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10.S: Spectroscopic Methods (Summary)

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  • 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 spectrum
    attenuated total reflectance
    background correction
    Beer’s law
    continuum source
    dark current
    effective bandwidth
    electromagnetic radiation
    electromagnetic spectrum
    emission spectrum
    excitation spectrum
    external conversion
    Fellgett’s advantage
    fiber-optic probe
    filter photometer
    fluorescent quantum yield

    graphite furnace
    internal conversion
    intersystem crossing
    ionization suppressor
    Jacquinot’s advantage
    line source
    method of continuous variations
    molar absorptivity
    mole-ratio method
    nominal wavelength
    phase angle
    phosphorescent quantum yield
    photodiode array

    protecting agent
    radiationless deactivation
    releasing agent
    signal averaging
    signal processor
    signal-to-noise ratio
    singlet excited state
    slope-ratio method
    spectral searching
    stray radiation
    triplet excited state
    vibrational relaxation



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