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Spectroscopy is used to obtain information about a sample. Sample is excited or stimulated by : heat, electrical,light, particles, chemical reaction etc. Radiation emitted and absorbed are measured as these contain information of analytes.
Spectroscopy is used to obtain information about a sample. Sample is excited or stimulated by : heat, electrical,light, particles, chemical reaction etc. Radiation emitted and absorbed are measured as these contain information of analytes.
Spectroscopy is used to obtain information about a sample. Sample is excited or stimulated by : heat, electrical,light, particles, chemical reaction etc. Radiation emitted and absorbed are measured as these contain information of analytes.
-It is for obtaining information about a sample. -Sample is excited or stimulated by : Heat, Electrical,Light, Particles, Chemical reaction etc -Prior to excitation the analyte is expected in the lowest energy state(Ground state). -The radiation emitted & absorbed are measured as these contain information of analytes.
Types of spectra: 1)Emission spectra 2)Absorption spectra
i)Emission spectra: -EM radiation is produced when excited particles (atoms,ions or molecules) relaxes to lower energy levels by giving up their excess energy as photons.
-The emitted radiation is passed through a prism or a grating & examined directly with a spectroscope.
-The spectrum thus obtained is Emission spectrum
-It is a plot of intensity of emitted radiation vs. WL or frequency.
i)Line spectra: -A line spectra consists of discrete irregular spaced lines. (produced in UV/Vis region) -Substances in gaseous atomic state give this spectra. -Width of a line is about 10 -5 nm. -When the atom gets excited by electric or thermal method, its electrons move from inner orbitals to outer orbitals(valence orbital to higher energy orbital). -The atom returns to ground state after 10 -8 s, emitting a photons. -The discrete spectral line because of the emitted radiation from the excited atoms is the basis of emission spectroscopy. -In order for any element to emit a single spectral line, energy equivalent to the excitation potential of the element must be absorbed.
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ii)Band emission spectra. - It is given by the gaseous excited molecules or radicals. -Group of lines are so close together that under ordinary conditions they appear into a continuous band. -In this, numerous quantised vibrational levels superimpose on the ground-state electronic energy level of molecule. -The band is also composed of various rotational energy levels as well.
-Relaxation from one electronic state to another electronic state is via slow collisional transfer of energy (Hence relaxation by photon transfer is favoured)
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iii)Continuous spectra -Incandescent solid like iron or carbon emits a continuous spectra. -These spectra are devoid of sharp lines or discrete bands. -Do not depend upon the chemical composition but rather on temperature of the emitting surface. -The spectra obtained whenever matter in the bulk is heated until they glow. -These spectra are avoided by volatilizing sample before the excitation.
2)Absorption spectra: a)Line spectra(atomic absorption) b)Band spectra(molecular absorption) -Sample may be solid, liquid & gas. -EM radiation is transferred to atoms , ions or molecules. -Layers of sample selectively remove radiation of certain frequency. -Energy difference between Gr.state & one of the excited state of substance is quantised & characteristic. -The frequencies of the absorbed radiation is useful for the characterisation of the constituent of a sample matter. -An absorption spectrum is a result of plotting absorbance Vs. frequency/WL. a)Line spectra(atomic absorption) -Upon passing UV/Vis radiation through monoatomic particles, absorption is a result. e.g, gaseous mercury or sodium -Absorption occurs only in few well-defined frequencies. -The simplicity is attributed to availability of small No. of possible energy states in the particles.
-In case of sodium, most intense absorption occur at 589.3 nm. followed by emission of yellow colour. 5
b)Band spectra(molecular absorption)
E int = E elect. + E vib. + E rot.
-The energy associated with the mentioned types are quantized. i.e. Each energy components assumes only certain value for a given molecule. -On irradiation with many wavelength, the molecules abstract from the incident beam those wavelengths corresponding to photons of energy appropriate for the permitted molecular energy transitions. -Radiation of other wavelengths are simply transmitted. -The relative energy required for electronic, vibrational & rotational transitions are approximately 10000:100:1 respectively. -Passage of molecules from higher to lower energy level is followed by the release of energy(emission) -The region of the absorption is determined by the electronic energy levels of the molecule in absorption of visible & UV radiation Hence, Increase of electronic energy level of a molecule is followed by absorption of visible & UV radiation.
-Vibrational & rotational transitions superimpose upon the electronic transition.
The resulting absorption involves a band of wavelengths rather than a single line(appears nearly continuous spectra)
-The variation of the gain of energy approximates to a Gaussian distribution. 6
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