SKA6014

ADVANCED ANALYTICAL CHEMISTRY

TOPIC 2
Introduction to Spectroscopy

Azlan Kamari, PhD
Department of Chemistry
Faculty of Science and Mathematics
Universiti Pendidikan Sultan Idris
What is Spectroscopy?
The study of the interaction between radiation
and matter

Analytical spectroscopy, as defined in this
class, covers applications of spectroscopy to
chemical analysis
History of Analytical Spectroscopy
1666: Isaac Newton (England) shows that white light
can be dispersed into constituent colors, and coins the
term spectrum
Newton also produced the first spectroscope based
on lenses, a prism, and a screen
1800: W. Herschel and J. W. Ritter show that infrared
(IR) and ultraviolet (UV) light are part of the spectrum
1814: Joseph Fraunhofer noticed that the suns
spectrum contains a number of dark lines, developed
the diffraction grating
1859: G. Kirchoff obtains spectra of the elements,
explains the suns spectrum
The Visible Spectrum of the Sun
(Black lines are absorption by elements in the cooler outer region of the star)
Figure from National Optical Astronomy Observatory/Association of Universities for Research in Astronomy/National Science Foundation, http://www.noao.edu/image_gallery/html/im0600.html
History of Analytical Spectroscopy
1870: J. C. Maxwell formalizes and combines
the laws of electricity and magnetism
1900 to present: More than 25 Nobel prizes
awarded to spectroscopists, including:
1902: H. A. Lorentz and P. Zeeman
1919: J. Stark
1933: P. A. M. Dirac and E. Schrodinger
1945: W. Pauli
.
1999: A. Zewail
Introduction to Spectroscopy
Figures from NASA (www.nasa.gov)
The electromagnetic
spectrum
Each color you see is a
specific (narrow) range of
frequencies in this
spectrum
The Electromagnetic Spectrum
Modern life (not just analytical spectroscopy) revolves
around the EM spectrum!
Properties of Electromagnetic Radiation
Wave/particle duality
Perpendicular E and B
components
E = electric field
B = magnetic field
Wave properties:
Wavelength (frequency)
Amplitude
Phase
1 2 3 4 5
-1
-0.5
0.5
1
1 2 3 4 5
-1
-0.5
0.5
1
Long wavelength
(low frequency)
Short wavelength
(high frequency)
c = the speed of light (~3.00 x 10
8
m/s)
v = the frequency in cycles/second (Hz)
= the wavelength in meters/cycle

v
c
=
Note this figure
shows polarized
radiation!
Interference of Radiation
Monochromatic: radiation containing a single frequency
Polychromatic: radiation containing multiple frequencies
Constructive interference:
when two waves reinforce
each other



Destructive interference: when
two waves cancel each other
The Interaction of Radiation and Matter
Electromagnetic radiation travels fastest in a vacuum

When not travelling in a vacuum, radiation and matter
can interact in a number of ways

Some key processes (for spectroscopy):
Diffraction
Refraction
Scattering
Polarization
Absorption
Transmission of Radiation
The velocity at which radiation travels (or propagates)
through a medium is dependent on the medium itself

When radiation travels through a medium and does not
undergo a frequency change, it cannot be undergoing a
permanent energy transfer

However, radiation can still interact with the medium
Radiation, an EM field, polarizes the electron clouds of
atoms in the medium
Polarization is a temporary deformation of the electron
clouds
Transmission and Refraction
The refractive index (n
i
) of a medium is given by:
i
i
c
n
v
=
c = the speed of light (~3.00 x 10
8
m/s)
v
i
= the velocity of the radiation in the medium in m/s
n
i
= the refractive index at the frequency i
Refractive index measures the degree of interaction
between the radiation and the medium
Liquids: n
i
~ 1.3 to 1.8
Solids: n
i
~ 1.3 to 2.5
Refractive index can be used to identify pure liquid
substances
Refraction
When radiation passes through an interface between two
media with different refractive indices, it can abruptly
change direction
Snells law:
1
2
2
1
2
1
sin
sin
v
v
n
n
= =
u
u
v
1
= the velocity of the radiation in medium 1 in m/s
n
1
= the refractive index in medium 1
Snells law is a consequence
of the change in velocity in
the media
Reflection always occurs at
an interface. Its extent
depends on the refractive
indices of the media
u
1

u
2

Medium 1
Medium 2
Diffraction
Fraunhofer diffraction:
Also known as far-field diffraction, parallel beam
diffraction
Important in optical microscopy






Fresnel diffraction
Also known as near-field diffraction

Diffraction
Diffraction gratings:
Widely used in
spectroscopic instruments
to separate frequencies
(can be made precisely)

u sin 2d n =
http://www.astro.virginia.edu/research/observatories/40inch/fobos/images/grating.jpg
Bragg diffraction multiple slit Fraunhofer diffraction:
Important for instrument design, crystallography
Scattering
Rayleigh scattering (an elastic process):
Scattering of small amounts of radiation by molecules
and atoms (whose size is near to the wavelength of
the radiation)



Mie scattering: applies to large particles, involves
scattering in different directions.
Practical use in particle size analysis

4
1

scattering
Polarization
Polarization of EM radiation a simple classical picture:
Coherent Radiation
Coherent radiation fulfils two
conditions: (1) it has the
same frequency or set of
frequencies, and (2) it has a
well-defined and constant
phase relationship
Coherent radiation is cross-
correlated in that the
properties of one beam can be
used to predict those of the
other beam

Examples of coherent
radiation:
Lasers
Microwave sources (masers)
Coherent radiation: different
frequencies (colors) with a defined
phase relationship interfere to produce
a pulse

Diagram from wikipedia.org (public domain)
Incoherent Radiation
Produced by random
emission, e.g. individual
atoms in a large sample
emitting photons
Actually is coherent, but just
to a tiny (undetectable)
extent
Also known as continuous
radiation
Examples of incoherent
radiation:
Incandescent light bulbs
Filament sources
Deuterium lamps
Incoherent radiation: different
frequencies (colors) combined to
produce continuous radiation with
varying phase, frequency and
amplitude

Diagram from wikipedia.org (public domain)
More Properties of Electromagnetic Radiation
Wave and particle behaviour: photons behave as
both waves and particles
Quantum mechanics developed around the concept of
the photon, the elementary unit of radiation
Plancks law:


E is the energy of the photon in joules
h is Planck's constant (6.624 x 10
-34
joule seconds)
v is the frequency of the radiation
h E v =
Absorption and Emission
Absorption is a process accompanied by an energy
change
involves energy transfer of EM radiation to a
substance, usually at specific frequencies
corresponding to natural atomic or molecular energies

Emission occurs when matter releases energy in the form
of radiation (photons)
AE = hv
Higher energy
Lower energy
Absorption Emission
Energy Levels
Several types of quantum-mechanical energy
levels occur in nature:
Electronic
Rotational
Vibrational (including phonons and heat)
Nuclear

For each of these, a discrete quantum state and
energy-driven transitions between these states can be
studied (as opposed to a continuous range of energies)
The Uncertainty of Measurements
Because the lifetimes of quantum states can
persist for short periods, it can be difficult to
measure their energies accurately

This is usually stated in the form of an energy-
time uncertainty:
t E > A A
The Uncertainty Principle
The uncertainty principle: it is not possible to know both
the location and the momentum of a particle exactly a
fundamental limit on all measurements

In Heisenbergs terms, the act of measuring a particles
position affects its momentum, and vice versa
In equation form:


In other words, if you know the position of a particle to within Ax,
then you can specify its momentum along x to Ap
x

As the uncertainty in x increases (Ax l), that of p
x
decreases (Ax
), and vice versa
p x
x

2
1
> A A
Spectra and Spectrometers
Spectra are usually plotted as frequency vs. amplitude
Instead of energy, wavelength or energy (related
properties) can also be used
The choice of x- and y-axes is often dependent on the
particular technique, its history, etc
Key parameter is frequency/energy/wavelength
resolution

Spectrometers: instruments that measure the interaction
of radiation with matter, so the properties of such
interactions can be studied

Spectroscopy in Analytical Chemistry
Widely used approach for characterizing systems ranging
from chemical physics to biology, from individual atoms to
the largest molecules

Some of the most common techniques are:
UV-Visible spectroscopy
IR spectroscopy
Raman spectroscopy
X-ray spectroscopy
NMR spectroscopy
EPR spectroscopy