ATOMIC SPECTROSCOPY

ATOMIC ABSORPTION
SPECTROPHOTOMETRY (AAS)
 THEORY
Absorption of very narrow band
electromagnetic radiation by free atoms
Electromagnetic spectrum is identified by its
wavelength() and frequency()

Energy (E) =
hc
h 

where h = Planck constant, c = 3.0x108m/s
 Absorption of radiation by free atoms

h +

Free atom at ground Free atom at excited

state state
 Origins of Spectral Transition

Example: Na atom
Atomic absorption Atomic emission
3p HS
Absorption of
thermal, radiant E = hƒ
E = hƒ or electrical energy
= hc/

3s LS
LS = lower energy state or ground state
HS = higher energy state
• Only valence electron(s) (optical electrons) is
involved

• amount of energy absorb is dependent on the

population of atoms at ground state.

• restriction on the number of absorption line

 Degree of Absorption
• Amount of light absorbed at frequency ()

e 2
   kv d v  2 Nf
mc
where kv = absorption coefficient at
frequency ()
e = electron charge
m = mass of the electron
C = speed of light
N = total number of atoms that absorb at
frequency () in the light path
f = oscillator strength of each atom

Note: , e, m, and c are constants

Total amount of radiation absorbed by
atoms = constant x Nf

Important conclusion
• Absorption is independent of both the
wavelength of radiation and
temperature
Atomic Absorption Spectrometry -
AAS

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 Atomic Absorption Spectroscopy
Skoog, Holler, Nieman Ch9-p206

• uses the absorption of light to measure the

concentration of gas-phase atoms
• analyte atoms or ions must be vaporized in a
flame or graphite furnace
• The analyte concentration is determined from
the amount of absorption - (Beer’s law)
 Light Sources
• Atoms absorb light of specific and narrow
wavelengths (0.002 - 0.005 nm)

• Light source must emit radiation at

wavelengths that can be absorbed by the
analyte atoms
 Atomic Line widths
• Beer’s law requires that the linewidth of the
radiation source should be substantially
narrower than the linewidth of the absorbing
sample

• Otherwise, the measured absorbance will not

be proportional to the sample concentration.
Atomic absorption lines are very sharp, with
an intrinsic width of only ~10-4 nm.

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 Atomic Linewidths
• Linewidth is governed by the Heisenberg
uncertainty principle, which says that the
shorter the lifetime of the excited state, the
more uncertain is its energy.

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 Atomic Linewidths
• Two mechanisms broaden the lines to 10-3 to
10-2 nm in atomic spectroscopy.

• One is the Doppler effect.

• The second is pressure broadening.

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Doppler effect
• Thermal motion of atoms in a gas introduce
additional broadening of line
• magnitude increases with the velocity at
which the emitting or absorbing species
approaches or recedes from a transducer
• No effect when atoms moves perpendicular to
the path of the transducer
 1. The Doppler Effect

• An atom moving toward

the radiation source
experiences more
oscillations of the
electromagnetic wave in
a given time period than
one moving away from
the source.

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 2. Pressure broadening
• Linewidth is also affected by pressure
broadening from collisions between atoms.

• Collisions shorten the lifetime of the excited

state.

• Uncertainty in the frequency of atomic

absorption and emission lines is roughly
numerically equal to the collision frequency
between atoms and is proportional to pressure.

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 The Hollow Cathode Lamp
• Monochromators generally cannot isolate
lines narrower than 10-3 to 10-2 nm.

• To produce narrow lines of the correct

frequency, we use a hollow-cathode lamp
containing a vapor of the same element as
that being analyzed.

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 The Hollow Cathode Lamp
• When ~500 V is applied between the anode and
the cathode, gas is ionized and positive ions are
accelerated toward the cathode.
– Resulting collisions remove atoms from the cathode.
– Eventually a cloud of atoms congregate around

• After ionization occurs, the lamp is maintained at

a constant current of 2–30 mA by a lower voltage.

Harris, p. 509 19
 The Hollow Cathode Lamp
• Cations strike the cathode with enough energy
to “sputter” metal atoms from the cathode
into the gas phase.

• Gaseous atoms excited by collisions with high-

energy electrons emit photons as they return
to GS.

Harris, p. 509 20
 The Hollow Cathode Lamp
• Atoms in the lamp are cooler than atoms in a
flame. Implications?

• Thus lamp emission is sufficiently narrower

than the absorption bandwidth of atoms in
the flame to be nearly “monochromatic”.

Harris, p. 509 21
 E.g. Cu hollow cathode lamp
• For such a lamp, the cathode has to be made of
Cu.

• When bombarded with energetic energetic Ne+

or Ar+ ions, the sputtered (Cu) atoms vaporize
and emit light.

• Because of matching frequencies (e.g. 324.8 nm),

this light can only be absorbed by Cu atoms that
are meanwhile in the flame.

Harris, p. 480 22
Hollow cathode lamp

Atomic Spectroscopy - Dr Shaneel Chandra 23

 E.g. Cu hollow cathode lamp
• The purpose of a monochromator in atomic
spectroscopy is to select one line from the
hollow-cathode lamp and to reject as much
emission from the flame or furnace as
possible.

• A different lamp is usually required for each

element, although some lamps are made with
more than one element in the cathode.

Harris, p. 480 24
 Background correction – atomic
absorption
• Beam chopping or electrical
modulation of the hollow-
cathode lamp (pulsing it on and
off) can distinguish the signal of
the flame from the atomic line at
the same wavelength.

• A rotating chopper periodically

blocks the light from the lamp.

• Signal reaching the detector while

the beam is blocked must be from
flame emission.
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 Background correction – atomic
absorption
• Signal reaching the detector when the beam is not
blocked is from the lamp and the flame. The difference
between the two signals is the desired analytical signal.

• Beam chopping corrects for flame emission but not for

scattering.

• Most spectrometers provide an additional means to

correct for scattering and broad background
absorption. Deuterium lamps and Zeeman correction
systems are most common.
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 SAMPLE ATOMISATION
Flame
• Air Acetylene
• Nitrous Oxide

Graphite furnace
• electrothermal atomizer
 Flame Atomisation
Nebulizer
• Suck up liquid sample at a controlled rate
• Create a fine aerosol for introduction into
the flame
• Mix the aerosol and fuel and oxidant
thoroughly for introduction into the flame
Function of the flame

• Destroy any analyte ions and breakdown

complexes

• Create atoms (the elemental form) of the

element of interest Fe0, Cu0, Zn0, etc.
 Flame Considerations:
• Flame must provide the temperature and
fuel/oxidant ratio required for “complete”
atomisation.
• Spectrum of the flame should not interfere
with the absorption lines of the analyte.
• Observation height and fuel/oxidant ratio
of the flame should be chosen to maximize
the number of free atoms present.
• A 50 mm laminar burner head is necessary
when utilizing nitrous oxide as an oxidant.
• What advantage does long slot burners had
for AAS?
• Why shorter (50 mm) laminar burner slot
required for nitrous oxide?
 TYPES OF FLAMES
Fuel Oxidant Temperatures, Maximum
C Burning
Velocity (cms-1)
Natural gas Air 1700-1990 39-43
Natural gas Oxygen 2700-2800 370-390
Hydrogen Air 2000-2100 300-440
Hydrogen Oxygen 2550-2700 900-1400
Acetylene Air 2100-2400 158-266
Acetylene Oxygen 3050-3150 1100-2480
Acetylene Nitrous 2600-2800 285
oxide
Graphite Furnace
 Atomisation Process
Drying
• Sample is heated for 20-30 seconds at 110-
125°C to evaporate any solvent or volatile
matrix components.

Ashing
• Performed at an intermediate temperature
to prevent loss of analyte
Atomization

• Temperature of furnace unit raised

instantaneously to bring about the
dissociation of residues into free atoms ( 2000
- 3000 K) that are responsible for absorption
 ADVANTAGES
• provide a reducing environment for easily
oxidized elements
• small sample sizes
• solid and liquid samples
• higher sensitivity
• samples placed directly in the graphite
furnace
 Low amounts of noise from the furnace
 Lower detection limits for many elements (10-
10 to 10-13 g of analyte)

• Sample solution is not wasted

 Disadvantages
 Much more time consuming
 More severe matrix effects
 Lower precision
 Analytical range is low compared to flame &
plasma atomization
• Analysis is usually limited to metals
 SAMPLE TYPES
• Clinical, food and organic samples
• Petrochemicals
• Agricultural samples
• Water and effluents
• Geochemical and mineralogical samples
• Metals
 SAMPLE PREPARATIONS
• Wet ashing (acid digestion)
• use of organic solvents
• extractions
• filtration
• fusion and dissolution in acid
• mineral acids
 Advantage of solution samples
• principal constituent in the sample solution is
the solvent
• samples in solution form are relatively easy to
handle and lend themselves readily to
automation
• permit relatively simple and straightforward
background correction
• Possible to perform procedures such as
standard additions (spiking) and internal
standardization.
CALIBRATION CURVE
Region 1
• Very low concentration - low absorption
due to IONIZATION. (Some atoms converted
back to ions.) eg K K+ + e-

Region 2
• Linear region
Region 3
• Negative deviation at high concentration due
to SELF ABSORPTION.

• Photons emitted by excited atoms partly

absorbed by ground state atoms in flame.
OVERCOMING INTERFERENCE

The clever chemist uses quality

control as a tool for obtaining
valid results.

NOT merely as a means to pass

off suspect data for validation

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 The method of standard additions
• This method compensates for many types of
interference by adding known quantities of
analyte to the unknown in its complete
matrix.

• E.g. the analysis of strontium in aquarium

water by standard addition.

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 The method of standard additions
Slope (abs units/ppm)
• Sr in distilled water: 0.03088
• St. Add. Curve (aquarium): 0.0188

• This means the response of Sr in

distilled water increases by 1.64
when compared to aquarium
water.
• We attribute the lower response in aquarium water to
interference by other species.

The absolute value of the x-intercept of the standard

addition curve, 7,41 ppm is the true, reliable measure
of Sr in the aquarium water.
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 The Standard Addition Technique
• Standard addition is employed when the
sample composition is unknown or complex
and is suspected to affect the analytical signal.

• A matrix effect is a change in the analytical

signal caused by anything in the sample other
than analyte.

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•
The Standard Addition Technique
Standard solutions of ClO4 in pure water show
15X greater sensitivity.

• Reduction of the ClO4 signal is a matrix effect

attributed to other anions present in the
groundwater.

• Note: adding a small volume of concentrated

standard to an existing unknown does not
change the concentration of the matrix very
much.

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 Calculations using Standard Addition
• Consider a standard addition in which a sample with
unknown initial concentration of analyte [X]i gives a signal
intensity IX.
• Then a known concentration of standard, S, is added to an
aliquot of the sample and a signal IS+X is observed for this
second solution.
• Addition of standard to the unknown changes the
concentration of the original analyte slightly because of
dilution. Let’s call the diluted concentration of analyte [X]f,
where “f” stands for “final.”
• We designate the concentration of standard in the final
solution as [S]f. (Bear in mind that the chemical species X
and S are the same.)

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Harris p. 106
 Calculations using Standard Addition
• Signal α [Analyte], so

[Analyte in initial solution] Signal from initial solution

=
[Analyte + standard in final solution] Signal from final solution

&

[X]i Ix
Stan dard Addition Equation: = Equation 6
[ S]f + [X]f Is+ x

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 Simplifying Equation 6
• Suppose
Vo is the initial volume of the sample
Vs is the added volume of the standard
[S]i is the concentration of the standard

Then total volume is V = Vo + Vs

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 Simplifying Equation 6
• Then concentrations in Equation 6 are

• See Tutorial Question

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