Atomic Absorption Spectroscopy

Tutorial 2
Saravanakumar a/l Maniam SGC 130019

Saravanakumar Maniam SGC130019

Topic 2 : Atomic Absorption Spectroscopy (AAS)

1. Define: a) Sputtering: a process whereby atoms are ejected from a solid target material due to bombardment of the target by energetic particles b) sensitivity in AAS : Sensitivity is concentration of sample which give 1% absorption

2. State and describe the various parts of an AAS spectrometer. a) Light Source (HCL): light beam from HCL passed through flame. Radiation absorbed transformed atoms from ground state to excited state. b) Burner: Sample is vaporized, atomized in flame. Transformed to unexcited ground state atoms, absorbed light at specific wavelengths. c) Monochromator: separate & transmit a narrow portion of optical signal chosen from a wider range of wavelengths available at input. d) Detector: photomultiplier, convert light signal into electrical signal. e) Amplifier: Amplified and process electrical signal. f) Readout: Display of signals by computer or printer.

3. Primary radiation sources are important in AAS. State the various conditions which are important for the primary radiation sources. a) Emit line spectrum of one or more analyte elements with line widths smaller than those of absorption lines in atomizers. b) Have high spectral radiance density (radiant power per unit area, solid angle, & unit wavelength) in center of spectral line. c) Their optical conductance must be high d) Radiance s of analytical line must be constant over along time.

4. Describe the mechanism of operation of a hollow cathode lamp a) When a discharge occurs between two electrodes via a gas at low pressure, the cathode is bombarded by the energetic, positively-charged gas ions (for example, ionized filler gas atoms) which are accelerated towards its surface by the potential existing in the discharge. b) The energy of these ions is such that atoms of the cathode material are ejected or sputtered into the plasma. c) Here they may collide with other high energy particles which are present. These collisions result in a transfer of energy causing the metal atoms to become excited. d) Since this excited state is not stable, the atoms relax back to their ground state, emitting radiation at the characteristic wavelength of that element. For most elements, more than one analytically useful spectral line is generated.

.
1

Saravanakumar Maniam SGC130019

5. How do we prolong the lifetime and efficiency of the AAS detectors? never exceed the saturation limit of PMT tube by flooding it with light, too much radiation from flame or high concentration of sample components Limit to measuring low power radiation because intense light causes irreversible damage to photoelectric surface Devise always housed in a light tight compartment Care is taken to eliminate possibility of being exposed to strong light while powered.

6. What are the advantages of using Nitrous Oxide Acetylene Flames in AAS? Provide higher atomization efficiencies, better detection limits for refractory elements. Use of N2O instead of O2 as oxidant reduces probability of metal atom becomes oxidized in flame. Minimizes interference effects for many elements. Useful for metals that difficult to reduce. Has zone of high concentration of CN & NH species, results in strongly reducing environment

7 State the advantages and disadvantage of a premix burner in atomization of samples. Advantages: a) Elongated flame introduces more atoms into light path, increasing analytical sensitivity. b) Burner encrustation is reduced because large sample droplets are eliminated from system in mixing chamber. c) Burner is quiet to operate & therefore reduces irritation to operator. d) Analytical signal is significantly less noisy than total-consumption burner because sample droplets are effectively removed from light path & light scattering is reduced. Disadvantage a) if sample contains more than one solvent, any volatile material is preferentially evaporated in mixing chamber & less volatile component drains off & does not reach burner. b) Hazard if volatile combustible samples are being analyzed. c) Special precautions must be taken if oxyacetylene flames due to danger of flashback of fuel-oxidant mixture. 8 State the advantages and disadvantage of a total consumption burner in the atomization of samples. Advantage: a) Inexpensive b) No fractionation of sample during aspiration

Saravanakumar Maniam SGC130019

Disadvantage: a) Analytical signal changes as rate of aspiration of sample changes. b) Very viscous sample cannot be aspirated at all & analyzed. c) Sample broken into droplets after introduction into flame. d) Burner tip became encrusted with salts left after evaporation of solvent. e) Burners are very noisy, physically & electronically. f) Electronic noise contributes to poor reproducibility in data. 9. How does the sample feed rate affect the atomization of samples in AAS? If sample feed rate is high, too much energy of flame is used up in nebulizing & disintegrating sample. Final atomization step is inefficient. Flame is swamped with sample. If sample rate is low, production of neutral atoms is reduced & absorption signal is diminished. For reproducible result, sample feed rate must be constant.

10. The graphite furnace atomic absorption spectrometric technique (GF AAS) involves three distinct steps in its operation. Describe each of the steps involved. a) Drying solvent is vaporized. Carried out in low temperature b) Ashing burn-off organic component in sample. Usually in range of 200500oC. c) Atomization applied current increased, temperature in range of 20003000oC. 11 How do the electro thermal atomizers result in better sensitivity in AAS? Use of flame atomizer limits sensitivity due to fact that the flame is dynamic. The flame gases is not static and the analyte atoms remain in the light path for only a very short time. The furnace, although utilizing a much smaller sample size, because of its confining cylindrical shape, keeps the atoms in the light path for a much longer time period

12 Explain why is radiation source in atomic absorption instruments is usually modulated? The monochromator bandpass is larger than the atomic line width so any radiation arising from other sources (such as wide band molecular emissions from flame components) will interfere. In order to distinguish between the desired atomic signal and the flame background the hollow cathode line source is modulated, so P will be modulated at the same frequency as P0, giving a modulated absorbance signal which can easily be distinguished from the constant, non-modulated, flame background signal.

Saravanakumar Maniam SGC130019

13. Write a short discussion on the following: a) glow discharge atomization Consists of cylindrical cell, 17cm in length, circular hole 2cm (diameter) cut near middle of cylinder. An O-ring surrounds hole. Sample pressed against hole with torque screw, sealed tube. 6 fine streams of Ar gas from tiny nozzles arranged in circular pattern impinge sample surface in hexagonal pattern. Argon ionized by current between anode supporting nozzle & sample (as cathode). Result: 6 craters formed on sample surface. Sputtered atoms drawn by vacuum to axis of cell, absorb radiation from spectrometer source. Sample must be electrical conductor or pelleted with powdered conductor. Solution samples analyzed by deposition on graphite, aluminium or copper cathode

b) cold vapor atomization. c) For elements: As, Se, Sb, Bi, Ge, Sn, Te, Pb. These elements are difficult to reduce to atoms in flame when in high oxidation states. Elements form hydrides in acidic solutions with NaBH4. Hydrides formed swept out of solution into atomizers (inert gas) & peakshaped response is obtained. Metallic hydrides are easily thermolysed around 1000K, liberate corresponding elements in atomic state. If borohydride is added to acidic solution, excess hydrogen is also produced: BH4Various atomizers used with hydride generation method; including cool combustion flames (eg. H2-air, Ar-H-entrained air) & heated quartz tubes. Quartz tubes can be heated directly with flame or wrapped with nichrome wire & heated electrically. Detection limits usually low, enhancement by 10-100 times hydride generation technique. Hg: only metal to possess considerable vapor pressure at room temperature. Mercury converted to Hg2+ by treatment with HNO3 & H2SO4. SnCl2 reduced mercuric ions to metal. Hgo swept out of solution with carrier gas (eg. N2) into long-path glass absorption tube cell. Analysis measured at 253.7nm. Detection limit: ppb. As with hydride method, this method removes analyte from sample matrix; concentrates all mercury in sample into a small plug of carrier gas & provides a long residence time. Water mist enter into observation cell can lead to false absorbance signal due to scattering.
4

Saravanakumar Maniam SGC130019

Trap: to remove water mist with trap. Alternative: vaporize water mist by heating mercury-containing carrier gas & observation tube to above 100oC.

14 State and describe the factors which affect the atomization efficiency of samples in AAS. Droplet size a) Sample is aspirated into base of flame by burner, broken down into small droplets, which pass through flame. b) If droplets are large, surface area per unit weight is small & evaporation is small. c) Droplets will pass through flame without completely evaporating & any metals contained in them are never reduced to free atomic state & never contribute to absorption signal. d) If droplets are small, surface area per unit weight is large & evaporation is rapid. e) Evaporation leaves a solid metal residue which is decomposed by thermal energy of flame. f) Another consideration is size of solid residue remaining after evaporation of drop. g) If size large, residue will be bulky & decomposition by thermal energy of flame will be slow & inefficient; cause loss of sensitivity. h) Efficiency of decomposition of residue is chemical stability of solvent involved. eg: solution of aluminium chloride solution will give stronger absorption signal compare to solution of aluminium hydroxide (chemical interference). i) Drop size dependent on design of nebulizer section of burner. Sample feed rate a) Droplet evaporation & residue disintegrations require energy, provided by flame in burner. b) Under controlled condition, flame produces energy at steady rate. c) If sample feed rate is high, too much energy of flame is used up in nebulizing & disintegrating sample. d) Final atomization step is inefficient. Flame is swamped with sample. e) If sample rate is low, production of neutral atoms is reduced & absorption signal is diminished. f) For reproducible result, sample feed rate must be constant. g) Change in solvent causes significant changes in droplet size because of viscosity change in sample. Flame Temperature a) Transformation from solution to free neutral atoms is achieved by absorbing energy from flame. b) Energy is directly related to temperature. c) Hotter flame, more efficient in reducing sample to free atoms. d) Efficiency of production is related to drop size & reduction of free atoms in residues formed.

Saravanakumar Maniam SGC130019

e) Low-temperature flames, small changes in chemical energy needed to bring reduction to atoms to atoms-cause significant changes in efficiency of atomization. f) High-temperature, efficiency greater, similar changes in chemical energy have reduced effect on atomization efficiency. g) Energy changes brought by chemical composition of sample are basis of chemical interference. h) Differences in chemical stability between 2 chemical forms affect ease of atomization & absorption signal. i) Low-temperature flames subject to chemical interference should be avoided. j) High-temperature flames much more free from chemical interference & to be recommended. k) Low T flames: easily reduced elements (Cu, Pb, Zn, Cd) l) High T flames: difficult to reduce elements (eg alkaline earths). m) Fuels: natural gas, propane, butane, H2 & acetylene; n) Oxidants - Air & O2 (low temperature flames), N2O (high temperature flames). Oxide Formation a) After metals in sample have been reduced to neutral atoms, they will stay in state for varying periods of time. b) Time period ends when atoms react with oxidant or other components flame. c) Oxidizing flame is one which there is excess oxidant & reducing flame is one in which there is excess fuel. d) Ease of metal atom oxidized depends on chemistry of metal. e) If oxide easily formed & stable, it will oxidize easily. f) Step is controlled by equilibrium: Keq metal + oxidant -----------metal oxide

15 Explain how the deuterium lamp can be used to provide a background correction in atomic absorption spectroscopy. HCL & D2 lamp directed through atomizers at different times. HCL measured AT, D2 lamp estimate background, AB. Corrected absorbance obtained by calculating difference between two

16. Write a short discussion on the following: a) Zeeman effect background correction Energy level of molecules split under influence of strong magnetic field. Analyte & background absorption separated due to their different polarization characteristics. Advantages: o normal source intensities can be used at all wavelength o background correction is more accurate b) Smith-Hieftje background correction system
6

Saravanakumar Maniam SGC130019

Based upon self-reversal or self-absorption behaviour of radiation emitted from HCL operated at high temperature. Production of large concentration of non-excited atoms, absorb radiation. Broaden emission line of species produce line that has minimum in its center. Correction: lamp programmed run alternately at low & high currents. Absorbance obtained during low current operation & background absorbance measurement when radiation at peak is minimum. System subtracts background absorbance to give corrected value.

17. Describe the processes involved in sample introduction and atomization in flame atomic absorption spectrometry. The sample enters into the nebulizer, a mixing chamber where the sample is broken into an aerosol mist. The droplet size of this aerosol formed in the nebulizer is of importance since this directly affects how much analyte reaches the flame. Droplets with diameters greater than 20 m are trapped in the spray chamber by attaching to surfaces and flow to the waste container. Only about 10% of the water that enters the nebulizer reaches the flame. After the sample is pulled into the nebulizer and turned into an aerosol mist, it is mixed with the fuel and oxidant by two mixing fins. Common fuels used in FAAS units are acetylene (for hotter flames) and hydrogen (for cooler flames). Oxygen in the air or nitrous oxide is used as the oxidant to regulate the temperature of the flame. Different elements require different flame conditions, including the choice of fuel and oxidant and the ratio of the fuel to oxidant mixtures. Hydrogen-air flames produce temperatures of about 2000 C, while acetylene-air flames yield temperatures of approximately 2300 C and acetylene-nitrous oxide yield temperatures of 2900 C. Within these fuel types, fuel-rich mixtures yield cooler flames and oxidant-rich mixtures yield hotter temperatures. Temperatures are optimized for a particular analyte since different metal elements are excited or atomized under different conditions. In addition, some metals readily form oxides in an oxygen rich atmosphere, a reducing (fuel rich) environment is necessary to produce atomic instead of molecular species (such as oxides). Other elements are stable in the atomic state under any fuel/oxidant mixture. After this specific mixture of fuel and oxidant are mixed together with the sample, they exit the burner head and pass into the flame. 18. Suggest the possible ways which could be employed to minimize or to eliminate chemical interferences in AAS analysis. use high-temperature atomizing system usage of complexing agent EDTA. Depends upon fact that metal is complexed & strength of bond is constant even with other chemical entities in samples 19. Write a short discussion on Standard addition method. What advantage can be claimed for standard addition method? What minimum condition is needed for the successful application of this method? Due to high viscosity or chemical reaction, problem in flame spectrometry is suppression (or enhancement) of signal.
7

Saravanakumar Maniam SGC130019

Most convenient when a small number of samples are to be analyzed. Useful when the analyte is present in a complicated matrix and no ideal blank is available. Make possible work in presence of interference without eliminating interference. Make use of concentration calibration in presence of interference. Specific amounts of analyte added/spiked to sample & standard.

20. Nickel exhibits an atomic absorption sensitivity of 0.040 ppm under a given set of conditions. What would be the expected absorption for a 0.75 ppm solution? Sensitivity is concentration of sample which give 1% absorption Therefore, 0.040 ppm give 1% absorption 0.75ppm / 0.040 x 1% = 18.75% absorption.