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Atomic Absorption Spectroscopy (AAS)
Reading:
Rouessac and Rouessac; Chapter 14
 
Introduction
The phenomenon of atomic absorption (AA) was first observed in 1802 with thediscovery of the Fraunhofer lines in the sun's spectrum. It was not until 1955 however that Walsh proposed that atomic absorption be used for quantitative chemical analysis.Atomic absorption analysis involves measuring the absorption of light by vaporizedground state atoms and relating the absorption to concentration. The incident light beamis attenuated by atomic vapor absorption according to Beer's law.To obtain the best results in AA, the instrumental and chemical parameters of thesystem must be geared toward the production of neutral ground state atoms of theelement of interest. Conversion of the sample from its native state to the atomic state can be achieved using a flame (flame-AAS) or an electric furnace (electrothermal or graphitefurnace AAS). The latter will be studied herein. In the furnace, the sample undergoes anumber of pretreatment steps prior to analysis. First the sample is dried by evaporatingthe solvent (in this case the water). Second the organic matrix is decomposed by heatingof the sample (often to temperatures exceeding 1000ºC). Care must be taken during thesesteps not to lose any of the analyte through evaporation processes (e.g., inclusion in a plume from flammable organics). Finally, the furnace is rapidly heated to temperaturesaround 2400ºC to produce vaporized neutral atoms with as many as possible in their inelectronic ground states.The absorption spectrum of the gas phase atoms is extremely narrow (
≤
10
-2
nm).Thus the light source used for absorbance measurements must be of precisely the correctwavelength and of narrow line width for Beer’s law to remain valid. The light sourceused in AAS is a hollow cathode lamp in which light is emitted from excited atoms of thesame element which is to be determined. This ensures that the radiant energycorresponds directly to the wavelength, which is absorbable by the atomized sample.This method provides both sensitivity and selectivity since other elements in the samplewill not generally absorb the chosen wavelength and thus, will not interfere with themeasurement. However, molecular species may also be formed during the atomizationstep. This can alter the spectral characteristics of the analyte metal or can cause spectralinterference at the wavelength being monitored. To reduce background interference, thewavelength of interest is isolated by a monochromator placed between the sample and thedetector. Additional techniques such as D
2
or Zeeman background correction may also be used for complex matrices such as beer.
 
Chem 313 Instrumental Analysis
AAS-2
Experiment Summary
In this experiment:
•
a graphite furnace atomic absorption spectrometer will be used
•
the ashing and atomization processes will be examined
•
the GF-AAS will be calibrated for copper using a series of standard solutions
•
copper in food products will be determined using 1) calibration curve and 2) standardadditions methods
•
the copper content will be compared to the specifications on the products
Instrumentation
The instrument used in this lab is the Varian SpectrAA-880Z AA spectrometer. It is asingle beam instrument which consists of four main building blocks or modules: a hollowcathode lamp turret and power supply, a graphite furnace equipped with Zeeman background correction, a monochromator, and an electronic readout system (computer and software). Some aspects of these modules are discussed below.
i. Hollow Cathode Lamp
AnodeInsulating disk Hollow cathodeQuartz or glasswindow
+-
 
Figure 1.
A typical hollow-cathode lamp (HCL)Hollow cathode lamps are used as the light source for AA measurements. A typicalhollow cathode lamp is shown in Figure 1. The majority of HCLs are single elementlamps with the hollow cathode coated with the desired element. The lamps are generallyfilled with neon under reduced pressure (1-5 torr), are operated at a few hundred volts(150 - 400 volts) and require currents anywhere from approximately 3 - 25 mA. When aneon filled tube is operating the hole in the cathode has an orange glow due to Neemission.
 
Chem 313 Instrumental Analysis
AAS-3
ii. Electrothermal Atomizer (Graphite Furnace)
Electrothermal atomizers generally provide a number of advantages compared toother atomization methods: enhanced sensitivity and lower detection limits, the capabilityto deal with extremely small samples (0.5-10
µ
L), the capability to directly treat solidsamples, and lower noise associated with the atomization process. Electrothermalatomizers work by heating the sample to the point of atomization. The heating profile isessential to the proper performance of the instrument. Typically there are three major stages to an atomization process: 1)
evaporation of solvents-
this step usually 30-60swith temperatures slowly ramping up to 100-120ºC; 2)
ashing
- this step usually lasts a 5-15s and involves heating the sample to 700-900ºC, at these temperatures most of theorganic matrix is removed; and finally 3)
atomization
-this step involves actualatomization of the sample, the temperature of this step may approach 2900ºC. The exactchoice of heating profiles depends on the matrix and the analyte. These profiles are oftendetermined empirically by systematically varying the times and temperatures for each of these steps.This particular graphite furnace is fitted with a Zeeman Background correctionassembly. The details of this method can be found in the text in section 9-C (pages219-220). Essentially, a magnetic field is used to cause Zeeman splitting of the energy levelsof the atomized analyte. The absorbance signal without the field and with the field may be compared to remove unwanted background noise from the signal. This is especiallyuseful in complex matrices.
iii. Monochromator 
The monochromator depicted in Figure 2 is placed between the graphite furnaceand the detector and is used to isolate the wavelength of interest and reduce backgroundinterference. This is a rather typical monochromators and a description of monochromators may be found in the textbook section 7C (pages 159-166).
Concave MirrorsReflectingGratingEntrance SlitExit Slit
λ
1
λ
2
 
Figure 2.
Czerny-Turner Grating Monochromator 
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