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Atomic Absorption Chapter 9

Topics
Another Intro to Atomic Spectroscopic Methods
The Complete Measurement System The Ideal Source

Sample History and Signal in AA Atomization Methods Source in AA/ Hollow Cathode Lamp Spectrophotometers Interferences in AA Figures of Merit in AA

Complete Measurement System for all Atomic Spectroscopy Methods


Sample feed system Source of atomic vapor Excitation source for AA and AF Wavelength isolation device Detector Readout Precision and accuracy of methods depends on atomization (efficiency) method of introduction of sample into the atomization region (reproducibility, sampling accuracy). Physical and Chemical properties of analyte and matrix

Goals for an Ideal Source in Atomic Spectroscopic Methods


The source is the first basic need in Atomic spectroscopy Desirable properties:
Convert any sample into gas phase atomic vapor with little or no sample pre-treament
do so for all elements at all concentrations

Identical operating conditions for all elements and samples Analytical signal should be a simple function of the concentration of the individual elements (i.e. no interferences, no matrix effects) Characterized and understood at a fundamental level Accurate and precise Low initial cost, low maintainance and running costs Simple to operate and reliable

AA- From sample solution to signal generation and detection

Long sample history! What is the overall efficiency?

From sample solution to signal generation and detection

Transport
sample solution to nebulizer (viscosity changes between sample and standard) [Nx]sln= NA [Cx]

Nebulization
Solution to spray in the flame spray transport 2-5 % efficient [Nx]spray= F Nb [Nx]sln F: flow rate Nb: nebulization efficiency

Desolvation
spray in the flame to salt particles [Nx]salts=f2[Nx]spray f2: fraction desolvated

From sample solution to signal generation and detection

Vaporization
salt particles to vapor in flame [Nx]vapor=f3[Nx]salt neutral atoms, ionic species, and molecules (Ca, Ca+, CaOH) [Nx]n=f4[Nx]vapor [Nx]ionic=f4'[Nx]vapor [Nx]molec=f4''[Nx]vapor A large number of variables

Equilibrium of vaporized species


Signal f5f4f3f2FNbNA[Cx]

From sample solution to signal generation and detection IT = I010-abc


I0: intensity of source that can be absorbed by the sample IT: intensity of transmitted radiation

BUTS
Source is not pure (Iua:unabsorbed source radiation) Flame can emit IE Sample induced scattering loss IS Sample induced background absorption IBA (absorption caused by sample matrix or flame, molecular absorption)

IT = I010-abc+ Iua+IE-IS-IBA Careful calibration is of outmost importance! Standard addition method recommended

Flame Atomization
What is a flame? A flame is a gaseous chemical reaction that proceeds with liberation of energy Analytical flames:
Oxidant-Fuel O2-H2 Air-propane Air -C2H2 O2-C2H2 N2O-C2H2 Temperature 2780C 1925C 2100-2400C 3050C 2600-2800C

Flame structure
The efficiency of atomization and the extent of the other accompanying processes depend on the temperature Precision in AA critically depends on reproducibility of "the atomic sample region in the flame". Primary combustion zone-not at equilibrium Interzonal region used Secondary combustion: molecular oxides formed

Electrothermal Atomization
Electrical heating of sample container for vaporization and atomization of the sample
Flameless AA

Graphite furnace is used (GFAAS) Atomizer cell is a graphite tube or cup


Heat tube by passing a current

Steps
drying (<100C) ~10-30 sec Ashing (~200C-1000C) ~15-60 sec Atomization (2000C-3000C) ~5sec

Transient signal

Electrothermal Atomization

Advantages of GFAA over Flame AA:


Higher sensitivity lower detection limit (2 to 3 orders of magnitude) 0.1 pg small sample size (1L) direct analysis of solids

Disadvantages of GFAA
matrix interference formation and dissociation of molecular species excitation of molecular species followed by emission
e.g PbCl2

sample furnace interactions


Carbide formation Solutions: use carbide forming element called modifiers: Ta, W, Mo Coat the inner surface of the furnace with a thermally stable carbide

poor precision

Sources: Hollow Cathode Lamps (HCL)


Element specific Cathode Anode (tungsten) Apply ~300 V across the electrodes
Current produced 5 15 mA

Argon or neon -Ionization of inert gas -Accelerated cations dislodge and excite atoms from cathode (Sputtering) Excited atoms emit radiation (elements emission spectrum) and relax to ground state Ground state atoms diffuse back to cathode

Effect of high potential on the Profile of the Spectrum of the Source Self Reversal
At very high current, a large number of unexcited atoms are produced which absorb the emitted radiation. This leads to self reversal of the emitted line Doppler broadening is also increased

Line width versus sample Absorption Profile


A = abc
a: absorptivity b: length of absorbing medium c: concentration

The bandwidth of the source must be narrow compared to the absorption band of sample.
HLC are perfect for meeting this requirement

Source temperature must be kept below temperature of the atomizer The term Iua due to unabsorbed radiation form the source is eliminated

Spectrophotometers
Single Beam Double beam
Eliminates interference due to flame emission Corrects for fluctuation in source intensity from sample to sample How? Signal from the source is modulated Only modulated signal is amplified IT/I0 is amplified

Interferences in Atomic Absorption


Spectral Interferences
Absorption of combustion products Absorption by matrix (molecular species formed with absorbance bands that overlap the absorbance line) Scattering by products of atomization (refractory oxides)

Interferences in Atomic Absorption


Chemical Interferences
Formation of compounds of low volatility
Example
Calcium in the presence of the anions sulfate or phosphate Mg in the presence of the cation Al3+ (MgAl? Compounds)

Use higher temperatures or Use releasing agents


These agents react with the interferent (Sr for Al)

Use protective agents (EDTA)


These agents form stable but volatile compounds

Dissociation-association equilibrium
Involving metal oxides and hydroxides mainly

Ionization equilibria Stay with low temperature flame or Use ionization suppressor

Figures of merit Detection limits


0.020 to 0.001 ppm for flame 0.00001 ppm to 0.000002 ppm for graphite furnace

Accuracy (1% to 2% for flame)

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1ng/mL = 0.001 ppm

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