ATOMIC ABSORPTION SPECTROSCOPY

AAS is the measurement of absorption of radiation by free atoms. The total amount of absorption depends on the number of free atoms present and the degree to which the free atoms absorb the radiation. The key to understanding the application of atomic absorption spectrometry to analytical chemistry lies in understanding the factors which affect (1) the ability of the atoms to absorb and (2) the factors which affect the generation and loss of free atoms from a particular atom population. 1. THE ABILITY OF FREE ATOMS TO ABSORB A given population of free atoms exists at various electronic energy levels. The distribution of atoms in the energy levels is given by the Boltzmann distribution equation, i.e. Ne/No= g.e ( E/kT). The equilibrium between atoms in the high energy state and atoms in the low energy state depends on the energy required to excite the atoms and the temperature of the system. If the energy is great, the number of excited atoms is small and vice versa. If the temperature is high, the number of excited atoms is increased. At room temperature and at the temperatures obtained by most flame atomisers the number of atoms in the excited state is a very small fraction of those in the ground state and for absorption purposes can be ignored. A. Absorption by free atoms. In order to measure absorption by free atoms it is first necessary to choose the correct wavelength at which this absorption can be measured. That wavelength is a critical property of the atoms and is given by the equation E = E 1 -E2 = h = hc/ (4) where El = the energy of the higher energy state, or the energy after absorption; E2 = the energy of the lower energy state, or the energy before absorption. The energy of the radiation which the atom can absorb must equal the energy difference between the ground state and the excited state the atom. Why transition between ground and excited state instead of any two states is considered for analysis? Theoretically, any transitions between two states permitted by quantum theory can be used in AAS. In practice, however, it is found that the number of atoms in the upper excited state is extremely small and the degree of absorption by these few excited atoms is scarcely measurable. Consequently, absorption lines relating to transitions between an excited state and a higher excited state are insensitive and not analytically useful. Moreover, if absorption by these few atoms was measured, many orders of magnitude in sensitivity would be lost. Thus, AAS invariably utilizes transitions between the ground state (where the vast majority of atoms reside) and an upper excited state.
i. Absorption laws: To a first approximation, absorption by free atoms is similar to absorption by molecules and there is a linear relationship between absorbance and the concentration of the sample. This relationship is given by the Beer-Lambert Law which can be written in several ways such as follows: T = Il / I o, where T = transmittance, I0 is the initial radiation intensity and Il is the intensity often passing through the sample. Note that the ratio I1 /Io is independent of the light intensity. A sample of concentration c and path length b may absorb 30% of the light in which case Io = 100, Il = 70. If we put a second sample in line, the light intensity entering it will be 70. This will be I0 for the second sample. But since T is constant for that sample the light intensity leaving the second sample will be 70 x 70/100 = 49. There is a logarithmic relationship between Il and path length. Similarly, there is a logarithmic relationship with concentration. This can be summarized as I 1 = I0 10 -abc or I1 / I0= 10 -abc where Q = absorptivity, b = sample pathlength, c = concentration. From this - log I1/Io = abc We define - log Il / Io as A, where A = absorbance. Hence A = -1ogT = abc ( 5 ) This can be summarized as A = abc, which is the Beer-Lambert Law stating that the relationship between concentration or path length and absorbance is linear. In atomic absorption this relationship holds true in the sense that if we have two samples, one with a concentration twice the other, then the absorbance of the former will be approximately twice the latter within the limits of Beers Law. However, in practice it is found that this relationship cannot be sustained because flame atomizers are generally used as the sample cell and

the population of free atoms in a flame is far from homogeneous. Homogeneity of the sample is a basic requirement for the application of Beers Law. What happens when the concentration of the sample increases? Beers law is limited to dilute solutions i.e. <0.01 M. So when we increase the concentration of the solution it will start interacting with each other and their electrostatic forces will start interfering with each other. Thus there will be a deviation. Also, equilibrium constant of a reaction is dependent on the concentration under a constant condition. Hence with a change in concentration there will be deviation from Beers Law. WORKING PRINCIPLE: As with the colorimeter, the intensity of radiation is measured without the sample in the cell and designated I0. Sample is then introduced into the flame, ground state atoms are produced and absorption takes place. The intensity of radiation is measured and designated I. The same relationship holds for this absorption: I0 - I = the amount of source radiation absorbed by the sample atoms. In order to understand quantitative analysis by atomic absorption we must know how this absorption increases or decreases as the concentration of atoms in the sample is varied. The quantitative relationship is expressed by the Beer-Lambert Law, A = abc, where A is absorbance, a the absorptivity constant, b the cell path length and c the sample concentration. More simply, it states that the amount of light that is absorbed by a sample is a function of the number of absorbing atoms in the light path. Clearly, the number of atoms is a function of the sample cell path length and the concentration of the sample. In atomic absorption analysis, the sample cell is an atomizer which in most cases has a very reproducible path length, b, and Beer's Law relationships are followed in most cases. The percentage absorption reading is converted to absorbance, log10 (I0/I1) and then related to the sample concentration. For example, a sample absorption of 12.9% = 0.06 absorbance, and 1% absorption = 0.0044 absorbance. The most important point to note about the Beer-Lambert Law is that the concentration of the sample is directly proportional to absorbance A and not to percentage absorption. The atomic absorption process can be summarized as follows: 1. Radiant energy is emitted from a hollow cathode lamp and passed through a flame. 2. The flame sampling system produces ground-state atoms from the sample. 3. The intensity of radiation before and after sample atomization is measured and the result shown on a meter readout or digitally. 1. Hollow cathode lamp: A typical hollow-cathode lamp is shown in cross section in . The lamp consists of a glass envelope containing a cathode and an anode. The cathode is a metal cup or cylinder which is made of the chemical element for whose analysis it will be used. Thus, for a copper analysis, a lamp will be used having a pure copper or brass cathode. In the second case the lamp spectrum will also contain zinc lines. The sealed glass envelope contains an inert gas, usually neon at low pressure. When a high voltage, 300+00V is applied across the electrodes, positively charged neon ions bombard the cathode and dislodge (sputter) atoms of the cathode element. These atoms are excited by collisional processes and the emission spectrum of the element or elements is produced. Thus, by choosing the appropriate chemical element for the cathode, the atomic spectrum of that element may be readily generated. The cathode is usually surrounded by an insulating shield of mica, ceramic material or glass. This ensures that the discharge is confined to the interior of the cathode and results in an improvement in the intensity of the emitted lines. The anode can be of almost any shape. The material used for the lamp window is important since it must transmit the spectral line(s) of the element being studied. Because quartz glass transmits over the full wavelength range it is suitable for all lamps. The other glasses are less expensive, and they can be used for elements whose resonance lines lie above 300 nm. The fill gas is usually argon or neon at a pressure of 10--15torr, i.e. about 1/50th of atmospheric pressure. Neon is preferred because it produces higher signal intensity than argon, but where a neon line occurs in close proximity to the elements resonance line, argon is used instead.

Electrodeless discharge lamps : The biggest claimed advantage of EDLs is the increased intensity of the line spectrum, by several orders of magnitude compared with the hollow-cathode lamp. They consist of a sealed quartz tube several centimeters in length and about 5-10mm in diameter, filled with a few milligrams of the element of interest (as pure metal, halide or metal with added iodine) under an argon pressure of a few to^. The tube is mounted within the coil of a high-frequency generator at around 2400 MHz and excited by an output of a few Watts up to 200 Watts. Various views exist on the advantages or otherwise of electrodeless discharge lamps in AAS, Higher radiation intensity does not influence the sensitivity but the signal-to-noise ratio can occasionally be improved leading to better precision. 2. Flame : The flame is so controlled that the following reaction in fixed proportion will occur. 2 C2H2 + 50 2 = 4 CO2+ 2H2O + HEAT When C2H2 increased, the flame condition is reducing. Some carbon particle will form and thus the flme will glow with a high temperature. For stable oxide forming element a reducing flame is required. Elements like Si, Cr, Mo, Al, Sn. However, excess of C2H2 might lower the temperature. In this raction free radicals are formed which reaches the diffusion zone and react to form H2O and CO2.
Secondary diffusion zone (blue)

3. Burner: Made up of Tantalum. It is less corrosive. 4. Nebuliser: 10% of the original solution is nebulised. Efficient nebulisation is required

inorder to get a steady signal (steady density) Minimizing Chemical Interferences The quantitative analysis of some elements is complicated by chemical interferences occurring during atomization. The two most common chemical interferences are the 1. formation of nonvolatile compounds containing the analyte and 2. Ionization of the analyte. Formation of nonvolatile compounds containing the analyte (alkali metals Ca, Mg, REEs) : One example of a chemical interference due to the formation of nonvolatile compounds is observed when PO4 3 or Al3+ is added to solutions of Ca2+. These interferences were attributed to the formation of refractory particles of Ca3(PO4)2 and an AlCaO oxide. The formation of nonvolatile compounds often can be minimized by increasing the temperature of the flame, either by changing the fuel-to-oxidant ratio or by switching to a different combination of fuel and oxidant (air-acetylene flame can be replaced by N2OAcetylene flame.However this can cause ionisation of Ca, Mg. So 0.1% KCl solution is used). Another approach is to add a releasing agent or protecting agent to solutions containing the analyte. A releasing agent is a species whose reaction with the interferent is more favourable than that of the analyte. Adding Sr2+ or La3+ to solutions of Ca2+, for example, minimizes the effect of PO43 and Al3+ by reacting in place of the analyte. Thus, adding 2000 ppm SrCl2 to the Ca2+ /PO4 3 and Ca2+/Al3+ mixtures discussed in the preceding paragraph gave absorbances for each of 0.48, whereas a solution of 2000 ppm SrCl2 and Ca2+ alone gave an absorbance of 0.49. Protecting agents react with the analyte to form a stable volatile complex. Adding 1% w/w EDTA to the Ca2+/PO4 3 solution discussed in the preceding paragraph gave an absorbance of 0.52, compared with an absorbance of 0.55 for just the Ca2+ and EDTA. On the other hand, EDTA does not serve

as a protecting agent for solutions of Ca2+ and Al3+. Uranium can also be used as a releasing agent s it is having high affinity for oxygen and low atomic absorption affinity. Ionization of the analyte (alkali elements) : Ionization interferences occur when thermal energy from the flame or electrothermal atomizer is sufficient to ionize the analyte M t M+ + e where M is the analyte in atomic form, and M+ is the cation of the analyte formed by ionization. Since the absorption spectra for M and M+ are different, the position of the equilibrium in reaction 10.28 affects absorbance at wavelengths where M absorbs. If another species is present that ionizes more easily than M, then the equilibrium in reaction 10.28 shifts to the left. Variations in the concentration of easily ionized species, therefore, may have a significant effect on a samples absorbance, resulting in a determinate error. The effect of ionization can be minimized by adding a high concentration of an ionization suppressor, which is simply another species that ionizes more easily than the analyte. If the concentration of the ionization suppressor is sufficient, then the increased concentration of electrons in the flame pushes reaction 10.28 to the left, preventing the analytes ionization. Potassium and cesium are frequently used as ionization suppressors because of their low ionization energy. Na Na+ + eCs Cs + + e- ionizes first Na+ + e- = Na (atomic Na). Also low temperature flame air- butane can be used to remove the interferences. Titanium and Aluminium: They form stable monoxides which have a very high energy of dissociation (5eV). So we use N2o-C2H2 flame. The reducing properties of CN* are helpful in reducing Ti anal. Specifically for Ti, ions of Fe , Al and fluroboric acid interferes. (origin of fluroboric acid: F from HF used for dissolving the salts and B from boric acid used for neutralising HF action to protect the glass). The suppression of ionisation is done u8siong LaCl3 or KCl at high temperature. Silicon: It forms SiO which is very stable. Dissociation energy is 8.3 eV. So, N2o-C2H2 flame is used. But absorption signal of Si is very very sensitive to the flow-rates of oxidants and fuel. Flow rate N2O 7.7 Si absorption 0.004 0.040 0.090 0.120 0.140 0.147 Remark

C2H2 (l/min) 4.5 4.65 4.85 5.00 5.15 5.30

very very luminescent, very noisy, clogging of burner by SiC .

5.50 0.135 Best possible way is to reduce the concentration of silicon in the solution. It should be of within 100200g/ml (ppm). We can use HF, LiCO3, H3PO3 to break down silicate. But HF is sufficient to dissolve silicate. References: 1. Web sites 2. A Handbook of Silicate Rock Analysis.