Instrumentation of Infrared Spectrometer

1 SAROJ POUDYAL M. PHARM INDUSTRIAL PHARMACY ROLL NO. 18 1 ST S E M . 2011- 2013

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Introduction
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Spectroscopy is the study of the interaction of electromagnetic radiation with a chemical substance. The nature of the interaction depends upon the properties of the substance. When radiation passes through a sample (solid, liquid or gas), certain frequencies of the radiation are absorbed by the molecules of the substance leading to the molecular vibrations. The frequencies of absorbed radiation are unique for each molecule which provide the characteristics of a substance.

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Contd
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Infrared spectrometer utilizes the light of infrared region for the analysis of sample. Mostly this method is utilized for the identification of the material and is qualitative analytical work. Infra Red means beyond the red region (as shown in below figure)

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There are different types of instruments available, primarily single beam infra red spectrophotometer were in use and latter on it has changed to double beam infrared spectrophotometer. In these days most are using the double beam spectrometer and in addition to this FTIR is in abundant use. Here in this presentation only double beam Infra red spectrophotometer is described.

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Instrumention
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Basically, following components are present in a infra red spectrophotometer. These are the basic components which are found in both single and double beam spectrophotometer.
    

Light Source Sample holder Monochromator Detectors Miscellaneous items

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Light source
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There are different light source available or are in use to produce the Infra Red lights of different regions, i.e. inside infra red region there are three regions of infrared lightNear Infrared 12500 to 4000cm-1 (0.8 to 2.5um) Mid Infrared 4000 to 200cm-1 (2.5 to 50um) Far Infrared 200 to 12.5cm-1 (50 to 800um)
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Instrumentation of IR
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Rotary chopper Sample cell

Detector

Reference cell

Monochromator source
4/1/2012 Three dimensional view of IR spectrophotometer, simplified

Instrumentation of IR
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Simplified diagram of Infra Red Spectrophotometer

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Light source
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The main light sources which are in use can be listed as follows
     

Nernst Glower Silicon (Globar) Mercury Arc Incandescent wire Carbondioxide Laser Tungsten Lamp

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Nernst Glower
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Nernst glower are made up of oxides of elements like, Zn, Th, Ce, Y, Er etc and these are available in 12 mm diameter and up 20 mm length. From the both side of filaments, electricity are passed and are heated up to 18000C, then it starts glowing i.e. emitting light of infra red region. This lamp is used to produce near IR lights and used for analysis of carbohydrate and proteins.

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Silicon (Globar)
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It is the rod of sintered Silicon carbide and are of length 50 mm length ,5 mm in diameter. These rods are electrically heated at 1300-17000C. These rod may get bend, so water cooling required to prevent arcing. Spectral energy is comparable with nernst glower. They are self starters. used in middle IR region. used to detect simple functional groups.

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Mercury arc
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Mercury in high pressures are used. Used in far IR region. Intensity of radiation is greater. Used to detect inorganic complexes.

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Incandescent lamp or Nichrome wire

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It is made up of nichrome wire. Used in near IR instruments. Has a low spectral emissivity. It is heated up to 10000C. This light source is used to detect complex organic molecules.

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Carbondioxide laser
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A tunable co2 laser is used as an IR source for monitoring the concentration of certain atmospheric pollutants and for determine absorbing species in aqueous solution, in the Range 900-1100 cm-1 which consist of about 100 of closely spaced discreet line. And are important for quantitative determination of number of species like ammonia, butadiene, benzene, ethanol, nitrogen dioxide, trichloroethylene An important property of the laser source is the radiant power available in each line which is several order of magnitude greater than that of black body source
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Tungsten lamp
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Heated up to 30000C and they emit the IR radiation of mid IR region and are used for the detection 0f organic functional groups.

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Sample holder/cell
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According to sample handling technique, there are 3 different kinds of sample cells available.
  

Cell to accommodate solid sample Cell to accommodate liquid sample Cell to accommodate gas sample

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Solid Sample cell

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The universal type of sample holder usable for films, pellets, windows, mulls, etc in sample sizes from 13mm up to 40 mm diameter and 13 mm thickness.

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Liquid sample cell

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Gas sample cell

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These are made up of different materials, which are mostly inert to the infra red lights i.e. at the time of exposure they didnt absorb the light. Both ends are covered with disc of metal halides, and are vacuum able. Infra red light are passed perpendicularly or in angle.
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Summary of sample apparatus

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Motor pestle Gas sample holder Liquid sample holders

Pellet forming die

Solid sample holder

Sample holders and the materials used for preparation of sample, at a glance.
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Sample handling
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y Solid samples

There are 2 common techniques for powder solids 1) KBr pellet technique - One of the most popular technique for handling solid samples has been KBr pelleting halide salts be come transparent when sufficient pressure is applied to the finally powder material. 2) MULLS technique - IR spectra of solid that are not soluble in IR transparent solvent or are not conveniently pelleted in KBr are often obtain by dispersing the analyte with mulling agent. E.g. Nujol, refined mineral oil etc.

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In addition to the above mentioned techniques, one another technique is also in use called as deposited film. In this technique, the solid films are deposited onto the NaCl plate, by allowing a solution in a volatile solvent to evaporate drop by drop on the flat surface. Sometimes, the solid materials can be observed by changing them in solution state, but the spectra produced are different than the spectra they produce in solid state.
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Mulling agents
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Mulling agents are substance that transmit a wide range of IR frequency and help to minimize scattering by surrounding the analyte with a medium whose refractive index more closely matches to that of the sample than does air. Nujol, refined mineral oil is commonly used mulling agents. Other mulling agent is FLOUROLUBE i.e. halogenated polymer, fluorinated HC mull,perflouro kerosene or hexa flourobutane.

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But the Nujol cant be used in whole range of IR, as due to the presence of H-C bond in it, and interfere with the absorption of C-H bond of sample in the range of IR below 1300cm-1. So, it is useable to the sample whose absorption is above 1300cm-1. Thus for the IR above 1300cm-1 range, other mulling agent like Flourolube is used. Flourolube doesnt absorb IR in IR range above 1300cm-1. But sometime for the unknown samples, both i.e. nujol oil and flourolube can be used so that absorption in whole range wont be disturbed.
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Drawback, The problem associates with solvent chosen are eliminated with both mulling agents. But the spectra generally can not be used for quantitative analysis. So, separate mull with both of the agent is prepared for the sample, covering the whole range of IR. Preparing separate mull in both of the mulling agent is somewhere called split mulling.

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y Liquid sample

Liquid can be sampled in no. of different way depending on the sample characteristics such as volatile, composition and corrosively (towards the cell material) and the overall absorptive. one of the simplest and most popular method i.e. to sandwich the liquid between 2 IR window typically made from NaCl or KBr thus producing a capillary film this is certainly and rapid procedure

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y Gas sample

Gas sample is directly inserted in vacuumed sample cell, and fitted to the instrument for analysis.

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Monochromator
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They convert polychromatic light into mono chromatic light. They must be constructed of materials which transmit the IR. They are of 2 types.
 

Prisms Gratings

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Prism Monochromator
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There are different kinds of prism available which can be used in IR. These prism works in the principle of diffraction of light. Glass and quartz prisms absorb light of IR region themselves, so, in IR Metal halides prisms are used which transmit in IR. E.g. NaCl prism are useful in region of 4000 650cm -1 Lithium fluoride ,calcium fluoride prisms are useful in region where significant stretching vibration is located.

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Grating Monochromator
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Grating Monochromator are used to separate light of desired wave length from the whole light, as light source provides not only the light of desired wavelength. The Monochromator consists of microscopically grooved triangles, in parallel and uniform sizes. The grooves may be 20 grooves per mm to 4000 grooves per mm and sometimes more than 5000 grooves per mm. There are different kinds of Monochromator available, they can be listed as follows
 

Interference type Refraction type

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Detectors/ Transducers
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These are the devices used to detect the IR light passed through the sample and compare the difference between light received from reference cell and sample cell. Three types of detectors are used in IR spectrophotometer.
  

Theremal Detectors Pyroelectric detector Photon (Quantum) detector

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Thermal detector
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Thermal detector whose response depend on heating effect. Which in terns alters the physical properties of transducers such as resistance. It is a transducer that changes thermal energy into an electric signal. The electric signal is amplified and routed to the read out device But the problem of measuring IR radiation by thermal means is compounded by thermal noise from the surrounding for this reason thermal transducers are housing in a vacuum and are carefully shielded from thermal radiation emitted by other near by objects. Therefore temperature of room is maintained
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There are 3 different types of thermal detectors available , which can be used in IR Spectrophotometer.
Thermocouple detector  Thermister or Bolometer detector  Pneumatic or Golay cell detector (Detail of these can be furnished, if required)


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Thermocouple detector
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This is the most widely used detector in IR. It consist of 2 metal pieces like Bi, which are joined with dissimilar metals like sb, and form a pair of junction. The junctions are usually black ended so heat absorption will be better. One end of the junction will receive the IR for detection which cause the heat change of the end and finally generate the electric impulse for recording.

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Thermister or bolometer
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In this instrument, resistance of two different metals are so managed that one end will receive the IR from the sample and these two resistance are connected with whetstone bridge potentiometer. When the IR radiation heat the resistance, heat generates and the electric potential is generated which will be finally recorded.

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Pneumatic or Golay cell detector

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Pneumatic detectors respond to change in volume of non absorbing gas or liquid with temperature change. In pneumatic device if gas is used as medium called golay detector Here the absorbing radiation heats an inert gas (usually xenon) in a pneumatic chamber behind the plate and cause the gas to expand As the gas expands the flexible diaphragm at the opposite end of the chamber from the metallic plate is pushed outward this effect will be responsible to generate and pass the signal for recording.
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Pyroelectric detector
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The most recently developed IR detector is pyroelectric detector. It is constructed from single crystalline wafers of pyroelectric material which are insulated (dielectric material ) with very thermal and electric properties having materials. Certain crystal such as TGS (tri glycine sulphate ((NH2,CH2,COOH)3.H2SO4) DTGS (deuterated triglycine sulfate Lithium tantalat(LITAO3) Lithium niobate (LINbO3) are the important Pyroelectric material used in IR detector This crystal possesses internal electric polarizations. This internal property is taken in account. Crystal is placed between 2 electrodes one of which is IR transparent .

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When IR radiation fall on crystal its temp. is change, which alters the charge distribution across the crystal, which can be detected as the current in the external electric circuit connecting the 2 side of the capacitor. The magnitude of this current is proportional to the surface area of crystal and the rate of change of polarization with temp. This is known as pyroelectric effect.

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Photon (quantum) detector

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These detector generate an output signal that is proportional to the number of photons absorbed in the device material rather than to their total energy. At the same time the energy of each single photon must be high enough to cause delocalization of carriers across the device structure, resulting in increasing the device conductivity (as in photoconductive detectors) or in generating potential difference across a junction (as in photovoltaic detectors). These detectors are characterized by selective energy (or, wavelength)dependent response.
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Other detectors
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In addition to these detectors, photovoltaic detectors using diode type can also be used. While utilizing this detector, it should be highly sensitive. Mercury cadmium telluride (MCT) detector of photoconductive type and high sensitive, is the common detector used in IR spectrophotometer.

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Miscellaneous items
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In addition to these main components, certain other components are used in instrumentation of IR spectrophotometer. Following components can be kept inside this


Mirrors
Concave  Plane


Rotating mirror or chopper

These components are used as per requirement and according to the suitability. But the rotating mirror or chopper mirror play a major role. This mirror allows to pass one light either from reference cell or sample cell at a time and in the basis of this received light the detector analyze the material.
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The Michelson interferometer

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Instrumentation of Fourier-transform infrared absorption spectrometers (FTIR).

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Application of IR Spectrophotometer
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Pharmaceutical applications include:

  

    

Identification of raw materials Product quality Moisture and solvent content in drying or solvent removal processes, Residual drug carryover in manufacturing facilities, Mixing quality evaluation, Imaging of tablets Packaging systems. Real-time monitoring of fermentation processes, and products

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Application
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Thank you for you your active participation

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