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    CHEM F313: Instrumental Methods of Analysis: Energy & Electromagnetic Spectrum

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    radhika
    This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

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    CHEM F313: Instrumental Methods of Analysis: Energy & Electromagnetic Spectrum

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    radhika
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    This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

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    IMA Lecture 02

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    This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

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    25 views7 pages

    CHEM F313: Instrumental Methods of Analysis: Energy & Electromagnetic Spectrum

    Uploaded by

    radhika
    This document discusses electromagnetic waves and spectroscopy. It covers: 1. Key terms related to electromagnetic waves like wavelength, frequency, and wave number. 2. The electromagnetic spectrum and the different types of molecular transitions that occur at different energy levels, such as molecular vibration, valence electrons, and spin orientation. 3. Factors that contribute to line broadening in spectra, including collision broadening, Doppler broadening, and the Heisenberg uncertainty principle. 4. Factors that control the intensity of spectral lines, including transition probability, population of states, and path length of the sample.

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    of 7

    CHEM F313: Instrumental Methods of Analysis

    Lecture 02
    Energy & Electromagnetic Spectrum
    BITSPilani, Pilani Campus
    Electromagnetic waves

    TWO principle methods for signal enhancement

    1. Wavelength, l 6. Monochromatic/Polychromatic
    2. Frequency, 7. Interference
    3. Wave number, 8. Polarised/non-polarized
    4. Radiant Power, P
    5. Intensity, I
    BITSPilani, Pilani Campus
    Electromagnetic spectrum
    Energy Change

    Nuclear Inner shell Ionization Molecular Spin Orientation


    electrons of Atoms & Vibration
    Molecules (stretch, bend)

    Valance Electrons
    BITSPilani, Pilani Campus
    Width of Spectral Lines
    Irrespective of the improvement of the instrumentation (thin slit) the
    line width of the spectra are often blurred. Natural line width is
    governed by,
    Collision Broadening: Due to continual motion in liquid & gas phase,
    molecules/atoms collide frequently. Vibration & rotation spectra are
    usually affected.
    Doppler Broadening: Due to collisions. Random motion creates both
    higher and lower frequencies. More effective in gases then liquids
    Heisenbergs Uncertainly Principle: E x t = /2 ~ 10-34 J.s ,
    which means that lowest energy state is most certain.
    E.g. lifetime of excited electronic state is ~ 10-8 s, so, E ~ 10-28 J,
    and hence = 108 Hz. This is typically small w.r.t. source (~ 1016
    Hz).
    For excited electronic spin state lifetime = 10-7 s, which shows
    = 107 Hz. But this is comparable with the frequency of such
    transitions ~109 Hz, hence a considerably broad signal.

    BITSPilani, Pilani Campus


    Intensity of Spectral Lines
    Three important factors controlling the intensity of lines
    Transition Probability: governed by the selection rules, easy to
    understand pictorially
    Population of States: Higher the population of the lower energy
    state, higher is the intensity of the line.
    Path Length of sample: The relation can be expressed as
    I/I0 = e-kcl This is certainly not linear.

    BITSPilani, Pilani Campus


    UV-Vis: Instrumentation
    (details later)

    BITSPilani, Pilani Campus


    Fundamental Laws
    If a monochromatic radiation of radiant power P0 travels an infinitesimal distance dx, of
    an absorber then, at a constant concentration,

    The number of absorbent is proportional to the distance but independent of P


    k depends on the wavelength

    or, Lamberts Law

    Also, the relation between radiant power and concentration can be found out at a
    constant distance travelled and a fixed wavelength,

    Beers Law
    The number of absorbent is proportional to the concentration, C

    Combining, and converting to base 10,

    or,
    is called absorptivity [Lg-1cm-1] if C is in g.L-1 and l is in cm
    Or, molar absorption coefficient [Lmol-1cm-1] if C is in molL-1 and l is in cm
    BITSPilani, Pilani Campus

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