Department of Chemistry

Analytical and Environmental Chemistry

(CH-204)

Atomic Spectroscopy

Michael J. Hynes

1
 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

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 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.

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 Compound Heat
Atoms
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.
Atomic Spectroscopy
High
Sample Vapour
Temperature
Measure absorbance or emission of the atomic vapour.
Atomic spectroscopy deals with atoms.
Fe2+ and Fe3+ will not be distinguished.
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5
 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 = 10-6g/g or 1g/g
• The density of dilute aqueous solutions is approximately
1.00 so that:
1 g/g of aqueous solution = 1g/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.
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Atomic Absorption Spectroscopy
Absorbance = -log(It/I0)
Io = incident radiation (on sample)
It = transmitted radiation.

Atomic Emission Spectroscopy

Absorbance = -log(It/I0)
I0 =intensity of radiation reaching detector
in the absence of sample.
It = intensity of radiation reaching detector
when sample is being aspirated.

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• 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

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 x
Abs W1/2 x


Band Width = W1/2 = width of band at half the height

Abs W1/2 =
25 nm+ 0.003 nm

 
Molecular Absorption Band Atomic Vapour
Absorption Band
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 Atomic Absorption and Emission Lines
Resonance Lines
E3(Excited state)

E2(Excited state)

E1(Excited state)
E
Eo(Ground state)
Absorption Emission
Most Intense Line

3 Absorption Lines E = E1 - E0 = h = hc/

6 Emission lines
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Comparison of the atomic emission spectrum of
silicon compared with the molecular absorption
spectrum of ethanal.
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 Sample (Atoms in flame)

Source Chopper
h h h Detector i
HCL Flame Monochromator Amplifier
Io It
Burner V

Cloud Output
Fuel Chamber e.g. PC/Printer

Oxidant Nebuliser
(Air) Waste
HCL = Hollow-cathode Lamp
Sample uptake

Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer

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13
14
Laminar Flow Burner

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EXAMPLES OF FLAME TEMPERATURES
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!
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 Effect of temperature in atomic spectroscopy

Boltzman Distribution
E1 (g = 2) (Excited state)
E1
E0 (g = 1) (Ground state)
E1
N1  g  g is the multiplicity
  1  e kT
No  go 

Na E1 = 3.37 x 10-19 J/atom

At 2600 K
-3.37 x 10-19
2 1.381 x 10- 23 )(2600)
N1
No  e  1.67 x 104
1

At 2610 K N1/No = 1.74 x 10-4

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Effect of Temperature on Sodium Atoms
Temp % Ground % Excited
K State 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

 0.0174 - 0.0167100  4 %
0.0167
So! 18
 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.

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 Evaporation
+ - + -
M X M X MX
Solution Mist Solid

Vapourisation

Thermal M (gas) Dissociation

*
M (g) MX
X (gas)
excitation Gas
Flame
emission Absorption of radiant Measure for atomic
energy h
h absorption spectroscopy
Measure for
flame emission *
spectroscopy M (g)

Re-emit radiation at 90o Measure for atomic

(Atomic fluorescence) fluorescence spectroscopy

Process by which gaseous atoms are produced in flames

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 Sample (Atoms in flame)

Source Chopper
h h h Detector i
HCL Flame Monochromator Amplifier
Io It
Burner V

Cloud Output
Fuel Chamber e.g. PC/Printer

Oxidant Nebuliser
(Air) Waste
HCL = Hollow-cathode Lamp
Sample uptake

Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer

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 Radiation Source
• Beer’s 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.

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 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)

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Monochromator bandwidth
(~100x greater than atomic lines

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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) + h

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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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28
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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31
 Stages in a Graphite Furnace
• Typical conditions for Fe:
– Drying stage: 125o for 20 sec
– Ashing stage 1200o for 60 sec
– Atomisation 2700o for 10 sec

• Requires high level of operator skill.

• Method development difficult.

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Schematic Diagram of a Graphite Furnace

h
HCL

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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 34
 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)
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 Sample (Atoms in flame)

Source Chopper
h h h Detector i
HCL Flame Monochromator Amplifier
Io It
Burner V

Cloud Output
Fuel Chamber e.g. PC/Printer

Oxidant Nebuliser
(Air) Waste
HCL = Hollow-cathode Lamp
Sample uptake

Figure 1. Schematic Diagram of an Atomic Absorption Spectrophotometer

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 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.

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 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.).

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A B

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 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.

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 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). 41
 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
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 Examples
• Determination of calcium in the presence of sulfate or
phosphate (e.g. in natural waters)
3Ca2+ + 2PO43- = Ca3(PO4)2
(stable compound)
• Release agent
Add 1000 ppm of LaCl3
2LaCl3 + Ca3(PO4)2 = 3CaCl2 + 2La(PO4)
CaCl2 readily dissociates
• Protective chelation
Ca3(PO4)2+3EDTA = 3Ca(EDTA) + 2PO43-
Ca(EDTA) dissociates readily. 43
 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.

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 Solution
• Add an ionisation suppressor
[M  ][e - ]
K
[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.
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 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
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 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

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

 It   99 
Abs  - log   - log   0.00436
 I0   100 
This corresponds to an absorption of 0.00436

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 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.
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 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

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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

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

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 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

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 Applications of AAS

• Lubricating oils
– Ba, Ca, Mg and Zn additives
• Greases
– Li, Na, Ca

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 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
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