ATOMIC SPECTROSCOPY

BASED ON FLAME
ATOMIZATION; THEORY,
INSTRUMENTATION AND
APPLICATION
CHAPTER 3
FLAME ATOMIC ABSORPTION
SPECTROSCOPY
LECTURE 7
This lecture covers:
 Fundamental Principals
 Sample Atomization
 Flame atomizer
 Properties of flame
 Instrumentation for Flame Atomic Absorption
Spectroscopy
 Interferences
 Quantitative Analysis by Atomic Absorption
Spectroscopy
 Detection Limits and Accuracy
Introduction
 Atoms are the simplest and purest form a matter
and cannot rotate or vibrate as a molecules does.
 Atoms only undergoes electronic transitions when
energy is absorbed.
 Because the electronic transitions are discrete
(quantized), line spectra are observed.
 Applications of atomic spectroscopy:
 Analysisof heavy metals contaminations in
environmental samples.
◼ Examples of heavy metals are the transition metals, some
metalloids, lanthanides and actinides.
 Metal impurities in pharmaceutical samples
 Three techniques (methods) included in atomic
spectroscopy:
 Atomic Absorption Spectroscopy (AAS)
 Atomic Emisssion Spectroscopy (AES)

 Atomic Fluorescene Spectroscopy

 AAS and AES are used to determine the

concentration of an element in solution.
 Atomic absorption spectroscopy:
Absorbance = -log(P/Po)
P = Power of transmitted radiation
Po = Power of incident radiation

 Atomic emission spectroscopy:

Transmission = -log(Po/P)
Po = Power of radiation that reaches the detector in the
absence of sample.
P = Power of radiation that reaches the detector in the
presence of sample.
Principles of Flame AAS
 Light is absorbed by atoms of an analyte.
 The sample is aspirated in the form of aerosol into
flame using nebulizer.
 In the flame, the liquid/solvent is evaporated while
the metal vaporized as atoms.
 The flame contains atoms of the metal.
 The flame is lined up in a beam of light of the
appropriate wavelength.
 The flame (thermal energy) causes the atom to undergo
a transition from ground state to the first excited state.
 When the atoms make their transition, they absorb
some of the light from the beam i.e. radiation of a
particular wavelength that produced by a special
source made from that element (example HCL).
Wavelengths of radiation given off by the source are
the same as those absorbed by the atoms in the flame.
 The more concentrated the solution, the more light
energy is absorbed.
 The lamp must be aligned perfectly to the hottest
part of the flame and travels to the detector.
 Detector measures the intensity of the beam of light.
 the intensity of beam will reduced when the light
absorb by the metal.
 the detector records the reduction as an absorption.

Absorbance = -log(P/Po)
P = Power of transmitted radiation
Po = Power of incident radiation
 A = -log(P/Po)

Po P

Nebulizer

Aspiration
Fine capillary
tube
 The absorption is shown on a read out by the data
system.
 This absorption follows Beer’s law i.e. absorbance is
directly proportional to the path length in the flame
and to the concentration of atomic vapor in the
flame.
 Concentration of atomic vapor directly proportional
to the concentration of the analyte in the solution
being aspirated.
Sample Atomization
 In order to perform atomic spectroscopy, atoms of the
analyte must first be formed, usually in the form of an
atomic vapor.
 Atomization: The process by which a sample is
converted to an atomic vapor or elementary ions.
 Atomizer: Device used to converted a sample to an
atomic vapor.
 Two common methods of sample atomization:
 Flame atomization
 Electrothermal atomization
 Process occurs during atomization
Nebulization
 Conversion of the liquid
sample to a fine spray.
Desolvation
 Solid atoms are mixed with
the gaseous fuel.
Volatilization
 Solid atoms are converted to
a vapor in the flame
(molecules/atoms/ions.)
 There are three types of particles that exist in the flame:
 Atoms
 Ions
 Molecules
QUESTION
1. Define the terms (3m – Mar 2016)
 Nebulization
 Atomizations
Types of Flames
 Acetylene / N2O flame is
the best for refractory
elements.
 Elements that form
stable compounds that
are not completely
atomised at the
temperature of the
flame or graphite
furnace.
 Selection of flame type depends on the depends on the
volatilization temperature of the atom of interest.
 Flames are only stable at certain flow rates:
 at low flow rates (less than the maximum burning
velocity) the flame propagates into the burner body
causing flashback and, in some cases, an explosion.
 when the flow rate is increased, the flame starts to rise
above the burner body.
 best flames are obtained when the flow rate of the gas
is equal to the maximum burning velocity. At this equity
ratio the flame is most stable.
 at higher ratios, flames will reach a point where they
will no longer form and blow off the burner.
Flame Structure
 Interzonal region is the hottest
part of the flame and best for
atomic absorption.
 Oxidation of the atoms occurs
in the secondary combustion
zone where the atoms will form
molecular oxides and are
dispersed into the surroundings.
Temperature Profile

Temperature profile in °C for a

natural gas-air flame
Flame Absorption Profiles
 Temperature of a flame depends on the position from its tip.
 It is necessary to concentrate on one spot in a flame and
adjust the height of the flame to get best signal.
 Each element has its own specific height above burner tip.
 Ag: Slow to oxidize. Use higher distances from the tip so that
higher temperatures are achieved to analyze the silver.
 Cr: best results occur at lower heights (fuel rich flames) since at
higher heights oxygen from atmosphere will force chromium to
convert to the oxide which will not be atomized at flame
temperatures.
 Mg: increasing the height above tip will increase the signal due to
increased atomization at higher temperatures. However, at higher
distances the oxide starts to form leading to a decrease in signal.
Flame Atomizer
1. Nebulizer
 Types of nebulizer
◼ Concentric tubes.
◼ Cross flow.
◼ Fritted disk.
◼ Babington.
2. Burners
 Function: Acts as the atomizer or converts the sample
into gas-phase atoms or elementary ions.
 Two types of burners in flame spectroscopy:
◼ Turbulent flow (total consumption burner)
◼ Laminar flow (premix burner)
◼ Turbulent flow burner
◼ Nebulizer and burner are
combined into a single unit.
◼ Sample solution is directly
aspirated into the flame.
◼ All desolvation, atomization,
and excitation occurs in the
flame.
◼ Sample is drawn up the
capillary and nebulized.
◼ Sample flow rate: 1 to 3
mL/min.
Advantage
1. introduce relatively large & representative sample into the
flame.

Disadvantages
1. A relatively short path length through flame.
2. Problems with clogging of the tip.
3. Burners noisy from electronic and auditory stand point.
◼ Laminar flow burner
◼ Sample is nebulized by the flow of oxidant past a capillary tip.
◼ Resulting aerosol then mixed with fuel and flows past a series of
spoilers (baffles) that allow only the finest droplets to reach the burner
head.
Fine
droplets
◼ The larger droplets of the resulting aerosol condense and drain out of
the chamber to a waste container (~90%).
◼ Aerosol, oxidant and fuel are burned in a slotted burner that provided
a flame, 5 – 10 cm in length.
Fine
droplets
 Function of nebulizer:
 Suck up liquid sample at a controlled rate.
 Create a fine aerosol (nebulization) for introduction into
the flame.
 Mix the aerosol and fuel and oxidant thoroughly for
introduction into the flame (desolvation).

 Function of the flame:

 Produce atoms (the elemental form) of the element of
interest.
Advantage
1. Provide quiet flame.
2. Provide longer path length that enhance the sensitivity &
reproducibility.

Disadvantages
1. Lower rate of sample introduction.
2. Possibility of selective evaporation of mixed solvents in the
mixing chamber could create analytical uncertainties.
3. Mixing chamber contains a potentially explosive mixture
that can flash back if the flow rates are too low.
Performance characteristics of flame
atomization
 Flame atomizers have good precision (<1% relative precision).
 Relatively low sensitivity compared to electrothermal
atomization.
 There are two reasons for the low sampling efficiency of flame
atomizers:
 Most of the sample is wasted due to the nebulization
process.
 Atoms have a short residence times in the flame (~10-4 s).
Instrumentation
The absorption of the lamps
emission spectrum by atoms
in the flame

Monochromator Detector

HCL Emission spectrum

of HCL: line Amplifier
spectra

Laminar- Readout
flow burner
(consist of
nebulizer)
chopper
Sample
 AAS

Furnace
AA Spectrophotometers
 Single Beam Instrument

** The modulated power can

detector
be replaced by a chopper
 Double Beam Instrument
❑ Radiation from HCL is split into 2 beams.
1. One passes through the flame.
2. The other around the flame.

❑ A half-silvered mirror returns both beams to a single path

then pass through the monochromator then detector.

❑ Monochromator is placed between sample and detector.

It used to eliminates most of the radiation originating
from the flame.
Radiation Sources
 AAS uses line sources with narrow emission bands.
 Common radiation source used in AAS
 Hollow cathode lamp (HCL)
 Electrodeless discharge lamp (EDL)
 Hollow cathode lamp (HCL)

◼ Components in HCL:
◼ A cylindrical hollow cathode made of the element to be
determined or an alloy of it.
◼ Tungsten anode.
◼ Enclosed in a glass tube usually with a quartz or pyrex window
since the lines of interest are often in UV region.
◼ Tube is under reduced pressure and filled with inert gas such as
Ne or Ar.
 Hollow cathode lamp element Na
 Ar + e- Ar+ + 2e-

◼ How does the Hollow Cathode Lamp works?

◼ When potentials of ≥300 volts are applied to the lamp, the Ne
or Ar in the lamp will ionize at the anode.
◼ The noble gas ions (positive ions) then accelerate towards the
cathode with sufficient kinetic energy to dislodge excited metal
atoms and produce an atomic cloud of metal atoms. This is known
as sputtering. The metal will become vaporized.
◼ The vaporized metal is excited to higher energy levels by
continued collision with the high-energy gas ions.
◼ When the electrons return to the ground state, the characteristic
lines that metallic element are emitted.
◼ The filler gas also emitted lines, but the lines are not close enough
to the element lines to interfere.
 Electrodeless discharge lamp (EDL)
◼ Constructed of a metal or salt of interest sealed in a quartz
tube filled with a noble gas (Ne or Ar) at low pressure (1 –
5 torr).
◼ The noble gas is ionized and accelerated by a strong radio-
frequency (RF) or microwave field.
◼ Ionized argon will hit the metal causing excitation of the
atoms of the metal of interest.
◼ Provide radiant intensities usually one to two orders of
magnitude greater than HCL’s.
Source Modulation
 Why source modulation is employed in AAS?
 To eliminate interference caused by emission of the
radiated flame from analyte atoms and flame gas
species.
 To distinguish between the component of radiation
arising from the source and the component of radiation
arising from the flame background.
 Source modulator: Light chopper (circular rotating metal
disk)
Light Chopper
 The function of light chopper is
to eliminate the effects of
radiation from the flame.
 Light is “chopped” with a
rotating half-mirror so that
detector could received two
alternating signals. One from
the radiation source and one
from the flame.
 At one moment (opaque), only
light emitted by flame is read
by the detector since the light
from the radiation source is cut
off.
 Next moment (transparent),
light from both the flame
emission and radiation source
is read. Transmission from the
source light is measured since
the source light is allowed to
pass.
 Absorbance of the sample is
determined by measuring the
difference in radiant power
between flame emission signal
and signal from the radiation
source.
a) Signal provide by radiation
source.
b) Sample absorbance.
c) Signal provide by the sample
after absorbing part of the
radiation power.
QUESTIONS
1. In flame atomic absorption spectroscopy, briefly describe the
'atomization' process which the analyte undergoes.
2. Why is source modulation employed in atomic absorption
spectroscopy? Name the device used for this purpose.
3. Name the common line source used in AAS.
Interferences in AAS
 Spectral interference
 Chemical interference
 Spectral interference
 Spectral interference occurs when the spectral line of
the elements being determined are overlaps with a
spectral line or band from another element present in
the sample.
 The effect of the element will also be measured and
therefore the results will be incorrect.
 How it is occurs?
◼ Scattering by combustion or particulate products.
◼ Arise from the combustion products or particulate matters from
the atomization scatters the radiation from the source. Both
products reduce the power of the transmitted beam.
◼ Scattering by sample matrix interference.
◼ Arise when the emission or absorption of an interfering species
overlaps or lies so close to the analyte absorption so that
resolution by the monochromator becomes impossible.
 How to solve the issues?
◼ Tunethe monochromator to a different spectral line for the
element of interest so that there is no overlap.
◼ Add excess of radiation buffer to samples and standards.
◼ A radiation buffer is a potential interferents (interfering
substance) that are intentionally added in large amounts to
samples and standards to swamp out their effects on atomic
absorption/emission measurements.
 Chemical interference
 Resultfrom various processes occurring during
atomization that alter the absorption characteristics of
the analyte.
 Types of chemical interferences:
◼ Formation of low volatility compounds
◼ Anions present in the flame or furnace can form compounds of
low volatility with analyte and reduce the fraction of the analyte
that is atomized.
◼ Outcome: Low results of analyte or the absorbance of analyte is
decreased.
1. Anion interferences
◼ Example: to determine the concentration of Ca in a sample

◼ The presence of SO42- or PO43-

◼ Ca will react with anions

◼ The products are difficult to volatilize

2. Cation interferences
◼ Example: Determination of Mg in the presence of Al

◼ Formation of heat stable Al-Mg compounds

◼ To minimize the effects of low volatility compounds:
◼ Use higher flame temperature to volatilize the products. It
can however lead to other interferences
◼ Add releasing agents. Cations that react preferentially with
the interferant. Prevents the analyte from reacting with the
interferant
◼ Example:
◼ Determination of Ca in a sample

◼ Determination of Mg in the presence of Al

◼ Add excess of Sr+ or La3+

◼ La3+ or Sr+ will react with the interferant, replacing the

analyte
QUESTION
1. Briefly explain the function of adding a releasing agent such
as La3+ during the analysis of calcium using flame absorption
spectroscopy (AAS). (2m –Mar 2016)
◼ Dissociation (separation) equilibria
◼ In the hot, gas environment of a flame or a furnace, dissociation
and association reactions lead to conversion of the metallic
constituents to the elemental state. Some of the reaction is
reversible.
◼ Example: MO M+O M = analyte
M(OH)2 M + 2OH OH = hydroxyl radical
◼ A shift in the equilibrium towards the metal oxide will result in a
reduction in absorption of radiation by the metal analyte.
◼ How to cure dissociation reactions?
◼ By the addition of Aluminium,Al and Titanium,Ti in the
analysis of Vanadium,V.
◼ Refractory elements such as Al, Ti, Mo and V will react with
O and OH species in the flame to produce thermally stable
metal oxides and hydroxides.
◼ Metal oxides and metal hydroxides can be decomposed by
using high-temperature flames such as nitrous oxide-
acetylene flame so that atomic vapor of the metal can be
produces.
◼ Ionization equilibria
M M+ + e - M = analyte
◼ Sample (liquid/solid) must be vaporized and atomized in a high
temperature source such as flame.
◼ This high temperature environment lead to ionization of the
analyte atoms.
◼ Problem in the analysis of alkali metal ions:
◼ Alkali metals have lowest ionisation energies and are
therefore most easily ionized in flames.
◼ Ionisation leads to reduced signal intensity, as energy levels
of ions are different from those of the parent ions.
◼ How to cure ionization?
◼ By the addition of ionization suppressor / ionization buffers

◼ An easily ionizable species

◼ Provides a relatively high concentration of electrons in the

flame
◼ Results in suppression of ionization of the analyte

◼ Eg. of ionization suppressor – CsCl or Al(NO3)3·9H20:CsCl

buffer, CsCl:LaCl3 buffer
◼ Adding an ionization suppressor will helps to provide an
easily ionizable species which could results in suppression of
ionization of analyte
Quantitative Analysis
1. Calibration curve
2. Standard Addition Method

Quantitative analysis still follows Beer’s Lambert Law and the

concentration of unknown are determined by the same way
using the formula( A = εbc).
Width of the flame is consider as the beam pathlength.
1. Calibration curve
◼ A general method for determining the concentration of a
substance in an unknown sample by comparing the unknown
to a set of standard of known concentration.
❖ Plot is a linear over a significant concentration range (the
dynamic range).
❖ Analysis should never be based on the measurement of a
single standard with assumption that Beer’s law is being
followed.
Standard Calibration Curve

How to measure the

concentration of unknown?
Practically, you have measure the
absorbance of your unknown.
Once you know the absorbance
value, you can just read the
corresponding concentration from
the graph .
2. Standard Addition Method
▪ Extensively used in AAS. This process is often called spiking
the sample.
▪ Compensate for variation caused by physical and chemical
interferences in analyte solution.
▪ Involves adding one or more increments of a standard
solution to sample aliquots of the same size.
▪ Each solution is then diluted to a fixed volume before
measurement.
If Beer’s law is obeyed,
A = εbVstdCstd + εbVxCx
Vt Vt
= kVstdCstd + kVxCx
A= (kCstd)Vstd + kCxVx

k is a constant equal to εb/Vt

Plot a graph of A vs Vstd
A = (kCstd)Vstd + kCxVx
Y = mX + C
where the slope m and intercept C are
m = kCstd
C = kCxVx
Cx can be obtained from the ratio of these two
quantities m and C

C = kVxCx
m kCstd

Cx = CCstd
mVx
For single-point standard addition
Dividing the 2nd equation by the first & then rearrange it
will give.

Cx = A1 Cs Vs
(A2 – A1 ) Vx
 Example
70

The chromium in an aqueous sample was determined by pipetting

10.0mL of the unknown into each of five 50.0mL volumetric flasks.
Various volumes of a standard containing 12.2 ppm Cr were
added to the flasks, following which the solutions were diluted to
the volume.

1. Plot the data.

2. Calculate the concentration of Cr in the sample.
 Advantages (Flame)
71

1. Inexpensive in term of the equipment and running

day-to-day analysis.
2. High sample throughput.
3. Easy to use.
4. High precision.
Flame atomization best for reproducibility (less than
1%)
 Disadvantages
72

1. Only solutions can be analyzed.

2. Relatively large sample quantities required (1 – 2
mL).
3. Less sensitivity compared to graphite furnace.
Flame AAS detection limit is >1ppm while
Graphite furnace is <1ppm.
4. Interference due to refractory compound
formation.
5. Only metal element can be analysed using AAS.
 Detection Limits
73