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INTRODUCTION TO
SPECTROSCOPY METHOD OF
ANALYSIS (Chapter 1)
CHM 260
Syllabus content
1. An Introduction to Spectroscopic Methods of Analysis
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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?
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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?
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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.
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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
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800 nm
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:
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
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Limitations to The Applicability of Beer’s Law
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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
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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
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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
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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).
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
Vibrational
absorption
Energy Level Diagram for Molecular Absorption
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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.
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