ATOMIC ABSORPTION SPECTROSCOPY (AAS)

I. PURPOSES a. Studying and understanding the principle of AAS analysis method. b. Determining concentration of metal in solution by using AAS analysis method. II. THEORY Atomic absorption spectroscopy is a technique for determining the concentration of a particular metal element in a sample. Atomic absorption spectroscopy can be used to analyze the concentration of over 62 different metals in a solution. Atomic-absorption (AA) spectroscopy uses the absorption of light to measure the concentration of gas-phase atoms. Since samples are usually liquids or solids, the analyte atoms or ions must be vaporized in a flame or graphite furnace. The atoms absorb ultraviolet or visible light and make transitions to higher electronic energy levels. The analyte concentration is determined from the amount of absorption. Applying the Beer-Lambert law directly in AA spectroscopy is difficult due to variations in the atomization efficiency from the sample matrix, and nonuniformity of concentration and path length of analyte atoms (in graphite furnace AA). Concentration measurements are usually determined from a working curve after calibrating the instrument with standards of known concentration. Schematic of an atomic-absorption experiment

Atomic absorption spectroscopy (AAS) determines the presence of metals in

liquid samples. Metals include Fe, Cu, Al, Pb, Ca, Zn, Cd and many more. It also measures the concentrations of metals in the samples. Typical concentrations range in the low mg/L range. In their elemental form, metals will absorb ultraviolet light when they are excited by heat. Each metal has a characteristic wavelength that will be absorbed. The AAS instrument looks for a particular metal by focusing a beam of uv light at a specific wavelength through a flame and into a detector. The sample of interest is aspirated into the flame. If that metal is present in the sample, it will absorb some of the light, thus reducing its intensity. The instrument measures the change in intensity. A computer data system converts the change in intensity into an absorbance. As concentration goes up, absorbance goes up. The researcher can construct a calibration curve by running standards of various concentrations on the AAS and observing the absorbance. Then samples can be tested and measured against this curve. Atomic absorption methods measure the amount of energy (in the form of photons of light, and thus a change in the wavelength) absorbed by the sample. Specifically, a detector measures the wavelengths of light transmitted by the sample (the "after" wavelengths), and compares them to the wavelengths, which originally passed through the sample (the "before" wavelengths). A signal processor then integrates the changes in wavelength, which appear in the readout as peaks of energy absorption at discrete wavelengths (see schematic of an atomic-absorption experiment). Any atom has its own distinct pattern of wavelengths at which it will absorb energy, due to the unique configuration of electrons in its outer shell. This allows for the qualitative analysis of a pure sample. In order to tell how much of a known element is present in a sample, one must first establish a basis for comparison using known quantities. It can be done producing a calibration curve. For this process, a known wavelength is selected, and the detector will measure only the energy emitted at that wavelength. However, as the concentration of the target atom in the sample increases, absorption will also increase proportionally. Thus, one runs a series of known concentrations of some compound, and records the corresponding degree of absorbance, which is an inverse percentage of light transmitted. A straight line can then be drawn between all of the known points. From this line, one can then extrapolate the concentration of the substance under investigation from its absorbance. The use of special light sources and specific wavelength selection allows the quantitative determination of individual components of a multielement mixture. The phenomenon of atomic absorption (AA) was first observed in 1802 with the discovery of the Fraunhofer lines in the sun's spectrum. It was not until 1953 that Australian physicist Sir Alan Walsh demonstrated that atomic absorption could be used as a quantitative analytical tool. Atomic absorption analysis involves measuring the absorption of light by vaporized ground state atoms and relating the absorption to concentration. The incident light beam is attenuated by atomic vapor absorption according to Beer's law.

The process of atomic absorption spectroscopy (AAS) involves two steps: 1. Atomization of the sample 2. The absorption of radiation from a light source by the free atoms The sample, either a liquid or a solid, is atomized in either a flame or a graphite furnace. Upon the absorption of ultraviolet or visible light, the free atoms undergo electronic transitions from the ground state to excited electronic states. Instrumentation 1. Light source a. Hollow-Cathode Lamp The light source is usually a hollow-cathode lamp of the element that is being measured. Lasers are also used in research instruments. Since lasers are intense enough to excite atoms to higher energy levels, they allow AA and atomic fluorescence measurements in a single instrument. The disadvantage of these narrow-band light sources is that only one element is measurable at a time. b. Diode lasers Atomic absorption spectroscopy can also be performed by lasers, primarily diode lasers because of their good properties for laser absorption spectrometry. The technique is then either referred to as diode laser atomic absorption spectrometry (DLAAS or DLAS), or, since wavelength modulation most often is employed, wavelength modulation absorption spectrometry. 2. Atomizer AA spectroscopy requires that the analyte atoms be in the gas phase. Ions or atoms in a sample must undergo desolvation and vaporization in a high-temperature source such as a flame or graphite furnace. Flame AA can only analyze solutions, while graphite furnace AA can accept solutions, slurries, or solid samples.

Flame AA uses a slot type burner to increase the path length, and therefore to increase the total absorbance (see Beer-Lambert law). Sample solutions are usually aspirated with the gas flow into a nebulizing/mixing chamber to form small droplets before entering the flame. The graphite furnace has several advantages over a flame. It is a much more efficient atomizer than a flame and it can directly accept very small absolute quantities of sample. It also provides a reducing environment for easily oxidized elements. Samples are placed directly in the graphite furnace and the furnace is electrically heated in several steps to dry the sample, ash organic matter, and vaporize the analyte atoms. Types of Atomizer The technique typically makes use of a flame to atomize the sample, but other atomizers such as a graphite furnace or plasmas, primarily inductively coupled plasmas, are also used. When a flame is used, it arranged so that it is laterally long (usually 10 cm) and not deep. The height of the flame above the burner head can be controlled by adjusting the flow of the fuel mixture. A beam of light passes through this flame at its longest axis (the lateral axis) and hits a detector. 3. Light separation and detection AA spectrometers use monochromators and detectors for uv and visible light. The main purpose of the monochromator is to isolate the absorption line from background light due to interferences. Simple dedicated AA instruments often replace the monochromator with a bandpass interference filter. Photomultiplier tubes are the most common detectors for AA spectroscopy.

Analysis of liquids A liquid sample is normally turned into an atomic gas in three steps: 1. Desolvation the liquid solvent is evaporated, and the dry sample remains

2. Vaporization the solid sample vaporizes to a gas 3. Atomization the compounds making up the sample are broken into free atoms. Interferences Since the concentration of the analyte element is considered to be proportional to the ground state atom population in the flame, any factor that affects the ground state population of the analyte element can be classified as interference. Factors that may affect the ability of the instrument to read this parameter can also be classified as interference. The following are the most common interferences: a. Spectral interferences are due to radiation overlapping that of the light source. The interference radiation may be an emission line of another element or compound, or general background radiation from the flame, solvent, or analytical sample. This usually occurs when using organic solvents, but can also happen when determining sodium with magnesium present, iron with copper or iron with nickel. b. Formation of compounds that do not dissociate in the flame. The most common example is the formation of calcium and strontium phosphates. c. Ionization of the analyte reduces the signal. This is commonly happens to barium, calcium, strontium, sodium and potassium. d. Matrix interferences due to differences between surface tension and viscosity of test solutions and standards. e. Broadening of a spectral line, this can occur due to a number of factors. The most common line width broadening effects are: 1. Doppler effect This effect arises because atoms will have different components of velocity along the line of observation. 2. Lorentz effect This effect occurs as a result of the concentration of foreign atoms present in the environment of the emitting or absorbing atoms. The

magnitude of the broadening varies with the pressure of the foreign gases and their physical properties. 3. Quenching effect In a low-pressure spectral source, quenching collision can occur in flames as the result of the presence of foreign gas molecules with vibration levels very close to the excited state of the resonance line. 4. Self absorption or self-reversal effect The atoms of the same kind as that emitting radiation will absorb maximum radiation at the center of the line than at the wings, resulting in the change of shape of the line as well as its intensity. This effect becomes serious if the vapor, which is absorbing radiation, is considerably cooler than that which is emitting radiation. Background Correction methods The narrow bandwidth of hollow cathode lamps makes spectral overlap rare. That is, it is unlikely that an absorption line from one element will overlap with another. Molecular emission is much broader, so it is more likely that some molecular absorption band will overlap with an atomic line. This can result in artificially high absorption and an improperly high calculation for the concentration in the solution. Three methods are typically used to correct for this:

Zeeman correction - A magnetic field is used to split the atomic line into two sidebands (see Zeeman effect). These sidebands are close enough to the original wavelength to still overlap with molecular bands, but are far enough not to overlap with the atomic bands. The absorption in the presence and absence of a magnetic field can be compared, the difference being the atomic absorption of interest.

Smith-Hieftje correction (invented by Stanley B. Smith and Gary M. Hieftje) - The hollow cathode lamp is pulsed with high current, causing a larger atom population and self-absorption during the pulses. This selfabsorption causes a broadening of the line and a reduction of the line

intensity at the original wavelength.

III.EXPERIMENTAL PROCEDURE 3.1 Devices and Materials A. Device One set of AAS device Burette Volumetric flask Drop pipette Sample solution (fishpond water) Standard solution (Ca)

B. Material

3.2 Scheme of experiment 1. Dilute standard solution Ca 1000 ppm to 100 ppm in volumetric flask 100 mL 2. Make standard series of Ca 0; 2; 4; 6; 8; 10 ppm by diluting 100 ppm standard solution in volumetric flask 50 mL 3. Fill each of them (standard solution and sample solution) in film bottle

and give a label on it 4. Turn on the AAS device, let it be stable in a minute, and then we can measure absorbance for each solution 5. Make the curve between standard solution and regression 6. Calculate the concentration of sample and nature sample solution

3.3 Scheme of Equipment

IV.

RESULT AND DISCUSSION 4.1 Data and Calculation 1. Making standard solution of Ca V1 . N1 100 mL . 100 ppm V2 = V2 . N2 = V2 . 1000 ppm = 10 mL

2. Diluting standard solution with various concentrations 0 ppm V1 . 100 ppm = 50 mL . 0 ppm V1 = 0 mL 2 ppm V1 . 100 ppm = 50 mL . 2 ppm V1 = 1 mL 4 ppm V1 . 100 ppm = 50 mL . 4 ppm V1 = 2 mL 6 ppm

V1 . 100 ppm = 50 mL . 6 ppm V1 = 3 mL 8 ppm V1 . 100 ppm = 50 mL . 8 ppm V1 = 4 mL 10 ppm V1 . 100 ppm = 50 mL . 10 ppm V1 = 5 mL

3. Data

Standard Solution (ppm) 0 2 4 6 8 10 Nature sample Sample solution 4. Regression Equation

Absorbance () 0 0.021 0.041 0.062 0.093 0.126 0.208 0.042

x = concentration (ppm) y = absorbance (A)

No 1

x 0

y 0

xy 0

x2 0

Cx

2 3 4 5 6

2 4 6 8 10 30 5

Average

0.021 0.041 0.062 0.093 0.126 0.343 0.05716666 7

0.042 0.164 0.372 0.744 1.26 2.582

4 16 36 64 100 220

B = n . xy - x . y n. x2 - (x)2 B = 6 (2.582) - (30 x 0.343) 6 (220) - (30)2 = 5.202 420 = 0.0123857 A = y - Bx = 0.057166667 (0.0123857 x 5) = -4.762x10-3 So, the regression equation is y = A + Bx y = -4.762x10-3 + 0.0123857x 5. Regression Equation

Curve Concentration vs Absorbance

0.14 0.12 Absorbance 0.1 0.08 0.06 0.04 0.02 0 0 2 4 6 [ ] ppm Standard Solution Regression Curve 8 10 12

6. Sample concentration Nature sample (fish pond water) y = -4.762x10-3 + 0.0123857(x) 0.208 = -4.762x10-3 + 0.0123857(x) x = 17.1780 So, the concentration of nature sample is 17.178 ppm My sample solution (Cx) y = -4.762x10-3 + 0.0123857(x) 0.042 = -4.762x10-3 + 0.0123857(x)

x = 3.7755 So, the concentration of my sample is 3.7755 ppm

4.2 Discussion The purposes in this experiment about atomic absorption spectroscopy (AAS) are to know how to use AAS device, to understand the principle of that analysis method, and also to determine metal concentration in sample solution. We use Ca solution as standard solution and HNO3 as blank solution. We make variation of standard solution based on the concentration, 0; 2; 4; 6; 8; and 10 ppm. The natural sample we used is pond fish water. Atomic-absorption (AA) spectroscopy uses the absorption of light

to measure the concentration of gas-phase atoms, so the sample must undergo desolvation and vaporization in a high-temperature source such as a flame or graphite furnace. Flame AA can only analyze solutions, while graphite furnace AA can accept solutions, slurries, or solid samples. AAS determines the presence of metals in liquid samples. Metals include Fe, Cu, Al, Pb, Ca, Zn, Cd and many more. After we measure the solution absorbances, we get that the higher concentration of Ca solution, so the higher absorbance value we get. The regression equation we get is y = -4.762x10-3 + 0.0123857x. By using this regression equation, we can calculate concentration of sample solution. For the fish pond water, we got that concentration is 17.178 ppm, while in my sample solution which has 0.042 of absorbance value, the concentration is 3.7755 ppm. Many advantages we get by using AAS analysis method, beside quick analysis with high accuracy, we can do analysis of sample which has low concentration and just need a little sample.

V. CONCLUSION AND SUGGESTION 5.1 Conclusion After we did this experiment, we get some conclusions, they are: We can use AAS analysis method both qualitatively and quantitatively. AAS analysis method and filter photometry have some similarities. For elements which easy to vapor, the analysis we do must be with cold vapor, not by using heating.

5.2.1 advises, they are:

Suggestion

In order to get best result in the next experiment, we can give some You have to understand the principle of this method and find the differences with flame photometry. Do dilution of sample and standard solution carefully.

REFERENCES http://weather.nmsu.edu/Teaching_Material/soil698/Student_Reports/Spectroscop y/report.htm#instrumentation

http://elchem.kaist.ac.kr/vt/chem-ed/spec/spectros.htm http://www.gmu.edu/departments/SRIF/tutorial/aas/aas.htm http://www.gmu.edu/departments/SRIF/tutorial/aas/aas2.htm http://www.gmu.edu/departments/SRIF/tutorial/aas/aas3.htm http://en.wikipedia.org/wiki/Atomic_absorption_spectrometer http://www.shsu.edu/~chemistry/primers/AAS.html