Atomic Absorption Spectroscopy, Page 1

MULTI-ELEMENTAL DETERMINATION OF METALS BY ATOMIC ABSORPTION SPECTROSCOPY (VERSION 1.3) I. BACKGROUND. Atomic absorption spectroscopy (AAS) is a widely used technique for determining a large number of metals. In the most common implementation of AAS, an aqueous sample containing the metal analyte is aspirated into an air-acetylene flame, causing evaporation of the solvent and vaporization of the free metal atoms. This process is called atomization. A line source (hollow cathode lamp) operating in the UV-visible spectral region is used to cause

electronic excitation of the metal atoms, and the absorbance is measured with a conventional UV-visible dispersive spectrometer with photomultiplier detector. Figure 1 above is a typical instrument block diagram. The narrow spectral lines of atomic samples necessitate the use of a line source as well as a high-resolution monochromator. This helps to prevent interference from adjacent spectral lines of other atomic species present in the sample matrix. In this experiment, AAS in conjunction with flame atomization will be used to determine specific metals in a solid sample. The availability of a spectrometer equipped with a lamp turret (allowing several line sources to be used in sequential fashion) will facilitate the measurement of multiple metals in the sample.

Atomic Absorption Spectroscopy, Page 2 II. REAGENTS. Certified 1000 ppm AAS standards (Fe, Zn, Mn, Sb, Cu) provided by instructor. Nitric acid (2% v/v), prepare 1 L. Unknown sample (solid) provided by instructor. III. PROCEDURE. A. Preparation of Unknown. The instructor will provide a solid unknown. Digest your sample by dissolving approximately 0.10 g (weigh accurately) in a mixture of 25 mL of concentrated nitric acid and 10 mL of concentrated sulfuric acid in a beaker. Do this operation in a fume hood. You may have to heat the sample (put a watch glass over the beaker) in order to get all material to dissolve. Once dissolved, add the mixture slowly to ~50 mL of distilled water in a 100 mL volumetric flask. Rinse the beaker several times to ensure that all material is transferred. Dilute to the mark with distilled water. B. Preparation of Standard Curves. The instructor will describe the components and appropriate settings of the instrument and provide a list of which metals will be studied in the current laboratory session. The data table below provides relevant information for several metals that can be measured quantitatively with AAS and atomization by an air-acetylene flame. Metal Absorption Wavelength (nm) 248.3 213.9 Optimal Spectral Bandpass (nm) 0.2 0.5 Flame Stoichiometry Lamp Current (mA) 5 5 Optimal Working Range (ppm) 2.5 - 10 0.4 - 1.6 Required Stock Solution 50 mL of 100 ppm 100 mL of 10 ppm 50 mL of 100 ppm 100 + 50 mL of 100 ppm 50 mL of 100 ppm

Fe Zn

* *

Mn Sb

279.5 217.6

0.2 0.2

Fuel-rich Fuel-rich

5 10

1.0 - 4.0 10.0 40.0

Cu

324.7

0.5

2.0 - 8.0

*Fuel-rich, stoichiometric, and lean flames give similar performance. Lists stock solution (prepared from 1000 ppm reference standard) required to produce five 100 mL standards that span the working range. Using the provided 1000 ppm reference standards, prepare five calibration solutions that span the working ranges in the table above for the elements to be studied in the current laboratory session. Use 100 mL volumetric flasks for these standards and perform all dilutions with volumetric pipettes. The solvent for all dilutions should be 2% (v/v) nitric acid. Note: this procedure will produce a total of five solutions (i.e., each calibration standard will be a mixture of the metals being studied). Verify your solution preparation scheme with the instructor before you begin. Zero the instrument while aspirating 2% (v/v) nitric acid into the flame. Aspirate each

Atomic Absorption Spectroscopy, Page 3 standard into the flame and record the absorbance; repeat three times. C. Unknown Determination. With identical instrument settings as for preparing the calibration in Part A, aspirate the unknown and record the absorbance for each metal. Repeat the measurement three times. Note that serial dilutions may be required to obtain an absorbance reading within the working range for each metal. IV. CALCULATIONS. 1. Calculate the exact concentrations of your calibration standards. 2. Tabulate the mean, standard deviation, and 95% confidence interval for your absorbance data. 3. Use least-squares procedures to determine the slope and intercept of the calibration model for each metal studied. Report the value of r2 and the standard error of estimate. 4. Include a plot of absorbance vs. concentration (with error bars) for each metal. 5. Use your calibration model together with your dilution scheme to compute the weight percent of each metal in your original solid sample. 6. The limit of detection of each metal can be estimated by use of the following procedure. The intercept of the calibration model is an estimate of the absorbance when no metal is present in the sample (i.e., the blank signal). The standard error of estimate is an estimate of the measurement noise (i.e., in the absence of systematic error, the variation about the least-squares line should be due solely to instrumental noise). A widely used definition of limit of detection is the concentration corresponding to an absorbance value equal to the blank signal plus three times the noise level. Thus, ALOD = b + 3s (1)

where ALOD is the absorbance corresponding to the limit of detection, b is the intercept of the calibration model, and s is the computed standard error of estimate. The limit of detection, CLOD, can then be estimated as CLOD = (ALOD - b)/m (2)

where ALOD are as defined above and m is the computed least-squares slope of the calibration model. Equations 1 and 2 can be combined to yield CLOD = 3s/m Use your calibration data to estimate the limit of detection for each metal studied. (3)