） E1带(185nm, 50000)； E2带(200nm, 6900)； B带(230nm~270nm, 170)；结构精细； B带：芳环特征吸收带； 含取代基时，B带简化， 红移。 Inorganic Chelates (螯合的): How Do They Absorb So Intensely?金属配合物的紫外—可见吸收光谱 金属离子与配位体反应生成配合物的颜色一般不同于游离金属离子(水合离子)和配位体本身的颜色。金属配合物的生色机理主要有以下三种类型： ⑴ Excitation of the metal ion 配位体微扰的金属离子d?d电子跃迁和f?f电子跃迁:摩尔吸收系数ε很小(1~100) 。 CuSO4 ⑵ Excitation of the ligand 金属离子微扰的配位体内电子跃迁。配体多数为有机化合物。 ⑶ Charge transfer transitions 电荷转移跃迁（荷移吸收光谱 ） 邻二氮杂菲 A metal ion in a lower oxidation state, complexed with a high electron affinity ligand, may be oxidized without destroying the complex. An important example is the 1,10-phenanthroline chelate of iron (II). 9.5 Applications：Foundamental variables The wavelength (or energy) of the radiation.（辐射的波长；定性） 定性分析（qualitative analysis确定未知化合物） 有机化合物分子结构的推断 3. 某羰基化合物在近紫外和可见光区只产生一个204nm （60）的弱吸收带。该化合物可能是酯；醛酮；?，?－不饱和醛酮；?，?－不饱和酯； 在下列化合物中同时含有???*、 n??*跃迁的化合物是 三氯甲烷、丙酮、丁二烯、二甲苯 在下列化合物中，那一个化合物能吸收波长较长的辐射（ ） 苯、二甲苯、对氯代甲苯、萘 某化合物分子式为 C9H10O，如右图，指出 发色团。 The UV-Vis spectrum and Beer’ laws The UV-Vis spectrum typically represents the absorption of light as a plot (Figure 3.2) of energy (as wavelength, λ , in nanometers, from E = hc/λ) versus the intensity of absorption (as absorbance, A, or molar extinction coefficient, ε). A =? (cm-1 mol-1 L) b(cm) c(mol L-1) 摩尔吸光系数 9.3 Instrumentation Example 1（P7）； Example 2 Potassium dichromate(重铬酸盐) and potassium permanganate have overlapping absorption spectra in 1 M H2SO4. K2Cr2O7 has an a