-UV/Vis & IR spectrophotometer are called optical instruments. -Human eye is not sensitive to UV & IR wavelength , hence -Optical spectroscopic methods based on following phenomena: i)absorption, ii)fluorescence, iii)phosphorescence, iv)scattering, v)emission, & vi)chemiluminescence.
-Instruments for measurement of the phenomena differ somewhat in configuration. -Their basic components are similar. -The required properties of the instruments are same regardless for UV/Vis & IR portion of the spectrum. -Instruments for measurement of the phenomena differ somewhat in configuration. -Their basic components are similar. -The required properties of the instruments are same regardless for UV/Vis & IR portion of the spectrum. Configuration of the components: -Components are similar for absorption, fluorescence & emission measurement. -Differences lie in their configuration.
-The first configuration is for the absorption. -The second is for fluorescence & phosphorescence measurement. -The source is 90
to the detector.
-The third configuration is for the measurement of emission & chemiluminescence. Here, the container is a spark, a plasma & a flame. -The source is sample.
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Sources of radiation -The generated beam of radiation should be with sufficient power for detection & measurement, should be stable for reasonable periods.
-The problem of the source stability can sometimes be minimized by double beam design.
Following are the spectroscopic sources of radiation:
i)Continuum:
ii)Line sources:
iii)Lasers
i)Continuum: -Widespread use in absorption & fluorescence spectroscopy -Intensity changes with WL.
a) Infrared radiation -Common sources of IR radiations:- Globar & Nernst glower. -The Globar is an electrically heated rod of silicon carbide. -Nernst glower is a small rod of refractory oxides. -At 1200-1500
C it starts to conduct electricity and maintains its glow(incandescence).
b)Visible radiation: -Common source of radiation for visible region is a tungsten filament lamp. -It emits radiation of 350-2,000nm. -Tungsten/halogen lamp , a newer efficient version is increasingly used nowadays. c)Ultraviolet radiation: -The convenient light source for ultraviolet region is a deuterium discharge lamp. -Continuous spectrum covers 185-380nm. -Construction: two electrodes in a deuterium filled silica envelope. -High voltage is applied across the electrodes causes emission. -Pressure in the envelope should be low. -In UV/Vis spectrophotometer both tungsten halogen & deuterium lamps are used.
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ii)Line sources: -Emit a limited No. of lines, or bands of radiation & span a limited range of WL.
-Used in Atomic Absorption Spectroscopy, Atomic & Fluorescence Spectroscopy, Raman Spectroscopy, Refractometry Polarimetry. -Mercury & sodium vapour lamp: Used in refractometry, polarimetry. -Low pressure mercury arc lamps used in liquid chromatography.(Dominant line at 253.7-nm Hg line) -Hollow cathode lamps & electrodeless discharge lamps:
Used in AAS , in fluorescence.
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iii)Lasers: Highly useful in analytical instruments for due to : -high intensities, -narrow bandwidth. -coherent nature. Transparent sample holder -Required for all spectroscopic techniques except emission spectroscopy. -The states of samples in solid, liquid & gaseous. -The material of the sample container ideally should be transparent at the wavelength of measurement. -In UV/Vis spectrophotometer: *Above 320nm, the cuvette(cell) should be flat fused glass/fused silica or quartz/plastic. *Below 320nm, the container should be fused silica/quartz cell. -The standard pathlength of cells used in molecular absorption & fluorescence measurements is 10mm. -However, 1-50mm are also available for special applications -The material for sample containers in Infrared spectrometry are sodium chloride(2.5-17m) & potassium bromide (2.5-30)m. -In flame spectroscopic technique(AAS, flame photometry) the sample container is flame itself.
Wavelength selectors -Ideally, most spectroscopic analyses call for radiation of a single wavelength or frequency. *it is because enhances the sensitivity of absorbance measurements.(It is to require for Abs. Conc.) -But no wavelength selector approaches this ideal.
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-Hence, in practice the radiation consists of a limited, continuous group of wavelengths. -These groups of radiation are called a band.
Types of Wavelength selectors 1)Filters 2)Monochromators a)Prisms b)Gratings
1.Filters: -This type includes glass, gelatin & interference (interferometric) filter. -The glass filters are pieces of coloured glass. -In the gelatin filters mixture of dyes are incorporated in gelatin. -The interference filters consist of two parallel glass plates.
2)Monochromators: -Variation of the wavelength of the radiation over a wide range is called scanning a spectrum. -Monochromators are designed for spectral scanning. -Monochromators for UV/Vis, infrared radiation are all similar in mechanical construction.
Components of monochromators: -Slits, lenses, mirrors, windows, gratings or prisms -Fabrication of the components depends on the wavelength region of intended use.
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i)Slits: for a rectangular optical image & reducing the incident beam of radiation to a suitable area
ii)Collimating lens/mirror: that produces a parallel beam of radiation.
iii)Prism/grating: for dispersion of the radiation into its component wavelength.
iv)Focusing element: reforms the image of the entrance slit & focuses it on a planar surface called a focal plane.
v)Exit slit in the focal plane: isolates the desired spectral band or WL of radiation
Radiation transducers -Human eye & a photographic plate or film were detectors for early spectroscopic instruments. -Later detectors or transducers replaced the early means of radiation detection & measurement. -Transducer is to measure & convert radiant energy/light intensities to usable electric signal. -Precise determination of the light intensities are required for accurate determination of substance.
Properties of the ideal transducer -High sensitivity. -High signal - to noise ratio. -Constant response over a considerable range of wave L -Fast response time. -Zero output signal in the absence of illumination.
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-The electrical signal produced by the ideal transducer would be directly proportional to the radiant power P, i.e. S =kP
Where, S is the current or voltage output of detector, & k is the calibration sensitivity.
Types of radiation transducers Two kinds of transducers: 1)Photon transducer: responds to light. Barrier-layer cells, Phototubes, Photomultipliers, Photodiodes etc. 2)Thermal detectors: responds to heat Thermocouples, Bolometres , Thermistors , Golay detector etc.
Signal Processors & Readouts The signal processor is a device to : -amplify the electrical signal from the transducer -alter the signal from dc to ac or vice-versa -change the phase of the signal -filter the signal to remove the unwanted components
-Perform mathematical operations on the signal e.g. differentiation, integration or conversion to logarithm.
-Read out devices are:
DArsonval meter, digital meters, recorders, cathode-ray tubes, LCD panels, computer displays etc.