1

Department of Chemistry

Analytical and Environmental Chemistry
(CH-204)

Atomic Spectroscopy
Michael J. Hynes
2
Atomic Spectroscopy
Lecturer
Michael J. Hynes
Texts
(1) Quantitative Chemical Analysis , by Daniel C. Harris
Pub. Freeman. Chapter 21 (4th Edition)
(2) Atomic Absorption and Emission Spectroscopy by
E. Metcalfe & F.E. Prichard, Pub. Wiley (ACOL series).
(3) Most Analytical Chemistry Textbooks.
(4) Handout


3
Principle of Atomic Absorption pectroscopy
Atomic Absorption (AA) is based on the principle that a
ground state atom is capable of absorbing light of the
same characteristic wavelength as it would emit if
excited to a higher energy level.
In flame AA, a cloud of ground state atoms is formed by
aspirating a solution of the sample into a flame of a
temperature sufficient to convert the element to its atomic
state.
The degree of absorption of characteristic radiation
produced by a suitable source will be proportional to the
population of ground state atoms in the flame, and hence
to the concentration of the element in the analyte.
4
Spectra of atoms consist of SHARP LINES.
Each element has a characteristic spectrum.
Due to sharpness of lines, there is little overlap between the
spectral lines of different elements.
Therefore, there is little interference.
Heat
Compound
Atoms
Atomic Spectroscopy
Sample
High
Temperature
Vapour
Measure absorbance or emission of the atomic vapour.
Atomic spectroscopy deals with atoms.
Fe
2+
and Fe
3+
will not be distinguished.
5
6
Sensitivity
Atomic spectroscopy is very sensitive for most elements.
Concentrations at the ppm level may be routinely
determined using flame atomisation.
Using electrothermal atomisation, concentrations at the
ppb may be determined.
1 ppm = 10
-6
g/g or 1g/g
The density of dilute aqueous solutions is approximately
1.00 so that:
1 g/g of aqueous solution = 1g/ml = 1 ppm
1 ppm Fe = 1 x 10
-6
g Fe/ml = 1.79 x 10
-5
mol dm
-3

1 ppm = 1 second in 11.6 days
1 ppb = 1 second in 31.7 years.
7
Atomic Absorption Spectroscopy
Absorbance = -log(I
t
/I
0
)
I
o
= incident radiation (on sample)
I
t
= transmitted radiation.
Atomic Emission Spectroscopy
Absorbance = -log(I
t
/I
0
)
I
0
=intensity of radiation reaching detector
in the absence of sample.
I
t
= intensity of radiation reaching detector
when sample is being aspirated.
8
Both methods are used to determine the
concentration of an element in solution.
Both methods use a standard curve.
Difference between UV and IR spectroscopy
is that sample must be atomised.
Sample may be atomised by:
(1) A flame
(2) Electrically heated furnace
(3) A Plasma
9
x
x
W
1/2

Abs

Band Width = W
1/2
= width of band at half the height
25 nm+
Abs

Molecular Absorption Band

W
1/2
=
0.003 nm
Atomic Vapour
Absorption Band
10
E
3
(Excited state)
E
2
(Excited state)
E
1
(Excited state)
E
o
(Ground state)
Absorption Emission
Resonance Lines
Most Intense Line
3 Absorption Lines
6 Emission lines
Atomic Absorption and Emission Lines
AE = E
1
- E
0
= hv = hc/
AE
11
Comparison of the atomic emission spectrum of
silicon compared with the molecular absorption
spectrum of ethanal.
12
HCL
hv
Chopper
Cloud
Chamber
Fuel
Nebuliser
Sample uptake
Oxidant
(Air)
Monochromator
hv
Detector
hv
Amplifier
Output
e.g. PC/Printer
Source
Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer
Waste
HCL = Hollow-cathode Lamp

I
o I
t
i
V
Sample (Atoms in flame)
Burner
Flame
13
14
15
Laminar Flow Burner
16
Fuel Oxidant Temperature
(K)
Acetylene Air 2400-2700
Acetylene Nitrous Oxide 2900-3100
Acetylene Oxygen 3300-3400
Hydrogen Air 2300-2400
Acetylene flow rate: 1000 ml/minute
Air flow rate: 5000 ml/minute
Sample uptake: 2 ml/minute
~ 80% of sample goes to waste.
Therefore, dilution factor = ~ 15,000
Highly inefficient!
EXAMPLES OF FLAME TEMPERATURES
17
Effect of temperature in atomic spectroscopy
E
1
(g = 2)
E
0
(g = 1)
Boltzman Distribution
(Ground state)
(Excited state)
kT
o
N
N
1
E
o
1 1
e
g
g

A
|
|
.
|

\
|
=
AE
1

Na AE
1
= 3.37 x 10
-19
J/atom
4 )(2600) 10 x 1.381
10 x -3.37
N
N
10 x 1.67 e
1
2

23 -
-19
o
1

=
|
.
|

\
|
=
At 2600 K
At 2610 K N
1
/N
o
= 1.74 x 10
-4

g is the multiplicity
18
Temp
K
% Ground
State
% Excited
State
2600 99.9833 0.0167
2610 99.9826 0.0174
The effect of a 10 K temperature rise on the
ground state population is negligible (~0.02 %).
In the excited state the fractional change is
( )
% 4
0167 . 0
100 0.0167 - 0.0174
=
Effect of Temperature on Sodium Atoms
So!
19
Effect of Temperature
Small changes in flame temperature
(~10 K) have little effect in atomic
absorption but have significant effects in
atomic emission spectroscopy.
Must have good flame control in atomic
emission spectroscopy.
20
M
+
X
-
M
+
X
-
Solution
Mist
Evaporation
MX
Solid
Vapourisation
MX
Gas
Dissociation M (gas)
X (gas)
Thermal
excitation
M
*
(g)
Flame
emission
hv
Measure for
flame emission
spectroscopy
Absorption of radiant
energy
hv
Measure for atomic
absorption spectroscopy
M
*
(g)
Re-emit radiation at 90
o
(Atomic fluorescence)
Process by which gaseous atoms are produced in flames
Measure for atomic
fluorescence spectroscopy

21
HCL
hv
Chopper
Cloud
Chamber
Fuel
Nebuliser
Sample uptake
Oxidant
(Air)
Monochromator
hv
Detector
hv
Amplifier
Output
e.g. PC/Printer
Source
Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer
Waste
HCL = Hollow-cathode Lamp

I
o I
t
i
V
Sample (Atoms in flame)
Burner
Flame
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Radiation Source
Beers Law only applies to monochromatic radiation.
In practice, monochromatic implies that the linewidth of
the radiation being measured is less than the bandwidth
of the absorbing species.
Atomic absorption lines very sharp with an inherent
linewidth of 0.0001 nm.
Due to Doppler effect and pressure broadening, linewidths
of atoms in a flame are typically 0.001 - 0.01 nm.
Therefore, we require a source having a linewidth of less
than 0.01 nm.
Typical monochromator has a bandwidth of 1 nm i.e. x100
greater than the linewidth of the atom in a flame.
23
Hollow Cathode Lamp
Used because of the requirement for a source
of narrow lines of the correct frequency.
Hollow Cathode lamp
filled with argon or neon at a pressure of 130
- 170 Pa (1 - 5 torr)
24
Monochromator bandwidth
(~100x greater than atomic lines
25
Hollow Cathode Lamp
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Reactions in the Hollow Cathode Lamp
Apply sufficiently high voltage between the cathode and
the anode:
(1) Ionization of the filler gas:
Ne + e
-
= Ne
+
+ 2e
-

(2) Sputtering of the cathode element (M):
M(s) + Ne
+
= M(g) + Ne
(3) Excitation of the cathode element (M)
M(g) + Ne
+
= M
*
(g) + Ne
(4) Emission of radiation
M
*
(g) (M(g) + hv
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Hollow Cathode Lamp
The cathode of the hollow cathode lamp (HCL)
contains the element being analysed.
Therefore the atomic radiation emitted by the HCL
has the same frequency as that absorbed by the
analyte atoms in the flame or furnace.
The linewidth from the HCL is relatively narrow
(compared to linewidths of atoms in the flame or
furnace) because of low pressure in lamp and lower
temperature in lamp (less Doppler broadening).
Thus the linewidth from the HCL is nearly
monochromatic (vs sample).
Different lamp required for each element although
some are mulit-element.
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29
Hollow Cathode Lamp - The Filler Gas
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Electrothermal Atomisation - Graphite Furnace
Sample holder consists of a graphite tube.
Tube is heated electrically
Beam of light passes through the tube.
Offers greater sensitivity than flames.
Uses smaller volume of sample
typically 5 - 50 l (0.005 - 0.05 ml).
All of sample is atomised in the graphite tube.
Atomised sample is confined to the optical path for several
seconds (residence time in flame is very short).
Uses a number of stages as shown on next slide.
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32
Stages in a Graphite Furnace
Typical conditions for Fe:
Drying stage: 125
o
for 20 sec
Ashing stage 1200
o
for 60 sec
Atomisation 2700
o
for 10 sec

Requires high level of operator skill.
Method development difficult.

33
Schematic Diagram of a Graphite Furnace
HCL
hv
34
Advantages and Disadvantages of Flame AAS
Advantages
equipment relatively cheap
easy to use (training easy compared to furnace)
good precision
high sample throughput
relatively facile method development
cheap to run
Disadvantages
lack of sensitivity (compared to furnace)
problems with refractory elements
require large sample size
sample must be in solution
35
Advantages and Disadvantages of
Electrothermal Atomisation
Advantages
very sensitive for many elements
small sample size
Disadvantages
poor precision
long cycle times means a low sample throughput
expensive to purchase and run (argon, tubes)
requires background correction
method development lengthy and complicated
requires a high degree of operator skill (compared to
flame AAS)
36
HCL
hv
Chopper
Cloud
Chamber
Fuel
Nebuliser
Sample uptake
Oxidant
(Air)
Monochromator
hv
Detector
hv
Amplifier
Output
e.g. PC/Printer
Source
Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer
Waste
HCL = Hollow-cathode Lamp

I
o I
t
i
V
Sample (Atoms in flame)
Burner
Flame
37
Monochromator
The operation and sensitivity of the atomic absorption
spectrometer spectrometer depends on the spectral
band width of the resonance line emitted by the
primary radiation source (the hollow cathode lamp).
The function of the monochromator is to isolate the
resonance line from non-absorbing lines close to it in
the source spectrum and from background continua
and molecular emissions originating in the flame.
Hollow cathode lamps emit a number of lines, in the
case of multi-element lamps, the number can be
quite large and it is necessary to isolate the line of
interest.
38
Detector/Measuring System
The intensity of the line source is measured with a
photomultiplier, which produces an electrical signal
proportional to the intensity of the incident light.
This signal is amplified and processed electronically to produce
an output which on older instruments was read on a digital or
analogue meter in either absorbance or concentration mode.
In modern instruments, the output is usually displayed on the
computer screen of the PC controlling the instrument.
In order to eliminate the unwanted emissions from the flame, the
light source is modulated by a chopper which is located
between the hollow cathode lamp and the flame. The amplifier
which modifies the signal from the photomultiplier is tuned in to
the same frequency .
(Alternatively, the hollow cathode lamp may be modulated by
applying an AC voltage at say 50 Hz.).

39
A B
40
Interferences
Interference is any effect that changes
the signal when analyte concentrations
remain unchanged.
While atomic absorption spectroscopy is
relatively free from interferences, there
are a number of interferences which
must be dealt with.
41
Spectral Interference
This refers to overlap of analyte signals
with signals originating from other
elements in the sample or with signals due
to the flame or furnace.
Example:
Al 308.216 nm
V 308.211 nm
Solution:
Separate elements or use a different line
(which may be less sensitive).
42
Chemical Interference
Formation of Stable or Refractory Compounds
Elements that form very stable compounds
are said to be refractory because they are
not completely atomised at the temperature
of the flame or furnace.
Solution
Use a higher flame temperature (nitrous
oxide/acetylene)
Use a release agent
Use protective chelation
43
Examples
Determination of calcium in the presence of sulfate or
phosphate (e.g. in natural waters)
3Ca
2+
+ 2PO
4
3-
= Ca
3
(PO
4
)
2

(stable compound)

Release agent
Add 1000 ppm of LaCl
3

2LaCl
3
+ Ca
3
(PO
4
)
2
= 3CaCl
2
+ 2La(PO
4
)
CaCl
2
readily dissociates
Protective chelation
Ca
3
(PO
4
)
2
+3EDTA = 3Ca(EDTA) + 2PO
4
3-

Ca(EDTA) dissociates readily.

44
Ionisation Interference
M(g) M
+
(g) + e
-

A problem in the analysis of alkali metal ions at low flame
temperatures and other elements at higher temperatures.
Because alkali metals have the lowest ionisation
potentials, they are most extensively ionised in flames.
At 2450 K and a pressure of 0.1 Pa, sodium is 5% ionised.
Potassium is 33% ionised under the same conditions.
Ionised atoms have energy levels which are different to
the parent atoms
therefore the analytical signal is reduced.
45
Solution
Add an ionisation suppressor

K
] ][e [M
[M]
[M]
] ][e [M
K
-
-
+
+
=
=
Add an easily ionised element such as Cs.
Add 1000 ppm of CsCl when analysing Na or K.

Cs is more readily ionised than either Na or K.
This produces a high concentration of electrons in the
flame.
46
Matrix effects
The amount of sample reaching the flame is
dependent on the physical properties of the solution:
viscosity
surface tension
density
solvent vapour pressure.
To avoid differences in the amount of sample and
standard reaching the flame, it is necessary that the
physical properties of both be matched as closely as
possible.
Example:
Analysis of blood
47
Non-Atomic Absorption
Non-atomic absorption is caused by molecular
absorption or light scattering by solid particles in the
flame.
The absorption measurement obtained with a hollow
cathode lamp is the sum of the atomic absorption and
the non-atomic absorption.
The interference is corrected for by making a
simultaneous measurement of the non-atomic
absorption using a continuum source (usually
deuterium)
this is called background correction


48
Operational Parameters
Sensitivity
the concentration of an element which will
reduce the transmission by 1%


0.00436
100
99
log -
I
I
log - Abs
0
t
=
|
.
|

\
|
=
|
|
.
|

\
|
=
This corresponds to an absorption of 0.00436
49
Calculations
For an absorbance of 1.0 we require
1.0/0.00436 = 230 times the sensitivity.
For Cu, sensitivity = 0.05 ppm
For an absorbance of 1 we require a
concentration of 11.5 ppm.
Using scale expansion of 10 we can usually
obtain an absorbance of 1 using a 1 ppm
solution of copper.
50
Detection Limit
The concentration of an element that
gives a signal equal to three times the
peak to peak noise level of the baseline.
Measure the baseline while aspirating a
blank solution.
Absorbance
Peak to peak noise level
Time
51
Terms to understand in atomic spectroscopy (1)
Atomic absorption spectroscopy
Atomic emission spectroscopy
Atomisation
Background correction
Boltzman distribution
Chemical interference
Detection limit
Graphite furnace
Hollow-cathode lamp

52
Terms to understand in atomic spectroscopy (2)
Inductively coupled plasma
Ionisation interference
Ionisation suppressor
Matrix
Matrix modifier
Nebulisation
Premix burner
Releasing agent
Spectral interference

53
Applications of AAS
Agricultural analysis
soils
plants
Clinical and biochemistry
whole blood, plasma and serum Ca, Mg,
Li, Na, K, Cu, Zn, Fe etc.
Metallurgy
ores, metals and alloys

54
Applications of AAS
Lubricating oils
Ba, Ca, Mg and Zn additives
Greases
Li, Na, Ca
55
Applications of AAS
Water and effluents
many elements e.g. Ca, Mg, Fe, Si, Al, Ba
Food
wide range of elements
Animal feedstuffs
Mn, Fe, Co, Cu, Zn, Cr, Se
Medicines
range of elements