Atomic Absorption

Spectroscopy (AAS)
Lestyo Wulandari

Elemental Analysis - Atomic Spectroscopy

A) Introduction
Based on the breakdown of a sample into atoms, followed by the measurement of the
atoms absorption or emission of light.
i. deals with absorbance fluorescence or emission (luminescence) of atoms or
elemental ions rather then molecules
- atomization: process of converting sample to gaseous atoms or
elementary ions
ii. Provides information on elemental composition of sample or compound
- UV/Vis, IR, Raman gives molecular functional group information, but no
elemental information.
iii. Basic process the same as in UV/Vis, fluorescence etc. for molecules

E1
Eo

Absorbance

Fluorescence

iv. Differences for Molecular Spectroscopy

- no vibration levels much sharper absorbance, fluorescence, emission
bands
- position of bands are well-defined and characteristic of a given element
- qualitative analysis is easy in atomic spectroscopy (not easy in molecular
spectroscopy)
Examples:
carbon

oxygen

nitrogen

B) Energy Level Diagrams

energy level diagram for the outer electrons of an element describes atomic spectroscopy
process.
i. every element has a unique set of atomic orbitals
ii. p, d, f split by spin-orbit coupling
iii. Spin (s) and orbital (l) motion create magnetic fields that perturb each other (couple)

Similar pattern between atoms but

different spacing
Spectrum of ion different to atom
Separations measured in
electronvolts (eV)
1eV =1.602x10-19 J
= 96.484 kJ mol-1

Na

Mg+

As number of electrons increases,

number of levels increases
emission spectra more complex
Li 30 lines
Cs 645 lines
Cr 2277 lines
Note slight differences in energy due to
magnetic fields caused by spin

C) Desire narrow lines for accurate identification

Broadened by
i. Doppler effect
Doppler effect
- emitted or absorbed wavelength changes as a result of
atom movement relative to detector
- wavelength decrease if motion toward receiver
- wavelength increases if motion away from receiver

C) Desire narrow lines for accurate identification

Broadened by
ii. Pressure broadening
Pressure broadening:
Collisions with atoms/molecules transfers small quantities of vibrational energy
(heat) - ill-defined ground state energy
Effect worse at high pressures:
For high pressure Xe lamps (>10,000 torr) turns lines into continua!

D) Effect of Temperature on Atomic Spectra

- temperature changes number of atoms in ground and excited states
- need good temperature control

Boltzmann equation

N1 and No are the number of atoms in excited and ground states

k Boltzmann constant (1.28x10-23 J/K)
T temperature
E energy difference between ground and excited states
P1 and Po number of states having equal energy at each quantum level

Na atoms at 2500 K, only 0.02 % atoms in first excited state!

Less important in absorption measurements - 99.98 % atoms in ground state!

E) Atomic Absorption Spectroscopy (AAS)

commonly used for elemental analysis
expose sample to flame or high-temperature
characteristics of flame impact use of atomic absorption spectroscopy

Flame AAS:
simplest atomization of gas/solution/solid
laminar flow burner - stable "sheet" of flame
flame atomization best for reproducibility (precision) (<1%)
relatively insensitive - incomplete volatilization, short time in flame

F) Basic instrument design (Flame atomizer)

Single beam

Double beam

FLAME
i.

Different mixes and flow rates give different temperature profile in flame
- gives different degrees of excitation of compounds in path of light source

ii. Types of Flame/Flame Structure selection of right region in flame important for
optimal performance
a) primary combustion zone blue inner cone (blue due to emission from C2, CH &
other radicals)
- not in thermal equilibrium and not used
b) interconal region
- region of highest temperature (rich in free atoms)
- often used in spectroscopy
- can be narrower in some flames (hydrocarbon)
tall in others
(acetylene)
Temperature
varies
significantly across
c) outer cone
flame need to focus on part of the flame
- cooler region
- rich in O2 (due to surrounding air)
- gives metal oxide formation
Primary region
for spectroscopy
Not in thermal equilibrium
and not used for
spectroscopy

Flame profile: depends on type of fuel

and oxidant and mixture ration

Most sensitive part of flame for AAS varies with analyte

Consequences:
- Sensitivity varies with element
- must maximize burner position
- makes multi-element detection difficult

Sample Atomization expose sample to flame or high-temperature

i.

Need to break sample into atoms to observe atomic spectra

ii.

Basic steps:
a) nebulization solution sample, get into fine droplets by spraying thru thin nozzle or
passing over vibrating crystal.
b) desolvation - heat droplets to evaporate off solvent just leaving analyte and other
matrix compounds
c) volatilization convert solid analyte/matrix particles into gas phase
d) dissociation break-up molecules in gas phase into atoms.
e) ionization cause the atoms to become charged
f) excitation with light, heat, etc. for spectra measurement.

Sample Atomization expose sample to flame or high-temperature

iii.

Types of Nebulizers and Atomizers

atomizer
1) Laminar Flow Burner
- adjust fuel/oxidant mixture for optimum excitation of desired
compounds
- usually 1:1 fuel/oxidant mix but some metals forming oxides use
increase fuel mix
- different mixes give different temperatures.

Laminar nonturbulent streamline flow

i.
ii.

sample, oxidant and fuel are mixed

only finest solution droplets reach
burner
iii. most of sample collects in waste
iv. provides quite flame and a long
path length

atomizer
2) Electrothermal
Graphite furnace (rod or tube)
Small volumes measured, solvent evaporated, ash,
sample flash volatilized into flowing gas
Hydride generator
cold vapour method

2) Electrothermal (Graphite furnace)

- place sample drop on platform inside tube
- heat tube by applying current, resistance to current creates heat
- heat volatilizes sample, atomizers, etc. inside tube
- pass light through to measure absorbance

Po

P
Place sample
droplet on platform

Electrothermal atomic absorption (AKA

Graphite furnace AA)
Introduce sample
(solid, liquid, gas, slurry)

Pulse heat the ETV

Temp

Absorbance
signal

time

Closeup of graphite furnace

Controls for graphite furnace

Schematic of an hydride reactor

used for particular elements

Comparison of atomizers

b) Laminar Flow Burner

advantages:
- good b (5-10 cm)
- good reproducibility
disadvantages:
- not sample efficient (90-99% sample loss before flame)
- small amount of time that sample is in light path (~10-4 s)
- needs lots of sample

Light source
- need light source with a narrow bandwidth for light output
- AA lines are remarkably narrow (0.002 to 0.005 nm)
- separate light source and filter is used for each element

1) problem with using typical UV/Vis continuous light source

- have right , but also lots of others (non-monochromatic light)
- hard to see decrease in signal when atoms absorb in a small bandwidth
- only small decrease in total signal area
- with large amount of elements bad sensitivity

2) Solution is to use light source that has line emission in range of interest
- laser but hard to match with element line of interest
- hollow cathode lamp (HCL) is common choice

Hollow Cathode Lamp

Coated with element

to be analyzed

Process: use element to detect element

1. ionizes inert gas to high potential (300V)
Ar Ar+ + e2. Ar+ go to - cathode & hit surfaces
3. As Ar+ ions hit cathode, some of deposited element is excited and
dislodged into gas phase (sputtering)
4. excited element relaxes to ground state and emits characteristic radiation
- advantage: sharp lines specific for element of interest
- disadvantage: can be expensive, need to use different lamp for each element tested.

Source Modulation (spectral interference due to flame)

- problem with working with flame in AA is that light from flame and light source
both reach detector
- measure small signal from large background
- need to subtract out flames to get only light source signal (P/Po)
i. done by chopping signal:
Flame + P

Flame only

Flame + P

ii. or modulating P from lamp:

Flame only
time

Corrections For Spectral Interferences Due to Matrix

- molecular species may be present in flame
- problem if absorbance spectra overlap since molecular spectrum is much
broader with a greater net absorbance
- need way of subtracting these factors out

Methods for Correction

1) Two-line method
- monitor absorbance at two close together
one line from sample one from light source
second from impurity in HCL cathode, Ne or Ar gas in HCL, etc
- second must not be absorbed by analyte
absorbed by molecular species, since spectrum much broader
- A & are ~ constant if two close
- comparing A1, A2 allows correction for absorbance for molecular species

A1 (atom&molecule) A2 (molecule) = A (atom)

Problem: Difficult to get useful second with desired characteristics

2) Continuous source method (HCL plus D2)

- alternatively place light from HCL or a continuous source D2 lamp thru flame
- HCL absorbance of atoms + molecules
- D2 absorbance of molecules

advantage:
-available in most instruments
-easy to do
disadvantage:
-difficult to perfectly match lamps (can give + or errors)

3) Zeeman Effect
- placing gaseous atoms in magnetic field causes non-random orientation of
atoms
- not apparent for molecules
- splitting of electronic energy levels occurs (~ 0.01 nm)
- sum of split absorbance lines original line
Background
- only absorb light with same orientation
- can use Zeeman effect to remove background
place flame polarized light through

sample in magnetic field get

absorbance (atom+molecule) or
absorbance (molecule) depending
on how light is polarized
Background+Absorbance

6) Chemical Interference - more common than spectral interference

1) Formation of Compounds of Low Volatility
- Anions + Cations Salt
Ca2+ +SO42- CaSO4 (s)
- Decreases the amount of analyte atomized decreases the absorbance signal
- Avoid by:
increase temperature of flame (increase atom production)
add releasing agents other items that bind to interfering ions
eg. For Ca2+ detection add Sr2+
Sr2+ + SO42- SrSO4 (s)
increases Ca atoms and Ca absorbance
add protecting agents bind to analyte but are volatile
eg. For Ca2+ detection add EDTA4Ca2+ + EDTA4- CaEDTA2- Ca atoms
2) Formation of Oxides/Hydroxides
M + O MO
non-volatile & intense molecular absorbance

M + 2OH M(OH)2
- M is analyte
- Avoid by:
increase temperature of flame (increase atom production)
use less oxidant

3) Ionization
M M+ + e- M is analyte
- Avoid by:
lower temperature
add ionization suppressor creates high concentration of e- suppresses
M+ by shifting equilibrium.

3) Ionization

Ringkasan evolusi aerosol yang mungkin terjadi didalam nyala

Rouessac F and Rouessac A. 2007. Chemical Analysis. Modern Instrumentation
Methods and Techniques. Second Edition. John Wiley & Sons Ltd. England p.289

Analisis kuantitatif dengan SSA

sampel harus dalam bentuk larutan
Ada beberapa cara untuk melarutkan sampel yaitu:
Langsung dilarutkan dengan pelarut yang sesuai
Sampel dilarutkan dalam suatu asam
Sampel dilarutkan dalam suatu basa atau dilebur dahulu dengan
basa kemudian hasil leburan dilarutkan dalam pelarut yang
sesuai.

Metode pelarutan apapun yang akan dipilih untuk

dilakukan analisis dengan SSA, yang terpenting adalah
bahwa larutan yang dihasilkan harus jernih, stabil, dan
tidak menganggu zat-zat yang akan dianalisis.

Analisis kuantitatif dengan SSA

1. Kuantifikasi dengan kurva baku (kurva
kalibrasi)
2. Kuantifikasi dengan cara perbandingan
langsung
3. Cara standar adisi (cara penambahan
baku)

Standard additions