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ATOMIC SPECTROSCOPY

Discuss the differences between molecular and atomic spectroscopy

analysis of atomic not molecular species
line not band spectra
methods - emission, absorption, fluorescence
transitions - electronic energy levels (no vibrational and/or rotational energy
levels)
instrumentation - draw / wavelength selector after sample compartment

ATOMIC SPECTROSCOPIC THEORY

In 1917 Albert Einstein introduced three transition probability coefficients, Aij, Bji, and Bij,
for transitions between two atomic states with energy levels i and j, where Ei > Ej, and
the states are non-degenerate.

Place diagram here

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Emission

the intensity (Iemiss) of the emitted spectral line depends on the number of transitions
per unit time (second) and on the energy of the emitted radiation and is given by:
Iemiss = hn Aij Ni

The numbers of atoms in higher excitation states are much less, particularly because
of the greater energy required for excitation, but mainly because of the low transition
probabilities, leading to lower emission intensities at these lines.

Absorption

If the system is in the presence of a uniform field of electromagnetic radiation of

wavelength l, and a sharp line radiation source is used, the absorbance, A, is given
by:
A = [0,434bK (pe2)/(mc)] fji Nj L
K = Ikn dn = hn/c BjiNj
fji = oscillator strength
Nj = number of atoms in the ground state in the radiation path
L = radiation path length
b, e, m, c = constants

where,

Note: The oscillator strength is a measure of the degree to which an atom resembles
an oscillating electron in its ability to emit and absorb a particular line.
It is also defined for the transition i > j as the number of harmonically vibrating
electrons that would together have the same absorption as one atom in the
state i and is given by:
fij = (hcme /le2) Bji
Fluorescence

If the system is in the presence of a uniform field of electromagnetic radiation of

wavelength l, the fluorescence intensity, Ifluor, is given by:
Ifluor = Io (hn/c) BijNi

The fluorescence intensity is directly proportional to the incident (exciting) radiation on

the atom population. As such, the fluorescence intensity (i.e., analyte signal) can be
increased by increasing Io.

This behaviour is advantageous for the analysis for elements for which detection limits
are not sufficiently low in AES or AAS at the trace and ultra-trace concentration levels.

Bending of the calibration curve due to absorption of the fluorescing line, however, may
be severe and may lead to double-valued analytical curves.

ATOMIC SPECTROSCOPIC INSTRUMENTATION

The instrumentation used for atomic emission, absorption, and fluorescence have certain
components in common.
The arrangement of the various components in space differ from instrument to instrument.

INSTRUMENT CONFIGURATIONS

1.

Atomic Emission

Insert diagram here.

2.

Atomic Absorption

Insert diagram here.

3.

Atomic Fluorescence

Insert diagram here.

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INSTRUMENT COMPONENTS
Most spectroscopic instruments are comprised of several basis components:
1. source (of radiation)
2. atomizer (converts analyte species to atoms)
3. wavelength selector (discussed previously)
4. detector (discussed previously)

SOURCES
The radiation sources used in atomic spectroscopy are narrow line sources.
The sources available are:
1. vapour discharge lamps
2. hollow cathode lamps
3. electrodeless discharge lamps
4. lasers

1. Vapour discharge lamps

An arc is struck between two electrodes in the vapour of the element interest. The
element must be volatile, e.g., alkali elements.
These were the first lamps that were used in atomic spectroscopy. They are no longer
used.

2. Hollow cathode lamps (HCLs)

Insert diagram here.

the above is a simple diagram of a hollow cathode lamp

the cathode is a hollow cylinder made from the element of interest in the form of a
metal, composite material, or film
the anode is made from any involatile metal, e.g., tungsten
both the anode and the cathode are placed in a glass (pyrex) jacket which has a
quartz end-window
the lamp is evacuated and filled with a mono-atomic gas, e.g., Ne, Ar, to about 1 - 5
Torr.

the lamps are operated at currents below ~30 mA but at voltages up to ~300V
under these conditions electrons are stripped from the filler gas at the anode
the positive inert gas ions are accelerated towards the cathode by the high potential
field
they strike the cathode (inside the cylinder) and atoms from the cathode are ejected
from the surface (SPUTTERING), many in an excited state
a discharge is initiated inside the cathode, and this excites the ejected atoms
further
as the excited atoms relax to the ground state, they emit radiation that is
characteristic of the cathode element, i.e., the element of interest
the nature of the hollow cathode lamp used depends on the element to be analyzed

Advantages
narrow lines
intense lines
long life-times and low cost
discharge is limited to the area of the hollow cathode
Disadvantages
the cathode element is lost over time and is deposited on the walls of glass walls of
the lamp
this leads to arcing and shortened life-times
Note
higher currents and potentials have been used to obtain higher line intensities and
reportedly lower detection limits. This is offset by greater line broadening due to
the Doppler effect and self-absorption mainly.

3. Electrodeless Discharge Lamps (EDLs)

Insert diagram here.

the EDL consists of a sealed quartz bulb (~1.5 x 0.6 cm) in which is placed a small
quantity of a volatile element (plus iodine) or the volatile halide of more involatile
elements
the bulb is evacuated and argon is added to a low pressure (~ 1 - 5 Torr)
the bulb is placed in a resonance cavity which is made by winding an rf antenna (in
the form of a coil) around a ceramic tube
- placement of the bulb is crucial for good operation
an rf current of high frequency ~27.1 MHZ is applied to the coil

the large initial potential (due to the high impedance present at one end of the coil)
is sufficient to cause ionization of the argon atoms, producing ions and electrons
the rf power is magnetically coupled to the magnetic fields of these species and
they are accelerated back and forth at high velocities within the bulb
as they move back and forth, they collide with more argon atoms exciting them and
causing a discharge to be initiated
(No electrodes are required - thus the name electrodeless)
the high electronic excitation temperatures within the discharge are sufficient to
vaporize and excite the atoms of the analyte element
as the excited atoms relax to the ground state, they emit radiation that is
characteristic of the analyte element, i.e., the element of interest

Advantage
very high intensity source
very narrow lines
Both of the above lead to higher sensitivities and to lower detection limits.

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ATOMIZERS

The radiation from the source is focused on to the atomization cell by quartz and/or
fused silica lenses.

The purpose of the atomizer is to provide a population of atoms of the analyte element
- in AAS, preferably in the ground state - from the sample

The sample may be in the form of a gas, solution, or solid.

There are a number of different types of atomizers that have been used for this
purpose, as follows:
1. flames
2. electrothermal
3. plasmas, e.g., ICP, MIP, DC
4. specific, e.g., hydride generators, Hg cold vapour

1. Flame Atomizer
General:

there are several types of flame atomizers where the main differences have been
with respect to:
a) flame temperature
b) background spectral emission
c) oxidizing or reducing environment

four commonly available flame atomizers are:

I) air/methane & air/propane (not widely used)
ii) air/acetylene
2100-2400 oC
moderate spectral background
iii) nitrous oxide/
acetylene
2600-3000 oC
high spectral background
o
iv) air/hydrogen
1700-2000 C
low spectral background
Note: other types and variations of the above have been used.

a typical flame is maintained on a burner head.

- in AAS, a long slot burner is used for greater path length, and thus, for a higher
analyte absorbance signal
- in AES, a circular burner head is used to generate a less dispersed atom
population, and thus, a higher analyte emission signal.

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Typical Burner Assembly
Insert diagram here.

nebulizer
- the analyte solution is aspirated into the flame due to the pressure difference
across a venturi, caused by supersonic flow of air across the venturi

burner (spray) chamber

- is a pre-mixed system, i.e., the fuel and oxidant are mixed prior to entering
the chamber (provides a laminar flow)
- the stream of aspirated solution breaks up into droplets by the fast moving
gas as it passes through the burner chamber
- only the smallest droplets enter the flame as an aerosol (consisting of the
analyte specie, concomitants and the solvent)
- these droplets have diameters ranging from 5 - 20 mm. The larger droplets
fall out of the gas stream and go to drain
- only ~10% of the sample aspirated finally enters the flame

burner head
- maintains the flame in which atomization of the analyte specie takes place
- three main processes occur during the atomization process in the flame:
I) desolvation - the aerosol particle loses its solvent and a solid particle is
formed
ii) vaporization - the solid particle vaporizes to give molecular species
iii) dissociation - the molecular species dissociate to give atomic species
(flame gases and radical species take part in this dissociation)

Note: the actual process of dissociation (atomization) is more complex than

described, because of the non-equilibrium conditions occurring in the flame.
By assuming local thermodynamic equilibrium, we assume that in a small
region of the flame, dissociation of analyte species in solutions of different
concentrations lead to a direct proportionality between the number of atoms
formed and the concentration of the solution.

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Typical Flame Structure

flames are described as having three main regions

Insert diagram here.

i) primary reaction zone - low in the flame/low temperature/non-equilibrium

conditions/high concentration of radical species/excess of electrons/high
background spectral emission
ii) interconal zone or interzonal region - high temperature/local thermodynamic
equilibrium/low concentrations of radical species/near equilibrium concentrations
of electrons/low background spectral emission/ incompletely combusted species
iii) secondary reaction zone - at the edges of the interconal zone/low
temperature/high background spectral emission/incompletely combusted
products burn to completion with entrained air/completely oxidized species

the best zone for measuring the signal the atom population is the interconal zone,
thus this is the zone that is used for analysis

the signals measured with a flame atomizer are continuous in nature

Insert diagram here.

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2. Electrothermal Atomizers

Characteristics:

Electrothermal atomizers utilize electrical energy to generate thermal energy, which

in turn atomizes the species of interest.

All such atomizers are based on passing a high electrical current through a resistive
device.

A number of different designs, using graphite, Ta, W, Ti, Mo, have been developed
over the years.

Today, the graphite furnace (an enclosed system) is used in the main.

Procedure for analysis using an electrothermal atomizer

The atomizer then goes through programmed heating cycle that consists of three
main steps:

Note: The signals obtained with electrothermal atomizers are transient in nature.

Advantages:

high sensitivity

low detection limits

small sample size required

can analyze many involatile elements

solid sampling possible

Disadvantage:

analysis time per element is long

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3. Inductively Coupled Plasma (ICP)
Characteristics:

consists of three concentric quartz tubes through which argon gas flows

spectral observations are carried out ~ 10 - 30 mm above the core

residence time of the atom population ~ 2 ms (fairly long)

temperature of the plasma ~ 4000 - 8000 K (high)

sample argon flow ~ 0.5 - 1.5 L/min (expensive)

rf-coil

- powered by an rf generator capable of producing ~ 0.5 - 2 kW of power

at 27.1 or 41 MHz
- water-cooled induction coil

Advantages:

long residence times and high temperatures lead to more complete atomization of
the analyte element than in flames

fewer chemical interferences

inert atmosphere - longer life time/little or no oxide formation

self-absorption and self-reversal effects are not encountered, since the temperature
across the plasma (horizontally) is relatively uniform

linear calibration curves of several orders of magnitude are obtained

lower detection limits than flame atomizers - not as good as electrothermal

atomizers

many involatile elements can be atomized in the plasma as compared to flame

atomizers

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WAVELENGTH SELECTORS
The wavelength selectors used in UV-VIS spectroscopic instruments have been discussed
previously (see lecture notes).

DETECTORS
The detectors used in UV-VIS spectroscopic instruments have been discussed previously
(see lecture notes).

ATOMIC SPECTROSCOPIC INTERFERENCES

General
Interferences with the signal detected in atomic spectroscopy (emission, absorption and
fluorescence) is complex and depends on many variables, including the particular type of
atomizer used in the analysis.
For a rigorous discussion of interferences, it is best to discuss them with regards to the
type of atomizer and the particular method employed.
In this section, we will discuss interferences in a very general manner, pointing out to
which system our discussion applies.

Physical
Physical interferences are usually governed by the type of atomizer used and the type of
sample being analyzed.

sample introduction - nebulization - flames: viscosity, surface tension, density >>

sample aspiration rates, droplet sizes, amount of sample entering the flame, errors in
signal

sample atomization - flames & electrothermal: due to the form of analyte & the matrix
composition (concomitants) >> effect (decrease/increase) on sample volatilization and
atomization, lead to errors in signal

correction >> make all samples the same with respect to species present (reagents &
concomitants), use matrix modifiers, extract analyte from solution, use standard
addition method of analysis

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Chemical
Chemical interferences are due to the reaction of the analyte species with concomitants
and/or reagents.

may lead to formation of involatile or volatile species and thus to decreased or

enhanced analyte signals

correction >> make all samples the same with respect to species present (reagents &
concomitants), use matrix modifiers, extract analyte from solution, use standard
addition method of analysis

Ionization
Atomic species in the atomizer may gain sufficient energy to lose an electron and become
ionized.

M + energy
at equilibrium,

ki

M+ + e

{[M+] [e ]/[M]}

When this occurs, the ionic specie may absorb and/or emit emr at wavelengths that are
different from those of the neutral atomic specie.
Thus, when measurements of emr intensities are being made at a particular
wavelength, the loss of neutral atomic species will show up as a decrease in the
measured intensity.
Ionization interferences are significant in high temperature atomizers, e.g., fuel lean
flames.
Correction: Add an excess of an easily ionizable element, e.g., an alkali element.
The large electron concentration thus generated, suppresses ionization of
the analyte.

Spectral
1. spectral lines from other species

2. Non-specific spectral background absorption