Thursday, January 30, 2014

Spectrophotometry - IR Spectroscopy - Instrumentation

In the earlier post, we have tried to understand the basic concepts and a little theory about the infra-red (IR) spectrophotometer. The basic instrumentation of IR spectrometer consists of the components which will be explained here briefly. 

Sources: The IR spectrometer consists of a source of infrared light, emitting radiation throughout the whole frequency range of the instrument. An inert solid is electrically heated to a temperature in the range of 1500-2000K. This heated material will then emit IR radiation. Following are some of the sources:

The Nerst Glower: It is a cylinder of rare earth oxides. Platinum wires are sealed to the ends and a current is passed through the cylinder and can reach temperatures of around 2200K.

The Globar source: It is a silicon carbide rod which is electrically heated to around 1500K. The spectral output is comparable with the Nerst glower, except at short wavelengths (less than 5mm) where it’s output becomes larger.

The Incandescent wire source: This is a tightly wound coil of nichrome wire, which is electrically heated to 1100K. It produces a lower intensity of radiation than the above mentioned Nerst or Globar sources, but it has a longer working life.

Light from these sources is split into two beams of equal intensity. One beam is allowed to pass through the sample while other is allowed to behave as reference beam. Now, you might be thinking that why there is a need of double beam? So, the function of such a double beam operation is to measure the difference in the intensities between the two beams at each wavelength. 

Chopper: The two beams are reflected to a chopper which is rotating at a speed of 10 rotations per second.  This chopper makes the reference and the sample beam to fall on the monochromator grating alternately.

Monochromator grating: The grating also rotates, though slowly. This rotation sends individual frequencies to the detector. 

Detector:At the wavelength where the sample has absorbed, the detector will receive a weak beam from the sample while the reference beam will retain full intensity. This leads to a pulsating or alternating current to flow from detector to amplifier. On the other hand, at the frequencies where the sample doesn’t absorb, both the beams will have equal intensities and the current flowing from the detector to the amplifier will be direct and not alternating. The amplifier is designed to amplify only the alternating current. 
There are three different types of detectors.

Thermocouples: They consist of a pair of junctions of different metals. The potential difference (i.e.; the voltage) between the junction changes according to the difference in temperature between the junctions.

Pyroelectric detectors: They are made from a single crystalline wafer of a pyroelectric material (eg; triglycerine sulphate). The properties of a pyroelectric material are such that when an electric field is applied across it, electric polarisation occurs. In a pyroelectric material, when the field is removed, the polarisation persists.  This degree of polarisation is temperature dependent.

Photoelectric detectors: They comprise a film of semiconducting material deposited on a glass surface, sealed in an evacuated envelope (such as mercury cadmium telluride detector).

The above mentioned description is that of a “dispersive infra-red spectrometer”. Most of the modern IR absorption instruments use Fourier transform techniques with Michelson interferometer (about which we will not discuss here) which is referred to as Fourier Transform Infra-red Spectroscopy or FTIR Spectroscopy.

In the next post, we will discuss about the various sampling techniques for IR spectroscopy.

Tuesday, January 28, 2014

Spectrophotometry - IR Spectroscopy - Theory and Concepts

Welcome back.! :) My sincere apologies to all my readers for not having posted for a long time.

We were discussing the different types of spectrophotometers. We have already discussed about the instrumentation and applications of UV-visible spectrophotometry. In this post, we will have a look at (infra-red) IR spectrophotometry.

As we have seen earlier that visible light that we are able to see is just a small part of electromagnetic radiation spectrum. On the immediate lower side of this visible spectrum lies the infrared and on the other side lies the ultraviolet. So, in this post, we will be discussing about the absorption on the lower side of this spectrum. This infrared covers the range of 0.78nm and 1000nm of the electromagnetic spectrum.
We will try to understand the theory of infra-red absorption. So, to start with, we know that the infra-red radiation is of higher wavelength as compared to UV-visible region, so the electromagnetic radiation of this region constantly has low energy. Thus, infra-red radiation is associated with vibrational transitions of molecules. The atoms in molecules are in continuous vibration with respect to each other at temperatures above absolute zero.

Remember that the bond distance between the atoms in a molecule fluctuate to about ±0.5A˚.
Now, there are two kinds of vibrations as:
a. Stretching vibrations
b. Bending vibrations

The stretching vibrations are those where there is an increase or decrease in the bond length but the atoms remain in the same bond axis. The bending type of vibrations involves the changes in the positions of the atoms with respect to bond axis (here, such variations in bond angles may be about ±0.5˚). These vibrational transitions are low energy transitions and these energy levels correspond to the energies of the electromagnetic radiation in the infra-red region of the spectrum.
So, now we can ask a question as to ‘When does the molecule absorb radiation?' So, the answer is, when the frequency of a specific vibration equals the frequency of the IR radiation directed on the molecule, then the molecule absorbs radiation. 

Note: Difference in the presentation of IR spectra and UV-visible spectra:
Firstly, in the IR spectra, wave number is used rather than wavelength. Secondly, IR spectra are typically presented as percent transmission (transmittance x 100) versus wave number.

Modes of Vibration:

Each of the atoms has three degrees of freedom which corresponds to the motions along any of the three Cartesian coordinate axes (x, y, z). The theory of molecular vibrations predicts that an asymmetrical molecule will have 3n – 6 modes of fundamental vibrations where n is the number of atoms in that molecule. So, by this, the molecule methane (CH4) will have 3 (5) - 6 i.e.; 9 fundamental modes of vibration.

The diagram shown above depicts the vibrational modes available for AX2 systems (were any atom is joined to two other atoms eg., NO2, CH2 etc.)

Normally each vibration mode absorbs at a different frequency. Thus, a CH2 group will give rise to two C - H stretch bands which maybe symmetric or asymmetric. However, this is not always true. There will be some vibrations that may absorb at the same frequency and naturally, their absorption bands will overlap. Such vibrations are said to be degenerate. Also, there are vibrations whose absorption frequency may lie outside the normal infrared examined.

Till now we have seen about the vibrations which are fundamental. There are many other frequencies at which the bands can appear in an infra-red absorption spectrum.  Some of them are:
Overtone bands: These bands are generated by modulation of fundamental vibrations. Like, strong absorption at 800 cm-1 may give rise to a weaker absorption at 1600 cm-1.

Combinations or Beats: Another kind of modulation is when the two different frequencies x and y interact with each other (combinations). Such interactions may take place as x + y or as x - y. These resulting weaker absorptions are called beats.

You would agree that a particular kind of combination can occur in that particular compound and in none other. It is so because each compound has its own particular arrangement of atoms and so we can say that the combination bands are unique to a compound. Thus, the combination bands have extreme importance because they maybe signature or the fingerprint of a given compound. In other words, the IR spectra of no two compounds are alike or we can say conversely that substances giving the same IR spectra are identical. A large number of compounds fall in 900cm-1 and 1400cm-1. For this reason, this region is called the “fingerprint region”.

So, these were certain concepts and theory of IR spectrometry. In the next post, we will have a look at the instrumentation followed by sampling techniques for IR spectroscopy and lastly, applications of IR spectrophotometry.