Research AAS
Research AAS
CONTENTS
I. Overview …………………………………..page 1
V. Atomization process………………………..page 10
PAGE
VI. Chemical interference……………………...page 11
ATOMIC
ABSORPTION
UNDER SUP
ERVISION : DR.AHMED ABDULLAH
1
I.OVERVIEW
II.BRIEF HISTORY:
THE EARLIEST SPECTROSCOPY DATES BACK TO 1648, WHEN MARCUS
MARCI VON KRONLAND ANALYZED SUNLIGHT PASSING THROUGH
WATER DROPLETS, CREATING A RAINBOW.
III.PRINCIPLES OF AAS:
PAGE
THE TECHNIQUE USES THE ATOMIC ABSORPTION SPECTRUM OF THE
SAMPLE, ESTABLISHING A RELATIONSHIP BETWEEN MEASURED
ABSORBANCE AND ANALYTE CONCENTRATION BASED ON THE BEER–
LAMBERT LAW.
PAGE 1
IV.SOURCE OF RADIATION
THERE ARE TWO TYPES OF RADIATION SOURCES ARE USUALLY USED IN
AAS :
LINES SOURCES AND CONTINUUM SOURCES .
IV.I. LINE SOURCES
THE TWO MOST USUAL LINES SOURCES EMPLOYED IN AAS ARE
HOLLOWCATHODE LAMPS (HCLS) AND ELECTRODELESS DISCHARGE
LAMPS.
IV.I.I. HOLLOW-CATHODE LAMPS
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IT IS ADVISABLE THAT THE LENGTH OF THE HOLLOW CATHODE
SHOULD BE
AT LEAST THREE TIMES GREATER THAN THE CATHODE DIAMETER. THE
OPTIMUM DISTANCE BETWEEN THE CATHODE AND ANODE IS USUALLY
AROUND 20 MM TO 25 MM.
ACCORDING TO BEER’S LAW, ANALYTICAL SENSITIVITY INCREASES
LOGARITHMICALLY WITH THE ELECTROMAGNETIC RADIATION
INTENSITY EMPLOYED TO EXCITE THE ANALYTE ATOMS. FOR THIS
REASON, ATTEMPTS TO IMPROVE THE INTENSITY OF THE ANALYTICAL
SIGNAL GIVEN OFF WHEN HCLS ARE USED HAVE BEEN CARRIED OUT
BY:
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(A) SCHEMATIC DIAGRAM OF A HIGH FREQUENCY (HF) ELECTRODELESS
DISCHARGE LAMP EDL:
(1)LAMP BULB
(2)SIDE-ARM CONTAINING THE WORKING ELEMENT
(3)HF-INDUCTION COIL
(4)TEMPERATURE STABILIZATION
(5)INSULATION
(6)WINDOW
(B) EDL AND STRUCTURE OF THE MAGNETIC FIELD WITHIN THE LAMP
THE EDLS ARE CONSTITUTED BY A QUARTZ BULB WITH THE ANALYTE
SURROUNDED BY A RADIO FREQUENCY (RF) GENERATOR INSIDE A
GLASS TUBE FILLED WITH AN INERT GAS, USUALLY ARGON, UNDER
LOW PRESSURE.
THE SHORT HALF-LIFE TIME AND THE HIGH TEMPERATURE OF
OPERATION OF
HCL MAKE THEM INAD-EQUATE FOR VOLATILE SPECIES . HOWEVER, IN
EDLS, A
HF ELECTROMAGNETIC FIELD (RF OR MICROWAVES (MW): (300–3000
MHZ) ACCELERATES FREE ELECTRONS OF THE FILL MATERIAL
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COLLIDING WITH THE GAS ATOMS AND IONIZING THEM TO RELEASE
MORE ELECTRONS.
THE ENERGETIC ELECTRONS COLLIDE WITH THE ANALYTE-ATOM
PARTICLES
PRESENT IN THE QUARTZ BULB, THUS EXCITING THEM FROM THE
GROUND
STATE TO HIGHER ENERGY LEVELS. THEN, THE EXCITATION ENERGY IS
RELEASED AS A CHARACTERISTIC ELECTROMAGNETIC RADIATION OF
THE
FILL MATERIAL. THE EDL PERFORMANCE IS AFFECTED BY
TEMPERATURE, THE
NATURE AND PRESSURE OF THE FILL GAS, FILL MATERIAL, DIMENSIONS
AND
QUALITY OF THE LAMP ENVELOPE, THE NATURE AND CHARACTERISTICS
OF THE MW ENERGY COUPLING DEVICE, AND THE FREQUENCY AND
INTENSITY OF THE MW ENERGY.
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GENERALLY REPRODUCIBLE FROM ONE INSTRUMENT TO ANOTHER. THE
PRINCIPAL DIFFICULTIES ASSOCIATED WITH NON-MONOCHROMATIC
RADIATION ARE WELL KNOWN.
THE MOST IMPORTANT ADVANTAGES OF USING CONTINUUM RADIATION
SOURCES (CS) IN AAS WOULD BE THE FOLLOWING :
(I) ONLY ONE SINGLE RADIATION SOURCE IS USED FOR ALL ELEMENTS
AND
LINES.
(II) CS MAKES AAS A TRULY SIMULTANEOUS MULTI-ELEMENT
TECHNIQUE.
(III) FOR MOST ELEMENTS, THE RADIATION INTENSITY OF THE XENON
SHORT ARC LAMP IS AT LEAST ONE OR TWO ORDERS OF
MAGNITUDE HIGHER THAN THAT OF THE CORRESPONDING LINE
SOURCES.
(IV)THE PROBLEM OF “WEAK” LINES DISAPPEARS USING CS, ALLOWING
SECONDARY LINES TO BE USED.
(V) IT IS POSSIBLE TO DETERMINE ELEMENTS WITH CSAAS FOR WHICH
NO LINE SOURCES ARE AVAILABLE.
(VI)THE DETERMINATION OF ISOTOPE RATIOS IS ALSO POSSIBLE.
V. ATOMIZATION PROCESS :
V.I.WHAT IS ATOMIZATION IN AAS?
- ATOMIZATION REFERS TO THE PROCESS OF CONVERTING AN ANALYTE
(USUALLY IN LIQUID FORM) INTO FREE GASEOUS ATOMS. IN AAS, THIS
STEP IS CRUCIAL FOR ACCURATE ELEMENTAL ANALYSIS.
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- THE GOAL IS TO CREATE A VAPOR CONTAINING THE FREE ATOMS OF
THE
ELEMENT OF INTEREST. THESE ATOMS WILL ABSORB LIGHT AT SPECIFIC
WAVELENGTHS, ALLOWING US TO QUANTIFY THEIR CONCENTRATION.
V.II.WHY IS ATOMIZATION NECESSARY?
- SAMPLE PREPARATION: INITIALLY, THE ANALYTE IS DISSOLVED IN A
SUITABLE SOLVENT (OFTEN WATER OR ACIDS) TO CREATE A LIQUID
SOLUTION.
- DESOLVATION: THE SOLVENT MUST BE REMOVED TO LEAVE BEHIND
SOLID PARTICULATES OF THE ANALYTE. FOR EXAMPLE, CONVERTING
AN AQUEOUS SOLUTION OF CUCL₂ TO SOLID CUCL₂ REQUIRES
THERMAL ENERGY:
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- ELECTROTHERMAL ATOMIZATION INVOLVES HEATING THE
SAMPLE DIRECTLY (E.G., USING A GRAPHITE FURNACE) TO
GENERATE FREE ATOMS.
- SOME ELEMENTS MAY REQUIRE SPECIFIC ATOMIZATION
TECHNIQUES, BUT FLAME AND ELECTROTHERMAL METHODS
COVER MOST APPLICATIONS.
VI. CHEMICAL INTERFERNCE IN AAS :
A SPECTRAL INTERFERENCE OCCURS WHEN AN ANALYTE’S
ABSORPTION LINE
OVERLAPS WITH AN INTERFERENT’S ABSORPTION LINE OR BAND.
BECAUSE
ATOMIC ABSORPTION LINES ARE SO NARROW, THE OVERLAP OF TWO
SUCH
LINES SELDOM IS A PROBLEM. ON THE OTHER HAND, A MOLECULE’S
BROAD ABSORPTION BAND OR THE SCATTERING OF SOURCE
RADIATION IS A POTENTIALLY SERIOUS SPECTRAL INTERFERENCE.
AN IMPORTANT CONSIDERATION WHEN USING A FLAME AS AN
ATOMIZATION SOURCE IS ITS EFFECT ON THE MEASURED
ABSORBANCE.
AMONG THE PRODUCTS OF COMBUSTION ARE MOLECULAR SPECIES
THAT
EXHIBIT BROAD ABSORPTION BANDS AND PARTICULATES THAT
SCATTER
RADIATION FROM THE SOURCE. IF WE FAIL TO COMPENSATE FOR
THESE
SPECTRAL INTERFERENCES, THEN THE INTENSITY OF TRANSMITTED
RADIATION IS SMALLER THAN EXPECTED. THE RESULT IS AN APPARENT
INCREASE IN THE SAMPLE’S ABSORBANCE. FORTUNATELY, ABSORPTION
AND SCATTERING OF RADIATION BY THE FLAME ARE CORRECTED BY
ANALYZING A BLANK THAT DOES NOT CONTAIN THE SAMPLE.
SPECTRAL INTERFERENCES ALSO OCCUR WHEN COMPONENTS OF THE
SAMPLE’S MATRIX OTHER THAN THE ANALYTE REACT TO FORM
MOLECULAR
PAGE 9
SPECIES, SUCH AS OXIDES AND HYDROXIDES. THE RESULTING
ABSORPTION
AND SCATTERING CONSTITUTES THE SAMPLE’S BACKGROUND AND
MAY
PRESENT A SIGNIFICANT PROBLEM, PARTICULARLY AT WAVELENGTHS
BELOW
300 NM WHERE THE SCATTERING OF RADIATION BECOMES MORE
IMPORTANT. IF WE KNOW THE COMPOSITION OF THE SAMPLE’S MATRIX,
THEN WE CAN PREPARE OUR SAMPLES USING AN IDENTICAL MATRIX.
IN THIS
CASE THE BACKGROUND ABSORPTION IS THE SAME FOR BOTH THE
SAMPLES AND THE STANDARDS. ALTERNATIVELY, IF THE BACKGROUND
IS DUE TO A
KNOWN MATRIX COMPONENT, THEN WE CAN ADD THAT COMPONENT
IN
EXCESS TO ALL SAMPLES AND STANDARDS SO THAT THE
CONTRIBUTION OF
THE NATURALLY OCCURRING INTERFERENT IS INSIGNIFICANT. FINALLY,
MANY INTERFERENCES DUE TO THE SAMPLE’S MATRIX ARE ELIMINATED
BY
INCREASING THE ATOMIZATION TEMPERATURE. FOR EXAMPLE,
SWITCHING TO A HIGHER TEMPERATURE FLAME HELPS PREVENTS THE
FORMATION OF INTERFERING OXIDES AND HYDROXIDES.
IF THE IDENTITY OF THE MATRIX INTERFERENCE IS UNKNOWN, OR IF IT
IS
NOT POSSIBLE TO ADJUST THE FLAME OR FURNACE CONDITIONS TO
ELIMINATE THE INTERFERENCE, THEN WE MUST FIND ANOTHER
METHOD TO COMPENSATE FOR THE BACKGROUND INTERFERENCE.
SEVERAL METHODS
HAVE BEEN DEVELOPED TO COMPENSATE FOR MATRIX
INTERFERENCES, AND MOST ATOMIC ABSORPTION
SPECTROPHOTOMETERS INCLUDE ONE OR MORE OF THESE METHODS.
ONE OF THE MOST COMMON METHODS FOR BACKGROUND
CORRECTION IS
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TO USE A CONTINUUM SOURCE, SUCH AS A D2 LAMP. BECAUSE A D2
LAMP IS A
CONTINUUM SOURCE, ABSORBANCE OF ITS RADIATION BY THE
ANALYTE’S NARROW ABSORPTION LINE IS NEGLIGIBLE. ONLY THE
BACKGROUND,
THEREFORE, ABSORBS RADIATION FROM THE D2 LAMP. BOTH THE
ANALYTE
AND THE BACKGROUND, ON THE OTHER HAND, ABSORB THE HOLLOW
CATHODE’S RADIATION. SUBTRACTING THE ABSORBANCE FOR THE D 2
LAMP
FROM THAT FOR THE HOLLOW CATHODE LAMP GIVES A CORRECTED
ABSORBANCE THAT COMPENSATES FOR THE BACKGROUND
INTERFERENCE.
ALTHOUGH THIS METHOD OF BACKGROUND CORRECTION IS
EFFECTIVE, IT
DOES ASSUME THAT THE BACKGROUND ABSORBANCE IS CONSTANT
OVER
THE RANGE OF WAVELENGTHS PASSED BY THE MONOCHROMATOR. IF
THIS IS NOT TRUE, THEN SUBTRACTING THE TWO ABSORBANCES
UNDERESTIMATES OR OVERESTIMATES THE BACKGROUND.
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A TYPICAL OPTICAL ARRANGEMENT
ILLUSTRATION SHOWING A MODIFICATION TO THE OPTICAL BENCH TO
ALLOW FOR BACKGROUND CORRECTION USING A CONTINUOUS
SOURCE,
SUCH AS A D2-LAMP. THE CHOPPER ALTERNATES BETWEEN ALLOWING
LIGHT FROM THE HOLLOW CATHODE LAMP AND LIGHT FROM THE D 2-
LAMP TO PASS THROUGH THE FLAME AND REACH THE DETECTOR.
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Illustration of using the Zeeman effect to compensate for
background absorption when using an electrothermal atomizer: panel
(a) explains the origin of the Zeemen effect; panel (b) shows the
modification to the instrument; and panel (c) shows the resulting
absorption lines.
Chemical Interferences
The quantitative analysis of some elements is complicated by chemical
interferences that occur during atomization.
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The most common chemical interferences are the formation of
nonvolatile compounds that contain the analyte and ionization of the
analyte.
One example of the formation of a nonvolatile compound is the effect
of PO3−4
or Al3+ on the flame atomic absorption analysis of Ca2+. In one
study, for example, adding 100 ppm Al3+ to a solution of 5 ppm Ca2+
decreased calcium ion’s absorbance from 0.50 to 0.14, while adding
500 ppm PO3−4 to a similar solution of Ca2+ decreased the
absorbance from 0.50 to 0.38. These interferences are attributed to
the formation of nonvolatile particles of Ca3(PO4)2 and an Al–Ca–O
oxide .
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M(s)⇌ M+(aq)+e−
where M is the analyte. Because the absorption spectra for M and M+
are different, the position of the equilibrium affects the absorbance at
wavelengths where M absorbs. To limit ionization we add a high
concentration of an ionization suppressor, which is a species that
ionizes more easily than the analyte. If the ionization suppressor's
concentration is sufficient, then the increased concentration of
electrons in the flame pushes to the left, preventing the analyte’s
ionization. Potassium and cesium frequently are used as an ionization
suppressor because of their low ionization energy.
PAGE 15
Comparison between flame atomic absorption spectroscopy
and graphite furnace or electrothermal atomic absorption
spectroscopy .
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sample
Atomization :
Process of convertion of analyte from liquid to vapour in atom scale
Need high temperature
Flame atomic absorption spectroscopy :
Steps :
I. Nebulization : solution sample before against it to flame must
convert it to droplets (spray)
II. Desolvation : separation of analyte from solution (solvent) to be
easy to separate and continue process
III. Vaporization : convertion of analyte to gas phase and as it is in
molecule
IV. Dissociation : break up gas phases molecule into atoms
V. Ionization : break up gas phases into atom but in charged shape
*Both IV and V are types of Atomization
VI. Excitation : continue process with light or heat
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PAGE 18
Refrences :
"TAS-990 Atomic Absorption Spectrophotometer-纳米材料工程研
究中心". ercn.henu.edu.cn. Retrieved 2022-10-12.
"Robert Bunsen and Gustav Kirchhoff". Science History
Institute. Retrieved 20 March 2018.
McCarthy, G.J. "Walsh, Alan - Biographical entry".
Encyclopedia of Australian Science. Retrieved 22 May
2012.
Koirtyohann, S. R. (1991). "A History of Atomic
Absorption Spectrometry". Analytical Chemistry. 63 (21):
1024A–1031A. doi:10.1021/ac00021a716. ISSN 0003-
2700.
L'vov, Boris (1990). "Recent advances in absolute
analysis by graphite furnace atomic absorption
spectrometry". Spectrochimica Acta Part B: Atomic
Spectroscopy. 45 (7): 633–655.
Bibcode:1990AcSpe..45..633L. doi:10.1016/0584-
8547(90)80046-L.
"Analytical Methods for Graphite Tube Atomizers" (PDF).
agilent.com. Agilent Technologies. Archived (PDF) from
the original on 2022-10-09.
"Atomic Spectroscopy - GF-AAS". sites.chem.utoronto.ca.
Retrieved 2021-03-08.
Harvey, David (2016-05-25). "Atomic Absorption
Spectroscopy". chem.libretexts.org. Archived from the
original on 2017-10-06. Retrieved 2017-10-06.
"Sample Atomization – Atomic Absorption Spectroscopy
Learning Module". blogs.maryville.edu. Retrieved 2017-
11-02.
Walsh, Alan; Becker-Ross, Helmut; Florek, Stefan;
Heitmann, Uwe (19 January 2006). High-Resolution
PAGE 19
Continuum Source AAS. Weinheim: Wiley-VCH Verlag
GmbH & Co. KGaA. p. 2. ISBN 9783527307364.
Rakshit, Amitava. "Basics of Laboratory Safety: Common
laboratory rules and regulations". The International
Association for Ecology. Intecol. Archived from the
original on 27 September 2016. Retrieved 26 September
2016.
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