1

CHAPTER 3
Atomic Spectroscopy based
on Flame Atomization:
Theory, Instrumentation and
Application

HANANI YAZID
Faculty of Applied Sciences,
UiTM (Perlis)
 OVERVIEW
• Study the electronic transition of valence shell electron in free
atoms  provide analytical information about the elemental
composition of a sample

2
 CONCEPTS IN AAS
• Light with specific frequencies is absorbed by different metals when they
vaporize in a flame.
• The energy absorbed excites electrons, moving them from their ground
state to a higher energy state.
• Atomic Absorption Spectroscopy uses hollow cathode lamps (source) to
emit light with these frequencies which is then absorbed by the sample
containing the metal ion.
• The amount of light absorbed is proportional to the concentration of the
metal ion in solution.
(Concentrations are often expressed as mg/L or ppm)
• The amount of light absorbed by the sample is compared to the amount of
light absorbed by a set of standards of known concentration (calibration
curve).

3
 Principles in AAS
• The technique makes use of absorption spectrometry to assess the
concentration of an analyte in a sample. It requires standards with known
analyte content to establish the relation between the measured
absorbance and the analyte concentration and relies therefore on the
Beer-Lambert Law

• The electrons of the atoms in the atomizer can be promoted to higher

orbitals (excited state) for a short period of time (nanoseconds) by
absorbing a defined quantity of energy (radiation of a given wavelength).

• This amount of energy, i.e., wavelength, is specific to a particular electron

transition in a particular element.

4
Aspiration: The uptake of liquid sample up
to tube and into the nebulizer chamber
5
 NEBULIZER
• Sample is introduced in form of an aerosol
• Device used to produce an aerosols from liquids (by the action of pressurized
gas) is called pneumatic nebulizers

• Nebulize - To convert a liquid into a fine spray or mist (aerosol)

• Nebulization – The transformation of a liquid into a spray of small droplets
• Aerosol - A suspension of finely divided liquid or solid particles in a gas

6
Nebulizer chamber
• sucks up the liquid sample (aspirate)
• creates a fine aerosol for introduction into flame
• mixes aerosol, fuel and oxidant thoroughly, creates a
heterogenous mixture
• the smaller the size of the droplets produced, the higher the
element sensitivity

Fuel  acetylene
Oxidant  air (or nitrous oxide)

7
Desolvation: Evaporation of the solvent (the dry nanoparticle
sample remains)
Volatilization: A process whereby a sample is vaporised
8
 ATOMIZATION

Atomization: The process

where the samples/molecules
are dissociated into free atoms
9
 Flame Atomic Absorption Spectroscopy (FAAS)
• Currently the most widely used because of its simplicity, effectiveness and relatively low cost
1. Instrumentation: Line sources, source modulation (chopper), atomizer, monochromator, detector
2. Interferences
3. Quantitative analysis
4. Detection limits and accuracy

10
INSTRUMENTATION

11
12
Electrodeless-discharge lamp
• Constructed form a sealed quartz tube containing an inert gas
(Ar) at a pressure of a few torr and a small quantity of analyte
metal (or its salt)
• The lamp contains no electrode but instead is energized by an
intense field of radio frequency or microwave radiation
• Available commercially for several elements (As, Se and Te) for
which hollow cathode lamp intensities are low.

13
2) Source Modulation
It is necessary to discriminate between radiation from HCL and
radiation from the atomizer

•Modulation: The changing of some property of a wave by the desired

signal in such a way that the carrier wave can be used to convey
information about the signal

•Function: Employed in AAS to distinguish between the component of

radiation arising from the source and the component of arising from the
flame background

How?  Using beam chopper/ light chopper

14
 Chopper
• A chopper or a modulated power supply is used to modulate the
source radiation that passes through the atomizer (flame)

• The chopper rotates

resulting in an
alternating atomic
absorption and atomic
emission signal.
• The signal from
emission of radiation
will be continuous and
can be substracted
from the modulated
AA signal.
15
 Chopper
• Function: Eliminate the effects of radiation from the flame
• 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
source’s light is measured since the source’s light is allowed to pass
• The elements of the detector is such that the emission signal is
substracted from the total signal & this difference is what we measured.

16
3) Atomizer

• Several types of atomizers:

1) Graphite furnace atomizer
2) Plasma atomizer (ICP)
3) Flame atomizer

17
Graphite furnace atomizer (Electrothermal atomizer)

18
Plasma atomizer (ICP)

19
Flame atomizer

20
 Properties Flame

• A lower region: primary combustion

zone which is characterized by
existence of some non atomized
species and presence of fuel species (C2
and CH, etc.) that emit in the blue
region of the electromagnetic spectrum

• The second well region: interzonal region. This region is rich in

free atoms and is the region of choice for performing atomic
spectroscopy. It also contains the regions of highest
temperatures.

• The third region: secondary combustion region. It is characterized

21
4) Monochromator and 5) Detector (Photomultiplier, PMT)
• Monochromator: Tuned to a specific wavelength and with a specified
slit width chosen, isolates the hollow cathode lamp analytical line.
• Since the basis for the AAS process is atomic ABSORPTION, the
monochromator seeks to only allow the light not absorbed by the
analyte atoms in the flame to reach the PMT.
• That is, before an analyte is aspirated, a measured signal is generated
by the PMT as light from the HCL passes through the flame.
• When analyte atoms are present in the flame (sample is aspirated),
some of that light is absorbed by those atoms (remember it is not the
ionic but elemental form that absorbs).
• This causes a decrease in PMT signal that is proportional to the
amount of analyte.

22
Photomultiplier, PMT

23
Summary

24
 INTERFERENCES FAAS

1. Chemical Interference: Formation of stable or refractory

compound
Problem situation
• Analyte metal forms bond with an anion (refractory compound) which won't
dissociate in flame.
• Usually Group II elements (Ca2+ & Mg2+) with phosphate

Refractory: Element that forms stable compound that are not

completely atomised at the temperature of the flame of
graphite furnace

25
Solutions:

26
Solution:

27
3. Spectral Interference

• Spectral interferences are due to radiation overlapping that of

the light source. The interference radiation may be an emission
line of another element or compound, or general background
radiation from the flame, solvent, or analytical sample.

• Example: The interference of Na emission at 285.28 nm on

determination of Mg at 285.21 nm

Solutions:
• Can be reduced by improving the resolution of the spectrometer
• Choose another wavelength for analysis
• Use D2 and Zeeman background correction
• Two line correction?
28
 QUANTITATIVE ANALYSIS
Sample preparation:
• The sample is weighed and made into a solution by suitable dilution.

• When making reference solutions of the element under analysis, for

calibration, the chemical environment of the sample should be
matched as closely as possible – ie: the analyte should be in the
same compound and the same solvent.

• Teflon containers may be used when analysing very dilute solutions

because elements such as lead are sometimes leached out of glass
vessels and can affect the results.

29
In flame spectrometry comprehensive calibration and standard
addition calibration are the two most often used evaluation
techniques.
Calibration curve

•The comprehensive solution Calibration curve

series (standards) contain
increasing quantity of the
examined elements. (Standards
may contain other components
present in the samples - cations,
anions, organic compounds,
solvents)
•The parts of the calibration series
are usually diluted from a stock
solution with exactly known
concentration.

30
Standard Addition Calibration
• Standard addition method is applied primarily in case of:
 exponential interfering effects, when we do not know the cause
of interfering effect or we do not know the quality and
concentration of interfering components respectively
 complicated sample matrix (Example: an environmental water
sample (from a well, creek, pond) - no quantitative idea of what
the total or even partial matrix composition might be)
How??
• The samples are divided into 3 - 5 equal parts. We give to each
portion increasing amount of examined metal ion.
• To the first portion we do not add any metal ion solution thus it
contains the examined metal ion in the original
• The results should be plotted as follow:

31
Standard Addition Calibration

32
DETECTION LIMIT AND ACCURACY
• The relative error of FAAS is on the order of 1 % to 2 %
• The flame AA detection limit are generally better than flame AE detection limit
except for easily excited alkali metals

• Refer Table 28-4 (pg 864) in text book (Fundamentals of Analytical Chemistry)

33
Flame AAS

34
 Flame Atomic EMISSION Spectroscopy (FAES)
• Atoms and molecules are raised to excited states via thermal
collisions with the constituents of the partially burned flame gases.
• Upon their return to a lower or ground electronic state, the excited
atoms and molecules emit radiation characteristic of the sample
components.
• The emitted radiation passes through a monochromator that
isolates the specific wavelength for the desired analysis.
• A photodetector measures the radiant power of the selected
radiation, which is then amplified and sent to a readout device,
meter, recorder, or microcomputer system

35
Limitation of FES
• The number of excited atoms in flame is very small. It is the
alkaline and alkaline earth metals that can be practically
determined.
• It needs perfect control of flame temperature.
• Interference by other elements is not easy to be eliminated
• Heavy and transition metals, the number of absorption
and emission lines is enormous and the spectra are complex
36
Effect of Flame Temperature

37
 FES FAAS
Measurement of the intensity of Analysis of absorption of specific
light emitted when a metal is wavelength of radiation by neutral
introduced into a flame atoms in the ground state
Excitation of neutral atoms is
Excitation of Excitation of neutral atom is
brought only by the thermal
neutral atom brought only by radiation from HCL
energy
Temperature of flame is
Temperature important because of the
Temperature of flame is not critical
of flame intensity is greatly influenced by
temperature
Obey Beer Law (the relation
Beer Law Does not obey Beer Law between the absorbance and
concentration is linear)
Analytical signal in flame emission The signal is obtained from the
is the sum of all energies emitted difference between the intensity of
Signal as excited atoms drops to the the source in the absence and
ground state. The signal comes presence of metallic elements in
entirely from the emitting atoms liquids presence in the optical path
38
 39

Standard Addition Method

- Ideally, calibration standards should approximate the
composition of the samples to be analysed with respect to
NOT ONLY the analyte concentration, BUT also the
concentrations of other species in the sample matrix, in
order to minimize the effects of various components of the
sample on the measured absorbance.
- Example: Absorbance maximum of color complexed metal
ions is decreased in the presence of sulphate and phosphate
ions  lowered the absorbance  apply standard addition
method Can get from
the graph (y-
Graph: Plot As vs Vs intercept)
Equation: As = mVs + b where m = k = slope, b = kVxcx
cx = bcs/mVx
cs = concentration of std (known), Vs = volume of std added
 40

Cunk = - CSA (Vflask/Vunk) if Cs is not given

where CSA is the value of x-intercept