Write a short description on the basis of a single-beam and double-beam AAS spectrophotometer.

State the differences between the two spectrophotometers.

Atomic absorption spectroscopy (AAS) and Atomic Emission Spectroscopy is among first instrumental techniques and one of the commonest instrumental methods for analyzing for metals and some metalloids. They are based on the pioneering work of Bunsen and Kirchhoff in the middle of the 19th century who discovered that elements which are brought into a hot flame emit light of a characteristic wavelength. (Rosenberg & Panne, 2003). The spectrophotometers measure the ratio of the incident to transmitted light, which really is the energy of the light beam before it passes through the sample divided by the energy of the light beam after it passes through the sample. The measurement logarithm is absorbance, log I0/I. Single - Beam Atomic Absorption Spectrometry A single beam AAS is used to measure the intensity of a beam of light before and then after the addition of a sample and uses a light source, a prism(mirror) and a photocell(detector) as well as a sample holder for the material being analyzed by means of spectrophotometer. The instrument comprises a single beam of radiation emanating from the source (hollow cathode lamp) and travelling through the various components mention earlier and sample until ultimately reaching the detector. In other words, the light from the beam follows only one path - through the flame (figure 1).

Figure 1: Single Beam Spectrophotometer

It is build using an absolute minimum of optical components with the evident advantage of high optical throughput (radiation losses are lower) and relatively low cost. The simplicity of this system is however at the price of limited stability of the system, since any fluctuation in light source intensity will result in baseline variation. The single beam system relies on the light source remaining stable between blank and sample measurements. The incident beam should not drift or fluctuate. This is overcome with the introductions of modern hollow cathode lamps are suitably stable after warm up.

The single beam design is well suited to measuring absorbance at a particular wavelength however it is not as well suited to multiple wavelength measurements. The zero absorbance must be reset on the blank solution whenever the wavelength is altered i.e. there is no automatic blank correction. There is also the possibility that drifts in lamp intensity could mean significant errors over long periods of time.

The dynamic range of a single beam instrument tends to be larger and the instrument itself more compact as well as simpler in optical terms, which make these spectrophotometers easier to maintain and slightly less costly to operate, generally speaking. The single beam spectrophotometer is relatively low in cost and this is a significant advantage in smaller laboratories or those with low AAS sample throughput.

Double - Beam Atomic Absorption Spectrometry

The basic principle of double beam spectrophotometer is the instruments gather data from the difference in light intensity of two beams of light. One beam's path contains a reference sample with known properties, the other containing the sample being tested. Double beam models have their own set of advantages. Since these instruments are used with a reference sample, they do not typically need to be zeroed in between taking readings. These instruments also offer somewhat easier operation and the results tend to be more reproducible.

Figure 2: Double Beam Spectrophotometer

The light from the Hollow Cathode Lamp (HCL) is split into two paths using a rotating mirror where one pathway passes through the flame and another around. Both beams are recombined in space so they both hit the detector which is usually photomultiplier but separated in time. The beams alternate quickly back and forth along the two paths: one instant the photomultiplier beam is split by the rotating mirror and the sample beam passes through the flame and hits the photomultiplier. The next instance, the HCL beam passes through a hole in the mirror and passes directly to the photomultiplier without passing through the flame. The difference between these beams is the amount of light absorbed by atoms in the flame.

The purpose of a double beam instrument is to help compensate for drift of the output of the hollow cathode lamp or photomultiplier. If the HCL output drifts slowly the subtraction process described immediately above will correct for this because both beams will drift equally on the time scale of the analysis. Likewise if the photomultiplier response changes the double beam arrangement take this into account.

Double beam instruments were originally designed to overcome poor hollow cathode lamp characteristics, noisy Power Supplies, drifting detectors & amplifiers,

thermal expansion variations in optical components (mirrors, beam splitters, mounts, etc.) By using a high light-loss optical component, the beam splitter, to divide the signal beam from the hollow cathode lamp, served to correct for these low performance components; thus halving the available energy to make a sample measurement, compensation between the reference and sample beams was maintained. However, the same features which lend it its greatest strengths are also the source of its weaknesses. A double beam spectrophotometer is more costly to purchase and maintain and slightly more costly to operate than a single beam instrument as well.

Conclusion

A spectrophotometer, single beam or double suitability for a given application depends on the sample to be tested and the demands of the application. For some purposes, one instrument is a better choice than the other. Both types of instrument are used to determine some of the physical properties of the sample being tested by providing information about the amount of light absorbed by the sample and at which wavelengths, data which can reveal much about the sample's characteristics.

Modern spectrophotometer techniques are of course done in conjunction with software which is designed to assist in interpreting the information yielded by the spectrophotometer. Single or double beam, this part of the analytical process is much the same. The data is uploaded to a computer for reporting, analysis and manipulation including plotting the information to a grid, conversion of transmittance data to absorbency, baseline correction and other procedures which allow researchers to learn more about the sample.