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Flame Emission Spectrometry

       Nurul Auni binti Zainal Abidin
        Faculty of Applied Science,
          UiTM Negeri Sembilan.
Flame Emission Spectroscopy

     Measure the intensity of emitted radiation

                        Excited State


                      Emits Special
                      Electromagnetic Radiation




                            Ground State
Instruments

 Consists of:

 1.   Nebulizer
 2.   Burner
 3.   Monochromator
 4.   Detector
 5.   Readout device / computer
Introduction
    Basic Schematic
        Atomizer
                          Wavelength
                           Selector
                                                 Detector

    Scanning instruments can detect multiple elements.

    Many lines detected so sometimes it is a quantitatively
     difficult method.

    Source can be flame, but more commonly plasma
     because it is much hotter.
   Each element emit its own characteristics line
    spectrum
   Quantitative analysis can be performed here by
    observing what are emitted & comparing these
    with various standards.

   Detector permits qualitative as well as quantitative
    analysis

   Wavelength of emitted radiation indicates what
    element is present and the radiation intensity
    indicates how much of the element is present
   Intensity of the emitted light increase with
        concentration
       Relationship between intensity and concentration is
        usually linear

I
                                 I = kc
                               Unknown concentration can
                               be detected by comparison
                               with one or a series of
                               standards in the same manner
                               for the molecular techniques
                       c
Types of Atomizer

  Flame
  Plasma
  Arc and spark
Flame Atomization


                  Slit              Slit


 Emitted
                                           Detector



           Lens
 Flame                   Filterer
Process
    Sample is sprayed by the nebulizer into the burner.

    Carried into the flame

    Atomized & excited

    The emission from the excited atoms passes into the
     monochromator where the selected wavelength is passed
     through for measurement.

    Intensity of the emitted wavelength is measured by the
     detection system & indicated on the readout/computer.
Relationship Between AA and FES
     Flame Emission     it measures the radiation emitted by the
      excited atoms that is related to concentration.

     Atomic Absorption    it measures the radiation absorbed by
      the unexcited atoms that are determined.

     Atomic absorption depends only upon the number of
      unexcited atoms, the absorption intensity is not directly
      affected by the temperature of the flame.

     The flame emission intensity in contrast, being dependent
      upon the number of excited atoms, is greatly influenced by
      temperature variations.
Flame Emission Spectroscopy
    Flame Emission Spectroscopy is based upon those particles
     that are electronically excited in the medium.

 The Function of Flame

  To convert the constituents of liquid sample into the vapor
   state.
  To decompose the constituents into atoms or simple
   molecules:
        M+ + e- (from flame)           M + hv
  To electronically excite a fraction of the resulting atomic or
   molecular species
               M       M*
Interference

              INTERFERENCES



      Spectral                              Chemical
                                          interference
    interference


   NOTE: same interference which occur in AAS
Comparison btw AAS & AES
         (Based on Flame)
                  Flame Atomic        Flame Atomic
                  Absorption          Emission
Process measured Absorption (light    Emission (light
                 absorbed by          emitted by excited
                 unexcited atoms in   atoms in a flame)
                 flame)
Use of flame     Atomization          Atomization &
                                      excitation
Instrumentation   Light source        No light source
Beer’s Law        Applicable          Not applicable
Data obtained     A vs c              I vs c
2. Plasma
    Plasma – highly ionized, electrically neutral gaseous
     mixture of cations and electrons that approaches
     temperature 10, 000 K.

    There are three types of plasma sources:
     a) Inductively coupled plasma (ICP)
     b) Direct current plasma (DCP)
     c) Microwave induced plasma (MIP)

    ICP is the most common plasma source.
Inductively Coupled Plasma (ICP)
     Constructed of three concentric quartz tube.

     RF current passes through the water-cooled
      Cu coil, which induces a magnetic field.

     A spark generates argon ions which are held
      in the magnetic field and collide with other
      argon atoms to produce more ions.

     Argon in outer tube swirls to keep plasma
      above the tube.

     The heat is produced due to the formation of
      argon ions.
Inductively Coupled Plasma (ICP)
   Plasma Appearance
   a. Excitation Region
      The bright, white, donut shaped region at
       the top of the torch.
      Radiation from this region is a continuum
       with the argon line spectrum superimposed.
      Temperature: 8000 – 10 000 K
   b. Observation Region
      The flame shaped region above the torch
       with temperatures 1000 – 8000 K.
      The spectrum consists of emission lines
       from the analyte along with many lines from
       ions in the torch.
Inductively Coupled Plasma (ICP)
 1. Sample Introduction
   a. Liquid Sample
        - Nebulizer similar to FAAS
        - Sample nebulized in a stream of
        argon with a flow rate of 0.3 – 1.5 L/min.
        - Sample aerosol enters the plasma at
        the base through the central tube.

   b. Solid Samples
       - Sample atomized by
       electrothermal atomization a and carried
       into the plasma by a flow of argon gas.
Advantage of ICP-AES over
Flame AES
  1.   Temperature is two to three times higher than
       in a flame or furnace, which results in higher
       atomization and excitation efficiencies.
  2.   There is little chemical interference.
  3.   Atomization in the inert (argon) atmosphere
       minimizes oxidation of the analyte.
  4.   Short optical path length minimizes the
       probability of self-absorption by argon atoms
       in the plasma.
  5.   Linear calibration curves can cover up to five
       orders of magnitude.
ICP-AES over Flame AES
    Much lower detection limit because:

        Higher temperature with the plasma will increase
         the population of excited state atoms.

        The plasma environment is relatively chemically
         inert due to the higher population of electrons which
         will minimize the interference of ionization.
AAS and AES
    Both methods use atomization of a sample and therefore
     determine the concentrations of elements.

    For AAS, absorption of radiation of a defined wavelength is
     passed through a sample and the absorption of the
     radiation is determined. The absorption is defined by the
     electronic transition for a given element and is specific for
     a given element. The concentration is proportional to the
     absorbed radiation.

    In AES, the element is excited. A rapid relaxation is
     accompanied by emission of UV or visible radiation is used
     to identify the element. The intensity of the emitted
     photon is proportional to element concentration.

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CHM260 - AAS (ii)

  • 1. Flame Emission Spectrometry Nurul Auni binti Zainal Abidin Faculty of Applied Science, UiTM Negeri Sembilan.
  • 2. Flame Emission Spectroscopy  Measure the intensity of emitted radiation Excited State Emits Special Electromagnetic Radiation Ground State
  • 3. Instruments Consists of: 1. Nebulizer 2. Burner 3. Monochromator 4. Detector 5. Readout device / computer
  • 4. Introduction  Basic Schematic Atomizer Wavelength Selector Detector  Scanning instruments can detect multiple elements.  Many lines detected so sometimes it is a quantitatively difficult method.  Source can be flame, but more commonly plasma because it is much hotter.
  • 5. Each element emit its own characteristics line spectrum  Quantitative analysis can be performed here by observing what are emitted & comparing these with various standards.  Detector permits qualitative as well as quantitative analysis  Wavelength of emitted radiation indicates what element is present and the radiation intensity indicates how much of the element is present
  • 6. Intensity of the emitted light increase with concentration  Relationship between intensity and concentration is usually linear I I = kc Unknown concentration can be detected by comparison with one or a series of standards in the same manner for the molecular techniques c
  • 7. Types of Atomizer  Flame  Plasma  Arc and spark
  • 8. Flame Atomization Slit Slit Emitted Detector Lens Flame Filterer
  • 9. Process  Sample is sprayed by the nebulizer into the burner.  Carried into the flame  Atomized & excited  The emission from the excited atoms passes into the monochromator where the selected wavelength is passed through for measurement.  Intensity of the emitted wavelength is measured by the detection system & indicated on the readout/computer.
  • 10. Relationship Between AA and FES  Flame Emission it measures the radiation emitted by the excited atoms that is related to concentration.  Atomic Absorption it measures the radiation absorbed by the unexcited atoms that are determined.  Atomic absorption depends only upon the number of unexcited atoms, the absorption intensity is not directly affected by the temperature of the flame.  The flame emission intensity in contrast, being dependent upon the number of excited atoms, is greatly influenced by temperature variations.
  • 11. Flame Emission Spectroscopy  Flame Emission Spectroscopy is based upon those particles that are electronically excited in the medium. The Function of Flame  To convert the constituents of liquid sample into the vapor state.  To decompose the constituents into atoms or simple molecules: M+ + e- (from flame) M + hv  To electronically excite a fraction of the resulting atomic or molecular species M M*
  • 12. Interference INTERFERENCES Spectral Chemical interference interference NOTE: same interference which occur in AAS
  • 13. Comparison btw AAS & AES (Based on Flame) Flame Atomic Flame Atomic Absorption Emission Process measured Absorption (light Emission (light absorbed by emitted by excited unexcited atoms in atoms in a flame) flame) Use of flame Atomization Atomization & excitation Instrumentation Light source No light source Beer’s Law Applicable Not applicable Data obtained A vs c I vs c
  • 14. 2. Plasma  Plasma – highly ionized, electrically neutral gaseous mixture of cations and electrons that approaches temperature 10, 000 K.  There are three types of plasma sources: a) Inductively coupled plasma (ICP) b) Direct current plasma (DCP) c) Microwave induced plasma (MIP)  ICP is the most common plasma source.
  • 15. Inductively Coupled Plasma (ICP)  Constructed of three concentric quartz tube.  RF current passes through the water-cooled Cu coil, which induces a magnetic field.  A spark generates argon ions which are held in the magnetic field and collide with other argon atoms to produce more ions.  Argon in outer tube swirls to keep plasma above the tube.  The heat is produced due to the formation of argon ions.
  • 16. Inductively Coupled Plasma (ICP) Plasma Appearance a. Excitation Region  The bright, white, donut shaped region at the top of the torch.  Radiation from this region is a continuum with the argon line spectrum superimposed.  Temperature: 8000 – 10 000 K b. Observation Region  The flame shaped region above the torch with temperatures 1000 – 8000 K.  The spectrum consists of emission lines from the analyte along with many lines from ions in the torch.
  • 17. Inductively Coupled Plasma (ICP) 1. Sample Introduction a. Liquid Sample - Nebulizer similar to FAAS - Sample nebulized in a stream of argon with a flow rate of 0.3 – 1.5 L/min. - Sample aerosol enters the plasma at the base through the central tube. b. Solid Samples - Sample atomized by electrothermal atomization a and carried into the plasma by a flow of argon gas.
  • 18. Advantage of ICP-AES over Flame AES 1. Temperature is two to three times higher than in a flame or furnace, which results in higher atomization and excitation efficiencies. 2. There is little chemical interference. 3. Atomization in the inert (argon) atmosphere minimizes oxidation of the analyte. 4. Short optical path length minimizes the probability of self-absorption by argon atoms in the plasma. 5. Linear calibration curves can cover up to five orders of magnitude.
  • 19. ICP-AES over Flame AES  Much lower detection limit because:  Higher temperature with the plasma will increase the population of excited state atoms.  The plasma environment is relatively chemically inert due to the higher population of electrons which will minimize the interference of ionization.
  • 20. AAS and AES  Both methods use atomization of a sample and therefore determine the concentrations of elements.  For AAS, absorption of radiation of a defined wavelength is passed through a sample and the absorption of the radiation is determined. The absorption is defined by the electronic transition for a given element and is specific for a given element. The concentration is proportional to the absorbed radiation.  In AES, the element is excited. A rapid relaxation is accompanied by emission of UV or visible radiation is used to identify the element. The intensity of the emitted photon is proportional to element concentration.