Flame Emission and

Atomic Absorption Spectroscopy

Spectroscopy (seeing the invisible)

It is the branch of science that deals with the
study of interaction of matter with light.
OR
It is the branch of science that deals with the
study of interaction of electromagnetic radiation
with matter.
To know the molecular structure (qualitative
analysis)
To determine the quantity of species present
(quantitative analysis)

Spectroscopy

Atomic

Molecular

Examples:

Examples:

Atomic absorption

UV-Visible

Flame emission

Infra Red
NMR, etc.

Electromagnetic
Radiation

Electromagnetic Radiation
Electromagnetic radiation consist of discrete
packages of energy which are called as
photons.
A photon consists of an oscillating electric field
(E) & an oscillating magnetic field (M) which
are perpendicular to each other.

Electromagnetic Radiation
Frequency ():
It is defined as the number of times electrical field
radiation oscillates in one second.
The unit for frequency is Hertz (Hz).
1 Hz = 1 cycle per second

Wavelength ():
It is the distance between two nearest parts of the
wave in the same phase i.e. distance between two
nearest crest or troughs.

Electromagnetic Radiation

The relationship between wavelength &

frequency can be written as:
c=
As photon is subjected to energy, so
E=h=hc/

Electromagnetic Radiation and

spectroscopy
Radiation
Radiowave

Wavelength
(nm)
109-107

microwave
Infrared
UV-Visible

107-106
106-104
10-103

X-ray

10-10-3

spectroscopy
Nuclear magnetic
resonance
microwave
IR spectroscopy
Absorption/ UV-Vis
spectroscopy
X-ray diffraction

Electromagnetic Radiation

Violet

400 - 420 nm Yellow

570 - 585 nm

Indigo

420 - 440 nm Orange

585 - 620 nm

Blue

440 - 490 nm Red

620 - 780 nm

Green

490 - 570 nm

Principles of
Spectroscopy

Spectrum (s)/spectra(p)
A graph of intensity of absorbed or emitted
radiation by sample verses frequency () or
wavelength ().
Emission
Intensity

An emission spectrum
n

Frequency

Spectrophotometer is an instrument design to

measure the spectrum of a compound.
Example: UV-Vis spectrophotometer, FTIR
spectrophotometer,
Atomic
absorption
spectrophotometer, etc.,

Origin of Atomic Spectra

Atomic spectra
An atom on absorbing the
appropriate energy radiation go to
the excited state

energy

n=1

DE

n=2
n = 3,
etc.

Excited state atom on emitting the

radiation may come back to the
ground state
n=4

Energy

Atomic spectra (absorption as well

as emission) is recorded mostly in
UV (sometime in visible) regions

4f
4d

n=3
n=2
n=1

4p
3d
4s
3p
3s
2p
2s
1s

0.01 %

99.99 %

Signal is proportional to number of atoms

AES - low noise (background)
AAS - high signal
The energy gap for emission is exactly the same as for
absorption.
Most of the atoms in Ground state (~99.99%)
Even in flame, very few (~0.01%) will be in excited state.

1. Absorption Spectroscopy:
Radiation absorbed by a molecule/atom is recorded.
Example: UV-Vis spectroscopy, Atomic Absorption spec
FTIR spectroscopy,
E =hn

E2

E2

E1

E1

Can only occur if E = hn = E2 - E1

Photon with energy (E = hn = E2 - E1) excites electron from
lower energy level.

2. Emission Spectroscopy
Emitted electromagnetic radiation by atom or molecule
is measured
Examples: Flame emission, Fluorescence, phosphorescence
spectroscopy, etc.,
E2

E2

E1

E1

E =hn

Emitted photon has energy E = hn = E2 - E1

Emission
Intensity

Absorption and emission intensity is

proportional to the no of atoms in
ground and excited state respectively

Frequency

Energy levels in a molecule E=2

'=2

Erotational < Evibrational < Eelectronic

=1
'=0
E=1

Electronic transitions
(UV-Vis radiation required)

"=2
"=1

Vibrational transitions
(IR radiation required)

Rotational transitions
(microwave radiation required)

E=0

=0

J=1
J=0

Interaction of EMR with matter

1. Electronic Transitions: movement of electron
from ground to excited state
At room temperature the molecules are in the
lowest energy levels E0.
When the molecules absorb UV-visible light
from EMR, one of the outermost bond / lone
pair electron is promoted to higher energy
state such as E1, E2, En, etc is called as
electronic transition and the difference is as:
E = h = En - E0 where (n = 1, 2, 3, etc)
E = 35 to 71 kcal/mole (UV-Vis region)

Interaction of EMR with matter

2. Vibrational Energy Levels: Energy required to
vibrate a bond
These required less energy (Infra red region)
than electronic energy levels.

The spacing between energy levels are

relatively small i.e. 0.01 to 10 kcal/mole.
e.g. when IR radiation is absorbed, molecules
are excited from one vibrational level to
another or it vibrates with higher amplitude.

Interaction of EMR with matter

3. Rotational Energy Levels: Energy required for
the rotation of bond
The spacing between energy levels are even
smaller than vibrational energy levels.
Required energy of microwave region for
rotational transitions
Erotational < Evibrational < Eelectronic

Atomic Absorption Spectroscopy (AAS) and Flame

Emission Spectroscopy (FES): Atomic spectroscopy

The solution sample is aspirated into a flame that is hot

enough to break the molecules into their atomic states.
The concentration of the analyte in the flame may be
measured by either its absorption or emission of the
radiation.

Origin of Absorption and Emission

spectra

Flame test to identify the metals:

Qualitative analysis

In FES the flame also provides the excitation energy along

with atomization, but in AAS it provides only for the
atomization .

Relationship between
concentration and
absorbance:
Beer-Lamberts Law

Lamberts Law

When a monochromatic radiation is passed through

a solution, the decrease in the intensity of radiation
with thickness of the solution is directly
proportional to the intensity of the incident light.
Let I0 and I be the intensity of incident and
transmitted radiation, respectively and x be the
thickness of the solution.

I0

cuvette

dI

I
dx

Lamberts Law
dI

I
dx
So,

dI

KI
dx

Integrate equation between the limits

I = I0 at x = 0 and
I = I at x=x,
We get,

I
ln
Kx
I0

(i)

Beers Law
When a monochromatic radiation is passed
through a solution, the decrease in the
intensity of radiation is directly proportional
to the concentration of the solution.
I0

Con = C

Let C be the concentration of the solution.

Then

Beers Law
dI

I
dC
So,

dI

KI
dC

Integrate equation between limits

I = I0 and I
C = 0 and C,
We get,

I
ln
KC
I0

(ii)

BeerLamberts Law: Thickness as

well as conc. are variable
Combining equation (i) and (ii)

I
ln
KCl
I0

I0
2.303 log K .C.l
I
I0
K
log

C.l
I
2.303
A E.C.l
Where, log I0/I = A
K/2.303 = E or

Beer-Lamberts Law

Absorbance
Molar extinction coefficient

Beer-Lamberts Law
A E.C.l

I
T
I0

OR

I0

I0
log T log
A
I

T will be < 1, or < 100 (%T)

Absorbance is also known as optical density (OD)

Deviation from Lambert-Beer Law

Applicable only for dilute solutions
Monochromatic radiation must be used
Absorbing molecules must not undergo any
chemical change in solution
Molecules must not undergo
dissociation/association in solution

AAS and FES

Flame Photometer: Quantitative

analysis (emission/absorption)

FES: Instrumentation
Flame
Photomultiplier
(detector)

sample
slit

O2

prism

Monochromator

Fuel

amplifier
Recorder

Flame Structure

Secondary
combustion zone

Interzonal region
Primary
combustion zone
Fuel- oxidant mixture

Flame Photometry
Events occur in FES
molecules ions

Solution of metal
salt (NaCl)

Ground state atoms

Na

Solvent evaporation

Emission and
return to G

Solid aerosol of
metal salt (NaCl)

Excited atoms
Na*

Volatilization or decomposition

Gaseous metal
salt (NaCl)

Atomization

Excitation

Free atoms
Na

Flame Photometry
Functions of Flame
1. To convert the constituents of liquid sample into the vapor state.
2. To decompose the constituents into atoms or simple molecules:
M+ + e- (from flame) > M + hn
3. To electronically excite a fraction of the resulting atomic or
molecular species
M > M*
The flame is composed of :
a fuel gas and oxidant gas

Flame Photometry
Effect of the solvent used to dissolve the sample; if the solvent is
water the process is slow and if it is organic solvent the process
is fast and emission intensity is increased.
It is therefore very important that calibration curves be
prepared using the same solvent.
The stochiometric ratio of fuel to oxidant in the flame must be
used, in which both fuel to oxidant are totally consumed.

Principle:
Wavelength of a Radiant energy -

E2E1 DE = hn = hc/l
l= hc/ E2E1
l of the emitted radiation is characteristic of atoms of a
particular element from which it is emitted.
For example,
Na -------> Na* (energy from flame)
Na* -------> Na + hn (at 590 nm)

Sodium vapor exhibits sharp absorption peaks at

590.0 nm due to excitation of 3s electron to 3p states.

The fraction of free atom that are thermally excited is

governed by Boltzmann distribution law-

N*/N0 = A e-DE/kT
N* = no of atoms in excited state;
N0 = of atoms in ground state;
A =(g*/g0) = relative degeneracy
E = energy difference between ground and excited state;
k = Boltzmann distribution constant;
T = temperature of system

Flame Photometry
Factors affecting intensity of flame emission :
1- The concentration of the analyte in solution
2- The rate at which excited atoms are formed in the flame.
3- The rate at which the sample is introduced into the flame.
4- Temperature of the flame.
5- Composition of the flame.
6- The ratio of fuel to oxidant in the flame.
7- Solvent used to dissolve the sample.

Flame Photometry
Increase in flame temperature causes an increase in
emission intensity.
This is controlled by composition of the flame.
High temperature flames should not be used for elements
that ionized easily e.g. Na, K, Li or Ce.

Flame Temperature and Fuel gas composition

Fuel

Oxidant

Flame temperature
(0C)

Propane

Air

1900 oC

Propane

Oxygen

2800 oC

Hydrogen

Air

2100 oC

Hydrogen

Oxygen

2800 oC

Acetylene

Air

2200 0C

Acetylene

Oxygen

3000 0C

Types of Burners
Mecker Burner-

Natural gas and oxygen are used as fuel and oxidant.

Produces relatively low temp, and low excitation energies.
Used for alkali metals only.

Flame Photometry
2. Total consumption burner

Fuel

Advantages
1. Simple to manufacture
2. Allows a total representative sample
to reach the flame
3. Free from explosion hazards

Disadvantages
1.
2.

Aspiration rate varies with different solvents

Suitable only for AES

Sample

Used mainly for FES (short bath)

Oxidant

3 concentric tubes, the sample, fuel and

oxidant only mix at the tip of burner

Oxidant

Fuel

45

Flame Photometry
Chemical interferences: can often be overcome by simple
dilution with a suitable reagent solution e.g. serum is diluted by
EDTA solution for the determination of calcium in order to
prevent interference from phosphate.

Deviations from
linearity may occur

Absorbance,
Intensity

3. Standard curves

Concentration, c

Applications of FES:
1. Detection of elements from group I and II .

2. In clinical field, Na+ and K+ in body fluids, muscles and

heart can be determined by diluting the blood serum
3. Soft drinks, fruit juices and alcoholic beverages can

also be analyzed by using flame photometry.

4. In agriculture, the fertilizer requirement of the soil is
analyzed by flame test analysis of the soil.

5. Natural and Industrial waste water analysis

Advantages of FES:
1. Simple and inexpensive
2. Alkali and alkaline earth metal analysis is performed
with reliability
3. Fast, selective and sensitive to even parts per million
(ppm) to parts per billion (ppb) range.

Disadvantages of FES:
1. The concentration of the metal ion in the solution
can not be measured directly.
2. A set of standard solutions is required for
determining the concentration of unkown solution
3. It is difficult to obtain the accurate results of ions
with higher concentration.
4. The information about the molecular structure of the
compound present in the sample solution can not
be determined.
5. Non radiating elements (C, H, halides) cannot be
detected.

Sodium atom absorb at a wavelength of 589 nm. What is

the energy difference between (in J) between the ground
and excited state?
At a temperature of 2500 K, what is the ratio of excited
state to ground state population (N*/N0) if the relative
degeneracy (g*/g0) is 2 ?
E = hc/ = 3.37 x 10-19 J
N*/N0 = A e-DE/kT = 1.15 x 10-4
A = g*/g0