DETERMINATION OF NICKEL BY ATOMIC ABSORPTION SPECTROPHOTOMETRY

OBJECTIVES:

1. The student will analyze a sample of nickel ore using atomic absorption spectrophotometry.
2. The student will use the calibration curve method of analysis.
3. The student will use the method of standard addition for this analysis.
4. This method also depends on the fact that the entire sample is dissolved.
5. A known and unknown are treated alike.
6. Learn how to operate the Perkin-Elmer 2280 atomic absorption (AA) spectrophotometer.

INTRODUCTION:
In atomic absorption spectroscopy, metal atoms are vaporized into a flame, and the metal vapor will absorb radiation from the specific hollow cathode lamp in proportion to the number of atoms present. Beer's Law is followed in the part-per-million range (remember that ppm means mg of metal/liter of solution).

Each student will need to prepare a series of solutions of the metal that you wish to determine. The concentration of metal should be between 1 and 10 ppm of metal. You will need to prepare a series of standards in the desired concentration range. Each student will need to be checked out on the AA this term. You will need to run your standard solutions and your unknown solutions. The instrument will read directly in ppm if you do the proper standardization, but it is recommended that you use the absorbance values and Beer's Law for the calculations.

PROCEDURE:

1. Solutions that each student should prepare:

FOR BOTH THE KNOWN AND THE UNKNOWN NICKEL SOLUTION, dissolve the metal sample in a 150-ml beaker on a hot plate under the hood. Cover the beaker with a watch glass. Quantitatively transfer the solution to a volumetric flask.

a (Ni). Standard nickel stock solution (1000 ppm Ni). Place 0.2000 g of pure Ni wire (or shot) (weighed on an analytical balance) in a 100 ml. beaker. Add 15-ml. conc. HNO3 and 1 ml. conc. H2SO4. Place a watch glass over the beaker. Boil until dense white fumes of SO3 cease. Transfer carefully to a 200-ml. volumetric flask. Remember to rinse the watch glass. Dilute to the mark. Check with Dr. Sherren, she may have a standard Nickel stock solution.

b (Ni) Preparation of unknown nickel solution. Weigh a 1-gram sample of dry unknown into a 400-ml. beaker. Cover and add 35 ml. of 15 M nitric acid. Warm gently then boil until red fumes no longer come off (UNDER THE HOOD), all black particles should be dissolved and the volume should be about 5 ml. If not, add 5 ml. of 12 M HCl and heat for a few minutes under the hood. Cool and add 20 ml. 12 M HCl. Take to dryness, add 10-ml. hydrochloric acid and again take to dryness. Bake at 110o for one hour. Cool, add 10 ml. HCl, heat easily a few seconds, transfer to a 100 ml. volumetric flask and dilute with hot deionized water, cool to room temperature and adjust volume to mark. Stopper the flask and mix the solution thoroughly. If you did the EDTA Nickel you may take the unknown solution and dilute this solution to use for your unknown.

c. 1% (V/V) HCl for dilutions. 1 ml concentrated HCl per 99 ml H2O. An easy way is to dilute your solutions in a 100-mL volumetric flask and add 1 mL of concentrated HCl to the mixture before the final dilution.

3. In 100 mL volumetric flasks prepare a series of standard solutions containing 1.00, 2.00, 4.00, 5.00, 6.00, 7.00 8.00 and 10.00 ppm of standard nickel ion. (Use either a buret or a EPPENDORF pipet to measure the standard solution). Dilute to the mark with 1% HCl SOLUTION. After determining the absorbance, make a plot of absorbance vs. concentration USING EXCEL. The best results are obtained by using the regression equation of the data. Discard obviously bad points before doing the regression.

4. In 100 mL volumetric flasks prepare a series of unknown solutions containing 1.00, 2.00, 2.50, 3.00, 4.00, and 5.00 mL of the unknown nickel solution. (Use either a buret or a EPPENDORF pipet to measure the standard solution). Dilute to the mark with 1% HCl SOLUTION. Determine the absorbance of each solution. Using the data from the standard determine the concentration of each unknown solution. Also calculate the % of metal in the unknown.

5. Before making the first spectral measurement, you should receive instructions from Dr. Sherren on the use of the spectrophotometer. Set the wavelength for Ni [use 232 nm]. Sets slit width at 0.2 nm and maximize the wavelength. Read the section on the AA operation in the appendix.

6. Calculate the %metal in the unknown sample. Best results are obtained by calculating the best straight line on the computer.

CAUTION: Most solutions for the AA are prepared in dilute acid. Each ion will have a given recipe. Use 1% HCl for all dilutions.

CAUTION: Solutions of this dilute nature do not keep. You should prepare and do the determination the same day. All of you cannot use the instrument at once. It does go rapidly, but until you get the hang of it, it will take some time and some individual instruction.

CAUTION: Between each run, determination, or standardization; you will need to aspirate 1% HCl for a minimum of one (1) minute to clean out the burner chamber. After finishing, you will also need to aspirate 1% HCl into the flame to clean out the mixing chamber. If in doubt, come get Dr. Sherren.

CAUTION: Often it is necessary to take a solution in the AA and use the technique of standard addition. If your unknown values are much lower that the Absorbance values for the standards, check with Dr. Sherren on the directions for standard addition.

EXPERIMENT:

This experiment is to be done during regular laboratory hours. Dr. Sherren needs to check you out on the instrument before you begin the first and second times.

SAFETY AND DISPOSAL INFORMATION: Dispose of all test solutions and in the "AA EXPERIMENT WASTE" container. CAUTION: Remember to treat all chemicals with respect.

REFERENCES

Skoog, West, Holler: Fundamentals of Analytical Chemistry (1996) pp. 614-638.
Sawyer, Heineman, & Beebe: Chemistry Experiments for Instrumental Methods (1984) pp. 242-253.
"General Information" section of manufacturer's Analytical Methods book.

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Instrument Operating Guidelines

    1. Make sure the GAIN and LAMP 1 dials are turned fully counterclockwise, then turn on the instrument and the air compressor. Find the logbook and sign in.
    2. Turn on the AA. (It takes 30 minutes for the lamp to warm up for max. use.) Set the Lamp current (see instrument manual): The proper lamp current can be found, circled in ink, on the base of the lamp.

    3. 3. Turn on the acetylene tank. It must read over 90 on the tank gage.

    4. Set the wavelength  for Ni -- use 232 nm. Set slit width at 0.2 nm and maximum nm. [for Cu -- use 324.8 nm. Set slit width at 0.7 nm and maximum nm.;for Fe -- use 248.3 nm. Set slit width at 0.2 nm and maximum nm. ]
    5. Check the fuel gage. It should read 17 or 18.
    6. Check the oxidant gage. It should read 33 or 34.
    7.  Light the flame.
    8. Aspirate a 1% HCl blank for about 1 minute.
    9. Set AZ (autozero). Set the average = 3 and t = 2.
    10. Aspirate the standard for 1 minute. Read the absorbance.
    11. Aspirate 1% (v/v) HCl for one minute (or 90 seconds). Does it read 0.00? If way off (0.4 or more), repeat steps 7 to 11.
    12. To read your solution, aspirate for one minute, and then take at least 3 readings
    13. Average the readings for each solution.
    14. Calculate the % metal for each of your solutions.
    15. Reject bad data and calculate the mean and relative standard deviation for your unknown.
INTRODUCTION TO THE OPERATION OF THE INSTRUMENT

The Perkin-Elmer 2280 is a microprocessor controlled, single beam atomic absorption spectrophotometer. Among its principle components are a hollow cathode lamp (in our case it also happens to be a multielement lamp), a premix burner, and a grating monochromater.

The parts of the instrument manual, which will be of most use to you, are the following:

topic section in manual

- instrument controls and indicators 7A
- normal operating procedure 9C,1
- controls for the digital readout Appendix 2, sec. 3
    burner control
- operation of the digital readout Appendix 2, sec. 4
    burner control
- averaging and statistical operations 10I

The burner height and fuel/air ratio must be optimized. This may be done for you or you will be shown how to do it.

INSTRUMENT SHUTDOWN

1. Before shutting off the flame, aspirate deionized water for at least 5 minutes to prevent possible explosions (see section 12B,4). Then shut off the flame by carrying out the following steps in sequence:
a) close the main valve of the acetylene tank,
b) press the FLAME OFF button or let the flame die out by itself,
c) turn off the air compressor,
d) press CHK FUEL long enough to depressurize the acetylene lines.
2. Turn the GAIN and LAMP 1 dials fully counterclockwise. Turn off the instrument power and sign out of the log book.

REFERENCES
Skoog, West, Holler: Fundamentals of Analytical Chemistry (1996) pp. 611-638.
Sawyer, Heineman, & Beebe: Chemistry Experiments for Instrumental Methods (1984) pp. 242-253.
"General Information" section of manufacturer's Analytical Methods book.