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INTRODUCTION TO
SPECTROSCOPY METHOD OF
ANALYSIS (Chapter 1)

CHM 260
Syllabus content
1. An Introduction to Spectroscopic Methods of Analysis

 1.1 Properties of Electromagnetic Radiation


 1.2 The Electromagnetic Spectrum
 1.3 Spectroscopic Measurements
 1.3.1 Radiation Absorption
Transmittance
Absorbance
 1.3.2 Beer’s Law
Theory and Application
Limitations to the Applicability of Beer’s Law
 1.3.3 Absorption Spectra Atomic Absorption Molecular Absorption
 1.3.4 Emission of Electromagnetic Radiation
Line spectrum
Band spectrum
Continuum spectrum

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This is a high resolution spectrum of the Sun
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Lesson Outcomes
Identify & explain the different types of
electromagnetic radiation
Explain the interaction of electromagnetic
radiation with matter

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WHAT IS SPECTROSCOPY?

The study of the interaction between


ELECTROMAGNETIC (EM) RADIATION
and MATTER

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SPECTROSCOPIC ANALYSIS

covers

ATOMIC MOLECULAR
SPECTROSCOPY SPECTROSCOPY
(atomic absorption) (molecular absorption)

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1.1 PROPERTIES OF
ELECTROMAGNETIC RADIATION

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What is Electromagnetic Radiation?

is a form of energy that has both Wave and


Particle properties.
For example: Ultraviolet, visible, infrared,
microwave, radio wave.

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i. Wave Properties
EM radiation is conveniently modeled as waves
consisting of perpendicularly oscillating electric
and magnetic fields, as shown below.

At 90° to the direction of propagation is an


oscillation in the ELECTRIC FIELD.

At 90° to the direction of propagation and 90°


from the electric field oscillation (orthagonal) is
the MAGNETIC FIELD oscillation.

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Wave nature of a beam of single-frequency electromagnetic radiation

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Wave Parameters (Definitions)
 Period (p)
the time required for one cycle to pass a fixed point in
space.
 Frequency (ν @ f )
the number of cycles which pass a fixed point in space per
second. Unit in Hz or s-1
 Amplitude (A)
The maximum length of the electric vector in the wave
(Maximum height of a wave).
 Wavelength (λ)
The distance between two identical adjacent points in a
wave (usually maxima or minima).
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 Wavenumber (ṽ)
The number of waves per cm in units of cm-1
 Radiant Power ( P )
The amount of energy reaching a given area per second.
Unit in watts (W)
 Intensity ( I )
The radiant power per unit solid angle.

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Speed of light = Frequency x Wavelength
c = ν
 c is the speed of light
 ν is the frequency of the waves
  is the wavelength of the waves

c = 3.00 x 108 m/s = 3.00 x 1010 cm/s

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800 nm

Infrared radiation Ultraviolet radiation


V = 3.75 x 1014 s-1 V = 7.50 x 1014 s-1

Wavelength is inversely proportional to


frequency 1


The higher the ν, the shorter the λ & vice
versa
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ii. Particle Properties
EMR is viewed as a stream of discrete particles of
energy called photons.
We can relate the energy, E of photon to its
wavelength, frequency and wavenumber by,


hc
E = hν = = hcṽ
h = Planck’s constant 6.63 x 10-34 Js
Therefore wavenumber, ṽ

ṽ = 1/ = ν/c
Unit of wavenumber is cm-1
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Example:
What is the energy of a 500 nm photon?

ν = c/
= (3 x 108 m s-1)/(5.0 x 10-7 m)
= 6 x 1014 s-1 @ Hz

E = hν
= (6.626 x 10-34 J•s)(6 x 1014 s-1)
= 4 x 10-19 J

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1.2 THE ELECTROMAGNETIC
SPECTRUM

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Electromagnetic Spectrum

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Spectrum Region
Region Wavelength
Range
γ-ray <0.01 nm
X-ray 0.01-10 nm
UV 10-380 nm
Visible 380-700 nm
IR 700 nm-1 mm
Microwave 1 mm-1 m
Radio 1 nm-100000 km
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1.3 SPECTROSCOPIC
MEASUREMENTS

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1.3.1 The Absorption Methods
Absorption is the measure of the decrease in radiant
power.
Quantitative absorption methods require 2 power
measurements:
- Po = incident radiant power
- P = transmitted radiant power

P0 P

Absorbing solution
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i. Tansmittance
The fraction of incident radiation transmitted
through the sample medium.

Transmittance, P
T
P
Transmittance is commonly expressed in %.
% Transmittance,
P
%T  100
P
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ii. Absorbance
A measurement of the amount of radiant power
absorbed by the sample defined as the -ve log of
T.

P
A   log 10T  log
P

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Question:
Convert the following absorbance data
into percent transmittance:

i) 0.375 ii) 1.325 iii) 0.012


Ans:
i) 42.2%

ii) 4.73%

iii) 97.3%

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1.3.2 Beer’s Law
Shows linear relationship between
absorbance (A), concentration (c) of the
species measured, sample path length (b) and
the absorptivity (proportionality
constant) (a) of the species,
A  abc
-1
When the c is expressed in mol L and b in cm,
the proportionality constant, called the
molar absorptivity is given by ε
A  bc
* ε has the unit of L mol -1 cm-1
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Applications of Beer’s Law
Determination of unknown concentration by
measuring absorbance.

Example:
b = path length (cm)
A tea solution in a 0.5 cm sample cell gave an absorbance
A = absorbance
reading of 0.64 in blue light (420-440 nm).If the molar
ε = molar absorptivity
absorptivity for the tea is 120 cm-1mol-1L, using the same
light filter, calculate the concentration and the
transmittance of the solution. 1
2

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Answer:
i) c  A  0.64  0.011M
b 120  0.5
ii) T = 10-A = 10-0.64 = 0.23

23% of the power of the incident beam is


transmitted.

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Limitations to The Applicability of Beer’s Law

Deviations are frequently observed from the direct


proportionality between absorbance, A and
concentration, c when pathlength, b is constant.
Deviations may be due to:
i. Fundamental
ii. Instrumental
iii. Chemical deviations

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i. Fundamental Deviations
Real limitation to the law.
At high concentration (> 0.01M) each particle
affects the charge distribution of its neighbours.
Therefore, this interaction alter the ability of
analyte species to absorb a given wavelength of
radiation.
Causing deviation from the linear
relationship between absorbance and
concentration.

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ii. Instrumental Deviations

a. Due to polychromatic radiation:


Beer’s Law strictly applies when measurements
are made with monochromatic source radiation.
In practice, polychromatic sources that have a
continuous distribution of wavelengths are being
used.
Deviations occur if the radiation is
polychromatic since the relationship between A
and c is no longer linear when ε is differ.

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b. Due to the presence of stray radiation:
Due to instrument imperfections.
This stray radiation is the result of scattering
and reflection off the surfaces of gratings, lenses
or mirrors, filters and windows.
The wavelength of stray radiation differs greatly
from the principal radiation & may not have
passed through the sample.

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When measurements are made in the presence
of stray radiation,
logP o  logP s
A' 
P  Ps

Ps – power of non absorbed stray radiation

% stray radiation = Ps  100


Po

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iii. Chemical Deviations
Occur when the analyte undergo dissociation,
association or reaction with the solvent to give
products that absorb differently than the analyte.
Analyte undergoes dissociation as absorbance is
recorded.
Cr2O72- + H2O 2H+ + CrO42-
CrO42-

Cr2O72-
A550 A446

300 400 500 concentration concentration


wavelength 35
How EMR interacts with matter?

Atoms are the basic blocks of matter.


They consist of heavy particles (called protons
and neutrons) in the nucleus, surrounded by
lighter particles called electrons.

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Type of EM Interactions
 The interaction of radiation with matter can cause
redirection of the radiation and/or transitions
between the energy levels of the atoms or molecules.
1. Absorption: EMR energy transferred to absorbing
molecule (transition from low energy to high
energy state).

2. Emission: EMR energy transferred from emitting


molecule to space (transition from high energy to
low energy state).

3. Scattering: Redirection of light with no energy transfer.


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When a species (atoms/molecules) changes its
state, it absorbs or emits an amount of energy
exactly equal to the energy difference between
the states.
When atoms/molecules absorb or emit radiation in
making the transition from one energy state to
a second, the frequency (ʋ) or the wavelength (λ)
of the radiation is related to the energy difference
between the states.
hc
E1  E 0  hv 

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Absorption vs Emission

h

En En

h h

Eo Eo

Absorption Emission
1.3.3 Absorption of Radiation
 An electron will interact with a photon.
 An electron that absorbs a photon will gain
energy.
 An electron that loses energy must emit a
photon.
 For absorption to occur, the energy of the
photon must exactly match the energy level
in the atom (or molecule) it contacts.
Ephoton = Eelectronic transition
 We distinguish two types of absorption
i) Atomic
ii) Molecular
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i. Atomic Absorption
 Electrons bound to atoms
have discrete energies
(i.e. not all energies are
allowed).
 Thus, only photons of certain
energy can interact with the
electrons in a given atom.
 Transitions between
electronic levels of the
electrons produce line
spectra.

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 The energy of photon that can promote electrons
to excite/jump to a higher energy level depends on
the energy difference between the electronic levels.

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 Each atom has a specific set of energy levels, and
thus a unique set of photon wavelengths with
which it can interact.

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Molecular Absorption
The energy, E, associated with the molecular bands:
Etotal = Eelectronic + Evibrational + Erotational

In general, a molecule may absorb energy in 3 ways:


1. By raising an electron (or electrons) to a higher
energy level. (electronic)
2. By increasing the vibration of the constituent nuclei.
(vibrational)
3. By increasing the rotation of the molecule about the
axis. (rotational)
Rotational
absorption

Vibrational
absorption
Energy Level Diagram for Molecular Absorption

Partial energy-level diagrams for a fluorescent organic molecule

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Types of Spectra

Absorption spectrum
 A plot of the absorbance as a function of
wavelength or frequency.

Emission spectrum
 A plot of the relative power of the emitted
radiation as a function of wavelength or
frequency.

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Absorption Spectrum Emmission Spectrum

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Line spectrum: a series of sharp, well-defined
peaks caused by excitation of individual atoms.

Band spectrum: several groups of lines so


closely spaced that they are not completely
resolved.

Continuum spectrum: a beam of light that


contains a broad, smooth distribution of photon
wavelength.

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