10.S: Spectroscopic Methods (Summary)

The spectrophotometric methods of analysis covered in this chapter include those based on the absorption, emission, or scattering of electromagnetic radiation. When a molecule absorbs UV/Vis radiation it undergoes a change in its valence shell configuration. A change in vibrational energy results from the absorption of IR radiation. Experimentally we measure the fraction of radiation transmitted, T, by the sample. Instrumentation for measuring absorption requires a source of electromagnetic radiation, a means for selecting a wavelength, and a detector for measuring transmittance. Beer’s law relates absorbance to both transmittance and to the concentration of the absorbing species (A = –logT = εbC).

In atomic absorption we measure the absorption of radiation by gas phase atoms. Samples are atomized using thermal energy from either a flame or a graphite furnace. Because the width of an atom’s absorption band is so narrow, the continuum sources common for molecular absorption can not be used. Instead, a hollow cathode lamp provides the necessary line source of radiation. Atomic absorption suffers from a number of spectral and chemical interferences. The absorption or scattering of radiation from the sample’s matrix are important spectral interferences that may be minimized by background correction. Chemical interferences include the formation of nonvolatile forms of the analyte and ionization of the analyte. The former interference is minimized by using a releasing agent or a protecting agent, and an ionization suppressor helps minimize the latter interference.

When a molecule absorbs radiation it moves from a lower energy state to a higher energy state. In returning to the lower energy state the molecule may emit radiation. This process is called photoluminescence. One form of photoluminescence is fluorescence in which the analyte emits a photon without undergoing a change in its spin state. In phosphorescence, emission occurs with a change in the analyte’s spin state. For low concentrations of analyte, both fluorescent and phosphorescent emission intensities are a linear function of the analyte’s concentration. Thermally excited atoms also emit radiation, forming the basis for atomic emission spectroscopy. Thermal excitation is achieved using either a flame or a plasma.

Spectroscopic measurements may also involve the scattering of light by a particulate form of the analyte. In turbidimetry, the decrease in the radiation’s transmission through the sample is measured and related to the analyte’s concentration through an equation similar to Beer’s law. In nephelometry we measure the intensity of scattered radiation, which varies linearly with the analyte’s concentration.

10.9.1 Key Terms

absorbance absorbance spectrum absorptivity amplitude attenuated total reflectance atomization background correction Beer’s law chemiluminescence chromophore continuum source dark current double-beam effective bandwidth electromagnetic radiation electromagnetic spectrum emission emission spectrum excitation spectrum external conversion Fellgett’s advantage fiber-optic probe filter filter photometer fluorescence fluorescent quantum yield

fluorimeter frequency graphite furnace interferogram interferometer internal conversion intersystem crossing ionization suppressor Jacquinot’s advantage lifetime line source method of continuous variations molar absorptivity mole-ratio method monochromatic monochromator nephelometry nominal wavelength phase angle phosphorescence phosphorescent quantum yield photodiode array photoluminescence photon plasma polychromatic

protecting agent radiationless deactivation relaxation releasing agent resolution self-absorption signal averaging signal processor signal-to-noise ratio single-beam singlet excited state slope-ratio method spectral searching spectrofluorimeter spectrophotometer spectroscopy stray radiation transducer transmittance triplet excited state turbidimetry vibrational relaxation wavelength wavenumber

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Contributors

David Harvey (DePauw University)