Atomic Absorption Spectroscopy

Atomic Absorption Spectroscopy

Fundamental Principle
Instrumentation
Qualitative and Quantitative Analysis
Applications
2

Atomic Spectroscopy
atomic spectroscopy is the determination of elemental
composition by its electromagnetic or mass spectrum.
the study of the electromagnetic spectrum of elements is
called Optical Atomic Spectroscopy.
electrons exist in energy levels within an atom
these levels have well defined energies
electrons moving between them must absorb or emit
energy equal to the difference between them.

Atomic Spectroscopy
in optical spectroscopy, the energy absorbed to move an

electron to a more energetic level and/or the energy emitted as

the electron moves to a less energetic energy level is in the form
of a photon.

the wavelength of the emitted radiant energy is directly related

to the electronic transition which has occurred.

Atomic Spectroscopy
every element has a unique electronic structure, therefore the

wavelength of light emitted is a unique property of each

individual element.

as the orbital configuration of a large atom may be complex,

there are many electronic transitions which can occur, each

transition resulting in the emission of a characteristic wavelength

of light
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Atomic Spectroscopy

Atomic Spectroscopy
divided into

Atomic
Absorption

Atomic
Emission

Atomic
Fluorescence

Atomic Spectroscopy
Atomic absorption spectra
energy of radiation absorbed by a vaporized atom is identical with
that needed to bring about excitation to a higher electronic state
transitions: excitation of an electron from ground state to a higher
energy level

Atomic Absorption Spectroscopy (AAS)

Atomic-absorption (AA) spectroscopy uses the absorption of light
to measure the concentration of gas-phase atoms.
since samples are usually liquids or solids, the analyte atoms or
ions must be vaporized in a flame or graphite furnace.
the atoms absorb ultraviolet or visible light and make transitions to
higher electronic energy levels.

Atomic Absorption Spectroscopy

the analyte concentration is determined from the amount of
absorption.
concentration measurements are usually determined from a
working curve (Beers Law) after calibrating the instrument
with standards of known concentration.

Atomic Absorption Spectroscopy

1. Desolvation the liquid solvent is
evaporated, and the dry sample remains
2. Vaporizations the solid sample vaporizes to
a gas

3. Volatilization the compounds making up

the sample are broken into free atoms.
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Atomic Spectroscopy
Method: Atomization
A process in which the constituents of a solution are
converted into gaseous atoms / elementary ions.
Applicable to perhaps 70 of the elements in the periodic
table
Quite sensitive
Determine analyte concentration ppm to ppb range

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Instrument

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Atomic Absorption Spectroscopy

Spectrophotometers
contain same basic components as an instrument designed
for absorption analysis of solution

source, sample container (flame or hot surface), l selector,

detector-readout system
instrument provide sufficiently narrow band width to isolate
the line chosen for measurement from other lines that may
interfere with or diminish the sensitivity of the analysis

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Block diagram of basic instrumental parts of atomic

absorption spectrometer.

Block diagram

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Schematic of basic instrumental parts of

atomic absorption spectrometer.

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Block diagram of basic instrumental parts of

atomic absorption spectrometer.

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Atomic Absorption Spectroscopy

(based on Flame Atomization)

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Atomic Absorption Spectroscopy

Flame Absorption Spectrometer with attached graphite furnace

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Atomic (Flame) Absorption Spectrometer

Components

Functions

(i)

Hollow cathode lamp

emit a spectral line source of radiation

(ii)

Nebulizer

to introduce a solution sample in the form of fine

spray/aerosol

(iii)

Burner head

where sample is introduced into the flame and

atomization occurs

(iv)

Monochromator

to isolate a single atomic resonance line from the

spectrum of lines emitted by the hollow cathode lamp or
for spectrum (light dispersion) scanning

(v)

Photomultiplier tube

to convert radiant energy into an electrical signal

(for measurement of low radiant power) OR to
measure light intensity and amplifies the signal
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Atomic Spectroscopy
(based on Flame Atomization)
Spectrophotometer (AA); double beam

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Atomic Absorption Spectroscopy

(based on Flame Atomization)
large % of atoms are in the G.S., available to be excited by a beam of light
from a light source
AA uses a light beam to excite these ground state atoms in the flame
AA is much like the molecular absorption spectroscopy in that light is
measured & related to concentration
Major difference: instrument design
Light source
sample container
placement of monochromator

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Atomic Spectroscopy
(based on Flame Atomization)

Spectrophotometers
Radiation from hollow cathode lamp is split into 2 beams
One passes thru the flame
The other around the flame
A half-silvered mirror returns both beams to a single path then pass thru the
monochromator then detector
Note: monochromator placed between sample and detector
Eliminates most of the radiation emanating from the flame
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Atomic Absorption Spectroscopy

Line sources

i.

Hollow Cathode Lamp

ii.

Electrodeless Discharge Lamps

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1. Light Source (Hollow Cathode Lamp)

A cathode lamp (1), is a stable light source, which is necessary to

emit the sharp characteristic spectrum of the element to be
determined.
A different cathode lamp is needed for each element, although
there are some lamps that can be used to determine three or four
different elements if the cathode contains all of them.
Each time a lamp is changed, proper alignment is needed in order
to get as much light as possible through the flame, where the
analyte is being atomized, and into the monochromator.

@Zarila Mohd Shariff

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Hollow Cathode Lamp

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Atomic Spectroscopy
(based on Flame Atomization)
Light source
called hollow cathode tube
lamp emits exact l required for the analysis (without the use of
monochromator)
light directed at the flame, containing sample (aspirated)
flame wide ( 4 6 inches)
Reasonably long path length for detecting small concentration of atoms in the
flame

light beam enters monochromator, tuned to a l absorbed by the sample

detector measures light intensity (after adjusting for the blank)
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Atomic Spectroscopy
(based on Flame Atomization)
1. Hollow Cathode Lamp
light source in AA instrument
light from this lamp exactly light required for the analysis, even no
monochromator is used
atoms of metal tested are present within the lamp

So how does the Hollow Cathode Lamp works?

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Atomic Spectroscopy
(based on Flame Atomization)
So how does the Hollow Cathode Lamp works?
lamp on, atoms are supplied with energy

causes atoms elevate to excited states

upon returning to GS, exactly the same ls that are useful in the analysis are
emitted

since the analyzed metal with exactly the same energy levels that undergoes
excitation

Hollow cathode lamp MUST contain the element to be determined

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Atomic Spectroscopy
(based on Flame Atomization)

Illustration of the fact that the light emitted by hollow cathode lamp is exactly the
l needed by the atoms in the flame

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Atomic Absorption Spectroscopy

Detector AA measures ONLY the intensity of light
that does not get absorbed & NOT measure the light
emitted by the same atoms in the flame.

Use of light chopper

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Atomic Absorption Spectroscopy

Line Source used for AA: Hollow Cathode Lamp
Source of Modulation:
employed in flame AAS to distinguish between the
component of radiation arising from the source and
the component of radiation arising from flame
background
device: light chopper

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Atomic Absorption Spectroscopy

(based on Flame Atomization)

Light chopper (source of modulation)

eliminate the effects of radiation from the flame

mirror

open

light is chopped with a rotating half-mirror so that detector sees

alternating light intensities
one moment, only light emitted by flame is read since the light from
the source is cut off
next moment, light from both the flame emission & transmission of
the sources light is measured since the sources light is allowed to
pass
The elements of the detector is such that the emission signal is
subtracted from the total signal & this difference is then, is T (what is
measured)
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2. Atom Cell
the atom cell (2), is the part with two major functions:
1. nebulization of sample solution into a fine aerosol solution,
2. dissociation of the analyte elements into free gaseous ground
state form.

Not all the analyte goes through the flame, part of it is

disposed.

@Zarila Mohd Shariff

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2(a) Flame Atomizers

Two types of burners in flame spectroscopy

i.

Turbulent flow (total consumption burner)

ii.

Laminar flow (premix burner)

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Flame Atomizers
Turbulent flow burner:
Nebulizer & burner are combined into a single unit
Sample is drawn up the capillary & nebulized
caused by the flow of gases around the capillary tip

Sample flow rate: 1 to 3 mL/min

Advantage: introduce relatively large & representative sample into the flame
Disadvantage: a relatively short path length through flame
problems with clogging of the tip
burners noisy from electronic and auditory stand point

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Flame Atomizers
Turbulent flow burner:

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Flame Atomizers
Laminar flow (premix ) burner:
Sample is nebulized by the flow of oxidant past a capillary tip
Resulting aerosol then mixed with fuel & flows past a series of baffles that
remove all but the finest droplets

Majority of the sample collects in the bottom of mixing chamber, drained to a

waste container
Aerosol, oxidant & fuel are burned in a slotted burner that provides a flame, 5
10 cm in length

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Flame Atomizers

Laminar flow (premix ) burner

Advantage: provide quiet flame
longer path length; enhance sensitivity & reproducibility
clogging is not a problem

Disadvantage:
Lower rate of sample introduction
Possibility of selective evaporation of mixed solvents in the mixing chamber;
create analytical uncertainties
Mixing chamber contains a potentially explosive mixture that can be ignited
by flashback (overcome: pressure-relieve vents)

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Flame Atomizers
Laminar flow
(premix burner)

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3. Monochromator & 4. Detector

as the sample passes through the flame, the beam of light
passes through it into the monochromator (3).
the monochromator isolates the specific spectrum line
emitted by the light source through spectral dispersion, and
focuses it upon a photomultiplier detector (4), whose function
is to convert the light signal into an electrical signal.

@Zarila Mohd Shariff

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 The processing of electrical signal is fulfilled by a signal

amplifier (5). The signal could be displayed for readout (6), or
further fed into a data station (7) for printout by the
requested format

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Atomic Absorption Spectroscopy

The technique of flame atomic absorption spectroscopy (FAAS) requires
a liquid sample to be aspirated, aerosolized, and mixed with
combustible gases, such as acetylene and air or acetylene and nitrous
oxide.
The mixture is ignited in a flame whose temperature ranges from 2100
to 2800 oC.
During combustion, atoms of the element of interest in the sample are
reduced to free, unexcited ground state atoms, which absorb light at
characteristic wavelengths.

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 the characteristic wavelengths are element specific and accurate

to 0.01-0.1nm.
to provide element specific wavelengths, a light beam from a lamp
whose cathode is made of the element being determined is passed
through the flame.
a device such as photomultiplier can detect the amount of
reduction of the light intensity due to absorption by the analyte,
and this can be directly related to the amount of the element in
the sample
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Flame Atomization Process

Aqueous solution
(sample)

burner
(laboratory type)

dispersed/
nebulized

swept
into

gaseous fuel
+
oxidant

into small
droplets
mixed
with

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@Zarila Mohd Shariff

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Atomic Absorption Spectroscopy

Process: Atomization

Solution of the analyte is evaporated rapidly at an

elevated temperature to yield a finely divided solid

Further heating: breaks down into gaseous atoms

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Flame Atomization Process

Evaporation of solvent at base of the flame (above tip of burner)
Finely divided solid particles
Carried to center region of flame
Inner cone
Hottest part of flame

Inner cone: atoms & elementary ions formed from solid particles
Atoms/ elementary ions carried to outer cone (outer edge)
Oxidation process occur
Then atomized particles disperse into atmosphere

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Flame Atomization Process

Flame Temperatures : 1700 3100 oC
Depend upon fuels & oxidants used
Lowest T: Natural gas-air flames
Highest T: acetylene oxygen
acetylene nitrous oxide
2500 oC to 2700 oC: hydrogen oxygen flame

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Atomic Spectroscopy
Typical Gases for flames
Fuel Gas

Oxidizer gas

Maximum flame
temperature, oC

Natural gas

Air

1700

Acetylene (C2H2)

Air

2500

H2

O2

2940

Acetylene

N2O

2970

Acetylene

O2

3400

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Atomic Spectroscopy
proper flame temperature
fuel gas must be compound that can be burned in a controllable
manner to give a reproducible, as well as a hot flame
e.g. 1 Natural gas used in Bunsen burners

low flame
capable of exciting alkali metals (Group 1A) & some
alkaline metals (Group IIA)

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Atomic Spectroscopy
proper flame temperature
fuel gas must be compound that can be burned in a controllable
manner to give a reproducible, as well as a hot flame
e.g. 2 Acetylene nitrous oxide flame

used for the determination of many metals

because it prevents oxide formation & other interfering
reactions
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Flame Atomization Process

Effects of flame temperature
AA & AE spectra series of discrete lines whose
wavelength are unique for each element
Line spectra arise from excitation of the outer electron of
the atom;
energy of a radiant source
energy of a hot flame
higher flame temperature, increase in atom population
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Atomic Spectroscopy
Atomic absorption spectroscopy
(based on flames)
currently the most widely used of all the atomic methods
simplicity, effectiveness, relatively low cost

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Atomizer (Flame)
AA spectroscopy requires that the analyte atoms be in the gas phase.
Ions or atoms in a sample must undergo desolvation and vaporization
in a high-temperature source such as a flame or graphite furnace.
Flame AA can only analyze solutions, while graphite furnace AA can
accept solutions, slurries, or solid samples.
Flame AA uses a slot type burner to increase the path length, and
therefore to increase the total absorbance.

Sample solutions are usually aspirated with the gas flow into a
nebulizing/mixing chamber to form small droplets before entering
the flame.
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Atomizer (graphite furnace)

The graphite furnace has several advantages over a flame.
It is a much more efficient atomizer than a flame
it can directly accept very small absolute quantities of sample.

samples are placed directly in the graphite furnace and the furnace
is electrically heated in several steps to (i) dry the sample, (ii) ash
organic matter, and (iii) vaporize the analyte atoms.

Graphite furnace atomic

absorption spectrometer.
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Atomizer (graphite
furnace)
http://faculty.plattsburgh.edu/robert.fuller/437web/lec7graphitefurnace
/TempProgram.htm

http://faculty.sdmiramar.edu/fgarces/LabMatters/Instruments/
AA/AAS_Instrument/AASInstruments.htm

Graphite furnace atomic

absorption spectrometer.

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Graphite Furnace AAS vs Flame AAS

Graphite Furnace Advantages

Flame Advantages
Simple

Superior sensitivity - detect analytes at concentrations 10 - 100 times

lower than flame
High conversion efficiency of sample into free atoms

Low sample volumes ~20 L

Convenient
Excellent Results
Relatively short measurement time ~14 seconds

Absorption signal is a well defined peak

Peak heights and areas can be used for quantitative measurements

Temperature is only factor involved in production of free atoms

compared with flame which also must factor in the composition of the
flame, gas flow and oxidant-fuel ratio

Directs analysis of some types of liquid sample that would be

inappropriate for flame AAS

Low spectral interference due to generally higher temperatures

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Graphite Furnace AAS vs Flame AAS

Graphite Furnace Disadvantages
Longer measurement time than flame up
to ~330 seconds depending on the
temperature program used

Flame Disadvantages
Sensitivity Limitations

Restricted Analytical Scope

Limited dynamic range

High matrix interference

Loss of sample during process hence

higher initial sample volumes required

Short residence time of analyte in optical

path
Flame composition and temperature have
a bearing on the results obtained

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Atomic Spectroscopy
(based on Flame Atomization)
Absorption behavior follows Beers Law & concentration of unknown
are determined the same way
All atomic species have an absorptivity, a
Pathlength, b is width of the flame
A = abc

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Atomic Absorption Spectroscopy

Interferences

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Atomic Absorption Spectroscopy

Interferences
Spectral interference
Chemical interference

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Atomic Absorption Spectroscopy

Spectral interference
arise when particulate matter from atomization scatters
the incident radiation from the source
or when the absorption or emission of an interfering
species either overlaps or lies so close to the analyte
absorption that resolution by the monochromator
becomes impossible.

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Atomic Absorption Spectroscopy

Spectral interference (simple words)
is one in which the spectral line of the elements
being determined overlaps with a spectral line (or
band) from another element present in the
sample.
the effect of the element will also be measured &
thus the results will be incorrect
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Atomic Absorption Spectroscopy

Spectral interference
the most common method of solving this problem
tune the monochromator to a different spectral
line for the element of interest so that there is no
overlap
secondary lines (can be found in the literature)

@Zarila Mohd Shariff

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Atomic Absorption Spectroscopy

Chemical interference

2 common types of chemical interferences (that

reduce the concentration of free gaseous atoms)
(i) Ionization
(ii) Formation of molecular species

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Atomic Absorption Spectroscopy

Chemical interference Ionization
Sample (liquid/solid) must be vaporized & atomized in a high
temperature source such as flame
this high T environment lead to ionization of the analyte atoms
analyte ionization can be suppressed by adding a source of
electrons, which shifts the equilibrium of the analyte from the
ionic to the atomic form
Cesium & potassium are common ionization suppressors that
are added to analyte solutions

Analyte

+
Analyte

e66

Atomic Absorption Spectroscopy

Chemical interference - Ionization
Cesium & potassium are common ionization
suppressors that are added to analyte
solutions
these atoms (Cs & K) are easily ionized & produce a
high concentration of free electrons in the flame

Analyte

+
Analyte

e67

Atomic Absorption Spectroscopy

Chemical interference Refractory Formation
Some elements can form refractory compounds that are not
atomized in flames
e.g. in the presence of phosphates, which interferes with
calcium measurements due to formation of refractory calcium
phosphate
Formation of refractory compounds can be prevented or
reduced by adding a releasing agent

3 CaCl2

(aq)

2 PO43(aq)

Ca3(PO4)2

(s)

6 Cl

(aq)
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Atomic Absorption Spectroscopy

Chemical interference Refractory Formation
For calcium measurement
adding lanthanum to the sample (and standard) solutions binds
the phosphates as LaPO4
LaPO4 has a very high formation constant, Kf and effectively ties
up the phosphate interferent.

3 CaCl2

(aq)

2 PO43(aq)

Ca3(PO4)2

(s)

6 Cl

(aq)
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Atomic Absorption Spectroscopy

Quantitative Analysis

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Atomic Absorption Spectroscopy

Quantitative Analysis
Calibration curve
Standard Addition Method

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Atomic Absorption Spectroscopy

A
x
x

Calibration curve

x
x
x

Concentration

in principal linear
analysis should NEVER be based on the measurement of
a single standard with assumption that Beers law is
being followed

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Atomic Absorption Spectroscopy

Standard Addition Method
Extensively used in AAS
Compensate for variation caused by physical & chemical
interferences in the analyte solution
AA: two or more aliquots of the sample are transferred to
volumetric flasks
One is diluted to volume directly while a known amount of
analyte is introduced to the other before dilution to the same
volume
Several different standard addition are recommended if the
method is unfamiliar
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Atomic Absorption Spectroscopy

Example: Standard Addition Method
A multiple standard solution addition method was used for determining
Fe3+ in a natural water sample. Ten milliliter aliquots of the sample were
pipetted into 50.00mL volumetric flasks. Exactly 0.00, 5.00, 10.00, 15.00,
and 20.00 mL of a standard solution containing 11.1 ppm of Fe3+ were
added to each followed by an excess of thiocyanate ion to give the red
complex Fe(SCN)2+.
After dilution to volume, absorbances of the five solutions were
measured in a 0.982-cm cell at 480 nm and found to be 0.240, 0.437,
0.621, 0.809, and 1.009, respectively.
What is the concentration of Fe3+ in the water sample?

74

Atomic Absorption Spectroscopy

Example Standard Addition Method

bVs cs
Vt

bVx cx
Vt

A kVs cs kVx cx

cs = known concentration
As = absorbance after each
addition
Vt = total volume of each flask
Vs = variable volume of standard
added
cx = unknown concentration
k = constant = b/Vt

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Atomic Absorption Spectroscopy

Example Standard Addition Method
A plot of A as a function of Vs should yield a straight
line of the form

A mVs b
Concentration of unknown:

slope;

m = kcs

intercept;

b = kVxcx

bcs
cx
mVx
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Atomic Absorption Spectroscopy

Example Standard Addition Method
A plot of A as a function of Vs should yield a straight line of
the form
Standard Addition Method (example)
1.200

Absorbance

1.000
0.800
0.600
0.400
0.200
0.000
-0.200

-10.000

-5.000

0.000

5.000

10.000

15.000

20.000

Concentration
unknown?
Volume of
of standard
solution
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Atomic Absorption Spectroscopy

What is the concentration of the unknown?

Slope, m = 0.0382
Intercept (at y-axis),
b = 0.2412

Standard Addition Method (example)

1.200

Concentration of unknown:

Absorbance

1.000

bcs
cx
mVx

0.800
0.600
0.400
0.200
0.000
-0.200

-10.000

-5.000

0.000

5.000

10.000

15.000

Volume of standard solution (mL)

20.000

Substitute the values:

Cx = 7.01ppm

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Atomic Absorption Spectroscopy

Quantitative Analysis
Detection Limits (ng/mL)*
Element

AAS Flame

Element

AAS Flame

Al

30

Cu

As

100

Fe

Ca

Hg

500

Cd

Pb

10

Cr

Zn

Nanogram/milliliter = 10-3 mg/mL = 10-3 ppm

* V.A. Fassel and R.N. Kniseley, Anal Chem., 1974, 46, 1111A. Copyright 1974 American Chemical Society

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Atomic Absorption Spectroscopy

Quantitative Analysis
Accuracy
relative error associated with a flame absorption
analysis is of the order of 1% to 2%.

with special precautions, this figure can be lowered to

a few tenths of one percent
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