Atomic Absorption Training Course Flame Techniques

Practical experiments.

Varian Australia Pty Ltd 1988 Prepared by John Sanders Version .0 (1999)

1. SETUP AND OPTIMISATION.......................................................................................2 CALIBRATION AND CURVE FIT ALGORITHM.............................................................3 2. CHARACTERISTIC CONCENTRATION AND DETECTION LIMIT............................5 3. CHEMICAL INTERFERENCES....................................................................................6 4. NON-SPECIFIC ABSORBANCE INTERFERENCE.....................................................8 5. FLAME EMISSION........................................................................................................9 6. STANDARD ADDITIONS............................................................................................10

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1. Setup and Optimisation

Aim
This experiment is designed to illustrate the techniques and operations required to optimise for different modes of flame operation: Air/Acetylene flames Nitrous Oxide Acetylene Flames Each at the following nebuliser settings High Dissolved Solids and Maximum Sensitivity settings

Solutions

Standard Copper solutions 5ppm in 0.1% HNO 3 Standard Calcium Solution 1.0ppm in 0.1% HNO 3 2000ppm CsCl2 Standard Chromium Solution 5ppm

Procedure
Create a manual sampling worksheet with the three elements Cu, Ca, and Cr. Select the following conditions: Cu Cr and Ca the following: Max Sensitivity Air/Acet N2O/Acet air acet N2O acet Gas Flows Copper Calcium Chromium Absorbance Copper Calcium Chromium Discussion 1. 2. 3. Describe the different readings and when to use each nebuliser mode Describe the limitations of each nebuliser setting. Would you expect to see differences in gas flow settings for the different nebuliser settings? High Solid Setting Air/Acet N2O/Acet air acet N2O acet Air/Acetylene Gases Nitrous Oxide Gases

For each Gas combination determine the gas flows and nebuliser settings to provide

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Calibration and Curve Fit Algorithm

Aim This exercise illustrates the different calibration curvature and the algorithms used in producing linear calibration Solutions Multielement standards prepared in 0.01% HNO3 Copper 2 4 6 8 Hollow Cathode Lamps Cu, Fe, and Ni hollow cathode lamps Multielement Cu, Cr, Fe, Ni, Co, Mn Multielement Lamp Setup Create a worksheet with methods for Fe, Ni and Cu, for manual sampling with Concentration Readout and PROMT mode with 0.5% precision In Sequence control turn OFF the QC Tests Procedure Optimise each method, for maximum sensitivity. Start an autorun and read each calibration set , read the standards as samples After the run has finished, use the Curve Fit setting in the calibration graph and record the results for each of the calibration algorithms. Which provide better readback of the standards as samples? Fill in the table below for each calibration algorithm. New Rational Copper 2 4 6 8 Iron 5 10 15 20 Nickel 5 10
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Iron 5 10 15 20

Nickel 5 10 15 20

Rational

Linear

Linear Origin

Quadratic

Quadratic Origin

Cubic

Cubic Origin

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15 20 Discussion 1. Explain the difference between the value of the standards and the readback of the standards as samples. 2. How would you choose the "BEST" algorithm? 3. Why did we turn OFF the QC Test in the Sequence protocol?

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2. Characteristic Concentration and Detection Limit

Aim To measure the characteristic concentration and detection limit of the instrument for copper, iron and nickel.. Solutions Standard Solutions: Multi Element Standard Copper 2 4 6 8 Procedure Setup a worksheet with 15 samples and the three elements shown above. Optimise each element for maximum sensitivity and run the autorun. Using Deionised Water for the samples From the parameters read the Characteristic Concentration for each method Read the concentration of the DI water for all 15 samples. Calculate the standard Deviation of each method, and calculate the Detection Limit. Discussion 1. 2. 3. 4. 5. What would you expect the precision of the detection limit solution? At what concentration would you limit the reading of solutions, ie the sample reading is significantly different to a blank? At what concentration would you expect a precision of 10% RSD? Does the Characteristic Concentration differ from the published figure? What effect would you expect to see on the detection limit and characteristic concentration if you used the high solids setting of the nebuliser? Iron 5 10 15 20 Nickel 5 10 15 20

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3. Chemical Interferences
AIM To illustrate the problems seen with chemical interferences and means of reducing the effects. Solutions Calcium Standards: 0,1,2,3,5 mg/L Calcium standards 0,1,2,3,5 mg/L Calcium standards each with 2000mg/L Cesium Chloride Samples: 3mg/L Ca Solution 3mg/L Ca solution with 10mg/L P 3mg/L Ca solution with 10mg/L P, 2000mg/L Cs 3mg/L Ca solution with 10mg/L P, 2000mg/L Cs, 2000mg/l LaCl3. 3mg/L Ca solution with 100mg/L Al and 2000mg/L CsCl, and 2000mg/l LaCl3. Procedure Create a worksheet with four identical Calcium methods all manual sampling, use the following method details and layout: Method1 Gas Mixture Air/Acetylene Matrix/Standard Set No Cesium Create a label set of 13 Samples Method 2 N2O/Acetylene No Cesium Methods 3 Air/Acetylene Cesium Method 4 N2O/Acetylene Cesium

Using each standard set matrix record a calibration using the relevant standard solutions and readback the standards and 3ppm samples. Record the results.

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Method1 Air/Acetylene Standard 1 Standard 2 Standard 3 Standard 5 Standard 1+Cs Standard 2+Cs Standard 3+Cs Standard 5+Cs 3 Ca 3 Ca+10P 3 Ca + 10P +2000Cs 3 Ca + 10P +2000Cs+2000 La 3 Ca + 100 Al +2000Cs+2000 La

Method 2 N2O/Acetylene

Method 3 Air/Acetylene

Method 3 N2O/Acetylene

Discussion 1. 2. 3. 4. 5. Discuss the differences in calibration curvature.? Why is there a difference in the signal noise with the different gases.? What types of interferences are shown? Would you expect the effect to increase or decrease with changes in relative concentrations of the interferent and analyte.? Discuss the differences in the results when nitrous oxide/acetylene is used relevant to air/acetylene?

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4. Non-Specific Absorbance Interference

Aim To illustrate the effect of background absorbance on the analytical process. Solutions 0, 0.1, 0.2, 0.3 Zn standards Samples 0.2mg/L Zn 0.2mg/L Zn + 5%KBr 0.2mg/L Zn + 5%NaCl Procedure Create a worksheet with two Zinc methods and six samples, The only difference between the two methods will be the OPTICS page where the second method will have Background Correction BC=On, in the other method Background Correction BC=Off Optimise the instrument and adjust for maximum sensitivity. Start and autorun and read the standards and samples. Record the results: BC=Off 0.1 Standard 0.2 Standard 0.3 Standard 0.2 mg/L Zn Sample 0.2mg/l Zn 5%KBr 0.2mg/l Zn 5%NaCl Discussion 1. 2. 3. 4. What is causing the apparent difference in readings? Could the non-zero calibration algorithms be used to correct for the offset in the results caused by the non-specific absorbance? Will the use of background correction improve the accuracy of any measurements? What affect will background correction have on the detection limit and sensitivity of the instrument.? BC=On

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5. Flame Emission
Aim To illustrate the use of flame emission measurements for alkali elements Solutions 0, 0.5, 1.0 and 1.5 mg/l Sodium solutions. Procedure Create a worksheet with two methods for Sodium, in one method set the Instrument mode to Absorbance in the other set the mode to emission. Independently optimise each method and create a calibration, reading the calibration solutions as samples. Rotate the burner 90o and repeat the measurements Discussion 1. 2. 3. 4. Are the calibrations linear? What effect did burner rotation have on the calibrations and the precision of the readings? Which method would you expect to give the better precision? Why? Which method would you expect to give the better accuracy? Why?

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6. Standard Additions.
Aim To illustrate the use of the standard Additions calibration method and illustrate where it can be used. Solutions 0, 1.0, 2.0, 4.0 mg/l Iron Standards Spiking solution 10mg/l iron standard Samples 10% Solution of ethyl alcohol in water samples spiked with 1.0 and 2.0mg/L of iron. Procedure Create a worksheet with four iron methods. In the first two use normal concentration mode for calibration one method with background correction, the other with no background correction, In the remaining two methods select standard additions calibration mode, one method with background correction, the other with no background correction, You will need to take care in using the correct label sequence and naming of solutions. Also be careful in selecting the samples to be analysed in the worksheet. Measure the iron concentration of the samples using both procedures. Measure the nebuliser uptake of the blank water and the sample. Conc Mode Sample Sample + 1mg/l Fe Sample + 2mg/l Fe Sample + 4mg/l Fe Discussion 1. 2. 3. 4. Are the graphs for the standard addition calibration and the normal concentration calibration parallel? Why? Are the results different if background correction is used? Does standard additions correct for background interference? What does analytical problems does the method of standard additions correct for? Std Add Mode Std Add + BCG

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