Ultraviolet-visible molecular absorption spectrometry

The basic instrumentation used for spectrometric measurements has already been described in Chapter 7 (p. 277). The natures of sources, monochromators, detectors, and sample cells required for molecular absorption techniques are summarized in Table 9.1. The principal difference between instrumentation for atomic emission and molecular absorption spectrometry is in the need for a separate source of radiation for the latter. In the infrared, visible and ultraviolet regions, white sources are used, i.e. the energy or frequency range of the source covers most or all of the relevant portion of the spectrum. In contrast, nuclear magnetic resonance spectrometers employ a narrow waveband radio-frequency transmitter, a tuned detector and no monochromator. 

The spectrophotometric methods to be discussed (methods of molecular absorption spectrometry) are based on the measurement of absorption of radiation, in the visible and near ultraviolet regions, owing to coloured compounds formed, before the determination, by the elements to be determined. Only seldom is use made of the intrinsic colour of the element itself, in its ionic form. In cases where an element neither forms coloured compounds nor occurs in a coloured form, indirect spectrophotometric methods are applied. 

Materials characterization techniques, ie, atomic and molecular identification and analysis, are discussed in articles the tides of which, for the most part, are descriptive of the analytical method. For example, both infrared (ir) and near infrared analysis (nira) are described in Infrared and raman SPECTROSCOPY. Nudear magnetic resonance (nmr) and electron spin resonance (esr) are discussed in Magnetic spin resonance. Ultraviolet (uv) and visible (vis), absorption and emission, as well as Raman spectroscopy, circular dichroism (cd), etc are discussed in Spectroscopy (see also Chemh.itmtnescence Electro-analytical technique Immunoassay ZvIass spectrometry Microscopy Microwave technology. Plasma technology and X-ray technology). 

Spectra by the Thousands 575 Infrared Spectra 576 Characteristic Absorption Frequencies Ultraviolet-Visible (UV-VIS) Spectroscopy Mass Spectrometry 584 Molecular Formula as a Clue to Structure 589 Summary 590 Problems 593... 

Ultraviolet/visible spectrometry Electronic molecular absorption in solution Quantitative determination of unsaturated organic compounds... 

The selection rules help to predict the probability of a transition but are not always strictly followed. If the transition obeys the rules it is allowed, otherwise it is forbidden. A molecule can become excited in a variety of ways, corresponding to absorption in different regions of the spectrum. Thus certain properties of the radiation that emerges from the sample are measured. The fraction of the incident radiation absorbed or dissipated by the sample is measured in optical (ultraviolet and visible) absorption spectroscopy and some modes of nuclear magnetic resonance spectrometry (NMR). Because the relative positions of the energy levels depend characteristically on the molecular structure, absorption spectra provide subtle tools for structural investigation. 

---