Graphite Furnace AAS

SpectrAA Basic Principles

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 Objectives

 Introduction to atomic absorption

 Fundamentals of atomic absorption

 Introduction to graphite furnace AAS

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 Early History of Optical Spectra

Sunlight Prism


 Sir
Sir Isaac
Isaac Newton
Newton discovers
discovers the
the solar
solar
spectrum
spectrum in in the
the late
late 1600’s
1600’s

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 Fraunhofer Lines
 1802
1802Wollaston
Wollastondiscovered
discovereddark
darklines
linesininsolar
solar
spectrum
spectrum
 Fraunhofer
Fraunhoferinvestigated
investigatedlines
linesin
indetail
detail

 Lines
Linesdue
dueto
tosun’s
sun’sown
ownatmosphere
atmosphereabsorbing
absorbinglight
light

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 Kirchhoff & Bunsen’s Experiment (1)
Light Source
Lens

Lens

Place Salt on Wire Loop

White
and Hold in Flame
Card
Burner

Dark
Lines
Prism

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 Kirchhoff & Bunsen’s Experiment (2)

Used to Discover the

Place Salt on Wire Loop Elements Rb and Cs
and Hold in Flame Lens

White
Card
Burner

Emission
Prism
Lines

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 Absorption vs Emission

Fraunhofer
Absorption
Lines

Cu Ba Na K
Elemental
Emission
Lines

190 nm 900 nm

 Qualitative analysis of elements

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 Alan Walsh

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 Varian AA Time Line
1952-53 Sir Alan Walsh Develop & Patent AAS
& CSIRO
1962 Techtron First commercially available AAS
under license from CSIRO
1966 John Willis Nitrous Oxide/Acetylene flame AAS
& Phil Thomas developed
1967 Varian-Techtron Varian Associates acquires Techtron
1971 Varian-Techtron Zeeman Patents, GFAAS developed
1987 Varian-Techtron Zeeman furnace introduced
1991-92 Varian-OSI ISO-9001 certified factory-Optical
Spectroscopy
Instruments

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 Periodic Table
H He
Flame Only
Li Be B C N O F Ne
Flame & Furnace
Na Mg Al Si P S Cl Ar
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
Fr Ra Ac
Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu

Th Pa U Np Pu AmCmBk Cf Es Fm Md No Lr

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 Flame vs Furnace AAS
Criteria Flame Furnace
Elements 67 48
Sensitivity ppm-% ppt-ppb
Precision good fair
Interferences few many
Speed rapid slow
Simplicity easy more complex
Flame Hazards yes no
Automation yes yes (unattended)
Operating Cost low medium

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 Ground State Atom

Orbitals

Neutrons

Protons
Electrons

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 Absorption of Energy by Atom

Valence (Outer)
Electrons
Excited State
h Atom
Energy
Ground State Absorbed
Atom

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 Energy Level Diagram
Electron Energy Transitions
E4

E3
E2
E1

Eo
1 2 3 4 5 6

 Resonance lines originate from ground state (Eo)

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 Atomic Absorption Process
Sunlight Sun’s Atmosphere Energy Transitions

E3

E2

E1

Eo
3 2 1 4 1 2 3 4
 Resonance lines must originate from ground state

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 Energy Level Diagram for Pb
Electron Energy Transitions
E4

E3
E2
E1

Eo
202.2 217.0 261.4 283.3
Wavelength in Nanometers

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 Absorption Energy Diagram
(Few Lines/Element)

Excitation
E Ionization

}
E3
Excited
E2 States
Energy

E1 c
b
a b c d
a
Eo Ground State

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 Emission Energy Diagram
(Many Lines/Element)

Emission
E Ionization

}
E3
Excited
E2 States
Energy

E1 c
b
a b c d
a
Eo Ground State

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 Atomic Absorption

Io It

Resonance
Non-resonance Resonance
Fill Gas

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 Beer-Lambert Absorbance
Calculation
Io
A = log ( ) = abc
It
Ac
Where:

A = Absorbance a = absorptivity
Io = Incident Light Intensity b = path length
It = Transmitted Light Intensity c = concentration

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 Beer-Lambert Law

Theoretical
A = abc
A
B Actual
S
A  abc

CONC

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 % Transmittance vs ABS

Transmittance Absorbance

100 % 0
10 % 1
1% 2
0.1 % 3

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 Flame vs Furnace Sensitivity
100 g/L Pb @ 217.0 nm

0.936
Furnace Signal
for 10 L
Absorbance

Flame Signal

0.004

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 Flame vs Furnace
Detection Limit Comparison
Element Flame (PPB) Furnace (PPB)*

Ag 3 0.035
As 450 0.25
Bi 50 0.45
Cd 3 0.01
Cr 9 0.075
Pb 15 0.2
Zn Based on 20 L Volume
*Results 1.5 & D2 Peak
0.0075
Height ABS

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 Furnace Thermal Stages

Clean
Out
Atomize

T
Cool E
Ash M
Down
P
Dry

T I M E

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 Summary
 Atomic absorption theory
 Excitation
 Emission
 Absorption
 Beer-Lambert
 Flame vs Furnace AA
 Detection Limit
 Sensitivity
 Function of the furnace

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