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Atomic Absorption Spectroscopy andAtomic Emission Spectroscopy
A. Evaluation of Analytical Parameters in Atomic AbsorptionSpectroscopy
Objective
The single feature that contributes most to making atomic absorption unique among energy absorptiontechniques is the use of a flame to produce the necessary neutral, ground-state atoms. This experimentinvolves a study of various instrumental and chemical parameters that are important to atomicabsorption spectroscopy because they are important to the processes that occur in the flame.Specifically, the parameters to be investigated are: (1) dependence of signal on position in flame; (2)effect of fuel-to-oxidant ratio; (3) effect of the state of the metal; and (4) effect of concentration.
Theory
Since atomic absorption obviously implies absorption by atoms, the processes by which we can produce atoms are of principal importance. The necessity of a steady signal (uniform production of atoms) and of a system easily suited for use with solutions has limited the methods of atom productionalmost exclusively to flames. A primary objective is to produce a large number of free atoms in theflame, but the conditions necessary to accomplish this are often different for different systems.Furthermore, the physical environment within a flame varies drastically, causing the atom compositionof the flame to vary according to the geometric region.Degradation of solvated molecules to neutral atoms in a flame is a complicated and often poorlyunderstood process. The efficient production of free atoms depends on the fuel-oxidant composition,the temperature, the sample feed rate, the type of burner, and the chemical system itself, includingsolvent and diverse substances. It is not always possible to sort out the individual effect of each of these parameters, but it is possible to determine empirically optimum analytical conditions. In fact, astudy of the effects of these parameters often leads to valuable conclusions about the chemical natureof the system.The mechanism of atom production is complex and apparently is not the same for all solvents andflames. For this reason, the effects of certain parameters are not always the same for all systems. Oneof the more important factors that must be considered is the possible formation of oxides. Many metaloxides are among the most stable of all known compounds, and consequently, once formed, are verydifficult to reduce, even in a high-temperature, fuel-rich flame. For this reason, the reducing nature of the flame (amount of fuel to oxidant) is of principal importance. Furthermore, certain regions in theflame are likely to be more reducing and thus contain a greater predominance of neutral atoms. Thefree-atom composition of the flame is determined by examining the signal as a function of the positionof the optical path in the flame. A plot of such data is referred to as a flame-atom profile.
 
  Experiment #1A: Introduction of PE AAnalyst 200
1.
Prepare chromium standards with the following chromium concentrations: 1, 2, 3, 4,and 5 ppm Cr.
2.
Prepare an unknown chromium solution that has an approximate concentrationbetween 1 and 5 ppm Cr.
3.
Dilute all solutions with distilled water.
4. Using distilled water as the blank,
read the absorbance for all solutions using manualand autosampling procedure.
 Experiment #2A: Dependence of Signal on Position in Flame
1. Using distilled water as the blank,
read the absorbance for 10 ppm Cr solution.
2.
Lower burner ½ turn and read absorbance for 10 ppm Cr again.
3.
Continue to lower burner ½ turn and read absorbance until absorbance equals 0.
4.
Set burner height to maximum absorbance position.
 Experiment #3A: Dependence of Signal on Fuel-to-Oxidant Ratio
1.
Set acetylene flow rate to 2.5 L/min and read absorbance of 10 ppm Cr solution.
2.
Raise flow rate of acetylene by increments of 0.1 L/min and read absorbance until flowrate equals 3.5 L/min.
3.
Set flow rate of acetylene to rate showing maximum absorbance.
 Experiment #4A: Dependence of Signal on State of Metal 
With the burner height at the position of maximum absorbance and the flow rate set at the rate thatgives the maximum absorbance,
record the absorbance for the following 10 ppm Cr solutions:chromium nitrate, sodium chromate, sodium dichromate, chromium acetate, and chromiumchloride.
 
Calculations
1. Prepare a flame-atom profile by plotting the burner position (in arbitrary units) vs. signalintensity of (Cr-water). Locate the burner position giving the maximum signal on the graph.2. Plot the signal vs. fuel/oxidant ratio.3. Discuss the effect of the state of the metal on results.-2-
 
 
B. Trace Analysis of Metals by Flame Emission
Objective
This part of the experiment is designed to acquaint the student with the techniques of atomic emissionfor the analysis of metals. The use of a multipurpose emission-absorption instrument is illustrated for the determination of Na+ by emission.
Theory
The energy available in a flame can be used to excite the elemental components of an unknownsample, and the emission of radiation can be used to both qualitatively and quantitatively identify theunknown sample. The irreproducible nature of a flame makes quantitative determination virtually100% empirical, but if conditions are accurately controlled, the emission intensity can be a quantitativeindication of the amount of material present. The amount of material can be measured in reference toa working curve established with standard solutions. Some of the difficulties involved in the variationof flame conditions can be circumvented by the inclusion of a known concentration of a similarlyemitting element and relating concentration of the unknown to the ratios of the emission intensities of the unknown and the standard.The techniques of atomic emission and absorption are complementary rather than competitive. Manymetals, notably the alkali and alkaline earths, are easily excited in flames and consequently can bedetermined at much lower concentrations by flame emission. Other metals, such as the transitionmetals, are easily atomized in flames but not so readily excited and thus have much lower detectionlimits in absorption. For some elements (Mg) the two techniques may have identical detection limits.This is illustrated below:
 Detection Limits in Flame Emissionand Absorption Spectroscopy
Element Emission (ppm) Absorption (ppm)
Al 0.01 0.5As 1.0 0.04Ba 0.01 1.0Cd 0.3 0.0004Cr 0.003 0.001Cu 0.01 0.0005Fe 0.03 0.003Mg 0.003 0.003K 0.00001 0.005Na 0.00001 0.005Zn 3.0 0.0002
The instrument used in this experiment is designed for both flame emission and absorption studies. Itutilizes an integrated aspirator burner with electric ignition, the burner being fed with air and-3-
 
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