What is Spectroscopy?

To study changes in the property of light

when it interacts with the matter.
How do we study changes in the property of light when it interacts
with the matter?

MATTER*

Emission
Spectroscopy

Detector

MATTER Absorption
Spectroscopy

Detector
Light Source

Atoms
Atomic Spectroscopy
Molecules
Molecular Spectroscopy
Electromagnetic Spectrum
Types of molecular spectra

Electronic or UV-Vis. Spectra

(Electronic spectroscopy)

Vibrational spectra or vibrational-

Rotational spectra or IR spectra
(IR/vibrational

spectroscopy)

Rotational Spectra
(Rotational/microwave
ESR spectra (ESR spectroscopy)
spectroscopy)
NMR spectra (NMR
spectroscopy
 Spectroscopy

Atomic Molecular
spectroscopy spectroscopy

Absorption Emission Absorption Emission

Atoms when absorb energy Molecules, when absorb
e le ct ro n ju m p t o h igh e energy transitions takes
re n e r g y l e v e l a n d t h e n j u m p place between molecular
b a c k by emission of energy ener gy levels
e q u a l to t h e e n e r g y different
b e t w e e n t w o e n e r g y levels Molecular spectrum

Atomic absorption Flame emission

U V- visible & IR
Absorption and emission spectra

Excited State

Ground State
Lambert Beer’s Law / Beer’s Law

I0 I

cuvette
x
• When a beam of monochromatic radiation passes through a solution of
an absorbing substance, then, rate of decrease of intensity of radiation
with the thickness of absorbing medium is directly proportional to
intensity of incident radiations and concentration of solution.
(OR)
• The intensity of a beam of monochromatic radiations decreases
exponentially with increase in the thickness and the concentration of the
absorbing solution
 I0 = Ia + It ; Ia = I0 – It
The probability that the photons of a beam of
intensity I will be absorbed by the sample is
directly proportional to the concentration and the
thickness of the absorbing solution.
dl/I = - α c dx
where dI is the change in intensity produced by the absorption of
radiation on passing through a thickness dx of the solution of
concentration c and α is the proportionality constant.
The minus sign is introduced because there is reduction in intensity.

Applying limits I = I0 at X=0 and I = I at X = b to the

above differential gives

Thus, Beer- Lambert law states that intensity (I) of a beam of

monochromatic light decreases exponentially with increase in the
thickness (x) and the concentration c of the absorbing medium.
Beer- Lambert law states that intensity (I) of a beam of monochromatic light
decreases exponentially with increase in the thickness (x) and the concentration
c of the absorbing medium.

Ln (I/I0) = 2.303 Log (I/I0) = - α b c

Ln (I/I0) = Log (I/I0) = - (α / 2.303) b c

Log (I/I0) = - ε b c A=εlc

Log (I0/I) = ε b (If Log (I0/I) = A)
c
A=εbc

ε
Absorption Coefficient or Extinction Coefficient of the absorbing
medium. ( Characteristic of the solute and depends upon the
nature of the solvent / medium , temperature and the wave length
of the light used.)
 Log I/Io = -ecx
Log Io/I =
ecx
A=Log I0/I = ecx

A=abc

Abs

Conc.
Absorbance:
• Logarithmic ratio of the intensity of incident radiation to
the intensity of transmitted radiation

• I0 – Intensity of incident radiation

• I - intensity of transmitted radiation

Transmittance:
• The ratio of the intensity of transmitted radiation
to the intensity of incident radiation
T = I / I0

Relation between Absorbance and Transmittance:

A = Log 1/T
 A=εlc
Molar Absorption Coefficient or Molar Extinction Coefficient
If concentration c is expressed in mol dm-3 and the path length l in cm
then ε = dm3 mol-l cm-l
Transmittance (T) = I/ I0 [ If A = Log (I0/I) ] A = - Log T

T = 10-A 10 – ε l c
=
 Limitations
Beer’s law is valid in the following
conditions
1. Beer’s law is applicable to dilute solutions only

2. Monochromatic radiations

3. Solute must not undergo association,

dissociation, polymerization, hydrolysis in the solvent

MeBI (MeBI)2 (MeBI)3

660nm 610nm 500nm
1x10-5M 1x10-5M-5x 10-3M 5x10-3M – above
 How do we use Beer-Lambert Law ?
1. Numerical
A monochromatic radiation is incident on a solution of 0.05 molar concentration of an absorbing
substance. The intensity of the radiation is reduced to one fourth of the initial value after passing
through 10 cm length of the solution. Calculate the molar extinction coefficient of the substance………..

2. Finding the unknown A=εlc

---

UnKn-2 UnKn # n
How many of you have done Flame Photometry ever
in life?
 Atomic Emission and
Atomic Absorption
Spectroscopy
• In atomic emission and absorption spectroscopic technique sample solution
is aspirated into a flame that is hot enough to break the ions or molecules
into their atomic states.

• The concentration of the analyte in the flame can be measured by either

through absorption or emission of the radiation.

• The absorption mode is known as atomic absorption spectroscopy (AAS)

whereas emission mode as flame emission Spectroscopy (FES) or Atomic
emission spectroscopy.
Upper Diagram shows FES while the lower one shows AAS. In FES the flame provides
energy for atomization and excitation, but in AAS it provides only atomization .
 Flame emission spectroscopy

• Flame emission spectroscopy (flame photometry) is a special area of emission

spectroscopy in which a flame is used to excite the atoms.

• For a few elements, such as the alkali metals Na and K, flame is hot enough
not only to produce ground state atoms, but to raise some of the atoms to an
excited electronic state.

• So Flame emission spectroscopy is used for the detection of alkali metals and
some of the alkaline earth metals.
 Flame emission spectroscopy

Sequence of events in flame

Nebulizatio Desolvatio Volatilizatio

Sample n
n n
solutio
n
Spray Heat Dry aerosol Free
atoms

• Heat
• Atomic absorption and atomic emission techniques involve introduction of
• sample solution into a flame.
• The solution of the metal salt in question is sprayed into the flame.
• Solvent evaporates leaving the finely powdered salt.
• Vaporization of the salt.
• Conversion of ions into free gaseous atoms.
• Valence electron ( ) is raised to a higher energy state.
 Flame emission spectroscopy
Nebulization– Conversion of
sample solution in fine droplets –
aerosol formation which
is aspirated to flame
Desolvation – Removal of solvent leaving dry sample

Sublimation- Transition of salt from solid to gaseous state Atomization – Conversion of

ions in to atoms

Excitation – Valence electrons of atoms get excited to higher energy state

Relaxation – Excited electrons relaxes from higher energy state to ground state
Measurement – Wavelength and intensity of emitted radiations is measured
 Flame emission spectroscopy

Principle
•Absorption of heat energy by ground state
atom present in the flame
results in the excitation of valence electron of atoms.
•This valence electron comes back to ground state with the emission
of photon.
•Wave length intensity of emitted photon helps in and
and
qualitative
quantitative analysis of the sample.
The energy emitted when this electron drops down into a vacant lower level
is given off as radiant energy of a wavelength determined by the Planck-
Einstein relationship:
E2-E1 = DE = hn = hc/l l = hc/ E2-E1

l of the emitted radiation is characteristic of atoms of a particular element

from which it is emitted. It tells us about the elements which are present in
the flame
For example,
Na -------> Na* (energy from flame) Na* -------> Na + hn (at 589 nm)
How do we determine the concentration in FES?
Boltzmann Distribution :
N* / N0 = A e - ∆E/k T
N* : Number of atoms in excited state( Intensity)
N0 : Number of atoms in ground state( Concentration ? )
∆E : E1-E0 = Difference between two energy
states k : Boltzmann Contant
T : Temprature of flame
A : Constant for particular atom

Thus, TEMPRATURE plays an important part

in FES.
High Temprature = High Excitation = High
Ratio Intensity( Caution )
Intensity of radiant energy emitted when the atoms return to the
ground state is proportional to the concentration and is the basis of
“TEMPRATURE OF THE FLAME” depends on a)
flame emission spectroscopy.
Fuel & Oxidant
 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

 Flame Photometry
Limitations
(i)Does not Give Information about the Molecular Form of the Metal :
due to atomization of all the forms of metal.
(ii)FES is not applicable to all the Metal Atoms : more applicable due to
alkali & alkaline earth metals.
(iii)Sometimes Sample Preparation is a Lengthy Process: because only
liquid samples have to be introduced into the flame.
(iv) Cannot be used to determine inert gasses?

Any Questions?

Flame Photometry
ICP-AES will be introduced here

Slides will be provided soon………….

ATOMIC ABSORPTION
SPECTROSCOPY
 Atomic Absorption Spectroscopy

• Most powerful technique for the determination

of trace metals in solution
• 70-80 elements can be detected
• Determination can be made in the presence of many
other elements
• No specific sample preparation is required
• Wide application
 Atomic Absorption Spectroscopy
Principle
A sample solution containing known metal atoms, when
irradiated introduced
with light of their own specific
into the flame, is
wavelength will absorb light proportional to the density of atoms in
the flame.

Flame

Specific Wavelength
(Hollow cathode lamp)

Thus, AAS measures Amount of Light Absorbed.

Atomic Absorption Spectroscopy
Hollow Cathode Lamp (HCL)

?
 Principle
Absorption of energy by ground state atoms
present in the gaseous state in flame

N*/N0 = A e-DE / kT

Receive same l which they emit in the excited state

Absorption a density of atoms in flame

Amount of light absorbed a concentration of
metallic species
 Differences between AAS and FES

FES AAS
Excitation of atoms – Signal is obtained in presence
emission of photon and and absence of element and
return to ground state. decrease in intensity of signal
Emission intensity is obtained.
measured Absorption is measured
Emission intensity a No. of Absorption intensity a No. of
atoms in excited state atoms in ground state

Emission intensity depends Absorption intensity does not

on flame temperature depend on flame temperature

Beer’s law is not obeyed Beer’s law is obeyed over a

over wide range of wide range
concentration
 Advantages of AAS
• AAS - specific – Atom of a particular element can absorb
radiation of their own wavelength – No spectral interference
• Much larger No. of atoms contribute in AAS signal so results
are more authentic
• Variation in flame temperature has less effect
• Absorption intensity does not depends on flame temperature
• 70-80 elements can detected
 Disadvantages of AAS

• Different (HCL) lamp for each element is required

• Elements which for stable oxides eg. Al, Ti, W, Mo, do not
give very good results